JP2000053849A - Liquid crystal polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition improved in low weld strength, surface separation due to fibrillation, warpage due to the anisotropy of shrinkage, etc., by mixing a thermotropic liquid crystal polymer with a thermoplastic polyester elastomer in a specified ratio. SOLUTION: This composition contains 0.5-40 wt.% thermoplastic polyester elastomer. The thermoplastic polyester elastomer used is the one in which the structural units derived from a dicarboxylic acid at least partially comprise structural units derived from a long-chain-alkyl-component-containing 30C or higher dicarboxylic acid, for example, dimer acid. The structural units derived from a dicarboxylic acid other than dimer acid are desirably ones derived from an aromatic dicarboxylic acid. The structural units derived from a diol are ones derived from an aliphatic diol. The amount of the 30C or higher dicarboxylic acid used is usually 0.1-30 mol.% based on the dicarboxylic acid structural units.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION Thermotropic liquid crystal polymer (hereinafter sometimes referred to as "LCP") compositions have low weld strength, surface fibrillated peeling,
In many cases, warpage or the like due to anisotropy of the shrinkage ratio becomes a problem, and the present invention relates to a thermotropic liquid crystal polymer composition in which these points are improved.

[0002]

2. Description of the Related Art A wide variety of engineering plastics have been put on the market. Resins having excellent heat resistance and mechanical strength are widely used in electric and electronic parts, automobile parts, precision machine parts, etc. according to their characteristics. ing. However, the demand for higher performance is increasing, and various materials are being studied. Among them, the thermotropic liquid crystal polymer composed of particularly rigid molecular chains is
It is known that it has a low apparent viscosity at the time of injection molding, good injection moldability, and excellent mechanical properties, chemical resistance, heat resistance, nonflammability, low outgas pollution, and the like.

[0003] LCP exhibits a high degree of orientation under shear stress, and solidifies rapidly due to low latent heat. And
Such properties appear as drawbacks such as low weld strength, surface fibrillation peeling, and warpage due to anisotropy in shrinkage, and as a result, may limit the degree of freedom in designing molded products. .

In recent years, an epoxy resin, which is a thermosetting resin used as a resin material for encapsulating elements in fields such as electricity, electronics, and optics, has been replaced with a thermoplastic LCP.
There is a great demand for replacement. The production of sealed parts
Usually, the device is placed in a cavity of a mold, and molten LCP is injected and injected from an injection molding machine into a remaining space. However, in many cases, the pressure required for injection injection and mold filling (hereinafter, sometimes referred to as “filling pressure”) is high, so that the element is deformed, damaged, disconnected, etc., and product defects are caused. May occur. In order to avoid this, it is necessary to lower the filling pressure of LCP. In addition, since a high filling pressure is an obstacle in the production of a thin molded product of LCP, a favorable effect can be obtained also in thin molding by lowering the filling pressure.

[0005] Many of the drawbacks of LCP as described above are LC
Due to the anisotropy of P, various methods for relaxing the anisotropy have been conventionally studied. For example, although the anisotropy is reduced by filling with glass fiber or an inorganic filler, the effect cannot be obtained unless several tens% of the filler is used in this method. Therefore, in injection molding, LCP
The inherent characteristic of low apparent viscosity during injection molding is not maintained, resulting in sacrificing processability. Further, in extrusion molding, it is practically difficult to incorporate a filler such as glass fiber in the case of a film or a fiber which occupies a large part of the extruded product, and therefore, it often shows insufficient performance in practical use. As another method, a method of blending various polymers with LCP has been studied. However, the compatibility problem and the reduction in processability caused by a compatibilizer used for the purpose of improving the compatibility are mainly considered. Due to the problems described above, satisfactory results have not always been obtained.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problems such as low weld strength inherent to LCP, fibrillation peeling of the surface, and warpage caused by anisotropy of shrinkage. An object of the present invention is to provide a thermotropic liquid crystal polymer composition that can be used as a sealing material for devices in fields such as electricity, electronics, and optics.

