JP6645180B2 - Polyamide resin composition and molded article obtained by molding the same - Google Patents

Description

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

  Polyamide resins have excellent mechanical properties, heat resistance, and chemical resistance, and are therefore preferably used for automobiles and electric / electronic parts. Among various uses, polyamide resins are used for parts to which heat of extremely high temperature is applied, such as engine covers, because of excellent heat aging resistance. 2. Description of the Related Art In recent years, the environmental temperature in an engine room has been increasing with the increase in the density of components in the engine room and the increase in engine output. Further, due to an increase in demand for weight reduction, resin components are also being reduced in size and modularized, and heat aging resistance under higher temperature conditions and fluidity during molding are required.

  Conventionally, as a technique for improving the heat aging resistance of a polyamide resin, for example, a polyamide resin composition in which a copper compound and a halogen compound are blended with a polyamide resin is known (for example, see Patent Document 1). However, the polyamide resin composition of Patent Document 1 has insufficient heat aging resistance and fluidity with respect to the recent increase in the use environment temperature, miniaturization of engine peripheral parts, and modularization.

  In response, a number of technical improvements have been attempted to improve the heat aging resistance and the fluidity at high temperatures. For example, a polyamide resin composition containing a polyamide resin, a polyhydric alcohol having a number average molecular weight of less than 2,000, a co-stabilizer such as a copper stabilizer and a hindered phenol, and a polymer reinforcing material (for example, see Patent Document 2) ), A polyamide resin composition containing a polyamide resin, polyethyleneimine, a lubricant, a copper-containing stabilizer, a filler, and nigrosine (for example, see Patent Document 3).

JP 2006-273945 A JP 2011-529991 A JP 2008-530290 A

  However, molded articles obtained from the polyamide resin composition of Patent Document 2 have excellent heat aging resistance in a temperature range of 150 ° C to 230 ° C, but heat aging in a temperature range of less than 150 ° C and 240 ° C or more. There was a problem that it was poor. In addition, although the polyamide resin composition of Patent Document 3 also has excellent heat aging resistance in a temperature range of 160 ° C to 180 ° C, there is a problem that heat aging resistance is poor in a temperature range of less than 150 ° C. . Although the environmental temperature of parts in an engine room of an automobile is increasing year by year, since the temperature is not always high, a material having heat resistance and aging resistance at a low temperature is required for parts in the engine room of an automobile. Further, these techniques have a certain degree of fluidity improving effect, but the improving effect is not sufficient. Furthermore, the polyamide resin compositions of Patent Documents 2 and 3 disclose (i) problems on the surface appearance such as bleed-out of a polyhydric alcohol or the like to a surface layer of a molded product, coloring due to liberation of copper ions, and (ii) retention. There was a problem that the stability and (iii) the color tone were inferior.

  The present invention has been made in view of these problems of the prior art, and provides a polyamide resin composition which is excellent in fluidity and retention stability, and which can obtain a molded article excellent in heat aging resistance, mechanical strength, surface appearance and color tone. Make it an issue.

上記一般式（１）中、Ｘ１〜Ｘ６はそれぞれ同一でも異なってもよく、ＯＨ、ＮＨ２、ＣＨ３またはＯＲを表す。ただし、ＯＨとＮＨ２とＯＲの数の和は３以上である。また、Ｒはアミノ基、エポキシ基またはカルボジイミド基を有する有機基を表し、ｎは０〜２０の範囲を表す。
［４］（ｂ）水酸基および／またはアミノ基含有化合物と、（ｂ’）エポキシ基および／またはカルボジイミド基含有化合物とを反応させて、水酸基またはアミノ基と、エポキシ基またはカルボジイミド基との反応率が２０〜７０％である（Ｂ）水酸基および／またはアミノ基と、エポキシ基および／またはカルボジイミド基とを有し、１分子中の水酸基およびアミノ基の数の和が、１分子中のエポキシ基およびカルボジイミド基の数の和よりも多い化合物を得、次いで（Ａ）ポリアミド樹脂１００重量部に対して、前記（Ｂ）化合物０．１〜２０重量部および（Ｃ）リン含有化合物を溶融混練するポリアミド樹脂組成物の製造方法であって、得られるポリアミド樹脂組成物の吸光光度分析法により求められるリン原子含有量がポリアミド樹脂含有量に対して１８０〜３５００ｐｐｍであるポリアミド樹脂組成物の製造方法。
［５］請求項［１］〜［３］のいずれかに記載のポリアミド樹脂組成物を成形してなる成形品。 In order to solve the above problems, the present invention mainly has the following configurations.
[1] The sum of the number of hydroxyl groups and amino groups in one molecule having (B) a hydroxyl group and / or an amino group and an epoxy group and / or a carbodiimide group with respect to 100 parts by weight of the polyamide resin (A). Contains 0.1 to 20 parts by weight of a compound which is larger than the sum of the number of epoxy groups and carbodiimide groups in one molecule, and (C) a phosphorus-containing compound, and has a phosphorus atom content determined by an absorption spectrophotometric method of polyamide. 180 to 3500 ppm with respect to the resin content , wherein the compound (B) is a reaction product of (b) a compound containing a hydroxyl group and / or an amino group and (b ′) a compound containing an epoxy group and / or a carbodiimide group. A polyamide resin composition, wherein the conversion between a hydroxyl group or an amino group and an epoxy group or a carbodiimide group is 20 to 70% .
[ 2 ] The polyamide resin composition according to [ 1 ], wherein the (C) phosphorus-containing compound is at least one selected from the group consisting of phosphorous acid, hypophosphorous acid, and metal salts thereof.
[ 3 ] The polyamide resin composition according to [1] or [2] , wherein the compound (B) is a compound having a structure represented by the following general formula (1) and / or a condensate thereof.

In the general formula (1), X1 to X6 may be the same or different and represent OH, NH2, CH3 or OR. However, the sum of the numbers of OH, NH2, and OR is 3 or more. R represents an organic group having an amino group, an epoxy group or a carbodiimide group, and n represents a range of 0 to 20.
[ 4 ] (b) A reaction between a hydroxyl group and / or an amino group and an epoxy group and / or a carbodiimide group by reacting a compound containing a hydroxyl group and / or an amino group with (b ′) an epoxy group and / or a carbodiimide group. (B) having a hydroxyl group and / or an amino group and an epoxy group and / or a carbodiimide group in which the total number of hydroxyl groups and amino groups in one molecule is 20 to 70%. And a compound larger than the sum of the number of carbodiimide groups is obtained, and then 0.1 to 20 parts by weight of the compound (B) and the phosphorus-containing compound (C) are melt-kneaded with respect to 100 parts by weight of the polyamide resin (A). A method for producing a polyamide resin composition, wherein a phosphorus atom content of the obtained polyamide resin composition determined by a spectrophotometric method is a polyamide resin composition. A method for producing a polyamide resin composition having a content of 180 to 3500 ppm with respect to the fat content.
[ 5 ] A molded article obtained by molding the polyamide resin composition according to any one of [1] to [3] .

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

  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 heat aging resistance, mechanical strength, surface appearance and color tone can be provided.

¹ H-NMR spectrum of a dry blend of dipentaerythritol and bisphenol A type epoxy resin. ¹ H-NMR spectrum of a melt-kneaded reaction product of a polyhydric alcohol and an epoxy compound obtained in Reference Example 9.

  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 has a hydroxyl group and an amino group in one molecule. Contains a compound (hereinafter sometimes referred to as “(B) compound”) in which the sum of the numbers is larger than the sum of the number of epoxy groups and carbodiimide groups in one molecule, and (C) a phosphorus-containing compound. . Hereinafter, each component will be described.

  In the polyamide resin composition of the embodiment of the present invention, it is considered that the carboxyl terminal group of the polyamide resin (A) 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 the carboxyl terminal group of the polyamide resin are the same as the hydroxyl group and / or the amino group, the epoxy group and / or the carbodiimide group in the compound (B). It is thought to react. For this reason, it is considered that the polyamide resin (A) has excellent compatibility with the compound (B).

  The (A) polyamide resin used in the embodiment of the present invention is a polyamide containing (i) an amino acid, (ii) a lactam or (iii) a diamine and a dicarboxylic acid as main raw materials. (A) Typical examples of the raw material of the polyamide resin include 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 Aliphatic diamines such as hexamethylenediamine, 5-methylnonamethylenediamine and 2-methyloctamethylenediamine; aromatic diamines such as meta-xylylenediamine and para-xylylenediamine; 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 Alicyclic diamines such as 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine; aliphatics such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid; 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, as a raw material of the polyamide resin (A), two or more kinds of polyamide homopolymers or polyamide copolymers derived from these raw materials may be blended.

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

  Particularly preferred polyamide resins are polyamide resins having a melting point between 240C and 330C. A polyamide resin having a melting point of 240 ° C to 330 ° C is excellent in heat resistance and strength. The polyamide resin having a melting point of 240 ° C. or more can be melt-kneaded under a high temperature condition under a high resin pressure, and can increase the reactivity with the compound (B) described below. For this reason, the dispersibility of the compound (B) in the polyamide resin composition can be further increased, and the fluidity, retention stability, mechanical strength, heat aging resistance, surface appearance, and color tone can be further improved. The melting point of the polyamide resin is more preferably 250 ° C. or higher. On the other hand, by using a polyamide resin having a melting point of 330 ° C. or less, the melt-kneading temperature can be appropriately suppressed, and the decomposition of the polyamide resin can be suppressed. Therefore, fluidity, retention stability, mechanical strength, heat aging resistance, surface appearance, and color tone can be further improved. Here, the melting point of the polyamide resin in the embodiment of the present invention is determined by using a differential scanning calorimeter after the polyamide resin is cooled from the molten state to 30 ° C. at a rate of 20 ° C./min under an inert gas atmosphere. , Defined as the temperature of an endothermic peak that appears when the temperature is raised to the melting point + 40 ° C. at a temperature rising rate of 20 ° C./min. 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.

  Examples of the polyamide resin having a melting point of 240 ° C. to 330 ° C. include nylon 66, nylon 46, nylon 410, nylon 56, nylon 6T / 66, nylon 6T / 6I, nylon 6T / 12, nylon 6T / 5T, and nylon 6T. And copolymers having hexamethyl terephthalamide units such as / M5T and nylon 6T / 6, nylon 5T / 10T, nylon 9T, nylon 10T, nylon 12T and the like.

  It is also practically suitable to mix two or more of these polyamide resins according to required properties such as fluidity, retention stability, mechanical strength, heat aging resistance, surface appearance, and color tone. It is preferable to mix nylon 6, nylon 11 and / or nylon 12 with a polyamide resin having a melting point of 240 ° C. to 330 ° C., and it is possible to further improve the heat aging resistance of a molded product. In this case, the total blending amount of nylon 6, nylon 11, and nylon 12 is preferably 5 to 55 parts by weight based on 100 parts by weight of the polyamide resin having a melting point of 240 to 330 ° C.

  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 strength and heat aging resistance of the obtained molded product can be further improved. The relative viscosity is more preferably 2.0 or more. On the other hand, when 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 numbers of the hydroxyl group and the amino group in one molecule is 1 It contains more compounds than the sum of the number of epoxy groups and carbodiimide groups in the molecule. The hydroxyl group and / or amino group-containing compound has an effect of improving the moldability such as fluidity and the heat aging resistance at 150 to 230 ° C., but (A) the compatibility with the polyamide resin is low, or less than 150 ° C. And the problem that the heat aging resistance at 240 ° C. or higher is insufficient. In addition, the compound containing a hydroxyl group and / or an amino group has a problem of bleeding out to the surface layer of a molded article. And there is also a problem that the retention stability and the color tone are inferior. Further, there is also a problem that the compound containing a hydroxyl group and / or an amino group plasticizes the polyamide resin (A) and the mechanical strength of the obtained molded product is reduced. On the other hand, in the embodiment of the present invention, the compound (B) may have a structure in which the hydroxyl group and / or amino group is considered to undergo a dehydration condensation reaction with the carboxyl terminal group of the polyamide resin (A), or may have a hydroxyl group, an amino group, Since it is considered that the epoxy group and / or the carbodiimide group reacts with the amino terminal group or the carboxyl terminal group of the polyamide resin (A), it is excellent in compatibility with the polyamide resin (A) and finely dispersed in the polyamide resin composition. A phase can be formed to improve the heat aging resistance at less than 150 ° C and at least 240 ° C. In addition, bleed out of the compound (B) to the surface layer of the molded article can be suppressed, and the surface appearance can be improved. Furthermore, the epoxy group and the carbodiimide group are more excellent in reactivity with the terminal group of the polyamide resin (A) than the hydroxyl group and the amino group, and therefore, (B) the sum of the number of the hydroxyl group and the amino group in one molecule of the compound. Is larger than the sum of the numbers of epoxy groups and carbodiimide groups, thereby appropriately forming a crosslinked structure, suppressing a decrease in the degree of polymerization due to hydrolysis of the amide bond, and improving the retention stability and color tone. It is considered that embrittlement due to the formation of a suitable crosslinked structure can be suppressed, and fluidity and mechanical strength can be improved. Compounds having a hydroxyl group and an epoxy group and / or a carbodiimide group are more preferred.

  In the embodiment of the present invention, the compound (B) may be contained in the polyamide resin composition as the compound (B). For example, a compound containing a hydroxyl group and / or an amino group (b) described below and a compound (b ′) ) Epoxy group and / or carbodiimide group-containing compounds may be individually compounded into (A) polyamide resin to form (B) compound in the polyamide resin composition, or (B) compound which has been reacted in advance. May be blended with the polyamide resin (A). It is preferable to blend the compound (B) obtained by reacting them in advance with the polyamide resin (A). The compound (B) is more compatible with the polyamide resin (A), and has excellent fluidity, retention stability, and mechanical strength. , Heat aging resistance, surface appearance, and color tone can be further improved. In particular, the heat aging resistance at a high temperature of 190 ° C. or more can be significantly improved. Although this factor is not clear, it is considered as follows. That is, the (b ') epoxy group and / or carbodiimide group-containing compound is linked by previously reacting the (b') hydroxyl group and / or amino group-containing compound with the (b ') epoxy group and / or carbodiimide group-containing compound. A compound (B) having a multi-branched structure is formed. It is considered that such a compound (B) has a multi-branched structure, whereby the self-cohesive force is further reduced, and the reactivity and compatibility with the (A) polyamide resin are improved. Further, it is considered that the dispersibility of the compound (B) in the polyamide resin composition is further improved because the melt viscosity of the compound having a multi-branched structure is improved.

