JPS62146925A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition improved in heat resistance and moldability, by mixing at least a furan ring-containing addition polycondensate with an N,N'-substituted bisimide unsaturated compound. CONSTITUTION:This thermosetting resin composition contains at least a furan ring-containing addition polycondensate (A) and an N,N'-substituted bisimide unsaturated compound (B). The mixing ratio between components A and B is preferably 5:1-1:2 by weight. As component A, a furan-modified novolak phenolic resin is desirable, and as component B, N,N'-substituted bis(maleimide) is desirable. A diamine, a polyepoxy compound or an unsaturated polyester resin or the like may be added to the composition as a crosslinking agent.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to a thermosetting resin composition having excellent heat resistance and moldability, and more specifically, it relates to a thermosetting resin composition having excellent heat resistance and moldability, and more specifically, it relates to an addition polycondensate having a furan ring, The present invention relates to a resin composition containing a '-substituted bisimide unsaturated compound as an essential component.

[Background of the invention]

Resin compositions consisting of addition-type bisimide compounds and polyfunctional epoxy compounds have excellent heat resistance and have a wide range of uses such as molding materials, laminated materials, prepregs, and adhesives.

However, in these applications, there has been a strong demand for improved molding processability, particularly rapid curing and solubility in common solvents. In order to meet this demand, conventional compositions are not sufficient, and it is necessary to develop a heat-resistant resin composition having a new curing system.

[Purpose of the invention]

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

[Summary of the invention]

The first aspect of the present invention is a thermosetting resin composition comprising at least an addition polycondensate having a furan ring and an N,N'-substituted bisimide compound. Furthermore, the second invention includes at least an addition polycondensate having a furan ring;
A thermosetting resin composition comprising an N,N'-substituted bisimide compound and a polyfunctional epoxy compound,
The third is a thermosetting resin characterized by containing at least a furan-modified phenolic resin or an addition polycondensate having a furan ring, an N,N'-substituted bisimide compound, and an unsaturated polyester resin. It is a synthetic resin composition.

That is, the first invention forms the basis of the present invention, and the second invention forms the basis of the present invention. The third invention has been established.

Next, the resin components will be explained in order.

In the present invention, the addition polycondensate having a furan ring is
For example, addition polycondensates produced from furfural and phenols by the reaction shown in the following formula, [wherein R represents H or an alkyl group] heated pre-crosslinked polymers of the above reactants, , a co-condensate of furfuryl alcohol and phenols [wherein R represents H or an alkyl group], a reaction product of the above-mentioned polycondensate and polyvinyl acetal, a furfural-modified phenol novolak resin, and the like.

In addition, if it is added further, it represents furfural or furfuryl alcohol and bisphenol, that is, a single bond,
Or CH2, C(CHll)2 tO,S, SO2
Reactants with any of the above agents are also effective in achieving the effects of the present invention.

In addition, examples of N,N'-substituted bisimide-based unsaturated compounds include N,N'-ethylene dimaleimide, N
, N'-ethylenebis(2-methylmaleimide), N
, N'-trimethylene dimaleimide, N, N'-tetramethylene dimaleimide, N.

N'-hexamethylene dimaleimide, N,N'-hexamethylenebis(2-methylmaleimide), N,N'-
Dodecamethylene dimaleimide, N.

N'-m-phenylene dimaleimide, N, N'-p-
Phenylenedimaleimide, N,N'-(oxy-p-
phenylene) simaleimide, N, N'-(methylene-
Di-P-phenylene) simalemide, N, N'-(methylene-di-p-phenylene) bis(2-methylmaleimide), N, N'-2,4-tolylene dimaleimide, N
, N'-2,6-tolylene dimaleimide, N, N' -
m-xylylene cymaleimide, N,N'-p-xylylene cymaleimide, N,N'-oxypropylene dimaleimide, N,N'-ethylene bis(oxypropylene maleimide), N,N'-oxydiethylene cymaleimide, etc. There is an amine adduct of the above bisimide compound,
Phenol adducts, thiocol adducts, etc. are used. Moreover, a polyvalent N-substituted maleimide compound can be added or blended, or one or more of the above compounds can be used in combination.

In the present invention, the ratio of the addition polycondensate having a furan ring to the N,N'-bisimide unsaturated compound is not particularly limited, but the weight ratio of the former to the latter is approximately 5:1 to 1:
It is recommended to use 2.

