JPH1030052A - Liquid crystal resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid crystal resin composition which is excellent in flowability and mechanical characteristics, particularly improved in stiffness, anisotropy and abrasion. SOLUTION: This liquid crystal resin composition contains 100 pts.wt. of a liquid crystal resin comprising 99.5-50wt.% of a semi-aromatic liquid crystal polyester resin and 0.5-50wt.% of a wholly aromatic liquid crystal polyester resin and 5-200 pts.wt. of an inorganic filler where the average aspect ratio of the filler is 25-100 in the composition. The objective molded products are produced by molding this liquid crystal resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal resin composition which is excellent in fluidity and mechanical properties, in particular, has improved rigidity, anisotropy and abrasion, and a molded product thereof.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and a number of polymers having various new properties have been developed and marketed. Among them, optics characterized by a parallel arrangement of molecular chains. Attention is paid to the fact that anisotropic liquid crystalline polymers have excellent fluidity and mechanical properties,
In particular, it has high rigidity and moderate wear resistance,
In the field of electronics and office equipment, the demand for small molded products such as sliding members is increasing.

Examples of the polymer forming the anisotropic molten phase include a liquid crystalline polymer obtained by copolymerizing p-hydroxybenzoic acid with polyethylene terephthalate (Japanese Patent Laid-Open No.
No. 9-72393), p-hydroxybenzoic acid and 6
-Hydroxy-2-naphthoic acid copolymerized liquid crystal polymer (JP-A-54-77691), p-hydroxybenzoic acid copolymerized with 4,4'-dihydroxybiphenyl, terephthalic acid and isophthalic acid Polymers (JP-B-57-24407) are known. However, the liquid crystalline polymer has different molding shrinkage and mechanical properties in the direction perpendicular to the molecular chain orientation, and the filler such as glass fiber is used to improve the mechanical strength of the liquid crystalline polymer and the anisotropy of the molded product dimensions. It is known to mix.

As a method for further improving the physical properties of a liquid crystalline polymer, a method of blending two kinds of liquid crystalline polymers having different molecular structures (Japanese Patent Application Laid-Open Nos. 57-40550 and 62-220556, JP-A-63-1
32967, JP-A-2-88667, and JP-A-2-145463) are known, and according to this method, the elastic modulus of the blend is higher than the elastic modulus when used alone. It is disclosed. But,
Simply blending two kinds of liquid crystalline polymers has a large anisotropy and is difficult to put to practical use. As a method of adding glass fiber to further reduce anisotropy,
No. 173157, Japanese Patent Publication No. 3-95260, and Japanese Patent Publication No. 3-54250,
In these methods, the morphology formed in the two kinds of liquid crystalline polymers is broken, and the anisotropy is certainly reduced.
The mechanical properties did not improve so much.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and is particularly excellent in fluidity and mechanical properties when a filler having a specific aspect ratio is blended with a liquid crystalline polymer. It is an object to obtain a liquid crystalline resin composition having excellent rigidity and abrasion resistance.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.

That is, the present invention provides a liquid crystal comprising (1) 99.5 to 50% by weight of a semi-aromatic liquid crystalline polyester resin (A) and 0.5 to 50% by weight of a wholly aromatic liquid crystalline polyester resin (B). A liquid crystalline resin composition comprising 100 parts by weight of a conductive resin (C) and 5 to 200 parts by weight of an inorganic filler (D), and an average aspect ratio of the filler in the composition is 25 to 100. (2) The liquid crystallinity according to the above (1), wherein the semi-aromatic liquid crystalline polyester resin (A) is 95 to 55% by weight and the wholly aromatic liquid crystalline polyester resin (B) is 5 to 45% by weight. Resin composition, (3) ASTM method D
The flexural modulus measured at 790 (1/8 inch thickness) is 15 times higher than when the total amount of the wholly aromatic liquid crystalline polyester resin (A) in the composition was completely replaced with the semi-aromatic liquid crystalline polyester resin (B). % Or more, the liquid crystalline resin composition according to the above (1) or (2),
(4) The liquid crystalline resin composition according to any one of the above (1) to (3), wherein the filler (D) is subjected to a surface treatment with a silane coupling agent; When a plate-shaped molded product obtained from the resin composition was pressed against the center thereof with a load of 5 kg and pressed at the center and rotated at 20 rpm for 8 hours, the abrasion loss of the liquid crystalline resin composition was 100 μm / h or less than (h)
(1) to (4), wherein the weight average molecular weight of the wholly aromatic liquid crystalline polyester resin (B) is 10,000 to 200,000.
The liquid crystal resin composition according to any one of (5) and (7) the semi-aromatic liquid crystal polyester resin (A) has a weight average molecular weight of 10,000 to 200,000. (8) The liquid crystalline resin composition according to any one of the above (1) to (7), wherein the semi-aromatic liquid crystalline polyester resin (A) contains an ethylenedioxy unit. (9) A copolymer in which the semi-aromatic liquid crystalline polyester resin (A) has the following structural units (I), (III) and (IV), and / or (I), (II) and (III) )
, (IV) a liquid crystalline resin composition according to any one of the above (1) to (8), which comprises a copolymer having a structural unit;

