JP2002122193A - Polyamide resin tensioner of endless member for power transmission - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin tensioner superior in rigidity, impact abrasion and a fatigue strength characteristic, and further superior in heat resistance and oil proof, capable of providing the proper tension by inwardly pressing an endless member such as a chain and a timing belt stretched between the driving shaft side and the driven shaft side to transmit the torque of a driving shaft to a driven shaft in various devices such as an automobile, an electric/electronic device and an industrial machine. SOLUTION: In this polyamide resin tensioner of the endless member for transmitting the power, a polyamide composite composed of an apatite-type compound including polyamide and organic matter insoluble to a phenol solvent is used, and a content of the organic matter to 100 pts.wt. of the apatite-type compound is 5-100 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tensioner made of polyamide resin for an endless member for power transmission. Specifically, it is stretched between the drive shaft side and the driven shaft side to transmit the rotational force of the drive shaft having excellent rigidity, impact wear and fatigue strength characteristics, and also having excellent heat resistance and oil resistance to the drive shaft. The present invention relates to a tensioner made of a polyamide resin which applies an appropriate tension by pressing an endless member inward.

[0002]

2. Description of the Related Art Conventionally, endless members such as chains and toothed belts stretched between a drive shaft and a driven shaft have been used to transmit the rotational force of the drive shaft to the drive shaft. . For example, in the case of an automobile, in order to transmit the rotation of the crankshaft to the camshaft,
Chains and toothed belts (cogged belts) are used. Similarly, a chain or a toothed belt is used as a drive transmission endless member for a generator, various motors, and the like.

[0003] The camshaft is used to open and close the intake and exhaust valves of the engine at a predetermined timing synchronized with the operation of the engine. Therefore, it is necessary to open and close each valve at an accurate timing.
For this purpose, it is necessary to reliably prevent the chain or the toothed belt from causing lateral run-out or loosening. For this reason, a tensioner that presses the chain or the toothed belt inward to apply appropriate tension is required. Used. Since these tensioners are brought into contact with a chain or a toothed belt driven at a high speed with a high pressure, the tensioner is repeated with a strong impact force by the chain or the toothed belt in a very short cycle (eg, 25 to (Approximately 150 Hz) Continue to be beaten and scratched. For this reason, these tensioners are required to be excellent in impact wear and fatigue strength characteristics that can withstand hitting. In addition, these tensioners are used for assisting the driving of the chain or the toothed belt and accurately transmitting the rotation of the crankshaft to the camshaft so that the engine can be operated accurately. Is required to have high mechanical strength with little deterioration over time and sufficient mechanical strength even after long-term use.
Furthermore, since it is continuously exposed to high-temperature engine oil to which various additives are added for improving the performance of the engine, it is required to have excellent heat resistance, oil resistance, and chemical resistance. .

At present, as a tensioner material, nylon 66 or a resin mainly composed of nylon 46 is used as disclosed in JP-A-8-210448. However, nylon 66 and nylon 4
In No. 6, the impact wear and fatigue strength characteristics as described above are insufficient, and there is also a problem in durability. In addition, there has been an attempt to use a resin reinforced with nylon 66, nylon 46, or the like, which is filled with glass fiber, carbon fiber, or the like, but a tensioner made of nylon resin reinforced with glass fiber, etc. There is a problem that the teeth are damaged or worn. For the above reasons, the application of tensioners made of polyamide resin for chains, toothed belts and the like is currently severely restricted.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a drive shaft and a driven shaft for transmitting the rotational force of a drive shaft of various devices such as automobiles, electric / electronic devices, industrial machines, etc. to the drive shaft. Excellent in rigidity, impact wear, fatigue strength characteristics, and excellent heat resistance and oil resistance, suitable for applying inward tension to endless members such as chains and toothed belts that are stretched. It is to provide a tensioner made of polyamide resin.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a polyamide resin containing a specific amount of an apatite type compound in a polyamide. And found the present invention. That is, the present invention provides: Polyamide, and a polyamide composite comprising an apatite-type compound containing an organic substance insoluble in a phenol solvent, wherein the apatite-type compound converts the organic substance into 0.5 to 100 parts by weight per 100 parts by weight of the apatite-type compound. Including in proportion, a polyamide resin tensioner for an endless member for power transmission, characterized by using a polyamide composite,

[0007] 2. The power transmission according to the above item 1, wherein the polyamide composite contains an apatite type compound having an average particle diameter of 0.001 to 1 μm in a ratio of 1 to 30 parts by weight with respect to 100 parts by weight of the polyamide. 2. A tensioner made of an endless member made of polyamide resin. The polyamide according to the above 1 or 2, wherein the polyamide composite is obtained by blending a polyamide-forming component and an apatite-type compound-forming component, and advancing a polymerization reaction of the polyamide and a synthesis reaction of the apatite-type compound. Resin tensioner,

