JP2001234058A - Polyamide foam molding product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamide foam molding product suitable for an industrial material such as an automobile part, an electronic and an electric parts, an industrial mechanical part, etc. SOLUTION: This polyamide foam molding product is characterized in that the molding product comprises a polyamide or a polyamide resin compounded with another resin and 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 compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide foam molded article.

[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. By the way, for the purpose of weight reduction, a technique of adding a foaming agent to a polyamide resin and molding the polyamide resin has been conventionally known. For example, Japanese Patent Application Laid-Open No. 8-337671 discloses a polyamide resin composition comprising a polyamide, swellable fluoromica and a foaming agent. However, according to the studies of the present inventors, although the foamed molded article of polyamide resin is lightened to some extent, its level is still insufficient, and it is not possible to obtain a foam for practical use. Is currently severely constrained.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide foam molded article suitable for various parts such as automobile parts, electronic / electric parts, and industrial machine parts.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by using a polyamide resin containing a specific amount of an apatite type compound. The present inventors have found out what can be done, and have reached the present invention.

That is, the present invention relates to (1) a polyamide or a polyamide resin obtained by mixing other resins, and an apatite compound containing an organic substance insoluble in a phenol solvent, wherein the organic substance is an apatite compound 10
0.5 to 100 parts by weight per 0 parts by weight of a polyamide foam molded article, (2) a polyamide-forming component and an apatite-type compound-forming component, which are mixed to form a polyamide polymerization reaction and an apatite-type compound A polyamide foam molded article characterized by using a polyamide composite obtained by advancing the synthesis reaction of, or a polyamide resin composite obtained by blending another resin with the polyamide composite,

(3) The foamed molded article made of polyamide as described in (1) or (2) above, wherein the apatite compound has an average particle diameter of 0.001 to 1 μm. 0.0 in average particle size
The polyamide foam molded article according to the above item 2, wherein the apatite type compound is 0.5 to 300 parts by weight based on 100 parts by weight of the polyamide. 3. The polyamide foam molded article according to 1 or 2.

(6) Apatite-type compound-forming component is 0.5 to 300 parts by weight per 100 parts by weight of polyamide-forming component.
3. The foamed molded article made of polyamide according to the above item 2, which is in parts by weight. (7) The polyamide foam molded article according to the above (1), wherein at least a part of the organic substance is a polyamide, (8) the polyamide has a weight-average molecular weight of 1 to 1.
(1) wherein the molar ratio of the metal element to phosphorus constituting the apatite type compound is from 0.9 to 1;
3. The polyamide foam molded article according to the above 1 or 2, which is 0.0.

(10) The apatite type compound has a (002) plane peak having a diffraction angle (2θ) of 25.5 to 26.5 degrees due to wide-angle X-ray (CuKα: wavelength λ = 0.1542 nm) scattering, and a diffraction angle. (2θ) of (32.5-33.5 degrees)
(00) The foamed polyamide molded article as described in (1) or (2) above, which is a crystalline apatite compound having a plane peak, and (11) the above-mentioned (1), wherein the apatite compound is represented by the following general formula: Or the polyamide foam molded article according to 2 above, (A) _10-z (HPO ₄ ) _z (PO ₄ ) _6-z (X) _2-z · nH ₂
O (where 0 ≦ z <2 and 0 ≦ n ≦ 16,
(A) is a metal element, and X is an anion or an anion compound. )

(12) The polyamide foam molded article as described in (9) above, wherein the metal element is one or more of Group 2A elements of the periodic table of elements, and (13) the metal element is calcium. (14) a polyamide-forming component selected from a polymerizable amino acid, a polymerizable lactam, a polymerizable diamine / dicarboxylate, or a polymerizable oligomer of the compound; The foamed molded article made of polyamide according to the above item 2, which is at least one kind,

(15) The apatite type compound-forming component is
3. A foamed polyamide article as described in (2) above, which is a phosphoric acid metal compound or a mixture of a phosphoric acid metal compound and a non-phosphoric acid metal compound, and (16) a metal for phosphorus of an apatite compound forming component. 3. The foam molded article made of polyamide according to the above item 2, wherein the molar ratio of the elements is 0.9 to 10.0, wherein (17) the metal element of the apatite type compound forming component is a group 2A element of the periodic table of the elements. The foamed polyamide product according to the above 15 or 16, wherein the foamed product is one or more kinds.

