KR910006133B1 - Lubricating composition - Google Patents

Abstract

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Description

Lubricity composition

1 is a graph showing the relationship between surface pressure and dynamic friction coefficient.

2 is a graph showing a threshold PV value.

* Explanation of symbols for main parts of the drawings

1, 2: composition of Example 1 3: composition of Comparative Example 1

4: composition of Comparative Example 2

The present invention relates to a lubricating composition suitably used in the manufacture of gears, bearings, sliding parts and the like.

Recently, metal parts have been replaced by plastic parts in all of you. In general, plastics can be molded by injection and the same parts can be produced in large quantities with high accuracy but have lower strength than metals and have a higher coefficient of thermal expansion, resulting in large temperature dependence of dimensions, making them unsuitable for precision bearing retainers or bearing manufacture Do. In addition, thermoplastic resins exhibit very high coefficients of friction at high temperatures, resulting in high surface pressure, and thus are not suitable for applications that generate heat. Thus, although plastics have been frequently used in the manufacture of low load components, metals are still used in the manufacture of most high load components.

Melt-processabel polyesters, which can form anisotropic molten phases (hereinafter abbreviated as liquid crystalline polyesters), have lower coefficients of linear expansion than aluminum, as well as other plastics, and are better mechanical than metals in terms of their specific strengths. Strength, for example stiffness, flexural or compressive strength. Therefore, such polyesters are believed to be useful in the manufacture of high precision bearing retainers or bearings which have been made of metals until now. However, although such polyesters exhibit excellent abrasion resistance, which is believed to be due to the mechanical properties, they do not always exhibit sufficient coefficients of kinetic friction and critical PV values for use in applications requiring self-lubrication even in plastics. Does not. Therefore, the frictional properties of molten eutectic polyesters that can form anisotropic molten phases must be further refined to use them in such applications.

The inventors of the present invention have studied in view of the above problems, and until now such parts made of engineering plastics such as nylon 66, fibrous glass-reinforced polyester resin, polyacetal resin, polyphenylene ether resin or polycarbonate resin have been Although somewhat problematic, it has been found that high load parts can be made of a mixture of liquid crystalline polyester and lubricant. The present invention has been completed based on this finding.

The present invention provides a lubricating composition composed of a liquid crystalline polyester and a lubricant as main components.

The lubricity composition of the present invention comprises (1) 100 parts by weight of polyester which is capable of forming an anisotropic phase in the molten state and is melt processable, and (2) 1 to 30 parts by weight of lubricant.

Lubricants include paraffin oil, naphthenic oil, synthetic oils, waxes, hydrocarbons, fatty acids, fatty acid amides, fatty acid esters, metal soaps, aliphatic alcohols, polyhydric alcohols, polyglycols, polyglycerols, esters between fatty acids and polyglycols or polyglycerols, and Silicone waxes are preferably included.

The liquid crystal polyester used in the present invention is characterized by melting processability and its molecular chain is regularly arranged in parallel in the molten state. Such arranged molecules are sometimes called liquid crystal states or pneumatic phases of liquid crystal materials. Such polymers are made from monomers that are thin and flat and have relatively high stiffness along the major axis of the molecule and generally have multiple chained bonds, each coaxial or parallel to each other, and inherent.

The properties of the anisotropic molten phase can be confirmed by conventional deflection methods using cross polarizers. In particular, anisotropic molten phase can be identified by observing a sample placed on the Leitz hot stage in a nitrogen atmosphere with a 40-fold Leitz polarization microscope. The polymer is optically anisotropic. That is, light is conducted when the polymer sample is tested between the crossholers. If the sample is optically anisotropic, the polarization must be conducted even at rest.

Examples of components constituting the polymer capable of forming an anisotropic molten phase include (1) one or more aromatic dicarboxylic acids and / or cycloaliphatic dicarboxylic acids, (2) one or more aromatic diols, cycloaliphatic diols, and And / or aliphatic diols, ③ one or more aromatic hydroxy carboxylic acids, ④ one or more aromatic diol carboxylic acids, ⑤ one or more aromatic dithiols and / or aromatic thiol phenols and ⑥ one or more aromatic hydroxides Examples of polymers that include hydroxylamines and / or aromatic diamines and the like, which can form an anisotropic molten phase are as follows. I) Polyester consisting of components ① and ②, II) Polyester consisting only of component ③, III) Polyester consisting of components ①, ② and ③, Polythiol consisting only of component ④, V) into components ① and ⑤ Polythiol ester consisting of VI, polythiol ester consisting of components ①, ④ and ⑤, polyesteramide consisting of VII) components ①, ③ and ⑥, polyesteramide consisting of components III, ②, ③ and ⑥, and The polymer capable of forming an anisotropic melt phase can be aromatic polyazo methane even if it does not fall within this category. Examples thereof include poly (nitrilo-2-methyl-1,4-phenylene nitriloethylidine-1,4-phenyleneethylidine); Poly (nitrilo-2-methyl-1,4-phenylene nitrilomethylidine-1,4-phenylenemethylidine) and poly (nitrilo-2-chloro-1,4-phenylene nitrilomethylidine- 1,4-phenylenemethylidine).