Embedded image (However, R ₁ in the formula is

Embedded image R ₂ represents one or more groups selected from

Embedded image R ₃ represents one or more groups selected from

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. (10) The semi-aromatic liquid crystalline polyester resin (A) comprises the above structural units (I), (II), (III) and (IV),
The sum of (I) and (II) is the structural unit (I), (II) and (II)
60 to 95 mol% with respect to the total of I)
(III) is 40 to 5 mol% based on the total of the structural units (I), (II) and (III), and the molar ratio of the structural units (I) and (II) [(I) / (II) ] Is 75/25 to 95/5, and
The liquid crystalline resin composition according to the above (9), wherein the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III), (11) a wholly aromatic liquid crystalline compound The polyester resin (B) comprises the copolymer having the structural unit (I) and / or the copolymer having the structural units (I), (II) and (IV) according to claim 9. (1) above
Liquid crystal resin composition according to any one of (1) to (10),
2) The wholly aromatic liquid crystalline polyester resin (B) is the above (I)
The liquid crystal resin composition according to claim 10, comprising a copolymer having a structural unit represented by the formula:
3) The wholly aromatic liquid crystalline polyester resin (B) comprises the above structural units (I), (II) and (IV), and the structural unit (I) is based on the total of the structural units (I) and (II). 15 to 90 mol%, the structural unit (II) is 85 to 10 mol% with respect to the total of the structural units (I) and (II), and the structural unit (II) is a structural unit.
(IV) is substantially equimolar.
0) or the liquid crystalline resin composition according to (11), (14)
The liquid crystal resin composition according to the above (13), wherein 5 to 100 mol% of the structural unit (IV) is the following structural unit (V):

Embedded image (15) The liquid crystalline resin composition according to any one of the above (1) to (14), wherein 50% or more of the inorganic filler (D) is fibrous, (16) the inorganic filler ( (D) is fibrous, (50) or more of the liquid crystalline resin composition according to any one of (1) to (15), and (17) the inorganic filler (D) is glass fiber. (18) The liquid crystalline resin composition according to any one of (1) to (16), wherein (18) the inorganic filler (D) is a glass fiber. The liquid crystal resin composition according to any one of the above, (19) the liquid crystal resin (C) 10
The liquid crystalline resin composition according to any one of the above (1) to (18), further comprising 0.5 to 60 parts by weight of an organic bromide with respect to 0 parts by weight, and (20) an organic bromide. One of the following structural units produced from a brominated styrene monomer
Species or more as the main constituent unit and a weight average molecular weight of 1 × 10 ³
(1) which is a polybrominated styrene of up to 120 × 10 ⁴
9) The liquid crystal resin composition according to the above.

[0008]

Embedded image (21) With respect to 100 parts by weight of the liquid crystal resin (C), a copolymer comprising polyethylene, polypropylene, ethylene or propylene and an α-olefin having 3 or more carbon atoms, and α or α having ethylene or propylene and 3 or more carbon atoms. −
At least one selected from copolymers comprising olefins and non-conjugated dienes, and having a weight average molecular weight of 10,000
Olefinic polymers in the range of 0 to 600,000.
(1) to (10) which are further blended with 01 to 10 parts by weight.
The liquid crystalline resin composition according to any one of (20) and (22)
The liquid crystalline resin molded product obtained by molding the liquid crystalline resin composition according to any one of the above (1) to (21), and (23) the liquid crystalline resin molded product according to the above (22), wherein the liquid crystalline resin molded product is a small molded product. It is a liquid crystalline resin molded product.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The semi-aromatic liquid crystalline polyester resin (A) used in the present invention has an aliphatic chain such as ethylene, propylene, butylene or cyclohexane dimethylene in the molecular chain, and forms an anisotropic molten phase. And preferably contains an ethylenedioxy unit. Specifically, for example, a copolymer having the following structural units (I), (III) and (IV), and / or (I), (II) and (III)
And a liquid crystalline polyester resin comprising a copolymer having the structural unit of (IV).

[0010]

Embedded image (However, R ₁ in the formula is

Embedded image R ₂ represents one or more groups selected from

Embedded image R ₃ represents one or more groups selected from

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. Note that the sum of structural units (II) and (III) and structural unit (IV)
Is preferably substantially equimolar.

The structural unit (I) of the preferred semi-aromatic liquid crystalline polyester resin (A) in the present invention is formed from a hydroxy aromatic carboxylic acid selected from p-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid. The structural unit is represented by structural unit (II): 4,4'-dihydroxybiphenyl,
3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2- Structural units formed from aromatic dihydroxy compounds selected from bis (4-hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl ether; structural unit (III) represents structural units formed from ethylene glycol; structural unit (IV) ) Is terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid Acid, 1,2-bis (2-chlorophenoxy) eta Respectively show a structural unit derived from selected aromatic dicarboxylic acids from 4,4'-dicarboxylic acid. Of these, R ₂ of the structural unit (II) is

Embedded image , And the by R ₁ and R ₃ in the structural unit (IV) of structural units (I),

Embedded image Is particularly preferred.

The semi-aromatic liquid crystalline polyester resin (A) which can be used in the present invention comprises the above structural units (I), (III), (IV),
And / or a copolymer consisting of (I), (II), (III) and (IV) is preferred, and the copolymerization amount of the above structural units (I) to (IV) is arbitrary. However, the following copolymerization amount is preferred from the viewpoint of fluidity and mechanical properties.

That is, the total of the structural units (I) and (II) is preferably from 60 to 95 mol%, more preferably from 75 to 93 mol%, based on the total of the structural units (I), (II) and (III). More preferred. The structural unit (III) is the structural unit (I), (II)
It is preferably from 40 to 5 mol%, more preferably from 25 to 7 mol%, based on the total of (III) and (III). Also, structural units
The molar ratio [(I) / (II)] between (I) and (II) is preferably 75/25 to 95/5, more preferably 78/22 to 93, from the viewpoint of the balance between heat resistance and fluidity. / 7. The structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III).

The weight average molecular weight of the semi-aromatic liquid crystalline polyester resin (A) preferably used in the present invention is from 10,000 to 20 in view of mechanical strength, moldability and fluidity.
Preferably it is 000, especially 11,000-
150,000, and 12,000-100,000
It is preferred that Such determination of molecular weight can be carried out by gel permeation chromatography and other standard techniques without solution formation of the polymer, for example by quantifying end groups on compression molded films by infrared spectroscopy. Alternatively, the molecular weight can be measured by using a pentafluorophenol solution and using a light scattering method. The above measurement method can be appropriately selected according to the type of the polymer to be measured.