  In the embodiment of the present invention, examples of the compound (B) include a reaction product of a compound (b) having a hydroxyl group and / or an amino group and a compound (b ′) having an epoxy group and / or a carbodiimide group described below. . (B) The compound may be a low molecular compound, a polymer, or a condensate. (B) The structure of the 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 indicating 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 article can be improved. By setting the degree of branching to 0.05 or more, a crosslinked structure in the polyamide resin composition is sufficiently formed, and the fluidity, retention stability, mechanical strength, heat aging resistance, and surface appearance 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 crosslinking structure in the polyamide resin composition is appropriately suppressed, the dispersibility of the compound (B) in the polyamide resin composition is further increased, and the fluidity and the retention stability are maintained. , Mechanical strength, heat aging resistance, and surface appearance can be further improved. The degree of branching is more preferably 0.35 or less. The branching degree is defined by the following equation (2).
Degree of branching = (D + T) / (D + T + L) (2)
In the above formula (2), D represents the number of dendric units, L represents the number of linear units, and T represents the number of terminal units. Note that D, T, and L can be calculated from integrated values of peak shifts measured by ¹³ C-NMR. D is derived from a tertiary or quaternary carbon atom, T is derived from a primary carbon atom and is a methyl group, and L is derived from a primary or secondary carbon atom. Derived from those excluding T.

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

  The hydroxyl value of the compound (B) used in a preferred embodiment of the present invention is preferably from 100 to 2000 mgKOH / g. By setting the hydroxyl value of the compound (B) to 100 mgKOH / g or more, it becomes easy to sufficiently secure the reaction amount between the polyamide resin (A) and the compound (B), so that fluidity, retention stability, Mechanical strength, heat aging resistance, and surface appearance can be further improved. The hydroxyl value of the compound (B) is more preferably 300 mgKOH / g or more. On the other hand, when the hydroxyl value of the compound (B) is 2000 mgKOH / g or less, the reactivity between the (A) polyamide resin and the compound (B) is moderately increased, and the fluidity, the retention stability, the mechanical strength, and the heat aging resistance are increased. Properties and surface appearance can be further improved. Further, by setting the hydroxyl value of the compound (B) to 2000 mgKOH / g or less, gelation due to an excessive reaction can be suppressed. The hydroxyl value of the compound (B) 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 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 setting the amine value of the compound (B) to 100 mgKOH / g or more, it is easy to sufficiently secure the reaction amount between the polyamide resin (A) and the compound (B). Mechanical strength, heat aging resistance, and surface appearance can be further improved. The amine value of the compound (B) is more preferably 200 mgKOH / g or more. On the other hand, when the amine value of the compound (B) is 2,000 mgKOH / g or less, the reactivity between the polyamide resin (A) and the compound (B) is moderately increased. Aging property and surface appearance can be further improved. Further, by setting the amine value of the compound (B) to 2000 mgKOH / g or less, gelation of the polyamide resin composition due to an excessive reaction can be suppressed. The amine value of the compound (B) 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 a neutralization titration with an ethanolic hydrochloric acid solution.

  Examples of the compound (B) having a hydroxyl value or an amine value in the above-mentioned range include, for example, the following (b) a compound containing a hydroxyl group and / or an amino group and a compound (b ′) containing an epoxy group and / or a carbodiimide group. Reactants and the like.

  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, thereby further improving (A) compatibility with the polyamide resin, and further improving fluidity, retention stability, mechanical strength, heat aging resistance, and surface appearance. be able to.

  As the hydroxyl group and / or amino group-containing compound (b) used in the embodiment of the present invention, an aliphatic compound having three or more hydroxyl groups or three or more amino groups in one molecule is preferable. An aliphatic compound having three or more hydroxyl groups or three or more amino groups in one molecule is excellent in compatibility with (A) a polyamide resin, and has fluidity, retention stability, mechanical strength, heat aging resistance, and surface properties. The appearance can be further improved. The number of hydroxyl groups or the number of 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 lower steric hindrance than an aromatic compound or an alicyclic compound, and has excellent compatibility with the polyamide resin (A). It is considered that the properties, retention stability, mechanical strength, heat aging resistance, and surface appearance 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 weight compound, the number of hydroxyl groups or amino 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.). be able to. In the case of a polymer, the ratio of the monomer containing a hydroxyl group and / or an amino group contained in the polymer is a wt%, the number average molecular weight of the polymer is b, and the molecular weight of the monomer containing a hydroxyl group and / or an amino group is b. Where c is the average number of hydroxyl groups and / or amino groups = (a / 100) × b / c.

  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-methylpropane Punt triol, tris (hydroxymethyl) aminomethane, and the like 2-methyl-1,2,4-butanetriol. Further, as the hydroxyl group-containing compound, a hydroxyl group-containing compound having a repeating structural unit can also be mentioned. Examples 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 at least one hydroxyl group in which the carbon atom adjacent to the carboxyl group is a saturated carbon atom and all hydrogen atoms on the carbon atom are substituted. And a monocarboxylic acid having two or more hydroxyl groups. A 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 composed of 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 preferred.

  The hydroxyl value of the hydroxyl group-containing compound used in the embodiment of the present invention is preferably from 100 to 2000 mgKOH / g from the viewpoint of compatibility with the polyamide resin (A). By setting the hydroxyl value of the hydroxyl group-containing compound to 100 mgKOH / g or more, it becomes easy to sufficiently secure the reaction amount between (A) the polyamide resin and the hydroxyl group-containing compound. , Heat aging resistance and surface appearance can be further improved. The hydroxyl value of the hydroxyl group-containing compound is more preferably 300 mgKOH / g or more. On the other hand, by setting the hydroxyl value of the hydroxyl group-containing compound to 2000 mgKOH / g or less, the reactivity between (A) the polyamide resin and the hydroxyl group-containing compound is moderately increased, and the fluidity, the retention stability, the mechanical strength, the heat aging resistance, The surface appearance can be further improved. Further, by setting the hydroxyl value of the hydroxyl group-containing compound to 2000 mgKOH / g or less, gelation due to an excessive reaction can be suppressed. 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-containing compound with a mixed solution of acetic anhydride and pyridine and titrating the acetylated compound 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. Compounds and amino groups such as 1,1,2,3-tetraaminopropane, 1,2,3-triamino-2-methylaminopropane, 1,2,3,4-tetraaminobutane and isomers thereof are substituted with 4 Compounds having five amino groups such as 3,6,9-triazaundecane-1,11-diamine, 3,6,9,12-tetraazatetradecane-1,14-diamine, 1,1,2,2,3,3-hexaaminopropane, 1,1,2,3,3-pentaamino-2-methylaminopropane, 1,1,2,2,3,4-hexaaminobutane and the like Isomer 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 (i) a compound having an alkylene oxide unit introduced into the above-mentioned compound having an amino group, and (ii) three compounds in one molecule such as trimethylolpropane, pentaerythritol, and dipentaerythritol. The compound obtained by reacting the above-mentioned compound having a hydroxyl group and / or a compound in which the hydroxyl group is methyl-esterified with an alkylene oxide and further aminating the terminal group can also be mentioned.

  The amine value of the amino group-containing compound used in the embodiment of the present invention is preferably from 100 to 2000 mgKOH / g from the viewpoint of compatibility with the polyamide resin (A). By setting the amine value of the amino group-containing compound to 100 mgKOH / g or more, it is easy to sufficiently secure the reaction amount between (A) the polyamide resin and the amino group-containing compound. Mechanical strength, heat aging resistance, and surface appearance can be further improved. The amine value of the amino group-containing compound is more preferably 200 mgKOH / g or more. On the other hand, by setting the amine value of the amino group-containing compound to 2000 mgKOH / g or less, the reactivity between the polyamide resin (A) and the amino group-containing compound is moderately increased. Properties and surface appearance can be further improved. Further, 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 an 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 the 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 the amino group. Other functional groups include, for example, 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 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-containing and / or amino group-containing compound is 50 or more, the compound is less likely to volatilize during melt-kneading, and thus is excellent in processability. (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, when the molecular weight of the (b) hydroxyl group and / or amino group-containing compound is 10,000 or less, the compatibility between the compound (B) and the polyamide resin (A) becomes higher, so that the effect of the present invention becomes more remarkable. Is played. (B) The molecular weight of the hydroxyl group and / or amino group-containing compound is preferably 6,000 or less, more preferably 4000 or less, and even more preferably 800 or less.

  (B) The molecular weight of the compound containing a hydroxyl group and / or an amino group 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.). When the compound containing a hydroxyl group and / or an amino group is a condensate, the weight average molecular weight is used as the 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 and polymethyl methacrylate (PMMA) is used as a standard substance, and the column is adjusted to the solvent, for example, when hexafluoroisopropanol is used, Shimadzu Using "Shodex GPC HFIP-806M" and / or "Shodex GPC HFIP-LG" manufactured by GL Corporation, 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 fluidity, retention stability, mechanical strength, heat aging resistance, and surface appearance 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 crosslinking structure in the polyamide resin composition is appropriately suppressed, the dispersibility of the compound (B) in the polyamide resin composition is further increased, and the fluidity and the retention stability are maintained. , Mechanical strength, heat aging resistance, and surface appearance can be further improved. The degree of branching is preferably 0.35 or less. In addition, by using a compound having a hydroxyl group and / or an amino group having the degree of branching (b), the compound (B) having the degree of branching in the preferable range can be easily obtained. The branching degree is defined by the above equation (2).

  The epoxy group and / or carbodiimide group-containing compound (b ′) used in the embodiment of the present invention preferably has two or more epoxy and / or carbodiimide groups in one molecule, more preferably four or more. Preferably, it has more than six. Since the epoxy group and the carbodiimide group have excellent compatibility with the polyamide resin (A), the compound having two or more epoxy and / or carbodiimide groups in one molecule is compatible with the polyamide resin (A) and the compound (B). Is considered to be effective. (B ') The epoxy group and / or carbodiimide group-containing compound may be a low molecular compound or a polymer.

  In the case of a low molecular weight compound, the number of epoxy groups or carbodiimide 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.). can do. In the case of a polymer, the ratio of the monomer containing an epoxy group and / or a carbodiimide group contained in the polymer is set to a weight%, the number average molecular weight of the polymer is set to b, and the monomer containing an epoxy group and / or a carbodiimide group is contained. Is the average molecular weight of the epoxy group and / or carbodiimide group = (a / 100) × b / c.

  Specific examples of the epoxy group-containing compound include epichlorohydrin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, and glycidyl group-containing vinyl resin. Combination and the like can be exemplified. Two or more of these may be used.

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

  As the glycidyl ester type epoxy resin, 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 Examples thereof include tetraglycidyl melitate.

  As the glycidylamine type epoxy resin, an epoxy resin produced from epichlorohydrin, aniline, diaminodiphenylmethane, p-aminophenol, meta-xylylenediamine or 1,3-bis (aminomethyl) cyclohexane, tetraglycidylaminodiphenylmethane , Triglycidyl-paraaminophenol, triglycidyl-metaaminophenol, tetraglycidyl metaxylenediamine, 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 polymer include those obtained by radical polymerization of a raw material monomer forming a glycidyl group-containing vinyl unit. Specific examples of the raw material monomer forming the glycidyl group-containing vinyl unit include glycidyl (meth) acrylates, glycidyl esters of unsaturated monocarboxylic acids such as glycidyl p-styrylcarboxylate, and unsaturated monomers such as maleic acid and itaconic acid. Examples include monoglycidyl esters or polyglycidyl esters of polycarboxylic acids, unsaturated glycidyl ethers 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 Yakuhin Kogyo Co., Ltd., "Denacol" manufactured by Nagase ChemteX Corporation). (Registered trademark) EX-521 "), a polyfunctional epoxy compound containing polyethylene as a main component (for example," Bondfast "(registered trademark) E" manufactured by Sumitomo Chemical Co., Ltd.), and a multifunctional epoxy compound containing acryl as a main component. Functional epoxy compounds (for example, "Reseda" (registered trademark) GP-301 "manufactured by Toagosei Co., Ltd.," "ARUFON" (registered trademark) UG-4000 "manufactured by Toagosei Co., Ltd., manufactured by Mitsubishi Rayon Co., Ltd.) "" METABLEN "(registered trademark) KP-7653", a polyfunctional epoxy compound containing an acrylic / styrene copolymer as a main component (for example, "" oncryl "(registered trademark) -ADR-4368", "ARUFON" (registered trademark) UG-4040 manufactured by Toagosei Co., Ltd.), and a polyfunctional epoxy compound containing a silicone-acrylic copolymer as a main component (for example, , "" METABLEN "(registered trademark) S-2200"), and a polyfunctional epoxy compound containing polyethylene glycol as a main component (for example, "Epiol" (registered trademark) "E-1000" manufactured by NOF Corporation) , Bisphenol A type epoxy resin (eg, “jER” (registered trademark) “1004” manufactured by Mitsubishi Chemical Corporation) and novolak phenol type modified epoxy resin (eg, “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-hexadiene). Methylenecarbodiimide), 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-fe Lencarbodiimide), poly (tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (1,3,5-triisopropylbenzene) polycarbodiimide, poly (1,3,5-triisopropyl) Examples thereof include polycarbodiimides such as benzene) polycarbodiimide, poly (1,5-diisopropylbenzene) polycarbodiimide, poly (triethylphenylenecarbodiimide), and poly (triisopropylphenylenecarbodiimide).

