JPH0721051B2 - Thermosetting resin composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a thermosetting resin composition having excellent heat resistance and moldability, and more specifically, a furan-modified novolak type phenol resin and N, N′- The present invention relates to a resin composition containing a substituted bisimide-based unsaturated compound as an essential component.

[Background of the Invention]

A resin composition composed of an addition type bisimide compound and a polyfunctional epoxy compound has excellent heat resistance and has a wide range of applications such as molding materials, laminating materials, prepregs, and adhesives.
However, in these applications, there has been a strong demand for improvement in molding processability, particularly rapid curing property and solubility in general solvents. In order to deal with this, conventional compositions cannot be said to be sufficient, and development of heat resistant resin compositions having a new curing system is required.

[Object of the Invention]

The present invention has been made in view of the above circumstances, and an object thereof is to provide a thermosetting resin composition having excellent heat resistance and molding processability.

[Outline of Invention]

The present invention is a thermosetting resin composition comprising at least a furan-modified novolak type phenol resin and an N, N′-substituted bisimide compound.

Next, the resin components will be sequentially described.

In the present invention, the furan-modified novolak type phenol resin is, for example, an addition polycondensate produced by a reaction as shown in the following formula from furafural and phenols, [In the formula, R represents H or an alkyl group] The above-mentioned heated pre-crosslinked polymer of the reaction product, or a cocondensation product of furfuryl alcohol and phenols [In the formula, R represents H or an alkyl group] Furthermore, a reaction product of the above polycondensation product and polyvinyl acetal, a furfural modified phenol novolak resin, and the like.

If further added, furfural or furfuryl alcohol and bisphenol (In the formula, X is absent, that is, represents a single bond, or is a member of any one of CH ₂ , C (CH ₃ ) ₂ , O, S, SO _{2 and the} like.) It is effective in achieving the effect.

Examples of the N, N'-substituted bisimide-based unsaturated compound include N, N'-ethylenedimaleimide, N, N'-ethylenebis (2-methylmaleimide), N, N'-trimethylenedimaleimide. , N, N'-tetramethylene dimaleimide, N, N'-hexamethylene dimaleimide, N, N'-hexamethylene bis (2-methylmaleimide), N, N'-
Dodecamethylene dimaleimide, N, N'-m-phenylenedimaleimide, N, N'-p-phenylenedimaleimide,
N, N '-(oxy-p-phenylene) dimaleimide, N,
N '-(methylene-di-p-phenylene) dimaleimide, N, N'-(methylene-di-p-phenylene) bis (2-methylmaleimide), N, N'-2,4-tolylenedimaleimide, N , N'-2,6-tolylene dimaleimide, N, N '
-M-xylylene dimaleimide, N, N'-p-xylylene dimaleimide, N, N'-oxypropylene dimaleimide, N, N'-ethylenebis (oxypropylene maleimide), N, N'-oxydiethylene dimaleimide , 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-bis [4- (4
-Maleimidophenoxy) phenyl] propane and the like, and the amine adducts, phenol adducts and thiochol adducts of the above bisimide compounds are used. Further, a polyvalent N-substituted maleimide compound may be added and blended, or one or more of the above compounds may be used in combination.

In the present invention, the ratio of the furan-modified novolak type phenol resin to the N, N′-bisimide unsaturated compound is not particularly limited, but the weight ratio of the former to the latter is generally 5: 1.
It is recommended to use it in a ratio of up to 1: 2.

In the resin composition of the present invention, N, N'-substituted bisimide-based unsaturated compound as a crosslinking agent, for example, 4,4'-methylenedianiline, 4,4'-oxydianiline, 4,4'-carbonyl An alkylene group, a cyclic alkylene group, an arylene group, a heterocyclic group such as dianiline, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and 4,4'-methylenedi (cyclohexylamine). Alternatively, a diamine having, as a nucleus, a plurality of arylene groups bonded by groups such as —O—, —CH ₂ —, —SO ₂ —, —CO— and the like may be included. The amount of the amines used is not particularly limited, but it is preferably used in the range of 50 to 500 parts by weight with respect to 100 parts by weight of the N, N′-substituted bisimide compound.

