JPH0142286B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition that has excellent adhesion to ceramics and the like and moisture resistance, and is effective for moisture-proof insulation treatment of hybrid ICs. If a hybrid IC is used without moisture-proofing, the pin feet and connectors of mounted components such as capacitors and transistors may corrode or form condensation due to humidity and dust in harsh environments. In such a state, the hybrid IC will not function properly. In order to prevent these problems and to strengthen the mounted electronic components, it is necessary to apply moisture-proof paint to part or all of the hybrid IC to form a protective film. Conventionally, powder coatings and solvent-based moisture-proof insulation paints have been used for hybrid ICs. However, since these paints are heat-curable, high temperatures and long hours are required for complete curing and insulation treatment. In addition, for short-term processing, ultraviolet curable resin compositions that cure within a few seconds to several minutes are advantageous, but ordinary ultraviolet curable resin compositions have problems in adhesion to substrates and moisture resistance. . As a result of various studies, the present inventors have discovered a resin composition that has excellent adhesion to a substrate and moisture resistance. Specifically, the present invention provides (A) reacting maleic anhydride with an animal or vegetable oil having a double bond capable of an addition reaction to obtain an addition reaction product, and then reacting the addition reaction product with the reaction product represented by the general formula (). per 100 parts by weight of the compound (hereinafter referred to as component A) obtained by the esterification reaction with the compound (However, in the formula, R ₁ and R ₂ are H or CH ₃ ,
(These may be the same or different) (B) 5 to 40 parts by weight of the compound represented by the general formula () (hereinafter referred to as component B) (However, in the formula, R ₃ is H or CH ₃ , R ₄ is a divalent hydrocarbon residue, and R ₅ is an alkyl group) (C) A compound represented by the general formula () and/or a compound represented by the general formula () 0.5 to 20 parts by weight of the compound shown (hereinafter referred to as component C) (However, in the formula, R ₆ is H or CH ₃ , R ₇ is a divalent hydrocarbon residue, and R ₈ is an alkyl group) and (D) contains 0.001 to 10 parts by weight of a photopolymerization initiator. The present invention relates to a resin composition. The addition reaction between maleic anhydride and an animal or vegetable oil that has a double bond capable of addition reaction is as follows:
This animal and vegetable oil is added to 1 mole of maleic anhydride.
As 0.5 to 2 mol, at 160℃ to 240℃, 30 minutes to 6
It is preferable to do it in hours. If necessary, a solvent such as toluene or xylene may be used. For 1 mole of this addition reaction product, approximately equimolar amount of the compound represented by the above general formula () was added at 60°C without a solvent.
Preferably, the reaction is carried out at ~120°C for 4 to 24 hours. Examples of animal and vegetable oils having double bonds capable of addition reaction with maleic anhydride of the present invention include linseed oil, tung oil, coconut oil, safflower oil, soybean oil, dehydrated castor oil, rice bran oil, cottonseed oil, and fish oil. , these can be used alone or in mixtures. The compounds represented by the above general formula () include 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate,
-Hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, etc., and these can be used alone or in combination. The compound represented by the above general formula () is methyltri(acryloyloxyethoxy)
Examples include silane, methyltri(methacryloyloxyethoxy)silane, methyltri(acryloyloxypropoxy)silane, and methyltri(methacryloyloxypropoxy)silane. Examples of the compounds represented by the above general formula () or general formula () include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, vinyl Examples include trimethoxysilane and vinyltriethoxysilane. As a photopolymerization initiator, benzyl dimethyl ketal, benzoin, benzoin ethyl ether,
Benzoin ethers such as benzoinpropyl ether and benzoin phenyl ether, benzinthioethers, benzophenone, acetophenone, 2-ethylanthraquinone furoin, benzoin ether Michler's ketone, chlorinated decylnothioxanthone, and the like are used. The blending ratio of the above components is 5 to 40 parts by weight of component B) and 0.5 parts by weight of component C) per 100 parts by weight of component A).
~20 parts by weight and the photoinitiator is in the range of 0.0001 to 10 parts by weight. If component B) is less than 5 parts by weight, the moisture resistance will be poor, and if it exceeds 40 parts by weight, the adhesion to ceramic will be poor. If the amount of component C) is less than 0.5 parts by weight, the adhesion to ceramic will be poor, and if it exceeds 20 parts by weight, the moisture resistance will be poor. In addition, the photopolymerization initiator
If it is less than 0.0001 parts by weight, the curing speed by light irradiation will be slow, and if it exceeds 10 parts by weight, it will tend to be difficult to form a film. The resin composition of the present invention is the above A), B),
It is obtained by blending a predetermined amount of components C) and D) and stirring and dissolving the mixture. The resin composition in the present invention may contain the various components described below as necessary. As a crosslinkable monomer, styrene, vinyltoluene, α-methylstyrene, p-tertiarybutylstyrene, chlorostyrene, divinylbenzene, diallyl phthalate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methyl methacrylate, Ethyl methacrylate, lauryl methacrylate, monofunctional methacrylic acid esters such as reaction products of methacrylic acid and Cardiura E-10 (trade name of glycidyl ester of higher fatty acids manufactured by Schiel Chemical Co., Ltd.), ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1, Bifunctional methacrylic esters such as 6-hexanediol dimethacrylate, trifunctional methacrylic esters such as trimethylolpropane trimethacrylate,
