JP2002294039A - Liquid crystal resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal resin composition having excellent adhesion between a metal and the liquid crystal resin while keeping excellent characteristics of the liquid crystal resin, such as moldability, heat resistance and properties of hardly generating a gas, and especially suitable for a composite obtained by carrying out an insert or outsert molding of a metal component by an injection molding. SOLUTION: This liquid crystal resin composition is obtained by compounding 0-300 pts.wt. filler with 100 pts.wt. liquid crystal resin comprising (A) 99-50 wt.% one or more kinds of liquid crystal resins selected from a liquid crystal polyester and a liquid crystal polyesteramide, capable of forming anisotropic molten phases, and (B) 50-1 wt.% liquid crystal polyester except the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in adhesion to metal, and can provide excellent adhesion to metal parts when obtaining a composite with metal by molding such as insert molding and outsert molding. The present invention relates to a liquid crystal resin composition.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and a number of polymers having various new properties have been developed and put on the market. Among them, liquid crystalline polymers that form an anisotropic molten phase characterized by parallel arrangement of molecular chains have excellent fluidity, dimensional accuracy, mechanical properties, heat resistance, low gas generation, electrical properties, etc. Its components are mainly focused on various electric / electronic parts and optical parts such as fine pitch connectors, floppy (registered trademark) disk drive related parts, hard disk drive related parts, CD drive related parts, DVD drive related parts, etc. Its use is increasing.

Further, composites in which metal parts are inserted into liquid crystalline resin, specifically, for example, metal terminals such as electric switches, relays, connectors, sockets, and motor stator cores, and parts in which metal parts are sealed with resin, etc. ,
Due to the above characteristics, the resin portion is thin and stable performance can be obtained even in a high-temperature atmosphere. Therefore, it is expected to be used as a highly functional and highly integrated member in various industrial fields.

A typical example of a resin forming an anisotropic molten phase is a liquid crystalline polymer obtained by copolymerizing p-hydroxybenzoic acid with polyethylene terephthalate (JP-A-49-723).
No. 93), a liquid crystalline polymer obtained by copolymerizing p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (JP-A-54-77691), and p-hydroxybenzoic acid having 4,4'-dihydroxy Liquid crystalline polymer obtained by copolymerizing biphenyl with terephthalic acid and isophthalic acid
No. 7-24407) and the like. As described above, these liquid crystalline resins have excellent fluidity, dimensional accuracy, mechanical properties, heat resistance, low gas generation properties, and electrical properties, but are chemically stable because they are chemically stable. Adhesion with other resins is insufficient.For example, in a composite in which metal parts are inserted or outsert molded by injection molding or the like, sufficient adhesion between the metal and the liquid crystalline resin cannot be obtained, and the composite There was a problem that the function could not be exhibited.

As a method for improving these disadvantages, for example, Japanese Patent Application Laid-Open No. 11-58604 discloses a method of bonding a metal body surface-treated with a triazinethiol compound and a thermotropic liquid crystal resin to form an adhesive composite. Discloses a method of modifying the surface of a metal to improve the adhesion between the resin and the metal.However, in this publication, copper or phosphor bronze which has been subjected to such a surface treatment is used as a glass fiber reinforced liquid crystal resin. It is shown that only poor adhesiveness can be obtained even when used.

[0006] Furthermore, the above-mentioned publication discloses that by incorporating an oxygen-containing terpene resin into the liquid crystal resin, the adhesiveness to a metal treated with a triazine thiol compound can be improved. In addition to the above, not only the original performance of the liquid crystal resin such as heat resistance and low gas characteristic of the liquid crystal resin was greatly impaired, but there was no effect when the metal was not subjected to the above surface treatment.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, while maintaining excellent properties such as moldability, heat resistance and low gas property of a liquid crystal resin. Accordingly, an object of the present invention is to obtain a liquid crystal resin composition having excellent adhesion between a metal and a liquid crystal resin, and particularly suitable for a composite obtained by insert or outsert molding of a metal part by injection molding.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a liquid crystal resin having a specific structure is mixed with a liquid crystal resin so that a liquid crystal meeting the above object can be obtained. Found that a reactive resin composition can be obtained,
The present invention has been reached.

