JP2016176060A - Polyamide resin composition and molded part obtained by molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition capable of obtaining a molded part excellent in fluidity and retention stability and excellent in fire retardancy, thermal aging resistance, surface appearance and hinge properties.SOLUTION: Provided is a polyamide resin composition obtained by blending 100 pts.wt. of a polyamide resin (A) with (B) 0.1 to 20 pts.wt. of a compound having a hydroxyl group and/or an amino group, an epoxy group and/or a carbodiimide group, in which the total number of the hydroxyl group and the amino group in one molecule is higher than the total number of the epoxy group and the carbodiimide group in one molecule and (C)0.1 to 50 pts.wt. of a fire retardancy.SELECTED DRAWING: None

Description

  The present invention relates to a polyamide resin composition and a molded product formed by molding the same.

  Polyamide resin has excellent heat resistance, mechanical properties, moldability, etc., so it has suitable properties as engineering plastics. Widely used in applications. In particular, it is preferably used for molded products having hinge portions such as connectors, clips, and binding bands, taking advantage of the characteristics of excellent toughness. Of these uses, particularly in electrical and electronic parts, there is a strong demand for flame retardancy, and studies have been made on imparting flame retardancy using various flame retardants.

  For example, a flame retardant polyamide resin composition comprising a polyamide resin and a melamine cyanurate flame retardant has been proposed as a technique for improving the flame resistance of polyamide resin. It is disclosed that it is suitable for a molded article having a hinge portion in a wide field such as automobile industrial parts such as materials, OA equipment, and home appliances (see, for example, Patent Document 1). However, such a flame retardant polyamide resin composition has a problem that the dispersibility of the melamine cyanurate-based flame retardant is insufficient and the fluidity, residence stability, and hinge characteristics are insufficient. In addition, from the viewpoint of dispersibility, the method includes a step of melting and kneading a polyamide resin and melamine cyanurate to form a master batch, and a step of further melting and kneading the polyamide resin to form a composition in the master batch. Although a method for producing a flame retardant polyamide resin composition is proposed (for example, see Patent Document 2), it is still insufficient for achieving both hinge characteristics and flame retardancy.

  On the other hand, due to the recent increase in the density of parts in the engine room in the automobile field, the increase in engine output, and the higher integration of semiconductor devices in the electric / electronic field, the environmental temperature has been rising, and the hinge part as described above is included. In addition to hinge characteristics and flame retardancy, parts are also required to have heat aging resistance under higher temperature conditions. In addition, the demand for fluidity is increasing with the increase in the number of products used to improve production efficiency. Numerous technical improvements have been attempted to improve the heat aging resistance of polyamide resins. For example, a polyamide resin composition containing a polyamide resin, a polyhydric alcohol having a number average molecular weight of less than 2000, a co-stabilizer such as a copper stabilizer or a hindered phenol, and a polymer reinforcing material (see, for example, Patent Document 3) ), A polyamide resin, a thermoplastic resin composition containing a polyhydric alcohol having a particle size of 70 microns or less (see, for example, Patent Document 4), a polyamide resin, polyethyleneimine, a lubricant, a copper-containing stabilizer, A polyamide resin composition containing a filler and nigrosine (see, for example, Patent Document 5) has been proposed.

JP 2000-26721 A Japanese Patent Laid-Open No. 08-245875 Special table 2011-529991 gazette Special table 2014-525506 gazette Special table 2008-530290

  However, the molded product obtained from the polyamide resin composition of Patent Documents 3 and 4 has excellent heat aging resistance in a temperature range of 150 ° C. to 230 ° C., but has heat aging resistance in a temperature range of less than 150 ° C. There was a problem of being inferior. Further, the polyamide resin composition of Patent Document 5 also has excellent heat aging resistance in a temperature range of 160 ° C. to 180 ° C., but has a problem of poor heat aging resistance in a temperature range of less than 150 ° C. . Furthermore, the polyamide resin compositions of Patent Documents 3, 4, and 5 are (i) problems on the surface appearance such as bleeding out of polyhydric alcohol and the like on the surface of the molded product, and coloring due to liberation of copper ions, (ii) There was a problem of inferior residence stability and (iii) hinge characteristics.

  In view of these problems of the prior art, the present invention provides a polyamide resin composition that is excellent in fluidity and retention stability, and can obtain a molded product excellent in heat aging resistance, flame retardancy, hinge characteristics, and surface appearance. This is the issue.

In order to solve the above problems, the present invention mainly has the following configuration.
[1] (A) The sum of the number of hydroxyl groups and amino groups in one molecule having (B) hydroxyl groups and / or amino groups and epoxy groups and / or carbodiimide groups with respect to 100 parts by weight of polyamide resin Is a polyamide resin composition comprising 0.1 to 20 parts by weight of a compound larger than the sum of the number of epoxy groups and carbodiimide groups in one molecule and 0.1 to 50 parts by weight of (C) a flame retardant.
[2] The compound (B) is a reaction product of (b) a hydroxyl group and / or amino group-containing compound and (b ′) an epoxy group and / or carbodiimide group-containing compound. The polyamide resin composition according to [1], wherein a reaction rate with a group or a carbodiimide group is 1 to 95%.
[3] The polyamide resin composition according to [1] or [2], wherein the compound (B) is a compound having a structure represented by the following general formula (1) and / or a condensate thereof.

In the general formula (1), X ^{1 to} X ⁶ may be the same or different and each represents OH, NH ₂ , CH ₃ or OR. However, the sum of the numbers of OH, NH ₂ and OR is 3 or more. Moreover, R represents the organic group which has an amino group, an epoxy group, or a carbodiimide group, and n represents the range of 0-20.
[4] A molded product formed by molding the polyamide resin composition according to any one of [1] to [3].
[5] The molded article according to [4], which has a hinge part.

  The polyamide resin composition of the present invention is excellent in fluidity and residence stability. According to the polyamide resin composition of the present invention, a molded product excellent in heat aging resistance, flame retardancy, hinge characteristics, and surface appearance can be provided.

¹ H-NMR spectrum of a dry blend product of dipentaerythritol and bisphenol A type epoxy resin. ¹ H-NMR spectrum of a melt-kneaded reaction product of a polyhydric alcohol and an epoxy compound obtained in Reference Example 9. The top view (a) and sectional drawing (b) of the molded article which have a hinge part used for hinge characteristic evaluation in the Example.

  Hereinafter, embodiments of the present invention will be described in detail. The polyamide resin composition of the embodiment of the present invention has (B) a hydroxyl group and / or an amino group, an epoxy group and / or a carbodiimide group with respect to 100 parts by weight of the (A) polyamide resin. 0.1 to 20 parts by weight of a compound in which the sum of the number of hydroxyl groups and amino groups in the molecule is greater than the sum of the number of epoxy groups and carbodiimide groups in one molecule (hereinafter referred to as “(B) compound”) And (C) 0.1-50 parts by weight of a flame retardant. Hereinafter, each component will be described.

  In the polyamide resin composition of the embodiment of the present invention, it is considered that (A) the polyamide resin has a carboxyl terminal group that undergoes a dehydration condensation reaction with a hydroxyl group and / or an amino group in the compound (B) described later. Furthermore, in the polyamide resin composition of the embodiment of the present invention, (A) the amino terminal group and carboxyl terminal group of the polyamide resin are the hydroxyl group and / or amino group, epoxy group and / or carbodiimide group in the compound (B). It is thought to react. For this reason, it is thought that (A) polyamide resin is excellent in compatibility with (B) compound.

  The (A) polyamide resin used in the embodiment of the present invention is a polyamide mainly composed of (i) amino acid, (ii) lactam or (iii) diamine and dicarboxylic acid. (A) As a typical example of the raw material of the polyamide resin, amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethyl Hexamethylenediamine, 5-methylnonamethylenediamine, aliphatic diamine such as 2-methyloctamethylenediamine, aromatic diamine such as metaxylylenediamine, paraxylylenediamine, 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 Aliphatic diamines such as 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, aliphatics such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid Dicarboxylic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid Aromatic dicarboxylic acids such as acids, 1, - cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, an alicyclic dicarboxylic acids such as 1,3-cyclopentane dicarboxylic acid. In the embodiment of the present invention, (A) two or more polyamide homopolymers or polyamide copolymers derived from these raw materials may be blended as raw materials for the polyamide resin.

  Specific examples of the polyamide resin include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide (nylon 410). , Polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (Nylon 106), polydecane methylene sebamide (nylon 1010), polydecane methylene dodecane (nylon 1012), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polycaproamide / polyhexamethylene azide Pamidocoli -(Nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipa Mido / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polyundecanamide copolymer (nylon 6T / 11) , Polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexame Lenisophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6), polyxylylene sebacamide (nylon XD10), polyhexamethylene terephthalamide / polypentamethylene terephthalamide copolymer (nylon 6T) / 5T), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T), polypentamethylene terephthalamide / polydecamethylene terephthalamide copolymer (nylon 5T / 10T), polynonamethylene terephthalate Examples include amide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), and polydodecamethylene terephthalamide (nylon 12T). In addition, specific examples of the polyamide resin include a mixture and a copolymer thereof. Here, “/” indicates a copolymer. The same shall apply hereinafter.

  A particularly preferred polyamide resin is a polyamide resin having a difference between the melting point and the cooling crystallization temperature of 30 ° C. or more. The polyamide resin having a difference between the melting point and the temperature-falling crystallization temperature of 30 ° C. or higher is excellent in fluidity because of its slow solidification rate, and can improve the dispersibility of the flame retardant (C) as described later. Variation in flame retardancy can be suppressed. Moreover, hinge characteristics can be further improved by forming a more uniform and fine dispersed structure in the resin composition. The difference between the melting point and the cooling crystallization temperature is preferably 50 ° C. or higher. Here, the melting point of the polyamide resin in the embodiment of the present invention is the temperature after the polyamide resin is cooled from the molten state to 30 ° C. at a temperature decreasing rate of 20 ° C./min in an inert gas atmosphere using a differential scanning calorimeter. The temperature of the endothermic peak that appears when the temperature is raised to the melting point + 40 ° C. at a rate of temperature increase of 20 ° C./min is defined. However, when two or more endothermic peaks are detected, the temperature of the endothermic peak having the highest peak intensity is defined as the melting point. In addition, the temperature decrease crystallization temperature of the polyamide resin in the embodiment of the present invention is as follows. The temperature of the polyamide resin is decreased from the molten state to 30 ° C. at a temperature decrease rate of 20 ° C./min using a differential scanning calorimeter. It is defined as the temperature of the exothermic peak that appears when However, when two or more exothermic peaks are detected, the temperature of the exothermic peak having the highest peak intensity is set as the temperature-falling crystallization temperature.

  The polyamide resin having a difference between the melting point and the temperature-falling crystallization temperature of 30 ° C. or higher is nylon 6, nylon 66, nylon 410, nylon 610, nylon 56, nylon 6/66, nylon 6 / 6T, nylon 66 / 6T, nylon 66 / 6I, nylon 66 / 6I / 6, nylon 6T / 11, nylon 6T / 12, nylon XD6, nylon XD10, nylon 6T / 5T, nylon 6T / M5T, nylon 10T, nylon 12T, and the like.

  The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity (ηr) measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g / ml is in the range of 1.5 to 5.0. Preferably there is. When the relative viscosity is 1.5 or more, the retention stability is excellent, and the hinge characteristics and heat aging resistance of the obtained molded product can be further improved. The relative viscosity is more preferably 2.0 or more, and further preferably 3.0 or more. On the other hand, if the relative viscosity is 5.0 or less, the fluidity can be further improved.

  The polyamide resin composition of the embodiment of the present invention has (B) a hydroxyl group and / or an amino group and an epoxy group and / or a carbodiimide group, and the sum of the number of hydroxyl groups and amino groups in one molecule is 1. Contains more compounds than the sum of the number of epoxy and carbodiimide groups in the molecule. The hydroxyl group and / or amino group-containing compound has an effect of improving molding processability such as fluidity and heat aging resistance at 150 to 230 ° C., but is less than 150 ° C. due to low compatibility with the (A) polyamide resin. There is a problem that the heat aging resistance is insufficient. In addition, the hydroxyl group and / or amino group-containing compound has a problem of bleeding out to the surface layer of the molded product, and the hydroxyl group and / or amino group of the hydroxyl group and / or amino group-containing compound is hydrolyzed of the amide bond of the (A) polyamide resin. There is also a problem in which the retention stability is inferior. Furthermore, the hydroxyl group and / or amino group-containing compound plasticizes the polyamide resin (A), and there is a problem that the hinge characteristics and flame retardancy of the resulting molded article are lowered. On the other hand, in the embodiment of the present invention, the compound (B) has a hydroxyl group and / or amino group considered to undergo a dehydration condensation reaction with the carboxyl terminal group of the (A) polyamide resin, or a hydroxyl group, amino group, Since the epoxy group and / or carbodiimide group is considered to react with the amino terminal group or carboxyl terminal group of the (A) polyamide resin, it is excellent in compatibility with the (A) polyamide resin and is finely dispersed in the polyamide resin composition. A phase can be formed and the heat aging resistance at less than 150 ° C. can be improved. Moreover, the bleeding out to the molded article surface layer of (B) compound can be suppressed and surface appearance can be improved. Furthermore, since the epoxy group and the carbodiimide group are excellent in reactivity with the terminal group of the (A) polyamide resin as compared with the hydroxyl group and amino group, the sum of the number of hydroxyl groups and amino groups in one molecule of the compound (B) By adding more than the sum of the number of epoxy groups and carbodiimide groups, it is possible to form an appropriate cross-linked structure to suppress a decrease in the degree of polymerization due to hydrolysis of the amide bond, and to improve the retention stability while excessive cross-linking. Since embrittlement due to structure formation can be suppressed, fluidity is improved, dispersibility of a flame retardant described later can be further improved, and flame retardancy and hinge characteristics can be improved. A compound having a hydroxyl group and an epoxy group and / or a carbodiimide group is more preferable.

  In the embodiment of the present invention, examples of the compound (B) include a reaction product of (b) a hydroxyl group and / or amino group-containing compound described later and (b ′) an epoxy group and / or carbodiimide group-containing compound. . The compound (B) may be a low molecular compound, a polymer, or a condensate. With such a compound (B), the heat aging resistance at a high temperature of 190 ° C. or more can be further improved. Although it is not certain about this factor, it is thought as follows. That is, (b ') an epoxy group and / or carbodiimide group-containing compound is linked by reacting (b) a hydroxyl group and / or amino group-containing compound with (b') an epoxy group and / or carbodiimide group-containing compound in advance. A compound (B) having a multi-branched structure as a point is formed. This (B) compound has a multi-branched structure, so that the self-aggregation force is further reduced, and (A) the reactivity and compatibility with the polyamide resin are improved. Moreover, since the melt viscosity of the compound having a multi-branched structure is improved, it is considered that the dispersibility of the compound (B) in the polyamide resin composition is further improved. The structure of the (B) compound can be specified by a usual analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.).

In the embodiment of the present invention, the degree of branching of the compound (B) is not particularly limited, but is preferably 0.05 to 0.70. The degree of branching is a numerical value representing the degree of branching in the compound. A linear compound has a degree of branching of 0, and a completely branched dendrimer has a degree of branching of 1. As this value is larger, a crosslinked structure can be introduced into the polyamide resin composition, and the hinge characteristics of the molded product can be improved. By setting the degree of branching to 0.05 or more, the crosslinked structure in the polyamide resin composition is sufficiently formed, and the compatibility with the (A) polyamide resin is further improved. Therefore, fluidity, residence stability, flame retardancy , Heat aging resistance, surface appearance and hinge characteristics can be further improved. The degree of branching is more preferably 0.10 or more. On the other hand, by setting the degree of branching to 0.70 or less, the crosslinked structure in the polyamide resin composition is moderately suppressed, the dispersibility of the compound (B) in the polyamide resin composition is further increased, and the fluidity and residence stability are increased. In addition, flame retardancy, heat aging resistance, surface appearance and hinge characteristics can be further improved. The degree of branching is more preferably 0.35 or less. The degree of branching is defined by the following formula (2).
Branch degree = (D + T) / (D + T + L) (2)

In the above formula (2), D represents the number of dendritic units, L represents the number of linear units, and T represents the number of terminal units. In addition, said D, T, and L can be calculated from the integrated value of the peak shift measured by ¹³ C-NMR. D is derived from a tertiary or quaternary carbon atom, T is derived from a primary carbon atom that is a methyl group, L is a primary or secondary carbon atom, Derived from except T.

  Examples of the (B) compound having a degree of branching in the above-described range include, for example, a reaction product of a preferable (b) hydroxyl group and / or amino group-containing compound described later and (b ′) an epoxy group and / or carbodiimide group-containing compound. Is mentioned.

  The hydroxyl value of the compound (B) used in a preferred embodiment of the present invention is preferably 100 to 2000 mgKOH / g. (B) By making the hydroxyl value of the compound 100 mgKOH / g or more, it becomes easy to ensure a sufficient amount of reaction between the (A) polyamide resin and the (B) compound. Flame retardancy, heat aging resistance, surface appearance and hinge characteristics can be further improved. (B) The hydroxyl value of the compound is more preferably 300 mgKOH / g or more. On the other hand, by setting the hydroxyl value of the (B) compound to 2000 mgKOH / g or less, the reactivity between the (A) polyamide resin and the (B) compound is moderately improved, and the fluidity, residence stability, flame retardancy, and heat resistance are improved. Aging property, surface appearance and hinge characteristics can be further improved. Moreover, the gelation by an excessive reaction can be suppressed by making the hydroxyl value of (B) compound into 2000 mgKOH / g or less. (B) The hydroxyl value of the compound is more preferably 1800 mgKOH / g or less. Here, the hydroxyl value of the compound (B) can be determined by acetylating the compound (B) with a mixed solution of acetic anhydride and anhydrous pyridine and titrating it with an ethanolic potassium hydroxide solution.