The wholly aromatic liquid crystalline polyester resin (B) used in the present invention is a wholly aromatic polyester which forms an anisotropic molten phase upon melting, and is preferably the above (I) and / or (I) or (I). A liquid crystalline polyester resin comprising a copolymer having the structural units of (II) and (IV).
When structural units (II) and (IV) are contained, it is preferable that the structural units (II) and (IV) are substantially equimolar.

The structural unit (I) of the wholly aromatic liquid crystalline polyester resin (B) preferred in the present invention is formed from a hydroxy aromatic carboxylic acid selected from p-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid. The structural unit (II) is 4,4'-dihydroxybiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, Methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-
At least one structural unit formed from an aromatic dihydroxy compound selected from dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, and 4,4′-dihydroxydiphenyl ether; the structural unit (IV) is terephthalic acid; Isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4
'-Diphenylether dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid,
2-bis (2-chlorophenoxy) ethane-4,4'-
The structural units generated from one or more aromatic dicarboxylic acids selected from dicarboxylic acids are shown below.

When the wholly aromatic liquid crystalline polyester resin (B) used in the present invention has the composition of (I), it is a copolymer comprising the following structural units (VI) and (VII). The structural unit (VI) is preferably 90 to 10 mol%, more preferably 85 to 65 mol%, based on the total of the structural units (VI) and (VII).

[0018]

Embedded image In the case of the compositions (I), (II) and (IV), the above structural unit (I) is 1% of the total of the structural units (I) and (II) from the viewpoint of fluidity.
It is preferably from 5 to 90 mol%, more preferably from 40 to 90 mol%, and the structural unit (IV) is the structural unit (II)
And are substantially equimolar. Of these, those in which 5 to 100 mol% of the structural units (IV) are the following structural units (V) are particularly preferred.

[0019]

Embedded image The weight average molecular weight of the wholly aromatic liquid crystalline polyester (B) preferably used in the present invention is preferably from 10,000 to 200,000, particularly from 12,000 to 150, from the viewpoint of mechanical strength and fluidity. 000, plus 1
Preferably it is 5,000 to 100,000. Such determination of molecular weight can be carried out by gel permeation chromatography and other standard techniques without solution formation of the polymer, for example by quantifying end groups on compression molded films by infrared spectroscopy.
Alternatively, the molecular weight can be measured by using a pentafluorophenol solution and using a light scattering method. The above measurement method can be appropriately selected according to the type of the polymer to be measured.

The liquid crystalline resin composition of the present invention has a specific aspect ratio to a liquid crystalline resin (C) comprising a semi-aromatic liquid crystalline polyester resin (A) and a wholly aromatic liquid crystalline polyester resin (B). The effect is exhibited only when the filler is blended.

When the above components (A) and (B), which can be preferably used in the present invention, are subjected to polycondensation, in addition to the above components, 3,3'-diphenyldicarboxylic acid, 2,2
Aromatic dicarboxylic acids such as' -diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecandioic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid; chlorohydroquinone; -Dihydroxydiphenyl sulfone,
4,4'-dihydroxydiphenyl sulfide, 4,4
Aromatic diols such as' -dihydroxybenzophenone and 3,4'-dihydroxybiphenyl, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol Aliphatic, alicyclic diols, aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid, and p-aminophenol, p-aminobenzoic acid, and the like can be further copolymerized within a range that does not impair the liquid crystallinity.

The method for producing a liquid crystalline resin in the present invention comprises:
There is no particular limitation, and it can be produced according to a known polycondensation method of a liquid crystalline polyester resin. For example, the wholly aromatic liquid crystalline polyester resin (B) is preferably (1) to (4), and the semi-aromatic liquid crystalline polyester resin (A) is preferably produced by the method (5).

(1) p-acetoxybenzoic acid and 4,
Diacylated aromatic dihydroxy compounds such as 4'-diacetoxybiphenyl, diacetoxybenzene, and 2,
A method of producing from 6-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and other aromatic dicarboxylic acids by deacetic acid condensation polymerization.

(2) p-hydroxybenzoic acid and 4,
4′-dihydroxybiphenyl, an aromatic dihydroxy compound such as hydroquinone and an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid are reacted with acetic anhydride to acylate a phenolic hydroxyl group. A method of producing by a deacetic acid polycondensation reaction

(3) Phenyl esters of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl, hydroquinone and 2,6
-A method of producing from a diphenyl ester of an aromatic dicarboxylic acid such as naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, etc. by a phenol removal polycondensation reaction.

(4) p-hydroxybenzoic acid and 2,
A predetermined amount of diphenyl carbonate is reacted with an aromatic dicarboxylic acid such as 6-naphthalenedicarboxylic acid, terephthalic acid, or isophthalic acid to form diphenyl esters, and aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl and hydroquinone And a production method by a dephenol polycondensation reaction.

(5) Polyester polymers such as polyethylene terephthalate, oligomers or bis (β-
(Hydroxyethyl) terephthalate and the like, and a method of producing the bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid by the method of (1) or (2).

Although these polycondensation reactions proceed without a catalyst, metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and metallic magnesium can also be used.

The semi-aromatic liquid crystalline polyester resin (A) and the wholly aromatic liquid crystalline polyester resin (B) used in the present invention can be measured for logarithmic viscosity in pentafluorophenol. At that time, the semi-aromatic liquid crystalline polyester resin (A) is preferably 0.5 to 15.0 dl / g as a value measured at 60 ° C. at a concentration of 0.1 g / dl,
1.0 to 3.0 dl / g is particularly preferred. The wholly aromatic liquid crystalline polyester resin (B) is 6 g at a concentration of 0.1 g / dl.
The value measured at 0 ° C. is preferably 1.0 to 15.0 dl / g, particularly preferably 2.5 to 10.0 dl / g.

