JP2020029538A - Polyamide composition - Google Patents

Abstract

To provide a polyamide composition having more excellent various physical properties including chemical resistance and high-temperature heat resistance.SOLUTION: There is provided a polyamide composition which comprises a polyamide (A) having a dicarboxylic acid unit and a diamine unit, a copper compound (B1) and a metal halide (B2), wherein more than 40 mol% and 100 mol% or less of the dicarboxylic acid unit is a naphthalenedicarboxylic acid unit, 60 mol% or more and 100 mol% or less of the diamine unit is a branched aliphatic diamine unit and a linear aliphatic diamine unit of an optional constitutional unit and the ratio of the branched aliphatic diamine unit to 100 mol% in total of the branched aliphatic diamine unit and the linear aliphatic diamine unit is 60 mol% or more.SELECTED DRAWING: None

Description

  The present invention relates to a polyamide composition and the like. More specifically, the present invention relates to a semi-aromatic polyamide having a dicarboxylic acid unit mainly composed of a naphthalenedicarboxylic acid unit and a diamine unit mainly composed of an aliphatic diamine unit, a polyamide composition containing a copper compound and a metal halide, and the like.

  Semi-aromatic polyamides using aromatic dicarboxylic acids such as terephthalic acid and aliphatic diamines, and crystalline polyamides such as nylon 6, nylon 66, etc., are suitable for clothing due to their excellent properties and ease of melt molding. Widely used as fibers for industrial and industrial materials and general-purpose engineering plastics. On the other hand, these crystalline polyamides have also been pointed out with problems such as insufficient heat resistance and poor dimensional stability due to water absorption. In particular, in recent years, resinization of engine room components has been actively studied for the purpose of improving fuel efficiency of automobiles, and is superior to conventional polyamides in high-temperature strength, heat resistance, dimensional stability, mechanical properties, and physical and chemical properties. Polyamides are desired.

  As a polyamide having excellent heat resistance, for example, Patent Document 1 discloses a semi-aromatic polyamide obtained from 2,6-naphthalenedicarboxylic acid and a linear aliphatic diamine having 9 to 13 carbon atoms. Patent Document 1 describes that the semi-aromatic polyamide is excellent not only in heat resistance but also in chemical resistance and mechanical properties. On the other hand, Patent Literature 1 describes that use of an aliphatic diamine having a side chain is not preferable because crystallinity of the obtained polyamide is reduced.

Patent Document 2 discloses that 60 to 100 mol% of dicarboxylic acid units are composed of 2,6-naphthalenedicarboxylic acid units, and 60 to 100 mol% of diamine units are 1,9-nonanediamine units and 2-methyl-1,8. A polyamide comprising -octanediamine units and having a molar ratio of 1,9-nonanediamine units to 2-methyl-1,8-octanediamine units of 60:40 to 99: 1 is disclosed. Patent Document 2 describes that the polyamide is excellent in mechanical properties, thermal decomposition resistance, low water absorption, chemical resistance, and the like, in addition to heat resistance.
Furthermore, a resin composition containing a semi-aromatic polyamide and uses of the semi-aromatic polyamide are disclosed (for example, Patent Documents 3 and 4).

JP-A-50-67393 JP-A-9-12715 International Publication No. 2012/098840 International Publication No. 2005/102681

As described above, conventional polyamides such as Patent Documents 1 and 2 have physical properties such as heat resistance, mechanical properties, low water absorption, and chemical resistance, and further improvement in these physical properties is required.
Patent Literature 2 describes that 1,9-nonanediamine and 2-methyl-1,8-octanediamine are used in combination as aliphatic diamines. However, 2-methyl-1,8-octanediamine having a side chain is described. No mention is made of polyamides in the high ratio region.

  Therefore, an object of the present invention is to provide a polyamide composition which is excellent in various physical properties including chemical resistance and high-temperature heat resistance, and a molded article comprising the same.

The present inventors have conducted intensive studies and as a result, a specific polyamide having a dicarboxylic acid unit mainly composed of a naphthalenedicarboxylic acid unit and a diamine unit mainly composed of a branched aliphatic diamine unit, a copper compound, and a metal halide. The present inventors have found that a polyamide composition containing the same can solve the above problems, and have further studied based on the findings to complete the present invention.
That is, the present invention is as follows.

[1] A polyamide (A) having a dicarboxylic acid unit and a diamine unit, a copper compound (B1) and a metal halide (B2),
Naphthalenedicarboxylic acid units account for more than 40 mol% and 100 mol% or less of the dicarboxylic acid units,
60 mol% or more and 100 mol% or less of the diamine unit are a branched aliphatic diamine unit and a linear aliphatic diamine unit of an optional constitutional unit, and the branched aliphatic diamine unit and the linear aliphatic diamine A polyamide composition, wherein the proportion of the branched aliphatic diamine unit to the total 100 mol% of the units is 60 mol% or more.
[2] A molded article comprising the polyamide composition.

  ADVANTAGE OF THE INVENTION According to this invention, the polyamide composition excellent in various physical properties including chemical resistance and high temperature heat resistance, and the molded article which consists of this can be provided.

For polyamides in which the dicarboxylic acid unit is a 2,6-naphthalenedicarboxylic acid unit and the diamine unit is a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit, the 2-methyl- It is the graph which plotted the melting point (degreeC) of polyamide with respect to the content rate (mol%) of a 1,8-octanediamine unit.

  Hereinafter, the present invention will be described in detail. In the present specification, a rule that is preferable can be arbitrarily adopted, and a combination of preferable ones is more preferable. In this specification, the description “XX to YY” means “XX or more and YY or less”.

<Polyamide composition>
The polyamide composition of the present invention contains a polyamide (A) having a dicarboxylic acid unit and a diamine unit, a copper compound (B1) and a metal halide (B2).
In the present specification, “to unit” (where “to” indicates a monomer) means “constituent unit derived from”, and for example, “dicarboxylic acid unit” refers to “derived from dicarboxylic acid”. "Structural unit" means, and "diamine unit" means "structural unit derived from diamine".

[Polyamide (A)]
The polyamide (A) contained in the polyamide composition of the present invention has a dicarboxylic acid unit and a diamine unit. And, more than 40 mol% and 100 mol% or less of the dicarboxylic acid units are naphthalenedicarboxylic acid units. Further, 60 mol% or more and 100 mol% or less of the diamine unit are a branched aliphatic diamine unit and a linear aliphatic diamine unit of an optional constitutional unit, and the branched aliphatic diamine unit and the linear aliphatic diamine The proportion of the branched aliphatic diamine unit to the total of 100 mol% with the aliphatic diamine unit is 60 mol% or more.

  As described above, the polyamide (A) has a dicarboxylic acid unit mainly composed of a naphthalenedicarboxylic acid unit and a diamine unit mainly composed of a branched aliphatic diamine unit, and thus has various chemical resistance and other properties. The polyamide composition of the present invention containing the polyamide (A), the copper compound, and the metal halide is excellent in physical properties, and the above-mentioned excellent properties are maintained, and additionally, excellent high-temperature heat resistance is exhibited. In addition, various molded articles obtained from the polyamide composition can maintain excellent properties of the polyamide composition.

