JPH06128462A - Thermosetting resin composition, adhesive sheet, polyimide film having adhesive and metal foil laminated polyimide film - Google Patents

Abstract

PURPOSE:To obtain a composition capable of bonding and curing at low temperature, having good heat resistance and used as a heat resistant adhesive useful for flexible printed-wiring board substrates, thin film multilayered substrates, etc., by including a specific polyimide and epoxy resin. CONSTITUTION:The composition is obtained by blending a polyimide containing a structural unit of formula I [X is O or C(=O)O; Ar<1> is divalent group containing aromatic ring; Ar<2> is composed of 10-90mol group of formula II (Z is SO2, NHCO, O, etc.; K is 0 or 1; H of each benzene ring may be substituted with a substituent group) and 90-10mol% group of formula III (R<1> to R<4> are H, 1-4C alkyl or alkoxy and $ 2 groups thereof are alkoxy or alkyl; X' is CH2, O, etc.)] with 10-50wt.% (preferably 25-40wt.%) epoxy resin and as necessary, polymaleimide, etc. Furthermore, polyimide of formula I is obtained by reacting an acid dianhydride of formula IV with a compound of formula V [Y is amino or isocyanate; (m) is 1-4] and a compound of formula VI.

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 used for printed circuit boards, 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]

The present invention is a thermosetting resin composition containing a polyimide containing a structural unit represented by the general formula 4 and an epoxy resin.

[0005]

[Chemical 4] (In general formula 4, X represents -O- or -C (= O) O-, Ar ¹ represents a divalent group containing an aromatic ring, and Ar ² is represented by general formula 5 or formula 6. The group represented by the general formula 5 is 10 to 90 mol%, and the group represented by the general formula 6 is 90 to 10 mol%).

[0006]

[Chemical 5] (In general formalized 5, Z is -C (= O) -, - SO 2 -, -
O -, - S -, - (CH 2) m -, - NHCO -, - C
_{(CH 3) 2 -, -} C (CF 3) 2 -, - C (= O) O- or showed binding, m and k is an integer of 1 or more, with or different from each plurality of Z same Or hydrogen of each benzene ring may be appropriately substituted with a substituent)

[0007]

[Chemical 6] (In the general formula 6, R ¹ , R ² , R ³ , and R ⁴ 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)
-, -NHCO- is shown)

In the general formula 5, 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 polyimide is produced by reacting the acid dianhydride represented by the general formula 7 with the compounds represented by the general formulas 8 and 9.

[0010]

[Chemical 7] (However, in the general formula 7, Ar ¹ is a divalent aromatic group, X
Represents -O- or -C (= O) O-)

[0011]

[Chemical 8] (However, in general formula 8, Z is -C (= O)-, -SO
_{2 -, - O -, -} S -, - CH 2 -, - NHCO -, - C
_{(CH 3) 2 -, -} C (CF 3) 2 -, - C (= O) O- or represents a bonding, Y represents an amino group or isocyanate group, n represents an integer of 1 to 4, a plurality Z may be the same or different, and hydrogen on each benzene ring may be substituted with an alkyl group or halogen) and a compound represented by the general formula 9 can get.

[0012]

[Chemical 9] (However, in the formula, Y represents an amino group or an isocyanate group, and R ¹ , R ² , R ³ , and R ⁴ each independently represent an alkyl group or an alkoxy group having 1 to 4 carbon atoms)

Specific examples of the acid dianhydride represented by the general formula 7 are catechol bis trimellitate dianhydride, resorcinol bis trimellitate dianhydride, dihydroxybenzene bis trimellitate dianhydride and bisphenol A bis trimellitate. Examples thereof include dianhydride, tetrachlorobisphenol A bis trimellitate dianhydride, tetrabromobisphenol A bis trimellitate dianhydride, biphenyl bis trimellitate dianhydride, and acid dianhydride represented by the following chemical formula 10.

[0014]

[Chemical 10] (In the formula, X represents -O- or -C (= O) -O-, two Xs may be the same or different, R represents an alkyl group or a fluoroalkyl group, and R may be the same or different, and p is 1 or 2.)

Examples of the acid dianhydride represented by the general formula 10 include compounds represented by the following chemical formulas 11 to 22.

