JP5714834B2 - Polyamide composition and molded article comprising polyamide composition - Google Patents

Description

  The present invention relates to a polyamide composition and a molded body comprising the polyamide composition.

  Polyamides typified by polyamide 6 and polyamide 66 (hereinafter sometimes abbreviated as “PA6” and “PA66”, respectively) are excellent in molding processability, mechanical properties, or chemical resistance. It is widely used as various parts materials for automobiles, electric / electronics, industrial materials, industrial materials, daily use and household goods.

In recent years, in the automobile industry, as an environmental measure, there is a demand for weight reduction of a vehicle body by metal replacement in order to reduce exhaust gas.
In order to meet these requirements, polyamides are increasingly used for exterior materials and interior materials, and the required levels of various properties such as heat resistance, strength, and appearance for polyamide materials are further improved. Yes.
In particular, since the temperature in the engine room is also increasing, there is an increasing demand for higher heat resistance for polyamide materials.
Further, in the electrical and electronic industries such as home appliances, in order to cope with the lead-free surface mount (SMT) solder, it is required to increase the heat resistance of the polyamide material that can withstand the rise in the melting point of the solder.
However, polyamides such as PA6 and PA66 have a low melting point and cannot satisfy these requirements in terms of heat resistance.

In order to solve the above-mentioned problems of conventional polyamides such as PA6 and PA66, high melting point polyamides have been proposed.
Specifically, a polyamide composed of terephthalic acid and hexamethylenediamine (hereinafter sometimes abbreviated as “PA6T”) has been proposed.
However, since the PA6T 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 pyrolysis of the polyamide even if a molded product is obtained by melt molding. .

  In order to solve the above-mentioned problems of PA6T, PA6T may be abbreviated as aliphatic polyamide such as PA6 and PA66, or amorphous aromatic polyamide (hereinafter referred to as “PA6I”) composed of isophthalic acid and hexamethylenediamine. ) And the like, and a high melting point semi-aromatic polyamide mainly composed of terephthalic acid and hexamethylenediamine (hereinafter referred to as “6T copolymer polyamide”) whose melting point is lowered to about 220 to 340 ° C. Have been proposed).

As a 6T copolymer polyamide, Patent Document 1 discloses an aromatic polyamide (hereinafter referred to as “a mixture of hexamethylene diamine and 2-methylpentamethylene diamine”), which is composed of an aromatic dicarboxylic acid and an aliphatic diamine. May be abbreviated as “PA6T / 2MPDT”).
Proposals for high melting point aliphatic polyamides (hereinafter sometimes referred to as “PA46”) composed of adipic acid and tetramethylenediamine, and alicyclic polyamides composed of alicyclic dicarboxylic acid and aliphatic diamine, etc. It has also been made.

Further, in Patent Documents 2 and 3, a semi-alicyclic ring of an alicyclic polyamide (hereinafter sometimes abbreviated as “PA6C”) composed of 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine and another polyamide. Group polyamides (hereinafter may be abbreviated as “PA6C copolymerized polyamides”) are disclosed.
Patent Document 2 discloses that the heat and heat resistance of semi-alicyclic polyamide blended with 1 to 40% of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit is improved in solder heat resistance. Is disclosed to be excellent in fluidity, toughness and the like in an automobile part.

Furthermore, Patent Document 4 discloses that a polyamide comprising a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine is light resistance, toughness, moldability, and lightness. In addition, as a method for producing polyamide, 1,4-cyclohexanedicarboxylic acid and 1,9-nonanediamine are reacted at 230 ° C. or lower to form a prepolymer. It is disclosed to produce a polyamide having a melting point of 311 ° C. by solid-phase polymerization at 230 ° C.
Furthermore, Patent Document 5 discloses that a polyamide using 1,4-cyclohexanedicarboxylic acid having a trans / cis ratio of 50/50 to 97/3 as a raw material has heat resistance, low water absorption, light resistance, and the like. It is disclosed that it is excellent.

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 Pamphlet

However, although the 6T copolymer polyamide described above has the characteristics of low water absorption, high heat resistance, and high chemical resistance, the fluidity is low and the moldability and the molded product surface appearance are insufficient. Inferior toughness and light resistance. Therefore, improvement is desired in applications where the appearance of a molded product such as an exterior part is required or exposed to sunlight or the like. In addition, the specific gravity is large, and improvement in lightness is also desired.
Further, the PA6T / 2MPDT disclosed in Patent Document 1 can partially improve the problems of the conventional PA6T copolymerized polyamide, but it has fluidity, moldability, toughness, surface appearance of the molded product, and light resistance. In terms of sex, the level of improvement is insufficient.
Furthermore, although PA46 has good heat resistance and moldability, it has a problem that the water absorption is high and the dimensional change due to water absorption and the deterioration of mechanical properties are remarkably large. The dimensional change required for automobile applications, etc. There are cases where the demand cannot be met.
Furthermore, PA6C copolymer polyamides disclosed in Patent Documents 2 and 3 also have problems such as high water absorption and insufficient fluidity.
Furthermore, the polyamides disclosed in Patent Documents 4 and 5 are still insufficiently improved in terms of toughness, rigidity, and fluidity.

  Therefore, an object of the present invention is to provide a polyamide composition that has a good fluidity, has a practically sufficient moldability, and can obtain a molded article excellent in toughness, reflow resistance, and heat discoloration. .

As a result of intensive studies to solve the above problems, the present inventors have obtained a polyamide obtained by polymerizing a predetermined amount of a dicarboxylic acid containing a predetermined amount of an alicyclic dicarboxylic acid and a predetermined diamine, titanium oxide, and an inorganic filler. It has been found that a polyamide composition specified with regard to the content of titanium oxide and inorganic filler, and further to the mass ratio thereof, can solve the above problems, and has completed the present invention.
That is, the present invention is as follows.

[1]
(A): (a) a dicarboxylic acid containing at least 70 mol% of an alicyclic dicarboxylic acid;
(B) a diamine containing more than 50 mol% of a linear diamine having a main chain;
A polymerized polyamide,
(B): titanium oxide;
(C) an inorganic filler (excluding talc) ;
(D) at least one crystal nucleating agent selected talc, and boron nitride hydride et al,
Containing,
The content of the (B) titanium oxide is 10% by mass or more, and the mass ratio between the (B) titanium oxide and the (C) inorganic filler is (B) / (C) ≧ 0.5. The polyamide composition in which the content of the crystal nucleating agent (D) is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyamide (A).

[2]
The polyamide composition according to [1], wherein the (A) polyamide is polymerized by adding an end-capping agent, and the end-capping rate of the (A) polyamide by the end-capping agent is 10% or more. object.
[3]
The polyamide composition according to [1] or [2] , wherein the (D) crystal nucleating agent is talc.
[4]
The polyamide composition according to any one of [1] to [3] , wherein the total content of (B) titanium oxide and (C) inorganic filler is 35 to 70% by mass.

[5]
The polyamide composition according to any one of [1] to [4] , wherein (a) the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.

[6]
[1] thru | or the said (b) main chain linear diamine is a C7-C13 diamine.
[5] The polyamide composition according to any one of [5] .

[7]
[1] The (A) polyamide end-capping agent is at least one selected from the group consisting of aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, aliphatic monoamines, and alicyclic monoamines. Thru | or the polyamide composition as described in any one of [6] .

[8]
The polyamide composition according to any one of [1] to [7] , wherein the trans isomer ratio of the alicyclic dicarboxylic acid structure in the (A) polyamide is 50 to 85 mol%.

[9]
The (B) titanium oxide has a number average particle size (by electron micrograph) of 0.1 to 0.8.
The polyamide composition according to any one of [1] to [8] , which is μm.

[10]
The (B) titanium oxide is inorganic and / or organic coated.
The polyamide composition according to any one of [1] to [9] .

[11]
The ignition loss of titanium oxide (B) (reduction when heated at 650 ° C. for 2 hours) is 0.7 to 2.5.
The polyamide composition according to any one of [1] to [10] , wherein the polyamide composition is mass%.

[12]
(C) At least one of the inorganic fillers is a fibrous filler and / or an acicular filler,
The polyamide composition according to any one of [1] to [11] .

[13]
Glass fiber is included as the (C) inorganic filler, and the (C) in the polyamide composition
) The polyamide composition according to any one of [1] to [12] , wherein the fiber length (weight average length) of the glass fiber is 250 to 500 μm.

[14]
After melt kneading the (A) polyamide and the (B) titanium oxide,
The polyamide composition according to any one of [1] to [13] , which is obtained by further kneading the inorganic filler (C).

[15]
The molded object shape | molded using the polyamide composition as described in any one of said [1] thru | or [14] .

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the polyamide composition from which the molded object which has favorable fluidity | liquidity, has practically sufficient moldability, and is excellent in toughness, reflow resistance, and heat-resistant discoloration property can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

[Polyamide composition]
The polyamide composition of this embodiment contains (A) polyamide, (B): titanium oxide, and (C): inorganic filler.

Hereinafter, the component which comprises the polyamide composition of this embodiment is demonstrated.
[(A) Polyamide]
First, (A) polyamide contained in the polyamide composition of the present embodiment will be described.
(A) Polyamide is a polyamide obtained by polymerizing the following (a) and (b).
(A) Dicarboxylic acid containing at least 70 mol% of alicyclic dicarboxylic acid (b) Diamine containing main chain exceeding 50 mol% of linear diamine In the present embodiment, polyamide is an amide in the main chain It means a polymer having a (—NHCO—) bond.

The (a) dicarboxylic acid which is a polymerization component of the (A) polyamide will be described.
<(A) Dicarboxylic acid>
Said (a) dicarboxylic acid contains at least 70 mol% of alicyclic dicarboxylic acid.
(A) By using a dicarboxylic acid containing at least 70 mol% of an alicyclic dicarboxylic acid, a polyamide that simultaneously satisfies heat resistance, fluidity, toughness, low water absorption, strength, and the like can be obtained. it can.

Examples of (a-1) alicyclic dicarboxylic acid (also referred to as alicyclic dicarboxylic acid) contained in (a) dicarboxylic acid include 1,4-cyclohexane dicarboxylic acid, 1,3- Examples thereof include alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid and 1,3-cyclopentane dicarboxylic acid having an alicyclic structure having 3 to 10 carbon atoms, preferably 5 to 10 carbon atoms.
The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.
Examples of the substituent include alkyl groups having 1 to 4 carbon atoms such as 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.
The alicyclic dicarboxylic acid is preferably 1,4-cyclohexanedicarboxylic acid from the viewpoints of heat resistance, low water absorption, rigidity, and the like.
As the alicyclic dicarboxylic acid, one kind may be used, or two or more kinds may be used in combination.

