JP2014111760A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition which excels in heat resistance, low water absorption, rigidity at high temperature, tensile physical property, thermal ageing resistance, chemical resistance and fluidity, develops sufficient crystallization even when molded in a mold at 80°C, and gives little mold contamination during manufacture.SOLUTION: The polyamide composition comprises the following polyamide resin (A), a copper compound (B1) and a metal halide compound (B2). The polyamide resin comprises 95 to 99.95 mass% of a polyamide (a-1) having a number average molecular weight of 2000 or more and 0.05 to 5 mass% of a polyamide oligomer (a-2) having a number average molecular weight of 500 or more and less than 2000, in which 25 mol% or more of the whole monomer units constituting the above polyamide (a-1) and the polyamide oligomer (a-2) are structural units derived from a specified alicyclic monomer, and a content percentage of trans isomer structural units derived from the alicyclic monomer is 50 to 85 mol%.

Description

  The present invention relates to a polyamide resin composition and a molded article comprising the same.

  Conventionally, polyamides represented by polyamide 6 (hereinafter abbreviated as PA6), polyamide 66 (hereinafter abbreviated as PA66) and the like are used for clothing and industrial materials because of their excellent characteristics and ease of melt molding. Widely used as fiber or general-purpose engineering plastic. On the other hand, the polyamide has been pointed out to have problems such as insufficient heat resistance and poor dimensional stability due to water absorption. Especially in the electrical and electronic fields that require reflow soldering heat resistance due to recent advances in surface mount technology (SMT), and in the engine room parts of automobiles, where demand for heat resistance is increasing year by year, the use of conventional polyamides Development of polyamides having excellent heat resistance, low water absorption, mechanical properties, and physicochemical properties has been desired. Furthermore, it has been desired to further improve the heat aging resistance of polyamides in cooling system parts such as radiator tanks, reservoir tanks or heater cores in which long life coolant is used.

  In order to solve the above-mentioned problems of conventional polyamides such as PA6 and PA66, development of high-melting-point polyamides having a rigid ring structure in the main chain has been advanced. For example, as a polyamide having an aromatic ring structure, various semi-aromatic polyamides mainly composed of a polyamide composed of terephthalic acid and 1,6-hexanediamine (hereinafter abbreviated as PA6T) have been proposed. Since PA6T has a melting point in the vicinity of 370 ° C. and exceeds the decomposition temperature, it is difficult to perform melt polymerization and melt molding. Therefore, PA6T is copolymerized with a dicarboxylic acid component such as adipic acid or isophthalic acid, or an aliphatic polyamide such as PA6. Therefore, it is used in a composition in which the melting point is lowered to an actually usable temperature range of about 280 to 320 ° C. Copolymerization of the third component in this way is effective for lowering the melting point of the polymer, but it is accompanied by a decrease in the crystallization speed and the ultimate crystallinity, resulting in rigidity, chemical resistance and heating at high temperatures. In addition to the reduced physical properties such as dimensional stability, there is a problem in that productivity is reduced as the molding cycle is extended. Although various physical properties such as dimensional stability accompanying water absorption have been improved as compared with conventional PA6 and PA66 by introduction of an aromatic group, they have not yet reached a practical level.

  In Patent Document 1, a semi-aromatic polyamide comprising an aromatic dicarboxylic acid unit containing 60 to 100 mol% of a terephthalic acid unit and a linear aliphatic alkylenediamine unit having 6 to 18 carbon atoms is added to 100 parts by mass of the polyamide. It is described that the polyamide composition containing 0.5 to 200 parts by mass of the filler has excellent performance in all of heat resistance, mechanical properties, chemical physical properties, and molding properties. Has been.

  On the other hand, as a polyamide having an alicyclic structure, Patent Document 2 includes a polyamide component composed of 1,4-cyclohexanedicarboxylic acid and 1,9-nonanediamine, and a polyamide component composed of terephthalic acid and 1,6-hexanediamine. Although a copolymerized polyamide obtained by copolymerization in a weight ratio of 25/75 to 85/15 is disclosed, the melting point is low, and the improvement effect in terms of heat resistance is insufficient. Polyamide composed of 1,4-cyclohexanedicarboxylic acid and aliphatic diamine having 6 to 18 carbon atoms described in Patent Document 3 is excellent in heat resistance, light resistance, toughness, and low water absorption, but in terms of fluidity. There is room for improvement.

  Furthermore, in the field of high melting point polyamide, knowledge about the relationship between moldability and crystallinity of high melting point polyamide has not been sufficient.

Japanese Examined Patent Publication No. 64-11073 Japanese Examined Patent Publication No. 47-42397 Japanese Patent Laid-Open No. 9-12868

  Therefore, the object of the present invention is excellent in heat resistance, low water absorption, rigidity at high temperature, tensile physical properties, heat aging resistance and fluidity, and crystallization proceeds sufficiently even when molded with a 80 ° C. mold. And it is providing the polyamide resin composition with few mold contamination at the time of manufacture.

（式中、Ｘはカルボキシル基またはアミノ基を表し、Ｚは炭素数３以上の脂環構造を表す。）

（式中、ＸおよびＺは前記定義の通りであり、Ｒ^１およびＲ^２はそれぞれ独立して炭素数１以上のアルキレン基を表す。）；
（２）前記ポリアミド樹脂（Ａ）１００質量部に対して銅化合物（Ｂ１）を０．０１〜１質量部、金属ハロゲン化物（Ｂ２）を０．０５〜２０質量部を含有する、上記（１）のポリアミド樹脂組成物；
（３）前記銅化合物（Ｂ１）がヨウ化銅および／または酢酸銅であり、前記金属ハロゲン化物（Ｂ２）がヨウ化カリウムである、上記（１）または（２）のポリアミド樹脂組成物；
（４）前記ポリアミド樹脂（Ａ）を構成する前記ポリアミド（ａ−１）および前記ポリアミドオリゴマー（ａ−２）の分子鎖の末端基の総量の１０％以上が末端封止剤によって封止されている、上記（１）〜（３）のいずれかのポリアミド樹脂組成物；
（５）前記脂環式モノマーが、前記一般式（I）または一般式（II）におけるＸがカルボキシル基である環状脂肪族ジカルボン酸である、上記（１）〜（４）いずれかのポリアミド樹脂組成物；
（６）前記環状脂肪族ジカルボン酸が１，４−シクロヘキサンジカルボン酸である、上記（５）のポリアミド樹脂組成物；
（７）前記ポリアミド（ａ−１）および前記ポリアミドオリゴマー（ａ−２）が、炭素数４〜１２の脂肪族ジアミンに由来する構造単位を含有する、上記（１）〜（６）のいずれかのポリアミド樹脂組成物；
（８）前記脂肪族ジアミンが１，４−ブタンジアミン、１，５−ペンタンジアミン、１，６−ヘキサンジアミン、２−メチル−１，５−ペンタンジアミン、１，８−オクタンジアミン、１，９−ノナンジアミン、２−メチル−１，８−オクタンジアミン、１，１０−デカンジアミン、１，１１−ウンデカンジアミンおよび１，１２−ドデカンジアミンからなる群より選ばれる少なくとも１種である、上記（７）のポリアミド樹脂組成物；
（９）１，４−シクロヘキサンジカルボン酸に由来する構造単位を２５モル％以上含有し、かつ脂肪族ジアミンに由来する構造単位として１，９−ノナンジアミンおよび／または２−メチル−１，８−オクタンジアミンを２５モル％以上含有する、上記（８）のポリアミド樹脂組成物；
（１０）さらに、ラクタムおよび／またはアミノカルボン酸に由来する構造単位を含有する、上記（１）〜（９）のいずれかのポリアミド樹脂組成物；
（１１）ポリアミド樹脂（Ａ）１００質量部に対してルイス塩基として作用する化合物（Ｃ）を０．１〜１０質量部含有する、上記（１）〜（１０）のいずれかのポリアミド樹脂組成物；
（１２）前記ルイス塩基として作用する化合物（Ｃ）がアルカリ金属酸化物、アルカリ金属水酸化物、アルカリ土類金属酸化物、アルカリ土類金属水酸化物、酸化亜鉛および水酸化亜鉛からなる群より選ばれる少なくとも１種である、上記（１１）のポリアミド樹脂組成物；
（１３）前記ルイス塩基として作用する化合物（Ｃ）が酸化カリウム、酸化マグネシウム、酸化カルシウム、酸化亜鉛、水酸化カリウム、水酸化マグネシウム、水酸化カルシウムおよび水酸化亜鉛からなる群より選ばれる少なくとも１種である、上記（１２）のポリアミド樹脂組成物；および
（１４）上記（１）〜（１３）のいずれかのポリアミド樹脂組成物からなる成形品；
を提供することにより達成される。 According to the present invention, the above object is
(1) A polyamide (a-1) having a number average molecular weight of 2000 or more is 95 to 99.95% by mass, and a polyamide oligomer (a-2) having a number average molecular weight of 500 to less than 2000 is in a range of 0.05 to 5% by mass. And an alicyclic ring in which 25 mol% or more of all the monomer units constituting the polyamide (a-1) and the polyamide oligomer (a-2) are represented by the following general formula (I) or general formula (II) A polyamide resin (A), a copper compound (B1), and a metal halide (the content of the trans isomer structural unit derived from the alicyclic monomer is 50 to 85 mol%, which is a structural unit derived from a formula monomer. Polyamide resin composition containing B2)

