JP6825289B2 - Resin composition, adhesive, film-like adhesive, adhesive sheet, multi-layer wiring board, copper foil with resin, copper-clad laminate, printed wiring board - Google Patents

Description

The present invention relates to a resin composition, an adhesive, a film-like adhesive, an adhesive sheet, a multilayer wiring board, a copper foil with resin, a copper-clad laminate, and a printed wiring board.

Flexible Printed Wiring Boards (FPWBs) and Printed Circuit Boards (PCBs), as well as multilayer wiring boards using them, are mobile communication devices such as mobile phones and smartphones, their base station devices, and servers. -It is widely used in network-related electronic devices such as routers and products such as large computers.

In recent years, high-frequency electric signals have been used in these products in order to transmit and process a large amount of information at high speed. However, since high-frequency signals are very easily attenuated, transmission loss can be as much as possible in the multilayer wiring board. Ingenuity to suppress is required.

As a means for suppressing transmission loss in a multi-layer wiring board, for example, when a printed wiring board or a printed circuit board is laminated, not only is it excellent in adhesive strength, but also the characteristic that both the relative permittivity and the dielectric loss tangent are small (hereinafter, It is conceivable to use a low-dielectric material having (also referred to as low-dielectric property).

The adhesive compositions that can be used as a low dielectric material, polyimide obtained by reacting aromatic tetracarboxylic acid dianhydride and dimer diamine, cross-linking agent such as an epoxy resin, and polyimide-based adhesive containing an organic solvent is known However, there were cases where the low dielectric property was insufficient (see Patent Document 1).

On the other hand, the polyimide-based adhesive excellent in low dielectric characteristics, polyimides obtained by reacting an aromatic tetracarboxylic acid dianhydride and diamino polysiloxane, crosslinking agent such as an epoxy resin, and polyimide-based adhesive comprising an organic solvent Although it is known (see Patent Document 2), the low dielectric property was insufficient as far as the applicant recognizes.

Japanese Unexamined Patent Publication No. 2013-199645 Japanese Unexamined Patent Publication No. 7-154042

A main object of the present invention is to provide a novel polyimide-based resin composition that provides an adhesive layer having good adhesiveness, heat resistance, and low dielectric properties.

The present inventor has conducted a study for further enhancing the adhesive strength and dielectric properties of the polyimide-based adhesives described in Patent Documents 1 and 2.

First, actually the aromatic tetracarboxylic dianhydride is free carboxylic acid derived from the raw material by noting that contains as impurities. Then, it was hypothesized that the carboxyl group of the free carboxylic acid directly increased the polarity of the polyimide and became a factor of moisture absorption of the polyimide, resulting in deterioration of the low dielectric property of the adhesive.

We also focused on the structure of the dimer diamine. Dimerdiamine is generally a multimer derived from dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid (see JP-A-9-12712, etc.), and has a conjugated double bond in the molecule. It was hypothesized that the low dielectric properties of the adhesive would be inadequate as a result of these π electrons increasing the polarity of the polyimide when contained in large amounts.

In addition, it has been newly found that diaminopolysiloxane has an adverse effect on the low dielectric loss tangent of polyimide when used in combination with dimer diamine. The reason is unknown, but it is probably because polysiloxane has a large surface energy and repels with polar groups (imide groups, etc.) in polyimide.

The present invention has been completed by the above studies. That is, the present invention relates to the following resin composition, adhesive, film-like adhesive, adhesive sheet, multilayer wiring board, copper foil with resin, copper-clad laminate, and printed wiring board.

1. 1. Free aromatic content is less than 1 wt% of a carboxylic acid dianhydride (a1) and hydrogenated dimer include diamine (a2), and diamino polysiloxane (a3) an included no monomer groups (1) A resin composition containing a reactive polyimide (A1).

2. 2. (A1) an aromatic tetracarboxylic acid dianhydride constituting a component is represented by the following structure, the resin composition the claim 1.
(In the formula, X is a single bond, -SO2-, -CO-, -O-, -O-C6H4-C (CH3) 2-C6H4-O- or -COO-Y-OCO- (Y is-(CH2). ) L- (l = 1-20) or -H2C-HC (indicating -OC (= O) -CH3) -CH2-.)

3. 3. The resin composition according to Item 1 or 2, wherein the molar ratio [(a1) / [(a2)] of the component (a1) and the component (a2) in the component (1) is 1 to 1.5.

4. Further, the resin composition according to any one of Items 1 to 3 above, which further contains a polyimide (A2) other than the component (A1).

5. (A2) component, (a1) component and / or the content of free carboxylic acid is 1 wt% or more aromatic tetracarboxylic acid dianhydride (a1 '), (a2) component and / or non-hydrogenated dimer Item 4. The resin composition according to Item 4, wherein the polyimide resin is obtained by reacting a monomer group (2) containing a diamine (a2').

6. Item 5. The resin composition according to Item 5, wherein the component (2) further contains the component (a3).

7. The resin composition according to any one of Items 4 to 6, wherein the solid content weight ratio [(A1) / (A2)] of the component (A1) to the component (A2) is 40/60 to 99/1.

8. The resin composition according to any one of Items 1 to 7, further containing a cross-linking agent (B).

9. Item 8 The resin composition according to Item 8, wherein the component (B) is a polyepoxy compound (B1) and / or a polyphenylene ether compound (B2).

10. Item 9. The resin composition according to Item 9, wherein the component (B1) is tetraglycidyl xylene diamine having the following structure.
(In the formula, Z ¹ represents a phenylene group or a cyclohexenyl group.)

