JPH0753821B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a lubricating composition suitable for producing gears, bearings, sliding parts and the like.

[Conventional technology and problems]

Recently, metal parts are being replaced by plastic parts in many fields. In general, plastics can be molded by injection molding, and the same parts can be mass-produced with high accuracy, but on the other hand, the strength is smaller than that of metal, and the coefficient of thermal expansion is large and the dimensional change due to temperature is large, so it is a precise bearing retainer. , Cannot be used for bearings. Further, in thermoplastics, the friction coefficient rapidly increases as the temperature rises, so that the surface pressure is large, and therefore it is not suitable when heat is easily held. Therefore, although plastics have come to be often used for light load parts, most heavy metals are still used for heavy load parts.

[Means for solving problems]

Melt-processable polyester (hereinafter abbreviated as "liquid crystalline polyester") capable of forming an anisotropic melt phase generally has not only a smaller linear expansion coefficient than other plastics but also smaller than aluminum. In addition, rigidity and mechanical strength such as tension, bending and compression are equal to or higher than metal in terms of specific strength, so it can also be used for high precision bearing retainers and bearings where only conventional metals could be used. However, the friction resistance and the limiting PV value are not so good, and it can be said that the self-lubricating property is excellent in plastics. Further, it has been found that it is not always sufficient for applications where self-lubricating property is required, and it is necessary to improve friction characteristics.

The present inventors have conducted intensive studies in view of the above problems, by blending a liquid crystal polyester with a lubricating substance as a main component, nylon 66 conventionally used for these parts, glass fiber reinforced polyester resin, The inventors have found that it is possible to manufacture heavy-duty parts, which have been somewhat difficult, even with materials conventionally called engineering plastics such as polyacetal resin, polyphenylene ether resin, and polycarbonate resin, and have completed the present invention.

That is, the present invention provides a lubricating composition containing a liquid crystalline polyester and a lubricating substance as main components.

The liquid crystalline polyester used in the present invention is a melt processable polyester and has a property that polymer molecular chains take a regular parallel arrangement in a molten state. The state in which the molecules are arranged in this manner is often called a liquid crystal state or a nematic phase of a liquid crystal substance. Made from such polymers, generally elongated, flat, fairly rigid along the long axis of the molecule, and having multiple chain extension bonds, usually in either coaxial or parallel relationship. To be done.

The properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using a crossed polarizer. More specifically, the confirmation of the anisotropic molten phase can be performed by using a Leitz polarization microscope and observing the sample placed on the Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. The polymer is optically anisotropic. That is, it transmits light when inspected between crossed polarizers. If the sample is optically anisotropic, polarized light will be transmitted even if it is stationary.

As the constituent component of the polymer forming the anisotropic molten phase as described above, one or more of aromatic dicarboxylic acid and alicyclic dicarboxylic acid is used. 1 of aromatic diol, alicyclic diol and aliphatic diol One or more Aromatic hydroxycarboxylic acids One or more Aromatic thiol carboxylic acids One or more Aromatic dithiols, aromatic thiol phenols 1
One or more of these include aromatic hydroxyamines, one or more of aromatic diamines, etc., and the polymer that forms the anisotropic melt phase consists only of polyester II) consisting of I) Polyester III) consisting of polyester IV) and polythiol ester consisting only of V) Polythiol ester consisting of V) VI) and polythiol ester VII) consisting of polyesteramide VIII) and a combination of polyesteramide consisting of Composed of.

Furthermore, although not included in the category of the combination of the above components,
Aromatic polyazomethine is contained in the polymer forming the anisotropic molten phase, and specific examples of such a polymer include poly (nitrilo-2-methyl-1,4-phenylenenitroethylidine-1,4-phenyleneethylene). Lysine); poly (nitrilo-2-methyl-1,4-phenylene nitrilomethylidine-1,4-phenylenemethylidine); and poly (nitrilo-2-chloro-1,4-phenylenenitromethylidine-
1,4-phenylenemethylidine).

Furthermore, although not included in the category of the combination of the above components,
Polyester carbonate is included as a polymer forming the anisotropic molten phase. It consists essentially of 4-oxybenzoyl units, dioxyphenyl units, dioxycarbonyl units and terephthaloyl units.

The compounds constituting the above-mentioned I) to VIII) are listed below.

