TWI809377B - Polyimide resin composition, adhesive composition, film-like adhesive material, adhesive sheet, copper foil with resin, copper-clad laminate, printed circuit board, and polyimide film - Google Patents

Abstract

The problem to be solved by the present invention is to provide a polyimide resin composition, the polyimide resin composition is easy to volatilize the organic solvent in drying under heating, and can obtain a kind of polyimide resin composition with low dielectric constant and low dielectric constant Polyimide resin layer with excellent electrical loss tangent and excellent solder heat resistance. The solution of the present invention is a polyimide resin composition comprising polyimide (A) and two or more different organic solvents (B), the polyimide (A) containing aromatic A reactant of a monomeric group of carboxylic anhydride (a1) and dimer diamine (a2), said diamine (a2) comprising dimer diamine; wherein, (B) None of the components contain a nitrogen atom, and the azeotropic point is 70°C to 120°C.

Description

Polyimide resin composition, adhesive composition, film-like adhesive material, adhesive sheet, copper foil with resin, copper-clad laminate, printed circuit board, and polyimide film

The present invention relates to a polyimide resin composition, adhesive composition, film-like adhesive material, adhesive sheet, copper foil with resin, copper-clad laminate, printed circuit board and polyimide film.

Flexible printed circuit boards (FPWB: Flexible Printed Wiring Board) and printed circuit boards (PCB: Printed Circuit Board) and multilayer circuit boards obtained by using them are widely used in mobile communication devices such as mobile phones and smart phones and their In products such as base station devices, network-related electronic equipment such as servers/routers, and large computers.

In addition, in recent years, in these products, high-frequency electrical signals are used for high-speed transmission and processing of large-capacity information, but high-frequency signals are very easy to attenuate, so it is sought to suppress transmission loss as much as possible on the aforementioned multilayer circuit boards. method.

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

As such a polyimide resin, a known polyimide is obtained by reacting tetracarboxylic anhydride containing pyromellitic dianhydride, dimer acid diamine and specific aromatic diamine (patent Literature 1). Since this polyimide has an aromatic ring, it exhibits excellent soldering heat resistance.

In addition, in the production of FPWB, etc., although the process of applying an adhesive composition to a support such as peeled polyethylene terephthalate (peeled PET) and release paper and drying it under heating, due to Such a support lacks heat resistance, so its drying is usually carried out at a temperature below 150°C. On this premise, when producing the polyimide of Patent Document 1, N,N-dimethylacetamide having a high boiling point is used as an organic solvent, and if the resin composition containing this solvent is made at the aforementioned temperature If dried, the organic solvent tends to remain, which adversely affects the low dielectric properties and soldering heat resistance of the polyimide resin layer. [Prior Art Literature] (patent documents)

Patent Document 1: Japanese Patent Laid-Open No. 2016-188298

[Problem to be solved by the invention]

The present invention provides a polyimide resin composition, the polyimide resin composition is easy to volatilize the organic solvent in drying under heating, and can obtain a kind of polyimide resin composition with low dielectric constant and low dielectric loss tangent, and excellent Polyimide resin layer for solder heat resistance. [Technical means to solve the problem]

In order to solve the aforementioned problems, the inventors of the present invention focused on the composition of the polyimide resin composition and intensively studied, found that the aforementioned problems were solved, and completed the present invention. That is, in the present invention, the following are provided.

1. A polyimide resin composition, said polyimide resin composition comprises polyimide (A) and two or more different organic solvents (B), and said polyimide (A) is A reactant of a group of monomers comprising an aromatic tetracarboxylic acid anhydride (a1) and a dimer diamine (a2), said diamine (a2) comprising a dimer diamine; wherein, (B) None of the components contain a nitrogen atom, and the azeotropic point is 70°C to 120°C.

2. The polyimide resin composition according to item 1 above, wherein the component (a2) further contains alicyclic diamine and/or aromatic diamine.

3. The polyimide resin composition according to item 1 or 2 above, wherein the component (B) is an organic solvent (B1) having a solubility of 1 g or more in 100 g of water and a solubility of 100 mg or less in 100 g of water organic solvent (B2).

4. The polyimide resin composition according to item 3 above, wherein the component (B1) is ketones and/or ethers.

5. The polyimide resin composition according to item 3 above, wherein the component (B2) is at least one selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

6. The polyimide resin composition according to any one of items 3 to 5 above, wherein the content ratio of (B1) component and (B2) component is (B1)/(B2)= 10/90～90/10.

7. An adhesive composition comprising the polyimide resin composition described in any one of items 1 to 6 and a crosslinking agent.

8. A film-like adhesive material comprising a hardened product of the adhesive composition described in item 7 above.

9. An adhesive sheet having the film-shaped adhesive material described in item 8 above on at least one side of a supporting film.

10. A resin-coated copper foil comprising the film-like adhesive material and copper foil described in item 8 above.

11. A copper-clad laminate comprising the resin-coated copper foil described in item 10 above, and the copper foil or insulating sheet.

12. A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate described in item 11 above.

13. A polyimide film, which is a dried product of the polyimide resin composition described in any one of items 1 to 6 above. [Efficacy of the invention]

According to the polyimide resin composition of the present invention, the organic solvent is easily volatilized during drying under heating, and a polyimide resin having a low dielectric constant and a low dielectric loss tangent, and excellent soldering heat resistance can be obtained. Amine resin layer. In addition, the polyimide resin layer also has high transparency.

The polyimide resin composition of the present invention contains polyimide (A) (hereinafter referred to as component (A)) containing aromatic tetracarboxylic anhydride (a1) (hereinafter referred to as It is a reactant of the monomer group of (a1) component) and dimer diamine (a2) (henceforth referred to as (a2) component) containing a dimer diamine.