Monofunctional acrylic esters such as methyl acrylate, ethyl acrylate, lauryl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, a reaction product of acrylic acid and Cardiura E-10, ethylene glycol diacrylate, Difunctional acrylic esters such as diethylene glycol diacrylate and 1,6 hexanediol diacrylate,
Trifunctional acrylic esters such as trimethylolpropane triacrylate can be used alone or in combination. As the solvent, aromatic solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl ethyl ketone and acetone can be used. As a radical polymerization initiator, acyl peroxides such as benzoyl peroxide and acetyl peroxide, ketone peroxides such as tert-butyl peroxide, methyl ethyl ketone peroxide, kyumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, etc. Oxyperoxides such as alkyl peroxides, tert-butyl peroxybenzoate, tert-butyl peroxy acetate, etc. can be used. As a hardening accelerator, naphthenates, octenoates, etc. of iron, cobalt, lead, manganese, nickel, tin, zinc, etc. can be used. As the polymerization inhibitor, quinones such as hydroquinone, paratertiary butylcatechol, pyrogallol, and other commonly used ones can be used. In addition, the resin composition of the present invention may optionally contain inorganic fillers such as quartz glass powder, hydrated alumina powder, talc, calcium carbonate, mica, mica powder, synthetic mica, synthetic mica powder, alumina oxide, and silica. , pigments, dyes, etc. may be added. Components such as the above-mentioned crosslinkable monomers are used in amounts commonly used in resin compositions, and there are no particular limitations on the amounts used. Further, the resin composition in the present invention includes an unsaturated polyester resin, an oil-modified unsaturated polyester resin,
It can be used in combination with dicyclopentadiene-modified unsaturated polyester resin, polybutadiene, acrylic acid and/or methacrylic acid-modified polybutadiene, unsaturated epoxy ester resin, epoxy resin, etc. The resin composition of the present invention is effective for moisture-proof insulation treatment of hybrid ICs, for example. Hybrid IC is made of alumina ceramic,
It is a board made of glass epoxy, paper phenol, etc., with resistors, wiring, etc. printed on it and various electronic components mounted on it. In the present invention, a hybrid IC of a resin composition
Application to the hybrid IC is carried out by dipping the hybrid IC in the above resin composition or by coating the hybrid IC with the above resin composition. For light irradiation, ultraviolet rays are the most efficient and easy to operate, so examples of light sources include low-pressure mercury lamps, high-pressure mercury lamps, and ultra-high-pressure mercury lamps. Next, examples and comparative examples will be explained. Parts in Examples and Comparative Examples indicate parts by weight. Example 1 708 g of linseed oil and 125 g of maleic anhydride were placed in a four-necked flask (1), reacted at 220°C for 4 hours while blowing nitrogen gas, and then cooled to 100°C to form 2-hydroxyethyl methacrylate 167
g, hydroquinone 0.2 g and reacted at 100℃ for 4 hours while blowing air, acid value 70,
A compound () having a viscosity of 32 poise (25°C) was obtained. Varnish A was obtained by mixing and stirring 80 parts of compound (), 20 parts of methyltri(methacryloyloxyethoxy)silane, 2 parts of γ-methacryloxypropyltrimethoxysilane, and 1 part of benzyl dimethyl ketal. Example 2 80 parts of the compound () used in Example 1, 20 parts of methyltri(methacryloyloxyethoxy)silane
Varnish B was obtained by mixing and stirring 1 part of vinyltrimethoxysilane, 2 parts of vinyltrimethoxysilane, and 1 part of benzyldimethyl ketal. Comparative Example 1 Varnish C was obtained by mixing and stirring 100 parts of the compound () used in Example 1, 2 parts of γ-methacryloxypropyltrimethoxysilane, and 1 part of benzyl dimethyl ketal. Comparative Example 2 60 parts of the compound () used in Example 1, 40 parts of methyltri(methacryloyloxyethoxy)silane
Varnish D was obtained by mixing and stirring 2 parts of γ-methacryloxypropyltrimethoxysilane and 1 part of benzyl dimethyl ketal. 15× for varnishes A to D obtained in Examples and Comparative Examples
Hybrid IC with 36×0.8mm alumina substrate
Dip and apply so that the flat part is about 50μm,
Ushio Inc. mercury lamp 50W/cm, irradiation distance 10
When it was cured by UV irradiation from cm for 120 seconds, it was completely cured. Next, the adhesion was evaluated by peeling off the tape according to the JIS K 5400 cross-cut test, and the results are shown in Table 1.

[Table] Test As shown in Table 1, the resin composition of the present invention has good adhesion to the substrate and excellent moisture resistance.

Claims (1)

[Scope of Claims] 1 (A) An addition reaction product is obtained by reacting maleic anhydride with an animal or vegetable oil having a double bond capable of an addition reaction, and then the addition reaction product is combined with the general formula () Based on 100 parts by weight of the compound obtained by esterification reaction with the compound shown in (However, in the formula, R ₁ and R ₂ are H or CH ₃ ,
(These may be the same or different) (B) 5 to 40 parts by weight of the compound represented by the general formula () (However, in the formula, R ₃ is H or CH ₃ , R ₄ is a divalent hydrocarbon residue, and R ₅ is an alkyl group) (C) A compound represented by the general formula () and/or a compound represented by the general formula () 0.5 to 20 parts by weight of the indicated compound (However, in the formula, R ₆ is H or CH ₃ , R ₇ is a divalent hydrocarbon residue, and R ₈ is an alkyl group) and (D) a resin containing 0.001 to 10 parts by weight of a photopolymerization initiator Composition.