[0008] 4. 4. The endless power transmission according to the above item 3, wherein an apatite type compound forming component having an average particle diameter of 0.001 to 10 μm is blended in a ratio of 1 to 30 parts by weight with respect to 100 parts by weight of the polyamide forming component. 4. A tensioner made of polyamide resin for the member; 5. The tensioner made of a polyamide resin for an endless member for power transmission according to any one of the above items 1 to 4, wherein the polyamide has a weight average molecular weight of 20,000 to 200,000. The polyamide composite further comprises, as a heat resistance improver, a halogen metal salt and a Group I transition series metal compound in a proportion of 0.001 to 20 parts by weight with respect to 100 parts by weight of the polyamide composite. 6. A tensioner made of a polyamide resin of an endless member for power transmission according to any one of the above 1 to 5, which is characterized by the following.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention relates to a tensioner made of a polyamide resin for an endless member for power transmission, comprising a polyamide resin and an apatite type compound. 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 are polycaprolactam (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), and polyhexamethylene sebacamide (nylon 610). Polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyundecalactam (nylon 11), polydodecalactam (nylon 12),
Polytrimethylhexamethylene terephthalamide (nylon TMHT), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene methylene terephthalamide (9T), polyhexamethylene terephthalamide (6
T), polybis (4-aminocyclohexyl) methandodecamide (nylon PACM12), polybis (3-methyl-aminocyclohexyl) methandodecamide (nylon dimethyl PACM12), polymethaxylylene adipamide (nylon MXD6), polyundeca Methylene hexahydroterephthalamide (nylon 11T
(H)), and polyamide copolymers containing at least two different polyamide components among these, and mixtures thereof.

Among these polyamides, more preferable 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, or a polymerizable diamine / dicarboxylate, and a polymerizable oligomer of the compound. Specific examples of the polymerizable amino acid include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid. In the present invention, these polymerizable amino acids may be used alone or in combination of two or more.

Examples of the polymerizable lactam include butyl lactam, pivalolactam, caprolactam, caprylactam, enantolactam, 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,
Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; cycloaliphatic 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 from 20,000 to 200,000. When the weight average molecular weight of the polyamide is out of the above range, the effect of improving physical properties such as impact wear, heat resistance and oil resistance of the obtained tensioner tends to be insufficient to satisfy the object of the present invention. The weight average molecular weight is determined, for example, by using hexafluoroisopropanol (HFI
P) and polymethyl methacrylate (PMMA) as a molecular weight standard sample, and can be determined by gel permeation chromatography (GPC).

The apatite type compound preferably used in the present invention is represented by the following general formula. (A) _10-z (HPO ₄ ) _z (PO ₄ ) _6-z (X) _2-z · nH ₂
O Here, 0 ≦ z <2, 0 ≦ n ≦ 16, (A) is a metal element, and X is an anion or an anion compound. From the viewpoint of moldability and physical properties, 0 ≦ z <1. , 0 ≦ n ≦
4 is more preferable. Preferred metal element (A)
Are 1, 2, 3, 4, 5, 6, and
Group 7, 8, 9, 10, 11, 12, and 13 elements, and tin and lead can be mentioned. These metal elements may be one kind or two or more kinds. In the present invention, from the viewpoints of economy, safety and physical properties of the obtained resin composition, it is particularly preferable that the resin composition is a group II element such as magnesium, calcium, strontium, barium, or a mixture of two or more thereof. .

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

In the present invention, among the apatite-type compounds, hydroxyapatite (X is a hydroxyl ion) in which the metal element (A) is calcium, fluorinated apatite (a part or all of X is a fluorine ion), Chlorinated apatite (X
Are partially or entirely chlorine ions), carbonate-containing hydroxyapatite, carbonate-containing fluorinated apatite, carbonate-containing chlorinated apatite, and mixtures thereof are most preferably used.

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. If the ratio is less than 0.9 or exceeds 10.0, the moldability may be significantly reduced or the effect of improving the physical properties may not sufficiently satisfy the object of the present invention.

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 viewpoint of excellent economic efficiency and physical properties, and particularly, calcium monohydrogen phosphate (CaHP)
O ₄ · mH ₂ O, where 0 ≦ m ≦ 2. ) Are more preferably used, especially anhydrous calcium monohydrogen phosphate (CaH
PO ₄ ) and calcium monohydrogen phosphate dihydrate (CaHP)
O ₄ · 2H ₂ O) is most preferably used. These phosphorus-based metal compounds may be used alone or in combination of two or more. When two or more kinds are combined, for example, calcium monohydrogen phosphate dihydrate (Ca
HPO ₄ · 2H ₂ O) and diphosphate dihydrogen calcium (Ca
H ₂ P ₂ O ₇ ), a combination of compounds containing the same kind of metal element, calcium monohydrogen phosphate dihydrate (CaHPO ₄ .2H ₂ O) and magnesium phosphate ₂ A combination of compounds containing different types of metal elements, such as a hydrate (MgHPO ₄ .3H ₂ O), is exemplified, but any of them may be used.

In the present invention, the phosphate metal compound is
Calcium hydrogen phosphate (CaHPO) _Four・ MH_TwoO, but 0
≦ m ≦ 2. ), Phosphoru
sanditsCompounds, 1 (1958)
CaO-H by VanWazer as described_TwoO
−P_TwoO_FivePhosphoric acid in the presence of water
Known by mixing compounds and calcium compounds
Can be obtained in a way. More specifically, for example, 2
Under a temperature of 0 to 100 ° C., in a potassium dihydrogen phosphate solution,
Add alkali phosphate solution and calcium chloride solution dropwise
Reaction and synthesis method, calcium carbonate or hydroxylation
According to the method of mixing calcium 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, fluoride) Lithium oxide,
Sodium fluoride, potassium fluoride, aluminum fluoride, etc.), metal bromide (such as calcium bromide), metal iodide (such as calcium iodide, potassium iodide, copper iodide), metal carbide (such as calcium carbide), metal Oxides (calcium oxide, magnesium oxide, aluminum oxide, etc.), metal carbonates (calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, aluminum carbonate, etc.), metal sulfates (calcium sulfate) Inorganic metal compounds such as metal nitrate (such as calcium nitrate) and metal silicate (such as calcium silicate and sodium hexafluorosilicate), and compounds of a metal element and a monocarboxylic acid (calcium acetate, copper acetate) , Calcium benzoate,
Examples thereof include a compound of a metal element and a dicarboxylic acid (such as calcium oxalate and calcium tartrate), and a compound of a metal element and a tricarboxylic acid (such as calcium citrate). In the present invention, these non-phosphate metal compounds may be used alone or in combination of two or more. When two or more kinds are combined, a compound containing the same kind of metal element may be combined, such as a mixture of calcium hydroxide and calcium carbonate, or a mixture of calcium carbonate and magnesium hydroxide, for example. May be combined with a compound containing a different metal element.