  Examples of commercially available carbodiimide group-containing compounds include "Carbodilite" (registered trademark) manufactured by Nisshinbo Holdings Inc. and "Stabaxol (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 ') When the molecular weight of the epoxy group and / or carbodiimide group-containing compound is 800 or more, volatilization during melt kneading becomes difficult, so that processability is excellent. In addition, 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 the (B) compound becomes higher, and the retention stability is improved. Properties, mechanical strength, heat aging resistance, and surface appearance are further improved. (B ') The molecular weight of the epoxy group and / or carbodiimide group-containing compound is more preferably 1,000 or more, and still more preferably 2,000 or more. By setting the molecular weight of the (b ′) epoxy group and / or carbodiimide group-containing compound to 2000 or more, the compound (B) or (b) a hydroxyl group and / or an amino group-containing compound can be added to the surface layer of the molded article even during wet heat treatment. Bleed out can be further suppressed, and the surface appearance can be further improved. On the other hand, by setting the molecular weight of the epoxy group and / or carbodiimide group-containing compound (b ') to 10,000 or less, the viscosity at the time of melt-kneading can be appropriately suppressed, and thus the processability is excellent. Further, high compatibility between the polyamide resin (A) and the compound (b ') containing an epoxy group and / or a carbodiimide group or the compound (B) can be maintained. (B ') The molecular weight of the epoxy group and / or carbodiimide group-containing compound is more preferably 8,000 or less.

  (B ′) The molecular weight of the compound containing an epoxy group and / or a carbodiimide group 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. When the compound containing an epoxy group and / or a carbodiimide group is a condensate, the weight average molecular weight is used as the 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 and polymethyl methacrylate (PMMA) is used as a standard substance, and the column is adjusted to the solvent, for example, when hexafluoroisopropanol is used, Shimadzu Using "Shodex GPC HFIP-806M" and / or "Shodex GPC HFIP-LG" manufactured by GL Corporation, the weight average molecular weight can be measured using a differential refractometer as a detector.

  The epoxy group and / or carbodiimide group-containing 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 the compatibility between the (A) polyamide resin and the (b ′) epoxy group and / or carbodiimide group-containing compound or the (B) compound becomes higher, Fluidity, retention stability, mechanical strength, heat aging resistance, and surface appearance are further improved.

  In the embodiment of the present invention, 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, is 50 to 3000. Is preferred. Here, the number of functional groups refers to the total number of epoxy groups and carbodiimide groups. The smaller the value is, the higher the functional group concentration is. However, when the value is 50 or more, gelation due to an excessive reaction can be suppressed, and (A) a polyamide resin and (b) a hydroxyl group and / or an amino group-containing Since the reaction with the compound is moderately enhanced, fluidity, retention stability, mechanical strength, heat aging resistance, and surface appearance can be improved. (B ') The value obtained by dividing the molecular weight of the compound containing an epoxy group and / or a carbodiimide group by the number of functional groups in one molecule is more preferably 100 or more, and still more preferably 1100 or more. (B ′) By setting the value obtained by dividing the molecular weight of the epoxy group and / or carbodiimide group-containing compound by the number of functional groups in one molecule to 1100 or more, the surface of the molded product can be treated with (B) Bleed-out of the compound or (b) a compound containing a hydroxyl group and / or an amino group can be further suppressed, and the surface appearance can be further improved. On the other hand, by setting the value obtained by dividing the molecular weight of the (b ′) epoxy group and / or carbodiimide group-containing compound by the number of functional groups in one molecule to 3000 or less, (A) the polyamide resin and (b) the hydroxyl group and / or Alternatively, the reaction with the amino group-containing compound can be sufficiently ensured, and the fluidity, retention stability, mechanical strength, heat aging resistance, and surface appearance can be further improved. From this viewpoint, the value obtained by dividing the molecular weight of the (b ′) epoxy group and / or carbodiimide group-containing compound by the number of functional groups in one molecule is more preferably 2,000 or less, more preferably 1,000 or less, and 300 or less. More preferred.

  In an 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 represent OH, NH ₂ , CH ₃ or OR. However, the sum of the numbers of OH, NH ₂ and OR is 3 or more. R represents an organic group having an amino group, an epoxy group or a carbodiimide group, and n represents a range of 0 to 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 which may have a substituent, and examples of the substituent include an alkylene oxide group and an aryl group. Examples of the organic group having an epoxy group include an epoxy group, a glycidyl group, a glycidyl ether type epoxy group, a glycidyl ester type epoxy group, a glycidylamine type epoxy group, a hydrocarbon group substituted with an epoxy group or a glycidyl group, and an epoxy group. And a heterocyclic group substituted with a glycidyl group. Examples of the organic group having a carbodiimide group include an alkylcarbodiimide group, a cycloalkylcarbodiimide group, and an arylalkylcarbodiimide group.

  N in the general formula (1) represents a range of 0 to 20. When n is 20 or less, plasticization of the polyamide resin (A) is suppressed, and retention stability, mechanical strength, and heat aging resistance can be further improved. n is more preferably 4 or less, and can further improve retention stability, mechanical strength, and heat aging resistance. On the other hand, n is more preferably 1 or more, and the molecular mobility of the compound (B) can be increased, and the compatibility with the polyamide resin (A) 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, (A) the compatibility with the polyamide resin is excellent, and the heat aging resistance, dimensional accuracy, chemical resistance and creep resistance of the obtained molded article can be further improved. Here, the sum of the numbers of OH, NH _2, and OR specifies the structural formula of the compound by a general analysis method (for example, a combination of NMR, FT-IR, and GC-MS) in the case of a low molecular weight compound. , Can be calculated.

In the case of a condensate, the number of OH or NH ₂ is determined by calculating the number average molecular weight and the hydroxyl value or the amine value of the compound having the structure represented by the general formula (1) and / or the condensate thereof, and calculating the following formula (3 ).
The 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 ORs 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 be. 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 gel permeation chromatography (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 a 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 adjusted to the solvent. For example, when hexafluoroisopropanol is used, “Shodex GPC HFIP-806M” and / or “Shodex GPC HFIP-LG” manufactured by Shimadzu GC Co., Ltd. are 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 based on 100 parts by weight of the polyamide resin (A). When the content of the compound (B) is less than 0.1 part by weight, the fluidity and the retention stability at the time of molding are reduced, and the mechanical strength, heat aging resistance and color tone of the obtained molded product are reduced. The content of the compound (B) is preferably at least 0.5 part by weight, more preferably at least 2 parts by weight, based on 100 parts by weight of the polyamide resin (A). On the other hand, when the content of the compound (B) exceeds 20 parts by weight, the dispersibility of the compound (B) in the polyamide resin composition decreases, and the compound (B) easily bleeds out to the surface layer of the molded article, and the surface appearance Decrease. In addition, plasticization and decomposition of the polyamide resin are promoted, and fluidity, retention stability, mechanical strength, heat aging resistance, and color tone are reduced. The content of the compound (B) is preferably 7.5 parts by weight or less, more preferably 6 parts by weight or less, based on 100 parts by weight of the polyamide resin (A).

  The method for producing the compound (B) used in the embodiment of the present invention is not particularly limited. A method of dry blending and melt-kneading at a temperature higher than the melting points of both components is preferred.

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

  Examples of the catalyst that promotes the reaction between the hydroxyl group and the epoxy group include phosphines, imidazoles, amines, and diazabicyclos. Specific examples of phosphines include triphenylphosphine (TPP). Specific examples of imidazoles include 2-heptadecyl imidazole (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 that promotes the reaction between the hydroxyl group and the carbodiimide group include trialkyl lead alkoxide, hydrofluoric acid, zinc chloride, and sodium alkoxide.

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

  When the (B) compound is prepared by reacting the (b) hydroxyl- and / or amino-group-containing compound with the (b ') epoxy-group and / or carbodiimide-group-containing compound, the compounding ratio thereof is not particularly limited, B) Compounds such 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 the compound (B) and / or its condensate. Is preferably blended. The epoxy group and the carbodiimide group are more excellent in reactivity with the terminal group of the polyamide resin (A) than the hydroxyl group and the amino group. For this reason, by making the sum of the number of hydroxyl groups and amino groups in one molecule of the compound (B) larger than the sum of the number of epoxy groups and carbodiimide groups in one molecule of the compound (B), excessive crosslinking is achieved. Embrittlement due to formation of a structure is suppressed, and fluidity, retention stability, mechanical strength, heat aging resistance, surface appearance, and color tone can be further improved.

  The weight ratio ((b) / (b ′)) of the (b ′) hydroxyl group and / or amino group-containing compound to the (b ′) epoxy group and / or carbodiimide group-containing compound to be reacted is 0.3 or more and less than 10,000. It is preferable that (A) Reactivity of polyamide resin and (b ') epoxy group and / or carbodiimide group-containing compound, and (b) hydroxyl group and / or amino group-containing compound and (b') epoxy group and / or carbodiimide group-containing compound The reactivity is higher than the reactivity between (A) the polyamide resin and (b) the compound containing a hydroxyl group and / or an amino group. For this reason, when the weight ratio ((b) / (b ')) is 0.3 or more, gel formation due to excessive reaction is suppressed, and fluidity, retention stability, mechanical strength, heat aging resistance, surface The appearance and color tone are further improved.

  When the compound (B) is prepared by reacting (b) a compound containing a hydroxyl group and / or an amino group with a compound containing a (b ′) epoxy group and / or a carbodiimide group, a hydroxyl group or an amino group, an epoxy group or a carbodiimide group Is preferably 1 to 95%. When the reaction rate is 1% or more, the degree of branching of the compound (B) can be increased, the self-cohesive force can be reduced, the reactivity with the polyamide resin (A) can be increased, and the fluidity and retention stability can be improved. , Mechanical strength, heat aging resistance and surface appearance are further improved. The reaction rate is more preferably at least 10%, further preferably at least 20%. 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 the polyamide resin (A) can be increased. The reaction rate is more preferably 90% or less, and further preferably 70% or less. The reaction rate of the compound (B) can be further increased by including the below-mentioned (C) phosphorus-containing compound.

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

As an example, FIG. 1 shows a ¹ H-NMR spectrum of a product obtained by dry blending dipentaerythritol and bisphenol A type epoxy resin (“jER” (registered trademark) 1004, manufactured by Mitsubishi Chemical Corporation) at a weight ratio of 3: 1. . FIG. 2 shows the ¹ H-NMR spectrum of the compound (B-6) and / or its condensate obtained in Reference Example 9 described later. Deuterated dimethyl sulfoxide was used as a solvent, the sample amount was 0.035 g, and the solvent amount was 0.70 ml. Symbol 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 at around 2.60 ppm and 2.80 ppm was obtained, and similarly, the total of the peak areas shown in FIG. 4) Calculate the reaction rate from the above. At this time, the peak area is normalized by the area of the peak of the benzene ring of the epoxy resin that does not contribute to the reaction.

  The polyamide resin composition of the embodiment of the present invention contains (C) a phosphorus-containing compound. BACKGROUND ART Conventionally, phosphorus-containing compounds such as sodium hypophosphite have been used as a polycondensation catalyst when polycondensing a polyamide, and are known to have an effect of shortening the polymerization time and suppressing yellowing. On the other hand, when a phosphorus-containing compound is added to the polyamide resin at the time of compounding, the effect of suppressing yellowing is obtained, but the condensation of the polyamide resin is promoted during melt-kneading, so that the polyamide resin thickens and the fluidity increases. There is a problem that it decreases. On the other hand, in the embodiment of the present invention, by containing the (B) compound and the (C) phosphorus-containing compound, the fluidity and the retention stability of the polyamide resin composition are improved, and the heat aging resistance and the mechanical aging property are improved. A molded product excellent in strength, surface appearance and color tone can be obtained. This is because the (C) phosphorus-containing compound is more effective in promoting the improvement of the reaction rate of the (B) compound than the self-condensation of the (A) polyamide resin. By increasing the degree of branching of the compound (B) and reducing the self-cohesive force of the compound (B), the reactivity and compatibility with the polyamide resin (A) are further improved, and It is considered that the dispersibility of the compound (B) can be further improved.

  In the polyamide resin composition of the embodiment of the present invention, the phosphorus atom content is 180 to 3500 ppm with respect to the polyamide resin content. Here, the phosphorus atom content in the embodiment of the present invention indicates a concentration of a phosphorus element determined by an absorptiometric analysis method described later. That is, in the polyamide resin composition of the embodiment of the present invention, the content of the (C) phosphorus-containing compound is 180 to 3500 ppm with respect to the (A) polyamide resin content in terms of phosphorus atoms (weight basis). When the concentration in terms of phosphorus atoms is less than 180 ppm, the fluidity and the retention stability are reduced. In addition, the heat aging resistance, mechanical strength, and color tone of the molded product decrease. The concentration of (C) the phosphorus-containing compound in terms of phosphorus atom is preferably at least 300 ppm, more preferably at least 800 ppm, based on the content of the polyamide resin (A). On the other hand, if the (C) phosphorus atom-converted concentration exceeds 3500 ppm, the viscosity of the (A) polyamide resin becomes remarkable, and the fluidity decreases. Further, the gas generated by the decomposition of the phosphorus-containing compound (C) due to the heat generated by the shearing accelerates the decomposition of the polyamide resin (A) and the compound (B), and the retention stability, heat aging resistance and mechanical strength are reduced. Further, the phosphorus-containing compound (C) easily bleeds out to the surface layer of the molded article, and the surface appearance and color tone are reduced. The content of the (C) phosphorus-containing compound is preferably 3,000 ppm or less in terms of phosphorus atom, based on the content of the (A) polyamide resin.

  Here, the concentration of the phosphorus atom derived from the phosphorus-containing compound (C) relative to the polyamide resin content in the polyamide resin composition, that is, the phosphorus atom content can be determined by the following method. First, the polyamide resin composition or a molded article thereof is dried under reduced pressure, and then heated in an electric furnace at 550 ° C. for 24 hours to incinerate, and the content of the inorganic substance in the polyamide resin composition or the molded article is determined. When the resin composition contains a resin component other than the polyamide resin (A) such as an impact modifier, a compound (B), a phosphorus-containing compound (C) and other additives, the resin (A) is extracted and separated by an organic solvent. The weight of the components other than the polyamide resin or the polyamide resin (A) is measured, and the content of the polyamide resin (A) in the polyamide resin composition or the molded product thereof is calculated. On the other hand, phosphoric acid is decomposed by dry ashing in the presence of sodium carbonate or by wet decomposing in a sulfuric acid / nitric acid / perchloric acid system or a sulfuric acid / hydrogen peroxide aqueous system to form 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. The phosphorous content in the polyamide resin composition is calculated by performing colorimetry by measuring the phosphor content in the polyamide resin composition. By dividing the phosphorus content calculated by the colorimetric determination by the polyamide resin content calculated above, the concentration in terms of the phosphorus atom in the polyamide resin can be obtained.

