JP2001234059A - Polyamide resin composition having excellent stability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamide resin composition suitable for an industrial material such as an automobile part, an electronic and an electric parts, an industrial mechanical part, etc., having excellent moldability and processability under a wide range of molding conditions, providing a molding having excellent rigidity, strength, toughness, surface appearance, weld strength, hot water resistance, reworkability, etc., and excellent stability of resistance to change in color by heat, weather resistance, etc., slightly causing change in color and deterioration in an excessive heat and light environment. SOLUTION: This polyamide resin composition is obtained by compounding (A) a polyamide with (B) a polyamide complex which comprises an apatite type compound containing an organic substance insoluble in a phenol solvent in an amount of 0.5-100 pts.wt. of the organic substance based on 100 pts.wt. of the apatite type compound or a polyamide resin complex obtained by compounding the polyamide complex with another resin and (C) a stabilizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin composition, and more particularly, to a molded article having excellent rigidity, strength, toughness, surface appearance, weld strength, hot water resistance, reworkability, and the like. The present invention relates to a polyamide resin composition which is excellent in heat discoloration resistance, weather resistance, and the like, which cause little discoloration or deterioration under heat or light environment.

[0002]

2. Description of the Related Art Polyamide resins have excellent properties such as mechanical properties, chemical resistance and moldability, and have been widely used in various parts such as automobile parts, electronic and electrical parts, and industrial machine parts. ing. However, in recent years, with the advancement of the industry, the level of mechanical properties required for a polyamide resin molded article has been further improved, and furthermore, various unprecedented properties have been demanded.

[0003] More specifically, from an economic viewpoint,
There is a strong demand for a polyamide resin material that can shorten the molding time and improve productivity. Further, from the viewpoint of component integration, there is a strong demand for a polyamide resin material that can cope with an increase in size and complexity. Furthermore, highly durable polyamide resin materials that can be used in harsh environments where excessive external force, heat, and light such as ultraviolet light are applied, and polyamide resin materials that can be recycled from the viewpoint of environmental issues are also strong. Requested.

The present inventors proposed a polyamide resin and a polyamide resin composition comprising a polyamide and apatite having a good interface in Japanese Patent Application Laid-Open No. H11-197977 in order to solve the above problems. Molded products obtained from this composition are certainly superior in rigidity, strength, toughness, surface appearance, weld strength, hot water resistance, reworkability, etc. compared to conventional polyamide resins, but they are used for a long time in a high temperature atmosphere In terms of the heat discoloration resistance in the case of repeated and reworking, and the stability such as the weather resistance in an environment such as ultraviolet rays, the results were not satisfactory.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a molded article having excellent rigidity, strength, toughness, surface appearance, weld strength, hot water resistance, reworkability, and excessive heat and light environment. An object of the present invention is to provide a polyamide resin composition which is excellent in stability such as heat discoloration resistance and weather resistance, which cause less discoloration and deterioration.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a stabilizer is added to a specific polyamide resin composite obtained by adding a specific amount of an apatite type compound to a polyamide resin. The present inventors have found that the above problems can be solved by the blended polyamide resin composition, and have accomplished the present invention.

That is, the present invention comprises (1) (A) a polyamide and (B) an apatite compound containing an organic substance insoluble in a phenol solvent, wherein the organic substance is present in an amount of 0.5 to 0.5 parts by weight per 100 parts by weight of the apatite compound. 100 parts by weight of a polyamide composite, or a polyamide resin composite obtained by mixing the polyamide composite with another resin,
(C) a polyamide resin composition comprising a stabilizer,

(2) A polyamide composite obtained by blending a polyamide-forming component and an apatite-type compound-forming component and allowing the polymerization reaction of the polyamide and the synthesis reaction of the apatite-type compound to proceed, A polyamide resin composition obtained by mixing a stabilizer with a polyamide resin composite obtained by mixing a resin; and (3) the apatite type compound has an average particle diameter of 0.001 to 1 μm. The polyamide resin composition according to 1 or 2,

(4) The polyamide resin composition as described in (2) above, wherein the apatite type compound-forming component has an average particle diameter of 0.001 to 10 μm. And (b) a phosphite-based stabilizer, (c) a hindered amine-based stabilizer, (d) a triazine-based stabilizer, and (e) a sulfur-based stabilizer. The polyamide resin composition according to any one of the above items 1 to 4. Less than,
The present invention will be described in detail.

[0010] The present invention relates to a polyamide resin composition comprising a polyamide resin composite comprising a polyamide resin and an apatite type compound, and a stabilizer mixed therein. The polyamide in the present invention may be a polymer having an amide bond (—NHCO—) in the main chain.

Polyamides preferably used in the present invention include polycaprolactam (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), and polyhexamethylene sebacamide (nylon 610). , Polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyundecalactam (nylon 11),

Polydodecalactam (nylon 12), polytrimethylhexamethylene terephthalamide (nylon TMHT), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene methylene terephthalamide (9T), polyhexamethylene terephthalamide (6
T), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-aminocyclohexyl) methane dodecamide (nylon dimethyl PACM12),

Polymetaxylylene adipamide (nylon MXD6), polyundecamethylene hexahydroterephthalamide (nylon 11T (H)), and a polyamide copolymer containing at least two different polyamide components among them; and And mixtures thereof.

Among these polyamides, more preferred polyamides for achieving the object of the present invention are polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene dodecamide (nylon 612), Hexamethylene isophthalamide (nylon 6I), and a polyamide copolymer containing at least two different polyamide components among them;
And mixtures thereof.

Furthermore, in the present invention, a polyamide resin obtained by mixing the polyamide with another resin can also be used. In this case, the content of the polyamide in the polyamide resin is preferably at least 50% by weight, more preferably at least 60% by weight, and most preferably at least 70% by weight. The polyamide content in the polyamide resin is 50
When the amount is less than% by weight, the improvement effect of the present invention may not be remarkable. As other resins to be blended with polyamide,
A thermoplastic resin or a rubber component can be added.

Other thermoplastic resins include, for example, polystyrene resins such as atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, AS resin and ABS resin, polyethylene terephthalate,
Polyester resins such as polybutylene terephthalate, polyether resins such as polycarbonate, polyphenylene ether, polysulfone, and polyether sulfone; condensation resins such as polyphenylene sulfide and polyoxymethylene; polyacrylic acid, polyacrylate, and polymethyl methacrylate Such as acrylic resins, polyethylene, polypropylene, polybutene, polyolefin resins such as ethylene-propylene copolymer, polyvinyl chloride, halogen-containing vinyl compound resins such as polyvinylidene chloride, phenolic resins, epoxy resins and the like. it can.

The rubber component includes rubber and modified products thereof. Examples of the rubber include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, shrimp chlorohydrin rubber, styrene-butadiene block copolymer (SB)
R), hydrogenated styrene-butadiene block copolymer (SEB),

Styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-
Styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS),
Hydrogenated styrene-isoprene-styrene block copolymer (SEPS),

Styrene-butadiene random copolymer,
Hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random copolymer, ethylene-
Propylene copolymer (EPR), ethylene- (1-butene) copolymer, ethylene- (1-hexene) copolymer,
Ethylene- (1-octene) copolymer,

Ethylene-propylene-diene copolymer (EPDM), butadiene-acrylonitrile-styrene-core-shell rubber (ABS), methyl methacrylate-butadiene-styrene-core-shell rubber (M
BS), methyl methacrylate-butyl acrylate-
Styrene-core shell rubber (MAS), octyl acrylate-butadiene-styrene-core shell rubber (MA
BS), core-shell rubbers such as alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (ABS), butadiene-styrene-core-shell rubber (SBR), and siloxane-containing core-shell rubber such as methyl methacrylate-butyl acrylate siloxane. .

The modified rubber is obtained by modifying the above rubber with a modifying agent having a polar group, such as maleic anhydride-modified SEBS and maleic anhydride-modified SEP.
S, maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-modified ethylene- (1-butene) copolymer, maleic anhydride-modified ethylene- (1-hexene)
Copolymer, maleic anhydride-modified ethylene- (1-octene) copolymer, maleic anhydride-modified EPDM, epoxy-modified SEBS, epoxy-modified ethylene-propylene copolymer, epoxy-modified ethylene- (1-butene) copolymer , An epoxy-modified ethylene- (1-hexene) copolymer, an epoxy-modified ethylene- (1-octene) copolymer and the like are preferably used. In the present invention, one kind of the above-mentioned thermoplastic resin and rubber component may be blended with the polyamide, or two or more kinds thereof may be combined and used.

