JP2001323126A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which is excellent in balance between storage stability and curability, and which has excellent properties such as low dielectric properties, low water absorption, heat resistance, adhesion and the like. A resin composition is provided. SOLUTION: 8-Ethyltetracyclo [4.4.1]
^2,5 . ^17.10 . A ring having a functional group obtained by introducing a functional group-containing unsaturated compound such as maleic anhydride into a polymer obtained by subjecting a norbornene-based monomer such as 0] -3-dodecene to ring-opening polymerization and hydrogenation by a modification reaction. A structure-containing polymer, a curing agent, and other additives are dissolved in a mixed solvent comprising at least one polar solvent and a nonpolar solvent selected from the group consisting of an amide compound, an ester compound, a nitrile compound, and a sulfoxide compound. To obtain a curable resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition,
More specifically, the present invention relates to a curable resin composition that is excellent in balance between storage stability and curability, and is suitable for obtaining a cured product having excellent properties such as low dielectric properties, low water absorption, heat resistance, and adhesion.

[0002]

2. Description of the Related Art High-temperature and high-humidity tests (85.degree. C. x 85% RH) and temperature cycle tests (-55.degree. C. to 120.degree. C.) are used for insulating and protective materials used in LSIs, printed circuit boards, thin film transistors, and the like. And other long-term reliability tests. For a protective material such as a cover coat material, a material having low water absorption, high heat resistance, and high adhesion is required. Insulating materials for build-up printed wiring boards used in computers and communication equipment that are growing rapidly in recent years require low dielectric properties in addition to low water absorption, high heat resistance, and adhesion. ing. In addition, coating materials used in the LCD field include:
Further, a resin material satisfying transparency has been demanded.

A polymer having a ring structure, such as a norbornene-based polymer, has attracted attention as a material excellent in low water absorption, low dielectric properties, and transparency. However, in order to satisfy the high reliability required for the materials for electronic components as described above, in addition to these characteristics, it is necessary to further improve various other characteristics. It has been done. For example, WO / 98/56011 discloses a curable resin composition in which a norbornene-based polymer graft-modified with maleic anhydride and an epoxy compound are dissolved or dispersed in a nonpolar organic solvent such as xylene. Has been proposed. It is reported that a cured product of this resin composition is excellent in low dielectric properties, low water absorption, high heat resistance, and adhesion properties. However, the curable resin composition conventionally proposed, even if it satisfies the preferable property that it can be quickly cured during the production of electronic parts and can shorten the production time, the composition undergoes natural curing and the like during storage before production. In some cases, this resulted in an undesirable behavior of becoming unstable.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent balance between storage stability and curability, low dielectric properties,
An object of the present invention is to provide a curable resin composition suitable for obtaining a cured product having excellent properties such as low water absorption, heat resistance, and adhesion.
The present inventors have conducted intensive studies to achieve the above object, and as a result, a mixed solvent comprising a polar solvent containing at least an amide compound, an ester compound, a nitrile compound or a sulfoxide compound, and a nonpolar organic solvent, such as maleic anhydride. A curable resin composition obtained by dissolving or dispersing a norbornene-based polymer obtained by graft-modifying an unsaturated polar compound and a curing agent has an excellent balance between storage stability and curability, and has low dielectric properties and low water absorption. It has been found that a cured product having excellent properties such as heat resistance, heat resistance, and adhesion is provided, and based on this finding, the present invention has been completed.

[0005]

Thus, according to the present invention, there is provided a mixture comprising at least one polar solvent selected from the group consisting of amide compounds, ester compounds, nitrile compounds and sulfoxide compounds, and a non-polar solvent. A curable resin composition containing a solvent, a polymer resin having a ring structure having a functional group, and a curing agent is provided.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The curable resin composition of the present invention contains a mixed solvent containing a specific polar solvent (A) and a nonpolar solvent, a polymer resin having a ring structure having a functional group, and a curing agent. Is what you do. The mixed solvent used in the present invention contains a non-polar solvent and a specific polar solvent (A). Examples of the non-polar solvent include aromatic hydrocarbons such as toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as n-pentane, hexane and heptane; cyclopentane;
Alicyclic hydrocarbons such as cyclohexane; Among them, aromatic hydrocarbons and alicyclic hydrocarbons are preferable from the viewpoint of compatibility with the ring-structure-containing polymer resin having a functional group. These non-polar solvents can be used alone or in combination of two or more.

The polar solvent (A) used in the present invention is at least one selected from the group consisting of amide compounds, ester compounds, nitrile compounds and sulfoxide compounds. Among these, a polar solvent having no active hydrogen is preferable. As the amide compound, N-
Methylpyrrolidone, N-ethylpyrrolidone, N-phenylpyrrolidone, N-benzylpyrrolidone, N, N-dimethylformamide, N, N-diethylformamide,
N, N-dimethylacetamide, N-methylcaprolactam and the like can be mentioned. Examples of the ester compound include methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, amyl butyrate, Examples include ethyl lactate, dimethyl carbonate, dimethyl phthalate, diethyl phthalate, and γ-butyl lactone. As nitrile compounds, acetonitrile, propionitrile,
Butyronitrile, benzonitrile, capronitrile and the like. Examples of the sulfoxide compound include dimethyl sulfoxide.

