JPH11286537A - Norbornene-based polymer having organic group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a norbornene-based polymer having excellent adhesive properties and fluidity while retaining excellent low water absorption, dielectric characteristics and heat resistance, and therefore esp. useful for the adhesion of electronic parts. SOLUTION: This norbornene-based polymer has pendant organic groups and a weigh-average molecular weight(Mw) of 1,000-1,000,000 calculated in terms of polystyrene when measured by gel permeation chromatography(GPC). The pendent organic groups contain 3-30 carbons, carboxyl group(s) and at least one of other polar groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a norbornene-based polymer, and more particularly, to a norbornene-based polymer having an organic group containing a carboxyl group and other specific polar groups, having excellent adhesiveness and fluidity, and having low water absorption. And a norbornene-based polymer having excellent dielectric properties and heat resistance. The norbornene-based polymer of the present invention has good adhesiveness to electronic components and the like, and can provide an adhesive excellent in adhesiveness particularly to fine uneven surfaces.

[0002]

2. Description of the Related Art Norbornene-based polymers are materials having low water absorption, excellent dielectric properties, and excellent heat resistance. However, since it does not have a polar group, it can be used as it is,
It does not have sufficient performance with respect to compatibility. As a method for solving these problems, Japanese Patent Application Laid-Open No. 5-148347
Japanese Patent Application Laid-Open Publication No. H11-157, pp. 147-143 discloses an example in which an amino group-containing ethylenically unsaturated compound is grafted to an addition (co) polymer of a norbornene-based monomer and ethylene. In addition, WO96
/ 37528 discloses an example in which an addition polymer of a norbornene-based monomer is modified by a graft reaction of maleic anhydride and further reacted with an amino group-containing polymer.
However, although the former has a certain improvement effect on the adhesive strength, it does not have sufficient adhesive strength required for electronic components, etc., and the latter has excellent fluidity at the time of melting. In addition, the wettability to electronic components having fine uneven surfaces was not sufficient, and a sufficiently satisfactory adhesive as an adhesive was not obtained. JP-A-6-100744 discloses that a random addition copolymer or a ring-opened polymer of a norbornene-based monomer or a hydrogenated product thereof is converted to an ethylenically unsaturated group-containing carboxylic acid, an anhydride thereof, and an ethylenically unsaturated group. A modified cyclic olefin-based polymer modified with any modifier of carboxylic acid hydroxyalkyl ester is disclosed. However, although it is described that these polymers are also effective as an adhesive, the types of polar groups contained therein are limited, and the degree required in the field of precision electronic components, which is the field of the present invention, is described. However, there is a problem that it does not have sufficient adhesiveness. From the above, no material has been found that has excellent properties in bonding electronic parts and the like while having excellent low water absorption, dielectric properties, and heat resistance.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a norbornene-based compound which is excellent in adhesiveness and fluidity while having excellent low water absorption, dielectric properties and heat resistance, and particularly suitable for bonding electronic parts. It is to provide a polymer.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a norbornene-based polymer having a specific structure in the side chain has excellent adhesiveness and fluidity, and has been used in electronic parts and the like. The present inventors have found that the material is particularly excellent in the bonding of, and have completed the present invention.

Thus, according to the present invention, there is provided (1) a norbornene-based polymer having an organic group in a side chain, the gel permeation chromatography (GP)
The weight average molecular weight (Mw) in terms of polystyrene measured according to C) is 1,000 to 1,000,000, and the organic group in the side chain contains 3 to 30 carbon atoms and has a carboxyl group and at least A norbornene-based polymer is provided, which contains one other polar group. According to the present invention, (2) the norbornene-based polymer according to (1), wherein the other polar group in the organic group of the side chain is a polar group containing at least one hetero atom selected from oxygen, nitrogen, and sulfur. Is provided.
According to the present invention, there is provided (3) the norbornene-based polymer according to any one of (1) and (2), wherein the other polar group in the organic group of the side chain has an ester bond or an amide bond. You. According to the present invention, there is provided (4) an adhesive resin containing the norbornene-based polymer according to any one of (1) to (3) as a main component. According to the present invention,
(5) reacting a norbornene-based polymer with a compound having active hydrogen after reacting a carboxylic anhydride having a carbon-carbon unsaturated bond in the presence of a radical generator. 3) A method for producing a norbornene-based polymer according to any one of the above is provided. According to the present invention, (6) after reacting a norbornene-based polymer with a carboxylic anhydride having a carbon-carbon unsaturated bond in the presence of a radical generator, an alkali metal salt or alkaline earth metal of a compound having active hydrogen The method for producing a norbornene-based polymer according to any one of (1) to (3), wherein the method comprises reacting a metal salt, followed by hydrolysis.
According to the present invention, (7) the compound having active hydrogen has at least one type of polar group selected from the group consisting of a hydroxyl group, an amino group, a mercapto group, a carboxyl group, and a sulfoxyl group. 6) A method for producing a norbornene-based polymer according to the above item is provided. According to the present invention, there is provided (8) a varnish obtained by dissolving or dispersing the norbornene-based polymer according to any one of (1) to (3) or the adhesive resin according to (4) in an organic solvent. .
According to the present invention, there is provided (9) a sheet formed by molding the norbornene-based polymer according to any one of (1) to (3) or the adhesive resin according to (4). According to the present invention, there is provided a method for bonding an electronic component by heating and melting the sheet according to (10) and (9).

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below by dividing them into items.

Norbornene-based polymer The norbornene-based polymer used in the present invention is not particularly limited. For example, a method disclosed in JP-A-3-14882 or JP-A-3-122137 may be used. And those obtained by polymerizing norbornene monomers. Specifically, a ring-opened polymer of norbornene-based monomer or other monomer copolymerizable with norbornene-based monomer and hydrogenated product thereof, norbornene-based monomer or norbornene-based monomer and Examples include addition polymers with other copolymerizable monomers. Among them, in order to highly balance heat resistance, dielectric properties, low water absorption and adhesiveness, hydrogenated ring-opening polymer of norbornene-based monomer, addition polymer of norbornene-based monomer, norbornene-based An addition copolymer of a vinyl compound copolymerizable with the monomer is preferred, and a hydrogenated ring-opening polymer of a norbornene monomer is particularly preferred.