  The amine value of the compound (B) used in the embodiment of the present invention is preferably 100 to 2000 mgKOH / g. By making the amine value of the (B) compound 100 mgKOH / g or more, it becomes easy to ensure a sufficient amount of reaction between the (A) polyamide resin and the (B) compound, so that fluidity, residence stability, Flame retardancy, heat aging resistance, surface appearance and hinge characteristics can be further improved. (B) The amine value of the compound is more preferably 200 mgKOH / g or more. On the other hand, by setting the amine value of the (B) compound to 2000 mgKOH / g or less, the reactivity between the (A) polyamide resin and the (B) compound is moderately improved, so that fluidity, residence stability, flame retardancy, Heat aging resistance, surface appearance, and hinge characteristics can be further improved. Moreover, gelatinization of the polyamide resin composition by an excessive reaction can be suppressed by making the amine value of (B) compound 2000 mgKOH / g or less. (B) The amine value of the compound is more preferably 1600 mgKOH / g or less. Here, the amine value of the compound (B) can be determined by dissolving the compound (B) in ethanol and performing neutralization titration with an ethanolic hydrochloric acid solution.

  Examples of the (B) compound having a hydroxyl value or an amine value within the above-mentioned range include, for example, a preferable (b) hydroxyl group and / or amino group-containing compound described later and (b ′) an epoxy group and / or carbodiimide group-containing compound. And reactants.

  The compound (B) used in the embodiment of the present invention is preferably a solid at 25 ° C. or a liquid having a viscosity of 200 mPa · s or more at 25 ° C. In that case, it becomes easy to obtain a desired viscosity at the time of melt-kneading, and (A) the compatibility with the polyamide resin is further improved, and the fluidity, residence stability, flame retardancy, heat aging resistance, surface appearance and hinge characteristics Can be further improved.

  The (b) hydroxyl group and / or amino group-containing compound used in the embodiment of the present invention is preferably an aliphatic compound having three or more hydroxyl groups or three or more amino groups in one molecule. An aliphatic compound having 3 or more hydroxyl groups or 3 or more amino groups in one molecule is excellent in compatibility with (A) polyamide resin, and has fluidity, residence stability, flame retardancy, heat aging resistance, The surface appearance and hinge characteristics can be further improved. The number of hydroxyl groups or amino groups in one molecule is preferably 4 or more, and more preferably 6 or more. An aliphatic compound having three or more hydroxyl groups or amino groups in one molecule has a lower steric hindrance than an aromatic compound or an alicyclic compound and is excellent in compatibility with (A) a polyamide resin. It is considered that the property, retention stability, flame retardancy, heat aging resistance, surface appearance and hinge characteristics can be further improved. (B) The hydroxyl group and / or amino group-containing compound may be a low molecular compound or a polymer.

In the case of a low molecular compound, the number of hydroxyl groups or amino groups in one molecule is calculated by specifying the structural formula of the compound by a usual analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). be able to. Further, in the case of a polymer, (b) the number average molecular weight and the hydroxyl value or amine value of the hydroxyl group and / or amino group-containing compound can be calculated and obtained by the following formula (3).
Number of OH or NH ₂ = (number average molecular weight × hydroxyl value or amine value) / 56110 (3)
Specific examples of the hydroxyl group-containing compound include 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,6-hexanetetrol, glycerin, Diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, ditrimethylolpropane, tritrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, methylglucoside, sorbitol, glucose, mannitol, sucrose, 1,3,5 -Trihydroxybenzene, 1,2,4-trihydroxybenzene, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, triethanolamine, trimethylolethane, trimethylolpropane, 2-methylpropyl Punt triol, tris (hydroxymethyl) aminomethane, and the like 2-methyl-1,2,4-butanetriol. Examples of the hydroxyl group-containing compound also include a hydroxyl group-containing compound having a repeating structural unit, such as an ester bond, an amide bond, an ether bond, a methylene bond, a vinyl bond, an imine bond, a siloxane bond, a urethane bond, a thioether bond, Examples thereof include a hydroxyl group-containing compound having a repeating structural unit having a silicon-silicon bond, a carbonate bond, a sulfonyl bond, and an imide bond. The hydroxyl group-containing compound may contain a repeating structural unit containing two or more of these bonds. As the hydroxyl group-containing compound having a repeating structural unit, a hydroxyl group-containing compound having a repeating structural unit having an ester bond, a carbonate bond, an ether bond and / or an amide bond is more preferable.

  A hydroxyl group-containing compound having a repeating structural unit having an ester bond is, for example, a compound having one or more hydroxyl groups, the carbon atom adjacent to the carboxyl group is a saturated carbon atom, and all the hydrogen atoms on the carbon atom are substituted. And can be obtained by reacting a monocarboxylic acid having two or more hydroxyl groups. The hydroxyl group-containing compound having a repeating structural unit having an ether bond can be obtained, for example, by ring-opening polymerization of a compound having one or more hydroxyl groups and a cyclic ether compound having one or more hydroxyl groups. A hydroxyl group-containing compound having a repeating structural unit having an ester bond and an amide bond can be obtained, for example, by a polycondensation reaction between an aminodiol and a cyclic acid anhydride. A hydroxyl group-containing compound having a repeating structural unit having an ether bond containing an amino group can be obtained, for example, by intermolecular condensation of trialkanolamine. A hydroxyl group-containing compound comprising a repeating structural unit having a carbonate bond can be obtained, for example, by a polycondensation reaction of an aryl carbonate derivative of trisphenol.

  Among the hydroxyl group-containing compounds, pentaerythritol, dipentaerythritol, and tripentaerythritol are preferable.

  The hydroxyl value of the hydroxyl group-containing compound used in the embodiment of the present invention is preferably 100 to 2000 mgKOH / g from the viewpoint of compatibility with the (A) polyamide resin. By setting the hydroxyl value of the hydroxyl group-containing compound to 100 mgKOH / g or more, it becomes easy to secure a sufficient amount of reaction between the (A) polyamide resin and the hydroxyl group-containing compound. , Heat aging resistance, surface appearance and hinge characteristics can be further improved. The hydroxyl value of the hydroxyl group-containing compound is more preferably 300 mgKOH / g or more. On the other hand, by setting the hydroxyl value of the hydroxyl group-containing compound to 2000 mgKOH / g or less, the reactivity between (A) the polyamide resin and the hydroxyl group-containing compound is moderately improved, and the fluidity, residence stability, flame retardancy, and heat aging resistance are increased. Further, the surface appearance and hinge characteristics can be further improved. Furthermore, the gelation by excessive reaction can also be suppressed by making the hydroxyl value of a hydroxyl-containing compound into 2000 mgKOH / g or less. The hydroxyl value of the hydroxyl group-containing compound is more preferably 1800 mgKOH / g or less. The hydroxyl value can be determined by acetylating a hydroxyl group-containing compound with a mixed solution of acetic anhydride and anhydrous pyridine and titrating it with an ethanolic potassium hydroxide solution.

  Specific examples of the amino group-containing compound include three amino groups such as 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane, and 1,2,4-triaminobutane. 4 amino groups such as compounds and 1,1,2,3-tetraaminopropane, 1,2,3-triamino-2-methylaminopropane, 1,2,3,4-tetraaminobutane and isomers thereof Compounds having 5, amino compounds such as 3,6,9-triazaundecane-1,11-diamine, 3,6,9,12-tetraazatetradecane-1,14-diamine, , 1,2,2,3,3-hexaaminopropane, 1,1,2,3,3-pentaamino-2methylaminopropane, 1,1,2,2,3,4-hexaaminobutane and these Isomers of And the amino group of the compound having 6, polyethylene imine obtained by polymerizing ethylene imine. Examples of the amino group-containing compound include three compounds in one molecule such as (i) a compound in which an alkylene oxide unit is introduced into the compound having the amino group, and (ii) trimethylolpropane, pentaerythritol, dipentaerythritol. A compound obtained by reacting a compound having the above hydroxyl group and / or a compound in which the hydroxyl group is methyl esterified with an alkylene oxide and amination of the terminal group can also be exemplified.

  The amine value of the amino group-containing compound used in the embodiment of the present invention is preferably 100 to 2000 mgKOH / g from the viewpoint of compatibility with the (A) polyamide resin. By making the amine value of the amino group-containing compound 100 mgKOH / g or more, it becomes easy to ensure a sufficient amount of reaction between the (A) polyamide resin and the amino group-containing compound. Flame retardancy, heat aging resistance, surface appearance and hinge characteristics can be further improved. The amine value of the amino group-containing compound is more preferably 200 mgKOH / g or more. On the other hand, by setting the amine value of the amino group-containing compound to 2000 mgKOH / g or less, the reactivity between the (A) polyamide resin and the amino group-containing compound is moderately increased, so that fluidity, residence stability, flame retardancy, heat resistance Aging property, surface appearance and hinge characteristics can be further improved. Furthermore, by setting the amine value of the amino group-containing compound to 2000 mgKOH / g or less, gelation of the polyamide resin composition due to excessive reaction can be suppressed. The amine value of the amino group-containing compound is more preferably 1600 mgKOH / g or less. The amine value can be determined by dissolving an amino group-containing compound in ethanol and performing neutralization titration with an ethanolic hydrochloric acid solution.

  The (b) hydroxyl group and / or amino group-containing compound used in the embodiment of the present invention may have another reactive functional group together with the hydroxyl group and / or amino group. Examples of other functional groups include aldehyde groups, sulfo groups, isocyanate groups, oxazoline groups, oxazine groups, ester groups, amide groups, silanol groups, silyl ether groups, and the like.

  The molecular weight of the (b) hydroxyl group and / or amino group-containing compound used in the embodiment of the present invention is not particularly limited, but is preferably in the range of 50 to 10,000. (B) If the molecular weight of the hydroxyl group and / or amino group-containing compound is 50 or more, it is difficult to volatilize during melt-kneading, and therefore, the processability is excellent. (B) The molecular weight of the hydroxyl group and / or amino group-containing compound is preferably 150 or more, more preferably 200 or more. On the other hand, if the molecular weight of the (b) hydroxyl group and / or amino group-containing compound is 10,000 or less, the compatibility between the (B) compound and the (A) polyamide resin will be higher, and the effect of the present invention will be more remarkable. Played. (B) The molecular weight of the hydroxyl group and / or amino group-containing compound is preferably 6000 or less, more preferably 4000 or less, and still more preferably 800 or less.

  (B) The molecular weight of the hydroxyl group and / or amino group-containing compound can be calculated by specifying the structural formula of the compound by an ordinary analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). The molecular weight when the hydroxyl group and / or amino group-containing compound is a condensate is the weight average molecular weight. The weight average molecular weight (Mw) can be calculated using gel permeation chromatography (GPC). Specifically, when a solvent in which the compound is dissolved, for example, hexafluoroisopropanol is used as a mobile phase, polymethyl methacrylate (PMMA) is used as a standard substance, and the column is matched to the solvent. For example, when hexafluoroisopropanol is used, Shimadzu Using “Shodex GPC HFIP-806M” and / or “Shodex GPC HFIP-LG” manufactured by GL Corp., the weight average molecular weight can be measured using a differential refractometer as a detector.

  The degree of branching of the (b) hydroxyl group and / or amino group-containing compound used in the embodiment of the present invention is not particularly limited, but is preferably 0.05 to 0.70. By setting the degree of branching to 0.05 or more, the crosslinked structure in the polyamide resin composition is sufficiently formed, and the compatibility with the (A) polyamide resin is further improved. Therefore, fluidity, residence stability, flame retardancy , Heat aging resistance, surface appearance and hinge characteristics are further improved. The degree of branching is preferably 0.10 or more. On the other hand, by setting the degree of branching to 0.70 or less, the crosslinked structure in the polyamide resin composition is moderately suppressed, the dispersibility of the compound (B) in the polyamide resin composition is further increased, and the fluidity and residence stability are increased. In addition, flame retardancy, heat aging resistance, surface appearance and hinge characteristics can be further improved. The degree of branching is preferably 0.35 or less. Further, by using the (b) hydroxyl group and / or amino group-containing compound having such a branching degree, the (B) compound having a branching degree within the above preferred range can be easily obtained. The degree of branching is defined by the equation (2).

  The (b ′) epoxy group and / or carbodiimide group-containing compound used in the embodiment of the present invention preferably has two or more epoxy and / or carbodiimide groups in one molecule, and further has four or more. Preferably, it has 6 or more. Since the epoxy group and the carbodiimide group are excellent in compatibility with the (A) polyamide resin, the compound having two or more epoxy and / or carbodiimide groups in one molecule is compatible with the (A) polyamide resin and the (B) compound. It is thought that there is an effect to increase (B ′) The epoxy group and / or carbodiimide group-containing compound may be a low molecular compound or a polymer.

  In the case of low molecular weight compounds, the number of epoxy groups or carbodiimide groups in one molecule is calculated by specifying the structural formula of the compound by an ordinary analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). can do. In the case of a polymer, it can be determined by dividing the number average molecular weight of the (b ′) epoxy group and / or carbodiimide group-containing compound by the epoxy equivalent or carbodiimide equivalent.

  Specific examples of epoxy group-containing compounds include epichlorohydrin, glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl group-containing vinyl heavy resins. Examples include coalescence. Two or more of these may be used.

  Examples of the glycidyl ether type epoxy resin include those produced from epichlorohydrin and bisphenol A, those produced from epichlorohydrin and bisphenol F, and phenol novolac type epoxy resins obtained by reacting novolak resin with epichlorohydrin. Examples thereof include orthocresol novolac type epoxy resins, so-called brominated epoxy resins derived from epichlorohydrin and tetrabromobisphenol A, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether and the like.

  Examples of the glycidyl ester type epoxy resin include epoxy resin produced from epichlorohydrin and phthalic acid, tetrahydrophthalic acid, p-oxybenzoic acid or dimer acid, trimesic acid triglycidyl ester, trimellitic acid triglycidyl ester, pyro An example is meritic acid tetraglycidyl ester.

  As the glycidylamine type epoxy resin, an epoxy resin produced from epichlorohydrin and aniline, diaminodiphenylmethane, p-aminophenol, metaxylylenediamine or 1,3-bis (aminomethyl) cyclohexane, tetraglycidylaminodiphenylmethane , Triglycidyl-paraaminophenol, triglycidyl-metaaminophenol, tetraglycidylmetaxylenediamine, tetraglycidylbisaminomethylcyclohexane, triglycidyl cyanurate, triglycidyl isocyanurate and the like.

  Examples of the alicyclic epoxy resin include compounds having a cyclohexene oxide group, a tricyclodecene oxide group, and a cyclopentene oxide group. Examples of the heterocyclic epoxy resin include an epoxy resin produced from epichlorohydrin and hydantoin or isocyanuric acid.

  Examples of the glycidyl group-containing vinyl-based polymer include those obtained by radical polymerization of raw material monomers that form glycidyl group-containing vinyl-based units. Specific examples of the raw material monomer for forming a glycidyl group-containing vinyl-based unit include glycidyl esters of unsaturated monocarboxylic acids such as glycidyl (meth) acrylate and glycidyl p-styrylcarboxylate, and unsaturated compounds such as maleic acid and itaconic acid. Examples thereof include monoglycidyl ester or polyglycidyl ester of polycarboxylic acid, unsaturated glycidyl ether such as allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-4-glycidyl ether.

  Commercially available epoxy group-containing compounds include polyglycidyl ether compounds that are low molecular polyfunctional epoxy compounds (for example, “SR-TMP” manufactured by Sakamoto Pharmaceutical Co., Ltd., “Denacol” manufactured by Nagase ChemteX Corporation). (Registered trademark) EX-521 ", etc.), polyfunctional epoxy compounds containing polyethylene as a main component (for example," "Bond Fast" (registered trademark) E "manufactured by Sumitomo Chemical Co., Ltd.), Functional epoxy compounds (for example, “Reseda” GP-301 manufactured by Toagosei Co., Ltd. “ARUFON” UG-4000 manufactured by Toagosei Co., Ltd., manufactured by Mitsubishi Rayon Co., Ltd. "" Methbrene "(registered trademark) KP-7653", etc.), a polyfunctional epoxy compound mainly composed of an acrylic / styrene copolymer (for example, "" manufactured by BASF oncryl "(registered trademark) -ADR-4368", "ARUFON" (registered trademark) UG-4040 "manufactured by Toagosei Co., Ltd.), a polyfunctional epoxy compound mainly composed of a silicone-acrylic copolymer (for example, , "" Methbrene "(registered trademark) S-2200", etc.), polyfunctional epoxy compounds mainly composed of polyethylene glycol (for example, "Epiol" (registered trademark) "E-1000" manufactured by NOF Corporation)) Bisphenol A type epoxy resin (for example, “jER” (registered trademark) “1004” manufactured by Mitsubishi Chemical Corporation), novolak phenol type modified epoxy resin (for example, “EPPN” (registered trademark) manufactured by Nippon Kayaku Co., Ltd.) ) "201").

  Examples of the carbodiimide group-containing compound include dicarbodiimides such as N, N′-diisopropylcarbodiimide, N, N′-dicyclohexylcarbodiimide, N, N′-di-2,6-diisopropylphenylcarbodiimide, and poly (1,6-hexa). Methylene carbodiimide), poly (4,4′-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4,4′-dicyclohexylmethanecarbodiimide) , Poly (4,4′-diphenylmethanecarbodiimide), poly (3,3′-dimethyl-4,4′-diphenylmethanecarbodiimide), poly (naphthalenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenol Lencarbodiimide), poly (tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (1,3,5-triisopropylbenzene) polycarbodiimide, poly (1,3,5-triisopropyl) Mention may be made of polycarbodiimides such as benzene) polycarbodiimide, poly (1,5-diisopropylbenzene) polycarbodiimide, poly (triethylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide) and the like.