(In the formula, X represents a carboxyl group or an amino group, and Z represents an alicyclic structure having 3 or more carbon atoms.)

(Wherein X and Z are as defined above, and R ¹ and R ² each independently represents an alkylene group having 1 or more carbon atoms);
(2) The above (1) containing 0.01 to 1 part by mass of the copper compound (B1) and 0.05 to 20 parts by mass of the metal halide (B2) with respect to 100 parts by mass of the polyamide resin (A). ) Polyamide resin composition;
(3) The polyamide resin composition according to (1) or (2), wherein the copper compound (B1) is copper iodide and / or copper acetate, and the metal halide (B2) is potassium iodide;
(4) 10% or more of the total amount of terminal groups of the molecular chain of the polyamide (a-1) and the polyamide oligomer (a-2) constituting the polyamide resin (A) is sealed with a terminal blocking agent. The polyamide resin composition according to any one of (1) to (3) above;
(5) The polyamide resin according to any one of (1) to (4), wherein the alicyclic monomer is a cyclic aliphatic dicarboxylic acid in which X in the general formula (I) or the general formula (II) is a carboxyl group. Composition;
(6) The polyamide resin composition according to (5), wherein the cycloaliphatic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid;
(7) Any of (1) to (6) above, wherein the polyamide (a-1) and the polyamide oligomer (a-2) contain a structural unit derived from an aliphatic diamine having 4 to 12 carbon atoms. A polyamide resin composition;
(8) The aliphatic diamine is 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, 1,8-octanediamine, 1,9 The above (7), which is at least one selected from the group consisting of -nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine and 1,12-dodecanediamine. A polyamide resin composition;
(9) 1,9-nonanediamine and / or 2-methyl-1,8-octane as a structural unit containing 25 mol% or more of a structural unit derived from 1,4-cyclohexanedicarboxylic acid and derived from an aliphatic diamine The polyamide resin composition according to (8), which contains 25 mol% or more of diamine;
(10) The polyamide resin composition according to any one of (1) to (9), further comprising a structural unit derived from lactam and / or aminocarboxylic acid;
(11) The polyamide resin composition according to any one of (1) to (10) above, containing 0.1 to 10 parts by mass of the compound (C) acting as a Lewis base with respect to 100 parts by mass of the polyamide resin (A). ;
(12) The compound (C) acting as a Lewis base is selected from the group consisting of alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, alkaline earth metal hydroxides, zinc oxide and zinc hydroxide. The polyamide resin composition of (11), which is at least one selected;
(13) The compound (C) acting as the Lewis base is at least one selected from the group consisting of potassium oxide, magnesium oxide, calcium oxide, zinc oxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and zinc hydroxide. (14) a molded article comprising the polyamide resin composition of any one of (1) to (13);
Is achieved by providing

  According to the present invention, heat resistance, low water absorption, rigidity at high temperature, tensile properties, heat aging resistance, fluidity are excellent, and crystallization proceeds sufficiently even when molded with a 80 ° C. mold, and A polyamide resin composition with less mold contamination during production can be provided.

4 is a GPC elution curve (vertical axis: signal intensity, horizontal axis: elution time) of the polyamide resin (A) obtained in Reference Example 1. It is a front view of the metal mold | die used for injection molding when evaluating metal mold | die contamination | contamination property. It is sectional drawing of the metal mold | die used for injection molding when evaluating metal mold | die contamination | contamination property.

  Hereinafter, the present invention will be described in detail.

[Polyamide resin (A)]
The polyamide resin (A) is surrounded by a baseline and an elution curve from the elution curve of each sample obtained under measurement conditions in Examples described later using gel permeation chromatography (hereinafter abbreviated as GPC). 95 polyamide (a-1) having a number average molecular weight of 2000 or more calculated from standard polymethyl methacrylate (standard PMMA) conversion, which can be calculated from the area of the region below the molecular weight at which the detection of the main peak is completed from the number average molecular weight of 2000 or more. -99.95 mass% is contained. Moreover, the polyamide resin (A) is 0.05-5 mass of polyamide oligomers (a-2) whose number average molecular weights calculated | required by GPC measurement on the conditions similar to the said polyamide (a-1) are 500-2000. %contains.

  When the content (mass%) of the polyamide (a-1) and the polyamide oligomer (a-2) is in the above range, the fluidity of the polyamide resin composition is improved, and the polyamide resin composition is molded with an 80 ° C. mold. However, crystallization proceeds sufficiently. Moreover, mold contamination derived from the polyamide oligomer (a-2) can be prevented.

  The reason why such an effect is obtained is not clear, but is estimated as follows, for example. That is, it is considered that the polyamide oligomer (a-2) in the melted state has a high molecular chain mobility and thus works advantageously for crystallization.

  In addition, it is preferable to contain 97-99.95 mass% of polyamide (a-1) from a viewpoint which can show | play the effect of this invention much more, and it is more preferable to contain 98-99.95 mass%. . Accordingly, the polyamide oligomer (a-2) is preferably contained in an amount of 0.05 to 3% by mass, and more preferably 0.05 to 2% by mass.

  In the polyamide resin (A), 25 mol% or more of all monomer units constituting the polyamide (a-1) and the polyamide oligomer (a-2) is represented by the following general formula (I) or general formula (II). The content of the trans isomer structural unit derived from the alicyclic monomer is 50 to 85 mol%.

(Wherein X, Z, R ¹ and R ² are as defined above.)

  Examples of the alicyclic structure having 3 or more carbon atoms represented by Z include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cycloundecylene group, Examples thereof include monocyclic or polycyclic cycloalkylene groups such as a cyclododecylene group, a dicyclopentylene group, a dicyclohexylene group, a tricyclodecalene group, a norbornylene group, and an adamantylene group.

Examples of the alkylene group having 1 or more carbon atoms represented by R ¹ and R ² include saturated aliphatic alkylene groups such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. Can be mentioned. These may have a substituent. Examples of such a substituent include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group, a hydroxyl group, and a halogen group.

  As the alicyclic monomer, a cycloaliphatic dicarboxylic acid in which X is a carboxyl group, and a cycloaliphatic diamine in which X is an amino group may be used alone or in combination.

  Examples of the cycloaliphatic dicarboxylic acid include cycloaliphatic dicarboxylic acids having 3 to 10 carbon atoms, preferably cycloaliphatic dicarboxylic acids having 5 to 10 carbon atoms, and more specifically 1,4. -Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid.

  The cycloaliphatic dicarboxylic acid may have a substituent other than a carboxyl group on the alicyclic skeleton. Examples of the substituent include preferably 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.