In the resin composition of the present invention, as a crosslinking agent for an N,N'-substituted bisimide unsaturated compound, for example, 4.4'-methylene dianiline, 4,4'-oxydianiline, 4.4
'-carbonyldianiline, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine,
4,4'-methylene di(cyclohexylamine) etc., alkylene group, cyclic alkylene group, arylene group, heterocyclic group, arui also 10-, -CHz -, -
SOx-.

Diamines whose core is a plurality of arylene groups linked by groups such as -C〇- may be included. The amount of the amine used is not particularly limited, but it is preferably used in the range of 50 to 500 parts by weight based on 100 parts by weight of the N,N'-substituted bisimide compound.

In the present invention, addition polycondensed metals having a furan ring and N
A useful composition can also be obtained by further adding a polyfunctional epoxy compound as a resin component to a resin composition containing an N'-substituted bisimide unsaturated compound.

Examples of polyfunctional epoxy compounds include diglycidyl ether of bisphenol A, butadiene diepoxide, and 3,4-epoxycyclohexylmethyl-(3,4-
epoxy)cyclohexane carboxylate, vinylcyclohexane dioxide, 4,4'-di(1,2-epoxyethyl)diphenyl ether, 4.4'-(1
,2-epoxyethyl)biphenyl, 2,2-bis(3
, 4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, 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-phenylenebis(4,5-epoxy-1,
Compounds with two epoxy groups in the molecule such as 2-cyclohexane)dicarboximide, triglycidyl derivatives of para-aminophenol, polyallyl glycidyl ether, 1,3.5-tri(1,2-epoxyethyl)benzene, 2.2',4.4'-tetraglycidoxybenzophenone, polyglycidyl ether of phenolformaldehyde novolak, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, etc. with three or more epoxy groups in the molecule. There are compounds that have the following properties, and one or more of them may be used.

Further, a tris(hydroxyphenyl)methane-based epoxy resin represented by the following formula is particularly effective in terms of heat resistance and imparting electrical properties, and is preferably used as appropriate depending on the use and purpose.

A curing agent is used in combination with these epoxy compounds. They are written by Hiroshi Kakiuchi; Epoxy Resin (published September 1970)
Pages 109-149, Lee.

Written by Neville; Epoxy Re5ins (M
e Gray-HillBook Company I
nc, New York, 1957) 63~
Page 141, by P. E. Brunis: E
poxyResins Technology (
Interscience Publishers,
Numerous compounds are well known as curing agents, including those described on pages 45 to 111 (New York, 1968). 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,
Examples include boron trifluoride-amine complexes, initial condensates of synthetic resins such as phenol resins, melamine resins, urea resins, and urethane resins, and their dicyandiamides, carboxylic acid hydrazides, and polyaminomaleimides.

In the present invention, from the viewpoint of heat resistance, phenolic compounds such as aromatic amines, carboxylic acid anhydrides, and phenol novolac resins are useful. Therefore, it is preferable to use a compound having such a reactive group in its molecule as the resin component of the composition, as it is particularly effective in promoting mutual crosslinking between the epoxy compound and them.

In such cases or when adding a curing catalyst as described below,
Addition of the aforementioned curing agents can be reduced.

The unsaturated polyester resin, which is another main component used in the present invention, contains unsaturated dibasic acids, saturated dibasic acids and their anhydrides, or lower alkyl ester derivatives thereof, and diols or alkylene monooxides and their A polyester containing an unsaturated group (resin base) synthesized from derivatives by condensation or addition polymerization using reactions such as esterification and ester conversion in the presence or absence of a catalyst, and an ethylene-based (
For example, it consists of a mixture of a polymerizable monomer (having a vinyl group, a furyl group, etc.) (a crosslinking agent), and usually contains a small amount of a polymerization inhibitor, and a polymerization initiator can be added as required. In addition to this type, vinyl ester resins obtained by reacting epoxy compounds such as bisphenol A type, novolac type, and tris(hydroxyphenyl)methane type with methacrylic acid and acrylic acid are also useful.

Here, typical unsaturated dibasic acids and saturated dibasic acids include maleic acid, maleic anhydride, fumaric acid, chloromaleic acid, dichloromaleic acid, citraconic acid, citraconic anhydride, mesaconic acid, and itaconic acid. acids, succinic acid, adipic acid, sepacic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, methylgeltanic anhydride, pimelic acid, hexahydrophthalic acid and its anhydrides, tetrahydrophthalic acid,
Het acid and its anhydride, tetrahyphthalic acid and its anhydride, tetrabromophthalic acid and its anhydride, lower alkyl esters thereof, etc. are used, and as the diol component, 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, dibromneopentyl 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, etc. are used.

