JPWO2016031257A1 - Polyamide, method for producing polyamide, polyamide composition, molded product of polyamide composition, and method for producing the same - Google Patents

Abstract

A polyamide composition molded article having excellent hot strength and hot stiffness is provided. A polyamide composition molded article comprising a polyamide obtained by polymerizing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine. The trans isomer ratio of the 1,4-cyclohexanedicarboxylic acid monomer unit is 71 to 100 mol%. [Selection figure] None

Description

  The present invention relates to polyamide, a method for producing a polyamide, a polyamide composition, a molded article of a polyamide composition, and a method for producing the molded article.

  Polyamides represented by polyamide 6 (hereinafter also referred to as “PA6”) and polyamide 66 (hereinafter also referred to as “PA66”) and the like are excellent in molding processability, mechanical properties, and chemical resistance. It is widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily necessities, and household goods.

In recent years, as an approach to the environment, for example, in the automobile industry, there is a demand for weight reduction of a vehicle body using a metal substitute material in order to reduce exhaust gas. In order to meet this requirement, polyamide materials are often used as exterior materials and interior materials, and the level of required properties such as heat resistance, strength and appearance of the polyamide materials are further improved. In particular, since the temperature in the engine room is on the rise, there is an increasing demand for higher heat resistance for polyamide materials.
In addition, in the electrical and electronic industries such as home appliances, a polyamide material having high heat resistance that can withstand the rise in melting point of solder is required to cope with lead-free surface mount (SMT) solder.

  However, conventional polyamides such as PA6 and PA66 have a low melting point, and further improvement is required in terms of heat resistance.

  Accordingly, in order to solve the problems of conventional polyamides such as PA6 and PA66, high melting point polyamides have been proposed. For example, a polyamide obtained by polymerizing terephthalic acid and hexamethylenediamine (hereinafter also referred to as PA6T) is proposed. Are known. Although PA6T has the characteristics of low water absorption, high heat resistance, and high chemical resistance, it is a high melting point polyamide having a melting point of about 370 ° C. It is difficult to obtain a molded product having sufficient characteristics due to severe thermal decomposition of the product.

  In order to solve the problems related to the thermal decomposition of PA6T, PA6T is composed of aliphatic polyamide such as polyamide 6 and polyamide 66 (hereinafter also referred to as PA6 and PA66, respectively), amorphous fragrance comprising isophthalic acid and hexamethylenediamine. A high melting point semi-aromatic polyamide (hereinafter also referred to as PA6T copolymer), which has been copolymerized with an aromatic polyamide (hereinafter also referred to as PA6I), etc. and has a melting point lowered to about 220 to 340 ° C. has been proposed. .

  As such a PA6T copolymer, Patent Document 1 discloses an aromatic polyamide (hereinafter referred to as a mixture of hexamethylenediamine and 2-methylpentamethylenediamine), which is composed of an aromatic dicarboxylic acid and an aliphatic diamine. , PA6T / 2MPDT). Although PA6T / 2MPDT can partially improve the problems of the conventional PA6T copolymer, the improvement level in terms of fluidity, moldability, toughness, molded product surface appearance and light resistance is insufficient. .

  As a polyamide having good heat resistance and moldability, a high-melting point aliphatic polyamide (hereinafter also referred to as PA46) composed of adipic acid and tetramethylenediamine is known, but PA46 has a high water absorption rate, and also absorbs water. There is a problem that the dimensional change and the deterioration of the mechanical properties due to the above are remarkably large, and the demand may not be satisfied in terms of the dimensional change required for automobile applications.

  As an alicyclic polyamide composed of an alicyclic dicarboxylic acid and an aliphatic diamine, for example, Patent Documents 2 and 3 include an alicyclic polyamide composed of 1,4-cyclohexanedicarboxylic acid and hexamethylene diamine (hereinafter referred to as PA6C). And semi-alicyclic polyamides (hereinafter also referred to as PA6C copolymers) with other polyamides. However, PA6C and PA6C copolymers disclosed in Patent Documents 2 and 3 also have problems such as high water absorption and insufficient fluidity.

  In Patent Document 4, a polyamide composed of a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine has light resistance, toughness, moldability, lightness, In addition, the polyamide is disclosed to be excellent in heat resistance and the like, but this polyamide is also insufficiently improved in terms of toughness, strength and fluidity.

  Patent Document 5 discloses a dicarboxylic acid component containing 10 to 80 mol% of 1,4-cyclohexanedicarboxylic acid having a trans ratio / cis isomer in a molar ratio of 50/50 to 97/3 in all carboxylic acid components; A polyamide obtained by thermal polycondensation with an aliphatic diamine component is described, and a polyamide having a ratio of a trans isomer / cis isomer of a raw material monomer within a predetermined range is excellent in toughness and chemical resistance and moldability It is described that it is excellent.

  Patent Document 6 describes a polyamide obtained by polymerizing a dicarboxylic acid containing an alicyclic dicarboxylic acid and a diamine containing a diamine having a substituent branched from the main chain. Dicarboxylic acid is isomerized at a high temperature and has a fixed ratio, and the cis isomer has a higher water solubility in the equivalent salt with diamine than the trans isomer. It is described that it is preferable that there are many cis-isomers, and that the trans isomer ratio of the entire alicyclic dicarboxylic acid in the polyamide is preferably 50 to 85 mol%.

  Furthermore, Patent Document 7 describes a copolymerized polyamide using a dicarboxylic acid containing an alicyclic dicarboxylic acid and a diamine having 8 or more carbon atoms as raw materials. Similarly, a cis isomer is used as a raw material monomer. It is described that a large amount is preferable, and that the trans isomer ratio in the portion derived from the alicyclic dicarboxylic acid of the copolymerized polyamide is preferably 65 to 80 mol%.

  Further, Patent Document 8 discloses a polyamide resin (hereinafter referred to as “dicarboxylic acid”) containing a terephthalic acid unit and a diamine containing a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit. , "PA9T"), and a polyamide composition comprising titanium oxide, magnesium hydroxide, and a specific reinforcing agent is disclosed, and it is disclosed that this polyamide composition is excellent in heat resistance. Has been.

  Furthermore, Patent Document 9 contains a semi-alicyclic polyamide blended with 70% or more of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit, titanium oxide, and an inorganic filler, and their mass ratio. A polyamide composition having a predetermined value is disclosed, and it is disclosed that this polyamide composition is excellent in reflow resistance, heat resistance and the like.

  However, the conventional polyamides or polyamide compositions disclosed in the above-mentioned patent documents are required to be further improved in order to obtain higher level characteristics in heat discoloration resistance, extrusion processability and molding process stability.

JP-T 6-503590 Japanese National Patent Publication No. 11-512476 Special table 2001-514695 gazette Japanese Patent Laid-Open No. 9-12868 International Publication No. 2002/048239 JP 2010-1111843 A International Publication No. 2012/093722 JP 2006-257314 A JP 2011-219697 A

  In the polyamide described in Patent Documents 6 and 7, in addition to the ratio of the trans isomer / cis isomer of the raw material monomer, the trans isomer ratio of the entire alicyclic dicarboxylic acid in the polyamide is within a predetermined range, In addition to the features of high melting point, toughness, and rigidity, it simultaneously achieves high-temperature rigidity due to high glass transition temperature, fluidity, which is usually opposite to heat resistance, and high crystallinity and low water absorption. It is described that it is possible.

  However, even if the ratio of the trans isomer / cis isomer of the raw material monomer is adjusted or the ratio of the trans isomer of the polyamide, which is the raw material of the molded product, is adjusted, the mechanical properties of the molded product are improved more than expected. It turned out not to. As a result of extensive studies by the present inventors, it has been found that the cause is that the trans isomer ratio of polyamide is not maintained in the molded product, and the present invention has been achieved.

  The present invention has been made in view of the above circumstances, and provides a polyamide composition molded article excellent in hot strength and hot rigidity, a method for producing the molded article, and such a polyamide composition molded article. It is an object of the present invention to provide a possible polyamide, a method for producing the polyamide, and a polyamide composition containing the polyamide.

The polyamide composition molded article of the present invention is
A dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, a diamine unit containing at least an aliphatic diamine, and
A polyamide composition molded article containing a polyamide comprising
The trans isomer ratio of the 1,4-cyclohexanedicarboxylic acid monomer unit in the molded product is 71 to 100 mol%.

  In the present invention and the present specification, the trans isomer ratio mol% may be described as a trans / cis ratio (molar ratio) or a trans / cis isomer ratio. From the description of the cis isomer ratio, the trans isomer ratio mol% can be uniquely derived. When the total of the trans isomer ratio and the cis isomer ratio is 100, when expressed as a trans / cis ratio (molar ratio), one ratio indicates one isomer ratio (mol%). For example, when the trans / cis ratio (molar ratio) is 71/29, the trans isomer ratio is 71 mol%.

  The content of 1,4-cyclohexanedicarboxylic acid is preferably at least 50 mol% in the dicarboxylic acid unit.

Moreover, the polyamide composition molded article of the present invention is obtained when the temperature is lowered at 20 ° C./min and the heat of fusion ΔHm obtained when the temperature is raised at 20 ° C./min in differential scanning calorimetry according to JIS-K7121. The ratio to the crystallization enthalpy ΔHc obtained is
ΔHm / ΔHc> 1.0
It is preferable that ΔHm / ΔHc ≧ 1.5.
It is preferable that

  Note that there are two measurement methods for differential scanning calorimetry according to JIS-K7121, input compensation DSC and thermal flow rate DSC. In the present invention, differential scanning calorimetry is measured by input compensation DSC.

  Further, the “trans isomer ratio” in the polyamide of the present invention is the sum of the respective trans isomer ratios of a plurality of types when (a) the dicarboxylic acid monomer unit includes a plurality of types of geometric isomers. means.

  The polyamide composition molded article of the present invention preferably has a melting peak temperature of 300 ° C. or higher in differential scanning calorimetry.

The polyamide composition molded article of the present invention preferably has a heat of fusion ΔHm of 40 J / g or more.
The trans isomer ratio mol% is more preferably 80-100.

  In the polyamide composition molded article of the present invention, the aliphatic diamine unit is preferably a saturated aliphatic diamine having 4 to 12 carbon atoms, and more preferably a saturated aliphatic diamine having 6 to 10 carbon atoms.

  The method for producing a polyamide composition molded article of the present invention comprises molding a polyamide composition containing a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine. The molded polyamide composition object is heat-treated at 200 ° C. or higher to produce a molded polyamide composition product.

  Further, as a result of intensive studies to solve the above-mentioned problems, the present inventors have further determined a polyamide having a specific trans isomer ratio and crystallinity ΔHm1 / ΔHc controlled, a polyamide composition thereof, and a polyamide composition molding. It was found that the product can solve the above problems.

That is, the first polyamide of the present invention is
(A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine;
A polyamide containing
In differential scanning calorimetry according to JIS-K7121, ΔHm1 / which is the ratio of the heat of fusion ΔHm1 obtained when the temperature is raised at 20 ° C./min and the crystallization enthalpy ΔHc obtained when the temperature is lowered at 20 ° C./min. ΔHc is
1.0 <ΔHm1 / ΔHc ≦ 2.2
And
The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is
71 <trans isomer ratio ≦ 75
It is.

  In the first polyamide of the present invention, the content of 1,4-cyclohexanedicarboxylic acid is preferably at least 50 mol% in the dicarboxylic acid unit.

  In the first polyamide of the present invention, all the dicarboxylic acid units are preferably 1,4-cyclohexanedicarboxylic acid.

  In the first polyamide of the present invention, the aliphatic diamine preferably has 6 to 12 carbon atoms.

  In the first polyamide of the present invention, the aliphatic diamine is hexamethylene diamine, 2-methyl-pentamethylene diamine, 2-methyl-1,8-octane diamine, nonamethylene diamine, decamethylene diamine, or dodecamethylene diamine. Preferably there is.

  In the first polyamide of the present invention, the aliphatic diamine is particularly preferably 2-methyl-pentamethylenediamine.

The first polyamide of the present invention is
(A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine;
A polyamide containing
The aliphatic diamine comprises a branched aliphatic diamine;
The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is
71 <trans isomer ratio ≦ 100
It may be.

  In the first polyamide of the present invention, the proportion of the branched aliphatic diamine in the (b) diamine unit is preferably 10 to 100 mol%.

In the first polyamide of the present invention, ΔHm1 / ΔHc is
1.0 <ΔHm1 / ΔHc ≦ 1.4
It is preferable that

Furthermore, when ΔHm1 / ΔHc is y and the trans isomer ratio is x,
y ≧ 0.04x−1.8
It is preferable that

In addition, the first polyamide of the present invention has a ratio [NH ₂ ] / ([NH ₂ ] + [COOH] which is a ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]). ])
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5
It is preferable that

In the first polyamide of the present invention, the total amount of active ends ([NH ₂ ] + [COOH]) μeq / g is
20 <[NH ₂ ] + [COOH] <60
It is preferable that

  In the first polyamide of the present invention, the sulfuric acid relative viscosity ηr is preferably 1.8 <ηr.

In the first polyamide of the present invention, the weight average molecular weight Mw / number average molecular weight Mn as the molecular weight distribution is:
Mw / Mn <3.5
It is preferable that

  In the first polyamide of the present invention, Tm1-Tc, which is the difference between the melting peak temperature Tm1 of the polyamide and the crystallization peak temperature Tc of the polyamide, is preferably 40 ° C <Tm1-Tc <90 ° C.

  The first polyamide composition of the present invention contains the first polyamide of the present invention and at least one selected from an inorganic filler, a nucleating agent, a heat stabilizer and a light stabilizer.

  The first polyamide composition of the present invention may further contain titanium oxide.

  The polyamide composition molded article of the present invention may be formed by molding the first polyamide composition of the present invention.

The method for producing the first polyamide of the present invention comprises:
(A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine,
[NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio of the amino terminal amount [NH ₂ ] to the total active terminal amount ([NH ₂ ] + [COOH]),
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5
And
Active terminal total amount ([NH ₂ ] + [COOH]) μeq / g is
60 ≦ [NH ₂ ] + [COOH] <110
Is heat-treated at 200 ° C. or higher and lower than the melting point for 10 hours or longer.

  In the method for producing a polyamide of the present invention, the “melting point” indicates a melting peak temperature Tm2 by differential scanning calorimetry (input compensation DSC) according to JIS-K7121.

The second polyamide of the present invention is
(A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine;
A polyamide containing
Sulfuric acid relative viscosity ηr is 2.5 or more,
In differential scanning calorimetry according to JIS-K7121, ΔHm1 / which is the ratio of the heat of fusion ΔHm1 obtained when the temperature is raised at 20 ° C./min and the crystallization enthalpy ΔHc obtained when the temperature is lowered at 20 ° C./min. ΔHc is
1.0 <ΔHm1 / ΔHc ≦ 2.2
And
The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is
75 <trans isomer ratio ≦ 100
It is.

  In the second polyamide of the present invention, the content of 1,4-cyclohexanedicarboxylic acid is preferably at least 50 mol% in the dicarboxylic acid unit.

  In the second polyamide of the present invention, all the dicarboxylic acid units are preferably 1,4-cyclohexanedicarboxylic acid.

  In the second polyamide of the present invention, the aliphatic diamine preferably has 6 to 12 carbon atoms.

  In the second polyamide of the present invention, the aliphatic diamine is hexamethylenediamine, 2-methylpentamethylenediamine, 2-methyl-1,8-octanediamine, nonamethylenediamine, decamethylenediamine, or dodecamethylenediamine. It is preferable.

  In the second polyamide of the present invention, the aliphatic diamine is preferably 2-methylpentamethylenediamine or decamethylenediamine.

The second polyamide of the present invention is
(A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine;
A polyamide containing
The aliphatic diamine comprises a branched aliphatic diamine;
Sulfuric acid relative viscosity ηr is 2.5 or more,
The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is
71 <trans isomer ratio ≦ 100
It may be.

  In the second polyamide of the present invention, the ratio of the (b) branched aliphatic diamine in the diamine unit is preferably 10 to 100 mol%.

  In the second polyamide of the present invention, ΔHm1 / ΔHc is preferably 1.4 <ΔHm1 / ΔHc ≦ 2.2.

In the second polyamide of the present invention, when ΔHm1 / ΔHc is y and the trans isomer ratio is x,
y ≧ 0.04x−1.8
It is preferable that

In a second polyamide of the present invention, the active end the total amount of amino-terminus weight [NH _2] is the ratio _{([NH 2] + [COOH} ]) [NH 2] / ([NH 2] + [COOH]) Is
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5
It is preferable that

In the second polyamide of the present invention, the weight average molecular weight Mw / number average molecular weight Mn indicating the molecular weight distribution is Mw / Mn <3.5.
It is preferable that

  The second polyamide composition of the present invention preferably contains the second polyamide of the present invention and at least one selected from an inorganic filler, a heat stabilizer, and a light stabilizer.

  The polyamide composition molded article of the present invention may be formed by molding the second polyamide composition of the present invention.

The method for producing a second polyamide of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine,
Active end the total amount of amino-terminus weight [NH _2] is the ratio _{([NH 2] + [COOH} ]) [NH 2] / ([NH 2] + [COOH]) _{is, [NH} 2] / _([ NH ₂ ] + [COOH]) <0.5, and the active terminal total amount ([NH ₂ ] + [COOH]) μeq / g is
110 ≦ [NH ₂ ] + [COOH] ≦ 200
Is heat-treated at 200 ° C. or higher and lower than the melting point for 10 hours or longer.

  The polyamide composition molded article of the present invention is a polyamide composition molded article containing a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine, Since the trans isomer ratio of the dicarboxylic acid monomer unit in this molded product is 71 to 100 mol%, it can be excellent in hot strength and hot stiffness.

  The method for producing a polyamide composition molded article according to the present invention comprises a polyamide composition containing a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine. Since the molded polyamide composition body is heat-treated at 200 ° C. or higher, the trans isomer ratio of the dicarboxylic acid monomer unit in the molded product is 71 to 100 mol%, and is excellent in heat strength and heat rigidity. Polyamide composition molded articles can be produced.

  The first polyamide of the present invention is a polyamide containing (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine, ΔHm1 / ΔHc, which is the ratio between the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc obtained when the temperature is lowered at 20 ° C./min, is 1.0 <ΔHm1 / ΔHc ≦ 2.2, and the dicarboxylic acid monomer in the polyamide The trans isomer ratio (mol%) of the unit is 71 <trans isomer ratio ≦ 75. By having such a configuration, in the polyamide composition molded article, the trans isomer ratio mol% can be made greater than 71 and 75 or less, and the heat resistance, reflow resistance, aging resistance, and release properties are excellent. The polyamide composition molded article of the invention can be obtained.

The first polyamide production method of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine. active end the total amount of end weight [NH _2] is the ratio _{([NH 2] + [COOH} ]) [NH 2] / ([NH 2] + [COOH]) _{is, [NH 2] / ([} NH ₂ ] + [COOH]) <0.5, and the active terminal total amount ([NH ₂ ] + [COOH]) μ equivalent / g is 60 ≦ [NH ₂ ] + [COOH] <110 , Heat treatment at 200 ° C. or higher and lower than the melting point for 10 hours or longer. By having such a configuration, ΔHm1 / ΔHc is 1.0 <ΔHm1 / ΔHc ≦ 2.2, and the trans isomer ratio (mol%) of the dicarboxylic acid monomer unit in the polyamide is 71 <trans isomer ratio. It can be set to ≦ 75, and a polyamide and a polyamide composition excellent in heat resistance, reflow resistance, aging resistance, and releasability can be provided.

  The second polyamide of the present invention is a polyamide containing (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine, and has a sulfuric acid relative viscosity. ηr is 2.5 or more, ΔHm / ΔHc is more than 1.0 and 2.2 or less, and the trans isomer ratio mol% of the dicarboxylic acid monomer unit is more than 75 and 100 or less. By having such a configuration, the polyamide composition of the present invention can have a trans isomer ratio mol% of more than 75 and 100 or less, and is excellent in hot strength, hot rigidity, and low water absorption. A composition molded article can be obtained.

The second polyamide production method of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine. active end the total amount of end weight [NH _2] is the ratio _{([NH 2] + [COOH} ]) [NH 2] / ([NH 2] + [COOH]) _{is, [NH 2] / ([} NH ₂ ] + [COOH]) <0.5, and the active terminal total amount ([NH ₂ ] + [COOH]) μ equivalent / g is 110 ≦ [NH ₂ ] + [COOH] ≦ 200 , Heat treatment at 200 ° C. or higher and lower than the melting point for 10 hours or longer. By having such a configuration, the sulfuric acid relative viscosity ηr is 2.5 or more, ΔHm / ΔHc is greater than 1.0 and 2.2 or less, and the trans isomer ratio mol% of the dicarboxylic acid monomer unit is 75%. Larger and less than 100 polyamides and polyamide compositions can be obtained.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, the following this embodiment is an illustration for demonstrating this invention, and is not the meaning which limits this invention to the following content. The present invention can be implemented with various modifications within the scope of the gist.

The polyamide composition molded article of the present invention is a polyamide composition molded article containing a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine, The trans isomer ratio of the dicarboxylic acid monomer unit in the molded product is 71 to 100 mol%.
Such a polyamide composition molded article can be obtained by the following method.

  One method is to mold a polyamide composition containing a polyamide obtained by polymerizing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine. A polyamide composition molded article is obtained by heat treatment at 200 ° C. or higher.

Another method is to mold the first polyamide composition or the second polyamide composition having a specific trans isomer ratio and ΔHm1 / ΔHc to obtain a polyamide composition molded article.
Hereinafter, these methods will be described as a first embodiment to a third embodiment.

First, the first embodiment of the present invention will be described.
A polyamide composition molded article according to the first embodiment is a molded polyamide composition containing a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine. Then, the molded polyamide composition object is heat-treated at 200 ° C. or higher to obtain a polyamide composition molded article.
Hereinafter, the polyamide contained in the polyamide composition for obtaining the polyamide composition molded product according to the first embodiment, its structural unit, the polyamide composition containing the polyamide, and the method for producing the polyamide composition molded product will be described.

〔polyamide〕
The polyamide in the polyamide composition molded article and the method for producing the same of the present invention is a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine.
In the present specification, polyamide means a polymer having an amide bond (—NHCO—) in the main chain.

(Dicarboxylic acid unit)
The dicarboxylic acid unit is a dicarboxylic acid containing at least 1,4-cyclohexanedicarboxylic acid. By including 1,4-cyclohexanedicarboxylic acid in the dicarboxylic acid unit, it is possible to obtain a polyamide that satisfies the strength, toughness and stability during heat, has a high melting point, and is excellent in fluidity and low water absorption. it can.
The content of 1,4-cyclohexanedicarboxylic acid is preferably at least 50 mol%. When the proportion of 1,4-cyclohexanedicarboxylic acid is at least 50 mol%, that is, 50 mol% or more, a polyamide having excellent strength and toughness and a high melting point can be obtained. The proportion of 1,4-cyclohexanedicarboxylic acid is more preferably 60 to 100 mol%, still more preferably 70 to 100 mol%, and most preferably 100 mol%.
The proportion of dicarboxylic acid other than 1,4-cyclohexanedicarboxylic acid in the dicarboxylic acid unit is 0 to 50 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol%.

In 1,4-cyclohexanedicarboxylic acid, there are trans isomers and cis geometric isomers. 1,4-Cyclohexanedicarboxylic acid as a raw material monomer for polyamide has a trans isomer and a cis isomer, and even if either a trans isomer or a cis isomer is used, there are various trans isomers and cis isomers. However, the raw material monomer is isomerized at a high temperature to have a certain ratio, and the cis isomer has higher water solubility in the equivalent salt with the diamine described later than the trans isomer. The trans / cis ratio in terms of molar ratio is preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and even more preferably 35/65 to 15/85. It is preferable.
The trans / cis ratio (molar ratio) of 1,4-cyclohexanedicarboxylic acid can be determined by nuclear magnetic resonance spectroscopy (NMR).

The dicarboxylic acid unit may contain a dicarboxylic acid other than 1,4-cyclohexanedicarboxylic acid, and examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.
Examples of the aliphatic dicarboxylic acid include malonic acid, dimethyl malonic acid, succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl glutaric acid, 2,2-diethyl succinic acid, and 2,3-diethyl glutaric acid. , Glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecane Examples thereof include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as diacid, eicosane diacid and diglycolic acid.

  Examples of the aromatic dicarboxylic acid include unsubstituted or various terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid and the like. Examples thereof include aromatic dicarboxylic acids having 8 to 20 carbon atoms and substituted with a substituent.

  Examples of the various substituents in the aromatic dicarboxylic acid include halogens such as alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, arylalkyl groups having 7 to 10 carbon atoms, chloro groups, and bromo groups. Group, a silyl group having 1 to 6 carbon atoms, and a sulfonic acid group and a sodium salt thereof.

  When copolymerizing dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid, from the viewpoints of heat resistance, fluidity, toughness, low water absorption, strength, etc., aliphatic dicarboxylic acids are preferred, and the number of carbon atoms is 6 or more. Aliphatic dicarboxylic acids are more preferred. Of these, aliphatic dicarboxylic acids having 10 or more carbon atoms are preferred from the viewpoints of heat resistance and low water absorption.

Examples of the aliphatic dicarboxylic acid having 10 or more carbon atoms include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Among them, sebacic acid or dodecanedioic acid is preferable from the viewpoint of heat resistance and the like.
Dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid may be used alone or in combination of two or more.

  The dicarboxylic acid may further contain a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, pyromellitic acid and the like within a range not impairing the object of the present invention. One type of polyvalent carboxylic acid may be used alone, or two or more types may be used in combination.

  The dicarboxylic acid other than 1,4-cyclohexanedicarboxylic acid is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid. The compound equivalent to the dicarboxylic acid is not particularly limited as long as it can be a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the dicarboxylic acid, and examples thereof include anhydrides and halides of dicarboxylic acids. .

  When the dicarboxylic acid other than 1,4-cyclohexanedicarboxylic acid includes an aliphatic dicarboxylic acid having 10 or more carbon atoms, preferably 50 to 99.9 mol% of 1,4-cyclohexanedicarboxylic acid and 10 or more carbon atoms are contained. The aliphatic dicarboxylic acid is 0.1 to 50 mol%, more preferably 1,4-cyclohexanedicarboxylic acid is 60 to 99 mol% and the aliphatic dicarboxylic acid having 10 or more carbon atoms is 1 to 40 mol%. More preferably, it is preferable that 1,4-cyclohexanedicarboxylic acid is 70 to 99 mol% and aliphatic dicarboxylic acid having 10 or more carbon atoms is 1 to 30 mol%.

(Diamine unit)
The diamine unit includes at least an aliphatic diamine. By using an aliphatic diamine-containing component as the diamine unit, it is possible to obtain a polyamide that simultaneously satisfies the strength, toughness and the like and has excellent moldability. The ratio of the aliphatic diamine in the diamine unit is preferably at least 50 mol%, more preferably 60 to 100 mol%, further 70 to 100 mol%, and particularly preferably 100 mol%. By containing at least 50 mol% of aliphatic diamine, a polyamide having higher strength and toughness and a high melting point can be obtained.

  The aliphatic diamine is preferably a saturated aliphatic diamine having 2 to 20 carbon atoms, more preferably a saturated fat having 4 to 12 carbon atoms, from the viewpoints of heat resistance, fluidity, toughness, low water absorption and strength. It is preferably an aliphatic diamine, and more preferably a saturated aliphatic diamine having 6 to 10 carbon atoms. One type of aliphatic diamine may be used alone, or two or more types may be used in combination.

Examples of the saturated aliphatic diamine include ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, 2-methylpentamethylenediamine, hexamethylenediamine, 2-methylhexamethylenediamine, 2,4-dimethylhexamethylenediamine, hepta Examples thereof include saturated aliphatic diamines having 2 to 20 carbon atoms such as methylene diamine, octamethylene diamine, nonamethylene diamine, 2-methyloctamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and tridecamethylene diamine. It is done.
From the viewpoints of heat resistance, fluidity, toughness, low water absorption, strength, and the like, 2-methylpentamethylenediamine, hexamethylenediamine, decamethylenediamine, and dodecamethylenediamine are more preferable.

As the diamine unit, a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine may be further included within a range not impairing the object of the present invention.
A polyvalent aliphatic amine may be used individually by 1 type, and may be used in combination of 2 or more types.

As the diamine unit, a diamine other than an aliphatic diamine such as an aromatic diamine or an alicyclic diamine may be included as long as the object of the present invention is not impaired.
Examples of the aromatic diamine include metaxylylenediamine, paraxylylenediamine, paraphenylenediamine, metaphenylenediamine, and the like.
Examples of the alicyclic diamine include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclopentanediamine, and the like.

(Lactam and / or aminocarboxylic acid)
The polyamide may be a polyamide obtained by further copolymerizing lactam and / or aminocarboxylic acid from the viewpoint of toughness. The lactam and / or aminocarboxylic acid means a lactam and / or aminocarboxylic acid that can be polymerized to polyamide.
The lactam and / or aminocarboxylic acid is preferably a lactam and / or aminocarboxylic acid having 4 to 14 carbon atoms, and more preferably a lactam and / or aminocarboxylic acid having 6 to 12 carbon atoms.

  Examples of the lactam include butyrolactam, pivalolactam, ε-caprolactam, caprilactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), and the like. Among these, from the viewpoint of toughness, ε-caprolactam and laurolactam are preferable, and ε-caprolactam is more preferable.

Examples of the aminocarboxylic acid include ω-aminocarboxylic acid and α, ω-amino acid that are compounds in which a lactam is ring-opened.
The aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted with an amino group at the ω position, such as 6-aminocaproic acid, 11-aminoundecanoic acid, Examples include 12-aminododecanoic acid, and examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.
A lactam and / or aminocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.
It is preferable that the addition amount of a lactam and / or aminocarboxylic acid is 0-20 mol% with respect to the molar amount of each monomer of a dicarboxylic acid unit, a diamine unit, and a lactam and / or aminocarboxylic acid.

(End sealant)
Polyamide may use a known end-capping agent for molecular weight adjustment when polymerizing using the above-described dicarboxylic acid unit, diamine unit and, if necessary, lactam and / or aminocarboxylic acid. You may have the residue of terminal blocker at the terminal.

Examples of the end-capping agent include monocarboxylic acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like, from the viewpoint of thermal stability. Monocarboxylic acids or monoamines are preferred.
As a terminal blocker, one type may be used alone, or two or more types may be used in combination.

The monocarboxylic acid that can be used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid , Caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; and benzoic acid, toluyl And aromatic monocarboxylic acids such as acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
As the monocarboxylic acid, one kind may be used alone, or two or more kinds may be used in combination.

The monoamine that can be used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, Aliphatic monoamines such as decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; and And cyclic amines such as pyrrolidine, piperidine, 3-methylpiperidine; and the like.
Monoamines may be used alone or in combination of two or more.

[Production method of polyamide]
The method for producing polyamide is not particularly limited, and examples thereof include the methods exemplified below.
1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter referred to as hot melt polymerization method).
2) A method of increasing the degree of polymerization while maintaining the solid state of the polyamide obtained by the hot melt polymerization method at a temperature below the melting point (hereinafter referred to as a hot melt polymerization / solid phase polymerization method).
3) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization (hereinafter referred to as prepolymer · Called the extrusion polymerization method).
4) A method in which an aqueous solution or suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated, and the degree of polymerization is increased while maintaining the solid state of the precipitated prepolymer at a temperature below the melting point of the polyamide , Called prepolymer / solid phase polymerization).
5) A method in which the dicarboxylic acid / diamine salt or a mixture thereof is polymerized in one step while maintaining the solid state (hereinafter referred to as a one-step solid phase polymerization method).
6) A method of polymerization using a dicarboxylic acid halide equivalent to a dicarboxylic acid and a diamine (hereinafter referred to as a solution method).

  The polyamide production method is preferably 1) hot melt polymerization, 2) hot melt polymerization / solid phase polymerization, 4) prepolymer / solid phase polymerization, more preferably 1) hot melt polymerization, 2) The hot melt polymerization / solid phase polymerization method is desirable, and the hot melt polymerization method is preferable in terms of shortening the polymerization cycle time of polyamide and improving the molecular weight.