In the present invention, a furan-modified novolak-type phenol resin and a resin composition containing an N, N′-substituted bisimide unsaturated compound are further useful compositions by adding a polyfunctional epoxy compound as a resin component. You can get things.

Examples of the polyfunctional epoxy compound include diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate, vinylcyclohexanedioxide, 4,4'-dioxide. (1,2-epoxyethyl) diphenyl ether, 4,4 '-(1,2-epoxyethyl) biphenyl, 2,2-bis (3,4-epoxycyclohexyl) propane, glycidyl ether of resorcin, bis- ( 2,3'-epoxycyclopentyl) ether, 2
-(3,4-Epoxy) cyclohexane-5,5-spiro (3,
4-epoxy) -cyclohexane-m-dioxane, bis- (3,4-epoxy-6-methylcyclohexyl) adipate, N, N'-m-phenylene bis (4,5-epoxy-1,2-cyclohexane) dicarboxy Compounds having two epoxy groups in the molecule such as imides, triglycidyl derivatives of paraaminophenol, polyallylglycidyl ether, 1,3,5-tri (1,2-epoxyethyl) benzene, 2,2 ', 4 , 4'-tetraglycidoxy benzophenone, phenol formaldehyde de novolak polyglycidyl ether, glycerin triglycidyl ether,
There are compounds having three or more epoxy groups in the molecule such as trimethylolpropane triglycidyl ether, and one or more of them are used.

Also, the following formula The tris (hydroxyphenyl) methane-based epoxy resin represented by is particularly effective from the viewpoint of imparting heat resistance and electrical characteristics, and it is preferably used as appropriate according to the application and purpose.

A curing agent is used in combination with these epoxy compounds. Hiroshi Kakiuchi; Epoxy resin (published in September, 1970) 10
9-149, Lee, Neville; Epoxy Resins (Mc Graw
−Hill Book Company Inc, New York, published 1957) 63〜1
41 pages, by PE Brunis; Epoxy Resins Technology (In
terscience Publishers, New York, 1968) 45-111
Many compounds are well known as a curing agent, including the compounds described in pages and the like. For example, aliphatic polyamines, aromatic polyamines, polybasic carboxylic acids, carboxylic acid anhydrides containing one or more anhydride rings per molecule, aliphatic or aromatic polyamide oligomers and polymers, boron trifluoride-amine complex. Synthetic resin initial condensates such as lux, phenol resin, melamine resin, urea resin, urethane resin, and other dicyandiamide,
Examples include carboxylic acid hydrazide and polyaminomaleimide. In the present invention, from the viewpoint of heat resistance, aromatic amines, carboxylic acid anhydrides, and phenol compounds such as phenol novolac resins are useful. Therefore, the use of a compound having such a reactive group in the molecule as the resin component of the composition is particularly effective and preferable for promoting mutual crosslinking between the epoxy compound and them. In such a case or in the case of adding a curing catalyst described later, the addition of the above-mentioned curing agents can be reduced.

The unsaturated polyester resin which is the other main component used in the present invention includes unsaturated dibasic acids, saturated dibasic acids and their anhydrides or their lower alkyl ester derivatives, and diols or alkylene monooxides and their A polyester (resin matrix) containing an unsaturated group synthesized from a derivative or the like in the presence or absence of a catalyst by condensation or addition polymerization utilizing a reaction such as esterification or ester conversion, It is composed of a mixture with an ethylene-based (for example, vinyl group, allyl group, etc.) polymerizable monomer (crosslinking agent), and usually contains a very small amount of a polymerization inhibitor, and a polymerization initiator may be added if necessary. In addition to this type, vinyl ester resins obtained by reacting bisphenol A type, epoxy compounds such as novolak type, tris (hydroxyphenyl) methane type, and methacrylic acid and acrylic acid are also useful.

