JP2016147919A - Polyamide resin composition and molded article obtained by molding same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition capable of obtaining a molded article which is excellent in flowability and retention stability, and is excellent in thermal aging resistance, mechanical strength, surface appearance and thermal conductivity.SOLUTION: A polyamide resin composition contains, with respect to (a) 100 pts.wt. of a polyamide resin, (B) 0.1-20 pts.wt. of a compound which has a hydroxy group and/or an amino group and an epoxy group and/or a carbodiimide group, and where the sum of the number of the hydroxy groups and/or the amino groups in one molecule is more than the sum of the number of the epoxy groups and/or the carbodiimide groups in one molecule; and (C) a thermal conductive filler.SELECTED DRAWING: Figure 2

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 recent years, the density of components in the engine room and the increase in engine output are increasing in the automobile field, and the integration of semiconductor devices is increasing in the electric / electronic field. Under such circumstances, polyamide resin has low thermal conductivity compared to metals, etc., so when used in components that generate heat or components that generate frictional heat, the generated heat can be efficiently diffused. There is a possibility that problems such as dimensional changes due to thermal expansion and deformation / deterioration of resin components over time may occur.

  On the other hand, as a method for improving the thermal conductivity of the polyamide resin, a method of blending a filler having excellent thermal conductivity is generally used. For example, 100 parts by weight of a thermoplastic resin, a specific metal and / or Or the thermoplastic resin composition which consists of 150-600 weight part of metal oxide powder is proposed (for example, refer patent document 1). Although high heat conductivity can be expressed by blending a large amount of heat conductive filler, the melt viscosity of the resin composition increases and the fluidity decreases, so the processability during injection molding decreases. In addition, there was a problem of strength reduction due to embrittlement. Therefore, as a method for improving the fluidity and thermal conductivity at the processing temperature, a thermoplastic resin composition containing a semi-aromatic polyamide, a thermal conductive filler, and a hyperbranched polyester amide having a terminal hydroxy group has been proposed. (For example, refer to Patent Document 2). However, the thermoplastic resin composition containing such hyperbranched polyester amide has problems such as a decrease in mechanical strength and retention stability of the obtained molded product and a deterioration in surface appearance due to bleeding out. In addition, it is difficult to suppress the oxidative deterioration of the resin member due to heat storage even by blending the heat conductive filler, and there is a need for a technology that suppresses the deterioration of mechanical properties (thermal aging) over time in the heat storage environment. Yes.

  On the other hand, as a technique for improving the heat aging resistance of polyamide resin, various technical improvements have been attempted so far. 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 composition containing a polyamide resin, polyethyleneimine, a lubricant, a copper-containing stabilizer, a filler, and nigrosine (see, for example, Patent Document 4).

JP-A-5-86246 Special table 2012-507601 gazette Special table 2011-529991 gazette Special table 2008-530290

  However, the molded product obtained from the polyamide resin composition of Patent Document 3 has excellent heat aging resistance in a temperature range of 150 ° C. to 230 ° C., but heat aging resistance in a temperature range of less than 150 ° C. and 240 ° C. or more. There was a problem of being inferior. Further, the polyamide resin composition of Patent Document 4 also has excellent heat aging resistance in a temperature range of 160 to 180 ° C., but has a problem of poor heat aging resistance in a temperature range of less than 150 ° C. In addition, these polyamide resin compositions are (i) problems in surface appearance such as bleeding out of polyhydric alcohol on the surface layer of molded products and coloring due to liberation of copper ions, and (ii) problems of poor residence stability. (Iii) There was a problem that the thermal conductivity was insufficient. SUMMARY OF THE INVENTION In view of the problems of these conventional techniques, the present invention has an object to provide a polyamide resin composition that is excellent in fluidity and retention stability, and can obtain a molded product excellent in heat aging resistance, surface appearance and thermal conductivity. And

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 containing 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 (C) a thermally conductive filler.
[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. 2. The polyamide resin composition according to claim 1, wherein the reaction rate with a group or a carbodiimide group is 1 to 95%.
[3] The polyamide resin composition according to [1], 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 product according to (4), wherein the molded product is a heat dissipation member.

  The polyamide resin composition of the present invention is excellent in fluidity and retention stability. According to the polyamide resin composition of the present invention, a molded article excellent in mechanical strength, heat aging resistance, surface appearance and thermal conductivity 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 6. The perspective view of the square pin type heat sink molded product used for fluidity | liquidity evaluation in an Example. Sectional drawing of the square pin type heat sink molded product used for fluidity | liquidity evaluation in an Example.

  Hereinafter, embodiments of the present invention will be described in detail. The polyamide resin composition of the embodiment of the present invention has (A) a polyamide resin, (B) a hydroxyl group and / or an amino group, an epoxy group and / or a carbodiimide group, and a hydroxyl group and an amino group in one molecule. A compound having a larger sum than the sum of the number of epoxy groups and carbodiimide groups in one molecule (hereinafter sometimes referred to as “(B) compound”), and (C) a thermally conductive filler. contains. 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 Polyamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6), polyhexamethylene terephthalamide / polyhexamethylene Isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polyundecanamide copolymer (nylon 6T / 11), polyhexamethylene terephthalamide / polydodeca Amide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6), polyxylylene Lensebacamide (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 terephthalamide (nylon 9T), polydecamethylene terephthalamide Examples include phthalamide (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. Since the polyamide resin having a difference between the melting point and the temperature-falling crystallization temperature of 30 ° C. or higher has a low solidification rate, the polyamide resin is excellent in fluidity and can improve the surface smoothness and gloss of a molded product made of the polyamide 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 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 mechanical properties of the obtained molded product can be further improved. The relative viscosity is more preferably 2.0 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. And there exists a subject that the heat aging resistance in 240 degreeC or more is inadequate. 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. There is also a problem inferior in retention stability and heat aging resistance. Furthermore, there is a problem that the hydroxyl group and / or amino group-containing compound plasticizes the (A) polyamide resin, and the mechanical strength of the resulting molded article is 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 heat aging resistance at less than 150 ° C. and 240 ° C. or more 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. It is considered that embrittlement due to structure formation can be suppressed and fluidity and mechanical strength 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, the (B) compound may be contained as the (B) compound in the polyamide resin composition. For example, (b) a hydroxyl group and / or amino group-containing compound described below and (b ′ ) Epoxy group and / or carbodiimide group-containing compound may be individually blended with (A) polyamide resin, and (B) compound may be formed in the polyamide resin composition, or these may be reacted in advance. (A) You may mix | blend with a polyamide resin. It is preferable to blend the (B) compound obtained by reacting these in advance with the (A) polyamide resin, and it is excellent in compatibility between the (B) compound and the (A) polyamide resin, and has fluidity, residence stability, and mechanical strength. Further, heat aging resistance and surface appearance can be further improved. Furthermore, the compatibility of (A) polyamide resin and (B) compound can improve the dispersibility of (C) thermal conductive filler as described later and suppress local thermal conductivity variation. can do. Moreover, since the heat conductive path is easily formed efficiently by the orientation of the heat conductive filler in the flow direction of the resin composition, the effect of the heat conductive filler is remarkably exhibited. In particular, the heat aging resistance at a high temperature of 190 ° C. or higher can be greatly 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.