Examples of the polyamide-forming component (raw material) include a polymerizable amino acid, a polymerizable lactam, or a polymerizable diamine / dicarboxylate, and a polymerizable oligomer of the compound. Specific examples of the polymerizable amino acid include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid. In the present invention, these polymerizable amino acids may be used alone or in combination of two or more.

Examples of the polymerizable lactam include butyl lactam, pivalolactam, caprolactam, caprylactam, enantholactam, undecanolactam,
Dodecanolactam and the like can be more specifically mentioned. In the present invention, these polymerizable lactams may be used alone or in combination of two or more.

Examples of the diamine of the polymerizable diamine dicarboxylate include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2-methylpentamethylene diamine, nonamethylene diamine, 2,2,4 -Trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, meta-xylylenediamine, para-xylylenediamine,

1,3-bis (aminomethyl) cyclohexane, 3,8-bis (aminomethyl) tricyclodecane, 1-amino-3-aminomethyl-3,5,5, -trimethylcyclohexane, bis (4- Aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine,
Aminoethylpiperazine and the like can be mentioned. In the present invention, these polymerizable diamines may be used alone or in combination of two or more.

Examples of the dicarboxylic acid of the polymerizable diamine / dicarboxylic acid salt include, for example, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2
-Dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, dodecanedioic acid,
Eicodioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid,
Hexahydroterephthalic acid, diglycolic acid and the like can be mentioned. In the present invention, these polymerizable dicarboxylic acids may be used alone or in combination of two or more.

The polyamide-forming component (raw material) of the present invention may further contain a known terminal blocking agent for controlling the molecular weight or improving the hot water resistance. As the terminal blocking agent, a monocarboxylic acid or a monoamine is preferable.
Other examples include acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols.

The monocarboxylic acid that can be used as a terminal blocking agent is not particularly limited as long as it has reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid,
Valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid,
Aliphatic monocarboxylic acids such as pivalic acid and isobutylic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid And the like. In the present invention, these monocarboxylic acids may be used alone or in combination of two or more.

The monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group. Examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine, and the like.
Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine, alicyclic monoamines such as cyclohexylamine and dicyclohexylamine, and aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine Can be mentioned. In the present invention, these monoamines may be used alone or in combination of two or more.

The molecular weight of the polyamide of the present invention is preferably 10,000 to 1,000,000 in terms of weight average molecular weight (Mw), and more preferably 20,000 to 500,000, because the moldability and physical properties are more excellent. And most preferably 30,000 to 200,000. The weight average molecular weight is determined by, for example, using hexafluoroisopropanol (HFIP) as a solvent,
Polymethyl methacrylate (PMM) as a molecular weight standard sample
It can be determined by gel permeation chromatography (GPC) using A).

The apatite type compound preferably used in the present invention is represented by the following general formula. (A) _10-z (HPO ₄ ) _z (PO ₄ ) _{6 -z} (X)
_2-z · nH ₂ O where 0 ≦ z <2, 0 ≦ n ≦ 16, (A) is a metal element, and X is an anion or an anion compound. From 0 ≦ z <1, 0 ≦ n ≦
4 is more preferable. Preferred metal element (A)
Are 1A, 2A, 3A, 4A, 5A of the periodic table of elements.
A, 6A, 7A, 8, 1B, 2B, 3B group element and tin, lead can be mentioned. These metal elements may be one kind or two or more kinds. In the present invention, from the viewpoints of economy, safety and physical properties of the obtained resin composition, it is particularly preferable that the resin composition is a group 2A element such as magnesium, calcium, strontium, barium, or a mixture of two or more thereof. .

Examples of the anion or anion compound represented by X in the above general formula include a hydroxyl ion (OH ⁻ ), a fluorine ion (F ⁻ ), and a chlorine ion (Cl ⁻ ). These anionic elements or anionic compounds may be one kind or two or more kinds. In the present invention, the hydrogen phosphate ion (HPO ₄ ^2- ) and the phosphate ion (P
O ₄ ^3- ) or part of X is carbonate ion (CO ₃
Carbonate-containing apatite substituted in ^2- ) may be used.

In the present invention, among the apatite type compounds, hydroxyapatite (X is a hydroxyl ion) in which the metal element (A) is calcium, fluorinated apatite (a part or all of X is a fluorine ion), Chlorinated apatite (X
Are partially or entirely chlorine ions), carbonate-containing hydroxyapatite, carbonate-containing fluorinated apatite, carbonate-containing chlorinated apatite, and mixtures thereof are most preferably used. Such apatite type compound forming component (raw material)
Examples thereof include a phosphate metal compound and a mixture of a phosphate metal compound and a non-phosphate metal compound. In the present invention, a phosphate metal compound and a non-phosphate metal compound More preferably, it is a mixture consisting of In the present invention, the molar ratio of the metal element to phosphorus in the apatite-type compound-forming component may be 0.9 to 10.0, more preferably 1.2 to 5.0, and still more preferably 1.5 to 2.0. 0.

As the phosphoric acids of the above-mentioned phosphoric acid metal compounds,
Is orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, meta
Phosphoric acid, phosphorous acid, hypophosphorous acid, etc.
You. More specifically, as the phosphate metal compound,
Calcium hydrogen phosphate (CaHPO)₄・ MH₂O, but
0 ≦ m ≦ 2. ), Calcium dihydrogen diphosphate (C
aH₂P₂O₇), Calcium dihydrogen phosphate monohydrate
(Ca (H₂PO₄) ₂・ H₂O), calcium phosphate diphosphate
(Α- and β-Ca₂P₂O₇), Tricalcium phosphate
(Α- and β-Ca₃(PO₄)₂),

Tetracalcium phosphate (Ca ₄ (PO ₄ ) ₂
O), octacalcium phosphate pentahydrate (Ca ₈ H ₂ (PO
_{4) 6 · 5H 2 O)} , calcium phosphite monohydrate (C
aHPO ₃ .H ₂ O), calcium hypophosphite (Ca
_{(H 2 PO 2) 2)} , magnesium phosphate second trihydrate _{(MgHPO 4 · 3H 2 O)} , magnesium phosphate third octahydrate _{(Mg 3 (PO 4) 2} · 8H 2 O ), Barium phosphate second (BaHPO ₄ ) and the like.

Among these, in the present invention, a compound of phosphoric acid and calcium is preferably used from the viewpoint of excellent economical properties and physical properties. Among them, calcium monohydrogen phosphate (CaHPO ₄ .mH ₂ O, where 0 ≦ m ≦ 2 Is.)
There is more preferably used, calcium hydrogen phosphate dihydrate (CaHPO ₄ · _2H 2 O) is most preferably used in particular as calcium hydrogen phosphate anhydrous (CaHPO _4). These phosphorus-based metal compounds may be used alone or in combination of two or more.

When two or more kinds are combined, for example,
Calcium hydrogen phosphate dihydrate (CaHPO ₄ · 2H
₂ O) and calcium dihydrogen diphosphate (CaH ₂ P)
_{2 O 7)} and to use the, or combination of compounds containing metallic elements of the same kind, magnesium phosphate and calcium hydrogen phosphate dihydrate (CaHPO 4 · 2H _{2 O)} Second trihydrate (MgHPO ₄ .3H ₂ O) is used, and a combination of compounds containing different metal elements is exemplified, but any of them may be used.

In the present invention, the phosphate metal compound is
Calcium hydrogen phosphate (CaHPO) ₄・ MH₂O, but
0 ≦ m ≦ 2. ), Phosphor
usand it Compounds, 1 (195
8) CaO by Van Wazer described in
-H₂OP₂O₅As the system phase diagram shows, the presence of water
Below, mixing the phosphate compound and the calcium compound
And a known method. More specifically,
For example, at a temperature of 20 to 100 ° C., potassium dihydrogen phosphate
Alkali solution and calcium chloride solution
The method of dropping and reacting the solution for synthesis, calcium carbonate or
Or a method of mixing calcium hydroxide and phosphoric acid aqueous solution.
Which is good.

By the way, the present inventors have obtained the same effect as the present invention by using a compound composed of arsenic (As) or vanadium (V), that is, arsenic acid or vanadium acid instead of the phosphoric acid. I guess it can be done. However, in the present invention, phosphoric acids are most preferably used because they are excellent in stability of raw material components, availability of forming components, and safety.