  The addition amount of the dicarboxylic acid unit and the addition amount of the diamine unit are preferably in the vicinity of the same molar amount. In consideration of the escape ratio of the diamine unit during the polymerization reaction to the outside of the reaction system in terms of the molar ratio, the molar amount of the entire diamine unit is preferably 0.9 to 1 with respect to the molar amount 1 of the entire dicarboxylic acid unit. .2, more preferably 0.95 to 1.1, and further preferably 0.98 to 1.05.

  In the polyamide production process, when polymerization is performed, it is preferable to add an additive during the polymerization. A diamine is mentioned as an additive at the time of superposition | polymerization. This diamine means a diamine to be added separately from the diamine unit used in the production of an equimolar amount of dicarboxylic acid / diamine salt, and the amount of diamine added as an additive is preferably 0.1 to 10 mol%. More preferably, it is 0.5-5.0 mol%, More preferably, it is 1.5-4.5 mol%, More preferably, it is 2.6-4.0 mol%. This diamine may be the same component as the diamine unit used in the production of the dicarboxylic acid / diamine salt or a different compound. By adding diamine or the like, the degree of polymerization can be increased or adjusted, which is effective as a method for controlling the molecular weight.

  In the method for producing polyamide, the polymerization form may be batch or continuous. Examples of the reactor used by a method other than the solid phase polymerization method include an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader. The reaction can be performed. In the case of the solid phase polymerization method, for example, a tumbler reactor, a vibration dryer reactor, a Nauter mixer reactor, a stirring reactor, or the like can be used.

  Specifically, polyamide pellets, flakes, or powder is placed in the reactor to polymerize the polyamide. At this time, it may be performed under a stream of inert gas such as nitrogen, argon or helium or under reduced pressure, or the inert gas may be supplied from the lower part of the reactor while pulling the internal gas to the reduced pressure at the upper part of the reactor. Often, the molecular weight of the polyamide can be improved by heating at a temperature below the melting point of the polyamide.

The reaction temperature of the solid phase polymerization is preferably 100 to 350 ° C, more preferably 120 to 300 ° C, and further preferably 150 to 270 ° C.
After the polymerization, heating is stopped, and the reaction temperature is preferably lowered from 0 to 100 ° C., more preferably from room temperature to 60 ° C., and then the polyamide can be taken out from the reactor.

  Although the said hot-melt-polymerization method can be performed by a well-known aspect, Preferably it is 100 degreeC or more, More preferably, it is 120 degreeC or more, It is preferable to carry out on the temperature conditions of 170 degreeC or more. For example, a mixture of 1,4-cyclohexanedicarboxylic acid and a dicarboxylic acid such as hexamethylene adipamide and a diamine, a solid salt or an aqueous solution is heated and concentrated at a temperature of 100 to 300 ° C., and the generated water vapor pressure is changed from normal pressure to The pressure is kept at about 5 MPa (gauge pressure), and finally the pressure is released, and polycondensation is performed at normal pressure or reduced pressure. Further, a solid phase polymerization method in which a mixture of dicarboxylic acid and diamine, a solid salt or a polycondensate is thermally polycondensed at a temperature below the melting point can be used. These methods may be combined as necessary.

  In the production process of the polyamide, the above-mentioned known end-capping agent is used for molecular weight adjustment when the polymerization is performed using the dicarboxylic acid unit and the diamine unit, and if necessary, lactam and / or aminocarboxylic acid. Further polymerization may be carried out by adding.

[Physical properties of polyamide]
(Molecular weight)
The molecular weight of the polyamide is based on the sulfuric acid relative viscosity ηr at 25 ° C., and the sulfuric acid relative viscosity ηr at 25 ° C. is preferably 2.3 or more. More preferably, it is 2.3-7.0, More preferably, it is 2.5-6.5, Most preferably, it is 3.0-6.5. Effective methods for controlling the relative viscosity ηr of sulfuric acid at 25 ° C. for polyamides include, for example, methods for controlling the addition amount of diamine and end-capping agent as additives during hot melt polymerization of polyamide, and polymerization conditions. Method.

When the relative viscosity ηr of sulfuric acid at 25 ° C. is 2.3 or more, the polyamide is excellent in mechanical properties such as toughness and strength. From the viewpoint of melt fluidity, a polyamide having excellent fluidity can be obtained when the sulfuric acid relative viscosity ηr at 25 ° C. of 7.0 is 7.0 or less.
The sulfuric acid relative viscosity at 25 ° C. can be measured at 25 ° C. in 98% sulfuric acid according to JIS-K6920.

<Molecular weight>
As an index of the molecular weight of the polyamide, a number average molecular weight Mn obtained by GPC (gel permeation chromatography), a weight average molecular weight Mw, and a molecular weight distribution Mw / Mn can be used. The larger the Mn, the higher the molecular weight of the (A) polyamide, and the smaller the Mn, the lower the molecular weight of the (A) polyamide.
The number average molecular weight Mn of the polyamide is preferably larger than 15000, more preferably 18000 or more, and further preferably 20000 or more.
Moreover, Mw / Mn which shows the molecular weight distribution of (A) polyamide becomes like this. Preferably it is less than 10, More preferably, it is 5 or less.
When the number average molecular weight Mn and the molecular weight distribution Mw / Mn are in the above ranges, it tends to be a polyamide composition having excellent mechanical properties such as toughness and rigidity, and moldability. In addition, Mn and Mw can produce | generate a calibration curve using the number average molecular weight Mn measured by PMMA (polymethylmethacrylate) standard sample (made by a polymer laboratory company), and can obtain | require the molecular weight of polyamide. More specifically, it can be measured by the method of Examples described later.

(Melting point)
The melting point Tm2 of the polyamide is preferably 280 to 350 ° C from the viewpoint of heat resistance.
Melting | fusing point Tm2 becomes like this. Preferably it is 280 degreeC or more, More preferably, it is 305 degreeC or more, More preferably, it is 315 degreeC or more. The melting point Tm2 is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.
When the melting point Tm2 of the polyamide is 280 ° C. or higher, a polyamide having excellent heat resistance can be obtained. Moreover, when the melting point Tm2 of the polyamide is 350 ° C. or less, the thermal decomposition of the polyamide in the melt processing such as extrusion and molding can be suppressed.

The heat of fusion ΔHm2 of the polyamide is preferably 10 to 100 J / g, more preferably 14 to 100 J / g, and still more preferably 20 to 100 J / g from the viewpoint of heat resistance.
The measurement of the melting point Tm2 and the heat of fusion ΔHm2 of polyamide can be performed according to JIS-K7121 as described in the following examples. Examples of the measuring device for the melting point and the heat of fusion include Diamond-DSC manufactured by PERKIN-ELMER.

[Polyamide composition]
The polyamide composition can contain an inorganic filler and other additives in addition to the polyamide. By including an inorganic filler as the polyamide composition, the polyamide composition is excellent in heat resistance and thermal stability, and without damaging the properties of the polyamide having a high melting point, the polyamide composition also has heat resistance and thermal stability. While satisfying the above, etc., it is particularly excellent in strength and moldability.

(Inorganic filler)
It does not specifically limit as an inorganic filler which comprises the polyamide composition of this embodiment, A well-known material can be used.
For example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica, hydrotalcite, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, phosphoric acid Calcium monohydrogen, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black , Carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, clay, montmorillonite, swellable fluorine mica, silicon nitride, and apatite.
One type of inorganic filler may be used alone, or two or more types may be used in combination.

Among the inorganic fillers, the glass fiber and the carbon fiber may have a round shape or a flat shape in cross section.
Examples of the flat cross section include a rectangle, an oval close to a rectangle, an ellipse, and a bowl shape with a narrowed central portion in the longitudinal direction.

  Among glass fibers and carbon fibers, from the viewpoint of imparting excellent mechanical properties to the polyamide composition, in the polyamide composition, the number average fiber diameter is 3 to 30 μm, and the weight average fiber length is 100 to 750 μm. Glass fibers or carbon fibers having an aspect ratio (L / D) of 10 to 100 between the weight average fiber length (L) and the number average fiber diameter (D) are preferably used.

  The number average fiber diameter of the inorganic filler in the polyamide composition is, for example, putting the polyamide composition in an electric furnace, incinerating the organic matter contained in the polyamide composition, and, for example, 100 or more glass fibers from the residue. The number average fiber diameter can be determined by arbitrarily selecting, observing with SEM, and measuring the fiber diameter.

As for the weight average fiber length of the inorganic filler in the polyamide composition, the glass fiber is arbitrarily selected in the same manner, and the weight average fiber length is measured by measuring the fiber length using an SEM photograph at a magnification of 1000 times. be able to.
As the inorganic filler, reinforcing fibers having a weight average fiber length of 1 to 15 mm are more preferable. The weight average fiber length of such reinforcing fibers is 1 to 15 mm, preferably 3 to 12 mm, from the viewpoint of improving mechanical strength, rigidity and moldability.

The weight average fiber length of the reinforcing fibers is the length of 400 reinforcing fibers arbitrarily selected using an image analyzer after observing with an optical microscope after burning or dissolving only the polyamide of the polyamide composition. It is calculated | required by measuring thickness and calculating an average value.
Here, when the length of each reinforcing fiber is L1, L2,..., L400, the calculation formula for the weight average fiber length for each reinforcing fiber is expressed by the following formula. In the following formula, “i” is an integer from 1 to 400.
Weight average fiber length = Σ (Li ² ) / ΣLi
In addition, a weight average fiber length is a value applied with respect to the reinforced fiber of the state contained in the polyamide composition of this embodiment. That is, the weight average fiber length of the reinforcing fiber before blending with the polyamide is not limited to the above.

The material of the reinforcing fiber is not particularly limited as long as it is a reinforcing fiber generally used for polyamide.
For example, inorganic fiber such as glass fiber, carbon fiber, boron fiber, metal fiber (eg, stainless fiber, aluminum fiber, copper fiber), polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaffin Organic materials such as phenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, wholly aromatic polyamide fiber such as fiber obtained from condensate of diaminodiphenyl ether and terephthalic acid or isophthalic acid, or wholly aromatic liquid crystal polyester fiber Is mentioned.

As reinforcing fiber, the said material may be used independently and 2 or more types may be used together. Especially, it is preferable that it is 1 or more types chosen from a glass fiber, a carbon fiber, a boron fiber, and a metal fiber from a viewpoint of an improvement of mechanical strength and rigidity, and a glass fiber and / or a carbon fiber are more preferable.
The reinforcing fiber is not particularly limited with respect to the average fiber diameter in the single fiber, but, for example, those having a diameter of 5 to 25 μm are generally used.

The average fiber diameter of single fibers is obtained by observing the reinforcing fibers to be used under an optical microscope and calculating the average value when measuring 400 fiber diameters arbitrarily selected using an image analyzer. It is done.
Further, as the reinforcing fiber, it is preferable to use roving which is a continuous fiber obtained by bundling single fibers.

<Surface treatment agent>
The inorganic filler such as glass fiber or carbon fiber may be surface-treated with a silane coupling agent or the like.
The silane coupling agent is not particularly limited, and examples thereof include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane. And aminosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes and the like. Of these, aminosilanes are preferable.
As the silane coupling agent, one kind may be used alone, or two or more kinds may be used in combination.

<Bundling agent>
Fibrous inorganic fillers such as glass fibers and carbon fibers are further used as sizing agents, copolymers and epoxy containing carboxylic anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers as constituent units. Compounds, polyurethane resins, and homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts with primary, secondary, or tertiary amines thereof may be included.

In particular, from the viewpoint of mechanical properties (particularly strength) of the polyamide composition, a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units (containing carboxylic acid anhydride) A copolymer containing an unsaturated vinyl monomer and an unsaturated vinyl monomer excluding an unsaturated vinyl monomer containing a carboxylic acid anhydride as a structural unit), an epoxy compound, and a polyurethane resin are preferred, and a carboxylic acid anhydride More preferred are a copolymer containing a contained unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units, and a polyurethane resin.
As the sizing agent, one type may be used alone, or two or more types may be used in combination.

  The carboxylic acid anhydride-containing unsaturated vinyl monomer constituting the copolymer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer as structural units is not particularly limited. Examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride, and maleic anhydride is preferred.

  Further, the unsaturated vinyl monomer constituting the copolymer containing carboxylic acid anhydride-containing unsaturated vinyl monomer and unsaturated vinyl monomer as structural units is not particularly limited, for example , Styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. Styrene and butadiene are preferred.

  Examples of the copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units include, for example, a copolymer of maleic anhydride and butadiene, a maleic anhydride and ethylene. Copolymers and copolymers of maleic anhydride and styrene are preferred.

The copolymer containing a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as constituent units has a weight average molecular weight of preferably 2,000 or more, and improves the fluidity of the polyamide composition. From this viewpoint, it is more preferably 2,000 to 1,000,000, and further preferably 2,000 to 900,000.
The weight average molecular weight can be measured by gel permeation chromatography (GPC).

  The epoxy compound is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, undecenoxide, and dodecene oxide. , Pentadecene oxide, eicosene oxide and the like; glycidol, epoxypentanol, 1-chloro-3,4-epoxybutane, 1-chloro-2-methyl-3,4-epoxybutane, 1,4 -Dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, methylcyclohexene oxide, vinylcyclohexene Alicyclic epoxy compounds such as oxide and epoxidized cyclohexene methyl alcohol; terpene epoxy compounds such as pinene oxide; aromatic epoxy compounds such as styrene oxide, p-chlorostyrene oxide and m-chlorostyrene oxide; epoxidized soybean oil; And epoxidized linseed oil.

  The polyurethane resin is not particularly limited, and those generally used as a sizing agent can be used. For example, isocyanates such as m-xylylene diisocyanate (XDI), 4,4′-methylenebis (cyclohexyl isocyanate) (HMDI), and isophorone diisocyanate (IPDI), polyester-based and polyether-based diols, Those synthesized from can be suitably used.

  As a homopolymer of acrylic acid (polyacrylic acid), the weight average molecular weight is preferably 1,000 to 90,000, more preferably 1,000 to 25,000.

The polyacrylic acid may be in the form of a salt with a primary, secondary, or tertiary amine.
The amine is not particularly limited, and examples thereof include triethylamine, triethanolamine, and glycine.

The degree of neutralization of polyacrylic acid by having a salt form means the ratio of the acrylic acid component forming a salt out of the acrylic acid component of polyacrylic acid, and other concomitant drugs (silane coupling agents, etc.) From the viewpoint of improving the stability of the mixed solution with) and reducing the amine odor, it is preferably 20 to 90%, more preferably 40 to 60%.
The weight average molecular weight of the salt-form polyacrylic acid is preferably 3,000 to 50,000, and is preferably 3,000 or more from the viewpoint of improving the converging property of glass fibers and carbon fibers. From the viewpoint of improving the mechanical properties of the product, it is preferably 50,000 or less.

  The other copolymerizable monomer in the copolymer of acrylic acid and other copolymerizable monomer is not particularly limited, and examples thereof include acrylic acid, maleic acid, and methacrylic acid, which are monomers having a hydroxyl group and / or a carboxyl group. Vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. As the other copolymerizable monomer, a monomer that is an ester of a monomer having a hydroxyl group and / or a carboxyl group can be suitably used.

The copolymer of acrylic acid and other copolymerizable monomers preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.
The copolymer of acrylic acid and other copolymerizable monomers may be in the form of a salt with a primary, secondary, or tertiary amine.
The amine is not particularly limited, and examples thereof include triethylamine, triethanolamine, and glycine.

The degree of neutralization of the copolymer by having a salt form means the proportion of the acid component forming a salt in the acid component of the copolymer, and the mixed solution with other concomitant drugs (such as a silane coupling agent) From the viewpoint of improving stability and from the viewpoint of reducing amine odor, it is preferably 20 to 90%, more preferably 40 to 60%.
The weight average molecular weight of the copolymer in the salt form is preferably 3,000 to 50,000, and preferably 3,000 or more from the viewpoint of improving the converging property of glass fiber or carbon fiber. From the viewpoint of improving the characteristics, it is preferably 50,000 or less.

The fibrous inorganic filler such as glass fiber and carbon fiber containing a sizing agent is obtained by using the above sizing agent in a known glass fiber or carbon fiber manufacturing process using a known method such as a roller type applicator. It is obtained by reacting continuously by drying fiber strands produced by applying to a fibrous inorganic filler such as carbon fiber.
The fiber strand may be used as it is as roving, or may be used as a chopped glass strand after further obtaining a cutting step.

  The sizing agent preferably imparts (adds) a solid content of 0.2 to 3% by mass with respect to 100% by mass of a fibrous inorganic filler such as glass fiber or carbon fiber. It is more preferable to apply (add) mass%.

  From the viewpoint of maintaining the bundling of fibrous inorganic fillers such as glass fibers and carbon fibers, the amount of sizing agent added is 100% by mass with respect to 100% by mass of fibrous inorganic fillers such as glass fibers and carbon fibers. Is preferably 0.2% by mass or more. From the viewpoint of improving the thermal stability of the polyamide composition, the addition amount of the sizing agent is preferably 3% by mass or less as the solid content. Moreover, drying of a strand may be performed after a cutting process, and you may cut | disconnect, after drying a strand.

When wollastonite is used as the inorganic filler constituting the polyamide composition, the polyamide composition has a number average fiber diameter of 3 to 30 μm, a weight average fiber length of 10 to 500 μm, and an aspect ratio (L / Those in which D) is 3 to 100 are preferably used.
As the inorganic filler, when talc, mica, kaolin, silicon nitride or the like is used, the polyamide composition preferably has a number average fiber diameter of 0.1 to 3 μm.

(Other additives)
In the polyamide composition, additives that are conventionally used for polyamide, for example, colorants such as pigments and dyes (including colored master batches), flame retardants, fibrillating agents, and lubricants, as long as the object of the present invention is not impaired. Agent, fluorescent bleaching agent, plasticizer, antioxidant, light stabilizer, UV absorber, antistatic agent, fluidity improver, filler, reinforcing agent, spreading agent, nucleating agent, rubber, reinforcing agent and Other polymers can also be contained.

  In addition, in the polyamide composition, as a heat stabilizer, phenol stabilizer, phosphorus stabilizer, amine stabilizer, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa of the periodic table One or more selected from the group consisting of metal salts of Group IVb and Group IVb elements and halides of alkali metals and alkaline earth metals can be blended.

The phenol-based stabilizer is not particularly limited, and examples thereof include hindered phenol compounds.
The phenol-based stabilizer has a property of imparting heat resistance and light resistance to resins and fibers such as polyamide.
The hindered phenol compound is not particularly limited, and examples thereof include N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide). )], Pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4) -Hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3- t-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undecane, 3 5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, And 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid. Among these, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable from the viewpoint of improving heat aging resistance.
As the phenol-based stabilizer, one type may be used alone, or two or more types may be used in combination.

  When using a phenol stabilizer, the compounding amount of the phenol stabilizer in the polyamide composition is preferably 0.01 to 1 part by mass, more preferably 0.1 to 100 parts by mass of the polyamide composition. -1 part by mass. When the blending amount is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

  The phosphorus stabilizer is not particularly limited, for example, pentaerythritol type phosphite compound, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl phosphite, Phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4- Di-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene-bis 3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, 4,4'-isopropylidenebis (2-t -Butylphenyl) -di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane Phosphite, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyl diphosphite, Tris (Mono, dimixed nonylphenyl) phosphite, 4,4'-isopropyl Bis (2-t-butylphenyl) .di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3 5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4′-isopropylidenediphenyl polyphosphite, bis (octylphenyl) bis (4,4′-butylidenebis (3-methyl-) 6-t-butylphenyl)) · 1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) diphosphite, tris (4 4′-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phos Phyto, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, Tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′-biphenylene diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenedi A phosphite etc. are mentioned. Of these, pentaerythritol phosphite compounds and tris (2,4-di-t-butylphenyl) phosphite are preferable from the viewpoint of further improving the heat aging resistance and reducing the generated gas.

  The pentaerythritol type phosphite compound is not particularly limited. For example, 2,6-di-t-butyl-4-methylphenyl phenyl pentaerythritol diphosphite, 2,6-di-t- Butyl-4-methylphenyl methyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2-ethylhexyl pentaerythritol diphosphite, 2,6-di-t-butyl- 4-methylphenyl isodecyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl lauryl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl Isotridecyl pentaerythritol diphosphite, 2,6-di-t-butyl -Methylphenyl stearyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl cyclohexyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl Benzyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl ethyl cellosolve pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl butyl carbitol Pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl octylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl nonylphenyl penta Erythritol diphosphite, bis (2,6-di-t Butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2,6-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl, 2,4-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl · 2,4-di-t-octylphenyl · pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl · 2-cyclohexyl Phenyl pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl phenyl pentaerythritol Tall diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos Fight etc. are mentioned. Among them, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite are preferred, and bis (2 , 6-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.

A phosphorus stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.
When using a phosphorus stabilizer, the compounding quantity of the phosphorus stabilizer in a polyamide composition is 0.01-1 mass part with respect to 100 mass parts of polyamide compositions, More preferably, it is 0.1-1. Part by mass. When the blending amount is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

  The amine stabilizer is not particularly limited, and examples thereof include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetra Methylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetra Methylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy)- 2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl)- Oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6 6-tetramethyl-4-piperidyloxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6) -Tetramethyl-4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2 , 6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4 -Tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl) -4-hydroxyphenyl Propionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β Examples include condensates with ', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.

One type of amine stabilizer may be used alone, or two or more types may be used in combination.
When the amine stabilizer is used, the compounding amount of the amine stabilizer in the polyamide composition is preferably 0.01 to 1 part by mass, more preferably 0.1 to 100 parts by mass of the polyamide composition. -1 part by mass. When the amount is within the above range, light resistance and heat aging resistance can be further improved, and the amount of generated gas can be further reduced.

The metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table is not particularly limited and is preferably a heat stabilizer. Copper salt.
The copper salt is not particularly limited. For example, copper halide (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, benzoic acid Examples thereof include copper oxide, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex salt in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid. Especially, it is preferable that it is 1 or more types selected from the group which consists of copper iodide, cuprous bromide, cupric bromide, cuprous chloride, and copper acetate. Copper iodide and / or copper acetate Is more preferable. When the above metal salt, especially copper salt, is used, a polyamide composition having excellent heat aging resistance and capable of suppressing metal corrosion (hereinafter also simply referred to as “metal corrosion”) of screws and cylinders during extrusion is obtained. be able to.

The said metal salt may be used individually by 1 type, and may be used in combination of 2 or more types.
When using a copper salt, the compounding amount of the copper salt in the polyamide composition is preferably 0.01 to 0.2 parts by mass, more preferably 0.02 to 0 parts per 100 parts by mass of the polyamide composition. 15 parts by mass. When the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

  Moreover, from the viewpoint of improving the heat aging resistance, the content of copper element is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, and still more preferably 50 to 300 ppm with respect to the total amount of the polyamide composition. .

Alkali metal and alkaline earth metal halides are not particularly limited, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. Among these, potassium iodide and potassium bromide, and a mixture thereof are preferable, and potassium iodide is more preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion.
As the halide, one kind may be used alone, or two or more kinds may be used in combination.

  When alkali metal and alkaline earth metal halides are used, the blending amount of alkali and alkaline earth metal halides in the polyamide composition is preferably 0.05 to 5 with respect to 100 parts by mass of the polyamide composition. It is a mass part, More preferably, it is 0.2-2 mass part. When the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

  In the polyamide composition of the present embodiment, a mixture of a copper salt and a halide of an alkali or alkaline earth metal can be suitably used as a heat stabilizer. The ratio of the copper salt to the alkali and alkaline earth metal halide may be included in the polyamide composition so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. Preferably, it is 5/1 to 30/1.

  When the molar ratio (halogen / copper) is within the above range, the heat aging resistance of the polyamide composition can be further improved. Moreover, when the molar ratio (halogen / copper) is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed. When the molar ratio (halogen / copper) is 40/1 or less, corrosion of the screws of the molding machine can be prevented without substantially impairing mechanical properties such as toughness, which is preferable.

[Production method of polyamide composition]
A method for producing the polyamide composition is not particularly limited as long as it is a method of mixing the above-described polyamide, an inorganic filler, and, if necessary, the above-described other additives.
As a method of mixing the constituent materials of the polyamide composition, for example, a method of mixing using a Henschel mixer and the like, supplying to a melt kneader and kneading, or a polyamide melted with a single screw or twin screw extruder, from a side feeder The method etc. which mix | blend an inorganic filler and another additive are mentioned.
In the method of supplying the components constituting the polyamide composition to the melt kneader, all the components (polyamide, inorganic filler, etc.) may be supplied to the same supply port at once, or the components may be supplied differently. You may supply from a mouth.

The melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature.
The melt kneading time is preferably about 0.5 to 5 minutes.
The apparatus for performing melt kneading is not particularly limited, and a known apparatus, for example, a melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, and a mixing roll can be used.

  The method for producing the polyamide composition when the inorganic filler contained in the polyamide composition is a reinforcing fiber having a weight average fiber length of 1 to 15 mm is not particularly limited. A pultrusion method in which polyamide is melt-kneaded with a twin screw extruder and the molten polyamide is impregnated into a roving of reinforcing fibers to obtain a polyamide-impregnated strand, or as described in JP 2008-221574 A There is a method of sufficiently impregnating polyamide by a step of twisting in a spiral shape.

[Physical properties of polyamide composition]
The polyamide composition preferably has a sulfuric acid relative viscosity ηr at 25 ° C. of 2.3 or more. More preferably, it is 2.3-7.0, More preferably, it is 2.5-6.5, Most preferably, it is 3.0-6.5. When the sulfuric acid relative viscosity ηr at 25 ° C. is 2.3 or more, the mechanical properties such as toughness and strength are excellent. From the viewpoint of melt fluidity, the polyamide relative viscosity ηr at 25 ° C. is preferably 7.0 or less.
The sulfuric acid relative viscosity at 25 ° C. can be measured at 25 ° C. in 98% sulfuric acid according to JIS-K6920.

The melting point of the polyamide composition is preferably 280 to 350 ° C. from the viewpoint of heat resistance. Melting | fusing point becomes like this. Preferably it is 280 degreeC or more, More preferably, it is 305 degreeC or more, More preferably, it is 315 degreeC or more. The melting point is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower. When the melting point of the polyamide composition is 280 ° C. or higher, the polyamide composition can have excellent heat resistance. Moreover, when the melting point is 350 ° C. or lower, thermal decomposition in melt processing such as extrusion and molding can be suppressed. The measurement of the melting point of the polyamide composition can be performed according to JIS-K7121, and basically has the same value as the melting point Tm2 of the polyamide.
The heat of fusion of the polyamide composition is preferably 10 to 100 J / g, more preferably 14 to 100 J / g, and still more preferably 20 to 100 J / g from the viewpoint of heat resistance. The measurement of the heat of fusion of the polyamide composition can be performed according to JIS-K7121. When determining the heat of fusion and crystallization enthalpy of the polyamide composition, if it contains an inorganic filler, nucleating agent, lubricant, stabilizer, etc., the value of the heat value is the ratio of the polyamide to the composition. Convert and calculate.
Examples of the measuring device for the melting point and the heat of fusion include Diamond-DSC manufactured by PERKIN-ELMER.

[Production Method of Polyamide Composition Molded Product]
The polyamide composition molded article of the present invention is a known molding method of the above-mentioned polyamide or polyamide composition, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding. It can be obtained by heat treatment at 200 ° C. or higher after molding using multilayer molding, melt spinning, etc., and molding the molded polyamide composition.

  The heat treatment method for the polyamide composition molded body is not particularly limited as long as heating at 200 ° C. or higher is possible. For example, an apparatus such as an electric furnace, a gear oven, a hot plate, or a molding die is used. Can be performed. The heat treatment may be performed in the air, may be performed in an inert gas atmosphere, for example, a nitrogen gas atmosphere, or may be performed in a reduced pressure environment. The heat treatment temperature is 200 ° C or higher, preferably 220 ° C to 300 ° C, more preferably 240 ° C to 300 ° C. By setting it as 200 degreeC or more, the trans isomer ratio of the 1, 4- cyclohexane dicarboxylic acid monomer unit in a molded article can be 71 mol% or more. On the other hand, by setting the temperature to 300 ° C. or lower, it is possible to satisfactorily prevent the molded product from melting, so that the trans isomer ratio can be set to 71 mol% or higher. The heat treatment time can be appropriately selected depending on the size and thickness of the molded product and the heat treatment temperature. For example, when the heat treatment time is 200 to 240 ° C., it is preferably 1 to 72 hours, more preferably about 1 to 48 hours.

[Properties of polyamide composition molded article]
The polyamide composition molded product of the present invention has a trans isomer ratio of the dicarboxylic acid monomer unit in the molded product of 71 to 100 mol%. Here, the dicarboxylic acid monomer unit means a unit derived from a dicarboxylic acid of a monomer as a raw material. The trans isomer ratio mol% is more preferably more than 75 and 100 or less, more preferably 80 or more and 100 or less, and still more preferably 85 or more and 100 or less.
The trans isomer ratio (mol%) of the dicarboxylic acid monomer unit of the polyamide composition molded article can be determined by nuclear magnetic resonance spectroscopy (NMR).

[The heat of fusion ΔHm, crystallization enthalpy ΔHc, melting peak temperature Tm of the polyamide composition molded product]
The heat of fusion ΔHm and the crystallization enthalpy ΔHc of the polyamide composition molded article of the present invention are each preferably 40 J / g or more, more preferably 45 J / g or more from the viewpoint of heat resistance, and 50 J / g. More preferably, it is the above. On the other hand, the heat of fusion ΔHm and the crystallization enthalpy ΔHc of the polyamide composition molded product are preferably 80 J / g or less from the viewpoint of moldability. When determining the heat of fusion ΔHm and crystallization enthalpy ΔHc of the polyamide composition molded article, if the inorganic filler, nucleating agent, lubricant, stabilizer, etc. are included, the value of the heat value is relative to the composition. Calculated by converting the ratio of polyamide.

  The ratio (ΔHm / ΔHc) between the heat of fusion ΔHm and the crystallization enthalpy ΔHc of the polyamide composition molded article of the present invention is preferably greater than 1.0, more preferably 1.5 or more, further from the viewpoint of heat resistance. Is more preferably 1.8 or more.

The measurement of the heat of fusion ΔHm and the crystallization enthalpy ΔHc of the polyamide composition molded product can be performed according to JIS-K7121, and the heat of fusion ΔHm is raised at a rate of temperature increase of 20 ° C./min. This is the Tm peak area when the endothermic peak appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time of the first temperature rise (melting peak) is the melting peak temperature Tm (° C.). When there are a plurality of endothermic peaks, a peak having ΔH of 1 J / g or more is regarded as a peak, the highest temperature is defined as a melting peak temperature Tm, and ΔHm is a sum of peak areas. The crystallization enthalpy ΔHc is the Tc value when the temperature of the exothermic peak (crystallization peak) that appears when the polyamide composition molded article is cooled at a temperature decrease rate of 20 ° C./min is the crystallization peak temperature Tc (° C.). It is the peak area. As the measuring device, Diamond-DSC manufactured by PERKIN-ELMER can be used.
The melting peak temperature Tm of the molded polyamide composition of the present invention is preferably 300 ° C. or higher, more preferably 310 ° C. or higher, from the viewpoint of heat resistance.

[Use of polyamide composition molded product]
The polyamide composition molded article of the present invention is excellent in heat resistance, strength, heat strength, rigidity, heat stiffness, heat stability, and has LLC (Long Life Coolant) resistance as shown in the following examples. Since it is improved, it can be suitably used as various parts materials for automobiles, electric and electronic, industrial materials, extrusion applications, daily necessities and household goods.

  It is not particularly limited for automobiles, and is used for, for example, intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, and electrical parts.

  Examples of the vehicle intake system parts include an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, and a throttle body.

  Examples of the automobile cooling system parts include a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil netter, and a delivery pipe.

  Examples of automobile fuel system parts include a fuel delivery pipe and a gasoline tank case.

  Examples of the interior parts include an instrument panel, a console box, a glove box, a steering wheel, and a trim.

Examples of exterior parts include a mall, a lamp housing, a front grille, a mud guard, a side bumper, a door mirror stay, and a roof rail.
In particular, when the trans isomer ratio mol% is more than 75 and 100 or less, it can be suitably used for automobile engine mounts, air ducts, cooling pipes, and vibration-proof components.

  The electrical component is not particularly limited, and examples thereof include a connector, a wire harness connector, a motor component, a lamp socket, a sensor on-vehicle switch, and a combination switch.

