JPH06345964A - Heat-resistant thermosetting resin composition, adhesive sheet, adhesive-backed polyimide film, and metal-foil-clad polyimide film - Google Patents

Abstract

PURPOSE:To obtain a resin composition which cures at a low temp. to give a cured adhesive layer with good heat resistance and is useful as a heat-resistant adhesive by mixing a specific polyimide with a specific polymaleimide and an epoxy resin. CONSTITUTION:A polyimide containing units represented by formula I [wherein 1-40wt.% of the Ar's are represented by formula II (where R is a divalent hydrocarbon residue; R1 to R4 each is a lower alkyl or phenyl; and (l) is 5-30) and 99-60mol% thereof are represented by formula III (where Z is C(=O), SO2, O, S, (CH2)m, NHC(=O), C(CH3)2, etc.; (n) and (m) each is an integer of 1 or larger; and the benzene rings are optionally substituted) or formula IV (where R5 to R8 each is H, a 1-4C alkyl, or an alkoxy and X is CH2, C(CH3)2, O, SO2, etc.)] is mixed with a polymaleimide represented by formula V (wherein k>=2 and R9 is a 2C or higher group having a valence of (k)) and an epoxy resin to obtain the objective composition. This composition can cure at 180 deg.C or lower to give a cured adhesive layer with good heat resistance. It is useful as a heat-resistant adhesive for use in producing a flexible printed circuit board or a thin laminate.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyimide resin composition which can be adhesively cured at a low temperature. The resin composition of the present invention is applied to a printed circuit board, TAB (Tape Automat).
ed Bonding) tape, composite lead frame
It is useful as a thermosetting adhesive having excellent heat resistance, which can be used for rubber, laminated materials and the like.

[0002]

2. Description of the Related Art Acrylic, phenolic, epoxy, polyimide, and other adhesives are known as insulating adhesives for electronic materials. Hot melt adhesives are also used for such applications.

[0003]

However, acrylic, phenolic, and epoxy adhesives are excellent in adhesiveness but inferior in heat resistance. The hot-melt adhesive has a high bonding temperature of around 300 ° C and is restricted by the adherend and the heating device. Since it is a hot-melt adhesive, when it is exposed to high temperature again after bonding, the adhesive softens and maintains its strength. Absent. The polyimide adhesive is 275 ° C for bonding,
It requires high temperature and high pressure of 5 MPa. The present invention provides a thermosetting resin composition which is excellent in heat resistance and adhesiveness and can be adhered at a low temperature of 180 ° C. or lower, and an application product of the thermosetting resin composition as an adhesive.

[0004]

DISCLOSURE OF THE INVENTION The present invention comprises a polyimide containing a constitutional unit represented by the general formula 6, a polymaleimide represented by the general formula 10 and an epoxy resin. Resin composition.

[0005]

[Chemical 6] (In the general formula 6, Ar is a group represented by the general formula 7, 8, or 9, and the group represented by the general formula 1 is 1 to 40.
Mol%, the group represented by the general formula 8 or 9 is 99 to 60
Mol%)

[0006]

[Chemical 7] (In the general formula 7, R represents a divalent hydrocarbon residue,
R ₁ , R ₂ , R ₃ , and R ₄ represent a lower alkyl group or a phenyl group, and l represents an integer of 5 to 30).

[0007]

[Chemical 8] (In general formalized 8, Z is -C (= O) -, - SO 2 -, -
O -, - S -, - (CH 2) m -, - NHC (= O) -,
_{-C (CH 3) 2 -,} - C (CF 3) 2 -, - C (= O) O
-Or a bond, n and m are integers of 1 or more, a plurality of Zs may be the same or different, and hydrogen of each benzene ring may be appropriately substituted with a substituent).

[0008]

[Chemical 9] (In the general formula 9, R ₅ , R ₆ , R ₇ , and R ₈ each independently represent hydrogen or an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and at least two or more of them are alkyl groups. Or an alkoxy group, X is —CH ₂ —, —
_{C (CH 3) 2 -,} - O -, - SO 2 -, - C (= O)
-, -NHC (= O)-is shown)

[0009]

[Chemical 10] (In general formula 10, k is an integer of 2 or more, and R ₉ is k
Indicates a group having a valence of 2 or more carbon atoms

In the general formula 8, the substituent that may be bonded to the benzene ring is a lower alkyl group such as a methyl group, an ethyl group or an isopropyl group, an alkoxy group such as a methoxy group or an ethoxy group, Fluorine-substituted alkyl groups such as trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, etc. and halogen elements such as fluorine, chlorine, bromine, etc., and these substituents When there are two or more, they may be the same or different.

