JP2018172521A - Polyamide resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition that has a small gas generation amount during molding and in which a molded product excellent in high temperature rigidity and in burst strength at low temperature and high temperature when heat treated at high temperature can be obtained.SOLUTION: Provided is a polyamide resin composition characterized in containing a compound (B) having three or more hydroxyl groups in one molecule in a proportion of 0.1 pts.wt. or more and 20 pts.wt. or less with respect to 100 pts.wt. of a first polyamide resin (A) and containing a second polyamide resin (C) having an amide group concentration smaller than the amide group concentration of the first polyamide resin (A) by 0.8 mmol/g or more in a proportion of 0.05 pts.wt. or more and less than 5 pts.wt.SELECTED DRAWING: None

Description

  The present invention relates to a polyamide resin composition and a molded product thereof.

  Polyamide resins have excellent mechanical properties, heat resistance, and chemical resistance, so they have suitable properties as engineering plastics, and are widely used in automobiles, electrical / electronic parts, and other precision equipment parts. Yes. In recent years, from the viewpoint of reducing the weight of automobiles, polyamide resins have also been used in engine room components such as intake manifolds and turbo ducts. Since these parts are hollow complex shapes manufactured using various welding techniques, high burst strength is required along with suppression of gas generation due to retention during molding.

  Furthermore, due to the recent increase in environmental temperature due to the increase in the density of engine compartment parts and the increase in engine output in the automotive field, engine compartment parts have high heat resistance under high temperature conditions as well as high temperature rigidity. There is a demand for a material having high burst strength in a wide temperature range while having properties. Numerous technical improvements have been attempted so far in order to improve the heat aging resistance (heat aging mechanical properties) related to the general mechanical properties of polyamide resins. For example, a polyamide resin composition (see Patent Document 1) having a polyamide resin having an amide group concentration of 8.2 mmol / g or less, a compound having a specific structure having an epoxy group or a carbodiimide group, and / or a condensate thereof, or a polyamide resin A thermoplastic polyamide resin composition (see Patent Document 2), a polyhydric alcohol having a number average molecular weight of less than 2000, and an anti-whitening agent such as polyethylene glycol, a polyamide resin, an impact resistance improving material, 2 A resin composition containing a polyhydric alcohol containing ˜8 hydroxyl groups has been proposed (see Patent Document 3).

JP 2016-164206 A Special table 2015-514849 gazette JP 2013-538927 A

  According to the polyamide resin composition described in Patent Document 1 described above, the high-temperature rigidity is high and the heat aging resistance is improved. However, the amount of gas generated is large, and the molded product is heated at low and high temperatures after heat treatment. There was a problem that the burst strength was insufficient. Further, according to the polyamide resin compositions described in Patent Documents 2 and 3, the heat aging resistance is improved, but the burst strength at low and high temperatures after heat treatment of the molded product is insufficient, There was a problem of inferior rigidity.

  Therefore, in view of the problems of these conventional techniques, the present invention provides a polyamide resin composition that can obtain a molded product that has a small amount of gas generation at the time of molding and has excellent burst strength and high-temperature rigidity at low and high temperatures after heat treatment. Is an issue.

In order to solve the above problems, the present invention mainly has the following configuration.
[1] Containing 100 parts by weight of the first polyamide resin (A), the compound (B) containing three or more hydroxyl groups in one molecule is contained in a proportion of 0.1 to 20 parts by weight. The second polyamide resin (C) having an amide group concentration of 0.8 mmol / g or less smaller than the amide group concentration of the first polyamide resin is contained in a proportion of 0.05 parts by weight or more and less than 5 parts by weight. A characteristic polyamide resin composition.
[2] The polyamide resin composition according to [1], wherein the second polyamide resin (C) is a crystalline polyamide.
[3] The polyamide resin composition according to [1] or [2], wherein the second polyamide resin (C) is an aliphatic polyamide.
[4] The second polyamide resin (C) is one selected from the group consisting of polyamide 410, polyamide 510, polyamide 610, polyamide 1010, polyamide 1012, polyamide 11, and polyamide 12, [1] to [3] ] The resin composition in any one of.
[5] The polyamide resin composition according to any one of [1] to [4], wherein the first polyamide resin (A) has a melting point of 300 ° C. or lower.
[6] The polyamide resin composition according to any one of [1] to [5], wherein the first polyamide resin (A) has an amide group concentration exceeding 8.2 mmol / g.
[7] The compound (B) contains an epoxy group and / or a carbodiimide group, and the number of hydroxyl groups in one molecule of the compound (B) is larger than the total number of epoxy groups and carbodiimide groups in one molecule of the compound (B). The polyamide resin composition according to any one of [1] to [6].
[8] A molded article comprising the polyamide resin composition according to any one of [1] to [7].
[9] A compound (B) containing three or more hydroxyl groups in one molecule is blended at a ratio of 0.1 to 20 parts by weight with respect to 100 parts by weight of the first polyamide resin (A). Polyamide containing a second polyamide resin (C) having an amide group concentration of 0.8 mmol / g or less smaller than the amide group concentration of the first polyamide resin in a proportion of 0.05 parts by weight or more and less than 5 parts by weight A method for producing a resin composition.

  The polyamide resin composition of the present invention is excellent in heat aging resistance, burst strength at low and high temperatures after heat treatment, and high temperature rigidity. According to the polyamide resin composition of the present invention, it is possible to provide a molded article excellent in burst strength and high-temperature rigidity at low and high temperatures after heat treatment.

¹ H-NMR spectrum of a dry blend product of dipentaerythritol and bisphenol A type epoxy resin. ¹ H-NMR spectrum of a melt-kneaded reaction product of a polyhydric alcohol and an epoxy compound obtained in Reference Example 6. In the Example of this invention, it is the schematic of the molded article (upper test piece: test piece 1) created for burst strength evaluation, A represents the top view of the test piece 1, B is the test piece 1 Represents a side view. In the Example of this invention, it is the schematic of the molded article (lower test piece: Test piece 2) created for burst strength evaluation, A represents the top view of the test piece 2, B is the test piece 2 The side view of is represented. In the Example of this invention, it is the schematic of the molded article 3 used for evaluation of burst strength, A represents the top view of the molded article 3, and B represents the side view of the molded article 3. FIG.

  Hereinafter, embodiments of the present invention will be described in detail. The polyamide resin composition of the embodiment of the present invention has a polyamide resin (A), a compound (B) containing three or more hydroxyl groups in one molecule, and an amide group concentration of 0.8 mmol as compared with the polyamide resin (A). A polyamide resin (C) that is smaller than / g and different from the polyamide resin (A) is contained. Hereinafter, each component will be described.

  In the polyamide resin composition according to the embodiment of the present invention, it is considered that the carboxyl terminal group of the polyamide resin (A) and the polyamide resin (C) undergoes a dehydration condensation reaction with a hydroxyl group in the compound (B) described later.

  The polyamide resin (A) used in the embodiment of the present invention is a polyamide resin mainly composed of amino acid (i), lactam (ii) or diamine and dicarboxylic acid (iii). Representative examples of the raw material of the polyamide resin (A) 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 Hexamethylenediamine, 5-methylnonamethylenediamine, aliphatic diamine such as 2-methyloctamethylenediamine, aromatic diamine such as metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane Aliphatic diamines such as 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, aliphatics such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid Dicarboxylic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid Aromatic dicarboxylic acids such as acids, 1, - cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, an alicyclic dicarboxylic acids such as 1,3-cyclopentane dicarboxylic acid. In the embodiment of the present invention, two or more polyamide homopolymers or polyamide copolymers derived from these raw materials may be blended as raw materials for the polyamide resin (A).

  Specific examples of the polyamide resin (A) include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide ( Nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sebamide (nylon 510), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene Adipamide (nylon 106), polydecane methylene sebamide (nylon 1010), polydecane methylene dodecane (nylon 1012), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polycaproamide / poly Hexamethylene adipamide Polymer (nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipa Polyamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6), polyhexamethylene terephthalamide / polyhexamethylene Isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polyundecanamide copolymer (nylon 6T / 11), polyhexamethylene terephthalamide / poly Decanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6), poly Xylylene 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 terephthalamide (nylon 9T), polydecamethylene Terephthalamide (nylon 10T), polydecamethylene terephthalamide / polyhexamethylene dodecanamide copolymer (nylon 10T / 612), polydecamethylene terephthalamide / polyhexamethylene adipamide copolymer (nylon 10T / 66) polydodecamethylene terephthalate Examples thereof include amide (nylon 12T). In addition, specific examples of the polyamide resin include these copolymers. Here, “/” indicates a copolymer. The same shall apply hereinafter. Further, a polyamide resin larger than the polyamide resin (C) described later by 0.8 mmol / g or more may be blended and used. Two or more of the polyamide resins (A) exemplified above may be blended, but the amide group concentration of the polyamide resin (A) when blending two or more is blended with the amide group concentration of the blended polyamide resin. .

  Among these, a polyamide resin having a melting point of 300 ° C. or lower is preferable. By using a polyamide resin having a melting point of 300 ° C. or less, decomposition of the polyamide resin (A), compound (B), and polyamide resin (C) during melt-kneading or molding can be suppressed, and the amount of gas generated during molding Therefore, mold contamination of the molding machine can be reduced. A polyamide resin having a melting point of 200 ° C. or higher is more preferable. A polyamide resin having a melting point of 180 ° C. or higher is preferable. If the melting point is 180 ° C. or higher, the heat resistance can be improved. The melting point can be measured using DSC (differential scanning calorimeter).

  Further, the polyamide resin (A) more preferably has an amide group concentration exceeding 8.2 mmol / g. Here, the amide group concentration represents the number of amide groups contained per structural unit of the polyamide resin, and is represented by the following mathematical formula (1).

  Amide group concentration [mmol / g] = (number of amide groups per structural unit / molecular weight of structural unit) × 1000 (1)

  In the above mathematical formula (1), the molecular weight of the structural unit refers to the molecular weight corresponding to the repeating structural unit constituting the polyamide resin. For example, in the case of a polyamide resin containing an amino acid as a constituent component, it is a numerical value obtained by subtracting the molecular weight of one water molecule from the molecular weight of the amino acid. In the case of a polyamide resin containing lactam as a constituent, it is a numerical value of the molecular weight of lactam. In the case of a polyamide resin having diamine and dicarboxylic acid residues as constituent components, the value is obtained by subtracting the molecular weight of two water molecules from the sum of the molecular weights of dicarboxylic acid and diamine. Here, the amide group concentration of the polyamide resin can be obtained from the mathematical formula (1) by specifying the structural unit by a general analysis method such as GC, calculating the molecular weight thereof, and the like.