In addition, the polymer capable of forming an anisotropic molten phase may be a polyester carbonate even if it does not fall within this category. Such polyester carbonates may consist essentially of 4-oxybenzoyl, dioxyphenyl, dioxycarbonyl and terephthaloyl units.

Examples of components constituting polymers I) to VIII) are now described.

Examples of aromatic dicarboxylic acids include terephthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid, 2,6-naphthalene dicarboxylic acid, diphenyl ether-4, 4'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid Acids, isophthalic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenoxyethane-3,3'-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid and naphthalene- Aromatic dicarboxylic acids such as 1,6-dicarboxylic acid and their alkyl-, alkoxyl- and Halogen substituted derivatives are included.

Examples of cycloaliphatic dicarboxylic acids include alicyclic dicarboxylic acids such as trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid. Acids and their alkyl-, alkoxy- and halogen substituted derivatives such as trans-1,4- (1-methyl) -cyclohexane dicarboxylic acid and trans-1,4- (1-chloro) -cyclohexanedicarboxylic acid Included.

Examples of aromatic diols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxytriphenyl, 2,6-naphthalenediol, 4,4'-dihydroxydi Phenyl ether, bis (4-hydroxyphenoxy) ethane, 3,3'-dihydroxydiphenyl, 3,3'-dihydroxydiphenyl ether, 1,6-naphthalenediol, 2,2-bis ( Aromatic diols such as 4-hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl) methane with chlorohydroquinone, methylhydroquinone, 1-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4- Alkyl-, alkoxy-, halogen-substituted derivatives thereof such as chlororesorcinol and 4-methylresorcinol are included.

Examples of cycloaliphatic diols include trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexanedimethanol, cis-1,4-cyclohexane dimethanol, trans- Alicyclic diols such as 1,3-cyclohexanediol, cis-1,2-cyclohexanediol and trans-1,3-cyclohexanedimethanol and trans-1,4- (1-methyl) cyclohexanediol and trans Alkyl-, alkoxy- and halogen-substituted derivatives thereof such as -1,4- (1-chloro) cyclohexanediol and the like.

Aliphatic diols may be straight or branched chains and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol and neopentylglycol.

Examples of aromatic hydroxy carboxylic acids include aromatic hydroxy carboxylic acids such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and 6-hydroxy-1-naphthoic acid and 3- Methyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 2,6-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-hydroxy Hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro-2-naphthoic acid and 6-hydroxy-5,7 Alkyl-, alkoxy- and halogen-substituted derivatives thereof such as -dichloro-2-naphthoic acid.

Examples of aromatic mercapto carboxylic acids include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-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 aromatic mercapto phenols include 4-mercaptophenol, 3-mercaptophenol, 6-mapcaptophenol and 7-mecaptophenol.

Examples of aromatic hydroxylamines and aromatic diamines include 4-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-nattol, 4-amino-4'-hydroxy Difetyl, 4-amino-4'-hydroxydiphenylether, 4-amino-4'-hydroxydiphenylmethane, 4-amino-4'-hydroxydiphenylsulphide, 4,4'-diamino Phenyl sulfide (thiodianiline), 4,4'-diaminodiphenylsulfone, 2,5-diaminotoluene, 4,4'-ethylenedianiline, 4,4'-diaminodiphenoxyethane, 4 , 4'-diaminodiphenylmethane (methylenedianiline) and 4 / 4'-diaminodiphenyl ether (oxydianiline).

It does not form any anisotropic molten phase depending on the kind, proportion or sequence distribution of some of the components of the polymers I) to VIII) consisting of the several components. The polymers used in the present invention are therefore limited only to those which can form anisotropic melt phases among the polymers I) to VIII).

The polyesters I), II) and III) and polyester amide VIII), which are preferably used in the present invention as a polymer capable of forming an anisotropic molten phase, have a functional group capable of forming certain repeating units by condensation. It can be prepared from various organic monomers by various esterification processes. For example, the functional groups of these organic monomers may be carboxy, hydroxy, ester, acryloxy, acryl halides or amino groups. The monomer can be reacted according to the melt acid decomposition process in the absence of all heat exchange fluids. According to this treatment, the monomer mixture is heated to obtain a melt. The reaction proceeds to cause the polymer to suspend the solid particles of the polymer in the liquid, so that the volatiles generated (eg acetic acid or water) are removed in the final stage of condensation. This removal can easily be carried out in vacuo.