  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. 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 mechanical properties 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 (A) the polyamide resin is further improved, so that the fluidity, residence stability, mechanical strength are increased. Further, heat aging resistance, surface appearance, and thermal conductivity 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. Further, the mechanical strength, heat aging resistance and surface appearance can be further improved. Furthermore, by improving the fluidity of the polyamide resin composition, the dispersibility of the heat conductive filler (C) can be further improved and orientation in the flow direction can be facilitated, so that the thermal conductivity 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. Mechanical strength, heat aging resistance, surface appearance and thermal conductivity 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, mechanical strength, and heat aging are increased. Property, surface appearance and thermal conductivity can be further improved. Furthermore, by improving the fluidity of the polyamide resin composition, the dispersibility of the heat conductive filler (C) can be further improved and orientation in the flow direction can be facilitated, so that the thermal conductivity 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, Mechanical strength, heat aging resistance, surface appearance and thermal conductivity 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 the fluidity, residence stability, mechanical strength, heat resistance are increased. Aging property, surface appearance and thermal conductivity 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, mechanical strength, heat aging resistance, surface appearance and thermal conductivity are improved. 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. Aliphatic compounds having 3 or more hydroxyl groups or 3 or more amino groups in one molecule have excellent compatibility with (A) polyamide resin, fluidity, retention stability, mechanical strength, heat aging resistance, surface Appearance and thermal conductivity 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, mechanical strength, heat aging resistance, surface appearance and thermal conductivity 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 making the hydroxyl value of the hydroxyl group-containing compound 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, so that fluidity, residence stability, mechanical strength Further, heat aging resistance, surface appearance, and thermal conductivity 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 of (A) the polyamide resin and the hydroxyl group-containing compound is moderately improved, and the fluidity, residence stability, mechanical strength, heat aging resistance, The surface appearance and thermal conductivity 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. Mechanical strength, heat aging resistance, surface appearance and thermal conductivity 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 of the (A) polyamide resin and the amino group-containing compound is moderately improved. Property, surface appearance and thermal conductivity 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 (A) the polyamide resin is further improved, so that the fluidity, residence stability, mechanical strength are increased. Further, heat aging resistance, surface appearance and thermal conductivity 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. Further, the mechanical strength, heat aging resistance, surface appearance and thermal conductivity 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 , Mechanical strength, heat aging resistance, surface appearance, and thermal conductivity are further improved. (B ′) The molecular weight of the epoxy group and / or carbodiimide group-containing compound is more preferably 1000 or more. 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, mechanical strength, heat aging resistance, surface appearance, and thermal conductivity are further improved.

  The value obtained by dividing the molecular weight by the number of functional groups in one molecule, which is an index indicating 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 2000. 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 increases moderately, the fluidity, retention stability, mechanical strength, heat aging resistance, surface appearance and thermal conductivity can be 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. 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 2000 or less, (A) polyamide resin and (b) hydroxyl group In addition, the reaction with the amino group-containing compound can be sufficiently ensured, and the fluidity, residence stability, mechanical strength, heat aging resistance, surface appearance, and thermal conductivity 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 preferably 1000 or less, and more preferably 300 or less.

  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 and a glycidyl group. 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, mechanical strength, heat aging resistance, and surface appearance 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 can improve the fluidity, residence stability, heat aging resistance, mechanical strength, surface appearance, and thermal conductivity of the obtained molded product. 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 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 during molding are lowered, and the mechanical strength, heat aging resistance and thermal conductivity 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. Moreover, plasticization and decomposition of the polyamide resin are promoted, and the residence stability, mechanical strength, and heat aging resistance 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. It is possible to suppress embrittlement due to structure formation and improve fluidity, retention stability, mechanical strength, heat aging resistance and surface appearance. Furthermore, by improving the fluidity of the polyamide resin composition, the dispersibility of the (C) thermally conductive filler can be further improved, and orientation in the flow direction can be facilitated, so that the thermal conductivity can be 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, mechanical strength, heat aging resistance, and surface are suppressed. Appearance is improved. Furthermore, by improving the fluidity of the polyamide resin composition, the dispersibility of the heat conductive filler (C) can be further improved and orientation in the flow direction can be facilitated, so that the thermal conductivity 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. , Mechanical strength, heat aging resistance, surface appearance, and thermal conductivity are further improved. 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 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-6) and / or its condensate obtained in Reference Example 6 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 further contains (C) a thermally conductive filler. Here, (C) a thermally conductive filler refers to a filler having a thermal conductivity of 5 W / m · K or more. (C) The heat conductive filler may be either conductive or insulating. By selecting a filler having a thermal conductivity of 5 W / m · K or more, the thermal conductivity of the obtained molded product can be highly enhanced.

  In an embodiment of the present invention, by containing (C) a thermally conductive filler together with (A) polyamide resin and (B) compound, fluidity due to high compatibility between (A) polyamide resin and (B) compound. Due to the improvement effect, the dispersibility of the heat conductive filler (C) can be improved, and local variations in heat conductivity can be suppressed. Further, since the heat conduction path is easily formed efficiently by the orientation of the heat conductive filler in the resin composition flow direction, the effect of the heat conductive filler is remarkably exhibited. Therefore, it is possible to obtain a molded article having excellent mechanical strength, heat aging resistance, surface appearance, and thermal conductivity while improving the fluidity and residence stability of the polyamide resin composition.