[0016]

[Chemical 11]

[0017]

[Chemical 12]

[0018]

[Chemical 13]

[0019]

[Chemical 14]

[0020]

[Chemical 15]

[0021]

[Chemical 16]

[0022]

[Chemical 17]

[0023]

[Chemical 18]

[0024]

[Chemical 19]

[0025]

[Chemical 20]

[0026]

[Chemical 21]

[0027]

[Chemical formula 22]

Acid dianhydrides other than the above-mentioned acid dianhydrides may be used in combination as long as the object of the present invention is not impaired. Examples of such acid dianhydride include 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride and 3,3 ′, 4,4 ′.
-Diphenylsulfone tetracarboxylic dianhydride, 4,
4 '-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis (1,2-benzenedicarboxylic acid anhydride) and the like. These are at most 50 mol% or less based on the total amount of acid dianhydride, and more preferably 30 mol% or less.
It should be at most mol%.

The compound represented by the general formula 8 is as follows:
In the general formula 8, in the combination of one Z and one Y and the combination of two Z, it is preferable that each is bonded to the same benzene ring at the para position or the meta position.

Among the compounds represented by the general formula 8, as the diamine in which the group Y is an amino group, bis (anilinoisopropylidene) benzene, bis (aminophenoxy) benzene, bis (aminophenoxyphenyl) propane, bis (Aminophenoxyphenyl) sulfone, bis (aminophenoxyphenyl) ketone, bis (aminophenoxyphenyl) hexafluoropropane, 4,
4'-bis [3- (4-amino-α, α'-dimethylbenzyl) phenoxy] diphenyl sulfone, 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 -Amino-
α, α'-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [3- (3-amino-α, α'-
Dimethylbenzyl) phenoxy] diphenyl sulfone,
4,4'-bis [3- (3-amino-α, α'-dimethylbenzyl) phenoxy] benzophenone, 4,4'-
Bis [2- (4-amino-α, α′-dimethylbenzyl) phenoxy] diphenyl sulfone, 4,4′-bis [2- (4-amino-α, α′-dimethylbenzyl) phenoxy] benzophenone, 3, 3'-bis [3- (4
-Amino-α, α'-dimethylbenzyl) phenoxy]
Examples thereof include diphenyl sulfone and 3,3′-bis [3- (4-amino-α, α′-dimethylbenzyl) phenoxy] benzophenone. You may mix and use these.

Among the compounds represented by the general formula 8, diisocyanates in which the group Y is an isocyanate group include 4,4'-bis [3- (4-isocyanate-α,
α'-Dimethylbenzyl) phenoxy] diphenyl ketone, 4,4'-bis [3- (4-isocyanate-α,
α′-Dimethylbenzyl) phenoxy] diphenyl sulfone and the like, and among the compounds represented by the general formula 8, there are diamines in which the group Y is an amino group, in which the amino group is replaced with an isocyanate group.

Of the compounds represented by the above general formula 9, those in which Y is an amino group include 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3', 5,5'-tetramethyldiphenylmethane, 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'-diisopropyldiphenylmethane,
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 and the like.

Among the compounds represented by the general formula 9 above, examples of compounds in which Y is an isocyanate group include diamines exemplified above in which “amino” is replaced with “isocyanate”. it can.

The compound represented by the general formula 8 and the compound represented by the general formula 9 have a molar ratio of the former / the latter of 10 /
It is preferably used so as to be 90 to 90/10.
If this ratio is too large, the solubility in a solvent having a small polarity tends to decrease, and if it is too large, the effect of decreasing the softening point of the polyimide by using the compound represented by the general formula 8 becomes small. The above ratio is 40/6
It is particularly preferably 0 to 10/90.

When a diamine is used as a reaction partner of the acid dianhydride, other diamines which may be used in combination with the above-mentioned diamine include diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone,
There are diaminodiphenylketone, diaminodiphenylpropane, phenylenediamine, toluenediamine, diaminodiphenylsulfide, diaminodiphenylhexafluoropropane, diaminodialkyldiphenylmethane, and the like, and these may be used in combination of two or more, within a range not impairing the object of the present invention. Used in.