  Examples of commercially available carbodiimide group-containing compounds include “Carbodilite” (registered trademark) manufactured by Nisshinbo Holdings, Inc., and “Stavaxol (registered trademark)” manufactured by Rhein Chemie.

  The molecular weight of the (b ′) epoxy group and / or carbodiimide group-containing compound of the embodiment of the present invention is not particularly limited, but is preferably in the range of 800 to 10,000. (B ′) By setting the molecular weight of the epoxy group and / or carbodiimide group-containing compound to 800 or more, it becomes difficult to volatilize during melt-kneading, and therefore, the workability is excellent. Moreover, since the viscosity at the time of melt-kneading can be increased, the compatibility between the (A) polyamide resin and the (b ′) epoxy group and / or carbodiimide group-containing compound or (B) compound becomes higher, and the residence stability , Heat aging resistance, and surface appearance are further improved. (B ') The molecular weight of the epoxy group and / or carbodiimide group-containing compound is more preferably 1000 or more, and further preferably 2000 or more. (B ′) The epoxy group and / or carbodiimide group-containing compound has a molecular weight of 2000 or more, so that even during wet heat treatment, the (B) compound and (b) hydroxyl group and / or amino group-containing compound on the surface of the molded product Bleed-out can be further suppressed, and the surface appearance can be further improved. On the other hand, when the molecular weight of the (b ′) epoxy group and / or carbodiimide group-containing compound is 10,000 or less, the viscosity at the time of melt-kneading can be moderately suppressed, so that the workability is excellent. Further, the compatibility between the (A) polyamide resin and the (b ′) epoxy group and / or carbodiimide group-containing compound or the (B) compound can be kept high. (B ′) The molecular weight of the epoxy group and / or carbodiimide group-containing compound is more preferably 8000 or less.

  (B ′) The molecular weight of the epoxy group and / or carbodiimide group-containing compound can be calculated by specifying the structural formula of the compound by a usual analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). it can. Moreover, the weight average molecular weight is used as the molecular weight when the epoxy group and / or carbodiimide group-containing compound is a condensate. The weight average molecular weight (Mw) can be calculated using gel permeation chromatography (GPC). Specifically, when a solvent in which the compound is dissolved, for example, hexafluoroisopropanol is used as a mobile phase, polymethyl methacrylate (PMMA) is used as a standard substance, and the column is matched to the solvent. For example, when hexafluoroisopropanol is used, Shimadzu Using “Shodex GPC HFIP-806M” and / or “Shodex GPC HFIP-LG” manufactured by GL Corp., the weight average molecular weight can be measured using a differential refractometer as a detector.

  The (b ′) epoxy group and / or carbodiimide group-containing compound used in the embodiment of the present invention is preferably solid at 25 ° C. or a liquid having a viscosity of 200 mPa · s or more at 25 ° C. In that case, it becomes easy to obtain a desired viscosity at the time of melt-kneading, and the compatibility between the (A) polyamide resin and the (b ′) epoxy group and / or carbodiimide group-containing compound or (B) compound becomes higher, Fluidity, retention stability, flame retardancy, heat aging resistance, surface appearance and hinge characteristics are further improved.

  The value obtained by dividing the molecular weight by the number of functional groups in one molecule, which is an indicator of the functional group concentration of the (b ′) epoxy group and / or carbodiimide group-containing compound in the embodiment of the present invention, is 50 to 3000. It is preferable. Here, the number of functional groups refers to the total number of epoxy groups and carbodiimide groups. The smaller the value, the higher the functional group concentration. By setting it to 50 or more, gelation due to excessive reaction can be suppressed, and (A) a polyamide resin and (b) a hydroxyl group and / or an amino group are contained. Since the reactivity with the compound is moderately improved, the fluidity, retention stability, flame retardancy, heat aging resistance, surface appearance and hinge characteristics can be further improved. (B ') The value obtained by dividing the molecular weight of the epoxy group and / or carbodiimide group-containing compound by the number of functional groups in one molecule is more preferably 100 or more, and further preferably 1100 or more. (B ') By setting the value obtained by dividing the molecular weight of the epoxy group and / or carbodiimide group-containing compound by the number of functional groups in one molecule to be 1100 or more, (B) Bleed out of the compound and (b) hydroxyl group and / or amino group-containing compound can be further suppressed, and the surface appearance can be further improved. On the other hand, by dividing the molecular weight of the (b ′) epoxy group and / or carbodiimide group-containing compound by the number of functional groups in one molecule to 3000 or less, (A) a polyamide resin and (b) a hydroxyl group and The reaction with the amino group-containing compound can be sufficiently ensured, and the fluidity, residence stability, flame retardancy, heat aging resistance, surface appearance and hinge characteristics can be further improved. From this viewpoint, the value obtained by dividing the molecular weight of the (b ′) epoxy group and / or carbodiimide group-containing compound by the number of functional groups in one molecule is more preferably 2000 or less, more preferably 1000 or less, and more preferably 300 or less. Further preferred.

  In the embodiment of the present invention, the compound (B) is preferably a compound having a structure represented by the following general formula (1) and / or a condensate thereof.

In the general formula (1), X ^{1 to} X ⁶ may be the same or different and each represents OH, NH ₂ , CH ₃ or OR. However, the sum of the numbers of OH, NH ₂ and OR is 3 or more. Moreover, R represents the organic group which has an amino group, an epoxy group, or a carbodiimide group, and n represents the range of 0-20.

  R in the general formula (1) represents an organic group having an amino group, an organic group having an epoxy group, or an organic group having a carbodiimide group. Examples of the organic group having an amino group include an alkylamino group and a cycloalkylamino group that may have a substituent, and examples of the substituent include an alkylene oxide group and an aryl group. Examples of the organic group having an epoxy group include an epoxy group, a glycidyl group, a glycidyl ether type epoxy group, a glycidyl ester type epoxy group, a glycidyl amine type epoxy group, a hydrocarbon group substituted with an epoxy group or a glycidyl group, and an epoxy group. Or the heterocyclic group substituted by the glycidyl group etc. are mentioned. Examples of the organic group having a carbodiimide group include an alkyl carbodiimide group, a cycloalkyl carbodiimide group, and an arylalkyl carbodiimide group.

  N in General formula (1) represents the range of 0-20. When n is 20 or less, (A) the plasticization of the polyamide resin is suppressed, and the fluidity, retention stability, flame retardancy, heat aging resistance, surface appearance and hinge characteristics can be further improved. n is more preferably 4 or less. On the other hand, n is more preferably 1 or more, (B) the molecular mobility of the compound can be increased, and (A) the compatibility with the polyamide resin can be further improved.

The sum of the numbers of OH, NH ₂ and OR in the general formula (1) is preferably 3 or more. Thereby, it is excellent in compatibility with (A) polyamide resin, and the fluidity, residence stability, flame retardancy, heat aging resistance, surface appearance and hinge characteristics of the obtained molded product can be further improved. Here, the sum of the numbers of OH, NH ₂ and OR is the low molecular weight compound, and the structural formula of the compound is specified by a usual analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). Can be calculated.

In the case of the condensate, the number of OH or NH ₂ is calculated by calculating the number average molecular weight and the hydroxyl value or amine value of the compound having the structure represented by the general formula (1) and / or the condensate thereof. ).
Number of OH or NH _{2 in} the general formula (1) = (number average molecular weight × hydroxyl value or amine value) / 56110 (3)

  In the case of a condensate, the number of OR is calculated by dividing the number average molecular weight of the compound having the structure represented by the general formula (1) and / or the condensate by an amine equivalent, an epoxy equivalent or a carbodiimide equivalent. Can do. The number average molecular weight of the compound having the structure represented by the general formula (1) and / or the condensate thereof can be calculated using a gel permeation chromatograph (GPC). Specifically, it can be calculated by the following method. A solvent in which the compound having the structure represented by the general formula (1) and / or the condensate thereof is dissolved, for example, hexafluoroisopropanol is used as a mobile phase, and polymethyl methacrylate (PMMA) is used as a standard substance. The column is matched to the solvent. For example, when hexafluoroisopropanol is used, “Shodex GPC HFIP-806M” and / or “Shodex GPC HFIP-LG” manufactured by Shimadzu GL Corporation is used as a detector. The number average molecular weight can be measured using a differential refractometer.

  In the polyamide resin composition of the embodiment of the present invention, the content of the compound (B) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the (A) polyamide resin. When the content of the compound (B) is less than 0.1 parts by weight, the fluidity and retention stability at the time of molding are lowered, and the heat aging resistance and hinge characteristics of the obtained molded product are lowered. The content of the compound (B) is preferably 0.5 parts by weight or more and more preferably 2 parts by weight or more with respect to 100 parts by weight of the (A) polyamide resin. On the other hand, when the compounding amount of the compound (B) exceeds 20 parts by weight, the dispersibility of the compound (B) in the polyamide resin composition is lowered, and the compound (B) is likely to bleed out to the surface layer of the molded product. Decreases. Further, the plasticization and decomposition of the polyamide resin are promoted, and the residence stability, flame retardancy, heat aging resistance, and hinge characteristics are lowered. The compounding amount of the (B) compound is preferably 7.5 parts by weight or less, more preferably 6 parts by weight or less with respect to 100 parts by weight of the (A) polyamide resin.

  The production method of the compound (B) used in the embodiment of the present invention is not particularly limited, but the above-mentioned (b) hydroxyl group and / or amino group-containing compound and (b ′) epoxy group and / or carbodiimide group-containing compound A method of dry blending and melt kneading at a temperature higher than the melting point of both components is preferred.

  In order to promote the reaction between the hydroxyl group and / or amino group and the epoxy group and / or carbodiimide group, it is also preferable to add a catalyst. The addition amount of the catalyst is not particularly limited, and is 0 to 1 part by weight based on 100 parts by weight of the total of (b) the hydroxyl group and / or amino group-containing compound and (b ′) the epoxy group and / or carbodiimide group-containing compound. Preferably, 0.01-0.3 weight part is more preferable.

  Examples of the catalyst for promoting the reaction between the hydroxyl group and the epoxy group include phosphines, imidazoles, amines, diazabicyclos and the like. Specific examples of phosphines include triphenylphosphine (TPP). Specific examples of imidazoles include 2-heptadecylimidazole (HDI), 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole and the like. Specific examples of amines include N-hexadecylmorpholine (HDM), triethylenediamine, benzyldimethylamine (BDMA), tributylamine, diethylamine, triethylamine, 1,8-diazabicyclo (5,4,0) -undecene-7. (DBU), 1,5-diazabicyclo (4,3,0) -nonene-5 (DBN), trisdimethylaminomethylphenol, tetramethylethylenediamine, N, N-dimethylcyclohexylamine, 1,4-diazabicyclo- (2 , 2, 2) -octane (DABCO).

  Examples of the catalyst for promoting the reaction between the hydroxyl group and the carbodiimide group include trialkyl lead alkoxide, borohydrofluoric acid, zinc chloride, sodium alkoxide and the like.

  By melting and kneading (b) a hydroxyl group and / or amino group-containing compound and (b ′) an epoxy group and / or carbodiimide group-containing compound, (b) a hydroxyl group and / or an amino-containing compound and / or The amino group reacts with the epoxy group and / or carbodiimide group in the (b ′) epoxy group and / or carbodiimide group-containing compound. When (b) is a hydroxyl group-containing compound, a dehydration condensation reaction also occurs between the hydroxyl group-containing compounds. In this way, the (B) compound having a multi-branched structure can be obtained.

  When (b) a hydroxyl group and / or amino group-containing compound and (b ′) an epoxy group and / or carbodiimide group-containing compound are reacted to produce (B) a compound, the compounding ratio is not particularly limited. B) These compounds so that the sum of the number of hydroxyl groups and amino groups in one molecule of the compound is greater than the sum of the number of epoxy groups and carbodiimide groups in one molecule of (B) compound and / or its condensate Is preferably blended. The epoxy group and the carbodiimide group are superior in reactivity with the terminal group of the (A) polyamide resin as compared with the hydroxyl group and the amino group. For this reason, excessive crosslinking is achieved by increasing the sum of the number of hydroxyl groups and amino groups in one molecule of (B) compound to the sum of the number of epoxy groups and carbodiimide groups in one molecule of (B) compound. The embrittlement due to the formation of the structure is suppressed, and the fluidity, residence stability, heat aging resistance and surface appearance are further improved. Furthermore, the dispersibility of the flame retardant (C) can be improved due to the fluidity improving effect, local variations in flame retardancy can be suppressed, and the hinge characteristics can be further improved.

  The weight ratio ((b) / (b ′)) of the (b) hydroxyl group and / or amino group-containing compound to the (b ′) epoxy group and / or carbodiimide group-containing compound to be reacted is 0.3 or more and less than 10,000. It is preferable that (A) Reactivity of polyamide resin and (b ′) epoxy group and / or carbodiimide group-containing compound, and (b) hydroxyl group and / or amino group-containing compound and (b ′) epoxy group and / or carbodiimide group-containing compound. The reactivity is higher than the reactivity of (A) the polyamide resin and (b) the hydroxyl group and / or amino group-containing compound. For this reason, when the weight ratio ((b) / (b ′)) is 0.3 or more, formation of gel due to excessive reaction is suppressed, and fluidity, retention stability, heat aging resistance and surface appearance are more improved. improves. Furthermore, the dispersibility of the flame retardant (C) can be improved due to the fluidity improving effect, local variations in flame retardancy can be suppressed, and the hinge characteristics can be further improved.

  When (b) a hydroxyl group and / or amino group-containing compound is reacted with (b ′) an epoxy group and / or carbodiimide group-containing compound to produce (B) a compound, a hydroxyl group or amino group and an epoxy group or carbodiimide group The reaction rate is preferably 1 to 95%. When the reaction rate is 1% or more, (B) the degree of branching of the compound can be increased, the self-aggregation force can be reduced, (A) the reactivity with the polyamide resin can be increased, and the fluidity and residence stability. Further, heat aging resistance is further improved. Furthermore, the dispersibility of the flame retardant (C) can be improved by the fluidity improving effect, and local variations in flame retardancy can be suppressed. Further, the hinge characteristics can be improved by forming a more uniform and fine dispersion structure in the resin composition. The reaction rate is more preferably 10% or more, and further preferably 20% or more. On the other hand, when the reaction rate is 95% or less, an epoxy group or a carbodiimide group can be appropriately left, and the reactivity with (A) the polyamide resin can be enhanced. The reaction rate is more preferably 90% or less, and further preferably 70% or less.

The reaction rate of the hydroxyl group and / or amino group and the epoxy group and / or carbodiimide group is determined by dissolving the compound (B) in a solvent (for example, deuterated dimethyl sulfoxide, deuterated hexafluoroisopropanol, etc.) In the case of the epoxy ring-derived peak by ¹ H-NMR measurement, the amount of decrease before and after the reaction with the (b) hydroxyl group and / or amino group-containing compound is determined. In the case of a carbodiimide group, a carbodiimide group is determined by ¹³ C-NMR measurement. The origin peak can be calculated by calculating the amount of decrease before and after the reaction with the hydroxyl group and / or amino group-containing compound (b). The reaction rate can be determined by the following formula (4).
Reaction rate (%) = {1- (e / d)} × 100 (4)
In the above formula (4), d represents the peak area of a dry blend of (b) a hydroxyl group and / or amino group-containing compound and (b ′) an epoxy group and / or carbodiimide group-containing compound, and e represents (B ) Represents the peak area of the compound.

As an example, FIG. 1 shows a ¹ H-NMR spectrum of a dry blend of dipentaerythritol and bisphenol A type epoxy resin (“jER” (registered trademark) 1004 manufactured by Mitsubishi Chemical Corporation) at a weight ratio of 3: 1. . In addition, FIG. 2 shows the ¹ H-NMR spectrum of the compound (B-7) and / or its condensate obtained in Reference Example 9 described later. Deuterated dimethyl sulfoxide was used as a solvent, the sample amount was 0.035 g, and the solvent amount was 0.70 ml. Reference numeral 1 indicates a solvent peak.

From the ¹ H-NMR spectrum shown in FIG. 1, the total of the peak areas derived from the epoxy ring appearing near 2.60 ppm and 2.80 ppm is obtained, and the sum of the peak areas shown in FIG. 4) Calculate the reaction rate. At this time, the peak area is normalized by the area of the peak of the benzene ring of the epoxy resin that does not contribute to the reaction.

  The polyamide resin composition of the embodiment of the present invention contains (C) a flame retardant. By blending (C) flame retardant together with (A) polyamide resin and (B) compound, (C) dispersion of flame retardant due to fluidity improvement effect due to high compatibility of (A) polyamide resin and (B) compound The local flame retardant variation can be suppressed. Further, the hinge characteristics can be improved by forming a more uniform and fine dispersion structure in the resin composition.

  In the embodiment of the present invention, the flame retardant (C) is not particularly limited as long as it can impart flame retardancy to the polyamide resin. For example, phosphorus flame retardant, nitrogen flame retardant, metal hydroxide flame retardant Non-halogen flame retardants such as flame retardants and halogen flame retardants such as bromine flame retardants can be exemplified. Two or more of these may be blended. However, when blending two or more of these, the blending amount of the flame retardant (C) means the total blending amount of the two or more flame retardants. Among these, non-halogen flame retardants are preferable, and nitrogen flame retardants are more preferable from the viewpoint of further improving heat aging resistance.