The semi-aromatic liquid crystalline polyester resin (A) and the wholly aromatic liquid crystalline polyester resin (B) used in the present invention.
Is the sum of (A) and (B) and (A) 99.
5 to 50% by weight, (B) 0.5 to 50% by weight, preferably (A) 95 to 55% by weight, (B) 5 to 45% by weight, more preferably (A) 90 to 60% by weight, B) 10-4
0% by weight. If the amount of the wholly aromatic liquid crystalline polyester resin (B) is less than 0.5% by weight, no special effect such as abrasion resistance is exhibited, and if it exceeds 50% by weight, fluidity and rigidity are reduced. The characteristics of the present composition cannot be exploited.

As the filler (D) used in the present invention, fibrous materials such as glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, gypsum fiber, aluminum borate fiber, brass fiber, stainless steel fiber, Fiber fillers such as steel fibers, ceramic fibers, boron whisker fibers, and asbestos fibers are preferably used. Glass fibers, carbon fibers, aromatic polyamide fibers and the like are more preferably used. Particularly preferred is glass fiber. The type of the glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, a chopped strand of a long fiber type or a short fiber type, a milled fiber, or the like can be used. In addition, powdery, granular or plate-like fillers include mica, talc, silica, calcium carbonate, calcium oxide, aluminum oxide, glass beads, glass flakes, glass microballoons, bentonite, clay, wollastenite, titanium oxide, sulfuric acid Barium, zinc oxide, graphite and the like are used. The filler (D) is an epoxy-based polymer, a urethane-based polymer,
It may be used after being coated with an acrylic polymer or treated with a sizing agent, and an epoxy polymer is particularly preferred. Although two or more fillers can be used in combination, it is particularly preferable that the filler (D) is a fibrous material, and at least 50% or more of the fibrous material can be preferably used. Further, as the filler (D), glass fiber is particularly preferable, and at least 50% or more of the filler is preferably glass fiber.

The filler (D) used in the present invention is required to maintain an average aspect ratio in the composition of 25 to 100, preferably more than 25 and less than 100.
More preferably more than 26 and less than 80, particularly preferably 30 to 80
70. When the aspect ratio is less than 25, the anisotropy is not sufficiently improved, and when the aspect ratio exceeds 100, the rigidity is certainly improved, but the surface of the molded article is roughened, and there is no effect on the wear resistance.

By subjecting the filler used in the present invention to a surface treatment with a silane coupling agent such as aminosilane or epoxysilane, the mechanical properties are further improved. Particularly, an epoxy silane coupling agent is preferably used. Further, it may be used after being treated with a titanate-based coupling agent or another surface treatment agent. The amount of the surface treatment of the silane coupling agent with respect to the filler is usually 0.1 to 5%, preferably 0.2 to 4%, more preferably 0.3 from the viewpoint of the rigidity improving effect and the handleability. ~ 3% is used.

The amount of the filler (D) used in the present invention is 5 to 200 parts by weight based on 100 parts by weight of the total amount of the semi-aromatic liquid crystalline polyester resin (A) and the wholly aromatic liquid crystalline polyester resin (B). Parts by weight, preferably 10 to 150 parts by weight. If the filling amount exceeds 200 parts by weight, mechanical properties and fluidity are significantly reduced.

Of the filler (D) used in the present invention, the weight average fiber length in the composition of the fibrous filler is preferably 0.5 to 0.001 m from the viewpoint of the surface appearance and abrasion resistance of the molded article.
m, more preferably 0.4 to 0.003 mm, even more preferably 0.35 to 0.005 mm.

In the filler (D) used in the present invention, the fiber diameter of the fibrous filler is preferably from 5 to 15 μm, more preferably from the viewpoint of rigidity and fluidity of the obtained composition. Of 6 to 13 μm is used.

The particle size of the filler other than the fibrous filler in the composition is usually from 100 to 0.1 μm from the viewpoint of fluidity.
m, preferably 80-0.5 μm, more preferably 60
０．８0.8 μm.

The average aspect ratio, weight average fiber length, and average fiber diameter of the fibrous filler in the composition of the present invention can be measured, for example, by the following methods. First, after about 5 g of the composition was incinerated in a crucible, 10% of the remaining filler was removed.
Collect 0 mg and disperse in 100 cc of soapy water.
Then, one to two drops of the dispersion are placed on a slide glass using a dropper, observed under a microscope, and photographed. The fiber length and fiber diameter of the fibrous filler photographed are measured. The measurement was performed for 500 fibers or more, and the weight average fiber length and the average fiber diameter were obtained.
Expressed as the average fiber diameter.

The average aspect ratio, average major axis and average thickness of the powdery, granular or plate-like filler in the composition of the present invention are as follows:
For example, it can be measured by the following method. First, after about 5 g of the composition is incinerated in a crucible, 100 mg is collected from the remaining filler and dispersed in 100 cc of soapy water. Then, one to two drops of the dispersion are placed on a slide glass using a dropper, observed under a microscope, and photographed. Measure the major axis of the plate-like filler photographed.
Similarly, the filler remaining after incineration is observed and photographed under a scanning electron microscope. The thickness of the plate-like filler photographed is measured. The measurement is performed for 500 or more pieces, and the average major axis and the average thickness are obtained. The average aspect ratio is represented by the average major axis / average thickness.

When two or more fillers are used in combination, the average aspect ratio of the filler in the composition can be determined from the weighted average of the respective average aspect ratios.

The molded article made of the liquid crystalline resin composition of the present invention can further improve the wear characteristics by adding a flame retardant or an olefin polymer described below.