  By using a polyamide resin having an amide group concentration exceeding 8.2 mmol / g as the polyamide resin (A), it is possible to obtain a polyamide resin having an excellent balance between high-temperature rigidity and low-temperature and high-temperature burst strength after heat treatment. . The upper limit of the amide group concentration is not limited, but is preferably 13.0 mmol / g or less and more preferably 10.5 mmol / g or less from the viewpoint of suppressing water absorption and further improving dimensional stability.

  Among these, aliphatic polyamides are preferable because of excellent reactivity with the compound (B) described later, and polyamide 6, polyamide 66, and polyamide 610 are particularly preferable. These aliphatic polyamide resins have an excellent balance of strength, toughness, and welding characteristics, and also have high thermal stability, so that the burst strength and high-temperature rigidity at low and high temperatures can be further improved when the molded product is heat-treated. it can. Among these, polyamide 66 has a relatively high melting point, and can be melt-kneaded at a high resin pressure. For this reason, the reactivity with the hydroxyl-containing compound mentioned later can be improved more, the dispersibility of the compound (B) in the polyamide resin composition is further improved, and the burst at low and high temperatures when the molded product is heat-treated The strength can be further improved.

  The degree of polymerization of these polyamide resins (A) 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 1.5 to 5.0. It is preferable that it is the range of these. If the relative viscosity is 1.5 or more, the burst strength can be further improved since the balance between strength and toughness is excellent. Therefore, the burst strength at low and high temperatures after the heat treatment can be further improved. The relative viscosity is more preferably 2.0 or more, and further preferably 2.5 or more. On the other hand, if the relative viscosity is 5.0 or less, the moldability is excellent. Moreover, shear heat generation at the time of plasticizing can be moderately suppressed, and generation of gas due to thermal decomposition of the polymer can be suppressed.

  The polyamide resin composition used in the embodiment of the present invention contains a compound (B) having three or more hydroxyl groups in one molecule. The first form of the compound (B) is the compound (b1) in general having three or more hydroxyl groups in one molecule. As a special second form, compound (b2) having three or more hydroxyl groups in one molecule obtained by reacting compound (b1) with an epoxy group and / or carbodiimide group-containing compound or a condensate thereof Is also included in the compound (B).

  First, the compound (b1) which is the first form will be described. The compound (b1) has an effect of improving moldability such as fluidity and mechanical properties after heat treatment at 150 to 230 ° C. As the compound (b1), an aliphatic compound is preferable. The aliphatic compound has lower steric hindrance than the aromatic compound and the alicyclic compound, and has excellent reactivity with the polyamide resin (A) and the polyamide resin (C), so that the polyamide resin (A) and the polyamide resin ( The compatibility with C) is excellent, and the burst strength at low and high temperatures after heat treatment can be further improved. Further, the number of hydroxyl groups in one molecule of the compound (b1) is preferably 4 or more, more preferably 6 or more. The compound (b1) may be a low molecular compound, a polymer, or a condensate.

  In the case of a low molecular compound, the number of hydroxyl groups in one molecule 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.). . In the case of a polymer, the number average molecular weight and the hydroxyl value of the compound (b1) are calculated, and can be obtained by the following mathematical formula (2).

  OH number = (number average molecular weight × hydroxyl value) / 56110 (2)

  Specific examples of the compound (b1) 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-methylpro Ntorioru, trishydroxymethylaminomethane, and the like 2-methyl-1,2,4-butanetriol. In addition, examples of the compound (b1) include a hydroxyl group-containing compound having a repeating structural unit, such as an ester bond, an amide bond, an ether bond, a methylene bond, a vinyl bond, an imine bond, a siloxane bond, a urethane bond, and a thioether bond. , A hydroxyl group-containing compound having a repeating structural unit having a silicon-silicon bond, a carbonate bond, a sulfonyl bond, and an imide bond. The hydroxyl group-containing compound may contain a repeating structural unit containing two or more of these bonds. As the hydroxyl group-containing compound having a repeating structural unit, a hydroxyl group-containing compound having a repeating structural unit having an ester bond, a carbonate bond, an ether bond and / or an amide bond is more preferable.

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

  Among these compounds (b1), pentaerythritol, dipentaerythritol, and tripentaerythritol are preferable.

  Next, the second form will be described. As a second form of the compound (B), a compound (b2) having at least three hydroxyl groups in one molecule obtained by reacting the compound (b1) described above with an epoxy group and / or carbodiimide group-containing compound Or the condensate can also be mentioned. Such a compound (b2) or a condensate thereof can further improve the burst strength at low and high temperatures after the heat treatment. Although it is not certain about this factor, it is thought as follows. That is, by reacting the compound (b1) with an epoxy group and / or carbodiimide group-containing compound in advance, the compound (b2) having a multi-branched structure having the epoxy group and / or carbodiimide group-containing compound as a connection point or condensation thereof Things are formed. Such a compound (b2) or a condensate thereof has a multi-branched structure, whereby self-aggregation force is further reduced, and the reactivity and compatibility with the polyamide resin (A) and the polyamide resin (C) are further improved. Moreover, since the melt viscosity of the compound (b2) having a multi-branched structure or its condensate is improved, the dispersibility of the compound (b2) or its condensate in the polyamide resin composition is further improved. For this reason, a fine dispersion structure can be formed in the polyamide resin composition, the amount of gas generated during molding can be reduced, and the burst strength and high temperature rigidity at low and high temperatures after heat treatment are further improved. It is considered possible.

  The epoxy group and / or carbodiimide group-containing compound preferably has two or more epoxy and / or carbodiimide groups in one molecule, more preferably four or more, and still more preferably six or more. Since the epoxy group and the carbodiimide group are excellent in compatibility with the polyamide resin (A) and the polyamide resin (C), the compound having two or more epoxy and / or carbodiimide groups in one molecule is a polyamide resin (A) and a polyamide. It is thought that there exists an effect which improves the compatibility of resin (C), a compound (b2), or its condensate. The epoxy group and / or carbodiimide group-containing compound may be a low molecular compound or a polymer.

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

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

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

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

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

  Examples of the alicyclic epoxy resin include compounds having a cyclohexene oxide group, a tricyclodecene oxide group, and a cyclopentene oxide group.

  Examples of the heterocyclic epoxy resin include an epoxy resin produced from epichlorohydrin and hydantoin or isocyanuric acid.

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

  Examples of commercially available epoxy group-containing compounds include polyglycidyl ether compounds that are low molecular polyfunctional epoxy compounds (for example, “SR-TMP” manufactured by Sakamoto Pharmaceutical Co., Ltd., “Denacol” manufactured by Nagase ChemteX Corporation). (Registered trademark) EX-521 ", etc.), polyfunctional epoxy compounds containing polyethylene as a main component (for example," "Bond Fast" (registered trademark) E "manufactured by Sumitomo Chemical Co., Ltd.), Functional epoxy compounds (for example, “Reseda” GP-301 manufactured by Toagosei Co., Ltd. “ARUFON” UG-4000 manufactured by Toagosei Co., Ltd., manufactured by Mitsubishi Rayon Co., Ltd. "" Methbrene "(registered trademark) KP-7653", etc.), a polyfunctional epoxy compound mainly composed of an acrylic / styrene copolymer (for example, "" manufactured by BASF oncryl "(registered trademark) -ADR-4368", "ARUFON" (registered trademark) UG-4040 "manufactured by Toagosei Co., Ltd.), a polyfunctional epoxy compound mainly composed of a silicone-acrylic copolymer (for example, , "" Methbrene "(registered trademark) S-2200", etc.), polyfunctional epoxy compounds mainly composed of polyethylene glycol (for example, "Epiol" (registered trademark) "E-1000" manufactured by NOF Corporation)) Bisphenol A type epoxy resin (for example, “jER” (registered trademark) “1004”, “1007”, “1010”, etc., manufactured by Mitsubishi Chemical Corporation), novolak phenol type modified epoxy resin (for example, manufactured by Nippon Kayaku Co., Ltd.) “EPPN” (registered trademark) “201”).

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

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

  The molecular weight of the epoxy group and / or carbodiimide group-containing compound is not particularly limited, but is preferably 800 to 10,000. By setting the molecular weight of the epoxy group and / or carbodiimide group-containing compound to 800 or more, it becomes difficult to volatilize during melt-kneading, so the amount of gas generated is reduced. Moreover, since the viscosity at the time of melt-kneading can be increased, the compatibility between the polyamide resin (A) and the polyamide resin (C) and the compound (b2) or the condensate thereof becomes higher, and the high-temperature rigidity and the heat treatment The burst strength at low and high temperatures can be further improved. The molecular weight of the epoxy group and / or carbodiimide group-containing compound is more preferably 1000 or more. On the other hand, by setting the molecular weight of the epoxy group and / or carbodiimide group-containing compound to 10,000 or less, the viscosity at the time of melt-kneading can be moderately suppressed, so that the amount of gas generated can be further reduced. Further, the compatibility of the polyamide resin (A) and the polyamide resin (C) with the compound (b2) or a condensate thereof can be kept higher. The molecular weight of the epoxy group and / or carbodiimide group-containing compound is more preferably 8000 or less.

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

  The epoxy group and / or carbodiimide group-containing compound is preferably solid at 25 ° C. or a liquid having a viscosity of 200 mPa · s or more at 25 ° C. In that case, it becomes easy to obtain a desired viscosity at the time of melt-kneading, the compatibility between the polyamide resin (A) and the polyamide resin (C), and the compound (B) becomes higher, and the low temperature and high temperature after the heat treatment after the heat treatment. The burst strength and high-temperature rigidity can be further improved.

  The value obtained by dividing the molecular weight by the number of functional groups in one molecule, which is an index indicating the functional group concentration of the epoxy group and / or carbodiimide group-containing compound, is preferably 50 to 3000. Here, the number of functional groups refers to the total number of epoxy groups and carbodiimide groups. This value indicates that the smaller the value, the higher the functional group concentration. By setting it to 50 or more, gelation due to excessive reaction can be suppressed, and the polyamide resin (A) and the compound (b2) or a condensate thereof can be suppressed. Since the reactivity increases moderately, the high-temperature rigidity and the burst strength at low and high temperatures after heat treatment can be further improved. The value obtained by dividing the molecular weight of the epoxy group and / or carbodiimide group-containing compound by the number of functional groups in one molecule is more preferably 100 or more, and further preferably 1100 or more. 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 compound (b2) or its condensation on the surface layer of the molded product even during wet heat treatment Bleed-out of objects can be further suppressed and the surface appearance can be further improved. On the other hand, by making the molecular weight of the epoxy group and / or carbodiimide group-containing compound divided by the number of functional groups in one molecule 3000 or less, the reaction with the polyamide resin (A) and the compound (B) is sufficient. The high-temperature rigidity and the burst strength at low and high temperatures after heat treatment can be further improved. From this viewpoint, the value obtained by dividing the molecular weight of the epoxy group and / or carbodiimide group-containing compound by the number of functional groups in one molecule is more preferably 2800 or less, and more preferably 2500 or less.