Aromatic dicarboxylic acids include terephthalic acid and 4,4'-
Diphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenoxyethane-
4,4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenylether-3,3'-dicarboxylic acid, diphenoxyethane-3, Aromatic dicarboxylic acids such as 3'-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, naphthalene-1,6-dicarboxylic acid,
Or chloroterephthalic acid, dichloroterephthalic acid,
Examples thereof include alkyl, alkoxy or halogen substitution products of the above aromatic dicarboxylic acids such as bromoterephthalic acid, methyl terephthalic acid, dimethyl terephthalic acid, ethyl terephthalic acid, methoxy terephthalic acid and ethoxy terephthalic acid.

Examples of the alicyclic dicarboxylic acid include trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids or trans-1,4- ( 1-methyl) cyclohexanedicarboxylic acid, trans-1,4-
Examples thereof include alkyl-, alkoxy- or halogen-substituted products of the above alicyclic dicarboxylic acids such as (1-chloro) cyclohexanedicarboxylic acid.

Aromatic diols include hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxytriphenyl, 2,6-naphthalenediol, 4,4'-
Dihydroxydiphenyl ether, bis (4-hydroxyphenoxy) ethane, 3,3′-dihydroxydiphenyl, 3,3′-dihydroxydiphenyl ether, 1,6-naphthalenediol, 2,2-bis (4-hydroxyphenyl) propane, 2, 2-bis (4-hydroxyphenyl)
Aromatic diols such as methane, chlorohydroquinone, methylhydroquinone, 1-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone: 4-chlororesorcin,
Examples thereof include alkyl-, alkoxy- or halogen-substituted products of the above aromatic diols such as 4-methylresorcin.

As the alicyclic diol, trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol,
Trans-1,4-cyclohexanedimethanol, cis-
Alicyclic diols such as 1,4-cyclohexanedimethanol, trans-1,3-cyclohexanediol, cis-1,2-cyclohexanediol, trans-1,3-cyclohexanedimethanol, or trans-1,4- ( 1-
Methyl) cyclohexanediol, trans-1,4-
Examples thereof include alkyl-, alkoxy- or halogen-substituted compounds of the alicyclic diols such as (1-chloro) cyclohexanediol.

Aliphatic diols include ethylene glycol and 1,3-
Examples thereof include linear or branched aliphatic diols such as propanediol, 1,4-butanediol and neopetyl glycol.

As aromatic hydroxycarboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-
Aromatic hydroxycarboxylic acids such as 2-naphthoic acid and 6-hydroxy-1-naphthoic acid, or 3-methyl 4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4 -Hydroxybenzoic acid, 3
-Methoxy-4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, 6-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid, 3-chloro -4-Hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid, 3,5-dichloro-4-
Hydroxybenzoic acid, 2,5-dichloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 6-
Hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro-2-naphthoic acid, 6-hydroxy-
Examples thereof include alkyl, alkoxy or halogen-substituted aromatic hydroxycarboxylic acids such as 5,7-dichloro-2-naphthoic acid.

As the aromatic mercaptocarboxylic acid, 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-
Examples thereof include 2-naphthoic acid and 7-mercapto-2-naphthoic acid.

Examples of aromatic dithiols include benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, and 2,7-naphthalene-dithiol.

Examples of the aromatic mercaptophenol include 4-mercaptophenol, 3-mercaptophenol, 6-mercaptophenol and 7-mercaptophenol.

4- as aromatic hydroxy amine and aromatic diamine
Aminophenol, N-methyl-4-aminophenol, 1,4-phenylenediamine, N-methyl-1,4-phenylenediamine, N, N'-dimethyl-1,4-phenylenediamine, 3-aminophenol, 3 -Methyl-4-aminophenol, 2-chloro-4-aminophenol, 4
-Amino-1-naphthol, 4-amino-4'-hydroxydiphenyl, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxydiphenylmethane, 4-amino-4'-hydroxydiphenylsulfide, 4, 4'-diaminophenyl sulfide (thiodianiline), 4,4'-diaminodiphenyl sulfone,
2,5-diaminotoluene, 4,4′-ethylenedianiline,
4,4'-diaminodiphenoxyethane, 4,4'-diaminodiphenylmethane (methylenedianiline), 4,4'-diaminodiphenylether (oxydianiline) and the like can be mentioned.