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 dianhydride, 3,3',4,4'- Diphenylphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)] Diphthalic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3, 3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl) ether Dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane Dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3, 4-dicarboxyphenyl)propane dianhydride, bis(2,3-dicarboxyphenoxyphenyl)pyridine dianhydride, bis(3,4-dicarboxyphenoxyphenyl)pyridine dianhydride, 1,4 ,5,8-naphthalene tetracarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic anhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid 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, 2,2-bis(3,4-dicarboxyphenyl)tetrafluoropropane dianhydride, 2,2-bis(3, 3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, etc. These may be used alone or in combination of two or more.

Among these, the component (a1) is preferably a compound represented by the following general formula (1) from the viewpoint of the flexibility of the polyimide resin layer and solder heat resistance. (In formula (1), X represents a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -C(CH ₃ ) ₂ -, -OC 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(-OC(=O)-CH ₃ )-CH ₂ -OCO-, p represents an integer of 1 to 20.)

Examples of the compound represented by the general formula (1) include 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride , 3,3',4,4'-diphenyl-tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4' -Diphenyl ether tetracarboxylic dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 4,4'-(hexafluoroisopropylidene ) diphthalic anhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic anhydride, 2,2-bis(2 ,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl) Pyrodianhydride, etc. These may be used alone or in combination of two or more. Among these, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-[propane -2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride.

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

In addition, in 100 mol% of the monomer group constituting (A) component, the usage amount of the tetracarboxylic anhydride represented by the general formula (1) is not particularly limited, but is usually 10 mol% to 90 mol%. Preferably, it is 25 mol% to 75 mol%.

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

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

The dimer diamine refers to a diamine obtained by substituting all carboxyl groups of a dimer acid with primary amino groups or primary aminomethyl groups (see, for example, JP-A-9-12712). Here, dimer acids mainly include dibasic acids with 36 carbon atoms obtained by dimerizing unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid, and dibasic acids with 18 carbon atoms depending on the degree of purification. Monomer acid with 54 carbon atoms, trimer acid with 54 carbon atoms, and polymerized fatty acid with 20 to 90 carbon atoms. In addition, although the said dimer acid contains a double bond, the degree of unsaturation can also be reduced by hydrogenation reaction, for example.

Although it does not specifically limit as said dimer diamine, For example, the compound represented by following General formula (2) is mentioned.

In addition, examples of commercially available dimer diamines include "Versamine 551", "Versamine 552" (manufactured by Nippon Konings Co., Ltd.), "PRIAMINE 1073", "PRIAMINE 1074", "PRIAMINE 1075 "(Above are manufactured by Korotar Co., Ltd., Japan) etc.

Furthermore, dimer diamine may be used as it is, and the dimer diamine subjected to purification processes, such as distillation, may be used.

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

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

Moreover, diamine (a2-1) (henceforth (a2-1) component) other than dimer diamine may be contained as (a2) component. As the component (a2-1), for example, aliphatic diamine, alicyclic diamine, aromatic diamine, diamino ether, and diamino polysiloxane can be contained. In addition, dimer diamine is excluded about these amines.

Examples of aliphatic diamines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamino Hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diamino Undecane, 1,12-diaminododecane, etc.

Examples of the alicyclic diamine include diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, tetramethyldiamine Dicyclohexylmethane, 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[5.2.1.02,6]decane, isophoronediamine wait.

Examples of aromatic diamines include: 2,2'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diamino Biphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 2,2'-di-n-propyl-4,4'-diaminobiphenyl and other diaminobiphenyls; 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane and other bisaminophenoxy Phenylpropane; 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and other diaminodiphenyl ethers; P-phenylenediamine, m-phenylenediamine and other phenylenediamines; 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, etc. ; 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone and other diaminodiphenylsulfone; 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone and other diaminobenzophenones; 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis[4-(3-aminophenoxy base) diaminodiphenylmethane such as phenyl]methane; 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl) ) diaminophenylpropane such as propane; 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1, Diamines such as 3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane Phenylphenylhexafluoropropane; 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl Diaminophenylphenylethane such as base)-1-(4-aminophenyl)-1-phenylethane; 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 other bisaminophenoxybenzenes; 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 other bisaminobenzylbenzene; 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, 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene and other bisaminobis methyl benzyl benzene; 1,3-bis(3-amino-α,α-di-trifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α,α-di-trifluoromethylbenzyl)benzene base) benzene, 1,4-bis(3-amino-α,α-di-trifluoromethylbenzyl)benzene, 1,4-bis(4-amino-α,α-di-trifluoro Diaminobis-trifluoromethylbenzylbenzene such as methylbenzyl)benzene; 2,6-bis(3-aminophenoxy)benzonitrile, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy ) biphenyl, bis[1-(3-aminophenoxy)]biphenyl and other aminophenoxybiphenyls; Bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone and other aminophenoxyphenylketones; Bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide and other aminophenoxyphenylsulfides; Bis[4-(3-aminophenoxy)phenyl]pyridine, bis[4-(4-aminophenoxy)phenyl]pyridine and other aminophenoxyphenylphenones; Bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether and other aminophenoxyphenyl ethers; 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3 , 3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane and other aminophenoxy phenylpropane; 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 other bis(amino (phenoxybenzoyl)benzene; 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 and other bis(aminophenoxy-α,α-dimethylbenzyl)benzene; 4,4'-bis[4-(4-aminophenoxy)benzoyl]diphenyl ether and other bis[(aminoaryloxy)benzoyl]diphenyl ethers; 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone and other bis(amino-α,α-dimethylbenzyl) phenoxy)benzophenone; 4,4'-Bis[4-(4-Amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone and other bis[amino-α,α-dimethylbenzyl Phenoxy]diphenylphenone; 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylsulfone and other bis[aminophenoxyphenoxy]diphenylsulfone; 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-diphenoxybenzophenone and other diamine groups Diaryloxybenzophenones; 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone and other diaminoaryloxybenzophenones; 1-(4-Aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, etc.

Examples of diaminoethers include bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether, bis[(2-aminomethoxy base) ethyl] ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]ether, 1,2-bis(amine methoxy)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, etc.

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 wait.

