JP6226704B2 - Polyamide resin composition - Google Patents

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.

  In particular, in the electric / electronic field, by incorporating various flame retardants into the above-mentioned aliphatic polyamide, materials that meet the high flame retardant requirements based on the UL-94 standard have been put into practical use. However, these aliphatic polyamides have large water absorption, and there are problems such as dimensional change of molded products and deterioration of mechanical properties. In recent years, along with the development of surface mounting technology (SMT) in the electric and electronic fields, it has excellent heat resistance and flame retardancy, and swelling of the molded product surface occurs due to reflow heating in the SMT process. Development of materials (blister resistance) that can prevent the phenomenon (blister) is required. In addition, in order to meet the demands for thinning and narrow pitch, materials having high fluidity (thin fluidity) are required.

  In order to meet the above requirements, development of a high melting point polyamide has been advanced as a polyamide containing a flame retardant. 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. The 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 the rigidity at high temperatures (for example, the glass transition of polyamide). In addition to a decrease in various physical properties such as chemical resistance and dimensional stability associated with water absorption, there is a problem of a decrease in productivity due to the extension of the molding cycle.

  While development of polyamides having an aromatic ring structure is underway, polyamides having an alicyclic structure have also been developed. For example, in Patent Document 1, 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 are used in a weight ratio of 25/75 to 85/15. Copolyamides obtained by copolymerization are disclosed, but 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 2 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. 47-42397 Japanese Patent Laid-Open No. 9-12868

  Therefore, the object of the present invention is excellent in heat resistance, flame retardancy, blister resistance, fluidity, rigidity at high temperature, and crystallization proceeds sufficiently even when molded with a 80 ° C. mold, and An object of the present invention is to provide a polyamide resin composition with less mold contamination during production.

（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）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）のポリアミド樹脂組成物；
（３） 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）または（２）のポリアミド樹脂組成物；
（４） 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（３）のポリアミド樹脂組成物；
（５） 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）〜（４）のいずれかのポリアミド樹脂組成物；
（６） 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（５）のポリアミド樹脂組成物；
（７） 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（６）のポリアミド樹脂組成物；
（８） 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）〜（７）のいずれかのポリアミド樹脂組成物；
（９） 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）〜（８）のいずれかのポリアミド樹脂組成物；
（１０） 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（９）のポリアミド樹脂組成物；
（１１） 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（１０）のポリアミド樹脂組成物；
（１２） 前記ポリアミド樹脂（Ａ）１００質量部に対して前記難燃剤（Ｂ）を５〜１００質量部含有する、上記（１）〜（１１）のいずれかのポリアミド樹脂組成物；
（１３） 前記ハロゲン系難燃剤（Ｂ２）が臭素系難燃剤である、上記（１）〜（１２）のいずれかのポリアミド樹脂組成物；
（１４） 前記臭素系難燃剤が臭素化ポリスチレンである、上記（１３）のポリアミド樹脂組成物；
（１５） 前記ポリアミド樹脂（Ａ）１００質量部に対して難燃助剤（Ｄ）を１〜３０質量部含有する、上記（１）〜（１４）のいずれかのポリアミド樹脂組成物；
（１６） 前記難燃助剤（Ｄ）が三酸化二アンチモン、四酸化二アンチモン、五酸化二アンチモン、アンチモン酸ナトリウム、オルソリン酸メラミン、ピロリン酸メラミン、ホウ酸メラミン、ポリリン酸メラミン、酸化アルミニウム、水酸化アルミニウム、ホウ酸亜鉛およびスズ酸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（１５）のポリアミド樹脂組成物；
（１７） 前記ポリアミド樹脂（Ａ）１００質量部に対して繊維状強化材（Ｅ）１〜２００質量部を含有する、上記（１）〜（１６）のいずれかのポリアミド樹脂組成物；
（１８） 上記（１）〜（１７）のいずれかのポリアミド樹脂組成物を含有する成形品；
（１９） 電気部品または電子部品である、上記（１８）の成形品；および
（２０） 製造工程にＳＭＴ工程を含む上記（１９）の成形品；
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 or more and less than 2000 is 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), which is a structural unit derived from a formula monomer, and the trans isomer structural unit content derived from the alicyclic monomer is 50 to 85 mol%, a phosphorus-based flame retardant (B1), and a halogen Polyamide resin composition containing at least one flame retardant (B) selected from a series flame retardant (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) 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 sealing agent. The polyamide resin composition of (1) above;
(3) The polyamide resin composition according to (1) or (2), 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;
(4) The polyamide resin composition according to (3), wherein the cycloaliphatic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid;
(5) Any of (1) to (4) 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;
(6) 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 (5), 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;
(7) 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 (6), which contains 25 mol% or more of diamine;
(8) The polyamide resin composition according to any one of (1) to (7), further comprising a structural unit derived from lactam and / or aminocarboxylic acid;
(9) The polyamide resin composition according to any one of (1) to (8) 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). ;
(10) 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 (9), which is at least one selected;
(11) 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 of (10) above;
(12) The polyamide resin composition according to any one of (1) to (11) above, containing 5 to 100 parts by mass of the flame retardant (B) with respect to 100 parts by mass of the polyamide resin (A);
(13) The polyamide resin composition according to any one of (1) to (12), wherein the halogen flame retardant (B2) is a bromine flame retardant;
(14) The polyamide resin composition according to (13), wherein the brominated flame retardant is brominated polystyrene;
(15) The polyamide resin composition according to any one of (1) to (14) above, containing 1 to 30 parts by mass of a flame retardant aid (D) with respect to 100 parts by mass of the polyamide resin (A);
(16) The flame retardant aid (D) is diantimony trioxide, diantimony tetroxide, diantimony pentoxide, sodium antimonate, melamine orthophosphate, melamine pyrophosphate, melamine borate, melamine polyphosphate, aluminum oxide, The polyamide resin composition of (15), which is at least one selected from the group consisting of aluminum hydroxide, zinc borate and zinc stannate;
(17) The polyamide resin composition according to any one of (1) to (16), comprising 1 to 200 parts by mass of the fibrous reinforcing material (E) with respect to 100 parts by mass of the polyamide resin (A);
(18) A molded article containing the polyamide resin composition according to any one of (1) to (17) above;
(19) The molded product according to (18), which is an electrical component or an electronic component;
Is achieved by providing

