JP2000186201A - Welded polyamide molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a welded molding excellent in strengths, elongation, rigidity, and weld strength by using a composition comprising a polyamide and an apatite compound containing organic matter insoluble in a phenolic solvent. SOLUTION: This molding comprises 50-99 wt.% polyamide and 1-50 wt.% apatite compound containing organic matter insoluble in a phenolic solvent. The organic matter is contained in an amount of 0.5-100 pts.wt. per 100 pts.wt. apatite compound. A production process for the polyamide resin composition consists of mixing 50-99 wt.% polyamide-forming component with 1-50 wt.% apatite-compound-forming component and accomplishing the polymerization into a polyamide and the synthesis into an apatite compound. Most desirably, this process consists of concurrently subjecting a mixture of both components to the polymerization into a polyamide and the synthesis into an apatite compound at about 40-300 deg.C under pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide welded molded product. More particularly, the present invention relates to a polyamide welded molded article comprising a polyamide and an apatite type compound, which is excellent in strength, elongation, rigidity and weld strength.

[0002]

2. Description of the Related Art Polyamides have excellent mechanical properties, heat resistance and chemical resistance, and are widely used as daily parts, automobile material parts and electric material parts. Accordingly, the shapes required for these various components have become larger and more complex, and the required physical properties have been advanced. As a method for satisfying the demand for the increase in size and complexity, a method of producing various parts by dividing and molding into two or more parts and then welding these divided molded articles is attracting attention. It has been widely used in recent years.

As the welding polyamide, a non-reinforced polyamide resin such as nylon 66 or nylon 6 or a reinforced polyamide resin composition containing a fibrous reinforcing material such as glass fiber or carbon fiber has been used. However, since the strength of the welded portion is not sufficient, attempts have been made to improve the strength. For example, JP-A-8-151517 and JP-A-8-151517
JP-A-2881827 and JP-A-8-294970 attempt to improve the strength of the weld by optimizing the viscosity, melting point, crystallinity and the like of nylon. However, although the strength of the welded portion of the welded molded product obtained by these inventions is improved compared to the prior art, it has not yet reached a sufficient level, and its use is currently severely restricted.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide welded molded article which is excellent in strength, elongation and rigidity, and which is excellent in welded part strength.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the use of a specific polyamide resin composition containing a specific amount of an apatite type compound in a polyamide has led to a It has been found that a welded molded article having excellent strength, elongation, rigidity, and excellent welded part strength can be obtained, and the present invention has been completed.

That is, the present invention relates to (1) polyamide 50
-99% by weight and 1-50% by weight of an apatite type compound containing an organic substance insoluble in a phenol solvent, wherein the organic substance is 0.5-0.5% by weight per 100 parts by weight of the apatite type compound.
(2) a polyamide-forming component of 50 to 99% by weight, which is 100 parts by weight;
A polyamide-welded molded article, characterized by using a polyamide resin composition obtained by mixing 1 to 50% by weight of an apatite-type compound-forming component and advancing a polyamide polymerization reaction and an apatite-type compound synthesis reaction;

(3) The polyamide-welded molded article according to the above (1), wherein at least a part of the organic substance is a polyamide, and (4) the polyamide has a weight average molecular weight of 1 to 10.
3. The polyamide welded molded article according to the above item 1 or 2, wherein the average particle diameter of the apatite type compound is 1 μm or less. (6) The polyamide-welded molded article according to (1) or (2), wherein the molar ratio of the metal element to phosphorus constituting the apatite type compound is 0.9 to 10.0.

(7) The polyamide welded molded article as described in (1) or (2) above, wherein the welded part strength is 800 kg / cm ² or more, and (8) 100 parts by weight of the polyamide resin composition as described in (2) above. 0.5 to 3 fibrous reinforcing agents
A polyamide welded molded article comprising a reinforced polyamide resin composition blended with 00 parts by weight, (9) an apatite type compound is formed by a wide-angle X-ray (CuKα: wavelength λ = 1.542).
Å) (002) plane peak with a diffraction angle (2θ) of 25.5 to 26.5 degrees due to scattering, and a diffraction angle (2θ) of 32.5 to
3. The polyamide-adhered molded article according to the above 1 or 2, which is a crystalline apatite type compound having a (300) plane peak of 33.5 degrees.

(10) The polyamide welded molded article according to the above 1 or 2, wherein the apatite type compound 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, and A
Is a metal element, and X is an anion or an anion compound. (11) The polyamide-welded molded article according to (6), wherein the metal element is at least one element from Group 2A of the Periodic Table of the Elements, and (12) the metal element is calcium. 6. The polyamide welded molded article according to 6,

(13) A polyamide-forming component comprising a polymerizable amino acid, a polymerizable lactam, a polymerizable diamine.
3. The polyamide-welded molded article according to the above item 2, which is at least one selected from the group consisting of dicarboxylates and oligomers of the above-mentioned polymerizable compounds, (14) a phosphate-based metal compound Or a mixture of a phosphate-based metal compound and a non-phosphate-based metal compound, wherein the polyamide-welded molded article according to the above item 2, wherein the molar ratio of the metal element to phosphorus in the (15) apatite-type compound-forming component is 0; 3. The polyamide welded molded product according to the above item 2, wherein the product is from 9.1 to 10.0.

(16) The polyamide welded molded article according to the above (14) or (15), wherein the metal element of the apatite type compound-forming component is at least one element from Group 2A of the Periodic Table of the Elements. 16. The polyamide-welded molded article according to the above 14 or 15, wherein the metal element of the compound-forming component is calcium, (18) the polymerization reaction of the polyamide and the synthesis reaction of the apatite type compound at a temperature of 40 to 300 ° C. 3. A polyamide-welded molded article according to the above item 2, wherein the molded article is formed.

Hereinafter, the present invention will be described in detail. The present invention relates to a polyamide welded molded product in which an apatite compound is added to a polyamide. The polyamide in the present invention may be a polymer having an amide bond (—NHCO—) in the main chain.

Polyamides preferably used in the present invention include polycaprolactam (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), and polyhexamethylene sebacamide (nylon 610). Polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyundecalactam (nylon 11), polydodecalactam (nylon 12),
Polytrimethylhexamethylene terephthalamide (nylon TMHT), polyhexamethylene isophthalamide (nylon 6I),

Polynonane methylene terephthalamide (9
T), polyhexamethylene terephthalamide (6T),
Polybis (4-aminocyclohexyl) methandodecamide (nylon PACM12), polybis (3-methyl-
Aminocyclohexyl) methandodecamide (nylon dimethyl PACM12), polymethaxylylene adipamide (nylon MXD6), polyundecamethylene hexahydroterephthalamide (nylon 11T (H)), and at least two different polyamides Polyamide copolymers containing components, 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.

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

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

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

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

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

The apatite type compound preferably used in the present invention is represented by the following general formula. (A) _10-z (HPO ₄ ) _z (PO ₄ ) _6-z (X) _2-z · nH ₂ O where 0 ≦ z <2, 0 ≦ n ≦ 16, A is a metal element, X is an anion or an anion compound,
From the viewpoint of moldability and physical properties, it is more preferable that 0 ≦ z <1, and 0 ≦ n ≦ 4.

Preferred metal elements (A) are 1A, 2A, 3A, 4A, 5A, 6A, 7A, and 1A in the periodic table of the elements.
8, 1B, 2B, and 3B group 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 III 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, 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.

Examples of the apatite type compound-forming component (raw material) include a phosphate metal compound and a mixture of a phosphate metal compound and a non-phosphate metal compound. More preferably, the mixture is a mixture of a phosphate metal compound and a non-phosphate metal compound. In the present invention, the molar ratio of the metal element to phosphorus in the apatite type compound-forming component is 0.9 to 10.0.
And more preferably 1.2 to 5.0, and still more preferably 1.5 to 2.0.

Examples of the phosphoric acids of the phosphoric acid 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 ), phosphoric acid Tetracalcium (C
a ₄ (PO ₄ ) ₂ O), octacalcium phosphate pentahydrate (C
_{a 8 H 2 (PO 4)} 6 · 5H 2 O), calcium phosphite monohydrate _{(CaHPO 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 secondary (BaHPO _4), and the like Can be.

Among them, in the present invention, a compound of phosphoric acid and calcium is preferably used from the viewpoints of economy and physical properties, and particularly, 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 phosphate (CaH ₂ P ₂ O ₇ ), such as 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 you can.

In the present invention, the phosphate metal compound is
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 composed of arsenic (As) or vanadium (V), that is, arsenic acid or vanadium acid instead of the phosphoric acid. I guess it can be done. However, in the present invention, phosphoric acids are most preferably used because they are excellent in stability of raw material components, availability of forming components, and safety.

The non-phosphate metal compound in the present invention is not particularly limited as long as it forms a compound with a metal element other than the 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, lithium fluoride, sodium fluoride, potassium fluoride, aluminum fluoride, etc.) ), Metal bromide (eg, calcium bromide), metal iodide (eg, calcium iodide, potassium iodide, copper iodide), metal carbide (eg, calcium carbide), metal oxide (eg, calcium oxide, magnesium oxide), carbonic acid Metal salts (calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, aluminum carbonate, etc.),

Inorganic metal compounds such as metal sulfates (such as calcium sulfate), metal nitrates (such as calcium nitrate), metal silicates (such as calcium silicate and sodium hexafluorosilicate), and metal elements and monocarboxylic acids (Calcium acetate, copper acetate, calcium benzoate, calcium stearate, etc.), compounds of metal elements with dicarboxylic acids (calcium oxalate, calcium tartrate, etc.), compounds of metal elements with tricarboxylic acids (calcium citrate, etc.) ).