  Compound (B) (compound (b2) having at least three hydroxyl groups in one molecule obtained by reacting compound (B1) with an epoxy group and / or carbodiimide group-containing compound used in the embodiment of the present invention Or when the condensate is used, the hydroxyl value of the compound (b1) used as the raw material is preferably 100 to 2000 mgKOH / g. By making the hydroxyl value of the compound (B) 100 mgKOH / g or more, it becomes easy to ensure a sufficient amount of reaction between the polyamide resin (A) and the polyamide resin (C) and the compound (B). Burst strength and high temperature rigidity at low and high temperatures after heat treatment can be further improved. The hydroxyl value of the compound (B) is more preferably 300 mgKOH / g or more. On the other hand, by setting the hydroxyl value of the compound (B) to 2000 mgKOH / g or less, the reactivity between the polyamide resin (A) and the polyamide resin (C) and the compound (B) is moderately improved, and gelation is caused by excessive reaction. Therefore, the burst strength at low and high temperatures after heat treatment can be further improved. The hydroxyl value of the compound (B) is more preferably 1800 mgKOH / g or less. The hydroxyl value can be determined by acetylating the compound (B) with a mixed solution of acetic anhydride and anhydrous pyridine and titrating it with an ethanolic potassium hydroxide solution.

  Compound (B) (compound (b2) having at least three hydroxyl groups in one molecule obtained by reacting compound (B1) with an epoxy group and / or carbodiimide group-containing compound used in the embodiment of the present invention Or when using the condensate, the compound (b1) used as the raw material may have other reactive functional groups with both hydroxyl groups. Examples of other functional groups include aldehyde groups, sulfo groups, isocyanate groups, oxazoline groups, oxazine groups, ester groups, amide groups, silanol groups, silyl ether groups, and the like.

  Compound (B) (compound (b2) having at least three hydroxyl groups in one molecule obtained by reacting compound (B1) with an epoxy group and / or carbodiimide group-containing compound used in the embodiment of the present invention Or when using the condensate, although there is no restriction | limiting in particular in the molecular weight of the compound (b1) used as the raw material, 50-10000 are preferable. If the molecular weight of the compound (B) is 50 or more, it is difficult to volatilize at the time of melt kneading, so that the processability is excellent. The molecular weight of the compound (B) is preferably 150 or more, and more preferably 200 or more. On the other hand, if the molecular weight of the compound (B) is 10000 or less, the compatibility with the polyamide resin (A) becomes higher, and thus the effect of the present invention is more remarkably exhibited. The molecular weight of the compound (B) is preferably 6000 or less, more preferably 4000 or less, and still more preferably 800 or less.

  The molecular weight of the compound (B) 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.). Moreover, the molecular weight in case a compound (B) is a condensate uses a weight average molecular weight as a molecular weight. The weight average molecular weight (Mw) can be calculated using gel permeation chromatography (GPC). Specifically, when a solvent in which the compound is dissolved, for example, hexafluoroisopropanol is used as a mobile phase, polymethyl methacrylate (PMMA) is used as a standard substance, and the column is matched to the solvent. For example, when hexafluoroisopropanol is used, Shimadzu Using “Shodex GPC HFIP-806M” and / or “Shodex GPC HFIP-LG” manufactured by GL Corp., the weight average molecular weight can be measured using a differential refractometer as a detector.

  In a more preferred embodiment of the present invention, compound (B2) (compound (b2) obtained by reacting compound (b1) with an epoxy group and / or carbodiimide group-containing compound (b2) ) Or a condensate thereof, the degree of branching of the compound (b1) as the raw material is not particularly limited, but is preferably 0.05 to 0.70. The degree of branching is a numerical value representing the degree of branching in the compound. A linear compound has a degree of branching of 0, and a completely branched dendrimer has a degree of branching of 1. The larger this value, the more the cross-linked structure can be introduced into the polyamide resin composition, the tensile strength and heat aging mechanical properties can be further improved, and the burst strength and high temperature rigidity at low and high temperatures after heat treatment can be further improved. . By setting the degree of branching to 0.05 or more, the crosslinked structure in the polyamide resin composition is sufficiently formed, and the compatibility with the polyamide resin (A) and the polyamide resin (C) is further improved. The heat aging mechanical properties can be further improved, and the burst strength and high temperature rigidity at low and high temperatures after heat treatment can be further improved. The degree of branching is more preferably 0.10 or more. On the other hand, by setting the degree of branching to 0.70 or less, the crosslinked structure in the polyamide resin composition is moderately suppressed, the dispersibility of the compound (B) in the polyamide resin composition is further increased, and the tensile strength and heat aging machine are increased. The characteristics can be further improved, and the burst strength and high temperature rigidity at low and high temperatures after heat treatment can be further improved. The degree of branching is more preferably 0.35 or less. The degree of branching is defined by the following mathematical formula (3).

  Branch degree = (D + T) / (D + T + L) (3)

In the above mathematical formula (3), D represents the number of dendritic units, L represents the number of linear units, and T represents the number of terminal units. In addition, said D, T, and L can be calculated from the integrated value of the peak shift measured by ¹³ C-NMR. D is derived from a tertiary or quaternary carbon atom, T is derived from a primary carbon atom that is a methyl group, L is a primary or secondary carbon atom, Derived from except T.

  Examples of the compound (B) having a degree of branching in the above-mentioned range include, for example, the above-mentioned preferable compound (b1), a reaction product (b2) of such a compound (b1) and an epoxy group and / or carbodiimide group-containing compound, or Examples include condensates.

  In a more preferred embodiment of the present invention, the compound (B) is preferably a compound having a structure represented by the following general formula (4) and / or a condensate thereof.

In the general formula (4), X ^{1 to} X ⁶ may be the same or different and each represents OH, CH ₃ or OR. However, the sum of the number of OH and OR is 3 or more, and the number of OH is 3 or more. R represents an organic group having an epoxy group or a carbodiimide group, and n represents a range of 0 to 20. Note that neither the number of OH nor the number of OR is zero.

  R in the general formula (4) represents an organic group having an epoxy group or an organic group having a carbodiimide group. Examples of the organic group having an epoxy group include an epoxy group, a glycidyl group, a glycidyl ether type epoxy group, a glycidyl ester type epoxy group, a glycidyl amine type epoxy group, a hydrocarbon group substituted with an epoxy group or a glycidyl group, and an epoxy group. Or the heterocyclic group substituted by the glycidyl group etc. are mentioned. Examples of the organic group having a carbodiimide group include an alkyl carbodiimide group, a cycloalkyl carbodiimide group, and an arylalkyl carbodiimide group.

  N in General formula (4) represents the range of 0-20. When n is 20 or less, the plasticization of the polyamide resin (A) and the polyamide resin (C) is suppressed, and the burst strength and high temperature rigidity at low and high temperatures after heat treatment can be further improved. n is more preferably 4 or less. On the other hand, n is more preferably 1 or more, the molecular mobility of the compound (B) can be increased, and the compatibility with the polyamide resin (A) and the polyamide resin (C) can be further improved.

  The sum of the numbers of OH and OR in the general formula (4) is preferably 3 or more. Thereby, it is excellent in compatibility with the polyamide resin (A) and the polyamide resin (C), and the burst strength and high temperature rigidity at low and high temperatures after the heat treatment can be further improved. Here, the sum of the number of OH and OR 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.) in the case of a low molecular compound. be able to.

  In the case of a condensate, the OH number can be obtained from the following formula (2) by calculating the number average molecular weight and the hydroxyl value of the compound having the structure represented by the general formula (4) and / or the condensate thereof.

  OH number = (number average molecular weight × hydroxyl value) / 56110 (2)

  In the case of a condensate, the number of ORs can be calculated by a value obtained by dividing the number average molecular weight of the compound having the structure represented by the general formula (4) and / or the condensate thereof by an epoxy equivalent or a carbodiimide equivalent. The number average molecular weight of the compound having the structure represented by the general formula (4) and / or the condensate thereof can be calculated using a gel permeation chromatograph (GPC). Specifically, it can be calculated by the following method. A solvent in which the compound having the structure represented by the general formula (4) and / or the condensate thereof is dissolved, for example, hexafluoroisopropanol is used as a mobile phase, and polymethyl methacrylate (PMMA) is used as a standard substance. The column is matched to the solvent. For example, when hexafluoroisopropanol is used, “Shodex GPC HFIP-806M” and / or “Shodex GPC HFIP-LG” manufactured by Shimadzu GL Corporation is used as a detector. The number average molecular weight can be measured using a differential refractometer.

  In the polyamide resin composition used in the embodiment of the present invention, the content of the compound (B) is 0.1 to 20 parts by weight (0.1 to 20 parts by weight with respect to 100 parts by weight of the polyamide resin (A). Part or less). When the content of the compound (B) is less than 0.1 parts by weight, the burst strength at low and high temperatures after the heat treatment decreases. The content of the compound (B) is preferably 0.5 parts by weight or more and more preferably 2.5 parts by weight or more with respect to 100 parts by weight of the polyamide resin (A). On the other hand, when the compounding amount of the compound (B) exceeds 20 parts by weight, the dispersibility of the compound (B) in the polyamide resin composition decreases, and the plasticization and decomposition of the polyamide resin (A) are promoted, and the amount of gas , And the burst strength and high-temperature rigidity at low and high temperatures after heat treatment decrease. The content of the compound (B) is preferably 7.5 parts by weight or less, and more preferably 6 parts by weight or less with respect to 100 parts by weight of the polyamide resin (A).

  In the polyamide resin composition used in the embodiment of the present invention, the compound (B) is obtained by reacting the aforementioned hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound. When a compound having two hydroxyl groups is used, its production method is not particularly limited. A method of dry blending a hydroxyl group-containing compound and an epoxy group and / or carbodiimide group-containing compound, and melt-kneading at a temperature higher than the melting point of both components Is preferred.

  It is also preferable to add a catalyst in order to promote the reaction between the hydroxyl group and the epoxy group and / or carbodiimide group. The addition amount of the catalyst is not particularly limited, and is preferably 0 to 1 part by weight, and 0.01 to 0.3 part by weight with respect to 100 parts by weight in total of the hydroxyl group-containing compound and the epoxy group and / or carbodiimide group-containing compound. More preferred.

