JP2000052489A - Bonded composite and sealing resin composition used therein - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bonded composite of a metal and a thermotropic liquid crystal resin excellent in adhesion and having high reliability and a sealing resin compsn. SOLUTION: A bonded composite is constituted by melting a thermotropic liquid crystal compsn. containing a non-crystalline liquid polyester resin to bond the same to a metal member 2. A sealing resin compsn. comprises the thermotropic liquid crystal compsn. containing a non-crystalline liquid polyester resin for sealing a member to be sealed at least a part of which comprises a metal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composite comprising a metal body and a thermotropic liquid crystal resin composition. More specifically, a non-liquid crystalline polyester-based resin in which a metal body, preferably a metal body surface-treated with a triazine thiol compound, has an interaction such as a hydrogen bond or a chemical bond between the metal surface and the triazine thiol compound. The present invention relates to a highly encapsulable adhesive composite in which a thermotropic liquid crystal resin composition containing is bonded in a molten state to increase the adhesive strength between the two materials. The obtained adhesive composite is used as various industrial parts mainly for electric parts, electronic parts and optical parts. For example, placing a metal body as a member to be bonded or a member to be sealed in a mold, and into the mold,
A method of injecting a thermotropic liquid crystal resin in a molten state can be employed. The most typical configuration of such an electric / electronic component is a resin-sealed component (a component sealed with a resin), for example, using a metal lead frame as a member to be sealed, and using a thermotropic liquid crystal resin (hereinafter, referred to as a thermotropic liquid crystal resin). ,
(Also called "LCP" or simply "liquid crystal resin")
And a lead frame sealing component formed using a sealing material.

[0002]

2. Description of the Related Art A composite of a resin material and a metal body is an industrial member used in various industrial fields such as the electric and electronic industries. In recent years, as the demands for higher functionality and higher integration for such composites have increased, ultrasonic fusion using a thermoplastic resin with excellent product design flexibility as a resin material,
Methods for producing a composite of a resin material and a metal body by various molding methods such as dielectric fusion, insert molding, and outsert molding have been studied. 2. Description of the Related Art Conventionally, thermosetting resins have been used as main materials in the electric and electronic fields, particularly in resin-sealed parts of lead frames used in semiconductor devices. However, the demand for simplified processes and recycling of materials has also been added, and sealing parts that have been sealed by insert molding or outsert molding using a thermoplastic resin instead of a thermosetting resin have become more reliable. It is strongly demanded as a complex having a high level. Above all, when a thermotropic liquid crystal resin is used as a sealing resin material, a stable heat-resistant composite can be obtained in various heating steps such as a soldering process after sealing. Is particularly high. In addition, a lead such as a lead wire is connected to the electric / electronic component, and when the electric / electronic component is sealed with a resin, it is necessary to seal these conductor portions as well.

[0003]

However, conventionally, it is difficult to bond a metal material and a liquid crystal resin, and a highly reliable bonded composite has not been obtained. For example, Japanese Patent Publication No. 1-60051 proposes a technique relating to injection bonding between a copper material surface-treated with a triazinethiol compound and polyethylene as an adhesive composite of a resin material and a metal body. However, in this technique, not only the metal as the bonding partner is limited to a copper material, but also the adhesiveness which is said to be improved is not necessarily sufficient. Japanese Patent Publication No. 60-41 discloses a bonded body of rubber and metal
The same applies to the method described in Japanese Patent Publication No. 08-856 which discloses a composite of plastic and metal. That is, the conventional invention is inadequate with respect to application to an adhesive composite of a wide range of highly reliable thermoplastic resins and metals, particularly to an application of an adhesive composite of a metal / thermotropic liquid crystal resin. Was. In view of the above, an object of the present invention is to provide a highly reliable adhesive composite that enables a wide range of applications to a metal / thermotropic liquid crystal resin adhesive composite.