The norbornene monomers 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, 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] hept-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
A bicyclic norbornene-based monomer having a norbornene (bicyclic) structure such as dicarboxylic imide; tricyclo [4.3.1 ^2,5 . 0 ^1,6 ] deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.
^12.5 . 0 ^1,6 ] dec-3-ene; tricyclo [4.
4.1 ^2,5 . 0 ^1,6 ] undeca-3,7-diene or tricyclo [4.4.1 ^2,5 . 0 ^1,6 ] Undeca-3,8
-Diene or a partially hydrogenated product thereof (or an adduct of cyclopentadiene and cyclohexene), tricyclo [4.4.1 ^2,5 . 0 ^1,6 ] 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] tricyclic norbornene monomers such as hept-2-ene and 5-phenyl-bicyclo [2.2.1] hept-2-ene; tetracyclo [4.4.1 ^2,5 . 1
^7,10 . 0] -dodec-3-ene (common name: tetracyclododecene), 8-methyltetracyclo [4.4.
^12.5 . ^17,10 . 0] -dodec-3-ene, 8-ethyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene, 8-methylidenetetracyclo [4.4.1
^2,5 . ^17,10 . 0] -dodec-3-ene, 8-ethylidenetetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene, 8-vinyltetracyclo [4.4.1
^2,5 . ^17,10 . 0] -dodec-3-ene, 8-propenyl-tetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene, 8-methoxycarbonyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene,
8-Hydroxymethyltetracyclo [4.4.1 ^2,5 .
^17,10 . 0] -dodec-3-ene, 8-carboxytetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodeca-3
-Cyclic norbornene-based monomer having a tetracyclododecene (tetracyclic) structure such as -ene (tetracyclododecene-based monomer); 8-cyclopentyl-tetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene,
8-cyclohexyl-tetracyclo [4.4.1 ^2,5 .
^17,10 . 0] -dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodeca-3
-Ene; tetracyclo [7.4.1 ^10,13 . 0 ^1,9 . 0
^2,7 ] trideca-2,4,6,11-tetraene (1,1)
4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [8.4.1 ^11,14 . 0
^1,10 . 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (1,4-methano-1,4,4a, 5,10,10
a- also referred to as hexahydro-anthracene), pentacyclo [6.5.1 ^{1,8. 13-6} . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, pentacyclo [7.4.
^13-6 . 1 ^10,13 . 0 ^1,9 . 0 ^2,7 ] pentadeca-4,11
A norbornene-based monomer such as a pentacyclic norbornene-based monomer such as -diene; a 6-ring or more norbornene-based monomer such as a cyclopentadiene tetramer;

The norbornene-based monomer may also have a polar group. Examples of the polar group include a hetero atom and an atomic group having a hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a halogen atom and the like, and from the viewpoint of adhesiveness, an oxygen atom and a nitrogen atom are preferable. Specific examples of such a polar group include an epoxy group, a carboxyl group, a hydroxyl group, an oxy group, an ester group, a carbonyloxycarbonyl group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group. Specific examples of the norbornene-based monomer having such a polar group include, for example, 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] Hept-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-methyloctanoate, 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 [4.4.1 ^2,5 . 1
^7,10 . 0] -dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.1 ^2,5 .
^17,10 . 0] -dodec-3-ene, 8-hydroxymethyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene, 8-carboxytetracyclo [4.4.
^12.5 . ^17,10 . 0] -dodec-3-ene and the like. These norbornene monomers can be used alone or in combination of two or more. The proportion of the norbornene-based monomer 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, and more preferably 70% by weight or more. It is suitable because fluidity and heat resistance are highly balanced.

The polymerization method and hydrogenation method of the norbornene monomer or other monomer copolymerizable with the norbornene monomer are not particularly limited, and can be carried out according to known methods. Ring opening of norbornene monomers (co)
The polymer is a norbornene-based monomer or another monomer copolymerizable with the norbornene-based monomer, and as a ring-opening polymerization catalyst, a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, and platinum. , A catalyst system comprising a nitrate or acetylacetone compound and a reducing agent, or titanium, vanadium, zirconium,
Using a catalyst system comprising a halide or acetylacetone compound of a metal such as tungsten or molybdenum, and an organoaluminum compound, in a solvent or without solvent, usually at a polymerization temperature of -50 ° C to 100 ° C, 0 to 50 kg / c.
It can be obtained by ring-opening (co) polymerization at a polymerization pressure of m ² . In the catalyst system, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound,
By adding a third component such as a halogen-containing compound, molecular iodine, and other Lewis acids, the polymerization activity and the selectivity of ring-opening polymerization can be increased. The hydrogenated norbornene-based polymer is prepared by converting a ring-opened (co) polymer into palladium,
It can be obtained by hydrogenation in the presence of a hydrogenation catalyst such as a homogeneous catalyst comprising a nickel compound and organoaluminum or a heterogeneous catalyst in which palladium or nickel is supported on a carrier such as alumina or silica. When the hydrogenation ratio is usually 50% or more, preferably 70% or more, more preferably 90% or more, the obtained polymer is excellent in fluidity and heat resistance and is suitable.

The content of these norbornene monomers in the ring-opening polymer may be appropriately selected according to the purpose of use, but is usually at least 50% by weight, preferably at least 80% by weight, more preferably at least 80% by weight. When the content is 90% by weight or more, heat resistance is excellent and suitable.

The norbornene-based monomer or the addition copolymer of the norbornene-based monomer and another monomer copolymerizable with the norbornene-based monomer may be prepared, for example, by mixing a monomer component in a solvent or without a solvent with titanium, In the presence of a catalyst system comprising a zirconium or vanadium compound and an organoaluminum compound, usually-
It can be obtained by a method of copolymerizing at a polymerization temperature of 50 ° C to 100 ° C and a polymerization pressure of 0 to 50 kg / cm ² .
As the norbornene-based monomer, for example, the above-mentioned norbornene-based monomer is used. The content of these norbornene monomers in the addition polymer may be 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. When it is, it is excellent in fluidity and heat resistance and is suitable.

The remainder of the norbornene-based polymer other than the norbornene-based monomer is not particularly limited as long as it is a copolymerizable monomer, and is a vinyl-based compound such as an α-olefin or an aromatic vinyl compound. Is used. Examples of the α-olefin include ethylene, propylene, 1-butene, 4-methyl-1-pentene, and the like, and examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, and p-chloro. Styrene and the like. As the copolymerizable monomer, a monocyclic cycloolefin monomer such as cyclopentene and cyclohexene; and a cyclic conjugated diene monomer such as cycloheptadiene and cyclohexadiene can also be appropriately used. . The content of other monomers other than these norbornene-based monomers in the norbornene-based polymer is appropriately selected depending on the purpose of use in the case of each of the norbornene-based ring-opened polymer and the norbornene-based addition polymer. In the case of a ring-opened polymer, it is usually 50% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, and in the case of an addition polymer, it is usually 70% by weight or less. Preferably 50% by weight or less, more preferably 30% by weight or less, is excellent in heat resistance and suitable. These norbornene-based polymers can be used alone or in combination.
More than one species can be used in combination.

[0014] norbornene-based polymer in the organic groups present invention for the purpose of improving the adhesion, each containing a carboxyl group and at least one other polar group, carbon atoms 3-3
Those having 0 organic groups in the side chain are used. That is, if the number of carbon atoms in the organic group is too small, the adhesiveness decreases, and if the number of carbon atoms is too large, the fluidity such as the melt viscosity and the solution viscosity of the polymer decreases, which is not preferable. Therefore, as described above, when the number of carbon atoms in the organic group is usually 3 to 30, preferably 4 to 25, and more preferably 5 to 20, the adhesiveness and fluidity of the polymer are highly balanced. It is preferred. At least one other polar group in the organic group, for the purpose of further improving the adhesion improved by the carboxyl group, preferably,
Those containing at least one heteroatom selected from oxygen, nitrogen and sulfur are selected. Specific examples of the polar group containing a hetero atom include, for example, a polar group having an ester bond, an amide bond, an imide bond, a sulfide bond, an ether bond, a thioether bond, and the like. And a polar group having an amide bond are preferred.