An alicyclic dicarboxylic acid 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 of various ratios of a trans isomer and a cis isomer may be used.
Since alicyclic dicarboxylic acids are isomerized at a high temperature to a certain ratio, and the cis isomer has higher water solubility in the equivalent salt with the diamine than the trans isomer, the trans isomer / cis cis is used as a raw material monomer. The body ratio in terms of molar ratio is preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and still more preferably 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).

Examples of the dicarboxylic acid other than the (a-1) alicyclic dicarboxylic acid (a-2): alicyclic dicarboxylic acid contained in the (a) dicarboxylic acid described above include: Aliphatic dicarboxylic acids and aromatic dicarboxylic acids are exemplified.
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, naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. And aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with the above-mentioned substituents.
Examples of the various substituents include, for example, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, a halogen group such as a chloro group and a bromo group, and 1 carbon atom. ˜6 silyl groups, and sulfonic acid groups and salts thereof such as sodium salts.

(A-2) The dicarboxylic acid other than the alicyclic dicarboxylic acid is preferably an aliphatic dicarboxylic acid, more preferably carbon in terms of heat resistance, fluidity, toughness, low water absorption, rigidity, and the like. It is an aliphatic dicarboxylic acid having a number of 6 or more.
In particular, 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.
In particular, in terms of heat resistance, sebacic acid and dodecanedioic acid are preferable.
(A-2) One dicarboxylic acid other than the alicyclic dicarboxylic acid may be used alone, or two or more dicarboxylic acids may be used in combination.

(A) The dicarboxylic acid component may further contain a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid as long as the object of the present embodiment is not impaired.
As the polyvalent carboxylic acid, one kind may be used alone, or two or more kinds may be used in combination.

The proportion (mol%) of (a-1) alicyclic dicarboxylic acid in (a) dicarboxylic acid is at least 70 mol%.
The ratio of alicyclic dicarboxylic acid is 70-100 mol%, it is preferable that it is 75-100 mol%, More preferably, it is 80-100 mol%, More preferably, it is 100 mol%.
When the ratio of (a-1) alicyclic dicarboxylic acid in (a) dicarboxylic acid is at least 70 mol%, a polyamide having excellent heat resistance, low water absorption, rigidity and the like can be obtained.

(A) The ratio (mol%) of dicarboxylic acids other than (a-2) alicyclic dicarboxylic acid in dicarboxylic acid is 0 to 30 mol%, and preferably 0 to 25 mol%.
(A-2) when an aliphatic dicarboxylic acid having 6 or more carbon atoms is included as a dicarboxylic acid other than the alicyclic dicarboxylic acid, (a-1) 70 to 99.9 mol% of the alicyclic dicarboxylic acid, and (A-2) 0.1 to 30 mol% of an aliphatic dicarboxylic acid having 6 or more carbon atoms, (a-1) 70 to 95 mol% of an alicyclic dicarboxylic acid, and (a-2) More preferably, the aliphatic dicarboxylic acid having 6 or more carbon atoms is 5 to 30 mol%, (a-1) the alicyclic dicarboxylic acid is 80 to 95 mol%, and (a-2) the fatty acid having 6 or more carbon atoms. It is more preferable that it is 5-20 mol% of group dicarboxylic acid.

The (a) dicarboxylic acid used for the polymerization of the polyamide (A) constituting the polyamide composition of the present embodiment is not limited to the compounds described as the dicarboxylic acid, but is a compound equivalent to the dicarboxylic acid. May be.
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. Can be mentioned.

<(B) Diamine>
The (b) diamine which is a polymerization component of the (A) polyamide will be described.
(B) The diamine contains more than 50 mol% of a diamine having a linear main chain.
Examples of (b-1) diamine having a linear main chain contained in (b) diamine include ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, and octamethylene. Examples thereof include linear saturated aliphatic diamines having 2 to 20 carbon atoms such as diamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.
These diamines may be used alone or in combination of two or more.

The diamine having a linear (b-1) main chain is preferably a linear aliphatic diamine having 4 to 16 carbon atoms from the viewpoints of heat resistance, fluidity, toughness, low water absorption, rigidity, and the like. More preferably a linear aliphatic diamine having 6 to 14 carbon atoms, still more preferably a linear aliphatic diamine having 7 to 13 carbon atoms, still more preferably a linear aliphatic diamine having 9 to 12 carbon atoms. It is a group diamine.
In addition, when using in combination of 2 or more types of linear diamine, it is preferable that an average carbon number is the said range. The average carbon number here represents the average carbon number calculated from the molar ratio.
For example, when a diamine having 12 carbon atoms and a diamine having 6 carbon atoms are used at a molar ratio of 80/20, the average carbon number is 10.8.

  (B) By using a diamine containing a diamine having a main chain of more than 50 mol%, a polyamide that simultaneously satisfies low water absorption and heat resistance can be obtained.

The (b-1) main chain contained in the (b) diamine is a diamine other than a linear diamine, and (b-2): And diamines having substituents branched from the main chain, alicyclic diamines, and aromatic diamines.
Examples of the substituent branched from the main chain of the diamine having a substituent branched from the main chain include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl. Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a group.
Examples of the diamine having a substituent branched from the main chain include 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylenediamine, Examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine.
The diamine having a substituent branched from the main chain is preferably 2-methylpentamethylenediamine or 2-methyloctamethylenediamine from the viewpoints of heat resistance and rigidity.
Examples of the alicyclic diamine (also referred to as alicyclic diamine) include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclopentanediamine, and the like.
The aromatic diamine is an aromatic diamine, such as metaxylylenediamine.

The diamine other than the (b-2) diamine having a linear main chain is preferably a diamine or fat having a substituent branched from the main chain from the viewpoints of heat resistance, fluidity, toughness, low water absorption and the like. It is a cyclic diamine, more preferably 2-methylpentamethylenediamine or 2-methyloctamethylenediamine.
(B-2) Diamines other than the diamine having a linear main chain may be used alone or in combination of two or more.

The (b) diamine component described above may further contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine within a range not impairing the object of the present embodiment.
A polyvalent aliphatic amine may be used individually by 1 type, and may be used in combination of 2 or more types.

As described above, the ratio (mol%) of (b-1) diamine having a linear main chain in (b) diamine is a ratio exceeding 50 mol%.
The proportion of the diamine having a linear main chain is more than 50 mol% to 100 mol%, and preferably 60 to 100 mol%. More preferably, it is 80-100 mol%, More preferably, it is 85-100 mol%, More preferably, it is 90-100 mol%, More preferably, it is 100 mol%.
(B) (b-1) In the diamine, when the ratio of the diamine having a linear main chain exceeds 50 mol%, the polyamide is excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity. it can.

  The proportion (mol%) of the diamine other than the diamine (b-2) in which the main chain is (b-2) in the diamine (b) is 50 mol% or less, and preferably 0 to 40 mol%.

The addition amount of the (a) dicarboxylic acid, which is a polymerization component of the (A) polyamide, and the addition amount of the (b) diamine are preferably around the same molar amount.
The amount of (b) diamine escaped from the reaction system during the polymerization reaction is also considered in terms of the molar ratio, and (a) the molar amount of (b) diamine as a whole is 0 It is preferable that it is 0.9-1.2, More preferably, it is 0.95-1.1, More preferably, it is 0.98-1.05.

<(C) Lactam and / or aminocarboxylic acid>
The (A) polyamide can be further copolymerized with (c) lactam and / or aminocarboxylic acid from the viewpoint of toughness.
The (c) lactam and / or aminocarboxylic acid used in this embodiment means a lactam and / or aminocarboxylic acid that can be condensed (condensed).
When the (A) polyamide is a polyamide obtained by polymerizing (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, the (c) lactam and / or aminocarboxylic acid is used. The 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.
In particular, from the viewpoint of toughness, ε-caprolactam, laurolactam and the like 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 the 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, And 12-aminododecanoic acid and the like, and examples of the aminocarboxylic acid include paraaminomethylbenzoic acid and the like.

(C) A lactam and / or aminocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more types.
(C) The addition amount (mol%) of lactam and / or aminocarboxylic acid is the molar amount of each monomer of (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid. It is preferable that it is 0-30 mol% with respect to.

<End sealant>
When (A) a polyamide is polymerized using (a) dicarboxylic acid and (b) diamine, and (c) lactam and / or aminocarboxylic acid as required, a known end-capping is used for molecular weight adjustment. An additional stop agent can be added.
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. And monocarboxylic acids and 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 Acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and aromatic monocarboxylic acid such as phenylacetic acid; and the like, and aliphatic monocarboxylic acid and alicyclic monocarboxylic acid are particularly preferable. .
Monocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more types.

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; and aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine And the like. In particular, an aliphatic monoamine and an alicyclic monoamine are preferable.
Monoamines may be used alone or in combination of two or more.

(A) As for polyamide, the terminal group of the molecular chain may be sealed with the terminal blocker mentioned above.
The ratio of the end groups of the molecular chain being sealed with the end-capping agent (end-capping rate) is preferably 10% or more from the viewpoint of the fluidity of the polyamide composition of the present embodiment. More preferably, it is -90%.
The terminal blocking rate of the molecular chain of the polyamide can be measured by the method described in Examples described later.

The combination of (a) dicarboxylic acid and (b) diamine described above is not limited to the following, but (a-1) at least 70 mol% or more of alicyclic dicarboxylic acid and (b-1) 50 mol. In combination with a linear saturated aliphatic diamine having 6 to 14 carbon atoms exceeding (%), (a-1) at least 70 mol% or more of 1,4-cyclohexanedicarboxylic acid and (b-1) exceeding 50 mol% A combination with a linear saturated aliphatic diamine having 7 to 13 carbon atoms is more preferred.
By polymerizing these combinations as polyamide components, it is possible to obtain a polyamide that simultaneously satisfies heat resistance, fluidity, toughness, low water absorption, and strength.

((A) Polyamide structure)
As described above, the (A) polyamide has (a) a dicarboxylic acid containing an alicyclic dicarboxylic acid as a component. In the (A) polyamide, the alicyclic dicarboxylic acid structure has a trans isomer and a cis isomer. It exists as a geometric isomer of the body.
The trans isomer ratio of the alicyclic dicarboxylic acid structure in the polyamide (A) constituting the polyamide composition of the present embodiment represents a ratio that is a trans isomer in the entire alicyclic dicarboxylic acid in the polyamide, preferably Is 50 to 85 mol%, more preferably 50 to 80 mol%, still more preferably 60 to 80 mol%.