  According to the present invention, heat resistance, flame resistance, blister resistance, fluidity, and rigidity at high temperatures are excellent, and crystallization proceeds sufficiently even when molded with a mold at 80 ° C. A polyamide resin composition with less mold contamination can be provided.

2 is a GPC elution curve (vertical axis: signal intensity, horizontal axis: elution time) of the polyamide resin (A) used in Example 1. It is a graph which shows the temperature profile (when measured peak temperature (variable) is 260 degreeC) in the infrared heating furnace of the test piece in evaluation of blister resistance. 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 the measurement conditions in Examples described later using a gel permeation chromatograph (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 where 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 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.

  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, and when two carboxyl groups are on different sides of the ring structure, the two carboxyl groups are on the same side of the trans isomer and ring structure. In some cases, it is cis.

  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 a trans isomer and a cis geometric isomer, and when two amino groups are on different sides of the ring structure, When two amino groups are on the same side, a cis form is obtained.

  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, the “trans isomer structural unit” derived from the alicyclic monomer of the polyamide resin (A) means a structural unit in which an amide bond exists on a different side with respect to 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 further solid-phase polymerization or polymerization using a melt 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.

  In addition, when performing polymerization after obtaining a prepolymer by solid phase polymerization, it is preferably performed in an inert gas atmosphere or under an inert gas flow, and the polymerization temperature is 200 ° C. or higher to 20 ° C. lower than the melting point of polyamide. If it is within the temperature range 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 polyamide are effective. It becomes easy to adjust the content (% by mass) of the oligomer (a-2) 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 compound (C) that acts as a Lewis base that is insoluble in a solvent for dissolving the polyamide resin (A) is dissolved in a solvent for dissolving the polyamide resin (A), and then filtered. GPC measurement may be performed after removing insoluble matter.

[Flame Retardant (B)]
From the viewpoint of imparting flame retardancy to the resin composition, the polyamide resin composition of the present invention is at least one flame retardant (B) selected from a phosphorus-based flame retardant (B1) and a halogen-based flame retardant (B2). Containing.

<Phosphorus flame retardant (B1)>
The phosphorus-based flame retardant (B1) is not particularly limited as long as it is a flame retardant containing a phosphorus element. For example, red phosphorus-based, phosphate ester-based, phosphate amide-based, (poly) phosphate-based, phosphazene-based and Examples include phosphine-based phosphorus flame retardants. Of these, phosphine is preferable. Examples of such phosphine-based flame retardants include phosphinates and / or diphosphinates (hereinafter, both may be collectively referred to as “phosphinates”). In addition, as content of a phosphorus flame retardant (B1), it is preferable to contain 5-100 mass parts with respect to 100 mass parts of polyamide resins (A), and it is more preferable to contain 10-75 mass parts, It is more preferable to contain 30-70 mass parts. By setting the content of the phosphorus flame retardant (B1) to 5 parts by mass or more, a polyamide resin composition having excellent flame retardancy can be obtained. In addition, by setting the content of the phosphorus-based flame retardant (B1) to 100 parts by mass or less, generation of decomposition gas at the time of melt-kneading, decrease in fluidity (particularly, thin-walled fluidity) at the time of molding, and molding metal. It is possible to suppress the adhesion of pollutants to the mold. Furthermore, it is possible to suppress the deterioration of the mechanical properties and the appearance of the molded product.

