JPH10273554A - Liquid-crystalline resin composition and precise molding prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which gives a molded article excellent in thin-wall flowability and mechanical properties and having a high vibration- damping capability, a smooth surface, and small variations in physical properties by compounding a liq.-crystalline resin with aluminum borate whisker having a particle size and a relative particle amt. satisfying a specific relation. SOLUTION: The liq.-crystalline resin (A) is a liq.-crystalline polyester, a liq.-crystalline polyesteramide, etc., capable of forming anisotropy when melted. A liq.-crystalline polyester is a polyester which have ethylenedioxy units as the essential units and comprises structural units represented by formulas I to IV (wherein R1 is at least one kind of a group selected from among groups represented by formula V; R2 is at least one kind of a group selected from among groups represented by formula VII; and X is H or Cl). The aluminum borate whisker (B) used has a particle size distribution (obtd. by laser diffraction) satisfying the relation: 7.5<=D90/D10<=20 [wherein D90 (μm) is the particle size at a relative particle amt. of 90%; and D10 (μm) is that at a relative particle amt. of 10%]. 100 pts.wt. ingredient A is compounded with 1-300 pts.wt. ingredient B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to electric / electronic parts,
The present invention relates to a liquid crystal resin composition having excellent thin fluidity and excellent mechanical properties useful as OA / AV parts, automobile parts, machine parts, housing parts, and the like, and a precision molded product comprising the same. In particular, the present invention relates to a liquid crystal resin composition that requires a vibration damping property and can stably produce a precision molded product that requires a surface smoothness.

[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. Among them, optical anisotropy during melting characterized by a parallel arrangement of molecular chains has been developed. Are attracting attention because they have excellent fluidity and mechanical properties. However, the mechanical properties of liquid crystalline resin alone are not enough to replace precision metal parts, and the development of liquid crystalline resin compositions with even better mechanical physical properties has been developed by blending fillers with high mechanical properties. It is becoming necessary.

[0003] Among them, a technique of blending aluminum borate whiskers as a filler having high mechanical properties is known (for example, JP-A-3-59067, JP-A-4-96965, and JP-A-Hei-4-96965). -198256, JP-A-6-220249). However, aluminum borate whiskers known so far do not provide the mechanical properties as high as expected when molding precision molded products such as optical pickup parts.
There was a problem that sufficient vibration damping properties could not be obtained, and physical property variations were large, resulting in an increase in the rate of occurrence of defective products having insufficient physical properties.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and is excellent in thin-wall fluidity and mechanical properties, has high vibration damping properties, has a smooth surface, and has a small variation in physical properties of molded articles. It is an object to obtain a small amount of a liquid crystalline resin composition and a precision molded product comprising the same.

[0005]

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 relates to (1) (A) a liquid crystalline resin 1
(B) The particle size at a relative particle amount of 90% in the particle size distribution determined by laser diffraction
(Μm), and the particle diameter at a relative particle amount of 10% is D10 (μm).
m), a liquid crystalline resin composition comprising 1 to 300 parts by weight of aluminum borate whiskers satisfying 7.5 ≦ D90 / D10 ≦ 20; (2) (A) 100 parts by weight of the liquid crystalline resin; (B) In a liquid crystalline resin composition containing 1 to 300 parts by weight of aluminum borate whiskers, when the relative particle amount is 90% in the particle size distribution obtained by laser diffraction of aluminum borate whiskers in the composition. Has a particle size of D90 (μm) and a relative particle amount of 1.
When the particle size at 0% is D10 (μm), 5 ≦ D90 / D10 ≦ 20, (3) the liquid crystalline resin (A) is a liquid crystalline polyester and And / or a liquid crystalline resin comprising a liquid crystalline polyesteramide
(1) The liquid crystalline resin composition according to (2), (4) the liquid crystalline resin wherein the liquid crystalline resin (A) comprises a liquid crystalline polyester and / or a liquid crystalline polyesteramide containing an ethylene dioxide unit as an essential component. The liquid crystal resin composition according to any one of the above (1) to (3), wherein (5) the liquid crystal resin (A) is composed of the following structural units (I), (II), (III) and (IV) The liquid crystalline resin composition according to any one of the above (1) to (4), which is a liquid crystalline polyester,

Embedded image (However, R ₁ in the formula is

Embedded image R ₂ represents one or more groups selected from

Embedded image And at least one group selected from In the formula, X represents a hydrogen atom or a chlorine atom. (6) The aluminum borate whisker (B) has a particle size distribution of 8 ≦ D90 / D determined by laser diffraction.
The liquid crystalline resin composition according to any one of the above (1), (3) to (5), which is an aluminum borate whisker satisfying 10 ≦ 14, and (7) an aluminum borate whisker (B) is obtained by laser diffraction. 1.0 μm in particle size distribution
The liquid crystalline resin composition according to any one of the above (1), (3) to (6), which is an aluminum borate whisker satisfying <D10 ≦ 2.0 μm, and (8) aluminum borate whisker (B) is subjected to laser diffraction. The liquid crystalline resin composition according to any one of the above (1), (3) to (7), which is an aluminum borate whisker having a particle size distribution of 8.0 μm <D90 ≦ 18 μm, (9) liquid crystal Resin (A) 100
The liquid crystalline resin composition according to any one of the above (1) to (8), further comprising 0.5 to 60 parts by weight of an organic bromide with respect to parts by weight, and (10) the organic bromide is bromine. One or more of the following structural units produced from a styrene monomer are used as main constituent units, and have a weight average molecular weight of 1 × 10 ^{3 to} 120 ×
The liquid crystalline resin composition according to the above (9), which is 10 ⁴ polybrominated styrene,