When diisocyanate is used as a reaction partner of the acid dianhydride, diisocyanate which may be used in combination with the above-mentioned diisocyanate includes diphenylmethane diisocyanate and toluylene diisocyanate. There is one in which the amino group of the above-mentioned other diamine such as nato is changed to an isocyanate group. Any of the above-mentioned diisocyanates can be produced by reacting the above diamine with phosgene according to a conventional method.

The polyimide used in the present invention is manufactured, for example, as follows.

1. When a diamine is used as a reaction partner of an acid dianhydride, the acid dianhydride and the diamine are mixed with each other in an organic solvent, if necessary, in the presence of a catalyst such as tributylamine, triethylamine or triphenyl phosphite at 100 ° C.
As described above, a method of directly heating by heating to 180 ° C. or more to imidization to directly obtain a polyimide (catalyst is preferably used in an amount of 0 to 15% by weight based on the total amount of the reaction components, particularly preferably 0. It is preferable to use 01 to 15% by weight).

2. An acid dianhydride and a diamine are reacted in an organic solvent at a temperature of less than 100 ° C. to once produce a varnish of a polyamide acid which is a precursor of a polyimide, and then the varnish is heated to imidize, or acetic anhydride, Propionic anhydride, acid anhydrides such as benzoic anhydride, ring-closing agents such as carbodiimide compounds such as dicyclohexylcarbodiimide, chemical ring-closing by adding a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole, etc. (A ring-closing agent and a ring-closing catalyst are each 1 to 8 per 1 mol of acid anhydride).
It is preferable to use it within a molar range).

As the organic solvent, N-methyl-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidone, etc. Aprotic polar solvents, phenolic solvents such as phenol, cresol, xylenol, and P-chlorophenol. In addition, raw material monomers and polyimides among benzene, toluene, xylene, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, diglyme, methyl cellosolve, cellosolve acetate, methanol, ethanol, isopropanol, methylene chloride, chloroform, trichlene, tetrachloroethane, etc. Alternatively, those which dissolve the polyamic acid may be used, and those which do not dissolve these may be used as a mixture with another solvent within the range not impairing the solubility.

In the production of the above-mentioned polyimide and its precursor polyamic acid, solid-phase reaction, 3
A melting reaction or the like at 00 ° C. or lower can be used. When a diisocyanate is used as a reaction partner of the acid dianhydride, it can be carried out according to the above-mentioned method for directly obtaining a polyimide. However, it is sufficient that the reaction temperature is room temperature or higher, particularly 60 ° C. or higher.

The acid dianhydride and the reaction partner are preferably used in about equimolar amounts, but the excess amount of either one is 1
Up to 0 mol%, particularly preferably up to 5 mol%, is acceptable.

As the epoxy resin to be blended with the polyimide represented by the general formula 4, 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.

Bisphenol type epoxy resin, halogenated bisphenol type epoxy resin, phenol novolac type epoxy resin, halogenated phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, polyphenol type epoxy resin, polyglycol type epoxy resin, returned aliphatic Epoxy resin.

The mixing ratio of the polyimide and the epoxy resin is preferably 10 to 50% by weight, more preferably 25 to 40% by weight, based on the polyimide.
Is. If the amount of the epoxy resin is less than 10% by weight, the curing will be insufficient and the adhesiveness will be reduced. If it exceeds 50% by weight, the resin composition becomes brittle and cannot be molded.

If necessary, polymaleimide may be added as a thermosetting component together with the epoxy resin. Specific examples of the polymaleimide include 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'-hexamethylene bismaleimide,
There are compounds represented by Chemical formulas 23 to 28, and these are used alone or in combination of two or more kinds.