  (C) Examples of the phosphorus-containing compound include a phosphite compound, a phosphate compound, a phosphonite compound, a phosphonate compound, a phosphinite compound, and a phosphinate compound. Two or more of these may be contained.

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

  Examples of the phosphate compound include phosphoric acid, alkyl phosphates, aryl phosphates, 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, alkyl phosphonite, aryl phosphonate, alkylated phosphonous acid, arylated phosphonous acid, their alkyl esters and aryl esters, and their metal salts. No. Specifically, phosphonous acid, dimethyl phosphonite, diethyl phosphonite, diphenyl phosphonite, methyl phosphonous acid, ethyl phosphonous acid, propyl phosphonous acid, isopropyl phosphonous acid, butyl phosphonous acid, phenyl Phosphonous 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, their alkyl esters or aryl esters, and their metal salts.

  Examples of the phosphonate compound include phosphonic acid, alkyl phosphonate, aryl phosphonate, alkylated phosphonate or arylated phosphonic acid, alkyl ester or aryl ester thereof, and metal salt thereof. Specifically, dimethyl phosphonate, diethyl phosphonate, diphenyl phosphonate, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic 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 phosphinous acid, alkyl phosphites, aryl phosphites, alkylated phosphinous acids, arylated phosphinous acids, their alkyl or aryl esters, and metal salts thereof. Can be Specifically, phosphinous acid, methyl phosphinite, ethyl phosphinite, phenyl phosphinite, methyl phosphinous acid, ethyl phosphinous acid, propyl phosphinous acid, isopropyl phosphinous acid, butyl phosphinous acid, phenyl Phosphinous acid, dimethyl phosphinous acid, diethyl phosphinous acid, dipropyl phosphinous acid, diisopropyl phosphinous acid, dibutyl phosphinous acid, diphenyl phosphinous acid, alkyl esters or aryl esters thereof, and metal salts thereof. Can be

  Examples of the phosphinate compound include hypophosphorous acid, alkyl hypophosphite, aryl hypophosphite, alkylated hypophosphorous acid, arylated hypophosphorous acid, their alkyl ester or aryl ester, and And the like. 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, dixylylphosphinic acid, dibiphenylylphosphinic acid, naphthylphosphinic acid, Examples include anthrylphosphinic acid, 2-carboxyphenylphosphinic acid, alkyl esters or aryl esters thereof, and metal salts thereof.

  Of these, phosphite compounds and phosphinate compounds are preferable, and these may be hydrates. It is more 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, the reaction rate of the compound (B) can be further increased while suppressing the thickening of the polyamide resin (A), and the degree of branching can be increased to reduce the self-cohesive force. Further, the fluidity and the retention stability during molding can be further improved, and the heat aging resistance, mechanical strength, surface appearance, and color tone 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 preferred.

  As a metal salt of phosphorous acid or hypophosphorous acid, specifically, lithium phosphite, sodium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, barium phosphite, hypophosphorous acid Examples 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. (A) While suppressing the thickening of the polyamide resin, B) Since the reaction rate of the compound can be further increased, and the degree of branching can be increased to reduce the self-cohesive force, the fluidity and retention stability at the time of molding can be further improved, and the heat aging resistance of the molded article, Mechanical strength, surface appearance, and color tone can be further improved.

  The polyamide resin composition of the embodiment of the present invention can further contain a copper compound. It is considered that the copper compound coordinates not only with the amide group of the polyamide resin (A) but also with the hydroxyl group and hydroxide ion of the compound (B). Therefore, it is considered that the copper compound has an effect of increasing the compatibility between the polyamide resin (A) and the compound (B).

  The polyamide resin composition of the embodiment of the present invention can further contain a potassium compound. The potassium compound suppresses release and precipitation of copper. Therefore, it is considered that the potassium compound has an effect of accelerating the reaction of the copper compound with the compound (B) and the polyamide resin (A).

  As the copper compound, for example, copper chloride, copper bromide, copper iodide, copper acetate, copper acetylacetonate, copper carbonate, copper borofluoride, copper citrate, copper hydroxide, copper nitrate, copper sulfate, copper oxalate And the like. Two or more of these may be contained as a copper compound. Among these copper compounds, industrially available ones are preferred, and copper halides are preferred. 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, potassium nitrate, and the like. Two or more of these may be contained as potassium compounds. Among these potassium compounds, potassium iodide is preferred. By including the potassium compound, the surface appearance, weather resistance and mold corrosion resistance of the molded article can be improved.

  The content (weight basis) of the copper element in the polyamide resin composition of the embodiment of the present invention is preferably 25 to 200 ppm. When the content of the copper element is 25 ppm or more, the compatibility between the polyamide resin (A) and the compound (B) is further improved, and the heat aging resistance of the molded article 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, when the content of the copper element is 200 ppm or less, coloring due to precipitation and release of the copper compound can be suppressed, and the surface appearance of the molded article can be further improved. Further, by setting the content of the copper element to 200 ppm or less, a decrease in the hydrogen bonding force of the amide group due to the excessive coordination bond between the polyamide resin and copper is suppressed, and the heat aging resistance of the molded article is further improved. be able to. The content (weight basis) of the copper element in the polyamide resin composition is preferably 190 ppm or less. The content of the copper element in the polyamide resin composition can be adjusted to the above-described desired range by appropriately adjusting the amount of the copper compound.

  The content of the 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 pellets are ashed in an electric furnace at 550 ° C. for 24 hours, concentrated sulfuric acid is added to the ash, and the mixture is heated and wet-decomposed to dilute the decomposition solution. The copper content can be determined by performing an atomic absorption analysis (calibration curve method) on the diluted solution.

  The ratio Cu / K of the content of the copper element to the content of the potassium element in the polyamide resin composition is preferably 0.21 to 0.43. Cu / K is an index indicating the degree of suppression of the precipitation and release of copper. As this value is smaller, the precipitation and release of copper are suppressed, and the copper compound, the compound (B) and the polyamide resin (A) Can promote the reaction. By setting Cu / K to 0.43 or less, the precipitation and release of copper can be suppressed, and the surface appearance of the molded article can be further improved. Further, by setting Cu / K to 0.43 or less, the compatibility of the polyamide resin composition is also improved, so that the heat aging resistance of the molded product can be improved. On the other hand, by setting Cu / K to 0.21 or more, the dispersibility of the potassium-containing compound is improved, and even in the case of deliquescent potassium iodide, it is difficult to form a lump, and the effect of suppressing the precipitation and release of copper is reduced. As a result, the reaction between the copper compound, the compound (B) and the polyamide resin (A) is sufficiently promoted, and the heat aging resistance of the molded product is further improved. The potassium element content in the polyamide resin composition can be determined by the same method as the above copper content.

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

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

  The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, it can be selected from long fiber type or short fiber type chopped strand, milled fiber and the like. 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. Further, the cross section of the glass fiber is not limited to a circular, flat gourd, cocoon, ellipse, ellipse, rectangle, or similar products. From the viewpoint of reducing the characteristic warpage of a molded product that is likely to occur in a glass fiber-containing polyamide resin composition, a flat fiber having a ratio of major axis / minor axis of 1.5 or more is preferable, and 2.0 or more is more preferable. , Preferably 10 or less, more preferably 6.0 or less. If the ratio of major axis / minor axis is less than 1.5, the effect of flattening the cross section is small, and if it is larger than 10, it is difficult to produce the glass fiber itself.

  Examples of the non-fibrous filler include, for example, non-swellable silicates such as talc, wollastenite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, calcium silicate, and Li-type fluorine Swellable layered silicate represented by teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluoromica, Li-type tetrasilicon fluoromica, silicon oxide, magnesium oxide, alumina, silica, diatomaceous earth, zirconium oxide, oxidation Metal oxides such as titanium, iron oxide, zinc oxide, calcium oxide, tin oxide and antimony oxide; metal carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dolomite, hydrotalcite, calcium sulfate, and barium sulfate Such as metal sulfates and hydroxides Metal hydroxides such as nesium, calcium hydroxide, aluminum hydroxide, and basic magnesium carbonate; smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and sauconite; vermiculite; halloysite; kanemite; Examples include various clay minerals such as zirconium phosphate and titanium phosphate, glass beads, glass flakes, ceramic beads, boron nitride, aluminum nitride, silicon carbide, calcium phosphate, carbon black, and graphite. In the above-mentioned swellable phyllosilicate, exchangeable cations existing between layers may be exchanged with organic onium ions, and examples of the organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Further, two or more of these fillers may be contained.

  The surface of the filler is a known coupling agent (for example, a silane-based coupling agent or a titanate-based coupling agent) or a known sizing agent (for example, a carboxylic acid-based, epoxy-based, or urethane-based). Or the like, and the mechanical strength and surface appearance of the molded product can be further improved. As the sizing agent, an epoxy sizing agent is preferable. As a method for treating the filler, for example, in the case of treatment with a coupling agent, a method in which the filler is subjected to a surface treatment with a coupling agent in advance according to a conventional method and then melt-kneaded with a polyamide resin is preferably used. When the filler and the polyamide resin are melt-kneaded without performing the surface treatment described above, an integrable blending method in which a coupling agent is added may be used. The processing amount of the coupling agent is preferably at least 0.05 part by weight, more preferably at least 0.5 part by weight, based on 100 parts by weight of the filler. On the other hand, the processing amount of the coupling agent is preferably 10 parts by weight or less, more preferably 3 parts by weight or less, based on 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 from 1 to 150 parts by weight based on 100 parts by weight of the polyamide resin (A). When the content of the filler is 1 part by weight or more, the mechanical strength and heat aging resistance of the molded product can be further improved. The content of the filler is more preferably at least 10 parts by weight, further preferably at least 20 parts by weight. On the other hand, when the content of the filler is 150 parts by weight or less, floating of the filler on the surface of the molded article is suppressed, and a molded article having more excellent surface appearance can be obtained. The content of the filler is more preferably 80 parts by weight or less, and further preferably 70 parts by weight or less.

  Furthermore, the polyamide resin composition of the embodiment of the present invention can contain a resin other than the polyamide resin and various additives depending on the purpose, as long as the effects of the present invention are not impaired.

  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, polyethersulfone resins, polyetherketone resins, and polythioethers. Ketone resin, polyether ether ketone resin, polyimide resin, polyamide imide resin, polyethylene tetrafluoride resin, and the like can be given. When these resins are blended, the content is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the polyamide resin (A) 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, coupling agents such as epoxy compounds, polyalkylene oxide oligomers. -Based compounds, plasticizers such as thioether-based compounds and ester-based compounds, crystal nucleating agents such as polyetheretherketone, montanic acid waxes, metal soaps such as lithium stearate and aluminum stearate, ethylenediamine / stearic acid / sebacic acid heavy Examples thereof include condensates, release agents such as silicone compounds, lubricants, UV inhibitors, coloring agents, flame retardants, impact modifiers, and foaming agents. When these additives are contained, the content is preferably at most 10 parts by weight, more preferably at most 1 part by weight, based on 100 parts by weight of the polyamide resin (A) in order to make full use of the characteristics of the polyamide resin.

  Examples of the heat stabilizer other than the copper compound include a phenol compound, a sulfur compound, and an amine compound. As the heat stabilizer other than the copper compound, two or more of these may be used.

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

  Examples of the sulfur compound include an organic thioacid compound, a mercaptobenzimidazole compound, a dithiocarbamic acid compound, and a thiourea compound. Among these sulfur compounds, mercaptobenzimidazole compounds and organic thioacid compounds are preferred. 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 the thioether compound include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, ditetradecylthiodipropionate, dioctadecylthiodipropionate, and 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 exemplified. More preferred are N, N′-di-2-naphthyl-p-phenylenediamine and 4,4′-bis (α, α-dimethylbenzyl) diphenylamine.

  As the combination of the sulfur compound or the 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 according to 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. Can be preferably used. For production in a molten state, melt kneading using an extruder or melt kneading using a kneader can be used, but from the viewpoint of productivity, melt kneading using an extruder capable of continuous production is preferable. For the melt kneading by an extruder, one or more extruders such as a multi-screw extruder such as a single-screw extruder, a twin-screw extruder, and a 4-screw extruder, and a twin-screw single-screw extruder can be used. From the viewpoint of improvement in 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 the polyamide resin composition of the embodiment of the present invention, the compound (B) prepared in advance from (b) a compound containing a hydroxyl group and / or an amino group and (b ′) a compound containing an epoxy group and / or a carbodiimide group is used. (A) a method of melt-kneading with a polyamide resin and (C) a phosphorus-containing compound, and (A) a polyamide resin containing (b) a compound containing a hydroxyl group and / or an amino group and (b ′) a compound containing an epoxy group and / or a carbodiimide group. , (C) a phosphorus-containing compound and melt-kneading 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 color tone. In the embodiment of the present invention, the (C) phosphorus-containing compound is preferably compounded together with the (A) polyamide resin and the (B) compound at the time of compounding. By blending the (C) phosphorus-containing compound at the time of compounding, the fluidity and retention stability during molding of the polyamide resin composition are further improved, and the heat aging resistance, mechanical strength, surface appearance, and color tone are further improved. Can be.

