CN114958287A

CN114958287A - Adhesive composition, cured product, adhesive sheet, copper foil with resin, copper-clad laminate, and printed wiring board

Info

Publication number: CN114958287A
Application number: CN202210183420.2A
Authority: CN
Inventors: 山口贵史; 中村太阳; 盐谷淳; 杉本启辅; 山下真花; 田崎崇司
Original assignee: Arakawa Chemical Industries Ltd
Current assignee: Arakawa Chemical Industries Ltd
Priority date: 2021-02-26
Filing date: 2022-02-24
Publication date: 2022-08-30
Also published as: TW202239821A; JP2022132145A; KR20220122502A

Abstract

The invention provides an adhesive composition which gives a layer of the adhesive composition having both a low dielectric constant and a low dielectric loss tangent. The present invention relates to an adhesive composition, a cured product of the composition, an adhesive sheet having the cured product, a copper foil with resin, a copper-clad laminate, and a printed wiring board, wherein the adhesive composition comprises: a polyimide (A) which is a reaction product of a monomer group containing an aromatic tetracarboxylic acid anhydride (a1) and a dimer diamine-containing diamine (a2), a liquid crystal polymer filler (B), and a crosslinking agent (C).

Description

Adhesive composition, cured product, adhesive sheet, copper foil with resin, copper-clad laminate, and printed wiring board

Technical Field

The invention relates to an adhesive composition, a cured product, an adhesive sheet, a copper foil with resin, a copper-clad laminate, and a printed wiring board.

Background

Flexible Printed Wiring Boards (FPWB) and Printed Circuit Boards (PCBs) and multilayer Wiring boards using the same are widely used in mobile communication devices such as mobile phones and smartphones, network-related electronic devices such as base station devices and servers and routers, and products such as large computers.

In recent years, in these products, high-frequency electric signals are used for transmitting and processing a large amount of information at high speed, but since high-frequency signals are extremely easily attenuated, it is necessary to suppress transmission loss as much as possible even in the multilayer wiring board.

As a means for suppressing the transmission loss in a multilayer wiring board, for example, a composition containing a polyimide resin is considered as an adhesive composition having a characteristic of small dielectric constant and dielectric loss tangent (hereinafter, also referred to as low dielectric characteristic) when a printed wiring board or a printed circuit board is laminated.

As such an adhesive composition, a composition is known in which a thermosetting resin, a flame retardant and an organic solvent are blended with a polyimide resin obtained by reacting an aromatic tetracarboxylic acid with a diamine containing 30 mol% or more of a dimer diamine (patent document 1). However, in this adhesive composition, the dielectric loss tangent may be high.

As a technique for reducing the dielectric loss tangent, for example, a resin composition for an adhesive containing an inorganic filler such as fused silica in a polyimide resin is also known (patent document 2), but when this filler is used, the dielectric constant becomes high, and a low dielectric property cannot be sufficiently satisfied.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2013-199645

Patent document 2: japanese patent laid-open publication No. 2016-041797

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide an adhesive composition that gives a layer of an adhesive composition having both a low dielectric constant and a low dielectric loss tangent (hereinafter also referred to as an "adhesive layer").

Means for solving the problems

The present inventors have conducted extensive studies in order to solve the above problems, and as a result, have found that an adhesive composition containing a specific filler can solve the above problems, and have completed the present invention. That is, in the present invention, the following aspects are provided.

1. An adhesive composition comprising: a polyimide (A) which is a reaction product of a monomer group containing an aromatic tetracarboxylic acid anhydride (a1) and a dimer diamine-containing diamine (a2), and a liquid crystal polymer filler (B).

2. The adhesive composition according to item 1 above, wherein the component (a2) further comprises an alicyclic diamine and/or an aromatic diamine.

3. The adhesive composition according to item 1 or 2, wherein the content of the component (B) is 20 to 300 parts by weight based on100 parts by weight of the component (A) in terms of nonvolatile components.

4. The adhesive composition according to any one of the preceding items 1 to 3, further comprising a crosslinking agent (C).

5. The adhesive composition according to any one of the preceding items 1 to 4, wherein the content of the component (C) is 1 to 20 parts by weight based on100 parts by weight of the component (A) in terms of nonvolatile components.

6. A cured product of the adhesive composition described in any one of the aforementioned items 1 to 5.

7. An adhesive sheet comprising a cured product of the above item 6 on at least one surface of a support film.

8. A copper foil with resin, which comprises the cured product of the aforementioned item 6 and a copper foil.

9. A copper-clad laminate comprising the resin-coated copper foil according to item 8 above, and a copper foil or an insulating sheet.

10. A printed wiring board having a circuit pattern on a copper foil surface of the copper-clad laminate according to the above 9.

Effects of the invention

The adhesive composition of the present invention has both a low dielectric constant and a low dielectric loss tangent.

Detailed Description

The adhesive composition of the present invention comprises: a polyimide (a) (hereinafter referred to as component (a)), which is a reaction product of a monomer group containing an aromatic tetracarboxylic acid anhydride (a1) (hereinafter referred to as component (a 1)) and a dimer diamine-containing diamine (a2) (hereinafter referred to as component (a 2)), and a liquid crystal polymer filler (B) (hereinafter referred to as component (B)).

(A) The component is polyimide, and is used for the adhesive layer to show a low dielectric constant and a low dielectric loss tangent.

The component (a1) is not particularly limited, and examples thereof include: 2,2 ', 3, 3' -biphenyltetracarboxylic dianhydride, 2,3 ', 3, 4' -biphenyltetracarboxylic dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,2,3, 4-benzenetetracarboxylic anhydride, 3,3 ', 4, 4' -diphenylsulfone tetracarboxylic dianhydride, 4,4 '-oxydiphthalic anhydride, 4, 4' - [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] diphthalic dianhydride, 2 ', 3, 3' -benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4' -benzophenonetetracarboxylic dianhydride, 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 2,3 ', 3, 4' -diphenylethertetracarboxylic dianhydride, bis (2, 3-dicarboxyphenyl) ether dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, bis (2, 3-dicarboxyphenoxyphenyl) sulfone dianhydride, bis (3, 4-dicarboxyphenoxyphenyl) sulfone dianhydride, 1,4,5, 8-naphthalene tetracarboxylic anhydride, 2,3,6, 7-anthracene tetracarboxylic dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 4, 8-dimethyl-1, 2,3,5,6, 7-hexahydronaphthalene-1, 2,5, 6-tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2-bis (3,3 ', 4, 4' -tetracarboxyphenyl) tetrafluoropropane dianhydride, and the like. These may be used alone or in combination of 2 or more.

Among them, the component (a1) is preferably represented by the following general formula (1) from the viewpoint of flexibility of the adhesive layer and solder heat resistance.