Examples of electrical and electronic products include connectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, and motor end caps.
In particular, when the trans isomer ratio mol% is greater than 71 and 75 or less, it can be suitably used as an LED reflector.

  Examples of industrial materials include gears, cams, insulating blocks, valves, power tool parts, agricultural equipment parts, engine covers, and the like.

  Examples of daily goods and household goods include buttons, food containers, and office furniture.

  As an extrusion application, for example, it is used for a film, a sheet, a filament, a tube, a rod, and a hollow molded article.

Next, a second embodiment of the present invention will be described.
The polyamide composition molded article according to this embodiment is formed by molding a first polyamide composition containing a first polyamide having a specific trans isomer ratio and ΔHm1 / ΔHc.
Details of the first polyamide, the first polyamide composition, and the molded polyamide composition will be described below.

[(A1) Polyamide]
The first polyamide of the present invention (hereinafter also simply referred to as “polyamide”) is
(A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine,
In differential scanning calorimetry according to JIS-K7121, ΔHm1 / which is the ratio of the heat of fusion ΔHm1 obtained when the temperature is raised at 20 ° C./min and the crystallization enthalpy ΔHc obtained when the temperature is lowered at 20 ° C./min. ΔHc is
1.0 <ΔHm1 / ΔHc ≦ 2.2
And the trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is
71 <trans isomer ratio ≦ 75
It is.

The (A1) polyamide of the present invention contains as structural units (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine.
The total amount of the above (a) dicarboxylic acid unit and (b) diamine unit is preferably 20 to 100 mol%, and 50 to 100 mol%, based on 100 mol% of all structural units of (A1) polyamide. More preferably, it is more preferably 90 to 100 mol%, and most preferably 100 mol%.

The ratio of the predetermined monomer unit constituting (A1) polyamide can be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.
(A1) In the polyamide, the structural unit of (A1) polyamide other than the above (a) dicarboxylic acid unit and (b) diamine unit is not particularly limited. For example, (c) lactam and / or aminocarboxylic acid described later The unit which consists of is mentioned.

  The polyamide of the present invention having ΔHm1 / ΔHc, which is the ratio between the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc, and the trans isomer ratio as described above can be obtained by the polyamide structural unit and production method described below. .

First, the structural unit of (A1) polyamide will be described in detail.
((A) dicarboxylic acid unit)
(A) The dicarboxylic acid unit contains at least a 1,4-cyclohexanedicarboxylic acid unit. (A) The dicarboxylic acid unit preferably contains 50 to 100 mol% of 1,4-cyclohexanedicarboxylic acid units (based on the total number of dicarboxylic acids), more preferably 60 to 100 mol%, and 70 to 100 mol. % Is more preferable, and 100 mol% is most preferable.

  (A) When the ratio (mol%) of 1,4-cyclohexanedicarboxylic acid unit in the dicarboxylic acid unit is in the above range, the heat resistance, fluidity, toughness, low water absorption, rigidity, and the like are satisfied at the same time. A polyamide composition can be obtained.

  The units that may be contained in the (a) dicarboxylic acid unit other than 1,4-cyclohexanedicarboxylic acid include (a-1) an alicyclic dicarboxylic acid unit, (a-2) an aromatic dicarboxylic acid unit, and (A-3) Aliphatic dicarboxylic acid units. Hereinafter, unless it is described as (a-1), the term “alicyclic carboxylic acid unit” is used in the sense of including 1,4-cyclohexanedicarboxylic acid.

(A-1) Alicyclic dicarboxylic acid unit (a-1) Other than 1,4-cyclohexanedicarboxylic acid (a-1) The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit is not limited to the following. However, examples include alicyclic dicarboxylic acids having 3 to 12 carbon atoms in the alicyclic structure, and alicyclic dicarboxylic acids having 5 to 12 carbon atoms in the alicyclic structure are preferable.
Examples of such (a-1) alicyclic dicarboxylic acid units include, but are not limited to, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and the like. .

By including such (a-1) alicyclic dicarboxylic acid units, the heat resistance, low water absorption, rigidity, etc. of the polyamide composition tend to be more excellent.
In addition, (a-1) alicyclic dicarboxylic acid which comprises an alicyclic dicarboxylic acid unit may be used individually by 1 type, and may be used in combination of 2 or more types.

The alicyclic group of the alicyclic dicarboxylic acid unit may be unsubstituted or may have a substituent.
Examples of the substituent include, but are not limited to, for example, 1 to 1 carbon atoms of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. 4 alkyl groups and the like.

(A-2) Aromatic dicarboxylic acid unit (a-2) The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit is not limited to the following, but for example, a dicarboxylic acid having a phenyl group or a naphthyl group. Examples include acids. The aromatic group of the aromatic dicarboxylic acid unit may be unsubstituted or may have a substituent.
Although it does not specifically limit as a substituent, For example, halogen groups, such as a C1-C4 alkyl group, a C6-C10 aryl group, a C7-C10 aralkyl group, a chloro group, and a bromo group, carbon Examples thereof include silyl groups of 1 to 6, sulfonic acid groups and salts thereof (sodium salts, etc.).

Examples of the aromatic dicarboxylic acid unit include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, and 5-methylisophthalic acid. And an aromatic dicarboxylic acid having 8 to 20 carbon atoms which is unsubstituted or substituted with a predetermined substituent such as 5-sodium sulfoisophthalic acid.
(A-2) The aromatic dicarboxylic acid which comprises an aromatic dicarboxylic acid unit may be used individually by 1 type, and may be used in combination of 2 or more type.

(A-3) Aliphatic dicarboxylic acid unit (a-3) The aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit is not limited to the following, but examples thereof include malonic acid, dimethylmalonic acid, and succinic acid. Acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2- 3 to 3 carbon atoms such as methyl adipic acid, trimethyl adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid 20 linear or branched saturated aliphatic dicarboxylic acids and the like.

(A-3) When the aliphatic dicarboxylic acid unit contains an aliphatic dicarboxylic acid having 6 or more carbon atoms, the heat resistance, fluidity, toughness, low water absorption, rigidity, and the like of the polyamide composition are more excellent. This is preferable because of its tendency.
Among them, (a-3) the aliphatic dicarboxylic acid unit is preferably an aliphatic dicarboxylic acid having 10 or more carbon atoms. By using such a dicarboxylic acid, the heat resistance and low water absorption of the polyamide composition tend to be more excellent.

The aliphatic dicarboxylic acid unit having 10 or more carbon atoms is not particularly limited, and examples thereof include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Among these, sebacic acid and dodecanedioic acid are preferable from the viewpoint of heat resistance of the polyamide composition.
(A-3) As the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit, only one kind may be used alone, or two or more kinds may be used in combination.

  (A) The proportion (mol%) of dicarboxylic acid other than 1,4-cyclohexadicarboxylic acid unit in the dicarboxylic acid unit is preferably 0 to 50 mol%, and preferably 0 to 40 mol%. More preferably, it is more preferably 0 to 30 mol%.

When the aliphatic dicarboxylic acid unit (a-3) having 10 or more carbon atoms is contained, 1,4-cyclohexanedicarboxylic acid is 50 to 99.9 mol% and (a-3) the aliphatic dicarboxylic acid unit is It is preferably 0.1 to 50 mol%, more preferably 60 to 95 mol% of 1,4-cyclohexanedicarboxylic acid and (a-3) 5 to 40 mol% of an aliphatic dicarboxylic acid unit, More preferably, the 1,4-cyclohexanedicarboxylic acid is 80 to 95 mol% and the (a-3) aliphatic dicarboxylic acid unit is 5 to 20 mol%.
Polyamide that satisfies the excellent heat resistance, fluidity, toughness, low water absorption, rigidity, etc. at the same time when the ratio of the aliphatic dicarboxylic acid unit (a-3) having 10 or more carbon atoms is in the above range. There is a tendency to obtain a composition.

(A) The dicarboxylic acid constituting the dicarboxylic acid unit is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid.
Here, the “compound equivalent to dicarboxylic acid” refers to a compound that can have the same dicarboxylic acid structure as the dicarboxylic acid structure derived from the dicarboxylic acid. Examples of such compounds include dicarboxylic acid anhydrides and halides.

Moreover, (A1) polyamide may further contain the unit derived from polyvalent carboxylic acid more than trivalence, such as trimellitic acid, trimesic acid, and pyromellitic acid, as needed.
Trivalent or higher polyvalent carboxylic acids may be used alone or in combination of two or more.

The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit has a trans isomer and a cis geometric isomer.
As the alicyclic dicarboxylic acid as a raw material monomer, either a trans isomer or a cis isomer may be used, or a mixture containing a trans isomer and a cis isomer in a predetermined ratio may be used.

((B) diamine unit)
(B) The diamine unit includes at least an aliphatic diamine unit. The aliphatic diamine constituting the aliphatic diamine unit may be linear or branched. (B) The diamine unit is not limited to the following, but for example, (b-1) a diamine unit having a substituent branched from the main chain, and (b-2) a linear aliphatic diamine unit. Is mentioned. Other diamine units may include (b-3) alicyclic diamine units, (b-4) aromatic diamine units, and the like.

  (B) It is preferable that carbon number of a diamine unit is 6-12. A carbon number of 6 or more is preferable because of excellent heat resistance, and a carbon number of 12 or less is preferable because of excellent crystallinity and releasability. (B) As for carbon number of a diamine unit, 6-10 is more preferable.

(B-1) Aliphatic diamine unit having a substituent branched from the main chain (branched aliphatic diamine)
(B) The diamine unit preferably includes (b-1) an aliphatic diamine unit having a substituent branched from the main chain. (B) Since the diamine unit includes (b-1) a diamine unit having a substituent branched from the main chain, a polyamide having a high glass transition temperature Tg and high crystallinity (ie, high ΔHm1 / ΔHc) is obtained. Can be obtained. For this reason, the polyamide composition of the present invention using this polyamide tends to satisfy more excellent fluidity, toughness, rigidity and the like at the same time. Hereinafter, (b-1) an aliphatic diamine unit having a substituent branched from the main chain may be simply referred to as (b-1).
The “substituent branched from the main chain” in (b-1) is not limited to the following, but for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl Group, an alkyl group having 1 to 4 carbon atoms of a tert-butyl group, and the like.

The diamine constituting such (b-1) is not limited to the following, but for example, 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also referred to as 2-methyloctamethylenediamine), and 2,4-dimethylocta Examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as methylenediamine.
Among these, 2-methylpentamethylenediamine and 2-methyl-1,8-octanediamine are preferable, and 2-methylpentamethylenediamine is more preferable. By including such (b-1), it tends to be a polyamide composition that is superior in heat resistance and rigidity.
In addition, the diamine which comprises (b-1) may be used individually by 1 type, and may be used in combination of 2 or more type.

(B) The diamine unit preferably contains 10 mol% or more of (b-1). (B) The proportion (mol%) of (b-1) in the diamine unit is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, and still more preferably 60 to 100 mol%. Yes, more preferably 85 to 100 mol%, still more preferably 90 to 100 mol%, and most preferably 100 mol%.
(B) It is preferable that the ratio of (b-1) in the diamine unit is in the above range from the viewpoint of obtaining a polyamide having a high glass transition temperature Tg and ΔHm1 / ΔHc within the range of the present application. For this reason, the polyamide composition using this polyamide tends to be a polyamide composition that is superior in fluidity, toughness, and rigidity.

(B-2) Linear aliphatic diamine unit Hereinafter, the (b-2) linear aliphatic diamine unit may be simply referred to as (b-2).
The aliphatic diamine constituting (b-2) is not limited to the following, but for example, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine. , Straight-chain saturated aliphatic diamines having 2 to 20 carbon atoms such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.

(B-3) Alicyclic diamine unit Hereinafter, the (b-3) alicyclic diamine unit may be simply referred to as (b-3).
The alicyclic diamine (hereinafter, also referred to as “alicyclic diamine”) constituting (b-3) is not limited to the following, and examples thereof include 1,4-cyclohexanediamine and 1,3. -Cyclohexanediamine, 1,3-cyclopentanediamine, etc. are mentioned.

(B-4) Aromatic diamine unit Hereinafter, the (b-4) aromatic diamine unit may be simply referred to as (b-4).
Examples of the aromatic diamine constituting (b-4) include metaxylylenediamine, paraxylylenediamine, paraphenylenediamine, metaphenylenediamine, and the like.

Among the diamine units (b-2) to (b-4), preferably (b-2) and (b-3), more preferably a linear saturated aliphatic group having 4 to 13 carbon atoms. A diamine unit (b-2) having a straight-chain saturated aliphatic group having 6 to 12 carbon atoms, more preferably hexamethylenediamine or nonamethylenediamine. , Decamethylenediamine and dodecamethylenediamine.
By using such a diamine, the polyamide composition tends to be excellent in heat resistance, fluidity, toughness, low water absorption, rigidity, and the like.
In addition, diamine may be used individually by 1 type and may be used in combination of 2 or more types.

The total proportion (mol%) of the diamine units (b-2) to (b-4) is preferably 0 to less than 50 mol%, and 0 to 40 mol% with respect to the entire diamine unit (b). More preferably, it is more preferably 0 to 30 mol%.
(B) When the total ratio of the diamine units (b-2) to (b-4) in the diamine unit is within the above range, the polyamide composition tends to be excellent in fluidity, toughness, and rigidity.

The (A1) polyamide may further contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine, if necessary.
Trivalent or higher polyvalent aliphatic amines may be used alone or in combination of two or more.

((C) Lactam unit (c-1) and / or aminocarboxylic acid unit (c-2))
The (A1) polyamide of the present invention is the above (a) and (b), (c) lactam unit (c-1) and / or aminocarboxylic acid unit (c-), as long as the object of the present invention is not impaired. 2) can be further contained.
By including such a unit, a polyamide composition that is superior in toughness tends to be obtained. In addition, the lactam and aminocarboxylic acid which comprise a lactam unit (c-1) and aminocarboxylic acid (c-2) here mean the lactam and aminocarboxylic acid which can superpose | polymerize or condensation-polymerize.

  The lactam and aminocarboxylic acid constituting the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) are not limited to the following, but for example, lactam and amino having 4 to 14 carbon atoms Carboxylic acids are preferred, and lactams having 6 to 12 carbon atoms and aminocarboxylic acids are more preferred.

The lactam constituting the lactam unit (c-1) is not limited to the following. Noractam) and the like.
Among them, as the lactam, ε-caprolactam, laurolactam and the like are preferable, and ε-caprolactam is more preferable. By including such a lactam, it tends to be a polyamide composition having better toughness.

  The aminocarboxylic acid constituting the aminocarboxylic acid unit (c-2) is not limited to the following, and examples thereof include ω-aminocarboxylic acid and α, ω-amino acid which are compounds in which a lactam is opened. Is mentioned.

  As the aminocarboxylic acid, a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms in which the ω position is substituted with an amino group is preferable. Examples of such aminocarboxylic acids include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.

  The lactam and aminocarboxylic acid constituting the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) may each be used alone or in combination of two or more. .

The total ratio (mol%) of the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) is preferably 0 to 20 mol%, more preferably 0 to 0, based on the whole (A1) polyamide. It is 10 mol%, More preferably, it is 0-5 mol%.
When the total ratio of the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) is within the above range, effects such as improvement of fluidity tend to be obtained.

(End sealant)
The terminal of (A1) polyamide used in the present invention may be end-capped with a known end-capping agent.
Such an end-capping agent is also added as a molecular weight regulator in the production of (A1) polyamide from the above-described dicarboxylic acid and diamine and lactam and / or aminocarboxylic acid used as necessary. Can do.

Examples of end-capping agents include, but are not limited to, acid anhydrides such as monocarboxylic acids, monoamines, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. Etc.
Among these, monocarboxylic acid and monoamine are preferable. (A1) Since the end of the polyamide is sealed with an end-capping agent, the polyamide composition tends to be more excellent in thermal stability. Only one type of end capping agent may be used alone, or two or more types may be used in combination.

The monocarboxylic acid that can be used as the end-capping agent is not limited to the following as long as it has reactivity with the amino group that can be present at the terminal of the (A1) polyamide. For example, formic acid Aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; cyclohexanecarboxylic acid, etc. And aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid. Of these, acetic acid is particularly preferred.
A monocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.

In order to obtain the polyamide of the present invention, it is preferable to use a monocarboxylic acid as a terminal blocking agent. The addition amount of the monocarboxylic acid is preferably 0.1 to 2.0 mol%, more preferably 0.3 to 1.5 mol%, and still more preferably 0.5 to mol with respect to the charged diamine. -1.5 mol%. By setting such addition amount, the ratio [NH ₂ ] / ([NH ₂ ] + [COOH]) of the amino terminal amount to the total active terminal amount can be less than 0.5, and the trans isomer ratio Can be more than 71 mol% and 75 mol% or less.

The monoamine that can be used as the end-capping agent is not limited to the following as long as it has reactivity with the carboxyl group that can be present at the end of the (A1) polyamide, but for example, methylamine, Aliphatic monoamines such as ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aniline , Aromatic monoamines such as toluidine, diphenylamine, and naphthylamine.
Only one monoamine may be used alone, or two or more monoamines may be used in combination.

  A polyamide composition containing (A1) polyamide end-capped with a terminal capping agent tends to be excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity.

Next, a production method for obtaining the first polyamide of the present invention will be described.
[(A1) Polyamide Production Method]
The first polyamide production method of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine,
[NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio of the amino terminal amount [NH ₂ ] to the total active terminal amount ([NH ₂ ] + [COOH]),
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5,
Active terminal total amount ([NH ₂ ] + [COOH]) μeq / g is
60 ≦ [NH ₂ ] + [COOH] <110
Is heat-treated at 200 ° C. or higher and lower than the melting point for 10 hours or longer.

That is, the first method for producing a polyamide of the present invention is a method for obtaining a polyamide having a specific terminal structure (hereinafter referred to as a precursor polyamide), and further heat-treating it below the melting point (A1) to obtain a polyamide. . As such a production method, a “hot melt polymerization / solid phase polymerization method” is preferable.
Hereinafter, the method for obtaining the precursor polyamide (thermal melt polymerization method) and the heat treatment (solid phase polymerization method) will be described in detail.

<Method for obtaining precursor polyamide>
The method for obtaining the precursor polyamide is not particularly limited, and examples thereof include the methods exemplified below.
1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter referred to as hot melt polymerization method).
2) A method in which an aqueous solution or suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated, and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization (hereinafter referred to as prepolymer · Called the extrusion polymerization method).
3) A method of polymerizing using a dicarboxylic acid halide equivalent to a dicarboxylic acid and a diamine (hereinafter referred to as a solution method).
Among them, the hot melt polymerization method is preferable from the viewpoint of increasing the molecular weight by polymerization in a short time and suppressing gelation.
When the precursor polyamide is produced, it is preferable that (a) the addition amount of the dicarboxylic acid constituting the dicarboxylic acid unit and (b) the addition amount of the diamine constituting the diamine unit are about the same molar amount.
(A) The dicarboxylic acid unit preferably contains 50 to 100 mol% of 1,4-cyclohexanedicarboxylic acid units (based on the total number of dicarboxylic acids), more preferably 60 to 100 mol%, and 70 to 100 mol. % Is more preferable, and 100 mol% is most preferable.

It is known that alicyclic dicarboxylic acids are isomerized at high temperatures, and the trans isomer and cis isomer are in a certain ratio, and the cis alicyclic dicarboxylic acid is more trans alicyclic dicarboxylic acid. Compared with an acid, the water solubility of an equivalent salt of an alicyclic dicarboxylic acid and a diamine tends to be higher. From this, the trans isomer / cis isomer ratio (molar ratio) of the alicyclic dicarboxylic acid as the raw material monomer is preferably 50/50 to 0/100, more preferably 40/60 to 10/90. More preferably, it is 35/65 to 15/85.
The trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR).

  (B) The diamine unit preferably includes (b-1) an aliphatic diamine unit having a substituent branched from the main chain, and the proportion is preferably 10 to 100 mol%, more preferably 50 to 100 mol%. 60-100 mol% is more preferable, 85-100 mol% is still more preferable, 90-100 mol% is especially preferable, and 100 mol% is the most preferable. (B-1) is most preferably 2-methyl-5-pentamethylenediamine.

When the precursor polyamide is produced (thermal melt polymerization), a terminal blocking agent may be used for molecular weight and terminal adjustment. The terminal blocking agent is not particularly limited, but acetic acid is preferable. The amount of acetic acid added to the charged diamine is 0.1 to 2.0 mol%, more preferably 0.3 to 1.5 mol%, and still more preferably 0.5 to 1.5 mol% in molar ratio.
Moreover, when manufacturing precursor polyamide (thermal melt polymerization), you may add a diamine in addition to the (b) diamine unit. Such diamine is preferably 2-methyl-5-pentamethylenediamine. (B) The amount of added diamine with respect to the diamine unit is 1.0 to 5.0 mol%, more preferably 1.5 to 4.5 mol%, still more preferably 2.0 to 4.0 mol% in terms of molar ratio. It is.

Moreover, you may add a phosphorus compound as a heat stabilizer (catalyst) at the time of hot melt polymerization. The heat stabilizer is not particularly limited, but sodium hypophosphite is preferable.
In the method for producing the precursor polyamide, from the viewpoint of the color tone and fluidity of the polyamide, it is preferable to carry out hot melt polymerization while maintaining the trans isomer ratio of the dicarboxylic acid monomer unit in the polyamide at 85% or less. It is more preferable to perform hot melt polymerization while maintaining the trans isomer ratio of the dicarboxylic acid monomer unit at 80% or less.

  (A1) The method for producing polyamide preferably further includes a step of increasing the degree of polymerization of the polyamide. Moreover, the sealing process which seals the terminal of the obtained polymer with a terminal sealing agent may be included as needed.

<Physical properties of precursor polyamide>
The physical property of the precursor polyamide is the ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]) [NH ₂ ] / ([NH ₂ ] + [COOH]) is 0. Less than 5 is preferable, 0.2 or more and less than 0.5 is more preferable, and 0.2 to 0.4 is more preferable. The active terminal total amount ([NH ₂ ] + [COOH]) is preferably 60 or more and less than 110 μeq / g, more preferably 70 to 110 μeq / g, still more preferably 80 to 110 μeq / g, and 80 to 100 μm. Equivalent / g is particularly preferred.
In order to obtain such physical properties of the precursor polyamide, the terminal structure of the polyamide is controlled by adjusting the amount of the structural units (a) to (c) of the polyamide, the end-capping agent and the additional diamine. Can be obtained.

<Heat treatment>
The heat treatment in the production method of the present invention is a method of heating the precursor polyamide at 200 ° C. or higher and lower than the melting point (Tm 2).
The heat treatment method is not particularly limited as long as heating at 200 ° C. or more and less than the melting point (Tm2) is possible. For example, apparatuses such as a dryer, an autoclave, an electric furnace, a gear oven, a hot plate, and a molding die This can be done by using The heat treatment may be performed in the air, may be performed in an inert gas atmosphere, for example, a nitrogen gas atmosphere, or may be performed in a reduced pressure environment. As the heat treatment method, a solid phase polymerization method in which constituent units such as monomers and precursor polyamide are polymerized in a solid state at a temperature lower than the melting point is preferable.

  The heat treatment temperature is 200 ° C. to less than the melting point (Tm 2), more preferably 220 ° C. to less than the melting point (Tm 2), and even more preferably 240 ° C. to less than the melting point (Tm 2). By making it 200 degreeC or more, the trans isomer ratio of the 1, 4- cyclohexane dicarboxylic acid monomer unit in polyamide can be made larger than 71 mol%. On the other hand, when the melting point is less than (Tm2), it is possible to satisfactorily prevent the polyamide from melting, so that the trans isomer ratio can be made larger than 71 mol%. The heat treatment time can be appropriately selected depending on the heat treatment temperature. For example, when the heat treatment time is 200 to 240 ° C., it is preferably 10 to 72 hours, more preferably about 10 to 48 hours.

Next, physical properties of the polyamide of the present invention will be described.
[(A1) Physical properties of polyamide]
<Trans isomer ratio>
(A1) The trans isomer ratio of the dicarboxylic acid monomer unit in the polyamide is preferably more than 71 mol% and 75 mol% or less, more preferably 72 mol% or more and 75 mol% or less.
Since the polyamide of the present invention is highly crystallized because the trans isomer ratio is in the above range, the polyamide and the polyamide composition of the present invention have a high melting point, toughness and rigidity, in addition to the characteristics of being high. It tends to have the property of simultaneously satisfying the thermal rigidity due to the glass transition temperature (Tg), the fluidity, which is usually a property contrary to heat resistance, and the high crystallinity.

As described above, the trans isomer ratio of the dicarboxylic acid monomer unit in such a polyamide can be controlled by controlling the carboxyl terminal amount of the polyamide and the method for producing the polyamide of the present invention.
The trans isomer ratio (molar ratio) of the 1,4-cyclohexanedicarboxylic acid monomer unit of the polyamide composition molded product can be determined by nuclear magnetic resonance spectroscopy (NMR).

<Sulfuric acid relative viscosity ηr>
(A1) The sulfuric acid relative viscosity ηr of the polyamide is preferably larger than 1.8. More than 1.8 and 3.0 or less are more preferable, and 2.0 or more and 2.5 or less are more preferable. When it is larger than 1.8, the mechanical properties of toughness and rigidity are excellent, and when it is 3.0 or less, the fluidity and moldability are excellent.
The sulfuric acid relative viscosity ηr at 25 ° C. can be measured at 25 ° C. in 98% sulfuric acid according to JIS-K6920.

<Molecular weight>
(A1) As an index of the molecular weight of polyamide, the number average molecular weight Mn, the weight average molecular weight Mw, and the molecular weight distribution Mw / Mn obtained by GPC (gel permeation chromatography) can be used. The larger the Mn, the higher the molecular weight of the (A1) polyamide, and the smaller the Mn, the lower the molecular weight of the (A1) polyamide.
(A1) The Mn of the polyamide is preferably greater than 15000, more preferably 18000 or greater, and even more preferably 19000 or greater.
Further, the Mw / Mn of the (A1) polyamide is preferably less than 3.5, more preferably 3.0 or less.
When the number average molecular weight Mn and the molecular weight distribution Mw / Mn are in the above ranges, it tends to be a polyamide composition having excellent mechanical properties such as toughness and rigidity, and moldability.
In addition, Mn and Mw can produce | generate a calibration curve using the number average molecular weight Mn measured by PMMA (polymethylmethacrylate) standard sample (made by a polymer laboratory company), and can obtain | require the molecular weight of polyamide. More specifically, it is measured by the method described in the following examples.

<Melting peak temperature Tm1, Tm2>
(A1) The melting peak temperature Tm1 of the polyamide is preferably 300 ° C. or higher, more preferably 320 ° C. or higher, and further preferably 325 ° C. or higher.
The melting peak temperature Tm1 of (A1) polyamide is preferably 350 ° C. or lower, more preferably 345 ° C. or lower, and further preferably 340 ° C. or lower.
(A1) When the melting peak temperature Tm1 of the polyamide is 300 ° C. or higher, a polyamide composition excellent in heat resistance tends to be obtained.
Moreover, when (A1) polyamide melting peak temperature Tm1 is 350 ° C. or less, (A1) thermal decomposition of polyamide in melt processing such as extrusion and molding tends to be further suppressed.

(A1) The melting peak temperature Tm2 of the polyamide is preferably 270 ° C. or higher, more preferably 275 ° C. or higher, and further preferably 280 ° C. or higher.
The melting peak temperature Tm2 of the (A1) polyamide is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.
(A1) When the melting peak temperature Tm2 of the polyamide is 270 ° C. or higher, a polyamide composition excellent in heat resistance tends to be obtained.
Moreover, when (A1) polyamide melting peak temperature Tm2 is 350 ° C. or less, (A1) thermal decomposition of polyamide in melt processing such as extrusion and molding tends to be further suppressed.
(A1) The melting peak temperatures Tm1 and Tm2 of the polyamide can be measured according to JIS-K7121 by the method described in Examples below.

<Heat of fusion ΔHm1, ΔHm2, crystallization enthalpy ΔHc>
(A1) The heat of fusion ΔHm1 and crystallization enthalpy ΔHc of the polyamide are each preferably 30 J / g or more, more preferably 35 J / g or more, and still more preferably 40 J / g or more. Moreover, the upper limit of the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc is not particularly limited and is preferably as high as possible.
(A1) When the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide are each 30 J / g or more, the heat resistance of the polyamide composition tends to be further improved.
(A1) The heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide can be measured according to JIS-K7121 by the method described in Examples below.
The heat of fusion ΔHm1 and crystallization enthalpy ΔHc of the (A1) polyamide described above can be measured according to JIS-K7121 by the method described later.
The heat of fusion ΔHm2 of the polyamide is preferably 20 J / g or more, more preferably 25 J / g or more, and further preferably 30 J / g or more. Moreover, the upper limit of the heat of fusion ΔHm2 is not particularly limited and is preferably as high as possible.
When the heat of fusion ΔHm2 of the polyamide is 20 J / g or more, the heat resistance of the polyamide composition tends to be further improved.

<Ratio of heat of fusion ΔHm1 and crystallization enthalpy ΔHc ΔHm1 / ΔHc>
The heat of fusion ΔHm1 is a heat of fusion reflecting the heat history received by the polyamide during heat treatment or cooling, and is different from the heat of fusion inherent in the polyamide. On the other hand, ΔHc is a crystallization enthalpy obtained through a cooling process (slow cooling) after complete melting, and is equal to the heat of fusion inherent in polyamide. Therefore, ΔHm1 / ΔHc means the ratio between the heat of fusion inherent in polyamide and the heat of fusion of polyamide subjected to a thermal history. For example, when heat treatment is performed at a temperature lower than the melting point, crystallization proceeds and ΔHm1 increases, so that ΔHm1 / ΔHc> 1.0. In the case of rapid cooling, crystallization does not proceed and ΔHm1 becomes small, so ΔHm1 / ΔHc ≦ 1.0.
(A1) Ratio ΔHm1 / ΔHc of polyamide heat of fusion ΔHm1 and crystallization enthalpy ΔHc is greater than 1.0 and less than or equal to 2.2, preferably greater than 1.0 and less than or equal to 1.4, more preferably 1 It is 1 or more and 1.4 or less, More preferably, it is 1.2 or more and 1.4 or less.
(A1) The ratio ΔHm1 / ΔHc between the heat of fusion ΔHm1 of the polyamide and the crystallization enthalpy ΔHc is greater than 1.0 and 2.2 or less, whereby the heat resistance of the polyamide composition tends to be improved.

  (A1) When the ratio ΔHm1 / ΔHc of the heat of fusion ΔHm1 and crystallization enthalpy ΔHc of the polyamide is y and the trans isomer ratio is x, it is preferable that y ≧ 0.04x−1.8. The heat resistance of the composition tends to be improved.

<Difference between melting peak temperature Tm1 and crystallization peak temperature Tc (Tm1-Tc)>
(A1) When the difference (Tm1−Tc) between the melting peak temperature Tm1 and the crystallization peak temperature Tc of the polyamide is in the range higher than 40 ° C. and lower than 90 ° C., the polyamide composition is excellent in fluidity and improved in releasability. Tend to. Tm1-Tc is preferably higher than 40 ° C and lower than 90 ° C, and more preferably 50 ° C to 80 ° C.

  The measurement of the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide can be carried out according to JIS-K7121, and the heat of fusion ΔHm1 is measured when the temperature of the polyamide is raised at a heating rate of 20 ° C./min (the first temperature rise). The endothermic peak appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time) is the peak area of Tm when the melting peak temperature is Tm (° C.). When there are a plurality of endothermic peaks, a peak having ΔH of 1 J / g or more is regarded as a peak, the highest temperature is defined as a melting peak temperature Tm1, and ΔHm1 is a sum of peak areas. The crystallization enthalpy ΔHc is the Tc value when the temperature of the exothermic peak (crystallization peak) that appears when the polyamide composition molded article is cooled at a temperature decrease rate of 20 ° C./min is the crystallization peak temperature Tc (° C.). It is the peak area. As the measuring device, Diamond-DSC manufactured by PERKIN-ELMER can be used as described in the following examples.