  As the (a-1) alicyclic dicarboxylic acid, an alicyclic dicarboxylic acid having a trans isomer / cis isomer ratio (molar ratio) of 50/50 to 0/100 is preferably used. The polyamide obtained by polymerization of the acid and (b) diamine preferably has a trans isomer ratio of 50 to 85 mol%.

(A) Since the trans isomer ratio of the alicyclic dicarboxylic acid structure in the polyamide is within the above range, (A) the polyamide has a high melting point, toughness and rigidity, and has a high Tg heat. It has the properties of satisfying both rigidity at the same time, fluidity, which is usually opposite to heat resistance, and high crystallinity.
These characteristics of (A) polyamide include (a) at least 70 mol% or more of 1,4-cyclohexanedicarboxylic acid and (b) linear saturated aliphatic diamine having 6 to 14 carbon atoms in excess of 50 mol%. This is particularly noticeable for polyamides comprising a combination with a diamine and having a trans isomer ratio of 50 to 85 mol%.
In addition, the trans isomer ratio of the alicyclic dicarboxylic acid structure in the polyamide (A) constituting the polyamide composition of the present embodiment can be measured by the method described in the following examples.

((A) Polyamide production method)
(A) Polyamide is not particularly limited, and exceeds (a) a dicarboxylic acid containing at least 70 mol% of an alicyclic dicarboxylic acid, and (b) a diamine having a main chain of linear chain exceeding 50 mol%. It can manufacture with the manufacturing method of polyamide including the process of superposing | polymerizing with the diamine containing.
(A) As a manufacturing method of polyamide, it is preferable to further include the process of raising the polymerization degree of polyamide.

(A) As a concrete manufacturing method of polyamide, various methods are mentioned, for example as illustrated 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 sometimes 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, sometimes abbreviated as “hot melt polymerization / solid phase polymerization method”). ,
3) A method in which an aqueous solution or a suspension of water of a diamine / dicarboxylate 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 “pre-polymerization”). Abbreviated as “polymer / extrusion polymerization method”).
4) A method of heating an aqueous solution or a suspension of water of a diamine dicarboxylate or a mixture thereof and increasing the degree of polymerization while maintaining the solid state of the precipitated prepolymer at a temperature below the melting point of the polyamide (hereinafter, And may be abbreviated as “prepolymer / solid phase polymerization method”).
5) A method of polymerizing a diamine dicarboxylate or a mixture thereof while maintaining a solid state (hereinafter sometimes abbreviated as “solid phase polymerization method”),
6) A “solution method” in which a dicarboxylic acid halide component equivalent to a dicarboxylic acid and a diamine component are used for polymerization.

(A) In the step of producing polyamide, from the viewpoint of the fluidity of the polyamide, it is preferable to carry out the polymerization while maintaining the trans isomer ratio of the alicyclic dicarboxylic acid at 85% or less, and particularly at 80% or less. By doing so, it is possible to obtain a polyamide having excellent color tone and tensile elongation and having a high melting point.
(A) In the process of producing a polyamide, in order to increase the degree of polymerization and raise the melting point of the polyamide, it is necessary to increase the heating temperature or lengthen the heating time. There is a case where the tensile elongation is lowered due to coloring of the polyamide or thermal deterioration. In addition, the rate at which the molecular weight increases may decrease significantly.

In addition, since (A) it is possible to prevent a decrease in tensile elongation due to polyamide coloring or thermal deterioration, the trans isomer ratio of the alicyclic dicarboxylic acid structure in the (A) polyamide is maintained at 80% or less. Polymerization is preferred.
As a method for producing (A) polyamide, it is easy to maintain the trans isomer ratio of the alicyclic dicarboxylic acid structure at 85% or less, and because the color tone of the obtained (A) polyamide is excellent, It is preferable to produce polyamide by 1) hot melt polymerization method and 2) hot melt polymerization / solid phase polymerization method.

(A) The polymerization form in the polyamide production process may be either a batch type or a continuous type.
The polymerization apparatus is not particularly limited, and examples thereof include known apparatuses such as an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader.

As an example of the first production method, an example in which polyamide is produced by a batch-type hot melt polymerization method will be described below, but the production method of polyamide is not limited to this example.
First, a solution of about 40 to 60% by mass containing a polyamide component ((a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid as required) using water as a solvent, In a concentration tank operated at a temperature of 110 to 180 ° C. and a pressure of about 0.035 to 0.6 MPa (gauge pressure), it is concentrated to about 65 to 90% by mass to obtain a concentrated solution.
Next, the concentrated solution is transferred to an autoclave, and heating is continued until the pressure in the container reaches about 1.5 to 5.0 MPa (gauge pressure).
Thereafter, while removing water and / or gas components, the pressure is maintained at about 1.5 to 5.0 MPa (gauge pressure), and when the temperature reaches about 250 to 350 ° C., the pressure is reduced to atmospheric pressure (gauge pressure). Is 0 MPa).
By reducing the pressure to atmospheric pressure and then reducing the pressure as necessary, by-product water can be effectively removed.
Then, it pressurizes with inert gas, such as nitrogen, and extrudes a polyamide melt as a strand.
The strand is cooled and cut to obtain (A) polyamide pellets.

As a second example of the production method, an example in which polyamide is produced by a continuous hot melt polymerization method will be described below.
First, a solution of about 40 to 60% by mass containing a polyamide component in water as a solvent is preheated to about 40 to 100 ° C. in a container of a preliminary apparatus, and then transferred to a concentrating tank / reactor. Concentrate to about 70-90% at a pressure of ˜0.5 MPa (gauge pressure) and a temperature of about 200-270 ° C. to obtain a concentrated solution.
This concentrated solution is discharged to a flasher maintained at a temperature of about 200 to 350 ° C., and then the pressure is reduced to atmospheric pressure (gauge pressure is 0 MPa). After reducing the pressure to atmospheric pressure, reduce the pressure as necessary.
Thereafter, the polyamide melt is extruded to form a strand, which is then cooled and cut to obtain (A) polyamide pellets.

((A) Polyamide molecular weight)
The molecular weight of the polyamide (A) constituting the polyamide composition of the present embodiment uses the relative viscosity ηr at 25 ° C. as an index.
The molecular weight of the polyamide (A) is preferably 1.5% in terms of mechanical properties such as toughness and rigidity, moldability and the like, in a 98% sulfuric acid concentration of 1% and a relative viscosity ηr at 25 ° C. measured according to JIS-K6810. It is -7.0, More preferably, it is 1.7-6.0, More preferably, it is 1.9-5.5.
The relative viscosity at 25 ° C. can be measured according to JIS-K6810 as described in the following examples.

((A) melting point of polyamide)
The melting point of the polyamide (A) constituting the polyamide composition of the present embodiment is preferably 270 to 350 ° C. as Tm2 from the viewpoint of heat resistance. Melting | fusing point Tm2 becomes like this. Preferably it is 270 degreeC or more, More preferably, it is 275 degreeC or more, More preferably, it is 280 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.
By setting the melting point Tm2 of the polyamide (A) to 270 ° C. or higher, the polyamide (A) having excellent heat resistance can be obtained. In addition, by setting the melting point Tm2 of the (A) polyamide to 350 ° C. or less, it is possible to suppress the thermal decomposition of the (A) polyamide in the melt processing such as extrusion and molding.

((A) Heat of fusion ΔH of polyamide)
The heat of fusion ΔH of the polyamide (A) constituting the polyamide composition of the present embodiment is preferably 10 J / g or more, more preferably 14 J / g or more, and still more preferably 18 J / g from the viewpoint of heat resistance. g or more, more preferably 20 J / g or more.

(A) Melting | fusing point (Tm1 or Tm2) of polyamide and the measurement of heat of fusion (DELTA) H can be performed according to JIS-K7121 as described in the following Example.
(A) As an apparatus for measuring the melting point and heat of fusion of polyamide, for example, Diamond-DSC manufactured by PERKIN-ELMER may be used.

((A) Glass transition temperature Tg of polyamide)
It is preferable that the glass transition temperature Tg of (A) polyamide which comprises the polyamide composition of this embodiment is 85-170 degreeC. More preferably, it is 90 degreeC or more, More preferably, it is 95 degreeC or more, More preferably, it is 100 degreeC or more. Further, the glass transition temperature is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
(A) By setting the glass transition temperature of the polyamide to 85 ° C. or higher, a polyamide having excellent heat resistance and chemical resistance can be obtained. Moreover, the molded article with a good external appearance can be obtained by setting the glass transition temperature of (A) polyamide to 170 ° C. or lower.
The glass transition temperature can be measured according to JIS-K7121 as described in the following examples.
Examples of the glass transition temperature measuring device include Diamond-DSC manufactured by PERKIN-ELMER.

[(B) Titanium oxide]
(B) Titanium oxide contained in the polyamide composition of the present embodiment will be described.
Examples of (B) titanium oxide include titanium oxide (TiO), dititanium trioxide (Ti ₂ O ₃ ), and titanium dioxide (TiO ₂ ). In particular, titanium dioxide is preferable.
(B) The crystal structure of titanium oxide is not particularly limited, but is preferably a rutile type from the viewpoint of light resistance.

(B) The number average particle diameter of titanium oxide is preferably 0.1 to 0.8 μm, more preferably 0.15 to 0.4 μm, and still more preferably 0 from the viewpoints of toughness and extrusion processability. .15 to 0.3 μm.
(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 contained organic matter is incinerated, for example, 100 or more titanium oxides are arbitrarily selected from the residue, and observed with an electron microscope to measure the particle diameter. Thus, the number average particle diameter can be measured and obtained.

  (B) Titanium oxide can be produced by, 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 vapor-phase oxidized, but is not limited thereto.

(B) It is preferable to coat the surface of the titanium oxide particles.
(B) The titanium oxide particles are preferably coated with an inorganic coating and / or an organic coating, more preferably with an inorganic coating first and then with an organic coating applied over the inorganic coating.
(B) The titanium oxide particles may be coated using any method known in the art.

The inorganic coating preferably contains a metal oxide.
Examples thereof include metal oxides and hydrated oxides including oxides and hydrated oxides of silicon, aluminum, zirconium, phosphorus, zinc, rare earth elements, and the like.
In particular, the metal oxide is preferably silica, alumina or zirconia from the viewpoint of light resistance, and more preferably silica or alumina.
These inorganic coatings may be one type of metal oxide or a combination of two or more types.
As an inorganic coating, it is preferable that it is 0.25-50 mass% with respect to 100 mass% of titanium oxide whole quantity, It is more preferable that it is 0.25-10 mass%, It is that it is 1-10 mass%. Further preferred.