  (C) Thermally conductive fillers include talc (5 to 10 W / m · K), magnesium hydroxide (8 W / m · K), aluminum oxide (36 W / m · K), magnesium oxide (60 W / m · K). K), zinc oxide (25 W / m · K), magnesium carbonate (15 W / m · K), silicon carbide (160 W / m · K), aluminum nitride (170 W / m · K), boron nitride (210 W / m · K) K), silicon nitride (40 W / m · K), carbon (10 to several hundred W / m · K), graphite (10 to several hundred W / m · K), silver (427 W / m · K), copper ( 398W / m · K), aluminum (237W / m · K), titanium (22W / m · K), nickel (90W / m · K), tin (68W / m · K), iron (84W / m · K) ), Stainless steel (15 W / m · K), and the like. Two or more of these may be used.

  Among these, from the viewpoint of thermal conductivity and fluidity, boron nitride, graphite, aluminum oxide, magnesium oxide, magnesium carbonate, zinc oxide, talc and magnesium hydroxide are preferable, and talc, magnesium hydroxide and boron nitride are more preferable. In these (C) thermally conductive fillers, the polar group on the surface forms a covalent bond or a hydrogen bond with the hydroxyl group and / or amino group, epoxy group and / or carbodiimide group of the compound (B). It is considered that the effect of the present invention is more remarkably achieved by the binder effect of the compound (B) with the (A) polyamide resin.

  Examples of the shape of boron nitride include a plate shape, a scale shape, and a flake shape. Of these, scaly and flakes are preferred. By setting it as scale shape and flake shape, it is easy to orient in a flow direction at the time of shaping | molding, and heat conductivity can be improved more. The average particle size of the flaky boron nitride is preferably 0.1 to 200 μm, and more preferably 0.1 to 100 μm. The crystal system of boron nitride is preferably a hexagonal crystal structure from the viewpoint of further improving thermal conductivity.

  Examples of the shape of graphite include a spherical shape, a powder shape, a fiber shape, a needle shape, a scale shape, a whisker shape, a microcoil shape, and a nanotube shape. Of these, scaly is preferable. By making it scale-like, thermal conductivity can be improved more. The average particle size of the flaky graphite is preferably 0.1 to 300 μm, and more preferably 0.1 to 150 μm.

  Examples of the shape of aluminum oxide, magnesium oxide, magnesium carbonate, and zinc oxide include a spherical shape, a plate shape, a fiber shape, a spindle shape, a rod shape, a needle shape, a cylindrical shape, and a column shape. Of these, spherical and plate shapes are preferred. By making it spherical or plate-shaped, it is possible to further improve the thermal conductivity while suppressing a decrease in fluidity and insulating properties of the resin composition. The average particle diameter of aluminum oxide, magnesium oxide, magnesium carbonate, and zinc oxide is preferably 0.1 to 150 μm, and more preferably 0.1 to 100 μm.

  Examples of the shape of talc include a plate shape, a scale shape, a scale shape, and a flake shape. Of these, scaly and lamellar shapes are preferred. By setting it as scale shape and flake shape, it is easy to orient in a flow direction at the time of shaping | molding, and heat conductivity can be improved more. The average particle size of the scaly talc is preferably from 0.1 to 200 μm, more preferably from 0.1 to 100 μm.

As magnesium hydroxide, high-purity magnesium hydroxide containing 80% by weight or more of an inorganic substance represented by the chemical formula Mg (OH) ₂ is preferable. From the viewpoint of further improving thermal conductivity and mechanical strength, high-purity magnesium hydroxide containing 80% by weight or more of an inorganic substance represented by Mg (OH) ₂ , having a CaO content of 5% by weight or less and a chlorine content of 1% by weight or less High-purity magnesium hydroxide containing 98% by weight or more of Mg (OH) _2, having a CaO content of 0.1% by weight or less and a chlorine content of 0.1% by weight or less is more preferred. Examples of the shape of magnesium hydroxide include a spherical shape, a plate shape, and a fiber shape. From the viewpoints of feed property and dispersibility during melt kneading, a spherical shape or a plate shape is preferable. The average particle diameter of magnesium hydroxide is preferably from 0.1 to 200 μm, more preferably from 0.1 to 100 μm, and even more preferably from 0.1 to 50 μm, from the viewpoints of fluidity and mechanical properties.

  The thermally conductive filler (C) used in the present invention is, for example, a vinylsilane compound such as vinyltriethoxysilane or vinyltrichlorosilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, Epoxysilane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- The surface treatment may be performed with an aminosilane compound such as aminopropyltrimethoxysilane, a long-chain fatty acid such as stearic acid, oleic acid, montanic acid, stearyl alcohol, or a long-chain aliphatic alcohol. In particular, the thermally conductive filler surface-treated with an epoxysilane compound and / or an aminosilane compound is used in combination with the (B) compound, so that (A) a polyamide resin and (C) a thermally conductive filler are used. Adhesion is further enhanced, embrittlement can be suppressed, and mechanical strength can be further improved.

  In the polyamide resin composition of the embodiment of the present invention, the capacity ratio ((A) / (C)) of (A) the polyamide resin to (C) the heat conductive filler is preferably 15/85 to 85/15. By setting the capacity ratio ((A) / (C)) to 15/85 or more, fluidity, mechanical strength, and thermal conductivity can be further improved. 30/70 or more is more preferable. On the other hand, by setting the capacity ratio ((A) / (C)) to 85/15 or less, thermal conductivity can be further improved while suppressing embrittlement. 70/30 or less is more preferable.

  The polyamide resin composition of the embodiment of the present invention can further contain a phosphorus-containing compound. 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 the 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 superior heat aging resistance, mechanical strength, surface appearance, and thermal conductivity 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 (C) and the thermally conductive filler (C) can be further improved.

  In the polyamide resin composition of the embodiment of the present invention, the content of the phosphorus-containing compound is not particularly limited, but is preferably 180 to 3500 ppm with respect to (A) the polyamide resin content in terms of phosphorus atoms. When the phosphorus atom equivalent concentration is 180 ppm or more, fluidity, retention stability, heat aging resistance, mechanical strength, and thermal conductivity can be further improved. On the other hand, when the phosphorus atom equivalent content is 3500 ppm or less, (A) the viscosity of the polyamide resin can be suppressed, and the (A) polyamide resin and the (B) compound due to the gas generated by the decomposition of the phosphorus-containing compound by shearing heat generation Decomposition can be suppressed, and fluidity, residence stability, heat aging resistance, mechanical strength, and thermal conductivity 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 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 modifier, (B) compound and (C) thermally conductive filler, phosphorus-containing compound and other additives, extraction with an organic solvent The weight of components other than (A) polyamide resin or (A) polyamide resin is measured by separation, and the content of (A) polyamide resin 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 amount calculated by colorimetric determination by the previously calculated polyamide resin amount, the phosphorus atom concentration relative to the polyamide resin can be obtained.

