JPH10316841A - Liquid crystalline resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, excellent in weld strength, toughness and mold releasability and having low anisotropy by including a liquid crystalline resin and a cyclic olefinic resin in a specific proportion therein. SOLUTION: This composition comprises (A) >50 and <=99.99 wt.% liquid crystalline resin composed of preferably a liquid crystalline polyester and/or a liquid crystalline polyester amide and (B) >=0.01 and <50 wt.% cyclic olefinic resin which is a thermoplastic cyclic olefinic resin having preferably >=80 deg.C glass transition temperature. Furthermore, (C) a filler in an amount of 1-300 pts.wt. based on 100 pts.wt. total amount of the components A and B and (D) a flame retardant in an amount of 0.01-60 pts.wt. based on 100 pts.wt. total amount of the component A and B are preferably compounded in the composition. Thereby, a precise molded product obtained by injection molding, a molded product, etc., having a welded part can be provided.

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 weld strength, toughness, and releasability and having small anisotropy, which is useful as OA / AV parts, automobile parts, machine parts, housing parts, and the like.

[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, liquid crystal resin has low weld strength and low toughness, so that the molded product is easily broken from the weld, and the elastic modulus difference between the flow direction and the vertical direction is large.
There is a disadvantage that the difference in rigidity is large depending on the part. In addition, liquid crystal resins are often used for thin-walled parts due to their excellent fluidity, and thus have a problem that they are difficult to release from a mold during molding.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to obtain a liquid crystalline resin composition having excellent weld strength, toughness, and releasability, and having small anisotropy.

[0004]

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 5
(B) a liquid crystalline resin composition comprising from 0.01% by weight to less than 50% by weight of (B) a cyclic olefin-based resin; (1) The liquid crystalline resin composition according to the above (1), which is a thermoplastic cyclic olefin resin at a temperature of not less than ° C, and (3) the above (1) or (2), wherein the cyclic olefin resin (B) is a thermoplastic norbornene resin. (4) The liquid crystalline resin according to any one of the above (1) to (3), wherein the liquid crystalline resin (A) is a liquid crystalline resin composed of a liquid crystalline polyester and / or a liquid crystalline polyesteramide. The composition (5) wherein the liquid crystal resin (A) is a liquid crystal resin comprising a liquid crystal polyester and / or a liquid crystal polyesteramide containing an ethylenedioxy unit as an essential component. - (4) liquid-crystalline resin composition of any one of (6) the liquid-crystalline resin (A) is the following structural unit
(I), (II), the liquid crystalline resin composition according to any one of the above (1) to (5), which is a liquid crystalline polyester comprising (III) and (IV),

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. The structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III). (7) The liquid crystalline resin (A) is composed of the structural units (I), (II) and (III)
And (IV), wherein the sum of the structural units (I) and (II) is 40 to 95 mol% of the total of the structural units (I), (II) and (III), and the structural unit (III) is a structural unit ( 60) of the sum of (I), (II) and (III)
5 mol%, molar ratio of structural unit (I) / structural unit (II)
The liquid crystal resin composition according to the above (6), wherein [(I) / (II)] is a liquid crystal polyester having a ratio of 75/25 to 95/5,
(8) The weight average molecular weight of the liquid crystalline resin (A) is 900 to 6
The liquid crystalline resin composition according to any one of the above (1) to (7), which is 0000, and (9) 100 parts by weight of the liquid crystalline resin (A), further comprising a metal phosphate and a metal phosphite. (1) wherein at least one compound selected from metal hypophosphites is contained in an amount of 0.001 to 10 parts by weight.
(8) The liquid crystalline resin composition according to any one of (1) to (8),
0) Fillers 1 to 300 are added to 100 parts by weight of liquid crystal resin (A) and cyclic olefin resin (B) in total.
The liquid crystalline resin composition according to any one of the above (1) to (9), which contains 100 parts by weight of the liquid crystalline resin (A) and the cyclic olefin resin (B). On the other hand, the liquid crystalline resin composition according to any one of the above (1) to (10), further containing 0.01 to 60 parts by weight of a flame retardant, (12) the liquid crystalline resin composition according to the above (1) to (11). A molded article having a weld portion formed by molding the composition from any one of the liquid crystalline resins.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Liquid crystalline resin (A) used in the present invention
Are resins capable of forming anisotropy when melted, and include liquid crystal polyester, liquid crystal polyester amide, liquid crystal polyester carbonate, liquid crystal polyester elastomer, etc. Among them, liquid crystal polyester, liquid crystal polyester amide and the like are preferably used.