(18) The foamed polyamide article as described in (15) or (16) above, wherein the metal element of the apatite type compound-forming component is calcium, (19) the polymerization reaction of polyamide and the synthesis reaction of apatite type compound. The polyamide foam molded article according to the above item 2, which is carried out at a temperature of 40 to 300 ° C. Hereinafter, the present invention will be described in detail.

The present invention relates to a polyamide foam molded article comprising a polyamide resin and an apatite type compound. The polyamide in the present invention has an amide bond (-NH
A polymer having CO-) may be used.

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.

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 Polymer,
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 modifier 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 polymerizable diamine of diamine / dicarboxylate include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, 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 / dicarboxylate include 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 Here, 0 ≦ z <2 and 0 ≦ n ≦ 16, (A) is a metal element, and X is an anion or an anion compound. From the viewpoint of moldability and physical properties, 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, hydrogen phosphate ion (HPO ₄ ²⁻ ), phosphate ion (PO ₄ ³ −), or part of X in the above general formula is replaced with carbonate ion (CO ₃ ²⁻ ). Carbonate-containing apatite 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.

Examples of the phosphoric acids of the phosphoric acid-based metal compound include orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, and the like. More specifically, as the phosphate metal compound, calcium monohydrogen phosphate (CaHPO ₄ .mH ₂ O;
≦ m ≦ 2. ), Calcium dihydrogen diphosphate (Ca
H ₂ P ₂ O ₇ ), calcium dihydrogen phosphate monohydrate (Ca
(H ₂ PO ₄ ) ₂ .H ₂ O), calcium diphosphate (α- and β-Ca ₂ P ₂ O ₇ ), tricalcium phosphate (α- and β-Ca ₃ (PO ₄ ) ₂ ),

Tetracalcium phosphate (Ca ₄ (PO ₄ )
₂ O), octacalcium phosphate pentahydrate (Ca ₈ H ₂ (P
_{O 4) 6 · 5H 2 O} ), calcium phosphite monohydrate (C
aHPO ₃ .H ₂ O), calcium hypophosphite (Ca (H
₂ PO ₂ ) ₂ ), magnesium phosphate di-trihydrate (M
gHPO ₄ · 3H ₂ O), magnesium phosphate third octahydrate _{(Mg 3 (PO 4) 2} · 8H 2 O), barium phosphate secondary (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 excellent economical properties and physical properties. Among them, calcium monohydrogen phosphate (CaHPO ₄ .mH ₂ O, where 0 ≦ m ≦ 2 in it.) are 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 one kind,
It may be a 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 ), a combination of compounds containing the same kind of metal element, or calcium monohydrogen phosphate dihydrate (CaH 2
Examples include a combination of compounds containing different types of metal elements, such as using PO ₄ .2H ₂ O) and magnesium phosphate dibasic trihydrate (MgHPO ₄ .3H ₂ O). But it doesn't hurt.

The phosphoric metal compound in the present invention comprises
Calcium hydrogen phosphate (CaHPO) _Four・ MH_TwoO, but 0
≦ m ≦ 2. ), Phosphoru
sand it Compounds, 1 (195
8) CaO- by VanWazer described in
H_TwoOP_TwoO_FiveAs the phase diagram of the system shows, in the presence of water,
By mixing phosphate compound and calcium compound
It can be obtained by a known method. More specifically, for example
For example, at a temperature of 20 to 100 ° C, dissolve potassium dihydrogen phosphate.
Add alkali phosphate solution and calcium chloride solution to the solution.
A method of dropping and reacting to synthesize, calcium carbonate or
For mixing calcium hydroxide and phosphoric acid aqueous solution
Good.

By the way, the present inventors have obtained the same effect as the present invention by using a compound consisting 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 metal compound and the non-phosphate metal compound which are the apatite type compound-forming components 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 proceed 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. The compounding amount of the polyamide-forming component and the apatite-type compound-forming component is 0.5 to 100100 parts by weight, more preferably 1 to 200 parts by weight, based on 100 parts by weight of the polyamide-forming component. Further, the amount is 3 to 100 parts by weight, particularly preferably 5 to 75 parts by weight. If the amount of the apatite type compound-forming component is less than 0.5 parts by weight or exceeds 300 parts by weight, problems such as difficulty in foam molding are likely to occur.