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

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

The phosphate-based metal compound and the non-phosphate-based metal compound which are the apatite type compound-forming components of the present invention have a preferable average particle diameter of 0.001 to 10 μm, more preferably 0.001 to 5 μm, and still more preferably. Is 0.00
1 to 1 μm. When the average particle size is out of the above range, the effect of improving the physical properties such as impact wear, heat resistance and oil resistance of the obtained tensioner tends not to sufficiently satisfy the object of the present invention. The measurement of the average particle diameter may be performed by dispersing the apatite-type compound-forming component in pure water or alcohols, performing ultrasonic treatment, and then measuring with a laser diffraction / scattering particle size distribution apparatus.

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

A more preferred method is a method in which the mixture of the two forming components is allowed to undergo a polyamide polymerization reaction and an apatite type compound synthesis reaction at a temperature of 40 to 300 ° C. This is a method in which a polyamide polymerization reaction and an apatite-type compound synthesis reaction are allowed to proceed simultaneously and in parallel at a temperature of 40 to 300 ° C. under a mixture of forming components under pressure. The compounding amount of the polyamide-forming component and the apatite-type compound-forming component is 1 to 30 parts by weight of the apatite-type compound-forming component, more preferably 1.5 to
It is 25 parts by weight, more preferably 2.5 to 20 parts by weight, particularly preferably 3 to 15 parts by weight. When the amount of the apatite type compound-forming component is less than 1 part by weight, the effect of improving impact wear, heat resistance and oil resistance tends to be low. The endless member tends to wear.

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

In the present invention, the kind of the dispersant is not particularly limited, and a known dispersant can be used. For example, "Elucidation of dispersion and aggregation and applied technology, 1992
Anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, 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. Among these, it is preferable to use an anionic surfactant or a nonionic surfactant. In particular, from the viewpoint of price and physical properties, sodium citrate, sodium polyacrylate, polyammonium ammonium, and styrene-maleic anhydride are preferably used. More preferably, polymers, olefin-maleic anhydride copolymers such as ethylene-maleic anhydride, and sucrose esters such as sucrose stearic acid ester are used.

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

A known method can be used for the polymerization of the polyamide. 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 The steam pressure to be applied is from normal pressure to about 1.
A hot-melt polycondensation method in which polycondensation is performed by maintaining the pressure at 96 MPa (gauge pressure) and finally releasing the pressure to normal pressure or reduced pressure to perform polycondensation can be used. Furthermore, diamine
A solid phase polymerization method performed at a temperature equal to or lower than the melting point of the dicarboxylic acid solid salt or polycondensate, a solution method in which a dicarboxylic acid halide component and a diamine component are polycondensed in a solution, and the like can also be used.

These methods may be combined as needed. Further, the polymerization form may be a batch type or a continuous type. The polymerization apparatus is not particularly limited, and a known apparatus, for example, an extruder-type reactor such as an autoclave-type reactor, a tumbler-type reactor, or a kneader can be used. The confirmation of the apatite type compound of the present invention, for example, using a polyamide composite, a polyamide resin composite, or a polyamide resin composition or a molded product thereof, wide-angle X-ray diffraction, a method of directly confirming by infrared absorption spectrum or the like, A method in which the polyamide is eluted with a phenol solvent in which the polyamide is soluble, the apatite-type compound component is separated, and the separated apatite-type compound is confirmed by wide-angle X-ray diffraction, infrared absorption spectrum, or the like.

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

The content of the apatite type compound of the present invention is
It is preferably 1 to 30 parts by weight, more preferably 1.5 to 25 parts by weight, based on 100 parts by weight of polyamide,
Further, the amount is 2.5 to 20 parts by weight, particularly preferably 3 to 15 parts by weight. The content of the apatite type compound, for example,
Using the polyamide composite, loss on ignition (Ig.loss) is measured in accordance with JISR3420, and can be determined from the weight loss. When the content of the apatite type compound is less than 1 part by weight with respect to 100 parts by weight of the polyamide, the effect of improving impact wear, heat resistance, and oil resistance tends not to be high, and when the content exceeds 30 parts by weight, However, endless members such as chains and toothed belts tend to wear easily.

The molar ratio of the metal element to phosphorus in the apatite type compound of the present invention is preferably 0.9 to 10.0, more preferably 1.2 to 5.0, particularly preferably 1.3 to 2.5. This ratio is 0.9
If it is less than 10.0 or more than 10.0, the moldability may be significantly reduced or the effect of improving the physical properties may not sufficiently satisfy the object of the present invention.