The organic bromide used in the present invention contains an organic bromine compound usually used as a flame retardant, and particularly preferably has a bromine content of 20% by weight or more. Specific examples include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane,
Low-molecular-weight organic bromine compounds such as ethylene-bis (tetrabromophthalimide) and tetrabromobisphenol A, brominated polycarbonate (for example, a polycarbonate oligomer produced from brominated bisphenol A or a copolymer thereof with bisphenol A), bromine Epoxy compounds (for example, diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin or epoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin), poly (brominated benzyl acrylate), brominated polyphenylene ether , Brominated bisphenol A, condensate of cyanuric chloride and brominated phenol, brominated polystyrene,
Examples include halogenated polymers and oligomers such as cross-linked brominated polystyrene and cross-linked brominated poly α-methylstyrene, and mixtures thereof. Among them, ethylene bis (tetrabromophthalimide), brominated epoxy oligomer or polymer, and brominated Polystyrene, cross-linked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are preferred, with brominated polystyrene being most preferred.

The above-mentioned preferred organic bromides will be described in more detail. As the brominated epoxy polymer, those represented by the following general formula (i) are preferred.

[0044]

Embedded image The polymerization degree n in the general formula (i) is preferably 15 or more,
More preferably, it is 50 to 80.

As the brominated polystyrene used in the present invention, brominated polystyrene and cross-linked brominated polystyrene produced by brominating polystyrene obtained by radical polymerization or anion polymerization, or brominated styrene monomer is subjected to radical polymerization or anion polymerization. Polymerization, preferably a polybrominated styrene having a brominated styrene unit represented by the formula (ii) and / or (iii) produced by radical polymerization. And / or (iii) a polybrominated styrene having a weight average molecular weight of 1 × 10 ^{3 to} 120 × 10 ⁴ as a main component.

[0046]

Embedded image The brominated styrene monomer as used herein is preferably a styrene monomer in which two to three bromine atoms have been introduced into the aromatic ring of the styrene monomer by a substitution reaction. In addition to dibrominated styrene and / or tribrominated styrene, May contain monobrominated styrene.

The polybrominated styrene preferably contains at least 60% by weight of dibrominated styrene and / or tribrominated styrene units, more preferably at least 70% by weight. 40% by weight of monobrominated styrene in addition to dibrominated styrene and / or tribrominated styrene
The polybrominated styrene copolymerized below, preferably 30% by weight or less, may be used. The weight average molecular weight of this polybrominated styrene is more preferably 1 × 10 ⁴ to 15 × 10 ⁴ . The weight average molecular weight is a value measured using a gel permeation chromatograph, and is a relative value based on polystyrene molecular weight.

As the cross-linked brominated polystyrene, polystyrene obtained by brominating porous polystyrene cross-linked with divinylbenzene is preferable.

As the brominated polycarbonate, those represented by the following general formula (iv) are preferred.

[0050]

Embedded image (R ₄ and R _{5 each} represent a substituted or unsubstituted aryl group, most preferably a pt-butylphenyl group.) In the general formula (iv), the polymerization degree n is preferably 4 or more, and 8 The above, especially 8 to 25 can be more preferably used.

The amount of the organic bromide is 0.5 to 60 parts by weight, especially 1 to 100 parts by weight of the liquid crystalline resin.
30 parts by weight are preferred.

Further, in the liquid crystalline resin composition of the present invention, the organic bromide is preferably dispersed in the composition at an average diameter of 25 μm or less, more preferably at 2.0 μm or less.

The olefin polymer used in the present invention includes polyethylene, polypropylene, a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, and propylene and an α-olefin having 4 or more carbon atoms. Copolymers, copolymers of ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene, and the like, and one or more of these may be used.

The α-olefin having 3 or more carbon atoms is preferably propylene, butene-1, pentene-
1,3-methylpentene-1, octacene-1 and the like, and propylene and butene-1 are more preferable, and these can be used in combination of two or more.

Examples of the α-olefin having 4 or more carbon atoms include the above α-olefins having 3 or more carbon atoms except for propylene, and these can be used in combination of two or more.

The non-conjugated diene is preferably 5-ethylidene-2-norbornene, dicyclopentadiene,
1,4-hexadiene and the like can be used.

The copolymerization ratio of ethylene and α-olefin having 3 or more carbon atoms in the copolymer comprising ethylene and α-olefin having 3 or more carbon atoms is usually 40 / 60-9.
9/1 (molar ratio), preferably 70/30 to 95/5
(Molar ratio).

The copolymerization amount of ethylene in the copolymer comprising ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene is usually 5 to 96.9 mol%, preferably 30 to 84.5 mol%. And α- having 3 or more carbon atoms
The copolymerization amount of the olefin is usually 3 to 80 mol%, preferably 15 to 60 mol%, and the copolymerization amount of the non-conjugated diene is usually 0.1 to 15 mol%, preferably 0.5 to 50 mol%.
10 mol%. Further, the copolymerization amount of propylene in the copolymer composed of propylene, an α-olefin having 4 or more carbon atoms and a non-conjugated diene is usually 5 to 96.9 mol%, preferably 30 to 84.5 mol%. The copolymerization amount of the α-olefin having 3 or more carbon atoms is usually 3 to 8
It is 0 mol%, preferably 15 to 60 mol%, and the copolymerization amount of the non-conjugated diene is usually 0.1 to 15 mol%, preferably 0.5 to 10 mol%.

Specific examples of these copolymers include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / pentene-1 copolymer, ethylene / propylene / butene-1 copolymer, propylene / Penten-
1 copolymer, propylene / butene-1 copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 1,4-hexadiene copolymer, propylene / butene-1 / 1,4 -A hexadiene copolymer, an ethylene / propylene / dicyclopentadiene copolymer and the like, and among them, an ethylene / propylene copolymer and an ethylene / butene-1 copolymer are more excellent in heat resistance and more preferable.

[0060] Two or more of the above olefin polymers can be used in combination.

In order to obtain excellent fluidity of the resulting composition, it is preferable that these olefin-based polymers have no copolymerization of a monomer containing an epoxy group, a carboxylic acid group or the like. .