Embedded image (11) For 100 parts by weight of the liquid crystalline resin (A), polyethylene, polypropylene, a copolymer of ethylene or propylene and an α-olefin having 3 or more carbon atoms, and an α-olefin of ethylene or propylene and 3 or more carbon atoms. −
Liquid crystallinity according to any one of the above (1) to (10), further comprising 0.01 to 10 parts by weight of at least one olefin polymer selected from a copolymer comprising an olefin and a non-conjugated diene. In the resin composition, (12) the liquid crystalline resin (A) in the molten state, (B) the particle size at a relative particle amount of 90% in the particle size distribution determined by laser diffraction was D90 (μ).
m), the particle diameter at a relative particle amount of 10% is D10 (μm)
Wherein the liquid crystalline resin composition according to any one of the above (1) to (11) is produced by adding and blending an aluminum borate whisker satisfying 7.5 ≦ D90 / D10 ≦ 20. (13) A liquid crystalline resin composition molded article comprising (A) 100 parts by weight of the liquid crystalline resin and (B) 1 to 300 parts by weight of aluminum borate whisker. In the particle size distribution obtained by laser diffraction of aluminum borate whiskers in the product, the particle size when the relative particle amount is 90% is D90 (μm), and the particle size when the relative particle amount is 10% is D10 (μm). Wherein: 5 ≦ D90 / D10 ≦ 20, (14) the liquid crystalline resin composition according to any one of the above (1) to (11), which is formed by molding Precision molded products, (15) (14) or (15) above, wherein the precision molded article comprising the liquid crystalline resin molded article according to (13) above, or (16) the precision molded article is for a member requiring vibration damping properties
(17) An optical pickup component formed by molding the liquid crystalline resin composition according to any one of (1) to (11).

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Liquid crystalline resin (A) used in the present invention
Is a resin capable of forming anisotropy upon melting, and examples thereof include liquid crystalline polyester, liquid crystalline polyester amide, liquid crystalline polyester carbonate, and liquid crystalline polyester elastomer, among which liquid crystalline polyester and liquid crystalline polyester amide are included. And the like are preferably used.

The liquid crystalline polyester comprises a structural unit selected from one or more of an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic dicarbonyl unit, an ethylenedioxy unit and the like. And a liquid crystalline polyester amide comprising the above structural unit and a structural unit selected from an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit, and anisotropically. Mention may be made of polyesteramides which form a molten phase.

The liquid crystalline polyester which can be preferably used in the present invention is a liquid crystalline polyester having an ethylenedioxy unit as an essential component.
(I), (III), (IV) or (I), (II), (III), (IV)
And most preferably a polyester comprising the structural units (I), (II), (III) and (IV).

[0010]

Embedded image (However, R ₁ in the formula is

Embedded image R ₂ 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) is a structural unit formed from p-hydroxybenzoic acid, and 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- Dihydroxynaphthalene,
Structural units formed from one or more aromatic dihydroxy compounds selected from 2,2-bis (4-hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl ether, and structural unit (III) formed from ethylene glycol The structural unit (IV) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid,
6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'- The structural units generated from one or more aromatic dicarboxylic acids selected from diphenyl ether dicarboxylic acids are shown below. Of these, R ₁ is

Embedded image And R ₂ is

Embedded image Is particularly preferred.

The liquid crystalline polyester which can be preferably used in the present invention includes the above structural unit (I), (III), (IV) or (I)
, (II), (III) and (IV). The copolymerization amount of the structural units (I), (II), (III) and (IV) is arbitrary. However, the following copolymerization amount is preferred from the viewpoint of fluidity.

That is, the structural units (I), (III) and (I
In the case of the copolymer comprising V), the structural unit (I) is preferably 30 to 95 mol%, more preferably 40 to 95 mol%, based on the total of the structural units (I) and (III). Further, the structural unit (IV) is preferably substantially equimolar to the structural unit (III).

On the other hand, the structural units (I), (II), (III),
In the case of the copolymer consisting of (IV), the sum of the above structural units (I) and (II) is structural units (I), (II) and (III) in terms of heat resistance, flame retardancy and mechanical properties. 60) for the sum of
-95 mol% is preferable, and 80-92 mol% is more preferable. Further, the structural unit (III) is preferably 40 to 5 mol%, preferably 2 to 5 mol%, based on the total of the structural units (I), (II) and (III).
0-8 mol% is more preferable. In addition, the structural units (I) and (I
The molar ratio of (I) [(I) / (II)] is preferably 75/25 to 95/5, more preferably 78/22 to 93/7, from the viewpoint of the balance between heat resistance and fluidity. Further, it is preferable that the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III).