[0007]

The present invention is characterized in that a polyester-based thermoplastic elastomer is blended with a thermotropic liquid crystal polymer, and that a terpene derivative is further contained as required. That is, the first aspect of the present invention relates to a thermotropic liquid crystal polymer composition containing 0.5 to 40% by weight of a polyester thermoplastic elastomer. A second aspect of the present invention is the first aspect of the present invention, wherein the structural unit derived from the dicarboxylic acid component in the polyester of the polyester-based thermoplastic elastomer is derived from an aromatic dicarboxylic acid and a hydrogenated dimer acid, and a diol component. The present invention relates to a thermotropic liquid crystal polymer composition wherein the structural unit derived from is derived from any of ethylene glycol, 1,4-butanediol and 1,4-cyclohexanediol. A third aspect of the present invention is the second aspect of the present invention, wherein the structural unit derived from the dicarboxylic acid component in the polyester is derived from terephthalic acid containing 0.1 to 30 mol% of hydrogenated dimer acid, The present invention relates to a thermotropic liquid crystal polymer composition in which a structural unit derived from a diol component is derived from 1,4-butanediol. The fourth aspect of the present invention is the second aspect of the present invention.
In a third aspect, the present invention relates to a thermotropic liquid crystal polymer composition, wherein the hydrogenated dimer acid has a structure represented by the following formula [I], [II] or [III].

Embedded image A fifth aspect of the present invention relates to the thermotropic liquid crystal polymer composition according to any one of the first to fourth aspects of the present invention, which contains 0.5 to 10% by weight of a terpene resin. Hereinafter, the present invention will be further described.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The thermotropic liquid crystal polymer used in the present invention is a polymer which exhibits optical anisotropy in a molten state. As described above, a polymer that exhibits optical anisotropy at the time of melting has a property that polymer molecular chains take a regular parallel arrangement in a molten state. The fact that the melt phase exhibits optical anisotropy can be confirmed by a normal polarization inspection method using an orthogonal polarizer. A general polymer becomes isotropic in a molten state, but when it shows anisotropy in a melting process, it changes from a solid phase to an isotropic phase through an anisotropic liquid crystal phase in a certain temperature range. In addition, mechanical anisotropy can be confirmed. That is, it is confirmed by the fact that the surface of the molded product is remarkably exfoliated and fibrillated when injection molding is performed, and the difference in physical properties between the direction of flow of the resin and the direction perpendicular thereto is large. Thermotropic liquid crystal polymers are generally made from monomers that are elongated, flat, rigid along the long chain of the molecule, and have multiple coaxial or parallel chain extension bonds.

The above-mentioned thermotropic liquid crystal polymer includes, for example, liquid crystalline polyester, liquid crystalline polyesterimide, etc., and more specifically, (whole) aromatic polyester, polyester amide, polyester carbonate and the like. Preferred is a liquid crystalline polyester, which is included in the category of polyester as long as it contains a plurality of ester bonds in the molecule. Preferred polyesters are aromatic polyesters.

In the thermotropic liquid crystal polymer used in the present invention, a part of one polymer chain is composed of a polymer segment forming an anisotropic molten phase, and the remaining part does not form an anisotropic molten phase. Also included are polymers composed of polymer segments. Further, a composite of a plurality of thermotropic liquid crystal polymers is also included.

Representative examples of the monomers constituting the thermotropic liquid crystal polyester include (a) at least one kind of aromatic dicarboxylic acid, (b) at least one kind of aromatic hydroxycarboxylic acid compound, and (c) aromatic diol. At least one of (d) (d ₁ ) aromatic dithiol, (d ₂ ) aromatic thiophenol and (d ₃ ) aromatic thiol carboxylic acid compound,
And (e) at least one of aromatic hydroxylamine and aromatic diamine compounds. These may be composed solely, but many are (a) and (c); (a) and (d); (a), (b) and (c); (a), (b) and (E); or (a),
(B), (c) and (e).

The aromatic dicarboxylic acid compound (a) includes terephthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,4- Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl ether-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-3,3'-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, 1,6
Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, or chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, dimethylterephthalic acid, ethylterephthalic acid, methoxyterephthalic acid,
Alkyl, alkoxy or halogen substituents of the above aromatic dicarboxylic acids represented by ethoxy terephthalic acid and the like.

(B) Examples of the aromatic hydroxycarboxylic acid compound include aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and 6-hydroxy-1-naphthoic acid. Carboxylic 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, 2-chloro-4-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid 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-5,7
And alkyl-, alkoxy-, or halogen-substituted aromatic hydroxycarboxylic acids such as -dichloro-2-naphthoic acid.