(Method for producing norbornene-based polymer having an organic group) The method for producing a norbornene-based polymer having an organic group in the present invention is not particularly limited. For example, (I) a norbornene-based polymer and its hydrogen To the additives,
A method in which a carbon-carbon unsaturated compound capable of forming a carboxyl group is introduced by a graft reaction, and then the introduced part is reacted with a compound having an active hydrogen-containing polar group. (II) Norbornene-based polymer and its hydrogen A method of introducing an unsaturated compound containing a carboxyl group and a polar group having a hetero atom into the additive by a graft reaction, (III) a norbornene-based polymer having a carbon-carbon unsaturated bond and a hydrogenated product thereof. A method of carboxyl-modifying a part of the carbon-carbon unsaturated bond, and further reacting a compound having an active hydrogen-containing polar group with all or part of the remaining carbon-carbon double bond,
(IV) A part of the norbornene-based polymer and its hydrogenated product obtained by polymerizing a norbornene-based monomer having a polar group other than a carboxyl group in the norbornene-based monomer, Oxidation, hydrolysis, solvolysis,
A method of converting to a carboxyl group by a reaction with an acid or a base, a reaction with hydrogen in the presence or absence of a hydrogenation catalyst, a reaction with a compound having active hydrogen, and the like,
(V) Among the norbornene-based monomers, a carboxyl-group-containing norbornene-based polymer obtained by polymerization using a carboxyl-group-containing norbornene-based monomer and a part of the carboxyl group site of a hydrogenated product thereof are known. Or a method of converting the compound into a target organic group by protecting with a protecting group or by reducing with an appropriate reducing agent. In the method (III), the norbornene-based polymer having a carbon-carbon unsaturated bond may be a norbornene-based monomer or dicyclopentadiene having a side chain having an unsaturated bond such as a vinyl group or a vinylidene group outside the ring. For example, it can be obtained by the polymerization method using a norbornene-based monomer having a carbon-carbon unsaturated bond that does not participate in the polymerization reaction, but the unsaturated compound can be introduced at a high modification rate, and the adhesiveness is reduced. The method of introducing a polar group by the above-mentioned method (I) or (II) is most preferable from the viewpoints of improvement and expansion of the selectivity of the polymer.

Therefore, the most preferable method among the methods (I) will be described in more detail. As a more detailed and specific method of the above method (I), the norbornene-based polymer or a hydrogenated product thereof used in the present invention may be added with (1) a carboxylic anhydride having a carbon-carbon unsaturated bond (hereinafter referred to as "unsaturated carboxylic acid"). (Hereinafter referred to as a saturated monomer), (2) a method of reacting with an active hydrogen-containing compound, or (1) after the reaction,
(2 ′) A method of reacting an alkali metal salt or an alkaline earth metal salt of an active hydrogen-containing compound, followed by hydrolysis. In the reaction (1), a conventionally known graft reaction can be used. For example, in the presence of a norbornene-based polymer and an unsaturated monomer, a method of irradiating radiation such as a gamma ray or an electron beam, a method of coexisting an unsaturated monomer after irradiating a radiation to the norbornene-based polymer,
Examples thereof include a method in which a norbornene-based polymer and an unsaturated monomer coexist in a solution state, a molten state, a dispersed state, or an impregnated state, and the reaction is performed in the presence or absence of a radical generator. Here, the polymerization in an impregnated state (impregnation polymerization) means dispersing a norbornene-based polymer in water or a solvent in a powder or pellet state, and then adding a radical generator and an unsaturated monomer to the dispersed norbornene-based polymer. It is a polymerization performed by impregnation. Among these, a norbornene-based polymer and an unsaturated monomer coexist in a solution state (solution method), a molten state (melt method) or an impregnated state (impregnation method), and in the presence or absence of a radical generator. A method in which both are reacted below is preferable, and a solution method is most preferable.

Specific examples of the unsaturated monomer (carboxylic anhydride having a carbon-carbon unsaturated bond) include, for example, acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid , Isocrotonic acid, nadic acid (endo-cis-bicyclo [2,
2,1] hept-5-ene-2,3-dicarboxylic acid). Among them, acid anhydrides of dicarboxylic acids such as maleic acid, itaconic acid, tetrahydrophthalic acid and nadic acid are preferred. From the viewpoint that the graft reaction rate can be controlled relatively freely and purification after the reaction is relatively easy, maleic anhydride is most preferred. These unsaturated monomers can be used alone or in combination of two or more.

As specific examples of the radical generator, for example, organic peroxides, organic peresters, azo compounds and the like can be used. Examples of the organic peroxide used herein include benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis- (tert-butyl). Peroxy) hexane, 2,5-dimethyl-2,5-bis- (t
tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxy-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (te
rt-butylperoxy) valerate, tert-butylperoxybenzoate, acetyl peroxide,
iso-butyryl peroxide, octanoyl peroxide, decanoyl peroxide, uranoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluoyl peroxide. Can be mentioned. Examples of organic peresters include tert
-Butyl peracetate, tert-butyl perphenyl acetate, tert-butyl peroxyisobutarate, tert-butyl perpivalate, cumyl perpivalate, and tert-butyl perdiethyl acetate. Further, examples of the azo compound include azobisisobutyronitrile and dimethylazoisobutyrate. Such radical initiators can be used alone or in combination of two or more. Among such radical initiators, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (ter
of t-butylperoxy) hexine-3, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, 1,4-bis (tert-butylperoxyisopropyl) benzene and dibenzoyl peroxide Such dialkyl peroxides are preferred. These radical generators can be used alone or in combination of two or more. The usage ratio of the radical generator is usually 0.001 to 30 parts by weight, preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the unmodified norbornene-based polymer.
Used in parts by weight.

Solvents that can be used in the above reaction include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane; cyclohexane and methylcyclohexane. And alicyclic hydrocarbon solvents such as decahydronaphthalene, and chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, and tetrachloroethylene. These solvents are
It can be appropriately selected depending on the unsaturated monomer used, reaction conditions, and the like. In the above reaction, a radical generator and an unsaturated monomer can be simultaneously charged and reacted, or the reaction can be performed while appropriately adjusting the concentration of the radical generator in the reaction system. If it is not necessary to broaden the molecular weight distribution, the latter reaction method is preferred. In the above reaction, the polymerization can be carried out in a molten state without a solvent or in a small amount, for example, in the presence of 30 parts by weight or less of a solvent per 100 parts by weight of a norbornene-based polymer.