The group represented by the general formula 8 has the general formula 11

[0012]

[Chemical 11] (In general formula 11, Z ₁ , Z ₂ and Z ₃ are each independently —SO ₂ —, —O—, —C (═O) — or —C (CH ₃ ).
_The group represented by (indicated by _2- ) is particularly preferable because the cured product obtained from the composition with maleimide described below has excellent solvent resistance.

The polyimide of the present invention is 3,3 ', 4,4.
It can be produced by reacting 4′-benzophenone tetracarboxylic acid dianhydride with the compound represented by the general formula 12 and the compounds represented by the general formulas 13 and 14.

[0014]

[Chemical 12] (In general formula 12, R, R ₁ , R ₂ , R ₃ , R ₄ and l are the same as in general formula 7, and Y represents an amino group.)

[0015]

[Chemical 13] (In the general formula 13, Z, n and m are the same as those in the general formula 8, Y represents an amino group or an isocyanate group, and hydrogen of each benzene ring is bonded to the benzene ring in the general formula 8. Optionally substituted with the substituents exemplified as the optional substituents)

[0016]

[Chemical 14] (In the general formula 14, R ₅ , R ₆ , R ₇ , R ₈ and X are the same as those in the general formula 9, and Y represents an amino group or an isocyanate group.)

In the above reaction, as an acid dianhydride,
Acid dianhydrides other than 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride may be used in combination as long as the object of the present invention is not impaired. Examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3.
3'-biphenyltetracarboxylic dianhydride, 3,
3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-diphenyloxytetracarboxylic dianhydride, 4,4 '-[2,2,2-trifluoro -1- (trifluoromethyl) ethylidene] bis (1,2-benzenedicarboxylic acid anhydride), ethylene bis trimellitate dianhydride, catechol bis trimellitate dianhydride, resorcinol bis trimellitate dianhydride, dihydroxybenzene bistri anhydride Melitate dianhydride, bisphenol A bis trimellitate dianhydride,
There are tetrachlorobisphenol A bis trimellitate dianhydride, tetrabromobisphenol A bis trimellitate dianhydride, biphenyl bis trimellitate dianhydride and the like. These are preferably used in 30 mol% or less so as not to exceed 50 mol% with respect to the total amount of the acid dianhydride.

The compounds represented by the general formula 12 include the following compounds. ω, ω'-bis (3-
Aminopropyl) polydimethylsiloxane, ω, ω'-
Bis (3-aminobenzyloxy) polydimethylsiloxane, ω, ω′-bis (4-aminobenzyloxy) polydimethylsiloxane, ω, ω′-bis [3- (3-aminobenzyloxy) propyl] polydimethylsiloxane , Ω, ω'-bis-3- (4-aminobenzyloxy)
Propyl] polydimethylsiloxane, ω, ω′-bis (3-aminopropyl) polydiphenylsiloxane,
ω, ω'-bis (3-aminobenzyloxy) polydiphenylsiloxane, ω, ω'-bis (4-aminobenzyloxy) polydiphenylsiloxane, ω, ω'-bis [3- (3-aminobenzyloxy) Propyl] polydiphenylsiloxane, ω, ω'-bis-3- (4-aminobenzyloxy) propyl] polydiphenylsiloxane.

Among the compounds represented by the above general formula 13, those in which Y is an amino group include the following compounds.