  Examples of the phosphinic acid salt include compounds represented by the following general formula (III).

ジホスフィン酸塩としては、例えば下記一般式（IV）で示される化合物が挙げられる。

Examples of the diphosphinate include compounds represented by the following general formula (IV).

In general formulas (III) and (IV), R ¹ , R ² , R ^3, and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 7 carbon atoms. Represents an arylalkyl group of ˜20. R ⁵ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 20 carbon atoms, or an arylalkylene group having 7 to 20 carbon atoms. M represents calcium (ion), magnesium (ion), aluminum (ion) or zinc (ion). m is 2 or 3, n is 1 or 3, and x is 1 or 2.

  As said alkyl group, a linear or branched saturated aliphatic group is mentioned. The aryl group may be unsubstituted or substituted with various substituents, and examples thereof include a phenyl group, a benzyl group, an o-toluyl group, and a 2,3-xylyl group.

  The phosphinic acid salt is a metal such as phosphinic acid and metal carbonate, metal hydroxide or metal oxide as described in European Patent Application No. 699708 and Japanese Patent Laid-Open No. 8-73720. It can be produced in aqueous solution using the components. Although these are monomeric compounds, depending on the reaction conditions, polymeric phosphinates having a degree of condensation of 1 to 3 are also included depending on the environment.

  Examples of the phosphinic acid and diphosphinic acid constituting the phosphinic acid salt include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4-di (Methylphosphinic acid), methylphenylphosphinic acid, diphenylphosphinic acid and the like.

  Examples of the metal component constituting the phosphinate include calcium ions, magnesium ions, aluminum ions, and zinc ions.

  Examples of phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate. , Calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propylphosphinate, methyl- n-propylphosphinic acid zinc, methylenebis (methylphosphinic acid) calcium, methylenebis (methylphosphoric acid) Finic acid) magnesium, methylene bis (methylphosphinic acid) aluminum, methylene bis (methylphosphinic acid) zinc, phenylene-1,4-bis (methylphosphinic acid) calcium, phenylene-1,4-bis (methylphosphinic acid) magnesium, phenylene -1,4-bis (methylphosphinic acid) aluminum, phenylene-1,4-bis (methylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate , Calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate and the like.

  Above all, from the viewpoint of flame retardancy and electrical properties of the obtained polyamide resin composition and availability of phosphinate, calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, ethyl Aluminum methylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate and zinc diethylphosphinate are preferred. These phosphinic acid salts may be used alone or in combination of two or more.

  As the phosphinate, it is used as a powder obtained by pulverizing the average particle diameter of the phosphinate to 100 μm or less in terms of mechanical properties (toughness, rigidity, etc.) of the polyamide resin composition and a molded product made from the same, and appearance of the molded product. It is preferable to use a powder pulverized to 50 μm or less. Use of a powdered phosphinate having an average particle size of 0.5 to 20 μm is preferable because not only a polyamide resin composition having excellent flame retardancy can be obtained, but also the rigidity of the molded product is improved.

  The phosphinic acid salt is not necessarily completely pure, and may contain unreacted substances or by-products as long as the effects of the present invention are not impaired.

[Halogen flame retardant (B2)]
As content of a halogenated flame retardant (B2), it is preferable to contain 5-100 mass parts with respect to 100 mass parts of polyamide resins (A), It is more preferable to contain 10-75 mass parts, 30- More preferably, 70 parts by mass is contained. By setting the content of the halogen-based flame retardant (B2) to 5 parts by mass or more, a polyamide composition having excellent flame retardancy can be obtained. Further, by setting the content of the halogen-based flame retardant (B2) to 100 parts by mass or less, generation of decomposition gas at the time of melt-kneading, lowering of fluidity (particularly, thin-walled fluidity) at the time of molding, and molding mold It is possible to suppress the adhesion of pollutants to the water. Furthermore, it is possible to suppress the deterioration of the mechanical properties and the appearance of the molded product.

  The halogen flame retardant (B2) is not particularly limited as long as it is a flame retardant containing a halogen element, and examples thereof include a chlorine flame retardant and a bromine flame retardant. These may be used alone or in combination of two or more.

  Examples of the chlorinated flame retardant include chlorinated paraffin, chlorinated polyethylene, dodecachloropentacyclooctadeca-7,15-diene (produced by Occidental Chemical Co., “Dechlorane Plus 25”), and anhydrous heptic acid. .