The polymers I) to VIII) composed of the above components may or may not form an anisotropic melt phase depending on the composition ratio in the components, the polymer, and the sequence distribution, but they are used in the present invention. The polymers are limited to those forming an anisotropic melt phase among the above polymers.

Polyesters of I), II), III) and V which are polymers forming an anisotropic melt phase suitable for use in the present invention.
The polyesteramide of III) can be produced by various ester forming methods that allow organic monomer compounds having functional groups that form the required repeating units by condensation to react with each other. For example, the functional groups of these organic monomer compounds may be carboxylic acid groups, hydroxyl groups, ester groups, acyloxy groups, acid halides, amine groups and the like. The organic monomer compound can be reacted by a molten acidolysis method without the presence of a heat exchange fluid. In this method, the monomers are first heated together to form a molten solution of the reactants. As the reaction continues, solid polymer particles become suspended in the liquid.
Volatile by-products of the final stage of condensation (eg acetic acid or water)
A vacuum may be applied to facilitate removal of the.

A slurry polymerization method can also be adopted to form a safe aromatic polyester suitable for use in the present invention. In this way, the solid product is obtained in suspension in the heat exchange medium.

Whichever of the above-mentioned molten acidolysis method and slurry polymerization method is adopted, the organic monomer reactant that induces a wholly aromatic polyester is in a modified form in which the hydroxyl group of such a monomer is esterified at room temperature (ie It can be subjected to the reaction (as an acyl ester). The lower acyl group preferably has about 2 to 4 carbon atoms. Preferably, the acetic acid ester of such an organic monomer reactant is subjected to the reaction.

Further, as typical examples of the catalyst that can be used with caution in either the molten acidolysis method or the slurry method, dialkyltin oxide (eg, dibutyltin oxide), diaryltin oxide, titanium dioxide, achimonium trioxide, alkoxytitanium silicate, titanium. Alkoxides, alkali and alkaline earth metal salts of carboxylic acids (eg zinc acetate),
Gaseous acid catalysts such as Lewis (eg, BF ₃ ) and hydrogen halide (eg, HC1) can be used. The amount of catalyst used is generally about 0.001 to 1% by weight, especially about 0.01 to 0.2% by weight, based on the total weight of the monomers.

The wholly aromatic polymers suitable for use in the present invention tend to be substantially insoluble in common solvents and therefore unsuitable for solution processing. However, as already mentioned, these polymers can be easily processed by conventional melt processing methods. Particularly preferred wholly aromatic polymers are somewhat soluble in pentafluorophenol.

The wholly aromatic polyesters suitable for use in the present invention generally have a weight average molecular weight of about 2,000 to 200,000, preferably about
It is 10,000 to 50,000, particularly preferably about 20,000 to 25,000. On the other hand, suitable wholly aromatic polyesteramides generally have a molecular weight of about 5,000 to 50,000, preferably about 10,000 to 30,
000, for example 15,000 to 17,000. The measurement of such a molecular weight can be carried out by a standard measurement method which does not involve solution formation of gel permeation chromatography and other polymers, for example, by quantifying an end group by infrared spectroscopy on a compression molded film. The molecular weight can also be measured by using a pentafluorophenol solution and using a light scattering method.

The above fully aromatic polyesters and polyesteramides also have an inherent viscosity (IV) of at least about 2.0 dl / g, for example about 2.0 to 10.0 dl / g when dissolved in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C. Is generally indicated.

The polymer exhibiting an anisotropic melt phase used in the present invention is preferably an aromatic polyester and an aromatic polyesteramide, and also preferably a polyester partially containing the aromatic polyester and the aromatic polyesteramide in the same molecular chain. Polyester partially contained in is also a preferred example.

Preferred examples of compounds constituting them are 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene and 1,4
-Naphthalene compounds such as dihydroxynaphthalene and 6-hydroxy-2-naphthoic acid, biphenyl compounds such as 4,4'-diphenyldicarboxylic acid and 4,4'-dihydroxybiphenyl, the following general formulas (I), (II) or ( III)
Compound represented by: (However, X: alkylene (C _{1 to} C ₄ ), alkylidene, -O
-, - SO -, - SO 2 -, - S -, - group Y :-( CH ₂ selected from _{CO-) n- (n = 1~4)} , - O (CH 2) n O- (n =
Groups selected from 1 to 4)) p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol, p-phenylenediamine and the like para-substituted benzene compounds and their nucleus-substituted benzene compounds (the substituents are chlorine, It is selected from bromine, methyl, phenyl, 1-phenylethyl), isophthalic acid, resorcin, and other meta-substituted benzene compounds.