That is, the liquid crystalline resin composition of the present invention comprises:
(A) one or more liquid crystal resins selected from liquid crystal polyesters and liquid crystal polyesteramides that form an anisotropic molten phase other than the following component (B), and (B) the following (a):
Liquid crystallinity comprising structural units of (b), (c) and (d), wherein the structural unit (c) is 25 to 60 mol% with respect to the total of the structural units (a), (b) and (c) Liquid crystallinity comprising a polyester and the following structural units (a), (c) and (d), wherein the structural unit (c) is 25 to 60 mol% based on the total of the structural units (a) and (c) With liquid crystalline polyester selected from polyester,
The component (A) and the component (B) are blended such that the component (A) is in a range of 99 to 50% by weight and the component (B) is in a range of 1 to 50% by weight based on the total of the components. I do.

[0010]

Embedded image (However, R1 in the formula is

[0011]

Embedded image R2 represents one or more groups selected from

[0012]

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the total of the structural units (b) and (c) and the structural unit (d) are substantially equimolar. In addition, in the liquid crystalline resin composition of the present invention, 300 parts by weight or less of a filler is further blended with respect to 100 parts by weight of the components (A) and (B) in total. ) The liquid crystalline resin as the component has the following structural unit
(I), (II) and (IV), and as a structural unit (II),
Liquid crystalline polyesters and / or structural units (I), (II), which are obtained by using two or more different aromatic dioxy units in combination.
Preferred conditions are a liquid crystalline polyester composed of (III) and (IV) and a liquid crystalline resin composition used for a composite with a metal.

[0013]

Embedded image (However, R1 in the formula is

[0014]

Embedded image R2 represents one or more groups selected from

[0015]

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural units (II) and (III)
And the structural units (IV) are substantially equimolar. As described above, since the liquid crystal resin composition of the present invention is composed of the specific liquid crystal resin (A) and the specific liquid crystal polyester (B), the liquid crystal resin has good moldability, heat resistance, low gas properties, and the like. A liquid crystal resin composition having excellent adhesion between the metal and the liquid crystal resin while maintaining excellent properties, and particularly suitable for a composite in which metal parts are inserted or outsert molded by injection molding can be obtained.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystalline polyester of the liquid crystalline resin (A) in the present invention is a polyester capable of forming an anisotropic molten phase and is other than the component (B) described later. And polyesters that form an anisotropic molten phase composed of structural units selected from aromatic oxycarbonyl units, aromatic dioxy units, aromatic dicarbonyl units, and ethylenedioxy units. Further, the liquid crystalline polyesteramide is a polyesteramide comprising the above structural unit and a structural unit selected from an aromatic iminocarbonyl unit, an aromatic diimino unit and an aromatic iminophenoxy unit, and forming an anisotropic molten phase. And so on.

Preferred examples of the liquid crystalline polyester include a liquid crystalline polyester comprising the above structural units (I), (II) and (IV), or structural units (I), (II), (III) and (IV) )).

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, 2,6-dihydroxynaphthalene, 2,7
-A structural unit formed from one or more aromatic dihydroxy compounds selected from dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl ether;
I) is a structural unit formed from ethylene glycol, and 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, 1,2-bis (2-chlorophenoxy)
The structural units generated from one or more aromatic dicarboxylic acids selected from ethane-4,4'-dicarboxylic acid and diphenyl ether dicarboxylic acid are shown. Of these, R1 is

[0019]

Embedded image And R2 is

[0020]

Embedded image Is particularly preferred.