The organic substance contained in the apatite type compound of the present invention is an organic substance incorporated into the inside or the surface of the apatite type compound by a physical or chemical interaction such as an ionic bonding reaction, an adsorption reaction or a grafting reaction. .
Therefore, even if the dissolving operation is performed using a phenol solvent in which the polyamide is soluble, the polyamide has a property that it does not dissolve or elute in the solvent, and this is the fixation between the apatite type compound and the polyamide as the matrix. Adhesion is greatly improved. It is necessary that the amount of the organic substance is 0.5 to 100 parts by weight per 100 parts by weight of the apatite type compound. It is more preferably 1 to 100 parts by weight, furthermore 3 to 75 parts by weight, particularly preferably 4 to 50 parts by weight. 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, physical properties such as impact abrasion are likely to be reduced, and when it exceeds 100 parts by weight, the moldability tends to be reduced. It is in.

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

The content of the organic substance of the present invention can be determined, specifically, by (i) an operation of separating an apatite type compound, (ii) measurement of a heat loss rate, (iii) quantification of an organic substance by measurement of a thermal decomposition component, Can be obtained. The details will be described below.

(I) Separation operation of apatite type compound: 10 g of polyamide composite, polyamide resin composite or molded article of the present invention is weighed, and 90% by weight of phenol 20
Then, the mixture is mixed with 0 ml, stirred at 40 ° C. for 2 hours, separated by a centrifuge, and the supernatant solvent is removed. Further, 200 ml of phenol was added, and the same dissolving operation and separation operation using a centrifuge were repeated four times. Subsequently, 200 ml of 99.5% by weight ethanol was added,
The mixture is stirred at 23 ° C. for 2 hours, and a separating operation is performed using a centrifugal separator to remove a supernatant solvent. After repeating this operation four more times, drying is performed in a vacuum dryer to obtain an apatite type compound. When the polyamide resin is a mixture of polyamide and another resin, before or after the above polyamide dissolving operation, the dissolving / separating operation of the mixed resin other than the polyamide using a solvent in which the other resin is soluble. Should be done.

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

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

The average particle size of the apatite type compound of the present invention is preferably 0.001 to 1 μm, more preferably 0.001 to 0.5 μm. The average particle 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 tensioner of the present invention: shooting (TEM photograph magnification 50,000 times), the particle size d _i of the apatite type compound, the number of particles n _i calculated, following The average particle diameter is calculated by the formula. Average particle size = Σd _i · n _i / Σn _i

In this case, if the particle diameter cannot be regarded as spherical, the minor axis and the major axis are measured, and 1/2 of the sum of the two is defined as the particle diameter. In addition, a minimum of 2000 is required for calculating the average particle diameter.
The particle size of each piece is measured. The molding method of the polyamide resin tensioner of the present invention is not particularly limited, but it can be molded by a usual molding method such as injection molding, extrusion molding, solvent molding, press molding, and thermoforming. In particular, injection molding is used as a preferred molding method.

In the tensioner made of polyamide resin of the present invention, the apatite type compound is uniformly and finely dispersed in the matrix or the polyamide as the matrix, and the interface between the polyamide and the apatite type compound is extremely well fixed and adhered. Compared to conventional polyamide resin tensioners, it has superior rigidity, impact wear, and fatigue strength characteristics, as well as excellent heat resistance and oil resistance, and the rotational force of the drive shaft of various devices such as automobiles, electric / electronics, and industrial machinery. Is expected to be applied to a tensioner to apply an appropriate tension by pressing inwardly endless members such as chains and toothed belts stretched between the drive shaft side and the driven shaft side to transmit the force to the driven shaft Is done.

In the present invention, if necessary, an inorganic filler may be added to the polyamide resin as long as the object of the present invention is not impaired. Examples of the inorganic filler include, but are not particularly limited to, glass fiber, carbon fiber, glass flake, barium sulfate, calcium carbonate, talc, kaolin, mica, wollastonite, boron nitride, molybdenum disulfide, and the like. In the present invention, in order to improve the heat resistance in a high-temperature atmosphere, a polyamide resin tensioner in which a heat resistance improver is mixed with a polyamide composite may be used. The heat resistance improver is not particularly limited, but preferred examples include a halogen metal salt and a Group I transition series metal compound.

The halogen metal salt is a salt of a halogen with a metal element belonging to Group 1 or 2 of the periodic table, and is preferably potassium iodide, potassium bromide, or the like.
Examples thereof include potassium chloride, sodium iodide, sodium chloride, and the like, and a mixture thereof. Among them, potassium iodide is most preferable.

The Group I transition series metal compound is a compound of the Group I transition group metal (Group 11) in the periodic table of the elements, and a preferable example is a metal compound of copper element (Cu). For example, copper halides, sulfates, acetates, propionates, benzoates,
Adipate, terephthalate, salicylate, nicotinate, stearate, ethylenediamine (e
n), chelate compounds such as ethylenediaminetetraacetic acid, and the like, and mixtures thereof. Among these, preferred are copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate.

The halogen metal salt, which is a heat resistance improving agent, and the Group I transition series metal compound are used in combination. In this case, from the viewpoint of further improving the heat resistance, halogen and the first transition series metal element are used. Is preferably in the range of 1 to 500, more preferably in the range of 5 to 200. The amount of the heat resistance improver of the present invention is preferably 0.001 to 20 parts by weight, more preferably 0.005 to 20 parts by weight, and more preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the polyamide.
~ 1 part by weight is most preferred. When the amount is less than 0.001, the effect of improving heat resistance tends to be insignificant, and when it exceeds 20 parts by weight, there is a concern that physical properties may be reduced.