The conditions for the graft modification reaction are not particularly limited, and the reaction can be carried out according to a conventional method. The reaction temperature is generally 0 to 400 ° C, preferably 60 to 350 ° C, and the reaction time is generally 1 minute to 24 hours, preferably 30 minutes to 10 minutes.
Time range. The graft modification rate of the graft modified product of the norbornene-based polymer is appropriately selected depending on the purpose of use, and is usually 0.1 to 100 mol%, preferably 0.1 to 100 mol%, based on the total number of monomer units in the polymer. It is in the range of 1 to 80 mol%, more preferably 5 to 50 mol%. When the graft modification rate of the norbornene-based polymer is in this range,
The dielectric constant and the peel strength (adhesion) between the metal layer are highly balanced and suitable. The graft modification rate is represented by the following formula (1). Graft modification rate (mol%) = (X / Y) × 100 (1) X: total number of moles of modified groups in the polymer due to the grafted unsaturated compound Y: total number of monomer units of the polymer X is a graft monomer It can be called the total number of moles of the denatured residue, and can be measured by ¹ H-NMR. Y
Is equal to (weight average molecular weight (Mw) of polymer / molecular weight of monomer). In the case of copolymerization, the molecular weight of the monomer is the average molecular weight of the monomer.

In the present invention, after the completion of the graft modification reaction of (1), the reaction of (2) or (2 ′) is carried out to obtain a norbornene-based polymer having an organic group in a target side chain. Can be generated. On this occasion,
After completion of the reaction (1), the modified polymer may be isolated and reacted with an active hydrogen-containing compound or an alkali metal salt or an alkaline earth metal salt of the active hydrogen-containing compound. It is also possible to directly react an active hydrogen-containing compound or an alkali metal salt or an alkaline earth metal salt of an active hydrogen-containing compound with the solution after the reaction. In the former method, after the modification rate of the polymer obtained after the reaction (1) is determined, the reaction amount of the active hydrogen-containing compound can be freely defined as required based on the determined degree. Further, in the latter method, although the amount of the active hydrogen-containing compound to be reacted cannot be accurately specified,
There is an advantage that a norbornene-based polymer can be synthesized without having to isolate and purify the modified polymer. The reaction amount of the active hydrogen-containing compound in the reaction (2) or (2 ′) is usually 0.1 to 100 equivalents, preferably 0.3 to 50 equivalents to the polar group introduced after the reaction (1). Equivalent,
It is more preferably 0.5 to 20 equivalents, most preferably 1.0 to 10 equivalents. If the reaction equivalent is too small, no adhesive force can be obtained, and if it is too large, unreacted active hydrogen-containing compounds remain undesirably at the time of polymer isolation.

The active hydrogen-containing compound used in the reaction (2) is not particularly limited as long as it is a substance capable of nucleophilic attack on electropositive carbon, but is not limited to a hydroxyl group, an amino group, a mercapto group, a carboxyl group and a sulfoxyl group. Compounds having at least one polar group selected from the group consisting of groups are preferred. Such compounds include water, alcohols, phenols, amines, thiols, organic acids (eg, aminocarboxylic acids, aminosulfonic acids,
Mercaptocarboxylic acids, etc.).

Specific examples of alcohols include methanol, ethanol, 1-propanol, 2-
Propanol, allyl alcohol, 1-butanol, 2
-Butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, methallyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol,
-Methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, 3-
Methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, cyclopentanol, 1-hexanol, cyclohexanol, geraniol, citronellol, benzyl alcohol, furfuryl alcohol, ethylene glycol, propylene glycol, Glycerin and the like. Among these, primary alcohols such as methanol, ethanol, allyl alcohol, and 1-butanol are preferred from the viewpoint of high reactivity. Also,
From the viewpoint of enhancing the adhesiveness, 2-propanol having a bulky substituent, 2-methyl-2-propanol,
Preferred are 2,2-dimethyl-1-propanol and their lithium, sodium, potassium salts and the like.

As the amines, in addition to inorganic amines such as ammonia, primary and secondary organic amines, aminocarboxylic acids, aminosulfonic acids and the like can be used. Specific examples of primary amines include ammonia,
Examples include monomethylamine, monoethylamine, n-propylamine, i-propylamine, cyclopentylamine, cyclohexylamine, geranylamine, benzylamine, aniline, ethanolamine and the like. Secondary amines include diethylamine, diphenylamine,
Diisopropylamine, di-n-butylamine, piperidine, pyrrolidine and the like. Of these, cyclic amines such as piperidine and pyrrolidine are preferred.

Examples of the thiols include methanethiol, ethanethiol, benzenethiol, thiophenol and the like.

Examples of the organic acids (eg, aminocarboxylic acids, aminosulfonic acids, mercaptocarboxylic acids, etc.) include 2-amino-2-norbornanecarboxylic acid and 2-amino-a- (methoxyimino) -4-acid.
Thiazoleacetic acid, 1-amino-1-cyclohexanecarboxylic acid, 1-amino-1
-Cyclopentanecarboxylic acid, 1-amino-1-cyclopropanecarboxylic acid, isonipecotic acid, nipecotic acid, pipecolic acid, p-aminobenzoic acid, 2-amino-1-naphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 5-amino-2-naphthalenesulfonic acid, 8-amino-2-naphthalenesulfonic acid, 3-amino-2-naphthoic acid, 3-amino-2,7-acid Naphthalenedisulfonic acid, 7-amino-1,
3-naphthalenedisulfonic acid, mercaptoacetic acid, 2-mercaptonicotinic
Acid, 2-mercaptobenzoic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, mercaptosuccinic acid, N- (2-mercaptopropionyl) glycine, and lithium, sodium, potassium salts thereof. No.

The reaction of the active hydrogen-containing compound in the method (2) may be carried out according to a conventional method, and the reaction temperature is not particularly limited. The reaction solvent, the type of the active hydrogen-containing compound, and the reaction time are taken into consideration. Temperature can be appropriately selected, but is usually 0 to 250 ° C, preferably 50 to 200 ° C.
The reaction time is usually 10 minutes to 15 hours, preferably 30 minutes to 5 hours.

As the alkali metal salt or alkaline earth metal salt of the active hydrogen-containing compound used in the reaction (2 '), for example, compounds of the above-mentioned active hydrogen-containing compounds such as lithium, sodium, potassium and calcium salts can be used. No. The reaction of the alkali metal salt or alkaline earth metal salt of the active hydrogen-containing compound may be carried out according to a conventional method, and the reaction conditions are such that the reaction temperature is usually -50 to 200 ° C, preferably 0 to 100 ° C, and the reaction time is usually It is 10 minutes to 24 hours, preferably 30 minutes to 10 hours. In the reaction of (2 ′), hydrolysis is carried out as a post-treatment step. However, usable hydrolysis reagents are not particularly limited, and water, diluted hydrochloric acid,
A saturated aqueous solution of ammonium chloride, organic acids and the like can be used. After completion of the reaction (including the hydrolysis step) of (2) or (2 ′), the reaction solution is filtered, if necessary, and the filtrate is dropped into a poor solvent such as acetone to coagulate the resin. Is dried to obtain an active hydrogen-containing norbornene-based polymer. However, some or all of these steps may be omitted as necessary.

The ratio (modification rate) of the organic groups in the norbornene-based polymer thus obtained may be appropriately selected depending on the purpose of use, and is usually 0.1 to 100 per polymer repeating unit. When it is in the range of mol%, preferably in the range of 0.2 to 50 mol%, more preferably in the range of 1 to 30 mol%, the adhesiveness and the fluidity are highly balanced and suitable.