Further, as the liquid crystalline polyesteramide,
Polyesteramides forming an anisotropic molten phase containing p-iminophenoxy units formed from p-aminophenol in addition to the structural units (I) to (IV) are preferred.

The liquid crystalline polyesters and liquid crystalline polyesteramides which can be preferably used include, in addition to the components constituting the structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid and 2,2'-diphenyl Aromatic dicarboxylic acids such as dicarboxylic acid, adipic acid, azelaic acid,
Aliphatic dicarboxylic acids such as sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylsulfone, 4,4'- Dihydroxydiphenyl sulfide,
Aromatic diols such as 4,4'-dihydroxybenzophenone and 3,4'-dihydroxybiphenyl, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol,
Aliphatic and alicyclic diols such as 4-cyclohexanedimethanol and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid and p-aminophenol and p-aminobenzoic acid are used as liquid crystalline compounds. Can be further copolymerized within a range that does not impair the above.

The method for producing a liquid crystalline resin in the present invention is not particularly limited. For example, a method for producing a liquid crystalline polyester or a liquid crystalline polyesteramide can be produced according to a known polyester or polyesteramide polycondensation method.

For example, in the production of the above-mentioned preferably used liquid crystalline polyester, the following production method is preferably mentioned.

(1) p-acetoxybenzoic acid, 4,4 '
Diacylated aromatic dihydroxy compounds such as diacetoxybiphenyl and diacetoxybenzene and aromatic dicarboxylic acids such as terephthalic acid and polyester polymers such as polyethylene terephthalate, oligomers or aromatic dicarboxylic acids such as bis (β-hydroxyethyl) terephthalate From the bis (β-hydroxyethyl) ester of the above by an acetic acid depolycondensation reaction.

(2) p-hydroxybenzoic acid, 4,4 '
Aromatic dihydroxy compounds such as dihydroxybiphenyl and hydroquinone; aromatic dicarboxylic acids such as acetic anhydride and terephthalic acid; polyester polymers such as polyethylene terephthalate; oligomers; and aromatic dicarboxylic acids such as bis (β-hydroxyethyl) terephthalate And a bis (β-hydroxyethyl) ester by a deacetic acid polycondensation reaction.

(3) A method in which 1,2-bis (4-hydroxybenzoyl) ethane is used as a part of the starting material in the production method of (1) or (2) as disclosed in JP-A-3-59024.

As the catalyst used for the polycondensation reaction, those known as polycondensation catalysts for liquid crystalline resins can be used.

The liquid crystalline resin used in the present invention is:
In some cases, the logarithmic viscosity can be measured in pentafluorophenol. In this case, the value measured at 60 ° C. at a concentration of 0.1 g / dl is preferably 0.3 or more. Particularly preferably, the content is 0.5 to 3.0 dl / g when it is contained, and 1.0 to 15.0 dl / g when it does not contain the structural unit (III).

The melt viscosity of the liquid crystalline resin in the present invention is preferably from 10 to 20,000 poise, more preferably from 20 to 20,000 poise.
10,000 poise is more preferred.

The aluminum borate whiskers (B) used in the present invention _{is, 9Al 2 0 3 · 2B 2} O 3 or 2
It refers to those having a needle-like shape shown in the chemical composition of _{Al 2 O 3 · B 2 O} 3. These aluminum borate whiskers are prepared, for example, by heating Al ₂ O ₃ or a raw material generating Al ₂ O ₃ and a raw material generating B ₂ O ₃ or B ₂ O ₃ at a temperature of 800 to 1200 ° C. in the presence of an alkali metal salt. The whisker is obtained by heating and reacting to grow whiskers.

The surface of the aluminum borate whisker (B) used in the present invention may be treated with a coupling agent such as a silane compound, a titanate compound or an aluminum compound. Examples of such a silane compound include amino silane, epoxy silane, vinyl silane, and mercapto silane. For example, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, γ-aniline Linopropyltrimethoxysilane, hydroxypropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, vinylacetoxysilane, isopropyltrisisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) Titanate,
Examples include tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl tridecyl benzene sulfonyl titanate, isopropyl tri (dioctyl phosphate) titanate, and acetoalkoxy aluminum diisopropylate.

The aluminum borate whisker (B) used in the present invention has a particle size D90 at a relative particle amount of 90% in the particle size distribution determined by laser diffraction.
(Μm), and the particle diameter at a relative particle amount of 10% is D10 (μm).
When m), 7.5 ≦ D90 / D10 ≦ 20, and more preferably 8 ≦ D90 / D10 ≦ 14. When D90 / D10 is in the above range, a molded product having good mechanical strength and surface smoothness, small variation in physical properties of the composition, and stable characteristics can be obtained.