The method of compounding the heat resistance improver is not particularly limited. For example, a method of compounding a heat resistance improver with a polyamide composite raw material (polyamide-forming component and / or apatite-type forming component), polyamide composite A method of blending a heat resistance improver during body preparation (either during polymerization of a polyamide or synthesis of an apatite type compound), and attaching the heat resistance improver to the surface of a polyamide composite (powder or pellet). Method, a method of blending a heat resistance improver by melt-kneading a polyamide composite, or a method of blending a master batch pellet and a polyamide composite pellet of a heat resistance improver, or a method of combining these methods, Either method may be used. In the case of blending, the heat resistance improving agent may be blended as it is, or may be blended by dissolving in a soluble solvent such as water.

In the present invention, if necessary, a polysiloxane may be blended with the polyamide resin in order to improve abrasion as long as the object of the present invention is not impaired. As polysiloxanes, for example, polydimethylsiloxane, and at least one methyl group on the side chain or terminal of polydimethylsiloxane is a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group,
Modified by at least one group selected from amino group, epoxy group, polyether group, carboxyl group, mercapto group, chloroalkyl group, alkyl higher alcohol ester group, alcohol group, aralkyl group, vinyl group, and trifluoromethyl group. Modified polysiloxane, or a mixture thereof.

In the present invention, if necessary, other resins may be mixed with the polyamide as long as the object of the present invention is not impaired. As other resins to be blended, a thermoplastic resin or a rubber component can be added. The other thermoplastic resin, for example, atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, polystyrene resin such as AS resin, polyethylene terephthalate, polyester resin such as polybutylene terephthalate, polycarbonate, polyphenylene ether, polysulfone, Polyether resins such as polyether sulfone, polyphenylene sulfide,
Condensation resins such as polyoxymethylene and other polyamides, acrylic resins such as polyacrylic acid, polyacrylates, and polymethyl methacrylate; polyolefin resins such as polyethylene, polypropylene, polybutene, and ethylene-propylene copolymer; Vinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene (PTF
Examples of the resin include a halogen-containing vinyl compound resin such as E), a phenol resin, and an epoxy resin.

Examples of the rubber component include rubber and modified products thereof. Examples of the rubber include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, shrimp chlorohydrin rubber, styrene-butadiene block copolymer (SB)
R), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-
Styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS),
Hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random copolymer Polymer,
Ethylene-propylene copolymer (EPR), ethylene-
(1-butene) copolymer, ethylene- (1-hexene)
Copolymer, ethylene- (1-octene) copolymer, ethylene-propylene-diene copolymer (EPDM), or butadiene-acrylonitrile-styrene-core-shell rubber (ABS), methyl methacrylate-butadiene-styrene-core-shell rubber ( MBS), methyl methacrylate-butyl acrylate-styrene-core-shell rubber (MAS), octyl acrylate-butadiene-styrene-core-shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (ABS), butadiene-styrene-
Core-shell types such as core-shell rubber (SBR) and siloxane-containing core-shell rubber such as methyl methacrylate-butyl acrylate siloxane can be mentioned.

The modified rubber is obtained by modifying the above rubber with a modifier having a polar group. Examples of the modified rubber include maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, and the like.
Maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-modified ethylene- (1-butene) copolymer,
Maleic anhydride-modified ethylene- (1-hexene) copolymer, maleic anhydride-modified ethylene- (1-octene) copolymer, maleic anhydride-modified EPDM, epoxy-modified S
EBS, epoxy-modified ethylene-propylene copolymer,
Epoxy-modified ethylene- (1-butene) copolymer, epoxy-modified ethylene- (1-hexene) copolymer, epoxy-modified ethylene- (1-octene) copolymer and the like are preferably used. In the present invention, the above-mentioned thermoplastic resin and rubber component may be used as a single compound in polyamide.
Two or more kinds may be combined and used.

In the polyamide resin of the present invention, fillers used in ordinary polyamide resins, for example, pigments and colorants such as carbon black, titanium white, and metallic pigments, and typical examples include sodium phosphite and hindered phenol. A heat stabilizer may be added.
Antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc hydroxystannate, ammonium polyphosphate, melamine cyanurate, succinoguanamine, melamine polyphosphate, melamine sulfate, melamine phthalate, fragrance Flame retardants such as group-based polyphosphates and composite glass powders, various plasticizers, moldability improvers, various additives such as weather resistance improvers and antistatic agents can be contained.

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

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

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

2. Characteristics of polyamide resin tensioner (2-1) Weight average molecular weight (Mw) of polyamide It was determined by gel permeation chromatography (GPC) using an evaluation molded product for a polyamide resin tensioner. 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 T manufactured by Tosoh Corporation.
Two SKgel-GMHHR-H and G1000HHR
Was 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 (M) was calculated in terms of polymethyl methacrylate (PMMA).
w) was calculated.

(2-2) Determination of the content of apatite type compound (weight / 100 parts by weight polyamide)
Dry at 20 ° C. for 8 hours and cool. 1 g of the tensioner was weighed on a platinum dish, ashed in an electric furnace at 650 ± 20 ° C., cooled, weighed, and the content of the apatite compound was determined.