  The compounding quantity of the (C) flame retardant in the polyamide resin composition of embodiment of this invention is 0.1-50 weight part with respect to 100 weight part of (A) polyamide resin. When the blending amount is less than 0.1 parts by weight, the flame retardancy tends to be inferior. 3 parts by weight or more is preferable. Moreover, when it exceeds 50 weight part, fluidity | liquidity, residence stability, heat aging resistance, surface appearance, and hinge characteristics will fall. The amount is preferably 40 parts by weight or less.

  The phosphorus-based flame retardant in the embodiment of the present invention is a compound containing a phosphorus element, specifically, a polyphosphoric acid-based compound such as red phosphorus, ammonium polyphosphate, or melamine polyphosphate, (di) phosphinic acid metal salt Phosphazene compounds, aromatic phosphate esters, aromatic condensed phosphate esters, halogenated phosphate esters, and the like. However, a phosphorus-containing compound (phosphorous acid, hypophosphorous acid or a metal salt thereof) described later is not included in the phosphorus-based flame retardant. Two or more of these may be blended. Among these, (di) phosphinic acid metal salts, phosphazene compounds, aromatic phosphate esters, aromatic condensed phosphate esters, and halogenated phosphate esters are preferred.

  (Di) phosphinic acid salt is a salt of phosphinic acid and metal, and can be obtained, for example, by reacting phosphinic acid and metal carbonate, metal hydroxide or metal oxide in an aqueous medium. The (di) phosphinate is essentially a monomeric compound, but depending on the reaction conditions, it may be a polymeric phosphinate having a degree of condensation of 1 to 3 depending on the environment. Examples of phosphinic acid include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (dimethylphosphinic acid), and methylphenylphosphine. Examples include acids and diphenylphosphinic acid. Examples of the metal component to be reacted with phosphinic acid include metal carbonates, metal hydroxides and metal oxides containing calcium ions, magnesium ions, aluminum ions and / or zinc ions. Examples of phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, ethylmethylphosphinic acid. Zinc, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propylphosphinate, methyl -Zinc n-propylphosphinate, calcium methylphenylphosphinate, methylphenylphosphinate Neshiumu, aluminum methylphenyl phosphinate, methyl phenyl phosphinate, zinc, calcium diphenyl phosphinate, magnesium diphenyl phosphinate, aluminum diphenyl phosphinate, and zinc diphenyl phosphinate and the like. Examples of the diphosphinate include, for example, methanedi (methylphosphinic acid) calcium, methanedi (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, benzene-1,4-di (methylphosphine). Acid) calcium, benzene-1,4-di (methylphosphinic acid) magnesium, benzene-1,4-dimethylphosphinic acid) aluminum, benzene-1,4-di (methylphosphinic acid) zinc and the like. Among these (di) phosphinic acid salts, aluminum ethylmethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are particularly preferable from the viewpoint of further improving flame retardancy and electrical characteristics.

  The phosphazene compound is an organic compound having —P═N— bond in the molecule, and examples thereof include cyclic phenoxyphosphazene, chain phenoxyphosphazene, and crosslinked phenoxyphosphazene compound. Examples of the cyclic phenoxyphosphazene compound include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffeoxycyclopentaphosphazene. These cyclic phenoxyphosphazene compounds are obtained by, for example, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene from a mixture of cyclic and linear chlorophosphazenes obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. It can be obtained by taking out a cyclic chlorophosphazene such as decachlorocyclopentaphosphazene and then substituting it with a phenoxy group. As the chain phenoxyphosphazene compound, for example, hexachlorocyclotriphosphazene obtained by the above method is subjected to reversion polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichlorophosphazene having a polymerization degree of 3 to 10,000 is converted into a phenoxy group. And a compound obtained by substituting with. Examples of the crosslinked phenoxyphosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a crosslinked structure of 4,4′-diphenylene groups, such as compounds, compounds having a crosslinked structure of 4,4′-oxydiphenylene groups, compounds having a crosslinked structure of 4,4′-thiodiphenylene groups, etc. Is mentioned. The content of the phenylene group in the crosslinked phenoxyphosphazene compound is usually 50 to 99.9%, preferably 70 to 90%, based on the total number of phenyl groups and phenylene groups in the cyclic phosphazene compound and / or the chain phenoxyphosphazene compound. It is. Further, the crosslinked phenoxyphosphazene compound is preferably a compound having no free hydroxyl group in the molecule.

  Aromatic phosphate esters are a group of compounds produced by the reaction of phosphorus oxychloride and phenols or a mixture of phenols and alcohols. Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, and bis- (t-butylphenyl). ), Butylated phenyl phosphates such as phenyl phosphate, tris- (t-butylphenyl) phosphate, propylated phenyl phosphates such as isopropylphenyl diphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate, and the like. It is done.

  The aromatic condensed phosphate ester is a reaction product of phosphorus oxychloride with a divalent phenolic compound and phenol (or alkylphenol). Examples of the aromatic condensed phosphate ester include resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, bisphenol A bis-diphenyl phosphate, and the like.

  The halogenated phosphate ester can be obtained, for example, by reacting alkylene oxide and phosphorus oxychloride in the presence of a catalyst. Examples of the halogenated phosphate ester include tris (chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) dichloroisopentyl diphosphate, polyoxyalkylene bis (dichloro). Alkyl) phosphate and the like.

  In embodiment of this invention, when mix | blending a phosphorus flame retardant as (C) a flame retardant, the compounding quantity is 0.1 weight part or more with respect to 100 weight part of (A) polyamide resin, and is 20 weight. Part or more is more preferable. On the other hand, it is preferably 50 parts by weight or less, more preferably 40 parts by weight or less.

  As a nitrogen-type flame retardant in embodiment of this invention, the salt of a triazine type compound and cyanuric acid or isocyanuric acid is mentioned, for example. A triazine compound and a salt of cyanuric acid or isocyanuric acid are adducts of a triazine compound and cyanuric acid or isocyanuric acid, usually 1 to 1 (molar ratio), sometimes 2 to 1 (molar ratio). ). Examples of the triazine compound include melamine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine, tri (hydroxymethyl) melamine, benzoguanamine, acetoguanamine, 2-amide-4,6-diamino-1,3, 5-Triazine and the like can be mentioned, and melamine, benzoguanamine and acetoguanamine are particularly preferable. Specific examples of salts of triazine compounds with cyanuric acid or isocyanuric acid include melamine cyanurate, mono (β-cyanoethyl) isocyanurate, bis (β-cyanoethyl) isocyanurate, tris (β-cyanoethyl) isocyanurate, etc. Among them, melamine cyanurate is particularly preferable.

  In embodiment of this invention, when mix | blending a nitrogen-type flame retardant as (C) a flame retardant, the compounding quantity is 0.1 weight part or more with respect to 100 weight part of (A) polyamide resin, and 3 weight is preferable. Part or more is more preferable. On the other hand, the amount is preferably 50 parts by weight or less, and more preferably 15 parts by weight or less.

Examples of the metal hydroxide flame retardant in the embodiment of the present invention include magnesium hydroxide and aluminum hydroxide, and magnesium hydroxide is more preferable. These are usually commercially available, and are not particularly limited, such as particle diameter, specific surface area, and shape, but the particle diameter is preferably 0.1 to 20 mm, and the specific surface area is preferably 3 to 75 m ² / g. The shape is preferably spherical, needle-like or platelet-like. The surface treatment of the metal hydroxide flame retardant may or may not be performed. Examples of the surface treatment method include treatment methods such as coating formation with a thermosetting resin such as a silane coupling agent, an anionic surfactant, a polyfunctional organic acid, and an epoxy resin.

  In the embodiment of the present invention, when a metal hydroxide flame retardant is blended as the flame retardant (C), the blending amount is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the (A) polyamide resin. 10 parts by weight or more is more preferable. On the other hand, it is preferably 50 parts by weight or less, more preferably 40 parts by weight or less.

  The brominated flame retardant in the embodiment of the present invention is a compound containing bromine. For example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylene-bis (tetrabromophthalimide) ), Monomeric organic bromine compounds such as tetrabromobisphenol A, brominated polycarbonates (for example, polycarbonate oligomers produced from brominated bisphenol A or copolymers thereof with bisphenol A), brominated epoxy compounds (for example brominated) For the reaction of diepoxy compounds and brominated phenols produced by the reaction of bisphenol A with epichlorohydrin and epichlorohydrin Monoepoxy compound), poly (brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, cyanuric chloride and brominated phenol condensate, brominated (polystyrene), poly (brominated styrene), Examples include brominated polystyrene such as cross-linked brominated polystyrene, and halogenated polymeric bromine compounds such as cross-linked or non-cross-linked brominated poly α-methyl styrene. Of these, ethylene bis (tetrabromophthalimide), brominated epoxy polymer, brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are preferred. Brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and bromine. Polycarbonate is more preferred.

  In the embodiment of the present invention, when a brominated flame retardant is blended as the flame retardant (C), the blending amount is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the (A) polyamide resin. Part or more is more preferable. On the other hand, it is preferably 50 parts by weight or less, more preferably 40 parts by weight or less.

  Moreover, it is also preferable to mix | blend the flame retardant adjuvant used in order to improve a flame retardance synergistically by using together with said (C) flame retardant. Examples of the flame retardant aid include antimony trioxide, antimony tetraoxide, antimony pentoxide, antimony deoxydioxide, crystalline antimonic acid, sodium antimonate, lithium antimonate, barium antimonate, antimony phosphate, zinc borate, and tin. Examples thereof include zinc oxide, basic zinc molybdate, calcium zinc molybdate, molybdenum oxide, zirconium oxide, zinc oxide, iron oxide, red phosphorus, swellable graphite, carbon black, hydrotalcite and the like. Among these, zinc stannate, antimony trioxide, antimony pentoxide, and hydrotalcite are preferable. The blending amount of the flame retardant aid is preferably 0.2 to 30 parts by weight with respect to 100 parts by weight of the (A) polyamide resin from the viewpoint of flame retardant improvement effect.

  The polyamide resin composition of the embodiment of the present invention can further contain a phosphorus-containing compound. Here, in the embodiment of the present invention, the “phosphorus-containing compound” refers to phosphorous acid, hypophosphorous acid or a metal salt thereof, and two or more kinds thereof may be blended. Conventionally, phosphorus-containing compounds such as sodium hypophosphite have been used as polycondensation catalysts for polycondensation of polyamides, and are known to shorten polymerization time and to suppress yellowing. In this embodiment, by containing a phosphorus-containing compound, the fluidity and residence stability of the polyamide resin composition are further improved, and a molded article having excellent flame retardancy, heat aging resistance, surface appearance, and hinge characteristics is obtained. be able to. This is because the phosphorus-containing compound is superior to the self-condensation of the (A) polyamide resin to promote the improvement of the reaction rate of the (B) compound, and (A) while suppressing the increase in the viscosity of the polyamide resin (B) The degree of branching of the compound can be increased, and by reducing the self-aggregation force of the compound (B), (A) the reactivity and compatibility with the polyamide resin can be further improved, and (B This is considered to be because the dispersibility of the compound) and the flame retardant (C) can be further improved.

  Examples of the metal constituting the metal salt of phosphorous acid or hypophosphorous acid include alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as magnesium, calcium and barium. Among these, sodium and calcium are preferable.

  Examples of the metal salt of phosphorous acid or hypophosphorous acid include lithium phosphite, sodium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, barium phosphite, lithium hypophosphite, Examples thereof include sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, calcium hypophosphite, barium hypophosphite and the like. Among these, sodium metal salts such as sodium hypophosphite and sodium phosphite, and calcium metal salts such as calcium phosphite and calcium hypophosphite are more preferable, and (A) B) Since the reaction rate of the compound can be further increased, the degree of branching can be increased and the self-aggregation force can be decreased, the fluidity and retention stability during molding are further improved, the flame retardancy of the molded product, Heat aging resistance, surface appearance, and hinge characteristics can be further improved.

  In the polyamide resin composition of the embodiment of the present invention, the compounding amount of the phosphorus-containing compound is not particularly limited, but the phosphorus atom content derived from the phosphorus-containing compound is (A) 180 to 3500 ppm with respect to the polyamide resin content. Preferably there is. Here, the phosphorus atom content in the embodiment of the present invention represents a phosphorus element concentration determined by an absorptiometric method described later. In the polyamide resin composition of the embodiment of the present invention, when the phosphorus atom equivalent concentration is 180 ppm or more, fluidity, residence stability, flame retardancy, heat aging resistance, surface appearance and hinge characteristics can be further improved. . On the other hand, if the phosphorus atom equivalent concentration is 3500 ppm or less, (A) the polyamide resin can be prevented from being thickened, and (A) the polyamide resin and (B) by the gas generated by the decomposition of the flame retardant and phosphorus-containing compound due to shearing Decomposition of the compound can be suppressed, and fluidity, residence stability, flame retardancy, heat aging resistance, surface appearance and hinge characteristics can be further improved.

  In addition, the phosphorus atom conversion density | concentration derived from a phosphorus containing compound with respect to the polyamide resin content in a polyamide resin composition here, ie, phosphorus atom content, can be calculated | required with the following method. First, the polyamide resin composition or a molded product thereof is dried under reduced pressure, and then heated and ashed in an electric furnace at 550 ° C. for 24 hours to determine the content of the inorganic substance in the polyamide resin composition or the molded product. In addition, when it contains resin components other than (A) polyamide resin, such as impact resistance improver, (B) compound, (C) flame retardant and phosphorus-containing compound, and other additives, extract by organic solvent The weight of components other than (A) polyamide resin or (A) polyamide resin is measured, and the (A) polyamide resin content in the polyamide resin composition or its molded product is calculated. On the other hand, the polyamide resin composition or a molded product thereof is subjected to dry ashing decomposition in the presence of sodium carbonate, or wet decomposition in sulfuric acid / nitric acid / perchloric acid system or sulfuric acid / hydrogen peroxide system to convert phosphorus into normal phosphoric acid. And Next, orthophosphoric acid is reacted with molybdate in a 1 mol / L sulfuric acid solution to form phosphomolybdic acid, which is reduced with hydrazine sulfate, and the absorbance of the resulting heteropolyblue at 830 nm is measured with an absorptiometer (calibration curve). The phosphorus content in the polyamide resin composition is calculated by colorimetric quantification by measurement in the method. By dividing the phosphorus content calculated by colorimetric determination by the previously calculated polyamide resin content, the phosphorus atom equivalent concentration for the polyamide resin can be obtained.

  The polyamide resin composition of the embodiment of the present invention can further contain a copper compound. The copper compound is considered to coordinate with the hydroxyl group and hydroxide ion of the compound (B) in addition to the coordination to the amide group of the (A) polyamide resin. For this reason, it is thought that a copper compound has the effect which further improves the compatibility of (A) polyamide resin and (B) compound.

  The polyamide resin composition of the embodiment of the present invention can further contain a potassium compound. Potassium compounds suppress the liberation and precipitation of copper. For this reason, it is thought that a potassium compound has an effect which accelerates | stimulates reaction with a copper compound, (B) compound, and (A) polyamide resin.

  Examples of the copper compound include copper chloride, copper bromide, copper iodide, copper acetate, copper acetylacetonate, copper carbonate, copper borofluoride, copper citrate, copper hydroxide, copper nitrate, copper sulfate, and copper oxalate. Etc. You may contain 2 or more types of these as a copper compound. Among these copper compounds, those commercially available are preferable, and copper halide is preferable. Examples of the copper halide include copper iodide, cuprous bromide, cupric bromide, cuprous chloride and the like. As the copper halide, copper iodide is more preferable.

  Examples of the potassium compound include potassium iodide, potassium bromide, potassium chloride, potassium fluoride, potassium acetate, potassium hydroxide, potassium carbonate, and potassium nitrate. You may contain 2 or more types of these as a potassium compound. Of these potassium compounds, potassium iodide is preferred. By including the potassium compound, the surface appearance, weather resistance and mold corrosion resistance of the molded product can be further improved.

  It is preferable that content (weight basis) of the copper element in the polyamide resin composition of embodiment of this invention is 25-200 ppm. By setting the copper element content to 25 ppm or more, the compatibility between the (A) polyamide resin and the (B) compound can be further improved, and the heat aging resistance of the molded product can be further improved. The content (weight basis) of the copper element in the polyamide resin composition is preferably 80 ppm or more. On the other hand, by setting the content of the copper element to 200 ppm or less, it is possible to suppress the coloration due to precipitation and liberation of the copper compound, and to further improve the surface appearance of the molded product. Moreover, by making content of copper element 200 ppm or less, the fall of the hydrogen bond strength of the amide group resulting from the excessive coordination bond of a polyamide resin and copper is suppressed, and the heat-resistant aging property of a molded article is improved more. be able to. The content (weight basis) of copper element in the polyamide resin composition is preferably 190 ppm or less. In addition, content of the copper element in a polyamide resin composition can be made into the above-mentioned desired range by adjusting the compounding quantity of a copper compound suitably.

  The content of copper element in the polyamide resin composition can be determined by the following method. First, the polyamide resin composition pellets are dried under reduced pressure. The pellet is incinerated for 24 hours in an electric furnace at 550 ° C., concentrated sulfuric acid is added to the incinerated product, and the mixture is heated and wet-decomposed to dilute the decomposition solution. The copper content can be determined by atomic absorption analysis (calibration curve method) of the diluted solution.