These (a2-1) components may be used individually or in combination of 2 or more types. Among them, from the viewpoint that the polyimide resin layer exhibits excellent soldering heat resistance, alicyclic diamines and aromatic diamines are preferable, and aromatic diamines are more preferable.

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

In addition, the usage-amount of (a2-1) component is not specifically limited in 100 mol% of (a2) component, Usually, it is 90 mol% or less, Preferably it is 70 mol% or less.

(A) component of this invention can be obtained by various well-known manufacturing methods. As its production method, for example, a method including the step of subjecting a monomer group comprising (a1) component and (a2) component to a temperature of preferably about 30°C to 120°C, more preferably 40°C to 100°C, etc. ℃ and the time is preferably about 0.1 hour to 2 hours, more preferably about 0.1 hour to 0.5 hours, to perform a polyaddition reaction to obtain a polyadduct; make the obtained polyadduct relatively Preferably, the imidization reaction, that is, the dehydration ring closure is carried out at a temperature of about 80°C to 250°C, more preferably at a temperature of about 80°C to 170°C for about 0.5 hours to 50 hours, more preferably about 1 hour to 20 hours The steps of the reaction. Moreover, the mixing method, order, etc. of (a1) component and (a2) component are not specifically limited.

In addition, in the step of performing the imidization reaction, various known reaction catalysts, dehydrating agents, and the following organic solvent (B) can be used; these may be used alone or in combination of two or more.

Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. In addition, examples of the dehydrating agent include aliphatic carboxylic acid anhydrides such as acetic anhydride and aromatic carboxylic anhydrides such as benzoic anhydride.

When the following organic solvent (B) is used in producing the component (A), the usage amount is adjusted so that the reaction concentration becomes 5% by mass to 60% by mass, preferably 20% by mass to 50% by mass.

The imide ring closure rate of the component (A) is not particularly limited, but is preferably 90% to 100%, more preferably 95% to 100%, from the viewpoint of obtaining the component (A) having a high softening point and flexibility. about. The reason is presumed to be that by setting the imide ring closure ratio of the component (A) within the above range, the component (A) is likely to form a hard segment and a soft segment structure, and both the softening point and the flexibility become high. Here, the "imide ring closure ratio" means the content of cyclic imide bonds in the polyimide resin of the component (A), which can be determined by various methods such as nuclear magnetic resonance (NMR) and infrared (IR) analysis. spectroscopically determined.

(A) The physical properties of the component are not particularly limited. (A) It is preferable that the weight average molecular weight of a component is 20000-100000. (A) The number average molecular weight of a component becomes like this. Preferably it is 5000-50000. The weight average molecular weight and the number average molecular weight are calculated|required as the polystyrene conversion value measured by gel permeation chromatography (GPC), for example.

The softening point of the component (A) of the present invention is preferably about 50°C to 250°C, more preferably about 80°C to 200°C, from the viewpoint of ease of processing by press hardening when manufacturing laminates such as copper-clad laminates. . In addition, the softening point refers to the temperature at which the storage modulus starts to decrease in the curve of the storage modulus measured using a commercially available measuring instrument (product name "ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific Co., Ltd.) .

The polyimide resin composition of the present invention contains two or more different organic solvents (B) (hereinafter referred to as (B) component).

(B) None of the components contain nitrogen atoms. That is, for example, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, diazabicycloundecene, etc. If such an organic solvent containing nitrogen atoms is used, the boiling point is high, so when the polyimide resin composition is dried under heating, the organic solvent contained in the composition cannot be completely volatilized, even if the polyimide resin composition will have After the imide resin layer laminate (such as copper-clad laminate, etc.) is hardened, the organic solvent will still remain, which will have a negative impact on low dielectric properties and soldering heat resistance, so it is not good.

As a physical property of (B) component, an azeotropic point is 70 degreeC - 120 degreeC. Here, the azeotropic point is the value measured under normal pressure using the liquid which mixed all (B) components.

If the azeotropic point of component (B) is less than 70°C, it will be difficult to dissolve component (A); if it exceeds 120°C, even if the polyimide resin composition is dried under heating, component (B) will remain, and polyamide The low dielectric properties and soldering heat resistance of the imide resin layer tend to deteriorate. Moreover, it is preferable that the azeotropic point of (B) component is 70 degreeC - 110 degreeC from a similar viewpoint.

The component (B) is not particularly limited as long as it does not contain a nitrogen atom and exhibits the aforementioned azeotropic point. When the component (B) is used in the production of the component (A), the resulting From the viewpoint of removing polyamic acid and polyimide resin and removing water produced as a by-product during the reaction, it is preferable to use an organic solvent (B1) having a solubility of 1 g or more with respect to 100 g of water (hereinafter referred to as (B1) component) and an organic solvent (B2) having a solubility of 100 mg or less in 100 g of water (hereinafter referred to as (B2) component) is combined. Further, the component (B1) has a solubility of 2 g or more in 100 g of water, and the component (B2) has a solubility of 50 mg or less in 100 g of water.

Examples of the component (B1) include ketones such as methyl ethyl ketone, diethyl ketone, cyclopentanone, cyclohexanone, and methyl cyclohexanone; ethylene glycol dimethyl ether, tetrahydrofuran, and dioxane Ethers such as methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, tertiary butanol and other alcohols; dimethylsulfoxide, etc. These may be used alone or in combination of two or more. Among these, ketones and ethers are preferable, and ethylene glycol dimethyl ether and cyclohexanone are more preferable from the viewpoint of sufficiently dissolving the polyamic acid generated in the production of the component (A).

Examples of the component (B2) include: aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene. Hydrocarbons; diisopropyl ether, ethyl acetate, etc. These may be used alone or in combination of two or more. Among them, in the production of component (A), aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic A group of hydrocarbons, more preferably toluene, methylcyclohexane.

As the content ratio of (B1) component and (B2) component, in the production of (A) component, the polyamic acid and polyimide resin produced can be sufficiently dissolved and the water produced as a by-product can be removed. From a viewpoint, in terms of mass ratio, (B1)/(B2)=10/90-90/10 is preferable, 15/85-85/15 is more preferable, 20/80-80/20 is more preferable .