  Examples of brominated flame retardants include hexabromocyclododecane, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, bis (tribromophenoxy) ethane, bis (pentabromophenoxy) ethane, and tetrabromobisphenol A epoxy resin. , Tetrabromobisphenol A carbonate, ethylene (bistetrabromophthal) imide, ethylenebispentabromodiphenyl, tris (tribromophenoxy) triazine, bis (dibromopropyl) tetrabromobisphenol A, bis (dibromopropyl) tetrabromobisphenol S, Brominated polyphenylene ether (including poly (di) bromophenylene ether), brominated polystyrene (polydibromostyrene, polytri (Including bromostyrene, crosslinked brominated polystyrene, etc.), brominated crosslinked aromatic polymers, brominated epoxy resins, brominated phenoxy resins, brominated styrene-maleic anhydride polymers, tetrabromobisphenol S, tris (tribromoneopentyl) ) Phosphate, polybromotrimethylphenylindane, tris (dibromopropyl) -isocyanurate and the like.

  The brominated flame retardant is a brominated polyphenylene ether from the viewpoint of reducing the amount of corrosive gas generated during melt processing such as extrusion and molding, and improving the flame retardancy and mechanical properties of electrical or electronic components. (Including poly (di) bromophenylene ether) and brominated polystyrene (including polydibromostyrene, polytribromostyrene, and crosslinked brominated polystyrene) are preferable, and brominated polystyrene is more preferable.

  For example, brominated polystyrene is produced by polymerizing a styrene monomer to produce polystyrene, and then brominating the benzene ring of polystyrene or brominated styrene monomers (bromostyrene, dibromostyrene, tribromostyrene, etc.) It can be produced by a polymerization method.

  The bromine content in the brominated polystyrene is preferably 55 to 75% by mass. By making the bromine content 55% by mass or more, it is possible to satisfy the bromine amount necessary for flame retardancy with a small brominated polystyrene content, and the decrease in mechanical properties of the polyamide resin (A) is small. A polyamide resin composition having excellent mechanical properties and heat resistance can be obtained. In addition, by setting the bromine content to 75% by mass or less, a polyamide resin composition that is less prone to thermal decomposition during melt processing such as extrusion and molding, can suppress gas generation, and is excellent in heat discoloration. Can be obtained.

[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.

[Flame Retardant (D)]
The polyamide resin composition of the present invention may contain a flame retardant aid (D). By using the flame retardant aid (D) in combination with the flame retardant (B), the polyamide resin composition of the present invention and a molded product comprising the same can exhibit further excellent flame retardancy.

  When the flame retardant aid (D) is contained, the content thereof is preferably 1 to 30 parts by mass, more preferably 1 to 25 parts by mass, and 3 to 20 parts by mass with respect to 100 parts by mass of the polyamide resin (A). Even more preferred.

  Examples of the flame retardant aid (D) include antimony compounds such as antimony trioxide, antimony tetroxide, antimony pentoxide, and antimony oxides such as sodium antimonate; melamine orthophosphate, melamine pyrophosphate, and boric acid Melamine compounds such as melamine and melamine polyphosphate; tin oxide such as tin monoxide and tin dioxide; iron oxide such as ferric oxide and gamma iron oxide; aluminum oxide, silicon oxide (silica), titanium oxide, zirconium oxide, Metal oxides such as manganese oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, nickel oxide, copper oxide and tungsten oxide; metal hydroxides such as aluminum hydroxide; aluminum, iron, titanium, manganese, Zinc, molybdenum, cobalt, bismuth, chromium, tin, aluminum Metal powder such as Timon, Nickel, Copper, Tungsten; Metal carbonate such as Zinc carbonate, Calcium carbonate, Magnesium carbonate, Barium carbonate; Metal borate such as Zinc borate, Calcium borate, Zinc stannate, Aluminum borate Silicone and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together. However, the compound acting as a Lewis base in the polyamide resin composition of the present invention is included in the compound (C) acting as a Lewis base in the present specification, and is distinguished from the flame retardant aid (D).

  Of these, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, melamine orthophosphate, melamine pyrophosphate, melamine borate, melamine polyphosphate, aluminum oxide, aluminum hydroxide, zinc borate and tin At least one selected from the group consisting of zinc acids is preferred.

  The flame retardant aid (D) is preferably contained in the polyamide resin composition of the present invention as a powder. The upper limit of the average particle diameter is preferably 30 μm, more preferably 15 μm, further preferably 10 μm, and most preferably 7 μm. On the other hand, the lower limit of the average particle size of the flame retardant aid (D) is preferably 0.01 μm. When the average particle size is 0.01 to 30 μm, the flame resistance of the obtained polyamide resin composition is improved.

[Fibrous reinforcement (E)]
The polyamide resin composition of the present invention may contain a fibrous reinforcing material (E). By using the fibrous reinforcing material (E), a polyamide resin composition having excellent heat resistance, rigidity at high temperature, and heat aging resistance can be obtained.

  Examples of the fibrous reinforcing material (E) include glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, and aramid fiber. Among these, glass fiber and carbon fiber are preferable from the viewpoint of strength and rigidity. These may be used alone or in combination of two or more.