  As the cycloaliphatic dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid is more preferable from the viewpoints of heat resistance, fluidity, rigidity at high temperature, and the like. In addition, cyclic aliphatic dicarboxylic acid may be used individually by 1 type, and may use 2 or more types together.

  Cycloaliphatic dicarboxylic acids have a trans isomer and a cis geometric isomer. In the case of general formula (I), when two carboxyl groups are on different sides of the ring structure, When two carboxyl groups are on the same side, a cis form is obtained. In the case of the general formula (II), the average value of the ratio of two pairs of X and Z trans isomer structural units was taken.

  For example, when 1,4-cyclohexanedicarboxylic acid is used as the cycloaliphatic dicarboxylic acid, Hyundai Organic Chemistry (4th edition), the first volume (KPC Volharddt, NE Schore, Co., Ltd. (April 1, 2004, page 174), when both of the two substituents occupy the axial position or the equatorial position, the trans form, and when the two substituents occupy the axial position or the equatorial position, respectively, Become a body.

  As the cycloaliphatic dicarboxylic acid, either the trans isomer or the cis isomer may be used, or a mixture of the trans isomer and the cis isomer in any ratio may be used.

When 1,4-cyclohexanedicarboxylic acid is used as the cycloaliphatic dicarboxylic acid, it is isomerized at a high temperature and the ratio of the trans isomer to the cis isomer converges, or the cis isomer is equivalent to the diamine compared to the trans isomer. From the viewpoint of high water solubility of the salt, the trans isomer / cis isomer ratio is preferably 50/50 to 0/100 (molar ratio) when used for polymerization, and is 40/60 to 10/90. Is more preferable, and 35/65 to 15/85 is even more preferable. In addition, the trans isomer / cis isomer ratio (molar ratio) of the cycloaliphatic dicarboxylic acid can be determined by ¹ H-NMR (see Examples described later).

  Examples of the cycloaliphatic diamine include cycloaliphatic diamines having 3 to 10 carbon atoms, preferably 5 to 10 carbon atoms, specifically 1,4-cyclohexanediamine and 1,3-bis. (Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl- 4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, methylcyclohexanediamine, isophoronediamine, norbornanediamine, tricyclodecanediamine and the like.

  The cycloaliphatic diamine may have a substituent other than an amino group on the alicyclic skeleton. Examples of the substituent include an alkyl group 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. In addition, cyclic aliphatic diamine may be used individually by 1 type, and may use 2 or more types together.

  Cycloaliphatic diamines, like cycloaliphatic dicarboxylic acids, have trans and cis geometric isomers. In the case of general formula (I), the two amino groups are on different sides of the ring structure. Is a cis form when two amino groups are on the same side of the trans form or ring structure. In the case of the general formula (II), the average value of the ratio of two pairs of X and Z trans isomer structural units was taken.

  For example, when 1,4-cyclohexanediamine is used as the cycloaliphatic diamine, Hyundai Organic Chemistry (4th edition), Vol. 1 (KPC Volharddt, NE Schore, Kagaku Dojin, 2004) (Published 1 April, page 174), when both of the two substituents occupy the axial position or the equatorial position, the trans form, and when the two substituents occupy the axial position and the equatorial position, respectively, Become.

  As the cycloaliphatic diamine, either the trans isomer or the cis isomer may be used, or a mixture of the trans isomer and the cis isomer in any ratio may be used.

When 1,4-cyclohexanediamine is used as the cycloaliphatic diamine, it is isomerized at a high temperature so that the ratio of the trans isomer and the cis isomer converges, or the cis isomer has an equivalent salt with a dicarboxylic acid compared to the trans isomer. From the viewpoint of high water solubility, the trans isomer / cis isomer ratio is preferably 50/50 to 0/100 (molar ratio) and more preferably 40/60 to 10/90 when used for polymerization. Preferably, it is 35/65 to 15/85. In addition, the trans isomer / cis isomer ratio (molar ratio) of the cycloaliphatic diamine can be determined by ¹ H-NMR.

  In the polyamide resin (A), the structural unit derived from the alicyclic monomer exists as a trans isomer structural unit and a cis isomer structural unit. The content of the trans isomer structural unit is 50 to 85 mol%, preferably 60 to 85 mol%, and preferably 70 to 85 mol% of the structural unit derived from the alicyclic monomer constituting the polyamide resin (A). Is more preferable, and 80-85 mol% is further more preferable. When the content of the trans isomer structural unit is within the above range, the polyamide resin (A) is excellent in rigidity and fluidity at high temperatures, and crystallization proceeds sufficiently even when molded with a 80 ° C. mold. . These are particularly remarkable in the case of the polyamide resin (A) using 1,4-cyclohexanedicarboxylic acid as the alicyclic monomer.

  In the present specification, in the case of the general formula (I), the “trans isomer structural unit” derived from the alicyclic monomer of the polyamide resin (A) is different from the alicyclic structure in terms of the amide bond. In the general formula (II), it means a structural unit in which an amide bond and Z are present on different sides of the alicyclic structure.

  The polyamide resin (A) contains a structural unit derived from an alicyclic monomer represented by the general formula (I) or the general formula (II), as well as a structural unit derived from another monomer capable of forming an amide bond. You may do it. Examples of such other monomers include dicarboxylic acids such as aliphatic dicarboxylic acids and aromatic dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, diamines such as aliphatic diamines and aromatic diamines, trivalent or higher polyvalent amines, A lactam and aminocarboxylic acid are mentioned, These may be used individually by 1 type and may use 2 or more types together.

  Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, speric acid, 3, 3 -Diethylsuccinic acid, azelaic acid, sebacic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, dimer acid, etc. And a linear or branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4-phenylenedioxydiacetic acid. 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4′-biphenyl And dicarboxylic acid. Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid, trimesic acid, and pyromellitic acid.

  Examples of the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, and 1,8-octanediamine. 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, Linear saturated aliphatic diamines such as 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosadecanediamine; 2-propanediamine, 1-butyl-1,2-ethanediamine, 1,1-di Til-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4- Dimethyl-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-hexanediamine, 2,2, 4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2,2-dimethyl-1,7-heptane Amine, 2,3-dimethyl-1,7-heptanediamine, 2,4-dimethyl-1,7-heptanediamine, 2,5-dimethyl-1,7-heptanediamine, 2-methyl-1,8-octane Diamine, 3-methyl-1,8-octanediamine, 4-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-octane Diamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, 3,7-dimethyl-1,1 Examples thereof include branched saturated aliphatic diamines such as 0-decanediamine and 7,8-dimethyl-1,10-decanediamine.

  Examples of aromatic diamines include metaxylylenediamine and paraxylylenediamine. Examples of the trivalent or higher polyvalent amine include bishexamethylene triamine.

  Examples of the lactam include ε-caprolactam, ω-laurolactam, butyrolactam, pivalolactam, caprylolactam, enantolactam, undecanolactam, laurolactam (dodecanolactam) and the like, among which ε-caprolactam and ω-laurolactam. Is preferred. Examples of the aminocarboxylic acid include α, ω-aminocarboxylic acid and the like. For example, the number of carbon atoms in which the ω position of 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like is substituted with an amino group. Examples thereof include 4-14 saturated aliphatic aminocarboxylic acids and paraaminomethylbenzoic acid. When it has a lactam and / or aminocarboxylic acid unit, there exists an effect | action which improves the toughness of the polyamide resin composition containing a polyamide resin (A).

  The polyamide resin (A) is an aliphatic diamine having 4 to 12 carbon atoms as a monomer unit constituting the polyamide (a-1) and the polyamide oligomer (a-2) from the viewpoint of heat resistance, low water absorption, and fluidity. It is preferable to contain the structural unit derived from. As structural units derived from aliphatic diamines having 4 to 12 carbon atoms, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, Any one or more of 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine It is preferable that it contains a structural unit derived from 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine, and is derived from an aliphatic diamine constituting the polyamide resin (A). 2 structural units derived from 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine It is further preferable to contain more than mole%. When 1,9-nonanediamine and 2-methyl-1,8-octanediamine are used in combination, 1,9-nonanediamine: 2-methyl-1,8-octanediamine = 99: 1 to 1:99 (molar ratio) ), And more preferably 95: 5 to 50:50.