  Examples of phosphorus-containing compounds include phosphite compounds, phosphate compounds, phosphonite compounds, phosphonate compounds, phosphinite compounds, and phosphinate compounds. Two or more of these may be contained.

  Examples of the phosphite compound include phosphorous acid, phosphorous acid alkyl ester, phosphorous acid aryl ester, and metal salts thereof. The alkyl ester or aryl ester may be a monoester, or may have a plurality of ester bonds such as a diester or triester, and so on. Specifically, phosphorous acid, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, Examples thereof include bis (2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite and metal salts thereof. The metal salt will be described later.

  Examples of the phosphate compound include phosphoric acid, phosphoric acid alkyl ester, phosphoric acid aryl ester, and metal salts thereof. Specific examples include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, and metal salts thereof.

  Examples of the phosphonite compound include phosphonous acid, phosphonous acid alkyl ester, phosphonous acid aryl ester, alkylated phosphonous acid, arylated phosphonous acid, their alkyl ester or aryl ester, and metal salts thereof. Can be mentioned. Specifically, phosphonous acid, dimethyl phosphite, diethyl phosphonite, diphenyl phosphite, methyl phosphonous acid, ethyl phosphonous acid, propyl phosphonous acid, isopropyl phosphonous acid, butyl phosphonous acid, phenyl Phosphorous acid, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, tetrakis (2,4-di-t-butyl-5-methyl) Phenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, alkyl esters or aryl esters thereof, and metal salts thereof.

  Examples of the phosphonate compound include phosphonic acid, phosphonic acid alkyl ester, phosphonic acid aryl ester, alkylated phosphonic acid or arylated phosphonic acid, their alkyl ester or aryl ester, and metal salts thereof. Specifically, dimethyl phosphonate, diethyl phosphonate, diphenyl phosphonate, methyl phosphonic acid, ethyl phosphonic acid, propyl phosphonic acid, isopropyl phosphonic acid, butyl phosphonic acid, phenyl phosphonic acid, benzyl phosphonic acid, tolyl phosphonic acid, xylyl Examples thereof include phosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid, anthrylphosphonic acid, alkyl esters or aryl esters thereof, and metal salts thereof.

  Examples of the phosphinite compound include phosphinic acid, phosphinic acid alkyl ester, phosphinic acid aryl ester, alkylated phosphinic acid, arylated phosphinic acid, their alkyl or aryl esters, and metal salts thereof. It is done. Specifically, phosphinic acid, methyl phosphite, ethyl phosphite, phenyl phosphite, methyl phosphinic acid, ethyl phosphinic acid, propyl phosphinic acid, isopropyl phosphinic acid, butyl phosphinic acid, phenyl Examples include phosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, diphenylphosphinic acid, alkyl esters or aryl esters thereof, and metal salts thereof. It is done.

  Examples of the phosphinate compound include hypophosphorous acid, hypophosphorous alkyl ester, hypophosphorous aryl ester, alkylated hypophosphorous acid, arylated hypophosphorous acid, their alkyl ester or aryl ester, and And metal salts thereof. Specifically, methyl phosphinate, ethyl phosphinate, phenyl phosphinate, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid, xylylphosphinic acid, Biphenylylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, diphenylphosphinic acid, ditolylphosphinic acid, dixylphosphinic acid, dibiphenylylphosphinic acid, naphthylphosphinic acid, Anthryl phosphinic acid, 2-carboxyphenyl phosphinic acid, alkyl or aryl esters thereof, and metal salts thereof can be mentioned.

  Among these, phosphite compounds and phosphinate compounds are preferable, and these may be hydrates. It is further preferable to contain at least one selected from the group consisting of phosphorous acid, hypophosphorous acid and metal salts thereof. By containing such a compound, it is possible to further increase the reaction rate of the compound (B) while suppressing the thickening of the (A) polyamide resin, and to increase the degree of branching and reduce the self-aggregation force. Further, the fluidity and retention stability during molding can be further improved, and the heat aging resistance, mechanical strength, surface appearance and thermal conductivity of the molded product can be further improved.

  Examples of the metal constituting the metal salt 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.

  As metal salts of phosphorous acid or hypophosphorous acid, specifically, lithium phosphite, sodium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, barium phosphite, hypophosphorous acid Examples thereof include lithium, sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, calcium hypophosphite, and barium hypophosphite. 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 residence stability during molding are further improved, and the heat aging resistance of the molded product, Mechanical strength, surface appearance, and thermal conductivity can be further improved.

  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 an effect which 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 the 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. Moreover, since compatibility of a polyamide resin composition also improves by making Cu / K into 0.43 or less, it can improve from the heat aging resistance of a molded article. 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 the heat aging resistance of a molded article improves 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 may further contain (C) a filler other than the thermally conductive filler. (C) As a filler other than the thermally conductive 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 organic fibers such as glass fibers and aromatic polyamide fibers, gypsum fibers, zirconia fibers, silica fibers, titanium oxide fibers, rock wool, potassium titanate whiskers, calcium carbonate whiskers, wollastonite whiskers, Examples thereof include fibrous or whisker-like fillers such as aluminum borate whisker. As the fibrous filler, glass 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 warp of the molded product that is likely to occur in the glass fiber-blended polyamide resin composition, the ratio of major axis / minor axis is preferably 1.5 or more, more preferably 2.0 or more, and more preferably 10 or less. Are preferable, and those of 6.0 or less are 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.

  The surface of the filler may be treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.), and the mechanical strength and surface appearance of the molded product are further improved. Can be improved. For example, 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, but the filler and the polyamide resin are melt-kneaded without performing a surface treatment of the filler in advance. In this case, an integral blend method in which a coupling agent is added may be used. 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 content of the filler is preferably 1 to 200 parts by weight with respect to 100 parts by weight of (A) the polyamide resin. If content of a filler is 1 weight part or more, fluidity | liquidity, mechanical strength, and heat aging resistance can be improved more. The content of the filler is more preferably 10 parts by weight or more, and further preferably 20 parts by weight or more. On the other hand, if the content of the filler is 200 parts by weight or less, the molded product having excellent surface appearance can be obtained by suppressing the float of the filler on the surface of the molded product. The content of the filler is more preferably 150 parts by weight or less, and even more preferably 100 parts by weight or less.