[0004]

SUMMARY OF THE INVENTION It is a feature of the present invention to find a broadly reliable technique for manufacturing a wide range of metal / LCP bonded composites with high reliability. That is, the first aspect of the present invention relates to an adhesive composite formed by melting and bonding a metal body and an LCP composition containing a non-liquid crystalline polyester resin. The second aspect of the present invention relates to the adhesive composite according to the first aspect of the present invention, wherein the metal body is surface-treated with a triazinethiol compound. A third aspect of the present invention relates to the adhesive composite according to the first aspect, wherein the non-liquid crystalline polyester resin is a polyester-based thermoplastic elastomer. A fourth aspect of the present invention relates to a sealing resin composition made of LCP containing a non-liquid crystalline polyester-based resin for sealing a member to be sealed at least partially made of metal. A fifth aspect of the present invention relates to the sealing resin composition used for sealing a member to be sealed, in which at least a part of the surface of the metal portion is surface-treated with a triazinethiol compound in the fourth aspect of the present invention. The sixth of the present invention is the fourth of the present invention.
Wherein the non-liquid crystalline polyester-based resin is a polyester-based thermoplastic elastomer.

SUMMARY OF THE INVENTION The present invention relates to the interaction between a metal and a thermotropic liquid crystal resin composition containing a non-liquid crystalline polyester resin, or the use of a triazine thiol compound to improve the adhesion (adhesion) between the metal and the LCP. It utilizes the interaction with these resins. Hereinafter, the present invention will be further described.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The material of the metal body is not particularly limited, but examples thereof include copper and copper alloys, steel materials, cold rolled steel sheets, cast iron, stainless steel, iron-nickel alloys, aluminum and its alloys, and the like. Can be. The shape of the metal body may be any shape such as a plate or a line. Further, a metal which has been appropriately subjected to a pretreatment such as a file finish or an oxide film formation treatment can also be used. As a more specific form of the metal product, for example, a lead frame used for semiconductor manufacturing can be cited. Normal,
Lead wires as circuit conductors or power supply conductors connected to electrical and electronic components are also examples of specific embodiments. Usually, it is necessary to seal them together when sealing the electric / electronic component. Therefore, copper, aluminum, gold, silver, tin, nickel and alloys containing these metals, which are the materials of these metal bodies, are also exemplified as the metal of the present invention. In addition to the linear shape, an arbitrary shape such as a plane having an opening is used.

The metal body does not need to be subjected to any pretreatment or the like, and can be subjected to the bonding operation only by appropriately performing ordinary solvent washing. However, by pre-treating the surface of the metal body with a triazine thiol compound in advance, it is possible to further improve the adhesion (adhesion) to the LCP. Here, the triazine thiol compound is a triazine compound in which the triazine basic skeleton is substituted with one to three thiol groups or a derivative thereof, and is usually water-soluble. More specifically, it is represented by the following structural formula [I].

[0008]

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In the formula [I], the substituent R is -OR ',-
SR ', -NHR' and -N (R ') ₂ . The substituent R ′ for R is a hydrogen atom, an alkyl group, an alkenyl group,
Examples include a phenyl group, an alkylphenyl group, and a cycloalkyl group. The total number of carbon atoms in R is preferably 36 or less. Those having more than 36 carbon atoms are not preferred because they are insoluble in water. M is H, Na,
Li, K, Rb, Cs, 1 / 2Ba, 1 / 2Ca, or aliphatic primary, secondary or tertiary amines, or quaternary ammonium salts. The two Ms may be the same or different. When R is specifically shown, -SH, -NHC _{6
H 5, -NHC 8 H 17,} -NHC 12 H 25, -NHC
_{18 H 35, -NHC 18 H 37} , -N (C 4 H 9) 2, -N (C 8 H
₁₇ ) ₂ and —N (C ₁₂ H ₂₅ ) ₂ .

The surface treatment of a metal body with a triazinethiol compound can be performed by bringing the metal body into contact with a solution or dispersion of the triazinethiol compound. These processes can be performed, for example, according to the methods described in Japanese Patent Publication No. 1-60051 and Japanese Patent Publication No. 8-856. Specific solutions or dispersions of triazine thiol compounds include water; water-soluble solvents such as triethylene glycol; alcohols such as methyl alcohol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and tetrahydrofuran; benzene, toluene and xylene. Organic solvents such as lower aromatic hydrocarbons, esters such as ethyl cellosolve, dimethylformaldehyde and ethyl acetate, ethers such as dimethyl ether; non-aqueous solvents insoluble or hardly soluble in water such as decalin, benzyl alcohol and benzyl acetate; By dissolving or dispersing the triazinethiol compound in a mixed solvent or the like depending on the ratio of At the time of preparing the solution, the solvent is appropriately heated to dissolve or disperse 0.0001 to 30% by weight of the triazinethiol compound.

