JP2017082203A - Plastic fastener composed of polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic fastener excellent in fitting characteristic, heat aging fitting resistance and regrind property.SOLUTION: There is provided a plastic fastener composed of a polyamide resin composition containing (B) a compound having at least 3 hydroxyl groups of 0.1 to 20 pts.wt. based on 100 pts.wt. of (A) a polyamide resin and having color tone change before and after a heat treatment ΔE* of 0 to 30 when a square plate with thickness of 2 mm is molded and heat treated at 190°C for 2 hours.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a plastic fastener made of a polyamide resin composition.

  Polyamide resin has excellent heat resistance, mechanical properties, moldability, etc., so it has suitable properties as engineering plastics. Widely used in applications. In particular, it is preferably used as a plastic fastener such as a clip, a cable clamp, a binding band, or a fixture for electric wiring, taking advantage of the feature of excellent balance between strength and toughness.

  When the resin composition is molded by the injection molding method, sprue, runners or molding defects are generated. In recent years, with the miniaturization and weight reduction of automobile parts and electrical / electronic parts, related parts such as plastic fasteners are also required to be miniaturized. In the case of such small parts, the weight ratio of the sprue or runner part to the weight of a single part is particularly large. ing.

  For such regrind, for example, a recycled resin obtained by compounding a mixture containing a raw material resin, at least one additive for resin, and a pulverized product of a recovered molded product generated in molding of the recycled resin composition A composition has been proposed (see, for example, Patent Document 1). However, there have been problems in regrind characteristics such as degradation of mechanical properties and discoloration due to thermal decomposition and thermal degradation of the raw material resin.

  On the other hand, due to the recent increase in the density of engine compartment parts in the automotive field, the increase in engine output, and the high integration of semiconductor devices in the electrical / electronic field, the environmental temperature is rising. Toughness (fitting characteristics) that is difficult to break when mated, toughness that is less likely to crack when mated even at higher temperatures (heat aging fitting characteristics), fitting characteristics and heat aging fitting even during regrind There is a demand for maintaining the combined characteristics and suppressing discoloration (regrind characteristics). As a technique for improving heat aging resistance (heat aging mechanical characteristics) related to general mechanical characteristics of polyamide resin, various technical improvements have been attempted so far. For example, a polyamide resin composition comprising a polyamide resin, a polyhydric alcohol having a number average molecular weight of less than 2000, a co-stabilizer such as a copper stabilizer or a hindered phenol, and a polymer reinforcing material (see, for example, Patent Document 2) ), A polyamide resin, a polyfunctional polyether polyol having a hydroxyl value of 3 to 1350 mg KOH / g, and other additives (see, for example, Patent Document 3), a polyamide resin, a hydroxyl group, an epoxy group, or A polyamide resin composition having a compound having a specific structure having a carbodiimide group and / or a condensate thereof (see, for example, Patent Document 4) has been proposed.

JP 2001-26719 A Special table 2011-529987 gazette Special table 2013-534549 gazette International Publication No. 2015/56393

  However, molded articles obtained from the polyamide resin compositions of Patent Documents 2 and 3 still have insufficient heat aging mechanical properties, and are inferior in heat aging fitting properties and regrind properties for plastic fastener applications. There was a problem. On the other hand, the molded product obtained from the polyamide resin composition of Patent Document 4 is excellent in heat aging mechanical properties and fitting properties, but is still insufficient in heat aging fitting properties and regrind properties for plastic fastener applications. There was a problem.

  In view of these problems of the prior art, an object of the present invention is to provide a plastic fastener excellent in fitting characteristics, heat aging fitting characteristics and regrind characteristics.

In order to solve the above problems, the present invention mainly has the following configuration.
[1] (A) 0.1-20 parts by weight of (B) compound having at least three hydroxyl groups per 100 parts by weight of polyamide resin, and molding a 2 mm thick square plate at 190 ° C. A plastic fastener made of a polyamide resin composition having a color change ΔE * before and after heat treatment of 2 to 30 when heat treated for 2 hours.
[2] The polyamide resin composition further comprises (C) a phosphorus-containing compound, and the phosphorus atom content determined by spectrophotometric analysis is at least 130 ppm with respect to the polyamide resin content. Plastic fastener.
[3] The plastic fastener according to [1] or [2], wherein the phosphorus atom content is at least 200 ppm with respect to the polyamide resin content.
[4] The plastic fastener according to any one of [1] to [3], wherein the polyamide resin composition further contains 0.1 to 50 parts by weight of (D) a nitrogen-containing compound with respect to 100 parts by weight of the polyamide resin. .
[5] The weight ratio ((B) / (D)) of (B) compound content having at least three hydroxyl groups to (D) nitrogen-containing compound content is 0.1-5. The plastic fastener according to [4], which is 0.
[6] The plastic fastener according to [4] or [5], wherein the average particle size of the (D) nitrogen-containing compound is 20 μm or less.

  ADVANTAGE OF THE INVENTION According to this invention, the plastic fastener excellent in the fitting characteristic, the heat aging fitting characteristic, and the regrind characteristic can be provided.

¹ H-NMR spectrum of a dry blend product of dipentaerythritol and bisphenol A type epoxy resin. ¹ H-NMR spectrum of a melt-kneaded reaction product of a polyhydric alcohol and an epoxy compound obtained in Reference Example 7. Before fitting (A), after fitting (B), at the time of cable fixing (C), after fitting (D), and after fitting (side view) (E) Overview diagram.

  Hereinafter, embodiments of the present invention will be described in detail. The plastic fastener according to the embodiment of the present invention refers to a plastic part for fixing a part or an electric wiring, and includes, for example, an automobile part, an electric / electronic part, a building member, various containers, daily necessities, household goods, sanitary goods, and the like. In the field, there are clips, clamps, bands, etc. that connect parts together and bundle electric wiring cables, cords, tubes, etc. Conventionally, when connecting and fixing multiple parts, it was common to use metal bolts, but in recent years, from the viewpoint of ease of installation, rust prevention, light weight, Plastic fasteners are becoming popular. The plastic fastener according to the embodiment of the present invention is excellent in fitting characteristics, heat aging fitting characteristics and regrind characteristics, and is therefore suitable for applications used in high temperature environments such as automobile parts and electrical and electronic parts. Further, taking advantage of the small discoloration due to heat treatment, it can be suitably used as a plastic fastener having a printing portion.

  In the plastic fastener of the embodiment of the present invention, (B) a compound having at least three hydroxyl groups (hereinafter, referred to as “(B) hydroxyl group-containing compound”) with respect to 100 parts by weight of the polyamide resin. Is formed of a polyamide resin composition having a color tone change ΔE * before and after heat treatment of 0 to 30 when formed into a square plate having a thickness of 2 mm and heat-treated at 190 ° C. for 2 hours. It is obtained by molding the polyamide resin composition. Hereinafter, each component which comprises a polyamide resin composition is demonstrated.

  In the polyamide resin composition used in the embodiment of the present invention, it is considered that (A) the polyamide resin has a carboxyl terminal group that undergoes a dehydration condensation reaction with a hydroxyl group in the (B) hydroxyl group-containing compound described later. For this reason, (A) polyamide resin is considered to be excellent in compatibility with (B) hydroxyl group-containing compound.

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

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

  Particularly preferred are polyamide 6, polyamide 66, polyamide 56, polyamide 610, polyamide 510, polyamide 410, polyamide 612, polyamide 11, polyamide 12, polyamide 6/66, polyamide 66 / 6T, polyamide 6T / 6I, polyamide 66. / 6I / 6, polyamide 6T / 5T, polyamide 9T, polyamide 10T, polyamide 12T, and the like. It is also practically suitable to blend two or more of these polyamide resins depending on the required properties such as moldability, heat resistance and toughness.

  Among these, aliphatic polyamides are preferable because they are excellent in reactivity with the (B) hydroxyl group-containing compound described later, and polyamide 6, polyamide 66, polyamide 610, and polyamide 410 are particularly preferable. These aliphatic polyamide resins have an excellent balance of strength, toughness, and injection moldability, and are not easily discolored by heat. Therefore, the fitting characteristics, heat aging fitting characteristics and regrind characteristics of plastic fasteners can be further improved. . 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 (B) hydroxyl-containing compound mentioned later can be improved more, the dispersibility of the (B) hydroxyl-containing compound in a polyamide resin composition is improved more, and the regrind characteristic of a plastic fastener is improved. Can be improved.

  The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity (ηr) measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g / ml is in the range of 1.5 to 5.0. Preferably there is. If the relative viscosity is 1.5 or more, since the balance between strength and toughness is excellent, chipping and deformation when mated with other components or wiring can be further suppressed, and the mating characteristics can be further improved. Moreover, the heat aging fitting characteristic 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. In addition, shear heat generation during regrind can be moderately suppressed, and alteration due to thermal decomposition of the polymer can be suppressed, so that regrind characteristics can be further improved.

  The polyamide resin composition used in the embodiment of the present invention contains (B) a compound having at least three hydroxyl groups. (B) The hydroxyl group-containing compound has an effect of improving molding processability such as fluidity and heat aging mechanical properties at 150 to 230 ° C. Furthermore, in the present invention, by changing the color tone before and after the heat treatment described later within a specific range, the compatibility of (A) the polyamide resin and (B) the hydroxyl group-containing compound is improved, and the fine dispersion in the polyamide resin composition is achieved. A structure can be formed, and in addition to heat aging mechanical properties, heat aging fitting properties and regrind properties can be improved.

