JPH11140297A - Resin composition, cured product and adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition satisfying heat resistance, mechanical properties, electrical properties, low water absorption, adhesion, solvent resistance, and moldability, each required for the interlaminar insulation films in electronic parts, to obtain a cured product from the above composition, and to obtain an adhesive film by using the above composition and cured product. SOLUTION: This resin composition is obtained by compounding 1-99.9 pts.wt. of a polyquinoline resin, 0.1-99 pts.wt. of a cyanate compound of the formula (Ar<1> is an n-valent organic group containing at least two carbon atoms, and (n) is an integer of >=2), and 0-95 pts.wt. of another organic compound or inorganic compound so as to be 100 pts.wt. as a whole. The second objective adhesive film is obtained by using the above composition and a cured product therefrom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive, a resin composition usable as an interlayer insulating film, a cured product, and an adhesive film.

[0002]

2. Description of the Related Art Hitherto, a dehydration-condensation type polyimide resin has been generally used as an interlayer insulating film of an electronic component (JP-A-63-222444). This is because the polyimide resin has excellent heat resistance and mechanical properties. However, in recent years, the requirements for heat resistance, mechanical properties, electrical properties, and low water absorption required for interlayer insulating films have become more severe, and polyimide resins cannot be used. Further, polyamic acid varnish, which is a precursor of the polyimide resin, has poor storage stability at room temperature.

On the other hand, polyquinoline resins containing a quinoline ring have been studied recently as resins to compensate for the disadvantages of polyimide resins (US Pat. No. 4,000,187, US Pat. No. 5,017,677). U.S. Pat.
247,050, etc.). Polyquinoline resins are excellent in electrical properties such as relative permittivity and dielectric loss tangent, heat resistance, mechanical properties, and low water absorption, but are inferior in adhesiveness. Therefore, it cannot be sufficiently adhered to an adherend such as copper or polyimide. In addition, since it is inferior in solvent resistance, it is difficult to form a multilayer by dissolving a previously formed insulating layer in a solvent when using it as an insulating material of a multilayer wiring board or an interlayer insulating film of an LSI. Further, in order to solve the above problem, a method of forming a semi-cured film from which the solvent has been removed and molding under heat and pressure can be considered. Not shown,
At present, it is difficult to apply as an insulating material for multilayering.

[0004]

As described above, heretofore, the heat resistance, mechanical properties, electrical properties, low water absorption, adhesiveness, solvent resistance, and moldability required for the interlayer insulating film have been satisfied. There was no resin composition and no adhesive film.

An object of the present invention is to provide a resin composition and a cured product satisfying the heat resistance, mechanical properties, electrical properties, low water absorption, adhesiveness, solvent resistance and moldability required for an interlayer insulating film of an electronic component. And an adhesive film.

[0006]

That is, the present invention provides a polyquinoline resin of 1 to 99.9 parts by weight, a cyanate compound of the general formula (I) of 0.1 to 99 parts by weight, and another organic compound or 10 to 95 parts by weight of inorganic compound
An object of the present invention is to provide a resin composition which is blended so as to be 0 parts by weight.

[0007]

Embedded image [However, in the general formula (I), Ar ¹ is an n-valent organic group containing at least two carbons, and n is an integer of 2 or more. ]

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The above-mentioned polyquinoline resin is a polymer having a quinoline ring in a repeating unit, and is described, for example, in US Pat. No. 4,000,187 and US Pat. No. 5,017,677. U.S. Pat.
7,050, Macromolecules (Macr)
omolecules) 14 (1981), 870
, Page 880 (JK Stille) and the like, together with the synthesis method. As an example, 4,4'-diacetyldiphenyl ether and 4,4'-diamino-3,
There is a method of forming a quinoline ring from 3'-dibenzoyldiphenyl ether to synthesize a polymer.

[0009] In addition to the above-mentioned method, the polyquinoline resin comprises a difluoromonomer having a quinoline ring, a diol monomer and optionally a monofluoromonohydroxy monomer and a base, and usually a fluoro group and a hydroxy group. By heating in an anhydrous solvent at a usage ratio such that it is almost equivalent, and removing water azeotropically,
It can also be manufactured. Alternatively, it can be produced by heating a monofluoromonohydroxy monomer and a base in an anhydrous solvent and azeotropically removing water.