In addition, if necessary, within the scope of not impairing the purpose of the present invention,
A trifunctional or higher functional polybasic acid and/or a polyhydric alcohol may be used in combination.

Examples of crosslinking agents include styrene, vinyltoluene, α-
Methyl styrene, divinylbenzene, diallyl phthalate, diallyl phthalate prepolymer, chlorstyrene,
Dichlorostyrene, diallylbenzene phosphonate, diallylaryl phosphylate, acrylate, methacrylate, triallyl cyanurate, triallyl cyanurate prepolymer, tribromophenol allyl ether, etc. are used.

The acid component, alcohol component, and crosslinking agent mentioned above are not limited to one type, and two or more types can be used in combination. Further, various modification treatments or addition of modifying agents are also possible. In addition, in the present invention, two or more types of unsaturated polyester resins may be used in combination).

In order to improve the storage stability at room temperature, unsaturated polyester resins contain quinones such as p-benzoquinone and naphthoquinone, phenols such as hydroquinone and 2,5-di-t-butylcatechol, and other compounds. Polymerization inhibitors such as 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 in order to complete the curing by short-term heating. Such polymerization initiators include benzoyl peroxide, P-chloro-benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, cabrylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide,
Cyclohexanone peroxide, bis(1-hydroxycyclohexyl peroxide), hydroxyhebutyl peroxide, t-butyl hydroperoxide, p-menthane hydroperoxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxide Octoate, t-butylperoxyisobutyrate, di-
Organic peroxides such as t-butylshiba-phthalate are useful, and one or more of them can be used. These polymerization initiators are effective in curing the resin composition of the present invention, and particularly significantly accelerate the crosslinking reaction of resin compositions containing unsaturated polyester resins.

Examples of curing catalysts include tetramethylalkanediamine, trialkanolamine, tris(dimethylaminomethyl)phenol, amino acids such as N-alkylmorpholine, cetyltrimethylammonium bromide, dodecyltrimethylammonium chloride, benzyldimethylstearylammonium chloride, Quaternary ammonium hydrochloric acid such as benzyldimethyltetradecylammonium acetate, 2-alkylimidazole, 2-methyl-4-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-azine-2-
imidazoles such as methylimidazole, triphenylphosphine tetraphenylborate, tetraphenylphosphonium tetraphenylborate, triethylaminetetraphenylborate, N-methylmorpholinetetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, etc. Tetraphenylboron salt is available and can be used. This type of compound is useful for accelerating the curing of the resin composition of the present invention, and acts particularly effectively in a composition containing an epoxy compound.

The polymerization initiator and curing catalyst are each 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.

In the present invention, depending on the purpose and use of the resin composition,
Various inorganic substances and additives can be mixed and used. Specific examples include zircon, silica, fused silica glass, alumina, aluminum hydroxide, glass, quartz glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay, kaolin, talc, iron powder, copper powder. , fillers such as mica, asbestos, silicon carbide, boron nitride, molybdenum disulfide, lead compounds, lead oxide, zinc white, titanium white, carbon black, higher fatty acids, mold release agents such as waxes, and epoxy silane. , vinylsilane, aminosilane, borane compounds, alkoxytitanate compounds, aluminum chelate compounds, and other coupling agents. Furthermore, known flame retardants containing antimony, neighboring compounds, bromine and chlorine can be used.

Various additives such as the resin component, crosslinking component compound, polymerization initiator, catalyst, filler, etc. described above are added to the rolls and kneader 1.
A homogeneous composition is produced through mixing and cross-mixing using equipment such as a twin-screw co-kneader or Henschel mixer.

Further, the resin composition of the present invention can also be used in the form of a solution, such as a varnish. Solvents used at that time include N-methyl-2-pyrrolidone, N,N-dimethylacetamine, N,N-dimethylformamide, N,
N-diethylformamide, N-methylformamide,
Dimethyl sulfoxide, N, N-diethylacetamide, N.

N-dimethylmethoxyacetamide, hexamethylphosphoramide, pyridine, dimethylsulfone, tetramethylsulfone, dimethyltetramethylenesulfone, etc., and the phenolic solvent group includes phenol,
Examples include cresol and xylenol.