A preferable example of the polyester partially containing the above-mentioned constituents in the same molecular chain is polyalkylene terephthalate, and the alkyl group has 2 to 4 carbon atoms.

Among the above-mentioned constituents, a compound containing one or more kinds of compounds selected from naphthalene compounds, biphenyl compounds and para-substituted benzene compounds as essential constituents is a further preferable example. Of the p-position-substituted benzene compounds, p-hydroxybenzoic acid, methylhydroquinone and 1-phenylethylhydroquinone are particularly preferable examples.

The following are exemplified as specific combinations of constituent components.

Wherein Z is-C1, a substituent -Br, selected from -CH _3,
X is alkylene (C ₁ ~C _4), alkylidene, -O -, -
_{SO -, - SO 2 -,} - S -, - it is a substituent selected from CO-.

Particularly preferred anisotropic melt phase forming polyesters for use in the present invention include repeating units containing naphthalene moieties such as 6-hydroxy-2-naphthoyl, 2,6-dihydroxynaphthalene and 2,6-dicarboxynaphthalene. It is contained in an amount of about 10 mol% or more. Preferred polyesteramides are those containing repeating units of the above-mentioned naphthalene moieties and moieties consisting of 4-aminophenol or 1,4-phenylenediamine. Specifically, it is as follows.

(1) A polyester consisting essentially of the following repeating units I and II.

This polyester contains about 10-90 mole% of Unit I and about 10-90.
It contains mol% of unit II. In one aspect unit I is about
It is present up to an amount of 65 to 85 mol%, preferably about 70 to 80 mol% (eg about 75 mol%). In another embodiment, the units II are present in much lower concentrations of about 15-35 mol%, preferably about 20-30 mol%. Further, at least some of the hydrogen atoms bonded to the ring are optionally selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and combinations thereof. It may be substituted with a selected substituent.

(2) A polyester consisting essentially of the following repeating units I, II and III.

This polyester contains about 30 to 70 mol% of Unit I. The polyester is preferably about 40-60 mol%
Unit I, about 20 to 30 mol% of unit II, and about 20 to 30 mol% of unit III. Moreover, at least a part of the hydrogen atoms bonded to the ring may have 1 to 4 carbon atoms.
May be substituted with a substituent selected from the group consisting of an alkyl group, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and combinations thereof.

(3) A polyester consisting essentially of the following repeating units I, II, III and IV: (In the formula, R means methyl, chloro, bromo or a combination thereof, and is a substituent for a hydrogen atom on the aromatic ring), and the unit I is about 20 to 60 mol%,
II in amounts of about 5 to 18 mol%, unit III in amounts of about 5 to 35 mol%, and unit IV in amounts of about 20 to 40 mol%. The polyester is preferably about 35-45 mole% of Unit I, about 10
Containing ~ 15 mol% Unit II, about 15-25 mol% Unit III, and about 25-35 mol% Unit IV. However, unit II
The total molarity of and III is substantially equal to the molarity of unit IV. In addition, at least a part of the hydrogen atoms bonded to the ring may be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof. It may be substituted with a substituent selected from This wholly aromatic polyester has 0.3w of pentafluorophenol at 60 ℃.
at least 2.0 dl / g when dissolved at a concentration of / v% eg
Logarithmic viscosities of 2.0 to 10.0 dl / g are generally indicated.