The content of the component (B) in the polyimide resin composition of the present invention is not particularly limited, but is preferably 50 to 1000 parts by mass based on 100 parts by mass of the component (A) (in terms of non-volatile components), More preferably, it is 100 mass parts - 400 mass parts.

[Adhesive composition] The adhesive composition of the present invention includes the polyimide resin composition of the present invention and a crosslinking agent.

The content of the polyimide resin composition in the adhesive composition of the present invention is not particularly limited, but the adhesive composition is 100% by mass, preferably about 10% by mass to 99.5% by mass.

The content of the component (A) in the adhesive composition of the present invention is not particularly limited, but the non-volatile content of the adhesive composition is 100% by mass, preferably about 2% by mass to 98% by mass.

As the cross-linking agent, various known cross-linking agents can be used without particular limitation as long as they function as a cross-linking agent of polyimide. The crosslinking agents may be used alone or in combination of two or more. The crosslinking agent is preferably at least one selected from the group consisting of epoxy, benzoxazine, bismaleimide and cyanate.

Epoxides include: phenol novolak type epoxy, cresol novolac type epoxy, bisphenol A type epoxy, bisphenol F type epoxy, bisphenol S type epoxy, hydrogenated bisphenol Phenol A-type epoxide, hydrogenated bisphenol F-type epoxide, stilbene-type epoxide, triazine-skeleton-containing epoxide, fennel-skeleton-containing epoxide, linear aliphatic epoxide, alicyclic Epoxides, glycidylamine-type epoxides, trisphenolmethane-type epoxides, alkyl-modified trisphenolmethane-type epoxides, biphenyl-type epoxides, epoxy containing dicyclopentadiene skeleton Compounds, naphthalene-skeleton-containing epoxides, arylalkylene-type epoxides, tetraglycidylxylylenediamine, dimer acid-modified epoxides that are dimer acid-modified products of the aforementioned epoxides , dimer acid diglycidyl ester, etc. In addition, examples of commercially available epoxy oxides include "jER828", "jER834", and "jER807" manufactured by Mitsubishi Chemical Corporation; "ST-3000" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "CELLOXIDE 2021P" manufactured by Nippon Steel Chemicals Co., Ltd.; "YD-172-X75" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd., etc. Among these epoxides, from the standpoint of a balance between soldering heat resistance and low dielectric properties, preferred are those selected from bisphenol A type epoxides, bisphenol F type epoxies, hydrogenated bisphenol A type epoxies At least one of the group consisting of compounds and alicyclic epoxides.

In particular, the tetraglycidyldiamine of the general formula (3) has good compatibility with the aforementioned polyimide. In addition, when this substance is used, it becomes easy to obtain a low-loss elastic modulus of the adhesive layer, and its soldering heat resistance and low dielectric properties also become favorable. (In the formula, Z represents phenylene or cyclohexylene.)

When an epoxy is used as a crosslinking agent, various known epoxy curing agents and active ester curing agents can be used in combination. These curing agents may be used alone or in combination of two or more.

Examples of hardeners for epoxy include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexa Hydrogen phthalic anhydride, 4-methyl-hexahydrophthalic anhydride, or mixtures of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride Anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride methylnadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, methyl Cyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride and other anhydride hardeners; Dicyandiamide (DICY), aromatic diamines (trade names "Lonzacure M-DEA", "Lonzacure M-DETDA", etc.; all manufactured by Japan's Lonza Co., Ltd.), aliphatic amines and other amine-based hardeners; Phenol novolac resin, cresol novolak resin, bisphenol A novolak resin, triazine-modified phenol novolak resin, phosphazene containing phenolic hydroxyl group (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd. etc.) and other phenolic hardeners; Rosin hardeners such as maleic acid modified rosin and its hydrogenated products; Cyclic phosphazene compounds, etc.

Examples of active ester-based hardeners include substances containing a biscyclopentadienyl diphenol structure, substances containing a naphthalene structure, acetylated phenol novolaks, and phenol novolacs described in JP 2019-183071. Benzoyl compounds, etc. Examples of commercially available active ester hardeners include: As substances containing dicyclopentadienyl diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H- 65TM", "EXB-8000L", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC Corporation); As a substance containing a naphthalene structure, "EXB9416-70BK" (manufactured by DIC Co., Ltd.); As acetylated phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); Examples of benzoyl compounds of phenol novolac include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) and the like.

Active ester-based hardeners can also be those produced by various known methods, and examples thereof include those obtained by reacting polyfunctional phenolic compounds with aromatic carboxylic acids described in Japanese Patent No. 5152445 .

Among the aforementioned hardeners, active ester-based hardeners and phenolic hardeners are preferred, and active ester-based hardeners are particularly preferred. The amount of the hardener used is not particularly limited, but the non-volatile content of the adhesive composition is 100% by mass, preferably about 0.1% by mass to 40% by mass, more preferably about 1% by mass to 10% by mass.

In addition, when an epoxy and a curing agent for epoxy are used in combination as a crosslinking agent, a reaction catalyst may be further used in combination. The reaction catalysts may be used alone or in combination of two or more. Reaction catalyst, can enumerate: 1,8-diaza-bicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng (Dimethylaminomethyl)phenol and other tertiary amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and other imidazoles; three Organic phosphines such as butylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine; tetraphenylphosphonium tetraphenylboride, 2-ethyl-4-tetraphenylboride Tetraphenylboron salts such as methylimidazole, tetraphenylboronated N-methylmorpholine, and the like. In addition, the usage amount of the reaction catalyst is not particularly limited, but the non-volatile content of the above-mentioned adhesive composition is 100% by mass, preferably about 0.01% by mass to 5% by mass.

Benzoxazine, for example: 6,6-(1-methylethylene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6 -(1-methylethylene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like. In addition, a phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to the nitrogen of the oxazine ring. In addition, examples of commercially available benzoxazines include "benzoxazine F-a type" and "benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd.; and "RLV type" manufactured by Air Water Corporation. -100", etc.