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

Examples 1 to 7 Furan-modified novolac type phenol resin (mp manufactured by Gunei Kagaku Co., Ltd., 120°C), N,N'-(methylenedi-p-phenylene) simaleimide, polyglycidyl ether of novolac type phenol as a polyfunctional epoxy compound ,
ESCN220L (manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent, 2
03), as well as tris(hydroxyphenyl)methane-based polyglycidyl ether XD-9053 (Dow
Chemical Co., Ltd., epoxy equivalent: 220) and unsaturated polyester resin PS-518 (Hitachi Chemical Co., Ltd., styrene content: 40%) were blended in predetermined amounts as shown in the table below to create seven types of blended compositions. did.

The above composition was rolled into two 8-inch diameter rolls at 70 to 85°C.
Alternatively, after kneading in a 70-80°C twin-screw kneader, the mixture was cooled to obtain a molding resin composition. Then, 160℃, 7
Transfer molding was performed under conditions of 0 kgf/cm for 2.5 minutes to prepare specimens for measuring bending strength. As a measure of the hardenability of the compound and the heat resistance of the molded product, we measured the Barcol hardness immediately after molding and the bending strength of the molded specimen at 200°C.
, the retention rate after 30 days of heat treatment was determined. The results are shown in the table.

The following materials were also used in carrying out these experiments.

Diamine 4,4'-methylene dianiline (MDA) Polymerization initiator Dicumyl peroxide (DCPO) Curing catalyst Triethylamine tetraphenylborate (Et
8N-BPh No.) Coupling agent Epoxy silane with BM303 (Shin-Etsu Chemical Co., Ltd.) Mold release agent Calcium stearate Hoechst Wax E Filler Fused silica glass powder Calcium carbonate Aluminum hydroxide In comparison with the comparative example values in the table, the furan ring was resin and N
, N'-substituted bismaleimide, and compositions further containing an epoxy resin or an unsaturated polyester resin.

Examples 8 and 9 Using the resin compositions of Examples 4 and 5, a 256-bit D-RAM memory LSI was molded under the same conditions as Examples 1 to 7.

The obtained resin-sealed LSI was left in supersaturated steam at 121°C and 2 atm (pressure hookah pot, PCT) for a predetermined period of time, and then taken out to check whether the LSI was functioning normally (corrosion of Afi wiring). The presence or absence of disconnection failures caused by

As a result, LSIs sealed with the compositions of Examples 4 and 5
In all cases, no defects were observed even after 2000 hours of PCT exposure, and it was found that these were highly effective in maintaining the moisture resistance reliability of LSI.

Note that the LSIs sealed with the compositions of Examples 4 and 5 were as follows:
P CT 2% at 2500 hours, respectively.

6% of defects occurred.

〔Effect of the invention〕

According to the present invention, as shown in the results of Examples, a thermosetting resin composition with improved molding curability and further thermal stability can be obtained, and can be easily molded and sealed.

It can provide a material useful for applications such as lamination.

Claims (1)

[Claims] 1. At least an addition polycondensate having a furan ring, and N
, an N'-substituted bisimide-based unsaturated compound. 2. The thermosetting resin composition according to claim 1, wherein the addition polycondensate having a furan ring is a furan-modified novolac type phenolic resin. 3.N,N'-substituted bisimide unsaturated compound is N,N'-substituted bisimido unsaturated compound
The thermosetting resin composition according to claim 1, which is a '-substituted bis(maleimide). 4. A thermosetting resin composition comprising at least a furan-modified novolak phenol resin, an N,N'-substituted bis(maleimide), and a diamine. 5. The thermosetting resin composition according to claim 4, wherein the addition polycondensate having a furan ring is a furan-modified novolac type phenolic resin. 6, N,N′-substituted bisimido unsaturated compound is N,N
5. The thermosetting resin composition according to claim 4, which is a '-substituted bis(maleimide). 7. At least an addition polycondensate having a furan ring, and N
, an N'-substituted bisimide-based unsaturated compound, and a polyfunctional epoxy compound. 8. The thermosetting resin composition according to claim 7, wherein the addition polycondensate having a furan ring is a furan-modified novolac type phenolic resin. 9, N,N′-substituted bisimido unsaturated compound is N,N
8. The thermosetting resin composition according to claim 7, which is a '-substituted bis(maleimide). 10. At least an addition polycondensate having a furan ring;
A thermosetting resin composition comprising an N,N'-substituted bisimide-based unsaturated compound and an unsaturated polyester resin. 11. The thermosetting resin composition according to claim 8, wherein the addition polycondensate having a furan ring is a furan-modified novolac type phenolic resin. 12, N,N'-substituted bisimido unsaturated compound is N,
9. The thermosetting resin composition according to claim 8, which is an N'-substituted bis(maleimide).