JP2001226581A - Flame-retardant polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant polyamide resin composition which is suitable in industrial materials such as automobile components, electronic and electric parts, and industrial machine components, and the molded products to be obtained from which excel in rigidity, strength, and also excel in flame retardance. SOLUTION: This flame-retardant composition comprises a polyamide composite material composed of (A) a polyamide and (B) an apatite compound containing a phenolic solvent-insoluble organic substance in an amount of the organic substance of 0.5-100 pts.wt. based on 100 pts.wt. apatite compound or a polyamide resin composite material obtained by mixing the polyamide composite material with other resins, and (C) a nonhalogen based flame- retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polyamide resin composition. More specifically, the present invention relates to a flame-retardant polyamide resin composition which is suitably used as a material for components such as connectors in the electric and electronic fields and electrical components in the automotive field, and relates to mechanical properties such as rigidity and strength. Excellent,
The present invention relates to a polyamide resin composition having excellent flame retardancy.

[0002]

2. Description of the Related Art Polyamide resins are blended with various polyamide resins and flame retardants because the molded articles have excellent mechanical properties, heat resistance, chemical resistance and self-extinguishing properties. BACKGROUND ART Flame-retardant polyamide resin compositions have been widely used in various parts such as automobile parts, electric and electronic parts, and industrial machine parts. For example, a polyamide resin, or a polyamide resin reinforced with glass fiber or the like, a flame-retardant polyamide resin composition containing a flame retardant,
It has been used for electrical and electronic parts such as printed laminates and connectors. More specifically, examples of the flame-retardant polyamide resin composition include, for example, a composition in which a polyamide resin and a chlorine-substituted polycyclic compound are blended (Japanese Patent Laid-Open No. 48-29).
No. 846) is disclosed. Many flame-retardant polyamide resin compositions in which a bromine-based flame retardant is blended with a polyamide resin have been proposed.

For example, blending of decabromodiphenyl ether (JP-A-47-7143) and blending of brominated polystyrene (JP-A-51-47044 and JP-A-Hei.
JP-A-175371), blending of brominated polyphenylene ether (JP-A-54-116054), blending of a brominated crosslinked aromatic polymer (JP-A-63-317552), brominated styrene-maleic anhydride A blend of a copolymer (JP-A-3-168246) and the like are disclosed. Also, many flame-retardant polyamide resin compositions in which a triazine-based flame retardant is blended with a polyamide resin have been proposed. For example, a blend of melamine (Japanese Patent Publication No. 47-1714) and a blend of cyanuric acid (JP-A-50-105744)
JP-A-53-31759, and the like, and the compounding of a salt of cyanuric acid and melamine (JP-A-53-31759).

[0004] However, when the halogen-based flame retardants are blended, there is a suspicion that harmful substances will be discharged during combustion, and there is a movement to regulate their use due to environmental problems. Further, although the triazine-based flame retardant is advantageous in terms of emission of harmful substances during combustion, for the purpose of increasing rigidity, strength, etc., a triazine-based flame retardant is blended with a polyamide resin reinforced with glass fiber or the like. Also,
There is a disadvantage that sufficient flame retardancy cannot be obtained. That is, a flame-retardant polyamide resin composition having excellent mechanical properties such as rigidity and strength of a molded article, and having little occurrence of harmful substances at the time of combustion, and having high flame retardancy has not been hitherto known. The development of such compositions has been strongly desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide resin composition whose molded article is excellent in rigidity, strength and flame retardancy.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific flame retardant is added to a polyamide resin composite in which a polyamide resin contains a specific amount of an apatite type compound. By blending the flame-retardant polyamide resin composition, they have found that the above problems can be solved,
The present invention has been reached.