As the liquid crystalline polyester comprising the structural units (I), (II) and (IV), a liquid crystalline polyester comprising two or more different aromatic dioxy units as the structural unit (II) is used. It is preferred that In this case, as the structural unit (II), it is preferable to combine a structural unit generated from 4,4′-dihydroxybiphenyl and one or more selected from other structural units, and particularly, from 4,4′-dihydroxybiphenyl. The generated structural unit and 3,3 ′, 5,5′-tetramethyl-4,
4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl ether And a combination of units formed from an aromatic dihydroxy compound selected from

Thus, when the liquid crystalline polyester does not contain the structural unit (III), the structural unit (I) is 40 to 90 mol% based on the total amount of the structural units (I) and (II). It is particularly preferably 60 to 80 mol%. The structural unit (IV) is substantially equimolar to the total of the structural units (II).

Further, the liquid crystal polyester has a structural unit (I),
In the case of (II), (III) and (IV), the sum of the structural units (I) and (II) is the sum of the structural units (I), (II) and (I)
It is more than 75 mol%, preferably not less than 82 mol%, based on the total of II). Further, it is preferably at most 93 mol%, more preferably at most 92 mol%.

The structural unit (III) is less than 25 mol% based on the total of the structural units (I), (II) and (III);
It is preferably at most mol%. Further, it is preferably at least 7 mol%, more preferably at least 8 mol%. Further, the structural unit (IV) includes the structural unit (II) and
It is substantially equimolar to the sum of (III).

Further, as the liquid crystalline polyesteramide, a polyesteramide which forms an anisotropic molten phase containing p-iminophenoxy units formed from p-aminophenol in addition to the structural units (I) to (IV) is mentioned. preferable.

In the polycondensation of the liquid crystalline polyester preferably used in the present invention, the above structural unit
In addition to the components constituting (I) to (IV), aromatic dicarboxylic acids such as 3,3′-diphenyldicarboxylic acid and 2,2′-diphenyldicarboxylic acid, adipic acid, azelaic acid,
Sebacic acid, aliphatic dicarboxylic acids such as dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone,
4,4'-dihydroxydiphenyl sulfone, 4,4 '
Aromatic diols such as dihydroxydiphenyl sulfide and 4,4′-dihydroxybenzophenone,
Butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol,
Aliphatic, alicyclic diols such as 1,4-cyclohexanedimethanol and m-hydroxybenzoic acid, 2,6-
Aromatic hydroxycarboxylic acids such as hydroxynaphthoic acid and p-aminophenol, p-aminobenzoic acid, and the like can be further copolymerized in a small proportion that does not impair the object of the present invention.

The method for producing the liquid crystalline resin which can be preferably used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method or the like.

For example, in the production of the liquid crystalline polyester which is preferably used, when the above structural unit (III) is not included, the following production methods (1) and (2) are used. The following method (3) is preferred. (1) Deacetic acid polycondensation from a diacylated product of an aromatic dihydroxy compound such as p-acetoxybenzoic acid and 4,4'-diacetoxybiphenyl or 4,4'-acetoxybenzene and an aromatic dicarboxylic acid such as terephthalic acid. A method for producing a liquid crystalline polyester by a reaction. (2) After reacting acetic anhydride with p-hydroxybenzoic acid and an aromatic dihydroxy compound such as 4,4′-dihydroxybiphenyl and hydroquinone, and an aromatic dicarboxylic acid such as terephthalic acid to acylate a phenolic hydroxyl group, A method for producing a liquid crystalline polyester by a deacetic acid polycondensation reaction. (3) Polyester polymers such as polyethylene terephthalate, oligomers or aromatic dicarboxylic acids such as bis (β-hydroxyethyl) terephthalate bis (β
-Hydroxyethyl) ester in the presence of (1)
Or a method of producing a liquid crystalline polyester by the method of (2).

Although these polycondensation reactions proceed without a catalyst, it is sometimes preferable to add a metal compound such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and metallic magnesium. .