Here, as the representative of the unsaturated dibasic acid and the saturated dibasic acid, maleic acid, maleic anhydride, fumaric acid, chloromaleic acid, dichloromaleic acid, citraconic acid, citraconic anhydride, mesaconic acid, and itacone Acid, succinic acid, adipic acid, cepasic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, methylglutanic acid, vimelic acid, hexahydrophthalic acid and their anhydrides, tetrahydrophthalic acid, hettic acid And its anhydrides, tetrachlorophthalic acid and its anhydrides, tetrabromophthalic acid and its anhydrides, lower alkyl esters thereof, etc. are used, and the diol component is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene. Glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethyl glycol, 2,2-diethylpropanediol, 1,3-neopentyl glycol, dipromeneopentyl glycol, bisphenol dioxyethyl ether, hydrogenated bisphenol A, 2,2-di (4-hydroxypropoxyphenyl) propane, ethylene oxide, propylene oxide, 3,3,3-trichloropropylene oxide, phenyl glycidyl ether, allyl glycidyl ether and the like are used. Further, if necessary, within a range not impairing the object of the present invention, 3
You may use together the polybasic acid and / or polyhydric alcohol more than functionality.

Examples of the cross-linking agent include styrene, vinyltoluene, α-
Methyl styrene, divinyl benzene, diallyl phthalate, diallyl phthalate prepolymer, chlorostyrene,
Dichlorostyrene, diallyl benzene phosphonate, diallyl aryl phosphyl acid ester, acrylic acid ester, methacrylic acid ester, triallyl cyanurate, triallyl cyanurate prepolymer, tripromophenol allyl ether and the like are used.

The above acid component, alcohol component, and crosslinking agent are not limited to one type, and two or more types can be used in combination. Further, various modification treatments or addition of modifiers are also possible.
In addition, in this invention, you may mix 2 or more types of unsaturated polyester resin.

Unsaturated polyester resins include, for example, quinones such as p-benzoquinone and naphthoquinone, hydroquinone, and 2,5-di-
Polymers such as t-butylcatechol and other phenols, other organic compounds, and metal salts are added.

It is desirable to add a polymerization initiator and a curing catalyst to the resin composition of the present invention for the purpose of completing the curing by heating for a short time. Examples of such a polymerization initiator include benzoyl peroxide, p-chloro-benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide. , Bis (1-hydroxycyclohexyl peroxide), hydroxyheptyl peroxide, t-butyl hydroperoxide, p-menthane hydroperoxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroctoate, t -Butyl peroxyisobutyrate, di-t
Organic peroxides such as -butyldiperphthalate are useful, and one or more of them can be used.
These polymerization initiators are effective for curing the resin composition of the present invention, and particularly accelerate the crosslinking reaction of the resin composition containing the unsaturated polyester resin.

Examples of the curing catalyst include tetramethylalkanediamine, trialkanolamine, tris (dimethylaminomethyl) phenol, amine acids such as N-alkylmorpholine, cetyltrimethylammonium bromide, dodecyltrimethylammonium chloride, benzyldimethylstearylammonium chloride, and the like. Quaternary ammonium hydrochloride such as benzyldimethyltetradecyl ammonium acetate, 2-alkylimidazole, 2-methyl-4-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-azine-2
-Imidazoles such as methylimidazole, triphenylphosphine tetraphenylborate, tetraphenylphosphonium tetraphenylborate, triethylamine tetraphenylborate, N-methylmorpholine tetraphenylborate, 2-ethyl-4-methylimidazole There are tetraphenylboron salts such as tetraphenylborate, which can be used. This type of compound is useful for accelerating the curing of the resin composition of the present invention, and particularly works effectively in a composition containing an epoxy compound.

The polymerization initiator and the curing catalyst are used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the resin content.

In the present invention, the resin composition, depending on the purpose and use,
Various inorganic substances and additives can be mixed and used. Specific examples thereof are zircon, silica, fused silica glass, alumina, aluminum hydroxide, glass,
Quartz glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay, kaolin, talc, iron powder,
Copper powder, mica, asbestos, silicon carbide, boron nitride, molybdenum disulfide, lead compounds, lead oxides, zinc white, titanium white, fillers such as carbon black, or release agents such as higher fatty acids and waxes, Coupling agents such as epoxy silane, vinyl silane, amino silane, borane compounds, alkoxy titanate compounds, aluminum chelate compounds and the like. Further, a known flame retardant containing antimony, a neighboring compound, bromine or chlorine can be used.

Various additives such as the above-mentioned resin component and cross-linking component compound, a polymerization initiator and a catalyst, a filler, a roll, a kneader,
After being mixed and kneaded by a device such as a twin-screw co-kneader or a Hensiel mixer, a homogeneous composition is produced.