The surface treatment can be performed by, for example, immersing the metal body in the above solution or dispersion. In addition, coating or the like can be performed. The time for the surface treatment may be at least 0.1 second. That is, after appropriately performing degreasing, acid washing, alkali washing and water washing, the dried metal body is immersed in the above solution or dispersion for a predetermined time, or the above solution or dispersion is applied to the metal body. ,
Thereafter, it is washed with an organic solvent such as alcohol or acetone, washed appropriately with water, and dried. During the treatment, the solvent can be appropriately heated within the boiling range of the solvent. Specifically, it is performed in a temperature range from normal temperature to 300 ° C.

Further, the surface treatment can be performed electrochemically. For example, it can be performed according to the method described in Japanese Patent Publication No. 5-51671. Specifically, an aqueous solution or an organic solvent solution of triazine thiol is used as an electrodeposition solution, a metal of a metal body is used as an anode, and an appropriate conductor such as a platinum plate or a titanium plate is used as a cathode, and a voltage of, for example, 20 V or less is used. , At a current density of 0.1 mA / dm ² or more and by applying a direct current for 0.1 second or more.

In the present invention, LCP is adhered to a metal body. The LCP referred to here is a polymer that exhibits optical anisotropy at the time of melting and has thermoplasticity. As described above, a polymer that exhibits optical anisotropy at the time of melting exhibits a property that the polymer molecular chains take a regular parallel arrangement in a molten state.
The optically anisotropic molten phase can be confirmed by a normal polarization inspection method using a crossed polarizer. Examples of the LCP include liquid crystalline polyesters and liquid crystalline polyesterimides, and specifically, (whole) aromatic polyesters, polyester amides, polyester carbonates, and the like. Preferred is a thermotropic liquid crystal polyester resin, which is included in the category of the polyester of the present invention as long as it contains a plurality of ester bonds in the molecule. Further preferred polyesters are aromatic polyesters. In the thermotropic liquid crystal polyester resin preferably used in the present invention, a part of one polymer chain is composed of a polymer segment forming an anisotropic molten phase, and the remaining part does not form an anisotropic molten phase. Also included are polymers composed of polymer segments.
Further, a composite of a plurality of thermotropic liquid crystal polyester resins is also included.

Representative examples of the monomers constituting the thermotropic liquid crystal polyester resin include (a) at least one kind of aromatic dicarboxylic acid, (b) at least one kind of aromatic hydroxycarboxylic acid compound, and (c) aromatic compound. at least one diol compound, (d) (d ₁₎ an aromatic dithiol, (d ₂₎ aromatic thiopheno - Le and (d ₃₎ at least one aromatic thiol carboxylic acid compound, (e) aromatic hydroxyl Aromatic compounds such as at least one of an amine and an aromatic diamine compound are exemplified. These may be used alone,
Many are (a) and (c); (a) and (d);
(A), (b) and (c); (a), (b) and (e); or (a), (b), (c) and (e)
And so on.

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

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

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

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

(E) As the aromatic hydroxylamine or aromatic diamine compound, 4-aminophenol, N-methyl-4-aminophenol, 1,4-phenylenediamine, N-methyl-1,4-phenylenediamine , N, N'-dimethyl-1,4-phenylenediamine, 3-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino-1-naphthol, 4-amino- 4'-hydroxybiphenyl, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxydiphenylmethane, 4-amino-4'-hydroxydiphenyl sulfide, 4,4'-diaminodiphenyl sulfide (thiodianiline), , 4'-diaminodiphenyl sulfone,
2,5-diaminotoluene, 4,4′-ethylenedianiline, 4,4′-diaminodiphenoxyethane, 4,4′-diaminodiphenylmethane (methylenedianiline),
4'-diaminodiphenyl ether (oxydianiline) and the like.

The thermotropic liquid crystal polyester resin used in the present invention can be produced from the above monomers by various ester forming methods such as a melt acidification method and a slurry polymerization method. Suitable thermotropic liquid crystal resin used in the present invention has a molecular weight of about 2,000 to 200,000.
0, preferably about 4,000 to 100,000. The value of the molecular weight can be determined, for example, by measuring end groups of the compressed film by infrared spectroscopy. GPC, which is a general measurement method performed in a solution state, can also be used.

Among the thermotropic liquid crystal polyester resins obtained from these monomers, fragrance which is a (co) polymer containing, as an essential component, a repeating unit represented by the following formula [II] derived from p-hydroxybenzoic acid: Group polyesters are preferred. About 30 mol% of the above monomer unit
Those containing the above are preferred. More preferably, it contains about 50 mol% or more.