  When melt-kneading using a twin-screw extruder, there is no particular limitation on the method of supplying raw materials to the twin-screw extruder. (B) When a compound is supplied as a raw material to a twin-screw extruder, or (b) a hydroxyl- and / or amino-group-containing compound and (b ') an epoxy-group and / or carbodiimide-group-containing compound are supplied to a twin-screw extruder In this case, the compound (B) or (b) a hydroxyl group and / or an amino group-containing compound easily promotes decomposition of the polyamide resin in a temperature range higher than the melting point of the polyamide resin. And / or the amino group-containing compound is supplied from the downstream side of the polyamide resin supply position to shorten the kneading time of (A) the polyamide resin and the (B) compound or (b) the hydroxyl group and / or the amino group-containing compound. preferable. Further, the method for supplying the (C) phosphorus-containing compound comprises: (A) a reaction rate of the compound (B) or (b) a compound containing a hydroxyl group and / or an amino group, while suppressing a viscosity increase of the polyamide resin. ) From the viewpoint of increasing the reaction rate of the epoxy group and / or carbodiimide group-containing compound, together with the (B) compound or (b) the hydroxyl group and / or amino group-containing compound, the (A) is supplied from the downstream side of the polyamide resin supply position. Is preferred. In addition, (b ′) the epoxy group and / or carbodiimide group-containing compound may be supplied to the twin screw extruder together with the polyamide resin (A), or may be supplied from the downstream side of the polyamide resin supply position. , Preferably from the downstream side. Here, the side of the twin-screw extruder where the raw material is supplied is defined as upstream, and the side where the molten resin is discharged is defined as downstream. Hereinafter, a case where the compound (B) and the phosphorus-containing compound (C) are supplied to a twin-screw extruder will be described by way of example, but (b) a hydroxyl- and / or amino-group-containing compound and (b ′) an epoxy group and / or a carbodiimide The same applies to the case where the group-containing compound is supplied to a twin-screw extruder.

  It is considered that the copper compound plays a role of protecting the amide group by coordinating to the amide group of the polyamide resin (A), and also serves as a compatibilizer of the polyamide resin (A) and the compound (B). Therefore, when compounding a copper compound, it is preferable to supply the mixture to the twin screw extruder together with the polyamide resin (A) and to sufficiently react the polyamide resin (A) with the copper compound.

  The ratio (L / D) of the total screw length L to the screw diameter D of the twin-screw extruder is preferably 25 or more, and more preferably more than 30. When the L / D is 25 or more, it becomes easy to supply the (B) compound and the (C) phosphorus-containing compound after sufficiently kneading the (A) polyamide resin and, if necessary, the copper compound. When a copper compound is blended, it becomes easy to supply the compound (B) and the phosphorus-containing compound (C) after sufficiently kneading the (A) polyamide resin and the copper compound. As a result, the decomposition of the polyamide resin (A) can be suppressed. Further, it is considered that the compatibility between the polyamide resin (A) and the compound (B) is further improved, and the fluidity and retention stability at the time of molding are further improved. Can be further improved.

  In the embodiment of the present invention, it is preferable that at least (A) the polyamide resin and, if necessary, the copper compound are supplied to the twin-screw extruder from an upstream side of ス ク リ ュ ー of the screw length and melt-kneaded. It is more preferable to supply from the upstream end. Here, the screw length is the length from the upstream end of the screw segment at the position (feed port) where the polyamide resin is supplied (feed port) at the root of the screw to the tip of the screw. The upstream end of the screw segment refers to the position of the screw piece located at the most upstream end of the screw segment connected to the extruder.

  The compound (B) and the phosphorus-containing compound (C) are preferably supplied to a twin-screw extruder from a downstream side of a half of the screw length and melt-kneaded. By supplying the compound (B) and the phosphorus-containing compound (C) from a downstream side of ス ク リ ュ ー of the screw length, the (A) polyamide resin and, if necessary, the copper compound are sufficiently kneaded, and then (B) ) And (C) the phosphorus-containing compound. As a result, the reaction rate of the compound (B) can be increased while suppressing the viscosity increase of the polyamide resin (A), the degree of branching can be increased, and the self-cohesive force can be reduced. It is considered that the compatibility of the compound (B) increases. As a result, the fluidity and the retention stability during molding are excellent, and the heat aging resistance, mechanical strength, surface appearance, and color tone of the molded product can be further improved.

  When manufacturing the polyamide resin composition of the embodiment of the present invention using a twin-screw extruder, from the viewpoint of improving kneading and reactivity, twin-screw extrusion having a plurality of full flight zones and a plurality of kneading zones. 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 disks.

Further, assuming that the maximum resin pressure among the resin pressures at a plurality of kneading zones is Pkmax (MPa) and the minimum resin pressure among the resin pressures at a plurality of full flight zones is Pfmin (MPa). ,
Pkmax ≧ Pfmin + 0.3
It is preferable to melt and 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 the kneading zone and the full flight zone indicates the resin pressure indicated by the resin pressure gauge installed in each zone.

  The kneading zone is more excellent in the kneadability and reactivity of the molten resin than the full flight zone. By filling the kneading zone with the molten resin, kneading properties and reactivity are dramatically improved. One index that indicates the state of filling of the molten resin is the value of the resin pressure, and the greater the resin pressure, the more an indicator that the molten resin is full. 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. The dispersibility of the contained compound can be increased. As a result, it is considered that the compatibility between the polyamide resin (A) and the compound (B) is increased, and the heat aging resistance, mechanical strength, surface appearance, and color tone of the molded product can be further improved.

  The method of increasing the resin pressure in the kneading zone is not particularly limited.For example, between the kneading zone or on the downstream side of the kneading zone, a reverse screw zone having an effect of pushing back the molten resin to the upstream side, A method of introducing a seal ring zone or the like having a storage effect can be preferably used. The reverse screw zone and the seal ring zone are formed from one or more reverse screws and one or more seal rings, and it is also possible to combine them.

  When the total length of the kneading zone on the upstream side of the supply position of the (B) compound and the (C) phosphorus-containing compound is Ln1, Ln1 / L is preferably 0.02 or more, and 0.03 or more. Is more preferable. On the other hand, Ln1 / L is preferably at most 0.40, more preferably at most 0.20. By setting Ln1 / L to 0.02 or more, the reactivity of the polyamide resin (A) can be increased, and by setting it to 0.40 or less, shear heat generation is appropriately suppressed to suppress thermal degradation of the resin. be able to. The melting temperature of the (A) polyamide resin is not particularly limited, but is preferably 340 ° C. or lower in order to suppress a decrease in the molecular weight of the (A) polyamide resin due to thermal degradation.

  Assuming that the total length of the kneading zone on the downstream side of the supply position of the (B) compound and the (C) phosphorus-containing compound 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, the decomposition of the polyamide resin (A) 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) the polyamide resin and the (B) compound are melt-kneaded with a twin-screw extruder to prepare a high-concentration premix, and the high-concentration premix is prepared. Is further melt-kneaded with a (A) polyamide resin and a (C) phosphorus-containing compound by a twin-screw extruder. (A) 100 parts by weight of the polyamide resin is melt-kneaded with 10 to 250 parts by weight of the compound (B) to prepare a high-concentration premix, and the high-concentration premix is further mixed with the (A) polyamide resin and (C). It is more preferable to melt-knead with a phosphorus-containing compound using a twin-screw extruder. Compared to a case where a high-concentration premix is not prepared, the fluidity during molding is more excellent, and the heat-aging resistance and mechanical strength of the obtained molded product can be further improved. The reason for this is not clear, but it is considered that the compatibility between the components is further improved by melt-kneading twice. Further, when preparing a high-concentration preliminary mixture, the compounding amount of the compound (B) increases with respect to the polyamide resin (A). In order to suppress a decrease in retention stability, the compound (B) is supplied from the downstream side of the polyamide resin supply position during melt-kneading with a twin-screw extruder, and the kneading time of the (A) polyamide resin and the (B) compound is reduced. Is preferably shortened. The polyamide resin (A) used for the high-concentration premix and the polyamide resin (A) further mixed with the high-concentration premix may be the same or different. As the polyamide resin (A) used for the high-concentration premix, nylon 6, nylon 11 and / or nylon 12 are preferred from the viewpoint of further improving the heat aging resistance of the molded article.

  The polyamide resin composition thus obtained can be molded by a known method, and various molded articles 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 and the molded article thereof are utilized for various uses such as automobile parts, electric / electronic parts, building members, various containers, daily necessities, household goods and sanitary goods, by utilizing the excellent properties. be able to. Polyamide resin composition of the embodiment of the present invention and molded articles thereof are, among others, fluidity, retention stability, heat aging resistance, mechanical strength, surface appearance and color tone are required for automobile engine peripheral parts, automobile underhood parts, It is particularly preferably used for automobile gear parts, automobile interior parts, automobile exterior parts, intake / exhaust system parts, engine cooling water system parts, automobile electric parts, and electric / electronic parts. Specifically, the polyamide resin composition of the embodiment of the present invention and a molded product thereof include an engine cover, an air intake pipe, a timing belt cover, an intake manifold, a filler cap, a throttle body, peripheral parts of an automobile engine such as a cooling fan, Automotive underhood parts such as cooling fans, radiator tank tops and bases, cylinder head covers, oil pans, brake piping, fuel piping tubes, exhaust gas system parts, gears, actuators, bearing retainers, bearing cages, chain guides, and chain tensioners Such as automotive gear parts, shift lever bracket, steering lock bracket, key cylinder, door inner handle, door handle cowl, interior mirror bracket, Automotive interior parts such as AC switches, instrument panels, console boxes, glove boxes, steering wheels, trims, front fenders, rear fenders, fuel lids, door panels, cylinder head covers, door mirror stays, tailgate panels, licensed garnishes, roof rails, engine mounts Automotive exterior parts such as brackets, rear garnish, rear spoiler, trunk lid, rocker molding, molding, lamp housing, front grill, mudguard, side bumper, air intake manifold, intercooler inlet, turbocharger, exhaust pipe cover, inner bush, bearing Retainer, engine mount, engine head cover, Intake / exhaust system parts such as a norator and throttle body, chain cover, thermostat housing, outlet pipe, radiator tank, oil cooler, engine cooling water system parts such as delivery pipe, connectors and wire harness connectors, motor parts, lamp sockets, sensors Automotive electrical components such as in-vehicle switches and combination switches, and electrical and electronic components include, for example, generators, motors, transformers, current transformers, voltage regulators, rectifiers, resistors, inverters, relays, power contacts, switching Breaker, circuit breaker, switch, knife switch, other pole rod, motor case, laptop housing and internal parts, CRT display housing and internal parts, printer housing and internal parts, mobile phone, mobile phone Mobile terminal housings and internal parts such as Sokon and handheld mobiles, IC and LED housings, condenser seats, fuse holders, various gears, various cases, cabinets and other electrical parts, connectors, SMT compatible connectors, card connectors, jacks , Coils, coil bobbins, sensors, LED lamps, sockets, resistors, relays, relay cases, reflectors, small switches, power supplies, coil bobbins, capacitors, variable condenser cases, optical pickup chassis, oscillators, various terminal boards, transformers, plugs , Printed circuit board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, Si power module and SiC power module, semiconductor, liquid crystal, FDD carrier , FDD chassis, motor brush holders, transformer members, parabolic antenna, is preferably used in electronic components such as computer-related parts.

  Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. Characteristic evaluation was performed according to the following method.

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

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

[Phosphorus atom content with respect to polyamide resin in polyamide resin composition]
The pellets obtained in each of the Examples and Comparative Examples 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. Next, the pellets were 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 weight of the inorganic substance and the additives from the weight of the polyamide resin composition.

  Next, the polyamide resin composition pellets were wet-decomposed in a sulfuric acid / hydrogen peroxide aqueous system, and the decomposition liquid was diluted with phosphorus as orthophosphoric acid. 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. The amount of phosphorus in the polyamide resin composition was calculated by colorimetric measurement by measuring with a linear method. The phosphorus content calculated by the colorimetric determination was divided by the polyamide resin content calculated above to obtain the phosphorus atom content with respect to the polyamide resin content. The spectrophotometer used was U-3000 manufactured by Hitachi, Ltd.

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

[Weight average molecular weight and number average molecular weight]
2.5 mg of the compound (B), the compound (B ′), the compound (b) containing a hydroxyl group and / or an amino group, and the compound (b ′) containing an epoxy group and / or a carbodiimide group were each added with hexafluoroisopropanol (0.005N- The resulting solution was dissolved in 4 ml of sodium trifluoroacetate (added with sodium trifluoroacetate) and filtered through a 0.45 μm filter to obtain a solution. The measurement conditions are shown below.
Apparatus: Gel permeation chromatography (GPC) (Waters)
Detector: Differential refractometer Waters410 (manufactured by Waters)
Column: Shodex GPC HFIP-806M (2) + HFIP-LG (Shimadzu GLC)
Flow rate: 0.5 ml / min
Sample injection volume: 0.1 ml
Temperature: 30 ° C
Molecular weight calibration: polymethyl methacrylate.

[Hydroxyl value]
(B) 0.5 g of a hydroxyl group-containing compound, a compound (B) and a compound (B ′) are collected and added to a 250 ml Erlenmeyer flask, and then acetic anhydride and pyridine anhydride are adjusted and mixed at 1:10 (mass ratio). 20.00 ml of the solution was collected, placed in the Erlenmeyer flask, fitted with a reflux condenser, refluxed with stirring for 20 minutes 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 through the condenser into the Erlenmeyer flask. 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 (excluding the sample) measured separately.
Hydroxyl value [mgKOH / g] = [((BC) × f × 28.05) / S] + E (5) where B: 0.5 mol / L of ethanolic potassium hydroxide solution used for titration Amount [ml], C: Amount [ml] of 0.5 mol / L ethanolic potassium hydroxide solution used for blank titration, f: Factor of 0.5 mol / L ethanolic potassium hydroxide solution, S: Mass [g] of sample, E: represents an acid value.

[Amine value]
0.5 to 1.5 g of the (b) amino group-containing compound and the (B) compound were precisely weighed and dissolved in 50 ml of ethanol, respectively. This solution was neutralized and titrated with a 0.1 mol / L ethanolic hydrochloric acid solution using a potentiometric titrator equipped with a pH electrode (AT-200, manufactured by Kyoto Electronics Industry Co., Ltd.). Using the inflection point of the pH curve as the titration end point, the amine value was calculated by the following equation (6).
Amine value [mgKOH / g] = (56.1 × V × 0.1 × f) / W (6)
Here, W represents the weighed amount of the sample [g], V represents the titer at the end of the titration [ml], and f represents the factor of a 0.1 mol / L ethanolic hydrochloric acid solution.