Generally, physical properties such as high-temperature strength, mechanical properties, heat resistance, low water absorption, and chemical resistance that a polyamide can have tend to be superior as the crystallinity of the polyamide increases. Further, between polyamides having similar primary structures, the melting point of the polyamide tends to increase as the crystallinity of the polyamide increases. Here, regarding the melting point of the polyamide, for example, a polyamide in which the diamine unit is a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit and the dicarboxylic acid unit is a terephthalic acid unit is taken as an example. And a graph showing the relationship between the melting point of the polyamide (vertical axis) and the composition of diamine units (content ratio of 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit) (horizontal axis). Indicates a minimal part. Then, the melting points at both ends on the horizontal axis of the graph, that is, the melting point A1 when the 1,9-nonanediamine unit having a linear structure is 100 mol%, and 100 mol of 2-methyl-1,8-octanediamine unit having a branched structure. %, The melting point A1 is usually higher than the melting point B1 depending on the molecular structure of the diamine unit.
On the other hand, in the case of a polyamide in which the diamine unit is a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit and the dicarboxylic acid unit is a 2,6-naphthalenedicarboxylic acid unit, While a minimal portion is shown in a graph having the same vertical axis and horizontal axis as the above, the melting point A2 when 1,9-nonanediamine unit having a linear structure is 100 mol%, and 2-methyl-1 having a branched structure are shown. In comparison with the melting point B2 when the octanediamine unit was 100 mol%, it was found that the melting point B2 was unexpectedly higher than the melting point A2.

Specifically, for a polyamide in which the dicarboxylic acid unit is a 2,6-naphthalenedicarboxylic acid unit and the diamine unit is a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit, FIG. 1 shows a graph in which the melting point (° C.) of the polyamide is plotted against the content ratio (mol%) of the 2-methyl-1,8-octanediamine unit.
According to FIG. 1, 2-methyl-1,8-octanediamine unit is 0 mol% (that is, 1,9-nonanediamine unit is 100 mol%). -It can be seen that the melting point of the polyamide decreases as the content ratio of the octanediamine unit increases. On the other hand, from the vicinity where the content of the 2-methyl-1,8-octanediamine unit exceeds 50 mol%, it can be seen that the melting point of the polyamide significantly increases as the content increases. Comparing the melting points near both ends on the horizontal axis in FIG. 1, the melting point when the content of the 2-methyl-1,8-octanediamine unit in the branched structure is around 100 mol% is more linear. It can be seen that the melting point is higher than the melting point when the content of 1,9-nonanediamine units in the structure is 100 mol%. The melting points in the left and right regions of the portion other than the vicinity of both ends on the horizontal axis are also compared with the vicinity of the vicinity where the content ratio of 2-methyl-1,8-octanediamine unit is 50 mol%. It can be seen that the melting point tends to be higher in the right region where the content of -1,8-octanediamine unit is high than in the left region where the content of 1,9-nonanediamine unit is high.

  As described above, it has been found that the polyamide having a diamine unit mainly composed of 1,9-nonanediamine unit and / or 2-methyl-1,8-octanediamine unit has different physical properties depending on the dicarboxylic acid unit to be combined. . As a result of further study by the present inventors, when the content ratio of the branched aliphatic diamine unit is larger than that of the linear aliphatic diamine unit, by adopting a naphthalenedicarboxylic acid unit as a dicarboxylic acid unit, the resistance to naphthalene dicarboxylic acid is improved. It has been found that various physical properties including chemical properties and high-temperature heat resistance are further improved. The reason for this is not necessarily clear, but it is presumed that the appropriate proportion of the branched structure in the diamine unit in the polyamide and the presence of the naphthalene skeleton in the dicarboxylic unit are interrelated.

(Dicarboxylic acid unit)
Of the dicarboxylic acid units, more than 40 mol% and not more than 100 mol% are naphthalenedicarboxylic acid units. When the content of the naphthalenedicarboxylic acid unit in the dicarboxylic acid unit is 40 mol% or less, it becomes difficult to exhibit various physical property improving effects such as chemical resistance and high-temperature heat resistance of the polyamide composition.
From the viewpoints of mechanical properties, heat resistance, and chemical resistance, the content of the naphthalenedicarboxylic acid unit in the dicarboxylic acid unit is preferably 50 mol% or more, more preferably 60 mol% or more, and 70 mol% or more. More preferably, it is at least 80 mol%, even more preferably at least 80 mol%, even more preferably at least 90 mol%, particularly preferably at least 100 mol%.

Examples of the naphthalenedicarboxylic acid unit include 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, And structural units derived from naphthalenedicarboxylic acids such as 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. Can be These structural units may include only one type, or may include two or more types. Among the above naphthalenedicarboxylic acids, 2,6-naphthalenedicarboxylic acid is preferred from the viewpoints of the development of various physical properties such as the chemical resistance and high-temperature heat resistance of the polyamide composition and the reactivity with the diamine.
From the same viewpoint as described above, the content of the structural unit derived from 2,6-naphthalenedicarboxylic acid in the naphthalenedicarboxylic acid unit is preferably 90 mol% or more, more preferably 95 mol% or more. , And 100 mol% (substantially 100 mol%).

The dicarboxylic acid unit can include a structural unit derived from a dicarboxylic acid other than naphthalenedicarboxylic acid, as long as the effects of the present invention are not impaired.
Examples of the other dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, dimethylmalonic acid, and dimethylmalonic acid. Aliphatic dicarboxylic acids such as 1,2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid and trimethyladipic acid; 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, cyclooctanedicarboxylic acid and cyclodecanedicarboxylic acid; terephthalic acid, isophthalic acid, diphenic acid, 4,4′-biphenyldicarboxylic acid, diphenylmethane-4, 4'-dicarboxylic acid, diphenylsul And aromatic dicarboxylic acids such as down-4,4'-dicarboxylic acid. One of these structural units derived from other dicarboxylic acids may be contained, or two or more of them may be contained.
The content of the structural unit derived from the other dicarboxylic acid in the dicarboxylic acid unit is preferably 50 mol% or less, more preferably 40 mol% or less, and still more preferably 30 mol% or less. , 20 mol% or less, even more preferably 10 mol% or less.