  Furthermore, the polyamide resin composition according to the embodiment of the present invention can contain a resin other than the polyamide resin and various additives depending on 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 content thereof 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 make full use of 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 include mold release agents such as condensates and silicone compounds, lubricants, UV inhibitors, colorants, flame retardants, impact resistance improvers, and foaming agents. When these additives are contained, the content 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.

  As a method for producing a polyamide resin composition of an embodiment of the present invention, (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 is used. (A) a polyamide resin, (C) a thermally conductive filler, a method of melt-kneading with components other than (A), (B), and (C) if necessary, and (b) a hydroxyl group and / or an amino group Compound (b ′) epoxy group and / or carbodiimide group-containing compound (A) polyamide resin, (C) thermally conductive filler, (A), (b), (b ′), (C ) And melt kneading with other components to form the compound (B) in the polyamide resin composition. The former method is preferable, and is excellent in fluidity and retention stability during molding, and can further improve heat aging resistance, mechanical strength, surface appearance, and thermal conductivity.

  Moreover, when the polyamide resin composition of embodiment of this invention contains 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 containing a phosphorus-containing compound at the time of compounding, the fluidity and residence stability during molding of the polyamide resin composition are further improved, and further, heat aging resistance, mechanical strength, surface appearance, thermal conductivity, and color tone are further improved. be able to.

  When melt-kneading using a twin-screw extruder, there is no particular limitation on the raw material supply method to the twin-screw extruder. (B) When supplying a compound as a raw material to a twin screw extruder, or (b) supplying a hydroxyl group and / or amino group-containing compound and (b ′) an epoxy group and / or carbodiimide group-containing compound to a twin screw extruder. In this case, the (B) compound or the (b) hydroxyl group and / or amino group-containing compound easily promotes the decomposition of the polyamide resin in a temperature range higher than the melting point of the polyamide resin. And / or supplying the amino group-containing compound from the downstream side of the polyamide resin supply position to shorten the kneading time of the (A) polyamide resin and the (B) compound or (b) the hydroxyl group and / or amino group-containing compound. preferable. In addition, (C) the method for supplying the thermally conductive filler is, together with (A) a compound or (b) a hydroxyl group and / or an amino group-containing compound, from the viewpoint of suppressing the thickening of the polyamide resin (A) It is preferable to supply from the downstream side of the polyamide resin supply position. The (b ′) epoxy group and / or carbodiimide group-containing compound may be supplied to the twin-screw extruder together with the (A) polyamide resin, or may be supplied from the downstream side of the polyamide resin supply position. Preferably, the supply is 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. In addition, when the polyamide resin composition of the embodiment of the present invention contains a phosphorus-containing compound, the phosphorus-containing compound increases the reaction rate of the compound (B) in addition to the catalytic effect that promotes self-condensation of the polyamide resin (A). Since it is thought that it plays the role which improves, it is preferable to supply to a twin-screw extruder with (B) compound and (C) heat conductive filler.

  Hereinafter, the case where (B) a compound is supplied to a twin screw extruder will be described as an example. (B) A hydroxyl group and / or amino group-containing compound and (b ′) an epoxy group and / or carbodiimide group-containing compound are twin-screw extruded. The same applies when supplying to the machine.

  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 is easy to supply (B) compound and (C) thermally conductive filler after sufficiently kneading (A) polyamide resin and various components to be blended if necessary. Become. As a result, (A) the decomposition of the polyamide resin can be suppressed.

  In the embodiment of the present invention, it is preferable that at least (A) the polyamide resin and, if necessary, the component to be blended are supplied to the twin screw extruder from the upstream side of 1/2 of the screw length and melt kneaded. It is more preferable to supply from the upstream end of the. 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.

  It is preferable that (B) the compound, (C) the thermally conductive filler and, if necessary, (D) the phosphorus-containing compound are supplied to the twin screw extruder from the downstream side of 1/2 of the screw length and melt kneaded. (B) Compound, (C) Thermally conductive filler and, if necessary, (D) Various components to be blended with (A) polyamide resin as required by supplying a phosphorus-containing compound from the downstream side of 1/2 of the screw length After being sufficiently kneaded, it becomes easy to supply the compound (B), (C) the thermally conductive filler, and (D) 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, (C) the dispersibility of the thermally conductive filler is improved, the fluidity and retention stability during molding are excellent, and the heat aging resistance, mechanical strength, surface appearance, and thermal conductivity of the molded product are further improved. be able to.

  When producing the polyamide resin composition of the embodiment of the present invention using a twin screw extruder, twin screw extrusion having a plurality of full flight zones and a plurality of kneading zones in terms of improving kneadability and reactivity. It is preferable to use a machine. 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 a twin screw extruder is used, the reaction can be effectively promoted by increasing the resin pressure in the kneading zone within a predetermined range from the resin pressure in the full flight zone. (A) Polyamide It is thought that the compatibility between the resin and the (B) compound and the dispersibility of the (C) thermally conductive filler are improved, and the fluidity, retention stability, heat aging resistance, mechanical strength, surface appearance and thermal conductivity are further improved. Can be 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 (B) compound and (C) the thermally conductive filler is Ln1, Ln1 / L is preferably 0.02 or more. More preferably, it is 03 or more. 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 of the (A) polyamide resin can be increased, and by setting it to 0.40 or less, shear heat generation is moderately suppressed and thermal degradation of the resin is suppressed. be able to. (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.

  When the total length of the kneading zone on the downstream side of the supply position of the compound (C) and the heat conductive filler (C) 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 thermally conductive filler, 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 heat conductive filler by a twin screw extruder. Compared with the case where a high-concentration premix is not produced, the fluidity at the time of molding is superior, and the heat aging resistance, mechanical strength, and thermal conductivity of the obtained 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 of the embodiment of the present invention is excellent in fluidity and retention stability, and can obtain a molded product excellent in heat aging resistance, mechanical strength, surface appearance, and thermal conductivity. It is useful for applications, ceramic substitute applications, electromagnetic shielding applications, high precision parts, high conductivity applications, automotive applications, and the like. Among them, motor members of automobiles and electric / electronic devices that generate heat due to friction during rotation, lighting device members that generate heat due to long-time lighting, electrical components, electric / electronic members that generate heat due to lightening and high density , Information communication member, automobile engine peripheral member, automobile under hood member, automobile gear member, automobile interior member, automobile exterior member, intake / exhaust system member, engine cooling water system member, etc., and generation thereof It is suitable for a heat radiating member such as a member in contact with a metal that dissipates heat, a component, a peripheral component, and a casing.