The molecular weight of the norbornene polymer of the present invention is not particularly limited and may be appropriately selected depending on the purpose of use.
The weight average molecular weight (Mw) in terms of polystyrene measured in C) is usually 1,000 to 1,000,000, preferably 5,000 to 500,000, more preferably 10,000 to 100,000. Range. When the weight average molecular weight (Mw) of the norbornene-based polymer is in this range, the adhesiveness, fluidity, and mechanical properties are highly balanced and suitable.

The glass transition temperature (Tg) of the norbornene-based polymer of the present invention may be appropriately selected according to the purpose of use, but is usually 50 to 300 ° C., preferably 100 to 280.
C., particularly preferably in the range from 120 to 250.degree. When in this range, the adhesiveness and the fluidity are highly balanced and suitable.

280 of the norbornene-based polymer of the present invention
The melt flow rate measured according to JIS K6719 at a temperature of 2.degree. C. and a load of 2.16 kgf may be appropriately selected according to the purpose of use, but is usually 1 to 100 g / 10 mi.
n. , Preferably in the range of 5 to 70 g / 10 min. If the melt flow rate is too high, the fluidity at the time of melting of the polymer is reduced, and the interface wettability with the adherend as an adhesive is reduced.If the melt flow rate is too low, problems such as the polymer overflowing as an adhesive occur. . Therefore, when the melt flow rate is in the above range, the adhesiveness is excellent and suitable.

Compounding Agents The norbornene-based polymer of the present invention may contain a soft polymer, another polymer, and other compounding agents, if necessary. The addition amount of the other polymer and other compounding agents is appropriately selected within a range that does not impair the purpose of the present invention.

The soft polymer is a polymer having a glass transition temperature of 40 ° C. or lower, and includes ordinary rubber polymers and thermoplastic elastomers. Specific examples of such a soft polymer include (a) α- such as ethylene and propylene.
Olefin-based soft polymer mainly composed of olefin,
(B) an isobutylene-based soft polymer mainly composed of isobutylene, (c) a diene-based soft polymer mainly composed of conjugated dienes such as butadiene and isoprene, and (d) a cyclic olefin ring-opening mainly composed of cyclic olefins such as norbornene and cyclopentene. Polymer, (e) a soft polymer (organic polysiloxane) having a silicon-oxygen bond as a skeleton, (f) a soft polymer derived from α, β-unsaturated acid and its derivative, (g) unsaturated polymer Examples include a soft polymer derived from an alcohol and an amine or an acyl derivative thereof or an acetal, and (h) a polymer of an epoxy compound. Specific examples of these soft polymers include, for example, (a) such as liquid polyethylene, atactic polypropylene, 1-butene, 4-methyl-1-butene, 1-hexene, 1-octene and 1-decene. A homopolymer of ethylene / α-olefin copolymer;
Copolymers such as propylene / α-olefin copolymer, ethylene / propylene / diene copolymer (EPDM), ethylene / cyclic olefin copolymer and ethylene / propylene / styrene copolymer are exemplified. (B)
Examples thereof include polyisobutylene, isobutylene / isoprene rubber, and isobutylene / styrene copolymer. (C) includes polymers of conjugated dienes such as polybutadiene and polyisoprene; butadiene / styrene random copolymer, isoprene / styrene random copolymer, acrylonitrile / butadiene copolymer, acrylonitrile / butadiene / styrene copolymer, etc. Conjugated diene random copolymers; conjugated dienes and aromatics such as butadiene / styrene block copolymers, styrene / butadiene / styrene block copolymers, isoprene / styrene block copolymers, and styrene / isoprene / styrene block copolymers And the like. Block copolymers of group III vinyl hydrocarbons, and hydrogenated products of these block copolymers are exemplified. Examples of (d) include norbornene-based monomers such as norbornene, vinylnorbornene, and ethylidene norbornene, and metathesis ring-opened polymers of monocyclic olefins such as cyclobutene, cyclopentene, and cyclooctene, and hydrogenated products thereof.
Examples of (e) include silicone rubbers such as dimethylpolysiloxane, diphenylpolysiloxane, and dihydroxypolysiloxane. (F) includes polymers of acrylic monomers such as polybutyl acrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide, and polyacrylonitrile; copolymers of acrylic monomers such as butyl acrylate / styrene copolymer with other monomers Polymers. Examples of (g) include polymers of (esterified) unsaturated alcohols such as polyvinyl alcohol, polyvinyl acetate, vinyl polystearate, polyvinyl benzoate, and polyvinyl maleate; and (esters) such as vinyl acetate / styrene copolymer. ) Copolymers of unsaturated alcohols and other monomers. (H) includes polyethylene oxide, polypropylene oxide,
Epichlorohydrin rubber, and the like. (I) includes natural rubber, polypeptides, proteins, and the like. These soft polymers may have a crosslinked structure, or may have a functional group introduced by modification.

Further, among the above soft polymers, (a)
(B) and (c) the soft polymers are particularly excellent in rubber elasticity,
It is preferable because of excellent mechanical strength and flexibility. Above all, soft polymers corresponding to these (a), (b) and (c), and more preferably a soft polymer having an aromatic vinyl monomer in a polymer repeating unit, are preferred. Specific examples of the soft polymer, for example, ethylene propylene
Random copolymers such as styrene copolymers, isobutylene / styrene copolymers, and hydrogenated products of the copolymers;
Butadiene / styrene block copolymer, styrene /
Block copolymers such as butadiene / styrene block copolymers, isoprene / styrene block copolymers, styrene / isoprene / styrene block copolymers, and hydrogenated products of the copolymers. Among these, from the viewpoint of heat resistance and weather resistance, a polymer containing no or only a small amount of a double bond in the main chain (a hydrogenated product of the above polymer) is most preferable.

(Other polymers) Examples of other polymers include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene,
Polyolefins such as ultra low density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, polypentene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer; polyesters such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, etc. And other resins such as polycarbonate, polyimide and epoxy resin.

(Other Compounding Agents) Other compounding agents include an adhesion aid, a filler, a flame retardant, a heat stabilizer, a weather stabilizer, a leveling agent, a lubricant and the like. When it is necessary to introduce a crosslinked structure when using the adhesive resin composition of the present invention, a curing agent, a curing accelerator, a curing aid, etc. suitable for each polar group of the alicyclic structure-containing polymer. May be appropriately compounded.