  (B) As a hydroxyl-containing compound, an aliphatic compound is preferable. Aliphatic compounds have low steric hindrance compared to aromatic compounds and alicyclic compounds, and are excellent in reactivity with (A) polyamide resin. Therefore, (A) compatibility with polyamide resin is excellent. The fitting characteristics, heat aging fitting characteristics, and regrind characteristics can be further improved. Moreover, the number of hydroxyl groups in one molecule of the (B) hydroxyl group-containing compound is preferably 4 or more, more preferably 6 or more. (B) The hydroxyl group-containing compound 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 (B) hydroxyl group-containing compound can be calculated and determined by the following formula (1).
OH number = (number average molecular weight × hydroxyl value) / 56110 (1)

  (B) Specific examples of the hydroxyl group-containing compound include 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,6-hexanetetrol. Glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, ditrimethylolpropane, tritrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, methylglucoside, sorbitol, glucose, mannitol, sucrose, 1, 3,5-trihydroxybenzene, 1,2,4-trihydroxybenzene, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, triethanolamine, trimethylol ethane, trimethylol propane, 2-methyl Le propanetriol, tris (hydroxymethyl) aminomethane, and the like 2-methyl-1,2,4-butanetriol. Examples of the hydroxyl group-containing compound (B) also include a hydroxyl group-containing compound having a repeating structural unit, such as an ester bond, an amide bond, an ether bond, a methylene bond, a vinyl bond, an imine bond, a siloxane bond, a urethane bond, Examples thereof include a hydroxyl group-containing compound having a repeating structural unit having a thioether bond, 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 (B) hydroxyl group-containing compounds, pentaerythritol, dipentaerythritol, and tripentaerythritol are preferable.

  Examples of the (B) hydroxyl group-containing compound include compounds having at least three hydroxyl groups obtained by reacting these hydroxyl group-containing compounds with an epoxy group and / or carbodiimide group-containing compound. The (B) hydroxyl group-containing compound can further improve the heat aging mechanical properties and further improve the heat aging fitting properties and the regrind properties. Although it is not certain about this factor, it is thought as follows. That is, by reacting a hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound in advance, a (B) hydroxyl group-containing compound having a multi-branched structure with the epoxy group and / or carbodiimide group-containing compound as a linking point is formed. Is done. The (B) hydroxyl group-containing compound has a multi-branched structure, so that the self-aggregation force is further reduced, and the reactivity and compatibility with the (A) polyamide resin are further improved. Moreover, since the melt viscosity of the (B) hydroxyl group-containing compound having a multi-branched structure is improved, the dispersibility of the (B) hydroxyl group-containing compound in the polyamide resin composition is further improved. For this reason, it is considered that a fine dispersion structure can be formed in the polyamide resin composition, and the tensile strength, heat aging mechanical properties, heat aging fitting properties, and regrind properties can be further improved.

  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 (A) polyamide resin, the compound having two or more epoxy and / or carbodiimide groups in one molecule is composed of (A) the polyamide resin and (B) the hydroxyl group-containing compound. It is considered that there is an effect of increasing the compatibility. 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” manufactured by Mitsubishi Chemical Corporation), novolak phenol type modified epoxy resin (for example, “EPPN” (registered trademark) manufactured by Nippon Kayaku Co., Ltd.) ) "201").

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

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

  The molecular weight of the 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 that the processability is excellent. Moreover, since the viscosity at the time of melt-kneading can be increased, the compatibility between (A) the polyamide resin and (B) the hydroxyl group-containing compound is increased, tensile strength, heat aging mechanical properties, heat aging fitting properties, The regrind characteristics 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, when the molecular weight of the epoxy group and / or carbodiimide group-containing compound is 10,000 or less, the viscosity at the time of melt-kneading can be moderately suppressed, so that the workability is excellent. Moreover, the compatibility of (A) polyamide resin and (B) hydroxyl group compound 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 (A) the polyamide resin and (B) the hydroxyl group-containing compound becomes higher, tensile strength, heat aging mechanical properties, heat aging fitting The characteristics and regrind characteristics 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 2,000. Here, the number of functional groups refers to the total number of epoxy groups and carbodiimide groups. The smaller this value, the higher the functional group concentration. By setting it to 50 or more, gelation due to excessive reaction can be suppressed, and the reactivity with (A) the polyamide resin and (B) the hydroxyl group-containing compound. Therefore, tensile strength, heat aging mechanical properties, heat aging fitting properties, and regrind properties 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. On the other hand, 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 2000 or less, (A) the polyamide resin and (B) the hydroxyl group-containing compound The reaction can be sufficiently secured, and the tensile strength, heat aging mechanical properties, heat aging fitting properties, and regrind properties 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 preferably 1000 or less, and more preferably 300 or less.

  (B) hydroxyl group-containing compound used in the embodiment of the present invention ((B) as the hydroxyl group-containing compound, at least three hydroxyl groups obtained by reacting a hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound) In the case of using a compound having a hydroxyl value, the hydroxyl value of the hydroxyl group-containing compound as a raw material is preferably 100 to 2000 mgKOH / g. (B) By setting the hydroxyl value of the hydroxyl group-containing compound to 100 mgKOH / g or more, it becomes easy to ensure a sufficient amount of reaction between (A) the polyamide resin and (B) the hydroxyl group-containing compound. Combined characteristics and regrind characteristics can be further improved. (B) The hydroxyl value of the hydroxyl group-containing compound is more preferably 300 mgKOH / g or more. On the other hand, by setting the hydroxyl value of the (B) hydroxyl group-containing compound to 2000 mgKOH / g or less, the reactivity between the (A) polyamide resin and the (B) hydroxyl group-containing compound is moderately increased, and gelation due to excessive reaction is suppressed. Therefore, the heat aging fitting characteristics and the regrind characteristics can be further improved. (B) The hydroxyl value of the hydroxyl group-containing compound is more preferably 1800 mgKOH / g or less. The hydroxyl value can be determined by acetylating the (B) hydroxyl group-containing compound with a mixed solution of acetic anhydride and anhydrous pyridine and titrating it with an ethanolic potassium hydroxide solution.

  (B) hydroxyl group-containing compound used in the embodiment of the present invention ((B) as the hydroxyl group-containing compound, at least three hydroxyl groups obtained by reacting a hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound) In the case of using a compound having a hydroxyl group-containing compound as a raw material), the hydroxyl group may have another reactive functional group. Examples of other functional groups include aldehyde groups, sulfo groups, isocyanate groups, oxazoline groups, oxazine groups, ester groups, amide groups, silanol groups, silyl ether groups, and the like.

  (B) hydroxyl group-containing compound used in the embodiment of the present invention ((B) as the hydroxyl group-containing compound, at least three hydroxyl groups obtained by reacting a hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound) The molecular weight of the compound containing the hydroxyl group-containing compound used as the raw material is not particularly limited, but is preferably 50 to 10,000. If the molecular weight of the (B) hydroxyl group-containing compound is 50 or more, it is difficult to volatilize during melt-kneading, so that the processability is excellent. (B) The molecular weight of the hydroxyl group-containing compound is preferably 150 or more, and more preferably 200 or more. On the other hand, if the molecular weight of the (B) hydroxyl group-containing compound is 10,000 or less, the compatibility with the (A) polyamide resin is further increased, and thus the effects of the present invention are more remarkably exhibited. (B) The molecular weight of the hydroxyl group-containing compound is preferably 6000 or less, more preferably 4000 or less, and still more preferably 800 or less.

  (B) The molecular weight of the hydroxyl group-containing compound can be calculated by specifying the structural formula of the compound by a usual analysis method (for example, a combination of NMR, FT-IR, GC-MS, etc.). In addition, as the molecular weight when the (B) hydroxyl group-containing compound is a condensate, the weight average molecular weight is used as the molecular weight. The weight average molecular weight (Mw) can be calculated using gel permeation chromatography (GPC). Specifically, when a solvent in which the compound is dissolved, for example, hexafluoroisopropanol is used as a mobile phase, 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, (B) hydroxyl group-containing compound (as (B) hydroxyl group-containing compound, at least three hydroxyl groups obtained by reacting a hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound) The degree of branching of the compound (including the hydroxyl group-containing compound 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. As this value is larger, a crosslinked structure can be introduced into the polyamide resin composition, the tensile strength and heat aging mechanical properties can be further improved, and the heat aging fitting property and regrind property of the plastic fastener 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 (A) the compatibility with the polyamide resin is further improved, so that the tensile strength and heat aging mechanical properties are further improved. It is possible to improve the heat aging fitting characteristics and regrind characteristics of the plastic fastener. 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 (B) hydroxyl compound in the polyamide resin composition is further increased, and the tensile strength and heat aging are increased. The mechanical characteristics can be further improved, and the heat aging fitting characteristics and regrind characteristics of the plastic fastener can be further improved. The degree of branching is more preferably 0.35 or less. The degree of branching is defined by the following formula (2).
Branch degree = (D + T) / (D + T + L) (2)

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

  Examples of the compound (B) having a degree of branching in the above-described range include the above-described preferable (B) hydroxyl group-containing compound and a reaction product of such a hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound. .

  In a more preferred embodiment of the present invention, the (B) hydroxyl group-containing compound is preferably a compound having a structure represented by the following general formula (3) and / or a condensate thereof.

In the above general formula (3), 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.

  R in the general formula (3) 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 (3) represents the range of 0-20. When n is 20 or less, (A) the plasticization of the polyamide resin is suppressed, the tensile strength and the heat aging mechanical property are further improved, and the heat aging fitting property and the regrind property of the plastic fastener are further improved. it can. n is more preferably 4 or less. On the other hand, n is more preferably 1 or more, (B) the molecular mobility of the hydroxyl group-containing compound can be increased, and (A) the compatibility with the polyamide resin can be further improved.

  The sum of the numbers of OH and OR in the general formula (3) is preferably 3 or more. Thereby, it is excellent in compatibility with the (A) polyamide resin, the tensile strength and the heat aging mechanical property can be further improved, and the heat aging fitting property and the regrind property of the plastic fastener 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 (1) by calculating the number average molecular weight and hydroxyl value of the compound having the structure represented by the general formula (3) and / or the condensate thereof.
OH number = (number average molecular weight × hydroxyl value) / 56110 (1)

  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 (3) 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 (3) 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 (3) 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 (B) hydroxyl group-containing compound is 0.1 to 20 parts by weight with respect to 100 parts by weight of (A) the polyamide resin. (B) If the content of the hydroxyl group-containing compound is less than 0.1 parts by weight, the fluidity during molding decreases, and the tensile strength, heat aging mechanical properties, heat aging fitting properties, and regrind properties decrease. The content of the (B) hydroxyl group-containing compound 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 (A) polyamide resin. On the other hand, if the blending amount of the (B) hydroxyl group-containing compound exceeds 20 parts by weight, the dispersibility of the (B) hydroxyl group-containing compound in the polyamide resin composition is lowered, so that (A) the polyamide resin is plasticized and decomposed. As a result, tensile strength, heat aging mechanical properties, heat aging fitting properties and regrind properties are reduced. The content of the (B) hydroxyl group-containing compound 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 (A) polyamide resin.