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 flame-retardant polyamide resin composition containing a non-halogen flame retardant, (2) a polyamide-forming component and an apatite-type compound-forming component, and a polymerization reaction of a polyamide and a synthesis reaction of an apatite-type compound A flame retardant polyamide resin composition obtained by blending a non-halogen flame retardant with a polyamide composite obtained by progressing, or a polyamide resin composite obtained by mixing another resin with the polyamide composite,

(3) The flame-retardant polyamide resin composition as described in (1) or (2) above, wherein the apatite compound has an average particle diameter of 0.001 to 1 μm.
(4) The apatite type compound-forming component has an average particle diameter of 0.001 to 10 μm.
The flame-retardant polyamide resin composition described above, wherein (5) a non-halogen flame retardant is (a) a phosphorus flame retardant, (b) an inorganic compound flame retardant, (c) a triazine flame retardant, and (d) a silicone flame retardant. 5. The flame-retardant polyamide resin composition according to any one of the above items 1 to 4, which is at least one selected from flame retardants. Hereinafter, the present invention will be described in detail.

The present invention relates to a flame-retardant polyamide resin composition obtained by blending a non-halogen flame retardant with a polyamide resin composite comprising a polyamide resin and an apatite type compound.
The polyamide in the present invention has an amide bond (-
A polymer having NHCO-) may be used.

Polyamides preferably used in the present invention are 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) and polyhexamethylene adipamide (nylon 6).
6), polyhexamethylene dodecamide (nylon 61
2), polyhexamethylene isophthalamide (nylon 6I), and polyamide copolymers containing at least two different polyamide components among these, and mixtures thereof.

Further, 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),

Alkyl acrylate-butadiene-acrylonitrile-styrene core shell rubber (ABS),
Core-shell types such as butadiene-styrene-core-shell rubber (SBR) and siloxane-containing core-shell rubber such as methyl methacrylate-butyl acrylate siloxane can be mentioned. The modified rubber is obtained by modifying the above rubber with a modifier having a polar group. Examples thereof include maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, maleic anhydride-modified ethylene-propylene copolymer, and maleic anhydride. Acid-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,
Epoxy-modified ethylene- (1-hexene) copolymer, 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, 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.

To the polyamide-forming component (raw material) of the present invention, a known terminal blocking agent can be further added 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 from 10,000 to 1,000,000 in terms of weight average molecular weight (Mw), more preferably from 20,000 to 500,000, since 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, and more preferably 0 ≦ z <1, 0 ≦ n ≦ 4 from the viewpoint of moldability and physical properties.

Preferred metal elements (A) are 1A, 2A, 3A, 4A, 5A, 6A, 7A, and 1A in the periodic table of the elements.
Group 8, 1B, 2B, and 3B elements, and tin and lead. These metal elements may be one kind or two or more kinds. In the present invention, from the viewpoint of economy, safety and physical properties of the obtained resin composition, 2A
It is particularly preferable to use a group 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 chloride 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 phosphoric acid metal compound,
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 them, in the present invention, a compound of phosphoric acid and calcium is preferably used from the viewpoint of economy 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 above-mentioned 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 above-mentioned phosphoric acids. 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.

In the present invention, among these compounds, metal hydroxides, metal fluorides, metal chlorides, metal carbonates, metal oxides, or mixtures thereof are used because of their better economy 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 product of a 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-based metal compound and the non-phosphate-based metal compound as the apatite type compound-forming component of the present invention have a preferred average particle diameter of 0.001 to 10 μm, more preferably 0.001 to 5 μm, 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. at a temperature of 40 to 300 ° C. 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.