  The ratio Cu / K of the content of copper element to the content of potassium element in the polyamide resin composition is preferably 0.21 to 0.43. Cu / K is an index representing the degree of suppression of copper precipitation and liberation, and the smaller the value, the more the copper compound, (B) compound and (A) polyamide resin are suppressed. The reaction with can be promoted. By setting Cu / K to 0.43 or less, copper precipitation and liberation can be suppressed, and the surface appearance of the molded product can be further improved. Further, by setting Cu / K to 0.43 or less, the compatibility of the polyamide resin composition is also improved, so that the retention stability and the heat aging resistance of the molded product can be further improved. On the other hand, by setting Cu / K to 0.21 or more, the dispersibility of the compound containing potassium is improved, and even if it is deliquescent potassium iodide, it is difficult to form a lump, and the effect of suppressing the precipitation and release of copper is improved. Since it improves, reaction with a copper compound, (B) compound, and (A) polyamide resin is fully accelerated | stimulated, and residence stability and the heat aging resistance of a molded article are improved more. The potassium element content in the polyamide resin composition can be determined by the same method as the above copper content.

  The polyamide resin composition of the embodiment of the present invention can further contain an impact resistance improving material. By incorporating an impact resistance improving material, it is possible to further improve the retention stability, heat aging resistance, and hinge characteristics. Impact modifiers generally refer to polymers whose glass transition temperature is lower than room temperature, and polymers in which some of the molecules are constrained to each other by covalent bonds, ionic bonds, van der Waals forces, entanglements, etc. It is. Examples of the impact resistance improving material include olefin resin, acrylic rubber, silicon rubber, fluorine rubber, urethane rubber, polyamide elastomer, and polyester elastomer. Two or more of these may be used. Among these, from the viewpoint of compatibility with (A) the polyamide resin, an olefin resin is preferably used.

  The olefin resin is a thermoplastic resin obtained by polymerizing or copolymerizing an olefin monomer having an unsaturated double bond such as unsaturated hydrocarbon, unsaturated carboxylic acid, acid anhydride or derivative thereof. The olefin resin is preferably used because it is excellent in compatibility with the (A) polyamide resin and can further improve the hinge characteristics of the molded product.

  Examples of the unsaturated hydrocarbon include ethylene, propylene, butene, isoprene, pentene and the like. Examples of unsaturated carboxylic acids, acid anhydrides, and derivatives thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, and glutacone. Acids and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl itaconic acid methyl, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, methacrylic acid 2-ethylhexyl, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5-heptene -2,3-dicarboxylic acid Endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate, glycidyl methacrylate, ethacryl Examples thereof include glycidyl acid, glycidyl itaconate, glycidyl citraconic acid, and 5-norbornene-2,3-dicarboxylic acid. Among these, unsaturated dicarboxylic acids and acid anhydrides thereof are preferable, and maleic acid and maleic anhydride are particularly preferable.

  Specific examples of olefin resins include homopolymers and copolymers such as polyethylene, polypropylene, polystyrene, poly 1-pentene, polymethylpentene, ethylene / α-olefin hydrocarbon copolymers, ethylene / unsaturated carboxylic acids. Acid ester copolymer, polyolefin obtained by hydrolyzing at least part of [copolymer of (ethylene and / or propylene) and vinyl alcohol ester], (ethylene and / or propylene) and (unsaturated carboxylic acid) And / or a copolymer of (unsaturated carboxylic acid ester), at least one of carboxyl groups of [a copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)] Polyolefins obtained by metallization of parts, conjugated die A block copolymer of a vinyl aromatic hydrocarbon, and the like hydride of the block copolymer. Among these, from the viewpoint of compatibility with (A) polyamide resin, ethylene / unsaturated carboxylic acid copolymer, ethylene / unsaturated carboxylic acid ester copolymer, ethylene / unsaturated carboxylic acid-unsaturated carboxylic acid metal A salt copolymer is preferably used.

  The ethylene / α-olefin hydrocarbon copolymer referred to in the present invention is preferably a copolymer of ethylene and at least one of α-olefin hydrocarbons having 3 to 20 carbon atoms. Specific examples of the α-olefin hydrocarbon having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3- Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and The combination of these, and the like. Among these α-olefin hydrocarbons, α-olefin hydrocarbons having 3 to 12 carbon atoms are preferable from the viewpoint of further improving the hinge characteristics of the molded product. (A) From the viewpoint of compatibility with the polyamide resin, a copolymer of an ethylene / α-olefin hydrocarbon and an unsaturated carboxylic acid and / or a derivative thereof is more preferable. Non-conjugated dienes such as 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5- (1′-propenyl) -2-norbornene At least one of these may be copolymerized. The α-olefin hydrocarbon content of the ethylene / α-olefin hydrocarbon copolymer is preferably 1 to 30 mol%, more preferably 2 to 25 mol%, and still more preferably 3 to 20 mol%.

  The ethylene / unsaturated carboxylic acid copolymer referred to in the present invention is a polymer obtained by copolymerizing ethylene and an unsaturated carboxylic acid, and examples thereof include (meth) acrylic acid. The number average molecular weight of the ethylene / unsaturated carboxylic acid copolymer is not particularly limited. However, since the fluidity and hinge characteristics are further improved, the MFR at 190 ° C. and the load of 2.16 kg is 0.9 to 5.5. Is preferred.

  The ethylene / unsaturated carboxylic acid ester copolymer referred to in the present invention is a polymer obtained by copolymerizing ethylene and an unsaturated carboxylic acid ester. Examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and glycidyl methacrylate. Specific examples of ethylene / unsaturated carboxylic acid ester copolymers include ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, ethylene / butyl acrylate copolymers, ethylene / methyl methacrylate copolymers. Copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / acrylic Examples include methyl acid / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, and the like. Of these, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, and ethylene / methyl methacrylate / glycidyl methacrylate copolymer are preferably used. The weight ratio of the ethylene component to the unsaturated carboxylic acid ester component in the ethylene / unsaturated carboxylic acid ester copolymer is not particularly limited, but is preferably 90/10 to 10/90, more preferably 85/15 to 15 / A range of 85. The number average molecular weight of the ethylene / unsaturated carboxylic acid ester copolymer is not particularly limited. It is preferable to be in the range.

  The ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid metal salt copolymer is a copolymer obtained by metallizing at least a part of the carboxyl group of the copolymer of ethylene and unsaturated carboxylic acid. . By chlorinating the metal, an ionomer structure is formed in which the copolymer molecules are cross-linked by metal ions. Examples of unsaturated carboxylic acid metal salts include (meth) acrylic acid metal salts. The metal constituting the unsaturated carboxylic acid metal salt is not particularly limited, and examples thereof include alkali metals such as sodium, alkaline earth metals such as magnesium, and zinc. The weight ratio of the unsaturated carboxylic acid component to the unsaturated carboxylic acid metal salt component in the ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid metal salt copolymer is not particularly limited, but preferably 95/5 to 5/95, More preferably, it is the range of 90/10-10/90. The number average molecular weight of the ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid metal salt copolymer is not particularly limited, but from the viewpoint of further improving fluidity and hinge characteristics, the MFR at 190 ° C. and a load of 2.16 kg is 0.1. It is preferable that it is 9-5.5.

  The method for introducing the unsaturated carboxylic acid, its acid anhydride or its derivative into the polyolefin resin is not particularly limited. For example, an olefin monomer containing an unsaturated carboxylic acid, its acid anhydride, or its derivative is used. Examples thereof include a polymerization method, and a method in which an unsaturated carboxylic acid, an acid anhydride or a derivative thereof is grafted onto a polyolefin-based hydrocarbon resin using a radical initiator. The introduction amount of the unsaturated carboxylic acid, its acid anhydride and its derivative is preferably in the range of 0.001 to 40 mol%, more preferably 0.01 to 35 mol% in the total olefin monomer of the polyolefin resin. Is within.

  The compounding amount of the impact resistance improving material in the polyamide resin composition of the present invention is 1 to 100 parts by weight with respect to 100 parts by weight of the (A) polyamide resin. By setting the blending amount to 1 part by weight or more, it is possible to further improve the retention stability, heat aging resistance, and hinge characteristics. On the other hand, by setting it to 100 parts by weight or less, fluidity and heat aging resistance can be improved. 5 to 50 parts by weight is preferred.

  The polyamide resin composition of the embodiment of the present invention can further contain a filler. As the filler, either an organic filler or an inorganic filler may be used, and either a fibrous filler or a non-fibrous filler may be used. As the filler, a fibrous filler is preferable.

  Examples of the fibrous filler include glass fiber, PAN (polyacrylonitrile) -based or pitch-based carbon fiber, stainless steel fiber, metal fiber such as aluminum fiber and brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, Ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, silicon nitride whisker And fibrous or whisker-like fillers. As the fibrous filler, glass fiber or carbon fiber is particularly preferable.

  The type of glass fiber is not particularly limited as long as it is generally used for reinforcing resin, and can be selected from, for example, long fiber type, short fiber type chopped strand, milled fiber, and the like. Further, the glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin. Furthermore, the cross-section of the glass fiber is not limited to a circular, flat gourd, eyebrows, oval, ellipse, rectangle, or similar products. From the viewpoint of reducing the specific warpage of the molded product that tends to occur in the glass fiber-containing polyamide resin composition, a flat fiber having a ratio of major axis / minor axis of 1.5 or more is preferred, and one having a ratio of 2.0 or more is more preferred. 10 or less is preferable, and 6.0 or less is more preferable. When the ratio of major axis / minor axis is less than 1.5, the effect of flattening the cross section is small, and when the ratio is larger than 10, it is difficult to produce the glass fiber itself.

  Non-fibrous fillers include, for example, non-swelling silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, calcium silicate, and Li-type fluorine. Teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, swellable layered silicate represented by swelling mica of Li-type tetrasilicon fluorine mica, silicon oxide, magnesium oxide, alumina, silica, diatomaceous earth, zirconium oxide, oxidation Metal oxides such as titanium, iron oxide, zinc oxide, calcium oxide, tin oxide, antimony oxide, metal carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dolomite, hydrotalcite, calcium sulfate, barium sulfate Metal sulfate such as montmorillo Smectite clay minerals such as knight, beidellite, nontronite, saponite, hectorite, and soconite and various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, glass beads, glass flakes, ceramic beads, boron nitride, aluminum nitride, Examples thereof include silicon carbide, carbon black, and graphite. In the swellable layered silicate, exchangeable cations existing between layers may be exchanged with organic onium ions, and examples of the organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Moreover, you may contain 2 or more types of these fillers.

  The surface of the filler has a known coupling agent (for example, silane coupling agent, titanate coupling agent) or a known sizing agent (for example, carboxylic acid, epoxy, urethane, etc.). The mechanical strength and surface appearance of the molded product can be further improved. As the sizing agent, an epoxy sizing agent is preferable. As a method for treating the filler, for example, in the case of treatment with a coupling agent, a method in which a filler is surface-treated with a coupling agent in accordance with a conventional method and then melt-kneaded with a polyamide resin is preferably used. An integral blend method in which a coupling agent is added may be used when the filler and the polyamide resin are melt-kneaded without performing the surface treatment. The treatment amount of the coupling agent is preferably 0.05 parts by weight or more, more preferably 0.5 parts by weight or more with respect to 100 parts by weight of the filler. On the other hand, the treatment amount of the coupling agent is preferably 10 parts by weight or less, and more preferably 3 parts by weight or less with respect to 100 parts by weight of the filler.

  In the polyamide resin composition of the embodiment of the present invention, the blending amount of the filler is preferably 1 to 150 parts by weight with respect to 100 parts by weight of the (A) polyamide resin. When the blending amount of the filler is 1 part by weight or more, the mechanical strength and heat aging resistance of the molded product can be further improved. As for the compounding quantity of a filler, 10 weight part or more is more preferable, and 20 weight part or more is further more preferable. On the other hand, when the blending amount of the filler is 150 parts by weight or less, it is possible to suppress the float of the filler on the surface of the molded product, and to obtain a molded product having a superior surface appearance. The blending amount of the filler is more preferably 80 parts by weight or less, and further preferably 70 parts by weight or less.

  Furthermore, the polyamide resin composition of the embodiment of the present invention can be blended with resins other than the polyamide resin and various additives according to the purpose within a range not impairing the effects of the present invention.

  Specific examples of resins other than polyamide resins include polyester resins, polyolefin resins, modified polyphenylene ether resins, polysulfone resins, polyketone resins, polyetherimide resins, polyarylate resins, polyether sulfone resins, polyether ketone resins, polythioethers. Examples thereof include ketone resins, polyether ether ketone resins, polyimide resins, polyamideimide resins, and tetrafluoropolyethylene resins. When these resins are blended, the blending amount is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the (A) polyamide resin, in order to fully utilize the characteristics of the polyamide resin.

  Specific examples of various additives include heat stabilizers other than copper compounds, isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, epoxy compounds and other coupling agents, polyalkylene oxide oligomers. Compounds, plasticizers such as thioether compounds and ester compounds, crystal nucleating agents such as polyether ether ketone, metal soaps such as montanic acid wax, lithium stearate, aluminum stearate, ethylenediamine, stearic acid, sebacic acid heavy Examples thereof include release agents such as condensates and silicone compounds, lubricants, ultraviolet light inhibitors, colorants, and foaming agents. When these additives are contained, the blending amount thereof is preferably 10 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the (A) polyamide resin in order to fully utilize the characteristics of the polyamide resin.

  Examples of heat stabilizers other than copper compounds include phenolic compounds, sulfur compounds, and amine compounds. Two or more of these may be used as a heat stabilizer other than the copper compound.

  As the phenolic compound, a hindered phenolic compound is preferably used, and N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane or the like is preferably used.

  Examples of sulfur compounds include organic thioacid compounds, mercaptobenzimidazole compounds, dithiocarbamic acid compounds, and thiourea compounds. Among these sulfur compounds, mercaptobenzimidazole compounds and organic thioacid compounds are preferable. In particular, a thioether compound having a thioether structure can be suitably used as a heat stabilizer because it receives oxygen from an oxidized substance and reduces it. Specific examples of thioether compounds include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate). ) And pentaerythritol tetrakis (3-laurylthiopropionate) are preferred, and pentaerythritol tetrakis (3-dodecylthiopropionate) and pentaerythritol tetrakis (3-laurylthiopropionate) are more preferred. The molecular weight of the sulfur compound is usually 200 or more, preferably 500 or more, and the upper limit is usually 3,000.

  As the amine compound, a compound having a diphenylamine skeleton, a compound having a phenylnaphthylamine skeleton, and a compound having a dinaphthylamine skeleton are preferable, and a compound having a diphenylamine skeleton and a compound having a phenylnaphthylamine skeleton are more preferable. Among these amine compounds, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine and N, N′-diphenyl-p-phenylenediamine are used. More preferred are N, N′-di-2-naphthyl-p-phenylenediamine and 4,4′-bis (α, α-dimethylbenzyl) diphenylamine.

  As a combination of a sulfur compound or an amine compound, a combination of pentaerythritol tetrakis (3-laurylthiopropionate) and 4,4′-bis (α, α-dimethylbenzyl) diphenylamine is more preferable.

  The method for producing the polyamide resin composition of the embodiment of the present invention is not particularly limited, but production in a molten state or production in a solution state can be used, and production in a molten state from the viewpoint of improving reactivity. Can be preferably used. For production in a molten state, melt kneading using an extruder, melt kneading using a kneader, or the like can be used. From the viewpoint of productivity, melt kneading using an extruder that can be continuously produced is preferable. For melt kneading by an extruder, one or more extruders such as a single screw extruder, a twin screw extruder, a multi screw extruder such as a four screw extruder, and a twin screw single screw compound extruder can be used. From the viewpoint of improving reactivity and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder is preferable, and a method by melt kneading using a twin-screw extruder is most preferable.

  In the embodiment of the present invention, the production method of the polyamide resin composition includes (b) a compound (B) prepared in advance from a hydroxyl group and / or amino group-containing compound and (b ′) an epoxy group and / or carbodiimide group-containing compound. And (A) a polyamide resin, (C) a flame retardant, and, if necessary, a method of melt kneading together with components other than (A), (B), and (C).

  Moreover, when the polyamide resin composition of embodiment of this invention mix | blends a phosphorus containing compound, it is preferable to mix | blend a phosphorus containing compound at the time of a compound with (A) polyamide resin and (B) compound. By blending a phosphorus-containing compound at the time of compounding, the fluidity and residence stability at the time of molding of the polyamide resin composition can be further improved, and the heat aging resistance and hinge characteristics can be further improved.

  When melt-kneading using a twin-screw extruder, there is no particular limitation on the raw material supply method to the twin-screw extruder. When supplying the compound (B) as a raw material to a twin screw extruder, the compound (B) tends to promote the decomposition of the polyamide resin in a temperature range higher than the melting point of the polyamide resin. It is preferable to supply from the downstream side of the supply position and shorten the kneading time of the (A) polyamide resin and the (B) compound. In addition, (C) the method of supplying the flame retardant is (A) from the viewpoint of suppressing the decomposition of the flame retardant accompanying shearing heat generation due to thickening of the polyamide resin, together with the (B) compound, than the (A) polyamide resin supply position. It is preferable to supply from the downstream side. Here, the side on which the raw material of the twin-screw extruder is supplied is defined as upstream, and the side on which molten resin is discharged is defined as downstream. Moreover, when the polyamide resin composition of the embodiment of the present invention is formed by blending a phosphorus-containing compound, the phosphorus-containing compound is added to the catalytic effect of (A) promoting the self-condensation of the polyamide resin, and the reaction of the (B) compound. Since it is thought that it plays the role which improves a rate, it is preferable to supply to a twin-screw extruder with (B) compound and (C) a flame retardant.

  It is considered that the copper compound plays a role as a compatibilizer between the (A) polyamide resin and the (B) compound while coordinating to the amide group of the (A) polyamide resin and protecting the amide group. From the above, when the copper compound is blended, it is preferable that (A) the polyamide resin and the copper compound be sufficiently reacted together with (A) the polyamide resin.