  Among them, a structural unit derived from 1,4-cyclohexanedicarboxylic acid is contained in an amount of 25 mol% or more, and a structural unit derived from an aliphatic diamine is 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine. The polyamide resin composition containing the polyamide resin (A) containing at least 25 mol% of the structural unit derived from is particularly excellent in heat resistance, low water absorption and fluidity.

  When 1,4-cyclohexanedicarboxylic acid or 1,4-cyclohexanediamine is used as the alicyclic monomer, the melting point of the polyamide resin (A) from which the higher trans isomer structural unit content is obtained is formed. Since it becomes preferable, as a content rate of a trans-isomer structural unit, 50-100 mol% is preferable, 50-90 mol% is more preferable, It is more preferable that it is 50-85 mol%, 60-85 mol% is More preferably, 70 to 85 mol% is particularly preferable, and 80 to 85 mol% is most preferable.

  In the polyamide resin (A), the structural units derived from the alicyclic monomers constituting the polyamide (a-1) and the polyamide oligomer (a-2) may be the same or different. From the viewpoint of moldability of the product in an 80 ° C. mold, it is preferably the same.

  When the polyamide resin (A) has 10% or more of the total amount of terminal groups of the molecular chain of the polyamide (a-1) and the polyamide oligomer (a-2), which are constituent components, sealed with an end-capping agent, The physical properties such as melt moldability are more excellent.

Here, the terminal blocking rate is the terminal carboxyl group, terminal amino group and terminal blocking of the molecular chain of polyamide (a-1) and polyamide oligomer (a-2), which are constituent components of the polyamide resin (A). The number of end groups sealed with the agent can be measured and calculated, for example, by ¹ H-NMR based on the integral value of the characteristic signal corresponding to each end group (see Examples described later).

  The end-capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group, and is monocarboxylic acid, monoamine, acid anhydride, monoisocyanate, monoacid halide, monoester. Examples include esters and monoalcohols. Of these, monocarboxylic acids or monoamines are preferable from the viewpoints of reactivity and stability of the sealing end, and monocarboxylic acids are more preferable from the viewpoint of easy handling.

  Examples of the monocarboxylic acid include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. Acid; cycloaliphatic carboxylic acid and other alicyclic monocarboxylic acids; benzoic acid, toluic acid, α-naphthalene carboxylic acid, β-naphthalene carboxylic acid, methyl naphthalene carboxylic acid, phenyl acetic acid and other aromatic monocarboxylic acids; any of these And the like. Among them, in terms of reactivity, stability of the sealing end, price, etc., acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, cyclohexane Hexanecarboxylic acid and benzoic acid are preferred.

  The end-capping agent may be added by any of a method of adding a terminal capping agent in advance during polymerization, a method of adding during polymerization, a method of adding in a melt-kneading or molding process, etc. It functions as an end-capping agent.

  The polyamide resin (A) preferably has a sample concentration of 0.2 g / dL in concentrated sulfuric acid and ηinh measured at 30 ° C. within the range of 0.4 to 3.0 dL / g. It is more preferably in the range of 0 dL / g, and further preferably in the range of 0.6 to 1.8 dL / g. When the polyamide resin (A) having ηinh within the above range is used, the resulting polyamide resin composition is more excellent in heat resistance, rigidity at high temperature, and the like.

  As a method for producing the polyamide resin (A), polyamides having different number average molecular weights and molecular weight distributions are produced and then mixed, and the content (mass%) of the polyamide (a-1) and the polyamide oligomer (a-2) is as follows. The method of adjusting suitably is mentioned so that it may become the range which the invention prescribes | regulates. The polyamide can be produced by a known method such as a melt polymerization method using a dicarboxylic acid and a diamine as raw materials, a solid phase polymerization method, or a melt extrusion polymerization method.

  Examples of the mixing method include a method in which polyamides having different number average molecular weights and molecular weight distributions described above are dry blended and charged simultaneously or separately into a melt kneader.

  As another method for producing the polyamide resin (A), the content of the polyamide (a-1) and the polyamide oligomer (a-2) is selected by selecting appropriate polymerization conditions when producing the polyamide resin (A) ( The method of superposing | polymerizing so that the mass%) may become the range prescribed | regulated by this invention is mentioned. Appropriate polymerization conditions include, for example, a dicarboxylic acid component, a diamine component constituting the polyamide resin (A), a catalyst and a terminal blocking agent as needed, and a nylon salt to produce a nylon salt. By heating at a temperature of 260 ° C., a solution containing a prepolymer having a water content of preferably 10 to 40% is obtained, and the sample is further sprayed into an atmosphere at 100 to 150 ° C. to obtain a sample in concentrated sulfuric acid. A powdery prepolymer having a concentration of 0.2 g / dL and ηinh of 0.1 to 0.6 dL / g at 30 ° C. is obtained. Further, a method of solid-phase polymerization or melt polymerization using an extruder can be mentioned.

  Examples of the catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid, salts or esters thereof, and specifically, phosphoric acid, phosphorous acid or hypophosphorous acid and potassium, sodium, magnesium, vanadium. , Calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony and other salts; phosphoric acid, phosphorous acid or hypophosphorous acid ammonium salt; phosphoric acid, phosphorous acid or hypophosphorous acid Examples include acid ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, and phenyl ester. Here, when ηinh of the prepolymer is in the range of 0.1 to 0.6 dL / g, there is little shift in the molar balance of the carboxyl group and amino group and a decrease in the polymerization rate in the subsequent polymerization stage, and various physical properties. A polyamide resin (A) excellent in the above can be obtained.

  When the polymerization after obtaining the prepolymer is performed by solid phase polymerization, it is preferably performed in an inert gas atmosphere or under an inert gas flow or under reduced pressure, and the polymerization temperature is 200 ° C. or higher to the melting point of the polyamide. When the polymerization temperature is within the range of 20 ° C. and the polymerization time is 1 to 8 hours, the polymerization rate is high, the productivity is excellent, coloring and gelation can be effectively suppressed, and polyamide (a-1 ) And the content (mass%) of the polyamide oligomer (a-2) can be easily adjusted within the range defined by the present invention. On the other hand, when the polymerization after obtaining the prepolymer is performed using a melt extruder, the polymerization temperature is preferably 370 ° C. or less, and the polymerization time is preferably 5 to 60 minutes. When polymerized under such conditions, a polyamide resin (A) with almost no decomposition of the polyamide and no deterioration is obtained, and the content (mass%) of the polyamide (a-1) and the polyamide oligomer (a-2) is determined in the present invention. It is easy to adjust to the range specified by.

  The content of the polyamide (a-1) and the polyamide oligomer (a-2) constituting the polyamide resin (A) is determined from the elution curve under the measurement conditions in Examples described later using GPC. In the case of the GPC measurement, when the polyamide resin (A) or the polyamide resin composition contains other components that are soluble in a solvent for dissolving the polyamide resin (A), for example, the polyamide resin (A) is insoluble. However, GPC measurement may be performed after the other components are extracted and removed using a soluble solvent. Further, for example, a copper compound (B1) and a metal halide (B2) that are insoluble in a solvent in which the polyamide resin (A) is dissolved, a compound (C) that acts as a Lewis base, the polyamide resin composition (A) ) Is dissolved in a solvent to be dissolved, and then filtered to remove insoluble matters, and then GPC measurement is performed.

[Copper compound (B1) and metal halide (B2)]
The polyamide resin composition of the present invention contains a copper compound (B1) and a metal halide (B2), so that the polyamide resin is excellent in heat resistance, low water absorption, rigidity under high temperature, tensile properties, fluidity, etc. A polyamide resin composition having further excellent heat aging resistance can be obtained without impairing the properties of (A). Each will be described below.