(Diamine unit)
As for the diamine unit, 60 mol% or more and 100 mol% or less are a branched aliphatic diamine unit and a linear aliphatic diamine unit of an optional constitutional unit. That is, the diamine unit contains a branched aliphatic diamine unit and does not contain a linear aliphatic diamine unit, or contains both a branched aliphatic diamine unit and a linear aliphatic diamine unit, and The total content of the branched aliphatic diamine unit and the linear aliphatic diamine unit as an optional constituent unit is 60 mol% or more and 100 mol% or less. When the total content of the branched aliphatic diamine unit and the linear aliphatic diamine unit in the diamine unit is less than 60 mol%, the effect of improving various physical properties such as chemical resistance and high temperature heat resistance of the polyamide composition is obtained. It is difficult to express.
From the viewpoints of chemical resistance, mechanical properties, and heat resistance, the total content of the branched aliphatic diamine unit and the linear aliphatic diamine unit in the diamine unit is preferably 70 mol% or more, and is preferably 80 mol% or more. %, More preferably 90 mol% or more, and particularly preferably 100 mol%.
In the present specification, the term "branched aliphatic diamine" refers to a linear aliphatic chain having a carbon atom to which two amino groups are bonded, each having a carbon atom at both ends. Means an aliphatic diamine having a structure in which one or more hydrogen atoms of an aliphatic chain (assumed aliphatic chain) are substituted by a branched chain. That is, for example, 1,2-propanediamine _{(H 2 N-CH (CH} 3) -CH 2 -NH 2) as one of branched-chain hydrogen atom of 1,2-ethylene group as contemplated aliphatic chain Is classified as a branched aliphatic diamine in this specification.

In the diamine unit, the ratio of the branched aliphatic diamine unit to the total of 100 mol% of the branched aliphatic diamine unit and the linear aliphatic diamine unit is 60 mol% or more. When the proportion of the branched aliphatic diamine unit is less than 60 mol%, it is difficult to exhibit various physical property improving effects such as chemical resistance and high temperature heat resistance of the polyamide composition.
From the viewpoint that various physical properties including chemical resistance and high temperature heat resistance are easily improved and the moldability of the polyamide composition is improved, the total of the branched aliphatic diamine unit and the linear aliphatic diamine unit is 100 in total. The ratio of the branched aliphatic diamine unit to the mol% is preferably 65 mol% or more, more preferably 70 mol% or more, further preferably 72 mol% or more, and more preferably 77 mol% or more. More preferably, it is even more preferably 80 mol% or more, and may be 90 mol% or more. The ratio may be 100 mol%, but in consideration of moldability, availability of diamine, and the like, it is preferably 99 mol% or less, 98 mol% or less, and even 95 mol% or less. Good.

  The carbon number of the branched aliphatic diamine unit is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, and preferably 18 or less, and 12 or less. Is more preferable. When the number of carbon atoms in the branched aliphatic diamine unit is within the above range, the polymerization reaction between the dicarboxylic acid and the diamine proceeds favorably, the crystallinity of the polyamide (A) also improves, and the polyamide composition containing the polyamide (A) The physical properties of the object are more easily improved. As an example of a preferred embodiment of the number of carbon atoms of the branched aliphatic diamine unit, the number of carbon atoms may be 4 to 18 or less, 4 to 12 or less, 6 to 18 or less, 6 to 12 or less, or 8 to 18 or less. , 8 or more and 12 or less.

The type of the branched chain in the branched aliphatic diamine unit is not particularly limited, and may be, for example, various aliphatic groups such as a methyl group, an ethyl group, and a propyl group. It is preferably a structural unit derived from a diamine having at least one selected from the group consisting of a methyl group and an ethyl group as a chain. When a diamine having at least one selected from the group consisting of a methyl group and an ethyl group is used as a branched chain, the polymerization reaction between the dicarboxylic acid and the diamine proceeds well, and the chemical resistance of the polyamide composition containing the polyamide (A) is improved. The property is easier to improve. From this viewpoint, the branched chain is more preferably a methyl group.
The number of the branched chains of the branched aliphatic diamine forming the branched aliphatic diamine unit is not particularly limited, but is preferably three or less because the effects of the present invention are more remarkably exhibited. , More preferably two or less, and even more preferably one.

  When the carbon atom to which any one of the amino groups is bonded is placed at position 1, the branched aliphatic diamine unit has a 2-position carbon atom adjacent thereto (a carbon atom on the assumed aliphatic chain) and the 2-position carbon atom. Is preferably a structural unit derived from a diamine having at least one of the branched chains on at least one of the carbon atoms at the 3-position adjacent to the carbon atom (the carbon atom on the assumed aliphatic chain). More preferably, it is a structural unit derived from a diamine having at least one of the branched chains at the carbon atom. Thereby, various physical properties including the chemical resistance and the high-temperature heat resistance of the polyamide composition are more likely to be improved.

Examples of the branched aliphatic diamine unit include 1,2-propanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, and 1-ethyl-1,4-diamine. Butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2-methyl-1,3- Propanediamine, 2-methyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2 , 5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2,2-dimethyl-1,6-hexane Amine, 2,4-diethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-ethyl-1 , 7-Heptanediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8 -Octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl-1 , 8-Octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, 5-methyl 1,9 structural units derived from branched aliphatic diamines, and the like. These structural units may be included alone or in combination of two or more.
Among the branched aliphatic diamine units, 2-methyl-1,5-pentanediamine, 3-methyl-1,2-methyl-1,5-pentanediamine is preferred from the viewpoints that the effects of the present invention are more remarkably exhibited and the raw material availability is excellent. Structural units derived from at least one diamine selected from the group consisting of 5-pentanediamine, 2-methyl-1,8-octanediamine and 2-methyl-1,9-nonanediamine are preferred, and 2-methyl-1 Structural units derived from 8,8-octanediamine are more preferred.

The carbon number of the linear aliphatic diamine unit is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, and preferably 18 or less, and 12 or less. More preferably, there is. When the number of carbon atoms in the linear aliphatic diamine unit is within the above range, the polymerization reaction between the dicarboxylic acid and the diamine proceeds well, the crystallinity of the polyamide becomes good, and the physical properties of the polyamide are easily improved. As an example of a preferred embodiment of the number of carbon atoms of the linear aliphatic diamine unit, the number of carbon atoms may be 4 to 18 or less, 4 to 12 or less, 6 to 18 or less, 6 to 12 or less, or 8 to 18 or less. It may be 8 or more and 12 or less.
The carbon numbers of the linear aliphatic diamine unit and the branched aliphatic diamine unit may be the same or different, but are the same because the effects of the present invention are more remarkably exhibited. Is preferred.

Examples of the linear aliphatic diamine unit include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1, Structural units derived from linear aliphatic diamines such as 15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, and 1,18-octadecanediamine. These structural units may be included alone or in combination of two or more.
Among the above-mentioned linear aliphatic diamine units, the effects of the present invention are more remarkably exhibited, and from the viewpoint of improving the heat resistance of the obtained polyamide composition containing polyamide (A), 1,4-butane is particularly preferred. Diamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, And a structural unit derived from at least one diamine selected from the group consisting of 1,12-dodecanediamine, and a structural unit derived from 1,9-nonanediamine is more preferable.