Further, the resin composition of the present invention can be used as a solution such as a varnish. As the solvent used at that time, N-methyl-2-pyrrolidone, N, N-dimethylacetamine, N, N-dimethylformamide, N, N-diethylformamide, N-methylformamide, dimethylsulfoxide, N, N -Diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosformamide, pyridine, dimethylsulfone, tetramethylsulfone, dimethyltetramethylenesulfone, and the like, and the phenolic solvent group includes phenol, cresol, xylenol, etc. There is.

The above substances may be used alone or in combination of two or more.

Examples 1 to 7 Furan modified novolak type phenol resin (manufactured by Gunei Chemical Co., Ltd.)
mp, 120 ° C), N, N '-(methylenedi-p-phenylene)
Dimaleimide, polyfunctional epoxidized novolak phenol polyglycidyl ether, ESCN220L
(Sumitomo Chemical Co., Ltd., epoxy equivalent, 203), and tris (hydroxyphenyl) methane-based polyglycidyl ether XD-9053 (Dow Chemical Co., epoxy equivalent, 220), unsaturated polyester resin PS-518 (Hitachi) Chemical composition, styrene content 40%) were blended in predetermined amounts shown in the following table to prepare 7 types of blended compositions.

The above composition was kneaded with an 8-inch diameter twin roll at 70 to 85 ° C. or a 70 to 80 ° C. twin-screw kneader and then cooled to obtain a molding resin composition. Then, transfer molding was performed under the conditions of 160 ° C., 70 kgf / cm ² and 5 minutes to prepare a test piece for measuring bending strength. Then, the barcol hardness immediately after molding and the bending strength of the molded sample after 200 ° C. and 30 days of heat treatment were determined as the scales of the curability of the compound and the heat resistance of the molded product. The results are shown in the table.

The following materials were also used in the implementation of these.

Diamine 4,4'-methylenedianiline (MDA) Polymerization initiator Dicumyl peroxide (DCPO) Curing catalyst Triethylamine tetraphenylborate (Et ₃ N ・ BPh ₄ ) Coupling agent Epoxysilane BM303 (Shin-Etsu Chemical Co., Ltd.) Release type Agent Calcium stearate Hoechst Wax E Filler Fused quartz glass powder Calcium carbonate Aluminum hydroxide In contrast to the values in the comparative example in the table, a resin having a furan ring and N,
It can be seen that the characteristic values of the examples for compositions with N'-substituted bismaleimides and also compositions containing epoxy resins or unsaturated polyester resins are excellent.

Examples 8 and 9 A 256k bit D-RAM memory LSI was molded using the resin compositions of Examples 4 and 5 under the same conditions as in Examples 1 to 7.

The resulting resin-sealed LSI was left in 121 ° C, 2 atm supersaturated water vapor (pressurizer / cutler pot, PCT) for a specified time and then taken out to determine whether the LSI was operating normally (corrosion of Al wiring). Check if there is a disconnection failure due to.

As a result, LSIs encapsulated with the compositions of Examples 4 and 5
No defects were found even after 2000 hours in PCT, and it was found that there was a great effect in maintaining the moisture resistance reliability of the LSI.

The LSI sealed with the compositions of Examples 4 and 5 was PCT.
At 2500 hours, defects of 2% and 6% occurred respectively.

〔The invention's effect〕

According to the present invention, as shown in the results of the examples, a thermosetting resin composition having improved molding curability and being further thermally stabilized is obtained, and molding, sealing, lamination, etc. It is possible to provide a material useful for the above-mentioned use.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Motoyo Wajima 4026, Kuji-cho, Hitachi City, Ibaraki Prefecture, Hitachi Research Laboratory, Hiritsu Manufacturing Co., Ltd. (56) References JP-A-52-129093 (JP, A)

Claims (2)

[Claims] 1. A thermosetting resin composition comprising at least a furan-modified novolak type phenol resin and an N, N′-substituted bisimide unsaturated compound. 2. An N, N′-substituted bisimide-based unsaturated compound
The thermosetting resin composition according to claim 1, which is an N, N′-substituted bis (maleimide).