The non-phosphate metal compound in the present invention is not particularly limited as long as it forms a compound with a metal element other than the phosphoric acids, and metal hydroxides (calcium hydroxide, magnesium hydroxide, water Strontium oxide, barium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, aluminum hydroxide, iron hydroxide,
Manganese hydroxide, etc.), metal chlorides (calcium chloride,
Magnesium chloride,

Strontium chloride, barium chloride, lithium chloride, sodium chloride, potassium chloride, aluminum chloride, iron chloride, manganese chloride, etc., metal fluorides (calcium fluoride, magnesium fluoride, barium fluoride, strontium fluoride, fluorine) Lithium iodide, sodium fluoride, potassium fluoride, aluminum fluoride, etc., metal bromide (such as calcium bromide), metal iodide (such as calcium iodide, potassium iodide, copper iodide), and metal carbide (such as calcium carbide) ), Metal oxides (calcium oxide, magnesium oxide, aluminum oxide, etc.),

Metal carbonates (calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, aluminum carbonate, etc.), metal sulfates (calcium sulfate, etc.), metal nitrate salts (calcium nitrate, etc.) , Inorganic metal compounds such as metal silicates (calcium silicate, sodium hexafluorosilicate, etc.) and compounds of metal elements and monocarboxylic acids (calcium acetate, copper acetate, calcium benzoate,
Examples thereof include a compound of a metal element and a dicarboxylic acid (such as calcium oxalate and calcium tartrate), and a compound of a metal element and a tricarboxylic acid (such as calcium citrate).

In the present invention, these non-phosphate metal compounds may be used alone or in combination of two or more. When two or more kinds are combined, a compound containing the same kind of metal element may be combined, such as a mixture of calcium hydroxide and calcium carbonate, or a mixture of calcium carbonate and magnesium hydroxide, for example. May be combined with a compound containing a different metal element.

According to the present invention, among these compounds, metal hydroxides, metal fluorides, metal chlorides, metal carbonates, metal oxides, or mixtures thereof are preferred because of their better economic efficiency and physical properties. It is preferably used. In particular, hydroxides, fluorides, chlorides, carbonates of calcium, magnesium, strontium, and barium, which are Group 2A elements of the periodic table, and mixtures thereof are more preferable. , Chlorides, carbonates, oxides, or mixtures thereof, among which calcium hydroxide, calcium carbonate, and calcium fluoride are most preferably used.

The method for producing the non-phosphate metal compound is not particularly limited. For example, in the case of calcium carbonate, even if it is a pulverized natural material, it may be a chemically synthesized product. It doesn't matter. The crystal form and shape are not particularly limited. For example, in the case of calcium carbonate, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, aragonite calcium carbonate, vaterite calcium carbonate, needle Any of calcium carbonate or a mixture thereof may be used.

The phosphate metal compound and the non-phosphate metal compound which are the apatite type compound-forming components of the present invention have a preferable average particle diameter of 0.001 to 10 μm, more preferably 0.001 to 5 μm or less, and still more preferably. Is 0.00
1 to 1 μm. The measurement of the average particle diameter may be performed by dispersing the apatite-type compound-forming component in pure water or alcohols, performing ultrasonic treatment, and then measuring with a laser diffraction / scattering particle size distribution apparatus.

The method for producing the polyamide composite of the present invention comprises:
It is preferable to use a method in which an apatite-type compound-forming component (raw material) is blended with a polyamide-forming component (raw material), and then polymerization of polyamide and synthesis of an apatite-type compound are performed. A more preferred method of polymerizing the polyamide and synthesizing the apatite-type compound is to heat the blend of the polyamide-forming component and the apatite-type compound-forming component, polymerize the polyamide-forming component in the presence of the apatite-type compound-forming component, and then apatite-type This is a method of synthesizing a compound, or a method of reacting an apatite-type compound-forming component in the presence of a polyamide-forming component and then polymerizing the polyamide.

A more preferred method is to advance the polymerization reaction of the polyamide and the synthesis reaction of the apatite type compound at a temperature of 40 to 300 ° C. with the mixture of the two forming components. This is a method in which a polyamide polymerization reaction and an apatite-type compound synthesis reaction are allowed to proceed simultaneously and in parallel at a temperature of 40 to 300 ° C. under a mixture of forming components under pressure.

Examples of the method of blending the polyamide-forming component and the apatite-type compound-forming component include a method of directly mixing the solid polyamide-forming component and the apatite-type compound-forming component, an aqueous solution of the polyamide-forming component and an apatite-type compound-forming component. And a method of blending with an aqueous solution or a suspension. Further, in order to improve the dispersibility of the apatite type compound, a compound such as a dispersant or a complexing agent may be added to the polyamide-forming component or the apatite-type compound forming component, if necessary. Further, the suspension of the apatite-type compound-forming component or the mixed solution of the apatite-type compound-forming component and the polyamide-forming component may be subjected to an ultrasonic treatment or a homogenizer.

In the present invention, the kind of the dispersant is not particularly limited, and a known dispersant can be used. For example, "Elucidation of dispersion and aggregation and applied technology, 1992
Anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and nonions, as described on pages 232 to 237 of "Year" (edited by Fumio Kitahara and published by Techno System Co., Ltd.) A system surfactant or the like can be used. Among them, it is preferable to use anionic surfactants and nonionic surfactants. Particularly, from the viewpoint of price and physical properties, sodium citrate, sodium polyacrylate, ammonium polyacrylate, and styrene-maleic anhydride are preferred. More preferably, polymers, olefin-maleic anhydride copolymers such as ethylene-maleic anhydride, and sucrose esters such as sucrose stearic acid ester are used.

The complexing agent is not particularly limited as long as it is a compound which forms a complex with a metal ion. Examples thereof include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, and glycol etherdiaminetetraacetic acid. Acetic acid, diethylenetriaminepentaacetic acid, citric acid, gluconic acid, tartaric acid, malic acid, succinic acid, aliphatic amines such as ethylenediamine, and urea can be used. Among them, citric acid, ethylenediaminetetraacetic acid (EDTA),
Ethylenediamine (en) is particularly preferred.

For the polymerization of the polyamide, a known method can be used. For example, a component hardly soluble in water such as 11-aminoundecanoic acid is used as a forming component,
A method of performing polycondensation by heating at ε, using ε-caprolactam as a forming component, adding an aqueous solution thereof to an end capping agent such as a monocarboxylic acid, or a reaction accelerator such as ε-aminocaproic acid as necessary, While distributing, 40
A ring-opening polycondensation method for lactams that is polycondensed by heating to ~ 300 ° C. Diamine / dicarboxylic acid such as hexamethylene adipamide is used as a forming component, and the aqueous solution is heated and concentrated at a temperature of 40 to 300 ° C to generate The steam pressure to be applied is from normal pressure to about 1.
A hot-melt polycondensation method in which polycondensation is performed by maintaining the pressure at 96 MPa (gauge pressure) and finally releasing the pressure to normal pressure or reduced pressure to perform polycondensation can be used. Furthermore, diamine
A solid phase polymerization method performed at a temperature equal to or lower than the melting point of the dicarboxylic acid solid salt or polycondensate, a solution method in which a dicarboxylic acid halide component and a diamine component are polycondensed in a solution, and the like can also be used.

These methods may be combined as needed. Further, the polymerization form may be a batch type or a continuous type. The polymerization apparatus is not particularly limited, and a known apparatus, for example, an extruder-type reactor such as an autoclave-type reactor, a tumbler-type reactor, or a kneader can be used. The method for producing the polyamide resin composite may be any method as long as the polyamide composite and the other resin are mixed together, and a polyamide composite powder or the pellet and the other resin powder or the pellet are mixed with a Henschel mixer or the like. A method of blending with a tumbler or the like, a polyamide composite powder or the pellet and another resin powder or the pellet, a Banbury mixer, a mixing roll,
A method of melt-kneading using a single-screw or twin-screw extruder or the like may be used.

The apatite type compound of the present invention can be confirmed directly by wide angle X-ray diffraction, infrared absorption spectrum or the like using a polyamide composite, a polyamide resin composite, or a polyamide resin composition or a molded product thereof. Elutes polyamide or other resin with a solvent in which polyamide or other compounded resin is soluble, separates apatite type compound component, wide-angle X-ray diffraction of separated apatite type compound, red A method of confirming with external absorption spectrum or the like may be used.

The solvent in which the polyamide or other resin is soluble is not particularly limited, and a known solvent can be used. For example, "POLYMERHANDBO
OK Third Edition "(J. Brandru
PandE. H. Supervision of Immergut / AWiley
-IntersciencePublication)
No. VII (SolventsNon-solv
entsForPolymers), but in the present invention, it is preferable to use a phenol solvent as a solvent for dissolving the polyamide.

When the polyamide resin is a mixture of a polyamide and a polyphenylene resin, for example, a chloroform solvent may be used as a soluble solvent for the polyphenylene resin, and a phenol solvent may be used as a soluble solvent for the polyamide. Specifically, the dissolving operation may be a multi-stage dissolving operation in which the polyphenylene-based resin is first dissolved using a sufficient amount of a chloroform solvent, and then the polyamide is dissolved using a sufficient amount of a phenol solvent.