In the aluminum borate whisker (B) used in the present invention, 1.0 μm <D10 ≦ 2.0 μm in the particle size distribution determined by laser diffraction indicates a high elastic modulus, excellent vibration damping properties, It is preferable in that a composition and a molded article having surface smoothness can be obtained.

In the particle size distribution of the aluminum borate whiskers (B) used in the present invention determined by laser diffraction, 8.0 μm <D90 ≦ 18 μm, high strength, excellent surface smoothness, and uneven physical properties. This is preferable in that a molded product having stable characteristics without any problem can be obtained.

The particle size distribution of the aluminum borate whisker (B) of the present invention can be measured by a general laser diffraction type particle size distribution analyzer. The particle size distribution measuring apparatus includes a wet method and a dry method, and any of them may be used. In the case of the wet method, water can be used as a dispersion medium for aluminum borate whiskers. At that time, the surface treatment of the whisker may be performed with an alcohol or a neutral detergent. It is also possible to use a phosphate such as sodium hexametaphosphate or sodium pyrophosphate as the dispersant. It is also possible to use an ultrasonic bath as a dispersing device. The measurement range of the particle size distribution depends on the performance of the apparatus, but it is desirable to measure a range of at least 0.1 μm to a maximum of 500 μm. More desirably, a range of at least 0.05 μm to a maximum of 700 μm is measured. The particle diameter D10 (μm) when the relative particle amount is 10% from the minimum particle diameter and the particle diameter D90 (μm) when the relative particle amount is 90% based on the cumulative particle size distribution data analyzed by the laser diffraction type particle size distribution analyzer. Can be requested.

The compounding amount of the aluminum borate whisker (B) used in the present invention is 1 to 300 parts by weight, preferably 1 to 100 parts by weight of the liquid crystalline resin (A).
0 to 200 parts by weight, more preferably 25 to 100 parts by weight.

It is also possible to use other fillers together with the liquid crystalline resin composition of the present invention. Other fillers include glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, asbestos fiber, graphite, mica, talc , Silica, calcium carbonate, glass beads,
Examples include fibrous, powdery, granular or plate-like inorganic fillers such as glass flakes, glass microballoons, clay, wollastenite, titanium oxide, and molybdenum disulfide. As these fillers, those treated with a silane-based, titanate-based coupling agent, or another surface treatment agent may be used.

In the present invention, an organic bromide can be further blended, and the organic bromide includes 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,
Low molecular weight organic bromine compounds such as octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylene-bis (tetrabromophthalimide), and tetrabromobisphenol A, and brominated polycarbonate (for example, manufactured using brominated bisphenol A as a raw material) Polycarbonate oligomer or its copolymer with bisphenol A),
Brominated epoxy compounds (eg, brominated bisphenol A
A diepoxy compound produced by the reaction of epichlorohydrin with a diepoxy compound or a monoepoxy compound obtained by the reaction of a brominated phenol with epichlorohydrin), poly (brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, cyanuric chloride and Halogenated polymers and oligomers such as condensates of brominated phenol, brominated polystyrene, cross-linked brominated polystyrene, cross-linked brominated poly-α-methylstyrene, and mixtures thereof, among which ethylene bis (tetrabromophthalimide) ), Brominated epoxy oligomers or polymers, brominated polystyrene, cross-linked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are preferred, and brominated polystyrene is most preferred. Ku can be used.

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.

[0035]

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 anionic polymerization, or brominated styrene monomer can be obtained by 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, etc., and especially the following (ii) produced from a brominated styrene monomer And / or (iii) a polybrominated styrene having a weight average molecular weight of 1 × 10 ^{3 to} 120 × 10 ⁴ as a main component.

[0037]

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 by a substitution reaction, and other than dibrominated styrene and / or tribrominated styrene. May contain monobrominated styrene.

The polybrominated styrene preferably contains dibrominated styrene and / or tribrominated styrene units in an amount of 60% by weight or more, more preferably 70% by weight or more. In addition to dibrominated styrene and / or tribrominated styrene, polybrominated styrene obtained by copolymerizing 40% by weight or less, preferably 30% by weight or less of monobrominated styrene 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.

[0041]

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 preferably 0.5 to 60 parts by weight, more preferably 1 to 30 parts by weight, per 100 parts by weight of the liquid crystalline resin (A).

In the liquid crystalline resin composition of the present invention, the organic bromide is preferably dispersed in the composition at an average diameter of 2.5 μm or less, more preferably at 2.0 μm or less. .

In the present invention, an olefin-based polymer can be blended. The olefin-based polymer is not particularly limited, but may be polyethylene, polypropylene, ethylene and / or propylene having 4 carbon atoms.
Copolymers composed of the above α-olefins, copolymers composed of ethylene and / or propylene and an α-olefin having 4 or more carbon atoms and a non-conjugated diene, and the like are preferably used, and one or more kinds are used. be able to.