(4) A polyester consisting essentially of the following repeating units I, II, III and IV: III General formula O-Ar-O (wherein Ar is at least 1
A dioxyaryl unit having four aromatic rings), IV a general formula (Wherein Ar ′ means a divalent group containing at least one aromatic ring), and the unit I is about 20 to 40 mol% and the unit II is 10 mol%. Above 50 mol%, unit III above 5 mol% and below about 30 mol% and unit IV above 5 mol%,
It is contained in an amount of about 30 mol% or less. This polyester is
Preferably, about 20-30 mol% (eg, about 25 mol%) of unit I, about 25-40 mol% (eg, about 35 mol%) of unit II, about 15
~ 25 mol% (eg, about 20 mol%) of unit III, and about 15
Contains ~ 25 mol% (eg, about 20 mol%) of unit IV. In addition, at least a part of the hydrogen atoms bonded to the ring may be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof. It may be substituted with a substituent selected from

Units III and IV have symmetrically arranged divalent bonds on one or more aromatic rings that connect these units to other units on either side within the polymer backbone (eg, on a naphthalene ring). When present, they are preferably symmetrical with respect to each other in the para position or arranged on a diagonal ring). However, asymmetric units such as those derived from resorcinol and isophthalic acid can also be used.

Preferred dioxyaryl units III are And a preferred dicarboxyaryl unit IV is Is.

(5) A polyester consisting essentially of the following repeating units I, II and III: II A dioxyaryl unit represented by the general formula O-Ar-O (wherein Ar represents a divalent group containing at least one aromatic ring), III General formula (Wherein Ar ′ means a divalent group containing at least one aromatic ring), and a unit I of about 10 to 90 mol% and a unit II of about 5 to
45 mol%, containing unit III in an amount of 5-45 mol%. The polyester preferably contains about 20-80 mol% Unit I, about 10-40 mol% Unit II, and about 10-40 mol% Unit III. More preferably, the polyester comprises about 60-80 mol% units I, about 10-20 mol% units.
II, and about 10-20 mol% of unit III. In addition, at least a part of the hydrogen atoms bonded to the ring may be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof. It may be substituted with a substituent selected from

Preferred dioxyaryl units II are And a preferred dicarboxyaryl unit III is Is.

(6) Polyesteramide consisting essentially of the following repeating units I, II, III and IV: II General formula (In the formula, A means a divalent group containing at least one aromatic ring or a divalent trans-cyclohexane group), III General formula Y-Ar-Z (wherein Ar is at least 1)
A divalent group containing one aromatic ring, Y means O, NH or NR, Z means NH or NR, respectively, and R means an alkyl group having 1 to 6 carbon atoms or an aryl group), IV in general Formula O-Ar'-O (wherein Ar 'means a divalent group containing at least one aromatic ring), and contains about 10 to 90 mol% of the unit I and about 5 units of the unit II.
~ 45 mol%, unit III about 5-45 mol%, and unit VI
In an amount of about 0 to 40 mol%. In addition, at least a part of the hydrogen atoms bonded to the ring may be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof. It may be substituted with a substituent selected from

Preferred dicarboxyaryl units II are And the preferred unit III is And a preferred dioxyaryl unit IV is Is.

Further, the polymer forming the anisotropic molten phase of the present invention,
A part of one polymer chain is composed of the polymer segment forming the anisotropic melt phase described above, and the remaining part is composed of the thermoplastic resin segment not forming the anisotropic melt phase. Polymers are also included.

The above-mentioned liquid crystalline polyester is a high-strength material in combination with the self-reinforcing effect, and has a small linear expansion coefficient and a small molding shrinkage ratio, so that there is little dimensional deviation. It has low melt viscosity and good flowability, but it can withstand high temperatures of 180-200 ℃. It has good chemical resistance, weather resistance, and hot water resistance, is chemically extremely inert, and at the same time does not affect other substances.

As the lubricating substance used in the present invention, those having a decomposition temperature of 270 ° C. or higher, which is generally difficult to decompose at the melt processing temperature of the liquid crystalline polyester used in the present invention, are preferable. Also, it is preferable that the viscosity is high to some extent.

Specifically, paraffin oil such as spindle oil, refrigerating machine oil, dynamo oil, turbine oil, machine oil, cylinder oil, gear oil, aviation piston engine lubricating oil, naphthenic mineral oil and grease, hydrocarbon, ester, polyglycol, A wide range of polyphenyl ether, silicone, halocarbon synthetic oils, etc. can be selected.

In addition, paraffin wax, low molecular weight polyolefin wax such as polyethylene wax, hydrocarbon type,
Fatty acid type, fatty acid amide type, fatty acid ester type, metal soap, aliphatic alcohol, polyhydric alcohol, polyglycol, polyglycerol, ester of fatty acid and polyhydric alcohol, ester of fatty acid and polyglycol or polyglycerol, dimethyl poly Wax-like or solid substances such as siloxane (so-called silicone wax) can be included in the selection target.