(C) As the aromatic diol, 4,4′-
Dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 4,4′-dihydroxyterphenyl, hydroquinone, resorcin, 2,6-naphthalenediol,
4'-dihydroxydiphenyl ether, bis (4-hydroxyphenoxy) ethane, 3,3'-dihydroxydiphenyl ether, 1,6-naphthalenediol, 2,2-
Bis (4-hydroxyphenyl) propane, aromatic diol such as bis (4-hydroxyphenyl) methane, or chlorohydroquinone, methylhydroquinone, tert-
Butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-
Alkyl, alkoxy or halogen-substituted aromatic diols such as chlororesorcin and 4-methylresorcin.

(D ₁ ) Examples of the aromatic dithiol include benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, and 2,7-naphthalene-dithiol. (D ₂ ) Examples of the aromatic thiophenol include 4-mercaptophenol, 3-mercaptophenol, and 6-mercaptophenol. (D ₃ ) Examples of the aromatic thiolcarboxylic acid include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid, and 7-mercapto-2-naphthoic acid.

(E) As the aromatic hydroxylamine or aromatic diamine compound, 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-naphthol, 4-amino- 4'-hydroxybiphenyl, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxydiphenylmethane, 4-amino-4'-hydroxydiphenyl sulfide, 4,4'-diaminophenyl sulfide (thiodianiline), , 4'-Diaminodiphenyl sulfone, 2,
5-diaminotoluene, 4,4′-ethylenedianiline,
4,4'-diaminodiphenoxyethane, 4,4'-diaminodiphenylmethane (methylene dianiline), 4,4'-
And diaminodiphenyl ether (oxydianiline).

The thermotropic liquid crystal polyester used in the present invention can be produced from the above monomers by various ester forming methods such as a melt acidification method and a slurry polymerization method. Suitable thermotropic liquid crystal polyesters for use in the present invention have a molecular weight of about 2,000 to
200,000, preferably about 10,000-100,0
00. The value of the molecular weight can be determined, for example, by measuring end groups of the compressed film by infrared spectroscopy. GP, which is a general measurement method performed in a solution state
C can also be used.

Of the thermotropic liquid crystal polymers obtained from these monomers, an aromatic polyester which is a (co) polymer containing a monomer unit represented by the following general formula [IV] as an essential component is preferable. It is preferable that the above monomer unit contains about 5 mol% or more.

[0019]

Embedded image

A particularly preferred aromatic polyester for use in the present invention is a compound represented by the following general formula [V] having a repeating unit having a structure derived respectively from three compounds of p-hydroxybenzoic acid, phthalic acid and dihydroxybiphenyl.
Is a polyester represented by In this polyester, part or all of the repeating units having a structure derived from dihydroxybiphenyl can be replaced with repeating units derived from dihydroxybenzene.
Further, a polyester represented by the following general formula [VI] having a repeating unit having a structure derived from two kinds of compounds, p-hydroxybenzoic acid and hydroxynaphthalenecarboxylic acid, is also preferably used.

[0021]

Embedded image

Embedded image

In the present invention, polyester-based thermoplastic elastomers to be added to the thermotropic liquid crystal polymer can be classified into the following two types from the viewpoint of a macroscopic structure. Any of these may be used alone or in combination with the LCP. First, PET (polyethylene terephthalate), PBT (polybutylene terephthalate), P
In a polyester of an aromatic dicarboxylic acid and an aliphatic diol such as CT (polycyclohexane dimethylene terephthalate) and PEN (polyethylene naphthalate), at least a part of the structural units derived from the dicarboxylic acid contains a long-chain alkyl component. And a structural unit derived from a dicarboxylic acid having 30 or more carbon atoms, for example, dimer acid. That is, in the polyester structure, the polyester contains a dicarboxylic acid structural unit derived from dimer acid as at least a part of the structural unit derived from dicarboxylic acid. The structural unit derived from a dicarboxylic acid other than dimer acid is preferably derived from an aromatic dicarboxylic acid such as terephthalic acid or naphthalenedicarboxylic acid. The structural unit derived from diol is ethylene glycol, 1,4-
It is derived from an aliphatic diol such as butanediol and 1,4-cyclohexanediol.