The apatite type compound of the present invention may be a crystalline apatite type compound or an amorphous apatite type compound. However, from the viewpoint of physical properties, it is more preferable that the apatite type compound is a crystalline apatite type compound. preferable. Confirmation that the apatite type compound is crystalline, specifically,
Copper Kα (wavelength λ = 0.542n) is used as an X-ray source.
m) was used to measure wide-angle X-ray diffraction, and the diffraction angle (2θ) was measured.
It is sufficient to confirm that a (002) plane peak exists at 25.5 to 26.5 degrees and a (300) plane peak exists at a diffraction angle (2θ) of 32.5 to 33.5 degrees.
In the present invention, the crystalline apatite type compound confirmed as described above is particularly preferable.

The content of the apatite type compound of the present invention is
It is preferably 0.5 to 300 parts by weight, more preferably 1 to 200 parts by weight, further preferably 3 to 100 parts by weight, particularly preferably 5 to 75 parts by weight, based on 100 parts by weight of polyamide.
Parts by weight. The content of the apatite type compound can be determined, for example, by measuring the loss on ignition (Ig.loss) using a polyamide composite according to JISR3420 and from the weight loss.

Further, the ignition loss and solvent extraction, NMR,
Alternatively, the content of the apatite compound can be determined from the polyamide resin composite or the polyamide resin composition of the present invention or a molded product thereof by combining the infrared absorption spectrum and the like as necessary. The content of the apatite compound is 100 parts by weight of the polyimide,
If the amount is less than 0.5 part by weight, the effect of improving the mechanical properties of the obtained molded article is not so significant as to achieve the object of the present invention, while if it exceeds 300 parts by weight, the toughness decreases. Problems such as fear of occurrence and difficulty in molding are likely to occur.

The molar ratio of the metal element to phosphorus in the apatite type compound of the present invention is preferably 0.9 to 10.0, more preferably 1.2 to 5.0, particularly preferably, 1.3 to 2.5. This ratio is 0.9
If it is less than 3, air bubbles are likely to be mixed or foamed during extrusion or molding, and the yield of the obtained molded article may be reduced. If this ratio exceeds 10.0, the toughness may be significantly reduced.

The organic substance contained in the apatite type compound of the present invention is 0.1 to 100 parts by weight of the apatite type compound.
It needs to be 5 to 100 parts by weight. It is more preferably 1 to 100 parts by weight, furthermore 3 to 75 parts by weight, particularly preferably 4 to 50 parts by weight. Since the organic substance is an organic substance that is taken into the inside or the surface of the apatite type compound by a physical or chemical interaction such as an ion bonding reaction, an adsorption reaction, or a grafting reaction, for example, a phenol solvent in which a polyamide is soluble is used. It has the property that it does not dissolve or elute in a solvent even when it is used for a dissolution operation, and this greatly improves the adhesion and adhesion between the apatite type compound and the matrix polyamide. When the amount of the organic substance is less than 0.5 part by weight per 100 parts by weight of the apatite type compound, there is a possibility that the toughness of the obtained molded article is greatly reduced. If the amount exceeds 100 parts by weight, moldability tends to decrease.

According to the study of the present inventors, the organic substance in the present invention is obtained from the pyrolysis gas chromatography of the separated apatite type compound, the mass spectrum (MS) of the pyrolysis component, and the measurement results of infrared absorption spectrum. , A polyamide-forming component, a polyamide, or a reaction product thereof. Therefore, it is preferable that at least a part of the organic substance is a polyamide from the viewpoint that the organic substance of the present invention particularly improves adhesion and adhesion to the matrix polyamide. Further, the organic substance may contain water.

The content of the organic substance of the present invention can be determined, specifically, by (i) separation operation of apatite type compound, (ii) measurement of heat loss rate, (iii) determination of organic substance by measurement of thermal decomposition component, Can be obtained. The details will be described below. (I) Separation operation of apatite type compound: 10 g of a polyamide composite, a polyamide resin composite, a polyamide resin composition or a molded product thereof is weighed, mixed with 200 ml of 90% by weight phenol, stirred at 40 ° C. for 2 hours, and centrifuged. The separation operation is performed using a separator, and the supernatant solvent is removed. Further, 200 ml of phenol was added, and the same dissolving operation and separation operation using a centrifuge were repeated four times.

Subsequently, 99.5% by weight of ethanol 20
After adding 0 ml, the mixture is stirred at 23 ° C. for 2 hours, and a separating operation is performed using a centrifugal separator to remove a supernatant solvent. After repeating this operation four more times, it was dried in a vacuum drier,
An apatite type compound is obtained. When the polyamide resin is a mixture of polyamide and another resin, before or after the above polyamide dissolving operation, the dissolving / separating operation of the mixed resin other than the polyamide using a solvent in which the other resin is soluble. Should be done.

(Ii) Measurement of heat loss (X (parts by weight / apatite type compound 100 parts by weight)): 5 to 15 mg of the obtained apatite type compound was weighed, and subjected to thermogravimetric analysis (TG).
A) Depending on the device, 99.9 ° C / 30 ° C to 550 ° C
After the temperature is raised at 550 ° C., the temperature is maintained at 550 ° C. for 1 hour. Using the initial weight (W ₀ ) at 30 ° C. and the final weight (W ₁ ) after holding at 550 ° C. for 1 hour, the heat loss rate X can be calculated by the following equation. Heat loss rate X (parts by weight / 100 parts by weight of apatite type compound) = (W ₀ −W ₁ ) × 100 / W ₁

(Iii) Quantification of organic substances by measuring pyrolysis components: 1 to 10 mg of the apatite type compound obtained in the above (i) was weighed, and pyrolysis gas chromatography was performed to determine a pyrolysis temperature of 550 ° C. and a column temperature of 50. ~ 320
It measures under the conditions of ° C (heating rate 20 ° C / min). The pyrogram obtained by pyrolysis gas chromatography is divided into a retention time of less than 2 min and a retention time of 2 min or more, and the peak area is calculated. Since the components of 2 min or less are low molecular weight components such as carbon dioxide, these low molecular weight components were subtracted from the whole to obtain the amount of organic substances. Specifically, the respective areas Sa (less than 2 min) and Sb (more than 2 min) are calculated, and the amount of organic matter is calculated by the following equation using the heat loss rate X of (ii). Amount of organic substance (parts by weight / 100 parts by weight of apatite type compound) = X · Sb / (Sa + Sb)

The average particle diameter of the apatite type compound of the present invention is preferably 0.001 to 1 μm, more preferably 0.001 to 0.5 μm. The average particle diameter in the present invention can be determined by an electron micrograph, and the average particle diameter can be calculated as follows. That is, a transmission electron microscope (TEM: 50,000 times or 100,000 times magnification) of a polyamide composite, a polyamide resin composite, or a polyamide resin composition or an ultrathin section cut out from a molded article obtained was photographed, and apatite was taken. particle size d _i of the mold _compound, obtains the number of particles n _i, to calculate the average particle diameter by the following equation. Average particle diameter = Σd _i · n _i / Σn _{i In} this case, if the particle diameter cannot be regarded as spherical, the minor axis and the major axis are measured, and の of the sum of both is defined as the particle diameter.
In calculating the average particle diameter, at least 2,000 particle diameters are measured.

The stabilizer of the present invention comprises (a) a phenol stabilizer, (b) a phosphite stabilizer, (c) a hindered amine stabilizer, (d) a triazine stabilizer, and (e) a sulfur stabilizer. Are preferably used, and these stabilizers will be described in detail below. The phenol-based stabilizer (a) of the present invention is not particularly limited, but a hindered phenol compound is preferably used. For example,
Pentaerythrityl-tetrakis 3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate {, N, N-hexamethylenebis (3,5-di-t-
Butyl-4-hydroxy-hydrocinnamamide,

Triethylene glycol-bis {3- (3
-T-butyl-5-methyl-4-hydroxyphenyl)
Propionate}, 3,9-bis {2- [3- (3-t
-Butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4.
8,10-tetraoxapyro [5,5] undecane,
3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4- (Hydroxybenzyl) benzene, 1,3,5-tris (4-t-butyl-3hydroxy-2,6-dimethylbenzyl) isocyanate, and the like, and mixtures thereof.