<Copper compound (B1)>
Examples of the copper compound (B1) used in the present invention include copper halide, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and stearic acid. Examples thereof include copper and copper complex salts coordinated to chelating agents such as ethylenediamine and ethylenediaminetetraacetic acid.

  Among these, copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate are preferred from the viewpoint of excellent heat aging resistance and suppression of metal corrosion of the screw and cylinder during extrusion. It is preferable that it is copper iodide and / or copper acetate. A copper compound (B1) may be used individually by 1 type, and may use 2 or more types together.

  The compounding amount of the copper compound (B1) in the polyamide resin composition of the present invention is preferably 0.01 to 1 part by mass, and 0.02 to 0.5 part by mass with respect to 100 parts by mass of the polyamide resin (A). More preferred. By controlling the blending amount of the copper compound (B1) within the above range, it is possible to improve the heat aging resistance while suppressing a decrease in the tensile properties of the resulting polyamide resin composition, and also to prevent copper precipitation and metal corrosion during molding. Can be suppressed.

<Metal halide (B2)>
As the metal halide (B2) used in the present invention, copper halide is excluded.
A salt of a group 1 or group 2 metal element of the periodic table of elements and a halogen is preferable, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium chloride, and the like. Preference is given to potassium bromide. A metal halide (B2) may be used individually by 1 type, and may use 2 or more types together. Among these, potassium iodide is more preferable from the viewpoint that the obtained polyamide resin composition is excellent in heat aging resistance and can suppress metal corrosion.

  0.05-20 mass parts is preferable with respect to 100 mass parts of polyamide resins (A), and, as for the compounding quantity of the metal halide (B2) in the polyamide resin composition of this invention, 0.2-10 mass parts is more. preferable. By controlling the blending amount of the metal halide (B2) within the above range, it is possible to improve the heat aging resistance while suppressing a decrease in the tensile properties of the obtained polyamide resin composition, and further, copper precipitation and metal corrosion during molding. Can also be suppressed.

  The ratio of the copper compound (B1) and the metal halide (B2) in the polyamide resin composition is such that the total amount of halogen and the molar ratio of copper (halogen / copper) is 2/1 to 50/1. It is preferable to contain a copper compound (B1) and a metal halide (B2) in the composition. Halogen / copper is more preferably 2/1 to 40/1, and further preferably 5/1 to 30/1. When the ratio of halogen / copper is 2/1 or more, it is preferable because copper precipitation and metal corrosion during molding can be suppressed. Moreover, when halogen / copper is 50/1 or less, corrosion of the screw etc. of a molding machine can be suppressed, without impairing mechanical physical properties, such as a tensile physical property, of the polyamide resin composition obtained.

The copper compound (B1) and the metal halide (B2) may be added alone, but are preferably used together from the viewpoint of excellent heat aging resistance of the obtained polyamide resin composition.
In order to disperse the copper compound (B1) and the metal halide (B2) in the polyamide resin (A), the polyamide resin composition of the present invention contains other components to the extent that the effects of the present invention are not impaired. May be. Examples of other components 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 ethylene bisstearyl amide, waxes such as polyethylene wax, and at least one amide group. And organic compounds having.

[Compound (C) acting as a Lewis base]
The polyamide resin composition of the present invention may contain 0.1 to 10 parts by mass of the compound (C) acting as a Lewis base with respect to 100 parts by mass of the polyamide resin (A), and 0.1 to 5 parts by mass. It is more preferable to contain a part. By setting the amount of the compound (C) acting as a Lewis base within the above range, the polyamide (a-1) and the polyamide oligomer (a-2) are constituted by the general formula (I) or the general formula (II). The content of the trans isomer structural unit derived from the represented alicyclic monomer can be increased, and a polyamide resin composition having a high melting point, that is, heat resistance and rigidity at high temperature is obtained. Furthermore, when the content of the trans isomer structural unit is increased, the resulting polyamide resin composition has a stronger crystal structure and chemical resistance is improved.

  The compound (C) acting as a Lewis base is selected from the group consisting of alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, alkaline earth metal hydroxides, zinc oxide and zinc hydroxide. It is preferable to use at least one kind.

  Examples of the alkali metal oxide and alkaline earth metal oxide include potassium oxide, magnesium oxide and calcium oxide. Examples of the alkali metal hydroxide and alkaline earth metal hydroxide include potassium hydroxide, water and the like. Examples thereof include magnesium oxide and calcium hydroxide. These may be used individually by 1 type and may use 2 or more types together.

[Other ingredients]
In the polyamide resin composition of the present invention, the above-mentioned polyamide resin (A), copper compound (B1) and metal halide (B2), and a compound that acts as a Lewis base as long as the effects of the present invention are not impaired as required Other components other than (C) may be included.
Examples of other components include thermoplastic resins other than polyamide (a-1) and polyamide oligomer (a-2), compatibilizers, fillers, silane coupling agents, crystal nucleating agents, copper-based heat stabilizers, oxidation Antioxidants (hindered amine antioxidants, phosphorus antioxidants, thio antioxidants, etc.), dyes, pigments, antistatic agents, plasticizers, flame retardants, flame retardant aids, processing aids, lubricants, fluorescence Examples include bleaching agents, rubbers and reinforcing agents.

[Production method of polyamide resin composition]
Examples of the method for producing the polyamide resin composition of the present invention include a method in which the polyamide resin (A) contains a copper compound (B1) and a metal halide (B2).

  As a method for containing the copper compound (B1) and the metal halide (B2) in the polyamide resin (A), the copper compound (B1) and the metal halide (B2) are each independently used during the polymerization step of the polyamide resin (A). Or a mixture (hereinafter sometimes abbreviated as “Production Method 1”) or melt kneading to each of the polyamide resin (A) and the copper compound (B1) and the metal halide (B2) alone. Or the method of adding with a mixture (Hereinafter, it may abbreviate as "the manufacturing method 2.") etc. are mentioned.

  When adding the copper compound (B1) and the metal halide (B2), they may be added in the form of a solid or in the form of an aqueous solution.

  The process of polymerizing the polyamide resin (A) in production method 1 is any process from the raw material monomer to the completion of polymerization of the polyamide resin (A), and may be at any stage. The apparatus for melt kneading in production method 2 is not particularly limited, and a known apparatus, for example, a melt kneader such as a single or twin screw extruder, a Banbury mixer, and a mixing roll can be used. A twin screw extruder is preferred. Although the melt-kneading conditions are not particularly limited, for example, the polyamide resin composition of the present invention is obtained by melt-kneading for 1 to 30 minutes in a temperature range 20 to 50 ° C. higher than the melting point of the polyamide resin (A).

[Containment method of other components]
The compound (C) acting as a Lewis base can be contained in the polyamide resin (A) in advance. The compound (C) that acts as a Lewis base and the above-mentioned other components include polyamide resin (A), copper compound (B1) and metal halide (B2), compound that acts as a Lewis base (C ) And other components can be mixed uniformly if necessary, and usually a method of melt-kneading using a single screw extruder, twin screw extruder, kneader, Banbury mixer, etc. is adopted. . The melt kneading conditions are not particularly limited, and examples thereof include a method of melt kneading for 1 to 30 minutes in a temperature range 30 to 50 ° C. higher than the melting point.

[Molded product made of polyamide resin composition]
The thermoplastic resin composition of the present invention, such as injection molding, extrusion molding, press molding, blow molding, calendar molding, casting molding, etc., depending on the type, application, shape, etc. of the target molded product Various molded products can be manufactured by applying a molding method generally used for a product. Moreover, you may employ | adopt the shaping | molding method combining said shaping | molding method. Furthermore, the polyamide resin composition of the present invention can also be made into a composite molded body that is bonded, welded, and bonded to various materials such as various thermoplastic resins, thermosetting resins, paper, metal, wood, and ceramics.

  The polyamide resin composition of the present invention undergoes the molding process as described above, and manufactures electrical and electronic parts, automobile parts, industrial parts, fibers, films, sheets, household goods, and other various shaped products of any shape and application. Can be used effectively.