[0022]

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A particularly preferred aromatic polyester for use in the present invention is represented by the following formula [III] having a repeating unit having a structure derived respectively from three compounds of p-hydroxybenzoic acid, phthalic acid and dihydroxybiphenyl. Polyester. In the polyester represented by the formula [III], part or all of the repeating units having a structure derived from dihydroxybiphenyl can be substituted with repeating units derived from dihydroxybenzene. Further, as a preferable aromatic polyester, a polyester represented by the following formula [IV] having a repeating unit having a structure derived from two kinds of compounds, p-hydroxybenzoic acid and hydroxynaphthalenecarboxylic acid, can also be mentioned.

[0024]

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The thermotropic liquid crystal polyester resin in the present invention may be used alone, or two or more of them may be used in combination.

In the present invention, a non-liquid crystalline polyester resin is blended with the thermotropic liquid crystal resin. This polyester resin has a lower melting point and a lower glass transition point than thermotropic liquid crystal polymer. Therefore, when the composition is solidified from a molten state, the non-liquid crystalline polyester resin has a low solidification rate, and has a high degree of freedom of molecular motion during the solidification process of the molten resin.
Alternatively, it is thought that there are many opportunities to interact with the triazine thiols on the metal surface, thereby providing an excellent adhesive composite. Non-liquid crystalline polyester resins include PBT (polybutylene terephthalate), PCT
(Polycyclohexane dimethylene terephthalate), P
High melting point polyester-based resins such as ET (polyethylene terephthalate) are exemplified, and these are preferable because they hardly impair the heat resistance of the liquid crystal polymer. In addition, polyester-based thermoplastic elastomers having a low melting point or a low glass transition point have an active molecular motion over a wide temperature range, so that the elastomer easily interacts with the metal body during melting, and has excellent adhesive properties. This is preferred because it provides an adhesive composite.

The polyester-based thermoplastic elastomer is
The macroscopic structure can be roughly classified into the following two types. Any of these may be used alone or in combination with the LCP. The first is PET, PBT, PCT, PEN
In a polyester of an aromatic dicarboxylic acid and an aliphatic diol such as (polyethylene naphthalate), at least a part of the structural units derived from the dicarboxylic acid is a dicarboxylic acid having a long-chain alkyl component and having 30 or more carbon atoms, For example, it comprises a structural unit derived from dimer acid. Structural units derived from dicarboxylic acids other than dimer acid are preferably aromatic dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid. Structural units derived from diols are ethylene glycol,
It is a structural unit derived from an aliphatic diol such as 1,4-butanediol and 1,4-cyclohexanediol.

A typical dimer acid used here is a dicarboxylic acid having 36 carbon atoms, which is obtained by thermally polymerizing a purified vegetable unsaturated fatty acid obtained from a dry oil such as tall oil or a semi-dry oil. It is obtained. By changing the raw materials, the presence or absence and the type of catalyst, the reaction conditions, the separation conditions after the reaction, etc., dimer acids having significantly different structures can be obtained according to the combination of various reactions such as polymerization, cyclization, and isomerization. . Preferably, a further hydrogenated dimer acid is used. In the present invention, a dimer acid having any structure can be used. Typical structures of hydrogenated dimer acids include three types of long-chains of linear aliphatic type, alicyclic type and aromatic type as shown in the following formulas [V], [VI] and [VII]. Carboxylic acids are exemplified.

[0029]

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Specific examples of the hydrogenated dimer acid include, for example, “PRIPOL 100” manufactured by Unichema.
8 "(trade name; C36, aromatic type: alicyclic type: linear aliphatic type, molar ratio = 9: 54: 37, dimer acid);
"PRIPOL 1009" (trade name; C36, aromatic type: alicyclic type: straight-chain aliphatic type molar ratio = 13: 6)
4: 23 dimer acids) and their ester derivatives, for example, "PRIPLAST 30 which is the dimethyl ester of the dimer acid of PRIPOL 1008 described above.
08 "(product name). These can be condensed alone or in combination with other dicarboxylic acids. As the dimer acid used in the present invention, for example, Harima Chemicals Co., Ltd. comprising a mixture represented by the following formula
"Haridimer 300" (trade name).