As the method of blending the polyamide-forming component and the apatite-type compound-forming component, a method of directly mixing a solid polyamide-forming component and an 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 glycoletherdiaminetetraacetic 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 confirmation of the apatite type compound of the present invention, for example, using a polyamide composite, a polyamide resin composite, or a polyamide resin composition or a molded product thereof, wide-angle X-ray diffraction, a method of directly confirming by infrared absorption spectrum or the like, Eluting polyamide or other resin with a solvent in which polyamide or other compounded resin is soluble, separating apatite type compound components, wide-angle X-ray diffraction, infrared absorption spectrum of separated apatite type compound For example, a method of confirming the above 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 compound of the present invention may be a crystalline apatite compound or an amorphous apatite compound, but from the viewpoint of physical properties, it is more preferably a crystalline apatite 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, by combining the above-mentioned loss on ignition and solvent extraction, NMR, or infrared absorption spectrum as necessary, apatite is obtained from the polyamide resin composite or the flame-retardant polyamide resin composition of the present invention or its molded product. The content of the type compound can be determined. Polyamide 1 content of apatite type compound
When the amount is less than 0.5 part by weight with respect to 00 parts by weight, the effect of improving the mechanical properties of the obtained molded article is not so remarkable as to achieve the object of the present invention, while exceeding 300 parts by weight. In such a case, problems such as 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, and 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 by the present inventors, the organic substance in the present invention is obtained from the results of pyrolysis gas chromatography of the separated apatite type compound, mass spectrometry (MS) of the pyrolysis component, and 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) quantification 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, and stirred at 40 ° C. for 2 hours. Then, a separating operation is performed using a centrifugal 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 rate (X (parts by weight / 100 parts by weight of apatite type compound)): 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 measurement of pyrolysis components: 1 to 10 mg of the apatite type compound obtained in the above (i) was weighed, and the pyrolysis temperature was 550 ° C. and the column temperature was 50 by pyrolysis gas chromatography. ~ 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 size 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 size = 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 1/2 of the sum of the two is defined as the particle diameter. In addition, a minimum of 2000 is required for calculating the average particle diameter.
The particle size of each piece is measured. The non-halogen flame retardant of the present invention is preferably selected from compounds comprising (a) a phosphorus flame retardant, (b) an inorganic compound flame retardant, (c) a triazine flame retardant, and (d) a silicone flame retardant. At least one
It is a kind of flame retardant. Hereinafter, the flame retardant will be described in detail.

(A) Phosphorus-based flame retardant As the phosphorus-based flame retardant of the present invention, red phosphorus, ammonium phosphate or ammonium polyphosphate is preferably used. As the red phosphorus, from the viewpoint of stability during handling, it is preferable to coat the surface thereof in advance with a coating of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. Treated, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, those coated with a coating comprising a metal hydroxide and a thermosetting resin selected from titanium hydroxide, aluminum hydroxide, magnesium hydroxide, Examples thereof include those in which a coating of a thermosetting resin is double coated on a coating of a metal hydroxide selected from zinc hydroxide and titanium hydroxide.

(B) Inorganic Compound Flame Retardants The inorganic compound flame retardants of the present invention include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, and water. Hydrates of metal hydroxides or inorganic metal compounds such as zirconium oxide, tin oxide, zinc stannate, and zinc hydroxystannate, and borate compounds such as zinc borate, zinc metaborate, and barium metaborate may be mentioned. it can. These may be used alone or in combination of two or more. Among these, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, hydrotalcite, or a mixture thereof is more preferable from the viewpoints of flame retardancy and economy.

(C) Triazine Flame Retardants The triazine flame retardants of the present invention include, for example, melamine, melam, melem, melon (product of deammonification of three to three molecules of melem at 300 ° C. or more), melamine cyanurate, Examples include melamine phosphate, melamine polyphosphate, succinoguanamine, adipoguanamine, methylglutaloganamin, and melamine resin. These may be used alone or in combination of two or more.

(D) Silicone Flame Retardant The silicone flame retardant of the present invention includes silicone resin, silicone oil and silica. The silicone resin is SiO ₂ , RSiO _3/2 , R ₂ SiO, R ₃
Examples of the resin include a resin having a three-dimensional network structure formed by combining structural units of SiO _1/2 . here,
R is a methyl group, an ethyl group, an alkyl group such as a propyl group,
Alternatively, it represents an aromatic group such as a phenyl group or a benzyl group, or a substituent having a vinyl group as the substituent. These silicone resins are obtained by co-hydrolyzing and polymerizing an organohalosilane corresponding to the above structural unit.