As the above liquid crystalline polyester, a polyester forming an anisotropic molten phase composed of structural units selected from aromatic oxycarbonyl units, aromatic dioxy units, aromatic dicarbonyl units, ethylenedioxy units and the like can be used. Examples of the liquid crystalline polyester amide include a polyester amide forming an anisotropic molten phase comprising the above structural unit and a structural unit selected from an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit, and the like. Can be mentioned.

The aromatic oxycarbonyl unit includes, for example, p-hydroxybenzoic acid, 6-hydroxy-2-
Structural units generated from naphthoic acid and aromatic dioxy units include, for example, 4,4′-dihydroxybiphenyl, structural units generated from hydroquinone, and aromatic dicarbonyl units include, for example, terephthalic acid, isophthalic acid, Examples of the structural unit generated from 6-naphthalenedicarboxylic acid and the aromatic iminooxy unit include:
Examples include structural units generated from 4-aminophenol.

Among them, 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, and more preferably the following structural units (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. The total 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,
A structural unit generated from an aromatic dihydroxy compound selected from 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, a structural unit (III) is a structural unit generated from ethylene glycol, The structural unit (IV) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, Structural units formed from aromatic dicarboxylic acids selected from -bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'-diphenyletherdicarboxylic acid 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),
It is a copolymer comprising (II), (III) and (IV), and 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 (IV)
In the case of a copolymer consisting of the above, 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, it is preferable that the structural unit (IV) is substantially equimolar to the structural unit (III).

On the other hand, the structural units (I), (II), (III) and (I)
In the case of the copolymer consisting of (V), the total 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. 40)
95 mol% is preferable, and 80 to 92 mol% is more preferable. Structural units (III) are structural units (I), (II) and (II)
It is preferably from 60 to 5 mol% based on the total of I), and
Molar% is more preferred. The molar ratio [(I) / (II)] of the structural units (I) / (II) is preferably 75/25 to 95/5, and more preferably 78 from the viewpoint of the balance between heat resistance and fluidity. / 22 to 93/7. In addition, 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-hydroxy-6-naphthoic acid and p-aminobenzoic acid impair the purpose of the present invention. Copolymerization can be further performed in a small proportion in a range that is not so large.

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 polymers such as polyethylene terephthalate and polymers, oligomers or aromatic compounds such as bis (β-hydroxyethyl) terephthalate A method of producing from a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid by a deacetic acid polycondensation reaction.

(2) aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid; aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl and hydroquinone; terephthalic acid;
Aromatic dicarboxylic acids such as isophthalic acid and 2,6-naphthalenedicarboxylic acid; polymers and oligomers of polyesters such as polyethylene terephthalate; and bis (β-hydroxyethyl) aromatic dicarboxylic acids such as bis (β-hydroxyethyl) terephthalate ) A method for producing an ester by an acetic anhydride polycondensation reaction in the presence of acetic anhydride as an acylating agent for a hydroxy group.

Although these polycondensation reactions proceed without a catalyst, those known as polycondensation catalysts for liquid crystalline resins such as potassium acetate, sodium acetate, stannous acetate, tetrabutyl titanate and antimony trioxide are used. be able to.

The melt viscosity of the liquid crystalline resin used in the present invention is preferably from 0.1 to 2,000 Pa · s, more preferably from 1 to 1,000 Pa · s.

The melt viscosity is calculated as melting point (Tm) +10
It is a value measured by a Koka type flow tester under the condition of ° C and a shear rate of 1,000 (1 / second).

Here, the melting point (Tm) refers to an endothermic peak temperature (Tm) observed when a polymer having undergone polymerization is measured from room temperature under a heating condition of 20 ° C./min.
After observation at m1), after holding at a temperature of Tm1 + 20 ° C. for 5 minutes, cooling once to room temperature at a temperature lowering condition of 20 ° C./min, and then endothermic observation observed when measuring again at a temperature rising condition of 20 ° C./min. Refers to the peak temperature (Tm2).