The weight-average molecular weight of the olefin polymer is not particularly limited, but is preferably 10,000 to 600,000 from the viewpoints of releasability, weld strength of the molded product, and appearance of the molded product.
And particularly preferably 30,000 to
500,000, more preferably 100,000-4
Desirably, it is in the range of 50,000. The weight average molecular weight is a value measured using gel permeation chromatography using tetrahydrofuran as a solvent, and is a relative value based on polystyrene molecular weight.

The amount of the olefin polymer added depends on the effect of improving the releasability and the weld strength.
0.01 to 10 parts by weight relative to 0 parts by weight is preferable,
0.1 to 5 parts by weight is particularly preferred.

The liquid crystal resin composition of the present invention may further contain an epoxy compound for improving physical properties. The structure is not necessarily limited. The number of epoxy groups in these epoxy compounds is preferably two or more, and most preferably two. The epoxy compounds include glycidyl ethers, glycidyl esters / ethers, glycidyl esters, epoxidized imide compounds, epoxy group-containing copolymers, epoxy silanes, and the like. More than one species may be used in combination.

The liquid crystalline resin composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and the like), and an ultraviolet absorber (for example, resorcinol, salicylate, benzoate). Triazole, benzophenone, etc.),
Lubricating agents (montanic acid and salts thereof, esters thereof, half esters thereof, stearyl alcohol, stearamide, polyethylene wax, etc.), coloring agents including dyes (eg, nigrosine, etc.) and pigments (eg, cadmium sulfide, phthalocyanine, etc.), crystal nucleating agents, Plasticizer,
Ordinary additives such as a flame retardant aid and an antistatic agent and other thermoplastic resins (such as fluororesins) can be added to impart predetermined characteristics.

For adjusting the liquid crystalline resin composition of the present invention, melt kneading is preferable, and various methods can be applied as a mixing method. Mixing rolls are used as melt mixing equipment,
Examples include a Banbury mixer, a kneader, and an extruder. Among them, an extruder is preferable. As the extruder, any one having a single screw or a screw having two or more screws can be used. In particular, since the aspect ratio of the filler is controlled, several kneading elements are used on the screw using a twin screw extruder. It is preferable to use by inserting or not inserting.

The flexural modulus of the molded article comprising the liquid crystalline resin composition of the present invention thus obtained is often such that the wholly aromatic liquid crystalline polyester resin (B) of the liquid crystalline resin composition is semi-aromatic. It can be improved by 15% or more compared to the case where the entire amount is replaced by the liquid crystalline polyester resin (A). The method for calculating the bending elastic modulus of the molded article made of the liquid crystalline resin composition of the present invention is 127 m in accordance with ASTM D790.
mx 12.7mm x 1/8 inch thickness (3.17mm)
Is a value measured at a sample span of 50 mm and a strain rate of 1 mm.

In many cases, the liquid crystalline resin composition of the present invention is obtained by pressing a plate-shaped molded product obtained therefrom by pressing a cylindrical aluminum applied with a load of 5 kg to the center thereof.
The amount of wear of the liquid crystalline resin composition when rotated at 0 rpm for 8 hours can be 100 μm / h or less. The wear characteristic value is to form a square plate of 30mm length × 30mm width × 3mm thickness, fix the square plate to a jig, apply a load of 5kg, and apply cylindrical aluminum with a diameter of 18mmφ × 2mm thickness to the center of the square plate. And rotating the cylindrical aluminum at 20 rpm for 8 hours to determine the amount of wear.

When used as a resin sliding member, wear characteristics are important, and the amount of wear is at most 100 μm / h or less, preferably 80 μm / h or less, more preferably 60 μm / h or less.
It is necessary to be less than μm / h.

In order to obtain a molded article from the liquid crystalline resin composition of the present invention, it can be molded by a usual method such as injection molding, extrusion molding, blow molding, compression molding, etc., and injection molding is particularly preferred.

The molded article of the present invention thus obtained has excellent fluidity and mechanical properties, and has excellent rigidity and slidability, and is excellent in three-dimensional molded articles and sheets having these characteristics. It can be used for applications such as container pipes. For example, various gears, various cases, various substrates, sensors, L
ED lamps, connectors, sockets, resistors, relay case switch coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers,
Plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage, FDD chassis, HDD parts, motor brush holder, parabolic antenna, computer related Electrical and electronic parts such as parts; VTR parts, TV parts, irons,
Home and office represented by hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Various bearings such as electrical product parts, office computer related parts, pagers, mobile phones, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, stern bearings, underwater bearings, etc., motor parts, Mechanical related parts such as lighters and typewriters, optical equipment such as microscopes, binoculars, cameras, watches, etc., precision mechanical related parts; alternator terminals, alternator connectors, IC regulators, potentiometer bases for light drier, Various valves, such as gas-gas valve,
Various pipes for fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor , Throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, Distributors, starter switches,
Starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, lamp reflector, lamp housing, brake It is useful for parts related to automobiles and vehicles, such as pistons, solenoid bobbins, engine oil filters, and ignition device cases, and various other uses.

Above all, it is extremely practical as a small molded product used for small parts, for example, small parts of 5 cc or less, because of its rigidity, and slidability is required by utilizing its slidability. Very practical for sliding parts.
In particular, it is extremely practical for molded products that are small built-in parts requiring slidability, such as pickup lens holders, paper separating claws of copiers and printers, and various small gears.

[0073]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the gist of the present invention is not limited to the following Examples.

Reference Example 1 (A-1) 995 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4'-dihydroxybiphenyl, terephthalic acid 112
Parts by weight, 216 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, and 960 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distillation tube, and polymerized. Liquid crystal onset temperature 293 ° C, logarithmic viscosity 1.49dl /
g, a resin having a weight average molecular weight of about 21,000 was obtained.