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, a metal hydroxide, a metal fluoride, a metal chloride, a metal carbonate, a metal oxide, or a mixture thereof is preferably used because of excellent economical properties and physical properties. .

Particularly preferred are hydroxides, fluorides, chlorides, carbonates of calcium, magnesium, strontium and barium which are Group 2A elements of the Periodic Table of the Elements, or mixtures thereof. , Fluoride, chloride, carbonate, oxide, or a mixture thereof is most preferably used.

The phosphate metal compound and the non-phosphate metal compound which are the apatite type compound-forming components of the present invention have a preferable average particle diameter of 100 μm or less, more preferably 50 μm or less.
μm or less, more preferably 25 μm or less. The average particle diameter is measured by dispersing an apatite-type compound-forming component in pure water or alcohol and measuring with a laser diffraction / scattering type particle size distribution apparatus, or by using a scanning electron microscope (S
A method of measuring using observation by EM) may be used.

The method for producing the polyamide resin composition of the present invention is a method in which an apatite-type compound-forming component (raw material) is blended with a polyamide-forming component (raw material), followed by polymerization of polyamide and synthesis of an apatite-type compound. Good.
A preferred method of polymerization of the polyamide and the apatite-type compound is to heat a 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 form the apatite-type compound. A method of synthesizing or reacting an apatite type compound forming component in the presence of a polyamide forming component,
Thereafter, the polyamide is polymerized.

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

Examples of the method of blending the polyamide-forming component and the apatite-type compound-forming component include a method of directly mixing the solid polyamide-forming component and the apatite-type compound-forming component, and an aqueous solution of the polyamide-forming component and 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 as needed.

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, nonionics, etc., as described on pages 232 to 237 of "Year" (supervised by Fumio Kitahara, published by Techno System Co., Ltd.) A system surfactant or the like can be used.

Of these, anionic surfactants and nonionic surfactants are preferably used. In particular, from the viewpoint of cost and physical properties, sodium citrate, sodium polyacrylate, ammonium polyacrylate, styrene-anhydrous. More preferably, maleic acid copolymers, 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, known methods can be used. For example, a component that is hardly soluble in water such as 11-aminoundecanoic acid is used as a forming component, and 40 to 300 ° C.
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 needed, and removing an inert gas. 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 A hot-melt polycondensation method or the like in which the steam pressure to be maintained is kept at a pressure between normal pressure and 20 atm, and finally the pressure is released and the pressure is reduced to normal pressure or reduced to perform polycondensation can be used.

Further, a solid phase polymerization method carried out at a temperature equal to or lower than the melting point of the diamine / 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. it can. 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 apatite type compound of the present invention can be confirmed by, for example, directly confirming the polyamide resin composition or the welded molded product by wide-angle X-ray diffraction, infrared absorption spectrum, or the like. The molded article may be dipped in a solvent in which polyamide such as phenol is soluble, the polyamide resin is eluted and separated, and the remaining components may be confirmed by wide-angle X-ray diffraction, infrared absorption spectrum, or the like. The apatite type compound contained in the polyamide welded molded article of the present invention may be a crystalline apatite type compound or an amorphous apatite type compound, but from the viewpoint of physical properties, a crystalline apatite type compound may be used. More preferably, it is a compound.

The crystallinity of the apatite type compound can be confirmed by measuring wide-angle X-ray diffraction of a polyamide resin composition or a welded molded product. In addition, the polyamide resin composition or a welded molded article is immersed in a solvent in which polyamide such as phenol is soluble, and the polyamide resin is eluted,
It can also be confirmed by measuring wide-angle X-ray diffraction of the remaining separated components. More specifically, wide angle X-ray diffraction of the separated component was measured using copper Kα (wavelength λ = 1.542 °) as an X-ray source, and the diffraction angle (2θ) was 2 °.
The (002) plane peak exists at 5.5 to 26.5 degrees, and the diffraction angle (2θ) becomes (30) at 32.5 to 33.5 degrees.
0) What is necessary is just to confirm that a plane peak exists. 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 must be 1 to 50% by weight, more preferably 2 to 50% by weight.
It is 45% by weight, particularly preferably 5 to 40% by weight. The content of the apatite type compound can be determined, for example, by measuring the loss on ignition (Ig.loss) of a polyamide resin composition or a welded molded product according to JIS R3420, and determining the weight loss. Specifically, after sufficiently drying the polyamide resin composition and the welded molded product, about 1 g
It is weighed, incinerated in an electric furnace at 650 ± 20 ° C., cooled, and weighed to determine the content of the apatite type compound. When the content of the apatite type compound is less than 1% by weight, the effect of improving the elastic modulus and the strength of the welded portion is not so remarkable as to achieve the object of the present invention, while when it exceeds 50% by weight, , The progress may be reduced.

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 2.0. The quantitative determination of the metal element will be specifically described in the case of calcium as the metal element. First, 0.5 g of a polyamide resin composition or a welded molded product is weighed on a platinum dish and carbonized at 500 ° C. using an electric furnace. After cooling the carbide, 5 ml of hydrochloric acid and 5 ml of pure water are added thereto and dissolved by boiling on a heater. It is cooled again, pure water is added to make 500 ml, and calcium in this sample may be quantified by high frequency inductively coupled plasma (ICP) emission analysis (characteristic wavelength: 317.933 nm).

The other metal elements can be quantified in a similar manner by selecting the characteristic wavelength. On the other hand, the amount of phosphorus was determined by 0.5 g of a polyamide resin composition or a welded molded product.
Is weighed, 20 ml of concentrated sulfuric acid is added thereto, and the mixture is wet-decomposed on a heater. After cooling, 5 ml of hydrogen peroxide is added, heated on a heater, and concentrated until the total amount becomes 2 to 3 ml.
This was cooled again, made up to 500 ml with pure water, and subjected to high frequency inductively coupled plasma (ICP) emission analysis (characteristic wavelength 213.6).
18 nm). The molar ratio of the metal element to phosphorus can be calculated based on the quantitative results obtained in this manner. If this ratio is less than 0.9, air bubbles are likely to be mixed in or foamed during extrusion or molding, and the yield of a welded molded article may be reduced. If the ratio exceeds 10.0, the elongation may be significantly reduced.

The polyamide resin composition and the welded molded product of the present invention contain an apatite type compound and are characterized in that the interface between the polyamide and the apatite type compound is extremely well fixed and adhered. The synthesis of the apatite type compound, for example, for example, taking hydroxyapatite as an example, generally,
A wet method in which calcium hydroxide and phosphoric acid are reacted in an aqueous solution of about PH8, and a hydrothermal method in which calcium monohydrogen phosphate or the like is performed at high temperature and high pressure of about 200 ° C. and 15 atm are used. The conditions for synthesizing this apatite type compound are very similar to the conditions for polymerizing polyamide.

The present inventors have paid attention to this point. That is, the polyamide composition used for the polyamide welded molded article of the present invention is obtained by mixing a polyamide-forming component and an apatite-forming component and synthesizing an apatite-type compound at any stage of the polyamide polymerization process. It is a thing. By doing so, between the polyamide to be polymerized and the apatite type compound to be synthesized,
Physical or chemical interaction such as ionic bonding reaction, adsorption reaction or grafting reaction occurs, and polyamide forming component (raw material) is formed inside or on the surface of apatite type compound particles.
And polyamide components.

The apatite-type compound synthesized via these reaction products (organic substances) is uniformly and finely dispersed in a polyamide as a matrix, and the interface between the polyamide and the apatite-type compound is surprisingly good. Adhere to and adhere to For this reason, the obtained polyamide welded molded product exhibits excellent rigidity, strength, elongation and welded portion strength.

The polyamide which is the matrix of the polyamide resin composition of the present invention elutes in a phenol solvent, whereas the reaction product (organic substance) does not elute or dissolve in the phenol solvent. That is, even when the organic substance is eluted / dissolved with a phenol solvent, the organic substance does not elute / dissolve and the organic substance remains together with the apatite type compound. In the present invention, the organic matter insoluble in the phenol solvent remaining in the apatite type compound needs to be 0.5 to 100 parts by weight per 100 parts by weight of the apatite type compound.

More preferably, the amount is 1 to 100 parts by weight, further 3 to 100 parts by weight, particularly preferably 4 to 50 parts by weight. 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 resulting welded product has a large decrease in elongation. On the other hand, when the amount exceeds 100 parts by weight, there is a concern that molding workability may be deteriorated.

The organic substance of the present invention is formed by a polyamide-forming component and / or a polyamide as a result of physical and chemical interaction with apatite, and has a property that it cannot be eluted into a phenol solvent. It is preferable that at least a part of the organic substance is a polyamide from the viewpoint of further improving adhesion and adhesion to the polyamide as the matrix. Further, the organic substance may contain water.