The liquid crystalline resin used in the present invention is:
The weight average molecular weight is preferably from 800 to 200,000, particularly preferably from 900 to 60000, and the structural unit (II
When containing (I): 1000 to 30,000, structural unit (III)
When it does not contain, 2000 to 60000 is preferable.
The molecular weight is determined using a solvent in which the liquid crystalline resin is soluble.
It can be measured by the LS (gel permeation chromatography-light scattering) method.

The metal phosphate, metal phosphite, and metal hypophosphite used as necessary in the liquid crystalline resin composition of the present invention include phosphoric acid, phosphorous acid, and hypophosphorous acid. There are alkali metal salts, alkaline earth metal salts, and transition metal salts. Specifically, lithium phosphate, potassium phosphate, sodium phosphate, calcium phosphate, magnesium phosphate, barium phosphate, aluminum phosphate, manganese phosphate, Lithium phosphite, potassium phosphite, sodium phosphite, calcium phosphite, magnesium phosphite, barium phosphite, aluminum phosphite, manganese phosphite, lithium hypophosphite, potassium hypophosphite, Sodium hypophosphite, calcium hypophosphite, magnesium hypophosphite, barium hypophosphite, aluminum hypophosphite, Such as manganese phosphate and the like. Among them, sodium phosphate, potassium phosphate, calcium phosphate, sodium phosphite, potassium phosphite, calcium phosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite are preferred, and sodium hypophosphite is particularly preferred. Particularly preferred.

The amount of the metal phosphate, metal phosphite, and metal hypophosphite used in the present invention is usually in the range of 100 parts by weight of the liquid crystalline resin (A).
0.001 to 10 parts by weight, preferably 0.01 to 10 parts by weight.
3 parts by weight, more preferably 0.02 to 1 part by weight.

At least one compound selected from the group consisting of metal phosphates, metal phosphites and metal hypophosphites used in the present invention is incorporated at the stage of polymerizing the liquid crystalline resin (A). Is effective in improving color tone and heat resistance.

For example, aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl and hydroquinone, terephthalic acid, isophthalic acid, Aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, polyester polymers such as polyethylene terephthalate, oligomers or bis (β
Bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as -hydroxyethyl) terephthalate in the presence of acetic anhydride as an acylating agent for a hydroxy group, and a metal phosphate, metal phosphite, hypophosphorous acid A method in which at least one compound selected from metal salts is added to produce a liquid crystalline resin (A) by a deacetic acid polycondensation reaction.

The cyclic olefin resin used in the present invention includes a thermoplastic norbornene resin.

As the above-mentioned thermoplastic norbornene resin,
Hydrogen such as a norbornene-based monomer, or a ring-opening polymer, an addition polymer, or a modified product of these polymers of a norbornene-based monomer and a monomer copolymerizable with the norbornene-based monomer Additional polymers are mentioned.

The norbornene-based monomer is an adduct of one or more cyclopentadiene and an olefin, and converts its hydrogen into an alkyl group, an alkylidene group, an aromatic group, a halogen, a hydroxyl group, an ester group, an alkoxy group, a cyano group. , An amide group, an imide group, a silyl group or the like. Specifically, norbornene (bicyclo [2.2.1]
-2-heptene), tricyclo [5.2.1.0 ^2,6 ]
-8-decene, tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, pentacyclo [6.5.1.1]
^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, and substituted products thereof. Specific examples include norbornene (bicyclo [2.2.1] -2-heptene) and 5-methylbicyclo [2.2.1]. -2-heptene, 5-methoxycarbonylbicyclo [2.2.1] -2-heptene,
5-methyl-5-methoxycarbonylbicyclo [2.
2.1] -2-Heptene, 6-methyl-5-methoxycarbonylbicyclo [2.2.1] -2-heptene, 5-
Cyanobicyclo [2.2.1] -2-heptene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 9-
Methyl-8-methoxycarbonyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, and the like. These norbornene monomers can be used as one or more copolymers.