The heating conditions at this time are appropriately determined in consideration of the azeotropic temperature / reflux temperature of the solvent used, but are usually 100 to 250 ° C. and 1 to 24 hours.

As the difluoro monomer having a quinoline ring, for example, 2- (2-fluorophenyl) -5-
Fluoro-4-phenylquinoline, 2- (4-fluorophenyl) -5-fluoro-4-phenylquinoline, 4
-(2-fluorophenyl) -5-fluoro-2-phenylquinoline, 2- (4-fluorophenyl) -7-fluoro-4-phenylquinoline, 2,4-difluoroquinoline, 2,7-difluoroquinoline, , 5-Difluoroquinoline, 2,7-difluoro-6-phenylquinoline, 4- (4-fluorophenyl) -7-fluoroquinoline, 6,6'-bis [2- (4-fluorophenyl) -4-phenyl Quinoline], 6,6'-bis [2-
(2-fluorophenyl) -4-phenylquinoline],
6,6'-bis [2- (4-fluorophenyl) -4-
tert-butylquinoline], 6,6′-bis [4-
(4-fluorophenyl) -2-phenylquinoline],
6,6'-bis-4-fluoroquinoline, 6,6'-bis [4- (fluorophenyl) -2- (2-pyridyl)
Quinoline], 6,6'-bis-2-fluoroquinoline,
6,6'-bis [4- (4-fluorophenyl) -2-
(Methyl) quinoline], 6,6'-bis [2-fluoro-4-phenylquinoline], oxy-6,6'-bis [2- (4-fluorophenyl) -4-phenylquinoline], 1,4 -Benzene-bis-2,2- [4- (4-
Fluorophenyl) quinoline], 1,4-benzene-bis-2,2- [4-fluoroquinoline], 1,4-benzene-bis-4,4- [2- (4-fluorophenyl)
Quinoline], 1,1,1,3,3,3-hexafluoroisopropylidene-bis [(4-phenoxy-4-phenyl) -2- (4-fluoroquinoline)] and the like. These are used alone or in combination of two or more.

Examples of the diol monomer include resorcinol, hydroquinone, 4,4'-dihydroxybiphenyl, 1,3-dihydroxynaphthalene, 2,6-
Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3,4-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, methyl-2,4-dihydroxybenzoate, isopropylidene diphenol (bisphenol A), hexafluoroisopropylidene diphenol ( Bisphenol AF), trifluoroisopropylidene diphenol, phenolphthalein, phenol red, 1,2-di (4-hydroxyphenyl) ethane, di (4-hydroxyphenyl) methane, 4,4-
Examples include dihydroxybenzophenone, 9,9-bis (4-hydroxyphenyl) fluorene, and the like. These are used alone or in combination of two or more.

Examples of the monofluorohydroxy monomer include 2- (4-fluorophenyl) -6-hydroxy-4-phenylquinoline, 2- (2-fluorophenyl) -6-hydroxy-4-phenylquinoline,
-(2-fluorophenyl) -6-hydroxy-2-phenylquinoline, 2,3-diphenyl-4- (2-fluorophenyl) -6-hydroxyquinoline, 2,3-diphenyl-4- (4-fluorophenyl ) -6-Hydroxyquinoline, 2,3-diphenyl-6- (2-fluorophenyl) -4-hydroxyquinoline, 7-fluoro-2-hydroxyquinoline, 7-fluoro-2-hydroxy-4-phenylquinoline, 7 -(4-fluorophenyl) -2-hydroxy-4-phenylquinoline, 7-
Fluoro-4-hydroxy-4-phenylquinoline, 7
-(4-fluorophenyl) -4-hydroxy-2-phenylquinoline, 2- (4-fluorophenyl) -4-
Hydroxy-3-phenylquinoline, 2- (4-fluorophenyl) -8-hydroxy-3-phenylquinoline, 2- (4-fluorophenyl) -8-hydroxyquinoline, 2- (2-fluorophenyl) -4- (4-hydroxyphenyl) quinoline and the like. These are used alone or in combination of two or more.

As the solvent used in the synthesis, for example,
N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, tetramethylurea, dimethylsulfoxide, sulfolane, diphenylsulfone, toluene, dichlorobenzene and the like. These are used alone or in combination of two or more.

Examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, metal hydride, metal amide, butyllithium and the like. These are used alone or in combination of two or more.

As the polyquinoline resin, the following general formula (III) or general formula (IV) is preferred from the viewpoints of handleability, electric characteristics, low hygroscopicity and the like.

[0017]

Embedded image

[0018]

Embedded image Wherein R ¹ and R ² are each independently preferably an alkyl group having 1 to 6 carbon atoms, preferably an aryl group having 6 to 12 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms, preferably an aryloxy group having 6 to 12 carbon atoms, a formyl group (-COH), ketone group (-COR ^3), ester group (-CO ₂ R ⁴ or -OCOR ^5), an amido group (-N
R ⁶ COR ⁷ or —CONR ⁸ R ⁹ ), preferably a heteroaryl group having 6 to 12 carbon atoms or a cyano group,
Alternatively, ^two of R ¹ and R ² may be connected to each other to contain an unsaturated bond, and
To form a monovalent hydrocarbon group (provided that R ^{3 to} R ⁹ are
It represents a hydrogen atom, preferably an alkyl group having 1 to 6 carbon atoms, preferably an aryl group having 6 to 12 carbon atoms, or a heteroaryl group having preferably 6 to 12 carbon atoms. ), M and p
Are each independently an integer of 0 to 5, X is a single bond,-
O -, - S -, - CO -, - SO -, - SO 2 -, - A
-,-(OA) _q -O- or -Q- (where q is 1
An -3 integer, A is, -Ar ³ - (arylene), - Hr ¹ - (heteroarylene group), - Ar ³ -O
^{-Ar 3 -, - Ar 3 -CO} -Ar 3 -, - Ar 3 -S-A
^{r 3 -, - Ar 3 -SO} -Ar 3 -, - Ar 3 -SO 2 -A
represents r ³ -or -Ar ³ -Q-Ar ^3- , and Q is

[0019]

Embedded image (L ¹ and L ² are a methyl group or a trifluoromethyl group, or L ¹ and L ² are preferably a divalent organic group having 2 to 12 carbon atoms which may be connected to each other and contain an unsaturated bond. Z ¹ and Z ² each independently represent a single bond or an arylene group having preferably 6 to 12 carbon atoms, and Y represents —O— or —O—A—O—. Is shown. And a polyquinoline resin having a repeating unit represented by the formula:

The above general formula (III) or general formula (IV)
In the definition of, as the alkyl group, for example, a methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, s
Examples include an ec-butyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a decyl group, an undecyl group, a dodecyl group, and a docosyl group.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group and a diphenylphenyl group.

Examples of the heteroaryl group include a pyridyl group, a quinolyl group, a pyrazinyl group and the like.

Two R ¹ , two R ² , and L ¹ and L ²
Examples of the divalent organic group which may include an unsaturated bond and are formed by connecting an alkylene group such as a 1,3-propylene group, a 1,4-butylene group, and a 1,5-pentylene group , -CH = CH-CH = CH-,

[0024]

Embedded image And the like.

Although the molecular weight of the polyquinoline resin is not particularly limited, gel permeation chromatography (GP
The number average molecular weight measured by C) using a standard polystyrene calibration curve is preferably from 5,000 to 20.
10,000, more preferably 10,000 to 10
It is 0000. If the molecular weight is too small, heat resistance and mechanical strength tend to decrease, and if it is too large, the melt viscosity tends to increase and moldability tends to decrease.

The amount of the polyquinoline resin used is 1 to 99.9 parts by weight based on 100 parts by weight of the resin composition. If the amount is less than 1 part by weight, thermal stability at high temperatures and mechanical strength are liable to decrease, and water absorption is liable to increase. If it exceeds 99.9 parts by weight, Tg, adhesiveness, and solvent resistance tend to decrease. In addition, the melt viscosity before curing is high, and the moldability tends to decrease.

The amount of the polyquinoline resin used is preferably at least 10 parts by weight based on 100 parts by weight of the resin composition in order to sufficiently improve the thermal stability at high temperatures, mechanical strength and low water absorption. In order to sufficiently improve Tg, adhesiveness, solvent resistance, and moldability, the content is preferably 90 parts by weight or less based on 100 parts by weight of the resin composition. For the same reason, it is more preferably from 20 to 80 parts by weight, particularly preferably from 40 to 70 parts by weight, based on 100 parts by weight of the resin composition.