  Examples of electrical and electronic parts include SMT connectors such as FPC connectors, BtoB connectors, card connectors, and coaxial connectors; SMT switches, SMT relays, SMT bobbins, memory card connectors, CPU sockets, LED reflectors, camera module bases, barrels, holders , Cable sheathing, optical fiber parts, muffler gear for AV / OA equipment, automatic flashing equipment parts, mobile phone parts, heat resistant gears for copiers, end caps, commutators, commercial outlets, command switches, noise filters, magnet switches, Examples include a solar cell substrate, a liquid crystal plate, an LED mounting substrate, a flexible printed wiring board, and a flexible flat cable.

  Automotive parts include cooling parts such as thermostat housing, radiator tank, radiator hose, water outlet, water pump housing, rear joint; intercooler tank, intercooler case, turbo duct pipe, EGR cooler case, resonator, throttle body, intake manifold Intake and exhaust system parts such as tail pipes; Fuel system parts such as fuel delivery pipes, gasoline tanks, quick connectors, canisters, pump modules, fuel piping, oil strainers, lock nuts, seal materials; mount brackets, torque rods, cylinder head covers Structural parts such as bearing retainers, gear tensioners, headlamp actuator gears, slide doors Drive system parts such as peripheral parts and clutch peripheral parts; brake system parts such as air brake tubes; automotive harness parts such as wire harness connectors, motor parts, sensors, ABS bobbins, combination switches, and in-vehicle switches in the engine room; sliding door dampers , Dora mirror stay, door mirror bracket, inner mirror stay, roof rail, engine mount bracket, air cleaner inlate pipe, door checker, plastic chain, emblem, clip, breaker cover, cup holder, air bag, fender, spoiler, radiator support And interior / exterior parts such as radiator grilles, louvers, air scoops, hood bulges, back doors and fuel sender modules.

  Industrial parts include, for example, gas pipes, oil field mining pipes, hoses, ant-proof cables (communication cables, pass cables, etc.), powder coating paint parts (inside coating of water pipes), subsea oil field pipes, pressure hoses, hydraulic pressure Tubes, paint tubes, fuel pumps, separators, supercharge ducts, butterfly valves, conveyor roller bearings, railway sleeper spring bearings, outboard engine covers, generator engine covers, irrigation valves, large switches ( Switch), and monofilaments (extruded yarn) such as fishing nets.

  Examples of the fiber include an airbag base fabric, a heat resistant filter, a reinforcing fiber, a brush bristle, a fishing line, a tire cord, an artificial grass, a carpet, and a seat sheet fiber.

  Examples of films and sheets include heat-resistant adhesive tapes such as heat-resistant masking tapes and industrial tapes; cassette tapes, magnetic tapes for data storage for digital data storage, magnetic tape materials such as video tapes; retort food pouches, confectionery Food packaging materials such as individual packaging and processed meat products packaging; electronic component packaging materials such as semiconductor packaging packaging.

  In addition, the polyamide resin composition of the present invention includes plastic magnets, shoe soles, tennis rackets, skis, bonded magnets, glasses frames, binding bands, tag pins, sash crescents, electric tool motor fans, and motor stator insulating blocks. , Lawn mower engine cover, lawn mower fuel tank, micro slide switch, DIP switch, switch housing, lamp socket, connector shell, IC socket, bobbin cover, relay box, condenser case, small motor case, gear, Cam, dancing pulley, spacer, insulator, fastener, caster, wire clip, bicycle wheel, terminal block, starter insulation, fuse box, air cleaner case, air conditioner fan, tar Null housing, wheel cover, bearing retainer over, water pipe impeller, clutch release bearing hub, a heat-resistant container, microwave oven parts, rice cooker parts, can be suitably used such as a printer ribbon guide.

  EXAMPLES Hereinafter, although an Example, a reference example, and a comparative example (henceforth an Example etc.) demonstrates this invention in detail, this invention is not limited to these. In the following examples, etc., melting point, solution viscosity, content (mass%) of polyamide (a-1) and polyamide oligomer (a-2), end-capping rate, trans isomerism derived from alicyclic monomer Body structure unit content, water absorption, load deflection temperature, tensile strength / tensile fracture strain, heat aging resistance, melt viscosity, relative crystallinity, and mold contamination were measured or evaluated by the following methods.

<Melting point>
The melting point of the polyamide (polyamide 9C-1 to 4 described below) used in each example etc. is measured under a nitrogen atmosphere using a differential scanning calorimeter (DSC822) manufactured by METTLER TOLEDO. Thus, the peak temperature of the melting peak that appears when the temperature was raised from 30 ° C. to 360 ° C. at a rate of 10 ° C./min was determined as the melting point (° C.). When there are a plurality of melting peaks, the melting point is the peak temperature of the melting peak on the highest temperature side.

<Solution viscosity>
The solution viscosity ηinh of the polyamide used in each example was obtained by dissolving 50 mg of polyamide in 25 mL of 98% concentrated sulfuric acid in a volumetric flask and dropping the obtained solution at 30 ° C. with an Ubbelohde viscometer (t ) And was calculated from the following formula (1) from the falling time (t ₀ ) of concentrated sulfuric acid.
ηinh (dL / g) = {ln (t / t ₀ )} / 0.2 (1)

<Contents of polyamide (a-1) and polyamide oligomer (a-2)>
The content (mass%) of the polyamide (a-1) and the polyamide oligomer (a-2) in the polyamide resin (A) used in each example or the like is an elution curve (vertical axis: vertical axis :) of each sample obtained using GPC. From the signal intensity obtained from the detector (horizontal axis: elution time), the area of a region with a number average molecular weight of 500 or more and less than 2000 surrounded by the baseline and the elution curve, and the number average molecular weight of 2000 or more surrounded by the baseline and the elution curve From the area of the region below the number average molecular weight where the detection of the main peak is completed. The measurement was performed under the following conditions.
・ Detector: UV detector (wavelength: 210 nm)
-Column: Showa Denko HFIP-806M (inner diameter 8 mm x length 300 mm)
Solvent: hexafluoroisopropanol containing sodium trifluoroacetate at a concentration of 0.01 mol / L Temperature: 40 ° C
・ Flow rate: 1 mL / min
・ Injection volume: 90μL
・ Concentration: 0.5 mg / mL
Sample preparation: Polyamide resin (A) or polyamide resin composition obtained in each example or the like in hexafluoroisopropanol containing 0.01 mol / L of sodium trifluoroacetate was converted to 0 in terms of polyamide resin (A). The solution was weighed to 5 mg / mL and stirred for 1 hour at room temperature to dissolve, and the resulting solution was filtered through a membrane filter (pore size 0.45 μm) to prepare a sample.
-PMMA standard sample: Standard elution curve (calibration curve) was prepared using STANDARD M-75 (number average molecular weight range: 1,800 to 950,000) manufactured by Showa Denko KK.
The elution curve when the polyamide resin composition obtained in Reference Example 1 described later (which actually corresponds to the polyamide resin (A) alone) was measured under the above-mentioned conditions is shown as polyamide (a-1) and polyamide oligomer ( It is shown in FIG. 1 together with the region a-2).

<End sealing rate>
Using the polyamide resin composition obtained in each example, etc., injection molding (mold temperature: 80 ° C.) was performed at a cylinder temperature about 20 ° C. higher than the respective melting points, and the length was 100 mm, the width was 40 mm, and the thickness was 1 mm. And 30-30 mg of the obtained test piece was scraped off and dissolved in 1 mL of trifluoroacetic acid-d (CF ₃ COOD), and the nuclear magnetic resonance apparatus JNM-ECX400 (400 MHz, manufactured by JEOL Ltd.) ) Was used to measure ¹ H-NMR under conditions of room temperature and 256 accumulations. Then, the carboxyl group terminal (a), the amino group terminal (b), and the terminal (c) sealed with the terminal blocking agent are obtained from the integral values of the characteristic signals of the terminal groups, respectively, and the terminal sealing is performed from Equation (2). The stopping rate (%) was determined.
Terminal sealing rate (%) = c / (a + b + c) × 100 (2)

<Trans isomer structural unit content>
Using the polyamide resin composition obtained in each example, etc., injection molding (mold temperature: 80 ° C.) was performed at a cylinder temperature about 20 ° C. higher than the respective melting points, and the length was 100 mm, the width was 40 mm, and the thickness was 1 mm. The test piece was prepared, 20-30 mg was scraped from the obtained test piece, dissolved in 1 mL of trifluoroacetic acid-d (CF ₃ COOD), filtered through a glass filter to remove insoluble matters, and a measurement sample ¹ H-NMR was measured using a nuclear magnetic resonance apparatus JNM-ECX400 (400 MHz) manufactured by JEOL Ltd. under conditions of room temperature and 256 integrations. From the ratio of the peak area of 2.10 ppm derived from β hydrogen of the cis isomer of the 1,4-cyclohexanedicarboxylic acid structural unit and the peak area of 2.20 ppm derived from β hydrogen of the trans isomer structural unit, trans isomerism The body structural unit content was determined.