[0031]

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

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

The second polyester-based thermoplastic elastomer is a thermoplastic elastomer composed of a block polyester copolymer of a hard segment and a soft segment because of its macroscopic structure. The hard segment is a block copolymer having a crystalline polyester structure, and the soft segment is a block copolymer having a polyether structure or an amorphous polyester structure. Examples of the structure constituting the hard segment include a polyester structure of an aromatic dicarboxylic acid and an aliphatic diol corresponding to PET, PBT, PEN, PCT and the like. Examples of the structure constituting the soft segment include a polyether structure corresponding to polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like. They are,
It can be easily obtained from the market, for example, “Thermoplastic Elastomer” (1991-2-15), Chemical Daily, p. 184-
207. The structure is, for example, B.
M. Walker, CP Rader, “Handbook of Thermoplasti
c Elastomers (second edition) ”(1988) Van Nostrand
Reinhold, New York, p. 181-223 (Chapter 6), and
“Thermop” edited by NR Legge, G. Holden, HESchroeder
lastic Elastomers ”(1987) Hanser, New York, p. 163
-196 (Chapter 8).

The first thermoplastic elastomer has a random structure in which soft segments are present uniformly and finely, and the second thermoplastic elastomer has a block structure in which the soft segments exist locally.

In order to obtain a composition of a non-liquid crystalline polyester resin and a thermotropic liquid crystal resin, known melt kneading can be employed. That is, the raw materials having an appropriate mixing ratio may be previously melt-kneaded by an extruder or a kneader, or may be melt-kneaded in a melting step of an injection molding machine. The mixing ratio is adjusted in consideration of the balance between heat resistance, rigidity and workability. In order to obtain a resin material for sealing an ordinary electrical member or optical member, it is preferable to use a composition comprising 1 to 40 parts by weight of a polyester-based thermoplastic elastomer and 99 to 60 parts by weight of a thermotropic liquid crystal resin. Here, the total of both components is 100 parts by weight.

In the present invention, a thermoplastic resin is bonded to a metal body, preferably a metal body subjected to a surface treatment with a triazinethiol compound. The thermoplastic resin preferably contains the non-liquid crystalline polyester resin. The compounding amount of the non-liquid crystalline polyester resin is 0.1 to 40 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of LCP.
0 parts by weight.

In the present invention, as described above, the interaction between the metal surface and the non-liquid crystalline polyester resin contained in the LCP, the interaction between the triazinethiol compound present on the metal surface and the LCP, An adhesive effect is obtained due to the interaction between the triazine thiol compound present on the surface and the non-liquid crystalline polyester resin contained in the LCP. Therefore, in order to sufficiently exert these interactions, it is necessary to bring the LCP in a molten state into contact with a metal body, preferably a metal body treated with a triazinethiol compound. In particular,
When utilizing the non-liquid crystalline polyester-based resin contained in the LCP, the molecular movement is actively performed to transfer the non-liquid crystalline polyester resin from the inside of the LCP to the surface, and by contact with the metal surface, The interaction can be further increased. Thus, in the present invention, it is important that the LCP composition is brought into contact with and adhered to the metal body in a molten state.

Various additives can be added to the resin composition of the present invention according to the purpose. For example, inorganic or organic fillers (glass fiber, carbon fiber, talc, mica, calcium carbonate, clay, calcium sulfate, magnesium hydroxide, silica, alumina, barium sulfate, titanium oxide, zinc oxide, graphite, wood powder, various whiskers , Metal powders, metal fibers, etc.), various stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, metal deactivators, etc.), pigments, dyes, plasticizers, oils, lubricants, nucleating agents, antistatic Agents, flame retardants and the like. The amount of the filler is generally in the range of 1 to 90% by weight, preferably 5 to 85% by weight, based on the total weight of the resin composition containing the various additives described above.

In the case of a thermoplastic resin, particularly a thermoplastic resin such as a liquid crystal resin, which has a large anisotropy of shrinkage upon solidification, reducing the anisotropy of the shrinkage also improves the adhesiveness (adhesion). Valid on That is, since the contraction anisotropy of the thermoplastic resin necessarily acts as a peeling force in a relative relationship with the metal body showing isotropic contraction, the contraction anisotropy of the thermoplastic resin is suppressed or alleviated. If this is the case, improvement in adhesion (adhesion) is expected. In order to suppress or alleviate the above-mentioned shrinkage anisotropy, a method of blending another thermoplastic resin having a small shrinkage anisotropy or a method of blending a filler having a small aspect ratio is effective. Taking a liquid crystal resin having a characteristic of high contraction anisotropy as an example, specific examples of another thermoplastic resin having low contraction anisotropy include a polycarbonate resin and a polyarylate resin. One to 30 parts by weight of another thermoplastic resin having a small shrinkage anisotropy can be blended per 100 parts by weight of the liquid crystal resin.