The organic substance can be confirmed by separating the separated apatite type compound by, for example, pyrolysis gas chromatography and measuring the mass spectrum (MS) of the pyrolysis component. It can also be confirmed by infrared absorption spectrum and nuclear magnetic resonance (NMR) of the separated apatite type compound. According to the study by the present inventors, the organic matter in the present invention is obtained from a pyrolysis gas chromatography and a measurement result of mass spectrometry (MS) or infrared absorption spectrum of the decomposition component. Is the reaction product of

The organic substance is identified by eluting a polyamide resin composition or a welded molded article with a 90% by weight aqueous phenol solution, and then separating a pyrolytic component such as a polyamide-forming component or a polyamide among the pyrolytic components of the separated apatite type compound. By confirming the presence of a characteristic component that matches

For example, in the case where adipic acid / hexamethylenediamine salt is used as a polyamide-forming component, the obtained polyamide resin composition or a welded molded product is separated by elution with a 90% by weight aqueous phenol solution. In the thermal decomposition component of the apatite type compound at 550 ° C., if cyclopentanone can be confirmed, it indicates that the organic substance contains adipic acid, and if adiponitrile can be confirmed, it indicates that the organic substance contains hexamethylenediamine. I have. Further, if cyclopentanone and adiponitrile can be simultaneously confirmed as the thermal decomposition components, it indicates that the organic substance contains polyhexamethylene adipamide (nylon 66).

The amount of the organic substance of the present invention is, specifically,
(A) separation operation of apatite type compound as follows,
(B) measurement of the heat loss rate of the separated apatite type compound,
(C) Quantification of organic matter by measurement of a thermal decomposition component can be obtained.

(A) Separation operation of apatite type compound: 10 g of a polyamide resin composition or a welded molded product was weighed, mixed with 200 ml of 90% by weight phenol, and heated at 40 ° C.
, And the mixture is separated using a centrifuge.
Remove the supernatant solvent. Further, 200 ml of phenol was added, and the same dissolving operation and separation operation using a centrifuge were repeated four times. Subsequently, 200 ml of 99.5% by weight ethanol was added, and the mixture was stirred at 23 ° C. for 2 hours.
The separation operation is performed using a centrifuge, and the supernatant solvent is removed. After repeating this operation four more times, drying is performed in a vacuum dryer to obtain an apatite type compound.

(B) Measurement of heat loss rate (X (parts by weight / 100 parts by weight of apatite type compound)) of the separated apatite type compound: 5 to 15 m of the obtained apatite type compound
g at 30 ° C. by thermogravimetric analysis (TGA).
To 550 ° C at a rate of 99.9 ° C / min.
Hold at C for 1 hour. Initial weight at 30 ° C. (W ₀ )
Using 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

(C) Quantification of organic matter by measurement of pyrolysis components: The apatite type compound obtained in (a) was
Weigh 10 mg, pyrolysis gas chromatography, pyrolysis temperature 550 ° C, column temperature 50-320 ° C
(Measurement rate is 20 ° C./min). The pyrolysis gas chromatography pyrogram obtained is
The peak area is calculated by dividing the retention time into less than 2 min and 2 min or more. 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 the above (b). 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 1 μm or less, more preferably 0.1 μm
It is as follows. The average particle size in the present invention can be determined by an electron micrograph, and the average particle size can be calculated as follows. That is, a transmission electron microscope of ultra-thin sections were cut from the polyamide resin composition or welded molded articles (TEM: Photography magnification 25,000 times) the photographing, the particle size d _i of the apatite type compound, the number of particles n _i Then, the average particle diameter is calculated 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 used for calculating the average
The particle size of each piece is measured. In the present invention, a welded molded article can be obtained by using a reinforced polyamide resin composition obtained by blending a fibrous reinforcing material, for example, glass fiber, carbon fiber, or the like, with the polyamide resin composition of the present invention. Among the fibrous reinforcing materials, glass fibers are particularly preferably used.

Specifically, the polyamide is 50 to 99% by weight.
And a polyamide resin composition comprising 1 to 50% by weight of an apatite type compound containing an organic substance insoluble in a phenol solvent, wherein the organic substance is 0.5 to 100 parts by weight per 100 parts by weight of the apatite type compound. It is a welded molded product comprising a reinforced polyamide resin composition with a material. The type of fibrous reinforcing material is not particularly limited, but those used for resin reinforcement are preferably used, and particularly, those subjected to surface treatment are preferably used. The surface treatment is performed using a coupling agent or a film forming agent. Examples of the coupling agent include a silane coupling agent and a titanium coupling agent.

As the silane coupling agent, triethoxysilane, vinyl tris (β-methoxyethoxy)
Silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β
-(1,1-epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane,
γ-aminopropyltrimethoxysilane, γ-aminopropyl-tris (2-methoxy-ethoxy) silane, N
-Methyl-γ-aminopropyltrimethoxysilane,

N-vinylbenzyl-γ-aminopropyltriethoxysilane, triaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3
-4,5 dihydroimidazolepropyltriethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) amide, N, N-bis (trimethylsilyl) urea and the like can be mentioned. Among them, γ-
Aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, β-
Aminosilanes and epoxysilanes such as (1,1-epoxycyclohexyl) ethyltrimethoxysilane are excellent in economy and easy to handle, and thus are preferably used.

Titanium-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) ) Titanate, tetra (1,1-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate,

Isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate isopropyl tricumyl phenyl titanate,
Isopropyl tri (N-amidoethyl, aminoethyl)
Titanate, dicumylphenyloxyacetate titanate, diisostearoylethylene titanate and the like can be mentioned.

Examples of the film-forming agent include urethane polymers, acrylic polymers, maleic anhydride and ethylene, styrene, α-methylstyrene, butadiene, isoprene, chloroprene, 2,3 dichlorobutadiene,
Examples thereof include copolymers with unsaturated monomers such as 1,3-pentadiene and cyclooctadiene, and polymers such as epoxy polymers, polyester polymers, vinyl acetate polymers, and polyether polymers. Of these, urethane polymers, acrylic acid polymers, butadiene maleic anhydride copolymers, ethylene maleic anhydride copolymers, styrene maleic anhydride copolymers, and mixtures thereof are particularly preferably used from the viewpoint of excellent economy and performance.

To perform a surface treatment of a fibrous reinforcing material using such a coupling agent and a film forming agent,
Any known method may be used, and a sizing treatment of applying the organic solvent solution or suspension of the coupling agent and the film forming agent to the surface of the fibrous reinforcing material as a so-called sizing agent, a Henschel mixer, a super mixer, a ready mixer, Examples include a dry mixing method using a V-type blender or the like, a spray method applying by spraying, an integral blending method, and a dry concentrate method. In addition, a method in which these methods are combined, for example, a method in which a coupling agent and a part of a film forming agent are applied by sizing treatment, and then the remaining film forming agent is sprayed can also be used. Among them, sizing, dry mixing, spraying, and a combination thereof are preferably used from the viewpoint of excellent economy.

The amount of the fibrous reinforcing material is 0.5 to 300 parts by weight based on 100 parts by weight of the polyamide resin composition of the present invention.
Parts by weight, preferably 5 to 200 parts by weight. If the amount is small, the strength and rigidity tend to be low,
If the amount is too large, problems such as molding failure may occur. The shape of the fibrous reinforcing material has an average diameter of 3 to 30 μm and an average length of 1 to 1 from the viewpoint of easy handling.
Chopped short fibers having a diameter of 10 mm and a number of bundles of 500 to 5,000 are most preferably used.

The apparatus for kneading the polyamide resin composition and the fibrous reinforcing material is not particularly limited, and a known apparatus can be used.
A melt kneader such as a shaft extruder, a Banbury mixer and a mixing roll is preferably used.

As a kneading method, a method of mixing a polyamide resin composition and a fibrous reinforcing material with Henschel and supplying the resulting mixture to a melt kneader or kneading the mixture or a method of melting the mixture with a single-screw or twin-screw extruder. For example, a method of blending a fibrous reinforcing material from a side feeder into the polyamide resin composition thus obtained can be exemplified. A particularly preferred method is to mix the polyamide resin composition and a part of the fibrous reinforcing material and supply the mixture to a single-screw or twin-screw extruder from the viewpoint of exhibiting high properties, and further to the remaining fibrous reinforcing material. Is supplied from the tip of the extruder.

The number average fiber diameter of the fibrous reinforcing material in the obtained polyamide welded molded article is 3 to 30 μm, the weight average fiber length is 100 to 750 μm, and the ratio of the weight average fiber length to the average fiber diameter ( When L / D) is in the range of 10 to 500, preferably 25 to 100, high properties can be exhibited. The number-average fiber diameter and weight-average fiber length of the fibrous reinforcing material are measured by dissolving the molded product in a solvent in which polyamide such as formic acid is soluble, and extracting, for example,
More than 00 fibrous reinforcements can be arbitrarily selected and observed and observed with an optical microscope, a scanning electron microscope, or the like.

The term “welding” in the present invention means that a plurality of molded products are melted by using a molded product obtained by injection molding, blow molding, extrusion molding, transfer molding, compression molding, or the like, and by partially melting the molded product. This is a bonding method, and examples thereof include hot plate welding, hot air welding, high frequency welding, friction welding, vibration welding, spin welding, and ultrasonic welding. Another example is injection welding in which a molded product is inserted into a mold and then newly injection-molded and welded.

The machine used for welding is not particularly limited.
A commercially available product can be used. Also, the welding conditions
There is no particular limitation, and a known method can be used. For example, in the case of a method of welding by vibration welding, for example, a vibration having a necessary frequency and amplitude is applied to a plurality of molded articles to be bonded, and the vibration is generated at a pressure bonding surface by holding under a predetermined pressure for a predetermined time. The surface of the molded product is melted by the frictional heat, and a welded molded product can be obtained. The frequency of the vibration applied to the pressing surface is usually 1 to 1000 Hz, and the amplitude is 0.01
~ 100mm, welding pressure is 1 ~ 1000Kg / cm ²
It is preferred to carry out under the conditions of

The polyamide resin composition of the present invention may contain, if necessary, fillers used in ordinary polyamide resins, for example, inorganic fillers such as mica, talc, clay minerals, alumina, silica and the like, as long as the object of the present invention is not impaired. , Antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc hydroxystannate,
Flame retardants such as ammonium polyphosphate, melamine cyanurate, succinoguanamine, melamine polyphosphate, melamine sulfate, melamine phthalate, aromatic polyphosphate, composite glass powder, pigments and coloring agents such as titanium white, phosphorous acid Heat stabilizers such as soda and hindered phenol, lubricants such as stearic acid and paraffin wax, various plasticizers, various additives such as weather resistance improvers and antistatic agents can be contained.