The phosphite-based stabilizer (b) of the present invention comprises:
Although there is no particular limitation, for example, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, tris isodecyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl Phosphite, diphenylisodecyl phosphite, diphenyltridecyl phosphite, triphenyl phosphite,

Tris (nonylphenyl) phosphite,
Tris (2,4-di-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, tetratridecyl-4, 4′-butylidenebis (3-methyl-6-t-butylphenol) -diphosphite, 4,4′-isopropylidene-diphenolalkyl phosphite (where alkyl is a carbon atom having 12 to 1 carbon atoms)
About 5),

4,4'-isopropylidenebis (2-t
-Butylphenol) .di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) 1,1,3-tris (2-methyl-5-t-
Butyl-4-hydroxyphenyl) butanediphosphite, tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, tetra (C1-C15 mixed alkyl) -4,4 '
-Isopropylidene diphenyl diphosphite, tris (mono, di-mixed nonylphenyl) phosphite,

4'-isopropylidenebis (2-t-
Butylphenol) di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-
10-phosphaphenanthrene-10-oxide, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4′-isopropylidenedifenyl polyphosphite, Bis (octylphenyl) bis (4,4'butylidenebis (3-methyl-
6-t-butylphenol)) 1,6-hexaneol diphosphite,

Hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) diphosphite, tris (4,4'-isopropylidenebis (2-t-butylphenol)) phospho Phytite, tris (1,3-stearoyloxyisopropyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite,

2,2-methylenebis (3-methyl-4,
6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-
Methylphenyl) -4,4'-biphenylenediphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphite, and the like, and mixtures thereof can be mentioned.

Further, pentaerythritol type phosphite compounds are preferred as phosphite compounds. Specific examples of the pentaeristol type phosphite compound include 2,6-di-t-butyl-4-methylphenyl phenyl pentaerythritol diphosphite and 2,6-di-t-butyl-4-. Methylphenyl
Methyl pentaerythritol diphosphite, 2,6
-Di-t-butyl-4-methylphenyl-2-ethylhexyl pentaerythritol diphosphite, 2,6
-Di-t-butyl-4-methylphenyl isodecyl.
Pentaerythritol diphosphite,

2,6-di-t-butyl-4-methylphenyl lauryl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl isotridecyl pentaerythritol diphosphite,
2,6-di-t-butyl-4-methylphenyl stearyl pentaerythritol diphosphite, 2,6-
Di-t-butyl-4-methylphenyl cyclohexyl pentaerythritol diphosphite, 2,6-di-
t-butyl-4-methylphenyl benzyl pentaerythritol diphosphite,

2,6-di-t-butyl-4-methylphenyl-ethyl cellosolve pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-butyl carbitol pentaerythritol diphosphite Phyto, 2,6-di-t-butyl-4-methylphenyl octylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl nonylphenyl pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,

Bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite,
2,6-di-t-butyl-4-methylphenyl 2,6
-Di-t-butylphenylpentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylphenylpentaerythritol diphosphite, 2,6- Di-t-butyl-4
-Methylphenyl 2,4-di-t-octylphenyl pentaerythritol diphosphite,

2,6-di-t-butyl-4-methylphenyl-2-cyclohexylphenyl pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl phenyl pentaerythritol Diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl)
Pentaerythritol diphosphite and the like.

Among them, bis (2,6-di-t-butyl-
4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) ) Pentaerythritol diphosphite, bis (2,6-di-)
t-octyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is particularly preferred.

The hindered amine stabilizer (c) of the present invention is, for example, 4-acetoxy-2,2,6,6
-Tetramethylpiperidine, 4-stearoyloxy-
2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4- Benzoyloxy-2,
2,6,6-tetramethylpiperidine, 4-methoxy-
2,2,6,6-tetramethylpiperidine,

4-stearyloxy-2,2,6,6-
Tetramethylpiperidine, 4-cyclohexyloxy-
2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine,
4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2
6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine,

4- (phenylcarbamoyloxy)-
2,2,6,6-tetramethylpiperidine, bis (2
2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -oxalate, bis (2,2,6,6-tetramethyl-4) -Piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl)-
Sebacate, bis (2,2,6,6-tetramethyl-4
-Piperidyl) -adipate, bis (2,2,6,6-
Tetramethyl-4-piperidyl) -terephthalate,
1,2-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -ethane, α, α′-bis (2,2,
6,6-tetramethyl-4-piperidyloxy) -p-
Xylene, bis (2,2,6,6-tetramethyl-4-
Piperidyl tolylene-2,4-dicarbamate,

Bis (2,2,6,6-tetramethyl-4
-Piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2, 6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionyloxydibutyl]
-4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid 1,2,2,6,6-pentamethyl-4-
Piperidinol and β, β, β ', β'-tetramethyl-
Condensates with 3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol,
Alternatively, a mixture thereof can be mentioned.

The (d) triazine-based stabilizer of the present invention is preferably a hydroxyphenyltriazine, such as 2,4,6-tris (2-hydroxy-4).
-Octyloxy-phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy-phenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy -4-octyloxy-phenyl) -4,6-bis (2,4-dimethylphenyl)-
1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,

2,4-bis (2-hydroxy-4-propyloxy-phenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyl) Oxy-phenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine,
-(2-hydroxy-4-dodecyloxy-phenyl)
-4,6-bis (2,4-dimethylphenyl) -1,
3,5-triazine, 2,4,6-tris (2′-hydroxy-4′-isopropyloxyphenyl) -1,
3,5-triazine, 2,4,6-tris (2′-hydroxy-4′-n-hexyloxyphenyl) -1,
3,5-triazine and 2,4,6-tris (2 ′
-Hydroxy-4'-ethoxycarbonylmethoxyphenyl) -1,3,5-triazine and the like, and mixtures thereof.

The (e) sulfur-based stabilizer of the present invention includes:
Examples thereof include pentaerythrityltetrakis (3-
Lauryl thiopropionate), dilauryl 3,3'-
Examples thereof include thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, and the like, and mixtures thereof.

The stabilizer of the present invention comprises (a) a phenol stabilizer, (b) a phosphite stabilizer, (c) a hindered amine stabilizer, (d) a triazine stabilizer,
(E) selected from compounds comprising a sulfur-based stabilizer,
Any compound may be used as long as it is at least one kind of compound.
The amount is 0.01 to 20 parts by weight, preferably 0.02 to 15 parts by weight, more preferably 0.025 to 10 parts by weight, most preferably 0.3 to 5 parts by weight with respect to 0 parts by weight. When the amount of the stabilizer is less than 0.01 part by weight, the stability such as heat discoloration resistance and weather resistance is not improved until the object of the present invention is achieved, and is not preferable. It is not preferable to exceed the value, because silver tends to be generated on the surface of the molded article or the mechanical properties of the molded article tend to be reduced.

The method for producing the polyamide resin composition of the present invention is not particularly limited. For example, a method of blending a stabilizer with a polyamide composite material (polyamide-forming component and / or apatite-type forming component), polyamide A method of compounding a stabilizer during the preparation of the composite (either during the polymerization of the polyamide or the synthesis of the apatite type compound), or during the preparation of the polyamide resin composite (when mixing the polyamide composite with another resin). A method of blending a stabilizer, a method of attaching a stabilizer to the surface of a polyamide composite or a polyamide resin composite (powder or pellet), a method of blending a stabilizer with a polyamide composite or a polyamide resin composite by melt-kneading, Method of compounding masterbatch of stabilizer into polyamide composite or polyamide resin composite Or a method of blending a combination of these methods, may be used any method.

The polyamide resin composition of the present invention is a polyamide resin in which an apatite type compound is uniformly and finely dispersed in a polyamide or a polyamide resin as a matrix, and the interface between the polyamide and the apatite type compound is extremely well fixed and adhered. It is a blend of a stabilizer and a composite, and the resulting molded article is superior in rigidity, strength, toughness, surface appearance, weld properties, reworkability, and excessive heat and light compared to conventional polyamide resin compositions. It is characterized in that it is excellent in heat discoloration resistance and weather resistance with little discoloration and deterioration under the above environment. Therefore, application to various parts such as automobile parts, electronic / electric parts, and industrial machine parts is expected.