The α-olefin having 4 or more carbon atoms is preferably butene-1, pentene-1, 3-methylpentene-1, octene-1, and the like, and more preferably butene-1. These can be used in combination.

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 preferably 40/6.
0 to 99/1 (molar ratio), particularly 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 preferably 5 to 96.9 mol%, particularly preferably 30 to 84.5 mol. %, And the copolymerization amount of the α-olefin having 3 or more carbon atoms is preferably from 3 to 80.
Mol%, particularly preferably 15 to 60 mol%, and the copolymerization amount of the non-conjugated diene is preferably 0.1 to 15 mol%, particularly preferably 0.5 to 10 mol%. Also,
The copolymerization amount of propylene in the copolymer comprising propylene, an α-olefin having 4 or more carbon atoms and a non-conjugated diene is preferably 5 to 96.9 mol%, particularly preferably 30 to 84.5 mol%. , Α- having 4 or more carbon atoms
The copolymerization amount of the olefin is preferably 3 to 80 mol%,
Particularly preferably, it is 15 to 60 mol%, and the copolymerization amount of the non-conjugated diene is preferably 0.1 to 15 mol%, particularly 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 are more preferable.

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

Further, these olefin polymers are preferable in that a monomer having excellent fluidity can be obtained when a monomer containing an epoxy group, a carboxylic acid group or the like is not copolymerized.

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 mold release effect, weld strength, appearance of the molded product and fluidity.
0, preferably 30,000 to 500,000, and more preferably 100,000 to 450,000.

The amount of the olefin polymer to be added is not particularly limited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the liquid crystalline resin (A) from the viewpoint of releasability and weld strength. 0.1-5 parts by weight are particularly preferred.

The liquid crystal resin composition of the present invention may further contain an epoxy compound for improving the 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.

Further, the liquid crystal resin composition of the present invention may contain an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and the like) to such an extent that the object of the present invention is not impaired. Substituents), UV absorbers (eg resorcinol, salicylate,
Benzotriazole, benzophenone, etc.), lubricants and release agents (montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide, polyethylene and polyethylene wax, etc.),
A conventional additive such as a coloring agent including a dye (eg, nitrosine) and a pigment (eg, cadmium sulfide, phthalocyanine, carbon black), a plasticizer, an antistatic agent, a crystal nucleating agent, a flame retardant, etc. Properties can be imparted.

The method for producing the liquid crystalline resin composition of the present invention is not particularly limited, and examples thereof include a method of melting and kneading the components.

The method of mixing the liquid crystalline resin (A), the aluminum borate whisker (B), and the filler used together is preferably melt-kneading, and a known method can be used for melt-kneading. For example, a composition can be obtained by melt-kneading using a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder, or the like.

As a preferred method, a method in which an aluminum borate whisker (B) is added to and blended with the liquid crystalline resin (A) in a molten state, specifically, using a twin-screw extruder, the liquid crystalline resin (B) is used. There is a method in which aluminum borate whiskers (B) are supplied by a side feeder and kneaded, where A) is melted with the raw materials. As for the screw arrangement of the twin-screw extruder, it is desirable that kneading after the side feeder supply section is not so strong so that the aluminum borate whisker (B) is not broken as much as possible.

The method for adding the other additives is not particularly limited, and it is preferable to carry out melt-kneading. A known method can be used for the melt-kneading. For example, in the preferred method described above, a method using a liquid crystalline resin to which an additive has been added in advance, or the compound is added together with the component (B) or at any other position different therefrom And the like.

In the present invention, when the particle size distribution of the aluminum borate whiskers (B) in the composition satisfies 5 ≦ D90 / D10 ≦ 20, the liquid crystal resin composition has the mechanical strength and the surface smoothness. It is preferable because a molded article having good properties, small variation in physical properties, and stable properties can be obtained.

As a preferred method for producing the liquid crystalline resin composition having such a particle size distribution, specifically, a twin screw extruder is used to melt the liquid crystalline resin (A). Then, a method of supplying and kneading the aluminum borate whiskers (B) having the above-described particle size distribution by a side feeder can be mentioned. As for the screw arrangement of the twin-screw extruder, it is desirable that kneading after the side feeder supply section is not so strong so that the aluminum borate whisker (B) is not broken as much as possible.

The method of adding the other additives is not particularly limited, and it is preferable to carry out melt-kneading. A known method can be used for the melt-kneading. For example, in the preferred method described above, a method using a liquid crystalline resin to which an additive has been added in advance, or the compound is added together with the component (B) or at any other position different therefrom And the like.

The liquid crystalline resin composition of the present invention thus obtained has excellent moldability and can be formed by a usual molding method (injection molding,
Extrusion molding, blow molding, press molding, injection press molding, etc.) can be processed into three-dimensional molded products, sheets, container pipes, etc., and are particularly effective for precision molded products obtained by injection molding.