The organic coating preferably contains one or more of carboxylic acids, polyols, alkanolamines and / or silicon compounds. In particular, polyols and silicon compounds are more preferable from the viewpoints of light resistance and film processability, and silicon compounds are more preferable from the viewpoint of reducing generated gas during processing.
Examples of carboxylic acids that can be used as the organic coating include adipic acid, terephthalic acid, lauric acid, myristic acid, palmitic acid, stearic acid, polyhydroxystearic acid, oleic acid, salicylic acid, malic acid, and maleic acid. . These carboxylic acid esters and metal salts may be used. Examples of the metal salt include aluminum salt, zinc salt, magnesium salt, calcium salt, barium salt and the like.

Examples of the alkanolamines that can be used as the organic coating include monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, tripropanolamine, and derivatives thereof include acetates thereof, Organic acid salts such as oxalate, tartrate, formate, benzoate and the like can be mentioned.
Examples of polyols that can be used as the organic coating include trimethylolpropane, trimethylolethane, ditrimethylolpropane, trimethylolpropane ethoxylate, pentaerythritol and the like, and trimethylolpropane and trimethylolethane are preferable.

Examples of the silicon compound that can be used as the organic coating include organosilanes, organopolysiloxanes, and organosilazanes.
Specifically, as organosilanes, (a) aminosilane (aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc.) , (B) epoxy silane (γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.), (c) methacrylsilane (γ- (methacryloyloxypropyl) trimethoxysilane Etc.), (d) vinylsilane (vinyltrimethoxysilane, vinyltriethoxysilane etc.), (e) mercaptosilane (3-mercaptopropyltrimethoxysilane etc.), (f) chloroalkylsilane (3-chloropropyltriethoxysilane) Etc.), (g) alkylsilane (n-butyl) Rutriethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexylmethyldimethoxysilane, hexylmethyldiethoxysilane, cyclohexylmethyldiethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane Etc.), (h) phenylsilane (phenyltriethoxysilane etc.), (i) fluoroalkylsilane (trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane etc.) etc., or their hydrolysis products. It is done.
Organopolysiloxanes include (a) straight polysiloxane (dimethylpolysiloxane, methylhydrogen polysiloxane, methylmethoxypolysiloxane, methylphenylpolysiloxane, etc.), (b) modified polysiloxane (dimethylpolysiloxane diol). , Dimethylpolysiloxane dihydrogen, side-chain or both-end amino-modified polysiloxane, side-chain or both-end or one-end epoxy-modified polysiloxane, both-end or one-end methacryl-modified polysiloxane, side-chain or both-end carboxyl-modified polysiloxane , Side chain or both ends or one end carbinol modified polysiloxane, both ends phenol modified polysiloxane, side chain or both ends mercapto modified polysiloxane, both ends or side chain polyether modified polysiloxane, side chain alkyl Polysiloxane, side chain methylstyryl modified polysiloxane, side chain higher carboxylic acid ester modified polysiloxane, side chain fluoroalkyl modified polysiloxane, side chain alkyl / carbinol modified polysiloxane, side chain amino / both end carbinol modified polysiloxane Siloxane etc.) or their copolymers.
Furthermore, examples of organosilazanes include hexamethylsilazane and hexamethylcyclotrisilazane.

Among the silicon compounds, hydrophobic functional groups such as a methacryl group (—OCOC (CH ₃ ) ═CH ₂ ), a vinyl group (—CH═CH ₂ ), an alkyl group (—R), an aryl group (—Ph , -Ar, etc.), a carboxylic acid ester group (-OCOR), an acyl group (-COR), a polyether group _{^{(- (R 1 O) n}} (R 2 O) m R 3), the fluorine-containing group (- (CH _{2) n CF 3, - (} CF 2) is more preferably a silicon compound having an _n CF _3, etc.) and the like, more preferably as long as organosilanes or organopolysiloxanes having a hydrophobic functional group.

Among these silicon compounds, at least one selected from alkylsilanes having 4 to 10 carbon atoms, hydrolysis products thereof, dimethylpolysiloxane, and methylhydrogenpolysiloxane is even more preferable.
When an alkylsilane having 6 (hexyl group) having the largest number of carbon atoms in the alkyl group is used as the alkylsilane, the dispersibility and heat resistance are further improved. The hydrolyzed products of organosilanes are those in which hydrolyzable groups of organosilanes are hydrolyzed into silanols, and those in which silanols are polycondensed into dimers, oligomers, and polymers. say.

From the viewpoint of extrusion processability, the (B) titanium oxide constituting the polyamide composition of the present embodiment has an ignition loss of 0.7 to 2.5% by mass with respect to 100% by mass of the total amount of titanium oxide. More preferably, it is 0.7-2.0 mass%, More preferably, it is 0.8-1.5 mass%.
Here, the loss on ignition can be calculated from the weight loss rate when the titanium oxide is dried at 120 ° C. for 4 hours to remove moisture adhering to the surface and then heat-treated at 650 ° C. for 2 hours.
In addition, as (B) titanium oxide, 1 type may be used and it may be used in combination of 2 or more types.

The blending amount of (B) titanium oxide in the polyamide composition of the present embodiment is 10% by mass or more with respect to 100% by mass of the polyamide composition from the viewpoint of whiteness.
From a viewpoint of fluidity | liquidity and toughness, Preferably it is 10-50 mass%, More preferably, it is 15-40 mass%, More preferably, it is 15-30 mass%.

[(C) Inorganic filler]
The (C) inorganic filler contained in the polyamide composition of the present embodiment will be described.
(C) Examples of the inorganic filler include glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate. , 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 black Furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, mica, montmorillonite, swellable fluorine mica, and apatite.
(C) It is preferable from a viewpoint of mechanical strength that at least one inorganic filler is a fibrous filler and / or an acicular filler.

(C) As an inorganic filler, a glass fiber and a carbon fiber are mentioned as a typical example, These 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.
The flatness ratio is expressed by D2 / D1, where D2 is the major axis of the fiber cross section and D1 is the minor axis of the fiber cross section. The perfect circle has a flatness ratio of about 1.
Among glass fibers and carbon fibers, from the viewpoint that excellent mechanical strength characteristics can be imparted to the polyamide composition, the number average fiber diameter is 3 to 30 μm, and in the polyamide composition, the weight average fiber length is 250 to More preferably, it is 500 μm and the aspect ratio (L / D) between the weight average fiber length and the number average fiber diameter is 10 to 100.

In addition, when (C) a glass fiber or carbon fiber having a flat cross-sectional shape is contained as the inorganic filler, reduction of warpage, heat resistance, and toughness of the plate-like molded product obtained by molding the polyamide composition of the present embodiment. From the viewpoint of low water absorption and heat aging resistance, the flatness is preferably 1.5 or more. More preferably, it is 1.5-10.0, More preferably, it is 2.5-10.0, More preferably, it is 3.1-6.0.
When the aspect ratio is extremely large, in addition to mixing with other components, it may be crushed during processing such as kneading and molding, and the desired effect may be reduced.
The thickness of the glass fiber or carbon fiber having an aspect ratio of 1.5 or more is arbitrary, but the minor axis D1 of the fiber cross section is 0.5 to 25 μm, and the major axis D2 of the fiber cross section is 1.25 to 250 μm. Preferably there is.
If it is too thin, spinning of the fiber may be difficult. If it is too thick, the strength of the molded product may be reduced due to a decrease in the contact area with the polyamide resin or the like. From this viewpoint, the short diameter D1 is preferably 3 μm or more, and the short diameter D1 is preferably 3 μm or more, and the flatness is preferably a value larger than 3.
These glass fibers and carbon fibers having a flatness ratio of 1.5 or more are produced, for example, by the method described in Japanese Patent Publication No. 3-59019, Japanese Patent Publication No. 4-13300, Japanese Patent Publication No. 4-32775, and the like. be able to.
In particular, in an orifice plate having a large number of orifices on the bottom surface, an outer periphery of an orifice plate surrounding a plurality of orifice outlets and having a convex edge extending downward from the bottom surface of the orifice plate, or a nozzle tip having one or more orifice holes A glass fiber having a flatness ratio of 1.5 or more manufactured by using a nozzle chip for deformed cross-section glass fiber spinning provided with a plurality of convex edges extending downward from the tip of the part is preferable.
In these fibrous reinforcing materials, fiber strands may be used as rovings as they are, or a cutting step may be obtained and used as chopped glass strands.

  In addition, in this specification, (C) As a measuring method of the number average fiber diameter and weight average fiber length of an inorganic filler, for example, a polyamide composition is put into an electric furnace, an organic substance contained is incinerated, and a residue From the above, for example, 100 or more glass fibers are arbitrarily selected, observed with a scanning electron microscope (SEM), and the number average fiber diameter is measured by measuring the fiber diameter of these glass fibers, and the magnification is 1000. There is a method for obtaining the weight average fiber length by measuring the fiber length using an SEM photograph at a magnification.

The glass fiber or carbon fiber as the (C) inorganic filler may be surface-treated with a silane coupling agent or the like.
Although it does not restrict | limit especially as said silane coupling agent, For example, aminosilanes, such as (gamma) -aminopropyl triethoxysilane, (gamma) -aminopropyl trimethoxysilane, and N- (beta)-(aminoethyl) -gamma-aminopropylmethyldimethoxysilane. And the like; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. Especially, it is preferable that it is 1 or more types selected from said enumeration component, and aminosilanes are more preferable.

Moreover, about the glass fiber and carbon fiber as said (C) inorganic filler, a carboxylic acid anhydride containing unsaturated vinyl monomer and the said carboxylic acid anhydride containing unsaturated vinyl monomer are further excluded as a sizing agent. Copolymers containing unsaturated vinyl monomers as constituent units, epoxy compounds, polycarbodiimide compounds, polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and primary grades thereof , Salts with secondary and tertiary amines, and co-polymers containing unsaturated vinyl monomers containing carboxylic acid anhydrides and unsaturated vinyl monomers excluding the unsaturated vinyl monomers containing carboxylic acid anhydrides Coalescence etc. may be included.
These may be used individually by 1 type and may be used in combination of 2 or more type.
In particular, from the viewpoint of mechanical strength of the polyamide composition, the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as structural units. A copolymer, an epoxy compound, a polycarbodiimide compound, a polyurethane resin, and a combination thereof are preferable, and the carboxylic acid anhydride-containing unsaturated vinyl monomer and the carboxylic acid anhydride-containing unsaturated vinyl monomer A copolymer containing a saturated vinyl monomer as a structural unit, a polycarbodiimide compound, a polyurethane resin, and a combination thereof are more preferable.