[ chemical formula 1]

(in the formula (1), X represents a single bond or-SO ₂ －、－CO－、－O－、－O－C ₆ H ₄ －C(CH ₃ ) ₂ －C ₆ H ₄ －O－、－C(CH ₃ ) ₂ －、－O－C ₆ H ₄ －SO ₂ －C ₆ H ₄ －O－、－C(CHF ₂ ) ₂ －、－C(CF ₃ ) ₂ －、－COO－(CH ₂ ) _p -OCO-, or-COO-H ₂ C－HC(－O－C(＝O)－CH ₃ )－CH ₂ -OCO-, p represents an integer of 1 to 20. )

Examples of the substance represented by the general formula (1) include: 2,2 ', 3,3 ' -biphenyltetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic dianhydride, 3,3 ', 4,4 ' -benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenylether tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2-bis (3,3 ', 4,4 ' -tetracarboxyphenyl) tetrafluoropropane dianhydride, 4,4 ' - [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] diphthalic dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2, 2' -bis (3, 4-dicarboxyphenoxyphenyl) sulfone dianhydride, and the like. These may be used alone or in combination of 2 or more. Among them, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride and 4, 4' - [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] diphthalic dianhydride are preferable from the viewpoint of good solubility of the component (a) in an organic solvent.

The amount of the component (a1) used in 100 mol% of the monomer group constituting the component (a) is not particularly limited, but is usually 10 to 90 mol%, preferably 25 to 75 mol%.

The amount of the tetracarboxylic anhydride represented by the general formula (1) to be used in 100 mol% of the monomer group constituting the component (a) is not particularly limited, but is usually 10 to 90 mol%, preferably 25 to 75 mol%.

(a1) The amount of the tetracarboxylic anhydride represented by the general formula (1) to be used in 100 mol% of the component (a) is not particularly limited, but is usually 10 to 100 mol%, preferably 50 to 100 mol%.

(a2) The component (B) is diamine containing dimer diamine.

The dimer diamine is obtained by substituting all carboxyl groups of a dimer acid with a primary amino group or a primary aminomethyl group (see, for example, Japanese patent application laid-open No. 9-12712). Here, the dimer acid is a substance mainly containing a dibasic acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid such as oleic acid, linoleic acid, linolenic acid, and the like, and contains a monomer acid having 18 carbon atoms, a trimer acid having 54 carbon atoms, and a polymerized fatty acid having 20 to 90 carbon atoms depending on the degree of purification. The dimer acid may contain a double bond, but the degree of unsaturation may be reduced by hydrogenation, for example.

The dimer diamine is not particularly limited, and examples thereof include those represented by the following general formula (2). In the general formula (2), m + n is preferably 6 to 17, p + q is preferably 8 to 19, and the dotted line indicates a carbon-carbon single bond or a carbon-carbon double bond.

[ chemical formula 2]

Further, commercially available dimer diamines include: "Versamine 551", "Versamine 552" (manufactured by Cognis Japan, Inc.) and "PRIAMINE 1073", "PRIAMINE 1074" and "PRIAMINE 1075" (manufactured by Croda Japan, Inc.) are mentioned.

The dimer diamine may contain an amine derived from the monomer acid, trimer acid and/or polymerized fatty acid, and the content of the amine is 10 wt% or less, preferably 5 wt% or less, more preferably 3 wt% or less, and still more preferably 2 wt% or less in the dimer diamine.

The dimer diamine may be used as it is, or may be purified by distillation or the like.

The amount of the dimer diamine in 100 mol% of the monomer group constituting the component (a) is not particularly limited, but is usually 5 mol% or more, preferably 25 to 75 mol%.

The amount of the dimer diamine used in 100 mol% of the component (a2) is not particularly limited, but is usually 10 mol% or more, and preferably 30 to 100 mol%.

Further, the component (a2) may contain a diamine (a2-1) (hereinafter referred to as a component (a 2-1)) other than dimer diamine. Examples of the component (a2-1) include aliphatic diamines, alicyclic diamines, aromatic diamines, diamino ethers, and diamino polysiloxanes. It is noted that dimer diamine is excluded for these amines.

Examples of the aliphatic diamine include: ethylenediamine, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 11-diaminoundecane, 1, 12-diaminododecane, and the like.

Examples of the alicyclic diamine include: diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, tetramethyldiaminodicyclohexylmethane, 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] heptane, 3(4),8(9) -bis (aminomethyl) tricyclo [5.2.1.0(2,6) ] decane, isophoronediamine, and the like.

Examples of the aromatic diamine include:

diaminobiphenyls such as 2,2 ' -diaminobiphenyl, 3 ' -diaminobiphenyl, 4 ' -diaminobiphenyl, 2 ' -dimethyl-4, 4 ' -diaminobiphenyl, 2 ' -diethyl-4, 4 ' -diaminobiphenyl, and 2,2 ' -di-n-propyl-4, 4 ' -diaminobiphenyl;

bisaminophenoxyphenylpropanes such as 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane;

diaminodiphenyl ethers such as 3,3 ' -diaminodiphenyl ether, 3,4 ' -diaminodiphenyl ether, and 4,4 ' -diaminodiphenyl ether;

phenylenediamines such as p-phenylenediamine and m-phenylenediamine;

diaminodiphenyl sulfides such as 3,3 ' -diaminodiphenyl sulfide, 3,4 ' -diaminodiphenyl sulfide, and 4,4 ' -diaminodiphenyl sulfide;

diaminodiphenyl sulfones such as 3,3 ' -diaminodiphenyl sulfone, 3,4 ' -diaminodiphenyl sulfone and 4,4 ' -diaminodiphenyl sulfone;

diaminobenzophenones such as 3,3 ' -diaminobenzophenone, 3,4 ' -diaminobenzophenone, and 4,4 ' -diaminobenzophenone;

diaminodiphenylmethane such as 3,3 ' -diaminodiphenylmethane, 3,4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylmethane, bis [4- (3-aminophenoxy) phenyl ] methane;

diaminophenylpropanes such as 2, 2-bis (3-aminophenyl) propane, 2-bis (4-aminophenyl) propane, and 2- (3-aminophenyl) -2- (4-aminophenyl) propane;

diaminophenylhexafluoropropane such as 2, 2-bis (3-aminophenyl) -1,1,1,3,3, 3-hexafluoropropane, 2-bis (4-aminophenyl) -1,1,1,3,3, 3-hexafluoropropane and 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3, 3-hexafluoropropane;

diaminophenylphenylethane such as 1, 1-bis (3-aminophenyl) -1-phenylethane, 1-bis (4-aminophenyl) -1-phenylethane and 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane;

bisaminophenoxybenzenes such as 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, and the like;

bis-aminobenzoylbenzenes such as 1, 3-bis (3-aminobenzoyl) benzene, 1, 3-bis (4-aminobenzoyl) benzene, 1, 4-bis (3-aminobenzoyl) benzene, 1, 4-bis (4-aminobenzoyl) benzene, and the like;

bisaminodimethylbenzyl benzenes such as 1, 3-bis (3-amino- α, α -dimethylbenzyl) benzene, 1, 3-bis (4-amino- α, α -dimethylbenzyl) benzene, 1, 4-bis (3-amino- α, α -dimethylbenzyl) benzene, and 1, 4-bis (4-amino- α, α -dimethylbenzyl) benzene;