  Examples of the motor member include a hybrid vehicle in which a drive mechanism that has been developed in recent years uses both a gasoline and a motor, a fuel cell vehicle in which the drive mechanism is a motor only, and a heat-dissipating member for cooling a motor of an electric vehicle. Specifically, the motor cooling heat-dissipating member is used for motor cooling methods such as air cooling, water cooling circulation, and oil circulation. And / or heat radiating member of cooling oil circulation path, heat radiating pipe, pipe holding fixture, cap, heat radiating from motor heat generating part to air and / or cooling water, cooling oil via metal, ceramics and other cooling members Cooling parts that require various heat dissipation properties such as fins are included. Illumination equipment members include a mounting base encapsulating lighting elements (especially LEDs), a heat dissipation plate in contact with the mounting base, a light source, a housing for housing the mounting base for lighting and / or a heat dissipation plate, and an LED power supply circuit Cases, LED packages, LED spacers, LED sockets, LED base connectors, LED element frames, connectors, connector sockets, reflectors, lamp sockets, lamp holders, capacitors, circuits, and the like. Examples of the electrical member include an ECU case and a power module. Electrical and electronic components include connectors, relay cases, switches, variable capacitor cases, various inverters, various terminal boards, transformers, printed wiring boards, liquid crystal panel frames, plastic magnets, semiconductors, liquid crystal display parts, lamp covers for projectors, etc. , FDD carriage, FDD chassis, actuator, HDD parts such as chassis, computer related parts, personal computer housing, mobile phone housing optical pickup parts, LED substrate, flat display parts and the like. Examples of the information communication member include a chip antenna, a wireless LAN antenna, an ETC (Electronic Toll Collection System) antenna, a satellite communication antenna, and the like. Examples of the automobile engine peripheral member include an engine cover, an air intake pipe, a timing belt cover, an intake manifold, a filler cap, a throttle body, and a cooling fan. Examples of the automobile underhood member include a cooling fan, a top and a base of a radiator tank, a cylinder head cover, an oil pan, a brake pipe, a fuel pipe, an exhaust gas system component, and the like. Examples of the automobile gear member include a gear, an actuator, a bearing retainer, a bearing cage, a chain guide, and a chain tensioner. Automotive interior components include shift lever brackets, steering lock brackets, key cylinders, door inner handles, door handle cowls, interior mirror brackets, air conditioner switches, instrument panels, console boxes, glove boxes, steering wheels, trims, etc. . Automotive exterior components include front fender, rear fender, fuel lid, door panel, cylinder head cover, door mirror stay, tailgate panel, license garnish, roof rail, engine mount bracket, rear garnish, rear spoiler, trunk lid, rocker molding, molding, lamp Examples include housings, front grilles, mudguards, and side bumpers. Examples of the intake / exhaust system members include an air intake manifold, an intercooler inlet, a turbocharger, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, and a throttle body. Examples of the engine cooling water system member include a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil netter, and a delivery pipe.

  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 and temperature-falling crystallization temperature of polyamide resin]
About 5 mg of the polyamide resin was sampled, and under a nitrogen atmosphere, using a robot DSC (differential scanning calorimeter) RDC220 manufactured by Seiko Instruments Inc., the melting point and the cooling crystallization temperature of the (A) polyamide resin were measured under the following conditions. After the temperature was raised to the melting point of the polyamide resin + 40 ° C. to obtain a molten state, the temperature of the exothermic peak (temperature-falling crystallization temperature) observed when the temperature was lowered to 30 ° C. at a temperature lowering rate of 20 ° C./min was determined. Furthermore, after maintaining at 30 ° C. for 3 minutes, the temperature (melting point) of the endothermic peak observed when the temperature was raised to the melting point + 40 ° C. at a rate of temperature increase of 20 ° C./min 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 Examples 22 and 24 were dried under reduced pressure at 80 ° C. for 12 hours, and the pellets were ashed in an electric furnace at 550 ° C. for 24 hours 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. By dividing the phosphorus amount calculated by colorimetric determination by the previously calculated polyamide resin amount, the phosphorus atom content relative to the polyamide resin content was determined. U-3000 manufactured by Hitachi, Ltd. was used as the absorptiometer.

[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)
However, B: amount of 0.5 mol / L ethanolic potassium hydroxide solution used for titration [ml], C: amount of 0.5 mol / L ethanolic potassium hydroxide solution used for blank titration [ml ], F: Factor of 0.5 mol / L ethanolic potassium hydroxide solution, S: Mass of sample [g], E: 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 shows. the ¹ H-NMR spectrum from ¹ H-NMR spectrum shown in. Figure 1 shown in FIG. 2 of the obtained (B-6) compound in reference example 6, the 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, where the peak area does not contribute to the reaction benzene of epoxy resin 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).

[Mechanical strength]
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. This test piece was subjected to a tensile test at a crosshead speed of 10 mm / min by a tensile tester Tensilon UTA2.5T (manufactured by Orientec Co., Ltd.) according to ASTM D638. The measurement was performed three times, and the average value was calculated as the tensile strength before the heat aging resistance test treatment. The greater the tensile strength, the better the mechanical strength.

[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 heat-treated at 135 ° C. in a gear oven under the atmosphere for 3000 hours or 190 ° C. under a gear oven under the atmosphere for 2000 hours (heat aging resistance test treatment). The same tensile test was performed, and 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.

[Thermal conductivity]
Using the injection molding machine (Sumitomo Heavy Industries, Ltd., SG75H-MIV), the cylinder temperature: (A) Melting point of polyamide resin + 15 ° C. The mold temperature was set to 80 ° C., and a square plate (film gate) having a thickness of 50 mm × 50 mm × 3 mm was produced by injection molding under the condition of the lower limit pressure (minimum filling pressure) +0.49 MPa. Both surfaces of the obtained square plate were cut to a depth of 0.5 mm to obtain a test piece having a thickness of 2 mm, and the thermal conductivity was measured with a heat flow meter method thermal conductivity measuring device (GH-1S manufactured by Rigaku Corporation). It shows that it is excellent in thermal conductivity, so that heat conductivity is high.