  In the present invention, it is preferable that the fibrous reinforcing material (E) has a cross-section major axis D2 and a minor axis D1 having a flatness expressed by D2 / D1 of 1.5 or more. If there is a nominal value by the manufacturer, the flatness can be used as it is, but if there is no nominal value, D2 and D1 can be calculated by observing the cross section of the fibrous reinforcing material (E) with a microscope.

  Examples of the cross-sectional shape of the fibrous reinforcing material (E) include a rectangle, an oval close to a rectangle, an ellipse, a saddle shape, and a saddle shape with a narrowed central portion in the longitudinal direction. Among these, the cross-sectional shape of the fibrous reinforcing material (E) is preferably a rectangle, an oval close to a rectangle, an ellipse, or a bowl.

  When a plate-shaped molded article is produced from the polyamide resin composition of the present invention, from the viewpoints of reduction of warpage (shape stability), heat resistance, toughness, flame resistance, blister resistance, and fluidity of the plate-shaped molded article. The flatness of the fibrous reinforcing material (E) is preferably 1.5 or more, more preferably 1.5 to 10.0, still more preferably 2.5 to 10.0, Most preferably, it is 3.1-6.0. When the aspect ratio is as large as about 15 to 20, the desired effect of the present invention may not be obtained in some cases, such as mixing with other components, and crushing during processing such as kneading and molding.

  The fiber diameter of the fibrous reinforcing material (E) is not particularly limited, but it is usually preferable that the cross-sectional minor axis D1 is 0.5 to 25 μm and the cross-sectional major axis D2 is 1.25 to 250 μm. If the fiber diameter is smaller than the above range, spinning of the fiber may be difficult. If it is larger than the above range, the mechanical strength of the molded product may decrease due to a decrease in the contact area with the resin. The short diameter D1 is preferably 3 μm or more, more preferably the short diameter D1 is 3 μm or more and the flatness is a value larger than 3.

  The fibrous reinforcing material (E) can be produced by a method described in, for example, Japanese Patent Publication No. 3-59019, Japanese Patent Publication No. 4-13300, Japanese Patent Publication No. 4-32775, and the like. Particularly, in an orifice plate having a large number of orifices on the bottom surface, an orifice plate which surrounds a plurality of orifice outlets and has a convex edge extending downward from the bottom surface of the orifice plate, or a nozzle chip having one or a plurality of orifice holes. A glass fiber having a flatness ratio of 1.5 or more, which is manufactured using a nozzle chip for deformed cross-section glass fiber spinning provided with a plurality of convex edges extending downward from the front end of the outer peripheral portion is preferable. In the fibrous reinforcing material (E), the fiber strand may be used as a roving as it is, or may be used as a chopped glass strand through a cutting process.

  The compounding amount of the fibrous reinforcing material (E) is preferably 0.1 to 200 parts by mass, more preferably 1 to 180 parts by mass, and further preferably 100 parts by mass of the polyamide resin (A). 5 to 150 parts by mass. By setting the blending amount of the fibrous reinforcement (E) to 0.1 parts by mass or more with respect to 100 parts by mass of the polyamide resin (A), the toughness, mechanical strength, etc. of the polyamide resin composition of the present invention are improved. Moreover, the polyamide resin composition with easy moldability is obtained by setting the blending amount to 200 parts by mass or less.

When the fibrous reinforcing material (E) is a glass fiber, specific examples of the composition include an E glass composition, a C glass composition, an S glass composition, and an alkali-resistant glass composition. Moreover, although the tensile strength of glass fiber is arbitrary, it is usually 290 kg / mm ² or more. Among these, E glass is preferable from the viewpoint of easy availability. These glass fibers are preferably surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like. The amount is usually 0.01% by mass or more based on the glass fiber weight (total amount of glass fiber and surface treatment agent).

  If necessary, the fibrous reinforcing material (E) can be treated with a sizing agent. As the sizing agent, polymers containing carboxylic acid anhydride-containing unsaturated vinyl monomers as constituent units, epoxy compounds, polyurethane resins, homopolymers / copolymers of acrylic acid, their primary and secondary And salts with tertiary or tertiary amines. These may be used alone or in combination of two or more.

  The polyamide resin composition of the present invention may contain a fibrous inorganic filler other than the fibrous reinforcing material (E).

  Examples of such other fibrous inorganic fillers include carbon fiber and wollastonite. In the case of these carbon fibers, the average fiber diameter is 3 to 30 μm, the weight average fiber length is 100 to 750 μm, and the aspect ratio (L / D) between the weight average fiber length and the average fiber diameter is 10 to 100. Some are preferably used from the viewpoint of excellent rigidity and fluidity at high temperatures. In the case of wollastonite, it is more preferable that the average fiber diameter is 3 to 30 μm, the weight average fiber length is 10 to 500 μm, and the aspect ratio (L / D) is 3 to 100.