  In the polyamide resin composition used in the embodiment of the present invention, (B) at least three hydroxyl groups obtained by reacting the aforementioned hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound as the hydroxyl group-containing compound. In the case of using a compound having a compound, its production method is not particularly limited, but a method in which a hydroxyl group-containing compound and an epoxy group and / or carbodiimide group-containing compound are dry blended and melt kneaded at a temperature higher than the melting point of both components is preferable. .

  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 (B) hydroxyl group-containing compound having a multi-branched structure can be obtained.

  When (B) a hydroxyl group-containing compound is produced by reacting a hydroxyl group-containing compound with an epoxy group and / or carbodiimide group-containing compound, the blending ratio thereof is not particularly limited, but (B) in one molecule of the hydroxyl group-containing compound. These compounds are preferably blended so that the sum of the number of hydroxyl groups is larger than the sum of the number of epoxy groups and carbodiimide groups in one molecule of the (B) hydroxyl group-containing compound and / or its condensate. The epoxy group and carbodiimide group are excellent in reactivity with the terminal group of the (A) polyamide resin as compared with the hydroxyl group. For this reason, by making the sum of the number of hydroxyl groups in one molecule of the (B) hydroxyl group-containing compound larger than the sum of the number of epoxy groups and carbodiimide groups in one molecule of the (B) hydroxyl group-containing compound, excess It is possible to suppress embrittlement due to the formation of a cross-linked structure, to further improve the tensile strength and heat aging mechanical properties, and to further improve the heat aging fitting properties and regrind properties of the plastic fastener.

  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. (A) Reactivity of polyamide resin and epoxy group and / or carbodiimide group-containing compound, and reactivity of hydroxyl group-containing compound and epoxy group and / or carbodiimide group-containing compound are: (A) polyamide resin and (B) hydroxyl group-containing compound Higher than the reactivity. 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, and the heat aging fitting properties and regrind properties of the plastic fastener are improved. It can be improved further. When a hydroxyl group-containing compound is reacted with an epoxy group and / or a carbodiimide group-containing compound (B) to produce a hydroxyl group-containing compound, the reaction rate of the hydroxyl group and the epoxy group or carbodiimide group is 1 to 95%. preferable. When the reaction rate is 1% or more, (B) the degree of branching of the hydroxyl group-containing compound can be increased, the self-aggregation force can be reduced, (A) the reactivity with the polyamide resin can be increased, and heat aging mechanical properties And the heat aging fitting characteristics and regrind characteristics of the plastic fastener can be further improved. The reaction rate is more preferably 10% or more, and further preferably 20% or more. On the other hand, when the reaction rate is 95% or less, an epoxy group or a carbodiimide group can be appropriately left, and the reactivity with (A) the polyamide resin can be enhanced. The reaction rate is more preferably 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 (B) hydroxyl group-containing compound obtained by the reaction in a solvent (for example, deuterated dimethyl sulfoxide, deuterated hexafluoroisopropanol, etc.) In the case of a group, by determining the amount of decrease before and after the reaction with the hydroxyl group-containing compound used as a raw material for the epoxy ring-derived peak by ¹ H-NMR measurement, in the case of a carbodiimide group, the peak derived from carbodiimide group by ¹³ C-NMR measurement 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. The reaction rate can be determined by the following formula (4).
Reaction rate (%) = {1- (e / d)} × 100 (4)

  In the above formula (4), d represents the peak area of a dry blend of a hydroxyl group-containing compound used as a raw material and an epoxy group and / or carbodiimide group-containing compound, and e is (B) hydroxyl group-containing obtained by reaction. Represents the peak area of the compound.

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

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

  The polyamide resin composition used in the embodiment of the present invention preferably further contains (C) a phosphorus-containing compound. Conventionally, phosphorus-containing compounds such as sodium hypophosphite have been used as polycondensation catalysts for polycondensation of polyamides, and are known to shorten polymerization time and to suppress yellowing. In a more preferred embodiment of the present invention, by containing (C) a phosphorus-containing compound together with (B) a hydroxyl group-containing compound, the tensile strength and heat aging mechanical properties are further improved while maintaining the fluidity of the polyamide resin composition. Further, the heat aging fitting characteristic and the regrind characteristic of the plastic fastener can be further improved. This is because the (C) phosphorus-containing compound improves the reactivity and compatibility between the (B) hydroxyl group-containing compound and the (A) polyamide resin more than the self-condensation of the (A) polyamide resin, and the polyamide resin composition This is considered to be because the dispersibility of the (B) hydroxyl group-containing compound therein can be further improved. Note that (C) the phosphorus-containing compound does not include a phosphorus-based flame retardant.

  In the polyamide resin composition used in the embodiment of the present invention, the content of the (C) phosphorus-containing compound is preferably 130 ppm or more and more preferably 200 ppm or more with respect to the (A) polyamide resin content in terms of phosphorus atoms. When the phosphorus atom equivalent concentration is 130 ppm or more, the tensile strength and heat aging mechanical properties of the plastic fastener can be further improved, and the heat aging fitting property and regrind property of the plastic fastener can be further improved. (C) As for the phosphorus atom conversion density | concentration of a phosphorus containing compound, 300 ppm or more is preferable with respect to (A) polyamide resin content, 800 ppm or more is more preferable, 1000 ppm or more is more preferable. On the other hand, the phosphorus atom equivalent concentration of the (C) phosphorus-containing compound is preferably 25000 ppm or less relative to the (A) polyamide resin content.

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

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

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

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

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

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

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

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

  Among these, phosphite compounds and phosphinate compounds are preferable, and these may be hydrates. It is further preferable to contain at least one selected from the group consisting of phosphorous acid, hypophosphorous acid and metal salts thereof. By containing such a compound, the reactivity and compatibility of the (B) hydroxyl group-containing compound can be further increased while suppressing the thickening of the (A) polyamide resin, and the tensile strength and heat aging mechanical properties are further improved. Thus, the heat aging fitting characteristic and the regrind characteristic of the plastic fastener can be further improved.

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

  Specific examples of the metal salt of phosphorous acid or hypophosphorous acid include lithium phosphite, sodium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, barium phosphite, hypophosphorous acid Examples thereof include lithium, sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, calcium hypophosphite, and barium hypophosphite. Among these, sodium metal salts such as sodium hypophosphite and sodium phosphite, and calcium metal salts such as calcium phosphite and calcium hypophosphite are more preferable.

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

  The polyamide resin composition used in the embodiment of the present invention preferably further contains (D) a nitrogen-containing compound. Here, (D) Nitrogen-containing compound in the embodiment of the present invention excludes (A) to (C) among compounds containing nitrogen. That is, for example, compounds containing both phosphorus and nitrogen, such as phosphazene compounds, are classified as (C) phosphorus-containing compounds. (D) By containing a nitrogen-containing compound, the tensile strength and heat aging mechanical properties can be further improved, and the heat aging fitting properties and regrind properties of the plastic fastener can be further improved. The reason for this is not clear, but (A) the nitrogen-containing compound reacts and traps the carboxylic acid that causes coloration caused by decomposition when the polyamide resin is heat-treated or melted in the atmosphere. presume.

  The content of the (D) nitrogen-containing compound in the polyamide resin composition of the embodiment of the present invention is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of (A) the polyamide resin. (D) By making content of a nitrogen-containing compound into 0.1 weight part or more, heat-resistant aging mechanical characteristics can be improved more, and heat-aging fitting characteristics and regrind characteristics can be improved more. 1 part by weight or more is preferable, and 5 parts by weight or more is more preferable. On the other hand, when the content of the (D) nitrogen-containing compound is 50 parts by weight or less, the heat aging mechanical properties can be further improved, and the heat aging fitting properties and regrind properties of the plastic fastener can be further improved. 40 parts by weight or less is preferable.

  (D) Although it does not specifically limit as a nitrogen-containing compound, The salt of a triazine type compound and a triazine type compound, and cyanuric acid or isocyanuric acid is mentioned preferably. A triazine compound and a triazine compound and a salt of cyanuric acid or isocyanuric acid are adducts of a triazine compound and cyanuric acid or isocyanuric acid, usually in a 1 to 1 (molar ratio), optionally 2 pair 1 (molar ratio). Examples of the triazine compound include melamine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine, tri (hydroxymethyl) melamine, benzoguanamine, acetoguanamine, 2-amide-4,6-diamino-1,3, 5-Triazine and the like can be mentioned, and melamine, benzoguanamine and acetoguanamine are particularly preferable. Specific examples of salts of triazine compounds with cyanuric acid or isocyanuric acid include melamine cyanurate, mono (β-cyanoethyl) isocyanurate, bis (β-cyanoethyl) isocyanurate, tris (β-cyanoethyl) isocyanurate, etc. Among them, melamine cyanurate is particularly preferable.

(D) The average particle diameter (D ₅₀ ) of the nitrogen-containing compound is preferably 20 μm or less, and more preferably 10 μm or less. (D) By setting the average particle size (D ₅₀ ) of the nitrogen-containing compound to 20 μm or less, the tensile strength and the heat aging mechanical properties are improved, and the heat aging fitting properties and regrind properties of the plastic fastener are further improved. Can do. (D) The average particle size (D ₅₀ ) of the nitrogen-containing compound is preferably 1 μm or more. (D) By setting the average particle size of the nitrogen-containing compound to 1 μm or more, it is possible to further improve the fitting characteristics, heat aging fitting characteristics, and regrind characteristics of the plastic fastener. The average particle diameter (D ₅₀ ) can be measured by a laser diffraction scattering method. Specifically, by the laser diffraction scattering method, the particle diameter is plotted on the horizontal axis and the frequency (mass) is plotted on the vertical axis, and the cumulative mass becomes 50% when the total sum of the cumulative masses is 100%. It can be measured as the particle size.