Of these polar solvents (A), amide compounds, especially N-methylpyrrolidone, are preferred from the viewpoint of the balance between solution storage stability and curing properties. In addition, an ester compound, particularly t-butyl acetate, is suitable for a technique of obtaining a B-stage film from a curable resin composition, laminating it on a substrate, and curing. These polar solvents (A) can be used alone or in combination of two or more. When the storage stability is particularly important, it is preferable to use the polar solvent (A) in combination. Specifically, the amide compound and the ester compound such as a combination of N-methylpyrrolidone and t-butyl acetate are preferably used. A combination or a combination of one amide compound and another amide compound such as a combination of dimethylacetamide and N-methylpyrrolidone is preferred. The polar solvent (A) is not particularly limited depending on its molecular weight, but is usually 50 to 500, preferably 60, from the viewpoint of excellent balance between storage stability and curing properties and excellent cured properties.
To 400, particularly preferably 70 to 300.

The weight ratio of the nonpolar solvent to the polar solvent (A) depends on whether the storage stability of the composition is important or the ease of forming a B-stage film is important. When emphasizing storage stability, the nonpolar solvent: polar solvent (A) is usually 99: 1 to 1:99, 97:
3 to 10:90, more preferably 95: 5 to 15: 8
5, most preferably 93: 7 to 20:80. When importance is attached to the formation of the B-stage film, the nonpolar solvent: polar solvent (A) is usually 99: 1 to 1: 1 by weight.
99, 97: 3 to 5:95, more preferably 95: 5
The ratio is 10:90, most preferably 90:10 to 15:85.

In the present invention, a halogenated hydrocarbon,
At least one polar solvent (B) selected from ketones, ethers and carbonates can be included in the mixed solvent. Examples of the halogenated hydrocarbon include chlorobenzene, dichlorobenzene, and trichlorobenzene.Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, benzophenone, and acetophenone.Examples of the ether include tetrahydrofuran and
Examples include tetrahydropyran, anisole, and the like. Examples of the carbonate include ethylene carbonate and propylene carbonate.

These polar solvents (B) can be used alone or in combination of two or more.
Of these polar solvents (B), carbonates and ethers are preferred from the viewpoint of enhancing storage stability, and ketones are preferred from the viewpoint of enhancing the ease of forming a B-stage film. The amount of the polar solvent (B) is appropriately selected depending on the type and use of the solvent. When emphasizing storage stability, the polar solvent (A): polar solvent (B) is usually 99: 1 to 1:99, 97: 3 to 5:95, more preferably 95: 5 by weight ratio. -10: 90, most preferably 90: 1
0:15:85. When importance is attached to the formation of the B-stage film, the polar solvent (A):
By weight ratio, usually 99: 1 to 1:99, 90:10 to 3:
97, more preferably 80:20 to 5:95, most preferably 70:30 to 10:90. The amount of the mixed solvent contained in the composition of the present invention is such that the amount of the polar solvent (A) is usually 1 to 1,000 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the functional group-containing polymer resin having a ring structure. -500 parts by weight, more preferably 10-200 parts by weight, most preferably 20-100 parts by weight.

The polymer resin having a ring structure having a functional group used in the present invention is a resin having a portion having a ring structure and a functional group portion. The ring structure in the polymer resin may be present in any of the main chain and / or the side chain, but preferably has a ring structure in the main chain from the viewpoint of heat resistance and solvent resistance. Examples of the ring structure include an aromatic ring structure and an alicyclic structure, and an alicyclic structure is preferable from the viewpoint of low dielectric properties and low water absorption. Monocyclic, polycyclic, fused polycyclic,
A bridged ring, a combination of these, and a polycyclic ring are exemplified.
The number of carbon atoms constituting the ring structure is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15, from the viewpoint of balancing heat resistance, solvent resistance and moldability.

The proportion of the repeating unit having a ring structure in the ring structure-containing polymer resin is appropriately selected according to the purpose of use, but is usually 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight. % Or more, and the upper limit is 100% by weight. If the proportion of the monomer unit having a ring structure in the ring structure-containing polymer resin is excessively small, low dielectric properties, low water absorption, and poor heat resistance may be unfavorable. Specific examples of the polymer resin having a ring structure include a norbornene-based polymer, a monocyclic cyclic olefin-based polymer,
Examples include a cyclic conjugated diene polymer, a vinyl cyclic hydrocarbon polymer, an aromatic polymer having a repeating unit of an aromatic ring in the main chain, and hydrogenated products thereof. Among these, norbornene-based polymers and hydrogenated products thereof, cyclic conjugated diene-based polymers and hydrogenated products thereof are preferable in fields requiring high reliability, particularly strength properties, and norbornene-based polymers and hydrogenated products thereof. Are more preferred.

There is no particular limitation on the norbornene-based polymer, and for example, a polymer obtained by polymerizing a norbornene-based monomer by a method disclosed in JP-A-3-14882 or JP-A-3-122137 is used. . Specific examples include ring-opening polymers of norbornene-based monomers and hydrogenated products thereof, addition polymers of norbornene-based monomers, and addition copolymers of norbornene-based monomers and vinyl compounds. Among these, in fields requiring high reliability, particularly strength properties, hydrogenated ring-opening polymers of norbornene-based monomers, addition polymers of norbornene-based monomers, and addition of vinyl compounds copolymerizable with norbornene-based monomers. Polymers are preferred, and hydrogenated ring-opening polymers of norbornene monomers are more preferred.