4,4'-bis (3-aminocumyl) benzene, 4,3'-bis (3-aminocumyl) benzene,
3,3'-bis (3-aminocumyl) benzene, 4,
4'-bis (3-aminophenoxy) benzene, 4,
3'-bis (3-aminophenoxy) benzene, 3,
3'-bis (3-aminophenoxy) benzene, bis [4- (3-aminophenoxy) phenyl] sulfone,
Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl]
Ketone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2, 2-bis [4-
(4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxyphenyl) hexafluoropropane, bis [4- (4-aminophenoxyphenyl) hexafluoropropane, bis [4- (3-aminobenzoyl) Phenyl] sulfone, bis [4- (4-aminobenzoyl) phenyl] sulfone, bis [4- (3
-Aminobenzoyl) phenyl] ketone, bis [4-
(4-Aminobenzoyl) phenyl] ketone, bis [4
-(3-aminobenzoyl) phenyl] ether, bis [4- (4-aminobenzoyl) phenyl] ether,
2,2-bis [4- (3-aminobenzoyl) phenyl] propane, 2,2-bis [4- (4-aminobenzoyl) phenyl] propane, bis [4- (3-aminophenylsulfonyl) phenyl] ether , Screw [4-
(4-Aminophenylsulfonyl) phenyl] ether, bis [3- (3-aminophenylsulfonyl) phenyl] sulfone, bis [3- (3-aminophenylsulfonyl) phenyl] ketone, 2,2-bis [4- ( 3-
Aminophenylsulfonyl) phenyl] propane, 2,
2-bis [4- (4-aminophenylsulfonyl) phenyl] propane, bis [3- (3-aminophenoxy)
Phenyl] ether, bis [3- (3-aminobenzoyl) phenyl] sulfone, bis [3- (3-aminobenzoyl) phenyl] ketone, bis [3- (3-aminobenzoyl) phenyl] ether, bis [3- (3-Aminophenylsulfonyl) phenyl] ether, 2,2-
Bis [3- (3-aminophenoxy) phenyl] propane, 4,4′-bis [3- (4-amino-α, α′-dimethylbenzyl) phenoxy] diphenylsulfone,
4,4'-bis [3- (4-amino-α, α'-dimethylbenzyl) phenoxy] benzophenone, 4,4'-
Bis [4- (4-amino-α, α′-dimethylbenzyl) phenoxy] diphenyl sulfone, 4,4′-bis [4- (4-amino-α, α′-dimethylbenzyl) phenoxy] benzophenone, 4- [3- (4-amino-
α, α'-Dimethylbenzyl) phenoxy] -4'-
[4- (4-amino-α, α'-dimethylbenzyl) phenoxy] diphenyl sulfone, 4- [3- (4-amino-α, α'dimethylbenzyl) phenoxy] -4'-
[4- (4 amino-α,α'-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [3- (3 amino-α,α'-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4'- Bis [3- (3 amino-
α, α′-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [2- (4 amino-α,α′-dimethylbenzyl) phenoxy] diphenylsulfone,
4,4′-bis [2- (4 amino-α,α′-dimethylbenzyl) phenoxy] benzophenone, 3,3′-bis [3- (4 amino-α,α′-dimethylbenzyl) phenoxy] diphenylsulfone , 3,3'-bis [3-
(4 amino-α, α'-dimethylbenzyl) phenoxybenzophenone.

Among the compounds represented by the above general formula 13, those in which Y is an isocyanate group include the diamines exemplified above in which an amino group is replaced with an isocyanate group. Some examples are given below.

Diphenylmethane diisocyanate, toluylene diisocyanate, 4,4'-bis [3- (4-
Isocyanate-α, α'-dimethylbenzyl) phenoxy] diphenyl ketone, 4,4'-bis [3- (4-
Isocyanate-α, α'-dimethylbenzyl) phenoxy] diphenyl sulfone.

Among the compounds represented by the above general formula 14, those in which Y is an amino group include the following compounds.