  In the polyamide resin composition used in the embodiment of the present invention, the weight ratio ((B) / (D)) of (B) hydroxyl group-containing compound content to (D) nitrogen-containing compound content is 0.1-5. 0.0 is preferred. By setting the weight ratio ((B) / (D)) to 0.1 or more, (A) the carboxylic acid generated by the decomposition of the polyamide resin can be reacted and captured more efficiently, and the tensile strength and heat aging mechanical properties can be further improved. It is possible to improve the heat aging fitting characteristics and regrind characteristics of the plastic fastener. On the other hand, by setting the weight ratio ((B) / (D)) to 5.0 or less, it is possible to suppress plasticization and retention stability deterioration, and to further improve the tensile strength and heat aging mechanical properties. Further, the heat aging fitting characteristic and the regrind characteristic of the plastic fastener can be further improved.

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

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

  Examples of the copper compound include copper chloride, copper bromide, copper iodide, copper acetate, copper acetylacetonate, copper carbonate, copper borofluoride, copper citrate, copper hydroxide, copper nitrate, copper sulfate, and copper oxalate. Etc. You may contain 2 or more types of these as a copper compound. Among these copper compounds, industrially available ones are preferred, and copper halide and / or derivatives thereof are preferred.

  As a copper halide derivative, for example, complex salts of these copper halides with a nitrogen-based ligand and / or a thiol-based ligand are preferable.

  The type of the nitrogen-based ligand is not particularly limited as long as it contains a nitrogen atom as a ligand in the molecule, but a preferable one is a compound having an oxygen atom together with a nitrogen atom in the molecule, for example, 8 -Quinolinol, 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, picolinic acid, alanine, aminocaproic acid, quinaldic acid, pyrazine acid, anthranilic acid, aminophenol, 4-amino-n-butyric acid, Quinolin-2-carboxylic acid, etc .; compounds having nitrogen and sulfur atoms in the molecule, such as 8-mercaptoquinoline; compounds having two or more nitrogen atoms in the molecule, such as xylylenediamine, ethylenediamine, diethylenetriamine, triethylene Tetramine, etc., or their various derivatives, which can be used alone. Other capable, may be used in combination of two or more if necessary.

  Although it does not specifically limit as a thiol type ligand, As a preferable thing, it is a compound which has a nitrogen atom or an oxygen atom as another ligand with a thiol in a molecule | numerator, for example, 2-mercaptoimidazole, 2-mercapto- 1-methylimidazole, 2-mercaptobenzothiazole, 6-amino-2-mercaptobenzothiazole, 5-mercapto-1-methyltetrazole, 2-mercaptothiazoline, 2-mercaptopyridine, 2-mercapto-4-pyrimidone, 2- Examples include mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercaptobenzoxazole, ortho-aminothiophenol, and various derivatives thereof. It is also possible to use together.

  Among these, copper iodide and copper bromide are preferable as the copper halide, and the complex salt of 2-mercaptobenzimidazole and copper iodide and / or copper bromide is preferable as the copper halide derivative.

  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 a potassium compound, the heat aging mechanical properties can be further improved, and the regrind properties of the plastic fastener can be further improved.

  The content (weight basis) of copper element in the polyamide resin composition used in the embodiment of the present invention is preferably 25 to 200 ppm. By setting the copper element content to 25 ppm or more, the compatibility of the (A) polyamide resin and the (B) hydroxyl group-containing compound is further improved, the heat aging mechanical properties are further improved, and the regrind properties of the plastic fastener are further improved. Can be improved. The content (weight basis) of the copper element in the polyamide resin composition is preferably 80 ppm or more. More preferably, it is 140 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 plastic fastener. In addition, by controlling the content of copper element to 200 ppm or less, a decrease in the hydrogen bond strength of the amide group due to excessive coordination bond between the polyamide resin and copper can be suppressed, and the heat aging mechanical properties can be further improved. The regrind characteristic of the fastener can be further 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 compound and (B) the hydroxyl group-containing compound and (A) are suppressed. The reaction with the polyamide resin 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 plastic fastener can be further improved. Moreover, the compatibility of a polyamide resin composition improves by making Cu / K into 0.43 or less, Therefore The regrind characteristic of a plastic fastener can be improved more. 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. Because of the improvement, the reaction between the copper compound, the (B) hydroxyl group-containing compound and the (A) polyamide resin is sufficiently promoted to further improve the heat aging mechanical properties and further improve the regrind properties of the plastic fastener. Can do. 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 used in the embodiment of the present invention can further contain an impact resistance improving material. Impact modifiers generally refer to polymers with glass transition temperatures below room temperature or copolymers below and above room temperature, with some intermolecular bonds being covalent, ionic, van der Waals forces, entanglement These are polymers that are constrained by each other. Examples of the impact resistance improving material include olefin resin, acrylic rubber, silicon rubber, fluorine rubber, urethane rubber, polyamide elastomer, and polyester elastomer. Two or more of these may be used. Among these, from the viewpoint of compatibility with (A) the polyamide resin, an olefin resin is preferably used.

  Examples of the olefin resin include an ethylene / unsaturated carboxylic acid copolymer, an ethylene / unsaturated carboxylic acid ester copolymer, and an ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid metal salt copolymer.

  The content of the impact resistance improving material in the polyamide resin composition used in the embodiment of the present invention is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the (A) polyamide resin.

  The polyamide resin composition used in 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, soconite and other smectite clay minerals and vermiculite, halloysite, kanemite, kenyanite, 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 may be treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.), and the mechanical strength and surface appearance of the snap fastener are further improved. Can be improved. For example, a method in which a filler is surface-treated with a coupling agent in accordance with a conventional method and then melt-kneaded with a polyamide resin is preferably used. In this case, an integral blend method in which a coupling agent is added may be used. The treatment amount of the coupling agent is preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the filler.

  In the polyamide resin composition used in 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 (A) polyamide resin. When the content of the filler is 1 part by weight or more, the tensile strength and heat aging mechanical properties can be further improved, and the regrind properties of the plastic fastener can be further improved. The content of the filler is more preferably 20 parts by weight or more. On the other hand, when the content of the filler is 150 parts by weight or less, the plastic fastener that suppresses the floating of the filler on the surface of the plastic fastener and has a superior surface appearance can be obtained. As for content of a filler, 70 weight part or less is more preferable.

  Furthermore, the polyamide resin composition used in the embodiment of the present invention can contain a resin other than the polyamide resin and various additives depending on the purpose within a range not impairing the effects of the present invention.

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

  Specific examples of various additives include heat stabilizers other than copper compounds, isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, epoxy compounds and other coupling agents, polyalkylene oxide oligomers. Compounds, plasticizers such as thioether compounds and ester compounds, crystal nucleating agents such as polyether ether ketone, metal soaps such as montanic acid wax, lithium stearate, aluminum stearate, ethylenediamine, stearic acid, sebacic acid heavy Examples thereof include release agents such as condensates and silicone compounds, lubricants, ultraviolet light inhibitors, colorants, flame retardants (excluding those contained in the (D) nitrogen-containing compound), and foaming agents. When these additives are contained, the content thereof is preferably 1 part by weight or less with respect to 100 parts by weight of the (A) polyamide resin in order to make full use of 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 polyamide resin composition used in the embodiment of the present invention is characterized in that a color tone change ΔE * before and after heat treatment becomes 0 to 30 when a square plate having a thickness of 2 mm is molded and heat treated at 190 ° C. for 2 hours. And Here, the color change ΔE * before and after the heat treatment when the square plate is heat-treated at 190 ° C. for 2 hours is an index of the dispersibility of the (B) hydroxyl group-containing compound in the polyamide resin composition. When the polyamide resin is heat-treated, a carboxylic acid that causes coloring is generated by decomposition, but the polyamide resin composition used in the embodiment of the present invention captures the carboxylic acid that causes coloring by the (B) hydroxyl group-containing compound. be able to. The better the dispersibility of the (B) hydroxyl group-containing compound in the polyamide resin composition, the higher the carboxylic acid scavenging action. Therefore, the color change ΔE * before and after heat treatment when heat treated at 190 ° C. for 2 hours is ) The degree of dispersibility of the hydroxyl group-containing compound can be expressed.

  As described above, when a plastic fastener made of a polyamide resin composition is heated, it is considered that embrittlement of the polyamide resin progresses from the surface of the plastic fastener in contact with oxygen due to oxidative deterioration and low molecular weight. For this reason, the thinner the molded product, the more easily affected by heating. Moreover, the higher the heating temperature and the longer the heating time, the more susceptible to the influence of heating. In the present invention, assuming that various general polyamide resins are used, a heating temperature of 190 ° C. is selected as a condition that is lower than the melting point, and the influence of heating can be evaluated in a short time as much as possible. As a condition for sufficiently expressing the characteristics of the color change ΔE * before and after, a heating time of 2 hours was selected experimentally, and a condition for a thickness of 2 mm was set as a condition for evaluating the influence of heating in a short time. Selected.

  (B) The hydroxyl group-containing compound has an effect of improving molding processability such as fluidity and heat aging mechanical properties, but when (A) the compatibility with the polyamide resin is low, (A) the amide bond of the polyamide resin In order to promote hydrolysis, it may cause deterioration of mechanical properties, discoloration during melt-kneading or heat treatment, and deterioration of regrind properties due to thermal decomposition during regrind. In the embodiment of the present invention, (B) the hydroxyl group in the hydroxyl group-containing compound and (A) the carboxyl terminal group of the polyamide resin are further promoted, the compatibility is increased, and the fineness in the polyamide resin composition is increased. By forming the dispersion structure, the fitting characteristics, the heat aging fitting characteristics, and the regrind characteristics can be improved. When the color tone change ΔE * before and after the heat treatment is 0 to 30, a fine dispersion structure is formed in the polyamide resin composition, and the heat aging fitting property and the regrind property are excellent. On the other hand, when the color tone change ΔE * before and after the heat treatment exceeds 30, it means that the dispersibility of the (B) hydroxyl group-containing compound is insufficient, and the heat aging fitting property and the regrind property are deteriorated. The cause of this is not clear, but when a plastic fastener made of a polyamide resin composition is heated in the atmosphere, the deterioration of the polyamide resin on the surface of the plastic fastener in contact with oxygen and the embrittlement due to low molecular weight proceed, and the cause of coloring This is thought to be due to the formation of substances.