  Measurement of the average fiber diameter and the weight average fiber length of the other fibrous inorganic filler is obtained by dissolving the molded article of the polyamide resin composition with a solvent such as formic acid in which the polyamide is soluble, Observation with an optical microscope, a scanning electron microscope, or the like, for example, can be calculated by obtaining an average of 100 or more.

  The other fibrous inorganic filler can be treated with a sizing agent, if necessary. As the sizing agent, the same sizing agent that can be used for the above-described fibrous reinforcing material (E) can be used.

  In the molded article containing the polyamide resin composition of the present invention, in addition to the fibrous reinforcing material (E), the other fibrous inorganic material is used from the viewpoint of reducing the occurrence of warpage and reducing the dimensional anisotropy. An inorganic filler different from the filler may be included. Examples of such inorganic fillers include glass flakes, glass beads, hollow glass beads, talc, kaolin, mica, silicon nitride, hydrotalcite, calcium monohydrogen phosphate, zeolite, boehmite, silicon oxide, calcium silicate, Examples thereof include sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, calcium fluoride, mica, montmorillonite, swellable fluorine mica, and apatite. These inorganic fillers may be surface-treated. One kind of the inorganic filler described above may be used alone, or two or more kinds may be used in combination.

[Other ingredients]
The polyamide resin composition of the present invention includes a polyamide resin (A), a flame retardant (B), a compound acting as a Lewis base (C), and a flame retardant aid, as long as the effects of the present invention are not impaired. Components other than (D) and the fibrous reinforcing material (E) may be included. Examples of other components include thermoplastic resins other than polyamide (a-1) and polyamide oligomer (a-2), compatibilizers, organic fillers, silane coupling agents, crystal nucleating agents, dyes, pigments, and light stabilizers. Agents, antistatic agents, plasticizers, lubricants, processing aids, lubricants, fluorescent bleaches, rubbers and reinforcing agents.

[Production method of polyamide resin composition]
As a method for containing the flame retardant (B), any method can be used as long as it is uniformly mixed with the polyamide resin (A). Usually, melt-kneading is performed using a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, or the like. Is adopted. Although the melt-kneading conditions are not particularly limited, for example, the polyamide resin composition of the present invention can be obtained by melt-kneading for 1 to 30 minutes in a temperature range 30 to 50 ° C. higher than the melting point of the polyamide resin (A). In addition, when the viscosity of the polyamide resin (A) is high, the dispersion of the flame retardant (B) in the polyamide resin composition becomes insufficient, and sufficient flame retardancy and resistance to the resulting polyamide resin composition and a molded product comprising the polyamide resin composition are obtained. Blister properties cannot be imparted, and whitening of the product surface tends to occur.

  The compound (C) acting as a Lewis base, the flame retardant aid (D), the fibrous reinforcing material (E), and other components may be previously contained in the polyamide resin composition. Moreover, as a method of containing these components, any method may be used as long as these components are uniformly mixed. Usually, melt kneading is performed using a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, or the like. The method of supplying the components constituting the polyamide resin composition to which the method is applied to the melt kneader may be that all the components may be supplied to the same supply port at once, or the components may be supplied from different supply ports. May be. The melt kneading temperature is preferably about 5 ° C. to about 375 ° C. higher than the melting point of the polyamide resin (A). The melt kneading time is preferably about 0.5 to 15 minutes.

[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 which combined 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.

  Among them, the polyamide resin composition of the present invention can be suitably used for electric parts or electronic parts, and particularly from the viewpoint of excellent heat resistance, electric parts or electronic parts including an SMT process, more specifically, SMT compatible. It can be suitably used for connectors, switches, coil bobbins, breakers, electromagnetic switches, holders, plugs, and switches. Moreover, since it is excellent in thin-wall fluidity | liquidity, even if it contains a thin part with a thickness of 0.4 mm or less, manufacture is possible preferably.

  EXAMPLES Hereinafter, although an Example and a comparative example (henceforth an Example etc.) demonstrate 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, flame retardancy, blister resistance, fluidity, deflection temperature under load, 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.
An elution curve when the polyamide resin (A) used in Example 1 described later is measured under the above conditions is shown in FIG. 1 together with regions of the polyamide (a-1) and the polyamide oligomer (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 (D) sealed with the terminal blocking agent are obtained from the integral value of the characteristic signal of each terminal group, respectively, and the terminal sealing is performed from the mathematical formula (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.