On the other hand, the wholly aromatic polyester which is preferably used in the present invention may be prepared by a slurry polymerization process. According to this process, the solid product can be obtained in a suspended state in a heat exchange medium.

According to either of the two processes, an organic monomer capable of forming a wholly aromatic polyester can be used in the reaction in the form of a modification in which the hydroxyl group is esterified (ie as a lower acyl ester). Lower acyl groups preferably have 2 to 4 carbon atoms.

Representative examples of catalysts used in the melt acid decomposition process and the slurry process include dialkyl tin oxide (eg, dibutyltin oxide), diaryltin oxide, titanium dioxide, antimony trioxide, alkoxytitanium silicate, titanium alkoxylated, and carbon Gas acid catalysts such as alkali and alkaline earth metal salts of acids (eg zinc acetate), Lewis acid (eg BF ₃ ), and hydrogen halides (eg HCl) are included. The amount of catalyst used is about 0.001 to 1% by weight, preferably about 0.01 to 0.2% by weight, based on the total amount of monomers used.

The wholly aromatic polymers preferably used in the present invention are generally insoluble in organic solvents and are therefore not suitable for solution processes. However, as described above, the polymer can be easily processed by conventional melting processes. Preferred examples of wholly aromatic polymers are those that are somewhat soluble in pentafluorophenols.

Fully aromatic polyesters preferably used in the present invention have a weight average molecular weight of about 2,000 to 200,000, preferably about 10,000 to 50,000 and particularly preferably about 20,000 to 25,000, while the preferred fully aromatic polyesters used in the present invention Amides 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. Determination of these molecular weights can be carried out by gel permeation chromatography or by other standard methods that do not involve the formation of polymer solutions, for example by means of testing the compression molded films of such polymers to end group content by infrared spectroscopy. . Instead, it can also be carried out by the light scattering method using such a polymer solution in pentafluorophenol.

Generally 0.1% (by weight) solution of the fully aromatic polyester or polyesteramide in pentafluorophenol has a logarithmic viscosity of at least about 2.0 dl / g, for example, about 2.0 to 10.0 dl / g at 60 ° C. (IV) is shown.

The polymer capable of forming the anisotropic molten phase used in the present invention is preferably an aromatic polyester or an aromatic polyesteramide. Moreover, the polyester which partially contains the aromatic polyester unit and aromatic polyesteramide used for the molecular chain is also used preferably for this invention.

Preferred examples of components constituting the polymer include naphthalenes such as 2,6-naphthalene dicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene and 6-hydroxy-2-naphthoic acid. derivative; Biphenyl compounds such as 4,4'-diphenyldicarboxylic acid and 4,4'-dihydroxybiphenyl; The compounds represented by the following formulas (I), (II) and (III);

[Where X represents a group selected from an alkylene group having 1 to 4 carbon atoms, an alkylidene group, -O-, -SO-, -SO _2- , -S- and -CO-, and Y represents-(CH ₂ ) _n And -O (CH ₂ ) _n O-, where n is 1-4.] P- such as p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol and p-phenylenediamine Substituted benzene derivatives and their derivatives substituted in their rings, wherein the substituents are selected from chlorine, bromine, methyl, phenyl and 1-phenylethyl, and m-substituted benzene derivatives such as isophthalic acid and resorcinol Included.

Preferred examples of polyesters which partially contain the component in the molecular chain are polyalkylene terephthalates in which the alkyl group has 2 to 4 carbon atoms.

Particularly preferred examples include those containing as main components one or more compounds selected from the group consisting of naphthalene compounds, biphenyl compounds and p-substituted benzene derivatives. Among the p-substituted benzene derivatives, p-hydroxybenzoic acid, methyl hydroquinone and 1-phenylethylhydroquinone are particularly preferred.

Examples of special combinations of components are as follows.

Wherein Z is a substituent selected from -Cl, -Br and -CH ₃ and X is alkylene, alkylidene, -O-, -SO-, -SO ₂ , -S- and -CO having from 1 to 4 carbon atoms Selected substituent.

Preferred examples of polyesters capable of forming anisotropic molten phases used in the present invention are naphthalene constituents such as 6-hydroxy-2-naphthoyl, 2,6-dihydroxy naphthalene or 2,6-dicarboxynaphthalene. While those containing at least 10 mole% of the repeating units containing the above, preferred examples of the polyesteramide are those containing the repeating units constituting the naphthalene structure and 4-aminophenol or 1,4-phenylenediamine. .

Preferred examples of polyesters and polyesteramides are now described.

및

로 대략 이루어지는 폴리에스테르.(1) next repeat unit

And

Polyester which consists of approximately.