The color tone change ΔE * before and after the heat treatment can be obtained by the following method. First, a polyamide resin composition is molded to obtain a square plate having a thickness of 2 mm. About the obtained square plate, L *, a *, and b * are measured on 23 degreeC and 50% RH conditions using a color computer (SM color computer model SM-3 by Suga Test Instruments Co., Ltd.). Further, after the obtained square plate is heat-treated at 190 ° C. for 2 hours, L *, a *, and b * are similarly measured under the conditions of 23 ° C. and 50% RH. From each measured value, a color tone change ΔE * is calculated by the following equation (5).
ΔE * = [(ΔL *) ² + (Δa *) ² + (Δb *) ² ] ^1/2 (5)
ΔL * L * _{After heat treatment-Before} L * _{heat treatment}
Δa * = a * _{after heat treatment} -a * _{before heat treatment}
Δb * = b * _{after heat treatment} -b * _{before heat treatment}

  In the embodiment of the present invention, the means for setting the color change ΔE * before and after the heat treatment of the polyamide resin composition to 0 to 30 is, for example, a method using the above-mentioned preferable polyamide resin composition or a preferable production method described later. Examples thereof include a method for producing a resin composition. From the viewpoint of the composition of the polyamide resin composition, for example, by containing the above-mentioned preferred (B) hydroxyl group-containing compound, (C) containing a phosphorus-containing compound and / or (D) a nitrogen-containing compound, Examples thereof include a method in which the compatibility between the A) polyamide resin and the (B) hydroxyl group-containing compound is further improved to form a finely dispersed structure in the polyamide resin composition. Moreover, as a viewpoint of the manufacturing method of a polyamide resin composition, the resin pressure at the time of melt-kneading is raised by selection of kneading | mixing temperature or screw arrangement, it melt-kneads through a multiple times extruder, (A) polyamide A high-concentration premix of resin and (B) hydroxyl group-containing compound is prepared, and this is melt-kneaded with (A) polyamide resin, so that the compatibility between (A) polyamide resin and (B) hydroxyl group-containing compound is increased. And a method of forming a fine dispersion structure in the polyamide resin composition.

  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.

  In the embodiment of the present invention, as a method for producing a polyamide resin composition using a twin-screw extruder, (B) a hydroxyl group-containing compound and (A) a polyamide resin, if necessary, other than (A) and (B) The method of melt-kneading with these components is mentioned.

  When melt-kneading using a twin-screw extruder, there is no particular limitation on the raw material supply method to the twin-screw extruder. When supplying the (B) hydroxyl group-containing compound to the twin screw extruder, the (B) hydroxyl group-containing compound tends to promote the decomposition of the polyamide resin in a temperature range higher than the melting point of the polyamide resin. It is preferable to supply the compound from the downstream side of the polyamide resin supply position and shorten the kneading time of (A) the polyamide resin and (B) the hydroxyl group-containing compound. 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.

  Further, when the polyamide resin composition used in the embodiment of the present invention contains a (C) phosphorus-containing compound, (C) the phosphorus-containing compound facilitates the condensation of the (A) polyamide resin during melt kneading, (B) It is preferable to supply the phosphorus-containing compound (C) from the downstream side of the (A) polyamide resin supply position together with the hydroxyl group-containing compound.

  When the polyamide resin composition used in the embodiment of the present invention contains (D) a nitrogen-containing compound, (D) the nitrogen-containing compound promotes decomposition of the polyamide resin in a temperature range higher than the melting point of the polyamide resin. Since it is easy, it is preferable to supply the (D) nitrogen-containing compound from the downstream side of the (A) polyamide resin together with the (B) hydroxyl group-containing compound and the (C) phosphorus-containing compound.

  Further, the copper compound serves to protect the amide group by coordinating to the amide group of the (A) polyamide resin, and also serves as a compatibilizing agent for the (A) polyamide resin and the (B) hydroxyl group-containing compound. Therefore, when a copper compound is blended, it is preferable to supply the (A) polyamide resin and the copper compound sufficiently by supplying them to the twin screw extruder together with the (A) polyamide resin.

  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, (B) a hydroxyl group-containing compound, if necessary (C) a phosphorus-containing compound, (D) a nitrogen-containing compound after sufficiently kneading the (A) polyamide resin and, if necessary, the copper compound And it becomes easy to supply other components. As a result, (A) the decomposition of the polyamide resin can be suppressed. Further, the dispersibility of (A) the polyamide resin and (B) the hydroxyl compound can be further improved, and the color tone change ΔE * before and after the heat treatment can be easily adjusted to the above desired range.

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

  (B) The hydroxyl group-containing compound, and optionally (C) the phosphorus-containing compound and (D) the nitrogen-containing compound are preferably supplied to the twin screw extruder from the downstream side of 1/2 of the screw length and melt-kneaded. . (B) A hydroxyl group-containing compound, if necessary (C) a phosphorus-containing compound, and (D) a nitrogen-containing compound are supplied from the downstream side of 1/2 of the screw length, so that (A) a polyamide resin and, if necessary, a copper compound are sufficient (B) a hydroxyl group-containing compound, and (C) a phosphorus-containing compound and (D) a nitrogen-containing compound, if necessary. As a result, the reactivity between the (B) hydroxyl group-containing compound and the (A) polyamide resin can be improved and the dispersibility can be further improved while suppressing the thickening of the (A) polyamide resin. As a result, the color tone change ΔE * before and after the heat treatment can be easily adjusted to the desired range described above.

  In order to express the effect of the present invention more remarkably, it is preferable to increase the dispersibility of the (B) hydroxyl group-containing compound in the polyamide resin composition. Specifically, a method of further promoting the dehydration condensation reaction between (B) the hydroxyl group in the hydroxyl group-containing compound and (A) the carboxyl end group of the polyamide resin is preferable, and (A) a finely dispersed structure is formed in the polyamide resin composition. By forming, the change in color tone ΔE * before and after the heat treatment of the polyamide resin composition can be easily adjusted to the above-mentioned desired range. (B) Examples of means for increasing the dispersibility of the hydroxyl group-containing compound in the (A) polyamide resin composition include, for example, a method of increasing the resin pressure during melt kneading by selecting a kneading temperature and screw arrangement, and melting through a plurality of extruders. Preferable examples include a kneading method, (A) a polyamide resin and (B) a high-concentration preliminary mixture of a hydroxyl group-containing compound, and (A) a melt kneading method with the 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 (B) hydroxyl group-containing compound in the product can be further improved, and as a result, the color tone change ΔE * before and after the heat treatment can be easily adjusted to the above-mentioned desired range.

  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.

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

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

  Also, (A) polyamide resin and (B) hydroxyl group-containing compound, (C) phosphorus-containing compound, (D) nitrogen-containing compound and other components are melt-kneaded as necessary, and the resulting resin composition is repeatedly passed through an extruder. And a method of improving the dispersibility of the (B) hydroxyl group-containing compound in the polyamide resin composition by repeating melt kneading a plurality of times.

  When a high concentration premix of (A) polyamide resin and (B) hydroxyl group-containing compound is prepared, and a polyamide resin composition is produced by a method of melt-kneading this with (A) polyamide resin, (A) 100 weight of polyamide resin (B) 10 to 250 parts by weight of a hydroxyl group-containing compound is melt-kneaded to prepare a high-concentration premix, and the high-concentration premix is further (A) a polyamide resin, and (C) a phosphorus-containing compound if necessary. (D) It is more preferable to melt and knead together with the nitrogen-containing compound and other components by a twin screw extruder. Compared with the case where a high-concentration premix is not prepared, the color change ΔE * before and after the heat treatment can be easily adjusted to the above-mentioned desired range. For this reason, it is excellent in the fluidity | liquidity at the time of shaping | molding, and residence stability, it can improve the tensile strength and the heat aging mechanical characteristic more, and can further improve the heat aging fitting characteristic and regrind characteristic of a plastic fastener.

  Although it is not certain about this factor, the phase of (A) the polyamide resin and (B) the hydroxyl group-containing compound is obtained by previously melt-kneading the (B) hydroxyl group-containing compound at a high concentration with respect to the (A) polyamide resin. It is considered that a large number of components that contribute to solubility improvement, that is, a compatibilizing agent, are generated, and the compatibility between the (A) polyamide resin and the (B) hydroxyl group-containing compound is further improved.

  On the other hand, when preparing a high concentration premix, the content of the (B) hydroxyl group-containing compound is increased with respect to (A) the polyamide resin. In order to suppress a decrease in residence stability, during melt kneading in a twin-screw extruder, (B) a hydroxyl group-containing compound is supplied from the downstream side of the polyamide resin supply position, and (A) the polyamide resin and (B) a hydroxyl group are contained. It is preferable to shorten the kneading time of the compound. 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 (A) used in the high-concentration premix is made of nylon 6, nylon 11 from the viewpoint of further improving the tensile strength and heat aging mechanical properties, and further improving the heat aging fitting properties and regrind properties of plastic fasteners. And / or nylon 12 is preferred.

  The polyamide resin composition thus obtained can be molded by a known method, and a plastic fastener can be obtained from the polyamide resin composition. Examples of the molding method include injection molding, injection compression molding, extrusion molding, compression molding, blow molding, and press molding.

  The shape of the plastic fastener is not particularly limited, but from the viewpoint of facilitating fixing of components and electrical wiring, it is preferable to have a fitting portion and a mechanism for press-contacting the fixed components and wiring. Moreover, it is preferable to have a marking space from a viewpoint of distinguishability.