A typical dimer acid used here is a dicarboxylic acid having 36 carbon atoms, which is obtained by thermally polymerizing a purified vegetable unsaturated fatty acid obtained from a dry oil such as tall oil or a semi-dry oil. It can be obtained by By changing the raw materials, the presence or absence of a catalyst and the type, reaction conditions, separation conditions after the reaction, etc., when used, the structure varies greatly depending on the combination of various reactions such as polymerization, cyclization, isomerization, etc. A dimer acid is obtained. Preferably, a further hydrogenated dimer acid is used. In the present invention, a dimer acid having any structure can be used. Representative structures of hydrogenated dimer acids include:
Three types of long-chain carboxylic acids of linear aliphatic type, alicyclic type and aromatic type as shown in the above formulas [I], [II] and [III] are exemplified. Specific hydrogenated dimer acids include, for example, “PRIPOL 100” manufactured by Unichema.
8 "(trade name; C36, aromatic type: alicyclic type: linear aliphatic type, mol% ratio = 9: 54: 37, dimer acid);
"PRIPOL 1009" (trade name; C36, aromatic type: alicyclic type: straight-chain aliphatic type mole% ratio = 13: 6)
4:23 dimer acid) and their ester derivatives, such as “PRIPLAST 300, which is the dimethyl ester of the dimer acid of PRIPOL 1008 described above.
8 "(product name). These can be condensed alone or in combination with other dicarboxylic acids. As the dimer acid used in the present invention, for example, Harima Chemicals Co., Ltd. comprising a mixture represented by the following formula
"Haridimer 300" (trade name).

[0024]

Embedded image

When the carbon number of the long-chain alkyl component is 3
The amount of 0 or more dicarboxylic acids used, for example, dimer acid,
The amount is 0.1 to 30 mol%, preferably 1 to 20 mol%, more preferably 3 to 10 mol%, based on the total number of moles of the structural units corresponding to the dicarboxylic acid of the polyester elastomer.

As a specific example, a polyester elastomer produced by mixing dimer acids as described above alone or in a mixture as described above in the above ratio when producing PBT from dimethyl terephthalate and 1,4-butanediol as raw materials. Is mentioned. These are disclosed in JP-A-5-515.
No. 20, JP-A-5-117512, JP-A-5-117512
No. 171015, JP-A-5-214219,
JP-A-5-295240, JP-A-6-73277
And Japanese Patent Application Laid-Open No. 8-217965. Commercially available hydrogenated dimer acid-containing thermoplastic elastomers include “PO 2120” and “PO 2121” manufactured by Kanebo Gosen Co., Ltd.
(Both are trade names). In addition, the polyester-based thermoplastic elastomer obtained by copolymerizing such a dimer acid reduces the required filling pressure at the time of injection molding by improving the fluidity of the thermotropic liquid crystal resin. It also has the effect of avoiding damage to members.

The second polyester-based thermoplastic elastomer is a thermoplastic elastomer composed of a block polyester copolymer of a hard segment and a soft segment because of its macroscopic structure. The hard segment is a block copolymer having a crystalline polyester structure, and the soft segment is a block copolymer having a polyether structure or an amorphous polyester structure. Examples of the structure constituting the hard segment include a polyester structure of an aromatic dicarboxylic acid and an aliphatic diol corresponding to PET, PBT, PEN, PCT and the like. Examples of the structure constituting the soft segment include a polyether structure corresponding to polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like. These can be easily obtained from the market, for example, “Thermoplastic Elastomer” (1991-2-15) Kagaku Kogyo Nippo p. 184-20
7 The structure is described in, for example,
M. Walker, C.W. P. Rader, “Handbook of Thermoplastic
Elastomers (second edition) ”(1988) Van Nostrand
Reinhold, New York, p. 181-223 (Chapter 6); R. Legge, G. Holden, H.C. E. "Ther" edited by Schroeder
moplastic Elastomers "(1987) Hanser, New York, p.
163-196 (Chapter 8).

The first thermoplastic elastomer has a random structure in which soft segments exist uniformly and finely, and the second thermoplastic elastomer has a block structure in which soft segments exist locally. It is believed that there is.

The amount of the polyester-based thermoplastic elastomer is from 0.5 to 40% by weight, preferably from 3 to 20% by weight, based on the whole composition. If the amount is less than 0.5% by weight, the effect of the present invention cannot be sufficiently exhibited, and if it exceeds 40% by weight, mechanical properties and the like are significantly reduced.

The effects of improving low weld strength, surface fibrillation peeling, and warpage caused by anisotropy of shrinkage, which are the objects of the present invention, are the effects of the block structure of the two types of thermoplastic polyester elastomers. Those having a random structure are better than those having the above, and a great effect can be obtained particularly by using a hydrogenated dimer acid-containing thermoplastic elastomer.