[Reaction rate of compound (B)]
(B) 0.035 g of the compound was dissolved in 0.7 ml of deuterated dimethyl sulfoxide, and ¹ H-NMR measurement was performed for an epoxy group, and ¹³ C-NMR measurement was performed for a carbodiimide group. Each analysis condition is as follows.
(1) ¹ H-NMR
Apparatus: JEOL Ltd. nuclear magnetic resonance apparatus (JNM-AL400)
Solvent: deuterated dimethyl sulfoxide Observation frequency: OBRQ 399.65 MHz, OBSET 124.00 KHz, OBFIN 105000.00 Hz
Number of integrations: 256 (2) ¹³ C-NMR
Apparatus: JEOL Ltd. nuclear magnetic resonance apparatus (JNM-AL400)
Solvent: deuterated dimethyl sulfoxide Observation frequency: OBRQ 100.40 MHz, OBSET 125.00 KHz, OBFIN 105000.00 Hz
Number of integration: 512 times.

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

As an example, dipentaerythritol and bisphenol A type epoxy resin "Mitsubishi Chemical Co., Ltd. Ltd." jER "(registered trademark) 1004 3: ¹ H-NMR spectrum but was dry blended in a weight ratio of 1 shown. also from ¹ H-NMR spectrum shows a ¹ H-NMR spectrum of the obtained in reference example 9 (B-6) compounds in. Figure 1 shown in FIG. 2, an epoxy ring appearing in the vicinity of 2.60ppm and 2.80ppm The total area of the peaks derived was determined, the total of the peak areas shown in Fig. 2 was similarly calculated, and the reaction rate was calculated from the reaction rate calculation formula (4), where the peak area did not contribute to the reaction. It was normalized by the area of the ring peak.

[Branch degree]
After the compound (B) and the compound (B ′) were analyzed by ¹³ C-NMR under the following conditions, the degree of branching (DB) was calculated by the following formula (2).
Degree of branching = (D + T) / (D + T + L) (2)
In the above formula (2), D represents the number of dendric units, L represents the number of linear units, and T represents the number of terminal units. The above D, T, and L were calculated from the peak areas measured by ¹³ C-NMR. D is derived from a tertiary or quaternary carbon atom, T is derived from a primary carbon atom and is a methyl group, and L is derived from a primary or secondary carbon atom. Derived from those excluding T. The peak area was calculated by integrating the area of the portion 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: JEOL Ltd. nuclear magnetic resonance apparatus (JNM-AL400)
Solvent: Deuterated dimethyl sulfoxide measurement sample amount / solvent amount: 0.035 g / 0.70 ml
Observation frequency: OBFRQ100.40MHz, OBSET125.00KHz, OBFIN10500.00Hz
Number of integration: 512 times.

[Sum of the number of hydroxyl groups and amino groups and sum of the number of epoxy groups and carbodiimide groups of the compounds (B) and (B ')]
The number of OH or NH ₂ was calculated by calculating the number average molecular weight and the hydroxyl value or the amine value of the compound (B) and the compound (B ′) and using the following formula (3).
OH or NH ₂ number = (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 compound (B) or compound (B ') by the epoxy equivalent or carbodiimide equivalent.

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

The carbodiimide equivalent was calculated by the following method. (B) 100 parts by weight of the 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 hot-pressed at about 200 ° C. for 1 minute to prepare a sheet. Thereafter, the infrared absorption spectrum of the sheet was measured by a transmission method using an infrared spectrophotometer (IR Prestige-21 / AIM8800, manufactured by Shimadzu Corporation). The measurement conditions were a resolution of 4 cm ^-1 and a cumulative number of 32 times. In the infrared absorption spectrum by 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 an internal standard peak. A value was calculated by dividing the absorbance of the peak derived from the carbodiimide group appearing around 2140 cm ^{-1 by} the absorbance of the CN group absorption peak of potassium ferrocyanide appearing around 2100 cm ^-1 . In order to calculate the carbodiimide equivalent from this value, IR measurement is performed using a sample whose carbodiimide equivalent is known in advance, and a calibration curve is created using the ratio of the absorbance of the peak derived from the carbodiimide group to the absorbance of the internal standard peak, B) The carbodiimide equivalent was calculated by substituting the absorbance ratio of the compound into a calibration curve. In addition, as a sample whose carbodiimide equivalent is known, aliphatic polycarbodiimide (manufactured by Nisshinbo, "Carbodilite" (registered trademark) LA-1, carbodiimide equivalent 247 g / mol), aromatic polycarbodiimide (manufactured by Rhine Chemie, "Stabaxol" (registered trademark) ) P, carbodiimide equivalent 360 g / mol).

[Tensile strength]
The pellets obtained in each of the Examples and Comparative Examples were dried under reduced pressure at 80 ° C. for 12 hours, and the cylinder temperature of the polyamide resin (A) was determined using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.). An ASTM No. 1 dumbbell specimen having a thickness of 3.2 mm was prepared by injection molding under the conditions of a melting point of + 15 ° C. and a mold temperature of 80 ° C. (160 ° C. in Example 26). This test piece was subjected to a tensile test at a crosshead speed of 10 mm / min using a tensile tester Tensilon UTA2.5T (manufactured by Orientec) in accordance with 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 higher the tensile strength, the better the mechanical properties.

[Liquidity]
The pellets obtained in each of the Examples and Comparative Examples were vacuum-dried at 80 ° C. for 12 hours, and cylinder temperature: (A) melting point of polyamide resin + 15 using an injection molding machine (ROBOSHOT α-30C, manufactured by FANUC). C., mold temperature: 80.degree. C. (160.degree. C. in Example 26), injection pressure: 98 MPa, and injection molding using a mold having a length of 200 mm.times.10 mm.times.0.5 mm. A 5 mm thick rod flow test piece was prepared. The rod flow length at a holding pressure of 0 was measured for each of the five samples, the average value was determined, and the fluidity was evaluated. The longer the flow length, the better the fluidity.

[Heat aging resistance]
The pellets obtained in each of the Examples and Comparative Examples were dried under reduced pressure at 80 ° C. for 12 hours, and the cylinder temperature of the polyamide resin (A) was determined using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.). An ASTM No. 1 dumbbell specimen having a thickness of 3.2 mm was prepared by injection molding under the conditions of a melting point of + 15 ° C. and a mold temperature of 80 ° C. (160 ° C. in Example 26). This test piece was subjected to a tensile test at a crosshead speed of 10 mm / min using a tensile tester Tensilon UTA2.5T (manufactured by Orientec) in accordance with 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. Then, the ASTM No. 1 dumbbell test piece was heat-treated at 135 ° C. in an air-gear oven for 3000 hours, or 190 ° C. in an air-gear oven for 2000 hours, or 240 ° C. in an air-gear oven for 2000 hours (heat aging). Test), the same tensile test was performed on the treated test piece, and the average value of three measurements was calculated as the tensile strength after the heat aging test. The ratio of the tensile strength after the treatment to the tensile strength before the heat aging test was calculated as the tensile strength retention. The higher the tensile strength retention, the better the heat aging resistance.

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

[Surface appearance]
The pellets obtained in each of the Examples and Comparative Examples were dried under reduced pressure at 80 ° C. for 12 hours, and the cylinder temperature of the polyamide resin (A) was determined using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.). Melting point + 15 ° C, Mold temperature: 80 ° C (Example 26: 160 ° C), Injection / cooling time: 10/10 seconds, Screw rotation speed: 150 rpm, Injection pressure: 100 MPa, Injection speed: 100 mm / sec. A square plate (film gate) having a thickness of 80 mm x 80 mm x 3 mm was injection molded. The obtained square plate was heat-treated at 140 ° C. for 1 hour in the atmosphere, and the state of the surface of the square plate after the treatment was visually observed and evaluated according to the following criteria.
A: The color tone of the molded product is white, and no bleeding is observed on the surface.
B: The color tone of the molded product is slightly bluish white or reddish brown, and no bleeding is observed on the surface.
C1: The color tone of the molded product is bluish white or reddish brown, and no bleeding is observed on the surface.
C2: The color tone of the molded product is white, and bleeding is observed on the surface.
Here, the bleeding refers to a material that has emerged on the surface of the molded article. When the (b) compound containing a hydroxyl group and / or an amino group, or the compound (B) or the compound (B ′) is solid at room temperature, it is like a dusting cloth. When the compound (b) containing a hydroxyl group and / or an amino group, the compound (B) or the compound (B ′) is liquid at room temperature, it becomes a viscous liquid.

[Tone]
The pellets obtained in each of the Examples and Comparative Examples were dried under reduced pressure at 80 ° C. for 12 hours, and the cylinder temperature of the polyamide resin (A) was determined using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.). Melting point + 15 ° C, Mold temperature: 80 ° C (Example 26: 160 ° C), Injection / cooling time: 10/10 seconds, Screw rotation speed: 150 rpm, Injection pressure: 100 MPa, Injection speed: 100 mm / sec. A square plate (film gate) having a thickness of 80 mm x 80 mm x 3 mm was injection molded. The YI value (yellowness) of the square plate was measured using SM Color Computer Model SM-3 manufactured by Suga Test Instruments Co., Ltd. The larger the YI value, the stronger the yellow tint, and the smaller the YI value, the better the color tone.

The pellets obtained in Examples 3 to 4, Comparative Examples 20 to 21 , and Examples 27 to 28 were dried under reduced pressure at 80 ° C. for 12 hours, and used with an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.). Then, a 3.2 mm thick ASTM No. 1 dumbbell test piece was prepared by injection molding under the conditions of cylinder temperature: A) melting point of polyamide resin + 15 ° C., mold temperature: 80 ° C. This test piece was subjected to a tensile test at a crosshead speed of 10 mm / min using a tensile tester Tensilon UTA2.5T (manufactured by Orientec) in accordance with ASTM D638. The measurement was performed three times, and the average value was calculated as the tensile strength before the hot water test treatment. Then, the ASTM No. 1 dumbbell test piece was charged into a pressure-resistant autoclave, ion-exchanged water was added so that the test piece was sufficiently immersed, and the pressure-resistant autoclave was placed in a 90 ° C. gear oven and subjected to a hot water resistance test for 6 hours. The test piece was dried under reduced pressure at 80 ° C. for 12 hours. The same tensile test was performed on the dried test specimen, and the average of three measurements was calculated as the tensile strength after the hot water test treatment.
The ratio (percentage) of the tensile strength after the hot water test to the tensile strength before the hot water test was calculated as the tensile strength retention. The higher the tensile strength retention, the better the hot water resistance.

[Moisture and heat resistance]
The pellets obtained in Examples 13 to 15, Comparative Examples 21 to 22 , Examples 28 to 29, and Comparative Example 4 were dried under reduced pressure at 80 ° C. for 12 hours, and were injected with an injection molding machine (SG75H- manufactured by Sumitomo Heavy Industries, Ltd.). Using MIV), cylinder temperature: (A) melting point of polyamide resin + 15 ° C., mold temperature: 80 ° C., injection / cooling time: 10/10 seconds, screw rotation speed: 150 rpm, injection pressure: 100 MPa, injection speed: Under a condition of 100 mm / sec, a square plate (film gate) having a thickness of 80 mm × 80 mm × 3 mm was injection-molded. The obtained square plate was subjected to wet heat treatment at 80 ° C. and 95% RH for 1 hour, and the state of the surface of the square plate after the treatment was visually observed and evaluated according to the criteria described in the above “Surface appearance”.

Reference Example 1 ((A-2) nylon 410)
700 g of an equimolar salt of tetramethylenediamine and sebacic acid, 700 g, 21.2 g of a 10% by weight aqueous solution of tetramethylenediamine (1.00 mol% based on the 410 salt), 0.3065 g of sodium hypophosphite (weight of polymer produced) (0.05% by weight based on the weight of the polymerization vessel) was charged in a polymerization vessel, sealed, and purged with nitrogen. After the heating was started and the internal pressure of the can reached 0.5 MPa, the internal pressure of the can was maintained at 0.5 MPa for 1.5 hours while releasing water out of the system. Thereafter, the internal pressure of the vessel was returned to normal pressure over 10 minutes, and the reaction was further performed under a nitrogen flow for 1.5 hours to complete the polymerization. Thereafter, the polymer was discharged from the polymerization can in a gut shape and pelletized, followed by vacuum drying at 80 ° C. for 24 hours to obtain nylon 410 having ηr = 2.84 and a melting point of 252 ° C.

Reference Example 2 ((A-4) nylon 4T / 6T = 40/60 (weight ratio))
A 4T salt, which is an equimolar salt of tetramethylenediamine and terephthalic acid, and a 6T salt, which is an equimolar salt of hexamethylenediamine and terephthalic acid, were blended in a weight ratio of 40:60. 0.5 mol% of tetramethylenediamine and hexamethylenediamine were added in excess of the total aliphatic diamine, respectively. Further, 30 parts by weight of water was added to and mixed with 70 parts by weight of these raw materials in total. This was charged into a polymerization vessel, sealed, and purged with nitrogen. After the heating was started and the internal pressure of the container reached 2.0 MPa, the internal pressure of the container was maintained at 2.0 MPa and the internal temperature of the container at 240 ° C. for 2 hours while releasing water out of the system. Thereafter, the content was discharged from the polymerization can onto a cooling belt, and this was vacuum-dried at 100 ° C. for 24 hours to obtain a polyamide resin oligomer. The obtained polyamide resin oligomer was pulverized and dried, and subjected to solid phase polymerization at 50 Pa and 240 ° C. to obtain nylon 4T / 6T = 40/60 having ηr = 2.48 and a melting point of 336 ° C.