11. Item 9. The polyimide resin composition according to Item 9 or 10, wherein the component (B2) is a hydroxyl group-containing polyphenylene ether having the following structure.
(In the formula, Z ² represents an alkylene group or a single bond having 1 to 3 carbon atoms, m represents 0 to 20, n represents 0 to 20, and the sum of m and n represents 1 to 30. )

12. The polyimide resin composition according to any one of Items 1 to 11, further containing an organic solvent (C).

13. Further general formula: Q-Si (R ¹ ) _a (OR ² ) _3-a (In the formula, Q is a group containing a functional group that reacts with an acid anhydride group, and R ¹ is hydrogen or having 1 to 8 carbon atoms. Item 1 to the above, which contains a hydrocarbon group, R ² is a hydrocarbon group having 1 to 8 carbon atoms, and a is a reactive alkoxysilyl compound (D) represented by 0, 1 or 2). 12 of any resin composition.

14. An adhesive comprising the resin composition according to any one of Items 1 to 13.

15. A film-like adhesive made of a cured product of the adhesive according to Item 14.

16. An adhesive sheet using the cured product of the adhesive according to Item 14 as an adhesive layer.

17. A multilayer wiring board obtained by using at least one selected from the group consisting of the adhesive of item 14, the film-like adhesive of item 15, and the adhesive sheet of item 16.

18. A copper foil with a resin obtained by using at least one selected from the group consisting of the adhesive of item 14, the film-like adhesive of item 15, and the adhesive sheet of item 16.

19. A copper-clad laminate obtained by using the resin-attached copper foil according to Item 18.

20. A printed wiring board obtained by using the copper-clad laminate of Item 19.

The resin composition of the present invention has good adhesive strength as well as initial adhesiveness to various substrates. Further, the cured product (adhesive layer) has a low tack, does not foam when heated, hardly causes adhesive residue, and is excellent in adhesive strength and low dielectric properties.

The resin composition and cured product are adhesives for manufacturing printed circuit boards (build-up boards, flexible printed circuit boards, etc.) and copper-clad boards for flexible printed circuit boards, carrier tapes such as TAB tapes and COF tapes, and carrier sheets. It is useful as an adhesive, a semiconductor interlayer material, a coating agent, an electrically insulating material such as a resist ink, and the like.

Further, the multilayer wiring board, the copper foil with resin, the copper-clad laminate, and the printed wiring board of the present invention all have a cured product (adhesive layer) of the adhesive of the present invention, which has adhesive strength and low dielectric constant. Products that require a high degree of low-dielectric characteristics due to their excellent characteristics, such as mobile communication devices such as smartphones and mobile phones, their base station devices, network-related electronic devices such as servers and routers, and large computers. It is useful as a material for products that handle high-frequency signals.

The resin composition of the present invention, an aromatic tetracarboxylic acid dianhydride content of less than 1% by weight of free carboxylic acid (a1) (hereinafter, (a1) also referred to as components.) And hydrogenated dimer diamine (a2) The monomer group (1) (hereinafter, also referred to as (1) component) containing (hereinafter, also referred to as (a2) component) and not containing the diaminopolysiloxane (a3) (hereinafter, also referred to as (a3) component). ) Is reacted to contain a polyimide (A1) (hereinafter, also referred to as a component (A1)).

The component (a1), any of various known aromatic tetracarboxylic acid dianhydride, content of less than 1% by weight of free carboxylic acid, preferably from 0.5% or less, most preferably 0.2 weight Use less than%. By using the component (a1), it is possible to enhance the low dielectric property of the adhesive according to the present invention while maintaining the adhesive strength.

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,2,3,4-benzene tetracarboxylic acid anhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic acid Anhydroide, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenone Tetetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis ( 3,3', 4,4'-tetracarboxyphenyl) tetrafluoropropanedianhydride, 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfonate dianhydride, 2,2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride and 4,4'-[propane-2,2-diyl bis (1,4-phenyleneoxy) )] Diphthalic acid dianhydride and the like can be mentioned, and two or more types may be combined.

(In the formula, X is a single bond, -SO _2- , -CO-, -O-, -O-C ₆ H _4- C (CH ₃ ) _2- C ₆ H _4- O- or -COO-Y- It represents OCO- (Y indicates − (CH ₂ ) _l − (l = 1 to 20) or −H ₂ C—HC (−OC (= O) −CH ₃ ) −CH ₂₋ ). )

Examples of the aromatic tetracarboxylic dianhydride, from the viewpoint of adhesion and low dielectric properties of the adhesive according to the present invention, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 4,4 '- [propane-2,2-diyl bis (1,4-phenyleneoxy)] diphthalic dianhydride, and 4,4'-oxydiphthalic least one anhydride selected from the group consisting of compounds are preferred.

Examples of the free carboxylic acid include aromatic tetracarboxylic acid, aromatic tetracarboxylic acid monoanhydride, aromatic tricarboxylic acid, aromatic tricarboxylic acid anhydride, aromatic dicarboxylic acid, and aromatic dicarboxylic acid anhydride. Be done. For example, the 3,3 ', in the case of 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid or a monoanhydride, and 3,3 ' , 4-Benzophenone tricarboxylic acid (see structure below; molecular weight about 356) and the like.

The content of the free carboxylic acid in the component (a1) can be quantified by various known analytical means such as high performance liquid chromatography (HPLC) and mass spectrometer (GC-MASS).

The component (a2) is a hydride of a multimer (see JP-A-9-12712, etc.) derived from dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid, and hereinafter, non-dimer acid. Shows a limited structural formula. In each structural formula, m + n = 6 to 17 and p + q = 8 to 19, and the broken line portion means a carbon-carbon single bond or a carbon-carbon double bond. The component (a2) is one in which at least one or all of the carbon-carbon double bonds are single bonds.

Examples of commercially available products of the component (a2) include PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.). The following is an example of hydrogenated dimer diamine.

The molar ratio of the component (a1) to the component (a2) in the component (1) [(a1) / (a2)] is not particularly limited, but is usually 1 to 1 from the viewpoint of the balance between the adhesive force and the low dielectric property. It is about 5, preferably about 1 to 1.2.

In the present invention, the component (a3) is not included in the component (1) from the viewpoint of low dielectric properties. Specific examples of the component (a3) will be described later.