Bismaleimide, for example: 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide , 3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide Amide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4 '-Diphenylbismaleimide, etc. Moreover, as a commercial item of bismaleimide, "BAF-BMI" by JFE Chemical Co., Ltd., "BMI-1000H" by Daiwa Chemical Industry Co., Ltd., etc. are mentioned.

Cyanate, for example: 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-cyanatophenol)-1,1,1,3,3 ,3-Hexafluoropropane, bisphenol A cyanate, diallyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-paraffin (4-cyanatophenyl) Ethane, 4-cumylphenol cyanate, 1,1-bis(4-cyanatophenyl)ethane, 4,4'-bisphenol cyanate, and 2,2-bis(4 - cyanatophenyl) propane and the like. Moreover, "PRIMASET BTP-6020S (made by Nippon Lonza Co., Ltd.)" etc. are mentioned as a commercial item of cyanate ester.

The content of the crosslinking agent in the adhesive composition of the present invention is not particularly limited. The content of the crosslinking agent is preferably about 1 to 900 parts by mass relative to 100 parts by mass (in terms of non-volatile matter) of the component (A) of the present invention in the adhesive composition.

Assuming that the non-volatile content of the adhesive composition is 100% by mass, the content of the crosslinking agent in the adhesive composition of the present invention is preferably about 1% by mass to 80% by mass.

A flame retardant may be contained in the adhesive composition of the present invention. The flame retardants may be used alone or in combination of two or more. As a flame retardant, a phosphorus flame retardant, the following inorganic filler, etc. are mentioned, for example.

Examples of phosphorus-based flame retardants include polyphosphoric acid, phosphoric acid ester, and phosphazene derivatives that do not have a phenolic hydroxyl group. Among the phosphazene derivatives, cyclic phosphazene derivatives are preferred from the viewpoint of flame retardancy, heat resistance, bleeding resistance, and the like. As a commercial item of a cyclic phosphazene derivative, SPB-100 by Otsuka Chemical Co., Ltd., Rabitle FP-300B by Fushimi Pharmaceutical Co., Ltd., etc. are mentioned.

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 mass relative to 100 parts by mass (in terms of non-volatile matter) of the component (A) of the present invention in the adhesive composition.

The adhesive composition of the present invention may also contain the formula W-Si(R ¹ ) _a (OR ² ) _3-a (wherein, W represents a group containing a functional group capable of reacting with an anhydride group, and R ¹ represents Hydrogen or a hydrocarbon group with 1 to 8 carbon atoms, ^R2 represents a hydrocarbon group with 1 to 8 carbon atoms, and a represents 0, 1 or 2) a reactive alkoxysilyl compound. The low dielectric properties of the adhesive layer composed of the adhesive composition of the present invention can be maintained and its melt viscosity can be adjusted by the reactive alkoxysilyl compound. As a result, the interface adhesion between the adhesive layer and the support (so-called anchoring effect) can be enhanced, and bleeding of the hardened layer from the end of the support can be suppressed.

Examples of the reactive functional group included in W in the general formula include an amine group, an epoxy group, and a thiol group.

W contains amino compounds, such as: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-amino Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-ureidopropyltrialkoxysilane, etc. As a compound containing an epoxy group in W, for example: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, etc. As a compound containing a thiol group in W, for example: 3-mercaptopropyltrimethoxysilane, or 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane, -Mercaptopropylmethyldiethoxysilane, etc. Among these groups, a compound containing an amine group is preferred because of its 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 mass relative to 100 parts by mass (in terms of non-volatile components) of the component (A) of the present invention in the adhesive composition.

The adhesive composition of the present invention may contain any material other than the polyimide resin composition, crosslinking agent, flame retardant, reactive alkoxysilyl compound, and the aforementioned organic solvent of the present invention as an additive .

Additives, such as: ring-opening esterification catalyst, dehydrating agent, plasticizer, weather resistance agent, antioxidant, heat stabilizer, lubricant, antistatic agent, whitening agent, colorant, conductive agent, mold release agent , surface treatment agent, viscosity modifier, silica filler, and fluorine filler, etc.

The content of the aforementioned additives is not particularly limited, but examples include less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, and 0 part by mass based on 100 parts by mass of the non-volatile components of the adhesive composition.

The content of the aforementioned additives is not particularly limited, but examples thereof include less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, and 0 part by mass relative to 100 parts by mass (in terms of non-volatile content) of the component (A) of the present invention.

The adhesive composition of the present invention can be obtained by dissolving the above-mentioned crosslinking agent, and if necessary, the above-mentioned flame retardant, reactive alkoxysilyl compound, and additives in the polyimide resin composition of the present invention. In addition, in the preparation of the above-mentioned adhesive composition, the above-mentioned (B) component may be further blended.

[Film Adhesive Material] The film-form adhesive material of this invention contains the hardened|cured material of the adhesive composition of this invention. As a method for producing a film-like adhesive material, a method including the steps of applying the above-mentioned adhesive composition on a suitable support, a step of volatilizing the organic solvent by heating to harden it, and the like, etc., can be cited. The steps of the support, etc. In addition, the thickness of the adhesive material is not particularly limited, but is preferably about 3 μm to 40 μm. As a support body, a release paper, a release film, the following support film, etc. are mentioned. In addition, when producing the aforementioned film-like adhesive material, the aforementioned adhesive composition and various known adhesive compositions other than the aforementioned adhesive composition may be used in combination.

[adhesive sheet] The adhesive sheet of the present invention contains the film-form adhesive material of the present invention on at least one side of a support film.

The aforementioned adhesive sheet can be obtained by, for example, coating the adhesive composition of the present invention on a support film and hardening it by heating; or laminating the film-like adhesive material of the present invention on a support film.