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

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

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

[Phosphorus atom content relative to polyamide resin content in polyamide resin composition]
The pellets obtained in Examples 9 to 36 and Comparative Example 6 were dried under reduced pressure at 80 ° C. for 12 hours, and the pellets were ashed in an electric furnace at 550 ° C. for 24 hours to determine the inorganic content. Subsequently, the pellet was stirred in DMSO at 60 ° C. to extract additive components other than the polyamide resin, and the additive content was determined. Thereafter, the content of the polyamide resin in the composition was determined by subtracting the inorganic and additive weights from the weight of the polyamide resin composition.

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

[Copper content and potassium content in polyamide resin composition]
The pellets obtained in Example 35 were dried under reduced pressure at 80 ° C. for 12 hours. The pellet was incinerated for 24 hours in an electric furnace at 550 ° C., concentrated sulfuric acid was added to the incinerated product, and the mixture was heated and wet-decomposed to dilute the decomposition solution. The diluted solution was subjected to atomic absorption analysis (calibration curve method) to determine the copper content and the potassium content. AA-6300 manufactured by Shimadzu Corporation was used as the atomic absorption spectrometer.

[Weight average molecular weight and number average molecular weight]
A solution obtained by dissolving 2.5 mg of the (B) hydroxyl group-containing compound obtained in Reference Example 1 in 4 ml of hexafluoroisopropanol (added with 0.005N sodium trifluoroacetate) and filtering through a 0.45 μm filter. Used for measurement. The measurement conditions are shown below.
Apparatus: Gel permeation chromatography (GPC) (manufactured by Waters)
Detector: differential refractometer Waters 410 (manufactured by Waters)
Column: Shodex GPC HFIP-806M (2 pieces) + HFIP-LG (Shimadzu GL Corp.)
Flow rate: 0.5 ml / min
Sample injection volume: 0.1 ml
Temperature: 30 ° C
Molecular weight calibration: polymethylmethacrylate.

[Hydroxyl value]
(B) 0.5 g of a hydroxyl group-containing compound was sampled and added to a 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 calculated by the following formula (5) by subtracting the measurement result of the blank (not including the sample) separately measured.
Hydroxyl value [mgKOH / g] = [((BC) × f × 28.05) / S] + E (5) where B: 0.5 mol / L ethanolic potassium hydroxide solution used for titration Amount [ml], C: Amount of 0.5 mol / L ethanolic potassium hydroxide solution used for titration of blank [ml], f: Factor of 0.5 mol / L ethanolic potassium hydroxide solution, S: Sample mass [g], E: represents acid value.

[(B) Compound reaction rate]
0.035 g of the (B) hydroxyl group-containing compound obtained in Reference Examples 2 to 7 was dissolved in 0.7 ml of deuterated dimethyl sulfoxide, respectively. In the case of an epoxy group, ¹ H-NMR measurement, 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 dry blend of a hydroxyl group-containing compound and an epoxy group and / or carbodiimide group-containing compound used as raw materials is defined as d, the peak area of the compound (B) is defined as e, and the reaction rate is calculated by the following formula (4). did.
Reaction rate (%) = {1- (e / d)} × 100 (4)

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

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

[(B) Sum of number of hydroxyl groups of compound and sum of number of epoxy groups and carbodiimide groups]
About the (B) compound obtained by the reference examples 2-7, the number average molecular weight and the hydroxyl value of (B) compound were computed, and the number of OH was computed by following formula (1).
Number of OH = (number average molecular weight × hydroxyl value) / 56110 (1)
The number of epoxy groups or carbodiimide groups was calculated by dividing the number average molecular weight of the compound (B) by the epoxy equivalent or carbodiimide equivalent.

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

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

[Color change ΔE * before and after heat treatment]
The pellets obtained in each example and comparative example were vacuum-dried at 80 ° C. for 12 hours, and using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: (A) of polyamide resin Melting point + 15 ° C., mold temperature: 80 ° C., injection / cooling time: 10/15 seconds, screw rotation speed: 150 rpm, injection pressure: 100 MPa, injection speed: 50 mm / second, 70 mm × 70 mm × 2 mm thick corner A plate (film gate) was injection molded. At any five points of the obtained square plate, using a color computer (SM color computer model SM-3 manufactured by Suga Test Instruments Co., Ltd.), at 23 ° C. and 50% RH, L * (lightness), a *, B * (hue and saturation) were measured, and the average value was calculated.

In addition, the obtained 2 mm square plate was heat-treated in a gear oven under the atmosphere at 190 ° C. for 2 hours, and then at any 5 points in the same manner under the conditions of 23 ° C. and 50% RH, L *, a *, b * Was measured and the average value was calculated. From the obtained average value, the color tone change ΔE * was calculated by the following formula (5).
ΔE * = [(ΔL *) ² + (Δa *) ² + (Δb *) ² ] ^1/2
Here, ΔL * = L * _{after heat treatment} −L * _{before heat treatment} , Δa * = a * _{after heat treatment} −a * _{before heat treatment} , Δb * = b * _{after heat treatment} −b * _{before heat treatment} .

[Heat-resistant mechanical properties]
The pellets obtained in each example and comparative example were vacuum-dried at 80 ° C. for 12 hours, and using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: (A) of polyamide resin An ASTM No. 1 dumbbell test piece having a thickness of 3.2 mm was produced by injection molding under the conditions of melting point + 15 ° C. and mold temperature: 80 ° C. This test piece was subjected to a tensile test at a crosshead speed of 10 mm / min by a tensile tester Tensilon UTA2.5T (manufactured by Orientec Co., Ltd.) according to ASTM D638. The measurement was performed three times, and the average value was calculated as the tensile strength before heat aging treatment. Next, ASTM No. 1 dumbbell test piece was heat-treated at 190 ° C. in the atmosphere for 3000 hours (heat aging treatment). The test piece after treatment was subjected to the same tensile test, and the average value of the three measurements was heat aging. The tensile strength after the treatment was calculated. The ratio of the tensile strength after the treatment to the tensile strength before the heat aging treatment was calculated as the tensile strength retention rate. The higher the tensile strength retention, the better the heat aging mechanical properties.

[Mating characteristics]
The pellets obtained in each example and comparative example were vacuum-dried at 80 ° C. for 12 hours, and using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature: (A) of polyamide resin By injection molding under the conditions of melting point + 15 ° C. and mold temperature: 80 ° C., the plastic fastener shown in FIG. 3 (W1: 14.2 mm, W 2: 19.6 mm, W 3: 6.0 mm, H 1: 2.0 mm, (H2: 8.5 mm) 30 molded products were obtained. 3A shows a plastic fastener after fitting, FIG. 3B shows a plastic fastener after fitting, FIG. 3D shows a top view after fitting, and FIG. 3E shows a side view after fitting. Next, 30 pieces of the obtained plastic fasteners were used to fix the wires 2 each having a diameter of 4.5 mm, and the presence or absence of cracks in the fitting portion 3 or the inner spring portion 4 at the time of fitting and fitting was visually observed. The number that was not counted was counted. The greater the number of cracks not recognized in 30, the better the fitting characteristics.

[Heat aging mating characteristics]
Plastic fasteners (up to 30 pieces) that were not cracked at the time of mounting and fitting in the above evaluation were subjected to 2000 hours (heat aging treatment) in a gear oven at 170 ° C. in the atmosphere, and the plastic fastener fitting part 3 after the treatment Alternatively, the presence or absence of cracks in the inner spring 4 was visually observed, and the number of cracks not observed was counted. The greater the number of cracks not found, the better the heat aging fitting characteristics.

  Further, the value of (number of cracks not recognized after heat aging treatment / 30) was calculated. The closer this value is to 1, the better the heat aging fitting characteristics.

[Regrind characteristics]
The plastic fasteners obtained in the examples and comparative examples and the sprue runner generated during molding were pulverized to obtain pulverized products. The ground product was passed through an ASTM 16 mesh sieve to remove fines. Also, pulverized products having a maximum length exceeding 50 mm were excluded. Subsequently, the obtained pulverized product was subjected to the conditions of cylinder temperature: (A) melting point of polyamide resin + 15 ° C., mold temperature: 80 ° C. using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.). The plastic fastener (W1: 14.2 mm, W2: 19.6 mm, W3: 6.0 mm, H1: 2.0 mm, H2: 8.5 mm) regrind shown in FIG. 3 was obtained by injection molding.

  Using 30 plastic fastener regrinds, fixing the wire with a diameter of 4.5 mm in the same manner as above, visually observing whether there is a crack in the fitting part or the inner spring part during mounting fitting, no cracking was observed The number was counted. The greater the number of cracks not recognized in 30, the better the regrind characteristics (fitting characteristics).

  Subsequently, the plastic fastener regrind (up to 30 pieces) that was not cracked during fitting in the evaluation was subjected to 2000 hours (heat aging treatment) in a gear oven under the atmosphere at 170 ° C., and the processed plastic fastener The regrind fitting part or inner spring was visually observed for cracks, and the number of cracks not observed was counted. The greater the number of cracks not found, the better the regrind characteristics (heat aging fitting characteristics).

  Further, the value of (number of cracks not recognized after heat aging treatment / 30) was calculated. The closer this value is to 1, the better the regrind characteristics (heat aging fitting characteristics).

For each of the plastic fastener and the plastic fastener regrind obtained by the above method, the fitting part is cut, and at any five points of the remaining square plate part (W1: 15 mm, W2: 20 mm, H1: 2 mm), the color Using a computer (SM color computer model SM-3 manufactured by Suga Test Instruments Co., Ltd.), L *, a *, and b * were measured under the conditions of 23 ° C. and 50% RH, and the average value was calculated. The average value obtained and L *, a *, b * before heat treatment measured by the method described in [Color change before and after heat treatment ΔE *] (L *, a *, b * before regrind treatment) From the following formula, a change in color tone ΔE _R * before and after regrinding was calculated according to the following formula. The closer the ΔE _R * is to 0, the less the change in color tone during regrinding, and the better the regrind characteristics (color tone).
ΔE _R * = [(ΔL *) ² + (Δa *) ² + (Δb *) ² ] ^1/2
Here, ΔL * = L * _{after regrind treatment} -L * _{regrind pretreatment,} Δa * = a * _{after regrind treatment} -a * _{regrind pretreatment,} Δb * = b * _{regrind processed} -b * _{Li Before grinding} .