As the monomer copolymerizable with the norbornene-based monomer, various olefins can be exemplified. Examples of the olefin include ethylene, propylene, butene, styrene, butadiene, pentadiene, isoprene, acrylic acid, methacrylic acid, vinyl acetate, vinyl chloride, acrylonitrile, chloroprene, allyl alcohol, allyl glycidyl ether, maleic anhydride, cyclobutene, cyclopentene, and cyclohexene. , Cycloheptene, cyclooctene and the like. One or more of these monomers can be used as a copolymerizable monomer.

Known methods can be used for ring-opening polymerization and addition polymerization of the norbornene-based monomer or a monomer copolymerizable with the norbornene-based monomer and the norbornene-based monomer.

The ring-opening polymerization includes, for example, ruthenium,
The reaction can be carried out in the presence of a platinum group catalyst such as rhodium, palladium or platinum, or in the presence of a catalyst such as tungsten chloride or molybdenum chloride and an organic metal compound such as n-butyllithium or diethylaluminum chloride. In the case of ring-opening polymerization, monomers that can be copolymerized include:
Cycloolefins such as cyclobutene, cyclopentene, cyclohexene, cycloheptene and cyclooctene are exemplified.

The ring-opened polymer of a norbornene-based monomer or a monomer copolymerizable with a norbornene-based monomer and a norbornene-based monomer is subjected to hydrogenation in order to improve oxidation resistance. Desirably a body. A known method can be used for the hydrogenation. For example, in the presence of a heterogeneous catalyst such as ruthenium, rhodium, palladium, platinum, and nickel, under a hydrogen gas atmosphere at normal pressure to 200 atm, at room temperature to 200 ° C. Can be done with

As the addition polymerization, for example, a transition metal complex catalyst such as titanium, zirconium, or hafnium is mixed with triethylaluminum, diethylaluminum chloride,
It can be performed in the presence of an organometallic compound such as n-butyllithium. In the case of addition polymerization, monomers that can be copolymerized include α-olefins such as ethylene and propylene.

The cyclic olefin resin used in the present invention is preferably a thermoplastic cyclic olefin resin having a glass transition temperature of 80 ° C. or higher. In particular, those having a glass transition temperature of 100 ° C. or higher are preferable, and those of 150 ° C. or higher are more preferable.

The cyclic olefin resin used in the present invention has a weight average molecular weight of 20,000 to 400,000.
Is preferable, and 50,000 to 300,000 is preferable. The molecular weight can be determined, for example, using GPC-LS using a toluene solvent.
(Gel permeation chromatograph-light scattering) method.

The composition ratio of the liquid crystalline resin (A) to the cyclic olefin resin (B) in the liquid crystalline resin composition of the present invention is such that the content of the liquid crystalline resin (A) is more than 50% by weight and 99.99% by weight or less. Preferably, it is 70% by weight or more and 99.9% by weight or less, more preferably 80% by weight or more and 99.8% by weight or less, and the cyclic olefin-based resin (B) is 0.01% by weight or more and less than 50% by weight. , Preferably at least 0.1% by weight
0% by weight or less, more preferably 0.2% by weight or more and 20% by weight or less.

The filler used as the liquid crystalline resin composition of the present invention includes glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, aluminum borate fiber, gypsum fiber, brass fiber, stainless steel fiber, and steel fiber. , Ceramic fiber, boron fiber, asbestos fiber, alumina fiber, silica alumina fiber, graphite, mica, talc, silica, calcium carbonate, glass beads,
Examples thereof include fibrous (including whisker), powdery, granular, and plate-like organic and inorganic fillers such as glass flakes, glass microballoons, clay, wollastenite, titanium oxide, and molybdenum disulfide. Among them, glass fiber, carbon fiber, potassium titanate fiber, aluminum borate fiber, mica, and talc are preferable. As these fillers, those treated with a silane-based, titanate-based coupling agent, or another surface treatment agent may be used.

When the filler is used in the present invention, the compounding amount thereof is 1 to 300 parts by weight, preferably 5 to 100 parts by weight of the liquid crystal resin (A) and the cyclic olefin resin (B) in total. ~ 200 parts by weight, more preferably 10
１００100 parts by weight.