Among the copolymers containing carboxylic acid anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers excluding the carboxylic acid anhydride-containing unsaturated vinyl monomers as constituent units, the carboxylic acid anhydride-containing copolymer Examples of the unsaturated vinyl monomer include, but are not limited to, maleic anhydride, itaconic anhydride, and citraconic anhydride, and maleic anhydride is particularly preferable.
On the other hand, the unsaturated vinyl monomer excluding the carboxylic anhydride-containing unsaturated vinyl monomer means an unsaturated vinyl monomer different from the carboxylic anhydride-containing unsaturated vinyl monomer.
Examples of the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer include, but are not limited to, for example, styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2, Examples include 3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. Styrene and butadiene are particularly preferable.
Among these combinations, selected from the group consisting of a copolymer of maleic anhydride and butadiene, a copolymer of maleic anhydride and ethylene, a copolymer of maleic anhydride and styrene, and a mixture thereof. It is more preferable that it is 1 type or more.

  In addition, a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units has a weight average molecular weight of 2 1,000 or more. Moreover, from a viewpoint of the fluidity | liquidity improvement of a polyamide composition, More preferably, it is 2,000-1,000,000, More preferably, it is 2,000-500,000. In addition, the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC).

  Examples of the epoxy compound as the sizing agent include, but are not limited to, ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, undecenoxide, and dodecoxide. Aliphatic epoxy compounds such as decene oxide, pentadecene oxide, and eicosene oxide; 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, vinylcyclohexane Alicyclic epoxy compounds such as xene 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.

Moreover, it is preferable that the said polycarbodiimide compound is a polycarbodiimide compound which has a polyol segment partially. By having a polyol segment, the polycarbodiimide compound is easily water-soluble and can be more suitably used as a glass fiber sizing agent.
These carbodiimide compounds can be obtained by subjecting a diisocyanate compound to a decarboxylation reaction in the presence of a known carbodiimidization catalyst such as 3-methyl-1-phenyl-3-phospholene-1-oxide.
As the diisocyanate compound, aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates, and mixtures thereof can be used.
Although not limited to the following, for example, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4 -Tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate , Dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl Isocyanate and 1,3,5-triisopropylbenzene 2,4-diisocyanate, and the like. And the polycarbodiimide compound which has two isocyanate groups at the terminal is obtained by carbodiimidizing these diisocyanate compounds. Of these, dicyclohexylmethane carbodiimide can be suitably used from the viewpoint of improving reactivity.
For a polycarbodiimide compound having two isocyanate groups at the terminal, a method of further converting the monoisocyanate compound to an equimolar amount carbodiimide, or a method of reacting an equimolar amount with a polyalkylene glycol monoalkyl ether to generate a urethane bond, etc. A polycarbodiimide compound having one isocyanate group at the terminal is obtained.
Examples of the monoisocyanate compound include, but are not limited to, hexyl isocyanate, phenyl isocyanate, cyclohexyl isocyanate, and the like. The polyalkylene glycol monoalkyl ether described above is not limited to the following, and examples thereof include polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether.

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

  The homopolymer of acrylic acid (polyacrylic acid) as the sizing agent preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.

The polymer of acrylic acid may be a copolymer of acrylic acid and other copolymerizable monomers.
Examples of the monomer that forms a copolymer with acrylic acid include, but are not limited to, for example, among monomers having a hydroxyl group and / or a carboxyl group, acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, and isocrotone. One or more selected from the group consisting of acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid are included (except for acrylic acid alone). Preferably, it has 1 or more types of ester monomers among the above-mentioned monomers.

The polymer of acrylic acid (including both homopolymers and copolymers) may be in the form of a salt.
The salt of the acrylic acid polymer includes, but is not limited to, primary, secondary or tertiary amines.
Although not limited to the following, specific examples include triethylamine, triethanolamine, and glycine.
The degree of neutralization is preferably 20 to 90%, and preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor. Is more preferable.

  The weight average molecular weight of the acrylic acid-forming polymer (including both homopolymers and copolymers) that forms a salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. (C) 3,000 or more is preferable from the viewpoint of improving the converging property of glass fibers or carbon fibers which are inorganic fillers, and 50,000 or less is preferable from the viewpoint of improving mechanical properties when a polyamide composition is obtained.

(C) As a method for imparting the above-described sizing agent to glass fiber or carbon fiber as an inorganic filler, in a known glass fiber or carbon fiber manufacturing process, sizing is performed using a known method such as a roller-type applicator. It is obtained continuously by applying the agent and drying the fiber strands.
The fiber strand may be used as a roving as it is, or may be used as a chopped glass strand by further obtaining a cutting step.
The sizing agent preferably imparts (adds) 0.2 to 3% by mass, more preferably 0, to 100% by mass of (C) glass fiber or carbon fiber as the inorganic filler. 3 to 2% by mass (added).
(C) From the viewpoint of maintaining the bundling of glass fibers or carbon fibers as the inorganic filler, the amount of sizing agent added is 100% by mass with respect to 100 mass% of the glass fibers or carbon fibers as the inorganic filler (C). Is preferably 0.2% by mass or more. On the other hand, from the viewpoint of improving the thermal stability of the polyamide composition, it is preferably 3% by mass or less. The strand may be dried after the cutting step, or may be cut after the strand is dried.

  (C) inorganic fillers other than glass fibers and carbon fibers include wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate, aluminum borate, from the viewpoint of strength and rigidity, and surface appearance. Clay can be preferably used. More preferred are wollastonite, kaolin, mica and talc, still more preferred are wollastonite and mica, and even more preferred is wollastonite. These (C) inorganic fillers may be used individually by 1 type, and may be used in combination of 2 or more type.

The number average particle diameter of the inorganic filler (C) other than glass fiber or carbon fiber is preferably 0.01 to 38 μm from the viewpoint of toughness and surface appearance. 0.03-30 micrometers is more preferable, 0.05-25 micrometers is more preferable, 0.1-20 micrometers is still more preferable, 0.15-15 micrometers is the most preferable.
By setting the number average particle diameter to 38 μm or less, a polyamide composition having excellent toughness and surface appearance can be obtained. Further, when the thickness is 0.1 μm or more, the balance between cost, powder handling surface and physical properties is excellent.
Further, among the inorganic fillers (C), those having a needle-like shape such as wollastonite have an average fiber diameter as an average particle diameter. Furthermore, when the cross section is not a circle, the maximum value of the length is taken as the fiber diameter.

Regarding the aspect ratio (L / D) between the weight average fiber length and the number average fiber diameter of (C) inorganic fillers other than glass fibers and carbon fibers having a needle shape, the appearance of the molded product, injection From the viewpoint of wear of metallic parts such as a molding machine, 1.5 to 10 is preferable, 2.0 to 5 is more preferable, and 2.5 to 4 is even more preferable.
In this specification, as a method for measuring the number average particle diameter (number average fiber diameter) and the weight average fiber length of the inorganic filler (C), for example, a polyamide composition is placed in an electric furnace and contained in an organic substance. From the residue, for example, 100 or more inorganic fillers are arbitrarily selected and observed with a scanning electron microscope (SEM), and the particle diameter of these inorganic fillers is measured to determine the number average particles. There is a method of determining the weight average fiber length by measuring the diameter and measuring the fiber length in the same manner.

The inorganic filler (C) other than the glass fiber and carbon fiber is subjected to a surface treatment with a usual surface treatment agent, for example, a coupling agent such as a silane coupling agent or a titanate coupling agent. Can be used.
Preferred examples of the silane coupling agent include epoxy silane coupling agents.
Further, a mixture of a polyalkoxysiloxane and an epoxy silane coupling agent and / or a reaction product of a polyalkoxy siloxane and an epoxy silane coupling agent can also be preferably used.
Such a surface treating agent can be pretreated on the surface of the inorganic filler, or may be added when the polyamide and the inorganic filler are mixed.
Moreover, the quantity of a preferable surface treating agent is the range of 0.05 mass%-1.5 mass% with respect to (C) inorganic filler.

The total content of (B) titanium oxide and (C) inorganic filler is 35 to 70 mass% with respect to 100 mass% of the polyamide composition. % Is preferred.
(B) The total amount of titanium oxide and (C) inorganic filler is 35% by mass or more, so that the toughness and reflow resistance are excellent, and that it is 70% by mass or less, the fluidity and extrusion processability are excellent. The resulting polyamide composition is preferably 35 to 60% by mass, more preferably 35 to 50% by mass.
Further, the blending ratio of (B) titanium oxide and (C) inorganic filler is (B) / (C) ≧ 0.5 in terms of mass ratio from the viewpoint of toughness, whiteness and extrusion processability. Preferably (B) / (C) is 0.5-3, More preferably, it is 1-2.

The polyamide composition of the present embodiment may further contain the following (D) crystal nucleating agent from the viewpoint of reflow resistance.
[(D) Crystal nucleating agent]
(D) Although it does not specifically limit as a crystal nucleating agent, The effect which makes a crystallinity degree and crystallization temperature high by mix | blending with a polyamide composition is exhibited. A well-known thing can be used, For example, a talc, a calcium silicate, a calcium carbonate, a boron nitride, carbon black etc. are mentioned.
(D) It is preferable from a viewpoint of toughness and reflow resistance that the compounding quantity of a crystal nucleating agent is 0.001-1 mass part with respect to 100 mass parts of (A) polyamide.

The polyamide composition of this embodiment may further contain the following (E) amine light stabilizer from the viewpoint of light stability.
[(E) amine light stabilizer]
Examples of (E) amine light stabilizers include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethyl. Piperidine, 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-tetramethylpiperidine Gin, 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-pentameth) Ru-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) -Tetramethi -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-piperidyl ) Butylamine polycondensate, 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-butyl- 4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol Examples include condensates with β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.
These may be used alone or in combination of two or more.

Among these (E) amine light stabilizers, a low molecular type having a molecular weight of less than 2,000 is preferable from the viewpoint of further improving the light stability.
When a polymer type having a molecular weight of 2,000 or more is used, it is necessary to increase the amount of addition in order to achieve equivalent light stability, which may increase the amount of gas generated.

In addition, (E) amine light stabilizers are NH type (indicating that hydrogen is bonded to an amino group), NR type (indicating that an alkyl group is bonded to an amino group). There are types such as NOR type (indicating that an alkoxy group is bonded to an amino group), and among others, the NH type is preferable from the viewpoint of further improving light stability.
Specifically, among the amine light stabilizers, 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, 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 preferred, and 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 is more preferred, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3 More preferred is benzenedicarboxamide.