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

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

  By melting and kneading the hydroxyl group-containing compound and the epoxy group and / or carbodiimide group-containing compound, the hydroxyl group in the hydroxyl group-containing compound reacts with the epoxy group and / or carbodiimide group in the epoxy group and / or carbodiimide group-containing compound. To do. In addition, a dehydration condensation reaction occurs between the hydroxyl group-containing compounds. In this way, a compound (B) having a multi-branched structure can be obtained.

  When a compound (B) is prepared by reacting a hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound, the compounding ratio thereof is not particularly limited, but the number of hydroxyl groups in one molecule of the compound (B) is not limited. These compounds are preferably blended so that the sum is larger than the sum of the number of epoxy groups and carbodiimide groups in one molecule of the compound (B). The epoxy group and carbodiimide group are excellent in reactivity with the end groups of the polyamide resin (A) and the polyamide resin (C) as compared with the hydroxyl group. For this reason, by forming the sum of the number of hydroxyl groups in one molecule of the compound (B) more than the sum of the number of epoxy groups and carbodiimide groups in one molecule of the compound (B), an excessive crosslinked structure is formed. It is possible to suppress embrittlement due to, and to further improve the burst strength and high temperature rigidity at low and high temperatures after heat treatment.

  The weight ratio of the hydroxyl group-containing compound to the epoxy group and / or carbodiimide group-containing compound to be reacted ((epoxy group and / or carbodiimide group-containing compound) / (hydroxyl group-containing compound)) is preferably 0.3 or more and less than 10,000. The reactivity of the polyamide resin (A) and the polyamide resin (C) with the epoxy group and / or carbodiimide group-containing compound, and the reactivity of the hydroxyl group-containing compound with the epoxy group and / or carbodiimide group-containing compound are as follows. And higher than the reactivity of the polyamide resin (C) and the compound (B). For this reason, when the weight ratio is 0.3 or more, the formation of gel due to excessive reaction is suppressed, the tensile strength and the heat aging mechanical properties are further improved, the burst strength and the high temperature rigidity at low and high temperatures after heat treatment. Can be further improved. When a compound (B) is produced by reacting a hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound, the reaction rate between the hydroxyl group and the epoxy group or 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-aggregation force can be reduced, and the reactivity with the polyamide resin (A) and the polyamide resin (C) can be increased. The heat aging mechanical properties can be further improved, and the burst strength and high temperature rigidity at low and high temperatures after heat treatment can be further improved.

  When a compound (B) is produced by reacting a hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound, the reaction rate of the epoxy group or 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-aggregation force can be reduced, and the reactivity with the polyamide resin (A) and the polyamide resin (C) can be increased. The burst strength at low and high temperatures after heat treatment is further improved. The reaction rate is more preferably 10% or more, and further preferably 20% or more. On the other hand, when the reaction rate is 95% or less, an epoxy group or a carbodiimide group can be appropriately left, and the reactivity of the polyamide resin (A) and the polyamide resin (C) can be increased. The reaction rate is more preferably 90% or less, and further preferably 70% or less.

The reaction rate between the hydroxyl group and the epoxy group and / or carbodiimide group is determined by dissolving the compound (B) obtained by the reaction in a solvent (for example, deuterated dimethyl sulfoxide, deuterated hexafluoroisopropanol, etc.) In this case, the peak derived from the epoxy ring can be calculated by determining the amount of decrease before and after the reaction with the hydroxyl group-containing compound used as a raw material by ¹ H-NMR measurement. In the case of a carbodiimide group, the carbodiimide group-derived peak can be calculated by determining the amount of decrease before and after the reaction with the hydroxyl group-containing compound used as a raw material by ¹³ C-NMR measurement. The reaction rate can be obtained by the following mathematical formula (5).

  Reaction rate [%] = {1- (e / d)} × 100 (5)

  In the above mathematical formula (5), d represents the peak area of a dry blend of the hydroxyl group-containing compound used as the raw material and the epoxy group and / or carbodiimide group-containing compound, and e represents the compound (B) obtained by the reaction. Represents the peak area.

As an example, FIG. 1 shows a ¹ H-NMR spectrum of a dry blend of dipentaerythritol and bisphenol A type epoxy resin (“jER” (registered trademark) 1004 manufactured by Mitsubishi Chemical Corporation) at a weight ratio of 3: 1. . Further, FIG. 2 shows a ¹ H-NMR spectrum of a melt-kneaded reaction product (B-8) of a polyhydric alcohol and an epoxy compound obtained in Reference Example 6 described later. Deuterated dimethyl sulfoxide was used as a solvent, the sample amount was 0.035 g, and the solvent amount was 0.70 ml. Reference numeral 1 indicates a solvent peak.

Formula from ¹ H-NMR spectrum shown in Figure 1, obtains the sum of the epoxy ring from the peak area appearing in the vicinity of 2.60ppm and 2.80 ppm, to find the total peak area shown in FIG. 2 as well, to calculate the reaction rate The reaction rate is calculated from (5). 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 (C) used in the embodiment of the present invention is a polyamide resin mainly composed of amino acid (i), lactam (ii) or diamine and dicarboxylic acid (iii), and is an amide of the first polyamide resin. This is a polyamide resin having an amide group concentration of 0.8 mmol / g or more smaller than the group concentration. In other words, the polyamide resin (C) is a polyamide resin different from the polyamide resin (A) that satisfies the following mathematical formula (6). When 3 or more types of polyamide resins are mix | blended in a resin composition, a polyamide resin with the lowest amide group density | concentration is made into a polyamide resin (C). The amide group concentration can be determined in the same manner as in the polyamide resin (A) described above.

  Amide group concentration of polyamide resin (A) −0.8 ≧ amide group concentration of polyamide resin (C) Formula (6)

  By blending a polyamide resin (C) different from the polyamide resin (A) that satisfies the mathematical formula (6), the resin phase of the polyamide resin (C) is dispersed in the polyamide resin (A). ) Is more compatible with the compound (B) than the polyamide resin (A), so that the dispersibility of the compound (B) can be further improved and the generation of gas during molding can be suppressed. it can. Moreover, since the polyamide resin (C) has toughness even in a low temperature region as compared with the polyamide resin (A), the burst strength at a low temperature after the heat treatment of the molded product can be further improved.

  A typical example of the raw material of the polyamide resin (C) is the same raw material as the polyamide resin (A). Specific examples of the polyamide resin (C) include polyamide resins similar to the polyamide resin (A). The polyamide resin (C) is preferably a crystalline polyamide. Among these, the polyamide resin (C) is preferably an aliphatic polyamide.

  As the polyamide resin (C), the resin exemplified above can be used as long as the following mathematical formula (6) is satisfied, but it is more preferable to satisfy the following mathematical formula (7).

  Amide group concentration of polyamide resin (A) −0.8 ≧ amide group concentration of polyamide resin (C) Formula (6)

  Amide group concentration of polyamide resin (A) −1.0 ≧ amide group concentration of polyamide resin (C) (7)

  Among these, the polyamide resin composition is preferred because of its high-temperature rigidity, low temperature after heat treatment and excellent burst strength at high temperature, and crystalline polyamide is preferred. Reactivity with the aforementioned compound (B) and low-temperature burst after heat treatment Aliphatic polyamides are preferred because of their excellent strength and low gas properties. Among these, one selected from the group consisting of polyamide 410, polyamide 510, polyamide 610, polyamide 1010, polyamide 1012, polyamide 11 and polyamide 12 is preferable. Since these crystalline aliphatic polyamide resins have an excellent balance between high-temperature rigidity and low-temperature toughness and high thermal stability, the burst strength and high-temperature rigidity at low and high temperatures after heat treatment of molded products can be further improved. .

  In addition, as the polyamide resin (A), two or more kinds of the polyamide resins exemplified above may be blended, but the polyamide resin (C) satisfies the formula (6), and the polyamide resin exemplified above (polyamide resin) (Except (A)) is contained only 1 type. That is, in a composition containing a plurality of polyamide resins, the polyamide resin (C) always has the lowest amide group concentration, and the other polyamide resins correspond to the polyamide resin (A).

  The following is mentioned as a preferable combination of a polyamide resin (A) and a polyamide resin (C). When the polyamide resin (A) is polyamide 6, examples of the polyamide resin (C) include polyamide 410, polyamide 510, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 66, examples of the polyamide resin (C) include polyamide 410, polyamide 510, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 46, examples of the polyamide resin (C) include polyamide 66, polyamide 6, polyamide 410, polyamide 510, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 56, examples of the polyamide resin (C) include polyamide 66, polyamide 6, polyamide 410, polyamide 510, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 6/66, examples of the polyamide resin (C) include polyamide 410, polyamide 510, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 66 / 6T, examples of the polyamide resin (C) include polyamide 410, polyamide 510, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 6T / 6I, examples of the polyamide resin (C) include polyamide 410, polyamide 510, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 66 / 6I, examples of the polyamide resin (C) include polyamide 410, polyamide 510, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 66 / 6I / 6, examples of the polyamide resin (C) include polyamide 410, polyamide 510, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 6 / 6T, examples of the polyamide resin (C) include polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 5T / 6T, examples of the polyamide resin (C) include polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 410, examples of the polyamide resin (C) include polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 11, and polyamide 12.

  When the polyamide resin (A) is polyamide MXD6, examples of the polyamide resin (C) include polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 6T / M5T, examples of the polyamide resin (C) include polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 12.

  When the polyamide resin (A) is polyamide 610, examples of the polyamide resin (C) include polyamide 1010, polyamide 1012, polyamide 11, and polyamide 12.

  When the polyamide resin (A) is polyamide 9T, examples of the polyamide resin (C) include polyamide 11 and polyamide 12. (A) When the polyamide resin is polyamide 10T, examples of the (C) polyamide resin include polyamide 11, polyamide 12, and the like.

  In the polyamide resin composition used in the embodiment of the present invention, the content of the polyamide resin (C) different from the polyamide resin (A) satisfying the mathematical formula (6) is 0 with respect to 100 parts by weight of the polyamide resin (A). 0.05 parts by weight or more and less than 5 parts by weight. When the blending amount of the polyamide resin (C) is less than 0.05 parts by weight, since the resin phase of the polyamide resin (C) is not formed in the polyamide resin (A), the dispersibility of the compound (B) decreases, As the amount of gas increases, the burst strength at low and high temperatures after heat treatment decreases. The blending amount of the polyamide resin (C) is preferably 0.1 parts by weight or more, and more preferably 2.0 parts by weight or more with respect to 100 parts by weight of the polyamide resin (A). On the other hand, when the compounding amount of the compound (B) is 5 parts by weight or more, the amide exchange reaction between the polyamide resin (A) and the polyamide resin (C) proceeds excessively in the polyamide resin composition, and the polyamide resin composition Since the degree of crystallinity is reduced, plasticization and decomposition of the polyamide resin composition are promoted, the amount of gas is increased, and the burst strength and high temperature rigidity at low and high temperatures after heat treatment are reduced. The amount is preferably 4.95 parts by weight or less, and more preferably 4.90 parts by weight or less.