4,4'-diamino-3,3 ', 5,5'
-Tetramethyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3', 5,5'-tetra-n-propyldiphenylmethane, 4, 4'-diamino-
3,3 ', 5,5'-tetraisopropyldiphenylmethane, 4,4'-diamino-3,3', 5,5'-tetrabutyldiphenylmethane, 4,4'-diamino-3,
3'-dimethyl-5,5'-diethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,
5'-diisopropyldiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-diisopropyldiphenylmethane, 4,4'-diamino-3,5-dimethyl-3 ', 5'-diethyldiphenylmethane, 4,
4'-diamino-3,5-dimethyl-3 ', 5'-diisoprobi-diphenylmethane, 4,4'-diamino-
3,5-diethyl-3 ', 5'-diisopropyldiphenylmethane, 4,4'-diamino-3,5-diethyl-
3 ', 5'-dibutyldiphenylmethane, 4,4'-diamino-3,5-diisopropyl-3', 5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-
Diisopropyl-5,5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,
5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino- 3,3'-diethyldiphenylmethane, 4,4'-diamino-3,3'-
Di-n-propyldiphenylmethane, 4,4'-diamino-3,3'-diisopropyldiphenylmethane, 4,
4'-diamino-3,3'-dibutyldiphenylmethane, 4,4'-diamino-3,3 ', 5-trimethyldiphenylmethane, 4,4'-diamino-3,3', 5-
Triethyldiphenylmethane, 4,4'-diamino-
3,3 ′, 5-tri-n-propyldiphenylmethane,
4,4'-diamino-3,3 ', 5-triisopropyldiphenylmethane, 4,4'-diamino-3,3', 5
-Tributyldiphenylmethane, 4,4'-diamino-
3-methyl-3'-ethyldiphenylmethane, 4,4 '
-Diamino-3-methyl-3'-isopropyldiphenylmethane, 4,4'-diamino-3-ethyl-3'-n
-Propyldiphenylmethane, 4,4'-diamino-3
-Ethyl-3'-isopropyldiphenylmethane, 4,
4'-diamino-3-isopropyl-3'-butyldiphenylmethane, 4,4'-diamino-2,2'-bis (3,3 ', 5,5'-tetramethyldiphenyl) isopropane, 4,4'-Diamino-2,2'-bis (3,3
3 ', 5,5'-tetraethyldiphenyl) isopropane, 4,4'-diamino-2,2'-bis (3,3',
5,5'-tetra-n-propyldiphenyl) isopropane, 4,4'-diamino-2,2'-bis (3,3 ',
5,5'-tetraisopropyldiphenyl) isopropane, 4,4'-diamino-2,2'-bis (3,3 ',
5,5′-tetrabutyldiphenyl) isopropane,
4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenyl ether, 4,4'-diamino-3,
3 ', 5,5'-tetraethyldiphenyl ether,
4,4'-diamino-3,3 ', 5,5'-tetra n-
Propyl diphenyl ether, 4,4'-diamino-
3,3 ', 5,5'-tetraisopropyl diphenyl ether, 4,4'-diamino-3,3', 5,5'-tetrabutyl diphenyl ether, 4,4'-diamino-
3,3 ', 5,5'-tetramethyldiphenyl sulfone, 4,4'-diamino-3,3', 5,5'-tetraethyldiphenyl sulfone, 4,4'-diamino-3,
3 ', 5,5'-tetra-n-propyldiphenyl sulfone, 4,4'-diamino-3,3', 5,5'-tetraisoprobyl diphenyl sulfone, 4,4'-diamino-3,3 ', 5,5'-tetrabutyldiphenyl sulfone, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenyl ketone, 4,4'-diamino-3,
3 ', 5,5'-tetraethyldiphenylketone, 4,
4'-diamino-3,3 ', 5,5'-tetra n-propyl diphenyl ketone, 4,4'-diamino-3,
3 ', 5,5'-tetraisopropyldiphenylketone, 4,4'-diamino-3,3', 5,5'-tetrabutyldiphenylketone, 4,4'-diamino-3,
3 ', 5,5'-tetramethylbenzanilide, 4,
4'-diamino-3,3 ', 5,5'-tetraethylnesanilide, 4,4'-diamino-3,3', 5,5 '
-Tetra n-propylbenzanilide, 4,4'-diamino-3,3 ', 5,5'-tetraisopropylbenzanilide, 4,4'-diamino-3,3', 5,5'-tetrabutylbenz Anilid.

Among the compounds represented by the above general formula 14, those in which Y is an isocyanate group include the diamines exemplified above in which the amino group is replaced with an isocyanate group.

The compound represented by the general formula 13 and another diamine or diisocyanate, and the compound represented by the general formula 14 and another diamine or diisocyanate may be used in combination within the range not impairing the object of the present invention. In this case, the amount of the other diamine or diisocyanate is preferably 30 mol% or less based on the total amount of the reaction partners of the acid dianhydride.

Examples of such diamines include diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl ketone, diaminodiphenylpropane, phenylenediamine, toluylenediamine, diaminodiphenylsulfone, diaminodiphenylhexafluoropropane, diaminodialkyldiphenylmethane, and the like. Examples of the diisocyanate include those in which the amino group of the diamine is replaced with an isocyanate group.

The compounds represented by the general formula 12 and the compounds represented by the general formula 13 and the general formula 14 are represented by the general formula 1
1 to 40 mol% of the compound represented by 2, preferably 5 to
20 mol%, the total of both compounds represented by general formulas 13 and 14 is 99 to 60 mol%, preferably 50 to 70 mol% of the compound represented by general formula 13, The compound represented by is used in an amount of 45 to 10 mol%.

When the acid dianhydride and diamine are reacted, the polyimide represented by the general formula 6 is produced, for example, as follows.

Acid dianhydride and diamine in an organic solvent, if necessary, in the presence of a catalyst such as tributylamine, triethylamine and triphenyl phosphite, at 100 ° C. or higher,
Preferably, it is heated to 180 ° C. or higher to directly form a polyimide. The catalyst is preferably used in an amount of 0 to 15% by weight, more preferably 0.01 to 15% by weight, based on the total amount of the reaction components.