  The ratio of the total screw length L to the screw diameter D (L / D) of the twin screw extruder is preferably 25 or more, more preferably more than 30. When L / D is 25 or more, it becomes easy to supply the compound (B) and the flame retardant (C) after sufficiently kneading the (A) polyamide resin and, if necessary, the copper compound. As a result, (A) the decomposition of the polyamide resin can be suppressed. Moreover, it is considered that the compatibility between the (A) polyamide resin and the (B) compound is further improved, so that the retention stability at the time of molding can be further improved, and the heat aging resistance and hinge characteristics can be further improved.

  In the embodiment of the present invention, it is preferable to supply at least (A) the polyamide resin and, if necessary, the copper compound to the twin-screw extruder from the upstream side of 1/2 of the screw length and melt knead, It is more preferable to supply from the upstream end. The screw length here is the length from the upstream end of the screw segment at the position (feed port) where the (A) polyamide resin is supplied to the screw tip. The upstream end portion of the screw segment refers to the position of the screw piece located at the most upstream end of the screw segment connected to the extruder.

  The compound (B) and the flame retardant (C) and, if necessary, the phosphorus-containing compound are preferably supplied to the twin screw extruder from the downstream side of 1/2 of the screw length and melt-kneaded. (B) A compound and (C) a flame retardant, and if necessary, a phosphorus-containing compound is supplied from the downstream side of 1/2 of the screw length, so that (A) a polyamide resin and, if necessary, a copper compound are sufficiently kneaded, After that, it becomes easy to supply the compound (B) and the flame retardant (C), and if necessary, the phosphorus-containing compound. As a result, it is possible to increase the reaction rate of the compound (B) while suppressing the thickening of the polyamide resin (A), to increase the degree of branching and to reduce the self-aggregation force, (B) It is thought that the compatibility of a compound increases. As a result, the fluidity and retention stability during molding are excellent, and the heat aging resistance of the molded product can be further improved. Moreover, the dispersibility of (C) a flame retardant can be improved by the fluidity improvement effect by the compatibility improvement of (A) polyamide resin and (B) compound, and the local flame-retardant variation is suppressed. Can do. Further, the hinge characteristics can be improved by forming a more uniform and fine dispersion structure in the resin composition.

  When producing the polyamide resin composition of the embodiment of the present invention using a twin screw extruder, a twin screw extruder having a plurality of full flight zones and a plurality of kneading zones in terms of kneadability and reactivity. Is preferably used. The full flight zone is composed of one or more full flights, and the kneading zone is composed of one or more kneading discs.

Further, the maximum resin pressure among the resin pressures in the plurality of kneading zones is Pkmax (MPa), and the minimum resin pressure in the plurality of full flight zones is Pfmin (MPa). ,
Pkmax ≧ Pfmin + 0.3
It is preferable to melt-knead under the following conditions,
Pkmax ≧ Pfmin + 0.5
It is more preferable to perform melt kneading under the following conditions. In addition, the resin pressure of a kneading zone and a full flight zone refers to the resin pressure which the resin pressure gauge installed in each zone shows.

  The kneading zone is superior in the kneadability and reactivity of the molten resin compared to the full flight zone. By filling the kneading zone with the molten resin, kneadability and reactivity are dramatically improved. As an index indicating the state of filling of the molten resin, there is a value of the resin pressure. As the resin pressure is larger, it becomes one standard indicating that the molten resin is filled. That is, when using a twin-screw extruder, kneadability and reactivity can be further improved by increasing the resin pressure in the kneading zone within a predetermined range from the resin pressure in the full flight zone. The dispersibility of the compound and the flame retardant (C) can be increased, and as a result, the fluidity, residence stability, flame retardancy, heat aging resistance, surface appearance and hinge characteristics of the molded product can be further improved.

  The method for increasing the resin pressure in the kneading zone is not particularly limited. For example, a reverse screw zone that has the effect of pushing back the molten resin upstream or between the kneading zones and a molten resin can be used. A method of introducing a seal ring zone or the like having an effect of accumulating can be preferably used. The reverse screw zone and the seal ring zone are formed of one or more reverse screws and one or more seal rings, and they can be combined.

  When the total length of the kneading zone on the upstream side of the supply position of the compound (B) and the flame retardant (L) is Ln1, Ln1 / L is preferably 0.02 or more, and 0.03 or more. More preferably it is. On the other hand, Ln1 / L is preferably 0.40 or less, and more preferably 0.20 or less. By setting Ln1 / L to 0.02 or more, the reactivity and kneadability of the (A) polyamide resin can be improved. By setting it to 0.40 or less, shear heat generation is moderately suppressed and the resin is thermally deteriorated. Can be suppressed. (A) Although there is no restriction | limiting in particular in the melting temperature of a polyamide resin, in order to suppress the molecular weight fall by the thermal deterioration of (A) polyamide resin, 340 degrees C or less is preferable.

  (B) When the total length of the kneading zone on the downstream side of the compound supply position is Ln2, Ln2 / L is preferably 0.02 to 0.30. By setting Ln2 / L to 0.02 or more, the reactivity of the compound (B) can be further increased. Ln2 / L is more preferably 0.04 or more. On the other hand, by setting Ln2 / L to 0.30 or less, (A) decomposition of the polyamide resin can be further suppressed. Ln2 / L is more preferably 0.16 or less.

  As a more preferable production method of the polyamide resin composition of the embodiment of the present invention, a high concentration premix is prepared by melt-kneading (A) the polyamide resin and the (B) compound with a twin screw extruder. And (A) a polyamide resin and (C) a flame retardant, and a method of melt-kneading with a twin screw extruder. (A) 10 to 250 parts by weight of (B) compound is melt-kneaded with respect to 100 parts by weight of polyamide resin to prepare a high concentration premix, and the high concentration premix is further added to (A) polyamide resin and (C) It is more preferable to melt and knead together with the flame retardant with a twin screw extruder. Compared with the case where a high-concentration premix is not prepared, the fluidity and retention stability during molding are excellent, and the heat aging resistance of the resulting molded product can be further improved. Although it is not certain about this factor, it is considered that the compatibility between each component is further improved by melt-kneading twice. Moreover, when preparing a high concentration premix, the compounding quantity of (B) compound increases with respect to (A) polyamide resin. In order to suppress a decrease in residence stability, at the time of melt kneading in a twin screw extruder, (B) the compound is supplied from the downstream side of the polyamide resin supply position, and (A) the kneading time of the polyamide resin and (B) compound Is preferably shortened. The (A) polyamide resin used in the high concentration premix and the (A) polyamide resin further blended in the high concentration premix may be the same or different. Nylon 6, nylon 11 and / or nylon 12 is preferable as the (A) polyamide resin used in the high-concentration premix from the viewpoint of further improving the heat aging resistance of the molded product.

  The polyamide resin composition thus obtained can be molded by a known method, and various molded products such as sheets, films and fibers can be obtained from the polyamide resin composition. Examples of the molding method include injection molding, injection compression molding, extrusion molding, compression molding, blow molding, and press molding.

  The polyamide resin composition and molded product thereof according to an embodiment of the present invention are utilized for various uses such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, daily life goods and sanitary goods, taking advantage of their excellent characteristics. be able to. The polyamide resin composition and molded product thereof according to an embodiment of the present invention are excellent in fluidity, residence stability, flame retardancy, heat aging resistance, surface appearance, and hinge characteristics, and are therefore used in automobile parts and electrical / electronic parts. In particular, it is effective when a molded article having a hinge portion is used. Here, the hinge portion is thinner than the peripheral portion and refers to a portion where the molded product can be bent, and is particularly useful for use in clips, clamps, and bands for bundling wires, cords, and tubes in a high temperature environment.

  The embodiment of the present invention will be described more specifically with reference to the following examples. The characteristic evaluation was performed according to the following method.

[Melting point of polyamide resin]
About 5 mg of the polyamide resin was sampled, and the melting point of the (A) polyamide resin was measured under the following conditions using a Seiko Instruments robot DSC (differential scanning calorimeter) RDC220 under a nitrogen atmosphere. After melting to a melting point of the polyamide resin + 40 ° C. to obtain a molten state, the temperature is lowered to 30 ° C. at a rate of temperature drop of 20 ° C./min, held at 30 ° C. for 3 minutes, and then melted at a rate of temperature rise of 20 ° C./min The temperature (melting point) of the endothermic peak observed when the temperature was raised to + 40 ° C. was determined.

[Relative viscosity of polyamide resin]
The relative viscosity (ηr) was measured using an Ostwald viscometer at 25 ° C. in 98% concentrated sulfuric acid having a polyamide resin concentration of 0.01 g / ml.

[Phosphorus atom content relative to polyamide resin in polyamide resin composition]
The pellets obtained in Example 18 were dried under reduced pressure at 80 ° C. for 12 hours, and the pellets were ashed for 24 hours in an electric furnace at 550 ° C. to determine the inorganic content. Subsequently, the pellet was stirred in DMSO at 60 ° C. to extract additive components other than the polyamide resin, and the additive content was determined. Thereafter, the content of the polyamide resin in the composition was determined by subtracting the inorganic and additive weights from the weight of the polyamide resin composition.

  Next, the pellets of the polyamide resin composition were wet-decomposed in a sulfuric acid / hydrogen peroxide system to convert phosphorus into normal phosphoric acid, and the decomposition solution was diluted. Next, the orthophosphoric acid is reacted with molybdate in a 1 mol / L sulfuric acid solution to form phosphomolybdic acid, which is reduced with hydrazine sulfate, and the absorbance of the resulting heteropolyblue at 830 nm is measured with an absorptiometer (calibration). The phosphorus content in the polyamide resin composition was calculated by colorimetric quantification by measurement using a linear method. The phosphorus atom content relative to the polyamide resin content was determined by dividing the phosphorus content calculated by colorimetric determination by the previously calculated polyamide resin content. U-3000 manufactured by Hitachi, Ltd. was used as the absorptiometer.

[Copper content and potassium content in polyamide resin composition]
The pellets obtained in Example 15 were dried under reduced pressure at 80 ° C. for 12 hours. The pellet was incinerated for 24 hours in an electric furnace at 550 ° C., concentrated sulfuric acid was added to the incinerated product, and the mixture was heated and wet-decomposed to dilute the decomposition solution. The diluted solution was subjected to atomic absorption analysis (calibration curve method) to determine the copper content and the potassium content. AA-6300 manufactured by Shimadzu Corporation was used as the atomic absorption spectrometer.

[Weight average molecular weight and number average molecular weight]
(B) Compound, (B ′) compound, (b) Hydroxyl group and / or amino group-containing compound, (b ′) Epoxy group and / or carbodiimide group-containing compound (2.5 mg) were added to hexafluoroisopropanol (0.005N- A solution obtained by dissolving in 4 ml of sodium trifluoroacetate and filtering through a 0.45 μm filter was used for the measurement. The measurement conditions are shown below.
Apparatus: Gel permeation chromatography (GPC) (manufactured by Waters)
Detector: differential refractometer Waters 410 (manufactured by Waters)
Column: Shodex GPC HFIP-806M (2 pieces) + HFIP-LG (Shimadzu GL Corp.)
Flow rate: 0.5 ml / min
Sample injection volume: 0.1 ml
Temperature: 30 ° C
Molecular weight calibration: polymethylmethacrylate.

[Hydroxyl value]
(B) 0.5 g of the hydroxyl group-containing compound, (B) compound, and (B ′) compound was collected and added to each 250 ml Erlenmeyer flask, and then acetic anhydride and anhydrous pyridine were adjusted and mixed to 1:10 (mass ratio). 20.00 ml of the solution was collected, put into the Erlenmeyer flask, attached with a reflux condenser, refluxed for 20 minutes with stirring in an oil bath adjusted to 100 ° C., and then cooled to room temperature. Further, 20 ml of acetone and 20 ml of distilled water were added to the Erlenmeyer flask through a condenser. A phenolphthalein indicator was added thereto, and titrated with a 0.5 mol / L ethanolic potassium hydroxide solution. In addition, the hydroxyl value was calculated by the following formula (5) by subtracting the measurement result of the blank (not including the sample) separately measured.
Hydroxyl value [mgKOH / g] = [((BC) × f × 28.05) / S] + E (5) where B: 0.5 mol / L ethanolic potassium hydroxide solution used for titration Amount [ml], C: Amount of 0.5 mol / L ethanolic potassium hydroxide solution used for titration of blank [ml], f: Factor of 0.5 mol / L ethanolic potassium hydroxide solution, S: Sample mass [g], E: represents acid value.

[Amine number]
(B) 0.5-1.5 g of amino group-containing compound and (B) compound were precisely weighed and dissolved in 50 ml of ethanol. This solution was neutralized and titrated with an ethanolic hydrochloric acid solution having a concentration of 0.1 mol / L using a potentiometric titrator (Kyoto Electronics Industry Co., Ltd., AT-200) equipped with a pH electrode. The inflection point of the pH curve was taken as the titration end point, and the amine value was calculated by the following formula (6).
Amine value [mg KOH / g] = (56.1 × V × 0.1 × f) / W (6)
However, W: Weighed amount of sample [g], V: Titration amount at the end of titration [ml], f: Factor of 0.1 mol / L ethanolic hydrochloric acid solution.

[(B) Compound reaction rate]
(B) 0.035 g of the compound was dissolved in 0.7 ml of deuterated dimethyl sulfoxide, and in the case of an epoxy group, ¹ H-NMR measurement was performed, and in the case of a carbodiimide group, ¹³ C-NMR measurement was performed. Each analysis condition is as follows.
(1) ¹ H-NMR
Apparatus: Nuclear magnetic resonance apparatus (JNM-AL400) manufactured by JEOL Ltd.
Solvent: Deuterated dimethyl sulfoxide Observation frequency: OBFRQ 399.65 MHz, OBSET 124.00 KHz, OBFIN 10500.00 Hz
Integration count: 256 times (2) ¹³ C-NMR
Apparatus: Nuclear magnetic resonance apparatus (JNM-AL400) manufactured by JEOL Ltd.
Solvent: Deuterated dimethyl sulfoxide Observation frequency: OBFRQ 100.40 MHz, OBSET 125.00 KHz, OBFIN 10500.00 Hz
Integration count: 512 times.

From the obtained ¹ H-NMR spectrum, the area of the peak derived from the epoxy ring was determined. Moreover, the area of the peak derived from a carbodiimide group was calculated | required from the obtained ¹³ C-NMR spectrum. The peak area was calculated by integrating the area surrounded by the baseline and the peak using analysis software attached to the NMR apparatus. (B) The peak area of a dry blend of a hydroxyl group and / or amino group-containing compound and (b ′) an epoxy group and / or carbodiimide group-containing compound is defined as d, and the peak area of the compound (B) is defined as e. Was calculated by the following formula (4).
Reaction rate (%) = {1- (e / d)} × 100 (4)

As an example, dipentaerythritol and bisphenol A type epoxy resin "Mitsubishi Chemical Co., Ltd. Ltd." jER "(registered trademark) 1004 3: ¹ H-NMR spectrum but was dry blended in a weight ratio of 1 shown. also from ¹ H-NMR spectrum shows a ¹ H-NMR spectrum of the obtained in reference example 9 (B-7) compound. Figure 1 shown in FIG. 2, an epoxy ring appearing in the vicinity of 2.60ppm and 2.80ppm The sum of the peak areas derived was similarly obtained, and the sum of the peak areas shown in Fig. 2 was also obtained, and the reaction rate was calculated from the calculation formula (4) for the reaction rate, in which case the peak area is an epoxy resin benzene that does not contribute to the reaction. Normalized by the area of the peak of the ring.

[Degree of branching]
The compound (B) and the compound (B ′) were subjected to ¹³ C-NMR analysis under the following conditions, and the degree of branching (DB) was calculated from the following formula (2).
Branch degree = (D + T) / (D + T + L) (2)
In the above formula (2), D represents the number of dendritic units, L represents the number of linear units, and T represents the number of terminal units. Said D, T, and L were computed from the peak area measured by ¹³ C-NMR. D is derived from a tertiary or quaternary carbon atom, T is derived from a primary carbon atom that is a methyl group, L is a primary or secondary carbon atom, Derived from except T. The peak area was calculated by integrating the area surrounded by the baseline and the peak using analysis software attached to the NMR apparatus. The measurement conditions are as follows.
(1) ¹³ C-NMR
Apparatus: Nuclear magnetic resonance apparatus (JNM-AL400) manufactured by JEOL Ltd.
Solvent: Deuterated dimethyl sulfoxide measurement sample amount / solvent amount: 0.035 g / 0.70 ml
Observation frequency: OBFRQ 100.40MHz, OBSET125.00KHz, OBFIN10500.00Hz
Integration count: 512 times.

[(B) Compound, (B ′) Sum of Number of Hydroxyl and Amino Groups of Compound and Sum of Number of Epoxy Group and Carbodiimide Group]
The number of OH or NH ₂ was calculated by the following formula (3) by calculating the number average molecular weight and the hydroxyl value or amine value of the (B) compound and (B ′) compound.
Number of OH or NH ₂ = (number average molecular weight × hydroxyl value or amine value) / 56110 (3)

  The number of epoxy groups or carbodiimide groups was calculated by dividing the number average molecular weight of the (B) compound and (B ′) compound by the epoxy equivalent or carbodiimide equivalent.