(E) When using an amine light stabilizer, the compounding amount of the (E) amine light stabilizer with respect to the polyamide composition of the present embodiment is preferably 0.01 to 1 with respect to 100% by mass of the polyamide composition. It is mass%, More preferably, it is 0.1-1 mass%.
In the above range, light stability and heat aging resistance can be further improved, and the amount of generated gas can be reduced.

The polyamide composition of this embodiment may further contain the following (F) phenol-based heat stabilizer from the viewpoint of heat stability.
[(F) Phenolic heat stabilizer]
(F) Although it does not restrict | limit as a phenol type heat stabilizer below, For example, a hindered phenol compound is mentioned.
Phenol-based heat stabilizers, 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-hydroxyphenylpropionamide), 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-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.
These may be used alone or in combination of two or more.
In particular, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] from the viewpoint of improving heat aging resistance.
When using a phenol-based heat stabilizer, the blending amount of the phenol-based heat stabilizer in the polyamide composition is preferably 0.01 to 1% by mass, more preferably 0 to 100% by mass of the polyamide composition. 0.1 to 1% by mass. When it is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

The polyamide composition of this embodiment may further contain the following (G) phosphorus heat stabilizer from the viewpoint of heat stability.
[(G) Phosphorus heat stabilizer]
(G) The phosphorus-based heat stabilizer is not limited to the following. For example, pentaerythritol phosphite compound, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl phosphite 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) butane Diphosphite, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, Tris (mono, dimixed nonylphenyl) phosphite, 4,4'-isopropylidenebis 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′-isopropylidene diphenyl 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) phosphite, 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′-biphenylene diphosphite Can be mentioned.
These may be used alone or in combination of two or more.

Among the phosphorus-based heat stabilizers listed above, pentaerythritol phosphite compound, tris (2,4-di-t-butylphenyl) phosphite is used from the viewpoint of further improving heat aging resistance and reducing generated gas. preferable.
Examples of the pentaerythritol phosphite compound include, but are not limited to, 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-4 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 pentaerythritol Diphosphite, bis (2,6-di-t- Til-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 Diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos Fight is mentioned.
These 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, and bis (2,6-di-t-octyl-4-methylphenyl) Pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.

  When using the phosphorus heat stabilizer, the blending amount of the phosphorus heat stabilizer in the polyamide composition of the present embodiment is preferably 0.01 to 1% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 0.1-1 mass%. When it is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

The polyamide composition of the present embodiment may further contain other components as necessary within a range not impairing the effects of the invention.
[Other components that can be included in the polyamide composition]
Other components that can be contained in the polyamide composition of the present embodiment are not limited to the following, but include, for example, colorants (including colored master batches) such as pigments and dyes, mold release agents, flame retardants, and fibrillation. Agent, lubricant, brightening agent, plasticizer, copper compound, alkali metal halide compound, antioxidant, stabilizer, UV absorber, antistatic agent, fluidity improver, filler, reinforcing agent, exhibition Adhesives, nucleating agents, rubber, reinforcing agents, and other polymers may be mixed.
Here, since each of the above-mentioned various components has greatly different properties, a suitable content rate for each component shall be selected according to the property, and those skilled in the art will have a suitable content for each of the other components described above. The rate can be easily set.

[Production method of polyamide composition]
The polyamide composition of this embodiment comprises the above-mentioned (A) polyamide, (B) titanium oxide, (C) inorganic filler, and (D) crystal nucleating agent, (E) amine-based light stability, if necessary. And (F) a phenol-based heat stabilizer, (G) a phosphorus-based heat stabilizer, and the above-mentioned other predetermined components.
The mixing method is not particularly limited, and a conventionally known method can be applied.
For example, (i) a method of obtaining the polyamide composition by mixing each material constituting the polyamide composition using a tumbler, a Henschel mixer, etc., and feeding and kneading to a single or twin screw extruder, or (ii) Using a single-screw or twin-screw extruder, (A) polyamide is supplied from the upstream side and melted, and then (B) titanium oxide and (C) inorganic filler are added from the side feeder and further kneaded. (Iii) a method of obtaining a polyamide composition by (iii) supplying (A) polyamide and (B) titanium oxide from the upstream side, melt kneading, (C) adding an inorganic filler, and further kneading; iv) (A) Polyamide is supplied and melted from the upstream side, (B) Titanium oxide is added and kneaded from the first side feeder, and (C) Inorganic filling is performed from the second side feeder. It was added, methods and the like to obtain a polyamide composition by further kneading. Above all, from the viewpoint of toughness and extrudability, (A) polyamide and (B) titanium oxide are melt-kneaded and melted by adding (C) inorganic filler as in (iii) and (iv) above. A method of kneading is preferred.
In addition, (D) crystal nucleating agent, (E) amine-based light stabilizer, (F) phenol-based heat stabilizer, (G) phosphorus-based heat stabilizer, and other predetermined components are mixed as necessary. There is no particular limitation on the supply method in the case of (A) adding from the same supply port as (A) polyamide, (B) adding from the same supply port as titanium oxide, (C) inorganic filler You may add from the same supply port. Among these, from the viewpoint of extrusion processability and heat discoloration resistance, the method of adding (A) from the same supply port as the polyamide and melt-kneading is preferable.

The melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature.
The melt kneading time is preferably about 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 polyamide composition]
The polyamide composition of the present embodiment can be measured for the relative viscosity ηr at 25 ° C., the melting point Tm2, the heat of fusion ΔH, and the glass transition temperature Tg by the same methods as those for (A) polyamide.
(A) About the measuring method of relative viscosity (eta) r of 25 degreeC of polyamide, melting | fusing point Tm2, heat of fusion (DELTA) H, and glass transition temperature Tg, it shows in [Example] mentioned above.
Moreover, the polyamide composition having excellent heat resistance, moldability, and chemical resistance is obtained when these measured values in the polyamide composition are in the same range as the preferred value for the measured value of the polyamide (A). Can do.

[Molded body]
The molded body of the polyamide composition of the present embodiment can be obtained by molding the polyamide composition by a predetermined molding method.
A known method can be applied as the molding method, and is not particularly limited. For example, generally known plastic molding methods such as press molding, injection molding, gas-assisted injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melt spinning method can be used.
The molded article of the polyamide composition of this embodiment is excellent in heat resistance, moldability, mechanical strength, and low water absorption, for automobiles, electric / electronic use, industrial materials, daily use / household use etc. It can be suitably used for various parts materials and for extrusion applications.
In particular, it is suitable for electric and electronic use, and is used for, for example, an LED reflector.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

The raw materials and measurement methods used in Examples and Comparative Examples are shown below.
1 kg / cm ² means 0.098 MPa.
〔raw materials〕
((A) Polyamide)
The polyamide (A) used in the examples and comparative examples was prepared using the following (a) to (d) as appropriate.
<(A) Dicarboxylic acid>
(1) 1,4-cyclohexanedicarboxylic acid (CHDA)
Product name: 1,4-CHDA HP grade (trans isomer / cis isomer = 25/75)
(Eastman Chemical)
(2) Terephthalic acid (TPA) (manufactured by Wako Pure Chemical Industries, Ltd.)
(3) Adipic acid (ADA) (Wako Pure Chemical Industries, Ltd.)
<(B) Diamine>
(4) 1,12-diaminododecane (dodecamethylenediamine) (C12DA)
(5) 1,10-diaminodecane (decamethylenediamine) (C10DA) (manufactured by Tokyo Chemical Industry)
(6) 1,9-Diaminononane (nonamethylenediamine) (C9DA) (manufactured by Tokyo Chemical Industry)
(7) 1,7-diaminoheptane (heptamethylenediamine) (C7DA) (manufactured by Tokyo Chemical Industry)
(8) 1,6-diaminohexane (hexamethylenediamine (C6DA) (manufactured by Tokyo Chemical Industry)
(9) 2-Methyloctamethylenediamine (2MC8DA) The 2-methyloctamethylenediamine was produced with reference to the production method described in JP-A No. 05-17413.
<(C) Lactam and / or aminocarboxylic acid>
(10) ε-caprolactam (CPL) (manufactured by Wako Pure Chemical Industries)
<(D) End sealant>
(11) Acetic acid (Wako Pure Chemical Industries)

((B) Titanium oxide)
(12) TiO ₂ -1
Average particle size: 0.21 μm
Coating: Alumina, silica, siloxane compound Loss on ignition: 1.21% by mass
(13) TiO ₂ -2
Product name: Taipei (registered trademark) CR-63 (Ishihara Sangyo Co., Ltd.)
Average particle size: 0.21 μm
Coating: Alumina, silica, siloxane compound Loss on ignition: 0.43% by mass

((C) inorganic filler)
(14) Glass fiber Product name: ECS 03T-275H (manufactured by Nippon Electric Glass Co., Ltd.)
Average fiber diameter 10μmφ, cut length 3mm
(15) Wollastonite Product name: Nygros8 (manufactured by NYCO)
Average fiber diameter 8μmφ

((D) Crystal nucleating agent)
(16) Talc Product name: Microace L-1 (Nippon Talc)
(17) Boron nitride (BN)
Product name: DENKABORON NITRIDE (registered trademark) SP-2 (manufactured by Denki Kagaku)
(18) Carbon black (CB)
Product name: Mitsubishi Carbon Black (registered trademark) RCF # 50 (Mitsubishi Chemical Corporation)

((E) amine light stabilizer (HALS))
(19) Product name: Nylostab (registered trademark) S-EED (manufactured by Clariant)

((F) Phenolic heat stabilizer)
(20) Product name: IRGANOX (registered trademark) 1098 (manufactured by Ciba)

((G) phosphorus compound)
(21) Product name: Sodium hypophosphite monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.)

[Calculation of polyamide content]
(A-1) The mol% of the alicyclic dicarboxylic acid is (the number of moles of (a-1) alicyclic dicarboxylic acid added as a raw material monomer / the number of moles of all (a) dicarboxylic acids added as raw material monomers. ) × 100.
(B-1) The mole% of the diamine having a linear main chain is ((b-1) the number of moles of the diamine having a linear main chain / all the diamines added as the raw material monomer) The number of moles) was determined by calculation as 100.
In addition, when calculating by the above formula, the denominator and numerator do not include the number of moles of (b-1) main chain linear diamine added as an additional component.