<Glass transition temperature Tg>
(A1) The glass transition temperature Tg of the polyamide is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, even more preferably 130 ° C. or higher, and even more preferably. Is 135 ° C. or higher.
The glass transition temperature Tg of (A1) polyamide is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
(A1) When the glass transition temperature Tg of polyamide is 90 ° C. or higher, a polyamide composition excellent in heat discoloration resistance and chemical resistance tends to be obtained. Moreover, when the glass transition temperature Tg of (A1) polyamide is 170 ° C. or lower, a molded product having a good appearance tends to be obtained.
(A1) The glass transition temperature Tg of polyamide can be measured according to JIS-K7121, as described in the following examples.
Examples of the measuring device for the glass transition temperature Tg include Diamond-DSC manufactured by PERKIN-ELMER.

<Polymer end>
Although it does not specifically limit as a polymer terminal of (A1) polyamide used for this invention, It can classify | categorize and define as follows.
That is, 1) amino terminal, 2) carboxyl terminal, 3) cyclic amino terminal, 4) terminal by sealing agent, and 5) other terminal.

1) the amino terminus is a polymer end with an amino group (-NH ₂ group), derived from (b) diamine units of the raw material.
Amino-terminal amount _([NH 2]), to the (A1) Polyamide 1g, preferably 5~100μ eq / g, more preferably from 5~70μ eq / g, more preferably 5~50μ equivalents / G, even more preferably 5 to 30 μ equivalent / g, and particularly preferably 5 to 20 μ equivalent / g.
When the amino terminal amount is in the above range, the whiteness, reflow resistance, heat discoloration resistance, light discoloration resistance, hydrolysis resistance, and heat retention stability of the polyamide composition tend to be more excellent. The amino terminal amount can be measured by neutralization titration. Specifically, 3.0 g of polyamide is dissolved in 100 mL of a 90 mass% phenol aqueous solution, and the obtained solution is titrated with 0.025N hydrochloric acid to obtain the amino terminal amount (μ equivalent / g). The end point is determined from the indicated value of the pH meter.

2) The carboxyl terminal is a polymer terminal having a carboxyl group (—COOH group) and is derived from the raw material (a) dicarboxylic acid.
The carboxyl terminal amount ([COOH]) is preferably 5 to 100 μequivalent / g, more preferably 5 to 70 μequivalent / g, and further preferably 5 to 50 μequivalent / g with respect to 1 g of (A1) polyamide. g, even more preferably 5 to 30 μequivalent / g, and particularly preferably 5 to 20 μequivalent / g. When the carboxyl end amount is in the above range, the whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance of the polyamide composition tend to be more excellent. The carboxyl end amount can be measured by neutralization titration. Specifically, 4.0 g of polyamide is dissolved in 50 mL of benzyl alcohol, and the obtained solution is titrated with 0.1 N NaOH to obtain the carboxyl terminal amount (μ equivalent / g). The end point is determined from the discoloration of the phenolphthalein indicator.

Here, the total amount of the amino terminal amount ([NH ₂ ]) and the carboxyl terminal amount ([COOH]) is defined as the active terminal total amount ([NH ₂ ] + [COOH]). The total amount of active terminals is preferably 10 to 200 μeq / g, more preferably 10 to 150 μeq / g, and still more preferably 10 to 100 μeq / g, based on 1 g of (A1) polyamide. Most preferably, it is 20-60 microequivalent / g.
[NH ₂ ] / ([NH ₂ ] + [COOH]), which is a ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]), is preferably 0.5. It is less than, More preferably, it is 0.2 or more and less than 0.5, More preferably, it is 0.2 or more and 0.4 or less, Most preferably, it is 0.2 or more and 0.3 or less. It is possible to control ΔHm1 / ΔHc to be larger than 1.0 and 2.2 or less because the ratio of the total amount of amino terminal and carboxyl terminal and the ratio of amino terminal to the total active terminal is within the above range. The whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance of the polyamide composition tend to be more excellent.

  Examples of the method for controlling the ratio of the amino terminal amount to the total active terminal amount include a method of controlling the addition amount of diamine and terminal blocking agent as additives during hot melt polymerization of polyamide, and the polymerization conditions. .

3) The cyclic amino terminus is a polymer terminus having a cyclic amino group (a group represented by the following (formula 1)).
In the following (Formula 1), R represents a substituent bonded to the carbon constituting the piperidine ring. Specific examples of R include a hydrogen atom, a methyl group, an ethyl group, and a t-butyl group.
Further, for example, even when piperidine cyclized by a deammonia reaction of a diamine having a pentamethylenediamine skeleton as a raw material is bonded to the polymer terminal, it becomes the terminal of this cyclic amino group. These structures may be taken when a monomer having a pentamethylenediamine skeleton is included.

・・・（式１）

... (Formula 1)

3) The amount of the cyclic amino terminal is preferably 30 μeq / g or more and 100 μeq / g or less, more preferably 30 μeq / g or more and 80 μeq / g or less, with respect to 1 g of (A1) polyamide. Preferably they are 35 microequivalent / g or more and 70 microequivalent / g or less.
When the amount of the cyclic amino terminus is in the above range, the polyamide composition of the present invention tends to have better toughness, hydrolysis resistance, and processability.

The amount of the cyclic amino terminus can be measured using ¹ H-NMR. For example, there is a method of calculation based on the integral ratio of hydrogen bonded to carbon adjacent to the nitrogen atom of the heterocyclic ring of nitrogen and hydrogen bonded to carbon adjacent to the nitrogen atom of the amide bond of the polyamide main chain.

  Cyclic amino terminal can be generated by dehydration reaction of cyclic amine and carboxyl terminal, and can also be generated by deammonia reaction of amino terminal in the polymer molecule. Cyclic amine is added as end-capping agent. It can also be produced by the diamine having a pentamethylenediamine skeleton, which is a raw material for polyamide, and cyclizing by deammonia reaction.

In the present invention, the cyclic amino terminal is preferably derived from a raw material diamine.
Without adding cyclic amine as an end-capping agent at the initial stage of polymerization, the cyclic amino terminal is generated from the raw material diamine, so that the low molecular weight carboxylic acid terminal is prevented from being blocked at the initial stage of polymerization. Thus, the polymerization reaction rate of the polyamide is maintained high, and as a result, a high molecular weight product tends to be easily obtained. As described above, when a cyclic amine is generated during the reaction, the carboxylic acid terminal is sealed with the cyclic amine at a later stage of the polymerization, so that a high molecular weight polyamide is easily obtained.

  Cyclic amines that generate a cyclic amino terminus can be generated as a by-product during the polymerization reaction of the polyamide. In this cyclic amine formation reaction, the higher the reaction temperature, the higher the reaction rate. Therefore, in order to make the cyclic amino terminal of the (A1) polyamide constant, it is preferable to promote the formation of a cyclic amine. Therefore, the reaction temperature for the polymerization of the precursor polyamide is preferably 300 ° C. or higher, and more preferably 320 ° C. or higher.

  As a method for adjusting these cyclic amino ends to a certain amount, control is performed by appropriately adjusting the polymerization temperature, the holding time of the reaction temperature of 300 ° C. or more during the polymerization step, the addition amount of the amine forming the cyclic structure, and the like. The method of doing is mentioned.

  4) The terminal by a sealing agent is a terminal formed when a sealing agent is added at the time of superposition | polymerization. Examples of the sealing agent include the above-described end sealing agents.

  5) The other terminal is a polymer terminal not classified in the above 1) to 4), such as a terminal generated by deammonia reaction at the amino terminal or a terminal generated by decarboxylation from the carboxylic acid terminal. It is done.

[First polyamide composition]
The first polyamide composition contains the first polyamide and at least one of an inorganic filler, a nucleating agent, a heat stabilizer and a light stabilizer. Furthermore, titanium oxide may be included. By containing such a structural component, a polyamide composition excellent in heat resistance, whiteness, reflow resistance, aging resistance and releasability can be obtained.
Hereinafter, the components of the first polyamide composition will be described.

((B) Titanium oxide)
The first polyamide composition of the present invention may further contain (B) titanium oxide.
Examples of (B) titanium oxide include, but are not limited to, titanium monoxide (TiO), dititanium trioxide (Ti ₂ O ₃ ), and titanium dioxide (TiO ₂ ). Of these, titanium dioxide is preferable.

  The crystal structure of (B) titanium oxide is not particularly limited, but is preferably a rutile type from the viewpoint of light resistance of the polyamide composition.

(B) Titanium oxide is preferably in the form of particles, and the number average particle diameter of (B) titanium oxide is preferably 0.1 to 0.8 μm, more preferably 0.15 to 0.4 μm. More preferably, it is 0.15-0.3 micrometer.
(B) When the number average particle diameter of titanium oxide is 0.1 μm or more, the extrusion processability of the polyamide composition tends to be further improved.
(B) When the number average particle diameter of titanium oxide is 0.8 μm or less, the toughness of the polyamide composition tends to be further improved.
(B) The number average particle diameter of titanium oxide can be measured by an electron micrograph. For example, the polyamide composition is put in an electric furnace, the organic matter contained in the polyamide composition is incinerated, and, for example, 100 or more arbitrarily selected titanium oxides from the residue are observed with an electron microscope. By measuring the particle diameter, it is possible to determine the number average particle diameter of (B) titanium oxide.

  (B) Although the manufacturing method of titanium oxide is not limited to the following, for example, a so-called sulfuric acid method in which a titanium sulfate solution is hydrolyzed, or a so-called chlorine method in which titanium halide is oxidized in a gas phase can be mentioned.

(B) It is preferable that the titanium oxide has an inorganic coating layer and / or an organic coating layer on the surface.
In particular, (B) titanium oxide having an inorganic coating layer on the surface of titanium oxide and an organic coating layer on the inorganic coating layer is preferable.

(B) Titanium oxide may be coated using any known method.
The inorganic coating is not limited to the following, but preferably includes, for example, a metal oxide.

The organic coating is not limited to the following, but for example, it preferably contains one or more organic substances selected from the group consisting of carboxylic acids, polyols, alkanolamines, and organosilicon compounds.
Among these, from the viewpoint of light resistance and extrusion processability of the polyamide composition, the surface of (B) titanium oxide is more preferably coated using polyols and organosilicon compounds. From the viewpoint of reducing generated gas, it is more preferable that coating is performed using an organosilicon compound.

  In addition, as (B) titanium oxide, only 1 type may be used independently and 2 or more types may be used in combination.

The content of (B) titanium oxide in the first polyamide composition is preferably 5% by mass to 70% by mass with respect to 100% by mass of the first polyamide composition, and is 20% by mass to 70% by mass. More preferably, it is 25-60 mass%, More preferably, it is 30-50 mass%.
(B) When the content of titanium oxide is in the above range, the whiteness of the polyamide composition tends to be more excellent.

((C) inorganic filler)
The first polyamide composition may further contain (C) an inorganic filler other than (B) titanium oxide described above from the viewpoint of mechanical properties such as strength and rigidity.
(C) The inorganic filler is not limited to the following, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, hydrotalcite, carbonic acid Zinc, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene Examples thereof include black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluorine mica, and apatite.

  Among these, as the inorganic filler (C), at least one selected from the group consisting of glass fiber, potassium titanate fiber, wollastonite, and clay is preferable, and wollastonite is more preferable.

(C) The number average particle diameter of the inorganic filler is preferably from 0.1 to 20 μm, more preferably from 0.15 to 15 μm, from the viewpoint of whiteness, toughness and extrusion processability of the first polyamide composition. Preferably it is 0.15-10 micrometers.
By including such an inorganic filler (C), the mechanical strength, appearance, whiteness and the like of the first polyamide composition tend to be more excellent.
(C) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the inorganic filler (C) in the first polyamide composition is preferably 1 to 30% by mass, more preferably 1 to 20% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 1-10 mass%.
(C) When content of an inorganic filler exists in said range, the intensity | strength of the 1st polyamide composition, rigidity, and toughness can be maintained with a sufficient balance.
From the above viewpoint, the content of the (C) inorganic filler is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 5% by mass or more.

((D) Nucleator)
The first polyamide composition preferably further contains a nucleating agent from the viewpoint of releasability.
“Nucleating agent” refers to a substance that can increase the crystallization peak temperature measured by differential scanning calorimetry when added, and can improve the spherulites of the resulting molded product or make the size uniform. Means that.

Examples of the nucleating agent include, but are not limited to, talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, carbon black, potassium titanate, and molybdenum disulfide. It is done.
A nucleating agent may be used individually by 1 type, and may combine 2 or more types.
Among these, talc, boron nitride, and carbon black are preferable from the viewpoint of the nucleation effect, more preferably talc and boron nitride, and still more preferably talc.

The nucleating agent is preferably in the form of particles, and the number average particle diameter of the nucleating agent is preferably 0.01 to 10 μm, more preferably 0.5 to 5 μm.
When the number average particle diameter of the nucleating agent is within the above range, the nucleating effect tends to be further improved.
For the measurement of the number average particle size of the nucleating agent, the molded article of the polyamide composition is dissolved in a polyamide-soluble solvent such as formic acid, and, for example, 100 or more nucleating agents are obtained from the obtained insoluble components. It can be selected arbitrarily and observed and obtained with an optical microscope or a scanning electron microscope.

The blending amount of the nucleating agent is preferably 0.001 to 15% by mass, more preferably 0.001 to 5% by mass, and still more preferably 0.001 to 100% by mass of the polyamide composition. It is -3 mass%, More preferably, it is 0.5-2.5 mass%.
By making the blending amount of the nucleating agent 0.001% by mass or more with respect to 100% by mass of the polyamide composition, the heat resistance of the polyamide composition is improved favorably, and the blending amount is made 15% by mass or less. As a result, a polyamide composition having excellent toughness can be obtained.

(Heat stabilizer)
The first polyamide composition may contain a heat stabilizer from the viewpoint of heat stability. As the heat stabilizer, the following (E) metal hydroxide, (F) phosphorus compound, (G) phenol antioxidant and / or amine antioxidant can be mentioned.

<(E) Metal hydroxide>
The first polyamide composition may contain (E) a metal hydroxide as a heat stabilizer.
(E) The metal hydroxide is represented by a general formula M (OH) x (M represents a metal element, and x represents a number corresponding to the multivalent value of M).
The metal element M is preferably a monovalent or higher metal. Examples of the monovalent or higher metal include, but are not limited to, sodium, potassium, lithium, calcium, magnesium, barium, zinc, aluminum, strontium, and the like. As the metal element M, an alkaline earth metal is preferable.

The (E) metal hydroxide contained in the first polyamide composition is not limited to the following. For example, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, hydroxide Aluminum, zinc hydroxide, manganese hydroxide, etc. are mentioned. Among these, from the viewpoint that the polyamide composition is excellent in reflow resistance, extrusion process stability, and molding process stability, calcium hydroxide and magnesium hydroxide are preferable, and calcium hydroxide is more preferable.
(E) A metal hydroxide may be used individually by 1 type, and may use 2 or more types together.
Moreover, you may use these (E) metal hydroxide which performed the surface treatment in order to improve adhesiveness and a dispersibility.
Examples of the surface treatment agent include, but are not limited to, for example, silane coupling agents such as aminosilane and epoxysilane, organosilicon compounds such as silicone; organic titanium compounds such as titanium coupling agents; organic acids and polyols And organic substances such as

  The (E) metal hydroxide in the first polyamide composition is preferably particulate, and the average particle diameter is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm. When the average particle diameter is in the above range, the effects of reflow resistance and heat discoloration can be obtained in the polyamide composition.

Moreover, the mass ratio of the particle | grains of 30 micrometers or more with respect to the whole particle | grains of (E) metal hydroxide becomes like this. Preferably it is 1 mass% or less, More preferably, it is 0.1 mass% or less.
(E) By making the mass ratio of the particle | grains 30 micrometers or more with respect to the whole metal hydroxide into the said range, in the 1st polyamide composition, the effect of reflow resistance and heat-resistant discoloration property is acquired.

  The purity of the (E) metal hydroxide in the first polyamide composition is preferably 99% or more, more preferably 99.5% or more, and further preferably 99.9% or more. Due to the high purity, the whiteness, reflow resistance, and light discoloration resistance of the first polyamide composition tend to be excellent.

The content of the metal hydroxide (E) described above is 0.1 to 20% by mass, preferably 0.1 to 10% by mass, more preferably 100% by mass with respect to 100% by mass of the first polyamide composition. Is 0.3-5% by mass, more preferably 0.3-2% by mass, even more preferably 0.5-1.5% by mass, and still more preferably 0.5-1. 0% by mass.
(E) When the content of the metal hydroxide is within the above range, the polyamide composition tends to be more excellent in heat discoloration resistance, extrusion processing stability, and molding processing stability.

The first polyamide composition may further contain a metal compound other than the above-described (C) metal hydroxide from the viewpoint of whiteness and heat discoloration.
(E) The metal compound other than the metal hydroxide is not limited to the following, and examples thereof include metal carbonates and metal halides.
(E) Although it does not specifically limit as a metal element contained in metal compounds other than a metal hydroxide, For example, a monovalent or more metal element is preferable. Examples of such metal elements include, but are not limited to, sodium, potassium, lithium, calcium, magnesium barium, zinc, aluminum, strontium, and the like. As the metal element, an alkaline earth metal is preferable.

  (E) The metal hydroxide may be added during the polymerization of (A1) polyamide, but is preferably added during the production of the polyamide composition mixed with (A1) polyamide after the polymerization of (A1) polyamide. By adding it during the production of the polyamide composition, the thermal history can be reduced, (E) the decomposition of the metal hydroxide can be suppressed, whiteness, reflow resistance, heat discoloration resistance, extrusion processing And a polyamide composition excellent in molding process stability can be obtained.

<(F) Phosphorus compound>
The polyamide composition may contain (F) a phosphorus compound as a heat stabilizer.
Examples of (F) phosphorus compounds include, but are not limited to, 1) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof, 2) Examples thereof include phosphoric acid, phosphorous acid, hypophosphorous acid, and metal salts of intramolecular and / or intermolecular condensates thereof.
In addition, (F) phosphorus type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof in 1) are not limited to the following, but examples include phosphoric acid, pyrophosphoric acid, and metalin. Examples thereof include acids, phosphorous acid, hypophosphorous acid, pyrophosphorous acid, and diphosphorous acid.
The metal salts of the above-mentioned 2) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof are not limited to the following. Mention may be made of salts of the compounds with Group 1 and 2 of the periodic table, manganese, zinc and aluminum.

  More preferable (F) phosphorus compounds are selected from the group consisting of metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts. One or more selected. By using such a phosphorous compound (F), the polyamide composition tends to be more excellent in whiteness, heat discoloration resistance, heat reflow resistance, and light discoloration resistance.

More preferable (F) phosphorus compound is a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid, group 1 (alkali metal) and group 2 (alkaline earth metal) of the periodic table, manganese , Zinc, and a metal selected from aluminum, or an intramolecular condensate of these metal salts or an intermolecular condensate of these metal salts.
More preferably (F) phosphorus compound is a metal salt containing a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid, and a metal selected from Groups 1 and 2 of the periodic table. is there.

The metal salt as such a (F) phosphorus compound is not particularly limited. For example, monosodium phosphate, disodium phosphate, trisodium phosphate, monocalcium phosphate, dicalcium phosphate, phosphoric acid Tricalcium, sodium pyrophosphate, sodium metaphosphate, calcium metaphosphate, sodium hypophosphite, calcium hypophosphite and the like; their anhydrous salts; and their hydrates.
Among these, sodium hypophosphite, calcium hypophosphite, and magnesium hypophosphite are preferable, and calcium hypophosphite and magnesium hypophosphite, which are alkaline earth metal salts, are more preferable. By using such a phosphorus compound (F), it tends to be more excellent in whiteness, heat discoloration resistance, light discoloration resistance and extrusion processability.

  (F) Phosphorus compound selected from the group consisting of the above-mentioned metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts Is more preferably a metal hypophosphite salt. (F) When a phosphorus compound is a hypophosphite metal salt, the 1st polyamide composition excellent in extrusion processability and shaping | molding process stability can be obtained.

Metal of (F) phosphorus compound selected from the group consisting of metal phosphate, metal phosphite, metal hypophosphite, intramolecular condensate of these metal salts, and intermolecular condensate of these metal salts The species is preferably the same as the metal species of (E) the metal hydroxide.
In particular, the metal species of the (F) phosphorus compound is preferably an alkaline earth metal.
(F) The phosphorus compound is selected from the group consisting of metal salts, intramolecular condensates of metal salts, and intermolecular condensates of metal salts, and (F) the metal species of the phosphorus compound is (E) metal When the metal species of the hydroxide are the same, it is possible to obtain a polyamide composition having improved thermal stability and excellent extrusion processability and molding process stability. Furthermore, by using an alkaline earth metal as the metal species of the (F) phosphorus compound, a more excellent effect can be obtained in the above characteristics.

(F) Phosphorus compound selected from the group consisting of metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts, A metal salt containing no anhydrous salt or hydrate is preferred.
(F) By using an anhydrous salt or a metal salt that does not contain a hydrate as the phosphorus compound, the amount of water generated during processing can be suppressed, and a decrease in the molecular weight of polyamide and gas generation can be suppressed. . (F) Polyamide composition having excellent whiteness, reflow resistance, heat discoloration resistance, extrusion processability, and molding process stability by using an anhydrous salt or a metal salt that does not contain hydrates as the phosphorus compound. You can get things.

As the phosphorus compound (F) selected from the group consisting of metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts, Those having low deliquescence are preferred, and those having no deliquescence are more preferred.
(F) By using a metal salt with low deliquescence as a phosphorus compound, processing is reduced when mixing each raw material component during production of the polyamide composition, and the amount of water in the raw material component is increased. It is possible to suppress the molecular weight reduction and gas generation of the polyamide at the time. By using a metal salt having low deliquescence, a polyamide composition excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion processability, and molding process stability can be obtained.

(F) The phosphorus compound may include an organic phosphorus compound.
Examples of organic phosphorus compounds include, but are not limited to, pentaerythritol phosphite compounds, trioctyl phosphites, trilauryl phosphites, tridecyl phosphites, octyl diphenyl phosphites, trisisodecyl phosphites. Phyto, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene -Bis (3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyldiphosphite, 4,4'-isopropylidenebis ( 2-t-butylphenyl) -di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) ) Butanediphosphite, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidenediphenyldiphos Phyto, tris (mono, dimixed nonylphenyl) phosphite, 9,10-di-hydro- 9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4′-isopropylidene Diphenyl polyphosphite, bis (octylphenyl) -bis (4,4′-butylidenebis (3-methyl-6-tert-butylphenyl)), 1,6-hexanol diphosphite, hexatridecyl-1,1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) diphosphite, tris (4,4′-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyl) Oxyisopropyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2- Tylene bis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphite And tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite.
An organophosphorus compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the organophosphorus compounds listed above, pentaerythritol phosphite compounds, tris (2,4-di-t-butylphenyl), from the viewpoint of further improving the heat aging resistance of the polyamide composition and reducing the generated gas. ) Phosphites are preferred, and pentaerythritol phosphite compounds are more preferred.

Examples of the pentaerythritol type phosphite compound include, but are not limited to, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di- t-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-t- Butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-isotridecyl-pentaerythritol diphosphite, 2,6-di-t-butyl -4-methylphenyl-stearyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-cyclohexyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methyl Phenyl-benzyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-ethyl cellosolve-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-butyl Carbitol-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-nonylphenyl -Pentaerythritol diphosphite, bis (2,6-di t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-2,6-di-t-butylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylphenyl-pentaerythritol diphosphite Phyto, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2 -Cyclohexylphenyl-pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl-phenyl-pentaeryth Tritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos And bis (2,4-dicumylphenyl) pentaerythritol diphosphite.
A pentaerythritol type phosphite compound may be used alone or in combination of two or more.

  Among the pentaerythritol type phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-) Ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) penta Erythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferred.

Content of the (F) phosphorus type compound in a 1st polyamide composition is 0.1-20.0 mass% with respect to 100 mass% of 1st polyamide compositions. Preferably it is 0.2-7.0 mass%, More preferably, it is 0.5-3.0 mass%, More preferably, it is 0.5-2.5 mass%, More preferably, it is 0.5 It is -2.0 mass%, More preferably, it is 0.5-1.5 mass%.
The content of the (F) phosphorus compound in the first polyamide composition is preferably greater than (E) the metal hydroxide.
(F) When the content of the phosphorus compound is within the above range, the first polyamide composition tends to be excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion stability, and molding stability. is there.

In the polyamide composition, the phosphorus compound (F) is preferably contained in an amount such that the phosphorus element concentration is 1,400 to 20,000 ppm relative to the first polyamide composition, and 2,000 to 20 More preferably, it is contained in an amount of 3,000 ppm, more preferably in an amount of 3,000 to 20,000 ppm, even more preferably in an amount of 3,000 to 10,000 ppm, More preferably, it is contained in an amount of 4,000 to 6,000 ppm.
When the phosphorus element concentration derived from the phosphorus compound (F) contained in the first polyamide composition is in the above range, the polyamide composition has whiteness, reflow resistance, heat discoloration resistance, extrusion stability, molding. Excellent processing stability.
(F) Phosphorus compound may be added during the polymerization of (A1) polyamide, but (A1) after the polyamide is polymerized, and added during the manufacture of the polyamide composition mixed with (E) the metal hydroxide described above. It is preferable to do. By adding it during the production of the polyamide composition, it is possible to reduce the heat history, (F) to suppress the decomposition of the phosphorus compound, etc., whiteness, reflow resistance, heat discoloration resistance, extrusion processability And a polyamide composition excellent in molding process stability can be obtained.

The metal element concentration can be measured by ICP emission spectroscopic analysis, and the metal element / phosphorus concentration derived from the (E) metal hydroxide and (F) phosphorus compound contained in the first polyamide composition.
In the first polyamide composition, (E) the metal hydroxide and (F) the phosphorus compound have a combined value of metal element concentrations derived from these components (excluding the phosphorus element) of 1,000 to 40, It is preferably included in an amount of 2,000 ppm, more preferably 2,000 to 30,000 ppm, more preferably 3,000 to 25,000 ppm, and more preferably 4,000. Even more preferably, it is contained in an amount of 20,000 ppm, and even more preferably in an amount of 5,000 to 10,000 ppm.
When the metal element concentration is in the above range, the first polyamide composition tends to be more excellent in reflow resistance and light discoloration resistance.

<(G) Phenol-based antioxidant and / or amine-based antioxidant>
The polyamide composition may contain a phenol-based antioxidant and / or an amine-based antioxidant as a heat stabilizer.
Examples of phenolic antioxidants include, but are not limited to, hindered phenolic compounds. Phenol-based antioxidants, particularly hindered phenol compounds, have the property of imparting heat resistance and light resistance to resins such as polyamide and fibers.

Examples of the hindered phenol compound include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropylene). Onamide), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl- 4-hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Examples include benzene and 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.
Among these, from the viewpoint of improving heat aging resistance, the hindered phenol compound may be N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide). )] Is preferred.
In addition, the phenolic antioxidant mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the phenolic antioxidant in the first polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the first polyamide composition. %, And more preferably 0.1 to 1% by mass.
When the content of the phenolic antioxidant is within the above range, the first polyamide composition tends to be superior in heat aging resistance and lower in the amount of generated gas.

Examples of amine-based antioxidants include, but are not limited to, poly (2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1,2-dihydro-2, 2,4-trimethylquinoline, phenyl-α-naphthylamine, 4,4-bis (α, α-dimethyldendyl) diphenylamine, (p-toluenesulfonylamido) diphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di-β-naphthyl-p-phenylenediamine, N, N′-di (1,4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine, N- (1-methylheptyl) -N′-phenyl-p-pheny Aromatic amines such as Njiamin the like.
The amine antioxidant includes an aromatic amine compound. Only one amine antioxidant may be used alone, or two or more amine antioxidants may be used in combination.

The content of the amine antioxidant in the first polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the first polyamide composition. %, And more preferably 0.1 to 1% by mass.
When the content of the amine-based antioxidant is within the above range, the first polyamide composition tends to be superior in heat aging resistance and have a lower generated gas amount.

(Light stabilizer)
The first polyamide composition may further contain a light stabilizer from the viewpoint of light stability. The light stabilizer has a property of imparting excellent heat resistance and light resistance to resins such as polyamide and fibers. Examples of the light stabilizer include amine light stabilizers.

<Amine-based light stabilizer>
Examples of the amine light stabilizer include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra. Methylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6 6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6 6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethyl Peridine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy)- 2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, Bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl) -4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pen) Methyl-4-piperidyl) carbonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis (2,2,6) , 6-Tetramethyl-4-piperidyloxy) ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6) -Tetra Methyl-4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6 , 6-Tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- ( N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5 -Triazine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4- Polycondensate with piperidyl) butylamine, poly [ {6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino } Hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4- Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tris (2,2,6,6-tetramethyl- 4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [ 3- (3,5-di-t- Til-4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4- Examples include condensates of piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.
Only one amine light stabilizer may be used alone, or two or more amine stabilizers may be used in combination.

Examples of amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, and bis (2, 2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedi Carboxamide and tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are preferred.
Among these, as the amine light stabilizer, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis-2,2,6,6-tetramethyl-4 -Piperidinyl-1,3-benzenedicarboxamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are more preferred, N, N ′ -Bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide is more preferred.

  The content of the amine light stabilizer in the first polyamide composition is preferably 0 to 2% by mass, more preferably 0.01 to 2% by mass with respect to 100% by mass of the first polyamide composition. %, And more preferably 0.1 to 2% by mass. When the content of the amine light stabilizer is within the above range, the light stability and heat aging resistance of the polyamide composition can be further improved, and the amount of generated gas can be further reduced.

(Other ingredients)
In addition to the above components, the first polyamide composition of the present invention may further contain other components as necessary.
Examples of other components include, but are not limited to, colorants such as pigments and dyes (including colored master batches), mold release agents, flame retardants, fibrillating agents, lubricants, and optical brighteners. , Plasticizers, copper compounds, alkali metal halide compounds, antistatic agents, fluidity improvers, reinforcing agents, spreader rubbers, reinforcing agents and other polymers.
Here, since the above-mentioned other components have greatly different properties, suitable content ratios for the respective components are various. A person skilled in the art can easily set a suitable content for each of the other components described above.

[Production method of first polyamide composition]
It does not specifically limit as a manufacturing method of the 1st polyamide composition of this invention, (A1) Polyamide, As needed, an inorganic filler, a nucleating agent, a heat stabilizer, a light stabilizer, titanium oxide, others The method of mixing each raw material component containing these components etc. can be used.

  For example, when (B) titanium oxide is contained in the first polyamide composition, the mixing method of (A1) polyamide and (B) titanium oxide is not limited to the following, but for example, (A1 ) Mixing polyamide, etc. and (B) titanium oxide using a tumbler, Henschel mixer, etc., supplying the resulting mixture to a melt kneader and kneading, or by using a single or twin screw extruder (A1) The method etc. which mix | blend (B) titanium oxide from a side feeder with polyamide etc. are mentioned.

The same method can also be used when blending a heat stabilizer. (A1) Polyamide or the like, (E) a metal hydroxide, and (F) a phosphorus compound are mixed, and the resulting mixture is obtained. A method of supplying and kneading to a melt kneader, (A1) polyamide or the like made molten by a single or twin screw extruder, (E) a metal hydroxide, (F) a phosphorus compound, (G) The method etc. which mix | blend a phenol type / amine type antioxidant are mentioned.
As a method of mixing the heat stabilizer (E) metal hydroxide, (F) phosphorus compound, and (G) phenol / amine antioxidant, a method of blending from a side feeder is preferred. By producing a polyamide composition by a method of blending from a side feeder, the polyamide composition tends to have excellent whiteness, reflow resistance, heat discoloration resistance, light discoloration resistance, and molding process stability.

  The same method can also be used when blending (C) inorganic filler, (A1) polyamide etc. and (C) inorganic filler are mixed, and the resulting mixture is fed to a melt kneader. Examples thereof include a kneading method and a method of blending (C) an inorganic filler from a side feeder into (A1) polyamide or the like that has been melted with a single or twin screw extruder.

  As a method of supplying each component of the first polyamide composition to the melt kneader, a method may be used in which all the components are supplied to the same supply port at a time, or each component is supplied from a different supply port. It is also possible to do it.

  The melt kneading temperature is preferably 250 to 375 ° C. as the resin temperature. The melt kneading time is preferably 0.25 to 5 minutes.

  The apparatus for performing melt kneading is not particularly limited, and a known apparatus, for example, a melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, and a mixing roll can be used.