  The degree of polymerization of these polyamide resins (C) 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 1.5 to 7.0. It is preferable that it is the range of these. If the relative viscosity is 1.5 or more, the burst strength can be further improved since the balance between strength and toughness is excellent. In addition, the burst strength after the heat treatment can be further improved. The relative viscosity is more preferably 2.0 or more, and further preferably 2.5 or more. On the other hand, if the relative viscosity is 7.0 or less, the moldability is excellent. Moreover, shear heat generation at the time of plasticizing can be moderately suppressed, and generation of gas due to thermal decomposition of the polymer can be suppressed.

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

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

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

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

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

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

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

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

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

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

  Non-fibrous fillers include, for example, non-swelling silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, calcium silicate, and Li-type fluorine. Teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, swellable layered silicate represented by swelling mica of Li-type tetrasilicon fluorine mica, silicon oxide, magnesium oxide, alumina, silica, diatomaceous earth, zirconium oxide, oxidation Metal oxides such as titanium, iron oxide, zinc oxide, calcium oxide, tin oxide and antimony oxide, metal carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dolomite and hydrotalcite, calcium sulfate, barium sulfate Metal sulfates, such as hydroxide Metal hydroxides such as nesium, calcium hydroxide, aluminum hydroxide, basic magnesium carbonate, montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite 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 swellable layered silicate, exchangeable cations existing between layers may be exchanged with organic onium ions, and examples of the organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Moreover, you may contain 2 or more types of these fillers.

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

  In the polyamide resin composition of the embodiment of the present invention, the content of the filler is preferably 1 to 150 parts by weight with respect to 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 of the molded product can be further improved. The content of the filler is more preferably 10 parts by weight or more, and further preferably 20 parts by weight or more. On the other hand, when the content of the filler is 150 parts by weight or less, a molded product having excellent fluidity and excellent weldability 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 according to the embodiment of the present invention can contain a resin other than the polyamide resin and various additives depending on the purpose within a range not impairing the effects of the present invention.

  Specific examples of resins other than polyamide resins include polyester resins, polyolefin resins, modified polyphenylene ether resins, polysulfone resins, polyketone resins, polyetherimide resins, polyarylate resins, polyether sulfone resins, polyether ketone resins, polythioethers. Examples thereof include ketone resins, polyether ether ketone resins, polyimide resins, polyamideimide resins, and tetrafluoropolyethylene resins. When these resins are blended, the content 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 fully utilize the characteristics of the polyamide resin.

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

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

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

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

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

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

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

  When melt kneading using a twin screw extruder, there is no particular limitation on the raw material supply method to the twin screw extruder, but when supplying the compound (B) to the twin screw extruder, the compound (B) is: In a temperature range higher than the melting point of the polyamide resin, it is easy to promote the decomposition of the polyamide resin. Therefore, the compound (B) is supplied from the downstream side of the polyamide resin supply position, and the polyamide resin (A) and the polyamide resin (C) It is preferable to shorten the kneading time of the compound (B). Here, the side on which the raw material of the twin-screw extruder is supplied is defined as upstream, and the side on which molten resin is discharged is defined as downstream.

  The copper compound plays a role of protecting the amide group by coordinating to the amide group of the polyamide resin (A) and the polyamide resin (C), and as a compatibilizer for the (A) polyamide resin and the compound (B). Therefore, when compounding a copper compound, (A) the polyamide resin is supplied to a twin-screw extruder, and the polyamide resin (A), the polyamide resin (C), and the copper compound are sufficient. It is preferable to make it react.

  The ratio (L / D) between the total screw length L and the screw diameter D (L / D) of the twin screw extruder is preferably 25 or more, more preferably more than 30. By setting the L / D to 25 or more, (the polyamide resin (A) and the polyamide resin (C) and, if necessary, the copper compound are sufficiently kneaded, and then the compound (B) and other components can be easily supplied if necessary. As a result, the decomposition of the polyamide resin (A) and the polyamide resin (C) can be suppressed, and the dispersibility of the polyamide resin (A) and the polyamide resin (C) and the compound (B) can be further increased. This improves the burst strength and high temperature rigidity at low and high temperatures after heat treatment of the molded product obtained.

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

  The compound (B) is preferably supplied to the twin-screw extruder from the downstream side of 1/2 of the screw length and melt-kneaded. By supplying the compound (B) from the downstream side of 1/2 of the screw length, the compound (A) and the polyamide resin (C) and, if necessary, the copper compound are sufficiently kneaded, the compound ( B) can be easily supplied. As a result, the reactivity of the compound (B) with the polyamide resin (A) and the polyamide resin (C) is improved while suppressing the thickening of the polyamide resin (A), and the dispersibility can be further improved. . As a result, the burst strength and high temperature rigidity at low and high temperatures after the heat treatment of the obtained molded product are further improved.

  In order to express the effect of the present invention more remarkably, it is preferable to increase the dispersibility of the compound (B) in the polyamide resin composition. Specifically, a method of further promoting the dehydration condensation reaction between the hydroxyl group in the compound (B) and the carboxyl terminal group of the polyamide resin (A) and the polyamide resin (C) is preferable, and the finely dispersed structure in the polyamide resin composition By forming, the burst strength and high temperature rigidity at low and high temperatures after the heat treatment of the molded product obtained are further improved. Means for increasing the dispersibility of the compound (B) in the polyamide resin composition include, for example, a method of increasing the resin pressure during melt-kneading by selecting a kneading temperature and screw arrangement, a method of melt-kneading through a plurality of extruders, a polyamide Preferred examples include a method of preparing a high-concentration preliminary mixture of the resin (A) and the polyamide resin (C) and the compound (B), and melt-kneading this with the (A) polyamide resin.

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

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

  The kneading zone is superior in the kneadability and reactivity of the molten resin compared to the full flight zone. By filling the kneading zone with the molten resin, kneadability and reactivity are dramatically improved. As an index indicating the state of filling of the molten resin, there is a value of the resin pressure. As the resin pressure is larger, it becomes one standard indicating that the molten resin is filled. That is, when using a twin screw extruder, the kneadability and reactivity can be further improved by increasing the resin pressure in the kneading zone within a predetermined range from the resin pressure in the full flight zone. The dispersibility of the compound (B) in the product can be further increased, and as a result, the burst strength and the high temperature rigidity at low and high temperatures after heat treatment of the obtained molded product are further improved.

  The method for increasing the resin pressure in the kneading zone is not particularly limited. For example, it is generally known that the cylinder set temperature during melt kneading is equal to or higher than the melting point of the resin. The zone, that is, the first plastic part is higher than the melting point, the cylinder temperature downstream from the first kneading zone is set to the melting point or lower, and the resin pressure is increased by increasing the viscosity of the molten resin. Alternatively, a method of introducing a reverse screw zone having an effect of pushing back the molten resin upstream, a seal ring zone having an effect of accumulating the molten resin, or the like can be preferably used on the downstream side of the kneading zone. The reverse screw zone and the seal ring zone are formed of one or more reverse screws and one or more seal rings, and they can be combined.

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

  When the total length of the kneading zone on the downstream side of the supply position of the compound (B) 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, decomposition of the polyamide resin (A) and the polyamide resin (C) can be further suppressed. Ln2 / L is more preferably 0.16 or less.

  Further, the polyamide resin (A) and the polyamide resin (C) and the compound (B) are melt-kneaded, the obtained resin composition is repeatedly passed through an extruder, and melt-kneading is repeated a plurality of times, in the polyamide resin composition. The method of improving the dispersibility of a compound (B) can also be mentioned.

  When preparing a polyamide resin composition by a method of preparing a high-concentration premix of the polyamide resin (A) and the polyamide resin (C) and the compound (B) and melt-kneading this with the (A) polyamide resin, (A ) To 100 parts by weight of the polyamide resin, 10 to 250 parts by weight of the compound (B) and 0.05 part by weight or more and less than 5 parts by weight of the polyamide resin (C) are melt-kneaded to prepare a high-concentration pre-mixture. More preferably, the concentration premix is further melt-kneaded with (A) a polyamide resin and, if necessary, other components together with a twin screw extruder. Compared with the case where a high-concentration premix is not produced, the burst strength and high temperature rigidity at low and high temperatures after the heat treatment of the molded product obtained are further improved.

  Although it is not certain about this factor, (A) the polyamide resin and the compound (B) are prepared by melt-kneading the compound (B) at a high concentration with the polyamide resin (A) and the polyamide resin (C) in advance. It is considered that a large number of components that contribute to the improvement of compatibility, that is, a compatibilizing agent, are generated, and the compatibility between the polyamide resin (A) and the polyamide resin (C) and the compound (B) is further improved.

  On the other hand, when producing a high concentration premix, the content of the compound (B) increases with respect to the polyamide resin (A) and the polyamide resin (C). In order to suppress a decrease in residence stability, during melt kneading in a twin screw extruder, the compound (B) is supplied from the downstream side of the polyamide resin supply position, and the polyamide resin (A) and the polyamide resin (C), It is preferable to shorten the kneading time of the compound (B). The (A) polyamide resin used in the high concentration premix and the (A) polyamide resin further blended in the high concentration premix may be the same or different.

  The polyamide resin composition thus obtained can be used to obtain various molded products by known methods. Examples of the molding method include injection molding, injection compression molding, extrusion molding, compression molding, blow molding, and press molding.