[Method for measuring physical properties]
(1) Melting points Tm1, Tm2 (° C.), heat of fusion ΔH (J / g)
According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER.
The measurement condition is that the temperature of an endothermic peak (melting peak) that appears when about 10 mg of a sample is heated to 300 to 350 ° C. according to the melting point of the sample at a heating rate of 20 ° C./min in a nitrogen atmosphere is Tm1 (° C.). After maintaining the temperature in the molten state at the highest temperature rise for 2 minutes, the temperature was lowered to 30 ° C. at a temperature drop rate of 20 ° C./min, held at 30 ° C. for 2 minutes, and the same at the temperature rise rate of 20 ° C./min. The maximum peak temperature of the endothermic peak (melting peak) that appears when the temperature is raised to is melting point Tm2 (° C.), and the total peak area is the heat of fusion ΔH (J / g).
When there were a plurality of peaks, those having ΔH of 1 J / g or more were regarded as peaks.
For example, when there are two peaks of melting point 295 ° C., ΔH = 20 J / g, melting point 325 ° C., ΔH = 5 J / g, the melting point Tm 2 was 325 ° C. and ΔH = 25 J / g.

(2) Glass transition temperature Tg (° C)
According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER.
Measurement conditions were such that a sample in a molten state obtained by melting a sample on a hot stage (EP80 manufactured by Mettler) was rapidly cooled using liquid nitrogen and solidified to obtain a measurement sample.
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) End sealing rate (%)
(A) The number average molecular weight (Mn) of the polyamide was measured by GPC, and the total number of molecular chain end groups was calculated using the relational expression: total number of molecular chain end groups (eq / g) = 2 / Mn.
The number of carboxyl group ends of the polyamide by titration (eq / g) [polyamide benzyl alcohol solution titrated with 0.1N sodium hydroxide] and the number of amino group ends (eq / g) [polyamide phenol solution 0.1N Titration with hydrochloric acid] was measured, and the end-capping rate was determined by the following formula (1).
Terminal sealing rate (%) = [(A−B) ÷ A] × 100 (1)
In the formula (1), A represents the total number of molecular chain end groups (this is usually equal to twice the number of polyamide molecules), and B represents the total number of carboxyl group terminals and amino group terminals.
The number average molecular weight (Mn) of the polyamide was determined by gel permeation chromatography (GPC).
The apparatus is HLC-8020 manufactured by Tosoh Corporation, the detector is a differential refractometer (RI), the solvent is hexafluoroisopropanol (HFIP) in which 0.1 mol% of sodium trifluoroacetate is dissolved, and the column is Tosoh ( Two TSKgel-GM HHR-H and one G1000 HHR manufactured by the same company were used.
The solvent flow rate was 0.6 mL / min, and the sample concentration was 1 to 3 (mg sample) / 1 (mL solvent).
Based on the obtained elution curve, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated in terms of polymethyl methacrylate (PMMA).

(4) Trans isomer ratio 30-40 mg of polyamide was dissolved in 1.2 g of hexafluoroisopropanol deuteride and measured by 1H-NMR.
In the case of 1,4-cyclohexanedicarboxylic acid, the trans isomer ratio is obtained from the ratio of 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. It was.

(5) Relative viscosity ηr at 25 ° C
It implemented according to JIS-K6810.
Specifically, a 1% concentration solution ((polyamide 1 g) / (98% sulfuric acid 100 mL)) was prepared using 98% sulfuric acid and measured under a temperature condition of 25 ° C.

(6) Loss on ignition of titanium oxide Titanium oxide was dried at 120 ° C. for 4 hours to remove water adhering to the surface, and then allowed to stand for 30 minutes in a desiccator and cooled.
Subsequently, about 10 g was precisely weighed in a magnetic crucible and heated in an electric furnace at 650 ° C. for 2 hours.
After heating, the mixture was allowed to stand for 30 minutes in a desiccator and cooled, and then the weight was measured.
The weight loss rate before and after heating was calculated and used as ignition loss.

(7) Weight average fiber length of glass fiber The polyamide composition pellets obtained in Examples and Comparative Examples were heated in an electric furnace at 650 ° C. for 2 hours and incinerated.
From the residue, 100 glass fibers were arbitrarily selected, and the weight average fiber length was determined by measuring the fiber length using an SEM photograph at a magnification of 1000 times.

(8) Bending amount (mm)
Using the injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], the polyamide composition pellets obtained in the examples and comparative examples were injected + pressure holding time 10 seconds, cooling time 15 seconds, and mold temperature. A strip-shaped molded piece having a length of 128 mm, a width of 12.8 mm, and a thickness of 0.7 mm was formed by setting the molten resin temperature to 120 ° C. and Tm2 + 20 ° C. of (A) polyamide.
Using the obtained test piece, a bending test was performed at a span distance of 28 mm and a compression speed of 5 mm / min, and the amount of deflection at the maximum load was measured.

(9) Spiral flow length (cm)
Using the injection molding machine [IS-100GN: manufactured by Toshiba Machine Co., Ltd.], the polyamide composition pellets obtained in the examples and comparative examples were injected + holding pressure time 10 seconds, cooling time 15 seconds, and mold temperature. Molded with a spiral flow mold of 120mm, molten resin temperature (A) Polyamide melting point Tm2 + 20 ° C, injection speed 100mm / s, injection pressure 100MPa, width 10mm, thickness 1.0mm. The flow length was measured.

(10) Whiteness Using the injection molding machine [PS-40E: manufactured by Nissei Plastic Co., Ltd.], the polyamide composition pellets obtained in the examples and comparative examples were injected and held for 10 seconds, and cooled for 15 seconds. The mold temperature was set to 120 ° C., the molten resin temperature was set to the melting point Tm2 + 20 ° C. of (A) polyamide, and a molded piece having a length of 60 mm × width of 60 mm × thickness of 2.0 mm was formed.
Using the spectral color difference meter [SE6000: manufactured by Nippon Denshoku Industries Co., Ltd.], the obtained molded piece is compliant with JIS Z8730, brightness (L value), redness (a value), yellow according to Hunter's color difference formula. The degree (b value) was obtained, and the whiteness (W) was calculated.
W = 100 − [(100−L) ² + a ² + b ² ] ^1/2

(11) Whiteness after heat treatment The molded piece of length 60 mm x width 60 mm x thickness 2.0 mm obtained above was heat-treated in a hot air dryer at 160 ° C for 24 hours.
The test specimen after the treatment was measured for color tone with a color difference meter in the same manner as described above, and the whiteness was calculated.

(12) Extrusion workability 3 kg of the polyamide composition pellets obtained in the examples and comparative examples were spread on a metal bat, and the number of foreign matters due to eyes was measured visually.

(13) Reflow resistance The polyamide composition pellets obtained in the examples and comparative examples were injected using an injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], injection + holding time 10 seconds, cooling time 15 Second, the mold temperature was set to 120 ° C., the molten resin temperature was set to (A) the melting point of polyamide Tm2 + 20 ° C., and a strip-shaped molded piece having a length of 60 mm × width of 60 mm × thickness of 0.7 mm was molded.
The obtained molded piece was heated in a hot air reflow furnace to confirm the change in shape of the test piece and the degree of discoloration, and the determination was made according to the following criteria.
<Shape change>
○: No deformation of the test piece.
Δ: Slight deformation is observed in the test piece.
X: The test piece has a clear deformation.
<Discoloration>
The test piece after reflowing was measured for color tone with a color difference meter in the same manner as the above-mentioned white color measurement, and the whiteness was calculated.
The hot-air reflow furnace used at this time was a lead-free solder compatible reflow furnace (UNI-6116H, manufactured by Nippon Antom Co., Ltd.). Set to ° C. The conveyor belt speed in the reflow furnace was set to 0.3 m / min.
Under this condition, the temperature profile in the furnace was confirmed. The heat exposure time at 140 ° C. to 200 ° C. was 90 seconds, the heat exposure time at 220 ° C. or higher was 48 seconds, and the heat exposure time at 260 ° C. or higher was 11 seconds. There was a maximum temperature of 265 ° C.

〔polyamide〕
(Production Example 1)
Polymerization reaction of polyamide was carried out by “hot melt polymerization method”.
(A) Dicarboxylic acid: CHDA 693 g (4.02 mol) and (b) diamine: C12DA 807 g (4.02 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50% by mass aqueous solution of the raw material monomer.
To this homogeneous aqueous solution, 16 g (0.08 mol) of (b) diamine: C12DA was added.
The aqueous solution of the raw material monomer thus obtained was charged into an autoclave with an internal volume of 5.4 L (manufactured by Nitto Koatsu) and 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 autoclave tank reached about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank was expressed as 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.).
Heating was continued until the final temperature reached −50 ° C. while removing water out of the system in order to keep the pressure in the tank at about 30 kg / cm ² . After the liquid temperature rises to a final temperature of −40 ° C. (here, 310 ° C., the final temperature is listed in Table 1), the pressure in the tank becomes atmospheric pressure (gauge pressure is 0 kg / cm ² ) while continuing heating. The pressure was lowered while taking about 90 minutes.
Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) (in the table, “the final temperature of the liquid temperature at the time of melt polymerization”, the same shall apply hereinafter) was about 350 ° C. With the resin temperature kept in this state, the inside of the tank was maintained for 30 minutes under a reduced pressure of 400 torr with a vacuum apparatus.
Thereafter, it 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 polyamide.
The polyamide thus obtained was dried in a nitrogen stream and the moisture content was adjusted to about 0.2% by mass, and then the above measurements (1) to (5) were performed on the polyamide.
The measurement results are shown in Table 1 below.

(Production Examples 2 to 9, Comparative Production Example 3)
(A) Dicarboxylic acid, (b) diamine, (c) Lactam and / or aminocarboxylic acid, and terminal blocker are used according to the compounds and amounts shown in Table 1 below, and the final resin temperature is shown in Table 1 below. Temperature.
For other conditions, the polyamide was polymerized by the same method as in Production Example 1 (“hot melt polymerization method”).
The polyamide thus obtained was dried in a nitrogen stream, and the moisture content was adjusted to about 0.2% by mass. With respect to this polyamide, the above measurements (1) to (5) were performed.
The measurement results are shown in Table 1 below.

(Comparative Production Example 1)
(A) Dicarboxylic acid and (b) diamine were used according to the compounds and amounts shown in Table 1 below, and the final resin temperature was set to the temperature shown in Table 1 below.
Although 1500 g of distilled water was added but did not dissolve at 25 ° C., it was placed in an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L as an equimolar 50 mass% heterogeneous slurry water of the raw material monomer (nonuniform) The slurry was replaced with nitrogen to initiate the polymerization.
In other conditions, polyamide was polymerized by the same method as in Production Example 1.
The polyamide thus obtained was dried in a nitrogen stream, and the moisture content was adjusted to about 0.2% by mass. With respect to this polyamide, the above measurements (1) to (5) were performed.
The measurement results are shown in Table 1 below.