[Physical properties of the first polyamide composition]
The physical properties of the polyamide in the first polyamide composition of the present invention are equivalent to the physical properties of the first polyamide of the present invention. That is, the first polyamide of the present invention maintains its original physical properties even after it is melt-kneaded with other additives as necessary to form the first polyamide composition. For this reason, the polyamide contained in it can be specified by measuring said each physical property about the 1st polyamide in a 1st polyamide composition.
Trans isomer ratio, sulfuric acid relative viscosity ηr, number average molecular weight Mn, molecular weight distribution Mw / Mn, melting peak temperature Tm1, Tm2, heat of fusion ΔHm1, ΔHm2, crystallization peak temperature Tc of the first polyamide composition of the present invention The ratio of crystallization enthalpy ΔHc, glass transition temperature Tg, amino terminal, carboxyl terminal, and amino terminal amount to the total amount of active terminals can be measured by the method for measuring the physical properties of the polyamide described in the examples described later.
When determining the heat of fusion and crystallization enthalpy of the polyamide composition, if it contains inorganic fillers, nucleating agents, lubricants, stabilizers, etc., the value of the heat value is the ratio of polyamide to the composition. Calculate by converting.
Since the measured values of the physical properties of the polyamide in the first polyamide composition of the present invention are in the same range as the measured values of the physical properties of the first polyamide of the present invention, the first polyamide composition of the present invention is Excellent heat resistance, whiteness, reflow resistance, aging resistance and releasability.

[Polyamide composition molded product]
The polyamide composition molded product of the present invention (hereinafter sometimes simply referred to as a molded product) is formed by molding the above-mentioned first polyamide composition.
The polyamide composition molded article maintains a high trans isomer ratio of dicarboxylic acid monomer units, is excellent in reflow resistance, heat discoloration resistance, and light discoloration resistance, and can be suitably used for a reflector or the like.

[Production Method of Polyamide Composition Molded Product]
The polyamide composition molded article can be obtained, for example, by molding the first polyamide composition described above by a known molding method.
Known molding methods include, but are not limited to, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melting. Commonly known plastic molding methods such as spinning can be listed.

[Physical properties of molded products]
The polyamide composition molded article is excellent in heat resistance, whiteness, reflow resistance, aging resistance, and mold releasability. The initial reflectance is preferably 96.5% or more. Furthermore, the reflection retention after the reflow process is preferably 95% or more, and more preferably 96.2% or more. The aging retention is preferably 86% or more, and more preferably 86.5% or more.

[Use of polyamide composition molded product]
By including the first polyamide composition, the polyamide composition molded article is excellent in heat resistance, moldability, mechanical strength, and low water absorption. Therefore, the above-mentioned polyamide composition can be suitably used as various component materials such as reflectors, automobiles, electric and electronic, industrial materials, daily necessities and household goods, and for extrusion applications. It can be used suitably. About these specific uses, the thing similar to said 1st embodiment is mentioned.

  The reflectance retention of the polyamide composition molded article can be measured by the method described in the examples described later.

[Method for suppressing reduction in reflectance due to heat of reflector]
As described above, the molded product containing the first polyamide composition of the present invention can be suitably used as a reflector.
In the reflector, by using a combination of (A1) polyamide, (E) metal hydroxide, and (F) phosphorus compound, it is possible to effectively suppress a decrease in reflectance due to heat.
About a reflectance, it can measure by the method described in the Example mentioned later. It has been verified in Examples to be described later that the above-described combination can effectively suppress a decrease in reflectance in a reflector containing the polyamide composition of the present invention.

Next, a third embodiment of the present invention will be described.
The polyamide composition molded article according to this embodiment is formed by molding a second polyamide composition containing a second polyamide having a specific trans isomer ratio and ΔHm1 / ΔHc.
Details of the second polyamide, the second polyamide composition, and the molded polyamide composition will be described below.

[(A2) Polyamide]
The second polyamide of the present invention contains (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine,
Sulfuric acid relative viscosity ηr is 2.5 or more, obtained in a differential scanning calorimetry according to JIS-K7121, when the temperature is lowered at 20 ° C./min and the heat of fusion ΔHm1 obtained when the temperature is raised at 20 ° C./min. ΔHm / ΔHc, which is a ratio to the crystallization enthalpy ΔHc obtained,
1.0 <ΔHm / ΔHc ≦ 2.2,
The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is
75 <trans isomer ratio ≦ 100.

The second polyamide of the present invention having the relative viscosity of sulfuric acid ηr, ΔHm1 / ΔHc, which is the ratio of the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc, and the trans isomer ratio as described above, is composed of the polyamide described below. It can be obtained by unit and manufacturing method.
First, the structural unit of (A2) polyamide is described in detail.
((A) dicarboxylic acid unit)
As the dicarboxylic acid unit constituting the polyamide of the present embodiment, the same dicarboxylic acid as in the second embodiment can be used.

((B) diamine unit)
(B) The diamine unit contains at least an aliphatic diamine. This aliphatic diamine may be linear or branched. (B) The diamine unit is not limited to the following. For example, (b-1) an aliphatic diamine unit having a substituent branched from the main chain (branched aliphatic diamine), and (b-2) ) Linear aliphatic diamine unit and the like. Other diamine units may include (b-3) alicyclic diamine units, (b-4) aromatic diamine units, and the like.

  (B) The aliphatic diamine unit preferably has 6 to 12 carbon atoms. A carbon number of 6 or more is preferable because of excellent heat resistance and low water absorption, and a carbon number of 12 or less is preferable because of high temperature strength and crystallinity. (B) As for carbon number of a diamine unit, 6-10 is more preferable.

(B-1) Aliphatic diamine unit having a substituent branched from the main chain (branched aliphatic diamine)
(B) The diamine unit preferably includes (b-1) an aliphatic diamine having a substituent branched from the main chain. (B) Since the diamine unit includes (b-1) a diamine unit having a substituent branched from the main chain, a polyamide having a high glass transition temperature Tg and high crystallinity (ie, high ΔHm1 / ΔHc) is obtained. Can be obtained. For this reason, the polyamide composition of the present invention using this polyamide tends to satisfy more excellent fluidity, toughness, rigidity and the like at the same time. Hereinafter, (b-1) an aliphatic diamine unit having a substituent branched from the main chain may be simply referred to as (b-1).
The “substituent branched from the main chain” in (b-1) is not limited to the following, but for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl Group, an alkyl group having 1 to 4 carbon atoms of a tert-butyl group, and the like.

The diamine constituting such (b-1) is not limited to the following, but for example, 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also referred to as 2-methyloctamethylenediamine), and 2,4-dimethylocta Examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as methylenediamine.
Among these, 2-methylpentamethylenediamine and 2-methyl-1,8-octanediamine are preferable, and 2-methylpentamethylenediamine is more preferable. By including such (b-1), it tends to be a polyamide composition that is superior in heat resistance and rigidity.
In addition, the diamine which comprises (b-1) may be used individually by 1 type, and may be used in combination of 2 or more type.

The (b) diamine unit more preferably contains 10 mol% or more of (b-1). (B) The proportion (mol%) of (b-1) in the diamine unit is preferably 10 to 80 mol%, more preferably 20 to 60 mol%, and still more preferably 30 to 50 mol%. is there.
(B) It is preferable that the ratio of (b-1) in the diamine unit is in the above range from the viewpoint of obtaining a polyamide having a high glass transition temperature Tg and ΔHm1 / ΔHc within the range of the present application. For this reason, the polyamide composition using this polyamide tends to be a polyamide composition that is superior in fluidity, toughness, and rigidity.

(B-2) Linear aliphatic diamine unit Hereinafter, the (b-2) linear aliphatic diamine unit may be simply referred to as (b-2).
The aliphatic diamine constituting (b-2) is not limited to the following, but for example, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine. , Straight-chain saturated aliphatic diamines having 2 to 20 carbon atoms such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.

(B-3) Alicyclic diamine unit Hereinafter, the (b-3) alicyclic diamine unit may be simply referred to as (b-3).
The alicyclic diamine (hereinafter, also referred to as “alicyclic diamine”) constituting (b-3) is not limited to the following, and examples thereof include 1,4-cyclohexanediamine and 1,3. -Cyclohexanediamine, 1,3-cyclopentanediamine, etc. are mentioned.

(B-4) Aromatic diamine unit Hereinafter, the (b-4) aromatic diamine unit may be simply referred to as (b-4).
Examples of the aromatic diamine constituting (b-4) include metaxylylenediamine, paraxylylenediamine, paraphenylenediamine, metaphenylenediamine, and the like.

Among the diamine units (b-2) to (b-4), preferably (b-2) and (b-3), more preferably a linear saturated aliphatic group having 4 to 13 carbon atoms. A diamine unit (b-2) having a straight-chain saturated aliphatic group having 6 to 12 carbon atoms, more preferably hexamethylenediamine or nonamethylenediamine. , Decamethylenediamine and dodecamethylenediamine, most preferably decamethylenediamine.
By using such a diamine, the polyamide composition tends to be excellent in heat resistance, fluidity, toughness, low water absorption, rigidity, and the like.
In addition, diamine may be used individually by 1 type and may be used in combination of 2 or more types.

The total proportion (mol%) of the diamine units (b-2) to (b-4) is preferably 50 mol% or more and 60 mol% or more with respect to the entire (b) diamine unit. More preferred.
(B) When the total ratio of the diamine units (b-2) to (b-4) in the diamine unit is within the above range, the polyamide composition tends to be excellent in fluidity, toughness, and rigidity.

The (A2) polyamide may further contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylene triamine, if necessary.
Trivalent or higher polyvalent aliphatic amines may be used alone or in combination of two or more.

((C) Lactam unit (c-1) and / or aminocarboxylic acid unit (c-2))
The (A2) polyamide of the present invention is within the range not impairing the object of the present invention, in addition to the above (a) and (b), (c) the lactam unit (c-1) and / or the aminocarboxylic acid unit (c -2) can further be contained.
By including such a unit, a polyamide composition that is superior in toughness tends to be obtained. In addition, the lactam and aminocarboxylic acid which comprise a lactam unit (c-1) and aminocarboxylic acid (c-2) here mean the lactam and aminocarboxylic acid which can superpose | polymerize or condensation-polymerize.

  As the lactam and aminocarboxylic acid constituting the lactam unit (c-1) and aminocarboxylic acid unit (c-2), the same lactam and aminocarboxylic acid as in the second embodiment can be used.

(End sealant)
The terminal of (A2) polyamide used in the present invention may be end-capped with a known end-capping agent.
Such an end-capping agent is also added as a molecular weight regulator in the production of (A2) polyamide from the above-described dicarboxylic acid and diamine, and lactam and / or aminocarboxylic acid used as necessary. Can do.

Examples of end-capping agents include, but are not limited to, acid anhydrides such as monocarboxylic acids, monoamines, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. Etc.
Among these, monocarboxylic acid and monoamine are preferable. (A2) Since the end of the polyamide is sealed with an end-capping agent, the polyamide composition tends to be more excellent in thermal stability. Only one type of end capping agent may be used alone, or two or more types may be used in combination.

The monocarboxylic acid that can be used as the end-capping agent is not limited to the following as long as it has reactivity with an amino group that can be present at the terminal of the (A2) polyamide. For example, formic acid Aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; cyclohexanecarboxylic acid, etc. And aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid. Of these, acetic acid is particularly preferred.
A monocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.

The monoamine that can be used as the end-capping agent is not limited to the following as long as it has reactivity with the carboxyl group that can be present at the terminal of the (A2) polyamide, but for example, methylamine, Aliphatic monoamines such as ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aniline , Aromatic monoamines such as toluidine, diphenylamine, and naphthylamine.
Monoamines may be used alone or in combination of two or more.

  The polyamide composition containing (A2) polyamide end-capped with a terminal capping agent tends to be excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity.

Next, the manufacturing method (the manufacturing method of 2nd polyamide) for obtaining the 2nd polyamide of this invention is demonstrated.
[(A2) Second Polyamide Production Method]
The method for producing a second polyamide of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine,
[NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio of the amino terminal amount [NH ₂ ] to the total active terminal amount ([NH ₂ ] + [COOH]),
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5,
Active terminal total amount ([NH ₂ ] + [COOH]) μeq / g is
110 ≦ [NH ₂ ] + [COOH] ≦ 200
Is heat-treated at 200 ° C. or higher and lower than the melting point for 10 hours or longer.

That is, the second method for producing a polyamide of the present invention is a method for obtaining a polyamide having a specific terminal structure (hereinafter referred to as a precursor polyamide) and further heat-treating it at a temperature lower than the melting point (A2) to obtain a polyamide. . As such a production method, a “hot melt polymerization / solid phase polymerization method” is preferable.
Hereinafter, the method for obtaining the precursor polyamide (thermal melt polymerization method) and the heat treatment (solid phase polymerization method) will be described in detail.

<Method for obtaining precursor polyamide>
The method for obtaining the precursor polyamide is not particularly limited, and examples thereof include the methods exemplified below.
1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter referred to as hot melt polymerization method).
2) A method in which an aqueous solution or suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated, and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization (hereinafter referred to as prepolymer · Called the extrusion polymerization method).
3) A method of polymerizing using a dicarboxylic acid halide equivalent to a dicarboxylic acid and a diamine (hereinafter referred to as a solution method).
Among them, the hot melt polymerization method is preferable from the viewpoint of increasing the molecular weight by polymerization in a short time and suppressing gelation.
When the precursor polyamide is produced, it is preferable that (a) the addition amount of the dicarboxylic acid constituting the dicarboxylic acid unit and (b) the addition amount of the diamine constituting the diamine unit are about the same molar amount.
(A) The dicarboxylic acid unit preferably contains 50 to 100 mol% of 1,4-cyclohexanedicarboxylic acid units (based on the total number of dicarboxylic acids), more preferably 60 to 100 mol%, and 70 to 100 mol. % Is more preferable, and 100 mol% is most preferable.

It is known that alicyclic dicarboxylic acids are isomerized at high temperatures, and the trans isomer and cis isomer are in a certain ratio, and the cis alicyclic dicarboxylic acid is more trans alicyclic dicarboxylic acid. Compared with an acid, the water solubility of an equivalent salt of an alicyclic dicarboxylic acid and a diamine tends to be higher. From this, the trans isomer / cis isomer ratio (molar ratio) of the alicyclic dicarboxylic acid as the raw material monomer is preferably 50/50 to 0/100, more preferably 40/60 to 10/90. More preferably, it is 35/65 to 15/85.
The trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR).

  (B) The diamine unit preferably includes (b-1) a diamine unit having a substituent branched from the main chain, and the proportion thereof is preferably 10 to 80 mol%, more preferably 20 to 60 mol%, 30 More preferred is ˜50 mol%. (B-1) is most preferably 2-methyl-5-pentamethylenediamine.

  When the precursor polyamide is produced (thermal melt polymerization), a diamine may be added in addition to (b) for adjusting the molecular weight and terminal. The diamine to be added is preferably 2-methyl-5-pentamethylenediamine. (B) The amount of added diamine with respect to diamine is 0-5.0 mol% by mole ratio, More preferably, it is 0-2.0 mol%, More preferably, it is 0-1.0 mol%.

Moreover, you may add a phosphorus compound as a heat stabilizer (catalyst) at the time of hot melt polymerization. The heat stabilizer is not particularly limited, but sodium hypophosphite is preferable.
In the method for producing the precursor polyamide, from the viewpoint of the color tone and fluidity of the polyamide, it is preferable to carry out hot melt polymerization while maintaining the trans isomer ratio of the alicyclic dicarboxylic acid unit in the polyamide at 85% or less. It is more preferable to perform hot melt polymerization while maintaining the trans isomer ratio of the alicyclic dicarboxylic acid unit at 80% or less.

  (A2) It is preferable that the manufacturing method of polyamide further includes the process of raising the polymerization degree of polyamide. Moreover, the sealing process which seals the terminal of the obtained polymer with a terminal sealing agent may be included as needed.

<Physical properties of precursor polyamide>
The physical property of the precursor polyamide is the ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]) [NH ₂ ] / ([NH ₂ ] + [COOH]) is 0. Less than 5 is preferable, 0.01 to less than 0.5 is more preferable, and 0.05 to 0.4 is more preferable. The total amount of active terminals ([NH ₂ ] + [COOH]) is preferably 110 to 200 μeq / g, more preferably 110 to 180 μeq / g, and still more preferably 110 to 160 μeq / g.
In order to obtain such physical properties of the precursor polyamide, the terminal structure of the polyamide is controlled by adjusting the amount of the structural units (a) to (c) of the polyamide, the end-capping agent and the additional diamine. Can be obtained.

<Heat treatment>
The heat treatment in the production method of the present invention can use the same method as the heat treatment in the second embodiment, and the preferred temperature range is also the same.

[(A2) Physical properties of polyamide]
Next, the physical properties of the second polyamide of the present invention will be described.
<Trans isomer ratio>
The trans isomer ratio of the dicarboxylic acid monomer unit in the second polyamide of the present invention is more than 75 mol% and not more than 100 mol%. The trans isomer ratio is more preferably more than 75 mol% and 100 mol% or less, further preferably more than 75 mol% and 90 mol% or less, and more preferably 80 mol% or more and 90 mol% or less.
Since the polyamide of the present invention is highly crystallized because the trans isomer ratio is in the above range, the polyamide and the polyamide composition of the present invention have a high melting point, toughness and rigidity, in addition to the characteristics of being high. It tends to have the property of simultaneously satisfying the thermal rigidity due to the glass transition temperature (Tg), the fluidity, which is usually a property contrary to heat resistance, and the high crystallinity.

As described above, the trans isomer ratio of the dicarboxylic acid monomer unit in such a polyamide can be controlled by controlling the carboxyl terminal amount of the polyamide and the method for producing the polyamide of the present invention.
The trans isomer ratio (molar ratio) of the 1,4-cyclohexanedicarboxylic acid monomer unit of the polyamide composition molded product can be determined by nuclear magnetic resonance spectroscopy (NMR).

<Sulfuric acid relative viscosity ηr>
(A2) Sulfuric acid relative viscosity ηr of polyamide uses sulfuric acid relative viscosity ηr at 25 ° C. as an index. The sulfuric acid relative viscosity ηr at 25 ° C. is 2.5 or more. Preferably it is 2.6-5.0, More preferably, it is 2.7-4.0. Effective methods for controlling the relative viscosity ηr of sulfuric acid at 25 ° C. for polyamides include, for example, methods for controlling the addition amount of diamine and end-capping agent as additives during hot melt polymerization of polyamide, and polymerization conditions. Method.

When the sulfuric acid relative viscosity ηr at 25 ° C. is 2.5 or more, the polyamide is excellent in mechanical properties such as toughness and strength. From the viewpoint of melt fluidity, a polyamide having excellent fluidity can be obtained when the sulfuric acid relative viscosity ηr at 25 ° C. of the polyamide is 5.0 or less.
The sulfuric acid relative viscosity at 25 ° C. can be measured at 25 ° C. in 98% sulfuric acid according to JIS-K6920.

<Molecular weight>
As an index of the molecular weight of the polyamide, a number average molecular weight Mn obtained by GPC (gel permeation chromatography), a weight average molecular weight Mw, and a molecular weight distribution Mw / Mn can be used. The larger the Mn, the higher the molecular weight of the (A2) polyamide, and the smaller the Mn, the lower the molecular weight of the (A2) polyamide.
The number average molecular weight Mn of the polyamide is preferably greater than 15000, more preferably 16000 or more, and even more preferably 17000 or more.
Moreover, Mw / Mn which shows the molecular weight distribution of (A2) polyamide becomes like this. Preferably it is less than 3.5, More preferably, it is 3.0 or less.
When the number average molecular weight Mn and the molecular weight distribution Mw / Mn are in the above ranges, it tends to be a polyamide composition having excellent mechanical properties such as toughness and rigidity, and moldability. In addition, Mn and Mw can produce | generate a calibration curve using the number average molecular weight Mn measured by PMMA (polymethylmethacrylate) standard sample (made by a polymer laboratory company), and can obtain | require the molecular weight of polyamide. More specifically, it can be measured by the method described in the following examples.

<Melting peak temperature Tm1, Tm2>
The melting peak temperature Tm1 of the polyamide is preferably 300 ° C. or higher, more preferably 310 ° C. or higher.
Further, the melting peak temperature Tm1 of the polyamide is preferably 350 ° C. or lower, more preferably 345 ° C. or lower, and further preferably 340 ° C. or lower.
When the melting peak temperature Tm1 of the polyamide is 300 ° C. or higher, a polyamide composition excellent in heat resistance tends to be obtained.
Moreover, when (A2) polyamide melting peak temperature Tm1 is 350 ° C. or less, (A2) thermal decomposition of polyamide in melt processing such as extrusion and molding tends to be further suppressed.

(A2) The melting peak temperature Tm2 of the polyamide is preferably 270 ° C. or higher, more preferably 275 ° C. or higher, and further preferably 280 ° C. or higher.
Further, the melting peak temperature Tm2 of (A2) polyamide is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.
(A2) When the melting peak temperature Tm2 of the polyamide is 270 ° C. or higher, a polyamide composition excellent in heat resistance tends to be obtained.
Moreover, (A2) When the melting peak temperature Tm2 of the polyamide is 350 ° C. or lower, the thermal decomposition of the (A2) polyamide in the melt processing such as extrusion and molding tends to be further suppressed.
(A2) The melting peak temperatures Tm1 and Tm2 of the polyamide can be measured according to JIS-K7121 by the method described in Examples below.

<Heat of fusion ΔHm1, ΔHm2, crystallization enthalpy ΔHc>
The heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide are each preferably 30 J / g or more, more preferably 35 J / g or more, and further preferably 40 J / g or more. Moreover, the upper limit of the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc is not particularly limited and is preferably as high as possible.
When the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide are each 30 J / g or more, the heat resistance of the polyamide composition tends to be further improved.
The heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide can be measured according to JIS-K7121 by the method described later.
The heat of fusion ΔHm2 of the polyamide is preferably 20 J / g or more, more preferably 25 J / g or more, and further preferably 30 J / g or more. Further, the upper limit of the heat of fusion ΔHm2 is not particularly limited and is preferably as high as possible.
When the heat of fusion ΔHm2 of the polyamide is 20 J / g or more, the heat resistance of the polyamide composition tends to be further improved.

<Ratio of heat of fusion ΔHm1 and crystallization enthalpy ΔHc ΔHm1 / ΔHc>
The heat of fusion ΔHm1 is a heat of fusion reflecting the heat history received by the polyamide during heat treatment or cooling, and is different from the heat of fusion inherent in the polyamide. On the other hand, ΔHc is a crystallization enthalpy obtained through a cooling process (slow cooling) after complete melting, and is equal to the heat of fusion inherent in polyamide. Therefore, ΔHm1 / ΔHc means the ratio between the heat of fusion inherent in polyamide and the heat of fusion of polyamide subjected to a thermal history. For example, when heat treatment is performed at a temperature lower than the melting point, crystallization proceeds and ΔHm1 increases, so that ΔHm1 / ΔHc> 1.0. In the case of rapid cooling, crystallization does not proceed and ΔHm1 becomes small, so ΔHm1 / ΔHc ≦ 1.0.
The ratio (ΔHm1 / ΔHc) between the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide of the present invention is greater than 1.0 and less than or equal to 2.2, preferably greater than 1.4 and less than 2.2 from the viewpoint of heat resistance. Or less, more preferably 1.5 or more and 2 or less, still more preferably 1.6 or more and 2.2 or less, and particularly preferably 1.7 or more and 2.2 or less.

  When the ratio of heat of fusion ΔHm1 of polyamide to crystallization enthalpy ΔHc ΔHm1 / ΔHc is y and the trans isomer ratio is x, it is preferable that y ≧ 0.04x−1.8. In this case, the heat resistance of the polyamide Tend to improve.

<Difference between melting peak temperature Tm1 and crystallization peak temperature Tc of polyamide (Tm1-Tc)>
(A2) When the difference (Tm1−Tc) between the melting peak temperature Tm1 and the crystallization peak temperature Tc of the polyamide is in the range higher than 40 ° C. and lower than 90 ° C., the polyamide composition has excellent fluidity and improved releasability. Tend to. Tm1-Tc is preferably higher than 40 ° C and lower than 90 ° C, and more preferably 50 ° C to 80 ° C.

  The measurement of the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide can be carried out according to JIS-K7121, and the heat of fusion ΔHm1 is measured when the temperature of the polyamide is raised at a heating rate of 20 ° C./min (the first temperature rise). The endothermic peak appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time) is the peak area of Tm when the melting peak temperature is Tm (° C.). When there are a plurality of endothermic peaks, a peak having ΔH of 1 J / g or more is regarded as a peak, the highest temperature is defined as a melting peak temperature Tm1, and ΔHm1 is a sum of peak areas. The crystallization enthalpy ΔHc is the Tc value when the temperature of the exothermic peak (crystallization peak) that appears when the polyamide composition molded article is cooled at a temperature decrease rate of 20 ° C./min is the crystallization peak temperature Tc (° C.). It is the peak area. As the measuring device, Diamond-DSC manufactured by PERKIN-ELMER can be used as described in the following examples.

Further, the melting peak temperature Tm2 and the heat of fusion ΔHm2 of polyamide can be measured as follows. After the first temperature increase, the temperature is maintained for 2 minutes in the molten state at the maximum temperature increase, then the temperature is decreased to 30 ° C. at a temperature decrease rate of 20 ° C./min, maintained at 30 ° C. for 2 minutes, and then the temperature increase rate is 20 The endothermic peak temperature that appears at the highest temperature side of the endothermic peak that appears when the temperature is similarly raised at the same temperature (° C./min) is the melting peak temperature Tm2 of the polyamide itself, and the peak area at this melting peak temperature. Is the heat of fusion ΔHm2 of the polyamide.
The measurement of the melting peak temperature Tm2 and the heat of fusion ΔHm2 of polyamide can be performed according to JIS-K7121 as described in the following examples. As an apparatus for measuring the melting peak temperature and the heat of fusion, for example, Diamond-DSC manufactured by PERKIN-ELMER may be used.

<Glass transition temperature Tg>
(A2) The glass transition temperature Tg of the polyamide is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, even more preferably 130 ° C. or higher, and even more preferably. Is 135 ° C. or higher.
Further, the glass transition temperature Tg of the (A2) polyamide is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
(A2) When the glass transition temperature Tg of the polyamide is 90 ° C. or higher, a polyamide composition excellent in heat discoloration resistance and chemical resistance tends to be obtained. Moreover, when the glass transition temperature Tg of (A2) polyamide is 170 ° C. or less, a molded product having a good appearance tends to be obtained.
(A2) The glass transition temperature Tg of polyamide can be measured according to JIS-K7121, as described in the following examples.
Examples of the measuring device for the glass transition temperature Tg include Diamond-DSC manufactured by PERKIN-ELMER.

<Polymer end>
Although it does not specifically limit as a polymer terminal of the polyamide used for this invention, It can classify | categorize and define as follows.
That is, 1) amino terminal, 2) carboxyl terminal, 3) cyclic amino terminal, 4) terminal by sealing agent, and 5) other terminal.

1) the amino terminus is a polymer end with an amino group (-NH ₂ group), derived from (b) diamine units of the raw material.
The amino terminal amount ([NH ₂ ]) is preferably 5 to 100 μequivalent / g, more preferably 5 to 70 μequivalent / g, and further preferably 5 to 50 μequivalent / g with respect to 1 g of polyamide. Yes, even more preferably 5-30 μeq / g, even more preferably 5-20 μeq / g.
When the amino terminal amount is in the above range, the whiteness, reflow resistance, heat discoloration resistance, light discoloration resistance, hydrolysis resistance, and heat retention stability of the polyamide composition tend to be more excellent. The amino terminal amount can be measured by neutralization titration. Specifically, 3.0 g of polyamide is dissolved in 100 mL of a 90 mass% phenol aqueous solution, and the obtained solution is titrated with 0.025N hydrochloric acid to obtain the amino terminal amount (μ equivalent / g). The end point is determined from the indicated value of the pH meter.

2) The carboxyl terminal is a polymer terminal having a carboxyl group (—COOH group) and is derived from the raw material (a) dicarboxylic acid.
The carboxyl end amount ([COOH]) is preferably 5 to 150 μeq / g, more preferably 5 to 140 μeq / g, and further preferably 5 to 130 μeq / g, relative to 1 g of polyamide. Even more preferably, it is 5 to 120 μeq / g, and even more preferably 5 to 110 μeq / g. When the carboxyl end amount is in the above range, the whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance of the polyamide composition tend to be more excellent. The carboxyl end amount can be measured by neutralization titration. Specifically, 4.0 g of polyamide is dissolved in 50 mL of benzyl alcohol, and the obtained solution is titrated with 0.1 N NaOH to obtain the carboxyl terminal amount (μ equivalent / g). The end point is determined from the discoloration of the phenolphthalein indicator.

The total amount of the amino terminal amount ([NH ₂ ]) and the carboxyl terminal amount ([COOH]) is defined as the active terminal total amount ([NH ₂ ] + [COOH]). The total amount of active terminals is preferably 10 to 200 µequivalent / g, more preferably 10 to 150 µequivalent / g, still more preferably 10 to 120 µequivalent / g, based on 1 g of (A2) polyamide.
In addition, [NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio of the amino terminal amount to the total active terminal amount, is preferably less than 0.5, more preferably less than 0.4, More preferably, it is less than 0.3, Most preferably, it is less than 0.1. ΔHm1 / ΔHc can be controlled to be greater than 1.0 and less than or equal to 2.2 because the ratio of the amino terminal amount and the carboxyl terminal amount and the ratio of the amino terminal amount to the active terminal total amount are within the above ranges. The heat discoloration resistance and light discoloration resistance of the polyamide composition tend to be more excellent.

  Examples of the method for controlling the ratio of the amino terminal amount to the total active terminal amount include a method of controlling the addition amount of diamine and terminal blocking agent as additives during hot melt polymerization of polyamide, and the polymerization conditions. .

3) The cyclic amino terminus is a polymer terminus having a cyclic amino group (a group represented by the following (formula 1)).
In the following (Formula 1), R represents a substituent bonded to the carbon constituting the piperidine ring. Specific examples of R include a hydrogen atom, a methyl group, an ethyl group, and a t-butyl group.
Further, for example, even when piperidine cyclized by a deammonia reaction of a diamine having a pentamethylenediamine skeleton as a raw material is bonded to the polymer terminal, it becomes the terminal of this cyclic amino group. These structures may be taken when a monomer having a pentamethylenediamine skeleton is included.

・・・（式１）

... (Formula 1)

3) The amount of the cyclic amino terminal is preferably 0 μe equivalent / g or more and 65 μe equivalent / g or less, more preferably 10 μe equivalent / g or more and 60 μequivalent / g or less, with respect to 1 g of (A2) polyamide. Preferably they are 20 microequivalent / g or more and 55 microequivalent / g or less.
When the amount of the cyclic amino terminus is in the above range, the polyamide composition of the present invention tends to have better toughness, hydrolysis resistance, and processability.

The amount of the cyclic amino terminus can be measured using ¹ H-NMR. For example, there is a method of calculation based on the integral ratio of hydrogen bonded to carbon adjacent to the nitrogen atom of the heterocyclic ring of nitrogen and hydrogen bonded to carbon adjacent to the nitrogen atom of the amide bond of the polyamide main chain.

  Cyclic amino terminal can be generated by dehydration reaction of cyclic amine and carboxyl terminal, and can also be generated by deammonia reaction of amino terminal in the polymer molecule. Cyclic amine is added as end-capping agent. It can also be produced by the diamine having a pentamethylenediamine skeleton, which is a raw material for polyamide, and cyclizing by deammonia reaction.

In the present invention, the cyclic amino terminal is preferably derived from a raw material diamine.
Without adding cyclic amine as an end-capping agent at the initial stage of polymerization, the cyclic amino terminal is generated from the raw material diamine, so that the low molecular weight carboxylic acid terminal is prevented from being blocked at the initial stage of polymerization. Thus, the polymerization reaction rate of the polyamide is maintained high, and as a result, a high molecular weight product tends to be easily obtained. As described above, when a cyclic amine is generated during the reaction, the carboxylic acid terminal is sealed with the cyclic amine at a later stage of the polymerization, so that a high molecular weight polyamide is easily obtained.