Further, if necessary, a thermoplastic resin or an elastomer, such as polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene rubber, which is usually blended with a polyamide resin within a range not to impair the object of the present invention.
Propylene copolymer, ethylene-propylene-diene copolymer, natural rubber and their acid-modified products such as maleic anhydride, styrene-maleic anhydride copolymer, styrene-phenylmaleimide copolymer, polyethylene,
Polypropylene, butadiene-acrylonitrile copolymer, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, other polyamide resins, aromatic polyester resins, polyphenylene ether resins, polyphenylene sulfide resins, phenol resins, and epoxy resins may be contained. .

[0083]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following examples unless it exceeds the gist. 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 Compound-Forming Component The molar ratio of metal component to phosphorus was calculated from the blending amount of the apatite-type compound forming component and its molecular weight.

2. Characteristics of polyamide resin composition (2-1) Weight average molecular weight (Mw) Determined by gel permeation chromatography (GPC). The apparatus is HLC-8020 manufactured by Tosoh Corporation, the detector is a differential refractometer (RI), the solvent is hexafluoroisopropanol (HFIP), and the column is TS manufactured by Tosoh Corporation.
Two Kgel-GMHHR-H and one G1000HHR were used. The solvent flow rate was 0.6 ml / min, the sample concentration was 1 to 3 (mg 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).
Was calculated.

(2-2) Determination of the content of the apatite type compound (% by weight) The polyamide resin composition and the welded molded product are dried at 100 ± 20 ° C. for 8 hours and cooled. 1 g of the composition is weighed in a platinum dish,
Ashing was performed in an electric furnace at 650 ± 20 ° C., 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 (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 resin composition and the welded molded product are weighed in a platinum dish and carbonized in an electric furnace at 500 ° C. After cooling, 5 ml of hydrochloric acid and 5 ml of pure water are added and dissolved by boiling on a heater. After cooling again, pure water was added to make up to 500 ml. The device is Thermo Jarrel
Using an IRIS / IP manufactured by Ash and a high frequency inductively coupled plasma (ICP) emission spectrometry, the wavelength was 317.933.
Quantified in nm.

(B) Determination of phosphorus: 0.5 g of a polyamide resin composition or a welded molded product was weighed, and 20 ml of concentrated sulfuric acid was added.
Wet decomposition on heater. After cooling, 5 ml of hydrogen peroxide
Was added, and the mixture was heated on a heater and concentrated to a total volume of 2 to 3 ml. It was cooled again and made up to 500 ml with pure water.
The device is an IRI made by Thermo Jarrell Ash
High frequency inductively coupled plasma (ICP) using S / IP
It was quantified at a wavelength of 213.618 (nm) by emission analysis.

(2-4) Amount of organic substance (parts by weight / 100 parts by weight of apatite type compound) a) Separation operation of apatite type compound: 10 g of a polyamide resin composition or a welded molded product was weighed and mixed with 200 ml of 90% by weight phenol. Then, the mixture was stirred at 40 ° C. for 2 hours and centrifuged using a centrifuge [H103RLH manufactured by Domestic Centrifuge Co., Ltd.].
Separation operation was performed at 0000 rpm for 1 hour, and the supernatant solvent was removed. 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, and subjected to a separating operation at 20,000 rpm for 1 hour using a centrifugal separator to remove a supernatant solvent. 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) device: HP-58 manufactured by HEWLETT PACKARD
90 column: DURABOND DB-1 (0.
25 mmI. D. × 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: AutoMS System II 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 was divided into a retention time of less than 2 min and a retention time of 2 min or more, and the respective peak areas Sa (less than 2 min) and Sb (2 min or more) were calculated. Heat loss rate X obtained in (b)
Was used to calculate the amount of the organic substance 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 Perkin Elm
er 1640, resolution was measured at 4 cm ^-1 .

(2-6) Confirmation of formation 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: 1.542Å 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. Physical Properties of General Part and Welded Part (3-1) Preparation of Injection Molded Product and General Physical Properties Molded product was prepared using an injection molding machine. The apparatus was set to PS40E manufactured by Nissei Plastics Co., Ltd., the cylinder temperature was set to 280 ° C., the mold temperature was set to 80 ° C., and the cycle was performed by 17 seconds of injection and 20 seconds of cooling. (3-2) Flexural modulus (Kg / cm ² ) This was performed according to ASTM D790. (3-3) Tensile strength (Kg / cm ² ) and tensile elongation (%) The test was performed according to ASTM D638.

(3-4) Preparation of Welded Molded Product and Strength of Welding Part Using an injection molding machine (IS150E manufactured by Toshiba Machine Co., Ltd.),
Cylinder temperature 290 ° C, mold temperature 80 ° C, length 114
× height 33 × thickness 3mm plate and length 114 × height 33 ×
A 10 mm wide flat plate was formed. The obtained two flat plates having different widths were combined with a vibration welding machine (Branson VIBRATIO).
N-WELDER, MODEL-2800)
Frequency 240Hz, pressure 6.4Mpa, amplitude 1.7m
As shown in FIG. 1 under the conditions of m and 2 mm, a flat plate having a welded portion was obtained by vibration welding in the width direction of the flat plate.
The obtained flat plate was cut out at intervals of 5 mm in the length direction.
Test piece (length: 64 mm, cross-sectional area of welded part: 15 m)
After creating the m ^2), it was performed a tensile test at a pulling speed of 5 mm / sec, was determined welded portion strength.

(3-5) Weight Average Fiber Length and Number Average Fiber Diameter (μm) of Fibrous Reinforcement The polyamide resin component of the welded molded product obtained by blending the fibrous reinforcement is dissolved in formic acid and precipitated. Get things. The resulting precipitate was observed under an optical microscope and randomly selected from 300 to
The length and diameter of 1,000 fibrous reinforcing materials were determined, and the weight average fiber length and the number average fiber diameter were calculated using an image analyzer IP-1000 manufactured by Asahi Kasei Corporation.

[0099]

Example 1 1.5 kg of a hexamethylenediamine / adipic acid equimolar solid salt was used as a polyamide-forming component. The solid salt was dissolved in 1.5 kg of pure water at 50 ° C. and used as an aqueous solution. As an apatite type compound forming component, an average particle diameter of 10 μm calcium monohydrogen phosphate dihydrate (CaHPO
₄ · 2H ₂ O) of 25 wt.% Suspension of 600 g (calcium monophosphate dihydrate: pure water = 150 g: 450
g), and 232 g of a 25% by weight suspension of heavy calcium carbonate (CaCO ₃ ) having an average particle diameter of 1.5 μm (calcium carbonate: pure water = 58 g: 174 g) were used. An aqueous solution of the polyamide-forming component and a suspension of the apatite-type compound-forming component were charged into a 5-liter autoclave,
The mixture was well stirred at a temperature of 50 ° C. From the amount of ingredients used,
The content of the apatite type compound-forming component was 12.2% by weight, and the ratio of the metal element to phosphorus was 1.67 in molar ratio.
Is calculated.

After sufficiently replacing the atmosphere with nitrogen, the temperature was raised from 50 ° C. to 270 ° C. At this time, the pressure in the autoclave became 18 kg / cm ² in gauge pressure, but heating was continued for 1 hour while removing water outside the system so that the pressure did not become 18 kg / cm ² or more. Thereafter, the heating was stopped, the mixture was cooled to room temperature, the autoclave was opened, about 1.5 kg of the polymer was taken out, pulverized by a pulverizer, and dried in a nitrogen stream at 80 ° C. for 24 hours. A welded molded product was produced using the ground polymer. The weight-average molecular weight (Mw) determined by using the welded molded product was 36000, and the content of the apatite type compound was 10.2% by weight based on measurement by incineration.
Met.

Further, as a result of quantification of calcium and phosphorus by high frequency inductively coupled plasma emission analysis, the molar ratio of calcium to phosphorus was calculated to be 1.67. From the result of observation with a transmission microscope, the average particle size of the apatite compound was 0.32 μm. FIG. 3 shows the measurement results of wide-angle X-ray diffraction of the apatite type compound obtained by the elution / separation operation using a 90% by weight aqueous phenol solution. As can be seen from this figure, formation of a crystalline apatite type compound can be confirmed. The apatite type compound obtained by the elution / separation operation has a thermal weight loss rate X by thermogravimetric analysis of 6.38.
(Parts by weight / 100 parts by weight of apatite type compound), Sb / (Sa +) by pyrolysis gas chromatography (GC)
Sb) = 0.80, and the amount of organic matter was calculated to be 5.1 (parts by weight / 100 parts by weight of apatite).

From the analysis results of the pyrolysis GC / mass spectrum, it was confirmed that cyclopentanone was one of the pyrolysis components of organic substances remaining in the apatite type compound.
Further, from the observation of the infrared absorption spectrum, a peak at 1548 cm ^−1, which was not observed in Comparative Example 1, indicating the presence of an organic substance was confirmed. However, this the infrared absorption spectrum, peaks indicating the carbonated apatite type compound to 1416cm ^-1 and 1455cm ^-1 were observed simultaneously. Table 1 shows the measurement results of the physical properties of the obtained welded molded product.