(Comparative Production Example 2)
Polyamide 9T (hereinafter abbreviated as “PA9T”) was produced with reference to the method described in Example 1 of JP-A-7-228689.
At that time, the terephthalic acid unit was a dicarboxylic acid unit.
On the other hand, 1,9-nonamethylenediamine unit and 2-methyloctamethylenediamine unit [1,9-nonamethylenediamine unit: 2-methyloctamethylenediamine unit = 80: 20 (molar ratio)] were used as diamine units.
The raw materials described in Table 1 below and 1500 g of distilled water were placed in an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L (non-uniform slurry state) and replaced 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 that time, the autoclave was pressurized 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 kept constant at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and maintaining 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.
This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was subjected to solid phase polymerization at 230 ° C. and 0.1 mmHg for 10 hours to obtain PA9T.
With respect to this polyamide, the above measurements (1) to (5) were performed.
The measurement results are shown in Table 1 below.

[Polyamide composition]
(Examples 1-3, Comparative Examples 1-3)
The polyamide produced according to the above production example or comparative production example was dried in a nitrogen stream to prepare a moisture content of about 0.2% by mass.
L / D (extruder cylinder length / extruder cylinder diameter) having an upstream supply port in the first barrel from the upstream side of the extruder and a downstream supply port in the ninth barrel = (A) Melting point Tm2 + 20 ° C. of polyamide (A) produced from the upstream supply port to the die in a production example using a 48 (barrel number: 12) twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)]. And at a screw rotation speed of 250 rpm and a discharge rate of 25 kg / h, polyamide, titanium oxide, crystal nucleating agent, amine light stabilizer, phenol heat A stabilizer and a phosphorus compound were dry-blended and then supplied and melt-kneaded, and then glass fibers were supplied from the downstream supply port and melt-kneaded to prepare polyamide composition pellets.
The obtained polyamide composition was dried in a nitrogen stream to reduce the water content to 500 ppm or less, and then molded and subjected to various evaluations.
The physical property values are shown in Table 2 below together with the composition.

From the results shown in Table 2 above, polyamides, titanium oxides, and inorganics obtained by polymerizing dicarboxylic acids containing at least 70 mol% of alicyclic dicarboxylic acids and diamines containing linear diamines having a main chain of more than 50 mol%. It was confirmed that a composition containing a filler and having a mass ratio of titanium oxide / inorganic filler ≧ 0.5 has a large bending deflection of the molded body and excellent toughness, and has a long spiral flow length and excellent fluidity.
Moreover, since the whiteness of the molded body and the whiteness after the heat treatment were high, it was confirmed that the thermal stability of the color tone was excellent and there were few foreign matters during extrusion. Furthermore, it confirmed that it was excellent also in the reflow resistance of a molded object.

(Examples 4 to 10, Comparative Examples 4 to 6)
Polyamide, titanium oxide, a crystal nucleating agent, an amine light stabilizer, a phenol heat stabilizer, and a phosphorus compound were supplied from the upstream supply port after dry blending so as to have the ratio shown in Table 3 below.
Other conditions were the same as in Example 1 to produce polyamide composition pellets.
The obtained polyamide composition was dried in a nitrogen stream to reduce the water content to 500 ppm or less, and then molded and subjected to various evaluations.
The physical property values are shown in Table 3 below together with the composition.

  From the results of Table 3 above, by using a polyamide obtained by polymerizing a dicarboxylic acid containing at least 70 mol% of an alicyclic dicarboxylic acid and a diamine containing a linear diamine having a main chain of more than 50 mol%, the structure is Similarly, it was confirmed that the polyamide composition was excellent in fluidity and extrusion processability, and the molded body was excellent in toughness and reflow resistance even in different cases.

(Examples 11 and 12)
The polyamide produced according to the above-described production example was dried in a nitrogen stream to prepare a moisture content of about 0.2% by mass.
L / D (of the extruder) having 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. Production example from upstream feed port to die using twin screw extruder [ZSK-26MC: Coperion (Germany)] with cylinder length / cylinder diameter of extruder = 48 (number of barrels: 12) (A) The melting point Tm2 + 20 ° C. of the polyamide produced by the process is set at a screw rotation speed of 250 rpm and a discharge amount of 25 kg / h. A nucleating agent, an amine-based light stabilizer, a phenol-based heat stabilizer, and a phosphorus compound are dry-blended and then supplied and melt-kneaded. Then, glass fibers are supplied from the second downstream supply port and melt-kneaded to obtain a polyamide composition. Food The Tsu door was fabricated.
The obtained polyamide composition was dried in a nitrogen stream to reduce the water content to 500 ppm or less, and then molded and subjected to various evaluations.
The physical property values are shown in Table 4 below together with the composition.

(Examples 13 and 14)
The polyamide produced according to the production example described above was dried in a nitrogen stream and the moisture content was adjusted to about 0.2% by mass and used.
L / D (of the extruder) having 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. Production example from upstream feed port to die using twin screw extruder [ZSK-26MC: Coperion (Germany)] with cylinder length / cylinder diameter of extruder = 48 (number of barrels: 12) (A) The melting point Tm2 + 20 ° C. of the polyamide produced in (1) was set at a screw rotation speed of 250 rpm and a discharge amount of 25 kg / h, and the polyamide, crystal nucleating agent, Amine-based light stabilizer, phenol-based heat stabilizer, and phosphorus compound are dry blended and then supplied and melt-kneaded, then titanium oxide is supplied from the downstream first supply port, melt-kneaded, and further downstream second supply port More glass fiber And melt-kneaded by supplying, to prepare a polyamide composition pellets.
The obtained polyamide composition was dried in a nitrogen stream to reduce the water content to 500 ppm or less, and then molded and subjected to various evaluations.
The physical property values are shown in Table 4 below together with the composition.

From the results of Table 4 above, when the type of titanium oxide is changed, and when the kneading method of the polyamide composition is changed, the polyamide composition is excellent in fluidity and extrudability, and the molded body is tough. It was confirmed that it was excellent in reflow resistance.
In particular, the loss on ignition of titanium oxide is in a specific range. Titanium oxide is supplied and kneaded in a melted state of polyamide, and further, glass fiber is supplied and melt kneaded. It was confirmed that the polyamide composition was excellent in extrusion processability.

(Examples 15 to 17, Reference Example 18, Example 19, Reference Example 20)
The polyamide produced according to the above production example was dried in a nitrogen stream, and the moisture content was adjusted to about 0.2% by mass and used.
L / D (of the extruder) having 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. Cylinder length /
Using the twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] with a cylinder diameter of the extruder = 48 (the number of barrels: 12), the production from the upstream supply port to the die was manufactured in the manufacturing example (
A) Polyamide, crystal nucleating agent, amine light stabilizer from the upstream supply port so that the melting point Tm2 + 20 ° C. of the polyamide is set, the screw rotation speed is 250 rpm, the discharge rate is 25 kg / h, and the ratio shown in Table 4 is obtained. Phenol heat stabilizer and phosphorus compound are dry-blended and then supplied and melt-kneaded, then titanium oxide is supplied from the downstream first supply port, melt-kneaded, and wollastonite is supplied from the downstream second supply port Then, it was melt-kneaded to produce polyamide composition pellets.
After drying the obtained polyamide composition in a nitrogen stream to reduce the moisture to 500 ppm or less,
Molded and subjected to various evaluations.
The physical property values are shown in Table 5 below together with the composition.

From the results shown in Table 5 above, it was confirmed that when a polyamide having a terminal blocking ratio of 10% or more was used, the polyamide composition was excellent in fluidity and a molded article having excellent color thermal stability.
Moreover, it confirmed that the molded object of the polyamide composition was excellent in reflow resistance by using a crystal nucleating agent.

  The polyamide composition of the present invention has industrial applicability as a molding material for various parts such as automobiles, electric and electronic, industrial materials, industrial materials, daily products and household products.

Claims (15)

(A): (a) a dicarboxylic acid containing at least 70 mol% of an alicyclic dicarboxylic acid;
(B) a diamine containing more than 50 mol% of a linear diamine having a main chain;
A polymerized polyamide,
(B): titanium oxide;
(C) an inorganic filler (excluding talc) ;
(D) at least one crystal nucleating agent selected talc, and boron nitride hydride et al,
Containing,
The content of the (B) titanium oxide is 10% by mass or more, and the mass ratio between the (B) titanium oxide and the (C) inorganic filler is (B) / (C) ≧ 0.5. The polyamide composition in which the content of the crystal nucleating agent (D) is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyamide (A).   The polyamide composition according to claim 1, wherein the (A) polyamide is polymerized by adding an end-capping agent, and the end-capping rate of the (A) polyamide by the end-capping agent is 10% or more. . The polyamide composition according to claim 1 or 2 , wherein the (D) crystal nucleating agent is talc. The polyamide composition according to any one of claims 1 to 3 , wherein a total content of the (B) titanium oxide and the (C) inorganic filler is 35 to 70 mass%. The polyamide composition according to any one of claims 1 to 4 , wherein the (a) alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid. The (b) diamine having a linear main chain is a diamine having 7 to 13 carbon atoms.
The polyamide composition according to any one of 5 . The end-capping agent for the polyamide (A) is at least one selected from the group consisting of aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, aliphatic monoamines, and alicyclic monoamines. The polyamide composition according to any one of 6 . The polyamide composition according to any one of claims 1 to 7 , wherein a ratio of the trans isomer of the alicyclic dicarboxylic acid structure in the polyamide (A) is 50 to 85 mol%. The (B) titanium oxide is
The polyamide composition according to any one of claims 1 to 8 , which has a number average particle diameter (by an electron micrograph) of 0.1 to 0.8 µm. The (B) titanium oxide is inorganic and / or organic coated.
The polyamide composition according to any one of claims 1 to 9 . The ignition loss of titanium oxide (B) (reduction when heated at 650 ° C. for 2 hours) is 0.7 to 2.5.
The polyamide composition according to any one of claims 1 to 10 , wherein the polyamide composition is in mass%. (C) At least one of the inorganic fillers is a fibrous filler and / or an acicular filler,
The polyamide composition according to any one of claims 1 to 11 . Glass fiber is included as the (C) inorganic filler, and the (C) in the polyamide composition
13 ) The polyamide composition according to any one of claims 1 to 12 , wherein the fiber length (weight average length) of the glass fiber is 250 to 500 µm. After melt kneading the (A) polyamide and the (B) titanium oxide,
The polyamide composition according to any one of claims 1 to 13 , which is obtained by further kneading the (C) inorganic filler. The molded object shape | molded using the polyamide composition as described in any one of the said Claims 1 thru | or 14 .