The acid dianhydride and the diamine are mixed in an organic solvent to give 10
A varnish of polyamic acid, which is a precursor of polyimide, is produced by reacting at a temperature lower than 0 ° C., and then the varnish is heated to imidize, or an acid anhydride such as acetic anhydride, propionic anhydride, or benzoic anhydride. Acids or carbodiimide compounds, for example, a ring-closing agent such as dicyclohexylcarbodiimide and, if necessary, a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole, etc. to form a polyimide by chemical ring-closing (imidization). . The ring-closing agent and the ring-closing catalyst are preferably used in the range of 1 to 8 mol per mol of the acid anhydride.

As the organic solvent, N-methyl-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-2-
Aprotic polar solvent such as imidazolidone, phenol
A phenol-based solvent such as phenol, cresol, xylenol or p-chlorophenol is used. In addition, benzene, toluene, xylene, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, methanol, ethanol, isopropanol, chloride Of the methylene, chloroform, trichloroethylene, tetrachloroethane, etc., those that dissolve the raw material monomer and the polyimide or the polyamic acid may be used, or even those that do not dissolve the raw material monomer and the polyimide or the polyamic acid, the solubility You may mix and use it in the range which does not impair.

The polyimide and its precursor polyamic acid can also be produced by a solid phase reaction or a melting reaction at 300 ° C. or lower.

In order to produce a polyimide represented by the general formula (6) by reacting an acid dianhydride with a diisocyanate, the acid dianhydride is reacted with a diamine to directly obtain a polyimide. It can be performed according to. However, it is sufficient that the reaction temperature is room temperature or higher, particularly 60 ° C. or higher.

Most preferably, the acid dianhydride and its reaction partner are reacted in approximately equimolar amounts, but one of them may be in excess, up to 10 mol%, particularly preferably 5 mol%.

As the polymaleimide to be added to the polyimide represented by the general formula 6, there are the following compounds,
These may be used alone or in combination of two or more.

N, N '-(4,4'-diphenylmethane) bismaleimide, N, N'-(4,4'-diphenyloxy) bismaleimide, N, N'-p-phenylene bismaleimide, N, N '-M-phenylene bismaleimide, N, N'-2,4-tolylene bismaleimide,
N, N'-2,6-tolylene bismaleimide, N, N '
-Ethylene bismaleimide, N, N '-[4,4'-
[2,2'-bis (4,4'-phenoxyphenyl) isopropylidene]] bismaleimide, N, N '-[4
4 '-[2,2'-bis (4,4'-phenoxyphenyl) hexafluoroisopropylidene]] bismaleimide, N, N'-[4,4'-bis (3,5-dimethylphenyl) methane ] Bismaleimide, N, N '-[4,
4′-bis (3,5-diethylphenyl) methane] bismaleimide, N, N ′-[4,4 ′-(3-methyl-5)
-Ethylphenyl) methane] bismaleimide, N, N '
-[4,4-bis (3,5-diisopropylphenyl)
Methane] bismaleimide, a maleimide represented by Chemical formulas 15 to 20.

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

[0042]

[Chemical 19]

[0043]

[Chemical 20] (In the chemical formula 18, r is an integer of 1 or more.)

Further, as the epoxy resin to be blended with the polyimide represented by the general formula 6, there are the following epoxy compounds having an average of two or more epoxy groups per molecule, and these may be used alone or in combination of two or more. Used as a mixture. Bisphenol-based epoxy resin, halogenated bisphenol-based epoxy resin, phenol novolac-based epoxy resin, halogenated phenol novolac-based epoxy resin, alkylphenol novolac-based epoxy resin,
Polyphenol epoxy resin, polyglycol epoxy resin, cycloaliphatic epoxy resin.

The mixing ratio of the polyimide represented by the general formula 6 and the thermosetting component, that is, polymaleimide and epoxy resin, is 10 to 6 with respect to the polyimide.
It is preferably 0% by weight, and more preferably 30 to 50% by weight. 10% by weight of thermosetting component
If the amount is less, the curing will not be sufficient, and if the amount is more than 60% by weight, the resin composition will become brittle and cannot be molded.

The ratio of the polymaleimide to the epoxy resin in the thermosetting component is optional, but in order to cure the resin composition of the present invention at 180 ° C. or lower, the epoxy resin is preferably 20% by weight or more. More preferably, the epoxy resin is 40 to 80% by weight.

180 of polymaleimide and epoxy resin
If necessary, a curing agent and a curing accelerator are used in order to carry out a curing reaction at a temperature of not higher than ° C. As the curing agent for curing the polymaleimide, there are the following diamines.