Examples of the cyanate compound represented by the above general formula (I) include 2,2'-di (4-cyanatophenyl) propane, di (4-cyanato-3,5-dimethylphenyl) methane, (4-cyanatophenyl) thioether, 2,2'-di (4-cyanatophenyl) hexafluoropropane, di (4-cyanatophenyl) ethane,
Phenol novolak cyanate, 1,1'-di (5-
t-butyl-2-methyl-4-cyanatophenyl) butane, 1,1'-di (5-tert-butyl-2-methyl-4-methyl-4-
Cyanatophenyl) sulfide, 4,4 '-[1,3-
[Phenylenebis (1-methyl-ethylidene)]], cyanate of bisphenol, cyanate of phenol and dicyclopentadiene copolymer, and the like, and these may be used alone or in combination of two or more.

The amount of the cyanate compound represented by the general formula (I) is 0.1 to 99 parts by weight based on 100 parts by weight of the resin composition. If less than 0.1 part by weight, T
g, adhesiveness and solvent resistance are apt to decrease. In addition, the melt viscosity before curing is high, and the moldability tends to decrease. If it exceeds 99 parts by weight, the thermal stability at high temperatures and the mechanical strength are liable to decrease, and the water absorption tends to increase.

The amount of the cyanate compound represented by the general formula (I) is 10 parts by weight with respect to 100 parts by weight of the resin composition in order to sufficiently improve Tg, adhesion, solvent resistance, and moldability. It is preferable that it is above. In order to sufficiently improve thermal stability at high temperatures, mechanical strength, and low water absorption, the content is preferably 90 parts by weight or less. For the same reason, the amount is more preferably from 20 to 80 parts by weight, particularly preferably from 30 to 60 parts by weight, based on 100 parts by weight of the resin composition.

By using the cyanate compound represented by the general formula (I), the adhesiveness, solvent resistance, and moldability can be improved without lowering the electrical characteristics, heat resistance and the like of the polyquinoline resin. .

Examples of the bismaleimide compound represented by the general formula (II) include N, N'-ethylenedimaleimide, N, N'-hexamethylenebismaleimide,
N'-dodecamethylene bismaleimide, N, N'-m-
Xylylenebismaleimide, N, N'-p-xylylenebismaleimide, N, N'-1,3-bismethylenecyclohexanebismaleimide, N, N'-1,4-bismethylenecyclohexanebismaleimide, N, N '-2,
4-tolylenebismaleimide, N, N'-2,6-tolylenebismaleimide, N, N'-3,3'-diphenylmethanebismaleimide, N, N'-4,4'-diphenylmethanebismaleimide, , 3'-Diphenylsulfonebismaleimide, 4,4'-diphenylsulfonebismaleimide, N, N'-4,4'-diphenylsulfidebismaleimide, N, N'-p-benzophenonebismaleimide, N, N'- Diphenylethane bismaleimide, N, N'-diphenylether bismaleimide,
N, N '-(methylene-ditetrahydrophenyl) bismaleimide, N, N'-(3-ethyl) -4,4'-diphenylmethanebismaleimide, N, N '-(3,3'
-Dimethyl) -4,4'-diphenylmethanebismaleimide, N, N '-(3,3'-diethyl) -4,4'-
Diphenylmethane bismaleimide, N, N '-(3,
3'-dichloro) -4,4'-diphenylmethanebismaleimide, N, N'-tolidinebismaleimide, N,
N'-isophorone bismaleimide, N, N'-p, p '
-Diphenyldimethylsilylbismaleimide, N, N '
-Benzophenone bismaleimide, N, N'-diphenylpropanebismaleimide, N, N'-naphthalenebismaleimide, N, N'-m-phenylenebismaleimide, N, N'-4,4 '-(1,1- Diphenyl-cyclohexane) -bismaleimide, N, N'-3,5-
(1,2,4-triazole) -bismaleimide, N,
N'-pyridine-2,6-diylbismaleimide, N,
N'-5-methoxy-1,3-phenylenebismaleimide, 1,2-bis (2-maleimidoethoxy) ethane,
1,3-bis (3-maleimidopropoxy) propane,
N, N'-4,4'-diphenylmethane-bis-dimethylmaleimide, N, N'-hexamethylene-bis-dimethylmaleimide, N, N'-4,4 '-(diphenylether) -bis-dimethylmaleimide, N , N'-4,
Bifunctional maleimide compounds typified by 4 '-(diphenylsulfone) -bis-dimethylmaleimide, N, N'-bismaleimide of N, N'-4,4'-(diamino) -triphenylphosphate, and aniline Polyfunctional maleimide compound obtained by the reaction of maleic anhydride with a reaction product (polyamine compound) with formalin, 3,4,4'-triaminodiphenylmethane, triaminophenol, etc., tris- (4-aminophenyl)- Maleimide compound obtained by reacting phosphate, tris- (4-aminophenyl) -thiophosphate with maleic anhydride, 2,2-bis [4- (4-maleimidophenoxy)
Phenyl] propane, 2,2-bis [3-chloro-4-
(4-maleimidophenoxy) phenyl] propane,
2,2-bis [3-bromo-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [ 3-propyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-isopropyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-butyl-
4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-sec-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methoxy-4- (4 -Maleimidophenoxy)
Phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,1-bis [3
-Methyl-4- (4-maleimidophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-maleimidophenoxy) phenyl] ethane, 1,1-bis [3-bromo-4- ( 4-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] methane, 1 1,1-bis [3-chloro-4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [3-bromo-4- (4-maleimidophenoxy) phenyl] methane, 3,3-bis [4 -(4-maleimidophenoxy) phenyl] pentane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,1,
1,3,3,3-hexafluoro-2,2-bis [4-
(4-maleimidophenoxy) phenyl] propane,
1,1,1,3,3,3-hexafluoro-2,2-bis [3-5-dibromo- (4-maleimidophenoxy)
Phenyl] propane and 1,1,1,3,3,3-hexafluoro-2,2-bis [3-5-methyl- (4-
Maleimidephenoxy) phenyl] propane, and these are used alone or in combination of two or more.