As the filler having a small aspect ratio to be compounded for the purpose of suppressing or relaxing the shrinkage anisotropy,
Specifically, a particulate filler such as talc, silica, calcium carbonate and the like can be mentioned. The aspect ratio is preferably 1
0 or less. The amount of the filler having a small aspect ratio is 1 to 90% by weight, preferably 5 to 85% by weight based on the total weight of the resin composition containing the above-mentioned various additives.
Range.

As described above, in order to lower the apparent glass transition temperature by blending a thermoplastic elastomer, and to extend the period (time) of substantially active molecular motion, the mold cooling temperature is usually set to a lower value. There is a way to make it higher than the set temperature. Specifically, the mold cooling temperature is set to be “(glass transition point of LCP−20 ° C.) to (melting point of LCP + 20 ° C.)”
Is preferably set in the range. In addition, such a temperature range is a temperature generally higher than a normally set mold cooling temperature.

In insert molding and the like, the insert member is often preheated. Making the preheating temperature higher than the temperature usually set is also effective for the above purpose. Specifically, similarly to the above, it is preferable to set the preheating temperature of the insert member in a range from “(glass transition point of LCP−20 ° C.) to (temperature of melting point of LCP + 20 ° C.)”. In addition, such a temperature range is generally a temperature higher than the preheating temperature usually set.

Further, by blending a low molecular weight compound having an interaction with a metal surface or a triazinethiol compound present on the metal surface, for example, an oxygen-containing hydrocarbon resin in the composition of the present invention, the adhesiveness to metal ( Adhesiveness) can be improved. As the oxygen-containing hydrocarbon resin that can be blended in the composition of the present invention, first,
Oxygen-containing hydrocarbon resins obtained by copolymerizing olefins with oxygen-containing compounds such as carboxylic acids, phenols and alcohols, or modifying hydrocarbon resins obtained by olefin polymerization with these oxygen-containing compounds are exemplified. Is done. It is preferable that oxygen atoms are contained in an average of 0.1 to 3 in one molecule. Specific examples include oxygen-containing terpene hydrocarbon resins derived from unsaturated terpene monomers such as α-pinene, β-pinene, dipentene, d-limonene, and l-limonene. Preferably, it is a free carboxylic acid or hydroxyl group-containing hydrocarbon resin. Free carboxylic acids or hydroxyl groups can be
It is preferable that the molecule contains an average of 0.1 to 3 molecules. More specifically, examples of the oxygen-containing terpene hydrocarbon resin include a reaction product of a terpene monomer and a phenol such as phenol, cresol, hydroquinone, and bisphenol A, or a hydrogenated product of the reaction product. In addition, the oxygenated terpene hydrocarbon resin may be a reaction product of a terpene monomer and an α, β-unsaturated dicarboxylic acid such as maleic acid or fumaric acid, or a hydrogenated product thereof. Furthermore, as an oxygen-containing terpene hydrocarbon resin, phenol,
It is also possible to use a phenol skeleton-containing polyvalent compound obtained by adding phenols such as cresol, hydroquinone and bisphenol A at a ratio of two or more molecules or a hydrogenated product thereof.

The reaction product of the terpene monomer and the phenol is subjected to a Friedel-Crafts reaction using, for example, the terpene monomer and the phenol. It is obtained by hydrogenation by a known method. These are referred to in the market as terpene diphenol, terpene phenolic resin, or terpene-phenol copolymer resin. For example, commercially available products such as “YS Polystar” and “Mighty Ace” (both are commercial products) Name, manufactured by Yashara Chemical Co., Ltd.).

The reaction product of the above-mentioned terpene monomer and α, β-unsaturated dicarboxylic acid is, for example, a terpene monomer and α, β-unsaturated dicarboxylic acid obtained by reacting Diels-Alder. The reaction can be carried out by reaction, and the hydrogenated product can be obtained by hydrogenating these compounds by a known method. These are called acid-modified terpene-based resins or acid-modified terpene copolymer resins on the market. For example, as a commercial product, "TM-60" (trade name, manufactured by Yashara Chemical Co., Ltd.)
Corresponds to this.