Various components include, for example, bumpers, spoilers, side covers, hood louvers, wheel covers, wheel caps, grill apron cover frames, roof rails, roof legs, door mirror stays,
Door mirror cover, door mirror bracket, rain channel, wiper blade, sunroof deflector,
Automotive exterior and skin parts such as outdoor handles, fenders, tail lamps, cylinder head covers, radiator tanks, timing belt covers,

Connectors, cable ties, motor fans, gear cams, hot air blower housings, tubes, hoses, power steering oil tanks, reservoir tanks, brake oil tanks, fuel strainers,
For air cleaners, paper casters, cooling fans, fan shrouds, oil pans, engine mounts, air suspension tanks, gasoline tanks, alcohol tanks, freon tanks, fuel tubes, fuel strainers, brake oil tanks, clutch oil tanks, power steering tanks, coolers Automotive underhood parts such as freon tubes, air cleaners, in-tech manifolds, surge tanks,

Moldings, wheel rims, wheels obtained from register blades, washer levers, window regulator handles, window regulator handle knobs, passing light levers, sun visor brackets, sun visor arms, seat lock parts, accelerator pedals, etc. Parts for bicycles such as bicycles such as spokes, saddles, saddle posts, handles, stands, luggage, parts for furniture such as desk legs, chair legs, seats, cabins, wagons, and OA for personal computer housings.
Equipment field equipment,

Switches, micro slide switch, D
IP switches, switch housings, lamp sockets, cable ties, connectors, connector housings, connector shells, IC sockets, coil bobbins, bobbin covers, relays, relay boxes, condenser cases, motor internal parts, small motor cases, dancing Electronic and electrical components such as pulleys,

Brush bristles for toothbrushes, magic fasteners, tire cords, belts, artificial grass,
Carpets, car seats, fishing nets, ropes, ropes, filter threads, hose reinforcing threads, valve housings,
Underfloor parts such as nails, screws, bolts, bolt nuts, spacers, insulators, fasteners, buckles, wire grips, adjusters, etc. Examples include industrial machine parts such as boxes, bottles for agricultural chemicals, and various bottles for drinking water and the like, and it can be expected to be useful for various other uses.

The polyamide resin composition of the present invention can be produced by a known molding method such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, melt spinning, and the like. Even when a generally known plastic molding method is used, good molding can be performed.

The polyamide resin composition of the present invention may contain, if necessary, a filler used in ordinary polyamide resins, for example, an inorganic filler such as glass fiber, glass flake, or carbon fiber within a range not to impair the object of the present invention. And antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc hydroxystannate, ammonium polyphosphate, melamine cyanurate, succinoguanamine, melamine polyphosphate, melamine sulfate, melamine phthalate, Flame retardants such as aromatic polyphosphate and composite glass powder, and pigments and colorants such as titanium white, carbon black, and metallic pigments can be contained.

Also, a moldability improving agent, for example, a phosphate compound such as triphenyl phosphate, a phosphite compound such as triphenyl phosphite, stearic acid,
Higher fatty acid compounds such as behenic acid and montanic acid; higher fatty acid metal salt compounds such as calcium stearate and calcium montanate; higher fatty acid ester compounds such as stearyl stearate; higher fatty acid amide compounds; An inorganic crystal nucleating agent such as high molecular weight polyethylene or oxidized low molecular weight polyethylene, substituted benzylidene sorbitol, caprolactone, or talc can be contained. Further, various additives such as an antistatic agent can be contained.

[0100]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by way of examples.
The present invention is not limited to the following embodiments. In addition, the physical property evaluation described in the following Examples and Comparative Examples was performed as follows. 1. Characteristics of polyamide-forming component and apatite-type compound-forming component (1-1) Content of apatite-type compound-forming component (% by weight) Calculated from the blending amount of polyamide-forming component and apatite-type compound-forming component. (1-2) Molar Ratio of Metal Element to Phosphorus in Apatite-Type Compound-Forming Component The metal element and phosphorus in the apatite-type compound-forming component were quantified and the molar ratio was calculated.

(A) Quantification of Metal Element: The case where calcium is used as the metal element will be described below, but other metal elements can be similarly determined. 0.5 g of the apatite-type compound forming component was weighed on a platinum dish,
Carbonize in an electric furnace. After cooling, 5 ml of hydrochloric acid and 5 m of pure water
Add 1 and dissolve by boiling on a heater. After cooling again, pure water was added to make up to 500 ml. The device is ThermoJarr
A high frequency inductively coupled plasma (ICP) emission spectrometry was performed using IRIS / IP manufactured by ellAsh to obtain a wavelength of 317.9.
It was quantified at 33 nm.

(B) Determination of phosphorus: 0.5 g of an apatite type compound-forming component was weighed, 20 ml of concentrated sulfuric acid was added, and the mixture was wet-decomposed on a heater. After cooling, 5 ml of hydrogen peroxide was added, and the mixture was heated on a heater and concentrated until the total amount became 2 to 3 ml. It was cooled again and made up to 500 ml with pure water. The device is IRIS / IP manufactured by Thermo Jarrel Ash
Was quantified by high frequency inductively coupled plasma (ICP) emission spectroscopy at a wavelength of 213.618 (nm).

2. Characteristics of Polyamide Resin Composition (2-1) Weight Average Molecular Weight (Mw) of Polyamide A polyamide composite was determined by gel permeation chromatography (GPC). The instrument was HLC-8020 manufactured by Tosoh Corporation, and the detector was a differential refractometer (R).
I), the solvent is hexafluoroisopropanol (HFI
P), the column is TSKgel-GMHH manufactured by Tosoh Corporation
Two RHs and one G1000HHR were used. The solvent flow rate was 0.6 ml / min, and the sample concentration was 1-3 (m
g sample) / 1 (ml solvent), and the mixture was filtered with a filter to remove insolubles and used as a measurement sample. Based on the obtained elution curve, the weight average molecular weight (Mw) was calculated in terms of polymethyl methacrylate (PMMA).

(2-2) Determination of the content of the apatite type compound (weight / 100 parts by weight polyamide) The polyamide composite is dried at 100 ± 20 ° C. for 8 hours and cooled. 1 g of the complex was weighed on a platinum dish, and 650 ± 20 ° C.
Was incinerated in an electric furnace, and after cooling, the weight was weighed to determine the content of the apatite type compound. (2-3) Molar ratio of metal element to phosphorus of apatite type compound The metal element and phosphorus of the apatite type compound were quantified and the molar ratio was calculated.

(A) Quantification of Metal Element: The case where calcium is used as the metal element will be described below, but other metal elements can be similarly determined. 0.5 g of the polyamide composite is weighed on a platinum dish and carbonized in a 500 ° C. electric furnace. After cooling, 5 ml of hydrochloric acid and 5 ml of pure water are added and dissolved by boiling on a heater. Cool again, add pure water and add 50
The volume was 0 ml. The device is ThermoJarrelAs
Quantification was performed at a wavelength of 317.933 nm by high frequency inductively coupled plasma (ICP) emission analysis using IRIS / IP manufactured by h.

(B) Determination of phosphorus: polyamide complex
5 g was weighed, 20 ml of concentrated sulfuric acid was added, and the mixture was wet-decomposed on a heater. After cooling, 5 ml of hydrogen peroxide was added, and the mixture was heated on a heater and concentrated until the total amount became 2 to 3 ml. It was cooled again and made up to 500 ml with pure water. The device is Therm
Quantification was performed at a wavelength of 213.618 (nm) by high-frequency inductively coupled plasma (ICP) emission analysis using IRIS / IP manufactured by oJarrel Ash.

(2-4) Amount of organic substance (parts by weight / 100 parts by weight of apatite type compound) (a) Separation operation of apatite type compound: 10 g of a polyamide composite was weighed, mixed with 200 ml of 90% by weight phenol, and heated at 40 ° C. With a centrifugal separator [H103RLH manufactured by Domestic Centrifuge Co., Ltd.] for 20,000 rpm.
For 1 hour to remove the supernatant solvent. Further, 200 ml of phenol was added, and the same dissolving operation and separation operation using a centrifugal separator were repeated four times. Subsequently, 200 ml of 99.5% by weight of ethanol was added, the mixture was stirred at 23 ° C. for 2 hours, and centrifuged for 2 hours.
The separation operation is performed at 0000 rpm for 1 hour, and the supernatant solvent is removed. After repeating this operation four more times, the resultant was dried at 80 ° C. for 12 hours in a vacuum dryer to obtain a target apatite compound.

(B) Measurement of heat loss rate (X (parts by weight / apatite type compound)) of the separated apatite type compound: (2)
-4) 10 mg of the apatite compound obtained in (a)
Is weighed, and the weight loss rate X is measured by a thermogravimetric analysis (TGA) device.
I asked. The equipment is TGA-50 manufactured by Shimadzu Corporation. The temperature condition is 99.9 ° C / min from 30 ° C to 550 ° C.
And then kept at 550 ° C. for 1 hour. Using the initial weight (W ₀ ) at 30 ° C. and the final weight (W ₁ ) after holding at 550 ° C. for 1 hour, the amount of organic matter was calculated by the following equation. Heat loss rate X (parts by weight / 100 parts by weight of apatite type compound) = (W ₀ −W ₁ ) × 100 / W ₁

(C) Determination of organic substances: (a) of (2-4)
3 mg of the apatite type compound obtained in the above was weighed, and subjected to pyrolysis chromatography (GC) and pyrolysis GC under the following conditions.
/ MS pyrogram was obtained.・ Pyrolysis device: Frontier Double Shot Pyrolyzer P
Y-2010D Thermal decomposition temperature: 550 ° C ・ Gas chromatography (GC) Equipment: HP-589 manufactured by HEWLETTPACKARD
0 Column: DURABONDDB-1 manufactured by J & W (0.25 mm ID × 30 m, film thickness 0.25 μm) Column temperature: 50 ° C. → 320 ° C. (heating rate 20 ° C./mi)
n) Inlet temperature: 320 ° C Detector temperature: 320 ° C

Mass spectrometry (MS) Apparatus: AutoMSSystemII manufactured by JEOL Ionization: EI (70 V) Measurement mass range: m / z = 10 to 400 Temperature: 200 ° C. Pyrogram of the obtained pyrolyzed GC is stored at a retention time of 2 mi.
The peak area Sa (less than 2 min) and Sb (more than 2 min) are calculated for each of the peak areas Sa and n, and the heat loss rate X obtained in (b) of (2-4) is used.
The amount of organic matter was calculated by the following equation. Amount of organic substance (parts by weight / 100 parts by weight of apatite type compound) = X · Sb / (Sa + Sb) Further, a thermal decomposition component was identified from a mass spectrum (MS).