As the adhesion aid, a low molecular weight compound having a molecular weight of about 300 to 3,000 in terms of polystyrene measured by gel permeation chromatography (GPC) for the purpose of further improving the fluidity of the polymer. Is used, specifically, for example, a polymerizable monomer oligomer,
Examples include hydrocarbon compounds (wax, paraffin oil, petroleum resin, etc.), phenols such as hindered phenol compounds, (phosphite) phosphates, esters and the like. The filler can be blended particularly for the purpose of improving mechanical strength (toughness) and further improving adhesive strength by reducing the coefficient of linear expansion. Examples of the filler include an inorganic or organic filler. As the inorganic filler,
Although not particularly limited, for example, calcium carbonate (light calcium carbonate, heavy or finely divided calcium, special calcium-based filler), clay (aluminum silicate; nepheline syenite fine powder, calcined clay, silane-modified clay) talc , Silica, alumina, diatomaceous earth, silica sand, pumice powder, pumice balloon, slate powder, mica powder, asbestos (asbestos), alumina colloid (alumina sol), alumina
White, aluminum sulfate, barium sulfate, lithopone, calcium sulfate, molybdenum disulfide, graphite (graphite), glass fiber, glass beads, glass flakes, foam glass beads, fly ash spheres, volcanic glass hollow bodies, synthetic inorganic hollow bodies, simple Crystalline potassium titanate, carbon fiber, carbon hollow spheres, anthracite powder, artificial cryolite (cryolite), titanium oxide, magnesium oxide, basic magnesium carbonate, domite, potassium titanate, calcium sulfite, mica, asbestos, silicate Calcium acid, montmorillonite, bentonite, graphite,
Aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber and the like can be mentioned. As the organic filler, for example, polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber, fluorine fiber, ebonite powder, thermosetting resin hollow sphere, Saran hollow sphere, shellac,
Wood flour, cork powder, polyvinyl alcohol fiber, cellulose powder, wood pulp and the like can be mentioned. The filler may have conductivity, particularly when the electronic components are bonded and electrically joined together, and as a specific example,
In addition to the above, nickel, aluminum, silver, copper, tin,
Metal plating such as nickel, gold, etc. is applied to metal particles such as lead, gold, zinc, platinum, cobalt, and alloys thereof (eg, solder), aggregated metal particles, molten metal particles, conductive carbon black, and resin particles. Metal-coated resin particles,
Examples thereof include particles obtained by coating a metal-coated resin particle with an insulating film, and composite resin particles obtained by compounding a resin and metal particles.

The form of use of the organic group-containing norbornene-based polymer of the present invention may be appropriately selected according to the purpose of use, and when used for bonding fine uneven surfaces such as circuit boards and electronic parts, varnish or varnish may be used. It is preferable to use it in the form of a sheet. Varnish The varnish of the present invention is prepared by dissolving or dispersing the organic group-containing norbornene-based polymer in an organic solvent. The organic solvent is not particularly limited as long as it dissolves or disperses the components.For example, toluene, xylene,
Aromatic hydrocarbons such as ethylbenzene; n-pentane;
Aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene; ketones such as methyl ethyl ketone, 21-pentanone and cyclohexanone; ethers; And the like. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used may be any ratio that is sufficient to uniformly dissolve or disperse the norbornene-based polymer and other components contained as necessary, but usually the solid content concentration is 1 to 80. %, Preferably 5 to 60% by weight, more preferably 10 to 50% by weight.

Sheet The sheet of the present invention can be obtained by molding a norbornene-based polymer into a sheet. The method of forming the sheet may be a conventional method, for example, a method of applying a varnish of the present invention to a smooth surface such as a mirror-finished metal plate or a resin carrier film and then drying the solvent, or A method of melt-extruding the norbornene-based polymer of the present invention from a T-die or the like is selected. The thickness of the sheet of the present invention,
It is appropriately selected according to the purpose of use.
0 μm, preferably 5 to 500 μm, more preferably 1 μm
When the thickness is in the range of 0 to 100 µm, the adhesiveness and the fluidity are highly balanced, which is preferable.

Adhesion Method The varnish and sheet of the present invention are excellent in adhesiveness and fluidity, and thus are suitable for use in bonding precision electronic parts having fine irregularities. As a method of bonding electronic components having a fine uneven surface as an adherend, for example,
(1) a method of applying the varnish of the present invention to one adherend, drying the solvent to form an adhesive resin layer, and then thermocompression bonding the other adherend to the adhesive resin layer; (2)
A method of laminating the sheet of the present invention on one adherend, placing the other adherend on the laminate, heat-melting the sheet, and pressing the sheet is adopted.

Although the adherend is not particularly limited, when the adherend is a wiring board or an electronic component having a fine uneven surface, the improvement effect of the present invention is remarkably exhibited. It is suitable. Examples of a wiring board or an electronic component having a fine uneven surface on its surface include, for example, a wiring board in which metal conductor wiring and electrodes are formed on an organic or inorganic material substrate (for example, a multilayer wiring board, a high-density wiring board). Printed wiring boards such as mounting boards and flexible printed boards, silicon wafer substrates, ceramic substrates), central processing units (CPU), IC chips such as semiconductor memory (DRAM), semiconductor elements such as LSI chips, ball grid arrays ( BGA), chip size package (CSP)
And other semiconductor packages. The adhesive resin composition of the present invention can be used as an adhesive resin material in electronics packaging technology. The adhesive resin composition of the present invention is suitable for, for example, fields such as adhesion and bonding of electronic components to a circuit board, sealing and insulation of electronic components, connection between substrates, interlayer insulating films, and transport of electronic components. Can be applied.

[0043]

The present invention will be specifically described below with reference to Synthesis Examples, Examples and Comparative Examples. (Evaluation method) (1) Unless otherwise specified, the molecular weight of gel permeation chromatography (G
(PC) as a standard polystyrene conversion value. (2) The copolymerization ratio and modification ratio of the polymer were determined by ¹ H-NMR.
Was measured by (3) The adhesive strength was measured according to the method described below. A varnish was prepared by dissolving the norbornene (co) polymer obtained in each of the examples in an organic solvent, and then formed into a film (thickness: 50 μm) by a cast film forming method. It was cut to a range of 1 cm. 0.8 cm thick, 8 cm long, 1 width
cm commercially available glass epoxy resin substrate (ANSI standard: F
R-4), and a thickness of 0.5 mm, a height of 8 cm,
Two silicon wafers each having fine wiring with a width of 1 cm formed thereon were prepared, and two glass epoxy resin substrates or end portions of two silicon wafers (vertical 1 c
The sample was prepared by sandwiching a film cut in the range of 1 m (width: 1 cm, width: 1 cm) and hot-melt-compression bonding at 250 ° C. and 30 kg / cm ^{2 using} a hot press. The peel strength obtained by a tensile test of the sample was defined as the adhesive strength. (4) The glass transition temperature was measured by DSC. (5) The melt flow rate is JIS K6719 (2
(Dissolution mass at 80 ° C. under a load of 2.16 kgf for 10 minutes).

[0044] [Synthesis Example 1] obtained by polymerization using a conventional Tegura catalysts 8-ethyl-tetracyclo [4.4.1 ^{2,5. 17,10} . 0] -Dodeca-3-ene ring-opening polymer hydrogenated product (hydrogenation ratio 99.91%, Mw
= 43400, Mw / Mn = 2.15) 100
Parts by weight were dissolved in 900 parts by weight of t-butylbenzene. To this solution was added 0.03 mol part of dicumyl peroxide and 0.3 mol part of maleic anhydride per repeating unit of the polymer. For 4 hours. The solution after the reaction was added dropwise to an excess amount of acetone to precipitate a modified polymer, which was collected by filtration, washed with an excess amount of acetone, and dried in vacuo at 100 ° C. for 48 hours. The resulting modified polymer was 95 parts by weight. The modified polymer was subjected to a GPC measurement (measurement solvent: toluene).
w = 43100 and Mw / Mn = 4.10. As a result of IR measurement of the modified polymer, the presence of a carbonyl bond (1780 cm ^-1 ) of the cyclic carboxylic anhydride was confirmed. As a result of ¹ H-NMR (CDCl 3, room temperature) measurement of the modified polymer, a peak derived from maleic anhydride was confirmed at δ 2.5 to 3.3 ppm. Judging from the overall integration ratio, the modification rate was 20.2 mol%. The modified polymer exhibited a glass transition temperature of 143 ° C.