와 약 10 내지 90몰%의 단위

로 이루어진다. 폴리에스테르의 구체예에 따르면 단위

은 약 65 내지 85몰%, 바람직하게는 약 70 내지 80몰%(예를 들면, 약 75몰%)의 양으로 내포되는 반면, 또다른 구체예에 따르면 단위

는 약 15 내지 35몰%, 바람직하게는 약 20 내지 30몰%의 매우 소량으로 내포된다. 또 고리에 결합된 하나 또는 그 이상의 수소원자는 1 내지 4탄소원자를 지니는 알킬기, 1 내지 4탄소원자를 지니는 알콕시기, 할로겐원자, 페닐기, 치환페닐기 및 그들의 조합으로 이루어지는 군으로부터 선택된 치환기로 치환될 수 있다.This polyester has a unit of about 10 to 90 mole percent

And from about 10 to 90 mole percent of units

Is made of. According to an embodiment of the polyester unit

Is contained in an amount of about 65 to 85 mole%, preferably about 70 to 80 mole% (eg, about 75 mole%), while in another embodiment the unit

Is contained in very small amounts of about 15 to 35 mole percent, preferably about 20 to 30 mole percent. One or more hydrogen atoms bonded to the ring may be substituted with a substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, phenyl groups, substituted phenyl groups, and combinations thereof. .

,

및

으로 대략 이루어지는 폴리에스테르.(2) next repeating unit

,

And

Polyester which consists of approximately.

을 내포한다. 그것은 약 40 내지 60몰%의 단위

, 약 20 내지 30몰%의 단위

및 약 20 내지 30몰%의 단위

으로 바람직하게 이루어진다. 또 고리에 결합된 하나 또는 그 이상의 수소원자는 1 내지 4탄소원자를 지니는 알킬기, 1 내지 4탄소원자를 지니는 알콕시기, 할로겐원자, 페닐기, 치환페닐기 및 그들의 조합으로 이루어지는 군으로부터 선택된 치환기와 치환될 수 있다.This polyester comprises about 30 to 70 mole percent of units

Implies It is a unit of about 40 to 60 mole percent

, About 20 to 30 mole percent of units

And about 20 to 30 mole percent of units

It is preferably made. One or more hydrogen atoms bonded to the ring may be substituted with a substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, phenyl groups, substituted phenyl groups, and combinations thereof. .

,

,

및

로 대략 이루어지는 폴리에스테르.(3) next repeating unit

,

,

And

Polyester which consists of approximately.

In the above, R is a substituent for substituting a hydrogen atom of the aromatic ring and represents methyl, chloro or bromo or a combination thereof.

, 약 5 내지 18몰%의 단위

, 약 5 내지 35몰%의 단위

및 약 20 내지 40몰%의 단위

으로 이루어지며, 그것은 바람직하게는 단위

의 몰%와 단위

의 몰%와의 총량이 단위

의 몰%와 대략 비슷하다는 조건으로 약 35 내지 45몰%의 단위

, 약 10 내지 15몰%단위

, 약 15 내지 25몰%단위

및 약 25 내지 35몰%단위

로 이루어진다. 또 고리에 결합된 하나 또는 그 이상의 수소원자가 1 내지 4탄소원자를 지니는 알킬기, 1 내지 4탄소원자를 지니는 알콕시기, 할로겐원자, 페닐기, 치환페닐기 및 그들의 조합으로 이루어지는 군으로부터 선택된 치환기와 치환될 수 있다. 펜타플루오로페놀에서 이 완전 방향족 폴리에스테르의 0.3%(w/v)용액은 일반적으로 60℃에서 적어도 2.0dl/g, 예를 들면 2.0 내지 10.0dl/g의 대수점도를 나타낸다.This polyester has a unit of about 20 to 60 mole percent

About 5-18 mole%

, About 5 to 35 mole percent of units

And from about 20 to 40 mole percent of units

Consisting of, preferably it is a unit

Molar% and units

Molar percentage of the unit

Units of about 35 to 45 mole percent, provided that they are approximately equal to mole percent of

About 10 to 15 mole%

About 15-25 mole%

And about 25 to 35 mole% units

Is made of. One or more hydrogen atoms bonded to the ring may be substituted with a substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, phenyl groups, substituted phenyl groups, and combinations thereof. The 0.3% (w / v) solution of this fully aromatic polyester in pentafluorophenols generally exhibits an algebraic viscosity of at least 2.0 dl / g, for example 2.0 to 10.0 dl / g, at 60 ° C.

및

로 대략 이루어지는 폴리에스테르.(4) Next repeating unit ①, ⑪,

And

Polyester which consists of approximately.