The norbornene-based monomers are described in the above publications, JP-A-2-227424 and JP-A-2-27684.
For example, monomers disclosed in Japanese Patent Publication No. 2 and the like can be used. Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and 5-methyl-bicyclo [2.2.1] hepta-
2-ene, 5,5-dimethyl-bicyclo [2.2.1]
Hept-2-ene, 5-ethyl-bicyclo [2.2.
1] Hept-2-ene, 5-butyl-bicyclo [2.
2.1] Hept-2-ene, 5-ethylidene-bicyclo [2.2.1] -hepta-2-ene, 5-hexyl-bicyclo [2.2.1] hepta-2-ene, 5-octyl -Bicyclo [2.2.1] hepta-2-ene, 5-octadecyl-bicyclo [2.2.1] hepta-2-ene,
5-ethylidene-bicyclo [2.2.1] hepta-2-
Ene, 5-methylidene-bicyclo [2.2.1] hepta-2-ene, 5-vinyl-bicyclo [2.2.1] hepta-2-ene, 5-propenyl-bicyclo [2.2.
1] Hept-2-ene, tricyclo [4.3.0.1
^2,5 ] deca-3,7-diene (commonly used dicyclopentadiene), tricyclo [4.4.0.1 ^2,5 ] undeca-3,8-diene, tricyclo [4.4.0.1]
^2,5 ] undec-3-ene, 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5
-Cyclohexenylbicyclo [2.2.1] hept-2
-Ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -dodec-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene,

8-ethyltetracyclo [4.4.0.1
^2,5 . 17, ¹⁰ ] -dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 .
17, ¹⁰ ] -dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . ^{17 , 10} ] -dodec-3-ene, 8-vinyltetracyclo [4.4.0.
^12,5 . 17, ¹⁰ ] -dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -dodec-3-ene, 8-cyclopentyl-
Tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ]-
Dodeca-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodeca-3-
Ene, 8-cyclohexenyl-tetracyclo [4.4.
0.1 ^2,5 . 1 ^{7,1 0]} - dodeca-3-ene, 8-
Phenyl-cyclopentyl-tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] - dodeca-3-ene; tetracyclo ^{[7.4.0.1 10,13.} 0 ^2,7] trideca -2,4,6,11- tetraene (1,4-methano -1,4,4a, also referred 9a- tetrahydrofluorene), tetracyclo ^{[8.4.0.1 11,14.} 0
^3,8 ] tetradeca-3,5,7,12-tetraene (1,4-methano-1,4,4a, 5,10,10a-
Also referred to as hexahydro-anthracene), pentacyclo ^{[6.5.1 3,6.} 0 ^2,7 . 0 ^{9, 13]} pentadeca-3,10-diene, pentacyclo [7.4.0.1
^3,6 . 1 ^{10, 13} . 0 ^2,7 ] pentadeca-4,1
1-diene, tetramer or higher adduct of cyclopentadiene, 5-phenylbicyclo [2.2.1] hept-2-
Ene, tetracyclo [6.5.0.1 ^2,5 . 0
^8,13] trideca -3,8,10,12- tetraene (1,4-methano -1,4,4a, also referred 9a- tetrahydrofluorene), tetracyclo [6.6.0.1
^2,5 . 0 ^8,13] tetradeca -3,8,10,12
-Tetraene (1,4-methano-1,4,4a, 5,1
Norbornene monomers having no functional group, such as 0,10a-hexahydroanthracene);

5-methoxy-carbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2.2.1] hept-2-ene, 5-methyl-5
Methoxycarbonyl-bicyclo [2.2.1] hepta
2-ene; 5-methoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, bicyclo [2.
2.1] Hept-5-enyl-2-methylpropionate, bicyclo [2.2.1] hept-5-enyl-2-
Methyl octanate, bicyclo [2.2.1] hept-
2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene,
5,6-di (hydroxymethyl) bicyclo [2.2.
1] Hept-2-ene, 5-hydroxy-i-propylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene;
5-Cyanobicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene-5,6
-Dicarboxylic acid imide, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 17, ¹⁰ ] -Dodeca-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 17, ¹⁰ ] -dodec-3-ene, 8-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodeca-3-
Ene, 8-carboxytetracyclo [4.4.0.1
^2,5 . Norbornene-based monomers having a functional group such as [ ^17,10 ] -dodec-3-ene.
These norbornene-based monomers are each independently,
Alternatively, two or more kinds can be used in combination.

The norbornene-based polymer may be a copolymer of a norbornene-based monomer and a vinyl compound copolymerizable therewith. The proportion of the norbornene-based monomer unit in the norbornene-based polymer is appropriately selected depending on the purpose of use, but is usually 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more. The low dielectric properties and the heat resistance properties are highly balanced and suitable.

Examples of the copolymerizable vinyl compound include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene and 3-ethyl- 1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,
4-dimethyl-1-hexene, 4,4-dimethyl-1-
Pentene, 4-ethyl-1-hexene, 3-ethyl-1
-Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, ethylene or α-olefin having 2 to 20 carbon atoms; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a,
5,6,7a-tetrahydro-4,7-methano-1H-
Cycloolefins such as indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-
Non-conjugated dienes such as 1,4-hexadiene and 1,7-octadiene; These vinyl compounds can be used alone or in combination of two or more.

The method of ring-opening polymerization or addition polymerization of a norbornene monomer, the method of addition polymerization of a norbornene monomer and a copolymerizable vinyl compound, and the method of hydrogenation are not particularly limited, and are known methods. Can be performed according to Ring-opening polymers of norbornene monomers include ruthenium, rhodium, palladium, osmium, iridium, metal halides such as platinum,
Using a catalyst system comprising a nitrate or acetylacetone compound and a reducing agent, or a catalyst system comprising a halide or acetylacetone compound of a metal such as titanium, vanadium, zirconium, tungsten or molybdenum, and an organoaluminum compound in a solvent, Or in the absence of solvent, usually at a polymerization temperature of -50 ° C to 100 ° C, 0 to 50k
It can be obtained by subjecting a norbornene-based monomer to ring-opening polymerization at a polymerization pressure of g / cm ² . In the catalyst system, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone,
Nitrogen-containing compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and other third components such as Lewis acids,
Polymerization activity and selectivity of ring-opening polymerization can be improved.