Examples of the flame retardant used in the present invention include organic bromides, organic phosphorus compounds, and red phosphorus.

As the organic bromide, an organic bromine compound usually used as a flame retardant, particularly one having a bromine content of 20% by weight or more is preferred. Specific examples include hexabromobenzene, pentabromotoluene, hexabromobiphenyl,
Low molecular weight organic bromine compounds such as decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, 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), a brominated epoxy compound (for example, a diepoxy compound produced by the reaction of brominated bisphenol A with epichlorohydrin, Epoxy compounds obtained by reaction of brominated phenols with epichlorohydrin), poly (brominated benzyl acrylate), brominated Halogenated polymers and oligomers such as phenylene ether, brominated bisphenol A, condensates of cyanuric chloride and brominated phenol, brominated polystyrene, cross-linked brominated polystyrene, cross-linked brominated poly-α-methylstyrene, or mixtures thereof Among them, ethylene bis (tetrabromophthalimide), brominated epoxy oligomer or polymer, brominated polystyrene, cross-linked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are preferable, and brominated polystyrene can be most preferably used. Among them, polybrominated styrene produced by polymerizing di- or tribrominated styrene monomer is preferable.

Examples of the organic phosphorus compound include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphate, phosphite, and hypophosphite. Among them, an aromatic phosphate compound is preferred.

As the red phosphorus, it may be used as it is, but it is coated with a metal hydroxide film such as magnesium hydroxide, paraffin, wax, phenolic, epoxy, or unsaturated polyester-based thermosetting resin. Or a mixture with titanium oxide can be suitably used.

When the flame retardant is used in the present invention, the compounding amount thereof is 0.01 to 60 parts by weight based on 100 parts by weight of the liquid crystal resin (A) and the thermoplastic norbornene resin (B) in total.
Parts by weight, preferably 0.03 to 20 parts by weight, more preferably 0.05 to 10 parts by weight.

When an organic bromide or an organic phosphorus compound is used, the amount is preferably 5 to 60 parts by weight. On the other hand, when red phosphorus is used, the amount is 0.01 to 10 parts by weight.
Preferably it is 20 parts by weight.

The liquid crystalline 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.

In the present invention, other thermoplastic resins include:
Nylon 6, nylon 66, nylon 46, aromatic nylon, polyacetal, polyethylene terephthalate,
Polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polyphenylene sulfide, polyphenylene oxide, polycarbonate, ABS, polyethylene, polypropylene, polystyrene, syndiotactic polystyrene, polymethyl methacrylate,
Polyethersulfone, polyetherketone, polyetheretherketone, polyetherimide, polyarylate and the like may be blended.

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.),
Add ordinary additives such as dyes (eg, nitrosine) and pigments (eg, titanium oxide, cadmium sulfide, phthalocyanine, carbon black, etc.), plasticizers, antistatic agents, crystal nucleating agents, flame retardants, etc. hand,
Predetermined characteristics can be provided.

The method of blending the liquid crystalline resin (A), the cyclic olefin resin (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 twin-screw extruder is used, and a liquid crystal resin (A), a cyclic olefin resin (B),
There is a method in which a filler is supplied to a place where a thermoplastic resin, a flame retardant, a pigment, and the like have been melted in a raw material by a side feeder and kneaded.

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.) to process into three-dimensional molded products, sheets, films, fibers, containers, pipes, etc.
It is particularly effective for precision molded products obtained by injection molding.

Since the liquid crystalline resin composition of the present invention has excellent weld strength, it is also effective for molded articles having a weld portion.

The liquid crystalline resin composition of the present invention comprises various optical lenses, glass substitutes, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors,
Variable condenser case, optical pickup, oscillator, various terminal boards, transformer, 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 holders, parabolic antennas, electrical and electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio parts・ Sound equipment parts such as laser discs and compact discs, lighting parts,
Home, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, such as refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. , Stern bearings, underwater bearings, and other various bearings, motor parts, mechanical parts such as lighters, typewriters, microscopes, binoculars, cameras,
Optical equipment such as watches, precision machinery related parts; alternator terminal, alternator connector,
IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, various pipes related to 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 for air conditioner Base, Heating hot air flow control valve, Brush holder for radiator motor, Water pump impeller, Turbine vane, Wiper motor related parts, Distributor, Starter switch, Starter relay, Wire harness for transmission,
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,
It is useful for automotive and vehicle related parts such as lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, and various other uses.