The number average molecular weight, the hydroxyl value, and the amine value of the (B) compound and (B ′) compound were measured by the methods described above. The epoxy equivalent was obtained by dissolving 400 mg of the compound (B) and the compound (B ′) in 30 ml of hexafluoroisopropanol, and then adding 20 ml of acetic acid and a tetraethylammonium bromide / acetic acid solution (= 50 g / 200 ml) to give a titration solution of 0. 1N perchloric acid and crystal violet were used as an indicator, and the titration amount when the color of the solution changed from purple to blue-green was calculated by the following formula (7).
Epoxy equivalent [g / eq] = W / ((FG) × 0.1 × f × 0.001) (7)
F: amount of 0.1N perchloric acid used for titration [ml], G: amount of 0.1N perchloric acid used for titration of blank [ml], f: 0.1N perchloric acid Acid factor, W: sample weight [g]

The carbodiimide equivalent was calculated by the following method. (B) 100 parts by weight of a compound and 30 parts by weight of potassium ferrocyanide (manufactured by Tokyo Chemical Industry Co., Ltd.) as an internal standard substance were dry blended and subjected to hot pressing at about 200 ° C. for 1 minute to produce a sheet. Thereafter, the infrared absorption spectrum of the sheet was measured by a transmission method using an infrared spectrophotometer (manufactured by Shimadzu Corporation, IR Prestige-21 / AIM8800). The measurement conditions were a resolution of 4 cm ⁻¹ and an integration count of 32 times. In the infrared absorption spectrum in the transmission method, since the absorbance is inversely proportional to the sheet thickness, it is necessary to normalize the peak intensity of the carbodiimide group using the internal standard peak. A value obtained by dividing the absorbance of the carbodiimide group-derived peak appearing in the vicinity of 2140 cm ^{−1 by} the absorbance of the CN group absorption peak of potassium ferrocyanide appearing in the vicinity of 2100 cm ⁻¹ was calculated. In order to calculate the carbodiimide equivalent from this value, IR measurement was performed in advance using a sample with a known carbodiimide equivalent, and a calibration curve was created using the ratio of the absorbance of the carbodiimide group-derived peak to the absorbance of the internal standard peak ( B) The absorbance ratio of the compound was substituted into a calibration curve, and the carbodiimide equivalent was calculated. In addition, aliphatic polycarbodiimide (manufactured by Nisshinbo Co., Ltd., “Carbodilite” (registered trademark) LA-1, carbodiimide equivalent 247 g / mol), aromatic polycarbodiimide (manufactured by Rhein Chemie, “Stabakuzol” (registered trademark)) ) P, carbodiimide equivalent 360 g / mol).

[Liquidity]
The pellets obtained in each Example and Comparative Example were vacuum-dried at 80 ° C. for 12 hours, and cylinder temperature: (A) Melting point of polyamide resin + 25 using an injection molding machine (FANUC Co., Ltd., ROBOSHOTα-30C). C., mold temperature: 80.degree. C., injection pressure: 98 MPa, injection molding was performed using a 200 mm long.times.10 mm width.times.0.5 mm thick mold, and a 10 mm wide.times.0.5 mm thick rod flow test piece was obtained. Produced. For each of the five samples, the rod flow length at a holding pressure of 0 was measured, the average value was obtained, and the fluidity was evaluated. The longer the flow length, the better the fluidity.

[Stay stability]
The pellets obtained in each Example and Comparative Example were dried under reduced pressure at 80 ° C. for 12 hours, and measured for relative viscosity after being melted and retained for 30 minutes at (A) melting point of polyamide resin + 20 ° C. in a nitrogen atmosphere. The value (percentage) divided by the previous relative viscosity was calculated as the relative viscosity retention rate, which was used as an indicator of residence stability. The closer the relative viscosity retention rate is to 100%, the better the retention stability.

[Flame retardance]
The pellets obtained in each Example and Comparative Example were dried under reduced pressure at 80 ° C. for 12 hours, and using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: (A) of polyamide resin A flame retardant evaluation test piece having a thickness of 1/64 as defined in UL94 was obtained by injection molding under the conditions of melting point + 15 ° C. and mold temperature: 80 ° C. The test piece was evaluated for flame retardancy according to the evaluation criteria defined in UL94. The flame retardancy level decreases in the order of V-0>V-1>V-2> HB.

[Heat aging resistance]
The pellets obtained in each Example and Comparative Example were dried under reduced pressure at 80 ° C. for 12 hours, and using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: (A) of polyamide resin An ASTM No. 1 dumbbell test piece having a thickness of 3.2 mm was produced by injection molding under the conditions of melting point + 15 ° C. and mold temperature: 80 ° C. The test piece was subjected to a tensile test according to ASTM D638 using a tensile tester Tensilon UTA2.5T (Orientec Co., Ltd.) at a crosshead speed of 10 mm / min. The measurement was performed three times, and the average value was calculated as the tensile strength before the heat aging resistance test treatment. Next, ASTM No. 1 dumbbell test piece was subjected to 135 hours at 135 ° C. in a gear oven under the atmosphere or 2000 hours (heat aging resistance test treatment) at 190 ° C. under a gear oven in the atmosphere. The average value of the three measurements was calculated as the tensile strength after the heat aging resistance test treatment. The ratio of the tensile strength after the treatment to the tensile strength before the heat aging resistance test treatment was calculated as the tensile strength retention rate. The greater the tensile strength retention, the better the heat aging resistance.

[Surface appearance]
The pellets obtained in each Example and Comparative Example were dried under reduced pressure at 80 ° C. for 12 hours, and using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: (A) of polyamide resin Melting point + 15 ° C., mold temperature: 80 ° C., injection / cooling time: 10/10 seconds, screw rotation speed: 150 rpm, injection pressure: 100 MPa, injection speed: 100 mm / second, corner of 80 mm × 80 mm × 3 mm thickness A plate (film gate) was injection molded. The obtained square plate was heat-treated in an atmosphere of 140 ° C. for 1 hour, and the state of the treated square plate surface was visually observed and evaluated according to the following criteria.
A: The color tone of the molded product is white, and no bleed is observed on the surface.
B: The color tone of the molded product is slightly bluish white or reddish brown, and no bleed is observed on the surface.
C1: The color tone of the molded product is bluish white or reddish brown, and no bleed is observed on the surface.
C2: The color tone of the molded product is white and bleed is observed on the surface.
Note that the bleed product refers to a material that is raised on the surface of the molded product. When the (b) hydroxyl group and / or amino group-containing compound, (B) compound, or (B ′) compound is solid at room temperature, it is like dusting. (B) When the hydroxyl group and / or amino group-containing compound, (B) compound or (B ′) compound is liquid at room temperature, it becomes a viscous liquid.

[Hinge characteristics]
The pellets obtained in each Example and Comparative Example were dried under reduced pressure at 80 ° C. for 12 hours, and using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: (A) of polyamide resin The molded article with hinge shown in FIG. 3 was obtained by injection molding under the conditions of melting point + 15 ° C. and mold temperature: 80 ° C. The hinge part was 20 mm long, 3 mm wide, and 0.5 mm thick.

  The obtained hinged molded product was cooled in a -20 ° C constant temperature bath for 3 hours. In addition, the thermostat used the prefabricated environmental test apparatus ROOMY by the ITEC company of the size which a tester can enter and can test in. After cooling for 3 hours, the measurer enters the room, waits for 10 minutes in the thermostatic bath to completely eliminate the influence of the temperature change at the time of entry, then bends the hinge part to 180 ° and returns it to the original position (0 °). The operation was performed. This operation was performed on 30 hinged molded articles, and the number of hinge parts broken was counted.

[Moisture and heat resistance]
The pellets obtained in Examples 12 to 14, 16, 17 and Comparative Example 2 were dried under reduced pressure at 80 ° C. for 12 hours, and the cylinder temperature was measured using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.). : (A) Melting point of polyamide resin + 15 ° C., mold temperature: 80 ° C., injection / cooling time: 10/10 seconds, screw rotation speed: 150 rpm, injection pressure: 100 MPa, injection speed: 100 mm / second, 80 mm A square plate (film gate) of × 80 mm × 3 mm thickness was injection molded. The obtained square plate was wet-heat treated for 1 hour under conditions of 80 ° C. and 95% RH, the state of the treated square plate surface was visually observed, and evaluated according to the criteria described in the “Surface appearance” above.

Reference Example 1 ((A-2) nylon 410)
700 g of 410 salt which is an equimolar salt of tetramethylene diamine and sebacic acid, 21.2 g of tetramethylene diamine 10 wt% aqueous solution (1.00 mol% with respect to 410 salt), 0.3065 g of sodium hypophosphite (weight of polymer produced) 0.05 wt%) was charged in a polymerization can and sealed, and the atmosphere was replaced with nitrogen. After heating was started and the internal pressure of the can reached 0.5 MPa, the internal pressure of the can was maintained at 0.5 MPa for 1.5 hours while releasing moisture out of the system. Thereafter, the internal pressure of the can was returned to normal pressure over 10 minutes, and the reaction was further continued for 1.5 hours under a nitrogen flow to complete the polymerization. Thereafter, the polymer was discharged from the polymerization can in a gut shape and pelletized, and this was vacuum dried at 80 ° C. for 24 hours to obtain nylon 410 having ηr = 2.84, Tm−Tc = 31 ° C., and a melting point of 252 ° C. .

Reference Example 2 (E-1: Nylon 6 masterbatch containing CuI / KI (weight ratio) = 0.23)
100 parts by weight of nylon 6 (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), ηr = 2.70) 2.0 parts by weight of copper iodide, 21.7% by weight of potassium iodide 40% aqueous solution After preliminarily mixing the parts, using a TEX30 type twin screw extruder (L / D: 45.5) manufactured by Nippon Steel Works, Ltd., melt kneading under conditions of a cylinder temperature of 245 ° C. and a screw rotation speed of 150 rpm, strand Pelletized with a cutter. Thereafter, it was vacuum-dried at 80 ° C. for 8 hours to produce a master batch pellet having a copper content of 0.60% by weight.

Reference Example 3 (B-1)
A phenol novolac type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.) is used with respect to 100 parts by weight of dipentaerythritol (Guangei Chemical Industry Co., Ltd., molecular weight / number of functional groups 42 per molecule). ) After pre-mixing 10 parts by weight, the mixture was melt-kneaded for 3.5 minutes under conditions of a cylinder temperature of 200 ° C. and a screw speed of 100 rpm using a PCM30 type twin screw extruder manufactured by Ikegai, and pelletized by a hot cutter. The obtained pellets were supplied again to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and / or its condensate. The reaction rate of the obtained compound was 53%, the degree of branching was 0.29, and the hydroxyl value was 1280 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 4 (B-2)
The compound represented by the general formula (1) and / or the same as in Reference Example 5 except that the screw speed of the twin screw extruder was changed to 300 rpm and the melt kneading time was changed to 0.9 minutes. Condensate pellets were obtained. The reaction rate of the obtained compound was 2%, the degree of branching was 0.15, and the hydroxyl value was 1350 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH and OR in the general formula (1) was 3 or more.

Reference Example 5 (B-3)
The compound represented by the general formula (1) and / or the same as in Reference Example 5 except that the screw speed of the twin screw extruder was changed to 200 rpm and the melt kneading time was changed to 2.4 minutes. Condensate pellets were obtained. The reaction rate of the obtained compound was 15%, the degree of branching was 0.20, and the hydroxyl value was 1300 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 6 (B-4)
10 parts by weight of phenol novolac type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.), 100 parts by weight of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.), 1,8-diazabicyclo After premixing 0.3 parts by weight of (5,4,0) -undecene-7 (manufactured by Tokyo Chemical Industry Co., Ltd.), cylinder temperature 200 ° C. using a PCM30 twin screw extruder manufactured by Ikegai Co., Ltd. The mixture was melt-kneaded for 3.5 minutes under the condition of a screw speed of 100 rpm and pelletized with a hot cutter. The obtained pellets were supplied to an extruder, and the remelt kneading step was further performed 6 times to obtain pellets of the compound represented by the general formula (1) and / or a condensate thereof. The reaction rate of the obtained compound was 96%, the degree of branching was 0.39, and the hydroxyl value was 1170 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 7 (B-5)
Aliphatic polycarbodiimide (Nisshinbo Chemical Co., Ltd. “Carbodilite” (registered trademark) LA-1) per 100 parts by weight of dipentaerythritol (Guangei Chemical Industry Co., Ltd.), average of carbodiimide groups in one molecule After 24 parts, molecular weight 6000, molecular weight / number of functional groups in one molecule) 10 parts by weight, using a PCM30 twin screw extruder manufactured by Ikegai Co., Ltd., cylinder temperature 200 ° C., screw rotation speed 100 rpm The mixture was melt-kneaded under conditions for 3.5 minutes and pelletized with a hot cutter. The obtained pellets were supplied again to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and / or its condensate. The reaction rate of the obtained compound was 89%, the degree of branching was 0.37, and the hydroxyl value was 1110 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of carbodiimide groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 8 (B-6)
In a 1 L autoclave equipped with a stirrer, 508 g (1.0 mol) of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.), 254 g of toluene, and 0.3 g of potassium hydroxide were charged, and the temperature was raised to 90 ° C. Stir to make a slurry liquid. Subsequently, it heated at 130 degreeC, 132 g (3 mol) of ethylene oxide was gradually introduce | transduced in the autoclave, and was made to react. With the introduction of ethylene oxide, the temperature inside the autoclave increased. Cooling was added as needed to keep the reaction temperature below 140 ° C. After the reaction, the pressure was reduced to 1.3 kPa or less at 140 ° C. to remove excess ethylene oxide and by-produced ethylene glycol polymer. Thereafter, the mixture was neutralized with acetic acid and adjusted to pH 6-7 to obtain ethylene glycol-modified dipentaerythritol.

  343 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol was weighed into an electromagnetic induction rotary stirring autoclave having an internal volume of 500 ml, and 3 g of 5% ruthenium-alumina powder catalyst manufactured by NE Chemcat, which had undergone external reduction treatment, was charged with nitrogen. Went. Subsequently, 26 g (1.53 mol) of ammonia was added, and hydrogen (0.18 mol) was injected so that the total pressure became 2.0 MPaG at room temperature (25 ° C.). While stirring at 1000 rpm, the reaction was heated until the reaction temperature reached 220 ° C. The initial maximum pressure at 220 ° C. was 9.8 MPaG. The pressure dropped from 9.8 MPaG to 8.4 MPaG in 4 hours. After confirming that there was no pressure drop, the reaction was further carried out for 0.5 hours. Thereafter, the reaction product was cooled and taken out, filtered to remove the catalyst, and dipentaerythritol polyethylenehexamine was obtained.

10 parts by weight of phenol novolac type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.) was premixed with 100 parts by weight of the obtained dipentaerythritol polyoxyethylenehexamine, ) Using a PCM30 type twin screw extruder manufactured by Ikegai, the mixture was melt kneaded for 3.5 minutes under the conditions of a cylinder temperature of 200 ° C. and a screw rotation speed of 100 rpm, pelletized with a hot cutter, and the compound represented by the general formula (1) / Or pellets of the condensate were obtained. The reaction rate of the obtained compound was 49%, the degree of branching was 0.25, and the amine value was 500 mgKOH / g. The number of amino groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in general formula (1) was 3 or more.

Reference Example 9 (B-7)
Bisphenol A type epoxy resin “jER” (registered trademark) 1004 manufactured by Mitsubishi Chemical Co., Ltd., 100 parts by weight of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.), two epoxy groups in one molecule, After premixing 33.3 parts by weight of molecular weight 1650, molecular weight / number of functional groups in one molecule 825), using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., conditions of cylinder temperature 200 ° C. and screw rotation speed 100 rpm And kneaded for 3.5 minutes and pelletized with a hot cutter. The obtained pellets were supplied again to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and / or its condensate. The reaction rate of the obtained compound was 56%, the degree of branching was 0.34, and the hydroxyl value was 1200 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 10 (B-8)
Bisphenol A type epoxy resin (“jER” (registered trademark) 1007, manufactured by Mitsubishi Chemical Corporation) per 100 parts by weight of dipentaerythritol (produced by Guangei Chemical Industry Co., Ltd.), the number of epoxy groups in two molecules , Molecular weight 2900, molecular weight / number of functional groups in one molecule 1450) 33.3 parts by weight were premixed, and then a PCM30 type twin screw extruder manufactured by Ikekai Co., Ltd. was used. The mixture was melt-kneaded for 3.5 minutes under the conditions, and pelletized with a hot cutter. The obtained pellets were supplied again to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and / or its condensate. The reaction rate of the obtained compound was 52%, the degree of branching was 0.32, and the hydroxyl value was 1160 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH2 and OR in the general formula (1) was 3 or more.

Reference Example 11 (B-9)
Bisphenol A type epoxy resin ("jER" (registered trademark) 1010, manufactured by Mitsubishi Chemical Corporation) per 100 parts by weight of dipentaerythritol (produced by Guangei Chemical Industry Co., Ltd.), the number of epoxy groups in two molecules , Molecular weight 5500, molecular weight / number of functional groups in one molecule 2750) 33.3 parts by weight were premixed, and then a PCM30 type twin screw extruder manufactured by Ikekai Co., Ltd. was used. The mixture was melt-kneaded for 3.5 minutes under the conditions, and pelletized with a hot cutter. The obtained pellets were supplied again to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and / or its condensate. The reaction rate of the obtained compound was 50%, the degree of branching was 0.29, and the hydroxyl value was 1100 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH2 and OR in the general formula (1) was 3 or more.

Reference Example 12 (B-10)
Bisphenol A diglycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., 2 epoxy groups in one molecule, molecular weight 340, molecular weight / 1) per 100 parts by weight of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.) The number of functional groups in the molecule 170) 33.3 parts by weight were premixed and then melted for 3.5 minutes under the conditions of a cylinder temperature of 200 ° C. and a screw rotation speed of 100 rpm using a Ikekai PCM30 twin screw extruder. It knead | mixed and pelletized with the hot cutter. The obtained pellets were supplied again to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and / or its condensate. The reaction rate of the obtained compound was 88%, the degree of branching was 0.32, and the hydroxyl value was 1290 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH2 and OR in the general formula (1) was 3 or more.