Comparative Example 1 Leona 1300 (nylon 66) manufactured by Asahi Kasei Kogyo Co., Ltd.
g, and 1 kg of hydroxyapatite manufactured by Taihei Chemical Industry Co., Ltd. having an average particle size of 25 μm, and melt-kneaded at a temperature of 280 ° C. with a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.). The kneaded material taken out in a shape was cooled with water and cut to obtain a polyamide resin composition. Using the polyamide resin composition, a welded molded product was produced in the same manner as in Example 1. The weight average molecular weight determined using the welded molded product was 36,000. From the measurement result by ashing, the content of the apatite type compound was 10.1% by weight.
Met. As a result of quantifying phosphorus and calcium by high-frequency inductively coupled plasma emission spectrometry, the molar ratio of calcium to phosphorus was calculated to be 1.66. From the results of transmission microscope observation, the average particle size of the apatite type compound was 3.2 μm.
m. FIG. 5 shows a wide-angle X-ray diffraction result of the apatite type compound obtained by the elution / separation operation using 90% by weight of phenol.

The apatite type compound had a thermal weight loss X by thermogravimetric analysis of 2.50 (parts by weight / apatite type compound 100 parts by weight), and Sb / (Sa) by pyrolysis GC / MS.
+ Sb) = 0.06, and the amount of the organic substance was calculated to be 0.15 (parts by weight / 100 parts by weight of the apatite compound). According to the analysis results of the pyrolysis GC / mass spectrum, the pyrolysis components of the organic substances present in the apatite type compound are the same as the pyrolysis components of the polyamide-forming components (hexamethylenediamine and adipic acid) and polyhexamethyleneadipamide. Could not be confirmed. In addition, the infrared absorption spectrum was almost the same as that of hydroxyapatite manufactured by Taihei Kagaku Sangyo Co., Ltd., which was a compounded apatite type compound, and no peak indicating the presence of organic substances could be confirmed. Table 1 shows the measurement results of the physical properties of the obtained welded molded product.

Reference Example 1 Hydroxyapatite (molar ratio of calcium to phosphorus: 1.67) manufactured by Taihei Kagaku Sangyo Co., Ltd. used in Comparative Example 1 was dried at 80 ° C. under reduced pressure.
The heat loss rate X was 2.23 (weight / apatite type compound 10).
0 parts by weight). No peak was detected in the pyrogram of pyrolysis GC for 2 minutes or more, and Sb / (Sa + S
b) = 0.0, and the amount of the organic matter was calculated to be 0.0 (parts by weight / 100 parts by weight of the apatite compound).

Example 2 As the polyamide-forming component, hexamethylenediamine
1.2 kg of equimolar solid salt of adipic acid and 0.3 kg of equimolar solid salt of hexamethylenediamine / isophthalic acid were used. The procedure was performed in the same manner as in Example 1 except that 1.5 kg of pure water was added to and dissolved in the solid salt and used as an aqueous solution. Table 1 shows the measurement results of the physical properties of the obtained welded molded product.

Example 3 As a polyamide-forming component, hexamethylenediamine
1.5 kg of an equimolar solid salt of dodecanoic acid was used. A pulverized polymer was obtained in the same manner as in Example 1 except that 1.5 kg of pure water was added to and dissolved in the solid salt and used as an aqueous solution. Using the pulverized polymer, the mixture was kneaded with an extruder having a diameter of 40 mm at a cylinder temperature of 260 ° C., extruded with a T-die having a width of 300 mm into a welded product, and solidified on a cooling roll at 30 ° C. to have a thickness of 40 μm. Was produced. Table 1 shows the measurement results of the physical properties of the obtained welded molded product.

Example 4 As the polyamide-forming component, hexamethylenediamine
1.2 kg of an equimolar adipic acid solid salt and 0.3 kg of ε-caprolactam were used. 1.5 kg of pure water in the solid salt
, And dissolved in the same manner as in Example 1, except that the resulting solution was used as an aqueous solution. Table 1 shows the measurement results of the physical properties of the obtained welded molded product.

Example 5 As a polyamide-forming component, ε-caprolactam 2.0
Kg was used. It was dissolved in 1.0 kg of pure water and used as an aqueous solution. As an apatite-type compound-forming component, 600 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate having an average particle diameter of 10 μm (calcium monohydrogen phosphate dihydrate: pure water = 150 g: 450 g), and an average A 25% by weight suspension of heavy calcium carbonate having a particle size of 1.5 μm was added to 2
32 g (calcium carbonate: pure water = 58 g: 174 g) was used. The polyamide-forming component and the apatite-type compound-forming component were charged into a 5-liter autoclave,
The mixture was stirred well at a temperature of 0 ° C.

Then, the temperature was raised to 260 ° C.
The mixture was stirred under a pressure of g / cm ² for 1 hour. Then release the pressure,
While removing water from the autoclave, 26
The reaction was performed at 0 ° C. for 2 hours, and further performed under reduced pressure of 400 mmHg for 1 hour. After the completion of the reaction, the product was taken out from the bottom nozzle in a strand form, cooled with water and cut to obtain pellets. The obtained pellet was dried in a nitrogen stream at 80 ° C. for 24 hours. A welded molded product was produced using the pellet. Table 1 shows the measurement results of the physical properties of the obtained welded molded product.

Example 6 As a polyamide-forming component, 3.0 kg of a hexamethylenediamine / adipic acid equimolar solid salt was used. 200 g of calcium monohydrogen phosphate dihydrate having an average particle diameter of 10 μm was used as an apatite type compound-forming component. The polyamide-forming component and the apatite-type compound-forming component were thoroughly stirred with a Henschel mixer and charged in a 5-liter autoclave. The content of the apatite-type compound-forming component is calculated to be 6.3 (% by weight), and the ratio of the metal element to phosphorus is calculated to be 1.00 in molar ratio. After replacing with enough nitrogen,
The pressure was set to a gauge pressure of 5 kg / cm ² , the temperature was raised from room temperature to 190 ° C., and the state was maintained for 2 hours. At this time, the pressure in the autoclave becomes 15 kg / cm ² in gauge pressure.

Subsequently, the pressure was reduced to 0.5 kg / cm ² , the temperature was raised to 240 ° C., and this state was maintained for 8 hours. In this series of operations, the pressure was set to 0.5 kg / cm.
^In order to keep at ² , the water formed was removed by means of a condenser.
After cooling, the autoclave was opened, and the polymer was taken out and pulverized. The pulverized polymer is treated in a nitrogen stream at 80 ° C. for 24 hours.
Dried for hours. Thereafter, pellets were formed using a small twin-screw extruder (Laboplast Mill ME, manufactured by Toyo Seiki Co., Ltd.) under the conditions of a cylinder temperature of 280 ° C., a screw rotation speed of 70 rpm, and an extrusion rate of 4 kg / hr. A welded molded product was produced in the same manner as in Example 1 using the pellets.

The obtained pellets were dried in a nitrogen stream at 80 ° C. for 24 hours. The weight average molecular weight of the obtained pellet was 210,000. From the result of measurement by incineration, the content of the apatite type compound was 5.2% by weight. As a result of quantification of calcium and phosphorus by high frequency inductively coupled plasma emission spectrometry, the molar ratio of calcium to phosphorus was 1.
01 was calculated. The average particle diameter of the apatite type compound was 0.25 μm from the result of observation with a transmission microscope. 9
FIG. 4 shows the X-ray diffraction results of the apatite type compound obtained by the elution / separation operation using a 0% by weight aqueous phenol solution.
Shown in

From this figure, the formation of the apatite type compound can be confirmed. The thermal weight loss rate X by thermogravimetric analysis is 5.67 (parts by weight / 100 parts by weight of apatite), and S by pyrolysis GC
b / (Sa + Sb) was 0.72, and the amount of organic matter was calculated to be 4.1 (parts by weight / 100 parts by weight of apatite). From the analysis result of the thermal decomposition GC / mass spectrum, adiponitrile was confirmed as a thermal decomposition component of the apatite type compound. From the observation of the infrared absorption spectrum, 165
A peak indicating the presence of an organic substance was observed at 0 cm ^-1 . Table 2 shows the measurement results of the physical properties of the obtained welded molded product.

Example 7 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m was performed in the same manner as in Example 6 except that 100 g of calcium hydrogen phosphate dihydrate was used. The weight-average molecular weight of the obtained welded molded product was 520000. From the measurement result by incineration, the content of the apatite type compound was 2.
It was 5% by weight. Table 2 shows the measurement results of the physical properties of the obtained welded molded product.

Comparative Example 2 As an apatite type compound-forming component, the average particle diameter was 10 μm.
Was performed in the same manner as in Example 6 except that 10.5 g of calcium monohydrogen phosphate dihydrate was used. The content of the apatite type compound-forming component is calculated to be 0.35% by weight, and the molar ratio of calcium to phosphorus is calculated to be 1.00. The weight-average molecular weight of the obtained welded molded product was 70,000.
From the measurement result by incineration, the content of apatite was 0.2
It was 1% by weight. As a result of quantifying calcium and phosphorus by high-frequency inductively coupled plasma emission spectrometry, the molar ratio of calcium to phosphorus was calculated to be 0.95. Table 2 shows the measurement results of the physical properties of the obtained welded molded product.