bisaminobistrifluoromethylbenzyl benzenes such as 1, 3-bis (3-amino- α, α -bistrifluoromethylbenzyl) benzene, 1, 3-bis (4-amino- α, α -bistrifluoromethylbenzyl) benzene, 1, 4-bis (3-amino- α, α -bistrifluoromethylbenzyl) benzene, and 1, 4-bis (4-amino- α, α -bistrifluoromethylbenzyl) benzene;

aminophenoxy biphenyls such as 4,4 '-bis (3-aminophenoxy) biphenyl, 4' -bis (4-aminophenoxy) biphenyl, and bis [1- (3-aminophenoxy) ] biphenyl;

aminophenoxyphenyl ketones such as bis [4- (3-aminophenoxy) phenyl ] ketone and bis [4- (4-aminophenoxy) phenyl ] ketone;

aminophenoxyphenyl sulfides such as bis [4- (3-aminophenoxy) phenyl ] sulfide and bis [4- (4-aminophenoxy) phenyl ] sulfide;

aminophenoxyphenyl sulfones such as bis [4- (3-aminophenoxy) phenyl ] sulfone and bis [4- (4-aminophenoxy) phenyl ] sulfone;

aminophenoxyphenyl ethers such as bis [4- (3-aminophenoxy) phenyl ] ether and bis [4- (4-aminophenoxy) phenyl ] ether;

aminophenoxyphenylpropanes such as 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2-bis [3- (3-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane and the like;

bis (aminophenoxybenzoyl) benzenes such as 1, 3-bis [4- (3-aminophenoxy) benzoyl ] benzene, 1, 3-bis [4- (4-aminophenoxy) benzoyl ] benzene, 1, 4-bis [4- (3-aminophenoxy) benzoyl ] benzene, 1, 4-bis [4- (4-aminophenoxy) benzoyl ] benzene and the like;

bis (aminophenoxy- α, α -dimethylbenzyl) benzene such as 1, 3-bis [4- (3-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 3-bis [4- (4-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 4-bis [4- (3-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 4-bis [4- (4-aminophenoxy) - α, α -dimethylbenzyl ] benzene;

bis [ (aminoaryloxy) benzoyl ] diphenyl ether such as 4, 4' -bis [4- (4-aminophenoxy) benzoyl ] diphenyl ether;

bis (amino- α, α -dimethylbenzylphenoxy) benzophenone such as 4, 4' -bis [4- (4-amino- α, α -dimethylbenzyl) phenoxy ] benzophenone;

bis [ amino- α, α -dimethylbenzylphenoxy ] diphenyl sulfone such as 4, 4' -bis [4- (4-amino- α, α -dimethylbenzyl) phenoxy ] diphenyl sulfone;

bis [ aminophenoxy phenoxy ] diphenyl sulfone such as 4, 4' -bis [4- (4-aminophenoxy) phenoxy ] diphenyl sulfone;

diaminodiaryloxybenzophenones such as 3,3 '-diamino-4, 4' -diphenoxybenzophenone and 3,3 '-diamino-4, 4' -biphenoxybenzophenone;

diaminoaryloxybenzophenones such as 3,3 '-diamino-4-phenoxybenzophenone and 3, 3' -diamino-4-biphenyloxybenzophenone;

1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-inden-5-amine, and the like.

Examples of the diamino ethers include: bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis [ (2-aminomethoxy) ethyl ] ether, bis [2- (2-aminoethoxy) ethyl ] ether, bis [2- (3-aminopropoxy) ethyl ] ether, 1, 2-bis (aminomethoxy) ethane, 1, 2-bis (2-aminoethoxy) ethane, 1, 2-bis [2- (aminomethoxy) ethoxy ] ethane, 1, 2-bis [2- (2-aminoethoxy) ethoxy ] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, and the like.

Examples of the diaminopolysiloxane include: α, ω -bis (2-aminoethyl) polydimethylsiloxane, α, ω -bis (3-aminopropyl) polydimethylsiloxane, α, ω -bis (4-aminobutyl) polydimethylsiloxane, α, ω -bis (5-aminopentyl) polydimethylsiloxane, α, ω -bis [3- (2-aminophenyl) propyl ] polydimethylsiloxane, α, ω -bis [3- (4-aminophenyl) propyl ] polydimethylsiloxane, and the like.

These (a2-1) components can be used alone or in combination of 2 or more. Among them, from the viewpoint that the adhesive layer shows excellent solder heat resistance, alicyclic diamines and aromatic diamines are preferable, and aromatic diamines are more preferable.

The amount of the component (a2-1) used in 100 mol% of the monomer group constituting the component (A) is not particularly limited, but is usually 90 mol% or less, preferably 50 mol% or less.

The amount of the component (a2-1) used in 100 mol% of the component (a2) is not particularly limited, but is usually 90 mol% or less, and preferably 70 mol% or less.

The component (A) of the present invention can be obtained by various known production methods. Examples of the production method include a method including the following steps: a step of obtaining an addition polymer by subjecting a monomer group containing the component (a1) and the component (a2) to an addition polymerization reaction at a temperature of preferably about 30 to 120 ℃, more preferably about 40 to 100 ℃, and for a time of preferably about 0.1 to 2 hours, more preferably about 0.1 to 0.5 hours; and (b) a step of subjecting the obtained addition polymer to imidization, i.e., a dehydration ring-closure reaction, at a temperature of preferably about 80 to 250 ℃, more preferably about 80 to 170 ℃ for preferably about 0.5 to 50 hours, more preferably about 1 to 20 hours. The method and the order of mixing the component (a1) and the component (a2) are not particularly limited.

In the step of conducting the imidization reaction, various known reaction catalysts, dehydrating agents and organic solvents can be used, and these can be used alone or in combination of 2 or more.

The reaction catalyst may be exemplified by: aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. Further, examples of the dehydrating agents include: aliphatic carboxylic acid anhydrides such as acetic anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride.

Examples of the organic solvent include: nitrogen-based organic solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-diethylacetamide, and diazabicycloundecene; ketones such as methyl ethyl ketone, diethyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone; ethers such as 1, 2-dimethoxyethane, 1, 2-diethoxyethane, tetrahydrofuran, and dioxane; alcohols such as methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, and tert-butanol; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; ethyl acetate, dimethyl sulfoxide, and the like. These may be used alone or in combination of 2 or more. When an organic solvent is used, the amount of the organic solvent is adjusted so that the reaction concentration is 5 to 60% by weight, preferably 20 to 50% by weight.

(A) The imide ring-closing ratio of the component (A) is not particularly limited, but is preferably 90 to 100%, more preferably about 95 to 100%, from the viewpoint of obtaining the component (A) having high softening point and high flexibility. The "imide ring-closure ratio" herein means the content of the cyclic imide bond in the polyimide as the component (a), and can be determined by various spectroscopic means such as NMR and IR analysis, for example.

(A) The physical properties of the components are not particularly limited. (A) The weight average molecular weight of the component (A) is preferably 20,000 to 100,000. (A) The number average molecular weight of the component (A) is preferably 5,000 to 50,000. The weight average molecular weight and the number average molecular weight are determined as polystyrene equivalent values measured by Gel Permeation Chromatography (GPC), for example.