In the silicone oil, polydimethylsiloxane and at least one methyl group on the side chain or at the terminal of the polydimethylsiloxane have a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group,
Modified by at least one group selected from amino group, epoxy group, polyether group, carboxyl group, mercapto group, chloroalkyl group, alkyl higher alcohol ester group, alcohol group, aralkyl group, vinyl group, and trifluoromethyl group. Modified polysiloxane, or a mixture thereof.

The silica is amorphous silicon dioxide. Among them, silicon dioxide surface-treated with a silane coupling agent or the like is most preferably used. The compounding amount of the non-halogen flame retardant of the present invention is polyamide 10
It is preferably from 1 to 300 parts by weight, more preferably from 3 to 200 parts by weight, most preferably from 5 to 100 parts by weight based on 0 parts by weight. If the amount is less than 1 part by weight,
The effect of improving flame retardancy tends to be insignificant.
If the amount exceeds 00 parts by weight, there is a concern that the moldability and mechanical properties may be reduced.

The method for producing the flame-retardant polyamide resin composition of the present invention is not particularly limited. For example, a flame retardant is blended with a polyamide composite raw material (a polyamide-forming component and / or an apatite-type forming component). Method, a method of blending a flame retardant during the preparation of a polyamide composite (either during the polymerization of a polyamide or during the synthesis of an apatite type compound), and a method of preparing a polyamide resin composite (mixing a polyamide composite with another resin) Method), a method of blending a flame retardant during melt-kneading of a polyamide composite or a polyamide resin composite, a method of preparing a master batch of a flame retardant in advance and blending it with a polyamide composite or a polyamide resin composite. Or any combination of these methods. There.

The flame-retardant polyamide resin composition of the present invention comprises:
The matrix or polyamide resin, the apatite type compound is uniformly and finely dispersed and the interface between the polyamide and the apatite type compound is fixed very well, and a flame retardant is blended with the bonded polyamide composite, Compared with the conventional flame-retardant polyamide resin composition, the obtained molded article has characteristics such as excellent mechanical properties such as rigidity and strength and excellent flame retardancy.

Therefore, application to various parts such as automobile parts, electronic / electric parts, and industrial machine parts is expected. Various parts include switches, micro slide switches, 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 Pulleys, electromagnetic switches, holders, plugs, breakers and the like can be mentioned.

The flame-retardant polyamide resin composition of the present invention comprises:
Known molding methods, such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, melt spinning, etc., using generally known plastic molding methods Can be formed well.

If necessary, the flame-retardant polyamide resin composition of the present invention may contain, as a moldability improving agent, a phosphoric ester compound such as triphenyl phosphate or a zinc oxide as long as the object of the present invention is not impaired. Phosphite compounds such as triphenyl phosphate, stearic acid, behenic acid, higher fatty acid compounds such as montanic acid, calcium stearate, metal salt compounds of higher fatty acids such as calcium montanate, higher fatty acid ester compounds such as stearyl stearate, Inorganic crystal nucleating agents such as higher fatty acid amide compounds, polyalkylene glycols or terminal modified products thereof, low molecular weight polyethylene or oxidized low molecular weight polyethylene, substituted benzylidene sorbitol, caprolactones and talc can be contained.

The flame-retardant polyamide resin composition of the present invention may contain, if necessary, fillers used in ordinary polyamide resins within the range not impairing the object of the present invention, such as glass fibers, glass flakes and carbon fibers. Such as inorganic fillers, pigments and colorants such as titanium white and carbon black, heat stabilizers represented by sodium phosphite and hindered phenol, various plasticizers, weather resistance improvers, antistatic agents, etc. Various additives can be contained.