The liquid crystalline polyester (B) which can be used in the present invention is a copolymer comprising the following structural units (a), (b), (c) and (d), wherein the structural unit (c) is 2 based on the sum of structural units (a), (b) and (c)
5 to 60 mol% of a liquid crystalline polyester and a copolymer comprising the following structural units (a), (c) and (d), wherein the structural unit (c) is composed of the structural units (a) and (c) Is at least one selected from liquid crystalline polyesters in an amount of 25 to 60 mol% based on the total of

[0031]

Embedded image (However, R1 in the formula is

[0032]

Embedded image R2 represents one or more groups selected from

[0033]

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the total of the structural units (b) and (c) and the structural unit (d) are substantially equimolar. ).

The structural unit (a) is a structural unit formed from p-hydroxybenzoic acid, and the structural unit (b) is 4,4'-dihydroxybiphenyl, 3,3 ', 5,5
'-Tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'-
A structural unit generated from one or more aromatic dihydroxy compounds selected from dihydroxydiphenyl ether,
The structural unit (c) is a structural unit formed from ethylene glycol, and the structural unit (d) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis ( It is formed from one or more aromatic dicarboxylic acids selected from phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and diphenyl ether dicarboxylic acid. Each structural unit is shown. Of these, R1

[0035]

Embedded image Is preferred. Also, as R2

[0036]

Embedded image Is particularly preferred.

The copolymerization amount of the above structural units (a), (b), (c) and (d) is preferably the following copolymerization amount in order to exert the effect of the present invention. That is, in the case of a copolymer composed of the structural units (a), (b), (c), and (d), the structural unit (c) is a copolymer of the structural units (a), (b), and (c). 25-60 for total
Mol%, preferably 30 mol% or more.
More preferably, it exceeds 0 mol%. 55 mol%
The following is preferred.

The total amount of the structural units (b) and (c) and the structural unit (d) are preferably substantially equimolar.

In the case of a copolymer comprising the structural units (a), (c) and (d), the structural unit (c)
Is 25 to 6 based on the sum of the structural units (a) and (c).
0 mol%, and the lower limit is preferably 30 mol% or more, and more preferably more than 40 mol%. Moreover, it is preferable that it is 55 mol% or less. 40 mol%
More preferably, Further, it is preferable that the structural units (c) and (d) are substantially equimolar.

Here, "substantially equimolar" means that the units constituting the polymer main chain excluding the terminal are equimolar, but the units constituting the terminal are not necessarily equimolar.

If the structural unit (c) is less than 25 mol% with respect to the total of the structural units (a) and (c), the effect of improving the adhesion to the metal body is poor, and if it exceeds 60 mol%, the heat resistance is reduced. Is not preferred.

In addition to the components constituting the above structural units (a) to (d), 3,3′-diphenyldicarboxylic acid,
Aromatic dicarboxylic acids such as 2'-diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecandioic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid; chlorohydroquinone; '-Dihydroxybiphenyl, 4,4'-
Aromatic diols such as dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxybenzophenone, 3,4'-dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol , Neopentyl glycol, 1,4-cyclohexanediol, 1,
Aliphatic and alicyclic diols such as 4-cyclohexyne dimethanol and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-aminobenzoic acid, etc. Copolymerization can be further performed within the range.

The compounding amounts of the liquid crystalline resin (A) and the liquid crystalline polyester (B) are 99 to 50% by weight of (A) and 1 (B) based on the total of (A) and (B). ~ 50
% (A) is from 95 to 60% by weight,
(B) is preferably 5 to 40% by weight. If the amount of the liquid crystalline polyester (B) is too large, the heat resistance is lowered, and if the amount is too small, the effect of improving the adhesion to the metal body is poor, so that neither is preferable.

Although not essential in the present invention, it is preferable to use a filler. Such fillers are not particularly limited, but fibrous, plate-like, powder-like, and granular fillers can be used. Specifically, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia Fibrous such as fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, whisker-like filler, mica, talc, Kaolin, silica,
Examples of the filler include powdery, granular, and plate-like fillers such as calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wallastenite, titanium oxide, zinc oxide, calcium polyphosphate, and graphite.