  The molded article according to the embodiment of the present invention can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, household goods, and hygiene articles by taking advantage of its excellent characteristics. The composite molded product according to the embodiment of the present invention includes, in particular, automotive engine peripheral parts, automobile underhood parts, automobile exterior parts, intake / exhaust system parts, engines that require low-temperature / high-temperature burst strength after heat treatment and high-temperature rigidity. It is particularly preferably used for cooling water system parts, automotive electrical parts, and electrical / electronic parts. Specifically, the polyamide resin composition and the molded product thereof according to the embodiment of the present invention include automotive engine peripheral parts such as an engine cover, an air intake pipe, a timing belt cover, an intake manifold, a filler cap, a throttle body, and a cooling fan. Cooling fan, radiator tank top and base, cylinder head cover, oil pan, brake piping, fuel piping tube, waste gas system parts and other automotive underhood parts, front fender, rear fender, fuel lid, door panel, cylinder head cover, door mirror stay , Tailgate panel, license garnish, roof rail, engine mount bracket, rear garnish, rear spoiler, trunk lid, rocker model Automotive exterior parts such as roof, molding, lamp housing, front grille, mudguard, side bumper, air intake manifold, intercooler inlet, turbocharger, exhaust pipe cover, inner bush, bearing retainer, engine mount, engine head cover, throttle body, etc. Intake / exhaust system parts, chain covers, thermostat housings, outlet pipes, radiator tanks, oil naters, delivery pipes and other engine cooling water system parts, connectors and wire harness connectors, motor parts, lamp sockets, sensor on-board switches, combination switches, etc. Examples of automotive electrical parts and electrical / electronic parts include generators, motors, transformers, current transformers, Pressure regulator, Rectifier, Resistor, Inverter, Relay, Power contact, Switch, 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 terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, IC and LED compatible housings, capacitor seats, fuse holders, various gears, various cases, cabinets and other electrical parts, connectors, SMT compatible connector, card connector, jack, coil, coil bobbin, sensor, LED lamp, socket, resistor, relay, relay case, reflector, small switch, power supply component, coil bobbin, condensate Sir, variable capacitor case, optical pickup chassis, oscillator, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, Si power modules and SiC power modules, It is preferably used for electronic parts such as semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, transformer members, parabolic antennas, computer-related parts and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The characteristic evaluation was performed according to the following method.

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

[Weight average molecular weight and number average molecular weight]
It is obtained by dissolving 2.5 mg of compound (B), epoxy group and / or carbodiimide group-containing compound in 4 ml of hexafluoroisopropanol (0.005N-sodium trifluoroacetate added) and filtering with a 0.45 μm filter. The solution was used for the measurement. The measurement conditions are shown below.

Apparatus: Gel permeation chromatography (GPC) (manufactured by Waters)
Detector: differential refractometer Waters 410 (manufactured by Waters)
Column: Shodex GPC HFIP-806M (2 pieces) + HFIP-LG (Shimadzu GL Corp.)
Flow rate: 0.5 ml / min
Sample injection volume: 0.1 ml
Temperature: 30 ° C
Molecular weight calibration: Polymethylmethacrylate

[Amide group concentration of polyamide resin]
0.06 g of polyamide resin was weighed into a vial and subjected to thermal decomposition with an aqueous hydrobromic acid solution at 150 ° C. for 3 hours. Subsequently, an aqueous sodium hydroxide solution is added to make the system alkaline, and then toluene and ethyl chloroformate are added and shaken. The supernatant liquid was taken out, measured under the following conditions, the structural unit constituting the polyamide was specified, the molecular weight thereof was calculated, and it was obtained from the mathematical formula (1).

Apparatus: Gas chromatograph (Shimadzu GC-14A: manufactured by Shimadzu Corporation)
Detector: Hydrogen flame ionization detector Column: NB-1 (filler methyl siloxane 100%, manufactured by J & W)
Carrier gas: He (3.0 ml / min) Column oven temperature: 150 ° C. to 330 ° C. (temperature rise at 10 ° C./min)

  Amide group concentration [mmol / g] = (number of amide groups per structural unit / molecular weight of structural unit) × 1000 (1)

[Hydroxyl value]
0.5 g of the compound (B) was sampled and added to each 250 ml Erlenmeyer flask, and then 20.00 ml of a solution prepared by adjusting and mixing acetic anhydride and anhydrous pyridine at 1:10 (mass ratio) was sampled. Then, a reflux condenser was attached, and the mixture was refluxed with stirring in an oil bath adjusted to 100 ° C. for 20 minutes, and then cooled to room temperature. Further, 20 ml of acetone and 20 ml of distilled water were added to the Erlenmeyer flask through a condenser. A phenolphthalein indicator was added thereto, and titrated with a 0.5 mol / L ethanolic potassium hydroxide solution. In addition, the hydroxyl value was computed by the following numerical formula (8) by subtracting the measurement result of the blank (sample is not included) measured separately.

Hydroxyl value [mgKOH / g] = [((B−C) × f × 28.05) / S] + E (8)
However, B: amount of 0.5 mol / L ethanolic potassium hydroxide solution used for titration [ml], C: amount of 0.5 mol / L ethanolic potassium hydroxide solution used for blank titration [ml ], F: factor of 0.5 mol / L ethanolic potassium hydroxide solution, S: sample mass [g], E: acid value

[Reaction rate of compound (B)]
0.035 g of the compound (B) was dissolved in 0.7 ml of deuterated dimethyl sulfoxide, and in the case of an epoxy group, ¹ H-NMR measurement was performed, and in the case of a carbodiimide group, ¹³ C-NMR measurement was performed. Each analysis condition is as follows.

(1) ¹ H-NMR
Apparatus: Nuclear magnetic resonance apparatus (JNM-AL400) manufactured by JEOL Ltd.
Solvent: Deuterated dimethyl sulfoxide Observation frequency: OBFRQ 399.65 MHz, OBSET 124.00 KHz, OBFIN 10500.00 Hz
Integration count: 256 times

(2) ¹³ C-NMR
Apparatus: Nuclear magnetic resonance apparatus (JNM-AL400) manufactured by JEOL Ltd.
Solvent: Deuterated dimethyl sulfoxide Observation frequency: OBFRQ 100.40 MHz, OBSET 125.00 KHz, OBFIN 10500.00 Hz
Integration count: 512 times

From the obtained ¹ H-NMR spectrum, the area of the peak derived from the epoxy ring was determined. Moreover, the area of the peak derived from a carbodiimide group was calculated | required from the obtained ¹³ C-NMR spectrum. The peak area was calculated by integrating the area surrounded by the baseline and the peak using analysis software attached to the NMR apparatus. The peak area of a compound obtained by dry blending the compound (B) and an epoxy group and / or carbodiimide group-containing compound was d, the peak area of the compound (B) was e, and the reaction rate was calculated by the following mathematical formula (5).

  Reaction rate [%] = {1- (e / d)} × 100 (5)

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. the compound ¹ H-NMR spectrum of (B-8) from ¹ H-NMR spectrum shown in FIG. 2. Fig. 1 obtained in reference example 6, the epoxy ring appearing in the vicinity of 2.60ppm and 2.80ppm The sum of the peak areas of origin was obtained, and the sum of the peak areas shown in Fig. 2 was similarly obtained, and the reaction rate was calculated from the mathematical formula (5) for calculating the reaction rate. Normalized by the peak area of the benzene ring.

[Degree of branching]
The compound (B) was analyzed by ¹³ C-NMR under the following conditions, and the degree of branching (DB) was calculated by the following mathematical formula (3).

  Branch degree = (D + T) / (D + T + L) (3)

In the above mathematical formula (3), D represents the number of dendritic units, L represents the number of linear units, and T represents the number of terminal units. Said D, T, and L were computed from the peak area measured by ¹³ C-NMR. D is derived from a tertiary or quaternary carbon atom, T is derived from a primary carbon atom that is a methyl group, L is a primary or secondary carbon atom, Derived from except T. The peak area was calculated by integrating the area surrounded by the baseline and the peak using analysis software attached to the NMR apparatus. The measurement conditions are as follows.

(1) ¹³ C-NMR
Apparatus: Nuclear magnetic resonance apparatus (JNM-AL400) manufactured by JEOL Ltd.
Solvent: Deuterated dimethyl sulfoxide measurement sample amount / solvent amount: 0.035 g / 0.70 ml
Observation frequency: OBFRQ 100.40MHz, OBSET125.00KHz, OBFIN10500.00Hz
Integration count: 512 times

[Sum of number of hydroxyl groups of compound (B) and number of epoxy groups and carbodiimide groups]
The number of OH was calculated by the following mathematical formula (2) from the number average molecular weight and the hydroxyl value of the compound (B).

  Number of OH = (number average molecular weight × hydroxyl number) / 56110 (2)

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

  The number average molecular weight and hydroxyl value of the compound (B) were measured by the methods described above. Epoxy equivalent is obtained by dissolving 400 mg of compound (B) in 30 ml of hexafluoroisopropanol, adding 20 ml of acetic acid and tetraethylammonium bromide / acetic acid solution (= 50 g / 200 ml), and adding 0.1N perchloric acid as a titrant and Crystal violet was used as an indicator, and calculated from the following formula (9) from the titration amount when the color of the solution changed from purple to blue-green.

Epoxy equivalent [g / eq] = W / ((F−G) × 0.1 × f × 0.001) (9)
F: amount of 0.1N perchloric acid used for titration [ml], G: amount of 0.1N perchloric acid used for titration of blank [ml], f: 0.1N perchloric acid Acid factor, W: sample weight [g]

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

[Burst strength after heat treatment]
The pellets obtained in each example and comparative example were dried under reduced pressure at 80 ° C. for 12 hours, and using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: polyamide resin (A) A test piece 1 shown in FIG. 3 and a test piece 2 shown in FIG. 4 were produced by injection molding under the conditions of melting point + 15 ° C. and mold temperature: 80 ° C. In addition, the horizontal length ((1) of FIG. 3) of the test pieces 1 and 2 is 148 mm, and the vertical length ((2) of FIG. 3) is 60 mm. About these molded articles, the test piece 1 is fixed to the upper part of the vibration welding machine, the test piece 2 is fixed to the lower part, and they are overlapped and rubbed by vibration to be melted and joined to form the molded article 3 shown in FIG. Produced. Specifically, welding was performed under the following conditions using a Branson 2850 type vibration welding apparatus.

・ Pressure: 0.7 MPa
・ Amplitude: 1.5mm
-Welding allowance: 1.5mm

  The welded molded article was left in a 230 ° C. hot air oven for 500 hours. Then, after standing for 1 hour in a -40 ° C. or 150 ° C. thermostatic bath, the molded product was taken out from the thermostatic bath and 10 seconds later, using a burst strength tester manufactured by Iwaki Pump Co., Ltd. (3) shown in FIG. A water pressure of 1.13 g / sec was applied from the inlet, and the average pressure at the time of rupture was set to a burst strength of −40 ° C. or 150 ° C.