It is not clear why polyester-based elastomers having a random structure, particularly thermoplastic elastomers containing hydrogenated dimer acid, exhibit excellent effects.
However, it is considered that the factor for improving the above problem of the thermotropic liquid crystal polymer is mainly the interaction between the soft segment portion existing in the polyester-based thermoplastic elastomer molecule and the thermotropic liquid crystal polymer molecule. Therefore, the hydrogenated dimer acid-containing thermoplastic elastomer having a random structure in which the soft segments are uniformly and finely dispersed is more uniform and broader than one having a block structure in which the soft segments are locally present. In order to be able to exert an interaction,
It is considered that the effect of improving the properties of CP is great.

A thermotropic liquid crystal resin composition which can be used as a sealing material for elements in fields such as electric, electronic and optical fields, or a thermotropic liquid crystal resin composition material which can obtain a thin molded product by low pressure molding. In order to provide this, a low molecular weight polyester-based thermoplastic elastomer may be used. In order to further improve this property, it is effective to add a terpene resin.

The terpene resin used in the present invention is a homopolymer of a terpene compound or a copolymer of a terpene compound and a polar monomer such as an aromatic vinyl monomer, a phenol compound or an unsaturated carboxylic acid. Wherein the main component is a polymer composed of 3 to 20 monomer molecules. These polymers are obtained, for example, by reacting a terpene compound with an aromatic vinyl monomer, a phenolic compound, an unsaturated carboxylic acid or a mixture thereof in an organic solvent in the presence of a Friedel-Crafts type catalyst. Can be Further, hydrogenated products of these polymers can also be used. In addition, in the case of a copolymer of a terpene compound and an unsaturated carboxylic acid, an effect of improving adhesion to a metal can be obtained in addition to the above effects.

Examples of the terpene compound include α-pinene, β-pinene, limonene, α-terpinene, β-terpinene, γ-terpinene, dipentene and the like.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, and vinyl toluene. Examples of the phenol compound include phenol, cresol, and bisphenol A. Examples of unsaturated carboxylic acids include α, β-unsaturated carboxylic acids and anhydrides thereof, such as maleic anhydride.

As the terpene resin thus obtained, for example, “YS Resin PX”, “YS Resin TO”, “YS Resin T” from Yashara Chemical Co., Ltd.
Products having trade names such as “R”, “Cloarin”, “YS Polystar”, “Mighty Ace”, “YP-90”, and “TM-60” are commercially available and can be easily obtained.

A petroleum resin having an alicyclic structure, obtained by hydrogenating an aromatic ring of a C ₉ petroleum resin, has a structure similar to a so-called terpene resin, and is expected to have the same effect. . Thus, the terpene resin used in the present invention also include hydrogenated C ₉ petroleum resin. Examples of such a petroleum resin include “Alcon P” (trade name, fully hydrogenated product) and “Alcon M” (trade name, partially hydrogenated) which are alicyclic saturated hydrocarbon resins manufactured by Arakawa Chemical Co., Ltd. Goods) can be obtained.

The amount of the terpene resin used in the present invention is 0.5 to 10% by weight, preferably 1 to 3% by weight, based on the whole composition. If it is less than 0.5% by weight,
The effect of lowering the filling pressure is poor, and if the amount exceeds 10% by weight, the mechanical properties and the like are significantly reduced.

The composition of the present invention may further contain another resin. The other resin to be blended may be any of a thermoplastic resin and a thermosetting resin, preferably a polyamide resin, a polycarbonate resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyphenylene sulfide resin,
So-called thermoplastic engineering plastics such as polyethersulfone resin, polysulfone resin, polyetherketone resin, and polyetheretherketone resin are exemplified. The blending amount of the other thermoplastic resin is
1 to 200 parts by weight per 100 parts by weight of the LCP of the present invention,
Preferably 1 to 100 parts by weight, more preferably 1 to 5 parts
0 parts by weight.