The softening point of the component (A) in the present invention is preferably about 50 to 250 ℃, more preferably about 80 to 200 ℃. The softening point is a temperature at which the storage modulus starts to decrease in a curve of the storage modulus measured by a commercially available measuring instrument (product name "ARES-2 KSTD-FCO-STD", manufactured by Rheometric Scientfic).

(B) The component (B) is a liquid crystalline polymer filler. By containing the component (B), the adhesive layer exhibits excellent solder heat resistance and also has low dielectric properties.

The "liquid crystal polymer" is a polymer having melt processability such that it can form a melt phase having optical anisotropy (if shear is applied to a molten liquid crystal polymer, molecular chains are oriented in the direction of shear to cause anisotropy).

The "liquid crystal polymer filler" refers to a filler (filler) containing a liquid crystal polymer, and examples of the shape include a powder, a sphere (including a substantially spherical filler), a spindle, an amorphous particle, a fiber, and the like, and a mixture thereof.

The type of the component (B) is not particularly limited, and examples thereof include aromatic polyesters and/or aromatic polyester amides. In addition, a polyester partially containing an aromatic polyester and/or an aromatic polyester amide in the same molecular chain is also included in the component (B).

As the constituent monomer of the component (B), aromatic hydroxycarboxylic acids, aromatic diols, aromatic dicarboxylic acids, and the like are mainly used.

Examples of the aromatic hydroxycarboxylic acid include: hydroxybenzoic acids such as p-hydroxybenzoic acid, m-hydroxybenzoic acid and o-hydroxybenzoic acid; hydroxynaphthoic acids such as 3-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, and 6-hydroxy-2-naphthoic acid; hydroxyphenyl benzoic acids such as 3 ' -hydroxyphenyl-4-benzoic acid, 4 ' -hydroxyphenyl-3-benzoic acid and 4 ' -hydroxyphenyl-4-benzoic acid; 4-hydroxy-4' -biphenylcarboxylic acid, and the like. In addition, anhydrides, acylates, esters, acid halides of these carboxylic acids may also be used. These may be used alone or in combination of 2 or more.

Examples of the aromatic diol include: resorcinol, hydroquinone, methylhydroquinone, 4 '-isopropylidenediphenol, 1, 4-dihydroxynaphthalene, 3' -dihydroxybiphenyl, 3,4 '-dihydroxybiphenyl, 4' -dihydroxybiphenyl ether, 1, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, and the like. In addition, an acylate, an ester, or an acid halide thereof may be used. These may be used alone or in combination of 2 or more.

Examples of the aromatic dicarboxylic acid include: terephthalic acid, methyl terephthalic acid, isophthalic acid, methyl isophthalic acid, 4 '-biphenyldicarboxylic acid, 2' -diphenylpropane-4, 4 '-dicarboxylic acid, diphenyl ether-4, 4' -dicarboxylic acid, diphenyl ketone-4, 4 '-dicarboxylic acid, diphenyl sulfone-4, 4' -dicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, and the like. In addition, anhydrides, acylates, esters, and acid halides of these carboxylic acids may also be used. These may be used alone or in combination of 2 or more.

As other constituent monomers, there may be used: aminocarboxylic acids such as anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-6-naphthoic acid, 2-amino-3-naphthoic acid, and 1-amino-4-naphthoic acid;

aminophenols such as 2-aminophenol, 3-aminophenol, 4- (N-methylamino) phenol, 3-methyl-4-aminophenol and acetoxyaminophenol;

and aromatic diamines such as 1, 3-phenylenediamine, 1, 4-phenylenediamine, and 4, 4' -diaminodiphenyl ether. These may be used alone or in combination of 2 or more.

The repeating units of the constituent monomers in the component (B) and the method for producing the component (B) are not particularly limited, and examples thereof include: japanese patent laid-open publication Nos. 2011-006629, 6295013, 2020/166651 and the like.

The physical properties of component (B) are, for example, melting point of about 260 to 340 ℃, more preferably about 290 to 340 ℃. The melting point herein means a value measured in accordance with JIS K-7121.

The volume average particle diameter of the component (B) is preferably about 20 μm or less, and more preferably about 0.1 to 7 μm. The volume average particle diameter herein means an arithmetic average particle diameter on a volume basis measured by a laser diffraction/scattering particle size distribution measurement method.

Examples of commercially available products of component (B) include "LF-31P" (manufactured by ENEOS, Inc.).

The content of the component (B) in the adhesive composition of the present invention is not particularly limited, but is preferably about 20 to 300 parts by weight, more preferably about 50 to 250 parts by weight, and further preferably about 80 to 200 parts by weight, in terms of nonvolatile components, relative to 100 parts by weight of the component (a), from the viewpoint of the adhesive layer exhibiting a low dielectric loss tangent.

The adhesive composition of the present invention may contain a crosslinking agent (C) (hereinafter referred to as component (C)). By containing the component (C), the solder heat resistance of the adhesive layer is easily increased.

As the component (C), various known crosslinking agents can be used without particular limitation as long as they function as a crosslinking agent for polyimide, and 2 or more kinds thereof can be used alone or in combination. Examples of the component (C) include: epoxy, benzoxazine, bismaleimide, cyanate ester, butadiene-based polymer, and the like.

Examples of epoxides are: phenol novolac type epoxy, cresol novolac type epoxy, bisphenol a type epoxy, bisphenol F type epoxy, bisphenol S type epoxy, hydrogenated bisphenol a type epoxy, hydrogenated bisphenol F type epoxy, stilbene type epoxy, triazine skeleton-containing epoxy, fluorene skeleton-containing epoxy, linear aliphatic epoxy, alicyclic epoxy, glycidyl amine type epoxy, triphenol methane type epoxy, alkyl-modified triphenol methane type epoxy, biphenyl type epoxy, dicyclopentadiene skeleton-containing epoxy, naphthalene skeleton-containing epoxy, aryl alkylene type epoxy, tetraglycidyl xylene diamine, dimer acid-modified epoxy which is a modification product of dimer acid of the above epoxy, dimer acid diglycidyl ester, and the like. Further, as a commercially available product of the epoxy compound, there can be mentioned: "jER 604", "jER 630", "jER 828", "jER 834" and "jER 807" manufactured by Mitsubishi Chemical corporation, "ST-3000" manufactured by NIPPON STEEL Chemical & Material corporation, "CELLOXIDE 2021P" manufactured by Daicel corporation, "YD-172-X75" manufactured by NIPPON STEEL Chemical & Material corporation, "TETRAD-X" manufactured by Mitsubishi gas Chemical corporation, and the like. Among these, from the viewpoint of the balance between the solder heat resistance and the low dielectric characteristics, at least 1 selected from the group consisting of bisphenol a type epoxy, bisphenol F type epoxy, hydrogenated bisphenol a type epoxy, and alicyclic epoxy is preferable.

In particular, the tetraglycidyl diamine of the general formula (3) has good compatibility with the above polyimide. In addition, when this is used, the adhesive layer can be easily molded with low loss, and the solder heat resistance and low dielectric characteristics thereof are also excellent.

[ chemical formula 3]

(wherein Z represents a phenylene group or a cyclohexylene group.)