4,4'-diaminodiphenyl ether,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4- Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3-methyl-
4- (4-aminophenoxy) phenyl] butane, 2,
2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] butane, 1,1, 1,3,3,3-hexafluoro-2,2
-Bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, bis [4 -(3-aminophenoxy) phenyl] sulfone, 4,4'-carbonylbis (p-phenyleneoxy) dianiline, 4,4 '
-Bis (4-aminophenoxy) biphenyl, metaphenylenediamine, hexamethylenediamine, tetramethylenediamine.

Among these, 2,2-bis [4-
(4-Aminophenoxy) phenyl] propane is preferred. Mixtures of the above diamines may be used if desired.

The curing accelerators for polymaleimide include the following peroxides.

T-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydro-oxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,
5-Dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexyne-3.

Of these, dicumyl peroxide is preferred.

The epoxy resin curing agent is not particularly limited as long as it is one generally used as an epoxy resin curing agent such as dicyandiamide, polyphenols and acid anhydrides. Further, the curing accelerator is also 2-methylimidazole, 2-methyl-4-ethylimidazole,
Imidazoles such as 2-undecylimidazole and 2-heptadecylimidazole and their derivatives, diethylamine, triethylamine, monoethanolamine,
Amines such as diethanolamine, BF ₃ -amine complex and the like can be used and are not particularly limited.

It is convenient that the resin composition of the present invention is molded into a sheet beforehand and used as a sheet adhesive. Further, the resin composition of the present invention is impregnated into a glass cloth, a glass mat, an aromatic polyamide fiber cloth, an aromatic polyamide fiber mat, etc. as a varnish, and the resin is semi-cured to form a fiber-reinforced sheet adhesive. It can also be used.

The resin composition of the present invention may be used as a varnish, which may be applied to an adherend as it is, dried, and heated and pressed to adhere to another adherend. Temperature 100-250 ° C, Pressure 0.1-1
It is preferable to heat and pressurize at 0 MPa for 20 minutes or more. Particularly, at a temperature of 150 to 200 ° C. and a pressure of 1 to 3 MPa, 60 to
It is more preferable to heat and press for 90 minutes.

The resin composition of the present invention is used as a varnish, and the varnish is applied to one side or both sides of a polyimide film and dried to obtain a polyimide film with an adhesive layer. It is useful for manufacturing printed circuit boards, TAB tapes, and the like. In addition, a polyimide film with a double-sided adhesive layer is adhered to printed circuit boards or to a printed circuit board and a metal foil, for example, a copper foil, an aluminum foil, or a 42 alloy foil, to form a thin film multilayer circuit board or a metal composite board. Can be manufactured.

The adhesive varnish of the present invention is coated on one side with a metal foil, and the polyimide film is coated on the surface of the polyimide film with no metal foil stretched. It is particularly useful for manufacturing a thin film multilayer circuit board, a composite lead frame and the like by heating and pressing the circuit board and 42 alloy foil.

[0058]

【Example】

Example 1 A four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube was charged with bis (4- (3-aminophenoxy)).
162 g (0.375 mol) of phenyl) sulfone and 9.15 g (0.025 mol) of 4,4′-methylenebis (2,6-diisopropylaniline) and ω, ω′-
Bis (3-aminopropyl) polydimethylsiloxane (n average 15.6, average molecular weight 1592) 159.2
g (0.1 mol) was added, and 991 g of a mixed solvent of N, N-dimethylformamide and diethylene glycol dimethyl ether at a ratio of 2/1 (weight ratio) was added and dissolved in a nitrogen atmosphere. To this solution was added 161 g (0.5 mol) of 3,3 ′, 4,4-benzophenonetetracarboxylic dianhydride.
Was added, taking care that the temperature does not exceed 30 ° C.

Thereafter, the mixture was stirred at room temperature for 3 hours, 330 g of N, N-dimethylformamide was added to dilute, 128 g of acetic anhydride and 99 g of pyridine were added, and then 30
The mixture was stirred at 0 ° C for 5 hours. The obtained reaction solution was poured into methanol to isolate the polymer. The isolated polymer was purified by refluxing in acetone for 30 minutes and dried under reduced pressure.

20 g of the obtained polymer powder, 5 g of brominated bisphenol epoxy resin, 5 g of bismaleimidediaminodiphenylmethane, 0.15 g of dicyanamide, 2
0.052 g of -ethyl-4-methylimidazole and 0.75 g of dicumyl peroxide were dissolved in 90 g of N, N-dimethylformamide to form a varnish.