The diamine unit may include a structural unit derived from a diamine other than the branched aliphatic diamine and the linear aliphatic diamine as long as the effects of the present invention are not impaired. Examples of the other diamine include an alicyclic diamine and an aromatic diamine.
Examples of the alicyclic diamine include cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, norbornanedimethylamine, and tricyclodecanedimethyldiamine.
As the aromatic diamine, for example, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4 '-Diaminodiphenyl ether and the like.
One of these structural units derived from other diamines may be contained, or two or more of them may be contained.
The content of the structural unit derived from the other diamine in the diamine unit is preferably at most 30 mol%, more preferably at most 20 mol%, further preferably at most 10 mol%.

(Dicarboxylic acid unit and diamine unit)
The molar ratio of dicarboxylic acid units to diamine units [dicarboxylic acid units / diamine units] in the polyamide (A) is preferably 45/55 to 55/45. When the molar ratio of the dicarboxylic acid unit to the diamine unit is in the above range, the polymerization reaction proceeds favorably, and a polyamide composition excellent in desired physical properties is easily obtained.
The molar ratio between the dicarboxylic acid unit and the diamine unit can be adjusted according to the mixing ratio (molar ratio) of the raw material dicarboxylic acid and the raw material diamine.

  The total ratio of dicarboxylic acid units and diamine units in the polyamide (A) (the ratio of the total number of moles of dicarboxylic acid units and diamine units to the number of moles of all the constituent units constituting the polyamide (A)) is 70 mol% or more. It is preferably at least 80 mol%, more preferably at least 90 mol%, even more preferably at least 95 mol%, and even more preferably at least 100 mol%. When the total ratio of the dicarboxylic acid unit and the diamine unit is in the above range, a polyamide composition having more desirable physical properties can be obtained.

(Aminocarboxylic acid unit)
The polyamide (A) may further include an aminocarboxylic acid unit in addition to the dicarboxylic acid unit and the diamine unit.
Examples of the aminocarboxylic acid unit include lactams such as caprolactam and lauryl lactam; and structural units derived from aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid. The content of the aminocarboxylic acid unit in the polyamide (A) is preferably 40 mol% or less, more preferably 20 mol% or less, based on 100 mol% in total of the dicarboxylic acid unit and the diamine unit constituting the polyamide (A). Is more preferable.

(Polyvalent carboxylic acid unit)
In the polyamide (A), a range in which a structural unit derived from a trivalent or higher polycarboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid can be melt-molded within a range that does not impair the effects of the present invention. Can also be included.

(Terminal sealant unit)
The polyamide (A) may contain a structural unit derived from a terminal blocking agent (terminal blocking unit).
The terminal blocking agent unit is preferably at least 1.0 mol%, more preferably at least 1.2 mol%, and preferably at least 1.5 mol%, based on 100 mol% of the diamine unit. Is more preferably 10 mol% or less, more preferably 7.5 mol% or less, and even more preferably 6.5 mol% or less. When the content of the terminal blocking agent unit is in the above range, a polyamide composition having excellent mechanical strength and fluidity is obtained. The content of the terminal capping agent unit can be adjusted to the above-mentioned desired range by appropriately adjusting the amount of the terminal capping agent at the time of charging the polymerization raw material. In consideration of the volatilization of the monomer component during the polymerization, fine adjustment of the charged amount of the terminal blocking agent is performed so that a desired amount of the terminal blocking agent unit is introduced into the obtained polyamide (A). Is desirable.
As a method for obtaining the content of the terminal blocking agent unit in the polyamide (A), for example, as described in JP-A-7-228690, the solution viscosity is measured, and the viscosity of the solution is compared with the number average molecular weight. A method of calculating the total terminal group amount from the relational expression and subtracting the amino group amount and the carboxyl group amount determined by titration from this, or using ¹ H-NMR, the signal corresponding to each of the diamine unit and the terminal blocking agent unit And the like, and the latter is preferable.

  As the terminal blocking agent, a monofunctional compound having reactivity with a terminal amino group or a terminal carboxyl group can be used. Specific examples include monocarboxylic acids, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and monoamines. From the viewpoints of reactivity and the stability of the capped end, a terminal capping agent for a terminal amino group is preferably a monocarboxylic acid, and a terminal capping agent for a terminal carboxyl group is preferably a monoamine. From the viewpoint of ease of handling and the like, a monocarboxylic acid is more preferable as the terminal blocking agent.

  The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group, and for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid Aliphatic monocarboxylic acids such as acids, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid; cycloaliphatic monocarboxylic acids such as cyclopentanecarboxylic acid and cyclohexanecarboxylic acid; benzoic acid, toluic acid, Aromatic monocarboxylic acids such as α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid; and arbitrary mixtures thereof. Among them, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid are preferred from the viewpoints of reactivity, sealed terminal stability, and price. And at least one selected from the group consisting of benzoic acid and benzoic acid.

  The monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearyl Aliphatic monoamines such as amine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; arbitrary mixtures thereof; Can be mentioned. Among these, at least one selected from the group consisting of butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline from the viewpoints of reactivity, high boiling point, stability of a sealed terminal, and price. Is preferred.

The polyamide (A) has an intrinsic viscosity [η _inh ] measured at a concentration of 0.2 g / dl and a temperature of 30 ° C. of 0.1 dl / g or more, preferably 0.4 dl / g or more, using concentrated sulfuric acid as a solvent. Is more preferably 0.6 dl / g or more, particularly preferably 0.8 dl / g or more, and further preferably 3.0 dl / g or less, and 2.0 dl / g or less. / G or less, more preferably 1.8 dl / g or less. When the intrinsic viscosity [η _inh ] of the polyamide (A) is within the above range, various properties such as moldability are further improved. The intrinsic viscosity [η _inh ] is determined based on the flow time t ₀ (second) of the solvent (concentrated sulfuric acid), the flow time t ₁ (second) of the sample solution, and the sample concentration c (g / dl) of the sample solution (that is, 0.2 g). / Dl) can be obtained from the relational expression of η _inh = [ln (t ₁ / t ₀ )] / c.

  The melting point of the polyamide (A) is not particularly limited, and may be, for example, 260 ° C. or higher, 270 ° C. or higher, and further 280 ° C. or higher. However, since the effects of the present invention are more remarkably exhibited, 290 ° C. ° C or higher, more preferably 295 ° C or higher, still more preferably 300 ° C or higher, even more preferably 305 ° C or higher, even more preferably 310 ° C or higher, It may be 315 ° C. or higher. The upper limit of the melting point of the polyamide (A) is not particularly limited, but is preferably 330 ° C. or lower, more preferably 320 ° C. or lower, further preferably 317 ° C. or lower in consideration of moldability and the like. . The melting point of the polyamide (A) can be determined as a peak temperature of a melting peak that appears when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter (DSC). It can be determined by the method described.

  The glass transition temperature of the polyamide (A) is not particularly limited, and may be, for example, 100 ° C. or higher, 110 ° C. or higher, and even 120 ° C. or higher, since the effects of the present invention are more remarkably exhibited. , 125 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 135 ° C. or higher, even more preferably 137 ° C. or higher, even more preferably 138 ° C. or higher. Preferably, it may be 139 ° C. or higher. Although the upper limit of the glass transition temperature of the polyamide (A) is not particularly limited, it is preferably 180 ° C or lower, more preferably 160 ° C or lower, and more preferably 150 ° C or lower in consideration of moldability and the like. More preferred. The glass transition temperature of the polyamide (A) can be determined as a temperature at an inflection point that appears when the temperature is raised at a rate of 20 ° C./min using a differential scanning calorimeter (DSC). It can be determined by the method described in the example.