(2-3) Molar Ratio of Metal Element to Phosphorus in Apatite Type Compound The metal element and phosphorus in the apatite type compound were quantified and the molar ratio was calculated. (A) Quantification of metal element: In the following, the case of calcium as the metal element will be described, but other metal elements can be similarly determined. Except that the evaluation molded product for a tensioner made of a polyamide resin was used, the measurement was carried out in the same manner as in (1-2) (a) Determination of the metal element. (B) Quantification of phosphorus: The same procedure as (1-2) (b) for quantification of phosphorus was carried out, except that an evaluation molded product for a tensioner made of a polyamide resin was used.

(2-4) Amount of organic matter (parts by weight / 100 parts by weight of apatite type compound) (a) Separation operation of apatite type compound: 10 g of a polyamide resin tensioner was weighed, mixed with 200 ml of 90% by weight phenol, and mixed with 40% by weight. And centrifuged at 20 ° C. for 2 hours using a centrifuge [H103RLH manufactured by Domestic Centrifuge Co., Ltd.].
Separation operation was performed at 000 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, 99.5% by weight of ethanol 2
Then, the mixture was stirred at 23 ° C. for 2 hours, and subjected to a separation operation using a centrifuge at 20,000 rpm for 1 hour.
Remove the 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 heat loss rate X 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 substance: (a) of (2-4)
3 mg of the apatite type compound obtained in the above was weighed, and subjected to pyrolysis chromatography (GC) and pyrolysis GC under the following conditions.
/ MS pyrogram was obtained. 1) Pyrolysis equipment: Frontier Double Shot Pyrolyzer P
Y-2010D Thermal decomposition temperature: 550 ° C 2) Gas chromatography (GC) Equipment: HP-589 manufactured by HEWLETTPACKARD
Column 0: J & W DURABONDDB-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. 3) Mass spectrum (MS) device: AutoMSSystem 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) Confirmation of generation of apatite type compound by X-ray diffraction X-ray diffraction of the apatite type compound obtained in (2-4) (a) was measured. The measurement conditions are as follows. X-ray: Copper Kα Wave number: 0.1542 nm Tube voltage: 40 KV Tube current: 200 mA Scanning speed: 4 deg. / Min divergence slit: 1 deg. Scattering slit: 1 deg. Light receiving slit: 0.15mm

3. Transmission Electron Microscope (TEM) Observation Using an evaluation molded product for a tensioner made of polyamide resin,
Ultra-thin sections of about 50 nm were made using a Reichert-Nissei cryomicrotome. Transmission electron microscope (TEM) observation was performed using HF- manufactured by Hitachi, Ltd.
Using a 2000, a bright-field image of 500000 times was taken and 10
Zero particles were arbitrarily selected to determine the weight average fiber diameter and average aspect ratio of apatite.

4. Preparation of Evaluation Molded Product for Polyamide Resin Tensioner and Measurement of Physical Properties Evaluation molded product for polyamide resin tensioner was prepared using an injection molding machine. The device is PS4 manufactured by Nissei Plastic Co., Ltd.
A molded product for evaluation was obtained under the conditions of 0E, a cylinder temperature of 300 ° C., a mold temperature of 80 ° C., and injection molding conditions of 17 seconds of injection and 20 seconds of cooling. (4-1) Flexural modulus (GPa) This was performed according to ASTM D790. (4-2) Amount of Wear (mg / 2Hr) and Dynamic Friction Coefficient Evaluation was performed using a flat plate having a thickness of 3 mm and a side of 6 cm × 6 cm. The measuring device is TRI-S-50D (Takachiho Seiki Co., Ltd.)
And a partner material was a ring-shaped steel material (S545C). The measurement conditions were a surface pressure of 2.0 MPa and a linear velocity of 20 c.
The test was performed under the conditions of m / sec.

(4-3) Deflection temperature under load (° C.) This was performed according to ASTM D648. Load is 1.83M
Pa was performed. (4-4) Oil resistance Evaluation was made based on the retention of tensile strength (ASTM D638) in oil (Mobil SHC629) around 1000 hours. (4-5) Heat Aging Resistance Evaluation was made based on the tensile strength (ASTM D638) retention rate in air at 180 ° C. for about 500 hours. (4-6) Fatigue Resistance Evaluation was made by compression creep. 10m on one side for injection molded products
m and cut into a cube, and a processed test piece was used. 23
At 100 ° C., under a stress of 30 MPa, a compressive strain (%) for 10 mm between chucks after 100 hours was measured and evaluated.

[0074]