In the above-mentioned filler, PAN-based carbon fibers are preferably used when glass fibers and conductivity are required. The type of the glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, a long fiber type or a short fiber type chopped strand, a milled fiber or the like can be used.

The above fillers can be used in combination of two or more kinds. The filler used in the present invention may be used after its surface is treated with a known coupling agent (for example, a silane-based coupling agent, a titanate-based coupling agent, or the like) or another surface treatment agent. .

When a filler is added, the amount of the filler is preferably 300 parts by weight or less based on 100 parts by weight of the total of the liquid crystalline resin (A) and the liquid crystalline polyester (B), and is preferably 5 to 150 parts by weight. Parts by weight are more preferred, and
00 parts by weight is particularly preferred.

The liquid crystal resin composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, hydroquinone, etc.) as long as the object of the present invention is not impaired.
Phosphites and their substituted products), ultraviolet absorbers (eg, resorcinol, salicylate, benzotriazole, benzophenone, etc.), release agents (montanic acid and its salts, esters, half esters, stearyl alcohol, stearamide and polyethylene) Coloring agents including waxes), lubricants (higher fatty acid metal salts, higher fatty acids and esters thereof), dyes (eg, nigrosine) and pigments (eg, cadmium sulfide, phthalocyanine, carbon black),
Plasticizers, flame retardants (for example, halogen-based flame retardants such as poly (brominated styrene)), red phosphorus and other general additives such as flame retardant aids, antistatic agents, and other thermoplastic resins (such as fluororesins) To impart predetermined properties.

The liquid crystalline resin composition of the present invention is preferably produced by melt kneading, and a known method can be used for melt kneading. For example, the composition can be melt-kneaded at a temperature of 200 to 400 ° C. using a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder, or the like to obtain a composition.

The thus obtained liquid crystalline resin composition of the present invention is particularly suitable for a composite of a metal body and a liquid crystalline resin composition because of its excellent adhesion to metal. Such a composite of the metal body and the liquid crystal resin composition can be obtained by bringing the liquid crystal resin composition into contact with the metal body in a molten state.
As a specific method, a metal body is mounted on a mold and injection-molded by injection molding, an outsert molding method, a method of co-extrusion molding a metal body with a liquid crystal resin, or a metal body-liquid crystal by blow molding or press molding. For example, a method of forming a composite with the conductive resin composition. The material of the metal body used for the composite of the above metal body-liquid crystalline resin composition is not particularly limited, and examples thereof include steel materials, cold-rolled steel sheets, cast iron, and iron such as stainless steel.
Examples include nickel-based alloys, copper and copper alloys, aluminum and aluminum alloys, gold, silver, tin, nickel, and alloys containing these metals. The shape of the metal body is not particularly limited, such as a plate, a line, and a sphere.

The metal body may be subjected to various chemical surface treatments. For example, the surface treatment method described in JIS may be mentioned, and specific examples of the aluminum alloy include a concentrated sulfuric acid / sodium dichromate aqueous solution treatment method, a chromate anodize method, a phosphate anodize method, and the like.
For stainless steel, a hydrochloric acid aqueous solution treatment method and a concentrated sulfuric acid / sodium dichromate aqueous solution treatment method and the like can be mentioned.

In addition, forming process Vol.5 No.12 No.87
5 to 880 (1993), a method of treating a metal surface with an aqueous solution of a triazine thiol to form a triazine thiol compound film on the metal surface.

By bringing the thus obtained liquid crystalline resin composition of the present invention into contact with a metal in a molten state, a composite of a metal and a liquid crystalline resin can be obtained. As a specific method, a metal body is mounted on a mold and injection-molded by injection molding, an outsert molding method, a method of co-extrusion molding a metal body with a liquid crystal resin, or a metal body-liquid crystal by blow molding or press molding. And a method of forming a composite with a conductive resin. By these molding methods, it is possible to obtain a metal-liquid crystalline resin composite having excellent adhesion.