When an epoxy compound is used as the component (C), various known curing agents for epoxy compounds and active ester curing agents can be used in combination. The curing agent can be used alone or in combination of 2 or more.

Examples of the curing agent for epoxy include: acid anhydride curing agents such as succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, or a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2, 3-dicarboxylic anhydride, methylnorbornane-2, 3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride, and the like;

dicyandiamide (DICY), aromatic diamines (trade names: "Lonzacure M-DEA" and "Lonzacure M-DETDA", all of which are amine-based curing agents manufactured by Lonza Japan, Ltd.), aliphatic amines, and the like;

phenol-based curing agents such as phenol novolak resins, cresol novolak resins, bisphenol A type novolak resins, triazine-modified phenol novolak resins, and phosphazenes containing a phenolic hydroxyl group (trade name: SPH-100 available from Otsuka chemical Co., Ltd.);

rosin curing agents such as maleic acid-modified rosins and hydrides thereof;

cyclic phosphazene compounds, and the like.

Examples of the active ester-based curing agent include: curing agents containing a dicyclopentadienyl diphenol structure described in Japanese patent laid-open publication No. 2019-183071, curing agents containing a naphthalene structure, acetylates of phenol novolak, and benzoylates of phenol novolak.

As a commercially available product of the active ester-based curing agent, for example,

examples thereof include: comprising a dicyclopentadienyl diphenol structure, "EXB 9451", "EXB 9460S", "HPC-8000H", "HPC-8000-65T", "HPC-8150-62T", "HPC-8000H-65 MT", "HPC-8000L-65 MT", "EXB-8150-65T" (manufactured by DIC Co., Ltd.);

naphthalene-containing, "EXB 9416-70 BK" (manufactured by DIC corporation);

"DC 808" (manufactured by Mitsubishi chemical corporation) which is an acetylate of phenol novolac;

examples of the benzoyl compound of phenol novolac include "YLH 1026", "YLH 1030" and "YLH 1048" (manufactured by Mitsubishi chemical corporation).

The active ester-based curing agent can be produced by various known methods, and examples thereof include those obtained by reacting a polyfunctional phenol compound with an aromatic carboxylic acid as described in japanese patent No. 5152445.

Among the above curing agents, active ester curing agents and phenol curing agents, particularly active ester curing agents, are preferable. The amount of the curing agent used is not particularly limited, and is preferably about 0.1 to 40% by weight, and more preferably about 1 to 10% by weight, based on 100% by weight of the nonvolatile matter of the adhesive composition.

In addition, in the case of combining an epoxy compound with a curing agent for an epoxy compound as the component (C), a reaction catalyst may be further used in combination. The reaction catalyst may be used alone or in combination of 2 or more. The reaction catalyst may be exemplified by: tertiary amines such as 1, 8-diaza-bicyclo [5.4.0] undec-7-ene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; tetraphenylboron salts such as tetraphenylphosphonium-tetraphenylboronate, 2-ethyl-4-methylimidazole-tetraphenylboronate and N-methylmorpholine-tetraphenylboronate. The amount of the reaction catalyst used is not particularly limited, and is preferably about 0.01 to 5% by weight, based on 100% by weight of the nonvolatile components of the adhesive composition.

Examples of benzoxazines are: 6,6- (1-methylethylidene) bis (3, 4-dihydro-3-phenyl-2H-1, 3-benzoxazine), 6- (1-methylethylidene) bis (3, 4-dihydro-3-methyl-2H-1, 3-benzoxazine), and the like. The oxazine ring may have a phenyl group, a methyl group, a cyclohexyl group, or the like bonded to the nitrogen. Further, as commercially available products of benzoxazines, there are exemplified: "benzoxazine F-a type", "benzoxazine P-d type" manufactured by four chemical industries, Ltd., "RLV-100" manufactured by AIR WATER, and the like.

The bismaleimides include: 4,4 ' -diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenylether bismaleimide, 3 ' -dimethyl-5, 5 ' -diethyl-4, 4 ' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1,6 ' -bismaleimide- (2,2, 4-trimethyl) hexane, 4 ' -diphenylether bismaleimide, 4 ' -diphenylsulfone bismaleimide, and the like. Further, as commercially available bismaleimides, there are exemplified: "BAF-BMI" manufactured by JFE Chemical Co., Ltd., and "BMI-1000H" manufactured by Dahe Kazakhstan Chemical Co., Ltd.).

Cyanate ester includes: 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2-bis (4-isocyanatophenyl) -1,1,1,3,3, 3-hexafluoropropane, bisphenol A cyanate, diallylbisphenol A cyanate, 4-phenylphenol cyanate, 1,1, 1-tris (4-cyanatophenyl) ethane, 4-cumylphenol cyanate, 1, 1-bis (4-cyanatophenyl) ethane, 4' -bisphenol cyanate, and 2, 2-bis (4-cyanatophenyl) propane, and the like. Further, as commercially available cyanate esters, there can be mentioned: "PRIMASET BTP-6020S" manufactured by Lonza Japan, Inc.

Examples of the butadiene-based polymer include: polybutadiene, 1, 2-butadiene homopolymer, butadiene-isoprene polymer, butadiene-acrylonitrile polymer, ethoxylated polybutadiene, epoxidized polybutadiene, butadiene-styrene polymer, styrene-butadiene-styrene polymer, and the like. Further, as commercially available products of the butadiene-based polymer, there can be mentioned: "Ricon 100" and "Ricon 184" manufactured by Cray Valley, and "NISSO-PB B-1000" and "NISSO-PB JP-200" manufactured by Nippon Kabushiki Kaisha.

The content of the component (C) in the adhesive composition of the present invention is not particularly limited. From the viewpoint of satisfying both excellent solder heat resistance and low dielectric characteristics of the adhesive layer, the content of the component (C) is preferably about 1 to 20 parts by weight, more preferably about 1.5 to 15 parts by weight, and still more preferably about 3 to 10 parts by weight, in terms of nonvolatile components, relative to 100 parts by weight of the component (a).

The adhesive composition of the present invention may further contain the above-mentioned organic solvent. The content thereof is preferably about 30 to 60% by weight based on 100% by weight of the adhesive composition.

The adhesive composition of the present invention may contain a flame retardant. The flame retardants may be used alone or in combination of 2 or more. Examples of the flame retardant include: phosphorus flame retardants, inorganic fillers, and the like.

Examples of the phosphorus-based flame retardant include: polyphosphoric acid, phosphoric acid esters, phosphazene derivatives having no phenolic hydroxyl group, and the like. Among these phosphazene derivatives, cyclic phosphazene derivatives are preferable from the viewpoints of flame retardancy, heat resistance, bleed-out resistance (Japanese: ブリードアウト resistance), and the like. Examples of commercially available cyclic phosphazene derivatives include: "SPB-100" manufactured by Otsuka chemical corporation and "Rabile FP-300B" manufactured by pharmaceutical institute corporation.

