JPS5842612A - Resin composition - Google Patents

Abstract

PURPOSE:An ultraviolet ray-curable composition excellent in adhesion to ceramics and moisture resistance and suitable for use in moisture-proof insulation of hybrid IC, comprising an unsaturated silane and a reaction product of maleic anhydride, an animal or vegetable oil and an OH-containing (meth)acrylate ester. CONSTITUTION:An addition reaction is carried out between (i) maleic anhydride and (ii) an animal or vegetable oil having a double bond which is addition- polymerizable with component (i), e.g., linsed oil, at 160-240 deg.C. The resulting product is further reacted with a compound of formulaI, wherein R1-2 are each H or CH3 (e.g., 2-hydroxyethyl methacrylate) at 60-120 deg.C to form a product. The titled composition is prepared by mixing 100pts.wt. above-prepared product with 0.0001-10pts.wt. photopolymerization initiator (e.g., benzyldimethylketal and 0.0001-20pts.wt. compounds of formulas II and/or III, wherein R<3> is H or CH3, R4 is a bivalent hydrocarbon radical and R5 is an alkyl, e.g., gamma-methacryloxypropyltrimethoxysilane.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has excellent adhesion to ceramics and 1 resistance.
The present invention relates to a resin composition suitable for moisture-proofing and insulating hybrid ICs.

Conventionally, a moisture-proof insulating paint of a powder-based paint/solvent type has been used as a one-coat-proof insulating cage material for hybrid ICs. However, these paints.

Because it is heat-curable, it took a long time to insulate it.

For short-time processing, ultraviolet curable resin compositions that cure within several seconds to several minutes are advantageous, but ordinary ultraviolet curable resin compositions have problems in adhesion to ceramics and moisture resistance.

As a result of various studies, the present inventors have discovered a resin composition that has excellent adhesion to ceramics and moisture resistance.

The present invention is A) a compound obtained by addition reaction of maleic anhydride and an animal or vegetable oil having a double bond capable of an addition reaction, and a compound having the formula or CH, which may be the same or different. )
A compound obtained by reacting the compound shown in (hereinafter referred to as A
) component) B) a photopolymerization initiator and 1 C) R represented by the formula (Jmu=C-CO-R4at(ORs)s).

Compounds and/i or CH*=CH-8i (ORs)
m (R, is H or C sweat, R1 is a divalent hydrocarbon residue,
R1 is an alkyl group) (hereinafter referred to as C)
Regarding the tree I11@ composition containing the following.

The addition reaction between maleic anhydride and maleic anhydride with an animal or vegetable oil having a double bond capable of an addition reaction is performed using α5 to 2 moles of this animal or vegetable oil per mole of Jl maleic acid.
It is preferable to carry out at 160°C to 240°C for 30 minutes to 6 hours.

If necessary, a laxative such as toluene or xylene may be used. per mole of this addition reactant.

1 Turtle OH The indicated compound was heated at 60°C to 120°C under a non-detergent agent for 4 to 2
It is preferable to react for 4 hours.

Examples of the animal and vegetable oils having a double bond capable of addition reaction with maleic anhydride of the present invention include linseed oil, tung oil, coconut oil, safflower oil, and soybean oil.

There are dehydrated oils, mustard oil, rice bran oil, and cottonseed oil, which can be used alone or in combination.

1 R,0H Hl or CH8) is 2-
Examples include hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, and 2-hydroxypropyl acrylate, and these can be used alone or in combination.

As a photopolymerization initiator, benzyl dimethyl ketal 1.
Benzoin ethers such as henzoin, benzoin ethyl ether, benzoin propyl ether, pen-diymphenyl ether.

Pen dithioethers, benzophenone.

Acetophenone, 2-ethylanthraquinone fucoin,
Benzoin ether-Michler's ketone series, decylnotiotins, and the like are used.

1 R1 compound t represented by the formula CH,=C-C-0-R, -8i (OR,) or compound represented by CHy=CH8i (ORs) (R8 is Hl or CH, R4 is divalent (R1 is an alkyl group), for example, disilane in r-methacryloxypropyltrimeth, cypcupyrtriethoxysilane in γ-methacrylo, r-acryloxypucvir Trimethoxy 7
Ran, vinyltrimethoxysilane, vinyltriethoxysilane, etc. A) For 100 parts by weight of component, 0.0001 to 10 parts by weight of photopolymerization initiator, C) 0 part by weight of component.
．． It is preferable to use it in a range of 0,001 to 20 parts by weight from the viewpoint of adhesion to ceramics and UV curability.

゛The resin composition of the present invention may contain the various components described below as necessary.

Styrene, vinyltoluene, α-
Methyl styrene, p-tert-butyl styrene, chlorstyrene, divinylbenzene, diallyl phthalate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, lauryl methacrylate, methacrylic acid and Cardura E Monofunctional methacrylic acid esters, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, such as reactants of -, 10 (trade name of dalicidyl ester of higher fatty acids manufactured by Shell Chemical Co., Ltd.).