The resulting varnish was cast on a glass plate and
After drying at 00 ° C for 10 minutes, peel it from the glass plate, fix it on an iron frame, and dry at 150 ° C for 20 minutes, thickness 25μ.
m sheets were obtained. Thickness 3 on the outside of the two sheets obtained
A copper foil having a thickness of 5 μm was placed and heated and pressed at a temperature of 180 ° C. and a pressure of 3 MPa for 60 minutes to obtain a double-sided copper-clad flexible laminate.

Example 2 The varnish obtained in Example 1 was applied to the film surface of a single-sided copper-clad polyimide film and heated at 100 ° C. for 10 minutes and then at 150 ° C. for 20 minutes to form an adhesive layer having a thickness of 10 μm. Provided. The obtained two single-sided copper-clad polyimide films with adhesive layers were bonded together with the adhesive layer surfaces and heated and pressed at a temperature of 180 ° C. and a pressure of 3 MPa for 60 minutes to obtain a double-sided copper-clad flexible laminate.

Example 3 The varnish obtained in Example 1 was applied to one surface of a polyimide film having a thickness of 75 μm and heated at 100 ° C. for 10 minutes and then at 150 ° C. for 20 minutes to form an adhesive layer having a thickness of 20 μm. did.

The obtained one-sided polyimide film with an adhesive layer and a 35 μm copper foil were laminated by a roll laminator under the conditions of a temperature of 180 ° C., a cylinder pressure of 0.5 MPa and a speed of 1 m / min. Then, it was cured for 60 minutes in a dryer at a temperature of 180 ° C. to obtain a single-sided copper-clad polyimide film.

Example 4 Bis (4- (3-aminophenoxy)) was placed in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube.
Phenyl) propane 82g (0.2mol) and 4,4 '
-Methylenebis (2,6-diisopropylaniline) 5
4.9 g (0.15 mol) and ω, ω'-bis (3-
Aminopropyl) polydimethylsiloxane (n average 8.4, average molecular weight 880) 132g (0.15mo
1), and under a nitrogen atmosphere, 2/1 of N, N-dimethylformamide and diethylene glycol dimethyl ether.
747 g of mixed solvent (weight ratio) was added and dissolved. To this solution was added 161 g (0.5 mol) of 3,3 ′, 4,4-benzophenonetetracarboxylic acid dianhydride at a temperature of 30 ° C.
It was added while being careful not to exceed the limit.

Then, the mixture was stirred at room temperature for 3 hours, diluted with 249 g of N, N-dimethylformamide, then added with 128 g of acetic anhydride and 99 g of pyridine, and then with 30
The mixture was stirred at 0 ° C for 5 hours. The obtained reaction solution was poured into methanol to isolate the polymer. The isolated polymer was purified by refluxing in acetone for 30 minutes and dried under reduced pressure.

22 g of the obtained polymer powder, 3 g of a bisphenol epoxy resin, 5 g of bismaleimidediaminodiphenylmethane, 0.09 g of dicyanamide, 0.024 g of 2-ethyl-4-methylimidazole and 0.75 g of dicumyl peroxide were added to N, A varnish was prepared by dissolving 90 g of N-dimethylformamide.

The obtained varnish was cast on a glass plate, and 1
After drying at 00 ° C for 10 minutes, peel it from the glass plate, fix it on an iron frame, and dry at 150 ° C for 20 minutes, thickness 25μ.
m sheets were obtained. Thickness 3 on the outside of the two sheets obtained
A copper foil having a thickness of 5 μm was placed and heated and pressed at a temperature of 180 ° C. and a pressure of 3 MPa for 60 minutes to obtain a double-sided copper-clad flexible laminate.

Example 5 The varnish obtained in Example 4 was applied to the film surface of a single-sided copper-clad polyimide film and heated at 100 ° C. for 10 minutes and then at 150 ° C. for 20 minutes to form an adhesive layer having a thickness of 10 μm. Provided. The obtained two single-sided copper-clad polyimide films with adhesive layers were bonded together with the adhesive layer surfaces and heated and pressed at a temperature of 180 ° C. and a pressure of 3 MPa for 60 minutes to obtain a double-sided copper-clad flexible laminate.

Example 6 The varnish obtained in Example 4 was applied to one surface of a polyimide film having a thickness of 75 μm and heated at 100 ° C. for 10 minutes and then at 150 ° C. for 20 minutes to form an adhesive layer having a thickness of 20 μm. did.