The polyamide-forming component and the apatite-type compound-forming component may be compounded by directly mixing the solid polyamide-forming component and the apatite-type compound-forming component, or by mixing the aqueous solution of the polyamide-forming component with the 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 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, for example, wide-angle X-ray diffraction or infrared absorption spectrum 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 an 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, but from the viewpoint of physical properties, it is more preferably 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.

The loss on ignition and solvent extraction, NMR,
Alternatively, the content of the apatite compound can be determined from the polyamide resin composite or the foamed molded article of the present invention by combining the infrared absorption spectrum and the like as necessary. When the content of the apatite type compound is less than 0.5 part by weight with respect to 100 parts by weight of the polyimide,
If the amount exceeds 00 parts by weight, foam moldability tends to decrease. The ratio of the metal element to phosphorus of the apatite type compound of the present invention is preferably 0.9 to 10.0 in terms of molar ratio, more preferably 1.2 to 5.0,
Particularly preferably, it is 1.3 to 2.5. This ratio is 0.
If it is less than 9, or more than 10.0, there is a possibility that the foaming moldability will 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. If the amount of the organic substance is less than 0.5 parts by weight or exceeds 100 parts by weight per 100 parts by weight of the apatite compound, the foaming 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 or a foam molded product of the present invention 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 vessel, and the supernatant solvent is removed. 200m more
Then, the same dissolving operation and the same separating operation using a centrifugal separator are 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 one 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 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 1/2 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 method of producing the polyamide foam molded article of the present invention is not particularly limited, but a foaming agent or a gas is blended into the polyamide composite or the polyamide resin composite, and the mixture is melt-extruded from an extruder die to form a foam. A method for obtaining a molded article can be mentioned. The foaming agent is not particularly limited, but specifically, for example, nitrogen, carbon dioxide, an inert gas such as helium, propane, butane, pentane, hexane, a saturated hydrocarbon such as cyclohexane, monochlorodifluoromethane, Dichloromonofluoromethane, trichloromonofluoromethane, dichlorotetrafluoroethane, trichlorotrifluoroethane,
Physical blowing agents such as halogenated hydrocarbons such as tetrafluoroethane; inorganic salts such as sodium carbonate and sodium bicarbonate; organic salts such as sodium citrate; azo compounds such as azodicarbonamide and hydrazonecarbonamide; -Chemical blowing agents such as tetrazole compounds such as phenyltetrazole and salts thereof.

The polyamide composite used in the polyamide foam molded article of the present invention has an apatite compound uniformly and finely dispersed in a matrix or polyamide resin, and has an extremely good interface between the polyamide and the apatite compound. It is a polyamide resin composite that is fixed and adhered to, compared to a conventional polyamide resin composition,
Because of excellent foam moldability, a foam molded article having good closed cells can be obtained. Therefore, the obtained molded article is expected to be applied to various parts such as automobile parts, electronic / electric parts, and industrial machine parts.

The polyamide resin composition of the present invention may contain, if necessary, fillers used in ordinary polyamide resins, for example, inorganic fillers such as glass fibers, glass flakes and carbon fibers, so long as the objects of the present invention are not impaired. 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, composite glass powder, titanium white, carbon black,
Contains pigments and colorants such as metallic pigments, heat stabilizers such as sodium phosphite and hindered phenol, various plasticizers, moldability improvers, various additives such as weather resistance improvers and antistatic agents Can be done.

[0071]

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 a 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 matter (parts by weight / 100 parts by weight of apatite type compound) (a) Separation operation of apatite type compound: 10 g of a polyamide complex 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 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 spectrum (MS) Apparatus: AutoMSSystem II 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 resolution was measured 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

[0084]

[Production Example 1] Production of polyamide composite (A): 50 weight
% Polyamide-forming components (hexamethylenediamine and
30 kg of an aqueous solution of equimolar salt with dipic acid) was prepared.
As an apatite type compound forming component, an average particle diameter of 1 μm
Calcium monohydrogen phosphate dihydrate (CaHPO_Four・ 2H_Two
6 kg (25% by weight suspension of O)
Dihydrate: pure water = 1.5 kg: 4.5 kg), and
And average particle size 1.5 μm heavy calcium carbonate (CaCO
_Three) Of 2.32 kg (calcium carbonate)
Water: 0.58 kg: 1.74 kg).