The amount of the bismaleimide compound represented by the general formula (II) is preferably 0.1 to 95 parts by weight based on 100 parts by weight of the resin composition. If it is less than 0.1 part by weight, Tg and adhesiveness tend to decrease, and if it exceeds 95 parts by weight, thermal stability at high temperature and mechanical strength decrease,
In addition, the water absorption tends to increase.

The amount of the bismaleimide compound represented by the general formula (II) is preferably at least 1 part by weight based on 100 parts by weight of the resin composition in order to sufficiently improve Tg and adhesiveness. . In order to sufficiently improve thermal stability at high temperatures, mechanical strength, and low water absorption, the content is preferably 80 parts by weight or less. For the same reason, the resin composition 10
The amount is preferably 5 to 60 parts by weight, more preferably 10 to 50 parts by weight, based on 0 parts by weight.

Examples of the other organic compounds include m-phenylenediamine, p-phenylenediamine, and 4,4 '.
-Diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfone, bis (4-aminophenyl) methylphosphine oxide, bis (4- Aromatic diamines such as aminophenyl) phosphine oxide and bis (4-aminophenyl) methylamine, diglycidyl ether of bisphenol A, 3,4-epoxycyclohexylmethyl-3,4-
Epoxycyclohexanecarboxylate, 4,4'-
(1,2-epoxyethyl) biphenyl, 4,4'-
(1,2-epoxyethyl) biphenyl ether, resorcin diglycidyl ether, bis (2,3-epoxycyclopentyl) ether, N, N'-m-phenylenebis (4,5'-epoxy-1,2-cyclohexanedi Bifunctional epoxy compounds such as carbodiimide), triglycidyl compounds of p-aminophenol, 1,3,5-
Contains a halogen atom such as tri (1,2-epoxyethyl) benzene, tetraglycidoxytetraphenylethane, phenol formaldehyde novolak resin or other trifunctional or higher functional epoxy compound, epoxy compound having hydantoin skeleton, or brominated epoxy compound. Epoxy compounds such as epoxy compounds, butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber,
Elastomers such as isoprene rubber, acrylic rubber, acrylonitrile-acryl rubber, hydrogenated butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, epoxy-modified butadiene rubber, carboxy-modified butadiene rubber, epoxy-modified acrylonitrile-acryl rubber, carboxy-modified acrylonitrile-acryl rubber, etc. Is mentioned.