The metal component and the liquid crystalline resin composite are specifically composed of a metal terminal or a metal component sealed with a resin, such as an electric switch, a relay, a connector, a socket, and a motor stator core. As a result, the resin portion is thin and stable performance can be obtained even in a high-temperature atmosphere. Therefore, it is expected to be a highly functional and highly integrated member in various industrial fields.

[0055]

The present invention will be described in more detail with reference to the following examples.

Reference Example 1 A-1 994 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4'-dihydroxybiphenyl, 112 terephthalic acid
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 distilling tube to perform polycondensation. 80 molar equivalents of aromatic oxycarbonyl units,
A liquid crystalline resin having a melting point of 314 ° C. comprising 7.5 molar equivalents of aromatic dioxy units, 12.5 molar equivalents of ethylenedioxy units, and 25 molar equivalents of aromatic dicarboxylic acid units was obtained.
The melt viscosity at 324 ° C. and a shear rate of 1000 / sec is 400
Poise.

Reference Example 2 A-2: 994 parts by weight of p-hydroxybenzoic acid, 4,
222 parts by weight of 4'-dihydroxybiphenyl, 2,6-
147 parts by weight of diacetoxynaphthalene, 107 acetic anhydride
8 parts by weight and 299 parts by weight of terephthalic acid,
The reaction vessel equipped with a distillation tube was charged and polycondensation was performed. A liquid crystalline resin having a melting point of 336 ° C., comprising 80 molar equivalents of aromatic oxycarbonyl units, 20 molar equivalents of aromatic dioxy units, and 20 molar equivalents of aromatic dicarboxylic acid units, was obtained. 3
The melt viscosity at 46 ° C. and a shear rate of 1000 / sec was 520 poise.

Reference Example 3 A-3: According to JP-A-54-77691, p-
921 parts by weight of acetoxybenzoic acid and 435 parts by weight of 6-acetoxynaphthoic acid were charged into a reaction vessel equipped with a stirring blade and a distillation tube, and polycondensation was performed. A liquid crystalline resin having a melting point of 283 ° C., comprising 57 molar equivalents of the structural unit generated from p-acetoxybenzoic acid and 22 molar equivalents of the structural unit generated from 6-acetoxynaphthoic acid, was obtained. The melt viscosity at 293 ° C. and a shear rate of 1000 / sec was 2000 poise.

Reference Example 4 B-1: 528 parts by weight of p-hydroxybenzoic acid, 4,4
126 parts by weight of '-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, 864 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 58 parts by weight of acetic anhydride
6 parts by weight were charged into a reaction vessel equipped with a stirring blade and a distillation tube, and polymerization was performed. Aromatic oxycarbonyl unit 42.
A liquid crystalline resin having a melting point of 213 ° C., comprising 5 molar equivalents, 7.5 molar equivalents of aromatic dioxy units, 50 molar equivalents of ethylenedioxy units, and 57.5 molar equivalents of aromatic dicarboxylic acid units was obtained.

Reference Example 5 B-2: 777 parts by weight of p-hydroxybenzoic acid, 4,4
126 parts by weight of '-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, 519 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 58 parts by weight of acetic anhydride
6 parts by weight were charged into a reaction vessel equipped with a stirring blade and a distillation pipe,
Polymerization was performed. 62.5 molar equivalents of aromatic oxycarbonyl units, 7.5 molar equivalents of aromatic dioxy units, 30 molar equivalents of ethylenedioxy units, 3 aromatic dicarboxylic acid units
A liquid crystalline resin having a melting point of 264 ° C. consisting of 7.5 molar equivalents was obtained.