<Water absorption rate>
Using the polyamide resin composition obtained in each example, etc., injection molding (mold temperature 80 ° C.) was performed at a cylinder temperature about 20 ° C. higher than the melting point of each, and the length was 60 mm and the width according to ISO 62 A test piece having a thickness of 60 mm and a thickness of 2 mm was produced. When the obtained test piece was immersed in water at 23 ° C. for 1 day, an increase in mass was measured, and an increase rate (%) with respect to the mass before immersion was calculated and used as an index of low water absorption. The smaller the value, the lower the water absorption.

<Load deflection temperature>
Using the polyamide resin composition obtained in each example etc., injection molding (mold temperature 80 ° C.) was performed at a cylinder temperature about 20 ° C. higher than the melting point of each, and ISO multipurpose test piece A type (length 80 mm) , Width 10 mm, thickness 4 mm). Using the obtained test piece, the deflection temperature under load (° C.) when a load of 1.8 MPa was applied according to ISO 75-2 / Af was measured and used as an index of rigidity under high temperature.

<Tensile strength / Tensile fracture strain>
Using the polyamide resin composition obtained in each example etc., injection molding (mold temperature 80 ° C.) was performed at a cylinder temperature about 20 ° C. higher than the melting point of each, and ISO multipurpose test piece A type (length 80 mm) , Width 10 mm, thickness 4 mm). Using the obtained test piece, the tensile strength (MPa) and the tensile fracture strain (%) at 23 ° C. were measured according to ISO 527, and used as an index of rigidity. The higher the tensile strength value and the smaller the tensile fracture strain value, the better the rigidity.

<Heat aging resistance>
Using the polyamide resin composition obtained in each of the Examples, etc., injection molding (mold temperature 80 ° C.) was performed at a cylinder temperature about 20 ° C. higher than the respective melting points, thereby producing an ISO multipurpose test piece A type. The tensile strength after leaving the obtained test piece in a drier at 120 ° C. for 1000 hours was measured according to ISO 527, and the ratio (%) to the tensile strength of the test piece before being left in the drier was calculated. Thus, it was used as an index of heat aging resistance.

<Melt viscosity>
About the polyamide resin composition obtained in each Example etc., using a capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a barrel temperature of 340 ° C., a shear rate of 121.6 sec ⁻¹ (capillary: inner diameter 1.0 mm × length 10 mm) The melt viscosity (Pa · s) was measured under conditions of an extrusion speed of 10 mm / min, and used as an index of fluidity.

<Relative crystallinity>
Using the polyamide resin composition obtained in each example etc., injection molding was performed under the following conditions to produce a test piece having a length of 100 mm, a width of 40 mm, and a thickness of 1 mm. About 10 mg was scraped from the obtained test piece, and the temperature was increased from 30 ° C. to 360 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere using DSC822. If there is an amorphous region in the polyamide resin (A) constituting the polyamide resin composition, the crystallization peak caused by the crystallization of the amorphous region in the temperature region of 80 to 150 ° C. in this temperature rising process. Is observed. In the present specification, the calorie calculated from the crystallization peak is referred to as “crystallization calorie ΔHc”. In the above-described temperature rising process from 30 ° C. to 360 ° C. at a rate of 10 ° C./min, a crystal melting peak is observed after the crystallization peak is detected or not detected. In this specification, the calorie calculated from the crystal melting peak is referred to as “crystal melting calorie ΔHm”. Using such ΔHc and ΔHm, the relative crystallinity (%) was calculated by the following mathematical formula (3), and used as an index of moldability in a 80 ° C. mold.
-Polyamide resin (A) or polyamide resin composition temperature during injection molding: 340 ° C
・ Mold temperature: 80 ℃
・ Injection speed: 60mm / sec
・ Injection time: 2 sec
・ Cooling time: 5 sec
Relative crystallinity (%) = (ΔHm−ΔHc) / ΔHm × 100 (3)

<Mold contamination>
Using the polyamide resin composition obtained in each of the examples, etc., the molds having the shapes shown in FIGS. 2 and 3 (FIG. 2: front view, FIG. 3: sectional view with the k-axis as the cut surface) are subjected to the following conditions. Injection molding was performed. The polyamide resin composition enters from the protruding end m in the figure, and flows from the outer periphery of the circle n in FIG. Contamination (discoloration) of the flow end О of the mold was visually confirmed after 500 shots of continuous injection, and when the mold did not show any deposits or fogging, the mold was fogged. The case was evaluated as Δ, and the case where deposits were found on the mold was evaluated as x, which was used as an index of mold contamination.
-Polyamide resin composition temperature during injection molding: 340 ° C
・ Mold temperature: 80 ℃
・ Injection speed: 60mm / sec
・ Injection time: 2 sec
・ Cooling time: 5 sec

  The polyamide resin (A), copper compound (B1), metal halide (B2) and compound (C) acting as a Lewis base used in each Example etc. are shown below.

<Polyamide resin (A)>
The following polyamides were blended in the proportions shown in Table 1 to obtain a polyamide resin (A).

Polyamide 9C-1:
1,4-cyclohexanedicarboxylic acid 5111.2 g (29.7 mol), 1,9-nonanediamine 4117.6 g (26.0 mol), 2-methyl, trans isomer / cis isomer ratio = 30/70 (molar ratio) -1,8-octanediamine 726.6 g (4.59 mol), acetic acid 110.4 g (1.84 mol) as end-capping agent, sodium hypophosphite monohydrate 10 g as catalyst, and distilled water 2.5 L was put into an autoclave with an internal volume of 40 L and purged with nitrogen. The internal temperature was raised to 200 ° C. over 2 hours. At this time, the autoclave was pressurized to 2 MPa. Thereafter, the reaction was continued for 2 hours while gradually removing water vapor and maintaining the pressure at 2 MPa. Next, the pressure was reduced to 1.2 MPa over 30 minutes to obtain a prepolymer. This prepolymer was pulverized and dried at 120 ° C. under reduced pressure for 12 hours. This was subjected to solid phase polymerization at 230 ° C. and 13.3 Pa for 10 hours to obtain polyamide 9C-1 having a solution viscosity ηinh of 0.87 dL / g.

Polyamide 9C-2:
1,4-cyclohexanedicarboxylic acid 5111.2 g (29.7 mol), 1,9-nonanediamine 4117.6 g (26.0 mol), 2-methyl, trans isomer / cis isomer ratio = 30/70 (molar ratio) -1,8-octanediamine 726.6 g (4.59 mol), acetic acid 110.4 g (1.84 mol) as end-capping agent, sodium hypophosphite monohydrate 10 g as catalyst, and distilled water 2.5 L was put into an autoclave with an internal volume of 40 L and purged with nitrogen. The internal temperature was raised to 200 ° C. over 2 hours. At this time, the autoclave was pressurized to 2 MPa. Thereafter, the reaction was continued for 2 hours while gradually removing water vapor and maintaining the pressure at 2 MPa. Next, the pressure was reduced to 1.2 MPa over 30 minutes to obtain a prepolymer. This prepolymer was pulverized and dried under reduced pressure at 120 ° C. for 12 hours to obtain polyamide 9C-2 having a solution viscosity ηinh of 0.23 dL / g.