Examples of the inorganic filler include a silica filler, a phosphorus filler, a fluorine filler, and an inorganic ion exchanger filler. The silica filler may be one whose surface is modified with a treating agent such as a silane coupling agent. Further, commercially available products of the inorganic filler include "FB-3 SDC" manufactured by DENKA, SFP-20M "," SC-2500-SPJ "," SC-2500-SXJ "," SC-2500-SVJ "manufactured by ADMATECHS," Exolit OP935 "manufactured by Clariant Plastics & Coatings (クラリアントケミカルズ), and" KTL-500F "manufactured by Shikohama, and" IXE "manufactured by Toyo Synthesis.

The content of the flame retardant in the adhesive composition of the present invention is not particularly limited. The content of the flame retardant is preferably 1 to 150 parts by weight based on100 parts by weight of the component (A) in terms of nonvolatile components.

The adhesive composition of the present invention may contain a compound represented by the general formula: W-Si (R) ¹ ) _a (OR ² ) _3－a (wherein W represents a group having a functional group reactive with an acid anhydride group, and R ¹ Represents hydrogen or a C1-8 hydrocarbon group, R ² Represents a C1-8 hydrocarbon group, and a represents 0, 1 or 2. ) The reactive alkoxysilyl compound shown. The reactive alkoxysilyl compound can adjust the melt viscosity of the adhesive layer formed from the adhesive composition of the present invention while maintaining the low dielectric characteristics thereof. As a result, the adhesive layer and the support can be improvedThe interfacial adhesion force of the body (so-called anchor effect), and the bleeding of the cured layer from the edge of the support body is suppressed.

Examples of the reactive functional group contained in W of the above general formula include: amino, epoxy, thiol, and the like.

Examples of the compounds wherein W contains an amino group include: n-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane and the like. Examples of the compound containing an epoxy group in W include: 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of the compound in which W contains a thiol group include: 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane and the like. Among these, W is preferably a compound containing an amino group, from the viewpoint of good reactivity and flow control effect.

The content of the reactive alkoxysilyl compound in the adhesive composition of the present invention is not particularly limited. The content of the reactive alkoxysilyl compound is preferably 0.01 to 5 parts by weight based on100 parts by weight of the component (A) in terms of nonvolatile components.

The adhesive composition of the present invention may contain, as an additive, a substance other than any of the component (a), the component (B), the component (C), the organic solvent, the flame retardant, and the reactive alkoxysilyl compound.

Examples of additives include: ring-opening esterification catalysts, dehydrating agents, plasticizers, weather-resistant agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, silica fillers, fluorine fillers, and the like.

The content of the additive is not particularly limited, and examples thereof include, relative to 100 parts by weight of nonvolatile components of the adhesive composition: less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, 0 part by weight, and the like.

The content of the additive is not particularly limited, and includes, in terms of nonvolatile components, 100 parts by weight of the component (a): less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, 0 part by weight, and the like.

The adhesive composition of the present invention can be obtained by mixing the component (a) and the component (B), and if necessary, the component (C), an organic solvent, a flame retardant, a reactive alkoxysilyl compound, and an additive.

[ cured product ]

The cured product of the present invention contains the adhesive composition. Examples of the method for producing a cured product include a method including the following steps: a step of applying the adhesive composition to an appropriate support; a step of heating to volatilize the organic solvent and thereby cure the adhesive composition; a step of peeling off the support. The thickness of the cured product is not particularly limited, but is preferably about 3 to 40 μm. Examples of the support include: release paper, release film, support film described later, and the like. In addition, when the cured product is produced, the adhesive composition may be used in combination with various known adhesive compositions other than the adhesive.

[ adhesive sheet ]

The adhesive sheet of the present invention contains the cured product of the present invention on at least one surface of the support film.

The adhesive sheet can be obtained by, for example, applying the adhesive composition of the present invention on a support film and curing the composition by heating, or by bonding a cured product of the present invention on a support film.

Examples of the support film include: polyimide, polyester, polyimide-silica dopant, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, aromatic polyester resin (so-called liquid crystal polymer; Vecstar, manufactured by Kuraray, inc.) obtained from ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, etc. and p-hydroxybenzoic acid, cycloolefin polymer, fluorine resin (polytetrafluoroethylene (PTFE), Perfluoroalkoxyalkane (PFA), polyvinylidene fluoride (PVDF), etc.), and the like.

When the adhesive composition of the present invention is applied to the support film, the application method is not particularly limited, and examples thereof include a method using a coater such as a comma coater, a die coater, a knife coater, or a lip coater. The thickness of the coating layer is not particularly limited, and the thickness after drying is preferably about 1 to 100 μm, more preferably about 3 to 50 μm. The adhesive layer of the adhesive sheet may be protected by various protective films.

[ copper foil with resin ]

The resin-coated copper foil of the present invention comprises the cured product of the present invention and a copper foil. Specifically, the adhesive composition of the present invention is obtained by applying the adhesive composition to a copper foil and heat-curing the composition, or by bonding the cured product of the present invention to a copper foil. Examples of the copper foil include rolled copper foil and electrolytic copper foil, and copper foil subjected to various surface treatments (roughening, rust prevention, and the like) may be used. Examples of the rust-proofing treatment include: plating treatment using a plating solution containing Ni, Zn, Sn, or the like, chromate treatment, or so-called mirror surface treatment.

The thickness of the copper foil is not particularly limited, but is preferably about 1 to 100 μm, and more preferably about 2 to 38 μm. The coating method may be the above method.

The adhesive layer of the resin-coated copper foil may be uncured, or may be partially cured or completely cured by heating. The partially cured adhesive layer is in a state called a so-called B-stage. The thickness of the adhesive layer is not particularly limited, and is preferably about 0.5 to 30 μm. Further, a resin may be bonded to the copper foil with resin to form a copper foil with resin on both sides.

[ copper-clad laminate ]

The copper-clad laminate of the present invention comprises the resin-coated copper foil of the present invention and a copper foil or an insulating sheet. The Copper Clad Laminate is also called CCL (Copper Clad Laminate). Specifically, the copper-clad laminate is obtained by bonding the resin-coated copper foil to at least one surface or both surfaces of various known copper foils or insulating sheets under heating. When the resin-attached copper foil is bonded to one surface, a material different from the resin-attached copper foil may be pressure-bonded to the other surface. The number of resin-attached copper foils, and insulating sheets in the copper-clad laminate is not particularly limited.

In one embodiment, the insulating sheet is preferably a prepreg or the support film. The prepreg is a sheet material (JIS C5603) obtained by impregnating a reinforcing material such as glass cloth with a resin and curing the resin to a B stage. The resin used is an insulating resin such as the component (a) of the present invention, a phenol resin, an epoxy resin, a polyester resin, a liquid crystal polymer, and an aramid resin. The thickness of the insulating sheet is not particularly limited, but is preferably about 20 to 500 μm. The heating and pressure bonding conditions are not particularly limited, but are preferably about 150 to 280 ℃ (more preferably about 170 to 240 ℃), and preferably about 0.5 to 20MPa (more preferably about 1 to 8 MPa).