[Synthesis Example 2] The same operation was performed as in Synthesis Example 1, except that the amounts of dicumyl peroxide and maleic anhydride were changed to 0.02 mol part and 0.1 mol part, respectively. The obtained modified polymer was 92 parts by weight.
GPC measurement of the modified polymer revealed that Mw =
44800, Mw / Mn = 2.48. Judging from the overall integral ratio of the modified polymer in ¹ H-NMR (CDCl 3, room temperature), the modification ratio was 3.3 mol%.

[Synthesis Example 3] In Synthesis Example 2, 8-ethyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodeca-3-ene ring-opening polymer
-Ethyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0]
-Hydrogenated ring-opening copolymer of dodeca-3-ene and dicyclopentadiene (hydrogenation ratio 99.89%, copolymerization ratio
7: 3, Mw = 41100, Mw / Mn
= 2.78), except that the same operation was performed. The obtained modified copolymer was 98 parts by weight. GPC measurement of the modified copolymer showed that Mw = 5100.
0, Mw / Mn = 3.21. Judging from the overall integral ratio of the modified copolymer in ¹ H-NMR (CDCl3, room temperature), the modification ratio was 3.9 mol%.

[Synthesis Example 4] In Synthesis Example 2, 8-ethyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0] - instead of dodeca-3-ene ring-opening polymer, 8-ethyl-tetracyclo [4.4.1 ^{2,5. 17,10} . 0] -dodeca-3
Hydrogenated ring-opening copolymer of -ene and dicyclopentadiene (hydrogenation ratio 99.88%, copolymerization ratio 5: 5,
(Mw = 39100, Mw / Mn = 3.01)
The same operation was performed except that was used. The resulting modified copolymer was 99 parts by weight. GPC measurement of the modified copolymer revealed that Mw = 49100, Mw / Mn.
= 3.20. ¹ H-NM of the modified copolymer
Judging from the overall integral ratio at R (CDCl3, room temperature), the denaturation rate was 3.1 mol%.

[Synthesis Example 5] In Synthesis Example 2, 8-ethyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0] - instead of dodeca-3-ene ring-opening polymer, 8-ethyl-tetracyclo [4.4.1 ^{2,5. 17,10} . 0] -dodeca-3
-Hydrogenated ring-opening copolymer of ene and dicyclopentadiene (hydrogenation ratio 99.91%, copolymerization ratio 3: 7,
(Mw = 35900, Mw / Mn = 2.99)
The same operation was performed except that was used. The obtained modified copolymer was 91 parts by weight. GPC measurement of the modified copolymer revealed that Mw = 40500 and Mw / Mn.
= 2.92. ¹ H-NM of the modified copolymer
Judging from the overall integral ratio at R (CDCl3, room temperature), the denaturation rate was 2.9 mol%.

Synthesis Example 6 Tetracyclo [4.4.1] obtained by polymerization using a conventionally known vanadium catalyst.
^2,5 . ^17,10 . 0] -dodec-3-ene (TCD) and an addition copolymer of ethylene (copolymerization ratio: TCD / ethylene = 29/71, Mw = 38500, Mw / Mn
= 2.11) Synthesis example 1 except that 100 parts by weight were used
87 parts by weight of the modified copolymer were obtained in the same manner as in the above.
When GPC measurement (measurement solvent: THF) of the modified copolymer was performed, Mw = 41000 and Mw / Mn =
It was 2.87. As a result of IR measurement of the modified copolymer,
Carbonyl bond of cyclic carboxylic anhydride (1780 cm
^-1 ) was confirmed. ¹ H-NMR of the modified copolymer
(CDCl3, room temperature) As a result of the measurement, δ 2.5 −
A peak derived from maleic anhydride was observed at 3.3 ppm. Judging from the overall integration ratio, the modification rate was 20.2 mol%. The modified copolymer exhibited a softening temperature of 111 ° C.

Example 1 100 parts by weight of the norbornene maleic anhydride polymer obtained in Synthesis Example 1 was added to THF 90
0 parts by weight, and 15 parts by weight of methanol was added.
The reaction was performed at 5 ° C. for 5 hours. This solution was poured into an excess amount of acetone to precipitate a polymer, which was collected by filtration, washed with an excess amount of acetone, and dried in vacuo at 100 ° C. for 24 hours.
The obtained polymer was 84 parts by weight. IR of the polymer
As a result of the measurement, a carbomethoxy group (1740 cm ⁻¹ , 1
052 cm ^-1 ) and a carboxyl group (1725 c
m ^-1 , 3200 cm ^-1 ). Of the polymer
¹ H-NMR (CDCl 3, room temperature) was measured, and peaks of a carbomethoxy group (δ 3.4 ppm) and a carboxyl group (broad centered on δ 12.5 ppm) were present at an intensity ratio of 3: 1. It was confirmed. Further, judging from the overall integration ratio, almost 100% of the maleic anhydride sites were converted into carbomethoxy groups and carboxyl groups. The glass transition temperature of the polymer was 142 ° C. A varnish was prepared by dissolving 25 parts by weight of the obtained polymer in 75 parts by weight of toluene, and then a sheet having a thickness of 50 μm was formed by a cast film forming method.
As a result of evaluating the adhesive strength under the conditions described in the above section, the adhesive strength was 63 kg / cm ² .

Example 2 In Example 1, Synthesis Example 1
In place of the norbornene maleic anhydride polymer obtained in the above, 100 parts by weight of the norbornene maleic anhydride polymer obtained in Synthesis Example 2 was used, 900 parts by weight of t-butylbenzene and 2.5 parts of methanol were used as a solvent. The same operation was performed except that the amount was changed to parts by weight. The obtained polymer was 96 parts by weight. As a result of IR measurement of the polymer, the presence of a carbomethoxy group (1740 cm ^-1 , 1152 cm ^-1 ) and a carboxyl group (1725 cm ^-1 , 3200 cm ^-1 ) were confirmed. ¹ H-NMR of the polymer (CDCl 3, room temperature)
As a result of the measurement, a carbomethoxy group (δ 3.4 ppm)
And a peak of a carboxyl group (broad centered at δ 11.8 ppm) at a ratio of intensity 3: 1. Further, judging from the overall integral ratio, almost 100% of the maleic anhydride sites were carbomethoxy groups. And that it was converted to a carboxyl group. The glass transition temperature of the polymer was 143 ° C., and the adhesive strength measured using the polymer in the same manner as in Example 1 was 68 kg / cm ² .