The addition polymer of a norbornene-based monomer and a vinyl compound can be prepared, for example, by subjecting the monomer component to -50 ° C. in a solvent or without a solvent in the presence of a catalyst system comprising a vanadium compound and an organoaluminum compound. -10
It can be obtained by a method of copolymerizing at a polymerization temperature of 0 ° C. and a polymerization pressure of 0 to 50 kg / cm ² .

The hydrogenated norbornene-based polymer can be obtained by hydrogenating a ring-opened polymer by adding hydrogen in the presence of a hydrogenation catalyst according to a conventional method. By hydrogenation, some or all of the carbon-carbon unsaturated bonds present in the main chain or side chains are hydrogenated and saturated. In the case of a norbornene-based polymer containing an aromatic ring, hydrogenation may be used to hydrogenate the aromatic ring, or only the non-aromatic carbon-carbon unsaturated bonds in the main chain and side chains may be selectively hydrogenated. Good.

Examples of the monocyclic cycloolefin polymer include:
For example, addition polymers of monocyclic cycloolefin monomers such as cyclohexene, cycloheptene and cyclooctene disclosed in JP-A-64-66216 can be exemplified.

Examples of the cyclic conjugated diene-based polymer include, for example, JP-A-6-136057 and JP-A-7-258.
No. 318, a polymer obtained by 1,2- or 1,4-addition polymerization of a cyclic conjugated diene-based monomer such as cyclopentadiene or cyclohexadiene, and a hydrogenated product thereof.

Examples of the vinyl cyclic hydrocarbon polymer include:
For example, a polymer obtained by polymerizing a vinyl cyclic hydrocarbon monomer such as vinylcyclohexene or vinylcyclohexane disclosed in JP-A-51-59989, and a hydrogenated product thereof, And polymers obtained by polymerizing vinyl aromatic monomers such as styrene and α-methylstyrene disclosed in JP-A-43910 and JP-A-64-1706, and hydrogenated products thereof. Can be.

Examples of the aromatic polymer having an aromatic ring in the main chain include polyphenylene sulfide, polyphenylene ether, polyether sulfone, and polysulfone.

The functional group in the polymer resin used in the present invention is appropriately selected according to the type of the curing agent. Examples of the functional group include a radical reactive functional group and an ion reactive functional group. From the viewpoint of not causing cure shrinkage, an ion-reactive functional group is preferable. Examples of the ion-reactive functional group include an epoxy group, a carboxyl group, a hydroxyl group, a carbonyloxycarbonyl group, a silanol group, an amino group, and a sulfone group. Among them, an epoxy group, a hydroxyl group, and a carbonyloxycarbonyl group are exemplified. Groups and amino groups are preferred, and carbonyloxycarbonyl groups are most preferred. These functional groups may be contained alone or in combination of two or more. The amount of the functional group in the polymer resin is usually 1 to 100 mol%, based on the total number of monomer units constituting the polymer,
Preferably 5 to 70 mol%, more preferably 20 to 50 mol%.
Mol%. When the functional group content of the polymer resin is within this range, low dielectric properties, low water absorption, and heat resistance are highly balanced and suitable.

The ring structure-containing polymer resin having a functional group is
There is no particular limitation on the production method. For example, 1) a compound having a functional group is introduced into the ring structure-containing polymer resin by a modification reaction, and 2) a monomer having a functional group is copolymerized as a copolymer component. It can be obtained by polymerization or 3) by copolymerizing a monomer containing a hydrolyzable functional group such as an ester group as a copolymerization component, and then hydrolyzing the functional group. Among these production methods, a modified ring structure-containing polymer resin obtained by introducing a functional group into a ring structure-containing polymer by a modification reaction is preferable because of its excellent curability and cured physical properties. The denaturation reaction can be performed according to a conventional method. Examples of the compound used for introducing a functional group by a modification reaction include an ion-reactive functional group-containing unsaturated compound.

The ion-reactive functional group-containing unsaturated compound is a compound having the above-mentioned ion-reactive functional group and a carbon-carbon unsaturated bond. Specifically, glycidyl acrylate, glycidyl methacrylate, endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid, endo-cis-bicyclo [2,2,1] hept -5-ene-2-methyl-2,3-dicarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, glycidyl ether of o-allylphenol, glycidyl ether of m-allylphenol, p-
Unsaturated epoxy compounds such as glycidyl ether of allylphenol; acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, endocis-bicyclo [2.2.1] hept-5-ene-
Unsaturated carboxylic acid compounds such as 2,3-dicarboxylic acid, methyl-endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid; maleic anhydride, chloromaleic anhydride, butenyl anhydride Unsaturated carboxylic anhydrides such as succinic acid, tetrahydrophthalic anhydride and citraconic anhydride; allyl alcohol, 2-allyl-6
-Methoxyphenol, 4-allyloxy-2-hydroxybenzophenone, 3-allyloxy-1,2-propanediol, 3-buten-1-ol, 4-pentene-1
Unsaturated alcohol compounds such as -ol and 5-hexen-1-ol; Among these, unsaturated epoxy compounds and unsaturated carboxylic anhydride compounds are preferred, and unsaturated carboxylic anhydride compounds are particularly preferred.