[High temperature stiffness]
The pellets obtained in each example and comparative example were dried under reduced pressure at 80 ° C. for 12 hours, and using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: polyamide resin (A) A rod-shaped test piece having a thickness of 1/4 inch was manufactured by injection molding under the conditions of melting point + 15 ° C. and mold temperature: 80 ° C. This test piece is subjected to a bending test under a condition of a crosshead speed of 3 mm / min in a thermostatic chamber adjusted to 150 ° C. using a bending tester Tensilon RTA-1T (manufactured by Orientec) according to ASTM D790. And the flexural modulus was measured. The measurement was performed three times, and the average value was calculated as the flexural modulus.

[Gas generation amount]
The pellets obtained in each example and comparative example were dried under reduced pressure at 80 ° C. for 12 hours, and 100 g of the pellets were weighed in an aluminum cup. After standing for 1 hour in a hot air oven having a melting point of the polyamide resin + 20 ° C., the weight of the pellet was weighed, and the weight loss was taken as the amount of gas generated.

<Reference Example 1> (A-3)
A 10T salt, which is an equimolar salt of decamethylenediamine and terephthalic acid, and 0.5 mol% of decamethylenediamine with respect to the total amount of decamethylenediamine were added in excess. Furthermore, 30 parts by weight of water was added to and mixed with 70 parts by weight of these raw materials. This was charged in a pressure vessel, sealed, and purged with nitrogen. Heating was started, and the pressure in the can was maintained at 2.0 MPa and the temperature in the can at 240 ° C. for 2 hours. Thereafter, the contents were discharged from the reaction vessel onto a cooling belt, which was vacuum dried at 100 ° C. for 24 hours to obtain a polyamide resin oligomer. The obtained polyamide oligomer was pulverized, dried, and solid-phase polymerized at 50 Pa and 240 ° C. to obtain nylon 10T (A-3) having ηr = 2.31, melting point 317 ° C., and amide group concentration 6.62 mmol / g. .

<Reference Example 2> (C-2)
700 g of 410 salt which is an equimolar salt of tetramethylene diamine and sebacic acid, 21.2 g of tetramethylene diamine 10 wt% aqueous solution (1.00 mol% with respect to 410 salt), 0.3065 g of sodium hypophosphite (weight of polymer produced) 0.05 wt%) was charged in a polymerization can and sealed, and the atmosphere was replaced with nitrogen. After heating was started and the internal pressure of the can reached 0.5 MPa, the internal pressure of the can was maintained at 0.5 MPa for 1.5 hours while releasing moisture out of the system. Thereafter, the internal pressure of the can was returned to normal pressure over 10 minutes, and the reaction was further continued for 1.5 hours under a nitrogen flow to complete the polymerization. Thereafter, the polymer was discharged from the polymerization can into pellets and pelletized, and this was vacuum-dried at 80 ° C. for 24 hours. Nylon 410 (ηr = 2.84, melting point 252 ° C., amide group concentration 7.86 mmol / g) C-2) was obtained.

<Reference Example 3> (B-5)
A phenol novolac epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.) is used for 100 parts by mass of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd., molecular weight / number of functional groups 42 per molecule). ) After preliminarily mixing 10 parts by mass, the mixture was melt-kneaded for 3.5 minutes under the conditions of a cylinder temperature of 200 ° C. and a screw rotation speed of 100 rpm using a Ikegai PCM30 type twin screw extruder, and pelletized by a hot cutter. The obtained pellets were again supplied to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (3) and / or its condensate. The reaction rate of the obtained compound (B-5) was 53%, the degree of branching was 0.29, and the hydroxyl value was 1280 mgKOH / g. There are three or more hydroxyl groups in one molecule, and the number of hydroxyl groups in one molecule is larger than the number of epoxy groups in one molecule, and the sum of the number of OH and OR in the general formula (4) is three or more. Met.

<Reference Example 4> (B-6)
The compound represented by the general formula (4) and / or the same as Reference Example 3 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 (B-6) was 2%, the degree of branching was 0.15, and the hydroxyl value was 1350 mgKOH / g. There are three or more hydroxyl groups in one molecule, and the number of hydroxyl groups in one molecule is larger than the number of epoxy groups in one molecule, and the sum of the number of OH and OR in the general formula (4) is three or more. Met.

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

<Reference Example 6> (B-8)
Bisphenol A type epoxy resin ("jER" (registered trademark) 1004 manufactured by Mitsubishi Chemical Corporation) per 100 parts by mass of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.), two epoxy groups in one molecule , Molecular weight 1650, molecular weight / number of functional groups in one molecule 825) After pre-mixing 33.3 parts by mass, using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., cylinder temperature 200 ° C., screw rotation speed 100 rpm The mixture was melt-kneaded for 3.5 minutes under the conditions, and pelletized with a hot cutter. The obtained pellets were again supplied to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (3) and / or its condensate. The reaction rate of the obtained compound (B-8) was 56%, the degree of branching was 0.34, and the hydroxyl value was 1200 mgKOH / g. There are three or more hydroxyl groups in one molecule, and the number of hydroxyl groups in one molecule is larger than the number of epoxy groups in one molecule, and the sum of the number of OH and OR in the general formula (4) is three or more. Met.

Reference Example 7 (B-9)
Aliphatic polycarbodiimide (Nisshinbo Chemical Co., Ltd. “Carbodilite” (registered trademark) LA-1) per 100 parts by mass of dipentaerythritol (Guangei Chemical Industry Co., Ltd.), average of carbodiimide groups in one molecule After 24 parts, molecular weight 6000, molecular weight / functional group number in one molecule 250) 10 parts by mass, using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., cylinder temperature 200 ° C., screw rotation speed 100 rpm The mixture was melt-kneaded for 3 minutes under the conditions described above and pelletized with a hot cutter. The obtained pellets were again supplied to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (3) and / or its condensate. The reaction rate of the obtained compound (B-9) was 68%, the degree of branching was 0.37, and the hydroxyl value was 1110 mgKOH / g. There are three or more hydroxyl groups in one molecule, the number of hydroxyl groups in one molecule is larger than the number of carbodiimide groups in one molecule, and the sum of the number of OH and OR in the general formula (4) is three or more. Met.

<Reference Example 8> (B-10)
After pre-mixing 500 parts by mass of a phenol novolac epoxy resin (“EPPN” (registered trademark) 201) manufactured by Nippon Kayaku Co., Ltd. with respect to 100 parts by mass of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.) Using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., melt-kneading for 3.5 minutes under the conditions of a cylinder temperature of 200 ° C. and a screw rotation speed of 100 rpm, pelletized by a hot cutter, and represented by the general formula (3) A pellet of the compound and / or its condensate was obtained. The reaction rate of the obtained compound (B-10) was 33%, the degree of branching was 0.23, and the hydroxyl value was 540 mgKOH / g. One molecule has three or more hydroxyl groups, the number of hydroxyl groups in one molecule is less than the number of epoxy groups in one molecule, and the sum of the number of OH and OR in the general formula (4) is 3 or more Met.

<Reference Example 9> (B-11)
After 100 parts by weight of diglycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd.) and 10 parts by weight of novolak phenol type modified epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.), Using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., the mixture was melt-kneaded for 3.5 minutes under conditions of a cylinder temperature of 100 ° C. and a screw rotation speed of 100 rpm, and pelletized by a hot cutter. The obtained pellets were supplied again to the extruder and melt-kneaded and pelletized under the same conditions as above to obtain pellets of the compound having no structure represented by the general formula (4). The reaction rate of the obtained compound (B-11) was 38%, the degree of branching was 0.02, and the hydroxyl value was 1240 mgKOH / g. One molecule has three or more hydroxyl groups, and the number of hydroxyl groups in one molecule is larger than the number of epoxy groups in one molecule, and has three or more hydroxyl groups in one molecule.

<Reference Example 10> (B-12)
Bisphenol A type epoxy resin (“jER” (registered trademark) 1007, manufactured by Mitsubishi Chemical Corporation) per 100 parts by mass of dipentaerythritol (Guangei Chemical Industry Co., Ltd.), 2 pieces of epoxy groups in one molecule , Molecular weight 2900, molecular weight / number of functional groups in one molecule 1450) After 33.3 parts by mass, using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., cylinder temperature 200 ° C., screw rotation speed 100 rpm The mixture was melt-kneaded for 3.5 minutes under the conditions, and pelletized with a hot cutter. The obtained pellets were again supplied to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (3) and / or its condensate. The reaction rate of the obtained compound (B-12) 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 (4) was 3 or more.

<Reference Example 11> (B-13)
Bisphenol A type epoxy resin ("jER" (registered trademark) 1010, manufactured by Mitsubishi Chemical Corporation) per 100 parts by mass of dipentaerythritol (Guangei Chemical Industry Co., Ltd.), the number of epoxy groups in two molecules , Molecular weight 5500, molecular weight / number of functional groups in one molecule 2750) 33.3 parts by mass were premixed, and then, using a PCM30 type twin screw extruder manufactured by Ikekai Co., Ltd., cylinder temperature 200 ° C., screw rotation speed 100 rpm The mixture was melt-kneaded for 3.5 minutes under the conditions, and pelletized with a hot cutter. The obtained pellets were again supplied to the extruder, and the remelting and kneading step was performed once to obtain pellets of the compound represented by the general formula (3) and / or its condensate. The reaction rate of the obtained compound (B-13) 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 (4) was 3 or more.

Reference Example 12 (F-1)
After 100 parts by mass of compound (B-5) is premixed with 100 parts by mass of polyamide 6 (nylon 6) (“Amilan” (registered trademark) CM1010, manufactured by Toray Industries, Inc.), then manufactured by Nippon Steel Works, Ltd. Using a TEX30 twin screw extruder (L / D: 45.5), the mixture was melt-kneaded under the conditions of a cylinder temperature of 245 ° C. and a screw rotation speed of 150 rpm, and pelletized with a strand cutter. Then, it vacuum-dried at 80 degreeC for 8 hours, and produced the high concentration pre-mixture pellet (F-1).

Reference Example 13 (F-2)
100 parts by mass of compound (B-12) is premixed with 100 parts by mass of polyamide 6 (nylon 6) (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), and then manufactured by Nippon Steel Works, Ltd. Using a TEX30 type twin screw extruder (L / D: 45.5), the mixture was melt-kneaded under conditions of a cylinder temperature of 240 ° C. and a screw rotation speed of 150 rpm, and pelletized by a strand cutter. Then, it vacuum-dried at the temperature of 80 degreeC for 8 hours, and produced the high concentration pre-mixture pellet (F-2).

  In addition, the polyamide resin (A), the compound (B), the epoxy group and / or carbodiimide group-containing compound (b-1), the polyamide resin (C), the filler (D), the resistance used in the examples and comparative examples. The impact property improving material (E) is as follows.