Production Example 1 Production of Polyamide Composite (A): 30 kg of an aqueous solution of 50% by weight of a polyamide-forming component (equimolar salt of hexamethylenediamine and adipic acid) was prepared.
As an apatite type compound forming component, an average particle diameter of 3 μm
750 g of calcium monohydrogen phosphate dihydrate (CaHPO ₄ .2H ₂ O) having a maximum particle diameter of 10 μm or less, and heavy calcium carbonate (CaCO ₃ ) having an average particle diameter of 1.5 μm
Was used in an amount of 1746 g (calcium carbonate: pure water = 291 g: 873 g). Mixing these polyamide-forming component and apatite-type compound-forming component,
Stir well. The molar ratio of calcium to phosphorus is 1.6
7 was calculated. The aqueous solution of the polyamide-forming component and the mixed suspension of the apatite-type compound-forming component were charged into a 70-liter autoclave having a stirring device and having a discharge nozzle at the bottom, and sufficiently stirred at a temperature of 50 ° C. . After purging with nitrogen, the temperature was raised from 50 ° C. to about 270 ° C. while stirring. At this time, the pressure in the autoclave becomes a gauge pressure of about 1.77 MPa,
Heating was continued for about 1 hour while removing water from the system so that the pressure did not become 1.77 MPa or more. Then, after about 1 hour, the pressure was reduced to atmospheric pressure, and after maintaining at about 270 ° C. and atmospheric pressure for about 1 hour, stirring was stopped, and the polymer was discharged in a strand form from the lower nozzle, and water-cooled / cutting Was performed to obtain a pellet. The obtained pellets were placed in a tumbler-type polymerization apparatus, and kept at 190 ° C. for 9 hours while flowing nitrogen, and after cooling, the pellets were taken out. As a result of evaluating the obtained polyamide composite (A), the weight average molecular weight (Mw) was 90000, and the content of the apatite type compound was 5.7 parts by weight based on 100 parts by weight of the polyamide. The molar ratio of calcium to phosphorus was calculated to be 1.67. According to the transmission electron microscope observation result of 50,000 times, the average particle diameter of the apatite type compound was 98
nm. Elution with 90% phenol aqueous solution
As a result of performing a separation operation and evaluating the obtained apatite type compound, formation of a crystalline apatite type compound was confirmed by wide-angle X-ray diffraction. The amount of the organic substance of the apatite type compound obtained by the elution / separation operation was calculated to be 6.5 (parts by weight / 100 parts by weight of apatite). Also, from the analysis results of the pyrolysis GC / mass spectrum, as one of the pyrolysis components of the organic matter remaining in the apatite type compound,
Cyclopentanone was identified.

[0075]

[Production Example 2] Production of polyamide complex (B): as apatite type compound-forming component, an average particle diameter of 3μm with a maximum particle size of 10μm or less of calcium hydrogen phosphate dihydrate (CaHPO ₄ · 2H ₂ O) 750 g, and 1148 g of a 25% by weight suspension of a mixture of heavy calcium carbonate (CaCO ₃ ) having an average particle diameter of 1.5 μm and calcium fluoride (CaF ₂ ) having an average particle diameter of 3 μm (calcium carbonate:
Calcium fluoride: pure water = 276 g: 11 g: 861
Except using g), it carried out similarly to Example 1, and obtained the polyamide composite (B).

[0076]

[Production Example 3] Production of polyamide composite (C): 50 kg of an aqueous solution of a polyamide-forming component (equimolar salt of hexamethylenediamine and adipic acid) was added to 30 kg of acetic acid in 30 kg.
3 g of endcapping agent was added. As an apatite type compound-forming component, calcium monohydrogen phosphate dihydrate (CaHPO ₄ .A) having an average particle diameter of 3 μm and a maximum particle diameter of 10 μm or less is used.
2H ₂ O), and 25% by weight of a mixture of heavy calcium carbonate (CaCO ₃ ) having an average particle size of 1.5 μm and calcium fluoride (CaF ₂ ) having an average particle size of 3 μm
A polyamide composite (C) was prepared in the same manner as in Example 1 except that 1100 g of the suspension (calcium carbonate: calcium fluoride: pure water = 218 g: 57 g: 825 g) was used.
I got

[0077]

Production Example 4 Production of polyamide composite (D): 50% by weight of polyamide-forming component (equimolar salt of hexamethylenediamine and adipic acid and isophthalic acid (adipic acid: isophthalic acid = 82: 18 by weight ratio) 30 kg of the aqueous solution of (2) was prepared. As apatite type compound-forming component, an average particle diameter of 3μm with a maximum particle size of 10μm or less of calcium hydrogen phosphate dihydrate (CaHPO ₄ · 2H ₂ O)
1500 g, and 2200 g of a 25% by weight suspension of a mixture of heavy calcium carbonate (CaCO ₃ ) having an average particle diameter of 1.5 μm and calcium fluoride (CaF ₂ ) having an average particle diameter of 3 μm (calcium carbonate: fluoride) Calcium: pure water = 436 g: 114 g: 1650 g) was used. these,
The polyamide-forming component and the apatite-type compound-forming component were mixed and sufficiently stirred. The molar ratio of calcium to phosphorus was calculated to be 1.67. An aqueous solution of the polyamide-forming component and a mixed suspension of the apatite-type compound-forming component,
70 having a stirring device and having a discharge nozzle at the bottom
The mixture was charged in a liter autoclave and sufficiently stirred at a temperature of 50 ° C. After purging with nitrogen, the temperature was raised from 50 ° C. to about 160 ° C. while stirring. At this time, heating was performed while removing water outside the system so that the pressure did not become about 0.2 MPa or more. When the temperature reached about 160 ° C., a 50% by weight aqueous solution containing 44 g of potassium iodide (KI) as a heat resistance improving agent and 2.6 g of cuprous iodide (CuI) was injected into the autoclave. Thereafter, the temperature is reduced to about 2
The temperature was raised to 70 ° C. At this time, the pressure in the autoclave becomes a gauge pressure of about 1.77 MPa, and heating is continued for about 1 hour while removing water from the system so that the pressure does not become 1.77 MPa or more. The pressure was reduced to atmospheric pressure. Thereafter, the mixture was further maintained at about 270 ° C. and atmospheric pressure for about 1 hour, then stirring was stopped, the polymer was discharged in a strand form from the lower nozzle, and water-cooled and cut to obtain pellets. The obtained pellets were placed in a tumbler-type polymerization apparatus, and kept at 190 ° C. for 9 hours while flowing nitrogen. After cooling, the pellets were taken out to obtain a polyamide composite (D).