In addition, the following substances can be used alone or in combination with the above substances.

(1) Saturated fatty acids Capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, etc.

(1) Unsaturated fatty acid linthenic acid, tudzuic acid, phytocetrainic acid, myristoleic acid, zomarinic acid, petroselinic acid, oleic acid
Elaidic acid, gadoleic acid, gondoic acid, whale oil acid, erucic acid, brassic acid, serragoleic acid, krillic acid,
Ximenic acid, linoleic acid, linoelysinic acid.

(3) Fatty acid ester Saturated fatty acid such as butyric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, lignoceric acid, cerotic acid, montanic acid, mericinic acid, or the like. Methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl of unsaturated fatty acids such as petroselinic acid, oleic acid, elaidic acid, linoleic acid, linoleic acid, araxidic acid, brassic acid, erucic acid and ricinoleic acid, heptyl,
Esters such as octyl, decyl, cosyl, contyl, oleyl alcohol, glycerin and sorbitan.

Further, dibasic fatty acid ester and the like are also preferable.

(4) fatty acid amide octyl amide, decyl amide, lauryl amide, myristyl amide, palmityl amide, stearyl amide,
Eicosylamide, docosylamide, ethylenebisstearic acid amide, methylenebisstearic acid amide, ethylenebis-3- (3,5-tert-butyl-4-hydroxyphenol) propanamide and the like.

(5) Metal soaps Stearic acid, oleic acid, palmitic acid, laurate, etc. and metals such as Na, Li, Be, Mg, Ca, Sr, Cu, Z
n, Cd, Al, Ce, Ti, Zr, Pb, Cr, Mn, Co, Ni, Fe, H
Soap with g, Ag, Tl and Sn (6) Higher alcohols Higher alcohols such as octyl, lauryl, cetyl, stearyl and oleyl.

The compounding amount of the lubricating substance is 1 to 30 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the liquid crystalline polyester.

As described above, the lubricating substance may be added alone or as a mixture of several types. In addition, a combination of these lubricating substances and other substances such as activated carbon and graphite, which have a high adsorption and occlusion property, or a substance which is compatible with the lubricating substance used, such as silicone oil, can be used. It is convenient to mix it with the rubber and then mix it with the liquid crystalline polyester, since it also has the function of retaining the lubricating substance, and can prevent excessive bleeding.

In order to further improve the strength performance of the composition of the present invention, various inorganic fillers may be added depending on the purpose. Examples of the inorganic substance include substances added to general thermoplastic resins and thermosetting resins, that is, general inorganic fibers such as glass fiber, carbon fiber, metal fiber, ceramic fiber, boron fiber, potassium titanate fiber, and asbestos. , Calcium carbonate, highly dispersible silicates, alumina,
Aluminum hydroxide, talc, clay, mica, glass flakes, glass powder, glass beads, quartz powder, silica sand,
Wollastonite, various metal powders, carbon black,
Barium sulfate, powdered substances such as calcined gypsum and silicon carbide,
Inorganic compounds such as alumina, boron nitrite, silicon nitride, and the like, and plate-like inorganic compounds, whiskers, metal whiskers, and the like are included.

These inorganic fillers may be used alone or in combination of two or more. In particular, it is preferable to use a conductive filler such as carbon fiber because it has an antistatic effect, improves the limit PV value, and does not wear the mating material such as glass fiber.

In addition, it is preferable to use a plate-shaped or powder-shaped material having a large surface area such as a powder as the above-mentioned filler, and to mix it after allowing the lubricating substance to soak into it, because it has a reinforcing effect and a retaining effect of the lubricating substance at the same time. .

The larger the amount of these fillers mixed, the better the strength,
From the viewpoint of moldability and the like, it is preferably 70% by weight or less based on the entire mixture with the resin.

In addition, the composition of the present invention is usually used together with a lubricating substance such as molybdenum disulfide, graphite, tungsten disulfide, a polymer substance, for example, a fluorine resin, which has been conventionally used for the purpose of reducing the friction coefficient. be able to.
Further, known substances added to general thermoplastic resins and thermosetting resins, that is, stabilizers such as plasticizers, antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments. Further, a lubricant for improving fluidity and difficulty, a crystallization accelerator (nucleating agent) and the like can be appropriately used depending on the required performance.