다음 일반식으로 표시된 디옥시아릴단위 :

여기서, Ar은 적어도 하나의 방향족 고리를 내포하는 이가기를 나타내고,

다음 일반식으로 표시된 디카르복시아릴단위 :

여기서, Ar'은 적어도 하나의 방향족 고리를 내포하는 이가기를 나타낸다.

Dioxyaryl units represented by the following general formula:

Here, Ar represents a divalent group containing at least one aromatic ring,

Dicarboxyaryl units represented by the following general formula:

Here, Ar 'represents a divalent group containing at least one aromatic ring.

, 10몰%를 초과하는 약 50몰%를 넘지 않는 양의 단위

, 5몰%를 초과하나 약 30몰%를 넘지 않는 양의 단위

와 5몰%를 초과하나 약 30몰%를 넘지 않는 양의 단위

를 내포하며, 또 그것은 약 20 내지 30몰%(예를 들면, 약 25몰%) 단위①, 약 25 내지 40몰(예를 들면, 약 35몰%)단위

, 약 15 내지 25몰%(예를 들면, 약 20몰%) 단위

와 약 15 내지 25몰%(예를 들면, 약 20몰%)단위

로 바람직하게 이루어진다. 또 고리에 결합된 하나 또는 그 이상의 수소원자는 1 내지 4탄소원자를 지니는 알킬기, 1 내지 4탄소원자를 지니는 알콕시기, 할로겐원자, 페닐기, 치환페닐기 및 그의 조합으로 이루어지는 군으로부터 선택된 치환기와 치환될 수 있다.This polyester is in units of about 20 to 40 mole percent

Unit of quantity not exceeding about 50 mol%, exceeding 10 mol%

, Unit of quantity exceeding 5 mol% but not exceeding about 30 mol%

And units in amounts exceeding 5 mol% but not exceeding about 30 mol%

Containing about 20 to 30 mole% (eg, about 25 mole%) units, and about 25 to 40 mole (eg, about 35 mole%) units.

About 15 to 25 mole% (eg, about 20 mole%) units

And about 15 to 25 mole percent (eg, about 20 mole percent)

It is preferably made. One or more hydrogen atoms bonded to the ring may be substituted with a substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, phenyl groups, substituted phenyl groups, and combinations thereof. .

와

가 대칭적인 것이 바람직하며, 여기서 ＂대칭적＂이라는 의미는 중합체의 주쇄의 양측으로 다른 단위와 각기 연결되는 두 결합이 하나 또는 그 이상의 고리에 대칭적으로 내재하는 것(예를 들면, 결합이 나프탈렌 고리에 내재할 때 그것들은 각기 서로에 대한 상호 p-위치에 또는 맞은편 고리에 내재한다)을 뜻한다. 그러나 레소르시놀 또는 이소프탈산으로부터 유도된 것과 같은 비대칭단위로 사용될 수 있다.unit

Wow

Is symmetrical, where “symmetric” means that two bonds, each of which is linked to the other unit on either side of the polymer's main chain, are symmetrically inherent in one or more rings (eg, the bonds are naphthalene When inherent in rings, they are either in mutual p-positions to each other or in opposite rings). However, it can be used as asymmetric units such as those derived from resorcinol or isophthalic acid.

의 바람직한 실예는

이고 디카르복시아릴 단위

의 바람직한 실예는

이다.Deoxyaryl units

Preferred examples of

And dicarboxyaryl units

Preferred examples of

to be.

,

,

으로 대략 이루어지는 폴리에스테르.(5) next repeating unit

,

,

Polyester which consists of approximately.

다음 일반식으로 표시된 디옥시아릴단위

Deoxyaryl unit represented by the following general formula

Here, Ar represents a divalent group containing at least one aromatic ring.

다음 일반식으로 표시된 디카르복시아릴단위

Dicarboxyaryl units represented by the following general formula

Here, Ar 'represents a divalent group containing at least one aromatic ring.

, 5 내지 45몰% 단위

및 5 내지 45몰% 단위

로 이루어지며, 반면에 약 20 내지 80몰% 단위

, 약 10 내지 40몰% 단위

및 약 10 내지 40몰% 단위

로 바람직하게 이루어진다.This polyester is about 10 to 90 mole percent units

, 5 to 45 mole% units

And 5 to 45 mole percent units

Consisting of about 20 to 80 mole%

, About 10 to 40 mole% units

And about 10-40 mole% units

It is preferably made.

, 약 10 내지 20몰% 단위

및 약 10 내지 20몰% 단위

로 이루어지는 것이 더 바람직하다.Especially when it is about 60 to 80 mole percent units

, About 10 to 20 mole% units

And about 10-20 mole% units

More preferably, it consists of.

One or more hydrogen atoms bonded to the ring may be substituted with a substituent selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, phenyl groups, substituted phenyl groups, and combinations thereof.