The above-mentioned supporting film can be exemplified: polyimide; polyester; polyimide-silicon dioxide mixture; polyethylene; polypropylene; polyethylene terephthalate; polyethylene naphthalate; Methyl acrylate resin; polystyrene resin; polycarbonate resin; Aromatic polyester resins obtained from benzoic acid (so-called liquid crystal polymers; "VECSTAR" manufactured by Kuraray Co., Ltd., etc.); cycloolefin polymers; fluorine-based resins (polytetrafluoroethylene (PTFE), perfluoroalkoxy alkanes (PFA), polyvinylidene fluoride (PVDF), etc.), etc. The polyimide includes the aforementioned polyimide film of the present invention.

When the adhesive composition of the present invention is coated on the aforementioned support film, the coating method is not particularly limited, and examples thereof include coating machines such as chipped wheels, dies, knives, and lips. The thickness of the coating layer is not particularly limited, but the thickness after drying is preferably about 1 μm to 100 μm, more preferably about 3 μm to 50 μm. In addition, the adhesive layer of the adhesive sheet can be protected with various protective films.

[Copper foil with resin] The copper foil with resin of this invention contains the film-form adhesive material of this invention, and copper foil. Specifically, it is obtained by applying the adhesive composition of the present invention on copper foil and heating and curing it, or by laminating the film-form adhesive material of the present invention on copper foil. Examples of the copper foil include rolled copper foil and electrolytic copper foil; copper foils subjected to various surface treatments (roughening, rust prevention, etc.) may also be used. Antirust treatment includes: plating treatment using a plating solution containing Ni, Zn, Sn, etc.; so-called mirror treatment such as chromate treatment.

The thickness of the copper foil is not particularly limited, but is preferably about 1 μm to 100 μm, and more preferably about 2 μm to 38 μm. Moreover, as a coating means, the said method is mentioned.

In addition, the adhesive layer of the resin-coated copper foil or the film-like adhesive material may be uncured, or may be partially cured or completely cured by heating. The partially cured adhesive layer or film-like adhesive material is in a so-called B-stage state. In addition, the thickness of the adhesive layer or the film-shaped adhesive material is not particularly limited, but is preferably about 0.5 μm to 30 μm. In addition, copper foil may be further bonded to the adhesive surface of this resin-coated copper foil to obtain resin-coated copper foil on both sides.

[Copper Clad Laminate Board] The copper-clad laminated board of this invention contains the resin-coated copper foil of this invention, and a copper foil or an insulating sheet. Copper Clad Laminate is also called CCL (Copper Clad Laminate). Specifically, the copper-clad laminate is formed by pressing and bonding the resin-coated copper foil to at least one or both surfaces of various known copper foils or insulating sheets under heating. In the case of bonding to one side, a material different from the aforementioned resin-coated copper foil may be crimped on the other side. In addition, the number of resin-coated copper foils, 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 aforementioned supporting film. A prepreg is a sheet-like material (JIS C 5603) in which a reinforcing material such as glass cloth is impregnated with a resin and cured to the B stage. As the resin, insulating resins such as component (A) of the present invention, phenolic resins, epoxy resins, polyester resins, liquid crystal polymers, and aramid resins are used. The thickness of the insulating sheet is not particularly limited, but is preferably about 20 μm to 500 μm. The heating and crimping conditions are not particularly limited, but are preferably about 150°C to 280°C (more preferably about 170°C to 240°C), and more preferably about 0.5MPa to 20MPa (more preferably about 1MPa to 8MPa).

[Printed Circuit 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. The patterning means for forming a circuit pattern on the copper foil surface of a copper-clad laminate includes a subtractive method and a semi-additive method. Examples of the semi-additive method include a method of patterning the copper foil surface of a copper-clad laminate with a resist film, performing electrolytic copper plating, removing the resist, and etching with an alkaline solution. In addition, the thickness of the circuit pattern layer in this printed wiring board is not specifically limited. In addition, a multilayer substrate can also be obtained by using the printed wiring board as a core base material and laminating the same printed wiring board, other known printed wiring boards or printed wiring boards on the core base material. For lamination, the aforementioned adhesive composition and other known adhesive compositions other than the aforementioned adhesive composition may be used in combination. In addition, the number of laminated layers in the multilayer substrate is not particularly limited. In addition, it is also possible to insert and provide a through hole every time a layer is built up, and to perform a plating process on the inside. The line width/space ratio of the aforementioned circuit pattern is not particularly limited, but is preferably about 1 μm/1 μm to 100 μm/100 μm. In addition, the height of the aforementioned circuit pattern is not particularly limited, but is preferably about 1 μm to 50 μm.

[Polyimide film] The polyimide film of the present invention is a dried product of the polyimide resin composition of the present invention.

As the method for producing the polyimide film of the present invention, it is possible to enumerate: after coating the aforementioned polyimide resin composition on the aforementioned support, drying it under heating to form a polyimide resin layer, The support and the like are peeled off from the polyimide resin layer.

The method of coating the polyimide resin composition on the support is not particularly limited, and the aforementioned coating means can be mentioned. In addition, the heat treatment conditions are not particularly limited, either, and examples thereof include a method of heating at a temperature of about 100° C. to 180° C. for about 0.5 hours to 3 hours.

The thickness of the heat-treated polyimide resin layer is not particularly limited, but the thickness after drying is preferably about 1 μm to 50 μm.

The polyimide resin composition used in the polyimide film of the present invention may contain various additives as long as the effect of the present invention is not impaired. The additives include: dehydrating agent, plasticizer, weather resistance agent, antioxidant, heat stabilizer, lubricant, antistatic agent, whitening agent, colorant, conductive agent, release agent, surface treatment agent, viscosity adjustment Agents, inorganic fillers, inorganic pigments, organic pigments, etc.

Examples of inorganic fillers include silica fillers, phosphorus-based fillers, fluorine-based fillers, inorganic ion-exchanger fillers, and the like. In addition, as the silica filler, a silica filler whose surface is modified with a treatment agent such as a silane coupling agent can also be used. In addition, examples of commercially available inorganic fillers include "FB-3SDC" and "SFP-20M" manufactured by Denka Co., Ltd., "SC-2500-SPJ" manufactured by Admatechs Co., Ltd., Clariant Chemicals Co., Ltd. "Exolit OP935" manufactured by Kitamura Co., Ltd., "KTL-500F" manufactured by Kitamura Co., Ltd., IXE manufactured by Toagosei Co., Ltd., etc.