1.6 Difunctional methacrylic esters such as hexanediol dimethacrylate, trifunctional methacrylic esters such as trimethylolpropane trimethacrylate, methyl acrylate, ethyl acrylate, lauryl acrylate, 2-hydroxyethyl acrylate, 2- l-functional acrylic esters such as hydroxypropyl acrylate, the reaction product of acrylic acid and Kershera E-10; di-functional acrylic esters such as ethylene glycol diacrylate, diethylene glycol diacrylate, and 1.6 hexanediol diacrylate; , trifunctional acrylic esters such as trimethylolpropane triacrylate can be used alone or in combination.

Examples of solvents that can be used include aromatic solvents such as toluene and xylene, ester-based detergents such as ethyl acetate and butyl acetate, and ketone-based solvents such as methyl ethyl ketone and acetone.

As a 5-dihydric polymerization initiator, acyl peroxides such as benzoyl peroxide and acetyl peroxide, tertiary-butyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide,
Ketone peroxides such as cyclohexanone peroxide, alkyl peroxides such as dicumyl peroxide, oxyperoxides such as tertiary-butylperoxybenzoate, tertiary-butylperoxybenzoate, and diacetate can be used.

Naphthenates of iron, cobalt, lead, manganese, nickel, tin, zinc, etc. as hardening accelerators.

Octenoic acid salts etc. can be used.

As a polymerization inhibitor, hydroquinone, paratertiary
Quinones such as butylcatechol and pyrogallol, and other commonly used ones can be used.

In addition, 9 Inventive products*@compounds include quartz glass powder, hydrated alumina powder, Merck, calcium carbonate, mica, mica powder 0 synthetic mica 1 synthetic mica powder, alumina oxide, silica, etc. You can add inorganic fillers such as pigments, dyes, etc.

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.

The resin composition of the present invention also includes unsaturated polyester resin,
It can be used in combination with oil-modified unsaturated polyester resin, dicyclopentadiene-modified unsaturated polyester resin, polybutadiene, acrylic acid-modified or methacrylic acid-modified polybutadiene, unsaturated epoxy ester resin, epoxy resin, etc.

Examples and comparative examples will be explained below, but the present invention is not limited to these examples. Actual example 9. In the comparative fold examples, the part is the direct part.

Comparative Example 1 EP-8211 (Shell Chemical Epoxy Tree 11) 29G
? , reacted with 140t1 of acrylic acid at 100°C for 4 hours,
Epoxy acrylate with an acid value of 1.5 was obtained. 70 parts of this epoxy acrylate and 30 parts of styrene.

One part of benzyl dimethyl ketal was stirred to obtain Varnish A.

Comparative Example 2 Acnicus 8060 (manufactured by Toagosei Co., Ltd., polyester acrylate) 70fflS, 30 parts of styrene.

Varnish B was obtained by stirring 1 part of benzyl dimethyl ketal.

Comparative Example 3 100 parts of EP-828, triphenylsulfonium hexafluoroantimony (5011 acid propylene solution) 6
Varnish C was obtained by mixing and stirring.

Comparison PJ4 Linseed oil 708 f, anhydrous maleic! 1t of 1125F
2-Hydroxyethyl methacrylate (167), hydroquinone (0.2f) and 0.2f of hydroquinone were charged, followed by reaction at 220°C for 4 hours while blowing nitrogen gas. While, 1
The reaction was carried out at 00°C for 4 hours, and the acid value was 70. Guest 32 poise (
Compound temperature (25°C) was obtained.

Varnish D was obtained by mixing and stirring 70 parts of Compound A, 30 parts of styrene, and 1 part of benzyl dimethyl ketal.

Example 1 Varnish E was obtained by mixing and stirring 70 parts of Compound A, 30 parts of styrene, 2 parts of r-methacryloxypropyltrimethoxysilane, and 1 part of benzyl dimethyl ketal.

Example 2 Varnish F was obtained by heating and stirring 70 parts of Compound A, 30 parts of styrene, 2 parts of vinyltrimethoxysilane, and 1 part of benzyldimethyl ketal.

For comparison, the varnish A-F of the actual example was applied to a thickness of 40 pm on an A4kjna ceramic substrate and cured by irradiating it with ultraviolet rays for 60 seconds using a 50 W/cm Ushio Denmei mercury lamp from an irradiation distance of 10 m. completely cured.

Next, adhesion was evaluated by peeling off the tape according to the cross-cut test according to JIS K 5400. The results are shown in Table 1.

Table 1 Adhesion test results * Value of 10 molecules is the first number left 12 121°C / 2 atm From Table 1 0 The resin composition of the present invention is UV curable, has good adhesion to ceramics and moisture resistance. It is shown that the quality is excellent.

Claims (1)

[Scope of Claims] 1. A) A compound obtained by addition reaction of maleic anhydride and an animal or vegetable oil having a double bond capable of an addition reaction, and having the formula Hl or CH, which are B) Photopolymerization initiator and 1 C) Formula CH, = C-C-0-Ra-8t (ORm~
Indicated by R. and /l or Cl=CH-8i (0Rsb
(R1 is In or CH, R, is a divalent hydrocarbon residue I
iii) A composition comprising a compound represented by R1 is an alkyl group.