Further, the phenol polyhydric compound having a terpene skeleton obtained by adding phenols to one molecule of the cyclic terpene compound at a ratio of two or more molecules is, for example, a terpene monomer and a phenol. The Friedel-Crafts reaction is performed at an equivalent ratio of 1: 2, and the hydrogenated product is obtained by hydrogenating these compounds by a known method. For example, as a commercially available product, "YP-90"
(Trade name, manufactured by Yashara Chemical Co., Ltd.) corresponds to this.

The second example of the oxygen-containing hydrocarbon resin is an oxygen-containing hydrocarbon wax, for example, a hydroxyl-containing hydrocarbon wax. This wax has a polyolefin-based hydrocarbon skeleton, and is a room-temperature solid having a hydroxyl group in a side chain or a terminal thereof. That is, it is an alcohol having a carbon number of about 100 to 500 in the main chain. These waxes can be produced, for example, by hydrogenating polybutadiene having a terminal hydroxyl group. As a commercially available product, "Polytail H" (trade name, manufactured by Mitsubishi Chemical Corporation)
Etc. correspond to this. In addition, the oxygen-containing wax can also be produced by subjecting a hydrocarbon wax to a peroxide treatment and introducing oxygen atoms.

The obtained LCP composition of the present invention is melt-injected by an appropriate melt-molding machine, for example, an injection molding machine, and is subjected to a surface treatment with a metal, preferably a triazinethiol compound, and a resin. Glue under melting. Taking a lead frame as an example of a specific member, a metal lead frame is preferably treated in advance with a triazine thiol compound in advance to form an insert member in sealing molding. This is set in a mold by a conventional method (fitting), and a resin is melt-injected and molded to perform sealing molding, thereby obtaining an adhesive composite as a sealing component. Alternatively, an adhesive composite can be obtained by using a metal body or a metal body subjected to a surface treatment as an outsert member and melt-injecting a resin by outsert molding. In addition, an adhesive composite can also be obtained by bringing a resin into contact with a metal body or a surface-treated metal body, heating and melting the resin, and performing hot press molding or the like.

The adhesive composite of the present invention is used as general industrial parts and various parts such as electricity, electronics and optics.
Representative forms of these parts include automotive parts such as lamp sockets, distributor caps, ignition coils, fuse cases, various switches, brackets, bobbins, intake temperature control panels, bimetal vacuum switching valves, gasoline tanks, etc. Electrical components such as coated steel plates, resin-coated metal tubes, connectors, block terminal pedestals, coil bobbins, tuner component relays, sockets, switches, sewing machine motor cases, relay terminal mounting terminals, fuse cases, capacitor cases, CD player chassis, HDD chassis, etc. Examples include general industrial parts such as pump casings and exterior parts such as cameras, and lead frame sealing members used in the fields of electricity, electronics, and optics.

[0051]

The present invention will be described below with reference to examples. <Surface treatment of metal body> Predetermined metal plate (50 mm x 50 mm x
(0.5 mm) was degreased and dried, then, if necessary, subjected to a surface treatment with a triazinethiol compound, dried and used. The kind of the used triazine thiol compound and the method of the surface treatment are as follows. (1) 1,3,5-Triazine-2,4,6-trithiol monosodium salt (TTN) A predetermined metal plate is placed in a 0.4% aqueous solution of TTN at 80 to 90 ° C.
, And then dried at 40 ° C. (2) 1,3,5-triazine-2,4,6-trithioltriethanolamine (TEA) A 1% aqueous solution of TEA is placed in an electrolytic cell, kept at 20 ° C., a predetermined metal plate is placed therein, and a constant voltage is applied. (At 0.6 V or less) for 2 minutes to perform an electrochemical treatment.

<Production of LCP composition> The thermotropic liquid crystal polymer, the non-liquid crystalline polyester resin and the filler were mixed with stirring, and then melted with a twin screw extruder to obtain the desired composition. In addition, the meaning of the symbol described in the table is as follows. -KFC (trade name): lead frame material made of iron-nickel alloy, manufactured by Kobe Steel Ltd. -PBT: polybutylene terephthalate-PETE1: PBT structure as a hard segment,
Polyester-based thermoplastic elastomer having a polyether structure as a soft segment; trade name: Perprene P-30B, manufactured by Toyobo Co., Ltd. -PETE2: PRIPLAST 3008 (trade name,
A copolymer obtained by subjecting 1,4-butanediol to transesterification with dimethyl terephthalate containing 10 mol% of a dimer acid mixture (manufactured by Unichema Co.), followed by polycondensation; trade name: Kanebo PBT PO2120, Kanebo Co., Ltd. Made.