The component (1) can include a diamine (hereinafter, also referred to as a component (a4)) other than the components (a1) to (a3). Specifically, for example, diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, 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, 1,3-bisaminomethylcyclohexane, isophoronediamine, etc. Alicyclic diamines; bisaminophenoxyphenyl propanes 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, 4,4'-diaminodiphenyl ether; phenylenediamines such as p-phenylenediamine, m-phenylenediamine; 3,3'- Diaminodiphenyl sulfides such as diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide; 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4' Diaminodiphenylsulfones such as −diaminodiphenylsulfone; diaminobenzophenones such as 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone; 3,3′-diaminodiphenylmethane, 4, Diaminodiphenylmethanes such as 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane; 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-) Diaminophenyl propanes such as aminophenyl) -2- (4-aminophenyl) propane; 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2, 2-Di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1, Diaminophenyl hexafluoropropanes such as 3,3,3-hexafluoropropane; 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenyl Diaminophenylphenyl ethanes such as ethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenyl ethane; 1,3-bis (3-aminophenoxy) benzene, 1,3-bis Bisaminophenoxybenzenes such as (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene; 1,3-bis (3-amino) Bisaminobenzoylbenzenes such as benzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, and 1,4-bis (4-aminobenzoyl) benzene; 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, Bisaminodimethylbenzenes such as α-dimethylbenzyl) benzene and 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene; 1,3-bis (3-amino-α, α-ditrifluoromethyl) Benzene) Benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4- Bisaminoditrifluoromethylbenzylbenzenes such as bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene; 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-amino) Aminophenoxybiphenyls such as phenoxy) pyridine, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl; bis [4- (3-aminophenoxy) phenyl] Aminophenoxyphenyl ketones such as ketones and bis [4- (4-aminophenoxy) phenyl] ketones; bis [4- (3-aminophenoxy) phenyl] sulfides, bis [4- (4-aminophenoxy) phenyl] sulfides Aminophenoxyphenyl sulfides such as; Aminophenoxyphenylsulfones such as bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone; Aminophenoxyphenyl ethers such as aminophenoxy) phenyl] ether and bis [4- (4-aminophenoxy) phenyl] ether; 2 , 2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, Aminophenoxyphenyl propanes such as 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane; and others, 1,3-bis [4- (4-aminophenoxy) phenyl] (3-Aminophenoxy) Benzene] 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, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino) Phenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -Α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) Phenoxy] Benzenephenone, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino -4-biphenoxybenzophenone, 6,6'-bis (3-aminophenoxy) 3,3,3,'3,'-tetramethyl-1,1'-spirobiindane, 6,6'-bis (4-amino) Phenoxy) 3,3,3,'3,'-tetramethyl-1,1'-spirobiindan, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) Tetramethyldisiloxane, 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-aminoprotoxy) ethyl] d -Tel, 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, ethyleneglycolbis (3-aminopropyl) ether, diethyleneglycorubis (3-aminopropyl) ether, triethyleneglycorubis (3-aminopropyl) ether, 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 can be mentioned, and two or more of them may be combined. Among these, the alicyclic diamine is preferable from the viewpoint of low dielectric properties. The amount of the component (a4) used is not particularly limited, but is usually less than 40 mol% when the total diamine component is 100 mol%.

The component (A1) can be produced by various known methods. Specifically, for example, the acid component and the diamine component used for each are subjected to a heavy addition reaction at a temperature of about 60 to 120 ° C. for about 0.1 to 2 hours. Then, the obtained heavy adduct may be further subjected to an imidization reaction, that is, a dehydration ring closure reaction at a temperature of about 80 to 250 ° C., preferably 100 to 200 ° C. for about 0.5 to 50 hours. Further, in those reactions, the component (C) described later, particularly an aprotic polar solvent, can be used as the reaction solvent.

In the imidization reaction, various known reaction catalysts, dehydrating agents, and solvents described later can be used. 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. The above may be combined. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride, and two or more kinds may be combined.

The imide ring closure rate is not particularly limited, but is usually 70% or more, preferably 85 to 100%. Here, the "imide ring closure rate" means the content of the cyclic imide bond in the component (A1) (hereinafter, the same applies), and can be determined by various spectroscopic means such as NMR and IR analysis.

The physical properties of the component (A1) are not particularly limited, but from the viewpoint of the balance between the adhesive strength and the low dielectric property, the number average molecular weight (refers to the polystyrene conversion value by gel permeation chromatography; hereinafter the same) is usually 5000 to It is about 50,000, preferably about 7,000 to 30,000, and the glass transition temperature (JIS-K7121) is about 30 to 160 ° C, preferably about 40 to 140 ° C. The concentration of the terminal acid anhydride group of the component (A1) is also not particularly limited, but is usually about 2000 to 40,000 eq / g, preferably about 3000 to 20000 eq / g.

The molecular terminal of the component (A1) may be further modified (sealed) with a low molecular weight primary alkyl monoamine. Specific examples thereof include ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopentylamine, tert-pentylamine, n-octylamine and n-. Examples thereof include decylamine, isodecylamine, n-tridecylamine, n-laurylamine, n-cetylamine, n-stearylamine, and those having an alkyl group having about 4 to 15 carbon atoms from the viewpoint of low dielectric properties. preferable. The amount of the primary alkyl monoamine used is also not particularly limited, but is usually about 0.8 to 1.2 mol, preferably 0.9 to 1, 1 mol with respect to 1 mol of the terminal acid anhydride group of the component (A1). It is about 1 mol.

The resin composition of the present invention may contain polyimide (A2) (hereinafter, also referred to as (A2) component) other than the component (A1).