의 바람직한 실예는

, 이고 디카르복시아릴 단위

의 바람직한 실예는

이다.Deoxyaryl units

Preferred examples of

, And dicarboxyaryl units

Preferred examples of

to be.

,

,

및

로 대략 이루어지는 폴리에스테르아미드 :(6) next repeating unit

,

,

And

Polyesteramide consisting roughly of:

다음 일반식으로 표시된 단위

Units represented by the following general formula

Here, A represents a divalent or divalent transcyclohexane group containing at least one aromatic ring.

다음 일반식으로 표시된 단위

Units represented by the following general formula

[-Y-Ar-Z-]

Wherein Ar is a divalent group containing at least one aromatic ring, Y represents O, NH or NR and Z represents NH or NR. (Where R represents an alkyl or aryl group having 1 to 6 carbon atoms)

다음 일반식으로 표시된 단위

Units represented by the following general formula

Here, Ar 'represents a divalent group containing at least one aromatic ring.

, 약 5 내지 45몰% 단위

, 약 5 내지 45몰% 단위

및 약 0 내지 40몰% 단위

로 이루어진다.This polyester amide is in the range of about 10 to 90 mole percent

, About 5 to 45 mole percent units

, About 5 to 45 mole percent units

And from about 0 to 40 mole percent units

Is made of.

One or more hydrogen atoms bonded to the ring may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a phenyl group, a substituted phenyl group, or a combination thereof. .

이 바람직한 실예는

이고, 단위

의 바람직한 실예는

또는

이며, 디옥시아릴단위

의 바람직한 실예는

이다.Dicarboxyl units

This preferred example is

, Unit

Preferred examples of

or

Deoxyaryl unit

Preferred examples of

to be.

In addition, a polymer capable of forming an anisotropic molten phase for use in the present invention is composed of segments of the polymer in which the polymer chains can form an anisotropic molten phase, the other of which is a thermoplastic resin which cannot form such a phase. It may be a polymer consisting of segments.

The liquid crystalline polyester is a high strength material in cooperation with its self-reinforcing effect and exhibits a low linear expansion coefficient and a small molding shrinkage factor, so that its dimensional distortion is small.

It is also resistant to high temperatures of 180-200 ° C. even though it shows good flowability because of its low melt viscosity. It also shows good resistance to chemicals, weather and hot water, which is chemically inert and has no effect on other substances.

The lubricant used in the present invention preferably has a decomposition temperature of 270 ° C. or higher so as not to be decomposed at the melting process temperature of the liquid crystal polymer. It is also desirable to have a somewhat high viscosity.

In particular, lubricants can be selected in a wide range, examples of which include paraffin and naphthalene mineral fibers such as spindle oil, refrigeration oil, dynamo milk, turbine oil, machine oil, cylinder oil, gear oil and lubricants for airplane piston engines; Synthetic oils such as oils and fats, hydrocarbons, esters, polyglycols, polyphenylethers, silicones and halocarbons.

Lubricants can also be selected from waxy solids, for example, low molecular weight polyolefin waxes such as paraffin waxes, polyethylene waxes, hydrocarbons, fatty acids, fatty acid amides, fatty acid esters, metal soaps, aliphatic alcohols, polyhydric alcohols, polyglycols, Polyglycerols, esters of polyhydric alcohols and fatty acids, polyglycol or esters of polyglycerols and fatty acids and dimethyl polysiloxanes (silicone waxes).

The following materials may also be used alone or in combination with the above.

(1) Saturated fatty acids: capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, lignoseric acid, sertric acid, montanic acid or meric acid.

(2) Unsaturated fatty acids: linderic acid, tzuzuic acid, phytocetoleic acid, myristoleic acid, jumaric acid, petroleic acid, oleic acid, elideic acid, gadoleic acid, gondonic acid, cetorelic acid, erucic acid, brasid Acids, ceracenic acid, taryric acid, cymenic acid, linoleic acid or linoleic acid.

(3) Fatty acid esters: saturated acids such as butyr, capro, enanth, capre, pelagon, undegano, lauric, myristic, palmitic, stearic, lignoser, serot, montan or mesiric acid or Unsaturated acids such as ferrocet, oleic, elide, linol, linolene, arachidonic, brasid, eruc or ricinolic acid and methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, decyl, kosyl, butyl or oleic Esters of monoalcohol, glycerin or sorbitan.

It can also be used as the basic fatty acid ester.

(4) Fatty acid amides: octylamide, decylamide, laurylamide, myristylamide, palmitylamide, stearylamide, eicosylamide, docosylamide, ethylene bisstearylamide, methylenebisstearylamide, ethylene- Bis-3- (3,5-t-butyl-4-hydroxyphenyl) propanamide.