[0047]

[Chemical formula 23]

[0048]

[Chemical formula 24]

[0049]

[Chemical 25]

[0050]

[Chemical formula 26]

[0051]

[Chemical 27]

[0052]

[Chemical 28] (In the formula, r represents an integer of 1 or more)

The ratio of the polymaleimide to the epoxy resin in the thermosetting component is arbitrary, but in order to cure the resin composition of the present invention at 180 ° C. or lower, the epoxy resin content is preferably 20% by weight or higher. 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′-bis (4-aminophenoxy) biphenyl, 4,4 ′ -Carbonylbis (p-phenyleneoxy) dianiline, 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. As the curing accelerator for polymaleimide, there are the following peroxides. t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydrooxide, di-t-butylperoxide, t-butylcumyl peroxide, dicumylperoxide, 2,5-dimethyl-2,5-di (T-Butylperoxy) hexane, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexyne-3,2,5-
Dimethyl-2,5-di (benzoylperoxy) hexane. 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 formed into a sheet shape in advance and used as a sheet adhesive. Further, the resin composition of the present invention may be used as a fiber-reinforced sheet adhesive by impregnating glass cloth, glass mat aromatic polyamide fiber cloth, aromatic polyamide fiber mat, etc. as a varnish and semi-curing the resin. it can.

The resin composition of the present invention may be used as a varnish, which is directly applied to an adherend, dried, and then 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. 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.

[0061]

【Example】

Example 1 4,4′-diamino-3, was added to a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a calcium chloride tube.
2.745 g (7.5 mmol) of 3 ', 5,5'-tetraisopropyldiphenylmethane (IPDDM) and 2,
1.025 g (2.5 mmol) of 2-bis [4- (4-aminophenoxy) phenylpropane] (BAPP) and 28.6 g of N, N-dimethylformamide (DMF).
And melted.

Next, while cooling so as not to exceed 5 ° C., bisphenol A bis trimellitate dianhydride (BAB
After adding 5.76 g (10.0 mmol) of T) little by little, polyamic acid was synthesized by reacting for 1 hour while cooling so as not to exceed 5 ° C. and then for 6 hours at room temperature.
2.55 g of acetic anhydride was added to the obtained polyamic acid varnish.
And 1.98 g of pyridine were added and reacted at room temperature for 3 hours to synthesize a polyimide.

The polyimide varnish thus obtained was poured into water, and the resulting precipitate was separated, pulverized and dried to obtain a polyimide powder. 21 g of the obtained polyimide powder, 9 g of brominated bisphenol epoxy resin, 0.2 of dicyandiamide.
g, 2-ethyl-4-methylimidazole 0.03 g was dissolved in 90 g of N, 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 2 The varnish obtained in Example 1 was applied to the film side 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 two adhesive-coated single-sided copper-clad polyimide films thus obtained 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 give a double-sided copper-clad flexible laminate.

Example 3 The one-sided copper-clad polyimide film with the adhesive layer and the one-sided copper-clad polyimide film obtained in Example 2 were heated to 180 ° C.
C., a cylinder pressure of 0.5 MPa, and a speed of 1 m / min were laminated by a roll laminator. Then, it was cured for 90 minutes in a dryer at a temperature of 180 ° C. to obtain a single-sided copper-clad polyimide film laminate.

Example 4 The one-sided copper-clad polyimide film with adhesive layer obtained in Example 2 and 42 alloy foil were laminated with a roll laminator under the conditions of a temperature of 180 ° C., a cylinder pressure of 1 MPa and a speed of 0.5 m / min. It was Then, it was cured for 90 minutes in a dryer at a temperature of 180 ° C. to obtain a single-sided copper-clad polyimide film-42 alloy laminated plate.

Example 5 The varnish obtained in Example 1 was applied to one side of a polyimide film having a thickness of 75 μm and dried by heating 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. Formed. The obtained polyimide film with an adhesive layer and a copper foil having a thickness of 35 μm were laminated with 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 in a dryer at a temperature of 180 ° C. for 90 minutes to obtain a single-sided copper-clad polyimide film.

Example 6 21 g of the polyimide powder obtained in Example 1, 4.5 g of bisphenol epoxy resin, 4.5 g of N, N '(4,4'-diphenylmethane) bismaleimide, 0.1 g of dicyandiamide, 2- Ethyl-4-methylimidazole 0.03 g and dicumyl peroxide 0.3 g were added to N, N-
It was dissolved in 90 g of 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 140 ° C for 20 minutes, thickness 25μ.
m sheets were obtained. Thickness 3 on the outside of the two sheets obtained
A copper foil of 5 μm was placed and heated and pressed at a temperature of 180 ° C. and a pressure of 3 MPa for 90 minutes to obtain a double-sided copper-clad flexible laminate.