  Cyclic amines that generate a cyclic amino terminus can be generated as a by-product during the polymerization reaction of the polyamide. In this cyclic amine formation reaction, the higher the reaction temperature, the higher the reaction rate. Therefore, in order to make the cyclic amino terminal of the polyamide (A2) constant, it is preferable to promote the generation of cyclic amine. Therefore, the reaction temperature for the polymerization of the precursor polyamide is preferably 300 ° C. or higher, and more preferably 320 ° C. or higher.

  As a method for adjusting these cyclic amino ends to a certain amount, control is performed by appropriately adjusting the polymerization temperature, the holding time of the reaction temperature of 300 ° C. or more during the polymerization step, the addition amount of the amine forming the cyclic structure, and the like. The method of doing is mentioned.

  4) The terminal by a sealing agent is a terminal formed when a sealing agent is added at the time of superposition | polymerization. Examples of the sealing agent include the above-described end sealing agents.

  5) The other terminal is a polymer terminal not classified in the above 1) to 4), such as a terminal generated by deammonia reaction at the amino terminal or a terminal generated by decarboxylation from the carboxylic acid terminal. It is done.

[Second polyamide composition]
The second polyamide composition of the present invention contains the first polyamide of the present invention and at least one selected from an inorganic filler, a heat stabilizer, and a light stabilizer. By containing an inorganic filler as the second polyamide composition, it has excellent heat resistance and stability under heat and has a high melting point. In addition, by containing the above components, the second polyamide composition does not impair the properties of the polyamide. It will be. Hereinafter, the components of the polyamide composition will be described.

(Inorganic filler)
It does not specifically limit as an inorganic filler which comprises the 2nd polyamide composition of this invention, A well-known material can be used.
For example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica, hydrotalcite, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, phosphoric acid Calcium monohydrogen, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black , Carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, clay, montmorillonite, swellable fluorine mica, silicon nitride, and apatite.
An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

Among the inorganic fillers, the glass fiber and the carbon fiber may have a round shape or a flat shape in cross section.
Examples of the flat cross section include a rectangle, an oval close to a rectangle, an ellipse, and a bowl shape with a narrowed central portion in the longitudinal direction.

  Among glass fibers and carbon fibers, from the viewpoint of imparting excellent mechanical properties to the polyamide composition, in the polyamide composition, the number average fiber diameter is 3 to 30 μm, and the weight average fiber length is 100 to 750 μm. Glass fibers or carbon fibers having an aspect ratio (L / D) of 10 to 100 between the weight average fiber length (L) and the number average fiber diameter (D) are preferably used.

  The number average fiber diameter of the inorganic filler in the polyamide composition is, for example, putting the polyamide composition in an electric furnace, incinerating the organic matter contained in the polyamide composition, and, for example, 100 or more glass fibers from the residue. The number average fiber diameter can be determined by arbitrarily selecting, observing with a SEM photograph, and measuring the fiber diameter.

As for the weight average fiber length of the inorganic filler in the polyamide composition, the glass fiber is arbitrarily selected in the same manner, and the weight average fiber length is measured by measuring the fiber length using an SEM photograph at a magnification of 1000 times. be able to.
As the inorganic filler, reinforcing fibers having a weight average fiber length of 1 to 15 mm are more preferable. The weight average fiber length of such reinforcing fibers is 1 to 15 mm, preferably 3 to 12 mm, from the viewpoint of improving mechanical strength, rigidity and moldability.

The weight average fiber length of the reinforcing fibers is the length of 400 reinforcing fibers arbitrarily selected using an image analyzer after observing with an optical microscope after burning or dissolving only the polyamide of the polyamide composition. It is calculated | required by measuring thickness and calculating an average value.
Here, when the length of each reinforcing fiber is L1, L2,..., L400, the calculation formula for the weight average fiber length for each reinforcing fiber is expressed by the following formula. In the following formula, “i” is an integer from 1 to 400.
Weight average fiber length = Σ (Li ² ) / ΣLi
In addition, a weight average fiber length is a value applied with respect to the reinforcing fiber of the state contained in the polyamide composition of this invention. That is, the weight average fiber length of the reinforcing fiber before blending with the polyamide is not limited to the above.

The material of the reinforcing fiber is not particularly limited as long as it is a reinforcing fiber generally used for polyamide.
For example, inorganic fiber such as glass fiber, carbon fiber, boron fiber, metal fiber (eg, stainless fiber, aluminum fiber, copper fiber), polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaffin Organic materials such as phenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, wholly aromatic polyamide fiber such as fiber obtained from condensate of diaminodiphenyl ether and terephthalic acid or isophthalic acid, or wholly aromatic liquid crystal polyester fiber Is mentioned.

As reinforcing fiber, the said material may be used independently and 2 or more types may be used together. Especially, it is preferable that it is 1 or more types chosen from a glass fiber, a carbon fiber, a boron fiber, and a metal fiber from a viewpoint of an improvement of mechanical strength and rigidity, and a glass fiber and / or a carbon fiber are more preferable.
The reinforcing fiber is not particularly limited with respect to the average fiber diameter in the single fiber, but, for example, those having a diameter of 5 to 25 μm are generally used.

The average fiber diameter of single fibers is obtained by observing the reinforcing fibers to be used under an optical microscope and calculating the average value when measuring 400 fiber diameters arbitrarily selected using an image analyzer. It is done.
Further, as the reinforcing fiber, it is preferable to use roving which is a continuous fiber obtained by bundling single fibers.

<Surface treatment agent>
An inorganic filler such as glass fiber or carbon fiber may be surface-treated with a surface treatment agent such as a silane coupling agent. As the silane coupling agent as the surface treatment agent, the same one as in the first embodiment can be used.

<Bundling agent>
The fibrous inorganic filler such as glass fiber or carbon fiber may further contain a sizing agent. As the sizing agent, the same sizing agent as in the first embodiment can be used.

(Heat stabilizer)
The polyamide composition may also contain a heat stabilizer. As a thermal stabilizer, phosphorus stabilizer (phosphorus compound), phenolic antioxidant, amine antioxidant, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa of the periodic table And one or more selected from the group consisting of metal salts of Group IVb elements and halides of alkali metals and alkaline earth metals. Specific examples of the heat stabilizer are shown below.

<Phosphorus stabilizer (phosphorus compound)>
Examples of phosphorus compounds include organic phosphorus compounds.
Examples of organic phosphorus compounds include, but are not limited to, pentaerythritol phosphite compounds, trioctyl phosphites, trilauryl phosphites, tridecyl phosphites, octyl diphenyl phosphites, trisisodecyl phosphites. Phyto, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene -Bis (3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyldiphosphite, 4,4'-isopropylidenebis ( 2-t-butylphenyl) -di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) ) Butanediphosphite, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidenediphenyldiphos Phyto, tris (mono, dimixed nonylphenyl) phosphite, 9,10-di-hydro- 9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4′-isopropylidene Diphenyl polyphosphite, bis (octylphenyl) -bis (4,4′-butylidenebis (3-methyl-6-tert-butylphenyl)), 1,6-hexanol diphosphite, hexatridecyl-1,1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) diphosphite, tris (4,4′-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyl) Oxyisopropyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2- Tylene bis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphite And tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite.
An organophosphorus compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the organophosphorus compounds listed above, pentaerythritol phosphite compounds, tris (2,4-di-t-butylphenyl), from the viewpoint of further improving the heat aging resistance of the polyamide composition and reducing the generated gas. ) Phosphites are preferred, and pentaerythritol phosphite compounds are more preferred.

Examples of the pentaerythritol type phosphite compound include, but are not limited to, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di- t-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-t- Butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-isotridecyl-pentaerythritol diphosphite, 2,6-di-t-butyl -4-methylphenyl-stearyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-cyclohexyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methyl Phenyl-benzyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-ethyl cellosolve-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-butyl Carbitol-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-nonylphenyl -Pentaerythritol diphosphite, bis (2,6-di t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-2,6-di-t-butylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylphenyl-pentaerythritol diphosphite Phyto, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2 -Cyclohexylphenyl-pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl-phenyl-pentaeryth Tritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos And bis (2,4-dicumylphenyl) pentaerythritol diphosphite.
A pentaerythritol type phosphite compound may be used alone or in combination of two or more.

  Among the pentaerythritol type phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-) Ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) penta Erythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferred.

Content of the phosphorus compound in a polyamide composition is 0.1-20.0 mass% with respect to 100 mass% of polyamide compositions. Preferably it is 0.2-7.0 mass%, More preferably, it is 0.5-3.0 mass%, More preferably, it is 0.5-2.5 mass%, More preferably, it is 0.5 It is -2.0 mass%, More preferably, it is 0.5-1.5 mass%.
When the content of the phosphorus compound is within the above range, the polyamide composition tends to be excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion process stability, and molding process stability.

<Phenolic antioxidant and / or amine antioxidant>
The polyamide composition may contain a phenol-based antioxidant and / or an amine-based antioxidant as a heat stabilizer.
Examples of phenolic antioxidants include, but are not limited to, hindered phenolic compounds. Phenol-based antioxidants, particularly hindered phenol compounds, have the property of imparting heat resistance and light resistance to resins such as polyamide and fibers.

Examples of the hindered phenol compound include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropylene). Onamide), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl- 4-hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Examples include benzene and 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.
Among these, from the viewpoint of improving heat aging resistance, the hindered phenol compound may be N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide). )] Is preferred.
In addition, the phenolic antioxidant mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the phenolic antioxidant in the polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass, further preferably 100% by mass with respect to 100% by mass of the polyamide composition. Is 0.1 to 1% by mass.
When the content of the phenolic antioxidant is within the above range, the polyamide composition tends to be superior in heat aging resistance and lower in the amount of generated gas.

Examples of amine-based antioxidants include, but are not limited to, poly (2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1,2-dihydro-2, 2,4-trimethylquinoline, phenyl-α-naphthylamine, 4,4-bis (α, α-dimethyldendyl) diphenylamine, (p-toluenesulfonylamido) diphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di-β-naphthyl-p-phenylenediamine, N, N′-di (1,4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine, N- (1-methylheptyl) -N′-phenyl-p-pheny Aromatic amines such as Njiamin the like.
The amine antioxidant includes an aromatic amine compound. Only one amine antioxidant may be used alone, or two or more amine antioxidants may be used in combination.

The content of the amine-based antioxidant in the polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass, further preferably 100% by mass with respect to the polyamide composition. Is 0.1 to 1% by mass.
When the content of the amine-based antioxidant is within the above range, the polyamide composition tends to be more excellent in heat aging resistance and lower in the amount of generated gas.

The metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table is not particularly limited and is preferably a heat stabilizer. Copper salt.
The copper salt is not particularly limited. For example, copper halide (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, benzoic acid Examples thereof include copper oxide, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex salt in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid. Especially, it is preferable that it is 1 or more types selected from the group which consists of copper iodide, cuprous bromide, cupric bromide, cuprous chloride, and copper acetate. Copper iodide and / or copper acetate Is more preferable. When the above metal salt, especially copper salt, is used, a polyamide composition having excellent heat aging resistance and capable of suppressing metal corrosion (hereinafter also simply referred to as “metal corrosion”) of screws and cylinders during extrusion is obtained. be able to.

The said metal salt may be used individually by 1 type, and may be used in combination of 2 or more types.
When using a copper salt, the compounding amount of the copper salt in the polyamide composition is preferably 0.01 to 0.2 parts by mass, more preferably 0.02 to 0 parts per 100 parts by mass of the polyamide composition. 15 parts by mass. When the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

  Moreover, from the viewpoint of improving the heat aging resistance, the content of copper element is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, and still more preferably 50 to 300 ppm with respect to the total amount of the polyamide composition. .

Alkali metal and alkaline earth metal halides are not particularly limited, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. Among these, potassium iodide and potassium bromide, and a mixture thereof are preferable, and potassium iodide is more preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion.
As said halide, 1 type may be used independently and 2 or more types may be used in combination.

  When alkali metal and alkaline earth metal halides are used, the blending amount of alkali and alkaline earth metal halides in the polyamide composition is preferably 0.05 to 5 with respect to 100 parts by mass of the polyamide composition. It is a mass part, More preferably, it is 0.2-2 mass part. When the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

  In the polyamide composition, a mixture of a copper salt and an alkali and alkaline earth metal halide can be suitably used as a heat stabilizer. The ratio of the copper salt to the alkali and alkaline earth metal halide may be included in the polyamide composition so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. Preferably, it is 5/1 to 30/1.

  When the molar ratio (halogen / copper) is within the above range, the heat aging resistance of the polyamide composition can be further improved. Moreover, when the molar ratio (halogen / copper) is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed. When the molar ratio (halogen / copper) is 40/1 or less, corrosion of the screws of the molding machine can be prevented without substantially impairing mechanical properties such as toughness, which is preferable.

(Light stabilizer)
The polyamide composition may contain a light stabilizer from the viewpoint of light stability. The light stabilizer has a property of imparting excellent heat resistance and light resistance to resins such as polyamide and fibers. Examples of the light stabilizer include amine light stabilizers.

Examples of the amine light stabilizer include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra. Methylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6 6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6 6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethyl Peridine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy)- 2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, Bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl) -4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pen) Methyl-4-piperidyl) carbonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis (2,2,6) , 6-Tetramethyl-4-piperidyloxy) ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6) -Tetra Methyl-4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6 , 6-Tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- ( N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5 -Triazine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4- Polycondensate with piperidyl) butylamine, poly [ {6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino } Hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4- Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tris (2,2,6,6-tetramethyl- 4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [ 3- (3,5-di-t- Til-4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4- Examples include condensates of piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.
Only one amine light stabilizer may be used alone, or two or more amine stabilizers may be used in combination.

Examples of amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, and bis (2, 2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedi Carboxamide and tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are preferred.
Among these, as the amine light stabilizer, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis-2,2,6,6-tetramethyl-4 -Piperidinyl-1,3-benzenedicarboxamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are more preferred, N, N ′ -Bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide is more preferred.

  The content of the amine light stabilizer in the polyamide composition is preferably 0 to 2% by mass, more preferably 0.01 to 2% by mass, further preferably 100% by mass with respect to 100% by mass of the polyamide composition. Is 0.1 to 2% by mass. When the content of the amine light stabilizer is within the above range, the light stability and heat aging resistance of the polyamide composition can be further improved, and the amount of generated gas can be further reduced.

(Other additives)
In the polyamide composition, additives that are conventionally used for polyamide, for example, colorants such as pigments and dyes (including colored master batches), flame retardants, fibrillating agents, and lubricants, as long as the object of the present invention is not impaired. Containing agents, fluorescent bleaching agents, plasticizers, ultraviolet absorbers, antistatic agents, fluidity improvers, fillers, reinforcing agents, spreading agents, nucleating agents, rubbers, reinforcing agents and other polymers You can also.

[Method for producing second polyamide composition]
The method for producing the polyamide composition is not particularly limited as long as it is a method of mixing the above-described second polyamide and, if necessary, the inorganic filler and other additives described above.
As a method for mixing the constituent materials of the second polyamide composition, for example, a method of mixing using a Henschel mixer or the like, supplying to a melt kneader and kneading, or a polyamide melted with a single screw or twin screw extruder, The method of mix | blending an inorganic filler and another additive from a side feeder is mentioned.
In the method of supplying the components constituting the second polyamide composition to the melt kneader, all the components (polyamide, inorganic filler, etc.) may be supplied to the same supply port at the same time. You may supply from a different supply port.

The melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature.
The melt kneading time is preferably about 0.5 to 5 minutes.
The apparatus for performing melt kneading is not particularly limited, and a known apparatus, for example, a melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, and a mixing roll can be used.

  The method for producing the polyamide composition when the inorganic filler contained in the second polyamide composition is a reinforcing fiber having a weight average fiber length of 1 to 15 mm is not particularly limited. For example, as described in the pultrusion method in which polyamide is melt-kneaded with a twin-screw extruder, and the molten polyamide is impregnated into a roving of reinforcing fibers to obtain a polyamide-impregnated strand, as described in JP-A-2008-221574. A method of sufficiently impregnating the polyamide by a process of twisting the impregnated strand in a spiral shape is mentioned.

[Physical properties of the second polyamide composition]
The physical properties of the polyamide in the second polyamide composition of the present invention are equivalent to the physical properties of the second polyamide of the present invention. In other words, the polyamide in the second polyamide composition maintains the physical properties of the second polyamide even after being melt-kneaded with other additives as necessary to obtain a composition. Has a measured value. Therefore, it is possible to specify the physical property of the polyamide contained in it by measuring each said physical property about a polyamide composition.
Trans isomer ratio, sulfuric acid relative viscosity ηr, number average molecular weight Mn, molecular weight distribution Mw / Mn, melting peak temperatures Tm1, Tm2, melting heat amounts ΔHm1, ΔHm2, crystallization peak temperature Tc of the second polyamide composition of the present invention. The ratio of crystallization enthalpy ΔHc, glass transition temperature Tg, amino terminal, carboxyl terminal, and amino terminal amount to the total amount of active terminals can be measured by the method for measuring the physical properties of the polyamide described in the examples described later.
Since the measured value in the second polyamide composition of the present invention is in the same range as the measured value of the second polyamide of the present invention, the polyamide composition of the present invention has low strength during heating, Excellent water absorption.

  When determining the heat of fusion and crystallization enthalpy of the second polyamide composition, if the inorganic polyamide, nucleating agent, lubricant, stabilizer, etc. are included, the value of the heat value is the value for the composition. Calculated by converting the ratio of the two polyamides.

[Polyamide composition molded product]
The polyamide composition molded article of the present invention (hereinafter sometimes simply referred to as a molded article) is formed by molding the above-mentioned second polyamide composition.
The polyamide composition molded article maintains a high trans isomer ratio of the dicarboxylic acid monomer unit, and is excellent in hot strength, hot stiffness, and low water absorption, so it can be suitably used for automotive parts. it can.

[Production Method of Polyamide Composition Molded Product]
The molded article of the polyamide composition of the present invention is a known molding method such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, and blow molding of the second polyamide or the second polyamide composition described above. , Film molding, hollow molding, multilayer molding, melt spinning and the like.

[Physical properties of molded products]
The polyamide composition molded article is excellent in mechanical properties and low water absorption during heating. The hot strength at 120 ° C. is preferably 120 MPa or more, and more preferably 125 MPa or more. Moreover, the thermal tensile elastic modulus at 120 ° C. is preferably 5.0 GPa or more, and more preferably 5.3 GPa or more.
The water absorption after 24 hours of 80 ° C. water is preferably less than 2.0%, more preferably 1.5% or less. Regarding the LLC resistance, the retention is preferably 75% or more, and more preferably 80% or more.

[Use of polyamide composition molded product]
The polyamide composition molded article of the present invention is excellent in heat resistance, strength, heat strength, rigidity, heat rigidity, heat stability, and has mold release and LLC resistance as shown in the following examples. Since it is improved, it can be suitably used as various parts materials for automobiles, electric and electronic, industrial materials, extrusion applications, daily necessities and household goods. About these specific uses, the thing similar to said 1st embodiment is mentioned.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to an Example. In the examples, 1 kg / cm ² means 0.098 MPa.
Examples of the first embodiment of the present invention will be described below.
[Example 1]
Measuring methods for raw materials and physical properties used in Examples and Comparative Examples are shown below.

[Raw material of polyamide]
<Raw material of dicarboxylic acid unit>
(1) 1,4-Cyclohexanedicarboxylic acid (CHDA) Product name: 1,4-CHDA HP grade (trans isomer / cis isomer (molar ratio) = 25/75) (2) Terephthalic acid (TPA) Wako Pure Chemical Industries, Ltd. Product name: Terephthalic acid <Raw material of diamine unit>
(3) 2-methylpentamethylenediamine (2MPD) manufactured by Tokyo Chemical Industry Co., Ltd. Product name: 2-methyl-1,5-diaminopentane (4) hexamethylenediamine (HMD) manufactured by Wako Pure Chemical Industries, Ltd. Product name: hexamethylenediamine ( 5) 1,9-nonanediamine (NMD) Aldrich product name: 1,9-nonanediamine (6) 2-methyl-1.8-octanediamine (2MODA) What was prepared with reference to Japanese Patent Laid-Open No. 05-17413 Using.
(7) 1,10-diaminodecane (decamethylenediamine) (C10DA) Product name: 1,10-decanamine (manufactured by Ogura Gosei Kogyo Co., Ltd.)

〔polyamide〕
(8) Polyamide 66 (PA66) manufactured by Asahi Kasei Chemicals Corporation: Leona (registered trademark) 1300-301

[Inorganic filler]
(9) Glass fiber (GF) Product name: NEC S03T275H Average fiber diameter (average particle diameter) 10 μm (circular shape), cut length 3 mm

[Calculation of polyamide content]
The mole% of 1,4-cyclohexanedicarboxylic acid is calculated by (Mole number of 1,4-cyclohexanedicarboxylic acid added as raw material monomer / Mole number of all dicarboxylic acid units added as raw material monomer) × 100. It was. The mol% of the aliphatic diamine was determined by calculation as (number of moles of aliphatic diamine added as a raw material monomer / number of moles of all diamine units added as a raw material monomer) × 100.
In addition, when calculating by the above formula, the denominator and numerator do not include the number of moles of aliphatic diamine added as an additive during melt polymerization.

[Method for measuring physical properties]
<(1) Glass transition temperature Tg, melting peak temperature Tm (° C.), heat of fusion ΔHm, crystallization enthalpy ΔHc>
According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER. The measurement conditions were as follows: when about 10 mg of the polyamide molded product obtained in Examples and Comparative Examples was heated to 300 to 350 ° C. according to the melting point of the sample at a heating rate of 20 ° C./min in the nitrogen atmosphere (first time) The melting peak temperature appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time of temperature rise was defined as Tm (° C.), and the peak area of Tm was defined as the heat of fusion ΔHm (J / g). The melting point Tm2 and the heat of fusion ΔHm2 of the starting polyamide can be measured from the DSC of the molded product as follows. After the first temperature increase, the temperature is maintained for 2 minutes in the molten state at the maximum temperature increase, then the temperature is decreased to 30 ° C. at a temperature decrease rate of 20 ° C./min, maintained at 30 ° C. for 2 minutes, and then the temperature increase rate is 20 The endothermic peak temperature that appears on the highest temperature side of the endothermic peak that appears when the temperature is similarly raised at the same temperature (° C./min) is the melting point of the polyamide itself, and the peak area at this melting point is the heat of fusion of the polyamide. ΔHm2.

In addition, when there were a plurality of endothermic peaks appearing at the first temperature increase, those having ΔH of 1 J / g or more were regarded as peaks. For example, when there are two endothermic peaks that appear at the first temperature rise, melting point 295 ° C., ΔH = 20 J / g, melting point 325 ° C., ΔH = 5 J / g, the melting peak temperature Tm is higher. The value of 325 ° C. and ΔHm were 25 J / g of the total value of all peaks.
The temperature of the exothermic peak (crystallization peak) that appears when the temperature is lowered at a rate of temperature decrease of 20 ° C./min is defined as the crystallization peak temperature Tc (° C.), and the total peak area of Tc is the crystallization enthalpy ΔHc (J / g). did.

  The glass transition temperature Tg (° C.) was measured using Diamond-DSC manufactured by PERKIN-ELMER according to JIS-K7121. The measurement conditions were that the polyamide composition molded products obtained in Examples and Comparative Examples were melted on a hot stage (EP80 manufactured by Mettler), and the molten sample obtained was rapidly cooled using liquid nitrogen and solidified. A measurement sample was obtained. Using 10 mg of the sample, the glass transition temperature was measured by raising the temperature in the range of 30 to 350 ° C. under a temperature raising speed of 20 ° C./min.

<(2) Trans isomer ratio>
30-40 mg of the polyamide composition molded product obtained in the examples and comparative examples was dissolved in 1.2 g of hexafluoroisopropanol deuterated and measured by ¹ H-NMR (ECA500 manufactured by JEOL). Trans isomer ratio mol% of 1,4-cyclohexanedicarboxylic acid monomer unit of molded product, peak area of 2.00 ppm derived from trans isomer and peaks of 1.77 ppm and 1.87 ppm derived from cis isomer It calculated | required from the area ratio.

<(3) Molecular weight>
Number average molecular weight Mn, weight average molecular weight Mw, molecular weight distribution Mw / Mn are GPC (gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA (polymethyl methacrylate) standard sample (Polymer Laboratories) A calibration curve was prepared using the number average molecular weight Mn measured in terms of conversion, and the molecular weight of the polyamide composition molded product obtained in this example and comparative example was determined.The GPC column is TSK-GEL GMHHR. -M and G1000HHR were used.

<(4) Tensile strength (MPa), tensile elastic modulus (GPa), tensile elongation (%)>
Using the polyamide composition molded articles (multipurpose test pieces) obtained in Examples and Comparative Examples, a tensile test was performed in accordance with ISO 527 under a 120 ° C. environment and a tensile speed of 5 mm / min, and the tensile strength and tensile elasticity. Rate and tensile elongation were measured.

<(5) Tensile strength retention after immersion (%)>
Tensile strength retention (%) after immersion of the polyamide composition molded articles obtained in Examples and Comparative Examples was measured as follows. The multipurpose test piece (3 mm thickness) of (4) above was immersed in a 120% ethylene glycol 50% aqueous solution for 24 hours and 720 hours and left at room temperature, and then the tensile test of the method of (4) was performed. Tensile strength was measured. The ratio of the tensile strength measured after immersion for 720 hours to the tensile strength measured after immersion for 24 hours was determined as the tensile strength retention after immersion.

[Example 1-1]
(Production of polyamide)
The polymerization reaction of polyamide was carried out as follows by a hot melt polymerization method.
CHDA 896 g (5.2 mol) as the dicarboxylic acid unit and 2PMD 604 g (5.2 mol) as the diamine unit were dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer.
The obtained aqueous solution was charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was purged with nitrogen. Until the pressure in the autoclave tank (hereinafter also referred to simply as “inside the tank”) reaches about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure). The liquid temperature was continuously heated from about 50 ° C. (the liquid temperature in this system was about 145 ° C.). In order to keep the pressure in the tank at about 2.5 kg / cm ² , heating was continued while removing water out of the system, and the solution was concentrated until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was about It was 160 ° C.). The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² (the liquid temperature in this system was about 245 ° C.). In order to keep the pressure in the tank at about 30 kg / cm ² , heating was continued until the final temperature (340 ° C. described later) −50 ° C. (here, 290 ° C.) was reached while removing water out of the system. After the liquid temperature rises to the final temperature (340 ° C. described later) −50 ° C. (here, 290 ° C.), while heating continues, the pressure in the tank reaches 30 at atmospheric pressure (gauge pressure is 0 kg / cm ² ). The pressure dropped while taking about a minute.

  Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 340 ° C. The resin temperature was kept at about 340 ° C., and the inside of the tank was maintained under a reduced pressure of about 79.9 kPa (about 600 torr) for 20 minutes by a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.

(Production of polyamide composition)
A polyamide composition was produced using the polyamide pellets and glass fibers obtained above.
Specifically, a twin screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd., L / D = 47.6 (D = 37 mmφ), set temperature Tm2 + 20 ° C. (when the polyamide obtained in Example 1-1 is used) 325 + 20 = 345 ° C.) and a screw rotation speed of 300 rpm) to produce a polyamide composition as follows. The polyamide (65 parts by mass) with the moisture content adjusted is supplied from a top feed port provided at the most upstream part of the twin screw extruder, and the downstream side of the twin screw extruder (resin supplied from the top feed port is Glass fiber (35 parts by mass) is supplied as an inorganic filler from the side feed port in a sufficiently melted state) at a mass ratio of (polyamide: glass fiber = 65: 35), and the melt-kneaded product extruded from the die head is supplied. It was cooled in a strand form and pelletized to obtain polyamide composition pellets.

(Manufacture of molded articles of polyamide composition)
In accordance with ISO 3167, the obtained polyamide composition was molded into a multi-purpose test piece (A type) by injection molding, and then heat treated at 240 ° C. in a reduced pressure environment at −0.1 MPa (gauge pressure) for 2 hours. Thus, a molded article of the polyamide composition was obtained. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 1-2]
A polyamide composition molded product was obtained in the same manner as in Example 1-1 except that the heat treatment time in (manufacturing the polyamide composition molded product) was set to 7 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 1-3]
(Production of polyamide)
The polymerization reaction of polyamide was carried out as follows by a hot melt polymerization method.
CHDA 795 g (4.62 mol) as a dicarboxylic acid unit, C10DA 517 g (3.00 mol) as a diamine unit, and 188 g (1.62 mol) of 2PMD are dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of the raw material monomer. Was made.
The obtained aqueous solution was charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was replaced with nitrogen. The liquid temperature was continuously heated from about 50 ° C. until the pressure in the tank was about 2.5 kg / cm ² as a gauge pressure (the liquid temperature in this system was about 145 ° C.). In order to keep the pressure in the tank at about 2.5 kg / cm ² , water was removed from the system while heating was continued until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It was about 160 ° C.). The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² (the liquid temperature in this system was about 245 ° C.). In order to keep the pressure in the tank at about 30 kg / cm ² , heating was continued until the final temperature (330 ° C. described later) −40 ° C. (here, 290 ° C.) was reached while removing water out of the system. After the liquid temperature rises to the final temperature (330 ° C. described later) −40 ° C. (290 ° C. here), the heating continues and the pressure in the tank reaches 30 at atmospheric pressure (gauge pressure is 0 kg / cm ² ). The pressure dropped while taking about a minute.

  Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 330 ° C. The resin temperature was kept at about 340 ° C., and the inside of the tank was maintained under a reduced pressure of about 79.9 kPa (about 600 torr) for 20 minutes by a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.

(Production of polyamide composition)
A polyamide composition was produced using the polyamide pellets and glass fibers obtained above.
Specifically, a twin-screw extruder (TEM 35 manufactured by Toshiba Machine Co., Ltd., L / D = 47.6 (D = 37 mmφ), set temperature Tm2 + 20 ° C. (when using the polyamide obtained in Example 3, 295 + 20) = 315 ° C.) and a screw rotation speed of 300 rpm), a polyamide composition was produced as follows. The polyamide (65 parts by mass) with the moisture content adjusted is supplied from a top feed port provided at the most upstream part of the twin screw extruder, and the downstream side of the twin screw extruder (resin supplied from the top feed port is Glass fiber (35 parts by mass) is supplied as an inorganic filler from the side feed port in a sufficiently melted state) at a mass ratio of (polyamide: glass fiber = 65: 35), and the melt-kneaded product extruded from the die head is supplied. It was cooled in a strand form and pelletized to obtain polyamide composition pellets.

(Production of polyamide composition molded product)
The obtained polyamide composition was formed into a multi-purpose test piece (A type) in accordance with ISO 3167, and then heat treated at 240 ° C. in a reduced pressure environment at −0.1 MPa (gauge pressure) for 2 hours to obtain a polyamide composition. A molded article was obtained. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 1-4]
A polyamide composition molded article was obtained in the same manner as in Example 1-3, except that the heat treatment time in (Manufacturing the polyamide composition molded article) was set to 7 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 1-5]
A polyamide composition molded article was obtained in the same manner as in Example 1-3, except that the heat treatment time in (manufacturing the polyamide composition molded article) was 24 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 1-6]
(Production of polyamide)
The polymerization reaction of polyamide was carried out as follows by a hot melt polymerization method.
CHDA 802 g (4.66 mol) as a dicarboxylic acid unit, C10DA 481 g (2.79 mol) as a diamine unit, 216 g (1.86 mol) of 2PMD are dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of the raw material monomer. Was made.
The obtained aqueous solution was charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was purged with nitrogen. The liquid temperature was continuously heated from about 50 ° C. until the pressure in the tank was about 2.5 kg / cm ² as a gauge pressure (the liquid temperature in this system was about 145 ° C.). In order to keep the pressure in the tank at about 2.5 kg / cm ² , water was removed from the system while heating was continued until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It was about 160 ° C.). The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² (the liquid temperature in this system was about 245 ° C.). In order to maintain the pressure in the tank at about 30 kg / cm ² , heating was continued until the final temperature (320 ° C. described later) −30 ° C. (here, 290 ° C.) was reached while removing water out of the system. After the liquid temperature rises to the final temperature (320 ° C. described later) -30 ° C. (here, 290 ° C.), the heating continues while the pressure in the tank reaches atmospheric pressure (gauge pressure is 0 kg / cm ² ). The pressure dropped while taking about a minute.

  Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 320 ° C. The resin temperature was kept at about 320 ° C., and the inside of the tank was maintained under a reduced pressure of about 79.9 kPa (about 600 torr) for 20 minutes with a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.

(Production of polyamide composition)
A polyamide composition was produced using the polyamide pellets and glass fibers obtained above.
Specifically, a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd., L / D = 47.6 (D = 37 mmφ), set temperature Tm2 + 20 ° C. (when the polyamide obtained in Example 1-6 is used) 325 + 20 = 345 ° C.) and a screw rotation speed of 300 rpm) to produce a polyamide composition as follows. The polyamide (65 parts by mass) with the moisture content adjusted is supplied from a top feed port provided at the most upstream part of the twin screw extruder, and the downstream side of the twin screw extruder (resin supplied from the top feed port is Glass fiber (35 parts by mass) is supplied as an inorganic filler from the side feed port in a sufficiently melted state) at a weight ratio of (polyamide: glass fiber = 65: 35), and the melt-kneaded product extruded from the die head is supplied. It was cooled in a strand form and pelletized to obtain polyamide composition pellets.

(Production of polyamide composition molded product)
The obtained polyamide composition was molded into a multi-purpose test piece (A type) in accordance with ISO 3167, and then heat-treated at a temperature of 240 ° C. under a reduced pressure environment at −0.2 MPa (gauge pressure) for 2 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 1-7]
A polyamide composition molded product was obtained in the same manner as in Example 1-6 except that the heat treatment time in (manufacturing the polyamide composition molded product) was set to 7 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 1-8]
A polyamide composition molded article was obtained in the same manner as in Example 1-6, except that the heat treatment time in (manufacturing the polyamide composition molded article) was 24 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 1-9]
(Production of polyamide)
The polymerization reaction of polyamide was carried out as follows by a hot melt polymerization method.
CHDA 795 g (4.62 mol) as a dicarboxylic acid unit, C10DA 517 g (3.00 mol) and HMD 188 g (1.62 mol) as a diamine unit are dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of the raw material monomer is obtained. Was made.
The obtained aqueous solution was charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was purged with nitrogen. The liquid temperature was continuously heated from about 50 ° C. until the pressure in the tank was about 2.5 kg / cm ² as a gauge pressure (the liquid temperature in this system was about 145 ° C.). In order to keep the pressure in the tank at about 2.5 kg / cm ² , water was removed from the system while heating was continued until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It was about 160 ° C.). The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² (the liquid temperature in this system was about 245 ° C.). In order to keep the pressure in the tank at about 30 kg / cm ² , heating was continued until the final temperature (330 ° C. described later) −40 ° C. (here, 290 ° C.) was reached while removing water out of the system. After the liquid temperature rises to the final temperature (330 ° C. described later) −40 ° C. (290 ° C. here), the heating continues and the pressure in the tank reaches 30 at atmospheric pressure (gauge pressure is 0 kg / cm ² ). The pressure dropped while taking about a minute.

  Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 330 ° C. The resin temperature was kept at about 340 ° C., and the inside of the tank was maintained under a reduced pressure of about 79.9 kPa (about 600 torr) for 20 minutes by a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.

(Production of polyamide composition)
Manufacture of the polyamide composition was implemented using said polyamide and glass fiber.
Specifically, a twin screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd., L / D = 47.6 (D = 37 mmφ), set temperature Tm2 + 20 ° C. (when the polyamide obtained in Example 1-9 is used) 295 + 20 = 315 ° C.) and a screw rotation speed of 300 rpm) to produce a polyamide composition as follows. The polyamide (65 parts by mass) with the moisture content adjusted is supplied from a top feed port provided at the most upstream part of the twin screw extruder, and the downstream side of the twin screw extruder (resin supplied from the top feed port is Glass fiber (35 parts by mass) is supplied as an inorganic filler from the side feed port in a sufficiently melted state) at a mass ratio of (polyamide: glass fiber = 65: 35), and the melt-kneaded product extruded from the die head is supplied. It was cooled in a strand form and pelletized to obtain polyamide composition pellets.

(Production of polyamide composition molded product)
The obtained polyamide composition was molded into a multi-purpose test piece (A type) in accordance with ISO 3167, and then heat-treated at a temperature of 240 ° C. under a reduced pressure environment at −0.2 MPa (gauge pressure) for 2 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 1-10]
A polyamide composition molded article was obtained in the same manner as in Example 1-9, except that the heat treatment time in (Manufacturing the polyamide composition molded article) was set to 7 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 1-11]
A polyamide composition molded article was obtained in the same manner as in Example 1-9, except that the heat treatment time in (Manufacturing the polyamide composition molded article) was 24 hours. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Comparative Example 1-1]
(Production of polyamide) and (Production of polyamide composition) were carried out in the same manner as in Example 1-1, and (Production of polyamide composition molded article) was carried out as follows.
The polyamide composition pellets obtained in (Production of polyamide composition) were heat-treated at a temperature of 150 ° C. under a reduced pressure environment at −0.2 MPa (gauge pressure) for 7 hours. This pellet had a trans isomer ratio of 70 mol%. Subsequently, in accordance with ISO 3167, a molded article of a polyamide composition was obtained by molding into a molded piece of a multipurpose test piece (A type). Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Comparative Example 1-2]
A polyamide composition molded article was obtained in the same manner as in Example 1-3, except that the heat treatment in (Manufacturing the polyamide composition molded article) was not performed. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Comparative Example 1-3]
(Production of polyamide)
It was prepared as follows according to the method described in Example 1 of JP-A-7-228689.
818.23 g (4.75 mol) of TPA, 712.30 g (4.50 mol) of NMD, 79.15 g (0.50 mol) of 2MODA, 18.32 g (0.15 mol) of benzoic acid, sodium hypophosphite monohydrate 1.63 g of the product (0.1 parts by mass with the total amount of raw material monomers being 100 parts by mass) and 1500 g of distilled water were placed in an autoclave (manufactured by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L and purged with nitrogen.
The resulting reaction liquid was stirred at a liquid temperature (internal temperature) of 100 ° C. for 30 minutes, and then heated to a liquid temperature of 210 ° C. over 2 hours. At this time, the pressure in the tank was increased to 22 kg / cm ² . The reaction was continued for 1 hour at a liquid temperature of 210 ° C. and a pressure in the tank of 22 kg / cm ² , then the temperature was raised to 230 ° C., and then the liquid temperature was maintained at 230 ° C. for 2 hours. The reaction was carried out while maintaining the internal pressure at 22 kg / cm ² . The pressure in the tank was lowered to 10 kg / cm ² over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer having a sulfuric acid relative viscosity [ηr] of 1.25.
The obtained prepolymer was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a size of 2 mm or less, and then subjected to solid phase polymerization at 230 ° C. and 0.1 mmHg for 10 hours to obtain a polyamide (hereinafter referred to as "PA9T") was obtained.

(Production of polyamide composition)
A polyamide composition was produced using the PA9T and glass fiber obtained above.
Specifically, a twin screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd., L / D = 47.6 (D = 37 mmφ), set temperature Tm2 + 20 ° C. (when using PA9T obtained in Comparative Example 1-3) 290 + 20 = 310 ° C.) and a screw rotational speed of 300 rpm), a polyamide composition was produced as follows. The polyamide (65 parts by mass) with the moisture content adjusted is supplied from a top feed port provided at the most upstream part of the twin screw extruder, and the downstream side of the twin screw extruder (resin supplied from the top feed port is Glass fiber (35 parts by mass) is supplied as an inorganic filler from the side feed port in a sufficiently melted state) at a mass ratio of (polyamide: glass fiber = 65: 35), and the melt-kneaded product extruded from the die head is supplied. It was cooled in a strand form and pelletized to obtain polyamide composition pellets.

(Production of polyamide composition molded product)
The obtained polyamide composition was molded into a multi-purpose test piece (A type) according to ISO 3167. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Comparative Example 1-4]
(Production of polyamide composition)
A polyamide composition was produced using polyamide 66 and glass fibers.
Specifically, a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd., L / D = 47.6 (D = 37 mmφ), set temperature Tm2 + 20 ° C. (when the polyamide obtained in Comparative Example 1-4 is used) 260 + 20 = 280 ° C.) and a screw rotation speed of 300 rpm), a polyamide composition was produced as follows. The polyamide (65 parts by mass) with the moisture content adjusted is supplied from a top feed port provided at the most upstream part of the twin screw extruder, and the downstream side of the twin screw extruder (resin supplied from the top feed port is Glass fiber (35 parts by mass) is supplied as an inorganic filler from the side feed port in a sufficiently melted state) at a mass ratio of (polyamide: glass fiber = 65: 35), and the melt-kneaded product extruded from the die head is supplied. It was cooled in a strand form and pelletized to obtain polyamide composition pellets.

(Production of polyamide composition molded product)
The obtained polyamide composition was molded into a multi-purpose test piece (A type) according to ISO 3167. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
Each physical property of the polyamide composition molded product obtained in Examples and Comparative Examples was measured based on the above method. The measurement results are shown in Table 1A and Table 1B.

  The polyamide composition molded article of the present invention is a trans-rich polyamide composition molded article obtained only by heat treatment after molding, regardless of the ratio of cis-trans in the raw material or polyamide state, and is apparent from the results shown in Table 1A. Thus, the polyamide composition molded articles of Examples 1-1 to 1-11 had excellent properties in hot strength and hot stiffness. In general, when the polymer absorbs water, degradation occurs due to hydrolysis and chemical penetration, and so-called LLC resistance decreases. However, the polyamide composition molded product of the present invention has improved LLC resistance as shown in the tensile strength retention after immersion. did. The penetration rate (degradation rate) of LLC differs between the amorphous part and the crystalline part of the molded product, and the amorphous part deteriorates faster than the crystalline part. However, the polyamide composition molded product of the present invention is not treated by heat treatment after molding. As a result of the decrease in the crystal portion and the increase in the crystal portion (ΔHm), it is considered that the LLC resistance was improved.

On the other hand, as shown in Table 1B, in Comparative Example 1-1, the composition pellets before molding had a trans isomer ratio of 70 mol%, and even after melt molding, the ratio was 70 mol%. As a result, the hot strength, the hot stiffness, and the LLC resistance were insufficient. In Comparative Example 1-2, the composition pellets before molding had a trans isomer ratio of 70 mol%, and even after melt molding, the trans isomer ratio was 70 mol%. It was insufficient in terms of LLC resistance.
On the other hand, Comparative Examples 1-3 and 1-4 were insufficient in terms of hot strength, hot stiffness, and LLC resistance because no isomers were present.

In the same manner as described above, the non-reinforced polyamide molded article not containing the inorganic filler was subjected to Examples and Comparative Examples as follows.
[Example 1-12]
In Example 1-1, a polyamide composition molded article was prepared in the same manner except that the glass fiber in (manufacturing the polyamide composition) was not added and the heat treatment time in (manufacturing the polyamide composition molded article) was 7 hours. Got. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 1-13]
In Example 1-3, a polyamide composition molded article was prepared in the same manner except that the glass fiber in (manufacturing the polyamide composition) was not added and the heat treatment time in (manufacturing the polyamide composition molded article) was 24 hours. Got. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Comparative Example 1-5]
In Example 1-1, a polyamide composition molded product was obtained in the same manner except that the glass fiber in (manufacturing the polyamide composition) was not added and heat treatment was not performed in (manufacturing the polyamide composition molded product). It was. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Comparative Example 1-6]
In Example 1-3, a polyamide composition molded product was obtained in the same manner except that the glass fiber in (manufacturing the polyamide composition) was not added and the heat treatment in (manufacturing the polyamide composition molded product) was not performed. It was. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.
Each physical property of the polyamide composition molded product obtained in Examples and Comparative Examples was measured based on the above method. The measurement results are shown in Table 1C.

  As shown in Table 1C, in Examples 1-12 and 1-13, in which heat treatment after molding was performed even in the case of a non-reinforced polyamide molded article not containing an inorganic filler, the strength during heating, the rigidity during heating, and the LLC resistance And had excellent characteristics. On the other hand, Comparative Examples 1-5 and 1-6 were insufficient in terms of hot strength, hot stiffness, and LLC resistance because the trans isomer ratio was 70 mol%.

Next, an example of the second embodiment will be described. The present example relates to a polyamide composition molded article obtained by molding the first polyamide composition using the first polyamide.
[Example 2]

  The raw materials used in the polyamide compositions of Examples and Comparative Examples, and methods for measuring physical properties of the polyamide and polyamide composition molded articles are shown below.

〔raw materials〕
(A) Polyamide The (A) polyamide used in the examples and comparative examples was produced using the following (a) and (b) as appropriate.
(A) Dicarboxylic acid (1) 1,4-cyclohexanedicarboxylic acid (CHDA) (manufactured by Eastman Chemical Co., Ltd., trade name: 1,4-CHDA HP grade (trans isomer / cis isomer = 25/75))
(B) Diamine (1) 2-Methylpentamethylenediamine (2MC5DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(2) Nonamethylenediamine (C9DA) (Aldrich)
(3) 2-methyloctamethylenediamine (2MC8DA) (manufactured with reference to the production method described in JP-A No. 05-17413)
(4) Hexamethylenediamine (C6DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(5) Undecamethylenediamine (C11DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(6) Dodecamethylenediamine (C12DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)

(C) Monocarboxylic acid (1) Acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
(2) Benzoic acid (Wako Pure Chemical Industries, Ltd.)

(B) Titanium oxide TiO ₂ (manufactured by Ishihara Sangyo Co., Ltd., trade name: Taipei (registered trademark) CR-63, number average particle size: 0.21 μm, coating: alumina, silica and siloxane compound)
In addition, the number average particle diameter of (B) titanium oxide was measured as follows by an electron micrograph method.
The polyamide compositions of Examples and Comparative Examples to be described later are placed in an electric furnace, the organic matter contained in the polyamide composition is incinerated, and 100 or more titanium oxides arbitrarily selected from the residue are observed with an electron microscope. And the number average particle diameter of (B) titanium oxide was calculated | required by measuring these particle sizes.

(C) Inorganic filler Wollastonite (number average fiber diameter 8 μm)
In addition, (C) The number average fiber diameter of an inorganic filler puts the polyamide composition of the Example and comparative example which are mentioned later into an electric furnace, and incinerates the organic substance contained in a polyamide composition. From the residue, 100 or more arbitrarily selected wollastonites were observed with an SEM, and the number average fiber diameter was determined by measuring the fiber diameters of these wollastonites.

(D) Nucleating agent Talc (made by Nippon Talc Co., Ltd., trade name: MICRO ACE (registered trademark) L-1 average particle size 5 μm)

(E) Metal hydroxide, calcium hydroxide, purity 99.9% (manufactured by Wako Pure Chemical Industries, Ltd.)

(F) Phosphorus compound Calcium hypophosphite (manufactured by Wako Pure Chemical Industries, Ltd., decomposition start temperature 340 ° C.)

(G) Phenol-based antioxidant Phenol-based antioxidant (manufactured by BASF, trade name: IRGANOX (registered trademark) 1098)

[Calculation of unit amount of structural unit in polyamide]
The mole% of 1,4-cyclohexanedicarboxylic acid is calculated by (Mole number of 1,4-cyclohexanedicarboxylic acid added as raw material monomer / Mole number of all dicarboxylic acid units added as raw material monomer) × 100. It was.
Further, the mol% of the aliphatic diamine was obtained by calculation as (number of moles of aliphatic diamine added as raw material monomer / number of moles of all diamine units added as raw material monomer) × 100.
In addition, when calculating by the above formula, the denominator and numerator do not include the number of moles of aliphatic diamine added as an additive during melt polymerization.

[Method of measuring physical properties of polyamide]
(1) Polyamide melting peak temperature Tm1 · Tm2 (° C.), heat of fusion ΔHm1 · ΔHm2 (J / g), crystallization peak temperature Tc (° C.), crystallization enthalpy ΔHc (J / g)
In accordance with JIS-K7121, using Diamond-DSC manufactured by PERKIN-ELMER, melting peak temperatures Tm1, Tm2 (° C.), heat of fusion ΔHm1 (J / g), crystallization peak temperature Tc (° C.), and The crystallization enthalpy ΔHc was measured.
Specifically, it measured as follows.

  First, an endothermic peak that appears when about 10 mg of a sample (polyamide) is heated to 300 to 350 ° C. in accordance with the melting point of the sample at a temperature increase rate of 20 ° C./min (at the first temperature increase) in a nitrogen atmosphere. The melting peak temperature that appeared on the highest temperature side of the melting peak) was Tm1 (° C.), and the peak area of Tm1 was the heat of fusion ΔHm1 (J / g). The melting point Tm2 and the heat of fusion ΔHm2 of the starting polyamide can be measured as follows. After the first temperature increase, the temperature is maintained for 2 minutes in the molten state at the maximum temperature increase, then the temperature is decreased to 30 ° C. at a temperature decrease rate of 20 ° C./min, maintained at 30 ° C. for 2 minutes, and then the temperature increase rate is 20 The endothermic peak temperature that appears at the highest temperature side of the endothermic peak that appears when the temperature is similarly raised at the same temperature (° C./min) is the melting peak temperature Tm2 of the polyamide itself, and the peak area at Tm2 is the polyamide area. The amount of heat of fusion ΔHm2.

In addition, when there were a plurality of endothermic peaks appearing at the first temperature increase, those having ΔH of 1 J / g or more were regarded as peaks. For example, when there are two endothermic peaks that appear at the first temperature increase, melting point 295 ° C., ΔH = 20 J / g, melting point 325 ° C., ΔH = 5 J / g, the melting peak temperature Tm1 is higher. The value of 325 ° C. and ΔHm1 were 25 J / g of the total value of all peaks.
The temperature of the exothermic peak (crystallization peak) that appears when the temperature is lowered at a rate of temperature decrease of 20 ° C./min is defined as the crystallization peak temperature Tc (° C.), and the total peak area of Tc is the crystallization enthalpy ΔHc (J / g). did.

(2) Glass transition temperature Tg (° C) of polyamide
The glass transition temperature Tg (° C.) was measured using Diamond-DSC manufactured by PERKIN-ELMER according to JIS-K7121. Specifically, it measured as follows. The sample was melted on a hot stage (EP80 manufactured by Mettler), and the obtained sample in a molten state was rapidly cooled using liquid nitrogen and solidified to obtain a measurement sample. 10 mg of the measurement sample was heated by DSC in the range of 30 to 350 ° C. under the condition of a heating rate of 20 ° C./min, and the glass transition temperature Tg (° C.) observed at the time of temperature increase was measured. did.

(3) Trans isomer ratio of polyamide The trans isomer ratio of the portion derived from 1,4-cyclohexadicarboxylic acid in the polyamide was measured as follows.
30-40 mg of polyamide was dissolved in 1.2 g of hexafluoroisopropanol deuteride, and the trans isomer ratio was measured by ¹ H-NMR (ECA500 manufactured by JEOL) using the resulting solution.
When the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid, the ratio between the peak area of 1.98 ppm derived from the trans isomer and the peak areas of 1.77 ppm and 1.86 ppm derived from the cis isomer From which the trans isomer ratio was determined.

(4) Polyamide sulfuric acid relative viscosity ηr
The relative viscosity ηr of sulfuric acid at 25 ° C. of the polyamides obtained in the examples and comparative examples was measured according to JIS-K6920. Specifically, a 1% concentration solution ((polyamide 1 g) / (98% sulfuric acid 100 mL)) was prepared using 98% sulfuric acid, and a temperature of 25 ° C. was obtained using the obtained solution. The sulfuric acid relative viscosity ηr was measured under the conditions.

(5) Polyamide molecular weight (Mn, Mw / Mn)
Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamides obtained in Examples and Comparative Examples is GPC (gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA (poly It was calculated using Mw and Mn measured by methyl methacrylate) standard sample (manufactured by Polymer Laboratories). In addition, TSK-GEL GMHHR-M and G1000HHR were used for the GPC column.

(6) Amino terminal amount ([NH ₂ ])
In the polyamides obtained in the examples and comparative examples, the amount of amino terminal bound to the polymer terminal was measured by neutralization titration as follows.
3.0 g of polyamide was dissolved in 100 mL of a 90 mass% phenol aqueous solution, and the obtained solution was titrated with 0.025N hydrochloric acid to determine the amino terminal amount (μ equivalent / g). The end point was determined from the indicated value of the pH meter.

(7) Carboxyl end amount ([COOH])
In the polyamides obtained in the examples and comparative examples, the amount of carboxyl terminal bound to the polymer terminal was measured by neutralization titration as follows.
4.0 g of polyamide was dissolved in 50 mL of benzyl alcohol, and the resulting solution was titrated with 0.1N NaOH to obtain the carboxyl end amount (μ equivalent / g). The end point was determined from the discoloration of the phenolphthalein indicator.

Based on the amino terminal amount ([NH ₂ ]) and carboxyl terminal amount ([COOH]) measured by (6) and (7), the total amount of active terminals ([NH ₂ ] + [COOH]) and the amount of amino terminal The ratio ([NH ₂ ] / ([NH ₂ ] + [COOH])) to the total amount of active terminals was calculated.

[Measurement method of physical properties of polyamide composition molded article]
(8) Initial reflectance (%)
The pellets of the polyamide composition produced in Examples and Comparative Examples to be described later are molded using an injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], so that length 60 mm × width 60 mm × thickness 1. A 0 mm molded piece was produced.
During molding, the total time of injection and pressure holding time was 5 seconds, the cooling time was 15 seconds, the mold temperature was set to Tg + 10 ° C., and the temperature of the molten polyamide composition was set to (A) the melting peak temperature Tm2 + 10 ° C. of polyamide.
The reflectance of the obtained molded piece with respect to light having a wavelength of 450 nm was measured with a Hitachi spectrophotometer (U-3310).

(9) Reflectance retention after reflow process (%)
The pellets of the polyamide composition produced in Examples and Comparative Examples to be described later are molded using an injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], so that length 60 mm × width 60 mm × thickness 1. A 0 mm molded piece was produced.
During molding, the total time of injection and holding time was 5 seconds, cooling time was 15 seconds, the mold temperature was set to Tg + 10 ° C., and the molten resin temperature was set to (A) the melting peak temperature Tm2 + 10 ° C. of polyamide. The obtained molded piece was heat-treated (reflow process) three times in a hot air reflow furnace (280 ° C. × 10 seconds).
The reflectance with respect to 450 nm light of the molded piece before and after the heat treatment (reflow process) was measured with a Hitachi spectrophotometer (U-3310), and the reflectance retention after the reflow process was calculated.

(10) Aging retention rate (%)
The molded piece after the reflow process obtained as described above was heat-treated in a hot air dryer at 150 ° C. for 300 hours.
The reflectance of the molded piece after heat treatment with respect to 450 nm light was measured with a Hitachi spectrophotometer (U-3310), and the aging retention was calculated in comparison with the reflectance before heat treatment.

(11) Releasability By molding the polyamide composition pellets produced in the examples and comparative examples described later using an injection molding machine (PS-40E: manufactured by Nissei Resin Co., Ltd.), the length is 60 mm × width. A molded product of 60 mm × 1.0 mm thickness was produced.
During molding, the total time of injection and holding time was 2 seconds, the mold temperature was set to Tg + 10 ° C., and the molten resin temperature was set to (A1) polyamide melting peak temperature Tm2 + 10 ° C.
The cooling time was adjusted, and the shortest cooling time for releasing the molded product from the mold without any problem was evaluated as the releasability. It was determined that shortening the cooling time would lead to improved productivity.

[(A) Production of polyamide]
(Production Example 1)
CHDA 896 g (5.20 mol) and 2MC5DA 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% water mixture of the raw material monomers.
The obtained water mixture, 21 g (0.18 mol) of 2MC5DA, 3.7 g (0.06 mol) of acetic acid and 1.3 g of sodium hypophosphite monohydrate, which are additives at the time of melt polymerization. An autoclave (manufactured by Nitto Koatsu) with an internal volume of 5.4 L was charged. The ratio of each material and the polymerization conditions are shown in Table 2A.

Next, it heated until the liquid temperature (internal temperature) in an autoclave became 50 degreeC. Thereafter, the inside of the autoclave was purged with nitrogen. The pressure inside the tank of the autoclave (hereinafter also simply referred to as “inside the tank”) is about 2.5 kg / cm ² as gauge pressure (hereinafter, all the pressure inside the tank is expressed as gauge pressure (G)). Heating was continued until At this time, the liquid temperature was about 145 ° C.
While maintaining the pressure in the tank at about 2.5 kg / cm ² (G), heating was continued while removing water out of the system, and the aqueous solution in the tank was concentrated to a concentration of about 85% by mass.

The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² (G).

In order to keep the pressure in the tank at about 30 kg / cm ² (G), heating was continued until the temperature reached about 50 ° C. (about 295 ° C.) lower than the final temperature (about 345 ° C.) while removing water from the system. While further heating, the pressure in the tank was reduced to atmospheric pressure (gauge pressure was 0 kg / cm ² ) over 60 minutes. The heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 340 ° C.

While maintaining the resin temperature in the tank, the inside of the tank was maintained under a reduced pressure of 100 torr (1.33 × 10 ⁴ Pa) for 10 minutes with a vacuum apparatus. Then, the inside of the tank was pressurized with nitrogen, and the product was discharged in a strand form from the lower nozzle (nozzle). Further, the strand-like product was cooled with water and cut to obtain a pellet-like precursor polyamide (precursor polyamide pellet). The total active terminal amount ([NH ₂ ] + [COOH]) of this precursor polyamide was 98 μeq / g, and the ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]). [NH ₂ ] / ([NH ₂ ] + [COOH]) was 0.37.

10 kg of the precursor polyamide pellets obtained by using melt polymerization was put into a conical ribbon vacuum dryer (trade name “ribocorn RM-10V” manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen.
The precursor polyamide pellets were heated at 240 ° C. for 10 hours with stirring while flowing nitrogen at 1 L / min in the vacuum dryer. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. while nitrogen was circulated to produce a pellet-like polyamide. The polyamide pellets were taken out from the vacuum dryer to obtain polyamide (hereinafter also referred to as “PA-1”).

  The obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.

(Production Example 2)
CHDA 896 g (5.20 mol) and 2MC5DA 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% water mixture of the raw material monomers.
The obtained water mixture, 18 g (0.16 mol) of 2MC5DA, 1.6 g (0.03 mol) of acetic acid and 1.3 g of sodium hypophosphite monohydrate, which are additives at the time of melt polymerization. An autoclave (manufactured by Nitto Koatsu) with an internal volume of 5.4 L was charged. The polymerization conditions were in accordance with Production Example 1. The total active terminal amount ([NH ₂ ] + [COOH]) of the obtained precursor polyamide was 91 μ equivalent / g, and the total active terminal amount of amino terminal amount [NH ₂ ] ([NH ₂ ] + [COOH]). [NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio to, was 0.49.

10 kg of precursor polyamide pellets obtained by using melt polymerization was placed in a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen.
The precursor polyamide pellets were heated at 250 ° C. for 10 hours with stirring while flowing nitrogen at 1 L / min in the vacuum dryer. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. with nitrogen flowing, and the polyamide pellets were removed from the vacuum dryer in the form of pellets to obtain polyamide (hereinafter also referred to as “PA-2”). .

  The obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.

(Production Example 3)
CHDA 896 g (5.20 mol) and 2MC5DA 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% water mixture of the raw material monomers.
The resulting water mixture, 15 g (0.13 mol) of 2MC5DA, 1.6 g (0.03 mol) of acetic acid and 1.3 g of sodium hypophosphite monohydrate, which are additives at the time of melt polymerization. An autoclave (manufactured by Nitto Koatsu) with an internal volume of 5.4 L was charged. The polymerization conditions were in accordance with Production Example 1. The total active terminal amount ([NH ₂ ] + [COOH]) of this precursor polyamide is 85 μeq / g, the ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]). [NH ₂ ] / ([NH ₂ ] + [COOH]) was 0.39.

10 kg of the precursor polyamide pellets obtained by using melt polymerization was put into a conical ribbon vacuum dryer (trade name “ribocorn RM-10V” manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen.
The precursor polyamide pellets were heated at 240 ° C. for 10 hours with stirring while flowing nitrogen at 1 L / min in the vacuum dryer. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. while circulating nitrogen, and the polyamide pellets were removed from the vacuum dryer in the form of pellets to obtain polyamide (hereinafter also referred to as “PA-3”). .

  The obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.

(Production Example 4)
CHDA 896 g (5.20 mol) and 2MC5DA 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% water mixture of the raw material monomers.
The resulting water mixture, 24 g (0.21 mol) of 2MC5DA, 3.7 g (0.06 mol) of acetic acid, and 1.3 g of sodium hypophosphite monohydrate, which are additives at the time of melt polymerization. An autoclave (manufactured by Nitto Koatsu) with an internal volume of 5.4 L was charged. The polymerization conditions were in accordance with Production Example 1. The total active terminal amount ([NH ₂ ] + [COOH]) of this precursor polyamide was 102 μeq / g, the ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]). [NH ₂ ] / ([NH ₂ ] + [COOH]) was 0.55.

10 kg of precursor polyamide pellets obtained by using melt polymerization was placed in a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen.
The precursor polyamide pellets were heated at 120 ° C. for 24 hours with stirring while flowing nitrogen at 1 L / min in the vacuum dryer. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. with nitrogen flowing, and the polyamide pellets were removed from the vacuum dryer in the form of pellets to obtain polyamide (hereinafter also referred to as “PA-4”). .

  The obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.

(Production Example 5)
The procedure was the same as in Production Example 4 except for the drying conditions.
10 kg of the precursor polyamide pellets obtained by using melt polymerization was put into a conical ribbon vacuum dryer (trade name “ribocorn RM-10V” manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen.
The precursor polyamide pellets were heated at 210 ° C. for 24 hours with stirring while flowing nitrogen at 1 L / min in the vacuum dryer. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. with nitrogen flowing, and the polyamide pellets were removed from the vacuum dryer in the form of pellets to obtain polyamide (hereinafter also referred to as “PA-5”). .

  The obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.

(Production Example 6)
CHDA 896 g (5.20 mol) and 2MC5DA 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% water mixture of the raw material monomers.
An autoclave (with an inner volume of 5.4 L) containing 1.6 g (0.03 mol) of acetic acid and 1.3 g of sodium hypophosphite monohydrate, which are additives during melt polymerization, was obtained. Nitto High Pressure). The polymerization conditions and drying conditions were in accordance with Production Example 1.

  The obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.

(Production Example 7)
The polymerization method was in accordance with the production method described in (Japanese Patent Publication No. 64-2131).
1007 g (5.85 mol) of CHDA, 832 g (4.46 mol) of C11DA, and 161 g (1.39 mol) of C6DA were dissolved in 500 g of distilled water to prepare an equimolar aqueous solution of about 80% by mass of raw material monomers.
The obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen. The liquid temperature was continuously heated from about 50 ° C. to 210 ° C., and heating was continued while removing water out of the system in order to keep the pressure in the autoclave tank at 17.5 kg / cm ² as a gauge pressure. Thereafter, the internal temperature was raised to 320 ° C., and the pressure was reduced while taking about 120 minutes until the pressure in the tank reached atmospheric pressure (gauge pressure was 0 kg / cm ² ). Thereafter, nitrogen gas was allowed to flow through the tank for 30 minutes, and the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 323 ° C. to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut and discharged in a pellet form to obtain copolymer polyamide pellets. Each physical property of the obtained polyamide was measured based on the above method.

(Production Example 8)
The polymerization method was in accordance with the production method described in (International Publication No. 2008-149862 pamphlet).
CHDA 726 g (4.22 mol), C12DA 675 g (3.37 mol), and C6DA 99 g (0.85 mol) were dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer.
The obtained aqueous solution was charged into an internal volume 5.4 L autoclave (manufactured by Nitto Koatsu), kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen.
The solution in the autoclave was stirred and the internal temperature was raised to 160 ° C. over 50 minutes. Thereafter, the internal temperature was maintained at 160 ° C. for 30 minutes, and while continuing to heat while removing the steam from the system, the solution was concentrated until the concentration of the aqueous solution reached 70% by mass. The removal of water was stopped and heating was continued until the internal pressure of the tank reached about 35 kg / cm ² (the liquid temperature in this system was about 250 ° C.). In order to keep the pressure in the tank at about 35 kg / cm ² , the prepolymer was obtained by reacting for 1 hour until the final temperature reached 300 ° C. while removing water out of the system.