In the present invention, when the particle size distribution of the aluminum borate whiskers (B) in the molded product is 5 ≦ D90 / D10 ≦ 20, the liquid crystalline resin molded product has a mechanical strength and a surface smoothness. It is preferable because a molded article having good properties, small variation in physical properties, and stable properties can be obtained.

As a method for producing such a molded product, there is a method of molding a liquid crystalline resin composition melt-kneaded using a liquid crystalline resin (A) and an aluminum borate whisker (B) having a specific particle size distribution. Among them, a method of molding a liquid crystalline resin composition in which the particle size distribution of aluminum borate whiskers in the composition is in the above-mentioned range is particularly preferred. Injection molding,
Extrusion molding, blow molding, press molding, injection press molding and the like may be used, but injection molding is particularly preferred. In particular, it is effective for precision molded products obtained by injection molding.

The liquid crystalline resin composition of the present invention can be used for various gears,
Various cases, sensors, LED lamps, connectors, sockets, resistors, relay case switch coil bobbins,
Capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal display parts, FD
D / carriage, FDD chassis, HDD parts, motor brush holders, parabolic antennas, electric / electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, sound parts Audio equipment parts such as audio, laser disk, compact disk,
Homes represented by lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc.
Office electrical product parts, office computer related parts,
Telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, various bearings such as oilless bearings, stern bearings, underwater bearings, etc., motor parts, machine parts such as lighters and typewriters, microscopes , Optical equipment such as binoculars, cameras, clocks, etc., precision machinery related parts; alternator terminal, alternator connector, IC regulator, potentiometer base for light drier, various valves such as exhaust gas valve, fuel related, exhaust system, intake system Various pipes, 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, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, Heating and hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust distributor, starter switch, 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 plate, Step motor rotor, lamp socket, lamp reflector, lamp housing,
It is useful for automotive and vehicle related parts such as brake piston, solenoid bobbin, engine oil filter, ignition device case, and other various uses. The liquid crystalline resin composition of the present invention has a high modulus of elasticity and is particularly useful for precision molded articles, especially precision molded articles for members requiring vibration damping properties. Among them, CD (compact disk) and CD-R
Optical pickup components, which are optical system driving devices such as OM, DVD, MO, and PD, are useful because they require excellent vibration characteristics.

[0067]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of 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 liquid crystalline 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 liquid crystalline 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, 149 parts by weight of hydroquinone
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 liquid crystalline 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 liquid crystal resin having 24 dl / g and a weight average molecular weight of about 35,000 was obtained.

The values of D90 / D10 of the aluminum borate whiskers (B) used in the present invention are shown below.

The particle size distribution of the aluminum borate whiskers (B) was measured by a laser diffraction / scattering type particle size distribution analyzer LA-700 manufactured by Horiba, Ltd. The measurement sample was prepared using pure water as a dispersion medium, dispersed using an ultrasonic bath, and adjusted to have a transmittance of about 80%. The cumulative particle size distribution was analyzed on a volume basis.

The particle size distribution of the composition and the aluminum borate whisker (B) of the molded product was determined by heating the composition (pellet) and the molded product in an electric furnace at 550 ° C. for 5 hours to incinerate the resin component. Later, the residue was measured.

B-1 is a commercially available aluminum borate whisker (trade name: Arbolex, Shikoku Chemical Industry Co., Ltd.)
Ltd., chemical _{composition: 9Al 2 O 3 · 2B 2} O 3, the fiber diameter 0.
5 to 1.0 μm, fiber length 10 to 30 μm), and B-
2 to B-7 were obtained by classifying commercially available products.

B-1: D90 / D10 = 5.8 (D90 = 10.5, D10 = 1.8) B-2: D90 / D10 = 8.1 (D90 = 13.0, D10 = 1.6) ) B-3: D90 / D10 = 9.5 (D90 = 9.5, D10 = 1.0) B-4: D90 / D10 = 12.6 (D90 = 17.6, D10 = 1.4) B -5: D90 / D10 = 17.0 (D90 = 17.0, D10 = 1.0) B-6: D90 / D10 = 25.0 (D90 = 20.0, D10 = 0.8) B-7 : D90 / D10 = 3.0 (D90 = 7.5, D10 = 2.5) The organic bromide used in the present invention is dibrominated styrene 80.
% By weight, a polybrominated styrene obtained by polymerizing a monomer mixture containing 15% by weight of monobrominated styrene and 5% by weight of dibrominated styrene (bromine content: 59% by weight), (weight average molecular weight: 30 × 10 ⁴ ) Copolymer (referred to as FR-1).

Examples 1 to 10 and Comparative Examples 1 to 6 100 parts by weight of the liquid crystalline resin (A) obtained in Reference Examples and aluminum borate whiskers (B) shown in Table 2 were prepared by L / D = 45.
And melt-kneaded under various conditions at 290 to 330 ° C. using a 30 mm φ twin screw extruder to form pellets. In addition, the liquid crystalline resin (A) was supplied from the starting position of the twin screw extruder, and the aluminum borate whisker (B) was supplied from the position where the liquid crystalline resin was melted by a side feeder. After drying with hot air, the pellets are supplied to a Sumitomo Nestar injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), and the cylinder temperature is set to 290 to 350 ° C. and the mold temperature is set to 90 ° C. The indicated test piece for measurement was obtained by injection molding. The measuring method is described below.