Example 7 Using the varnish obtained in Example 6, a single-sided copper-clad polyimide film with an adhesive layer was obtained in the same manner as in Example 2.
Further, using this, a double-sided copper-clad flexible laminate was prepared in the same manner as in Example 2.

Example 8 Using the adhesive layer-attached single-sided copper-clad polyimide film obtained in Example 7, a single-sided copper-clad polyimide film laminate was obtained in the same manner as in Example 3.

Example 9 A single-sided copper-clad polyimide film-42 alloy laminate was prepared in the same manner as in Example 4 using the adhesive layer-attached one-sided copper-clad polyimide film and 42-alloy foil obtained in Example 7. Obtained.

Example 10 Using the varnish obtained in Example 6, a polyimide film with an adhesive layer was obtained in the same manner as in Example 5. This and thickness 3
A 5 μm copper foil was laminated in the same manner as in Example 5 to obtain a single-sided copper-clad polyimide film.

Solder heat resistance (288 ° C.) was applied to the laminated plate and the single-sided copper-clad polyimide film obtained in each example.
The appearance after floated in the solder bath for 1 minute) was examined. The results were all good. The peeling strength is shown in Tables 1 and 2.

[0076]

[Table 1]

[0077]

[Table 2]

Comparative Example 1 A double-sided copper-clad flexible laminate was obtained by using an acrylic adhesive sheet and heating and pressing under the same structure and conditions as in Example 1. The peel strength of this flexible laminate at room temperature was 2.2 KN / m, but at 150 ° C., it fell to 0.5 KN / m. Also, after floating in a solder bath at 288 ° C., blistering occurred.

Comparative Example 2 A single-sided copper-clad polyimide film and a 42 alloy foil were bonded together using an epoxy adhesive under the same conditions as in Example 4, but they did not bond to the 42 alloy.

Comparative Example 3 A double-sided copper-clad flexible laminate was obtained by using a polyimide-based adhesive sheet and heating and pressing under the same structure and conditions as in Example 1. The peel strength of this flexible laminate at room temperature was very weak and could not be measured. Also, with this adhesive sheet, a single-sided copper-clad polyimide film and 42 alloy foil were tried to be bonded under the same conditions as in Example 4, but they were not bonded to either the polyimide film or 42 alloy.

[0081]

The thermosetting resin composition of the present invention can be bonded at a temperature of about 180 ° C. when used as an adhesive. Unlike conventional heat-resistant adhesives, high temperature is not required for adhesion, and roll-to-roll bonding is also possible, making it easy to handle. Moreover, it has excellent adhesive strength up to high temperatures,
It adheres to 42 alloy, which was difficult to bond. Further, it can be processed into a sheet shape in advance. Further, since it is soluble in a solvent, it can be applied to an adherend in advance and adhered to another adherend.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09J 163/00 JFP 8830-4J 179/08 JGE 9285-4J H05K 3/38 7011-4E

Claims (5)

[Claims] 1. A thermosetting resin composition comprising a polyimide containing a constitutional unit represented by the general formula 1 and an epoxy resin. [Chemical 1] (In general formula 1, X represents -O- or -C (= O) O-, Ar ¹ represents a divalent group containing an aromatic ring, and Ar ² is represented by general formula 2 or formula 3. The group represented by the general formula 2 is 10 to 90 mol%, and the group represented by the general formula 3 is 90 to 10 mol%. (In general formalized 2, Z is -C (= O) -, - SO 2 -, -
O -, - S -, - (CH 2) m -, - NHCO -, - C
(CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C (═O) O— or a bond, m is an integer of 1 or more, and a plurality of Zs may be the same or different, Hydrogen on each benzene ring may be appropriately substituted with a substituent). (In the general formula 3, R ¹ , R ² , R ³ , and R ⁴ each independently represent hydrogen or an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and at least two of them are alkyl groups. Or an alkoxy group, X ′ is —CH ₂ —,
_{-C (CH 3) 2 -,} - O -, - SO 2 -, - C (= O)
-, -NHCO- is shown) 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.