The (A) polyamide resin, (B) hydroxyl group-containing compound, (C) phosphorus-containing compound, and (D) nitrogen-containing compound used in the examples and comparative examples are as follows.
(A-1): nylon 66 resin having a melting point of 260 ° C. (“Amilan” (registered trademark) CM3001-N manufactured by Toray Industries, Inc.), ηr = 2.78.
(A-2): Nylon 6 resin having a melting point of 225 ° C. (“Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc.), ηr = 2.70, Tm−Tc = 55 ° C.
(A-3): Nylon 6 resin having a melting point of 225 ° C. (“Amilan” (registered trademark) CM1021T manufactured by Toray Industries, Inc.), ηr = 3.4.
(B-1): Dipentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight 254, hydroxyl value 1325 mgKOH / g.

Reference Example 1 (B-2)
In a four-necked flask equipped with a stirrer, pressure gauge, condenser and receiver, 50.5 g (0.14 mol) of pentaerythritol pentaethoxylate and 1.0 g (0.004 mol) of 3 fluorine A 50% by weight aqueous solution of borohydride diethyl ether complex was added at room temperature and heated to 110 ° C. To this, 450 g (3.87 mol) of 3-ethyl-3-oxetanemethanol was added over 35 minutes while maintaining the temperature in the system at 110 ° C. When the exotherm has subsided, the temperature is raised to 120 ° C., stirred for 2.5 hours, then cooled to room temperature, and contains a hydroxyl group having three or more hydroxyl groups, including a branched structure composed of repeating structural units having an ether bond A compound was obtained. The obtained hydroxyl group-containing compound had a weight average molecular weight of 2,620, a hydroxyl value of 810 mgKOH / g, and a degree of branching of 0.29.

  (B-3): 2,2,4-trimethyl-1,3-pentanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), molecular weight 146, hydroxyl value 767 mgKOH / g.

Reference Example 2 (B-4)
A phenol novolac type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.) is used with respect to 100 parts by weight of dipentaerythritol (Guangei Chemical Industry Co., Ltd., molecular weight / number of functional groups 42 per molecule). After premixing 10 parts by weight of an average number of epoxy groups in one molecule, molecular weight of 1330, molecular weight / functional number of molecules in one molecule of 190), a cylinder temperature of 200 using a PCM30 type twin screw extruder manufactured by Ikegai. The mixture was melt-kneaded for 3.5 minutes under the conditions of ° C and screw rotation speed of 100 rpm, 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 was 53%, the degree of branching was 0.29, and the hydroxyl value was 1280 mgKOH / g. The number of hydroxyl groups in one molecule was 3 or more, more than the number of epoxy groups in one molecule, and the sum of the number of OH and OR in the general formula (3) was 3 or more.

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

Reference Example 4 (B-6)
The compound represented by the general formula (3) and / or the same as in Reference Example 2 except that the screw rotation speed of the twin screw extruder was changed to 200 rpm and the melt kneading time was changed to 2.4 minutes. Condensate pellets were obtained. The reaction rate of the obtained compound was 15%, the degree of branching was 0.20, and the hydroxyl value was 1300 mgKOH / g. The number of hydroxyl groups in one molecule was 3 or more, more than the number of epoxy groups in one molecule, and the sum of the number of OH and OR in the general formula (3) was 3 or more.

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

Reference Example 6 (B-8)
Aliphatic polycarbodiimide (“Carbodilite” (registered trademark) LA-1 manufactured by Nisshinbo Chemical Co., Ltd.) and average number of carbodiimide groups in one molecule with respect to 100 parts by weight of dipentaerythritol (Guangei Chemical Industry Co., Ltd.) After 24 parts, molecular weight 6000, molecular weight / number of functional groups in one molecule 250) 10 parts by weight were premixed, 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 was 89%, the degree of branching was 0.37, and the hydroxyl value was 1110 mgKOH / g. The number of hydroxyl groups in one molecule was 3 or more, more than the number of carbodiimide groups in one molecule, and the sum of the numbers of OH and OR in general formula (3) was 3 or more.

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

Reference Example 8 (B-10)
After pre-mixing 500 parts by weight of a phenol novolac type epoxy resin (“EPPN” (registered trademark) 201 manufactured by Nippon Kayaku Co., Ltd.) with 100 parts by weight of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd.) Using a PCM30 type twin screw extruder manufactured by Ikegai Co., Ltd., melt-kneading for 3.5 minutes under 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 was 33%, the degree of branching was 0.23, and the hydroxyl value was 540 mgKOH / g. The number of hydroxyl groups in one molecule was 3 or more, which was less than the number of epoxy groups in one molecule, and the sum of the numbers of OH and OR in the general formula (3) was 3 or more.
(C-1): Sodium hypophosphite monohydrate (Wako Pure Chemical Industries, Ltd.), molecular weight 105.99
(C-2): Calcium hypophosphite (Wako Pure Chemical Industries, Ltd.), molecular weight 170.0
(C-3): Cyclophosphazene oligomer (SPB-100 manufactured by Otsuka Chemical Co., Ltd.)
(C-4): bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite (ADEKA Co., Ltd. PEP-36)
(D-1): Melamine cyanurate (MC-4000 manufactured by Nissan Chemical Industries, average particle size (D ₅₀ ) 14 μm)
(D-2): Melamine cyanurate (MC-6000 manufactured by Nissan Chemical Industries, average particle size (D ₅₀ ) 2 μm)
The average particle diameter (D ₅₀ ) was measured by a laser diffraction scattering method, plotted with the particle diameter on the horizontal axis and the frequency (mass) on the vertical axis, and the total accumulated mass of the frequencies was taken as 100%. It was measured as the particle size at which the cumulative mass was sometimes 50%.

Reference Example 9 (E-1) High Concentration Premixed Nylon 6 (“Amilan” (registered trademark) CM1010, ηr = 2.70) manufactured by Toray Industries, Inc., 100 parts by weight (B-1) dipentaerythritol After pre-mixing 100 parts by weight, the mixture was melt-kneaded using a TEX30 twin screw extruder (L / D: 45.5) manufactured by Nippon Steel, Ltd. under the conditions of a cylinder temperature of 240 ° C. and a screw rotation speed of 150 rpm. And pelletized with a strand cutter. Then, it vacuum-dried at 80 degreeC for 8 hours, and produced the high concentration pre-mixture pellet.

Reference Example 10 (E-2) High Concentration Premix (B-1) By the same method as Reference Example 9 except that (B-2) obtained in Reference Example 1 was used instead of dipentaerythritol A pellet of high concentration premix was obtained.

Reference Example 11 (E-3) High Concentration Premix (B-1) Except for using (B-4) obtained in Reference Example 2 instead of dipentaerythritol, the same procedure as in Reference 9 was used. A pellet of high concentration premix was obtained.

Reference Example 12 (E-4) High Concentration Premixture (B-4) 26.7 obtained in Reference Example 2 with respect to 100 parts by weight of nylon 66 (“Amilan” (registered trademark) CM3001-N manufactured by Toray) After pre-mixing the parts by weight, using a TEX30 type twin screw extruder (L / D: 45.5) manufactured by Nippon Steel, Ltd., melt kneading under conditions of a cylinder temperature of 235 ° C. and a screw rotation speed of 150 rpm, Pelletized with a strand cutter. Then, it vacuum-dried at 80 degreeC for 8 hours, and produced the high concentration pre-mixture pellet.

Reference Example 13 (Nylon 6 masterbatch containing F-1: CuI / KI (weight ratio) = 0.23)
To 100 parts by weight of nylon 6 (“Amilan” (registered trademark) CM1010, ηr = 2.70) manufactured by Toray Industries, Inc., 2.0 parts by weight of copper iodide and 21.7 parts by weight of potassium iodide 40% aqueous solution Is premixed and then melt-kneaded using a TEX30 twin screw extruder (L / D: 45.5) manufactured by Nippon Steel, Ltd. at a cylinder temperature of 245 ° C. and a screw rotation speed of 150 rpm, and a strand cutter Pelletized. Thereafter, it was vacuum-dried at 80 ° C. for 8 hours to produce a master batch pellet having a copper content of 0.60% by weight.

Reference Example 14 (F-2: CuI / 2-mercaptobenzimidazole equimolar complex)
Cuprous iodide is dissolved by stirring 11.43 g (0.06 mol) of cuprous iodide and 9.01 g (0.06 mol) of 2-mercaptobenzimidazole in 1 L of acetone at room temperature. Thus, a uniform light yellow solution was obtained. Subsequently, a part of insoluble matter was filtered and acetone was removed, thereby obtaining a complex having a molar ratio of cuprous iodide and 2-mercaptobenzimidazole of 1: 1.

(Examples 1 and 4)
The (A) polyamide resin shown in the table is a TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel, Ltd., in which the cylinder set temperature is set to the melting point of the polyamide resin + 15 ° C. and the screw rotation speed is set to 200 rpm. It was supplied from a main feeder to a twin screw extruder and melt kneaded. This main feeder was connected to a position of 0 when viewed from the upstream side when the total length of the screw was 1.0, that is, a position of an end portion on the upstream side of the screw segment. Subsequently, the hydroxyl group-containing compound (B) shown in the table 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 screw configuration of the twin screw extruder is (B) the total length of the kneading zone on the upstream side of the supply position of the hydroxyl group-containing compound is Ln1, (B) the kneading zone on the downstream side of the supply position of the hydroxyl group-containing compound 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 in a water bath and pelletized with a strand cutter. From the main feeder of a TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel, Ltd., the cylinder set temperature was set to the melting point of the polyamide resin + 15 ° C. and the screw rotation speed was set to 200 rpm. The mixture was supplied to a screw extruder, melted and kneaded, cooled with water and pelletized, and then again melt melted and kneaded with a twin screw extruder in the same manner to obtain a plurality of kneaded pellets.