As the component (A2), various known polyimides other than the component (A1) can be used, but preferably, an aromatic having a content of the component (a1) and / or a free carboxylic acid of 1% by weight or more. tetracarboxylic acid dianhydride (a1 ') (hereinafter, (a1') also referred to as components.) and, (a2) component and / or non-hydrogenated dimer diamine (a2 ') (hereinafter, (a2' also referred to as a) component ), And a polyimide obtained by reacting a monomer group (2) (hereinafter, also referred to as a component (2)) (however, excluding those corresponding to the component (A1)) can be mentioned.

(A1 ') As the component of the aromatic tetracarboxylic dianhydride, as long as the content of the free carboxylic acid is not less than 1 wt%, those of various known can be used without particular limitations. Further, a combination of the component (a1) and the free carboxylic acid so that the content thereof is 1% by weight or more can also be used as the component (a1'). The upper limit of the content of the free carboxylic acid in the component (a1') is usually 5% by weight or less from the viewpoint of improving the low dielectric property while maintaining the adhesive strength of the adhesive according to the present invention.

Examples of the component (a2') include those described in JP-A-9-12712, etc., and examples of commercially available products include Versamine 551 (manufactured by BASF Japan Ltd.) and PRIAMINE 1074 (Croda Japan). (Made by Co., Ltd.) can be exemplified.

The component (2) may also include the component (a3). Examples of the component (a3) include various known diaminopolysiloxanes, such as α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, and 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 can be exemplified.

Hereinafter, typical examples of combinations of raw materials in the component (2) are shown.
I. (A1) component, (a2) component and (a3) component b. (A1) component and (a2') component c. (A1) component, (a2') component and (a3) component d. (A1') component and (a2) component e. (A1') component, (a2) component and (a3) component f. (A1') component and (a2') component g. (A1') component, (a2') component and (a3) component chi. (A1) component, (a2) component and (a4) component l. (A1') component, (a2) component and (a4) component n. Component (a1), component (a2') and component (a4)

(2) Molar ratio of component (a1) and / or component (a1') to component (a2) and / or component (a2') [(a1, a1') / (a2, a2')] Is not particularly limited, but is usually about 1 to 1.5, preferably about 1 to 1.2.

When the component (a3) is included in the component (2), the amount used is not particularly limited, but it is usually about 0.1 to 5.0 mol% when the total diamine component is 100 mol%. ..

The component (2) may also include the component (a4). In this case, the amount of the component (a4) used is not particularly limited, but is usually less than 40 mol% when the total diamine component is 100 mol%.

The method for producing the component (A2) is the same as that of the component (A1). The imide ring closure rate of the component (A2) is also not particularly limited, but is usually 70% or more, preferably 85 to 100%.

The physical properties of the component (A2) are not particularly limited, but from the viewpoint of the balance between the adhesive strength and the low dielectric property, the number average molecular weight (refers to the polystyrene conversion value by gel permeation chromatography; hereinafter the same) is usually 5000 to It is about 50,000, preferably about 7,000 to 30,000, and the glass transition temperature (JIS-K7121) is about 30 to 160 ° C, preferably about 40 to 140 ° C. The concentration of the terminal acid anhydride group of the component (A2) is also not particularly limited, but is usually about 2000 to 40,000 eq / g, preferably about 3000 to 20000 eq / g.

The molecular end of the component (A2) may be modified (sealed) with the primary alkyl monoamine.

The solid content-weight ratio of the component (A1) to the component (A2) [(A1) / (A2)] is not particularly limited, but is usually 30 / from the viewpoint of particularly low dielectric properties of the cured product of the composition containing both. It is about 70 to 90/10, preferably about 40/60 to 99/1.

The resin composition of the present invention may further contain a cross-linking agent (B) (hereinafter, also referred to as a component (B)).

As the component (B), various known components can be used without particular limitation, for example, a polyepoxy compound (B1) (hereinafter, also referred to as (B1) component), a polyphenylene ether compound (B2) (hereinafter, (B2) component). (Also also referred to as), and cross-linking agents other than these (hereinafter, also referred to as (B3) component). Among these, the component (B1) and / or the component (B2) are preferable.

Examples of the component (B1) include phenol novolac type epoxy compound, cresol novolac type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, hydrogenated bisphenol A type epoxy compound, and hydrogenated bisphenol F. Type epoxy compound, stillben type epoxy compound, triazine skeleton-containing epoxy compound, fluorene skeleton-containing epoxy compound, linear aliphatic epoxy compound, alicyclic epoxy compound, glycidylamine type epoxy compound, triphenolmethane type epoxy compound, alkyl-modified tri Phenolmethane type epoxy compound, biphenyl type epoxy compound, dicyclopentadiene skeleton-containing epoxy compound, naphthalene skeleton-containing epoxy compound, arylalkylene type epoxy compound, tetraglycidylxylylene diamine, modified epoxy obtained by modifying these epoxy compounds with dimer acid. Examples thereof include compounds and diglycidyl esters of dimer acid, and two or more of them may be combined. Examples of commercially available products include "jER828" and "jER834", "jER807" and "jER630" manufactured by Mitsubishi Chemical Corporation, "ST-3000" manufactured by Nippon Steel Chemical Corporation, and Daicel Chemical Corporation (Daicel Chemical Corporation). Examples thereof include "Selokiside 2021P" manufactured by Nippon Steel Corporation and "YD-172-X75" manufactured by Nippon Steel Chemical Corporation.

Among the components (B1), tetraglycidyl xylene diamine having the following structure is preferable from the viewpoint of compatibility and heat resistance, and for example, a commercially available product such as "Tetrad-X" manufactured by Mitsubishi Gas Chemical Company, Inc. can be used.

(In the formula, Z ¹ represents a phenylene group or a cyclohexylene group.)