[0057]

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) 994 parts by weight of p-hydroxybenzoic acid, 134 parts by weight of 4,4'-dihydroxybiphenyl, 120 terephthalic acid
Parts by weight, 208 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, 944 parts by weight of acetic anhydride, and 3 parts by weight of sodium hypophosphite are charged into a reaction vessel equipped with a stirring blade and a distillation tube, and polymerization is carried out. went. Liquid crystal start temperature 29
A liquid crystalline resin having a weight average molecular weight of about 26,000 at 5 ° C. was obtained.

Reference Example 2 (A-2) 1296 parts by weight of p-acetoxybenzoic acid and polyethylene terephthalate 346 having an intrinsic viscosity of about 0.6 dl / g
The weight part was charged into a reaction vessel equipped with a stirring blade and a distilling tube, and polymerization was performed. A liquid crystalline resin having a liquid crystal onset temperature of 258 ° C. and a weight average molecular weight of about 28,000 was obtained.

Reference Example 3 (A-3) 932 parts by weight of p-hydroxybenzoic acid, 423 parts by weight of 6-hydroxy-2-naphthoic acid and 1011 parts by weight of acetic anhydride were placed in a reaction vessel equipped with a stirring blade and a distillation tube. Charge and polymerization were performed. Liquid crystal onset temperature 260 ° C, weight average molecular weight about 4
5,000 liquid crystalline resins were obtained.

Reference Example 4 (A-4) 1270 parts by weight of 6-hydroxy-2-naphthoic acid, p-
246 parts by weight of aminophenol, 374 parts by weight of terephthalic acid and 1263 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distilling tube, and polymerized. Liquid crystal start temperature 2
A liquid crystalline resin having a weight average molecular weight of about 44,000 at 40 ° C. was obtained.

Examples 1 to 17 and Comparative Examples 1 to 12 The liquid crystalline resin (A), thermoplastic norbornene resin (B), filler and flame retardant obtained in the reference examples shown in Tables 1 and 2 were L / D.
= 290 to 340 using a 30 mm φ twin screw extruder
The mixture was melt-kneaded at a temperature of ° C. to form pellets. After hot air drying,
These pellets are used for Sumitomo Nestor injection molding machine Promat 4
0/25 (manufactured by Sumitomo Heavy Industries, Ltd.), the cylinder temperature was set to 290 to 340 ° C., the mold temperature was set to 90 ° C., and the following test pieces for measurement were injection molded. The measuring method is described below.

(1) Weld strength Cylinder temperature of 290 to 340 using the above molding machine
1.6mm thick ASTM under the conditions of 90 ° C and mold temperature 90 ° C
No. 1 dumbbell was molded using a mold having gates at both ends, and the tensile strength was measured according to ASTM D790.

(2) Toughness A 6.4 mm thick × 12 mm wide test piece was molded using the molding machine described above, and the V specified in ASTM D256 was used.
The measurement was performed with a notch.

(3) Releasability The same method as that of the above-mentioned ASTM No. 1 dumbbell was used, and the length was 20 mm ×
A box-shaped test piece having a width of 20 mm, a height of 20 mm and a thickness of 20 mm was formed, and the releasing force at that time was measured.

(4) Anisotropy Using the above-mentioned molding machine, a rectangular plate having a length of 70 mm × width of 70 mm × thickness of 2 mm having a film gate with a thickness of 1 mm on one side was formed, and each of the plates was machined in the longitudinal and transverse directions. A test piece having a width of 12 mm was cut out, and the flexural modulus of each test piece was determined according to ASTM D.
The measurement was performed according to 790, and the elastic modulus ratio in the vertical and horizontal directions was determined.

The thermoplastic norbornene resin (B), filler and flame retardant in Tables 1 and 2 are as follows.