In order to efficiently modify the ion-reactive functional group-containing unsaturated compound, it is usually preferable to carry out the reaction in the presence of a radical initiator. Examples of the radical initiator include peroxides and azo compounds. As the peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t
tert-butyl peroxide, 2,5-dimethyl-2,
5-di (peroxidebenzoate) hexyne-3,
1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5
-Dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, t
tert-butyl perphenyl acetate, tert-butyl perisobutylate, tert-butyl per-se
c-octoate, tert-butyl perpiparate,
Examples include cumyl perpiparate and tert-butyl perdiethyl acetate, and examples of the azo compound include azobisisobutyronitrile and dimethylazoisobutyrate. These radical initiators
Each can be used alone or in combination of two or more. The usage ratio of the radical initiator is usually 0.001 to 100 parts by weight of the ring structure-containing polymer resin.
The range is 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.1 to 2.5 parts by weight. In the denaturation reaction, the reaction temperature is usually 0 to 400 ° C, preferably 60 to 400 ° C.
The temperature is raised to 350 ° C., and the reaction time is usually 1 minute to 24 hours, preferably 30 minutes to 10 hours.

The modified product of the polymer resin having a ring structure is not limited by the modification ratio, but is usually 1 to 150 mol%, preferably 5 to 70 mol%, more preferably 5 to 70 mol%, based on the total number of monomer units in the polymer. Preferably it is 20 to 50 mol%. When the modification ratio is in this range, the characteristics of low dielectric properties, low water absorption, and heat resistance are highly balanced and suitable. The graft modification rate can be measured by the following method or the like.
The modified product of the ring structure-containing polymer was measured by H ¹ -NMR, and the total A of the peak areas of hydrogen derived from the functional group-containing unsaturated compound was measured.
And the sum B of the peak areas of hydrogen derived from the ring structure-containing polymer in the modified ring structure-containing polymer is calculated.
/ A. Next, the modification rate X (= X ′ × 100) [mol%] is determined, and X is calculated from the following equation. (DX ′) / (C × X ′) = B / A where C is the number of hydrogen atoms in one molecule of the modified compound when the polar group-containing unsaturated compound is modified into a polymer. For example, in the case of maleic anhydride, C = 3. D is the number of hydrogens in one unit of the monomer of the ring structure-containing polymer. For example, in the case of a polymer obtained by ring-opening polymerization of ethyltetracyclododecene and hydrogenating it, D = 22.

The molecular weight of the polymer resin having a ring structure having a functional group used in the present invention is appropriately selected according to the purpose of use. For example, the molecular weight is determined by gel permeation chromatography (GPC) using toluene as a solvent. The measured polystyrene equivalent weight average molecular weight (Mw) is usually 1
0.00-1,000,000, preferably 20,000
00 to 500,000, more preferably 20,000 to
It is in the range of 100,000. When the weight average molecular weight (Mw) of the ring-structure-containing polymer resin having a functional group is in this range, it is particularly excellent in moldability and heat resistance and is suitable. The glass transition temperature of the ring-structure-containing polymer resin having a functional group used in the present invention is not particularly limited, but is usually 50 ° C or higher, preferably 100 ° C or higher, more preferably 120 ° C or higher.
When it is above, it is excellent in heat resistance and is suitable. The ring-structure-containing polymer resins having these functional groups are each alone,
Alternatively, two or more kinds can be used in combination.

As the curing agent used in the present invention, those used in ordinary curable resin compositions can be used.
Examples of the curing agent include an ionic curing agent and a radical curing agent, but an ionic curing agent is preferable because it has high adhesion and does not shrink upon curing. Examples of the ionic curing agent include aliphatic polyamines such as hexamethylenediamine, triethylenetetramine, diethylenetriamine and tetraethylenepentamine, diaminocyclohexane, diaminonorbornane, and 3 (4), 8 (9) -bis (aminomethyl). Tricyclo [5.2.1.0 ^2,6 ] decane, 1,3- (diaminomethyl) cyclohexane, mensendiamine, isophoronediamine N-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, Alicyclic polyamines such as bis (4-aminocyclohexyl) methane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane,
α, α′-bis (4-aminophenyl) -1,3-diisopropylbenzene, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, 4,4′-
Polyamines such as aromatic polyamines such as diaminodiphenylsulfone, metaphenylenediamine and metaxysilylenediamine; 4,4'-bisazidobenzal (4
-Methyl) cyclohexanone, 4,4'-diazidochalcone, 2,6-bis (4'-azidobenzal) cyclohexanone, 2,6-bis (4'-azidobenzal) -4
Bisazide compounds such as -methyl-cyclohexanone, 4,4'-diazidodiphenylsulfone, 4,4'-diazidodiphenylmethane, 2,2'-diazidostilbene;

Acid anhydrides such as phthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, nadic anhydride, 1,2-cyclohexanedicarboxylic acid, and maleic anhydride-modified polypropylene; fumaric acid, phthalic acid, maleic anhydride Acid, trimellitic acid, polyvalent dicarboxylic acid such as hymic acid; 1,3′-butanediol;
1,4'-butanediol, hydroquinone dihydroxy diethyl ether, tricyclodecane dimethanol, 1,
Polyols such as 1,1-trimethylolpropane; polyhydric phenols such as phenol novolak resin and cresol novolak resin; nylon-6, nylon-66, nylon-610, nylon-11, nylon-612,
Polyamides such as nylon-12, nylon-46, methoxymethylated polyamide, polyhexamethylenediamine terephthalamide and polyhexamethyleneisophthalamide; polyvalent isocyanates such as hexamethylene diisocyanate and toluylene diisocyanate; phenol novolak type epoxy compounds; cresol novolak Glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds such as type epoxy compounds, cresol type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, brominated bisphenol A type epoxy compounds, brominated bisphenol F type epoxy compounds, Polyvalents such as glycidylamine type epoxy compounds, alicyclic epoxy compounds and isocyanurate type epoxy compounds Epoxy compounds and the like can be mentioned.
Among these, particularly, when the resin polymer has a carbonyloxycarbonyl group as a functional group, from the viewpoint of heat resistance, solvent resistance, and storage stability, polyamines, polyols, polyhydric phenols, and polyhydric epoxy compounds are used. Preferred are, in particular, polyvalent epoxy compounds.