Reference Example 3 (E-1: Nylon 66 masterbatch containing CuI / KI (weight ratio) = 0.23)
2.0 parts by weight of copper iodide and 21.7 parts by weight of a 40% aqueous solution of potassium iodide were preliminarily mixed with 100 parts by weight of nylon 66 (“Amilan” (registered trademark) CM3001-N, manufactured by Toray Industries, Inc.). Thereafter, using a twin screw extruder (L / D: 45.5) manufactured by Nippon Steel Works, Ltd., the mixture was melt-kneaded at a cylinder temperature of 275 ° C. and a screw rotation speed of 150 rpm, and pelletized by a strand cutter. . Thereafter, vacuum drying was performed at 80 ° C. for 8 hours to produce master batch pellets having a copper content of 0.60% by weight.

Reference Example 4 (B-1)
For 100 parts by weight of pentaerythritol (manufactured by Koei Chemical Industry Co., Ltd., molecular weight / the number of functional groups in one molecule is 34), a phenol novolak type epoxy resin ("EPPN" (registered trademark) 201, manufactured by Nippon Kayaku Co., Ltd.) After premixing 10 parts by weight of the average number of epoxy groups in one molecule, 7 in molecular weight, 1330 in molecular weight, and 190 in molecular weight / the number of functional groups in one molecule, the cylinder was molded using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd. The mixture was melt-kneaded for 3.5 minutes at a temperature of 245 ° C. and a screw rotation speed of 100 rpm, and pelletized by a hot cutter. The obtained pellets are again supplied to an extruder, melt-kneaded under the above conditions, and a pelletizing step (remelting kneading step) is performed once, and the compound represented by the general formula (1) and / or a condensate thereof are obtained. Was obtained. The conversion of the obtained compound was 49%, the degree of branching was 0.27, and the hydroxyl value was 1,530 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 5 (B-2)
100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd., molecular weight / the number of functional groups in one molecule is 42), and a phenol novolak type epoxy resin (“EPPN” (registered trademark) 201, manufactured by Nippon Kayaku Co., Ltd.) After premixing 10 parts by weight, the mixture was melt-kneaded using a PCM30 twin screw extruder manufactured by Ikegai at a cylinder temperature of 200 ° C. and a screw rotation speed of 100 rpm for 3.5 minutes, and pelletized by a hot cutter. The obtained pellets were supplied to the extruder again, and the remelting kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and / or a condensate thereof. The conversion of the obtained compound was 53%, the degree of branching was 0.29, and the hydroxyl value was 1280 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 6 (B-3)
A compound represented by the general formula (1) and / or a compound thereof represented by the same manner as in Reference Example 5 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. A pellet of the condensate was obtained. The reaction rate of the obtained compound was 2%, the degree of branching was 0.15, and the hydroxyl value was 1350 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH and OR in the general formula (1) was 3 or more.

Reference Example 7 (B-4)
The compound represented by the general formula (1) and / or its compound was obtained in the same manner as in Reference Example 5 except that the screw rotation speed of the twin-screw extruder was changed to 200 rpm, and the melt-kneading time was changed to 2.4 minutes. A pellet of the condensate was obtained. The conversion of the obtained compound was 15%, the degree of branching was 0.20, and the hydroxyl value was 1,300 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

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

Reference Example 9 (B-6)
For 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), bisphenol A type epoxy resin (“jER” (registered trademark) 1004 manufactured by Mitsubishi Chemical Corporation), two epoxy groups in one molecule , Molecular weight 1650, molecular weight / functional group number per molecule 825) 33.3 parts by weight were preliminarily mixed, and then, using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., at a cylinder temperature of 200 ° C and a screw rotation speed of 100 rpm. Under the conditions, the mixture was melt-kneaded for 3.5 minutes and pelletized by a hot cutter. The obtained pellets were supplied to the extruder again, and the remelting kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and / or a condensate thereof. The obtained compound had a conversion of 56%, a degree of branching of 0.34, and a hydroxyl value of 1200 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 10 (B-7)
For 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), bisphenol A type epoxy resin (“jER” (registered trademark) 1007 manufactured by Mitsubishi Chemical Corporation), two epoxy groups in one molecule , Molecular weight 2900, molecular weight / functional number in one molecule 1450) 33.3 parts by weight were preliminarily mixed, and then, using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., at a cylinder temperature of 200 ° C and a screw rotation speed of 100 rpm. Under the conditions, the mixture was melt-kneaded for 3.5 minutes and pelletized by a hot cutter. The obtained pellets were supplied to the extruder again, and the remelting kneading step was performed once 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 52%, the degree of branching was 0.32, and the hydroxyl value was 1160 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 11 (B-8)
For 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), bisphenol A type epoxy resin (“jER” (registered trademark) 1010 manufactured by Mitsubishi Chemical Corporation), two epoxy groups in one molecule , Molecular weight 5500, molecular weight / functional group number per molecule 2750) 33.3 parts by weight were preliminarily mixed, and then, using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., at a cylinder temperature of 200 ° C and a screw rotation speed of 100 rpm. Under the conditions, the mixture was melt-kneaded for 3.5 minutes and pelletized by a hot cutter. The obtained pellets were supplied to the extruder again, and the remelting kneading step was performed once 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 50%, the degree of branching was 0.29, and the hydroxyl value was 1100 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 12 (B-9)
100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.) per 100 parts by weight of aliphatic polycarbodiimide ("Carbodilite" (registered trademark) LA-1 manufactured by Nisshinbo Chemical Inc.), average of carbodiimide groups in one molecule After premixing 10 parts by weight of 24 pieces, molecular weight of 6000, and molecular weight / the number of functional groups in one molecule of 250), using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., the cylinder temperature was 200 ° C. and the screw rotation speed was 100 rpm. Was melt-kneaded for 3.5 minutes under the conditions described above, and pelletized by a hot cutter. The obtained pellets were supplied to the extruder again, and the remelting kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and / or a condensate thereof. The conversion of the obtained compound was 89%, the degree of branching was 0.37, and the hydroxyl value was 1110 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of carbodiimide groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 13 (B-10)
In a 1 L autoclave equipped with a stirrer, 508 g (1.0 mol) of dipentaerythritol (manufactured by Koei 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. The mixture was stirred to obtain a slurry liquid. Next, the mixture was heated to 130 ° C., and 132 g (3 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. With the introduction of ethylene oxide, the temperature inside the autoclave rose. 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 the excess ethylene oxide and the by-produced polymer of ethylene glycol. Thereafter, the mixture was neutralized with acetic acid and adjusted to pH 6 to 7 to obtain ethylene glycol-modified dipentaerythritol.

  343 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol was weighed into a 500 ml electromagnetic induction rotary stirring type autoclave, charged with 3 g of a 5% ruthenium-alumina powder catalyst manufactured by NEC Chemcat, which had been subjected to an external reduction treatment, and replaced with nitrogen. Was done. Subsequently, 26 g (1.53 mol) of ammonia was added, and hydrogen (0.18 mol) was injected at room temperature (25 ° C.) so that the total pressure became 2.0 MPaG. While stirring under the condition of 1000 rpm, heating was performed 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 the pressure drop disappeared, the reaction was further performed for 0.5 hour. Thereafter, the reaction product was taken out by cooling, and the catalyst was removed by filtration to obtain dipentaerythritol polyethylenehexamine.

After premixing 10 parts by weight of a phenol novolak type epoxy resin ("EPPN" (registered trademark) 201, manufactured by Nippon Kayaku Co., Ltd.) with 100 parts by weight of the obtained dipentaerythritol polyoxyethylene hexamine, ) Using a PCM30 type twin screw extruder manufactured by Ikegai, melt kneading for 3.5 minutes at a cylinder temperature of 200 ° C and a screw rotation speed of 100 rpm, pelletize with a hot cutter, and prepare a compound represented by the general formula (1). And / or pellets of the condensate were obtained. The conversion of the obtained compound was 49%, the degree of branching was 0.25, and the amine value was 500 mgKOH / g. The number of amino groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 14 (B-11)
Bisphenol A diglycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) per 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), two epoxy groups per molecule, molecular weight 340, molecular weight / 1 After preliminarily mixing 33.3 parts by weight of the number of functional groups in the molecule (170), the mixture was melted for 3.5 minutes at a cylinder temperature of 200 ° C. and a screw rotation speed of 100 rpm using a PCM30 type twin screw extruder manufactured by Ikegai Corporation. It was kneaded and pelletized by a hot cutter. The obtained pellets were supplied to the extruder again, and the remelting kneading step was performed once to obtain pellets of the compound represented by the general formula (1) and / or a condensate thereof. The conversion of the obtained compound was 88%, the degree of branching was 0.32, and the hydroxyl value was 1290 mgKOH / g. The number of hydroxyl groups in one molecule was larger than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 15 (B'-1)
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, and 1.1 parts by weight of methanesulfonic acid (0.5 mol based on ethyleneimine) %) And subjected to ring-opening polymerization at 50 ° C. for 7 hours. After completion of the reaction, 1,4-dioxane and residual ethyleneimine were distilled off from the reaction solution to obtain polyethyleneimine. The degree of branching of polyethyleneimine was 0.31.

Reference Example 16 (B'-2)
50.5 g (0.14 mol) of pentaerythritol pentaethoxylate and 1.0 g (0.004 mol) of 3-fluoroethylene were added to a four-necked flask equipped with a stirrer, a pressure gauge, a condenser and a receiver. A 50% by weight aqueous solution of a boron fluoride diethyl ether complex was added at room temperature, and the mixture was 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., the mixture was stirred for 2.5 hours, and then cooled to room temperature to obtain a hydroxyl group-containing compound including a branched structure composed of a repeating structural unit having an ether bond. The weight-average molecular weight of the obtained hydroxyl-containing compound was 2,620, the hydroxyl value was 810 mgKOH / g, and the degree of branching was 0.29.

Reference Example 17 (B'-3)
In a four-necked flask equipped with a stirrer, pressure gauge, condenser and receiver, 2000 g (10.5 mol) of triisopropanolamine and 13.5 g (0.064 mol) of sodium diphosphite 50 were added. A wt% aqueous solution was added at room temperature and heated to 230 ° C. The reaction was allowed to proceed for 2 hours, and the condensate generated in the reaction solution was removed with a receiver under nitrogen gas. Further, the condensate was removed at 0.05 MPa, further cooled to 140 ° C., and the condensate was removed at 0.01 MPa. Thereafter, the mixture was cooled to room temperature to obtain a hydroxyl group-containing compound having a branched structure composed of a repeating structural unit having an ether bond containing an amino group. The weight average molecular weight of the obtained hydroxyl group-containing compound was 2,400, the hydroxyl value was 850 mgKOH / g, and the degree of branching was 0.42.

Reference Example 18 (B'-4)
617.8 g (1.70 mol) of pentaerythritol pentaethoxylate and 921.0 g (6.84 mol) of 2,8 were added to a four-necked flask equipped with a stirrer, a pressure gauge, a condenser and a receiver. 2-Dimethylolpropionic acid and 0.92 g (0.008 mol) of 96% by weight 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 while 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, and a reduced pressure of 4000 to 6666 Pa was added. The reaction was carried out for 5 hours to obtain a hydroxyl group-containing compound containing a branched structure composed of a repeating structural unit 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 2,050, the hydroxyl value was 590 mgKOH / g, and the degree of branching was 0.34.

Reference Example 19 (B'-5)
In a four-necked flask equipped with a stirrer, manometer, vacuum connection, condenser and receiver, 232.0 g (1.57 mol) of phthalic anhydride and 270.0 g (2.03 mol) of diphthalic anhydride were added. Isopropanolamine was added, and the temperature was raised to 70 ° C. while stirring. Next, the mixture was heated to 170 ° C. under a reduced pressure of 4000 to 6666 Pa, and reacted for 4.5 hours while removing water. Thereafter, the mixture was cooled to room temperature to obtain a hydroxyl group-containing compound having a branched structure composed of a repeating structural unit having an ester bond and an amide bond. The weight average molecular weight was 1950, the hydroxyl value was 505 mg KOH / g, and the degree of branching was 0.38.

Reference Example 20 (B'-6)
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 at an internal temperature. A 3000 ml 4-neck glass flask equipped with a vacuum, a gas inlet tube, a reflux condenser and a vacuum connection to a cooling trap was charged. After supplying nitrogen gas and adding 1.11 g of di-n-butyltin oxide, the mixture was heated to an internal temperature of 125 ° C. using an oil bath. Water generated during the reaction was separated under a reduced pressure of 0.02 MPa. The reaction mixture was kept 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 a repeating structural unit having an ester bond. The obtained branched compound containing a hydroxyl group and a carboxyl group 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 in the atmosphere. The weight average molecular weight of the compound after the heat treatment was 1950, the acid value was 277 mgKOH / g, the hydroxyl value was 504 mgKOH / g, the ratio of the acid value / hydroxyl value was 0.55, and the degree of branching was 0.40.

Reference Example 21 (B'-7)
After premixing 100 parts by weight of dipentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.) with 500 parts by weight of a phenol novolak type epoxy resin ("EPPN" (registered trademark) 201) manufactured by Nippon Kayaku Co., Ltd.) Using a PCM30 type twin screw extruder manufactured by Ikegai Corporation, melt kneading is performed for 3.5 minutes at a cylinder temperature of 200 ° C. and a screw rotation speed of 100 rpm, pelletized by a hot cutter, and represented by the general formula (1). A pellet of the compound and / or its condensate was obtained. The reaction rate of the obtained compound was 33%, the degree of branching was 0.23, and the hydroxyl value was 540 mgKOH / g. The number of hydroxyl groups in one molecule was smaller than the number of epoxy groups in one molecule, and the sum of the numbers of OH, NH ₂ and OR in the general formula (1) was 3 or more.

Reference Example 22 (F-1)
After preliminarily mixing 26.7 parts by weight of the compound (B-2) with 100 parts by weight of nylon 6 (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), TEX30 type manufactured by Japan Steel Works, Ltd. Using a twin screw extruder (L / D: 45.5), the mixture was melt-kneaded at a cylinder temperature of 245 ° C. and a screw rotation speed of 150 rpm, and pelletized by a strand cutter. Thereafter, vacuum drying was performed at 80 ° C. for 8 hours to produce high-concentration premix pellets.