[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, 80 mm × 80 mm A square plate (film gate) having a thickness of 3 mm was prepared. 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.

[Glossiness]
Using the injection molding machine (Sumitomo Heavy Industries, Ltd., SG75H-MIV), the cylinder temperature: (A) Melting point of polyamide resin + 15 ° C. The mold temperature was set to 80 ° C., and the square plate was formed by injection molding under the condition of the lower limit pressure (minimum filling pressure) +0.49 MPa using a mirror-finished mold of 80 mm × 80 mm × thickness 1 mm. Produced. About the obtained square plate, based on JIS-Z-8741, the glossiness of the incident angle of 60 degreeC was measured using the digital variable angle gloss meter (Suga Test Instruments Co., Ltd. make, UGV-5D). It shows that it is excellent in glossiness, so that this value is high.

[Surface smoothness]
Using the injection molding machine (Sumitomo Heavy Industries, Ltd., SG75H-MIV), the cylinder temperature: (A) Melting point of polyamide resin + 15 ° C. The mold temperature was set to 80 ° C., and the square plate was formed by injection molding under the condition of the lower limit pressure (minimum filling pressure) +0.49 MPa using a mirror-finished mold of 80 mm × 80 mm × thickness 1 mm. Produced. About 10 portions randomly selected from the obtained square plates, the average roughness (Ra) of the surface was measured using a surface roughness measuring device (manufactured by Kosaka Laboratory, Surfcorder SE-3400). . The smaller the average surface roughness, the better the surface smoothness.

[Liquidity]
Using the injection molding machine (Sumitomo Heavy Industries, Ltd., SG75H-MIV), the cylinder temperature: (A) Melting point of polyamide resin + 15 ° C. Mold temperature: set to 80 ° C., injection molding under the condition of lower limit pressure (minimum filling pressure) +0.49 MPa, square pin type heat sink molded product shown in FIGS. 3 and 4 (heat receiving surface: 19 mm × 19 mm, (Fin thickness: 1.45 mm, height: 20 mm, gap: 2.35 mm). Here, FIG. 3 is a perspective view of a square pin heat sink molded product, and FIG. 4 is a cross-sectional view of the square pin heat sink molded product. For each of the 10 square pin heat sink molded products obtained, the specific gravity was measured using a specific gravity measuring device AUW320 / SMK-401 (manufactured by Shimadzu Corporation), and the average value of the 10 pieces was taken as the specific gravity of the molded product. Moreover, theoretical specific gravity was computed based on the specific gravity of each compounding material, and the molded article filling rate was computed from the following formula.
Molded product filling ratio = (molded product specific gravity / theoretical specific gravity) × 100
It shows that the higher the molded product filling rate, the higher the filling rate in the thin wall portion and 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.

Reference Example 1 (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, the hydroxyl value was 1280 mgKOH / g, and the specific gravity was 1.050 g / cm ³ . 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 2 (B-2)
The compound represented by the general formula (1) and / or the same as in Reference Example 1 except that the screw rotation 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, the hydroxyl value was 1350 mgKOH / g, and the specific gravity was 1.050 g / cm ³ . 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 3 (B-3)
The compound represented by the general formula (1) and / or the same as in Reference Example 1 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, the hydroxyl value was 1300 mgKOH / g, and the specific gravity was 1.050 g / cm ³ . 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-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, the hydroxyl value was 1170 mgKOH / g, and the specific gravity was 1.050 g / cm ³ . 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 5 (B-5)
Aliphatic polycarbodiimide (“Carbodilite” (registered trademark) LA-1 manufactured by Nisshinbo Chemical Co., Ltd.) and average number of carbodiimide groups in one molecule with respect to 100 parts by weight of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.) 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., 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 89%, the degree of branching was 0.37, the hydroxyl value was 1110 mgKOH / g, and the specific gravity was 0.991 g / cm ³ . 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 6 (B-6)
Bisphenol A-type epoxy resin (“jER” (registered trademark) 1004, 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 1650, molecular weight / number of functional groups in one molecule 825) After pre-mixing 33.3 parts by weight, using a Ikegai PCM30 type twin screw extruder, cylinder temperature 200 ° C., screw rotation speed 100 rpm 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 56%, the degree of branching was 0.34, the hydroxyl value was 1200 mgKOH / g, and the specific gravity was 1.049 g / cm ³ . 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-7)
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 polyoxyethylenehexamine 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, the amine value was 500 mgKOH / g, and the specific gravity was 1.053 g / cm ³ . 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 8 (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, the hydroxyl value was 540 mgKOH / g, and the specific gravity was 1.172 g / cm ³ . 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 9 (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, and the specific gravity was 1.050 g / cm ³ .

Reference Example 10 (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, a degree of branching of 0.29, and a specific gravity of 1.010 g / cm ³ .

Reference Example 11 (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, the degree of branching was 0.34, and the specific gravity was 1.220 g / cm ³ .

Reference Example 12 (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 is 1950, the acid value is 277 mgKOH / g, the hydroxyl value is 504 mgKOH / g, the ratio of acid value / hydroxyl value is 0.55, the degree of branching is 0.40, and the specific gravity is 1. It was 250 g / cm ³ .

Reference Example 13 (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 1,950, the hydroxyl value was 505 mgKOH / g, the degree of branching was 0.38, and the specific gravity was 1.280 g / cm ³ .

Reference Example 14 (E-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.