Examples of the radical curing agent include methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis (t-butylperoxy) 3,
3,5-trimethylcyclohexane, 2,2-bis (t
-Butylperoxy) butane, t-butylhydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne- 3, organic peroxides such as α, α′-bis (t-butylperoxy-m-isopropyl) benzene, octanoyl peroxide, isobutyryl peroxide, and peroxydicarbonate;

The molecular weight of the curing agent may be appropriately selected according to the purpose of use, but is usually 50 to 4,000, preferably 100 to 3,000, more preferably 200 to 2,000.
00 range. These curing agents can be used alone or in combination of two or more. The mixing ratio of the curing agent is usually 0.1 to 20 parts by weight based on 100 parts by weight of the ring-structure-containing polymer resin having the functional group.
0 parts by weight, preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight.

The curable resin composition of the present invention may contain other polymers and other additives as required. Examples of other polymers include rubbery polymers and other resins. As the rubbery polymer, for example, natural rubber, polybutadiene rubber, polyisoprene rubber, acrylonitrile / butadiene copolymer rubber, styrene / butadiene copolymer rubber, styrene / isoprene copolymer rubber, styrene / butadiene / isoprene ternary Any diene rubber of copolymer rubber; hydrogenated product of these diene rubbers; saturation of ethylene / α-olefin copolymer such as ethylene / propylene copolymer, propylene / other α-olefin copolymer Polyolefin rubber; ethylene / propylene / diene copolymer, α-olefin / diene copolymer, isobutylene /
Α-olefin / diene polymer rubbers such as isoprene copolymer and isobutylene / diene copolymer; special rubbers such as urethane rubber, polyether rubber, acrylic rubber, propylene oxide rubber, and ethylene acrylic rubber;
Thermoplastic elastomers such as styrene / butadiene / styrene block copolymer rubber, hydrogenated styrene / isoprene / styrene block copolymer rubber; thermoplastic elastomer; urethane-based thermoplastic elastomer; polyamide-based thermoplastic elastomer; A polybutadiene-based thermoplastic elastomer;

Examples of the other resin include a ring-structure-containing polymer resin having no functional group and a polymer resin having no ring structure. Examples of the polymer resin having no ring structure include polyolefins such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, and polypentene; nylon 6, Polyamides such as nylon 66; ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polyamide resin, polyester resin and the like. These other polymers can be used alone or in combination of two or more. The mixing ratio of the other polymer is usually 100 parts by weight or less, preferably 70 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the ring-structure-containing polymer resin having the functional group. The lower limit is 0 parts by weight.

Other compounding agents include curing accelerators, curing assistants, fillers, flame retardants, heat stabilizers, weather stabilizers,
Leveling agent, thixotropic agent, antistatic agent,
Examples thereof include a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax, and an emulsifier, and the mixing ratio is appropriately selected within a range not to impair the object of the present invention.

In the present invention, in order to further enhance the cured physical properties, it is preferable to add a curing accelerator. The curing accelerator is not particularly limited, but when the curing agent is, for example, a polyvalent epoxy compound, a tertiary amine compound, a boron trifluoride complex compound, or the like is preferable. Above all, when a tertiary amine compound is used, lamination properties, insulation resistance, heat resistance, and chemical resistance to fine wiring are improved. Specific examples of the tertiary amine compound include linear tertiary amine compounds such as benzyldimethylamine, triethanolamine, triethylamine, tributylamine, tribenzylamine, and dimethylformamide; pyrazoles, pyridines, pyrazines, and pyrimidines. , Indazoles, quinolines, isoquinolines, imidazoles, triazoles and the like. Among these, imidazoles, particularly substituted imidazole compounds having a substituent, are preferred.

Specific examples of the substituted imidazole compound include 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole and 2-isopropylimidazole. Alkyl-substituted imidazole compounds such as 2,4-dimethylimidazole and 2-heptadecylimidazole; 2-phenylimidazole,
Phenyl-4-methylimidazole, 1-benzyl-2
-Methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole,
Benzimidazole, 2-ethyl-4-methyl-1-
(2′-cyanoethyl) imidazole, 2-ethyl-4
And imidazole compounds substituted with a hydrocarbon group having a ring structure such as an aryl group such as -methyl-1- [2 '-(3 ", 5" -diaminotriazinyl) ethyl] imidazole or an aralkyl group. Can be Among these, imidazole having a substituent having a ring structure is preferable from the viewpoint of compatibility with the polymer resin having a ring structure having the functional group, and 1-benzyl-2-phenylimidazole is particularly preferable. These curing accelerators are used alone or in combination of two or more. The amount of the curing accelerator is appropriately selected according to the purpose of use,
It is usually 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, based on 100 parts by weight of the polymer resin having a functional group-containing ring structure.