(5) Metal Soap: Na, Li, Be, Mg, Ca, Sr, Cu, Zn, Cd, Al, Ce, Ti, Zr, Pb, Cr, Mn, Co, Ni, Fe, Hg, Ag, Ti, Soaps such as stearic acid, oleic acid, palmitic acid or lauric acid with Sn.

(6) higher alcohols: octyl, lautyl, cetyl, stearyl, oleyl alcohol and the like.

The amount of lubricant is 1 to 30 parts by weight, preferably 5 to 25 parts by weight, per 100 parts by weight of the liquid crystal polymer. The lubricant may be used alone or as a mixture of two or more thereof.

It may also be used in combination with other materials, such as those having high absorption, occluding powers, such as activated carbon or graphite, or compatible with lubricants.

For example, when the silicone oil is added to the liquid crystalline polyester together with the silicone rubber, the silicone oil can be more effectively retained in the polyester, which preferably prevents bleeding of the oil.

The composition according to the present invention can further contain various inorganic fillers according to the object to further improve the strength characteristics. Inorganic fillers can be any conventional one for thermoplastic or thermoset resins. Examples thereof include inorganic fibers such as glass, carbon, metal, ceramic, boron and potassium titanate fibers and asbestos; Powders such as calcium carbonate, highly dispersible silicate, alumina, aluminum hydroxide, talc, clay, mica, glass flakes, glass powder, glass beads, quartz powder, silica sand, wollastonite, various metal powders, carbon black, barium sulfate and calcined gypsum ; Inorganic particles or platelets such as silicon carbide, alumina, boron nitride and silicon nitride, whiskers and metal whiskers.

These inorganic fillers may be used alone or as a mixture of two or more thereof. In particular, the use of conductive fillers, such as carbon fibers, is antistatic and improves critical PV values and is effective, whereas glass fibers are effective in circumventing the abrasion problems of materials in contact with them.

In addition, the use of fillers with large surface areas (such as in the form of plates or powders) impregnated with lubricants is also very effective in reinforcing the composition and maintaining it as a lubricant in the composition.

The larger the amount of the filler, the more advantageous it is in terms of strength, but in terms of moldability and the like, it is preferably at most 70% by weight based on its mixture with the resin.

The composition according to the invention may further contain other lubricants commonly used for the purpose of lowering the coefficient of friction, for example molybdenum disulfide, graphite, tungsten disulfide or polymeric lubricants (such as fluoro-resins).

The compositions may also be known additives generally added to thermoplastic or thermosetting resins, for example plasticizers, stabilizers (such as antioxidants or UV absorbers), antistatic agents, flame retardants, colorants (such as dyes and pigments), flowable or mold release properties. Lubricant or crystal promoter (nucleating agent) for improving the viscosity can be suitably contained depending on the finished product.

The manufacture of gears, bearings or sliding parts made of the compositions of the invention can be carried out by conventional injection molding processes for plastics according to the known art.

As described above, the liquid crystalline polyester has excellent moldability and mechanical strength, but its friction characteristics are not always sufficient for all applications.

According to the present invention, a composition which exhibits greatly improved friction properties and excellent mold holding properties and has a small coefficient of linear expansion so that no dimensional distortion occurs even when heat is generated in the use thereof does not adversely affect the excellent moldability and mechanical strength. It can be obtained by combining a lubricant and liquid crystalline polyester. Therefore, high-performance practical gears, bearings or sliding parts which have not been made of conventional plastics or engineering plastics or thermosetting resin compositions up to now can be produced with the composition according to the present invention.

The composition according to the present invention is characterized in that the coefficient of kinetic friction does not change with surface pressure as indicated by the curve (1) of FIG. 1, whereas the coefficient of kinetic friction of frequently used oil-containing phenol resins is shown in FIG. As indicated by the curve 3, it changes irregularly with the surface pressure.

The composition also exhibits a critically improved critical PV value with the addition of lubricants, which can be used sufficiently for the manufacture of high load parts.

The above characteristics of liquid crystalline polyesters are presumed to be due to very different molecules or crystal arrangements than other engineering plastics.

[Example 1 and Comparative Examples 1 and 2]

70 parts by weight of the liquid crystal polyester having a weight average molecular weight of 20,000 described later in more detail, 30 parts by weight of wollastonite and 5 parts by weight of lubricating oil were uniformly mixed and granulated. The resulting pellets were molded into plates to test the relationship between the dynamic friction coefficient and the surface pressure.

The results are shown in curve 1 of Table 1, where the coefficient of kinetic friction was measured using Suzuki's wear tester and steel as the counter material. In Comparative Example 1, phenolic resin containing 5 parts by weight of silicone oil was tested by treating in a similar manner as described above. The result is shown by the curve 3 of FIG.