Polyamide 9C-3:
Polyamide PA9C-1 was extracted in hot water at 80 ° C. for 8 hours. Then, it dried at 120 degreeC under pressure reduction for 12 hours, and obtained polyamide 9C-3 whose solution viscosity is (eta) inh0.89dL / g.

Polyamide 9C-4:
1,4-cyclohexanedicarboxylic acid 5111.2 g (29.7 mol), 1,9-nonanediamine 4117.6 g (26.0 mol), 2-methyl, trans isomer / cis isomer ratio = 30/70 (molar ratio) -1,8-octanediamine 726.6 g (4.59 mol), acetic acid 110.4 g (1.84 mol) as end-capping agent, sodium hypophosphite monohydrate 10 g as catalyst, and distilled water 2.5 L was put into an autoclave with an internal volume of 40 L and purged with nitrogen. The internal temperature was raised to 200 ° C. over 2 hours. At this time, the autoclave was pressurized to 2 MPa. Thereafter, the reaction was continued for 2 hours while gradually removing water vapor and maintaining the pressure at 2 MPa. Next, the pressure was reduced to 1.2 MPa over 30 minutes to obtain a prepolymer. This prepolymer was pulverized and dried at 120 ° C. under reduced pressure for 12 hours. This was polymerized at 350 ° C. under reduced pressure using an extrusion polymerization apparatus so that the residence time was 30 minutes, whereby polyamide 9C-4 having a solution viscosity ηinh of 0.78 dL / g was obtained.

<Copper compound (B1) and metal halide (B2)>
(1) Cuprous iodide, manufactured by Wako Pure Chemical Industries, Ltd. (2) Potassium iodide, manufactured by Wako Pure Chemical Industries, Ltd.

<Compound (C) acting as a Lewis base>
(1) Magnesium oxide:
“MF-150” manufactured by Kyowa Chemical Industry Co., Ltd. (average particle size: 0.71 μm)
(2) Calcium oxide:
“Calcium oxide” manufactured by Kanto Chemical Co., Ltd. (average particle size: 15 μm)
(3) Zinc oxide:
“Zinc oxide” manufactured by Wako Pure Chemical Industries, Ltd. (average particle size: 5.0 μm or less)

[Examples 1 to 12, Reference Example 1 and Comparative Example 1]
A mixture of polyamide 9C-1, polyamide 9C-2, polyamide 9C-3, and polyamide 9C-4 in amounts shown in Table 1 was dried under reduced pressure at 120 ° C. for 24 hours, and then the amount of copper compound shown in Table 1 (B1), metal halide (B2), and compound (C) acting as a Lewis base were dry blended, and the resulting mixture was twin-screw extruder (screw diameter: 30 mm, L / D = 28, cylinder temperature 350 ° C. The mixture was melt-kneaded by feeding from a hopper having a rotational speed of 150 rpm, extruded into a strand, and then cut by a pelletizer to obtain a pellet-like polyamide resin composition. Using the obtained polyamide resin composition, test pieces having a predetermined shape were prepared according to the above-described method, and various physical properties were evaluated. The results are shown in Table 1.

  In Examples 1 to 9, the content of the polyamide (a-1) and the polyamide oligomer (a-2), the trans isomer structural unit content, the content of the copper compound (B1) and the metal halide (B2) are specified. Since it is in the range, it has excellent heat resistance, low water absorption, rigidity at high temperatures, tensile properties, heat aging resistance, fluidity, and moldability, and no mold contamination occurs. Especially, since Examples 6-9 contain the compound (C) which acts as a Lewis base, the trans isomer structural unit content is high, and accordingly, rigidity at high temperature and heat aging resistance are more excellent. Example 10 is excellent in heat resistance, low water absorption, rigidity at high temperature, tensile properties, heat aging resistance, fluidity, and moldability, but there are slight differences in mold contamination. Examples 11 and 12 are excellent in heat resistance, low water absorption, rigidity at high temperature, heat aging resistance, fluidity and moldability, and no mold contamination occurs, but there are differences in tensile properties. Since Reference Example 1 does not contain a copper compound (B1) and a metal halide (B2), it is inferior in heat aging resistance. Since the comparative example 1 has few polyamide oligomers (a-2), it is inferior to low water absorption, fluidity | liquidity, and a moldability.

  The polyamide resin composition of the present invention is excellent in heat resistance, low water absorption, rigidity at high temperature, tensile physical properties, heat aging resistance and fluidity, and crystallization proceeds sufficiently even when molded in a 80 ° C. mold. In addition, there is little mold contamination at the time of manufacture, and it can be widely used as various parts materials for, for example, electric and electronic parts, automobile parts, industrial material parts, daily necessities and household goods.

Claims (14)

The polyamide (a-1) having a number average molecular weight of 2000 or more is contained in a range of 95 to 99.95% by mass, the polyamide oligomer (a-2) having a number average molecular weight of 500 or more and less than 2000 is contained in a range of 0.05 to 5% by mass, 25 mol% or more of all monomer units constituting the polyamide (a-1) and the polyamide oligomer (a-2) are alicyclic monomers represented by the following general formula (I) or general formula (II). A polyamide resin (A), a copper compound (B1), and a metal halide (B2), which are structural units derived from the cycloaliphatic monomer and have a trans isomer structural unit content of 50 to 85 mol%. A polyamide resin composition containing.

(In the formula, X represents a carboxyl group or an amino group, and Z represents an alicyclic structure having 3 or more carbon atoms.)

(In the formula, X and Z are as defined above, and R ¹ and R ² each independently represents an alkylene group having 1 or more carbon atoms.)   The copper compound (B1) is contained in 0.01 to 1 part by mass and the metal halide (B2) is contained in 0.05 to 20 parts by mass with respect to 100 parts by mass of the polyamide resin (A). Polyamide resin composition.   The polyamide resin composition according to claim 1 or 2, wherein the copper compound (B1) is copper iodide and / or copper acetate, and the metal halide (B2) is potassium iodide.   10% or more of the total amount of terminal groups of molecular chains of the polyamide (a-1) and the polyamide oligomer (a-2) constituting the polyamide resin (A) is sealed with a terminal blocking agent. Item 4. The polyamide resin composition according to any one of Items 1 to 3.   The polyamide resin composition according to any one of claims 1 to 4, wherein the alicyclic monomer is a cyclic aliphatic dicarboxylic acid in which X in the general formula (I) or the general formula (II) is a carboxyl group.   The polyamide resin composition according to claim 5, wherein the cycloaliphatic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.   The polyamide resin composition according to any one of claims 1 to 6, wherein the polyamide (a-1) and the polyamide oligomer (a-2) contain a structural unit derived from an aliphatic diamine having 4 to 12 carbon atoms. object.   The aliphatic diamine is 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, The polyamide according to claim 7, which is at least one selected from the group consisting of 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. Resin composition.   Containing 25 mol% or more of structural units derived from 1,4-cyclohexanedicarboxylic acid and 25,9,9-nonanediamine and / or 2-methyl-1,8-octanediamine as structural units derived from aliphatic diamine The polyamide resin composition according to claim 8, which contains at least mol%.   Furthermore, the polyamide resin composition in any one of Claims 1-9 containing the structural unit derived from a lactam and / or aminocarboxylic acid.   The polyamide resin composition in any one of Claims 1-10 containing 0.1-10 mass parts of compounds (C) which act as a Lewis base with respect to 100 mass parts of polyamide resins (A).   The compound (C) acting as a Lewis base is at least selected from the group consisting of alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, alkaline earth metal hydroxides, zinc oxide and zinc hydroxide. The polyamide resin composition of Claim 11 which is 1 type.   The compound (C) acting as the Lewis base is at least one selected from the group consisting of potassium oxide, magnesium oxide, calcium oxide, zinc oxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and zinc hydroxide. The polyamide resin composition according to claim 12.   A molded article comprising the polyamide resin composition according to any one of claims 1 to 13.

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