Examples of the inorganic pigment include cadmium red, cadmium tartrazine, cadmium orange, titanium dioxide, carbon black, black iron oxide, and black complex inorganic pigments.

Examples of organic pigments include aniline black, perylene black, anthraquinone black, benzidine-based yellow pigments, phthalocyanine blue, and phthalocyanine green.

The content of the additive in the polyimide resin composition of the present invention is not particularly limited, but is preferably 1 to 150 parts by mass with respect to 100 parts by mass (in terms of nonvolatile content) of the component (A). [Example]

Hereinafter, although an Example is given and this invention is demonstrated concretely, it is not limited to these Examples in particular. In addition, "%" is based on mass unless otherwise specified.

(Azeotropic point of organic solvent)

While stirring the solution obtained by mixing the organic solvents used in Examples 1 to 7, Reference Examples 1 to 3, and Comparative Examples 1 and 3, it was boiled, and the value of the thermometer was used to confirm the degree of steam generated. temperature.

(Example 1)

Add 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic acid to a reaction vessel equipped with a stirrer, water separator, thermometer and nitrogen gas introduction tube Diformic dianhydride (trade name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan LLC; hereinafter abbreviated as BisDA) 535.6 g, ethylene glycol dimethyl ether 716.92 g, and toluene 1672.81 g were heated to 60°C. Next, after slowly adding 540.0 g of dimer diamine (trade name "PRIAMINE 1075", manufactured by Nippon Korota Co., Ltd.; hereinafter referred to as PRIAMINE 1075), heat to 140° C. and carry out imidization over 10 hours. reaction to obtain a solution (30% of non-volatile content) of polyimide resin (A-1). The softening point of (A-1) is shown in Table 1 (the same applies hereinafter).

(Example 2～Example 7, Reference Examples 1～3, Comparative Example 1)

The composition and usage amount shown in Table 1 were changed to the same method as in Example 1 to obtain polyimide resins with 30% non-volatile content.

(Comparative Example 2, Comparative Example 3)

The type of solvent was changed to the solvent shown in Table 1, and the same method as in Example 1 was carried out, but the produced polyamic acid was not dissolved, and a polyimide resin was not obtained.

<Production of polyimide film (1)>

Coating the polyimide resin compositions of Examples 1 to 7, Reference Examples 1 to 3 and Comparative Example 1 on release paper (manufactured by Sun A. Kaken Co., Ltd.), respectively at 150 ° C for 5 minutes , 170°C x 5 minutes to dry it to obtain a laminated film with a polyimide resin layer formed thereon, and peel off the release paper from the film to obtain a polyimide film (1 ).

<Measurement of Relative Permittivity and Dielectric Loss Tangent>

Using a network analyzer ("ENA E5071C" manufactured by Agilent Technologies) and a separation-column dielectric resonator (manufactured by QWED) measuring a frequency of 10.124 GHz to measure the resonance frequency of a single resonator not inserted with any substance and its Q value of the peak.

Next, after cutting the polyimide film (1) into 4 cm x 5 cm to prepare a test piece, after stacking a plurality of test pieces so that the total thickness becomes 100 μm or more and inserting them into the resonator, the resonance when the test piece is inserted is measured frequency and Q value.

The relative permittivity (Dk) is calculated from the difference between the resonance frequency of a single resonator and when a test piece is inserted, and the dielectric loss tangent (Df) is calculated from the difference between the Q value of a single resonator and when a test piece is inserted The difference between the value and the resonant frequency is calculated. The results are shown in Table 1.

Abbreviations in Table 1 are as follows.

<Aromatic Tetracarboxylic Anhydride>

． BisDA: 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, trade name: "BisDA-1000", SABIC INNOVATIVE PLASTICS JAPAN Manufacturing LLC

． 6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, manufactured by Daikin Co., Ltd.

． BTDA: 3,3',4,4'-Benzophenone tetracarboxylic dianhydride, trade name: "BTDA", manufactured by Daicel Chemical Co., Ltd.

<Diamine>

． DDA: dimer diamine, trade name: "PRIAMINE 1075", manufactured by Japan Koluoda Co., Ltd.

． ODA: 4,4'-diaminophenyl ether, manufactured by Wakayama Seika Co., Ltd.

． 1,3-BAC: 1,3-bis(aminomethyl)cyclohexane, manufactured by Mitsubishi Gas Chemical Co., Ltd.

<Organic solvent>

(B1) Ingredients

． DMG: ethylene glycol dimethyl ether, solubility with respect to 100g of water: mixed

． CH: cyclohexanone, solubility relative to 100g water: 2.5g

． DMAc: N,N-Dimethylacetamide, solubility in 100g of water: mixed

． MEK: methyl ethyl ketone, solubility relative to 100g water: 29g

(B2) Ingredients

． Tol: toluene, solubility relative to 100g water: 45mg

． Xyl: xylene, solubility relative to 100g water: 17mg

． MCH: methylcyclohexane, solubility with respect to 100g of water: 1.4mg

． Hex: hexane, solubility relative to 100g water: 1.3mg

<Production of polyimide film (2)>

Coat the polyimide resin composition shown in Table 2 on a release paper (manufactured by Sun A. Kaken Co., Ltd.), and dry it at 120°C for 5 minutes to obtain After laminating the film of the resin layer, the release paper was peeled off from the film to obtain a polyimide film (2) with a film thickness of 25 μm. The relative permittivity (Dk) and dielectric loss tangent (Df) of the obtained polyimide film (2) were measured by the same method as in the preceding paragraph. The results are shown in Table 2.

<Production of polyimide film (3)>

Polyimide resin compositions shown in Table 2 were coated on glass plates, dried at 150°C for 1 hour, and then the glass plates were peeled off to obtain polyimide films with a film thickness of 25 μm. (3). The total light transmittance and yellowness index of the obtained polyimide film (3) were measured by the method described below.