  The prepolymer was pulverized to a size of 3 mm or less, and then dried at 100 ° C. for 24 hours in an atmosphere in which nitrogen gas was flowed at a flow rate of 20 L / min. Thereafter, a prepolymer was subjected to solid phase polymerization at 280 ° C. for 10 hours in an atmosphere in which nitrogen gas was flowed at a flow rate of 200 mL / min, to obtain a polyamide. The composition and polymerization conditions of this polyamide are shown in Table 2A.

(Production Example 9)
The polymerization method was in accordance with the production method described in (JP-A-9-12868).
CHDA 770 g (4.47 mol), C9DA (nonamethylenediamine) 609 g (3.85 mol), 2MC8DA (2-methyl-1,8-octanediamine) 107 g (0.68 mol), benzoic acid 13.8 g (0 .11 mol), 1.5 g of sodium hypophosphite monohydrate and 1500 g of distilled water were charged into an internal volume 5.4 L autoclave (manufactured by Nitto Koatsu) and purged with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 210 ° C. over 2 hours. At this time, the autoclave was heated up to 22 kg / cm ² . The reaction was continued as it was for 1 hour, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 22 kg / cm ² . Next, the pressure was reduced to 10 kg / cm ² over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. The prepolymer was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was solid-phase polymerized at 230 ° C. and 0.1 mmHg for 10 hours to obtain polyamide.

[Production of polyamide composition]
(Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-6)
Using the polyamides (PA-1) to (PA-9) obtained in Production Examples 1 to 9 and the above raw materials in the types and proportions described in Table 2B below, the polyamide composition is as follows. Manufactured.

  The polyamides (PA-1 to PA-9) obtained in Production Examples 1 to 9 were dried in a nitrogen stream and the moisture content was adjusted to about 0.2% by mass. Used as.

As an apparatus for producing the polyamide composition, a twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] was used.
The twin screw extruder has an upstream supply port in the first barrel from the upstream side of the extruder, a downstream first supply port in the sixth barrel, and a downstream second supply port in the ninth barrel. Had. In the twin-screw extruder, L / D (extruder cylinder length / extruder cylinder diameter) was 48, and the number of barrels was 12.
In the twin screw extruder, the temperature from the upstream supply port to the die is set to the melting peak temperature Tm2 + 10 ° C. of each (A) polyamide produced in the above production example, the screw rotation speed is set to 250 rpm, and the discharge amount is set to 25 kg / h. did.

(A) polyamide, (D) nucleating agent, (E) metal hydroxide, (F) phosphorus compound, and (G) phenolic antioxidant so as to have the types and ratios described in Table 2B. Was dry blended and then fed from the upstream feed port of the twin screw extruder.
Next, (B) titanium oxide was supplied from the downstream first supply port of the twin-screw extruder at the types and ratios shown in Table 2B below.
Furthermore, the inorganic filler (C) was supplied from the downstream second supply port of the twin-screw extruder in the types and proportions described in Table 2B below.
The raw materials supplied as described above were melt-kneaded with a twin-screw extruder to produce polyamide composition pellets.
The obtained polyamide composition pellets were dried in a nitrogen stream, and the water content in the polyamide composition was reduced to 500 ppm or less.
Various evaluations were performed as described above using the polyamide composition after adjusting the water content.
The evaluation results are shown in Table 2B below.

As shown in Table 2B, the polyamide compositions of Examples 2-1 to 2-3 have high initial reflectivity, reflectivity retention after the reflow process, reflectivity retention after heat treatment, and excellent releasability. I understood that.
On the other hand, the comparative example in which the trans isomer ratio is out of the scope of the present invention was inferior to the examples, particularly in the reflectance retention and the aging retention after the reflow process. Further, Comparative Examples 2-1 and 2-2 in which the ratio of the trans isomer was low and the ratio of the amino terminal amount to the total active terminal amount was 0.5 or more were inferior to the examples in terms of releasability.
From the above results, it was shown that the polyamide composition of the present invention is excellent in reflectance retention, aging retention and releasability, and therefore can be suitably used for LED reflectors.

Next, examples of the third embodiment will be described. The present example relates to a polyamide composition molded article obtained by molding the second polyamide composition using the second polyamide.
[Example 3]
Measuring methods for raw materials and physical properties used in Examples and Comparative Examples are shown below.

[Raw material of polyamide]
<(A) Raw material of dicarboxylic acid unit>
(1) 1,4-cyclohexanedicarboxylic acid (CHDA) manufactured by Eastman Chemical Co., Ltd. Product name: 1,4-CHDA HP grade (trans isomer / cis isomer (molar ratio) = 25/75)
<(B) Raw material of diamine unit>
(1) 2-methylpentamethylenediamine (2MC5DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(2) Nonamethylenediamine (C9DA) (Aldrich)
(3) 2-methyloctamethylenediamine (2MC8DA) (manufactured with reference to the production method described in JP-A No. 05-17413)
(4) Hexamethylenediamine (C6DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(5) Decamethylenediamine (C10DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(6) Undecamethylenediamine (C11DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(7) Dodecamethylenediamine (C12DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Inorganic filler]
Glass fiber (GF) manufactured by Nippon Electric Glass Co., Ltd. Product name: ECS03T275H Average fiber diameter (average particle diameter) 10 μm (circular shape), cut length 3 mm

[Calculation of polyamide unit amount]
The mole% of 1,4-cyclohexanedicarboxylic acid is calculated by (Mole number of 1,4-cyclohexanedicarboxylic acid added as raw material monomer / Mole number of all dicarboxylic acid units added as raw material monomer) × 100. It was.
The mol% of the aliphatic diamine was determined by calculation as (number of moles of aliphatic diamine added as a raw material monomer / number of moles of all diamine units added as a raw material monomer) × 100.
In addition, when calculating by the above formula, the denominator and numerator do not include the number of moles of aliphatic diamine added as an additive during melt polymerization.

[Method of measuring physical properties of polyamide]
(1) Polyamide melting peak temperature Tm1 · Tm2 (° C.), heat of fusion ΔHm1 · ΔHm2 (J / g), crystallization enthalpy ΔHc (J / g)
According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER. The measurement conditions were as follows: when about 10 mg of the polyamide obtained in Examples and Comparative Examples was heated to 300 to 350 ° C. according to the melting point (Tm) of the sample at a heating rate of 20 ° C./min in the nitrogen atmosphere (first time) The melting peak temperature appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time of temperature rise was Tm1 (° C.), and the peak area of Tm1 was the heat of fusion ΔHm1 (J / g). Further, the melting peak temperature Tm2 and the heat of fusion ΔHm2 of the starting polyamide can be measured as follows. After the first temperature increase, the temperature is maintained for 2 minutes in the molten state at the maximum temperature increase, then the temperature is decreased to 30 ° C. at a temperature decrease rate of 20 ° C./min, maintained at 30 ° C. for 2 minutes, and then the temperature increase rate is 20 The endothermic peak temperature that appears at the highest temperature side of the endothermic peak that appears when the temperature is similarly raised at the same temperature (° C./min) is the melting peak temperature Tm2 of the polyamide itself, and the peak area at Tm2 is the polyamide area. The heat of fusion ΔHm2

In addition, when there were a plurality of endothermic peaks appearing at the first temperature increase, those having ΔH of 1 J / g or more were regarded as peaks. For example, when there are two endothermic peaks that appear at the first temperature increase, melting point 295 ° C., ΔH = 20 J / g, melting point 325 ° C., ΔH = 5 J / g, the melting peak temperature Tm1 is higher. The value of 325 ° C. and ΔHm1 were 25 J / g of the total value of all peaks.
The temperature of the exothermic peak (crystallization peak) that appears when the temperature is lowered at a rate of temperature decrease of 20 ° C./min is defined as the crystallization peak temperature Tc (° C.), and the total peak area of Tc is the crystallization enthalpy ΔHc (J / g). did.

(2) Glass transition temperature Tg (° C) of polyamide
The glass transition temperature Tg (° C.) was measured using Diamond-DSC manufactured by PERKIN-ELMER according to JIS-K7121. The measurement conditions were as follows: a sample obtained by melting the polyamide obtained in Examples and Comparative Examples on a hot stage (EP80 manufactured by Mettler) was rapidly cooled and solidified using liquid nitrogen, and the measurement sample and did. Using 10 mg of the sample, the glass transition temperature was measured by raising the temperature in the range of 30 to 350 ° C. under a temperature raising speed of 20 ° C./min.

(3) Trans isomer ratio 30-40 mg of polyamides obtained in Examples and Comparative Examples were dissolved in 1.2 g of hexafluoroisopropanol deuterated and measured by ¹ H-NMR (ECA500 manufactured by JEOL). The trans isomer ratio of the 1,4-cyclohexanedicarboxylic acid monomer unit of the polyamide is 2.00 ppm peak area derived from the trans isomer, and 1.77 ppm and 1.87 ppm peak area ratio derived from the cis isomer. I asked for it.

(4) Polyamide sulfuric acid relative viscosity ηr
The relative viscosity ηr of sulfuric acid at 25 ° C. of the polyamides obtained in the examples and comparative examples was measured according to JIS-K6920. Specifically, a 1% concentration solution ((polyamide 1 g) / (98% sulfuric acid 100 mL)) was prepared using 98% sulfuric acid, and a temperature of 25 ° C. was obtained using the obtained solution. The sulfuric acid relative viscosity ηr was measured under the conditions.

(5) Molecular weight Number average molecular weight Mn, weight average molecular weight Mw, molecular weight distribution Mw / Mn are GPC (gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA (polymethyl methacrylate) standard sample. A calibration curve was prepared using the number average molecular weight Mn measured by Polymer Laboratories Co., Ltd., and the molecular weight of the polyamide obtained in this example and comparative example was determined.The GPC column was TSK-GEL GMHHR. -M and G1000HHR were used.

(6) Amino terminal amount ([NH ₂ ])
In the polyamides obtained in the examples and comparative examples, the amount of amino terminal bound to the polymer terminal was measured by neutralization titration as follows.
3.0 g of polyamide was dissolved in 100 mL of a 90 mass% phenol aqueous solution, and the obtained solution was titrated with 0.025N hydrochloric acid to determine the amino terminal amount (μ equivalent / g). The end point was determined from the indicated value of the pH meter.

(7) Carboxyl end amount ([COOH])
In the polyamides obtained in the examples and comparative examples, the amount of carboxyl terminal bound to the polymer terminal was measured by neutralization titration as follows.
4.0 g of polyamide was dissolved in 50 mL of benzyl alcohol, and the resulting solution was titrated with 0.1N NaOH to obtain the carboxyl end amount (μ equivalent / g). The end point was determined from the discoloration of the phenolphthalein indicator.

Based on the amino terminal amount ([NH ₂ ]) and carboxyl terminal amount ([COOH]) measured by (6) and (7), the active terminal total amount ([NH ₂ ] + [COOH]) and amino terminal amount activity The ratio ([NH ₂ ] / ([NH ₂ ] + [COOH])) relative to the total amount of terminals was calculated.

[Measurement method of physical properties of polyamide composition molded article]
(8) Tensile strength (MPa), tensile modulus (GPa), breaking strain (%)
Using the polyamide composition molded articles (multipurpose test pieces) obtained in Examples and Comparative Examples, a tensile test was performed in accordance with ISO 527 under a 120 ° C. environment and a tensile speed of 5 mm / min, and the tensile strength and tensile elasticity. The rate and breaking strain were measured.

(9) Water absorption rate (%)
The molded product of the polyamide composition obtained in Examples and Comparative Examples was immersed in distilled water at 80 ° C. for 24 hours, and the weight change rate before and after immersion was taken as the water absorption rate.

(10) Tensile strength retention (%) after immersion (indicated as LLC resistance (retention) in Tables 3A and 3B)
Tensile strength retention (%) after immersion of the polyamide composition molded articles obtained in Examples and Comparative Examples was measured as follows. The multipurpose test piece (3 mm thickness) of (8) above is immersed in an ethylene glycol 50% aqueous solution at 120 ° C. for 24 hours and 720 hours and left at room temperature, and then the tensile test of the method of (8) is performed. Tensile strength was measured. The ratio of the tensile strength measured after immersion for 720 hours to the tensile strength measured after immersion for 24 hours was determined as the tensile strength retention after immersion.

[Example 3-1]
(Production of polyamide)
The polymerization reaction of polyamide was carried out as follows by a hot melt polymerization method.
CHDA 802 g (4.66 mol) as a dicarboxylic acid unit, 2MC5DA 217 g (1.86 mol) and C10DA 482 g (2.79 mol) as a diamine unit are dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of the starting monomer is equimolar. Was made.

The obtained aqueous solution was charged into an autoclave having an internal volume of 5.4 L (manufactured by Nitto Koatsu), and 5.4 g of 2MC5DA was further added to the autoclave as an additional diamine. The temperature was maintained until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was purged with nitrogen. The pressure in the autoclave tank (hereinafter, also simply referred to as “inside the tank”) is about 2.5 kg / cm ² (G) as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure). The liquid temperature was continuously heated from about 50 ° C. until the temperature reached (the liquid temperature in this system was about 145 ° C.). In order to keep the pressure in the tank at about 2.5 kg / cm ² (G), heating was continued while removing water out of the system, and the solution was concentrated until the concentration of the aqueous solution reached about 75% by mass (the liquid in this system). The temperature was about 160 ° C.).

The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² (G) (the liquid temperature in this system was about 245 ° C.). In order to keep the pressure in the tank at about 30 kg / cm ² (G), heating was continued until the final temperature (330 ° C. described later) −40 ° C. (here, 290 ° C.) while removing water out of the system. . After the liquid temperature rises to the final temperature (330 ° C. described later) −40 ° C. (290 ° C. here), the heating continues and the pressure in the tank reaches 30 at atmospheric pressure (gauge pressure is 0 kg / cm ² ). The pressure dropped while taking about a minute.

Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 330 ° C. While the resin temperature was kept at about 330 ° C., the inside of the tank was maintained under a reduced pressure of about 50 kPa for 20 minutes with a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut and discharged in a pellet form to obtain a precursor polyamide pellet (precursor polyamide pellet). . The total active terminal amount ([NH ₂ ] + [COOH]) of this precursor polyamide was 115 μeq / g, the ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]). [NH ₂ ] / ([NH ₂ ] + [COOH]) was 0.39.

10 kg of the precursor polyamide pellets obtained by using melt polymerization was put into a conical ribbon vacuum dryer (trade name “ribocorn RM-10V” manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen.
The precursor polyamide pellets were heated at 240 ° C. for 10 hours with stirring while flowing nitrogen at a rate of 10 L / min in the vacuum dryer. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. while circulating nitrogen, and the polyamide pellets were taken out of the vacuum dryer in the form of pellets.

(Production of polyamide composition)
A polyamide composition was produced using the polyamide pellets and glass fibers obtained above.
Specifically, a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd., L / D = 47.6 (D = 37 mmφ), set temperature Tm2 + 10 ° C. (310 + 20 = 330 when the polyamide obtained above is used) C.) and a screw rotational speed of 250 rpm), a polyamide composition was produced as follows. The polyamide (65 parts by mass) with the moisture content adjusted is supplied from a top feed port provided at the most upstream part of the twin screw extruder, and the downstream side of the twin screw extruder (resin supplied from the top feed port is Glass fiber (35 parts by mass) is supplied as an inorganic filler from the side feed port in a sufficiently melted state) at a mass ratio of (polyamide: glass fiber = 65: 35), and the melt-kneaded product extruded from the die head is supplied. It was cooled in a strand form and pelletized to obtain polyamide composition pellets.

(Production of polyamide composition molded product)
The obtained polyamide composition was molded into a multi-purpose test piece (A type) by injection molding in accordance with ISO 3167 to obtain a molded polyamide composition product. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods. The measurement results are shown in Table 3A and Table 3B.

[Example 3-2]
A polyamide composition molded article was obtained in the same manner as in Example 3-1, except that the amount of 2MC5DA additional diamine was 4.3 g. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods. In addition, the active terminal total amount ([NH ₂ ] + [COOH]) of this precursor polyamide is 118 μ equivalent / g, the active terminal total amount of amino terminal amount [NH ₂ ] ([NH ₂ ] + [COOH]). The ratio to [NH ₂ ] / ([NH ₂ ] + [COOH]) was 0.29.

[Example 3-3]
A polyamide composition molded article was obtained in the same manner as in Example 3-1, except that the amount of 2MC5DA additional diamine was changed to 0 g. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods. In addition, the active terminal total amount ([NH ₂ ] + [COOH]) of this precursor polyamide is 135 μ equivalent / g, and the amino terminal amount [NH ₂ ] active terminal total amount ([NH ₂ ] + [COOH]). [NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio to, was 0.17.

[Example 3-4]
A polyamide composition molded article was obtained in the same manner as in Example 3-3, except that the precursor polyamide pellets obtained by melt polymerization were dried at 250 ° C. for 10 hours with a vacuum dryer. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Example 3-5]
CHDA 795 g (4.62 mol) as dicarboxylic acid units, 2MC5DA 188 g (1.62 mol) and C10DA 517 g (3.00 mol) as diamine units were dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of raw material monomers was obtained. A polyamide composition molded article was obtained in the same manner as in Example 3-3 except that was manufactured. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods. The total active terminal amount of the precursor polyamide ([NH2] + [COOH]) is 132 μeq / g, based on the total active terminal amount of the amino terminal amount [NH ₂ ] ([NH ₂ ] + [COOH]). The ratio [NH ₂ ] / ([NH ₂ ] + [COOH]) was 0.21.

[Example 3-6]
10 kg of the precursor polyamide pellet obtained by using melt polymerization was put in a vacuum dryer and sufficiently purged with nitrogen. After flowing nitrogen at 10 L / min, the precursor polyamide pellet was stirred at 235 ° C. for 10 hours while stirring. And heated. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. with nitrogen flowing, and the polyamide pellets were removed from the vacuum dryer in the form of pellets to obtain polyamide. Except these, it carried out similarly to Example 3-5, and obtained the polyamide composition molded article. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Comparative Example 3-1]
A polyamide composition molded article was prepared in the same manner as in Example 3-1, except that the amount of 2MC5DA additional diamine was 13 g, and the precursor polyamide pellets obtained by subsequent melt polymerization were dried at 150 ° C. for 10 hours in a vacuum dryer. Obtained. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods. The measurement results are shown in Table 3B. In addition, the active terminal total amount ([NH ₂ ] + [COOH]) of this precursor polyamide is 123 μ equivalent / g, the active terminal total amount of amino terminal amount [NH ₂ ] ([NH ₂ ] + [COOH]). [NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio to, was 0.55.

[Comparative Example 3-2]
A polyamide composition molded article was obtained in the same manner as in Comparative Example 3-1, except that the precursor polyamide pellets obtained by melt polymerization were dried at 200 ° C. for 10 hours with a vacuum dryer. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Comparative Example 3-3]
The polymerization method was in accordance with the production method described in Patent Document 7 (Japanese Patent Publication No. 64-2131).
1007 g (5.85 mol) of CHDA, 832 g (4.46 mol) of C11DA, and 161 g (1.39 mol) of C6DA were dissolved in 500 g of distilled water to prepare an equimolar aqueous solution of about 80% by mass of raw material monomers.
The obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen. The liquid temperature is continuously heated from about 50 ° C. to 210 ° C., and the pressure in the autoclave tank is referred to as gauge pressure (hereinafter, all the pressure in the tank is expressed as gauge pressure (G)), 17.5 kg / Heating was continued while removing water out of the system to maintain cm ² (G). Thereafter, the internal temperature was raised to 320 ° C., and the pressure was reduced while taking about 120 minutes until the pressure in the tank reached atmospheric pressure (gauge pressure was 0 kg / cm ² ). Thereafter, nitrogen gas was allowed to flow through the tank for 30 minutes, and the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 323 ° C. to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut and discharged in a pellet form to obtain copolymer polyamide pellets.
A polyamide composition and a polyamide composition molded article were produced based on Example 3-1. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Comparative Example 3-4]
The polymerization method was in accordance with the production method described in (International Publication No. 2008-149862 pamphlet).
CHDA 726 g (4.22 mol), C12DA 675 g (3.37 mol), and C6DA 99 g (0.85 mol) were dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer.
The obtained aqueous solution was charged into an internal volume 5.4 L autoclave (manufactured by Nitto Koatsu), kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen.

The solution in the autoclave was stirred and the internal temperature was raised to 160 ° C. over 50 minutes. Thereafter, the internal temperature was maintained at 160 ° C. for 30 minutes, and while continuing to heat while removing the steam from the system, the solution was concentrated until the concentration of the aqueous solution reached 70% by mass. The removal of water was stopped and heating was continued until the internal pressure of the tank reached about 35 kg / cm ² (the liquid temperature in this system was about 250 ° C.). In order to keep the pressure in the tank at about 35 kg / cm ² , the prepolymer was obtained by reacting for 1 hour until the final temperature reached 300 ° C. while removing water out of the system.

The prepolymer was pulverized to a size of 3 mm or less, and then dried at 100 ° C. for 24 hours in an atmosphere in which nitrogen gas was flowed at a flow rate of 20 L / min. Thereafter, a prepolymer was subjected to solid phase polymerization at 280 ° C. for 10 hours in an atmosphere in which nitrogen gas was flowed at a flow rate of 200 mL / min, to obtain a polyamide.
Manufacture of the polyamide composition and manufacture of the molded article of the polyamide composition were based on Example 3-1, and a polyamide composition and its molded article were obtained. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods.

[Comparative Example 3-5]
The polymerization method was in accordance with the production method described in (JP-A-9-12868).
CHDA 770 g (4.47 mol), C9DA (nonamethylenediamine) 609 g (3.85 mol), 2MC8DA (2-methyl-1,8-octanediamine) 107 g (0.68 mol), benzoic acid 13.8 g (0 .11 mol), 1.5 g of sodium hypophosphite monohydrate and 1500 g of distilled water were charged into an internal volume 5.4 L autoclave (manufactured by Nitto Koatsu) and purged with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 210 ° C. over 2 hours. At this time, the autoclave was heated up to 22 kg / cm ² . The reaction was continued as it was for 1 hour, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 22 kg / cm ² . Next, the pressure was reduced to 10 kg / cm ² over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. The prepolymer was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was solid-phase polymerized at 230 ° C. and 0.1 mmHg for 10 hours to obtain polyamide.

  A polyamide composition and a polyamide composition molded article were produced based on Example 3-1. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods. The evaluation results are shown in Table 3A and Table 3B below.

  As is clear from the results shown in Table 3A, the polyamide of the present invention increases the ratio of heat of fusion ΔHm1 / crystallization enthalpy ΔHc, which is an index of crystal growth, so that the polyamide compositions of Examples 3-1 to 3-6 The molded article had excellent properties in hot strength and hot stiffness. In general, when the polymer absorbs water, degradation occurs due to hydrolysis and chemical penetration, and so-called LLC resistance is lowered. However, the molded article containing the polyamide of the present invention is resistant to LLC as shown in the tensile strength retention after immersion. Improved. The penetration rate (degradation rate) of LLC differs between the amorphous part and the crystalline part of the molded product, and the amorphous part deteriorates faster than the crystalline part. However, in the polyamide of the present invention, the amorphous part after molding of the composition As a result of the decrease and increase in the crystal part (ΔHm), it is considered that the LLC resistance was improved.

  On the other hand, as shown in Table 3B, in Comparative Examples 3-1 and 3-2, since the trans isomer ratio of the polyamide is as low as 70 mol%, as a result, hot strength, hot stiffness, LLC resistance The sex was insufficient. Moreover, although the trans isomer ratio of the polyamides of Comparative Examples 3-3, 3-4, and 3-5 was 82 to 85 mol%, the crystal growth index ΔHm1 / ΔHc was 1.1 to 1.3. Since it was lower than the examples, it was insufficient in terms of hot strength, hot stiffness, and LLC resistance.

  The polyamide composition molded article of the present invention has industrial applicability as various parts such as LED reflectors, automobiles, electric and electronic, industrial materials, and daily and household products.

Claims (43)

A dicarboxylic acid unit comprising at least 1,4-cyclohexanedicarboxylic acid;
A diamine unit comprising at least an aliphatic diamine;
A polyamide composition molded article containing a polyamide comprising
A polyamide composition molded article in which the trans isomer ratio of the dicarboxylic acid monomer unit in the molded article is 71 to 100 mol%.   The polyamide composition molded article according to claim 1, wherein a content of the 1,4-cyclohexanedicarboxylic acid is at least 50 mol% in the dicarboxylic acid unit. In the differential scanning calorimetry according to JIS-K7121, the ratio between the heat of fusion ΔHm obtained when the temperature is raised at 20 ° C./min and the crystallization enthalpy ΔHc obtained when the temperature is lowered at 20 ° C./min is:
ΔHm / ΔHc> 1.0
The polyamide composition molded article according to claim 1 or 2.   The polyamide composition molded article according to claim 2 or 3, wherein a melting peak temperature in the differential scanning calorimetry is 300 ° C or higher.   The polyamide composition molded article according to claim 2, 3 or 4, wherein the heat of fusion ΔHm is 40 J / g or more.   The polyamide composition molded article according to any one of claims 1 to 5, wherein the trans isomer ratio mol% is greater than 71 and 75 or less.   The polyamide composition molded article according to any one of claims 1 to 6, wherein the trans isomer ratio mol% is greater than 75 and 100 or less.   The polyamide composition molded article according to any one of claims 1 to 7, wherein the aliphatic diamine unit is a saturated aliphatic diamine having 4 to 12 carbon atoms.   A polyamide composition containing a polyamide containing a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and a diamine unit containing at least an aliphatic diamine is molded, and the molded polyamide composition object is heat-treated at 200 ° C. or higher. To produce a polyamide composition molded article. (A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine;
A polyamide containing
In differential scanning calorimetry according to JIS-K7121, ΔHm1 / which is the ratio of the heat of fusion ΔHm1 obtained when the temperature is raised at 20 ° C./min and the crystallization enthalpy ΔHc obtained when the temperature is lowered at 20 ° C./min. ΔHc is
1.0 <ΔHm1 / ΔHc ≦ 2.2
And
The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is
71 <trans isomer ratio ≦ 75
Is a polyamide.   The polyamide according to claim 10, wherein a content of the 1,4-cyclohexanedicarboxylic acid is at least 50 mol% in the dicarboxylic acid unit.   The polyamide according to claim 11, wherein all of the dicarboxylic acid units are 1,4-cyclohexanedicarboxylic acid.   The polyamide according to any one of claims 10 to 12, wherein the aliphatic diamine has 6 to 12 carbon atoms.   14. The polyamide according to claim 13, wherein the aliphatic diamine is hexamethylene diamine, 2-methyl-pentamethylene diamine, 2-methyl-1,8-octane diamine, nonamethylene diamine, decamethylene diamine, or dodecamethylene diamine.   The polyamide according to claim 14, wherein the aliphatic diamine is 2-methyl-pentamethylenediamine. (A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine;
A polyamide containing
The aliphatic diamine comprises a branched aliphatic diamine;
The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is
71 <trans isomer ratio ≦ 100
Is a polyamide.   The polyamide according to claim 16, wherein the proportion of the branched aliphatic diamine in the (b) diamine unit is 10 to 100 mol%. The ΔHm1 / ΔHc is
1.0 <ΔHm1 / ΔHc ≦ 1.4
The polyamide according to any one of claims 10 to 17, which is When ΔHm1 / ΔHc is y and the trans isomer ratio is x,
y ≧ 0.04x−1.8
The polyamide according to any one of claims 10 to 18. [NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio of the amino terminal amount [NH ₂ ] to the total active terminal amount ([NH ₂ ] + [COOH]),
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5
The polyamide according to any one of claims 10 to 19, wherein Active terminal total amount ([NH ₂ ] + [COOH]) μeq / g is
20 <[NH ₂ ] + [COOH] <60
The polyamide according to any one of claims 10 to 20.   The polyamide according to any one of claims 10 to 21, wherein the sulfuric acid relative viscosity ηr is 1.8 <ηr. The weight average molecular weight Mw / number average molecular weight Mn as the molecular weight distribution is
The polyamide according to any one of claims 10 to 22, wherein Mw / Mn <3.5.   The polyamide according to any one of claims 10 to 23, wherein Tm1-Tc, which is a difference between a melting peak temperature Tm1 of the polyamide and a crystallization peak temperature Tc of the polyamide, is 40 ° C <Tm1-Tc <90 ° C.   A polyamide composition comprising the polyamide according to any one of claims 10 to 24 and at least one selected from an inorganic filler, a nucleating agent, a heat stabilizer and a light stabilizer.   The polyamide composition according to claim 25, further comprising titanium oxide.   28. A polyamide composition molded article obtained by molding the polyamide composition according to claim 25 or 26. (A) a dicarboxylic acid unit comprising at least 1,4-cyclohexane dicarboxylic acid, (b) containing a diamine unit comprising at least an aliphatic diamine, active end the total amount of amino-terminus weight [NH _2] ([NH ₂ ] + [COOH]), the ratio [NH ₂ ] / ([NH ₂ ] + [COOH])
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5, and the active terminal total amount ([NH ₂ ] + [COOH]) μeq / g is 60 ≦ [NH ₂ ] + [ COOH] <110 is a method for producing a polyamide in which a polyamide having a temperature of <110 is heat-treated at 200 ° C. or higher and lower than the melting point for 10 hours or longer. (A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine;
A polyamide containing
Sulfuric acid relative viscosity ηr is 2.5 or more,
In differential scanning calorimetry according to JIS-K7121, ΔHm1 / which is the ratio of the heat of fusion ΔHm1 obtained when the temperature is raised at 20 ° C./min and the crystallization enthalpy ΔHc obtained when the temperature is lowered at 20 ° C./min. ΔHc is
1.0 <ΔHm1 / ΔHc ≦ 2.2
And
The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is
75 <trans isomer ratio ≦ 100
Is a polyamide.   30. The polyamide according to claim 29, wherein a content of the 1,4-cyclohexanedicarboxylic acid is at least 50 mol% in the dicarboxylic acid unit.   The polyamide according to claim 30, wherein all of the dicarboxylic acid units are 1,4-cyclohexanedicarboxylic acid.   The polyamide according to any one of claims 29 to 31, wherein the aliphatic diamine has 6 to 12 carbon atoms.   The polyamide according to claim 32, wherein the aliphatic diamine is hexamethylenediamine, 2-methylpentamethylenediamine, 2-methyl-1,8-octanediamine, nonamethylenediamine, decamethylenediamine, or dodecamethylenediamine.   The polyamide according to claim 33, wherein the aliphatic diamine is 2-methylpentamethylenediamine or decamethylenediamine. (A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine;
A polyamide containing
The aliphatic diamine comprises a branched aliphatic diamine;
Sulfuric acid relative viscosity ηr is 2.5 or more,
The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is
71 <trans isomer ratio ≦ 100
Is a polyamide.   36. The polyamide according to claim 35, wherein the proportion of the branched aliphatic diamine in the (b) diamine unit is 10 to 100 mol%. The ΔHm1 / ΔHc is
1.4 <ΔHm1 / ΔHc ≦ 2.2
The polyamide according to any one of claims 29 to 36. When ΔHm1 / ΔHc is y and the trans isomer ratio is x,
y ≧ 0.04x−1.8
The polyamide according to any one of claims 29 to 37. [NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio of the amino terminal amount [NH ₂ ] to the total active terminal amount ([NH ₂ ] + [COOH]),
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5
The polyamide according to any one of claims 29 to 38. The weight average molecular weight Mw / number average molecular weight Mn indicating the molecular weight distribution is
Mw / Mn <3.5
40. The polyamide of any one of claims 29 to 39.   A polyamide composition comprising the polyamide according to any one of claims 29 to 40 and at least one selected from an inorganic filler, a heat stabilizer, and a light stabilizer.   42. A polyamide composition molded article obtained by molding the polyamide composition according to claim 41. (A) a dicarboxylic acid unit comprising at least 1,4-cyclohexane dicarboxylic acid, (b) containing a diamine unit comprising at least an aliphatic diamine, active end the total amount of amino-terminus weight [NH _2] ([NH ₂ ] + [COOH]), [NH ₂ ] / ([NH ₂ ] + [COOH]) is [NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5, A polyamide having a total active terminal amount ([NH ₂ ] + [COOH]) μ equivalent / g of 110 ≦ [NH ₂ ] + [COOH] ≦ 200 is heat-treated at a temperature of 200 ° C. or higher and lower than the melting point for 10 hours or longer. Production method.