(Production method of polyamide (A))
The polyamide (A) can be produced by using any method known as a method for producing a crystalline polyamide. For example, a melt polymerization method using a dicarboxylic acid and a diamine as raw materials, a solid phase polymerization method, It can be produced by a method such as an extrusion polymerization method. Among these, the method for producing the polyamide (A) is preferably a solid-phase polymerization method from the viewpoint that thermal degradation during polymerization can be more favorably suppressed.
In order to set the molar ratio between the branched aliphatic diamine unit and the linear aliphatic diamine unit to the above-mentioned specific numerical range, the branched aliphatic diamine and the linear aliphatic diamine used as the raw materials are preferably used. The molar ratio of the above units may be used.
When, for example, 2-methyl-1,8-octanediamine and 1,9-nonanediamine are used as the branched aliphatic diamine and the linear aliphatic diamine, respectively, these can be produced by a known method. Known methods include, for example, a method of distilling a crude diamine reaction solution obtained by performing a reductive amination reaction using dialdehyde as a starting material. Further, 2-methyl-1,8-octanediamine and 1,9-nonanediamine can be obtained by fractionating the diamine crude reaction solution.

  For example, the polyamide (A) is prepared by adding a diamine, a dicarboxylic acid, and, if necessary, a catalyst and an endcapping agent at a time to produce a nylon salt, and then heat-polymerizing at a temperature of 200 to 250 ° C. It can be produced by prepolymerization and then solid phase polymerization or polymerization using a melt extruder. When the final stage of the polymerization is carried out by solid-phase polymerization, it is preferably carried out under reduced pressure or under an inert gas flow.If the polymerization temperature is in the range of 200 to 280 ° C., the polymerization rate is large and the productivity is excellent. Coloring and gelation can be effectively suppressed. The polymerization temperature in the case where the final stage of the polymerization is carried out by a melt extruder is preferably 370 ° C. or lower. When the polymerization is carried out under such conditions, a polyamide which hardly decomposes and has little deterioration is obtained.

Examples of the catalyst that can be used when producing the polyamide (A) include phosphoric acid, phosphorous acid, hypophosphorous acid, and salts or esters thereof. Examples of the above salts or esters include, for example, phosphoric acid, phosphorous acid or hypophosphorous acid, and potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony and the like. Salts with metals; phosphoric acid, ammonium salts of phosphorous or hypophosphorous acid; ethyl, isopropyl, butyl, hexyl, isodecyl, octadecyl esters of phosphoric, phosphorous or hypophosphorous acid , Decyl ester, stearyl ester, phenyl ester and the like.
The amount of the catalyst used is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 1.0% by mass or less based on 100% by mass of the total mass of the raw materials. And more preferably 0.5% by mass or less. If the amount of the catalyst used is equal to or more than the above lower limit, polymerization proceeds favorably. When the content is equal to or less than the upper limit, impurities derived from the catalyst are less likely to be generated. For example, when a polyamide composition is formed into a film, problems due to the impurities can be prevented.

[Copper compound (B1) and metal halide (B2)]
The polyamide composition of the present invention contains a copper compound (B1) and a metal halide (B2), and thereby has excellent mechanical properties such as chemical resistance, low water absorption and tensile properties, and excellent fluidity. A polyamide composition having high-temperature heat resistance, specifically, excellent heat aging resistance and heat resistance at a high temperature of 150 ° C. or higher can be obtained without deteriorating properties. Hereinafter, the copper compound (B1) and the metal halide (B2) will be further described.

・ Copper compound (B1)
Examples of the copper compound (B1) include copper halide, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, copper stearate, ethylenediamine and ethylenediamine. Copper complex salts coordinated with a chelating agent such as tetraacetic acid and the like can be mentioned. Examples of the copper halide include copper iodide; copper bromide such as cuprous bromide and cupric bromide; and copper chloride such as cuprous chloride. Among these copper compounds, at least one selected from the group consisting of copper halides and copper acetate is preferable from the viewpoint of excellent heat aging resistance and suppression of metal corrosion of screws and cylinders during extrusion, At least one selected from the group consisting of copper iodide, copper bromide, copper chloride, and copper acetate is more preferable, and at least one selected from the group consisting of copper iodide, copper bromide, and copper acetate is more preferable. . As the copper compound (B1), one type may be used alone, or two or more types may be used in combination.

  The content of the copper compound (B1) in the polyamide composition of the present invention is preferably 0.01 part by mass or more and 1 part by mass or less, and more preferably 0.02 part by mass or more and 0.1 part by mass or less with respect to 100 parts by mass of the polyamide (A). 5 parts by mass or less is more preferable, and 0.06 parts by mass or more and 0.4 parts by mass or less is further preferable. By controlling the content of the copper compound (B1) within the above range, it is possible to improve the high-temperature heat resistance such as the heat aging resistance while suppressing the decrease in the tensile properties of the obtained polyamide composition, and to further precipitate copper during molding. And metal corrosion can also be suppressed.

.Metal halide (B2)
As the metal halide (B2), a metal halide not corresponding to the copper compound (B1) can be used, and a salt of a metal element belonging to Group 1 or Group 2 of the periodic table with a halogen is preferable. Examples include potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium chloride and the like. Among these, at least one selected from the group consisting of potassium iodide and potassium bromide is preferable from the viewpoint that the obtained polyamide composition is excellent in high-temperature heat resistance such as heat aging resistance and can suppress metal corrosion. Preferably, potassium iodide is more preferable. As the metal halide (B2), one type may be used alone, or two or more types may be used in combination.

  The content of the metal halide (B2) in the polyamide composition of the present invention is preferably from 0.05 to 20 parts by mass, and more preferably from 0.2 to 10 parts by mass, per 100 parts by mass of the polyamide (A). It is more preferably at most 0.5 part by mass, more preferably at most 0.5 part by mass and at most 9 parts by mass. By controlling the content of the metal halide (B2) within the above range, it is possible to improve the high-temperature heat resistance such as the heat aging resistance while suppressing the decrease in the tensile properties of the obtained polyamide composition, and to further improve the copper content during molding. Precipitation and metal corrosion can also be suppressed.

  Regarding the ratio between the copper compound (B1) and the metal halide (B2) in the polyamide composition, the ratio of the total molar amount of halogen to the total molar amount of copper (halogen / copper) is 2/1 to 50/1. It is preferable that the polyamide composition contains a copper compound (B1) and a metal halide (B2). The ratio (halogen / copper) is preferably at least 3/1, more preferably at least 4/1, even more preferably at least 5/1, preferably at most 45/1, more preferably at most 40/1, More preferably, it is 30/1 or less. When the ratio (halogen / copper) is not less than the above lower limit, copper precipitation and metal corrosion during molding can be more effectively suppressed. When the ratio (halogen / copper) is equal to or less than the upper limit, corrosion of screws of a molding machine can be more effectively suppressed without impairing mechanical properties such as tensile properties of the obtained polyamide composition. .