Comparative Example 3 A welded product was produced using only nylon 6 (SF1022, manufactured by Ube Industries, Ltd.) as a polyamide resin. Table 2 shows the physical property measurement results of the obtained welded molded products.
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Reference Example 2 Hexamethylenediamine / adipic acid equimolar solid salt
Only 3 kg of an aqueous solution in which 5 kg was dissolved in 1.5 kg of pure water, that is, only the polyamide-forming component was charged in a 5-liter autoclave. Thereafter, the operation was performed in the same manner as in Example 1. The weight-average molecular weight of the obtained welded molded product was 35,000. Table 2 shows the measurement results of the physical properties of the obtained welded molded product.

Example 8 As a polyamide-forming component, 1.0 kg of a hexamethylenediamine / adipic acid equimolar solid salt was used. The solid salt was dissolved in 1.0 kg of pure water at 50 ° C. and used as an aqueous solution. As an apatite type compound-forming component, 25% by weight of an average particle diameter of 10 μm calcium monohydrogen phosphate dihydrate
1.0 Kg of the suspension (calcium monohydrogen phosphate dihydrate: pure water = 250 g: 750 g) and 25 wt% suspension of heavy calcium carbonate having an average particle size of 1.5 μm were added to 3
87 g (calcium carbonate: pure water = 97 g: 290 g) was used. The polyamide-forming component and the apatite-type compound-forming component were charged into a 5-liter autoclave, and
The mixture was stirred well at a temperature of 0 ° C. The content of the apatite type compound-forming component is calculated to be 25.8% by weight, and the ratio of the metal element to phosphorus is calculated to be 1.67 in terms of molar ratio.

After sufficiently replacing with nitrogen, the temperature was raised from 50 ° C. to 270 ° C. At this time, the pressure in the autoclave became 18 kg / cm ² in gauge pressure, but heating was continued for 1 hour while removing water from the system so that the pressure did not become 18 kg / cm ² or more. Thereafter, the heating was stopped, the temperature was cooled to room temperature, the autoclave was opened, the polymer was taken out, pulverized by a pulverizer, and dried in a nitrogen stream at 80 ° C. for 24 hours. Using the obtained polymer, a welded molded product was produced in the same manner as in Example 1. The weight average molecular weight of the welded molded product was 35,000. From the result of measurement by incineration, the content of the apatite type compound was 22.3% by weight. As a result of quantification of calcium and phosphorus by high-frequency inductively coupled plasma emission analysis, the molar ratio of calcium to phosphorus was calculated to be 1.67. Table 3 shows the results of measuring the physical properties of the obtained welded molded product.

Example 9 An aqueous solution in which 750 kg of a solid salt of hexamethylenediamine / adipic acid, etc. was dissolved in 750 g of pure water at 50 ° C. was used as a polyamide-forming component. As an apatite type compound-forming component, 1.5 kg of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate having an average particle diameter of 10 μm (calcium monohydrogen phosphate dihydrate: pure water = 375 g: 11
25 g), and 580 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate:
Pure water = 145 g: 435 g) was used.

The polyamide-forming component and the apatite-type compound-forming component were charged into a 5-liter autoclave and stirred well at a temperature of 50 ° C. The content of the apatite type compound-forming component is calculated to be 40.9% by weight. Subsequent operations were performed in the same manner as in Example 8. The weight-average molecular weight of the obtained welded molded product was 32,000. According to the measurement result by incineration, the content of the apatite type compound was 3
9.1 (% by weight). Table 3 shows the measurement results of physical properties of the obtained molded article.

Comparative Example 4 As a polyamide-forming component, 400 g of a hexamethylenediamine / adipic acid equimolar solid salt was added to pure water 4 at 50 ° C.
An aqueous solution dissolved in 00 g was used. As an apatite-type compound-forming component, 2.0 kg of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate having an average particle size of 10 μm (calcium monohydrogen phosphate dihydrate: pure water = 500 g: 150 g)
0g) and 772 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate: pure water = 193 g: 435 g) were used.

The polyamide-forming component and the apatite-type compound-forming component were charged into a 5-liter autoclave and stirred well at a temperature of 50 ° C. The content of the apatite type compound-forming component is calculated to be 63.4% by weight. Subsequent operations were performed in the same manner as in Example 12. The polymer taken out of the autoclave, pulverized and dried, had a weight average molecular weight of 14,000. From the measurement result by incineration,
The content of the apatite type compound was 61.2% by weight. An attempt was made to pelletize the polymer using a twin-screw extruder, but the strand during extrusion was in an extremely unstable state, and could not be obtained as pellets.
Also, a molded product could not be obtained.

Example 10 As a polyamide-forming component, 1.5 kg of a hexamethylenediamine / adipic acid equimolar solid salt was used. The solid salt was dissolved in 1.5 kg of pure water at 50 ° C. and used as an aqueous solution. As an apatite-type compound-forming component, 600 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate having an average particle diameter of 10 μm (calcium monohydrogen phosphate dihydrate: pure water = 150 g: 450 g), and an average A 25% by weight suspension of heavy calcium carbonate having a particle size of 1.5 μm was added to 2
32 g (calcium carbonate: pure water = 58 g: 174 g) was used.

The polyamide-forming component and the apatite-type compound-forming component were charged into a 5-liter autoclave, and acetic acid (CH ₃ COO) was used as a molecular weight regulator.
H) 4.5 g was added and stirred well at a temperature of 50 ° C. After replacing with sufficient nitrogen, raise the temperature from 50 ° C to 270 ° C.
Temperature. At this time, the pressure in the autoclave becomes 18 kg / cm ² in terms of gauge pressure.
Heating was continued for 1 hour while removing water out of the system so as not to exceed g / cm ² .

Thereafter, the pressure was reduced to atmospheric pressure over 1 hour, and the polymer was drawn out in a strand form from the bottom, cooled with water, cut, and formed into pellets. The weight average molecular weight of the obtained polymer was 12,500. This polymer was placed in a 10-liter tumbler-type reactor,
At a temperature of 0 ° C., the mixture was maintained for 8 hours while constantly flowing nitrogen at 5 liter / min. After cooling, the polymer was removed. The weight average molecular weight of the obtained polymer was 42,000. Using the polymer, a welded molded product was produced in the same manner as in Example 1. Table 4 shows the measurement results of physical properties of the obtained welded molded product.

Example 11 As a polyamide-forming component, 1.5 kg of a hexamethylenediamine / adipic acid equimolar solid salt was used. The solid salt was dissolved in 1.5 kg of pure water at 50 ° C. and used as an aqueous solution. As an apatite type compound-forming component, 25% by weight of an average particle diameter of 10 μm calcium monohydrogen phosphate dihydrate
600 g of the suspension (calcium monohydrogen phosphate dihydrate:
Pure water = 150 g: 450 g), and an average particle size of 1.5
232 g of a 25% by weight suspension of μm heavy calcium carbonate
(Calcium carbonate: pure water = 58 g: 174 g) was used.
The polyamide-forming component and the apatite-type compound-forming component were charged into a 5-liter autoclave, and adipic acid (COOH (CH ₂ ) ₄ C) was further added as a molecular weight regulator.
OOH) was added, and the mixture was stirred well at a temperature of 50 ° C.

After sufficiently purging with nitrogen, the temperature was raised from 50 ° C. to 270 ° C. At this time, the pressure in the autoclave became 18 kg / cm ² in gauge pressure, but heating was continued for 1 hour while removing water outside the system so that the pressure did not become 18 kg / cm ² or more. Then, over 1 hour, the pressure was reduced to atmospheric pressure, the polymer was drawn out in a strand form from the bottom, cooled with water, cut, and formed into pellets.
The weight average molecule of the obtained polymer was 14,500. Kneader type reactor (Plastic BT-30-S2-60-L (L / D = 60), manufactured by Plastics Engineering Laboratory)
And extruded at a temperature of 290 ° C. at a discharge rate of 4 kg / hr. The weight average molecular weight of the obtained polymer is 370
00. Using the polymer, a welded molded product was produced in the same manner as in Example 1. Table 4 shows the measurement results of physical properties of the obtained welded molded product.

Example 12 The procedure of Example 10 was repeated, except that 20 g of stearylamine (CH ₃ (CH ₂ ) ₁₆ CH ₂ NH ₂ ) was used instead of acetic acid as a molecular weight regulator. Table 4 shows the measurement results of physical properties of the obtained welded molded product.

Example 13 As a molecular weight regulator, aniline (C ₆
Except for using H ₅ NH ₂₎ 14g was carried out in the same manner as in Example 11. Table 4 shows the physical property measurement results of the obtained welded molded products.
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Example 14 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g) and 104 g of a 25% by weight suspension of heavy calcium carbonate having an average particle diameter of 1.5 μm (calcium carbonate: pure water = 26 g: 78 g), and the same procedure as in Example 1 was carried out. The content of the apatite-type compound-forming component is calculated to be 10.4% by weight, and the ratio of the metal element to phosphorus is calculated to be 1.30 in terms of molar ratio. The weight-average molecular weight of the obtained welded molded product was 38,000, and the content of the apatite type compound was found to be 9.2% by weight based on measurement by incineration.
Met. Further, as a result of quantifying calcium and phosphorus by high frequency inductively coupled plasma emission analysis, the molar ratio of calcium to phosphorus was calculated to be 1.28. Table 5 shows the measurement results of physical properties of the obtained welded molded product.