(A-1): Polyamide 6 (nylon 6) resin having a melting point of 225 ° C. (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), amide group concentration: 8.84 mmol / g
(A-2): polyamide 66 (nylon 66) resin having a melting point of 260 ° C. (“Amilan” (registered trademark) CM3001-N manufactured by Toray Industries, Inc.), amide group concentration: 8.84 mmol / g
(A-4): Polyamide 610 (nylon 610) resin (“Amilan” (registered trademark) CM2001 manufactured by Toray Industries, Inc.) having a melting point of 223 ° C., amide group concentration of 7.08 mmol / g
(B-1): Dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.), molecular weight 254, hydroxyl value 1325 mg KOH / g, having 6 hydroxyl groups in one molecule (B-2): diglycerin (Sakamoto Yakuhin) Manufactured by Kogyo Co., Ltd.), molecular weight 166, hydroxyl value 1351 mg KOH / g; having 4 hydroxyl groups in one molecule. (B-3): 2,2,4-trimethyl-1,3-pentanediol (Tokyo Chemical ( Co., Ltd.), molecular weight 146, hydroxyl value 765 mgKOH / g; having two hydroxyl groups in one molecule. (B-4): polyethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight 10,000, hydroxyl value 11.2 mgKOH / g: having two hydroxyl groups in one molecule. (b-1): phenol novolac type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.), 1 minute Average number 7 epoxy groups in the molecular weight 1330, functionality 190 molecular weight / 1 molecule
(C-1): Polyamide 610 (nylon 610) resin (“Amilan” (registered trademark) CM2001 manufactured by Toray Industries, Inc.) having a melting point of 223 ° C., amide group concentration of 7.08 mmol / g
(C-3): Polyamide 12 (nylon 12) resin having a melting point of 180 ° C. (“Uvesta” (registered trademark) 3024U manufactured by Ube Industries, Ltd.), amide group concentration 5.08 mmol / g
(C-4): Polyamide 9T / M8T (nylon 9T / M8T) resin (Kuraray Co., Ltd. “Genesta” (registered trademark) N1000A) having a melting point of 295 ° C., amide group concentration 6.94 mmol / g
(C-5): Amorphous polyamide resin having a glass transition point of 160 ° C. (“grilamide” (registered trademark) TR55, manufactured by EMS Co., Ltd.), amide group concentration: 5.29 mmol / g
・ (D-1): Circular cross-section glass fiber (T-717H manufactured by Nippon Electric Glass Co., Ltd.), cross-sectional diameter of 10.5 μm, surface treatment agent: silane coupling agent, bundling agent: epoxy, fiber length of 3 mm
(E-1): Impact resistance improving material (MH7020 manufactured by Mitsui Chemicals, Inc.)

(Examples 1-21, 24-25, Comparative Examples 1-13)
After pre-mixing the polyamide resin (A), polyamide resin (C) and impact resistance improving material (E) shown in Tables 1 to 4, set the cylinder set temperature to the melting point of the polyamide resin + 15 ° C. and set the screw speed to 200 rpm. It was supplied from the main feeder of TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel, Ltd. to the twin screw extruder and melt kneaded. The main feeder was connected to a position 0 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position of an end portion on the upstream side of the screw segment. Subsequently, the compound (B), the epoxy group and / or carbodiimide group-containing compound and the filler (D) shown in Tables 1 to 4 were supplied from the side feeder to the twin screw extruder and melt-kneaded. This side feeder was connected to a position of 0.65 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position downstream of 1/2 of the screw length. The screw configuration of the twin-screw extruder is such that the total length of the kneading zone on the upstream side of the supply position of the compound (B) is Ln1, and the kneading zone on the downstream side of the supply position of the compound (B) etc. When the total length is Ln2, Ln1 / L is 0.14, and Ln2 / L is 0.07. The gut discharged from the die was immediately cooled by a water bath and pelletized by a strand cutter. The evaluation results of the above Examples and Comparative Examples are shown in Tables 1 to 4.

(Examples 22 and 23)
After preliminarily mixing the polyamide resin (A), the polyamide resin (C), and the high-concentration premix (F) shown in Table 2, 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 (stock) ) It was supplied from a main feeder of a TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel Works to a twin screw extruder and melt kneaded. This main feeder was connected to the position 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 filler (D) shown in Tables 2 and 3 was supplied from the side feeder to the twin screw extruder and melt-kneaded. This side feeder was connected to a position of 0.65 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position downstream of 1/2 of the screw length. The cylinder temperature, the screw rotation speed, and the screw configuration are the same as those in Example 13 or 20. Thus, the composition ratio of Example 22 is the same as that of Example 13, and the composition ratio of Example 23 is the same as that of Example 13. 20 is the same. The evaluation results of Examples 22 and 23 are shown in Table 2.

  Examples 1 to 25 contain a specific amount of compound (B) and a specific amount of polyamide resin (C) as compared with Comparative Examples 1 to 3, 5 to 7, 10, and 11. The compatibility of the resin (A) and the polyamide resin (C) with the compound (B) is further improved. As a result, the amount of gas generation during molding is small, and the burst strength and high temperature rigidity at low and high temperatures after heat treatment are obtained. It was possible to obtain a molded product excellent in.

  As a result of comparison between Example 2 and Comparative Example 8, since the compound (B) has at least three hydroxyl groups in one molecule, the phase of the polyamide resin (A) and the polyamide resin (C) and the compound (B) It was possible to obtain a molded product with improved solubility, a small amount of gas generation during molding, and excellent burst strength and high-temperature rigidity at low and high temperatures after heat treatment.

  Comparison between Example 2 and Comparative Example 4 shows that the use of the compound (B) instead of the elastomer improves the heat aging resistance of the polyamide resin, reduces the amount of gas generated during molding, and reduces the temperature and temperature after heat treatment. A molded product having excellent burst strength and high-temperature rigidity was obtained.

  A comparison between Example 2 and Comparative Example 2 shows that the use of the polyamide resin (C) improves the compatibility of the compound (B), reduces the amount of gas generated during molding, and at low and high temperatures after heat treatment. A molded product excellent in burst strength and high-temperature rigidity could be obtained.

  In Examples 2 and 3, the amount of polyamide resin (C) is in a more preferable range compared to Example 1, so that the amount of gas generated during molding is smaller, and the burst strength at low and high temperatures after heat treatment. In addition, a molded product superior in high-temperature rigidity could be obtained. Further, in Example 3, since the compounding amount of the compound (B) is in a more preferable range as compared with Examples 4 and 5, the amount of gas generated during molding is smaller, and at low and high temperatures after the heat treatment. A molded product having excellent burst strength and high-temperature rigidity could be obtained.

  Examples 13 to 21 use a reaction product of a hydroxyl group-containing compound and an epoxy group and / or carbodiimide group-containing compound as the compound (B), so that compared with Examples 2 and 11, the polyamide resin (A) Furthermore, the compatibility between the polyamide resin (C) and the compound (B) is further improved, it is possible to obtain a molded product that is superior in low gas properties, and excellent in low and high temperature burst strength and high temperature rigidity after heat treatment. It was.

  In Examples 13, 16 to 21, by using the compound (B) having a more preferable reaction rate compared to Examples 14 and 15, the polyamide resin (A), the polyamide resin (C), and the compound (B ), The amount of gas generated at the time of molding is smaller, and the molded product is superior in burst strength and high temperature rigidity at low and high temperatures after heat treatment.

  In Examples 13, 16-18, 20 and 21, the degree of branching of compound (B) falls within a more preferable range as compared with Example 19, so that polyamide resin (A), polyamide resin (C), and compound The compatibility with (B) was further improved, and a molded product superior in burst strength and high-temperature rigidity at low and high temperatures after heat treatment could be obtained.

  In Examples 13 to 17, 20 and 21, since the number of hydroxyl groups in one molecule is larger than the number of epoxy groups / carbodiimide groups in one molecule, compared with Example 18, the polyamide resin (A) and the polyamide The compatibility between the resin (C) and the compound (B) was further improved, and a molded product excellent in burst strength and high temperature rigidity at low and high temperatures after the heat treatment could be obtained.

  In Examples 22 and 23, compared to Examples 13 and 20, respectively, a high-concentration premix of polyamide resin (A) and compound (B) was prepared, and this was melt kneaded with polyamide resin (A). A molded product with improved compatibility between the polyamide resin (A) and the compound (B), less gas generation during molding, and excellent burst strength and high-temperature rigidity after heat treatment at low and high temperatures. I was able to get 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, etc., and processed and used for various molded products. be able to. In particular, the polyamide resin composition of the embodiment of the present invention has a small amount of gas generation at the time of molding, and can obtain a molded product having excellent low-temperature and high-temperature burst strength after heat treatment and high-temperature rigidity. Useful for electrical and electronic parts.

Claims (9)

  Containing 100 parts by weight of the first polyamide resin (A) in a proportion of 0.1 to 20 parts by weight of the compound (B) containing 3 or more hydroxyl groups in one molecule; The second polyamide resin (C) having an amide group concentration of 0.8 mmol / g or less smaller than the amide group concentration of the polyamide resin is contained in a proportion of 0.05 parts by weight or more and less than 5 parts by weight. Polyamide resin composition.   The polyamide resin composition according to claim 1, wherein the second polyamide resin (C) is a crystalline polyamide.   The polyamide resin composition according to claim 1 or 2, wherein the second polyamide resin (C) is an aliphatic polyamide.   The second polyamide resin (C) is one selected from the group consisting of polyamide 410, polyamide 510, polyamide 610, polyamide 1010, polyamide 1012, polyamide 11 and polyamide 12. Polyamide resin composition.   The polyamide resin composition according to any one of claims 1 to 4, wherein the first polyamide resin (A) has a melting point of 300 ° C or lower.   The polyamide resin composition according to any one of claims 1 to 5, wherein the first polyamide resin (A) has an amide group concentration exceeding 8.2 mmol / g.   Compound (B) contains an epoxy group and / or carbodiimide group, and the number of hydroxyl groups in one molecule of compound (B) is greater than the total number of epoxy groups and carbodiimide groups in one molecule of compound (B) Item 7. The polyamide resin composition according to any one of Items 1 to 6.   A molded article comprising the polyamide resin composition according to any one of claims 1 to 7.   Compound (B) containing three or more hydroxyl groups in one molecule is blended at a ratio of 0.1 to 20 parts by weight with respect to 100 parts by weight of the first polyamide resin (A). The second polyamide resin (C) having an amide group concentration of 0.8 mmol / g or less smaller than the amide group concentration of the polyamide resin is blended at a ratio of 0.05 parts by weight or more and less than 5 parts by weight. A method for producing a polyamide resin composition.

Images