Further, a reinforcing agent or a filler can be added to the resin composition of the present invention in order to further improve heat resistance and mechanical properties. Specific examples of reinforcing agents or fillers include fibrous materials, powdery and granular materials, and mixtures thereof. As the fibrous reinforcing agent or filler, glass fiber, Shirasu glass fiber, alumina fiber,
Examples include inorganic fibers such as silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, and metal fibers (for example, stainless steel fibers) and carbon fibers. In addition, wollastonite,
Silicates such as sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, alumina, silicon oxide, metal oxides such as magnesium oxide, zirconium oxide, titanium oxide, calcium carbonate, magnesium carbonate, dolomite, etc. Carbonate, calcium sulfate, calcium pyrosulfate, sulfate such as barium sulfate, glass beads, boron nitride, silicon carbide, Saroyan and the like, and these may be hollow. As hollow, for example, hollow glass fiber,
Glass microballoons, shirasu balloons, carbon balloons and the like can be mentioned. The reinforcing agent may be used after being subjected to a preliminary treatment with a silane-based or titanium-based coupling agent, if necessary. Up to 80% by weight, preferably 7% by weight, based on the total composition of the composition,
0% by weight or less can be blended.

Further, the resin composition of the present invention includes an antioxidant, a heat stabilizer, an ultraviolet absorber, a bone and a release agent, a dye (eg, nitrosine), and a pigment (eg, cadmium sulfide, phthalocyanine, Carbon black, etc.)
Ordinary additives such as a coloring agent, a flame retardant, a plasticizer, and an antistatic agent containing the same can be added to impart predetermined characteristics. Examples of the heat stabilizer include hindered phenol, hydroquinone, phosphites, and substituted products thereof. As the ultraviolet absorber, for example, resorcinol, salicylate, benzotriazole, benzophenone and the like are used. Nitrosine or the like can be added as a dye, and cadmium sulfide, phthalocyanine, carbon black, or the like can be added as a pigment.

The method for producing the composition of the present invention is not particularly limited, and it can be carried out by a conventionally known method. For example, a method in which each component is heated and melted at a predetermined ratio using an extruder and mixed, and a method in which a terpene-based resin is mixed in the process of melt-synthesizing LCP, and the like can be mentioned. In the present invention, a method of melt-kneading with an extruder is particularly preferred because it is simple and can be uniformly mixed. As a device for performing the melt kneading, a Banbury mixer, a static mixer roller, a kneader, or the like can be used continuously or batchwise, but it is effective to use a single-screw extruder or a twin-screw extruder continuously. is there.

As a method of mixing the above-mentioned other thermoplastic resin, it may be mixed at the same time as the production of the composition of the present invention, or may be mixed with a previously prepared LCP composition. Further, after another thermoplastic resin is previously mixed with the LCP, a polyester-based thermoplastic elastomer may be mixed.

[0043]

The present invention will be described below in detail with reference to examples. First, materials used in Examples and Comparative Examples will be described. <Materials> (1) Thermotropic liquid crystal polymer (LCP) LCP synthesized from phthalic acid, isophthalic acid, 4-hydroxybenzoic acid and 4,4-dihydroxybiphenyl
And the molar ratio of each of the above components is 0.75 / 0.2.
5/3/1. Observation of the optical anisotropy using a polarizing microscope equipped with a hot stage showed optical anisotropy in a molten state at 340 ° C. or higher. (2) Polyester-based thermoplastic elastomer (i) Transesterification reaction of dimethyl terephthalate containing 10 mol% of PETE-1 PRIPLAST 3008 (trade name, dimer acid dimethyl ester manufactured by Unichema) with 1,4-butanediol. Thereafter, a copolymer obtained by polycondensation; trade name: Kanebo PBT PO2120, manufactured by Kanebo Co., Ltd. (Ii) PETE-2 Polyester thermoplastic elastomer having a PBT structure as a hard segment and a polyether structure as a soft segment; trade name: Perprene P-30
B, manufactured by Toyobo Co., Ltd. (3) Terpene compound resin (i) Mighty Ace G-150 (trade name) Hydrogenated product of a Friedel-Crafts reaction product of a terpene compound and phenol, manufactured by Yashara Chemical Corporation. Abbreviated as "G-150" in the table. (Ii) YP-90 (trade name) terpene diphenol resin, Yashara Chemical Co., Ltd.
Made. (Iii) TM-60 (trade name) Diels-Alder reaction product of a terpene compound and maleic anhydride, manufactured by Yashara Chemical Corporation.