The production of gears, bearings, sliding parts and the like from the composition of the present invention can be easily carried out by molding the composition of the present invention by a conventional injection molding method conventionally used for molding plastics.

〔The invention's effect〕

As described above, the liquid crystalline polyester has excellent moldability and mechanical strength, but its frictional properties are not always sufficient depending on the application. By configuring as in the present invention, excellent moldability and mechanical properties are not impaired, frictional properties are remarkably improved, excellent shape stability is exhibited, a linear expansion coefficient is small, and heat is generated during use. Even if it is possible to obtain a composition having substantially no dimensional error, high-performance practical gears and bearings that could not be obtained with conventional plastics, so-called engineering plastics compositions or thermosetting resin compositions, It became possible to make sliding parts.

That is, the characteristics of the composition of the present invention are as shown in 1 of FIG.
The point is that the dynamic friction coefficient does not change due to the surface pressure. On the other hand, in FIG. 1C, for comparison, changes in dynamic friction coefficient of oil-containing phenolic resin, which is commonly used, are also shown. The dynamic friction coefficient changes irregularly due to surface pressure. I understand. Further, as shown in the examples described later, it is understood that the limiting PV value is greatly improved by blending the lubricating substance, and can be sufficiently used for heavy loads.

It is believed that such properties of liquid crystalline polyesters are due to the fact that the molecular or crystalline alignment is significantly different from other engineering plastics.

〔Example〕

The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 and Comparative Examples 1 and 2 70 parts by weight of a liquid crystalline polyester A having a weight average molecular weight of 20,000 (details described later), 30 parts by weight of wollastonite, and 5 parts by weight of silicone oil for lubricating were uniformly mixed to form pellets. Then, the relationship between the dynamic friction coefficient and the surface pressure was measured. The results are shown as 1 in FIG. 1 as Example 1. The coefficient of friction is measured with a steel using a Suzuki type friction and wear tester. For comparison, the same measurement results for a phenol resin containing 5 parts by weight of silicone oil are also shown as Comparative Example 1 in FIG. Further, the limiting PV value of the test piece composed of the composition of Example 1 was measured and shown in 2 of FIG. In the same figure, a composition having the composition obtained by removing 5 parts by weight of the lubricating silicone oil from the above composition is shown as Comparative Example 2 in 4.

After leaving a test piece of the composition of the present invention at 80 ° C. for 5 days,
The surface was observed, but no stickiness on the surface due to the lubricating substance was observed.

Examples 2 to 5 Instead of the liquid crystalline polyester A, the liquid crystalline polyester B,
A flat plate was prepared in the same manner as in Example 1 except that C, D and E (details described later) were used, and the dynamic friction coefficient was measured at a surface pressure of 10 kg / cm ^2. B; 0.016, C; 0.020, D 0.018, E, 0.021
Met.

The liquid crystalline polyesters A, B, C, D and E used had the following constitutional units.

A specific method for producing the liquid crystalline polyesters A, B, C, D and E will be described below.

<Liquid Crystal Polyester A> 4-acetoxybenzoic acid 1261 parts by weight, 6-acetoxy-
691 parts by weight of 2-naphthoic acid was charged into a reactor equipped with a stirrer, a nitrogen introducing tube and a distilling tube, and the mixture was heated to 250 ° C under a nitrogen stream. While distilling acetic acid from the reactor, the mixture was vigorously stirred at 250 ° C. for 3 hours and then at 280 ° C. for 2 hours. Furthermore, after raising the temperature to 320 ° C and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced and after 20 minutes the pressure was reduced to 0.1 m.
The pressure was lowered to mHg, and the mixture was stirred at this temperature and pressure for 1 hour.

The polymer obtained had an inherent viscosity of 5.4 measured in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C.