<Molding Method> A method of bonding a metal body and a resin will be described with reference to the drawings. FIG. 1A is a schematic cross-sectional view of a mold 1 used for molding, and FIG. 1B is a plan view of a metal body 2. (1) Metal body 2 (plate,
A double-sided tape 3 is applied to a part of one side of 50 mm × 50 mm × 0.5 mm), and the double-sided tape 3 is attached to a wall in a cavity 4 (100 mm × 100 mm × 1 mm) of a one-sided injection molding die 1. (2) The movable mold 5 is closed, and a predetermined thermoplastic resin is injected from a gate (not shown) into the cavity 4 to perform injection molding. (3) The movable mold 5 is opened, and the molded product (adhesive composite) is protruded with the protruding pin 6 and taken out.

<Evaluation Method of Adhesive Property> The adhesive property is represented by the ratio of A and B (A / B) shown below. That is, 3
/ 5 means that good adhesion was obtained in three of the five molding experiments. A: The number of times that a composite body of a metal body and a resin was removed from a mold in a removal operation of a molded product. In the case of poor adhesion, the metal adheres to the mold side, and only the molded resin plate is taken out. Therefore, taking out the integrated composite means that the adhesion is sufficient. B: Total number of molding experiments.

<Experimental Examples 101 to 142> Tables 1 to 8
Shows the thermotropic liquid crystal resin, filler, metal material, polyester-based thermoplastic elastomer, triazine thiol compound and oxygenated hydrocarbon resin used, and the evaluation results of adhesiveness. LCP is a thermotropic liquid crystal copolyester resin having repeating units each derived from phthalic acid / isophthalic acid / p-hydroxybenzoic acid / 4,4′-dihydroxybiphenyl, and each molar ratio is 0. .75 / 0.25 / 3/1. When this resin was observed for optical anisotropy using a polarizing microscope equipped with a hot stage, it showed optical anisotropy in a molten state at 340 ° C. or higher.

[0056]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[0057]

According to the present invention, by blending a non-liquid crystalline polyester resin with a thermotropic liquid crystal resin, the adhesion (adhesion) between the liquid crystal resin and the metal is improved, and good adhesion can be obtained. This effect is further improved when the metal is surface-treated with a triazinethiol compound.
This effect is considered to be due to the fact that the non-liquid crystalline polyester resin is well dispersed and produces an action such as a hydrogen bond on the metal surface or the triazinethiol compound. Also,
Polyester-based thermoplastic elastomers are particularly preferred because, during injection molding of the LCP composition, the LCP molecules can undergo molecular movement in the mixture even after they have solidified, and thus have a greater bonding effect with the metal surface.

[Brief description of the drawings]

FIG. 1A is a schematic sectional view of a mold, and FIG.
(B) is a top view of a metal body.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Mold 2 Metal body 3 Double-sided tape 4 Cavity 5 Moving mold 6 Projection pin

Continued on the front page F-term (reference) 4F100 AB01A AB17 AH03A AH04A AK41B AK41K AK42 AL09B BA02 BA07 BA26 EJ64A GB41 GB51 JA20B JB16B JL11 4J002 CF062 CF072 CF102 CF181 DA076 DA086 DC006 FB086 FD010 GN00 G00

Claims (6)

[Claims] 1. An adhesive composite formed by melting and bonding a metal body and a thermotropic liquid crystal resin composition containing a non-liquid crystalline polyester resin. 2. The adhesive composite according to claim 1, wherein the metal body is surface-treated with a triazinethiol compound. 3. The adhesive composite according to claim 1, wherein the non-liquid crystalline polyester resin is a polyester-based thermoplastic elastomer. 4. A sealing resin composition comprising a thermotropic liquid crystal resin containing a non-liquid crystalline polyester resin for sealing a member to be sealed at least partially composed of metal. 5. The resin composition for sealing according to claim 4, wherein at least a part of the surface of the metal portion is used for sealing the member to be sealed whose surface is treated with a triazinethiol compound. 6. The sealing resin composition according to claim 4, wherein the non-liquid crystalline polyester-based resin is a polyester-based thermoplastic elastomer.