Example 15 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 469 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
117 g: 351 g), and 232 g (calcium carbonate: pure water = 58 g: 174 g) of a 25% by weight suspension of heavy calcium carbonate having an average particle diameter of 1.5 μm was carried out in the same manner as in Example 1. The content of the apatite-type compound-forming component is calculated to be 10.4% by weight, and the ratio of the metal element to phosphorus is calculated to be 1.85 in molar ratio. The weight-average molecular weight of the obtained welded molded product was 32,000, and the content of the apatite type compound was 9.3% by weight, as measured by incineration. Further, as a result of quantification of calcium and phosphorus by high frequency inductively coupled plasma emission analysis, the molar ratio of calcium to phosphorus was calculated to be 1.88. Table 5 shows the measurement results of physical properties of the obtained welded molded product.

Example 16 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
100 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
25 g: 75 g) and 232 g (calcium carbonate: pure water = 58 g: 174 g) of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm was used in the same manner as in Example 1. The content of the apatite type compound-forming component is calculated to be 5.2% by weight, and the ratio of the metal element to phosphorus is calculated to be 5.0 in terms of molar ratio. The weight-average molecular weight of the obtained welded molded product was 26000, and the content of the apatite type compound was 4.3% by weight as measured by incineration. Further, as a result of quantifying calcium and phosphorus by high-frequency inductively coupled plasma emission analysis, the molar ratio of calcium to phosphorus was calculated to be 5.2. Table 5 shows the measurement results of physical properties of the obtained welded molded product.

Example 17 As an apatite type forming component, 600 g of a 25% by weight suspension of anhydrous calcium monohydrogen phosphate (CaHPO ₄ ) having an average particle size of 1.0 μm (anhydrous calcium hydrogen phosphate: pure water = 150 g: 450 g), and an average particle diameter of 10 μm
216 g of a 25% by weight suspension of calcium hydroxide (Ca (OH) ₂ ) (calcium hydroxide: pure water = 54 g: 16
2g) The procedure was the same as in Example 1 except that 2g) was used. Table 6 shows the physical property measurement results of the obtained welded molded product.

Example 18 As an apatite type forming component, phosphorus having an average particle diameter of 10 μm was used.
Tricalcium acid (Ca _Three(PO_Four)_Two25% suspension by weight)
600 g of the liquid (tricalcium phosphate: pure water = 150 g:
450 g), and an average particle diameter of 10 μm calcium hydroxide
60 g of a 25% by weight suspension of calcium hydroxide (calcium hydroxide: pure
Water = 12 g: 48 g) Except for using the same procedure as in Example 1.
I went. Table 6 shows the measurement results of the physical properties of the obtained welded molded products.
Show.

Example 19 As an apatite type forming component, 2 particles of calcium dihydrogen diphosphate monohydrate (CaH ₂ P ₂ O ₇ ) having an average particle size of 10 μm were used.
600 g of a 5% by weight suspension (calcium dihydrogen diphosphate: pure water = 150 g: 450 g), and an average particle size of 1
400 g of a 25% by weight suspension of 0 μm calcium hydroxide
(Calcium hydroxide: pure water = 100 g: 300 g) Except that it was used, it carried out similarly to Example 1. Table 6 shows the physical property measurement results of the obtained welded molded product.

Example 20 As an apatite type forming component, calcium dihydrogen phosphate monohydrate (Ca (HPO ₄ ) ₂ .H ₂
300 g of a 25% by weight suspension of O) (calcium dihydrogen phosphate monohydrate: pure water = 75 g: 225 g), and 288 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm. (Calcium carbonate: pure water = 72 g: 21
6g) The same procedure as in Example 1 was carried out except that the composition was used. Table 6 shows the physical property measurement results of the obtained welded molded product.

Example 21 As an apatite type forming component, an average particle diameter of 10 μm
Calcium phosphate (Ca _TwoP_TwoO₇) Of a 25% by weight suspension
600 g (calcium diphosphate: pure water = 150
g: 450 g), and heavy carbonic acid having an average particle size of 1.5 μm
320 g of a 25% by weight suspension of calcium (calcium carbonate)
Example 1 except that um: pure water = 80 g: 240 g) was used.
Was performed in the same manner as described above. Measurement of physical properties of the obtained welded molded product
The results are shown in Table 6.

Example 22 As a component for forming an apatite type compound, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 220 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate: pure water = 55 g: 165 g), and an average particle size of 5.
10 g of a 25% by weight suspension of 0 μm calcium fluoride (CaF ₂ ) (calcium fluoride: pure water = 2.5 g: 7.
The procedure was performed in the same manner as in Example 1 except that 5 g) was used. Table 7 shows the measurement results of physical properties of the obtained welded molded product.

Example 23 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 176 g of a 25% by weight suspension of heavy calcium carbonate having an average particle diameter of 1.5 μm (calcium carbonate: pure water = 44 g: 132 g), and an average particle diameter of 5.
44 g of a 25% by weight suspension of 0 μm calcium fluoride (CaF ₂ ) (calcium fluoride: pure water = 11 g: 33)
Except using g), it carried out similarly to Example 1. Table 7 shows the measurement results of physical properties of the obtained welded molded product.

Example 24 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 200 g of a 25% by weight suspension of heavy calcium carbonate having an average particle diameter of 1.5 μm (calcium carbonate: pure water = 50 g: 150 g), and an average particle diameter of 5.
The procedure was performed in the same manner as in Example 1 except that 36 g of a 25% by weight suspension of 0 μm calcium chloride (CaCl ₂ ) was used (calcium chloride: pure water = 9 g: 27 g). Table 7 shows the measurement results of physical properties of the obtained welded molded product.

Example 25 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 200 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate: pure water = 50 g: 150 g), and an average particle size of 10
248 g of a 25% by weight suspension of μm strontium carbonate (SrCO ₃ ) (strontium carbonate: pure water = 12 g:
The procedure was performed in the same manner as in Example 1 except that 36 g) was used.
Table 7 shows the measurement results of physical properties of the obtained welded molded product.

Example 26 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 200 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate: pure water = 50 g: 150 g), and an average particle size of 10
The procedure was performed in the same manner as in Example 1 except that 64 g (barium carbonate: pure water = 16 g: 48 g) of a 25% by weight suspension of μm barium carbonate (BaCO ₃ ) was used. Table 7 shows the measurement results of physical properties of the obtained welded molded product.

Example 27 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
540 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
135 g: 405 g), 60 g of a 25% by weight suspension of magnesium phosphate dibasic trihydrate (MgHPO ₄ .3H ₂ O) having an average particle size of 5.0 μm (magnesium phosphate
Trihydrate: pure water = 15 g: 45 g), average particle diameter 10 μm
172 g of a 25% by weight suspension of heavy calcium hydroxide
(Calcium hydroxide: pure water = 43 g: 129 g) was used in the same manner as in Example 1. Table 7 shows the physical property measurement results of the obtained welded molded product.

Example 28 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 160 g of a 25% by weight suspension of calcium hydroxide having an average particle diameter of 10 μm (calcium hydroxide: pure water = 40 g: 120 g), and an average particle diameter of 10 μm
m of iron (II) chloride tetrahydrate (FeCl ₂ .4H ₂ O)
32 g of a weight% suspension (iron (II) chloride tetrahydrate: pure water =
8 g: 24 g) was used in the same manner as in Example 1. Table 8 shows the measurement results of physical properties of the obtained welded molded product.

Example 29 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 160 g of a 25% by weight suspension of calcium hydroxide having an average particle diameter of 10 μm (calcium hydroxide: pure water = 40 g: 120 g), and an average particle diameter of 10 μm
m iron (III) chloride hexahydrate (FeCl ₃ · 6H ₂ O) of 2
The procedure was performed in the same manner as in Example 1 except that 44 g of a 5% by weight suspension (iron (III) chloride hexahydrate: pure water = 11 g: 33 g) was used. Table 8 shows the physical property measurement results of the obtained welded molded products.
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Example 30 As an apatite type compound-forming component, an average particle diameter of 10 μm was used.
m 600 g of a 25% by weight suspension of calcium hydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water =
150 g: 450 g), 160 g of a 25% by weight suspension of calcium hydroxide having an average particle diameter of 10 μm (calcium hydroxide: pure water = 40 g: 120 g), and an average particle diameter of 10 μm
m Example 1 except that 32 g of a 25% by weight suspension of copper iodide (CuI) (copper iodide: pure water = 8 g: 24 g) was used.
Was performed in the same manner as described above. Table 8 shows the measurement results of physical properties of the obtained welded molded product.

Example 31 As an apatite type compound-forming component, an average particle diameter of 25.
600 g of a 25% by weight suspension of 0 μm calcium monohydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water = 150 g: 450 g), and an average particle size of 1.5 μm The procedure was performed in the same manner as in Example 1 except that 232 g (calcium carbonate: pure water = 58 g: 174 g) of the weight% suspension was used. The average particle size of the apatite type compound was 0.52 μm from the result of observation of the welded molded product by a transmission microscope. Table 9 shows the measurement results of physical properties of the obtained welded molded product.

Example 32 As an apatite type compound-forming component, an average particle size of 75.
600 g of a 25% by weight suspension of 0 μm calcium monohydrogen phosphate dihydrate (calcium monohydrogen phosphate dihydrate: pure water = 150 g: 450 g), and an average particle size of 1.5 μm The procedure was performed in the same manner as in Example 1 except that 232 g (calcium carbonate: pure water = 58 g: 174 g) of the weight% suspension was used. From the result of observation of the welded molded product with a transmission microscope, the average particle size of the apatite compound was 0.88 μm. Table 9 shows the measurement results of physical properties of the obtained welded molded product.