The obtained one-sided polyimide film with an adhesive layer and a 35 μm copper foil were bonded together by a roll laminator under the conditions of a temperature of 180 ° C., a cylinder pressure of 0.5 MPa and a speed of 1 m / min. Then, it was cured for 60 minutes in a dryer at a temperature of 180 ° C. to obtain a single-sided copper-clad polyimide film.

The peel strength and solder heat resistance (appearance after floating in a solder bath at 288 ° C. for 1 minute) were examined for the flexible laminate and the one-sided copper-clad polyimide film obtained in each of the above examples. The results are shown in Tables 1 and 2.

[0073]

[Table 1]

[0074]

[Table 2]

Comparative Example 1 A commercially available acrylic adhesive sheet was used and heated and pressed under the same structure and under the same conditions as in Example 1 to obtain a double-sided flexible laminate. The peel strength of this flexible laminate at room temperature was 2.2 kN / m, but it was 150 ° C.
The peeling strength in No. 1 decreased to 0.5 kN / m.
Moreover, after floating in a solder bath at 288 ° C. for 1 minute, blistering occurred.

Comparative Example 2 A commercially available epoxy adhesive sheet was used and heated and pressed under the same structure and under the same conditions as in Example 1 to obtain a double-sided same-stretch flexible laminate. The peel strength of this flexible laminate at room temperature was 1.9 kN / m, but it was 150 ° C.
The peeling strength in No. 1 fell to 0.9 kN / m.
Moreover, after floating in a solder bath at 288 ° C. for 1 minute, blistering occurred.

Comparative Example 3 A commercially available polyimide-based adhesive sheet was used and heated and pressed under the same constitution and conditions as in Example 1, but no double-sided flexible laminated plate was obtained due to no adhesion.

[0078]

The thermosetting resin composition of the present invention can be adhered at a temperature of about 180 ° C. when used as an adhesive. Unlike conventional heat-resistant adhesives, it does not require high temperatures for adhesion, and roll-to-roll bonding is possible, making it easy to handle. Moreover, it has excellent adhesive strength even at high temperatures. Further, it can be processed into a sheet shape in advance. Furthermore, since it is soluble in a solvent, it can be applied to an adherend in advance and adhered to another adherend.

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[Procedure amendment]

[Submission date] July 15, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

[0043]

[Chemical 20] (In the chemical formula 20, r is an integer of 1 or more.)

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Claims (5)

[Claims] 1. A heat-resistant thermosetting resin composition comprising a polyimide containing a constitutional unit represented by the general formula 1, a polymaleimide represented by the general formula 5, and an epoxy resin. [Chemical 1] (In General Formula 1, Ar is a group represented by General Formula 2, Chemical Formula 3, or Chemical Formula 4, and the group represented by General Formula 2 is 1 to 40.
Mol%, the groups represented by the general formulas 3 and 4 are 99 to 60
Mol%) (In the general formula 2, R represents a divalent hydrocarbon residue,
R ₁ , R ₂ , R ₃ , and R ₄ represent a lower alkyl group or a phenyl group, and l represents an integer of 5 to 30) (In general formalized 3, Z is, -C (= O) -, - SO 2 -,
-O -, - S -, - (CH 2) m -, - NHC (= O)
_{-, - C (CH 3)} 2 -, - C (CF 3) 2 -, - C (=
O) represents O— or a bond, n and m are integers of 1 or more, a plurality of Zs may be the same or different, and hydrogen of each benzene ring may be appropriately substituted with a substituent. ) [Chemical 4] (In the general formula 4, R ₅ , R ₆ , R ₇ , and R ₈ each independently represent hydrogen or an alkyl group or an alkoxy group having 1 to 4 carbon atoms, at least two of which are alkyl groups. Or an alkoxy group, X is —CH ₂ —, —
_{C (CH 3) 2 -,} - O -, - SO 2 -, - C (= O)
-, -NHC (= O)-is shown) (In the general formula 5, k is an integer of 2 or more, and R ₉ represents a k-valent group having 2 or more carbon atoms.) 2. An adhesive sheet comprising the thermosetting resin composition according to claim 1 as a sheet. 3. An adhesive-attached polyimide film having an adhesive layer made of the thermosetting resin composition according to claim 1 on one side or both sides of a polyimide film. 4. A single-sided metal-clad polyimide film, wherein a polyimide film is provided with a metal foil on one side and an adhesive layer made of the thermosetting resin composition according to claim 1 is provided on the other side. 5. A metal-clad polyimide film obtained by laminating a metal foil with the resin composition according to claim 1 as an adhesive on one side or both sides of a polyimide film.