Examples 1 to 13 and Comparative Examples 1 to 9 The liquid crystalline resins obtained in Reference Examples 1 to 3, the liquid crystal polyesters obtained in Reference Examples 4 to 5, the fillers shown in Table 1, and others Are dry-blended in the proportions shown in Table 1 and then melt-kneaded using a 44 mm diameter twin screw extruder in which the cylinder temperature is set to the melting point of each liquid crystalline resin (A) plus 10 ° C. And

The pellets were converted into an injection molding machine NIIGATA NN-
75H4000 (manufactured by Niigata Iron Works Co., Ltd.), the temperature of the cylinder is + 20 ° C, and the width is 20mm x 2mm
× A 60mm long aluminum alloy (5056) plate or a phosphor bronze plate is attached, and the metal plate width 20mm × length 2
A resin molded product having the same size as a metal plate designed to be in contact with the resin in a range of 0 mm is insert-molded at a mold temperature of 130 ° C., thereby forming a composite (FIG. 1) ) Was molded. Also, 12.5 × 1
An Izod impact test piece of 25 × 3.2 (thickness) mm was formed.

FIG. 1 is a perspective view of such a molded product, in which 1 indicates a liquid crystal resin composition portion, and 2 indicates a metal body.

Using a composite of metal and resin, a shear peel test was performed on both ends of the composite with an Instron type tensile tester as shown in FIG. 1, and the shear peel strength was calculated from the measured tensile shear load. And the adhesion was compared.

Further, AST was performed using an Izod impact test piece.
The impact resistance was evaluated according to MD256. The results are shown in Table 1.

[0066]

[Table 1]

From Table 1, it can be seen that Examples 1 to 13 all have higher Izod impact strength and shear adhesion to metal than Comparative Examples 1 to 9, and that the liquid crystalline resin composition of the present invention has It turns out that it is excellent in adhesiveness.

[0068]

As described above, according to the present invention,
Excellent adhesion between metal and liquid crystal resin composition while maintaining excellent properties such as moldability, heat resistance and low gas properties of liquid crystal resin, especially composites where metal parts are inserted or outsert molded by injection molding A liquid crystalline resin composition suitable for the body is obtained.

[Brief description of the drawings]

FIG. 1 is a perspective view of a composite including a metal plate and a resin molded product.

[Explanation of symbols]

 1 Liquid crystalline resin composition part 2 Metal body

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shingo Fujino 1F, 9F, Oe-cho, Minato-ku, Nagoya-shi, Aichi F-term (reference) 4H017 AA04 AB13 AC16 AD06 AE05 4J002 CF041 CF042 CF181 CF182 CL081

Claims (4)

[Claims] (A) one or more liquid crystalline resins selected from liquid crystalline polyesters and liquid crystalline polyesteramides that form an anisotropic molten phase other than the following component (B):
(B) It comprises the following structural units (a), (b), (c) and (d), wherein structural unit (c) is structural unit (a),
The liquid crystalline polyester comprises 25 to 60 mol% based on the total of (b) and (c), and the following structural units (a), (c) and (d), and the structural unit (c) is a structural unit. A liquid crystalline polyester selected from liquid crystalline polyesters in an amount of 25 to 60 mol% with respect to the total of components (A) and (c), and (A) with respect to the total of components (A) and (B). Component is 99 to 50% by weight, component (B) is 1
A liquid crystal resin composition which is blended so as to be in a range of from 50% by weight to 50% by weight. Embedded image (However, R1 in the formula is And R2 represents one or more groups selected from Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the total of the structural units (b) and (c) and the structural unit (d) are substantially equimolar. ) 2. The liquid crystalline resin composition according to claim 1, further comprising 300 parts by weight or less of a filler based on 100 parts by weight of the total of the components (A) and (B). 3. The liquid crystalline resin as the component (A) comprises the following structural units (I), (II) and (IV), wherein the structural unit (II)
Liquid crystalline polyesters and / or structural units (I) obtained by combining two or more different aromatic dioxy units
3. The liquid crystalline resin composition according to claim 1, which is a liquid crystalline polyester comprising: (II), (III) and (IV). Embedded image (However, R1 in the formula is And R2 represents one or more groups selected from Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural units (II) and (III)
And the structural units (IV) are substantially equimolar. ) 4. The liquid crystalline resin composition according to claim 1, which is used for a composite with a metal.