(1) Bending Characteristics A test piece 3.2 mm thick × 12.7 mm wide × 127 mm long was formed using the above-mentioned forming machine.
The measurement was performed according to 790, and the minimum value, the maximum value, the difference between the maximum value and the minimum value, and the average value of the ten pieces of bending strength and flexural modulus were determined.

(2) Surface Smoothness The JIS (B0651) ten-point average roughness (Rz) of the test piece for bending characteristics was measured to determine the surface smoothness.

(3) Thin-wall fluidity Using the above molding machine, the cylinder temperature melting point + 10 ° C.
Mold temperature 120 ° C, injection speed 99%, injection pressure 500k
Under the condition of gf / cm ² , the rod flow length of a test piece of a 1.0 mmφ pin gate having a thickness of 0.5 mm × a width of 12.7 mm was measured.

Table 1 shows the results.

[0082]

[Table 1] From the results in Table 1, the liquid crystalline resin (A) and the specific D90 / D1
Excellent flexural strength only in the case of a specific liquid crystalline resin composition containing 0 aluminum borate whiskers (B),
It can be seen that it has a flexural modulus, its dispersion is small, and its surface smoothness is excellent. In addition, it is understood that the thin-wall fluidity useful for precision molded products is also excellent.

Example 11 In Example 3, aluminum borate whiskers (B-
Pellets of the composition were produced in the same manner as in Example 3, except that a product treated with an aminosilane coupling agent (γ-aminopropyltriethoxysilane) was used as 4).

Example 12 In Example 3, the above-mentioned organic bromide (FR-1) was further added.
The pellets of the composition were produced in the same manner as in Example 3, except that 100 parts by weight of the liquid crystal resin composition was mixed with the liquid crystal resin at the ratio shown in Table 2 from the starting position of the twin-screw extruder. did. 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.
0.5 mm (thickness) x 12.7 mm x 12 under the condition of ° C
A 7 mm combustion test piece is formed, and the combustion test piece is used
A vertical combustion test was performed in accordance with the L94 standard to evaluate the flame retardancy.

The results are shown in Table 2.

[0086]

[Table 2] Flame retardancy was imparted without lowering the thin-wall fluidity, bending characteristics and surface smoothness of the liquid crystalline resin composition.

Examples 13 to 17 In Example 3, the olefin polymer shown in Table 3 was added together with the liquid crystal resin in the ratio shown in Table 3 to 100 parts by weight of the liquid crystal resin composition together with the liquid crystal resin in a twin-screw extruder. Pellets of the composition were produced in the same manner as in Example 3 except that the mixture was supplied from the filling position and blended. These pellets are injected into a Toshiba IS55EPN injection molding machine (Toshiba Machine Plastic Engineering Co., Ltd.)
The temperature of the cylinder is 10 ° C. and the temperature of the mold is 90 ° C., and the size is 8 mm wide × 10 mm high × 100 mm long and 1 mm thick.
Forming a molded product provided with 4 8 mm partition walls at equal intervals,
Measure the ejection force when ejecting the molded product from the mold,
The releasability was evaluated.

The appearance of the molded product was observed, and the presence or absence of gas burn was evaluated.

[0089]

[Table 3] The mold releasability was imparted without lowering the mechanical properties and surface smoothness of the liquid crystalline resin composition and without impairing the surface appearance.

Example 18 In Example 12, the olefin polymer shown in Table 4 was added together with the liquid crystal resin in the ratio shown in Table 4 to 100 parts by weight of the liquid crystal resin composition together with the liquid crystal resin in the starting position of the twin-screw extruder. Pellets of the composition were produced in the same manner as in Example 12, except that they were supplied and blended. This pellet is used for Toshiba IS55EPN
It is supplied to an injection molding machine (manufactured by Toshiba Machine Plastic Engineering Co., Ltd.), and the size of the cylinder is 8 mm wide and 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 article was observed, and the presence or absence of gas burning was evaluated. The pellets were supplied to a Sumitomo Nestal injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), and the cylinder temperature was set at a melting point of + 10 ° C.
0.5 mm (thickness) x 1 at a mold temperature of 90 ° C
A combustion test specimen of 2.7 mm × 127 mm was molded, and a vertical combustion test was performed using the combustion test specimen in accordance with the UL94 standard to evaluate the flame retardancy.