[0077]

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 (parts by weight / 100 parts by weight of polyamide) The polyamide composite is dried at 100 ± 20 ° C. for 8 hours and cooled. 1 g of the composition was weighed in a platinum dish, ashed in an electric furnace at 650 ± 20 ° C., cooled, weighed, and the content of the apatite compound was determined. (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 in 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 5
00 ml. The device is ThermoJarrellA
The wavelength of 317.933 nm was determined by high frequency inductively coupled plasma (ICP) emission analysis using IRIS / IP manufactured by Sh.
Was determined.

(B) Determination of phosphorus: 0.5 g of the polyamide composite 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 Th
Quantification was performed at a wavelength of 213.618 (nm) by high frequency inductively coupled plasma (ICP) emission analysis using IRIS / IP manufactured by thermoJarrel 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: A polyamide complex was weighed, mixed with 200 ml of 90% by weight phenol, and heated at 40 ° C. The mixture was stirred for 2 hours and subjected to a separation operation at 20,000 rpm for 1 hour using a centrifugal separator [H103RLH manufactured by Kokusan Centrifuge Co., Ltd.] 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, and the mixture was stirred at 23 ° C. for 2 hours.
The separation operation is performed at 00 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 substance: (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) device: 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 spectrum (MS) Apparatus: AutoMSSystemII manufactured by JEOL Ionization: EI (70 V) Measurement mass range: m / z = 10 to 400 Temperature: 200 ° C. The 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 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 article (3-1) Flexural modulus and flexural strength (Mpa) The molded article was produced 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. Measurements were made according to ASTM D790
It went according to.

(3-2) Flame retardant UL94 (Under Writers Labo, USA)
ratifications Inc.). In addition, thickness 1/16 inch (UL9
4 standard) molded products using an injection molding machine (Nissei Plastic Co., Ltd. P
(S40E) and evaluated.

[0094]

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. 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 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 times, the average particle size of
It was 5 nm. As a result of performing elution and separation operations with a 90% aqueous phenol solution and evaluating the obtained apatite compound, formation of a crystalline apatite 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). Also,
From the analysis result of the pyrolysis GC / mass spectrum, cyclopentanone was confirmed as one of the pyrolysis 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 .

[0097]

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).

[0099]

[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.

[0100]

[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.

[0101]

[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).

[0102]

Example 1 Polyamide 1 in polyamide composite (A)
To 100 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), 15 parts by weight of melamine cyanurate as a flame retardant was mixed, and a twin screw extruder (Toshiba) TEM3 manufactured by Kikai Co., Ltd.
Using 5), the mixture was melt-kneaded at 280 ° C to obtain a polyamide resin composition. Table 1 shows the evaluation results.

[0103]

Example 2 Polyamide 1 in polyamide composite (B)
To 100 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), 15 parts by weight of melamine cyanurate as a flame retardant was mixed, and a twin screw extruder (Toshiba) TEM3 manufactured by Kikai Co., Ltd.
Using 5), the mixture was melt-kneaded at 280 ° C to obtain a polyamide resin composition. Table 1 shows the evaluation results.

[0104]

Example 3 Polyamide 1 in Polyamide Composite (C)
To 100 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), 15 parts by weight of melamine cyanurate as a flame retardant was mixed, and a twin screw extruder (Toshiba) TEM3 manufactured by Kikai Co., Ltd.
Using 5), the mixture was melt-kneaded at 280 ° C to obtain a polyamide resin composition. Table 1 shows the evaluation results.

[0105]

Comparative Example 1 15 parts by weight of melamine cyanurate as a flame retardant was mixed with 100 parts by weight of the polyamide of Production Example 4, and the mixture was heated at 280 ° C. using a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.). Was melt-kneaded under the following conditions to obtain a polyamide resin composition. Table 1 shows the evaluation results.

[0106]

Comparative Example 2 Polyamide 1 in Polyamide Composite (D)
To 100 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), 15 parts by weight of melamine cyanurate as a flame retardant was mixed, and a twin screw extruder (Toshiba) TEM3 manufactured by Kikai Co., Ltd.
Using 5), the mixture was melt-kneaded at 280 ° C to obtain a polyamide resin composition. Table 1 shows the evaluation results.