The above-mentioned other inorganic compounds include silica, alumina, calcium carbonate and the like, and these may be used alone or in combination of two or more.

The above other organic compound and other inorganic compound are contained in an amount of 0 to 95 parts by weight based on 100 parts by weight of the whole resin composition.
Preferably, it is blended in an amount of 0 to 30 parts by weight.

An anisotropic conductive adhesive may be prepared by blending a conductive substance such as silver powder, copper powder, silver or copper-plated plastic powder.

The resin composition of the present invention can be used by dissolving it in an organic solvent. Examples of the organic solvent include methylcellosolve, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, quinoline, cyclopentanone, m-
Cresol, chloroform, diethylene glycol dimethyl ether and the like can be mentioned, and these are used alone or in combination of two or more. From the viewpoint of solubility of the resin composition, N-methyl-2-pyrrolidone, quinoline, cyclopentanone,
m-Cresol, chloroform and diethylene glycol dimethyl ether are preferred, and N-methyl-2-pyrrolidone, cyclopentanone and diethylene glycol dimethyl ether are particularly preferred from the viewpoint of safety.

The composition obtained by dissolving the above resin composition in an organic solvent is coated on a support film, the organic solvent is removed by heating or the like, and the adhesive film or the like is removed by peeling off the support film. Obtainable. The thickness of the adhesive film is preferably 3 to 75 μm.

By heating and curing the resin composition and the adhesive film of the present invention, a cured product and a crosslinked film can be obtained. The heating temperature is not particularly limited, but is preferably 100 ° C. or higher to shorten the curing time,
500 ° C to prevent thermal deterioration of cured product and crosslinked film
It is preferable to set the following. 150-40 for similar reasons
The temperature is more preferably 0 ° C, particularly preferably 180 to 350 ° C.

For the purpose of low-temperature curing and short-time curing, a reaction accelerator such as an organic peroxide or a metal salt of an organic acid such as copper acetylacetonate can be added to the above resin composition, if necessary. is there.

[0043]

EXAMPLES The present invention will be described below in detail with reference to examples, but is not intended to limit the scope of the present invention.

Synthesis Example 1 (Synthesis of polyquinoline) 6,6'-bis [2- (4 "-fluorophenyl) -4
-Phenylquinoline] 74.3 g (0.124 mol,
1.03 equivalents), 4,4 '-(1,1,1,3,3,3
-Hexafluoro-2,2-propylidene) bisphenol 40.6 g (0.121 mol, 1.00 equivalent), anhydrous potassium carbonate 25 g (0.181 mol, 1.5 equivalent)
Was added to a 1-liter stainless steel flask, and 450 ml of N-methyl-2-pyrrolidone and 90 ml of toluene were further added as solvents. A water-cooled cooling tube equipped with a calcium chloride tube and a Dean-Stark tube for removing water, a dry nitrogen introduction tube, a mechanical stirrer, and a thermometer were installed. The mixture was heated under reflux for 24 hours using an oil bath, and water in the system was distilled off together with toluene for 24 hours. The solution was initially yellow, but gradually turned brown and black at this stage. Further, when the reaction temperature is 2
The temperature was raised to 00 ° C., and the reaction was performed for 6 hours. The reaction solution changed from black to deep blue as the viscosity increased. The reaction was stopped by adding 650 ml of N-methyl-2-pyrrolidone for dilution and cooling. The obtained polymer solution was poured into water and precipitated for purification.
Subsequently, washing and stirring in water at 50 ° C. for 2 hours were repeated three times, then, the polymer was separated by filtration and dried in a vacuum dryer at 60 ° C. all day and night. The polymer yield was 101.
1 g (89.0%). Its number average molecular weight was 45,000 in terms of polystyrene, and weight average molecular weight was 87,000 in terms of polystyrene.

The obtained polymer has a repeating unit represented by the following formula (V).