Reference Example 2 (A-2) 907 parts by weight of p-hydroxybenzoic acid, 117 parts by weight of 4,4'-dihydroxybiphenyl, hydroquinone 30
Parts by weight, 150 parts by weight of terephthalic acid, and an intrinsic viscosity of about 0.
294 parts by weight of 6 dl / g of polyethylene terephthalate and 940 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distilling tube to perform polymerization. Liquid crystal start temperature 291
A resin having a logarithmic viscosity of 1.28 dl / g and a weight average molecular weight of about 18,000 was obtained.

Reference Example 3 (A-3) 870 parts by weight of p-hydroxybenzoic acid, 251 parts by weight of 4,4'-dihydroxybiphenyl, hydroquinone 149
Parts by weight, 195 parts by weight of 2,6-naphthalenedicarboxylic acid, 299 parts by weight of terephthalic acid, and 1314 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distillation tube, and polymerized. Liquid crystal onset temperature 317 ° C, logarithmic viscosity 6.12d
1 / g and a resin having a weight average molecular weight of about 30,000 were obtained.

Reference Example 4 (A-4) A reaction vessel equipped with a distilling tube containing 1265 parts by weight of p-acetoxybenzoic acid and 456 parts by weight of 6-acetoxy-2-naphthoic acid according to JP-A-54-77691. And subjected to polycondensation. Liquid crystal onset temperature 293 ° C, logarithmic viscosity 5.
A resin having 24 dl / g and a weight average molecular weight of about 35,000 was obtained.

Table 1 shows the structure of the organic bromide used in the present invention.
Shown in

[0079]

[Table 1] Examples 1 to 11, Comparative Examples 1 to 9 Liquid crystalline polyester resin obtained in Reference Example and average fiber length of 3 m
As shown in Table 2, a predetermined amount of each glass fiber treated with aminosilane (Examples 1 to 3 and 5 to 11) and epoxysilane (Example 4) was weighed as shown in Table 2, and dry-blended. 290-330 using a 30 mmφ twin screw extruder
The mixture was melt-kneaded at a temperature of 50 ° C. at a screw rotation speed of 50 to 250 rpm to form pellets. After drying with hot air, the pellets were supplied to a Sumitomo Nestar injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.) and the cylinder temperature was 290.
The temperature was set at ~ 350 ° C and the mold temperature was 90 ° C, and the test pieces for measurement shown below were obtained by injection molding. The measuring method is described below.

(1) Bending characteristics Using the above molding machine, 1/8 inch (3.17 mm)
A test piece having a thickness of 12.7 mm and a width of 127 mm was molded and measured in accordance with ASTM D790 to determine a flexural modulus.

(2) Anisotropy Using the molding machine described above, the cylinder temperature was set to the melting point + 10 ° C.
Mold temperature 90 ° C, injection speed 99%, injection pressure 500kgf
A square plate having a thickness of 1 mm × 70 mm × 70 mm was molded under the condition of / cm 2, and the molding shrinkage in the direction perpendicular to the flow direction was determined.

(3) Sliding test A square plate having a length of 30 × width 30 × thickness 3 mm was formed using the above-mentioned molding machine, and the square plate was fixed to a jig, and a load of 5 kg was applied to 18 mmφ × 2 mm thickness. Of cylindrical aluminum is pressed against the center of the square plate,
After rotating at 8 rpm for 8 hours, the abrasion loss and dynamic friction coefficient of the liquid crystalline resin composition at that time were evaluated. Table 2 shows the results.

[0083]

[Table 2] From the results in Table 2, semi-aromatic liquid crystalline polyester resin (A)
And a wholly aromatic liquid crystalline polyester resin (B) having a specific composition ratio, and an aspect ratio of a filler compounded in the composition is excellent in fluidity only in the case of a specific liquid crystal resin composition,
It turns out that it has high elastic modulus, abrasion resistance and low anisotropy.

Example 12 A composition was prepared in the same manner as in Example 7 except that the organic bromide shown in Table 1 was further added in the proportion shown in Table 3 with respect to 100 parts by weight of the liquid crystalline resin composition. Was produced. The pellets are supplied to a Sumitomo Nestal injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), and the cylinder temperature is set to a melting point + 10 ° C. and the mold temperature is set to 90 ° C.
0.5mm (thickness) x 12.7mm x 127
mm of a combustion test piece, and UL
The same procedure as in Example 7 was carried out except that a vertical combustion test was carried out according to the 94 standard and the flame retardancy was evaluated. Table 3 shows the results.

[0085]

[Table 3] Flame retardancy was imparted without lowering the fluidity and mechanical properties of the liquid crystalline resin composition.

Examples 13 to 17 In the same manner as in Example 7, except that the olefin polymer shown in Table 4 was further added in the proportion shown in Table 4 with respect to 100 parts by weight of the liquid crystalline resin composition. To produce pellets of the composition. This pellet is supplied to a Toshiba IS55EPN injection molding machine (manufactured by Toshiba Machine Plastic Engineering Co., Ltd.), and the size is 8 mm wide × 10 m high under the conditions of a cylinder temperature of + 10 ° C. and a mold temperature of 90 ° C.
A projecting force when a molded product is formed in a box shape of mx 100 mm in length and 1 mm in thickness and provided with four 0.8 mm thick partitions at equal intervals, and the molded product is ejected from the mold. Was measured, and the releasability was evaluated. Further, the appearance of the molded product was observed, and the presence or absence of gas burning was evaluated.

[0087]

[Table 4] Mold releasability was imparted without lowering the fluidity and mechanical properties of the liquid crystalline resin composition and without impairing the surface appearance.