The composition of the present invention may further contain a curing aid. Examples of the curing assistant include oxime / nitroso curing assistants such as quinone dioxime, benzoquinone dioxime, and p-nitrosophenol;
Maleimide-based curing aids such as phenylene bismaleimide; allyl-based curing aids such as diallyl phthalate, triallyl cyanurate, and triallyl isocyanurate; methacrylate-based curing aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; Vinyl curing aids such as vinyl toluene, ethyl vinyl benzene, and divinyl benzene are exemplified. These curing aids can be used alone or in combination of two or more, and the compounding ratio is usually 1 to 1000 parts by weight, preferably 10 to 500 parts by weight, based on 100 parts by weight of the curing agent. Range of parts.

The curable resin composition of the present invention can be used, for example, after coating on a substrate, removing the solvent, drying and then curing. The substrate is not particularly limited, and for example, a printed wiring board, a silicon wafer substrate, a glass substrate, or the like can be used. The coating method may be a conventional method, for example, spin coating,
A die coating method, a doctor blade method, a screen printing method and the like can be mentioned. The drying conditions for removing the solvent include a drying temperature of usually 30 to 150 ° C, preferably 50 to 120 ° C, more preferably 60 to 100 ° C, and a drying time of usually 1 to 90 ° C.
Minutes, preferably 3 to 60 minutes, more preferably 5 to 30 minutes. The curing conditions are such that the curing temperature is usually 100 to 4
The curing time ranges from 00C, preferably from 110 to 350C, more preferably from 130 to 300C, usually from 10 minutes to 10 hours, preferably from 30 minutes to 5 hours.

[0044]

The present invention will be specifically described below with reference to examples and comparative examples. In the examples, “parts” means “parts by weight” unless otherwise specified. Example 1 Using a polymerization catalyst comprising tungsten hexachloride, triisobutylaluminum and isobutyl alcohol, 8-ethyltetracyclo [4.4.1 ^2,5 . 1 ^{7, 10.}
0] -3-dodecene (hereinafter abbreviated as ETD), and then hydrogenated using a hydrogenation catalyst composed of nickel acetylacetonate and triisobutylaluminum to give an ETD ring opening weight of 99% or more. A combined hydrogenated product was obtained. Then, in an autoclave, 100 parts of hydrogenated ETD ring-opening polymer, 35 parts of maleic anhydride, 3.5 parts of dicumyl peroxide, and 300 parts of t-butylbenzene
The resulting mixture was allowed to react at 135 ° C. for 4 hours, and the reaction solution was dropped into isopropanol, solidified, and dried to obtain a modified polymer. The modified polymer had a Tg of 158 ° C., a weight average molecular weight of 45,400 and a modification ratio of 26 mol%. 100 parts of the obtained modified polymer, 40 parts of a curing agent (dicyclopentadiene type epoxy resin: manufactured by Nippon Kayaku Co., Ltd.), 0.5 part of benzylimidazole and 20 parts of N-methylpyrrolidone (polar solvent (A)) were mixed with trimethyl Dissolve in benzene / dimethylacetamide (9/1 weight ratio) mixed solvent and add 3
A 0% by weight solution A and a 10% by weight solution B were obtained. The solution A was applied on a Teflon (registered trademark) substrate by a doctor blade method, preliminarily dried at 80 ° C. for 5 minutes, then left standing in a nitrogen atmosphere at 250 ° C. for 2 hours to be cured, and the thickness was 40 to 50.
A μm film was obtained. The dielectric constant, water absorption and glass transition temperature of this film were measured. In addition, curing properties were determined using the solution A. On the other hand, the solution B was evaluated for storage stability, heat resistance and adhesion. The results are shown in Table 1. Examples 2 to 6 and Comparative Examples 1 to 3 Example 1 except that the polar solvent (A) having the formulation shown in Table 1 was used.
A film was obtained and evaluated in the same manner as described above. The results are shown in Table 1.

<Test and Evaluation Methods> The Tg of the polymer resin was measured by the DSC method, and the Tg of the cured product obtained by thermally curing the curable resin composition was measured by the DMA method.
The peak top value of δ was used. The molecular weight (weight average molecular weight and number average molecular weight) of the polymer resin was measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. Ring structure-containing polymer (norbornene ring-opening polymer)
The hydrogenation rate of the main chain and the modification rate of the ring structure-containing polymer are ¹
It was measured by 1 H-NMR.

(Dielectric constant) The dielectric constant (ε) was measured according to JIS C6481, and ◎: ε ≦ 2.70, ○: 2. 7
0 <ε ≦ 2.85, Δ: 2.85 <ε ≦ 3.00, ×:
The evaluation was made on the basis of 3.00 <ε. (Water absorption) The water absorption (w) was measured according to JIS C6481, and ◎: w ≦ 0.10%, ：: 0.10% <w ≦ 0.
15%, Δ: 0.15% <w ≦ 0.20%, ×: 0.2
The evaluation was made on the basis of 0% <w. (Curing properties) Solution A was applied on a Teflon substrate by a doctor blade method, and preliminarily dried at 80 ° C for 5 minutes.
The film was cured by leaving it in a nitrogen atmosphere at 50 ° C. for 2 hours to obtain a film A having a thickness of about 45 μm. On the other hand, the solution A was applied by a doctor blade method, preliminarily dried at 80 ° C. for 5 minutes, and then left to cure in a nitrogen atmosphere at 230 ° C. for 1 hour to obtain a film B having a thickness of about 45 μm. The glass transition temperature of each of the films A and B was measured, and the temperature difference (ΔT) between them was calculated, and ：: ΔT <3 ° C., ○: 3 ° C. ≦ ΔT <
6 ° C., Δ: 6 ° C. ≦ ΔT <9 ° C., ×: 9 ° C. ≧ ΔT, and evaluated.