[0046]

Embedded image Synthesis Example 2 (Synthesis of polyquinoline) 6,6'-bis [2- (4 ") was placed in a 2 liter round bottom three-necked flask equipped with a mechanical stirrer, a Dean-Stark tube equipped with a condenser and a nitrogen inlet tube, and a thermometer. −
Fluorophenyl) -4-phenylquinoline] 114.
75 g (0.9225 mol, 1.03 equivalent), 9,9-
Bis (4-hydroxyphenyl) fluorene 66.04
72 g (0.18848 mol, 1.00 equivalent), potassium carbonate 39.1 g (0.28 mol, 1.5 equivalent), N-
Methyl-pyrrolidone 705 ml, toluene 42
1 ml was charged. The reaction mixture was heated under a nitrogen atmosphere for 15 hours. The toluene was removed via a Dean-Stark tube and the reaction mixture was heated at 200 ° C. for a further 12 hours. Then the reaction mixture was diluted with N-methyl-pyrrolidone and cooled to room temperature. The polymer was condensed by slowly pouring the resulting polymer solution into three volumes of acetone. The polymer was collected by filtration, dissolved in N-methyl-pyrrolidone and condensed with three volumes of water. The polymer was recovered and dried under vacuum at 130 ° C. for 12 hours. The polymer yield was 170 g (99%). Its number average molecular weight was 46,900 in terms of polystyrene, and its glass transition temperature was about 306 ° C.

The obtained polymer has a repeating unit represented by the following formula (VI).

[0048]

Embedded image Examples 1 to 8 To a resin composition having the composition shown in Table 1, 233 parts by weight of cyclopentanone was added as a solvent and uniformly mixed and dissolved at room temperature.

The varnish was coated with a 0.050 mm thick polyimide film (upilex 5 manufactured by Ube Industries, Ltd.).
0SGA) using a comma coater and apply evenly.
Heat drying was performed at 0 ° C. for 10 minutes and at 170 ° C. for 10 minutes to remove cyclopentanone. Thereafter, the obtained coating film was peeled off from the polyimide film to obtain an adhesive film having a thickness of 25 μm.

Example 9 To a resin composition having the composition shown in Table 1, 233 parts by weight of m-cresol was added as a solvent and uniformly mixed and dissolved at room temperature.

The varnish was uniformly applied to a 0.050 mm-thick polyimide film (UPILEX 50SGA) using a comma coater.
The solution was dried by heating at 10 ° C. for 10 minutes to remove cyclopentanone.
Thereafter, the obtained coating film was peeled off from the polyimide film to obtain an adhesive film having a thickness of 25 μm.

Comparative Example 1 To a resin composition having the composition shown in Table 2, 567 parts by weight of cyclopentanone was added as a solvent and uniformly mixed and dissolved at room temperature.

This varnish was uniformly applied to a 0.050 mm-thick polyimide film (UPILEX 50SGA) using a comma coater, and heated at 100 ° C. for 10 minutes at 170 ° C.
The solution was dried by heating at 10 ° C. for 10 minutes to remove cyclopentanone.
Thereafter, the obtained coating film was peeled off from the polyimide film to obtain an adhesive film having a thickness of 25 μm.

Comparative Example 2 To a resin composition having the composition shown in Table 2, 567 parts by weight of m-cresol was added as a solvent and uniformly mixed and dissolved at room temperature.

The varnish was uniformly applied to a 0.050 mm-thick polyimide film (UPILEX 50SGA) using a comma coater, and the coating was performed at 100 ° C. for 10 minutes at 170 ° C.
The solution was dried by heating at 10 ° C. for 10 minutes to remove cyclopentanone.
Thereafter, the obtained coating film was peeled off from the polyimide film to obtain an adhesive film having a thickness of 25 μm.

The adhesive films obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were pressed against copper, and the peel strength after heating at 280 ° C. for 2 hours was measured. Further, the adhesive film was heated in a dryer at 280 ° C. for 2 hours to obtain a cured film.
The relative permittivity at 1 MHz, dielectric loss tangent,
The glass transition temperature, 5% weight loss temperature, and solvent resistance were measured. The measured values are shown in Tables 3 and 4. Characteristic evaluation was based on the following method. -Peel strength: The adhesive film was pressure-bonded to copper at 300 ° C, 3 MPa, and 3 seconds, and further cured at 280 ° C for 2 hours, and then the peel strength was measured. Fluidity: The fluidity of the adhesive layer when the adhesive film was adhered to copper at 300 ° C., 3 MPa, and 3 seconds was evaluated.