<Measurement of total light transmittance>

Based on JIS K 7375:2008, it measured using the color haze meter. The results are shown in Table 2.

<Measurement of Yellow Index (YI)>

In accordance with JIS K 7373, the change in color was measured by a transmission method using a color difference meter (trade name: "ZE 6000", manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 2.

<Preparation of Adhesive Composition>

(Evaluation example 1)

30.0 g (non-volatile content 9.0 g) of the polyimide resin composition of Example 1 and 70.0 g (non-volatile content 21.0 g) of the polyimide resin composition of Example 4 were used as a multifunctional cross-linking agent. Epoxy resin (trade name: "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.) 1.0 g (non-volatile content 1.0 g), active ester resin (trade name: "EPICLON HPC-8000-65T" , manufactured by DIC Co., Ltd.) 9.2 g (non-volatile content 2.3 g) and imidazole-based epoxy resin (trade name: "Curazol 2E4MZ-A", manufactured by Shikoku Chemical Industry Co., Ltd.) 0.011 g (non-volatile content 0.011 g ), as an inorganic filler Silicon oxide (trade name: "SC-2500-SPJ", manufactured by Admatechs Co., Ltd.) 33.3 g (33.3 g of non-volatile content) and 65.4 g of methyl ethyl ketone as an organic solvent were mixed and stirred well to obtain Adhesive composition with 33% non-volatile content.

(Evaluation Example 2~Evaluation Example 4, Comparative Evaluation Example 1)

Using 100.0 g (non-volatile content 30.0 g) of the polyimide resin composition of Example 2, Example 5, Reference Example 1 and Comparative Example 1 respectively, the same method as Evaluation Example 1 was used to obtain the non-volatile content 33% adhesive composition.

<Preparation of Adhesive Sheet>

The obtained adhesive composition was coated on release paper (manufactured by Sun A. Kaken Co., Ltd.) with a gap coater so that the thickness after drying was 25 μm, and then dried at 150° C. for 5 minutes. , to obtain an adhesive sheet (release paper/adhesive layer).

<Measurement of Relative Permittivity and Dielectric Loss Tangent>

Peel off the release paper from the aforementioned adhesive sheet (release paper/adhesive layer), place the adhesive layer on the support for pressing, and then sandwich the same support for pressing on the side of the adhesive layer. It was cured by heating and pressing at 180° C. for 90 minutes, thereby producing a thermally cured adhesive sheet (support body/adhesive layer/support body). The support for pressing was removed from the adhesive sheet, and for the adhesive layer, the relative permittivity (Dk) and dielectric loss tangent (Df) were calculated in the same manner as in the preceding paragraph. The results are shown in Table 3.

<Production of copper clad laminate>

Peel the release paper from the aforementioned adhesive sheet (release paper/adhesive layer), and laminate it on a commercially available electrolytic copper foil (product name "F2-WS", manufactured by Furukawa Electric Co., Ltd.) (film thickness 18 μm) ) on the mirror side, the other side was superimposed on a commercially available polyimide film (trade name "Kapton 100EN", manufactured by Toray-DuPont Co., Ltd.; film thickness 25 μm; coefficient of thermal expansion: 15ppm/℃), Fabricate a laminate of polyimide film-adhesive layer-electrolytic copper foil. Next, it was placed on a support for pressing, and a support made of the same material was interposed from above, and it was solidified and hardened by heating and pressing at a pressure of 5 MPa and a temperature of 180°C for 90 minutes, thereby producing a copper-clad laminate. .

<Adhesion test>

About the said copper-clad laminated board, peeling strength (N/mm) was measured based on JIS C 6481 (the test method of the copper-clad laminated board for flexible printed wiring boards). The results are shown in Table 3.

<Soldering heat resistance test>

After placing the above-mentioned copper-clad laminate in a constant temperature room at a temperature of 23°C and a humidity of 50% for 24 hours, place the copper foil side down and float it in a solder bath at 288°C to check for foaming and evaluate according to the following criteria . The results are shown in Table 3.

(Evaluation Criteria)

○: No change in appearance

×: Blistering and swelling

[table 3]

none

Claims (10)

A kind of polyimide resin composition, it comprises polyimide (A) and two or more different organic solvents (B), and described polyimide (A) is to comprise aromatic tetracarboxylic acid anhydride (a1) and A reactant of a monomer group of diamine (a2), wherein the diamine (a2) includes dimer diamine; wherein, the components (B) do not contain nitrogen atoms, and the azeotropic point is 70°C~101°C, The aforementioned (B) component is an organic solvent (B1) having a solubility of 1 g or more in 100 g of water and an organic solvent (B2) having a solubility of 100 mg or less in 100 g of water, the aforementioned (B1) component is an ether, and the aforementioned ( B2) is an aromatic hydrocarbon, and the (A) component is obtained by subjecting a monomer group including the aforementioned (a1) component and the aforementioned (a2) component to an imidization reaction in the presence of the aforementioned (B) component. The polyimide resin composition according to Claim 1, wherein the component (a2) further contains alicyclic diamine and/or aromatic diamine. The polyimide resin composition according to any one of claim 1 or 2, wherein, in terms of mass ratio, the content ratio of (B1) component and (B2) component is (B1)/(B2)=10 /90~90/10. An adhesive composition comprising the polyimide resin composition and a crosslinking agent described in any one of claims 1-3. A film-like adhesive material, which includes the described in claim item 4 The hardened product of the adhesive composition. An adhesive sheet, which has the film-shaped adhesive material described in claim 5 on at least one side of a supporting film. A resin-coated copper foil comprising the film-like adhesive material and copper foil described in Claim 5. A copper-clad laminate, comprising the resin-coated copper foil and the copper foil or insulating sheet described in Claim 7. A printed circuit board having a circuit pattern on the copper foil surface of the copper-clad laminate described in Claim 8. A polyimide film, which is a dried product of the polyimide resin composition described in any one of claims 1 to 3.