Example 33 The average particle diameter of the component forming the apatite type compound was 3.0 μm.
25% by weight of calcium monohydrogen phosphate dihydrate and 25% of heavy calcium carbonate having an average particle size of 0.25 μm.
Each of the weight% suspensions was performed in the same manner as in Example 1 except that ultrasonic treatment was performed at a temperature of 40 ° C. for 30 minutes. Table 10 shows the physical property measurement results of the obtained welded molded product.

Example 34 An average particle diameter of 3.0 μm as a component for forming an apatite type compound
25% by weight of calcium monohydrogen phosphate dihydrate and 25% of heavy calcium carbonate having an average particle size of 0.25 μm.
Each of the weight% suspensions was performed in the same manner as in Example 1 except that the suspensions were each subjected to a treatment with a homogenizer at a temperature of 60 ° C. for 10 minutes. Table 10 shows the physical property measurement results of the obtained welded molded product.

Example 35 An average particle diameter of 3.0 μm as an apatite type compound-forming component
6 g of ammonium polyacrylate (Ceramo D-134, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a dispersant was added to a suspension of 25% by weight of calcium monohydrogen phosphate dihydrate. After adding 2.32 g of ammonium polyacrylate to a 25% by weight suspension of 0.25 μm heavy calcium carbonate, each was subjected to ultrasonic treatment at 40 ° C. for 30 minutes.
The procedure was performed in the same manner as in Example 1 except that the procedure was performed for one minute.

The weight loss rate X by thermogravimetric analysis of the apatite type compound obtained by eluting and separating the obtained welded molded product using a 90% by weight aqueous phenol solution was 12.
7 (parts by weight / 100 parts by weight of apatite), Sb / (Sa + Sb) by pyrolysis GC was 0.75, and the amount of organic matter was calculated to be 9.5 (parts by weight / 100 parts by weight of apatite). From the analysis results of pyrolysis GC / mass spectrum,
Both thermal decomposition components of cyclopentanone and adiponitrile were confirmed as thermal decomposition components of the apatite type compound. Also,
From the observation of the infrared absorption spectrum, 1550 cm ^-1 and 16
A peak indicating the presence of an organic substance was observed at 50 cm ^-1 .
Table 10 shows the physical property measurement results of the obtained welded molded product.

Example 36 The average particle diameter of the apatite type compound-forming component was 3.0 μm.
6 g of sodium polyacrylate (Sharol AN-103P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added as a dispersant to a 25% by weight suspension of calcium monohydrogen phosphate dihydrate. Sodium polyacrylate 2.3 in a 25% by weight suspension of .25 μm heavy calcium carbonate 2.3
After the addition of 2 g, each was carried out in the same manner as in Example 1 except that ultrasonic treatment was performed at a temperature of 40 ° C. for 30 minutes. Table 10 shows the physical property measurement results of the obtained welded molded product.

Example 37 The average particle size of the apatite type compound-forming component was 3.0 μm.
sodium citrate as a dispersant in a 25% by weight suspension of calcium monohydrogen phosphate dihydrate (Showa Kako Co., Ltd.)
1.2 g) and 0.46 g of sodium citrate to a 25% by weight suspension of heavy calcium carbonate having an average particle size of 0.25 μm, and then subjected to ultrasonic treatment at a temperature of 40 ° C. Was performed in the same manner as in Example 1 except that the measurement was performed for 30 minutes. Table 10 shows the physical property measurement results of the obtained welded molded product.

Example 38 The average particle size of the apatite type compound-forming component was 3.0 μm.
6 g of sucrose stearic acid ester (DK ester, Daiichi Kogyo Seiyaku Co., Ltd.) as a dispersant was added to a 25% by weight suspension of calcium monohydrogen phosphate dihydrate, and the average particle diameter was 0.25 μm weight. 2.32 g of sucrose stearic acid ester was added to a 25% by weight suspension of porous calcium carbonate, and each was subjected to ultrasonic treatment at a temperature of 40 ° C. for 30 minutes, except that each was performed in the same manner as in Example 1. Was. Table 10 shows the physical property measurement results of the obtained welded molded product.

Example 39 An aqueous solution obtained by dissolving 1.5 kg of a hexamethylenediamine / adipic acid equimolar solid salt in 1.5 kg of pure water at 50 ° C. was used as a polyamide-forming component. 600 g of a 25% by weight suspension of calcium monohydrogen phosphate dihydrate having an average particle diameter of 3.0 μm as an apatite type compound-forming component
(Calcium monohydrogen phosphate dihydrate: pure water = 150 g:
450 g) and 232 g of a 25% by weight suspension of heavy calcium carbonate having an average particle size of 1.5 μm (calcium carbonate: pure water = 58 g: 174 g). The polyamide-forming component and the apatite-type compound-forming component were charged in a 5-liter autoclave, and 6 g of ethylenediaminetetraacetic acid (EDTA) was added as a complexing agent.
Stir well at a temperature of ° C. Subsequent operations were performed in the same manner as in Example 1. Table 11 shows the measurement results of physical properties of the obtained welded molded product.

Example 40 Ethylenediaminetetraacetic acid (EDTA) 6 was used as a complexing agent.
Example 39 was carried out except that 1.3 g of ethylenediamine (en) was used instead of g. Table 11 shows the measurement results of physical properties of the obtained welded molded product.

Example 41 Polyamide resin composition 1 obtained in the same manner as in Example 1
50 parts by weight of glass fiber (JAAFT2A manufactured by Asahi Fiber Glass Co., Ltd.) was melt-kneaded at a temperature of 290 ° C. using a twin screw extruder (TEM35, Toshiba Machine Co., Ltd.) to give a glass fiber concentration of 100 parts by weight. 33% by weight of the reinforced polyamide resin composition pellets were obtained to form a welded molded product, and the properties of the welded molded product are shown in Table 12.

Example 42 Polyamide resin composition 1 obtained in the same manner as in Example 4
50 parts by weight of glass fiber (JAAFT2A manufactured by Asahi Fiber Glass Co., Ltd.) was melt-kneaded at a temperature of 290 ° C. using a twin screw extruder (TEM35, Toshiba Machine Co., Ltd.) to give a glass fiber concentration of 100 parts by weight. 33% by weight of the reinforced polyamide resin composition pellets were obtained to form a welded molded product, and the properties of the welded molded product are shown in Table 12.

Example 43 Polyamide resin composition 1 obtained in the same manner as in Example 1
50 parts by weight of glass fiber (JAFT2A manufactured by Asahi Fiber Glass Co., Ltd.) and 0.03 parts by weight of copper iodide with respect to 00 parts by weight.
Parts by weight, and 0.5 parts by weight of potassium iodide,
The mixture was melt-kneaded using a twin-screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.) to obtain a reinforced polyamide resin composition pellet having a glass fiber concentration of 33% by weight. Table 12 shows the physical property evaluation results.

Comparative Example 5 Nylon 66 (Leona 1300 manufactured by Asahi Kasei Corporation)
Except for using, a reinforced polyamide resin composition pellet having a glass fiber concentration of 33% by weight was obtained in the same manner as in Example 41, and a welded molded product was produced. Table 12 shows the results of evaluating the properties of the welded molded product.

Comparative Example 6 A reinforced polyamide resin composition pellet having a glass fiber concentration of 33% by weight was obtained and welded in the same manner as in Example 43, except that the polyamide resin composition obtained in the same manner as in Comparative Example 1 was used. A molded article was produced. Table 12 shows the results of evaluating the properties of the welded molded product.

[0165]

[Table 1]

[0166]

[Table 2]

[0167]

[Table 3]

[0168]

[Table 4]

[0169]

[Table 5]

[0170]

[Table 6]

[0171]

[Table 7]

[0172]

[Table 8]

[0173]

[Table 9]

[0174]

[Table 10]

[0175]

[Table 11]

[0176]

[Table 12]

[0177]

Industrial Applicability The polyamide welded molded article of the present invention has physical properties such as excellent strength, elongation and rigidity, and excellent welded part strength. Therefore, daily parts such as hot water tanks for toilet seats, various containers for water and hot water, car parts such as tail lamps, intech manifolds, surge tanks, oil tanks, gas tanks, canisters and various cylinders, washing machine balancers and speaker boxes It is suitably used for parts having complicated shapes such as home electric parts and hollow parts.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing a set state of a flat plate at the time of vibration welding in measuring a welded portion strength.

FIG. 2 is a conceptual diagram of a test piece shape used for measuring the strength of a welded portion.

FIG. 3 shows the results of wide-angle X-ray diffraction measurement of an apatite compound separated from the welded molded product of Example 1.

FIG. 4 is a result of wide-angle X-ray diffraction measurement of an apatite compound separated from the welded molded product of Example 6.

5 is a result of wide-angle X-ray diffraction measurement of an apatite type compound separated from the welded molded product of Comparative Example 1. FIG.

6 is a result of wide-angle X-ray diffraction measurement of the commercially available hydroxyapatite used in Reference Example 1. FIG.

[Explanation of symbols]

 a Vibration direction b Welding surface

Claims (2)

[Claims] 1. An apatite type compound containing 50 to 99% by weight of a polyamide and an organic substance insoluble in a phenol solvent, wherein the organic substance is 0.5 to 100 parts by weight per 100 parts by weight of the apatite type compound. A polyamide welded molded product characterized by the following. 2. Polyamide-forming component in an amount of 50 to 99% by weight.
And a 1-50% by weight of an apatite type compound-forming component, and a polyamide resin composition obtained by advancing a polymerization reaction of a polyamide and a synthesis reaction of an apatite type compound.