  The copper compound (B1) and the metal halide (B2) are used together from the viewpoint that the obtained polyamide composition is excellent in high-temperature heat resistance such as heat aging resistance. The total content of the copper compound (B1) and the metal halide (B2) relative to 100 parts by mass of the polyamide (A) is preferably 0.06 to 21 parts by mass, more preferably 0.1 to 15 parts by mass. It is at most 0.3 parts by mass, more preferably at most 0.3 parts by mass and at most 10 parts by mass, even more preferably at least 0.5 part by mass and at most 5 parts by mass. When the total content of the copper compound (B1) and the metal halide (B2) is within the above range, the polyamide composition can effectively suppress high-temperature heat resistance such as heat aging resistance while effectively suppressing problems such as metal corrosion. Can be improved.

[Other additives]
The polyamide composition may contain other additives as necessary in addition to the above-mentioned polyamide (A), copper compound (B1) and metal halide (B2).

  Other additives include, for example, antioxidants such as hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and thio antioxidants; coloring agents; ultraviolet absorbers; Agents; antistatic agents; flame retardants such as brominated polymers, antimony oxides, metal hydroxides, phosphinates; flame retardant aids; crystal nucleating agents; plasticizers; lubricants; Hydrogen sulfide adsorbent; inorganic or organic fibrous filler such as glass fiber, carbon fiber, wholly aromatic polyamide fiber; wollastonite, silica, silica alumina, alumina, titanium dioxide, potassium titanate, magnesium hydroxide, disulfide Powdery fillers such as molybdenum, carbon nanotubes, graphene, polytetrafluoroethylene, ultra high molecular weight polyethylene; hydrotalcite, glass Lake, mica, clay, montmorillonite, flaky fillers such as kaolin; alpha-olefin copolymer, and the like impact modifiers such as rubber.

  As the above dispersant, those capable of dispersing the copper compound (B1) and the metal halide (B2) in the polyamide (A) can be preferably used. Examples of the dispersant include higher fatty acids such as lauric acid; higher fatty acid metal salts composed of higher fatty acids and metals such as aluminum; higher fatty acid amides such as ethylenebisstearylamide; waxes such as polyethylene wax; An organic compound having an amide group is exemplified.

  The above fibrous filler may be subjected to a surface treatment with a silane coupling agent, a titanate coupling agent, or the like, if necessary. The silane coupling agent is not particularly limited. For example, aminosilane based agents such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane Coupling agents; mercaptosilane-based coupling agents such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilane-based coupling agents; vinylsilane-based coupling agents. One of these silane coupling agents may be used alone, or two or more thereof may be used in combination. Among the silane coupling agents, aminosilane-based coupling agents are preferred.

  The fibrous filler may be treated with a sizing agent as necessary. As the sizing agent, for example, a copolymer containing, as constituent units, a carboxylic anhydride-containing unsaturated vinyl monomer unit and an unsaturated vinyl monomer unit excluding the carboxylic anhydride-containing unsaturated vinyl monomer, Examples include epoxy compounds, polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts of these with primary, secondary or tertiary amines. One of these sizing agents may be used alone, or two or more thereof may be used in combination.

  The content of the other additives is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 0.02 to 200 parts by mass, and more preferably 0.03 to 100 parts by mass with respect to 100 parts by mass of the polyamide (A). Parts by mass are more preferred.

[Method for producing polyamide composition]
The method for producing the polyamide composition is not particularly limited, and the polyamide (A), the copper compound (B1), the metal halide (B2), and the above-mentioned other additives used as necessary may be uniformly mixed. A possible method can be preferably adopted.
As a method of including the copper compound (B1) and the metal halide (B2) in the polyamide (A), the copper compound (B1) and the metal halide (B2) may be used alone or independently during the polymerization step of the polyamide (A). A method of adding as a mixture (hereinafter, may be abbreviated as “Production Method 1”), or adding a polyamide (A), a copper compound (B1) and a metal halide (B2) alone or as a mixture at the time of melt-kneading. (Hereinafter, may be abbreviated as “Production Method 2”). When adding the copper compound (B1) and the metal halide (B2), they may be added as a solid or in the form of an aqueous solution. As for the other additives, the same addition method as in Production Method 1 or Production Method 2 can be adopted.

  The term “during the polymerization step of the polyamide (A)” in the production method 1 is any step from the starting monomer to the completion of the polymerization of the polyamide (A), and may be at any stage. In the case of performing the “melt kneading” in Production Method 2, usually, a method of adding the melt kneading using a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like is preferably adopted. The melt-kneading conditions are not particularly limited, and for example, a method in which melt-kneading is performed in a temperature range higher by about 10 to 50 ° C. than the melting point of the polyamide (A) for about 1 to 30 minutes.

<Molded product>
(Molding method)
A molded article comprising the polyamide composition of the present invention, using the polyamide composition of the present invention, injection molding, blow molding, extrusion molding, compression molding, stretch molding, vacuum molding, foam molding, It can be obtained by molding by various molding methods such as a rotational molding method, an impregnation method, a laser sintering method, and a hot melt lamination method. Furthermore, the polyamide composition of the present invention and another polymer or the like can be composite-molded to obtain a molded article.

(Application)
Examples of the molded article include films, sheets, tubes, pipes, gears, cams, various housings, rollers, impellers, bearing retainers, spring holders, clutch parts, chain tensioners, tanks, wheels, connectors, switches, sensors, and sockets. , Capacitors, hard disk components, jacks, fuse holders, relays, coil bobbins, resistors, IC housings, LED reflectors, and the like.
In particular, the polyamide composition of the present invention is suitable as an injection-molded member, a heat-resistant film, a tube for transporting various chemicals / chemicals, an intake pipe, a blow-by tube, a base material for a 3D printer, etc., which require high-temperature properties and chemical resistance. In addition, it is preferably used for molded articles for automobiles requiring high heat resistance and chemical resistance, for example, interior and exterior parts of automobiles, parts in an engine room, cooling system parts, sliding parts, electric parts and the like. Can be. In addition, the polyamide composition of the present invention can be made into a molded article that requires heat resistance corresponding to the surface mounting step. Such molded products include electrical and electronic components, surface mount connectors, sockets, camera modules, power supply components, switches, sensors, condenser seats, hard disk components, relays, resistors, fuse holders, coil bobbins, and ICs. It can be suitably used for surface mounting components such as a housing.

  Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Each evaluation in Production Examples, Examples, and Comparative Examples was performed according to the following methods.
-Intrinsic Viscosity The intrinsic viscosity (dl / g) at a concentration of 0.2 g / dl and a temperature of 30 ° C was determined for the polyamide (sample) obtained in the Production Example using concentrated sulfuric acid as a solvent from the following relational expression.
η _inh = [ln (t ₁ / t ₀ )] / c
In the above relational expression, η _inh represents an intrinsic viscosity (dl / g), t ₀ represents a flowing time (second) of a solvent (concentrated sulfuric acid), t ₁ represents a flowing time (second) of a sample solution, c Represents the concentration (g / dl) of the sample in the sample solution (ie, 0.2 g / dl).

-Melting point and glass transition temperature The melting point and glass transition temperature of the polyamide obtained in the production example were measured using a differential scanning calorimeter "DSC7020" manufactured by Hitachi High-Tech Science Corporation.
The melting point was measured based on ISO11357-3 (2011 2nd edition). Specifically, the sample (polyamide) is heated at a rate of 10 ° C./min from 30 ° C. to 340 ° C. in a nitrogen atmosphere, and is kept at 340 ° C. for 5 minutes to completely melt the sample. / Minute and cooled to 50 ° C. and kept at 50 ° C. for 5 minutes. The peak temperature of the melting peak that appears when the temperature is raised again to 340 ° C. at a rate of 10 ° C./min is defined as the melting point (° C.). did.
The glass transition temperature (° C.) was measured according to ISO11357-2 (2013, 2nd edition). Specifically, under a nitrogen atmosphere, the sample (polyamide) is heated from 30 ° C. to 340 ° C. at a rate of 20 ° C./min, and kept at 340 ° C. for 5 minutes to completely melt the sample. / Minute and cooled to 50 ° C. and kept at 50 ° C. for 5 minutes. The temperature at the inflection point that appeared when the temperature was raised again to 200 ° C. at a rate of 20 ° C./min was taken as the glass transition temperature (° C.).

<< Preparation of test piece >>
Using an injection molding machine (mold clamping force: 100 tons, screw diameter: φ32 mm) manufactured by Sumitomo Heavy Industries, Ltd., using the polyamide compositions obtained in Examples and Comparative Examples, With the cylinder temperature being 20 to 30 ° C. higher, the polyamide compositions of Examples 1 and 2 and Comparative Examples 1 and 5 had a mold temperature of 160 ° C., and the polyamide compositions of Comparative Examples 2 to 4 had a mold temperature of 140 ° C. The polyamide composition was molded using a T-runner mold under the conditions of (1), and a multipurpose test piece type A1 (a dumbbell-shaped test piece described in JIS K7139; 4 mm thick, 170 mm in total length, 80 mm in parallel portion length, parallel portion) (Width 10 mm).

-Tensile breaking strength Using an autograph (manufactured by Shimadzu Corporation) according to ISO527-1 (2012 second edition), using the multipurpose test piece type A1 (4 mm thick) produced by the above method. The tensile strength at break (MPa) at 23 ° C. was measured.

・ Chemical resistance (tensile strength retention)
Using the multipurpose test piece type A1 (4 mm thick) produced by the above method, a tensile test was performed at 23 ° C. in accordance with ISO527-1 (2012 second edition), and the tensile strength at break was calculated from the following equation (1). did. This value was defined as the initial tensile strength at break (a).
Tensile strength at break (MPa) = stress at break (N) / cross-sectional area of test piece (mm ² ) (1)
The test piece prepared by the above method was immersed in an antifreeze solution (aqueous solution obtained by diluting "Super Long Life Coolant" (pink) manufactured by Toyota Motor Corporation twice) in a pressure vessel, and the pressure vessel was set at 130 ° C. The sample was allowed to stand for 500 hours in a thermostat (“DE-303” manufactured by Mita Sangyo Co., Ltd.). After 500 hours, a tensile test was performed on the test piece taken out of the thermostat in the same manner as described above, and the tensile strength at break (b) of the test piece after heating was measured.
The tensile strength retention was determined from the following equation (2), and the long-term heat resistance and chemical resistance were evaluated.
Tensile strength retention (%) = {(b) / (a)} × 100 (2)

-Thermal deformation temperature A test piece (4 mm thick, total length 80 mm, width 10 mm) was prepared by cutting from the multipurpose test piece type A1 (4 mm thick) prepared by the above method, and an HDT tester manufactured by Toyo Seiki Seisaku-sho, Ltd. Using S-3M, the heat distortion temperature (° C.) was measured in accordance with ISO 75 (2013, 3rd edition).

-Water absorption The multipurpose test piece type A1 (4 mm thick) produced by the above method was weighed. Then, after immersion in water and immersion treatment at 23 ° C. for 168 hours, the weight increase was determined by weighing again, and this was divided by the weight before immersion to determine the water absorption (%).

Heat aging resistance Using a small kneader manufactured by Xplore Instruments, Inc. and an injection molding machine (“Xplore MC15”), using the polyamide compositions obtained in Examples and Comparative Examples, the melting point of the polyamide is 20 to 30 higher than the melting point of the polyamide. The polyamide composition was molded using a T-runner mold under the condition of a cylinder temperature of 170 ° C. and a mold temperature of 170 ° C., and a small test piece type 1BA (2 mm thick, total length 75 mm, parallel part length 30 mm, parallel part width) 5 mm). After the small test piece type 1BA (2 mm thick) was allowed to stand in a dryer at 170 ° C. for 250 hours, the tensile strength was measured in accordance with ISO 527-1 (2012, 2nd edition), and before being allowed to stand in the dryer. By calculating the ratio (%) to the tensile strength of the test piece, it was used as an index of heat aging resistance.

  The components used for preparing the polyamide compositions in Examples and Comparative Examples are shown.

"polyamide"
[Production Example 1]
Production of semiaromatic polyamide (PA9N-1) 9110.2 g (42.14 mol) of 2,6-naphthalenedicarboxylic acid, a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine [former / The latter = 4/96 (molar ratio)] 6833.7 g (43.30 mol), 210.0 g (1.72 mol) of benzoic acid, 16.2 g of sodium hypophosphite monohydrate (based on the total mass of the raw materials) 0.1% by mass) and 8.3 liters of distilled water were placed in an autoclave having an internal volume of 40 liters, followed by purging with nitrogen. The mixture was stirred at 100 ° C for 30 minutes, and the temperature inside the autoclave was raised to 220 ° C over 2 hours. At this time, the pressure inside the autoclave was increased to 2 MPa. Heating was continued for 5 hours while maintaining the pressure at 2 MPa, and steam was gradually removed to cause a reaction. Next, the pressure was reduced to 1.3 MPa over 30 minutes, and the reaction was further performed for 1 hour to obtain a prepolymer. The obtained prepolymer was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a particle size of 2 mm or less. This was subjected to solid-phase polymerization at 230 ° C. and 13 Pa (0.1 mmHg) for 10 hours to obtain a polyamide. This polyamide is abbreviated as "PA9N-1".