[ printed Wiring Board ]

The printed wiring board of the present invention has a circuit pattern on the copper foil surface of the copper-clad laminate of the present invention. Examples of the patterning means for forming a circuit pattern on the copper foil surface of the copper-clad laminate include: subtractive method, semi-additive method. Examples of the semi-addition method include the following methods: after patterning the copper foil surface of the copper-clad laminate with a resist film, electrolytic copper plating is performed to remove the resist, and etching is performed with an alkali solution. The thickness of the circuit pattern layer in the printed wiring board is not particularly limited. Further, a multilayer substrate may be obtained by stacking the same printed wiring board, other known printed wiring boards, or printed wiring boards on the printed wiring board as a core. When laminating, the adhesive composition may be used in combination with other known adhesive compositions other than the adhesive composition. The number of layers in the multilayer substrate is not particularly limited. In addition, a through hole may be inserted for each lamination to perform plating treatment on the inside. The line width/pitch ratio of the circuit pattern is not particularly limited, but is preferably about 1 μm/1 μm to 100 μm/100 μm. The height of the circuit pattern is not particularly limited, and is preferably about 1 to 50 μm.

[ examples ]

The present invention will be specifically described below with reference to examples, but the present invention is not particularly limited to these examples. In addition, "%" is based on weight unless otherwise specified.

Production example 1

In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas inlet, 280.00g of 4, 4' - [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] diphthalic dianhydride (trade name: "BisDA-1000", manufactured by SABIC Innovative Plastics Japan contract corporation, hereinafter abbreviated as BisDA.), 371.38g of 1, 2-dimethoxyethane and 866.56g of toluene were charged and heated to 70 ℃. Subsequently, 276.92g of dimer diamine (trade name: "PRIAMINE 1075", manufactured by Croda Japan, hereinafter, PRIAMINE1075) was added slowly, and then the mixture was heated to 110 ℃ to effect imidization for 12 hours, thereby obtaining a solution of polyimide (A-1) (30% nonvolatile content).

Production example 2

280.00g of BisDA-1000, 346.99g of 1, 2-dimethoxyethane and 809.65g of toluene were charged into the same reaction vessel as in preparation example 1, and the mixture was heated to 70 ℃. Then, 20.54g of 4, 4' -diaminophenyl ether (trade name: "ODA", manufactured by Hill Seiki Kogyo industries, Ltd.) and 242.08g of dimer diamine (PRIAMINE1075) were added slowly, and the mixture was heated to 110 ℃ for 12 hours to effect imidization, thereby obtaining a solution (nonvolatile content: 30%) of polyimide (A-2).

Production example 3

In a reaction vessel similar to that of production example 1, 260g of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (manufactured by Daikin corporation, hereinafter abbreviated as 6 FDA.) and 372.63g of 1, 2-dimethoxyethane and 869.47g of toluene were charged and heated to 70 ℃. Subsequently, 301.00g of dimer diamine (PRIAMINE1075) was added slowly, and the mixture was heated to 110 ℃ for 14 hours to effect imidization, thereby obtaining a solution of polyimide (A-3) (30% nonvolatile matter).

Example 1

Mixing: 100.0g (non-volatile matter 30.0g) and 233.3g (non-volatile matter 70.0g) of polyimide (A-1) (weight ratio in terms of non-volatile matter: (A-1)/(A-2) ═ 30/70), a liquid crystal polymer filler (trade name: "LF-31P", volume average particle diameter: 5 μm, melting point: 320 ℃, manufactured by ENEOS Co., Ltd.) 108.7g (non-volatile matter 108.7g), a polyfunctional epoxy resin (trade name: "TETRAD-X", manufactured by Mitsubishi gas chemical Co., Ltd.) 2.7g (non-volatile matter 2.7g) and an active ester resin (trade name: "EPICLON HPC-8000-65T", manufactured by Co., Ltd.) 9.2g (non-volatile matter 6.0g) as a crosslinking agent, a imidazole-based epoxy resin (trade name: "REZOL 2E4 MZ-A") as a reaction catalyst, 0.029g (nonvolatile content 0.029g) of the product of the four chemical industries, 53.3g of 1, 2-dimethoxyethane and 217.4g of methyl ethyl ketone as organic solvents were thoroughly stirred to obtain an adhesive composition having a nonvolatile content of 30%.

Examples 2 to 8, comparative examples 1 and 2

Adhesive compositions having the compositions shown in table 1 were obtained in the same manner as in example 1.

< production of adhesive layer >

Each adhesive composition was applied to release paper (manufactured by Sun a Kaken, ltd.) by a gap coater so that the thickness after drying became 25 μm, and then dried at 150 ℃ for 5 minutes to obtain an adhesive sheet (release paper/adhesive layer). Next, the release paper was peeled off from the adhesive sheet (release paper/adhesive layer), the adhesive layer was placed on a pressure-sensitive support, and the pressure-sensitive adhesive layer was further heated and pressed for 90 minutes at a pressure of 5MPa and 180 ℃ via the same pressure-sensitive support on the adhesive layer side to be cured, thereby producing a heat-cured adhesive sheet (support/adhesive layer/support). The support for pressing was removed from the adhesive sheet to obtain an adhesive layer.

< determination of relative dielectric constant and dielectric loss tangent >

The resonance frequency of the resonator alone without any insertion and the Q value of its peak were measured using a network analyzer (manufactured by Keysight Technologies, Inc.; device name: "P5003A") and a split column dielectric resonator (manufactured by QWED Inc.) for measuring the frequency 10.124 GHz.

Next, after a test piece was produced by cutting the adhesive layer to 4cm × 5cm, a plurality of test pieces were stacked so that the total thickness became 100 μm or more and inserted into a resonator, and then the resonance frequency and Q value when the test pieces were inserted were measured.

The relative dielectric constant (Dk) was calculated from the difference between the resonance frequencies when the resonator alone was inserted into the test piece, and the dielectric tangent (Df) was calculated from the difference between the Q values and the difference between the resonance frequencies when the resonator alone was inserted into the test piece. The results are shown in table 1.

[ Table 1]

*1: the parts by weight of each component means the weight based on the nonvolatile component.

The symbols shown in table 1 represent the following compounds.

< polyimide >

A-1-polyimide of production example 1

A-2-polyimide of production example 2

A-3-polyimide of production example 3

< Filler >

B-1-liquid crystalline Polymer Filler, trade name: "LF-31P", volume average particle diameter: 5 μm, melting point: 320 ℃ C, manufactured by ENEOS (strain)

D-1-unmodified silica, trade name: "SC 2500-SPJ", volume average particle diameter: 0.5 μm, manufactured by Admatechs

< crosslinking agent >

C-1-polyfunctional epoxy resin, trade name: TETRAD-X, manufactured by Mitsubishi gas chemical corporation

C-2-active ester resin, trade name: "EPICLON HPC-8000-65T", manufactured by DIC (strain)

C-3-active ester resin, trade name: "EPICLON HPC-8150-62T", manufactured by DIC corporation

The following tests were carried out to evaluate adhesive compositions containing a crosslinking agent.

Evaluation examples 1 to 7, comparative evaluation examples 1 and 2

< production of adhesive sheet >

The adhesive compositions of examples 1 to 7 and comparative examples 1 and 2 were applied to release paper (manufactured by Sun a Kaken, ltd.) using a gap coater so that the thickness after drying became 25 μm, and then dried at 150 ℃ for 5 minutes to obtain an adhesive sheet (release paper/adhesive layer).