[0107]

Comparative Example 3 100 parts by weight of the polyamide of Production Example 4 was mixed with glass fiber (JA4 manufactured by Asahi Fiberglass Co., Ltd.).
16: 10 parts by weight of a number average fiber diameter of 10 μm) and 15 parts by weight of melamine cyanurate as a flame retardant were mixed, and the mixture was mixed at 280 ° C. using a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.). To obtain a polyamide resin composition. Table 1 shows the evaluation results.

[0108]

Example 4 Polyamide 1 in Polyamide Composite (A)
To 100 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), 25 parts by weight of red phosphorus as a flame retardant was mixed, and a twin screw extruder (Toshiba Machine Co., Ltd.) 2) using TEM35 (manufactured by
The mixture was melt-kneaded at 80 ° C. to obtain a polyamide resin composition. Table 2 shows the evaluation results.

[0109]

Example 5 Polyamide 1 in Polyamide Composite (A)
To 100 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), 25 parts by weight of ammonium polyphosphate was mixed as a flame retardant, and a twin-screw extruder (Toshiba) TEM3 manufactured by Kikai Co., Ltd.
Using 5), the mixture was melt-kneaded at 280 ° C to obtain a polyamide resin composition. Table 2 shows the evaluation results.

[0110]

Example 6 Polyamide 1 in Polyamide Composite (A)
To 100 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), 25 parts by weight of zinc borate as a flame retardant was mixed, and a twin-screw extruder (Toshiba) The mixture was melt-kneaded at 280 ° C. using a TEM35 manufactured by Kikai Co., Ltd. to obtain a polyamide resin composition. Table 2 shows the evaluation results.

[0111]

Example 7 Polyamide 1 in Polyamide Composite (A)
To 100 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), 25 parts by weight of silica gel as a flame retardant was mixed, and a twin screw extruder (Toshiba Machine Co., Ltd. The mixture was melt-kneaded under the conditions of 280 ° C. using TEM35) (manufactured by KK) to obtain a polyamide resin composition. Table 2 shows the evaluation results.

[0112]

Example 8 Polyamide 1 in Polyamide Composite (A)
To 100 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), 25 parts by weight of magnesium hydroxide as a flame retardant was mixed, and a twin screw extruder (Toshiba) (TEM35 manufactured by Kikai Co., Ltd.)
Was melt-kneaded at 280 ° C. to obtain a polyamide resin composition. Table 2 shows the evaluation results.

[0113]

Example 9 Polyamide 1 in Polyamide Composite (A)
To 100 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), 25 parts by weight of melamine polyphosphate was mixed as a flame retardant, and a twin-screw extruder (Toshiba) (TEM35 manufactured by Kikai Co., Ltd.)
Was melt-kneaded at 280 ° C. to obtain a polyamide resin composition. Table 2 shows the evaluation results.

[0114]

[Table 1]

[0115]

[Table 2]

[0116]

Industrial Applicability According to the present invention, 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 an interface thereof is hardly halogen-free. It is a flame-retardant polyamide resin composition containing a flame retardant. Therefore, the obtained molded article has excellent rigidity, strength, and excellent flame retardancy as compared with the conventional flame-retardant polyamide resin molded article. It is expected to be very useful for various applications such as automobile underhood parts, motorcycle parts, furniture parts, OA equipment products, electronic and electronic parts, and industrial parts.

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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 flame-retardant polyamide resin composition obtained by mixing (C) a non-halogen flame retardant 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. A flame-retardant polyamide resin composition obtained by blending a non-halogen flame retardant with a polyamide resin composite obtained by mixing 3. The flame-retardant polyamide resin composition according to claim 1, wherein the apatite 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 at least one non-halogen flame retardant selected from (a) a phosphorus flame retardant, (b) an inorganic compound flame retardant, (c) a triazine flame retardant, and (d) a silicone flame retardant. The flame-retardant polyamide resin composition according to claim 1, wherein the composition is a seed.