[Production Example 2]
Production of semi-aromatic polyamide (PA9N-2) A mixture in which the ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine was [former / latter = 15/85 (molar ratio)] was used. Except for this, a polyamide was obtained in the same manner as in Production Example 1. This polyamide is abbreviated as "PA9N-2".

[Production Example 3]
Production of semi-aromatic polyamide (PA9N-3) A mixture in which the ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine was [former / latter = 85/15 (molar ratio)] was used. Except for this, a polyamide was obtained in the same manner as in Production Example 1. This polyamide is abbreviated as “PA9N-3”.

[Production Example 4]
Production of semi-aromatic polyamide (PA9T-1) 8190.7 g (49.30 mol) of terephthalic acid, a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine [former / latter = 4/96] (Molar ratio)] 7969.4 g (50.35 mol), benzoic acid 171.0 g (1.40 mol), sodium hypophosphite monohydrate 16.3 g (0.1 wt. % By mass) and 5.5 liters of distilled water were placed in an autoclave having an internal volume of 40 liters. Thereafter, a polyamide was obtained in the same manner as in Production Example 1. This polyamide is abbreviated as "PA9T-1".

[Production Example 5]
-Production of semi-aromatic polyamide (PA9T-2) A mixture in which the ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine was [former / latter = 80/20 (molar ratio)] was used. Except for the above, a polyamide was obtained in the same manner as in Production Example 4. This polyamide is abbreviated as “PA9T-2”.

<< Copper compounds and metal halides >>
"KG HS01-P" (molar ratio: CuI / KI = 10/1), manufactured by PolyAd Services << Other additives >>
-Lubricant "LICOWAX OP", manufactured by Clariant Chemicals-Crystal nucleating agent "TALC ML112", manufactured by Fuji Talc Co., Ltd.-Glass fiber "CS03JA-FT2A", manufactured by Owens Corning Japan GK-Colorant carbon black "# 980B" , Manufactured by Mitsubishi Chemical Corporation

[Examples 1 and 2 and Comparative Examples 1 to 5]
The components were mixed in advance in the proportions shown in Table 1, and were charged all at once into the upstream supply port of a twin-screw extruder ("TEM-26SS" manufactured by Toshiba Machine Co., Ltd.). The mixture was melt-kneaded at a cylinder temperature 20 to 30 ° C. higher than the melting point of the polyamide, extruded, cooled and cut to produce a pellet-shaped polyamide composition.

The above-mentioned various physical properties were evaluated using the polyamide compositions obtained in the above Examples and Comparative Examples. Table 1 shows the results.
In Table 1, C9DA indicates 1,9-nonanediamine unit, and MC8DA indicates 2-methyl-1,8-octanediamine unit.

From Table 1, it can be seen that the polyamide compositions of Examples 1 and 2 have higher tensile strength retention after immersion in an antifreeze and are more improved in chemical resistance than Comparative Examples 1 to 4. Furthermore, since the polyamide compositions of Examples 1 and 2 are more excellent in heat aging resistance than Comparative Example 5, it is understood that they have excellent high temperature heat resistance.
In addition, the polyamide compositions of Examples 1 and 2 are superior to Comparative Examples 1 to 5 in the evaluation of the tensile strength at break, the heat distortion temperature, and the water absorption rate, and are equal to or more excellent than those of the polyamide compositions of the present invention. It can be seen that is also excellent in mechanical properties, heat resistance and low water absorption.
As described in Patent Document 1, it is known that the use of an aliphatic diamine having a side chain reduces the crystallinity of the obtained polyamide, and is not preferable in terms of heat resistance, chemical resistance, and the like. . On the other hand, the polyamide composition of the present invention is characterized in that the polyamide (A) contained therein has a dicarboxylic acid unit mainly composed of a naphthalenedicarboxylic acid unit and a diamine unit mainly composed of a branched aliphatic diamine unit. With this configuration, chemical resistance is further improved, and in addition, mechanical properties, heat resistance including high-temperature heat resistance, and various physical properties such as low water absorption are further improved.

Claims (15)

A polyamide (A) having a dicarboxylic acid unit and a diamine unit, a copper compound (B1) and a metal halide (B2),
Naphthalenedicarboxylic acid units account for more than 40 mol% and 100 mol% or less of the dicarboxylic acid units,
60 mol% or more and 100 mol% or less of the diamine unit are a branched aliphatic diamine unit and a linear aliphatic diamine unit of an optional constitutional unit, and the branched aliphatic diamine unit and the linear aliphatic diamine A polyamide composition, wherein the proportion of the branched aliphatic diamine unit to the total 100 mol% of the units is 60 mol% or more.   The ratio of the said branched aliphatic diamine unit with respect to 100 mol% of the total of the said branched aliphatic diamine unit and the said linear aliphatic diamine unit is 60 mol% or more and 99 mol% or less. Polyamide composition.   The ratio of the said branched aliphatic diamine unit with respect to 100 mol% in total of the said branched aliphatic diamine unit and the said linear aliphatic diamine unit is 80 mol% or more and 99 mol% or less. Polyamide composition.   The polyamide composition according to any one of claims 1 to 3, wherein the branched aliphatic diamine unit has 4 to 18 carbon atoms.   The said branched aliphatic diamine unit is a structural unit derived from the diamine which has at least 1 type chosen from the group which consists of a methyl group and an ethyl group as a branched chain, The Claims any one of Claims 1-4. Polyamide composition.   The branched aliphatic diamine unit is derived from a diamine having a branched chain in at least one of the carbon atom at the 2-position and the carbon atom at the 3-position when the carbon atom to which any one of the amino groups is bonded is placed at the 1-position. The polyamide composition according to any one of claims 1 to 5, which is a constituent unit.   The branched aliphatic diamine units are 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, and 2-methyl-1,9 The polyamide composition according to any one of claims 1 to 3, which is a structural unit derived from at least one type of diamine selected from the group consisting of -nonanediamine.   The polyamide composition according to any one of claims 1 to 7, wherein the linear aliphatic diamine unit has 4 to 18 carbon atoms.   The linear aliphatic diamine unit is 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine The structural unit according to any one of claims 1 to 7, wherein the structural unit is derived from at least one diamine selected from the group consisting of, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. Item 6. The polyamide composition according to Item.   The polyamide composition according to any one of claims 1 to 9, wherein the polyamide compound (B1) is contained in an amount of 0.01 part by mass or more and 1 part by mass or less based on 100 parts by mass of the polyamide (A).   The polyamide composition according to any one of claims 1 to 10, wherein the copper compound (B1) is at least one selected from the group consisting of copper iodide, copper bromide, and copper acetate.   The polyamide composition according to any one of claims 1 to 11, wherein the polyamide (A2) contains 0.05 to 20 parts by mass of the metal halide (B2) based on 100 parts by mass of the polyamide (A).   The polyamide composition according to any one of claims 1 to 12, wherein the metal halide (B2) is at least one selected from the group consisting of potassium iodide and potassium bromide.   A molded article comprising the polyamide composition according to any one of claims 1 to 13.   The molded article according to claim 14, which is a film.