(2-5) Infrared absorption spectrum The infrared absorption spectrum of the apatite type compound obtained in (a) of (2-4) was measured. The device is PerkinElme
The measurement was performed at 1640, manufactured by r Company, at a resolution of 4 cm ^-1 . (2-6) Confirmation of generation of apatite type compound by X-ray diffraction X-ray diffraction of the apatite type compound obtained in (a) of (2-4) was measured. The measurement conditions are as follows.

X-ray: Copper Kα Wave number: 0.1542 nm Tube voltage: 40 KV Tube current: 200 mA Scanning speed: 4 deg. / Min divergence slit: 1 deg. Scattering slit: 1 deg. Light receiving slit: 0.15mm

3. Preparation and physical properties of molded products Molded products were prepared using an injection molding machine. The apparatus was set to PS40E manufactured by Nissei Plastic Co., Ltd., the cylinder temperature was set to 280 ° C., the mold temperature was set to 80 ° C., and a molded product was obtained under the injection molding conditions of 17 seconds of injection and 20 seconds of cooling. (3-1) Flexural modulus and flexural strength (Mpa) Performed according to ASTM D790. (3-2) Tensile strength (Mpa) and tensile elongation (%) Performed according to ASTM D638. (3-3) Notched Izod Impact Strength (J / m) This was performed according to ASTM D256.

(3-4) Deflection temperature under load (° C.) This was performed according to ASTM D648. Load is 1.82Mp
a. (3-5) Surface appearance Using HORIBA handy gloss meter IG320, JIS-
Gs60 ° C. was measured according to K7150. (3-6) Weld strength A molded product having a weld portion was prepared using the mold shown in FIG. 1, and the tensile strength was measured according to ASTM D-638.

(3-7) Hot Water Resistance After the test piece was immersed in water heated to 140 ° C. for 200 hours, the tensile strength was measured according to ASTM D-638 to evaluate the hot water resistance. (3-8) Reworkability The molded product (initial molded product) was pulverized by a pulverizer, and molding was performed using the obtained pulverized product. This operation was further repeated four times, and the tensile strength of the finally obtained molded product (rework molded product) was measured. (3-9) Discoloration due to rework The color tone of the molded product was measured using the initial molded product of (3-8) and the rework molded product. The device is a color difference meter ND manufactured by Nippon Denshoku
Using -300A, the color difference (Δb: change in b value) between the initial molded product and the rework molded product was determined. It can be determined that the smaller the color difference (Δb), the better the yellowing resistance.

(A) Phenolic stabilizer Stabilizer (A): 3,9-bis {2-3 [3- (t-butyl-4hydroxy-5-methylphenyl) propylniloxy] -1,1- Dimethylethyl｝ -2,4,8,10
-Tetraoxapyro [5,5] undecane (trade name: ADK STAB A-0
80)

(B) Phosphite stabilizer Stabilizer (B): bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name: ADK STAB PEP-36)

(C) Hindered amine stabilizer Stabilizer (C): bis- (2,2,6,6-tetramethyl-4-piperidyl) -sebacate (trade name: Sankyo Sanol 770)

(D) Triazine stabilizer Stabilizer (D): 2- (2-hydroxy-4-hexyloxy-phenyl) -4,6-diphenyl-1,3,5-
Triazine (Product name: TINUBIN 1577FF)

(E) Sulfur-based stabilizer Stabilizer (E): pentaerythrityltetrakis (3-laurylthiopropionate)

[0121]

Production Example 1 Production of Polyamide Composite (A): 30 kg of an aqueous solution of 50% by weight of a polyamide-forming component (equimolar salt of hexamethylenediamine and adipic acid) was prepared.
As an apatite type compound forming component, an average particle diameter of 1 μm
Calcium hydrogen phosphate dihydrate (CaHPO ₄ · 2H
₆ kg (calcium monohydrogen phosphate dihydrate: pure water = 1.5 kg: 4.5 kg) of a 25% by weight suspension of 2O) and heavy calcium carbonate (CaC) having an average particle size of 1.5 μm
2.32 kg (calcium carbonate: pure water = 0.58 kg: 1.74 kg) of a 25% by weight suspension of O ₃ ) was used.

The molar ratio of calcium to phosphorus is 1.67
It was calculated. An aqueous solution of the polyamide-forming component and a suspension of the apatite-type compound-forming component, having a stirring device,
The mixture was charged into a 70-liter autoclave having a discharge nozzle at the bottom, and stirred well at a temperature of 50 ° C.
After sufficiently replacing with nitrogen, the temperature was raised from 50 ° C. to about 270 ° C. while stirring. At this time, the pressure in the autoclave became a gauge pressure of about 1.77 Mpa, but heating was continued for about 1 hour while removing water from the system so that the pressure did not become 1.77 Mpa or more.

Thereafter, the pressure was reduced to atmospheric pressure over about one hour, and further maintained at about 270 ° C. and atmospheric pressure for about one hour. Then, stirring was stopped, and the polymer was discharged from the lower nozzle in a strand form. Water-cooling and cutting were performed to obtain pellets of the polyamide composite (A). As a result of evaluating the obtained polyamide composite (A), the weight average molecular weight (Mw) was 40000, and the content of the apatite type compound was 11.4 parts by weight based on 100 parts by weight of the polyamide. The molar ratio of calcium to phosphorus was calculated to be 1.67.
From the results of transmission electron microscopy observation at a magnification of 100,000, the average particle diameter of the apatite compound was 85 nm.

Elution and separation operations were carried out with a 90% aqueous phenol solution, and the obtained apatite type compound was evaluated. As a result, formation of a crystalline apatite type compound was confirmed by wide-angle X-ray diffraction. The amount of the organic substance of the apatite type compound obtained by the elution / separation operation was calculated to be 5.5 (parts by weight / 100 parts by weight of apatite). In addition, from the analysis result of the pyrolysis GC / mass spectrum, cyclopentanone was confirmed as one of the thermal decomposition components of the organic substance remaining in the apatite type compound. Further, from the observation of the infrared absorption spectrum, a peak indicating the presence of an organic substance was confirmed at about 1548 cm ^-1 .

[0125]

Production Example 2 Production of Polyamide Composite (B): 20 kg of an aqueous solution of 50% by weight of a polyamide-forming component (equimolar salt of hexamethylenediamine / adipic acid) was prepared. As apatite type compound-forming component, an average particle diameter of 1μm calcium hydrogen phosphate dihydrate (CaHPO ₄ · 2H
₁₂ kg of a 25% by weight suspension of 2O) (calcium monohydrogen phosphate dihydrate: pure water = 3 kg: 9 kg) and light calcium carbonate (CaCO ₃ ) having an average particle diameter of 100 nm
4.64 kg of a 25% by weight suspension of
Pure water = 1.16 Kg: 3.48 Kg) was used.

The aqueous solution of the polyamide-forming component and the suspension of the apatite-type compound-forming component were charged into a 70-liter autoclave having a stirrer and having a discharge nozzle at the bottom. Stirred. After the atmosphere was sufficiently replaced with nitrogen, the temperature was raised from 50 ° C. to about 270 ° C. At this time, the pressure in the autoclave is about 1.77 Mpa in gauge pressure, but the pressure is 1.77 Mpa.
Heating was continued for about 2 hours while removing water out of the system so as not to exceed pa. Then, after about 1 hour, the pressure was reduced to atmospheric pressure, and after maintaining at about 270 ° C. and atmospheric pressure for about 1 hour, stirring was stopped, and the polymer was discharged in a strand form from the lower nozzle, and water-cooled / cutting Was performed to obtain a polyamide composite (B).