(Example 2)
(A) Polyamide resin shown in the table is supplied to the twin screw extruder from the main feeder of TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel, Ltd. with a screw speed set to 200 rpm, Melt kneaded. Subsequently, the hydroxyl group-containing compound (B) shown in the table was supplied from the side feeder to the twin screw extruder, and melt kneaded. The positions of the main feeder and side feeder of the twin screw extruder and the screw configuration were the same as in Example 1. The cylinder set temperature is set to the melting point of the polyamide resin + 15 ° C. at the upstream side of the supply position of the (B) hydroxyl group-containing compound, and the downstream side of the supply position of the (B) hydroxyl group-containing compound is set to the melting point of the polyamide resin. The temperature of the discharge port was set to the melting point of the polyamide resin + 15 ° C. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter.

(Example 3)
The (A) polyamide resin shown in the table is a TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel, Ltd., in which the cylinder set temperature is set to the melting point of the polyamide resin + 15 ° C. and the screw rotation speed is set to 200 rpm. It was supplied from a main feeder to a twin screw extruder and melt kneaded. Subsequently, the hydroxyl group-containing compound (B) shown in the table was supplied from the side feeder to the twin screw extruder and melt kneaded. The positions of the main feeder and side feeder of the twin screw extruder were the same as those in Example 1. The screw configuration of the twin screw extruder was such that Ln1 / L was 0.14 and Ln2 / L was 0.14. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter.

(Examples 9 to 17, 20, 22 to 26, 28 to 34, Comparative Examples 1 to 7)
The (A) polyamide resin shown in the table is a TEX30 type twin screw extruder (L / D = 45) manufactured by Nippon Steel, Ltd., in which the cylinder set temperature is set to the melting point of the polyamide resin + 15 ° C. and the screw rotation speed is set to 200 rpm. It was supplied from a main feeder to a twin screw extruder and melt kneaded. Subsequently, (B) a hydroxyl group-containing compound, (C) a phosphorus-containing compound, and (D) a nitrogen-containing compound shown in the table were supplied from a side feeder to a twin-screw extruder and melt-kneaded. The positions of the main feeder and side feeder of the twin screw extruder and the screw configuration were the same as in Example 1. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter.

(Examples 5-8, 18, 19, 21, 27, 35-44)
(A) Polyamide resin and (E) high-concentration premix and (F) copper compound shown in the table were dry blended, the cylinder set temperature was set to the melting point of the polyamide resin + 15 ° C., and the screw rotation speed was set to 200 rpm. It was supplied from a main feeder of a TEX30 type twin screw extruder (L / D = 45) manufactured by Steelworks to a twin screw extruder and melt kneaded. Subsequently, (C) a phosphorus-containing compound and (D) a nitrogen-containing compound shown in the table were supplied from a side feeder to a twin-screw extruder and melt-kneaded. The positions of the main feeder and side feeder of the twin screw extruder and the screw configuration were the same as in Example 1. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter.

  The evaluation results of each Example and Comparative Example are shown in Tables 1-5.

  From the comparison between Examples 1 to 3 and 6 and Comparative Example 2 and from the comparison between Examples 4 and 8 and Comparative Example 4, the resin pressure at the time of melt-kneading is increased by selecting the kneading temperature and screw arrangement, multiple times extrusion (A) polyamide resin by melt kneading through a machine, preparing a high concentration premix of (A) polyamide resin and (B) hydroxyl group-containing compound, and melt kneading this with (A) polyamide resin And (B) improving the compatibility with the hydroxyl group-containing compound to form a finely dispersed structure in the polyamide resin composition, and setting the color change ΔE * before and after the heat treatment to 0-30, the tensile strength and heat aging It can be seen that a plastic fastener having improved mechanical characteristics and excellent heat aging fitting characteristics and regrind characteristics can be obtained.

  Further, from the comparison between Examples 9 to 15 and Comparative Example 2, (C) By containing a phosphorus-containing compound, the compatibility between (A) the polyamide resin and (B) the hydroxyl group-containing compound is improved, and the polyamide By forming a fine dispersion structure in the resin composition and setting the color change ΔE * before and after heat treatment to 0 to 30, the tensile strength and heat aging mechanical properties are improved, heat aging fitting properties and regrind properties. It can be seen that a plastic fastener excellent in the above can be obtained.

  In Example 6, compared with Examples 5 and 7, since the content of the (B) hydroxyl group-containing compound is in a more preferable range, the tensile strength and the heat aging mechanical properties are further improved, and the heat aging fitting properties and A plastic fastener superior in regrind characteristics could be obtained.

  In Examples 18, 21, 27, and 35, compared with Examples 13, 20, 23, and 28, respectively, a high-concentration premixed mixture of (A) polyamide resin and (B) hydroxyl group-containing compound was prepared. A) By melt-kneading with a polyamide resin, the compatibility between (A) the polyamide resin and (B) the hydroxyl group-containing compound is further improved. As a result, the tensile strength and the heat aging mechanical properties are further improved, and the heat aging is improved. A plastic fastener excellent in fitting characteristics and regrind characteristics could be obtained.

  Examples 22-26 contain (D) nitrogen-containing compounds as compared with Example 13 to further improve the tensile strength and heat aging mechanical properties, and by heat aging fitting properties and regrind properties. An excellent plastic fastener could be obtained.

  In Examples 22 to 24 and 26, the weight ratio of the (B) hydroxyl group-containing compound to the (D) nitrogen-containing compound is in a more preferable range as compared with Example 25. Therefore, the tensile strength and heat aging mechanical properties are high. It was possible to obtain a plastic fastener which was further improved and was superior in heat aging fitting characteristics and regrind characteristics.

  Examples 28-35, 40, and 44 are heat resistant by using a reaction product of a hydroxyl group-containing compound and an epoxy group and / or carbodiimide group-containing compound as the hydroxyl group-containing compound (B) as compared with Example 23. It was possible to obtain a plastic fastener with improved aging mechanical properties and superior heat aging fitting characteristics and regrind characteristics.

  Example 28 uses (B) a hydroxyl group-containing compound having a more preferable reaction rate as compared with Examples 29 to 32, thereby further improving the heat aging mechanical properties and the heat aging fitting properties and regrind properties. An excellent plastic fastener could be obtained.

  In Examples 28 and 32, compared with Example 33, the molecular weight of the compound having an epoxy and / or carbodiimide group used as the raw material for the (B) hydroxyl group-containing compound / the number of functional groups in one molecule is more preferable. Therefore, the tensile strength and heat aging mechanical properties were further improved, and a plastic fastener excellent in heat aging fitting properties and regrind properties could be obtained.

  Example 40 is compared with Example 35, Example 42 is compared with Example 38, and Example 43 is compared with Example 39. It was possible to obtain a plastic fastener with improved characteristics and superior regrind characteristics.

  In Example 35, compared to Example 44, by using a more preferable (A) polyamide resin, the tensile strength and heat-aging mechanical properties can be further improved, and a plastic fastener having excellent regrind properties can be obtained. It was.

  In Example 35, compared with Example 36, the content of the hydroxyl group-containing compound (B) is in a more preferable range, so that the tensile strength and heat aging mechanical properties are further improved, and heat aging fitting properties and regrind properties are improved. Thus, an excellent plastic fastener could be obtained.

  In Example 37, compared with Example 36, the average particle size of the (D) nitrogen-containing compound is in a more preferable range, so that the tensile strength and heat aging mechanical properties are further improved, and heat aging fitting properties and A plastic fastener superior in grind characteristics could be obtained.

  In Example 37, since the content of the (D) nitrogen-containing compound is in a more preferable range as compared with Example 38, the heat aging mechanical characteristics are further improved, and the heat aging fitting characteristics and the regrind characteristics are more excellent. A plastic fastener could be obtained.

  In Example 38, since the phosphorus atom content derived from the phosphorus-containing compound (C) is in a more preferable range as compared with Example 39, the tensile strength and heat aging mechanical properties are further improved, and heat aging fitting is achieved. A plastic fastener excellent in properties and regrind properties could be obtained.

  Example 41 contains a copper element derived from a copper compound at a more preferable concentration in the polyamide resin composition as compared with Example 40, thereby obtaining a plastic fastener that is superior in heat aging mechanical properties and color change after regrinding. I was able to.

  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 plastic fastener according to the embodiment of the present invention is excellent in fitting characteristics, heat aging fitting characteristics and regrind characteristics, and is therefore suitable for applications used in high temperature environments such as automobile parts and electrical and electronic parts. In addition, it can be suitably used as a plastic fastener having a printed portion, taking advantage of the small discoloration caused by heat treatment.

1 Solvent peak 2 Wiring 3 Fitting part 4 Inner spring

Claims (6)

(A) 0.1 to 20 parts by weight of (B) a compound having at least three hydroxyl groups per 100 parts by weight of polyamide resin, a 2 mm thick square plate is molded, and heat treated at 190 ° C. for 2 hours The plastic fastener which consists of a polyamide resin composition from which the color tone change (DELTA) E * before and behind heat processing becomes 0-30. 2. The plastic fastener according to claim 1, wherein the polyamide resin composition further contains (C) a phosphorus-containing compound, and a phosphorus atom content obtained by an absorptiometric analysis method is at least 130 ppm with respect to the polyamide resin content. The plastic fastener according to claim 1 or 2, wherein the phosphorus atom content is at least 200 ppm with respect to the polyamide resin content. The plastic fastener according to any one of claims 1 to 3, wherein the polyamide resin composition further contains 0.1 to 50 parts by weight of (D) a nitrogen-containing compound with respect to 100 parts by weight of the polyamide resin. In the polyamide resin composition, (B) the weight ratio of the compound content having at least three hydroxyl groups to the content of (D) nitrogen-containing compound ((B) / (D)) is 0.1 to 5.0. The plastic fastener according to claim 4. The plastic fastener according to claim 4 or 5, wherein (D) the average particle diameter of the nitrogen-containing compound is 20 µm or less.