[0057] ・ Relative permittivity, dielectric loss tangent: 1 MHz, relative permittivity at room temperature,
The dielectric loss tangent was measured. -Glass transition temperature: Dynamic viscoelasticity was measured using DVE Rheospectral (manufactured by Rheology), and Tg (glass transition temperature) was examined. , 5% weight loss temperature: Using a TG / DTA (manufactured by Seiko Denshi) was measured Td ⁵ (5% weight reduction temperature). Solvent resistance: The state after immersion in cyclopentanone at room temperature for 20 minutes was visually evaluated.

[0058] In the following, PQ1 is the polyquinoline resin obtained in Synthesis Example 1, PQ2 is the polyquinoline resin obtained in Synthesis Example 2, BC is 2,2'-di (4-cyanatophenyl) propane, and MC is di (4- Cyanato-3,5-dimethylphenyl) methane, FC is 2,2'-di (4-cyanatophenyl) hexafluoropropane, LC is di (4-cyanatophenyl) ethane, and XC is 4,4 '-[ 1,3-phenylenebis (1-methyl-ethylidene)] bisphenol cyanate, BMI is bis (4-maleimidophenyl) methane, BBMI is 2,2-bis [(4-maleimidophenoxy) phenyl] propane, AACu is copper Shows acetylacetonate.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

[Table 4] From the results of Examples 1 to 9 and Comparative Examples 1 and 2, it is clear that the adhesion, the fluidity and the solvent resistance are improved by blending the cyanate compound with the polyquinoline resin.

[0063]

The resin composition and the adhesive film of the present invention are excellent in adhesiveness, moldability, electrical properties, heat resistance, solvent resistance, mechanical properties and low water absorption, and are used for adhesives and interlayer insulation of electronic parts. It is suitably used for films and the like.

Claims (7)

[Claims] 1 to 99.9 parts by weight of a polyquinoline resin and 0.1% by weight of a cyanate compound represented by the following general formula (I):
1 to 99 parts by weight and another organic or inorganic compound 0
A resin composition prepared by mixing 95 parts by weight so that the total amount is 100 parts by weight. Embedded image [However, in the general formula (I), Ar ¹ is an n-valent organic group containing at least two carbons, and n is an integer of 2 or more. ] 2. A polyquinoline resin (1 to 99.8 parts by weight) and a cyanate compound (1) represented by the following general formula (I):
98 parts by weight, 0.1 to 95 parts by weight of a bismaleimide compound represented by the following general formula (II) and 0 to 95 parts by weight of another organic or inorganic compound are blended so that the total amount becomes 100 parts by weight. The resin composition according to claim 1. Embedded image [However, in the general formula (I), Ar ¹ is an n-valent organic group containing at least two carbons, and n is an integer of 2 or more. ] [However, in the general formula (II), Ar ² is a divalent organic group containing at least two carbons. ] 3. A polyquinoline resin (1 to 99.9 parts by weight) and a cyanate compound (0.1 to 0.1) represented by the following general formula (I):
99 parts by weight and other organic or inorganic compounds 0 to 95
A composition obtained by dissolving a resin composition prepared by mixing 100 parts by weight of a resin part in an organic solvent. Embedded image [However, in the general formula (I), Ar ¹ is an n-valent organic group containing at least two carbons, and n is an integer of 2 or more. ] 4. A polyquinoline resin in an amount of 1 to 99.8 parts by weight and a cyanate compound represented by the following general formula (I):
98 parts by weight, 0.1 to 95 parts by weight of a bismaleimide compound represented by the following general formula (II) and 0 to 95 parts by weight of another organic or inorganic compound are blended so that the total amount becomes 100 parts by weight. A resin composition obtained by dissolving the resin composition in an organic solvent. Embedded image [However, in the general formula (I), Ar ¹ is an n-valent organic group containing at least two carbons, and n is an integer of 2 or more. ] [However, in the general formula (II), Ar ² is a divalent organic group containing at least two carbons. ] 5. A resin composition obtained by removing an organic solvent from the composition according to claim 3 or 4. 6. A cured product obtained by heating and curing the resin composition according to claim 5. 7. An adhesive film using the resin composition according to claim 5.