(Storage Stability) Each of the resin composition solution B and the solution C obtained by placing the solution B in a glass ampoule and immersing it in a thermostat at 30 ° C. for one week was coated on a silicon substrate, And then heat-treated at 250 ° C. for 1 hour, and the thickness of the thin film obtained was measured. Solution B
The ratio of the thickness of the film obtained by the resin solution C to the thickness of the film obtained by (Pt = C / B) was calculated.
Pt <1.1, ：: 1.1 ≦ Pt <1.15, Δ: 1.
15 ≦ Pt <1.20, ×: 1.20 ≦ Pt (Heat resistance) The solution B of the curable resin composition is applied on a quartz glass substrate, preliminarily dried at 80 ° C for 5 minutes, and then heated at 250 ° C.
For 2 hours and thermally cured to obtain a thin film having a thickness of 2 μm.
ITO (indium tin oxide) is deposited on this thin film (ITO deposition conditions: discharge voltage 60 V, ITO film thickness 5).
00 °, glass substrate temperature 220 to 240 ° C.). IT
The appearance of the O film was observed, ◎: no wrinkles in the appearance, 微: fine wrinkles at one end of the glass substrate, Δ: wrinkles at the four ends of the glass substrate, ×: evaluation of wrinkles on the entire surface . (Adhesion) A solution B of the curable resin composition was applied to a glass epoxy substrate and a quartz glass substrate, preliminarily dried at 80 ° C. for 5 minutes, and then heat-treated at 250 ° C. for 2 hours to obtain a coating film. The adhesion of the coating film was determined in accordance with the grid test of JIS K 5400, and the score was obtained. ◎: 100
Or more, で: 95 to less than 100 points, Δ: 90 to less than 95 points, ×: less than 90 points.

[0048]

[Table 1]

Table Note) NMP: N-methylpyrrolidone NMCL: N-methylcaprolactam EB: Ethyl benzoate BL: γ-butyllactone BuAc: t-butyl acetate CHCN: acetonitrile THF: Tetrahydrofuran EtOH: Ethanol glass epoxy: glass epoxy Evaluation glass: Evaluation with quartz glass substrate

Example 7 100 parts of a modified polymer, 40 parts of a curing agent (dicyclopentadiene type epoxy resin: manufactured by Nippon Kayaku Co., Ltd.), 0.5 part of benzylimidazole and 20 parts of t-butyl acetate (polar solvent (A)) Was dissolved in a mixed solvent of trimethylbenzene / cyclopentanone (6/4 weight ratio) to obtain a 30% by weight solution A. A B-stage (semi-cured) film having a thickness of 40 μm was obtained in the same manner as in Example 5, except that the solution A was applied, preliminarily dried at 120 ° C. for 5 minutes, and then not thermally cured. This B-stage film is superimposed on a glass epoxy substrate, and is pressed with a vacuum press at 30 kg / cm ² and 180 kg / cm ² .
C. for 1 hour and laminated. On the other hand, the B-stage film obtained in the same manner as above was laminated on a quartz glass substrate, and pressed and laminated at 5 kg / cm ² at 250 ° C. for 2 hours using a vacuum press. The adhesion of the cured product on these substrates was evaluated. Further, the heat resistance of the film laminated on the quartz glass substrate was measured. In addition, only the B-stage film was treated with a vacuum press at 30 kg / cm ² and 180 ° C.
The cured film was obtained by pressure bonding for a time, and the dielectric constant and water absorption of the cured film were measured. The evaluation results were almost the same as in Example 5. Table 1 shows that storage stability is low when solvents such as THF and ethanol are mixed and used (Comparative Example). On the other hand, it can be seen that a mixed solvent using an amide compound or an ester compound has an excellent balance between storage stability and curing characteristics.

[0051]

The curable resin composition of the present invention has an excellent balance between curability and storage stability and can be used for a wide range of curable resin applications. Further, the curable resin composition of the present invention is excellent in cured physical properties such as low dielectric properties, low water absorption, heat resistance, transparency and adhesion, and therefore, for example, an insulating material for printed wiring boards; Interlayer insulating film; Insulating material for flexible printed wiring board; LSI, VL
Insulating materials such as interlayer insulating films for semiconductor devices such as SI devices; protective coating materials such as cover coats for semiconductor devices;
Solder resist materials for printed wiring boards; color filters for liquid crystal display substrates, flattening films for TFT arrays, flattening films for various wirings, transparent materials such as liquid crystal display cells (partition walls; also referred to as polymer cells); It can be suitably used for the purpose.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J002 BK001 CC062 CD042 CD052 CD102 CD132 CE001 CL002 EB027 EC048 EC058 ED017 EE037 EF118 EH036 EH146 EK018 EK038 EK048 EK078 EL138 EN038 EN048 EN078 EP016 EQ038 ER008 A06 EU06 A30 EF008 AA11 AB10 AB24 AB26 AB34 AB40 BA09 CA01 CA08 CA46 CA51 CB02 CB04 CB08 CB17 CB18 CB25 CD08 CD12

Claims (2)

[Claims] 1. A mixed solvent containing at least one polar solvent selected from the group consisting of an amide compound, an ester compound, a nitrile compound and a sulfoxide compound, and a non-polar solvent, and a polymer resin having a ring structure having a functional group. And a curable resin composition containing a curing agent. 2. The curable resin composition according to claim 1, further comprising a curing accelerator.