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 in a strand form from the lower nozzle. Water cooling and cutting were performed to obtain pellets. The obtained pellets are placed in a tumbler-type polymerization apparatus, and at a temperature of 200 ° C., while flowing nitrogen, 8
After holding for a while, the pellets were taken out after cooling. As a result of evaluating the obtained polyamide composite (A), the weight average molecular weight (Mw) was 120,000, 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 is 1.6
7 was calculated.

From the result of transmission electron microscopy observation at a magnification of 100,000, the average particle size of the apatite compound was 85 nm. 90
The resulting apatite-type compound was evaluated by performing elution / separation operations with a phenol aqueous solution, and the 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 6.5 (parts by weight / apatite 10
0 parts by weight). 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. Furthermore, from the observation of the infrared absorption spectrum,
A peak indicating the presence of an organic substance was observed at about 1548 cm ^-1 . Table 1 shows the properties of the polyamide composite (A).

[0088]

[Production Example 2] Production of polyamide composite (B): 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 polyamide composite (B) pellet was obtained in the same manner as in Example 1, except that the polyamide-forming component was used. Table 1 shows the properties of the polyamide composite (B).

[0089]

[Production Example 3] Production of polyamide 66: In Example 1, polymerization was carried out using only the polyamide-forming component without blending the apatite-forming component to obtain polyamide 66 pellets. The characteristics are shown in Table 1.

[0090]

[Production Example 4] Production of polyamide composite (C): 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 (C). Table 1 shows the properties of the polyamide composite (C).

[0091]

Example 1 A polyamide composite (A) was extruded from a single-screw extruder (diameter: 40 mm, L / D: 30, nozzle diameter: 2 mm).
And melted under a cylinder temperature condition of 280 ° C., and from the middle of the extruder, 100 parts by weight of the polyamide in the polyamide composite (A) (the weight obtained by subtracting the content of the apatite type compound from the polyamide composite is 100 parts by weight) butane gas (foaming agent)
A part by weight was press-fitted and passed through a mold at 280 ° C to obtain a rod-shaped foam molded product. The resulting foam has uniform cells,
The density was 300 kg / m ³ .

[0092]

Example 2 The procedure of Example 1 was repeated, except that the polyamide composite (B) was used instead of the polyamide composite (A). The resulting foam had uniform cells and a density of 220 Kg / m ³ .

[0093]

Comparative Example 1 The same procedure was performed as in Example 1, except that the polyamide obtained in Production Example 3 was used instead of the polyamide composite (A). The obtained foam molded article had a density of 650 Kg / m ³ and many voids were observed.

[0094]

Comparative Example 2 The same operation as in Example 1 was performed except that the polyamide composite (C) was used instead of the polyamide composite (A). The obtained foam molded article had a density of 600 kg / m ³ and many cavities were observed.

[0095]

[Table 1]

[0096]

According to the present invention, there is provided a polyamide foam comprising a polyamide resin 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 molded product, and is expected to be very useful for various applications such as automobile parts, motorcycle parts, furniture parts, OA equipment products, electronic and electronic parts, and industrial parts.

Continued on the front page F-term (reference) 4F074 AA00 AA71 AC04 AE01 AE06 AG20 BA37 CA22 CC03Y CC04X CC04Y DA02 DA35 DA37 DA47 4J001 DA01 EA06 EA07 EA08 EA15 EA16 EA17 EA28 EB05 EB06 EB07 EB08 EC46 EB09 EC37 EB09 EC48 GD10 JA02 JA04 JA05 JA07 JB01 JC03 4J002 AA002 AC012 AC022 BB032 BB122 BB152 BC032 BC062 BG012 BG042 BG062 BG102 BN152 BP012 CB002 CF052 CG002 CH072 CL003 CL011 CL031 CL051 CN012 CN03007 017 017 FD 017 017 020

Claims (4)

[Claims] An apatite compound containing an organic substance insoluble in a phenol solvent, wherein the organic substance is 0.5 to 1 per 100 parts by weight of the apatite compound.
A polyamide foam molded article characterized by being 00 parts by weight. 2. A polyamide composite obtained by blending a polyamide-forming component with 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 foam-formed article made of polyamide characterized by using a polyamide resin composite obtained by blending: 3. The polyamide foam molded article according to claim 1, wherein the apatite type compound has an average particle diameter of 0.001 to 1 μm. 4. The polyamide molded article according to claim 2, wherein the apatite type compound-forming component has an average particle diameter of 0.001 to 10 μm.