<Flame retardance>
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 each melting point, and a plate-shaped test piece having a thickness of 1 mm. Was made. And it was set as the flame-resistant parameter | index according to the prescription | regulation of UL-94 specification shown below. That is, the upper end of a test piece having a thickness of 1 mm was clamped to fix the test piece vertically, a predetermined flame was applied to the lower end for 10 seconds, and the burning time (first time) of the test piece was measured. After extinguishing the fire, flame was again applied to the lower end and released, and the burning time (second time) of the test piece was measured. The same measurement was repeated for 5 pieces, and a total of 10 data were obtained: 5 data for the first burning time (seconds) and 5 data for the second burning time. The total of 10 data is T, and the maximum value of 10 data is M. If T is 50 seconds or less, M is 10 seconds or less, does not burn up to the clamp, the flamed melt falls and does not ignite the cotton 12 inches below, “V-0”, T is 250 seconds In the following, M is 30 seconds or less, otherwise “V-1” if the same conditions as V-0 are satisfied, T is 250 seconds or less, M is 30 seconds or less, and does not burn up to the clamps. When the molten material dropped and ignited cotton 12 inches below, it was set as “V-2”. Moreover, it was set as "x" when not satisfying any evaluation criteria of said UL-94.

<Blister temperature resistance>
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 each melting point, and the length was 30 mm, the width was 10 mm, and the thickness was 0 A test piece (sheet) of 5 mm was produced. The obtained test piece was allowed to stand for 72 hours under conditions of a temperature of 40 ° C. and a relative humidity of 95%. Then, the reflow process of the temperature profile shown in FIG. 2 was performed with respect to the test piece using the infrared heating furnace (the Sanyo Seiko Co., Ltd. product, SMT scope). At that time, a sensor was installed on the test piece, and its temperature profile was measured. The reflow process was performed by changing the peak temperature in increments of 5 ° C in the interval from 240 ° C to 270 ° C. After completion of the reflow process, the appearance of the test piece was visually observed. The limit temperature at which the test piece does not melt and blisters are not generated is defined as the blister resistance temperature. The case where the blister resistance temperature exceeds 260 ° C. is “◯”, and the case where the blister resistance temperature is 240 ° C. or more and 260 ° C. or less is “ “Δ”, when the blister resistance temperature was less than 240 ° C., was set as “x”, and was used as an index of blister resistance.

<Fluidity>
Using the polyamide resin composition obtained in each example, etc., on an injection molding machine (SE18DU manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 340 ° C., an injection pressure of 90%, and a mold temperature of 140 ° C. A test piece having a length of 30 mm, a width of 30 mm, and a thickness of 0.3 mm was produced. The injection molding is performed 10 shots, 10 test pieces are produced, and when 10 test pieces having the above dimensions are obtained, “◯” indicates that one of the test pieces having the above dimensions is present due to insufficient filling of the polyamide resin composition. The case where it was not obtained was set as “Δ”, the case where the polyamide resin composition could not be filled, and the case where one of the test pieces having the above dimensions was not obtained was set as “x”.

<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.

<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 Example etc., the following conditions were satisfied with a mold having the shape shown in FIGS. 3 and 4 (FIG. 3: front view, FIG. 4: cross-sectional view with the k-axis as the cut surface). 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), flame retardant (B), compound (C) acting as a Lewis base, flame retardant aid (D), and fibrous reinforcing material (E) used in each example are shown below.

<Polyamide resin (A)>
The following polyamides were blended in the proportions shown in Tables 1 and 2 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 (eta) inh is 0.89 dL / 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.

<Flame retardant (B)>
[Phosphorus flame retardant (B1)]
“Exorit OP-930” (aluminum phosphinate), manufactured by Clariant Japan
[Halogen flame retardant (B2)]
“SAYTEX HP-7010G” manufactured by ALBEMARLE (brominated polystyrene: bromine content: 68%)

<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)

<Flame Retardant (D)>
(1) Borax Japan Co., Ltd., “Fire Break 415” (zinc borate)
(2) “MELAPUR200” (melamine polyphosphate), manufactured by Ciba Special Chemicals
(3) “MSA” (antimony trioxide) manufactured by Yamanaka Sangyo Co., Ltd.
(4) “FLAMARD-S” (Zinc stannate), manufactured by Nippon Light Metal Co., Ltd.

<Fibrous reinforcement (E)>
“CS-3J-256S” manufactured by Nitto Boseki Co., Ltd. (glass fiber: flatness = 1, diameter 11 μm, cut length 3 mm)

[Examples 1 to 17 and Comparative Examples 1 to 9]
After drying the mixture which mix | blended polyamide 9C-1-4 with the quantity shown in Table 1 and Table 2 under reduced pressure at 120 degreeC for 24 hours, the flame retardant (B) of the quantity shown in Table 1 and Table 2, and as needed The compound (C) acting as a Lewis base and the flame retardant aid (D) were dry blended, and the resulting mixture was twin screw extruder (screw diameter: 30 mm, L / D = 28, cylinder temperature 350 ° C., rotating Feed from a hopper of several 150 rpm), and further, if necessary, feed the fibrous reinforcing material (E) in the amount shown in Table 1 and Table 2 from the downstream supply port, melt knead, and extrude into a strand. A pelletized polyamide resin composition was obtained by cutting with a pelletizer. 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 Tables 1 and 2.