[0127]

[Production Example 3] Production of polyamide composite (C): 50% by weight of polyamide-forming components (1.2 kg of hexamethylenediamine / adipic acid equimolar salt and hexmethylenediamine /
30 kg of an aqueous solution of isophthalic acid equimolar salt (mixture with 0.3 kg) was prepared. A pellet of the polyamide composite (C) was obtained in the same manner as in Example 1 except that the polyamide-forming component was used.

[0128]

[Production Example 4] Production of polyamide 66: In Example 1, polymerization was carried out using only the polyamide-forming component without mixing the apatite-forming component to obtain a polyamide 66 pellet.

[0129]

[Production Example 5] Production of polyamide composite (D): 100 g of montmorillonite having an average thickness of 95 nm and a side length of about 0.1 μm per unit of the layered silicate is dispersed in 10 liters of water, To this, 51.2 g of 12-aminododecanoic acid and 24 ml of concentrated hydrochloric acid were added, and after stirring for 5 minutes,
Filtered. After washing this well, vacuum drying
A complex of ammonium ion of 2-aminododecanoic acid and montmorillonite was prepared. Repeat this operation,
About 2 kg of a complex of ammonium ion of 12-aminododecanoic acid and montmorillonite was obtained. 1.5 kg of a complex of ammonium ion of 12-aminododecanoic acid and montmorillonite was added to 30 kg of an aqueous solution of 50% by weight of a polyamide-forming component (equimolar salt of hexamethylenediamine / adipic acid), and a stirring device was provided. Into a 70-liter autoclave having a discharge nozzle, and stirred well at a temperature of 50 ° C. The subsequent operation was performed in the same manner as in Example 1 to obtain pellets of the polyamide composite (D).

[0130]

Example 1 Polyamide 1 in polyamide composite (A)
With respect to 00 parts by weight (the weight obtained by subtracting the content of the apatite type compound from the polyamide composite was taken as 100 parts by weight), the polyamide composite ( A) and the stabilizer (B) were mixed, and the mixture was mixed with a twin-screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.) to obtain 28%.
The mixture was melt-kneaded at 0 ° C. to obtain a polyamide resin composition. Table 1 shows the evaluation results.

[0131]

Example 2 The same procedure was performed as in Example 1 except that the polyamide composite (B) was used instead of the polyamide composite (A). Table 1 shows the evaluation results.

[0132]

Example 3 The same procedure as in Example 1 was carried out except that the polyamide composite (C) was used instead of the polyamide composite (A). Table 1 shows the evaluation results.

[0133]

Comparative Example 1 The same operation as in Example 1 was carried out except that the polyamide of Production Example 4 was used instead of the polyamide composite (A). Table 1 shows the evaluation results.

[0134]

Comparative Example 2 The same operation as in Example 1 was carried out except that the polyamide composite (D) was used instead of the polyamide composite (A). Table 1 shows the evaluation results.

[0135]

Comparative Example 3 Only the polyamide composite (A) (without blending of a stabilizer) was evaluated. Table 1 shows the evaluation results.

[0136]

Example 4 The procedure was performed in the same manner as in Example 1 except that the stabilizer (A) was used instead of the stabilizer (B). Table 2 shows the evaluation results.

[0137]

Example 5 The same procedure as in Example 1 was carried out except that stabilizer (C) was used instead of stabilizer (B). Table 2 shows the evaluation results.

[0138]

Example 6 Example 6 was repeated except that stabilizer (D) was used instead of stabilizer (B). Table 2 shows the evaluation results.

[0139]

Example 7 The same operation as in Example 1 was carried out except that stabilizer (E) was used instead of stabilizer (B). Table 2 shows the evaluation results.

[0140]

Example 8 Polyamide 1 in Polyamide Composite (A)
The stabilizer (A) and the stabilizer (B) were each 0.5 parts by weight with respect to 00 parts by weight (the weight obtained by subtracting the content of the apatite type compound from the polyamide composite was 100 parts by weight). Thus, the polyamide composite (A),
The stabilizer (A) and the stabilizer (B) were mixed and melt-kneaded at 280 ° C. using a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain a polyamide resin composition. . Table 3 shows the evaluation results.

[0141]

Example 9 Polyamide 1 in Polyamide Composite (A)
The stabilizer (B) and the stabilizer (D) are each 0.5 parts by weight with respect to 00 parts by weight (the weight obtained by subtracting the content of the apatite type compound from the polyamide composite is 100 parts by weight). Thus, the polyamide composite (A),
The stabilizer (B) and the stabilizer (D) were mixed and melt-kneaded at 280 ° C. using a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain a polyamide resin composition. . Table 3 shows the evaluation results.

[0142]

Example 10 100 parts by weight of polyamide in polyamide composite (A) (the weight obtained by subtracting the content of the apatite type compound from the polyamide composite was taken as 100 parts by weight).
To the polyamide composite (A), the stabilizer (A), and the stabilizer (B) such that the stabilizer (A), the stabilizer (B), and the stabilizer (C) each become 0.5 parts by weight. ) And the stabilizer (C) were mixed and melt-kneaded at 280 ° C using a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain a polyamide resin composition. Table 3 shows the evaluation results.

[0143]

Example 11 100 parts by weight of polyamide in polyamide composite (A) (the weight obtained by subtracting the content of the apatite type compound from the polyamide composite was taken as 100 parts by weight).
To the polyamide composite (A), the stabilizer (A), and the stabilizer (B) such that each of the stabilizer (A), the stabilizer (B), and the stabilizer (D) is 0.5 parts by weight. ) And the stabilizer (D) were mixed and melt-kneaded at 280 ° C using a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain a polyamide resin composition. Table 3 shows the evaluation results.

[0144]

[Table 1]

[0145]

[Table 2]

[0146]

[Table 3]

[0147]

According to the present invention, a stabilizer is added to a polyamide composite containing an apatite type compound which is uniformly and finely dispersed in a polyamide as a matrix, and is very well fixed and adhered to the polyamide at the interface. It is a polyamide fat composition composition. Therefore, the obtained molded product is characterized by being superior in rigidity, strength, toughness, surface appearance, weld properties, reworkability, heat discoloration resistance, weather resistance, and the like, as compared with conventional products. It is expected to be very useful for various applications such as automobile interior parts, automobile underhood parts, motorcycle parts, furniture parts, OA equipment products, electronic and electronic parts, and industrial parts.

[Brief description of the drawings]

FIG. 1 is a plan view of a mold for obtaining a molded product having a weld portion used in Examples and Comparative Examples of the present invention.

[Explanation of symbols]

 1; welded part 2: sprue 3: runner 4: molded product

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08K 5/17 C08K 5/17 5/3492 5/3492 5/36 5/36 5/524 5/524 7 / 18 7/18 F term (reference) 4J001 DA01 DB01 EA06 EA07 EA08 EB08 EB09 EB36 EB37 EC07 EC08 EC09 EC14 JA04 JA07 JA10 JA12 4J002 AC012 AC032 AC062 AC072 AC082 BB032 BB122 BB152 BB172 BB182 BG02 BG02 BG02 BG02 BG021 CB002 CC032 CD002 CF062 CF072 CG002 CH042 CH072 CK022 CL011 CL031 CN012 CN032 CP032 DH046 EJ017 EJ037 EJ047 EU077 EU087 EU187 EV097 EW067 FD016 FD037 GM00 GN00 GQ00

Claims (5)

[Claims] 1. A polyamide comprising (A) a polyamide and (B) an apatite compound containing an organic substance insoluble in a phenol solvent, wherein the organic substance is 0.5 to 100 parts by weight based on 100 parts by weight of the apatite type compound. Complex,
Alternatively, a polyamide resin composition obtained by mixing (C) a stabilizer with a polyamide resin composite obtained by mixing another resin with the polyamide composite. 2. A polyamide composite obtained by blending a polyamide-forming component and an apatite-type compound-forming component and advancing a polymerization reaction of a polyamide and a synthesis reaction of an apatite-type compound, or another resin added to the polyamide composite. The polyamide resin composition which mix | blends the stabilizer with the polyamide resin composite which mixes these. 3. The polyamide resin composition according to claim 1, wherein the apatite type compound has an average particle diameter of 0.001 to 1 μm. 4. The polyamide resin composition according to claim 2, wherein the apatite type compound-forming component has an average particle diameter of 0.001 to 10 μm. 5. The method according to claim 1, wherein the stabilizer is (a) a phenolic stabilizer,
It is at least one compound selected from (b) a phosphite-based stabilizer, (c) a hindered amine-based stabilizer, (d) a triazine-based stabilizer, and (e) a sulfur-based stabilizer. The polyamide resin composition according to any one of claims 1 to 4.