[0092]

[Table 4]

[0093]

The liquid crystalline resin composition of the present invention is excellent in thin-wall fluidity, mechanical properties and surface smoothness, in particular, there is little variation in mechanical properties and stable and excellent properties can be obtained. It is a material suitable for various applications such as electric / electronic related equipment, precision machine related equipment, office equipment, automobile, etc. In particular, it has excellent vibration damping properties due to its small variation and high elastic modulus, and is useful for small and precise parts that require vibration damping properties, such as optical pickup parts, such as lens holders. It is.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 101/00 C08L 101/00 G02B 1/04 G02B 1/04 // C09K 19/38 C09K 19/38

Claims (17)

[Claims] 1. A particle size distribution of 100% by weight of (A) a liquid crystalline resin and (B) a particle size distribution of 90% in a particle size distribution determined by laser diffraction is D90 (μm).
A liquid crystal resin composition comprising 1 to 300 parts by weight of aluminum borate whiskers satisfying 7.5 ≦ D90 / D10 ≦ 20, where the particle size at 0% is D10 (μm). 2. A liquid crystal resin composition comprising (A) 100 parts by weight of a liquid crystalline resin and (B) 1 to 300 parts by weight of aluminum borate whiskers, wherein laser diffraction of the aluminum borate whiskers in the composition is carried out. The particle size at a relative particle amount of 90% in the particle size distribution determined by
0 (μm), the particle size at a relative particle amount of 10% is D10
(Μm), wherein 5 ≦ D90 / D10 ≦ 20. 3. The liquid crystalline resin composition according to claim 1, wherein the liquid crystalline resin (A) is a liquid crystalline resin comprising a liquid crystalline polyester and / or a liquid crystalline polyesteramide. 4. The liquid crystal according to claim 1, wherein the liquid crystalline resin (A) is a liquid crystalline resin comprising a liquid crystalline polyester and / or a liquid crystalline polyesteramide containing an ethylene dioxide unit as an essential component. Resin composition. 5. The liquid crystalline resin (A) comprises the following structural units (I) and (I)
The liquid crystalline resin composition according to any one of claims 1 to 4, which is a liquid crystalline polyester consisting of (I), (III) and (IV). Embedded image (Where R ₁ in the formula is And R ₂ represents one or more groups selected from And at least one group selected from In the formula, X represents a hydrogen atom or a chlorine atom. ) 6. An aluminum borate whisker (B) having a particle size distribution of 8 ≦ D9 determined by laser diffraction.
The liquid crystalline resin composition according to claim 1, wherein the liquid crystalline resin composition is an aluminum borate whisker satisfying 0 / D10 ≦ 14. 7. An aluminum borate whisker (B) having a particle size distribution of 1.0 μm in a particle size distribution determined by laser diffraction.
7. The liquid crystalline resin composition according to claim 1, which is an aluminum borate whisker satisfying m <D10 ≦ 2.0 μm. 8. An aluminum borate whisker (B) having a particle size distribution of 8.0 μm as determined by laser diffraction.
8. The liquid crystalline resin composition according to claim 1, which is an aluminum borate whisker satisfying m <D90 ≦ 18 μm. 9. A liquid crystal resin (A) based on 100 parts by weight,
The liquid crystalline resin composition according to any one of claims 1 to 8, further comprising 0.5 to 60 parts by weight of an organic bromide. 10. 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 constituent unit and having a weight average molecular weight of 1 × 10 ^{3 to} 120 × 10 ^4. Item 10. A liquid crystalline resin composition according to item 9. Embedded image 11. Polyethylene, polypropylene, ethylene and / or 100 parts by weight of the liquid crystalline resin (A).
Or at least one kind selected from a copolymer consisting of propylene and an α-olefin having 4 or more carbon atoms and a copolymer consisting of ethylene and / or an α-olefin having 4 or more carbon atoms and a non-conjugated diene; The liquid crystalline resin composition according to any one of claims 1 to 10, further comprising 0.01 to 10 parts by weight of an olefin polymer. 12. A method according to claim 1, wherein the liquid crystal resin (A) in the molten state has a particle size D90 (μm) at a relative particle amount of 90% in a particle size distribution determined by laser diffraction, and a relative particle amount of 1
The liquid crystalline resin according to any one of claims 1 to 11, wherein an aluminum borate whisker satisfying 7.5 ≦ D90 / D10 ≦ 20 is added and blended when the particle size at 0% is D10 (μm). A method for producing a liquid crystalline resin composition, which comprises producing a composition. 13. (A) 100 parts by weight of a liquid crystalline resin, (B)
In a molded article of a liquid crystalline resin composition containing 1 to 300 parts by weight of aluminum borate whiskers, when the relative particle amount is 90% in the particle size distribution obtained by laser diffraction of aluminum borate whiskers in the molded article When the particle size is D90 (μm) and the particle size when the relative particle amount is 10% is D10 (μm), 5 ≦ D90 / D10 ≦ 20. 14. A precision molded product obtained by molding the liquid crystalline resin composition according to any one of claims 1 to 11. 15. A precision molded product comprising the liquid crystalline resin molded product according to claim 13. 16. The precision molded product according to claim 14, wherein the precision molded product is for a member requiring vibration damping properties. 17. An optical pickup component formed by molding the liquid crystalline resin composition according to any one of claims 1 to 11.