In addition, a test piece made of the composition of Example 1 was tested for a critical PV value, and the result is indicated by curve 2 in FIG. As Comparative Example 2, this experiment was repeated except that a test piece was prepared from the composition obtained by subtracting 5 parts by weight of lubricating silicone oil from the composition of Example 1. The result is shown by the curve 4 of FIG.

Test pieces made of the composition according to the invention were left at 80 ° C. for 5 days. The surface was observed, especially the surface tackiness due to the lubricant.

[Examples 2 to 4]

The plate was made of liquid crystal polyester B, C or D described in more detail in the same manner as described in Example 1 and tested for the coefficient of kinetic friction at a surface pressure of 10 kg / cm ² . The dynamic friction coefficients when using B, C or D were 0.016, 0.020 or 0.018, respectively.

The liquid crystal polyesters A, B, C and D each have the following structural units.

The process for producing the liquid crystalline polyesters A, B, C and D is described in more detail below.

[Liquid Crystal Polyester A]

1261 parts by weight of 4-acetoxybenzoic acid and 691 parts by weight of 6-acetoxy-2-naphthoic acid were fed to a reactor equipped with a stirrer, a nitrogen gas introduction tube, and a distillation tube. The contents were heated to 250 ° C. in a nitrogen atmosphere and the acetic acid was vigorously stirred at 250 ° C. for 3 hours and 280 ° C. for 2 hours with distillation from the reactor. The contents were heated to 320 ° C. After stopping the introduction of nitrogen, the internal pressure of the reactor was gradually reduced to 0.1 mm Hg over a 20 minute period. The contents were further stirred at this temperature under this pressure for 1 hour.

The polymer obtained had a 5.4 intrinsic viscosity as measured on pentafluorophenol at 60 ° C. with a concentration of 0.1% by weight.

[Liquid Crystal Polyester B]

1081 parts by weight of 4-acetoxybenzoic acid, 489 parts by weight of 2,6-diacetoxy naphthalene and 332 parts by weight of terephthalic acid were fed to a reactor equipped with a stirrer, a nitrogen gas introduction tube and a distillation tube. The contents were heated to 250 ° C. in a nitrogen atmosphere and stirred vigorously for 2 hours at 250 ° C. and 4 hours at 280 ° C. while distilling acetic acid from the reactor. The contents were heated to 320 ° C. After stopping the introduction of nitrogen, the internal pressure of the reactor was gradually reduced to 0.2 mmHg over a 30 minute period. The contents were further stirred at this temperature under this pressure for 1.5 hours.

The polymer obtained had a 2.5 intrinsic viscosity as measured on pentafluorophenol at 60 ° C. with a concentration of 0.1% by weight.

[Liquid Crystal Polyester C]

1081 parts by weight of 4-acetoxybenzoic acid, 460 parts by weight of 6-acetoxy-2-naphthoic acid, 166 parts by weight of isophthalic acid and 194 parts by weight of 1,4-diacetoxybenzene, equipped with a stirrer, nitrogen gas introduction pipe and distillation pipe. Fed to the reactor. The contents were heated to 260 ° C. in a nitrogen atmosphere and vigorously stirred for 2.5 hours at 260 ° C. and 3 hours at 280 ° C. while distilling acetic acid from the reactor. The contents were heated to 320 ° C. After stopping the introduction of nitrogen the internal pressure of the reactor was gradually reduced to 0.1 mm Hg over a 15 minute period. The contents were further stirred at this temperature under this pressure for 1 hour.

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

[Liquid Crystal 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 and 0.4 parts by weight of sodium acetate were fed to a reactor equipped with a stirrer, a nitrogen gas introduction tube and a distillation tube. The contents were heated to 250 ° C. in a nitrogen atmosphere and the acetic acid was stirred vigorously for 1 hour at 250 ° C. and 3 hours at 300 ° C. with distillation from the reactor. The contents were heated to 340 ° C. After introducing nitrogen, the internal pressure of the reactor was gradually reduced to 0.2 mm Hg over a 30 minute period. The contents were further stirred at this temperature under this pressure for 30 minutes.

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

Claims (3)

(1) A lubricating composition, characterized in that it can form an anisotropic phase in a molten state and comprises 100 parts by weight of polyester, which is melt processable, and (2) 1 to 30 parts by weight of a lubricant. The lubricity composition of claim 1, wherein the lubricant has a decomposition temperature of 270 ° C or higher. The method of claim 1 or 2, wherein the lubricant is paraffin oil, naphthenic oil, synthetic oil, wax, hydrocarbon, fatty acid, fatty acid amide, fatty acid ester, metal soap, aliphatic alcohol, polyhydric alcohol, polyglycol, polyglycerol, A lubricity composition, characterized in that it is selected from fatty acids and esters between polyglycols or polyglycerols and silicone waxes.

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