Example 3 In Example 2, Synthesis Example 2
The same operation was performed except that 100 parts by weight of the maleic anhydride-modified norbornene-based copolymer obtained in Synthesis Example 3 was used instead of the norbornene-maleic anhydride-based polymer obtained in (1). The obtained copolymer was 93 parts by weight. The glass transition temperature of the copolymer was 122 ° C., and the adhesive strength of the copolymer measured in the same manner as in Example 1 was 62 kg / cm ² .

Example 4 In Example 2, Synthesis Example 2
The same operation was performed except that 100 parts by weight of the maleic anhydride-modified norbornene-based copolymer obtained in Synthesis Example 4 was used instead of the maleic anhydride-norbornene-based polymer obtained in (1). The obtained copolymer was 97 parts by weight. The glass transition temperature of the copolymer was 109 ° C., and the adhesive strength measured using the polymer in the same manner as in Example 1 was 66 kg / cm ² .

[Example 5] In Example 2, synthesis example 2
The same operation was performed except that 100 parts by weight of the maleic anhydride-modified norbornene-based copolymer obtained in Synthesis Example 5 was used instead of the norbornene-maleic anhydride-based polymer obtained in (1). The obtained copolymer was 99 parts by weight. The glass transition temperature of the copolymer was 90 ° C., and the adhesive strength measured using the polymer in the same manner as in Example 1 was 69 kg / cm ² .

Example 6 The same operation as in Example 2 was performed using various alcohols instead of methanol. Table 1 shows the results.

[0056]

[Table 1]

Example 7 The same operation as in Example 2 was carried out except that various amines were used instead of methanol. Table 2 shows the results.

[0058]

[Table 2]

Example 8 The same operation was performed as in Example 2, except that 11 parts by weight of p-aminobenzoic acid was used instead of methanol. The obtained polymer was 95 parts by weight. As a result of IR measurement of the polymer, the amide group (32
50 cm ^-1 , 1690 cm ^-1 , 1400 cm ^-1 )
And carboxyl group (1724 cm ^-1 , 3250c
m ^-1 ) was confirmed. ¹ H-NMR (C
As a result of the measurement, the presence of a phenyl group was confirmed (δ 7.6 to 8.1 ppm). Further, judging from the overall integration ratio, it was confirmed that almost 100% of the maleic anhydride site of the base polymer was converted into an amide group and a carboxyl group. The glass transition temperature of the polymer is 150 ° C., and the adhesive strength measured using the polymer in the same manner as in Example 1 is> 150 kg / cm 2.
(Substrate destruction).

[Example 9] In Example 8, synthesis example 2
The same operation was performed except that 100 parts by weight of the maleic anhydride-modified norbornene-based copolymer obtained in Synthesis Example 6 was used instead of the maleic anhydride-modified norbornene-based copolymer obtained in (1). The obtained copolymer was 92 parts by weight. As a result of ¹ H-NMR (CDCl 3, room temperature) measurement of the copolymer, the presence of a phenyl group was confirmed (δ 7.6).
-8.2 ppm). Further, judging from the overall integral ratio, almost 100% of the maleic anhydride sites of the original copolymer
Was converted to an amide group and a carboxyl group. The softening temperature of the copolymer was 120 ° C., and the adhesive strength measured in the same manner as in Example 1 using the polymer showed an adhesive strength of> 150 kg / cm ² (substrate fracture).

[Comparative Example 1] According to the method described in Examples of JP-A-6-100744, Synthesis Examples 1, 3,
Each of 3.6 kg of the hydrogenated ring-opening (co) polymer used in 4, 5 and the addition copolymer used in Synthesis Example 6 was 2 kg.
The adhesive strength of each of the resins modified with -hydroxyethyl acrylate was measured. (2-hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 40 g; Perhexin 25B (manufactured by NOF Corporation), 4 g; divinylbenzene, 4 g, melt-mixed at 250 ° C.).
Table 3 shows the results.

[0062]

[Table 3]

Comparative Example 2 According to the method described in Example 41 of WO 96/37528, 100 parts by weight of the modified addition copolymer obtained in Synthesis Example 6 was replaced with a polypropylene oxide containing a terminal amino group-containing polypropylene oxide ( Jeffam
ine (registered trademark), hereinafter referred to as reagent A) or polybutadiene having a terminal amino group (Hycar (registered trademark) 1
300X45 (hereinafter referred to as Reagent B) was measured for adhesive strength (solvent used was ortho-dichlorobenzene). Table 4 shows the results.

[0064]

[Table 4]

From the results shown in Tables 1 to 4, the modified polymer in Comparative Example 1 had insufficient adhesive strength, and Comparative Example 2
In the modified polymer of the present invention, the modified polymer of Example has excellent adhesive strength, as compared with the fact that the adhesive strength is insufficient, because the melt flow rate is lowered and the fluidity is poor. Can be confirmed.

[0066]

According to the object of the present invention, a norbornene-based polymer which is excellent in adhesiveness and fluidity while having excellent low water absorption, dielectric properties and heat resistance is particularly suitable for bonding electronic parts. And an adhesive resin containing the polymer as a main component.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI C09J 151/08 C09J 151/08

Claims (10)

[Claims] 1. A norbornene-based polymer having an organic group in a side chain, wherein the polymer has a weight average molecular weight (Mw) in terms of polystyrene of 1,000 as measured by gel permeation chromatography (GPC). ~ 1,0
000, and the organic group in the side chain has 3 carbon atoms.
Containing at least one carboxyl group and at least one
A norbornene-based polymer containing two other polar groups. 2. The norbornene-based polymer according to claim 1, wherein the other polar group in the side chain organic group is a polar group containing at least one hetero atom selected from oxygen, nitrogen and sulfur. 3. The norbornene-based polymer according to claim 1, wherein the other polar group in the side chain organic group has an ester bond or an amide bond. 4. An adhesive resin comprising the norbornene-based polymer according to claim 1 as a main component. 5. The method according to claim 1, wherein a carboxylic anhydride having a carbon-carbon unsaturated bond is reacted with the norbornene-based polymer in the presence of a radical generator, and then a compound having active hydrogen is reacted. 4. The method for producing a norbornene-based polymer according to any one of claims 1 to 3. 6. After reacting a norbornene-based polymer with a carboxylic anhydride having a carbon-carbon unsaturated bond in the presence of a radical generator, an alkali metal salt or an alkaline earth metal salt of a compound having active hydrogen is added. React, then
The method for producing a norbornene-based polymer according to any one of claims 1 to 3, wherein the hydrolysis is carried out. 7. The norbornene-based compound according to claim 5, wherein the compound having active hydrogen has at least one polar group selected from the group consisting of a hydroxyl group, an amino group, a mercapto group, a carboxyl group and a sulfoxyl group. A method for producing a polymer. 8. A varnish obtained by dissolving or dispersing the norbornene-based polymer according to claim 1 or the adhesive resin according to claim 4 in an organic solvent. 9. A sheet formed by molding the norbornene-based polymer according to any one of claims 1 to 3 or the adhesive resin according to claim 4. 10. A method for bonding an electronic component by heating and melting the sheet according to claim 9.