When the component (B1) is used, various known curing agents for epoxy compounds can be used in combination. Specifically, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride Acid, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadicic anhydride, methylnadic anhydride, norbornan-2,3-dicarboxylic acid anhydride Acid anhydride-based curing agents such as methylnorbornan-2,3-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 3-dodecenyl phthalic anhydride, octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamine ( Product names "LonzacureM-DEA", "LonzacureM-DETDA", etc. All are manufactured by Lonza Japan Co., Ltd., amine-based curing agents such as aliphatic amines; Modified phenol novolak resin, phenolic curing agent such as phenolic hydroxyl group-containing phosphazene (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.), cyclic phosphazene compound, maleic anhydride-modified rosin and rosin such as hydride thereof. Examples include system cross-linking agents, and two or more types may be combined. Among these, a phenolic curing agent, particularly a phenolic hydroxyl group-containing phosphazene-based curing agent is preferable. The amount of these curing agents used is not particularly limited, but is usually about 0.1 to 120% by weight, preferably about 10 to 40% by weight, when the solid content of the adhesive of the present invention is 100% by weight. is there.

Further, when the component (B1) is used, a curing catalyst can also be used. Specifically, for example, 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and the like. Class amines; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole- Lus; Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine; tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholin -Tetraphenylborone salts such as tetraphenylborate; organic acids such as octanoic acid, stearic acid, acetylacetonate, naphthenic acid, and salicylic acid; organic metal salts such as Zn, Cu, and Fe, and two or more combinations thereof. May be. The amount of the catalyst used is not particularly limited, but is usually about 0.01 to 5% by weight when the solid content of the adhesive of the present invention is 100% by weight.

As the component (B2), various known components can be used without particular limitation. Specifically, those represented by the following general formulas are preferable.

(In the formula, Z ² represents an alkylene group or a single bond having 1 to 3 carbon atoms, m represents 0 to 20, n represents 0 to 20, and the sum of m and n represents 1 to 30. )

The physical properties of the component (B2) are not particularly limited, but from the viewpoint of adhesive strength and low dielectric properties, it is usually preferable that the terminal hydroxyl group concentration is about 900 to 2500 μmol / g and the number average molecular weight is about 800 to 2000.

As the component (B3), for example, at least one selected from the group consisting of a benzoxazine compound, a bismaleimide compound and a cyanate ester compound can be mentioned.

Examples of the benzoxazine compound include 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,6- (1-methylethylidene). ) Bis (3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like, and two or more kinds may be combined. A phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to the nitrogen of the oxazine ring. Examples of commercially available products include "benzoxazine FA type" and "benzoxazine Pd type" manufactured by Shikoku Chemicals Corporation, and "RLV-100" manufactured by Air Water Co., Ltd. Can be mentioned.

Examples of the bismaleimide compound include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane. Bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulphon Bismaleimide and the like can be mentioned, and two or more kinds may be combined. Moreover, as a commercial product, for example, "BAF-BMI" manufactured by JFE Chemical Co., Ltd. and the like can be mentioned.

Examples of the cyanate ester compound include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, and 2,2-bis (4-cyanatophenol) -1,1,1,3,3,3-hexafluoro. Propane, bisphenol A cyanate ester, diallyl bisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris (4-cyanatophenyl) ethane, 4-cumylphenol cyanate ester, 1,1-bis ( Examples thereof include 4-cyanatophenyl) ethane, 4,4'-bisphenol cyanate ester, and 2,2-bis (4-cyanatophenyl) propane, and two or more thereof may be combined. Examples of commercially available products include "PRIMASET BTP-6020S (manufactured by Lonza Japan Co., Ltd.)" and "CYTESTER TA (manufactured by Mitsubishi Gas Chemical Company, Inc.)".

The amount of the component (B) used is not particularly limited, but usually, 3 to 3 to 100 parts by weight of the total of the components (A1) and (A2) (hereinafter, both may be collectively referred to as the component (A)). It is about 30 parts by weight, preferably about 5 to 25 parts by weight.

The resin composition of the present invention may contain an organic solvent (C) (hereinafter, also referred to as a component (C)).

As the component (C), various known solvents can be used without particular limitation. Specific examples thereof include aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylcaprolactam, methyltriglime, and methyldiglyme, cyclohexanone, methylcyclohexane, and the like. Examples thereof include an alicyclic solvent, an alcohol solvent such as methanol, ethanol, propanol, benzyl alcohol and cresol, an aromatic solvent such as toluene, and two or more thereof may be combined. Among these, aromatic solvents are particularly preferable from the viewpoint of low dielectric properties.

The amount of the component (C) used is not particularly limited, but is usually about 0.1 to 10 parts by weight, preferably about 1 to 5 parts by weight, based on 100 parts by weight of the component (A).

The resin composition of the present invention further contains a general formula: Q-Si (R ¹ ) _a (OR ² ) _3-a (in the formula, Q is a group containing a functional group that reacts with an acid anhydride group, R ¹ Is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² is a hydrocarbon group having 1 to 8 carbon atoms, and a is a reactive alkoxysilyl compound (D) represented by 0, 1 or 2. ) (Hereinafter, also referred to as component (D)) can be included. Examples of the reactive functional group contained in Q include an amino group, an epoxy group and a thiol group.

The component (D) can adjust the melt viscosity of the cured layer of the adhesive according to the present invention while maintaining the low dielectric properties. As a result, it becomes possible to suppress the exudation of the cured layer generated from the edge of the substrate while increasing the interfacial adhesion between the cured layer and the substrate (so-called anchor effect) (hereinafter, such an operation is performed. Sometimes called control.)

Examples of the compound in which the functional group in Q is an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-. Examples thereof include aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and 3-ureidopropyltrialkoxysilane.

Examples of the compound in which the functional group in Q is an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3 -Glysidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and the like can be mentioned.

Examples of the compound in which the functional group in Q is a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Be done.

As the component (D), a compound having an amino group as the functional group in Q is preferable because it reacts rapidly with the terminal acid anhydride group of the component (A) and the effect of the flow control is good.

The amount of the component (D) used is not particularly limited, but is usually about 0.01 to 5 parts by weight, preferably about 0.1 to 3 parts by weight, based on 100 parts by weight of the component (A).