<Measurement Method> (1) Weld Strength FIG. 1 is a plan view of a test piece for measuring weld strength. 5
Using a mold with φ-pins installed, injection molding a resin material through the film gate from the opposite side of the 5φ-pins.
Test piece 1 having weld line 3 downstream of
Create The illustrated test piece 1 is in a state of being removed from a mold, and has a film gate portion 4. The dimensions of each part are as follows: a = 100 mm, b = 100 mm, c = 30
mm and d = 12.7 mm, and the thickness of the test piece is 3
mm. The portions A, B and C in the figure are cut out from the test piece, and the bending strength of each portion is measured. Subsequently, a test piece having no weld line is prepared by injection molding in the same manner except for removing the 5φ pin from the same mold, and a portion A is cut out to measure the bending strength. The bending strength of the three types of test pieces having a weld line is represented by a relative value (%) with the bending strength of the test piece having no weld line being 100. (2) Minimum filling pressure In FIG. 1, the minimum filling pressure required when preparing a test piece using a mold without the 5φ pin is measured. The results are relative values (%) with the value of the corresponding comparative example as 100.
Expressed by (3) Warpage FIG. 2 is a plan view of a test piece for measuring warpage. A resin material is injection-molded from the pin gate to produce a disk-shaped test piece 1a. The illustrated test piece 1a is in a state of being taken out of a mold, and has a pin gate portion 5. The diameter of the disk is 100 mm and the thickness is 1.6 mm. Height reference line 6
Height of each point of A, B, C and D with respect to (mm)
Are measured and compared. (4) Fibrillation and separation of the surface In FIG. 1, the surface of each test piece manufactured by injection molding using a mold without a 5φ pin was applied to a surface of a 5 kgf steel rod having a diameter of 5 mm wound with a commercially available adhesive tape. Rub it 10 times with force and observe the traces visually. Judgment is expressed in five stages of ◎, △, Δ, × and XX in order of appearance.

<Examples and Comparative Examples> Using a twin-screw extruder, the temperature of the kneading section was set at 350 ° C., and the raw materials shown in Tables 1 to 5 were melt-mixed, followed by extrusion to produce pellets. . Using the pellets, sample pieces for various measurements were prepared by injection molding. Table 1 shows the resin composition and measurement results.
To Table 5 below.

[0046]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[0047]

According to the present invention, by adding a polyester-based thermoplastic elastomer to LCP, a thermopowder having low weld strength, surface fibrillation peeling, and warpage caused by anisotropy of shrinkage are improved. A tropic liquid crystal polymer can be obtained. It is possible to solve the problems of LCP and expand the range of application, and it is industrially extremely useful.

[Brief description of the drawings]

FIG. 1 is a plan view of a test piece for measuring weld strength.

FIG. 2 is a plan view of a test piece for measuring warpage.

[Explanation of symbols]

 1, 1a Test piece 2 Pin hole 3 Weld line 4 Film gate 5 Pin gate 6 Height reference line

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 BK003 CE003 CF052 CF062 CF072 CF082 CF181 GN00 GQ00 GQ05 4J029 AA05 AB01 AC02 AD01 AD09 AE01 AE16 BB04A BB05A BB05B BB09A BB10A BB12A BB18 BB18B05B06 CB18 CB18 CB18 CB18 CC05A CC06A CF03 CF08 CF15 CG03 DB05 EB04A EB05A EB05B EC05A EC06A EC06B ED03 EE05 EE10 HA01 HB01 JE043 JE153 KH03

Claims (5)

[Claims] 1. A thermotropic liquid crystal polymer composition containing 0.5 to 40% by weight of a polyester thermoplastic elastomer. 2. The structural unit derived from a dicarboxylic acid component in the polyester portion of the polyester-based thermoplastic elastomer is derived from an aromatic dicarboxylic acid and a hydrogenated dimer acid, and the structural unit derived from a diol component is 2. The thermotropic liquid crystal polymer composition according to claim 1, wherein the composition is derived from any of ethylene glycol, 1,4-butanediol and 1,4-cyclohexanediol. 3. The structural unit derived from a dicarboxylic acid component in the polyester moiety is derived from terephthalic acid containing 0.1 to 30 mol% of a hydrogenated dimer acid, and is derived from a diol component. But,
3. The thermotropic liquid crystal polymer composition according to claim 2, which is derived from 1,4-butanediol. 4. The thermotropic liquid crystal polymer composition according to claim 2, wherein the hydrogenated dimer acid has a structure represented by the following formula [I], [II] or [III]. Embedded image 5. The thermotropic liquid crystal polymer composition according to claim 1, which contains 0.5 to 10% by weight of a terpene resin.