Reference Example 13 (B′-1)
After pre-mixing 500 parts by weight of a phenol novolac type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.) with 100 parts by weight of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.) Using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., melt-kneading for 3.5 minutes under conditions of a cylinder temperature of 200 ° C. and a screw rotation speed of 100 rpm, pelletized by a hot cutter, and represented by the general formula (1) A pellet of the compound and / or its condensate was obtained. The reaction rate of the obtained compound was 33%, the degree of branching was 0.23, and the hydroxyl value was 540 mgKOH / g. The number of hydroxyl groups in one molecule was smaller than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 14 (B′-2)
In a flask equipped with a reflux condenser, a thermometer and a stirrer, 100 parts by weight of ethyleneimine, 400 parts by weight of 1,4-dioxane, 1.1 parts by weight of methanesulfonic acid (0.5 moles relative to ethyleneimine) %) And ring-opening polymerization was carried out at 50 ° C. for 7 hours. After completion of the reaction, 1,4-dioxane and residual ethyleneimine were distilled off from the reaction solution to obtain polyethyleneimine. The degree of branching of polyethyleneimine was 0.31.

Reference Example 15 (B′-3)
In a four-necked flask equipped with a stirrer, pressure gauge, condenser and receiver, 50.5 g (0.14 mol) of pentaerythritol pentaethoxylate and 1.0 g (0.004 mol) of 3 fluorine A 50% by weight aqueous solution of borohydride diethyl ether complex was added at room temperature and heated to 110 ° C. To this, 450 g (3.87 mol) of 3-ethyl-3-oxetanemethanol was added over 35 minutes while controlling the heat generated by the reaction. When the heat generation stopped, the temperature was raised to 120 ° C., stirred for 2.5 hours, and then cooled to room temperature to obtain a hydroxyl group-containing compound containing a branched structure composed of repeating structural units having an ether bond. The obtained hydroxyl group-containing compound had a weight average molecular weight of 2,620, a hydroxyl value of 810 mgKOH / g, and a degree of branching of 0.29.

Reference Example 16 (B′-4)
In a four-necked flask equipped with a stirrer, pressure gauge, condenser and receiver, 617.8 g (1.70 mol) pentaerythritol pentaethoxylate and 921.0 g (6.84 mol) 2, 2-Dimethylolpropionic acid and 0.92 g (0.008 mol) of 96 wt% concentrated sulfuric acid were added. The temperature was raised to 140 ° C. to obtain a homogeneous transparent solution. At this time, the pressure was reduced to 4000 to 6666 Pa, and the reaction was performed for 4 hours with stirring. Thereafter, 921.0 g (6.84 mol) of 2,2-dimethylolpropionic acid and 0.14 g (0.014 mol) of 96% by weight concentrated sulfuric acid were added to obtain a reduced pressure state of 4000-6666 Pa with stirring. The reaction was conducted for 5 hours to obtain a hydroxyl group-containing compound containing a branched structure composed of repeating structural units having an ester bond. The obtained hydroxyl group-containing compound was pulverized and vacuum dried at 80 ° C. for 12 hours. The weight average molecular weight was 2050, the hydroxyl value was 590 mgKOH / g, and the degree of branching was 0.34.

Reference Example 17 (B′-5)
519.4 g (4.4 mol) of succinic acid, 277.0 g (1.92 mol) of 1,4-cyclohexanedimethanol and 393.4 g (2.89 mol) of pentaerythritol were added to a stirrer, internal temperature. A 3000 ml 4-neck glass flask equipped with a vacuum connection with a meter, gas inlet tube, reflux condenser and cold trap was charged. Nitrogen gas was supplied and after addition of 1.11 g of di-n-butyltin oxide, the mixture was heated to an internal temperature of 125 ° C. using an oil bath. The water produced during the reaction was separated under a reduced pressure of 0.02 MPa. The reaction mixture was held at the above temperature and pressure for 3.3 hours and then cooled to obtain a hydroxyl group- and carboxyl group-containing compound containing a branched structure composed of repeating structural units having an ester bond. The obtained hydroxyl group- and carboxyl group-containing branched compound was pulverized and vacuum dried at 80 ° C. for 12 hours. Next, the pulverized product was heat-treated in a gear oven at 190 ° C. for 400 hours under the atmosphere. The weight average molecular weight of the compound after heat treatment was 1950, the acid value was 277 mgKOH / g, the hydroxyl value was 504 mgKOH / g, the ratio of acid value / hydroxyl value was 0.55, and the degree of branching was 0.40.

Reference Example 18 (B′-6)
A four-necked flask equipped with a stirrer, pressure gauge, vacuum connection, condenser and receiver was charged with 232.0 g (1.57 mol) of phthalic anhydride and 270.0 g (2.03 mol) of dithiol. Isopropanolamine was added and the temperature was raised to 70 ° C. with stirring. Subsequently, it heated at 170 degreeC under pressure reduction of 4000-6666Pa, and made it react for 4.5 hours, removing a water | moisture content. Thereafter, the mixture was cooled to room temperature to obtain a hydroxyl group-containing compound containing a branched structure composed of repeating structural units having an ester bond and an amide bond. The weight average molecular weight was 1950, the hydroxyl value was 505 mgKOH / g, and the degree of branching was 0.38.

Reference Example 19 (F-1)
After preliminarily mixing 26.7 parts by weight of the compound (B-1) with 100 parts by weight of nylon 6 (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), TEX30 type manufactured by Nippon Steel Works, Ltd. Using a twin screw extruder (L / D: 45.5), the mixture was melt-kneaded under conditions of a cylinder temperature of 245 ° C. and a screw rotation speed of 150 rpm, and pelletized with a strand cutter. Then, it vacuum-dried at 80 degreeC for 8 hours, and produced the high concentration pre-mixture pellet.

Reference Example 20 (F-2)
After premixing 26.7 parts by weight of the compound (B-8) with 100 parts by weight of nylon 6 (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), TEX30 type manufactured by Nippon Steel Works, Ltd. Using a twin screw extruder (L / D: 45.5), the mixture was melt-kneaded under conditions of a cylinder temperature of 245 ° C. and a screw rotation speed of 150 rpm, and pelletized with a strand cutter. Then, it vacuum-dried at 80 degreeC for 8 hours, and produced the high concentration pre-mixture pellet.

In addition, (A) polyamide resin, (b) hydroxyl group and / or amino group-containing compound, (b ′) epoxy group and / or carbodiimide group-containing compound, (C) flame retardant, D) Phosphorus-containing compounds, (G) flame retardant aids, (H) impact resistance improvers are as follows.
(A-1): Nylon 6 resin having a melting point of 225 ° C. (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), ηr = 2.70, Tm−Tc = 55 ° C.
(A-3): Nylon 66 resin (“Amilan” (registered trademark) CM3001-N manufactured by Toray Industries, Inc.) having a melting point of 260 ° C., ηr = 2.78, Tm−Tc = 35 ° C.
(A-4): Nylon 6 resin having a melting point of 225 ° C. (“Amilan” (registered trademark) CM1021T manufactured by Toray Industries, Inc.), ηr = 3.4, Tm−Tc = 55 ° C.
(B-1): Dipentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight 254, hydroxyl value 1325 mgKOH / g.
(B-2): Dipentaerythritol polyoxyethylenehexamine, molecular weight 608, amine value 554 mgKOH / g.
(B′-1): Phenol novolak type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.), average number of epoxy groups in one molecule: 7, molecular weight: 1330, molecular weight: in one molecule 190 functional groups.
(C-1): Melamine cyanurate (MC-4000 manufactured by Nissan Chemical Industries, Ltd.)
(C-2): Melamine polyphosphate, melem, melam compound (manufactured by Nissan Chemical Industries, Ltd .: PMP-200)
(C-3): Brominated polystyrene (manufactured by Great Lakes Chemical Co., Ltd .: PDBS-80)
(C-4): Aluminum diethylphosphinate (manufactured by Clariant: Exolit OP1312)
(D-1): Sodium hypophosphite monohydrate (Wako Pure Chemical Industries, Ltd.), molecular weight 105.99
(G-1): Antimony trioxide (Nippon Seiko Co., Ltd .: ATOX)
(G-2): Hydrotalcite (Kyowa Chemical Industry Co., Ltd .: kw2100)
(H-1): Maleic anhydride modified ethylene-butene copolymer (Mitsui Chemicals, Inc .: “Toughmer” (registered trademark) MH7010)

(Examples 1-14, 19-21, Comparative Examples 1-6, 9-14)
The (A) polyamide resin shown in the table is a TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel, Ltd., in which the cylinder set temperature is set to the melting point of the polyamide resin + 15 ° C. and the screw rotation speed is set to 200 rpm. It was supplied from a main feeder to a twin screw extruder and melt kneaded. This main feeder was connected to a position of 0 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position of an end portion on the upstream side of the screw segment. Subsequently, (B) compound, (B ′) compound, (b) hydroxyl group and / or amino group-containing compound, and (C) flame retardant shown in the table were supplied from the side feeder to the twin screw extruder, and melt kneaded. This side feeder was connected to a position of 0.65 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position downstream of 1/2 of the screw length. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The evaluation results of each example and comparative example are shown in the table. Moreover, the evaluation results of the heat and humidity resistance were Example 12: C2, Example 13: A, Example 14: A, and Comparative Example 2: C2.

(Comparative Examples 7 and 8)
(A) Polyamide resin and (b ′) epoxy group and / or carbodiimide group-containing compound shown in the table were premixed, and then the cylinder set temperature was set to the melting point of the polyamide resin + 15 ° C., and the screw rotation speed was set to 200 rpm. The steel was fed from the main feeder of a TEX30 twin screw extruder manufactured by Nippon Steel, Ltd. to the twin screw extruder, and melt kneaded. This main feeder was connected to a position of 0 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position of an end portion on the upstream side of the screw segment. Subsequently, (b) a hydroxyl group and / or amino group-containing compound and (C) a flame retardant shown in the table were supplied from a side feeder to a twin screw extruder and melt-kneaded. This side feeder was connected to a position of 0.65 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position downstream of 1/2 of the screw length. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The evaluation results of each comparative example are shown in the table.

(Example 15)
(A) Polyamide resin and (E) copper compound shown in the table were premixed, and then the cylinder set temperature was set to the melting point of the polyamide resin + 15 ° C., and the screw rotation speed was set to 200 rpm. Supplied from the main feeder of the extruder to the twin screw extruder and melt kneaded. This main feeder was connected to a position of 0 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position of an end portion on the upstream side of the screw segment. Subsequently, the compound (B) and the flame retardant (C) shown in the table were supplied from the side feeder to the twin screw extruder, and melt kneaded. This side feeder was connected to a position of 0.65 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position downstream of 1/2 of the screw length. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The evaluation results are shown in the table.

(Examples 16 and 17)
Polyamide resin composition under the same conditions as in Example 2 and Example 13 except that the high-concentration premixes (F-1) and (F-2) shown in the table were supplied from the main feeder to the twin-screw extruder. Pellets were obtained. Thus, the composition ratio of Example 16 is the same as that of Example 13 and the composition ratio of Example 17 is the same as that of Example 13. The evaluation results of each example are shown in the table. Moreover, the evaluation result of heat-and-moisture resistance was Example 16: C2 and Example 17: A.

(Example 18)
The (A) polyamide resin shown in the table is a TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel, Ltd., in which the cylinder set temperature is set to the melting point of the polyamide resin + 15 ° C. and the screw rotation speed is set to 200 rpm. It was supplied from a main feeder to a twin screw extruder and melt kneaded. This main feeder was connected to a position of 0 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position of an end portion on the upstream side of the screw segment. Subsequently, the (B) compound, (C) flame retardant, and (D) phosphorus-containing compound shown in the table were supplied from the side feeder to the twin-screw extruder and melt-kneaded. This side feeder was connected to a position of 0.65 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position downstream of 1/2 of the screw length. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The evaluation results are shown in the table.

(Examples 22 to 24, Comparative Example 15)
TEX30 type twin screw extruder manufactured by Nippon Steel, Ltd., with (A) polyamide resin and (H) impact resistance improving material shown in the table, cylinder setting temperature set to the melting point of polyamide resin + 15 ° C. and screw rotation speed set to 200 rpm The mixture was supplied from the main feeder (L / D = 45) to the twin screw extruder and melt-kneaded. This main feeder was connected to a position of 0 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position of an end portion on the upstream side of the screw segment. Subsequently, the compound (B) and the flame retardant (C) shown in the table were supplied from the side feeder to the twin screw extruder, and melt kneaded. This side feeder was connected to a position of 0.65 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position downstream of 1/2 of the screw length. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The evaluation results of each example and comparative example are shown in the table.

  Examples 1-24 are compared with Comparative Examples 1-15, (B) A compound is contained in a specific amount, and (C) A flame retardant is mix | blended by specific concentration, (A) Polyamide resin and (B ) Compound compatibility and (C) Dispersibility of flame retardant are further improved. As a result, a molded product having excellent fluidity and residence stability, and excellent flame retardancy, heat aging resistance, surface appearance and hinge characteristics is obtained. I was able to.

  In Examples 1 and 2, compared with Example 3, the amount of the flame retardant (C) is in a more preferable range, so that a molded product excellent in fluidity and retention stability, and excellent in heat aging resistance and hinge characteristics is obtained. I was able to. Moreover, since Example 2 has the compounding amount of the compound (B) in a more preferable range as compared with Examples 4 and 5, it is possible to obtain a molded product that is excellent in retention stability, heat aging resistance, and hinge characteristics. I was able to.

  In Examples 2 and 10, since the reaction rate of the compound (B) is in a more preferable range as compared with Examples 7 to 9, the compatibility between the (A) polyamide resin and the (B) compound and (C) As a result, it was possible to obtain a molded article having excellent fluidity and retention stability, and excellent heat aging resistance and hinge characteristics.

  In Example 15, as compared with Example 2, (B) compound and (C) flame retardant were blended, and (E) copper compound was blended, whereby (A) polyamide resin and (B) compound As a result, it was possible to obtain a molded product that was more excellent in retention stability and heat aging resistance.

  Example 16 is compared with Example 2 and Example 17 is compared with Example 13 (F) by preparing a high-concentration premix and melt-kneading twice, so that (A) polyamide resin and (B) compound And (C) flame retardant dispersibility were improved, and as a result, a molded article excellent in fluidity and retention stability, and excellent in heat aging resistance and hinge characteristics could be obtained.

  In Example 18, as compared with Example 2, (B) compound and (C) flame retardant were blended, and (D) phosphorus-containing compound was blended, whereby (A) polyamide resin and (B) compound. And the dispersibility of the flame retardant (C) were further improved, and as a result, a molded article excellent in fluidity and retention stability, and excellent in heat aging resistance and hinge characteristics could be obtained.

  In Example 2, compared with Examples 19 and 20, since the difference between the melting point and the crystallization temperature of (A) the polyamide resin was in a more preferable range, the solidification rate could be slowed down, and the fluidity and hinge characteristics Thus, an excellent molded product could be obtained.

  Example 21 was able to obtain a molded article having excellent residence stability and excellent heat aging resistance and hinge characteristics by blending (A) polyamide resin having a more preferable viscosity as compared with Example 2. .

  In Example 22, as compared with Example 2, it was possible to obtain a molded article having excellent residence stability and excellent heat aging resistance and hinge characteristics by further blending (H) an impact resistance improving material.

  Examples 13 and 14 are compared with Example 12, and Example 17 is compared with Example 16. The molecular weight and the value obtained by dividing the molecular weight by the number of functional groups in one molecule are within preferable ranges. (B ′) Since the compound (B) obtained by reacting an epoxy group and / or carbodiimide group-containing compound was contained, a molded article having better moisture and heat resistance could be obtained.

  The polyamide resin composition of the embodiment of the present invention can be molded by any method such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, etc., and processed and used for various molded products. be able to. In particular, the polyamide resin composition of the embodiment of the present invention is excellent in fluidity and retention stability, and can provide a molded product excellent in flame retardancy, heat aging resistance, surface appearance, and hinge characteristics. It is effective when a molded product having a hinge portion, particularly of electrical and electronic parts. Here, the hinge portion is thinner than the peripheral portion and refers to a portion where the molded product can be bent, and is particularly useful for use in clips, clamps, and bands for bundling wires, cords, and tubes in a high temperature environment.

1 Solvent peak

Claims (5)

(A) With respect to 100 parts by weight of the polyamide resin, (B) a hydroxyl group and / or an amino group, an epoxy group and / or a carbodiimide group, and the sum of the number of hydroxyl groups and amino groups in one molecule is 1 A polyamide resin composition comprising 0.1 to 20 parts by weight of a compound larger than the sum of the number of epoxy groups and carbodiimide groups in the molecule and (C) 0.1 to 50 parts by weight of a flame retardant. The compound (B) is a reaction product of (b) a hydroxyl group and / or amino group-containing compound and (b ′) an epoxy group and / or carbodiimide group-containing compound, and the hydroxyl group or amino group, epoxy group or carbodiimide The polyamide resin composition according to claim 1, which has a reaction rate with a group of 1 to 95%. The polyamide resin composition according to claim 1 or 2, wherein the compound (B) is a compound having a structure represented by the following general formula (1) and / or a condensate thereof.
In the general formula (1), X ^{1 to} X ⁶ may be the same or different and each represents OH, NH ₂ , CH ₃ or OR. However, the sum of the numbers of OH, NH ₂ and OR is 3 or more. Moreover, R represents the organic group which has an amino group, an epoxy group, or a carbodiimide group, and n represents the range of 0-20. The molded article formed by shape | molding the polyamide resin composition in any one of Claims 1-3. The molded article according to claim 4, which has a hinge part.