The adhesive of the present invention comprises a resin composition, and the resin composition may be used as it is, and if necessary, the ring-opening esterification reaction catalyst, a dehydrating agent, a plasticizer, a weather resistant agent, and an oxidation are used. Inhibitors, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, phosphorus flame retardants, flame retardant fillers, silica fillers, fluorine fillers, etc. Additives and diluting solvents may be added.

The film-like adhesive of the present invention is obtained by curing the adhesive of the present invention by various known means. Specifically, for example, the adhesive is applied to various supports, heated, cured by volatilizing the component (C), and then peeled off from the support. It can be used as a film-like adhesive. Further, the coating means is not particularly limited, and examples thereof include a curtain coater, a roll coater, and a laminator. The thickness of the coating layer is also not particularly limited, but the thickness after drying is usually in the range of about 1 to 100 μm, preferably about 3 to 50 μm.

The adhesive sheet of the present invention is an article having the cured product as an adhesive layer. Specifically, it is composed of the cured product and various known sheet base materials, and the sheet base material includes, for example, polyester, polyimide, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, and poly. Aromatic polyester resin obtained from methyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, etc. and parahydroxybenzoic acid (so-called liquid crystal polymer; Examples include plastic films manufactured by Kuraray Co., Ltd., "Vexter", etc.). The thickness of the adhesive layer is also not particularly limited, but is usually in the range of about 1 to 100 μm, preferably about 3 to 50 μm.

The multilayer wiring board according to the present invention is an article obtained by using at least one selected from the group consisting of the polyimide-based adhesive, the film-like adhesive, and the adhesive sheet. Specifically, they are used to form an adhesive layer on at least one surface of a printed wiring board which is a core base material, another printed wiring board or a printed circuit board is laminated on the adhesive layer, and then pressure-bonded under heating and pressure. Can be obtained by doing. The heating temperature, crimping time and pressure are not particularly limited, but are usually about 70 to 200 ° C., about 1 minute to 3 hours, and about 0.5 to 20 MPa.

The copper foil with resin of the present invention is an article formed by forming an adhesive layer on the copper foil using at least one selected from the group consisting of the polyimide adhesive, the film-like adhesive, and the adhesive sheet. Examples of the copper foil include rolled copper foil and electrolytic copper foil, which may be subjected to various surface treatments (roughening, rust prevention, etc.). The thickness of the copper foil is not particularly limited, and is usually about 1 to 100 μm, preferably about 2 to 38 μm. The adhesive layer of the resin-attached copper foil may be uncured, or may be partially cured or completely cured under heating. The partially cured adhesive layer is in a so-called B stage. Further, the thickness of the adhesive layer is not particularly limited, and is usually about 0.5 to 30 μm. Further, the copper foil can be further attached to the adhesive surface of the obtained copper foil with resin to obtain a copper foil with double-sided resin.

The copper-clad laminate of the present invention is an article obtained by laminating a copper foil with a resin of the present invention and a copper foil or an insulating sheet, and is also called CCL (Copper Clad Laminate). Specifically, the resin-coated copper foil of the present invention is pressure-bonded to at least one or both sides of various known insulating sheets under heating. Further, in the case of one side, a material different from the resin-attached copper foil of the present invention may be pressure-bonded to the other side. Further, the number of resin-attached copper foils and insulating sheets in the copper-clad laminate is not particularly limited. Further, as the insulating sheet, a prepreg is preferable. The prepreg is a sheet-like material obtained by impregnating a reinforcing material such as glass cloth with a resin and curing it up to the B stage (JIS C 5603), and the resin is usually polyimide, phenol resin, epoxy resin, or polyester. Insulating resins such as resins, liquid crystal polymers, and aramid resins are used. The thickness of the prepreg is not particularly limited, and is usually about 20 to 500 μm. The heating / crimping conditions are not particularly limited, and are usually about 150 to 280 ° C. and about 0.5 to 20 MPa.

The printed wiring board of the present invention has a circuit pattern formed on the copper foil surface of the copper-clad laminate. Examples of the patterning means include a subtractive method and a semi-additive method. Examples of the semi-additive method include a method in which the copper foil surface of the copper-clad laminate of the present invention is patterned with a resist film, then electrolytically copper-plated to remove the resist, and then etched with an alkaline solution. Further, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. Further, a multilayer board can also be obtained by using the printed wiring board as a core base material and laminating the same printed wiring board or another known printed wiring board or printed circuit board on the printed wiring board. In laminating, not only the polyimide-based adhesive of the present invention but also other known polyimide-based adhesives can be used. Further, the number of layers in the multilayer board is not particularly limited. Further, a via hole may be inserted each time the lamination is performed, and the inside may be plated.

Hereinafter, the present invention will be specifically described through Examples and Comparative Examples, but the scope of the present invention is not limited thereto. In each example, parts and% are based on weight unless otherwise specified.

Manufacturing example 1
Commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-UP", manufactured by Ebonic Japan Co., Ltd .; 3,3) in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. 210.0 g of', 4,4'-benzophenone tetracarboxylic dianhydride content (99.9% or more), 1008.0 g of cyclohexanone, and 201.6 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Next, 341.7 g of hydrogenated dimer diamine (trade name "PRIAMINE 1075", manufactured by Crowder Japan Co., Ltd.) was added dropwise, and then an imidization reaction was carried out at 140 ° C. for 10 hours to obtain a softening point of about 80 ° C. and a weight. A solution (nonvolatile content: 30.0%) of a polyimide resin (A1-1) having an average molecular weight of about 35,000 was obtained. The molar ratio of the acid component / amine component was 1.03.