<Liquid Crystalline Polyester B> 1081 parts by weight of 4-acetoxybenzoic acid, 489 parts by weight of 2,6-diacetoxynaphthalene, and 332 parts by weight of terephthalic acid were charged into a reactor equipped with a stirrer, a nitrogen introducing pipe and a distilling pipe. ,
The mixture was heated to 250 ° C under a stream of nitrogen. While distilling acetic acid from the reactor, at 250 ° C for 2 hours, then at 280 ° C.
Stir vigorously for 2.5 hours. Furthermore, after raising the temperature to 320 ° C and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced and after 30 minutes the pressure was lowered to 0.2 mmHg, and at this temperature and pressure 1.5
Stir for hours.

The polymer obtained had an inherent viscosity of 2.5, measured in pentafluorophenol at a concentration of 0.1% by weight and at 60 ° C.

<Liquid Crystal Polyester C> 4-acetoxybenzoic acid 1081 parts by weight, 6-acetoxy-
2-naphthoic acid 460 parts by weight, isophthalic acid 166 parts by weight, 1,
194 parts by weight of 4-diacetoxybenzene was charged into a reactor equipped with a stirrer, a nitrogen introducing tube and a distilling tube, and the mixture was heated to 260 ° C under a nitrogen stream. While distilling acetic acid from the reactor, the mixture was vigorously stirred at 260 ° C. for 2.5 hours and then at 280 ° C. for 3 hours. Furthermore, after raising the temperature to 320 ° C. and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced and after 15 minutes the pressure was lowered to 0.1 mmHg, and stirring was carried out at this temperature and pressure for 1 hour.

The resulting polymer had an inherent viscosity of 5.0 as measured in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C.

<Liquid-Crystalline Polyester D> 1612 parts by weight of 6-acetoxy-2-naphthoic acid, 290 parts by weight of 4-acetoxyacetanilide, 249 parts by weight of terephthalic acid, 0.4 parts by weight of sodium acetate are provided with a stirrer, a nitrogen introducing pipe and a distilling pipe. The reactor was charged and the mixture was heated to 250 ° C. under a stream of nitrogen. While distilling acetic acid from the reactor, the mixture was vigorously stirred at 250 ° C. for 1 hour and then at 300 ° C. for 3 hours. Furthermore, after raising the temperature to 340 ° C. and stopping the introduction of nitrogen, the pressure in the reactor was gradually reduced and the pressure was reduced to 0 after 30 minutes.
It was lowered to 2 mmHg and stirred at this temperature and pressure for 30 minutes.

The polymer obtained had an inherent viscosity of 3.9 as measured in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C.

<Liquid Crystalline Polyester E> 768 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.62 and 1080 parts by weight of p-acetoxybenzoic acid were charged into a reactor equipped with a stirrer, a nitrogen introducing pipe and a distilling pipe, and 240 ° C under a nitrogen stream. Heated to. Raise the temperature to 275 ° C over 1 hour,
Stir vigorously for 1 hour. Next, after the introduction of nitrogen was stopped, the pressure inside the reactor was gradually reduced and after 30 minutes the pressure was reduced to 0.4 mmHg.
And further stirred for 4 hours.

The polymer obtained had an inherent viscosity of 0.66 as measured in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between surface pressure and dynamic friction coefficient. FIG. 2 is a graph showing the limit PV value. 1, 2 ... Composition of Example 1 ... Composition of Comparative Example 1 4 ... Composition of Comparative Example 2

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/101 KJV 7242-4J 5/20 KJY C08L 67/00 LPH C10M 107/00 9159-4H 107 / 32 9159-4H // (C08L 67/00 23:00 91:06 83:04) (C10M 107/00 107: 32 107: 50)

Claims (3)

[Claims] 1. A melt-processable polyester capable of forming an anisotropic melt phase and paraffinic mineral oil, naphthene mineral oil, polyglycol synthetic oil, silicone synthetic oil, halocarbon synthetic oil, paraffin wax, low molecular weight A main component is one or more lubricating substances selected from the group consisting of polyolefin wax, saturated fatty acid, unsaturated fatty acid, fatty acid ester, fatty acid amide, metal soap, higher alcohol and silicone wax. And a resin composition. 2. The resin composition according to claim 1, wherein the lubricating substance has a decomposition temperature of 270 ° C. or higher. 3. A blending amount of a lubricating substance is 1 with respect to 100 parts by weight of melt-processable polyester capable of forming an anisotropic molten phase.
The resin composition according to claim 1 or 2, which is -30 parts by weight.