< manufacture of copper-clad laminate >

The release paper was peeled off from the adhesive sheet (release paper/adhesive layer), and the resultant was laminated on the mirror surface side of a commercially available electrolytic copper foil (product name "F2-WS", manufactured by Kogawa electric industries, Ltd.) (film thickness: 18 μm) and the other side of the same was laminated on a commercially available polyimide film (product name: "Kapton 100 EN", manufactured by DU PONT-TORAY, manufactured by Ltd.; film thickness: 25 μm; thermal expansion coefficient; 15 ppm/. degree. C.) to obtain a laminate (polyimide film/adhesive sheet/copper foil).

Next, the laminate was placed on a support for pressing so that the copper foil surface was in contact with the support for pressing, and cured by heating and pressing for 90 minutes at a temperature of 180 ℃ and a pressure of 10MPa through the support made of the same material from above, thereby producing a copper-clad laminate (polyimide film/adhesive layer/electrolytic copper foil).

< adhesion test >

The peel strength (N/mm) of the copper-clad laminate was measured in accordance with JIS C6481 (test method for copper-clad laminates for flexible printed wiring boards). The results are shown in Table 2.

< solder Heat resistance test >

The copper-clad laminate was left in a thermostatic chamber at a temperature of 23 ℃ and a humidity of 50% for 24 hours, and then floated in a solder bath at 288 ℃ with the copper foil side down, and the presence or absence of foaming was confirmed, and evaluated according to the following criteria. The results are shown in Table 2.

(evaluation criteria)

O: no change in appearance

X: with foaming, expanding

[ Table 2]

Example 9 and comparative example 3

Adhesive compositions were obtained with the compositions shown in table 3, respectively. The relative dielectric constant and the dielectric loss tangent were measured by the same methods as described above. The results are shown in table 3.

[ Table 3]

*2: the parts by weight of each component means the weight based on the nonvolatile component.

The symbols shown in table 3 represent the following compounds.

< polyimide >

A-3-polyimide of production example 3

< Filler >

B-1-liquid crystalline polymer filler, trade name: "LF-31P", volume average particle diameter: 5 μm, melting point: 320 ℃ C, manufactured by ENEOS

< crosslinking agent >

C-2-active ester resin, trade name: "EPICLON HPC-8000-65T", manufactured by DIC (manufactured by KOKAI Co., Ltd.)

Evaluation example 8 and comparative evaluation example 3

The adhesive compositions of example 9 and comparative example 3 were applied to release paper (manufactured by Sun a Kaken, ltd.) by a gap coater so that the thickness after drying became 25 μm, and then dried at 150 ℃ for 5 minutes to obtain an adhesive sheet (release paper/adhesive layer).

A copper foil was removed by etching a double-sided copper-clad laminate (trade name: Pyralux TK125012R, manufactured by Dupont; film thickness: 75 μm) in which copper foil/fluororesin was laminated on both sides of a polyimide film, with a 40% ferric trichloride aqueous solution. Then, each adhesive sheet was laminated on one side of the exposed fluororesin, and further, a commercially available electrolytic copper Foil (trade name: "F2-WS", manufactured by ancient river Circuit Foil, 18 μm thick) was laminated thereon to prepare a laminate (fluororesin layer/polyimide film/fluororesin layer/adhesive layer/electrolytic copper Foil).

Next, the laminate was placed on a support for pressing so that the copper foil surface contacted the support for pressing, and was cured by heating and pressing for 90 minutes at a temperature of 180 ℃ and a pressure of 10MPa from above through a support made of the same material, thereby producing a copper-clad laminate. The peel strength (N/mm) of the obtained copper-clad laminate was measured by the same method as described above. The results are shown in Table 4.

[ Table 4]

Examples 10 and 11, and comparative example 4

Adhesive compositions having the compositions shown in Table 5 were obtained, and the relative dielectric constant and the dielectric loss tangent were measured by the same methods as described above. The results are shown in table 5.

[ Table 5]

*3: the parts by weight of each component means the weight based on the nonvolatile component.

The symbols shown in table 5 represent the following compounds.

< polyimide >

A-1-polyimide of production example 1

< Filler >

< crosslinking agent >

C-4-multifunctional epoxy resin, trade name: "jER 604", manufactured by Mitsubishi gas chemical corporation

C-5-active ester resin, trade name: "EPICLON HPC-8000-65M", manufactured by DIC corporation

C-6-4, 4' -diphenylmethane bismaleimide, trade name: "BMI-1000H", manufactured by Daihe Kangchi Kogyo Co., Ltd

C-7-butadiene-styrene polymer, trade name: "Ricon-100", manufactured by Cray Valley Co., Ltd

Evaluation examples 9 and 10, and comparative evaluation example 4

The adhesive compositions of examples 10 and 11 and comparative example 4 were applied to release paper (manufactured by Sun a Kaken, ltd.) by a gap coater so that the thickness after drying became 25 μm, and then dried at 150 ℃ for 5 minutes to obtain an adhesive sheet (release paper/adhesive layer).

Each adhesive sheet was laminated on the side of a liquid crystal polymer of a single-sided copper-clad laminate (trade name: "LDS-1250", manufactured by Azotech, Inc.; film thickness 50 μm) in which an electrolytic copper foil was laminated on one side of a liquid crystal polymer, and the same single-sided copper-clad laminate (LDS-1250) was further laminated on the side of the copper foil to prepare a laminate (electrolytic copper foil/liquid crystal polymer/adhesive layer/electrolytic copper foil/liquid crystal polymer).

Next, the laminate was placed on a support for pressing, and cured by heating and pressing for 90 minutes at a temperature of 180 ℃ under a pressure of 2.5MPa, with the support made of the same material interposed therebetween, to produce a copper-clad laminate. The peel strength (N/mm) and solder heat resistance of the obtained copper-clad laminate were measured by the same methods as described above. The results are shown in Table 6.

[ Table 6]

Claims

1. An adhesive composition comprising: a polyimide A which is a reaction product of a monomer group containing an aromatic tetracarboxylic anhydride a1 and a dimer diamine-containing diamine a2, and a liquid crystal polymer filler B.

2. The adhesive composition according to claim 1, wherein the component a2 further comprises an alicyclic diamine and/or an aromatic diamine.

3. The adhesive composition according to claim 1 or 2, wherein the content of the component B is 20 to 300 parts by weight based on100 parts by weight of the component A in terms of nonvolatile components.

4. The adhesive composition according to any one of claims 1 to 3, further comprising a crosslinking agent C.

5. The adhesive composition according to any one of claims 1 to 4, wherein the content of the component C is 1 to 20 parts by weight based on100 parts by weight of the component A in terms of nonvolatile components.

6. A cured product of the adhesive composition according to any one of claims 1 to 5.

7. An adhesive sheet comprising the cured product according to claim 6 on at least one surface of a support film.

8. A copper foil with resin, which comprises the cured product of claim 6 and a copper foil.

9. A copper-clad laminate comprising the resin-coated copper foil according to claim 8, and a copper foil or an insulating sheet.

10. A printed wiring board having a circuit pattern on a copper foil surface of the copper-clad laminate according to claim 9.