[0088]

Industrial Applicability The liquid crystalline resin composition of the present invention is excellent in fluidity and mechanical properties, and particularly improved in rigidity, abrasion and anisotropy. -It is a material suitable for various other uses such as electronic related equipment, precision machine related equipment, office equipment and automobiles.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08K 7/14 C08K 7/14 C08L 25/18 LEK C08L 25/18 LEK (72) Inventor Miki Sakai (72) Inventor Toshio Kurematsu, 9-9, Oecho, Minato-ku, Nagoya-shi, Aichi Nagoya Office

Claims (23)

[Claims] 1. A semi-aromatic liquid crystalline polyester resin (A) 9
Liquid crystalline resin (C) comprising 9.5 to 50% by weight and wholly aromatic liquid crystalline polyester resin (B) 0.5 to 50% by weight
100 parts by weight of the inorganic filler (D) is contained in an amount of 5 to 200 parts by weight, and the average aspect ratio of the filler in the composition is 25 to 1
A liquid crystalline resin composition characterized by being 00. 2. The liquid crystalline composition according to claim 1, wherein the content of the semi-aromatic liquid crystalline polyester resin (A) is 95 to 55% by weight and the content of the wholly aromatic liquid crystalline polyester resin (B) is 5 to 45% by weight. Resin composition. 3. An ASTM method D790 (1/8 inch thickness)
The flexural modulus measured by the method is improved by 15% or more compared to the case where the wholly aromatic liquid crystalline polyester resin (A) in the composition is completely replaced with the semi-aromatic liquid crystalline polyester resin (B). The liquid crystalline resin composition according to claim 1 or 2, wherein 4. The liquid crystalline resin composition according to claim 1, wherein the filler (D) is surface-treated with a silane coupling agent. 5. A liquid crystalline resin composition obtained by pressing a plate-shaped molded product obtained from a liquid crystalline resin composition onto a central portion thereof while applying a load of 5 kg thereto and rotating the same at 20 rpm for 8 hours. The liquid crystalline resin composition according to any one of claims 1 to 4, wherein an abrasion amount of the object is 100 µm / h or less. 6. The liquid crystalline resin composition according to claim 1, wherein the weight average molecular weight of the wholly aromatic liquid crystalline polyester resin (B) is 10,000 to 200,000. 7. The liquid crystalline resin composition according to claim 1, wherein the semi-aromatic liquid crystalline polyester resin (A) has a weight average molecular weight of 10,000 to 200,000. 8. The semi-aromatic liquid crystalline polyester resin (A) contains an ethylenedioxy unit.
8. The liquid crystalline resin composition according to any of 7. 9. A copolymer in which the semi-aromatic liquid crystalline polyester resin (A) has the following structural units (I), (III) and (IV), and / or (I), (II), The liquid crystalline resin composition according to any one of claims 1 to 8, comprising a copolymer having the structural units (III) and (IV). Embedded image (Where R ₁ in the formula is And R ₂ represents one or more groups selected from R ₃ represents one or more groups selected from Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. ) 10. A semi-aromatic liquid crystalline polyester resin (A).
Consists of the above structural units (I), (II), (III) and (IV), and the sum of the structural units (I) and (II) is the sum of the structural units (I), (II) and (III) 60 to 95 mol%, and the structural unit (III) is 40 to 5 mol% with respect to the total of the structural units (I), (II) and (III), and the structural units (I) and (II) ) Is 75/25 to 95/5, and the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III). The liquid crystalline resin composition according to claim 9, wherein: 11. A wholly aromatic liquid crystalline polyester resin (B)
Is a copolymer having the structural unit of (I) in claim 9,
The liquid crystal resin composition according to any one of claims 1 to 10, comprising a copolymer having structural units of (I), (II) and (IV). 12. A wholly aromatic liquid crystalline polyester resin (B).
Is a copolymer having the structural unit of the above (I). 13. A wholly aromatic liquid crystalline polyester resin (B).
Consists of the above structural units (I), (II) and (IV),
(I) is 15 to 9 with respect to the total of the structural units (I) and (II).
0 mol%, and the structural unit (II) is composed of the structural units (I) and (I)
85 to 10 mol% based on the total of the structural units (I)
The liquid crystalline resin composition according to claim 10, wherein I) is substantially equimolar to the structural unit (IV). 14. The liquid crystalline resin composition according to claim 13, wherein 5 to 100 mol% of the structural unit (IV) is the following structural unit (V). Embedded image 15. The liquid crystalline resin composition according to claim 1, wherein 50% or more of the inorganic filler (D) is fibrous. 16. The liquid crystalline resin composition according to claim 1, wherein the inorganic filler (D) is fibrous. 17. The liquid crystalline resin composition according to claim 1, wherein 50% or more of the inorganic filler (D) is glass fiber. 18. The liquid crystalline resin composition according to claim 1, wherein the inorganic filler (D) is glass fiber. 19. The liquid crystalline resin composition according to claim 1, further comprising 0.5 to 60 parts by weight of an organic bromide based on 100 parts by weight of the liquid crystalline resin (C). . 20. The organic bromide is a polybrominated styrene having at least one of the following structural units produced from a brominated styrene monomer as a main constitutional unit and having a weight average molecular weight of 1 × 103 to 120 × 104. The liquid crystal resin composition according to the above. Embedded image 21. A copolymer comprising polyethylene, polypropylene, ethylene or propylene and an α-olefin having 3 or more carbon atoms, and ethylene or propylene and 3 or more carbon atoms based on 100 parts by weight of the liquid crystalline resin (C). At least one selected from copolymers of α-olefins and non-conjugated dienes, and having a weight average molecular weight of 1
21. The liquid crystalline resin composition according to any one of claims 1 to 20, further comprising 0.01 to 10 parts by weight of an olefin polymer in a range of from 000 to 600,000. 22. A liquid crystalline resin molded article obtained by molding the liquid crystalline resin composition according to claim 1. 23. The liquid crystal resin molded product according to claim 22, wherein the liquid crystal resin molded product is a small molded product.