[0078]

[Production Example 5] Preparation of masterbatch (MB) pellets of heat resistance improver: Ny66 / 6 copolymer (weight ratio 90/1)
0) 100 parts by weight of potassium iodide (KI) 2
5 parts by weight and 1.5 parts by weight of cuprous iodide (CuI) were blended and melt-mixed with a twin-screw extruder (PCM45, manufactured by Ikegai Co., Ltd.) to prepare MB as a heat resistance improver.

[0079]

Example 1 To 100 parts by weight of the polyamide composite (A), 3 parts by weight of a master batch pellet of the heat resistance improver obtained in Production Example 5 was pellet-blended, and a molded article for evaluation was formed and evaluated. . Table 1 shows the results. A molded article for evaluation was molded and evaluated. Table 1 shows the results.

[0080]

Example 2 Masterbatch pellets 3 of the heat resistance improver obtained in Production Example 5 with respect to the polyamide composite (B)
A weight part was blended with a pellet, and a molded article for evaluation was molded and evaluated. Table 1 shows the results. A molded article for evaluation was molded and evaluated. Table 1 shows the results.

[0081]

Example 3 To 100 parts by weight of the polyamide composite (C), 3 parts by weight of a masterbatch pellet of the heat resistance improver obtained in Production Example 5 was pellet-blended, and a molded article for evaluation was formed and evaluated. . Table 1 shows the results.

[0082]

Example 4 A molded article for evaluation was molded using the polyamide composite (D) and evaluated. Table 1 shows the results.

[0083]

Example 5 3 parts by weight of a masterbatch pellet of the heat resistance improver obtained in Production Example 5 and 100 parts by weight of a black masterbatch pellet 3 with respect to 100 parts by weight of a polyamide composite (C)
To the parts by weight, 0.05 parts by weight of aluminum stearate as a moldability improver and 0.03 parts by weight of PEG (polyethylene glycol) as a spreading agent were blended with a Henschel mixer to form a molded article for evaluation and evaluated. Table 1 shows the results.

[0084]

Comparative Example 1 Polyamide 66 (Leona 1500, manufactured by Asahi Kasei Kogyo Co., Ltd.) was mixed with 3 parts by weight of a master batch pellet of the heat resistance improver obtained in Production Example 5 and 3 parts by weight of a black master batch pellet to formability. 0.05 parts by weight of aluminum stearate as an improving agent and 0.03 parts by weight of PEG (polyethylene glycol) as a spreading agent were blended with a Henschel mixer, and molded articles for evaluation were evaluated. Table 1 shows the results.

[0085]

[Table 1]

[0086]

According to the present invention, there is provided a polyamide resin comprising a polyamide resin containing an apatite type compound which is uniformly and finely dispersed in a polyamide as a matrix, and is very well fixed and adhered to the polyamide at the interface. A tensioner, a chain or toothed belt stretched between the drive shaft side and the driven shaft side to transmit the rotational force of the drive shaft of various devices such as automobiles, electric / electronics, industrial machines, etc. to the driven shaft side This is very useful for applying an appropriate tension to an endless member such as an endless member.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3J049 BB01 BE09 BF05 CA01 CA04 CA06 CA08 4J002 CL011 CL031 DD057 DD077 DD087 DG047 DH036 DH046 DH056 EG047 EG077 FD010 FD067 GM00

Claims (6)

[Claims] 1. A polyamide composite comprising a polyamide and an apatite-type compound containing an organic substance insoluble in a phenol solvent, wherein the apatite-type compound is obtained by adding the organic substance to the apatite-type compound in an amount of 0.1% by weight per 100 parts by weight of the apatite-type compound.
An endless power transmission member made of a polyamide resin, comprising a polyamide composite containing 5 to 100 parts by weight. 2. The polyamide composite has an average particle size of 0.1.
Apatite type compound of 001 to 1 μm
The polyamide resin tensioner for an endless member for power transmission according to claim 1, wherein the tensioner is contained in an amount of 1 to 30 parts by weight with respect to 00 parts by weight. 3. The polyamide composite is obtained by blending a polyamide-forming component and an apatite-type compound-forming component and proceeding a polymerization reaction of a polyamide and a synthesis reaction of an apatite-type compound. Or 2
The tensioner made of a polyamide resin described in 1. 4. The composition according to claim 3, wherein an apatite compound-forming component having an average particle diameter of 0.001 to 10 μm is compounded in a proportion of 1 to 30 parts by weight with respect to 100 parts by weight of the polyamide-forming component. The tensioner made of a polyamide resin of the endless member for power transmission according to the above. 5. A polyamide having a weight average molecular weight of 2
The tensioner made of a polyamide resin for an endless member for power transmission according to any one of claims 1 to 4, wherein the tension is from 10,000 to 200,000. 6. The polyamide composite further comprises a halogen metal salt and a Group I transition series metal compound as a heat resistance improver in an amount of 0.001 part by weight based on 100 parts by weight of the polyamide composite.
The tensioner made of a polyamide resin of an endless member for power transmission according to any one of claims 1 to 5, wherein the tensioner is blended at a ratio of 1 to 20 parts by weight.