  In Examples 1 to 9, since the content of the polyamide (a-1) and the polyamide oligomer (a-2) and the trans isomer structural unit content are in a specific range and include the phosphorus-based flame retardant (B1), Excellent in heat resistance, flame retardancy, blister resistance, fluidity, rigidity at high temperature, and moldability (relative crystallinity is large), and mold contamination does not occur. Especially, since Examples 7-9 contain the compound (C) which acts as a Lewis base, trans isomer structural unit content rate is high, and the rigidity under high temperature is more excellent in connection with it. Example 10 is excellent in heat resistance, flame retardancy, blister resistance, fluidity, rigidity at high temperatures, and moldability, but there are slight differences in fluidity and mold contamination. Since the comparative example 1 does not contain a phosphorus flame retardant (B1), it is inferior in flame retardancy. Since Comparative Examples 2-4 has few polyamide oligomers (a-2), it is inferior to fluidity | liquidity and a moldability. Furthermore, it is also inferior in blister resistance with fluidity | liquidity being bad.

  In Examples 11 to 16, since the content of the polyamide (a-1) and the polyamide oligomer (a-2) and the trans isomer structural unit content are in a specific range and include the halogen-based flame retardant (B2), Excellent in heat resistance, flame retardancy, blister resistance, fluidity, rigidity at high temperature, and moldability (relative crystallinity is large), and mold contamination does not occur. Especially, since Examples 13-16 contain the compound (C) which acts as a Lewis base, trans isomer structural unit content rate is high, and the rigidity in high temperature is more excellent in connection with it. Example 17 is excellent in heat resistance, flame retardancy, blister resistance, fluidity, rigidity at high temperature, and moldability, but there are slight differences in mold contamination. Since Comparative Example 5 does not contain the halogen-based flame retardant (B), the flame retardancy is inferior. Since Comparative Examples 6-9 have few polyamide oligomers (a-2), they are inferior in fluidity | liquidity and a moldability. Furthermore, it is inferior in flame retardancy and blister resistance due to poor fluidity.

  The polyamide resin composition of the present invention is excellent in heat resistance, flame retardancy, blister resistance, fluidity, rigidity at high temperature, and crystallization proceeds sufficiently even when molded with a 80 ° C. mold, and 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 (20)

The polyamide (a-1) having a number average molecular weight of 2000 or more is contained in a range of 95 to 99.95 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 mass%, Cycloaliphatic dicarboxylic acid in which 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) A polyamide resin (A) in which the content of the trans isomer structural unit derived from the cycloaliphatic dicarboxylic acid is 50 to 85 mol%, a phosphorus flame retardant (B1), and a halogen series Containing at least one flame retardant (B) selected from the flame retardant (B2) ,
In the polyamide resin (A), a polyamide resin composition having the same structural unit derived from the cyclic aliphatic dicarboxylic acid constituting the polyamide (a-1) and the polyamide oligomer (a-2) .

(In the formula, X represents a carboxyl 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.)   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 2. The polyamide resin composition according to Item 1. The polyamide resin composition according to claim 1 or 2, wherein the cycloaliphatic dicarboxylic acid has 5 to 10 carbon atoms . The polyamide resin composition according to any one of claims 1 to 3 , wherein the cycloaliphatic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.   The polyamide resin composition according to any one of claims 1 to 4, 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 5, 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 6, which contains at least mol%.   Furthermore, the polyamide resin composition in any one of Claims 1-7 containing the structural unit derived from a lactam and / or aminocarboxylic acid.   The polyamide resin composition in any one of Claims 1-8 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 9 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 10.   The polyamide resin composition in any one of Claims 1-11 containing 5-100 mass parts of said flame retardants (B) with respect to 100 mass parts of said polyamide resins (A).   The polyamide resin composition according to any one of claims 1 to 12, wherein the halogen flame retardant (B2) is a bromine flame retardant.   The polyamide resin composition according to claim 13, wherein the brominated flame retardant is brominated polystyrene.   The polyamide resin composition in any one of Claims 1-14 which contains 1-30 mass parts of flame retardant adjuvants (D) with respect to 100 mass parts of said polyamide resins (A).   The flame retardant aid (D) is antimony trioxide, diantimony tetroxide, diantimony pentoxide, sodium antimonate, melamine orthophosphate, melamine pyrophosphate, melamine borate, melamine polyphosphate, aluminum oxide, aluminum hydroxide The polyamide resin composition according to claim 15, which is at least one selected from the group consisting of zinc borate and zinc stannate.   The polyamide resin composition in any one of Claims 1-16 containing 1-200 mass parts of fibrous reinforcements (E) with respect to 100 mass parts of said polyamide resins (A).   A molded article containing the polyamide resin composition according to claim 1.   The molded article according to claim 18, which is an electrical part or an electronic part.   The molded article according to claim 19, wherein the manufacturing process includes an SMT process.

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