[0068] B-1: 8- methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3
A hydrogenated polymer of a ring-opening polymer of dodecene (hydrogenation rate 100%), a weight average molecular weight of 180,000, and a glass transition temperature of 165 ° C.

B-2: Random addition copolymer of 50 mol% of ethylene and 50 mol% of norbornene (bicyclo [2.2.1] -2-heptene), weight average molecular weight 20,000
0, glass transition temperature 120 ° C.

B-3: APL6013 (ethylene / norbornene random copolymer manufactured by Mitsui Petrochemical), glass transition temperature of 125 ° C. B-4: Arton F (hydrogenated polymer of norbornene ring-opening polymer manufactured by Japan Synthetic Rubber) ), Glass transition temperature 170
° C.

C-1: glass fiber (diameter 9 μm, fiber length 3 mm) aminosilane-treated chopped strand C-2: mica (particle diameter 9 μm) C-3: aluminum borate whisker (“Arbolex” manufactured by Shikoku Chemicals) D- 1: Poly (dibromostyrene) (GLB PDB)
S-80) D-2: Red phosphorus (“Nova Excel” 140 manufactured by Rin Kagaku)

[Table 1]

[Table 2] The results are shown in Tables 1 and 2. From the results in Tables 1 and 2, the specific liquid crystalline resin composition obtained by blending the cyclic olefin resin (B) with the liquid crystalline resin (A) has a higher eld strength, toughness, and releasability than those not blended. It can be seen that this is excellent and has low anisotropy.

[0072]

The liquid crystalline resin composition of the present invention is excellent in weld strength, toughness, and releasability, and has small anisotropy. It is a material suitable for various other uses such as equipment, OA / AV equipment, and automobile parts.

Claims (12)

[Claims] (A) More than 50% by weight of liquid crystal resin (99.99%)
(B) 0.01% by weight of cyclic olefin resin
A liquid crystalline resin composition comprising at least 50% by weight. 2. The liquid crystalline resin composition according to claim 1, wherein the cyclic olefin resin (B) is a thermoplastic cyclic olefin resin having a glass transition temperature of 80 ° C. or higher. 3. The liquid crystalline resin composition according to claim 1, wherein the cyclic olefin resin (B) is a thermoplastic norbornene resin. 4. 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. 5. A liquid crystalline polyester wherein the liquid crystalline resin (A) contains an ethylenedioxy unit as an essential component and / or
5. The liquid crystalline resin composition according to claim 1, which is a liquid crystalline resin comprising a liquid crystalline polyesteramide. 6. 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 5, which is a liquid crystalline polyester composed 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. The structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III). ) 7. The liquid crystalline resin (A) comprises a structural unit (I), (II),
(III) and (IV), wherein the total of the structural units (I) and (II) is 40 to 95 mol% of the total of the structural units (I), (II) and (III), and the structural unit (III) is 60 to 5 mol% of the total of the structural units (I), (II) and (III), and the structural unit (I) / the structural unit (II)
The liquid crystalline resin composition according to claim 6, wherein the liquid crystalline polyester has a molar ratio [(I) / (II)] of 75/25 to 95/5. 8. The weight average molecular weight of the liquid crystalline resin (A) is 90.
The liquid crystalline resin composition according to any one of claims 1 to 7, which has a molecular weight of 0 to 60000. 9. A liquid crystal resin (A) based on 100 parts by weight,
Further, at least one compound selected from a metal phosphate, a metal phosphite, and a metal hypophosphite is 0.001 to 0.001.
9. The method according to claim 1, wherein the composition contains 10 parts by weight.
Item 10. The liquid crystalline resin composition according to item 8. 10. The liquid crystal resin (A) and the cyclic olefin resin (B) in a total of 100 parts by weight, further containing 1 to 300 parts by weight of a filler. The liquid crystal resin composition according to the above. 11. The flame retardant is further contained in an amount of 0.01 to 60 parts by weight based on 100 parts by weight of the liquid crystalline resin (A) and the cyclic olefin resin (B) in total.
0. The liquid crystalline resin composition according to claim 1. 12. A molded article having a welded portion obtained by molding a composition from the liquid crystalline resin according to claim 1.