Manufacturing example 2
Commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA2000", manufactured by SABIC Japan GK; 4,4'-[Propane-2,2-diylbis (1,4)" in the same reaction vessel as in Production Example 1. -Phenyleneoxy)] The content of diphthalic dianhydride was 99.5% or more) 60.0 g, 165.0 g of cyclohexanone, and 27.5 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Next, 59.3 g of PRIAMINE 1075 was added dropwise, and then the imidization reaction was carried out at 140 ° C. for 10 hours to obtain a solution of a polyimide resin (A1-2) having a softening point of about 90 ° C. and a weight average molecular weight of about 30,000. (Non-volatile content 31.9%) was obtained. The molar ratio of the acid component / amine component was 1.05.

Comparative manufacturing example 1
A commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA-1000", manufactured by SABIC Japan GK; 4,4'-[Propane-2,2-diylbis (1)" is placed in the same reaction vessel as in Production Example 1. , 4-Phenyleneoxy)] The content of diphthalic dianhydride was 98.0%) 65.0 g, cyclohexanone 266.5 g, and methylcyclohexane 44.4 g were charged, and the solution was heated to 60 ° C. Next, 43.7 g of polyimideine 1075 and 5.4 g of 1,3-bisaminomethylcyclohexane were added dropwise, and then the imidization reaction was carried out at 140 ° C. for 10 hours to obtain a softening point of about 100 ° C. and a weight average molecular weight of about 30. A solution of 000 polyimide resin (A2-1) (nonvolatile content 29.2%) was obtained. The molar ratio of the acid component / amine component was 1.05.

Comparative manufacturing example 2
A commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-PF", manufactured by Ebony Japan Co., Ltd .; 3,3', 4,4'-benzophenone tetracarboxylic acid) is placed in the same reaction vessel as in Production Example 1. (98% content of dianhydride) 200.0 g, 960.0 g of cyclohexanone and 192.0 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Next, after dropping 319.2 g of PRIAMINE 1075, an imidization reaction was carried out at 140 ° C. for 10 hours to obtain a solution of a polyimide resin (A2-2) having a softening point of about 80 ° C. and a weight average molecular weight of about 25,000. Non-volatile content 29.8%) was obtained. The molar ratio of the acid component / amine component was 1.05.

Comparative manufacturing example 3
190.0 g of BTDA-PF, 277.5 g of cyclohexanone, and 182.4 g of methylcyclohexane were charged in the same reaction vessel as in Production Example 1, and the solution was heated to 60 ° C. Next, 23.8 g of PRIAMINE 1075 277.5 g and a commercially available polydimethylsiloxane (trade name "KF-8010", manufactured by Shin-Etsu Chemical Co., Ltd.) were added dropwise, and then the imidization reaction was carried out at 140 ° C. for 10 hours. A solution (nonvolatile content 29.8%) of a polyimide resin (A2-3) having a softening point of about 70 ° C. and a weight average molecular weight of about 15,000 was obtained. The molar ratio of the acid component / amine component was 1.09.

Comparative manufacturing example 4
In the same reaction vessel as in Production Example 1, 190.0 g of BTDA-UP, 912.0 g of cyclohexanone, and 182.4 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Next, 476.0 g of KF-8010 was added dropwise, and then the imidization reaction was carried out at 140 ° C. for 10 hours to obtain a solution of a polyimide resin (A2-4) having a softening point of about 20 ° C. and a weight average molecular weight of about 35,000. (Non-volatile content 36.7%) was obtained. The molar ratio of the acid component / amine component was 1.09.

Comparative manufacturing example 5
In the same reaction vessel as in Production Example 1, 200.0 g of BTDA-UP, 960.0 g of cyclohexanone, and 192.0 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Next, 319.2 g of a commercially available non-hydrogenated dimer diamine (trade name "PRIAMINE 1074", manufactured by Crowder Japan Co., Ltd.) was added dropwise, and then an imidization reaction was carried out at 140 ° C. for 10 hours to soften the softening point of about 70. A solution (nonvolatile content 29.8%) of polyimide (A2-5) at ° C. and a weight average molecular weight of about 25,000 was obtained. The molar ratio of the acid component / amine component was 1.05.

Comparative manufacturing example 6
In the same reaction vessel as in Production Example 1, 200.0 g of BisDA-1000, 700.0 g of cyclohexanone, and 175.0 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Next, 190.5 g of a commercially available hydrogenated dimer diamine (trade name "PRIAMINE 1075", manufactured by Crowder Japan Co., Ltd.) was added dropwise, and then an imidization reaction was carried out at 140 ° C. for 10 hours to soften the temperature at about 80 ° C. And a solution (nonvolatile content 29.9%) of polyimide (A2-6) having a weight average molecular weight of about 35,000 was obtained. The molar ratio of the acid component / amine component was 1.09.

<Measurement of relative permittivity and dielectric loss tangent of polyimide resin film>
The polyimide solutions of the production example and the comparative production example were subjected to Naflon PTFE tape TOMBO No. A cured product sheet having a film thickness of 50 μm was obtained by coating on 9001 (Nichias Corporation), drying at room temperature for 12 hours, and then curing at 200 ° C. for 1 hour. Next, with respect to the cured product sheet, the relative permittivity (Dk) and the dielectric loss tangent (Df) at 10 GHz are measured using a commercially available permittivity measuring device (cavity resonator type, manufactured by AET) according to JIS C2565. did. The results are shown in Table 1.

Example 1
100.00 g of solution of component (A1-1), 1.67 g of tetraglycidyl xylene diamine (trade name "Tetrad-X", manufactured by Mitsubishi Gas Chemical Company, Inc.) as component (B) and hydroxyl group-containing polyphenylene ether (trade name "" SA90 "SABIC Co., Ltd.) 1.67 g, (C) component 7.87 g of toluene, and (D) component commercially available amino group-containing silane coupling agent (trade name" KBM603 ", Shin-Etsu Chemical Co., Ltd. ); 0.07 g of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane) was mixed to obtain a resin composition (adhesive) having a non-volatile content of 30.0%.