Reference Example 23 (F-2)
After preliminarily mixing 26.7 parts by weight of the compound (B-7) with 100 parts by weight of nylon 6 (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), TEX30 type manufactured by Japan Steel Works, Ltd. Using a twin screw extruder (L / D: 45.5), the mixture was melt-kneaded at a cylinder temperature of 245 ° C. and a screw rotation speed of 150 rpm, and pelletized by a strand cutter. Thereafter, vacuum drying was performed at 80 ° C. for 8 hours to produce high-concentration premix pellets.

In addition, (A) a polyamide resin, (b) a compound containing a hydroxyl group and / or an amino group, (b ′) a compound containing an epoxy group and / or a carbodiimide group, and (D) a filler used in Examples and Comparative Examples are as follows. It is as follows.
(A-1): Nylon 66 resin having a melting point of 260 ° C. (“Amilan” (registered trademark) CM3001-N manufactured by Toray Industries, Inc.), ηr = 2.78.
(A-3): Nylon 6 resin having a melting point of 225 ° C. (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), ηr = 2.70.
(B-1): dipentaerythritol (large particle size) (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight 254, hydroxyl value 1325 mgKOH / g, average particle diameter 180 μm or more.
(B-2): dipentaerythritol polyoxyethylenehexamine, molecular weight 608, amine value 554 mgKOH / g.
(B′-1): Phenol novolak type epoxy resin (“EPPN” (registered trademark) 201, manufactured by Nippon Kayaku Co., Ltd.), average number of epoxy groups in one molecule, 7, molecular weight 1,330, molecular weight / one molecule 190 functional groups.
(B'-2): Bisphenol A type epoxy resin ("jER" (registered trademark) 1007, manufactured by Mitsubishi Chemical Corporation) Number of epoxy groups in one molecule, two, molecular weight 2,900, molecular weight / number of functional groups in one molecule 1450).
(C-1): sodium hypophosphite monohydrate (Wako Pure Chemical Industries, Ltd.), molecular weight 105.99
(C-2): calcium hypophosphite (Wako Pure Chemical Industries, Ltd.), molecular weight 170.05
(D-1): glass fiber with circular cross section (T-275H manufactured by NEC Corporation), cross-sectional diameter 10.5 μm, surface treatment agent: silane coupling agent, sizing agent: carboxylic acid, fiber length 3 mm
(D-2): Glass fiber with circular cross section (T-717H, manufactured by Nippon Electric Glass Co., Ltd.), cross-sectional diameter 10.5 μm, surface treatment agent: silane coupling agent, sizing agent: epoxy, fiber length 3 mm.

(Examples 1 9 13～15,17, 24-26, Comparative Example 1 to 19)
The (A) polyamide resin shown in the table was obtained by using a TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel Works Co., Ltd., in which 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 mixture was supplied from a main feeder to a twin-screw extruder and melt-kneaded. This main feeder was connected to the position of 0 when viewed from the upstream side when the total length of the screw was 1.0, that is, the position of the upstream end of the screw segment. Subsequently, the compound (B), the compound (B '), the compound (b) containing a hydroxyl group and / or an amino group, the compound (P) containing a phosphorus group and the filler (D) shown in the table are fed from a side feeder to a twin-screw extruder. The mixture was supplied 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 screw configuration of the twin-screw extruder is such that the total length of the kneading zone upstream of the supply position of the compound (B) is Ln1 and the total length of the kneading zone downstream of the supply position of the compound (B). When the length was Ln2, Ln1 / L was 0.14 and Ln2 / L was 0.07. Further, among the resin pressures indicated by the resin pressure gauges installed in a plurality of full flight zones, the minimum resin pressure Pfmin and the resin pressures indicated by the resin pressure gauges installed in a plurality of kneading zones, The difference from the maximum resin pressure Pkmax (Pkmax-Pfmin) was as shown in the table. The gut discharged from the die was immediately cooled in a water bath and pelletized by a strand cutter. Tables show the evaluation results of the examples and the comparative examples. The tensile strength retention before and after the hot water test was 82% in Example 3: 96% in Example 4. The results of evaluating the heat and moisture resistance were as follows: Example 13: C2, Example 14: A, Example 15: A, Comparative Example 4: C2.

( Comparative Examples 20 to 23 )
After premixing the (A) polyamide resin and the (b ') epoxy group and / or carbodiimide group-containing compound shown in the table, 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. It was supplied from a main feeder of a TEX30 type twin screw extruder manufactured by Nippon Steel Works to a twin screw extruder and melt-kneaded. This main feeder was connected to the position of 0 when viewed from the upstream side when the total length of the screw was 1.0, that is, the position of the upstream end of the screw segment. Subsequently, (b) a hydroxyl- and / or amino-group-containing compound, (C) a phosphorus-containing compound, and D) a filler shown in the table were supplied from a side feeder to a twin-screw extruder, and were 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 screw configuration of the twin screw extruder is such that (b) the total length of the kneading zone upstream of the supply position of the hydroxyl and / or amino group-containing compound is Ln1, and (b) the hydroxyl and / or amino group-containing compound is Assuming that the total length of the kneading zone downstream of the supply position is Ln2, Ln1 / L is 0.14 and Ln2 / L is 0.07. The difference between Pfmin and Pkmax (Pkmax-Pfmin) was as shown in the table. The gut discharged from the die was immediately cooled in a water bath and pelletized by a strand cutter. The evaluation results of each example are shown in the table. The tensile strength retentions before and after the hot water test were Comparative Example 20 : 72% and Comparative Example 21 : 83%, and the results of evaluating the moisture and heat resistance were Comparative Example 21 : C2 and Comparative Example 22 : A. Was.

(Example 22)
Pellets of the polyamide resin composition were obtained under the same conditions as in Example 3 except that the screw configuration of the twin-screw extruder was changed so that Ln1 / L was 0.01 and Ln2 / L was 0.01. The difference between Pfmin and Pkmax (Pkmax-Pfmin) was as shown in the table. The evaluation results are shown in the table.

(Example 23)
Pellets of the polyamide resin composition were obtained under the same conditions as in Example 3, except that the compound (B) and the phosphorus-containing compound shown in the table were supplied to the twin-screw extruder from the main feeder. The difference between Pfmin and Pkmax (Pkmax-Pfmin) was as shown in the table. The evaluation results are shown in the table.

(Examples 27 to 29)
Pellets of a polyamide resin composition were obtained under the same conditions as in Example 3 except that the (F) high-concentration premix and the (C) phosphorus-containing compound shown in the table were supplied from a main feeder to a twin-screw extruder. . Thereby, the composition ratios of Examples 27 to 29 are the same as those of Examples 3 to 4, and 14, respectively. The cylinder temperature, screw rotation speed, and screw configuration were the same as in Example 3. The difference between Pfmin and Pkmax (Pkmax-Pfmin) was calculated from the value of the resin pressure gauge when the high-concentration preliminary mixture was added and melt-kneaded, and was as shown in the table. The evaluation results of each example are shown in the table. The retention of tensile strength before and after the hot water test was Example 27: 88%, Example 28: 110%, and the evaluation results for wet heat resistance were Example 28: C2 and Example 29: A. Was.

(Example 30)
After preliminarily mixing the (A) polyamide resin and the (E) copper compound shown in the table, 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. TEX30 type biaxial manufactured by Japan Steel Works, Ltd. The mixture was fed from a main feeder of the extruder to a twin-screw extruder and melt-kneaded. This main feeder was connected to the position of 0 when viewed from the upstream side when the total length of the screw was 1.0, that is, the position of the upstream end of the screw segment. Subsequently, the compound (B), the phosphorus compound (C), and the filler (D) 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 screw configuration of the twin-screw extruder is such that the total length of the kneading zone upstream of the (B) compound supply position is Ln1, and the total length of the kneading zone downstream of the (B) compound supply position. Is Ln2, Ln1 / L is 0.14 and Ln2 / L is 0.07. The difference between Pfmin and Pkmax (Pkmax-Pfmin) was as shown in the table. The gut discharged from the die was immediately cooled in a water bath and pelletized by a strand cutter. The evaluation results are shown in the table.

Examples 1 to 9, 13 to 15, 17, 22 to 30 contain a specific amount of the compound (B) as compared with Comparative Examples 1 to 23 , and (
C) By containing the phosphorus atom derived from the phosphorus-containing compound at a specific concentration, the compatibility with the (A) polyamide resin is further improved, resulting in excellent fluidity and retention stability, heat aging resistance,
A molded article having excellent mechanical strength, surface appearance and color tone was obtained.

  Examples 1 to 8 contained 0.1 to 20 parts by weight of the compound (B) and (C) a phosphorus atom derived from the phosphorus-containing compound at a specific concentration. And (A) the compatibility between the polyamide resin and the (B) compound is further improved, and as a result, a molded article excellent in fluidity and retention stability, and excellent in heat aging resistance, mechanical strength, surface appearance and color tone is obtained. Was completed.

  In Example 3, the polyamide resin (A) and (A) contained the compound (B) and (C) the phosphorus atom derived from the phosphorus-containing compound at a specific concentration, as compared with Comparative Examples 8 to 15. B) A molded article having improved compatibility with the compound, excellent fluidity and retention stability, and excellent in heat aging resistance, mechanical strength, surface appearance and color tone was obtained.

In Example 3, since the reaction rate of the compound (B) is in a more preferable range as compared with Comparative Examples 16 to 18 , the compatibility between the polyamide resin (A) and the compound (B) is further improved. result,
A molded article excellent in fluidity and retention stability and excellent in heat aging resistance, mechanical strength, surface appearance and color tone was obtained.

  In Example 3, since the polyamide resin composition was manufactured by a more preferable method as compared with Examples 22 and 23, the compatibility between the polyamide resin (A) and the compound (B) could be further improved, and It was possible to obtain a molded article having excellent heat resistance and retention stability and excellent heat aging resistance, mechanical strength and color tone.

  Example 27 is compared with Example 3, Example 28 is compared with Example 4, Example 29 is compared with Example 14, and a high-concentration premix is prepared, twice melt-kneaded. As a result, the compatibility between the polyamide resin (A) and the compound (B) was further improved, and as a result, a molded article excellent in fluidity, heat aging resistance and mechanical strength was obtained.

  In Examples 3 and 24, as compared with Examples 25 and 26, the melting point of the polyamide resin (A) was in a preferable range, so that the compatibility between the polyamide resin (A) and the compound (B) was further improved, As a result, it was possible to obtain a molded article having excellent fluidity and retention stability, and having excellent heat aging resistance, mechanical strength and color tone.

Example 3 was compared with Comparative Example 20, and Example 17 was compared with Comparative Example 23 , because the compound (B) obtained by reacting in advance was used, so that (A) polyamide resin and (B) The compatibility with the compound was further improved, and as a result, a molded article having more excellent fluidity and retention stability, and having more excellent heat aging resistance, mechanical strength and color tone could be obtained.

  In Example 30, since the copper compound is further contained as compared with Example 3, the compatibility between the (A) polyamide resin and the (B) compound is further improved, and as a result, the molded article is more excellent in heat aging resistance. Could be obtained.

Example 4 is compared with Example 3, Comparative Example 21 is compared with Comparative Example 20, and Example 28 is compared with Example 27, because it contains glass fiber of an epoxy sizing agent. Thus, a molded article excellent in quality was obtained.

Examples 14 and 15 are compared with Example 13, Comparative Example 22 is compared with Comparative Example 21, and Example 29 is compared with Example 28, and the molecular weight and the molecular weight of the functional group in one molecule are compared. (B ′) a compound obtained by reacting an epoxy group and / or carbodiimide group-containing compound having a value obtained by dividing by a number, respectively, in a preferable range. Thus, it is possible to obtain a molded article having better moist heat resistance. did it.

  The polyamide resin composition of the embodiment of the present invention can be molded by any method such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, and is processed into various molded products and used. be able to. In particular, the polyamide resin composition of the embodiment of the present invention is excellent in fluidity and retention stability, and makes use of the fact that a molded article excellent in heat aging resistance, mechanical strength, surface appearance, and color tone can be obtained. Peripheral parts, automotive underhood parts, automotive gear parts, automotive interior parts, automotive exterior parts, intake / exhaust system parts, engine cooling water system parts, automotive applications such as automotive electrical components, and electric / electronic components such as LED reflectors and SMT connectors It is effective to process it into such as.

1 Solvent peak

Claims (5)

(A) 100 parts by weight of a 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 the hydroxyl group and the amino group in one molecule is 1 The compound contains 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 the phosphorus-containing compound (C), and the phosphorus atom content determined by absorptiometry is the polyamide resin content. 180 to 3500 ppm, and the compound (B) is a reaction product of (b) a compound containing a hydroxyl group and / or an amino group and (b ′) a compound containing an epoxy group and / or a carbodiimide group, A polyamide resin composition having a reaction rate between a hydroxyl group or an amino group and an epoxy group or a carbodiimide group of 20 to 70% . The polyamide resin composition according to claim 1 , wherein the (C) phosphorus-containing compound is at least one selected from the group consisting of phosphorous acid, hypophosphorous acid, and metal salts thereof. 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), X1 to X6 may be the same or different and represent OH, NH2, CH3 or OR. However, the sum of the numbers of OH, NH2, and OR is 3 or more. R represents an organic group having an amino group, an epoxy group or a carbodiimide group, and n represents a range of 0 to 20. (B) reacting a compound containing a hydroxyl group and / or an amino group with a compound containing a (b ′) epoxy group and / or a carbodiimide group, and the reaction rate between the hydroxyl group or the amino group and the epoxy group or the carbodiimide group is 20 to (B) having 70% of a hydroxyl group and / or an amino group and an epoxy group and / or a carbodiimide group, wherein the sum of the number of the hydroxyl group and the amino group in one molecule is equal to the number of the epoxy group and the carbodiimide group in one molecule; A polyamide resin composition obtained by melt-kneading 0.1 to 20 parts by weight of the compound (B) and phosphorus-containing compound (C) with respect to 100 parts by weight of the polyamide resin (A) is obtained. A method for producing a product, wherein the content of phosphorus atoms of the obtained polyamide resin composition is determined by spectrophotometry. Method for producing a polyamide resin composition which is 180~3500ppm respect. A molded article obtained by molding the polyamide resin composition according to any one of claims 1 to 3 .

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