In addition, (A) polyamide resin, (b) hydroxyl group and / or amino group-containing compound, (b ′) epoxy group and / or carbodiimide group-containing compound, (C) heat conductive filling used in this example and comparative example The materials, (D) phosphorus-containing compound, and (F) filler are as follows.
(A-1): Polyamide 66 resin having a melting point of 260 ° C., a specific gravity of 1.140 g / cm ³ , ηr = 2.78, and Tm−Tc = 35 ° C.
(A-2): Polyamide 6 resin having a melting point of 222 ° C., a specific gravity of 1.130 g / cm ³ , ηr = 2.70, and Tm−Tc = 55 ° C.
(A-3) Polyamide 66 / 6I / 6 (= 76/17/7% by weight) resin having a melting point of 228 ° C., a specific gravity of 1.130 g / cm ³ , ηr = 2.00, and Tm-Tc = 70 ° C.
(A-4) Polyamide 410 resin having a melting point of 250 ° C., a specific gravity of 1.090 g / cm ³ , ηr = 2.70, and Tm-Tc = 31 ° C.
(B-1): Dipentaerythritol (large particle size) (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight 254, hydroxyl value 1325 mgKOH / g, specific gravity 1.035 g / cm ³ , average particle diameter 180 μm or more.
(B-2): Dipentaerythritol polyoxyethylenehexamine, molecular weight 608, amine value 554 mgKOH / g, specific gravity 1.045 g / cm ³ .
(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 Of 190 functional groups and a specific gravity of 1.200 g / cm ³ .
(C-1): Talc (Nippon Talc Co., Ltd. average particle size: 23 μm, shape: scale, thermal conductivity: 5 W / m · K, specific gravity: 2.700 g / cm ³ )
(C-2): Magnesium hydroxide (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 0.83 μm, shape: particulate, thermal conductivity: 8 W / m · K, specific gravity: 2.360 g / cm ³ )
(C-3): Graphite (manufactured by Nippon Graphite Industry Co., Ltd., average particle size: 40 μm, shape: scale-like, thermal conductivity: 100 W / m · K, specific gravity: 2.250 g / cm ³ )
(C-4): Boron nitride (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size: 15 μm, shape: hexagonal scale, thermal conductivity: 210 W / m · K, specific gravity: 2.260 g / cm ³ )
(D-1): Sodium hypophosphite monohydrate (Wako Pure Chemical Industries, Ltd.), molecular weight 105.99
(F-1): Circular cross-section glass fiber (T-275H manufactured by Nippon Electric Glass Co., Ltd.), cross-sectional diameter 10.5 μm, surface treatment agent: silane coupling agent, fiber length 3 mm, specific gravity 2.550 g / cm ³ .

(Examples 1-16, 19-21, Comparative Examples 1-11)
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) thermally conductive filler shown in the table are supplied from the side feeder to the twin screw extruder and melted. 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.

(Examples 17 and 18)
(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 thermally conductive filler 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.

(Example 22)
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, (C) thermally conductive filler, 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.

(Example 23)
(E-1) Pellets of polyamide resin composition were obtained under the same conditions as in Example 4 except that the high-concentration preliminary mixture shown in the table was supplied from the main feeder to the twin-screw extruder. Thereby, the composition ratio of Example 23 becomes the same as that of Example 4.

(Example 24)
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) thermally conductive filler, (D) phosphorus-containing compound, and (F) glass fiber 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 result of each Example and a comparative example is shown to Tables 1-4.

  Examples 1-24 contain (A) polyamide resin and (B) by containing specific amount of (B) compound and containing (C) heat conductive filler compared with Comparative Examples 1-11. ) Improved compound compatibility and (C) Dispersibility and orientation of thermally conductive fillers, resulting in excellent fluidity and retention stability, heat aging resistance, mechanical strength, surface appearance and thermal conductivity An excellent molded product could be obtained.

  In Examples 3 to 5, compared with Examples 2 and 6, since the volume ratio of (A) polyamide resin and (C) thermally conductive filler is in a preferable range, the molding is superior in mechanical strength and thermal conductivity. I was able to get the goods.

  In Example 4, compared with Examples 14 to 16, since the reaction rate of the compound (B) is in a more preferable range, the compatibility between the (A) polyamide resin and the (B) compound and the dispersion of (C). As a result, it was possible to obtain a molded product that was more excellent in fluidity and retention stability and superior in heat aging resistance, mechanical strength, and thermal conductivity.

Since Examples 1, 4, and 10 use a more preferable (C) heat conductive filler as compared with Example 9, (B) the compound is (A) polyamide resin, and (C) heat conductivity. The adhesiveness of the filler was further improved, embrittlement was suppressed, and a molded product having excellent mechanical strength could be obtained.
In Example 23, compared with Example 4, a high-concentration premix was prepared and melted and kneaded twice, so that compatibility between (A) polyamide resin and (B) compound and dispersibility and orientation of (C) were obtained. As a result, it was possible to obtain a molded product having excellent fluidity and excellent heat aging resistance, mechanical strength, and thermal conductivity.

  In Examples 11 and 12, compared with Examples 4 and 13, the difference between the melting point and the crystallization temperature of (A) the polyamide resin was in a more preferable range. An excellent molded product having excellent surface smoothness and glossiness could be obtained.

  Since Example 4 used the compound (B) obtained by reacting in advance compared with Example 18, Example 21 compared with Example 17, (A) Polyamide resin and (B) The compatibility with the compound and the dispersibility and orientation of (C) are further improved, and as a result, it is possible to obtain a molded article that is superior in fluidity and retention stability, and superior in heat aging resistance, mechanical strength and thermal conductivity. did it.

  Since Example 22 further contains a phosphorus-containing compound as compared with Example 4, the compatibility between the (A) polyamide resin and the (B) compound and the dispersive orientation of (C) are further improved. As a result, it was possible to obtain a molded article which was excellent in fluidity and residence stability and excellent in heat aging resistance, mechanical strength and thermal conductivity.

  Since Example 24 further contained a phosphorus-containing compound and glass fiber as compared with Example 4, it was possible to obtain a molded article having excellent retention stability and excellent mechanical strength.

  The polyamide resin composition of the embodiment of the present invention is excellent in fluidity and retention stability, and can obtain a molded product excellent in heat aging resistance, mechanical strength, surface appearance, and thermal conductivity. It is useful for applications, ceramic substitute applications, electromagnetic shielding applications, high precision parts, high conductivity applications, automotive applications, and the like. Among them, motor members of automobiles and electric / electronic devices that generate heat due to friction during rotation, lighting device members that generate heat due to long-time lighting, electrical components, electric / electronic members that generate heat due to lightening and high density , Information communication member, automobile engine peripheral member, automobile under hood member, automobile gear member, automobile interior member, automobile exterior member, intake / exhaust system member, engine cooling water system member, etc., and generation thereof It is suitable for a heat radiating member such as a member in contact with a metal that dissipates heat, a component, a peripheral component, and a casing.

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 containing 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) a thermally conductive filler. 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 product according to claim 4, wherein the molded product is a heat dissipation member.