Example 2
A resin composition having a non-volatile content of 30.0% (adhesion) by mixing 100.00 g of a solution of the component (A1-2), 1.78 g of Tetrad-X and 1.78 g of SA90, 14.78 g of toluene, and 0.07 g of KBM603. Agent) was obtained.

Example 3
100.00 g of the solution of the component (A1-1), 25.17 g of the solution of the component (A2-3), 2.09 g of Tetrad-X and 2.09 g of SA90, 9.59 g of toluene, and 0.08 g of KBM603 were mixed. A resin composition (adhesive) having a non-volatile content of 30.0% was obtained.

Example 4
100.00 g of the solution of the component (A1-1), 25.17 g of the solution of the component (A2-3), 3.32 g of Tetrad-X and 3.32 g of SA90, 15.32 g of toluene, and 0.09 g of KBM603 were mixed. A resin composition (adhesive) having a non-volatile content of 30.0% was obtained.

Example 5
100.00 g of the solution of the component (A1-2), 26.76 g of the solution of the component (A2-3), 2.21 g of Tetrad-X and 2.21 g of SA90, 16.58 g of toluene, and 0.08 g of KBM603 were mixed. A resin composition (adhesive) having a non-volatile content of 30.0% was obtained.

Example 6
30.00 g of the solution of the component (A1-1), 30.82 g of the solution of the component (A2-1) and 15.10 g of the solution of the component (A2-3), a commercially available polyfunctional epoxy resin (trade name "jER630", Mitsubishi Chemical Co., Ltd .; N, N-diglycidyl-4-glycidyloxyaniline) 1.20 g and phenol novolac resin (trade name "T759", manufactured by Arakawa Chemical Industry Co., Ltd.) 1.30 g, toluene 3.81 g, 1.30 g of methyl ethyl ketone and 0.05 g of KBM603 were mixed to obtain a resin composition (adhesive) having a non-volatile content of 30.0%.

Example 7
(A1-1) component solution 30.00 g, (A2-1) component solution 30.82 g and (A2-3) component solution 15.10 g, jER630 0.57 g and T759 0.62 g, toluene 1.33 g , 0.62 g of methyl ethyl ketone and 0.05 g of KBM603 were mixed to obtain a resin composition (adhesive) having a non-volatile content of 30.0%.

Example 8
100.00 g of a solution of the component (A1-1), 1.67 g of Tetrad-X, and 3.90 g of toluene were mixed to obtain a resin composition (adhesive) having a non-volatile content of 30.0%.

Example 9
(A1-1) component solution 30.00 g, (A2-1) component solution 30.82 g and (A2-6) component solution 15.05 g, jER630 0.57 g and T759 0.62 g, toluene 1.37 g , 0.62 g of methyl ethyl ketone and 0.05 g of KBM603 were mixed to obtain a resin composition (adhesive) having a non-volatile content of 30.0%.

Example 10
30.00 g of the solution of the component (A1-1), 30.82 g of the solution of the component (A2-1) and 15.05 g of the solution of the component (A2-6), jER630 3.30 g and Bis-A type cyanate ester (trade name). "CYTESTER TA", manufactured by Mitsubishi Gas Chemical Company, Ltd. (2.34 g), toluene (8.96 g), methyl ethyl ketone (3.51 g) and KBM603 (0.05 g) are mixed to form a resin composition (adhesive) having a non-volatile content of 30.0%. Obtained.

Example 11
(A1-1) component solution 30.00 g, (A2-1) component solution 30.82 g and (A2-6) component solution 15.05 g, jER630 0.70 g and CYTESTER TA 0.49 g, toluene 1. 39 g, 0.74 g of methyl ethyl ketone and 0.05 g of KBM603 were mixed to obtain a resin composition (adhesive) having a non-volatile content of 30.0%.

Example 12
100.00 g of the solution of the component (A1-1) and 25.17 g of the solution of the component (A2-3), 0.58 g of Tetrad-X and 0.58 g of SA90, 2.54 g of toluene, and 0.08 g of KBM603 were mixed. A resin composition (adhesive) having a non-volatile content of 30.0% was obtained.

Comparative Example 1
A resin composition having a non-volatile content of 30.0% (adhesion) by mixing 100.00 g of a solution of the component (A2-2), 1.65 g of Tetrad-X and 1.65 g of SA90, 7.05 g of toluene, and 0.07 g of KBM603. Agent) was obtained.

Comparative Example 2
A resin composition having a non-volatile content of 30.0% (adhesion) by mixing 100.00 g of a solution of the component (A2-3), 1.65 g of Tetrad-X and 1.65 g of SA90, 7.05 g of toluene, and 0.07 g of KBM603. Agent) was obtained.

Comparative Example 3
A mixture of 20.00 g of the solution of the component (A1-1), 80.54 g of the component (A2-3), 1.67 g of Tetrad-X and 1.67 g of SA90, 7.47 g of toluene, and 0.07 g of KBM603 are mixed to form a non-volatile component. A 30.0% resin composition (adhesive) was obtained.

Comparative Example 4
A mixture of 100.00 g of the solution of the component (A1-1), 25.17 g of the component (A2-3), 6.26 g of Tetrad-X and 6.26 g of SA90, 29.00 g of toluene, and 0.09 g of KBM603 are mixed to form a non-volatile component. A 30.0% resin composition (adhesive) was obtained.

Comparative Example 5
A mixture of 100.00 g of the solution of the component (A1-1), 25.17 g of the component (A2-3), 0.19 g of Tetrad-X and 0.19 g of SA90, 0.71 g of toluene, and 0.08 g of KBM603 are mixed to form a non-volatile component. A 30.0% resin composition (adhesive) was obtained.

Comparative Example 6
A resin composition having a non-volatile content of 30.0% (adhesion) by mixing 100.00 g of a solution of the component (A2-4), 2.04 g of Tetrad-X and 2.04 g of SA90, 32.04 g of toluene, and 0.08 g of KBM603. Agent) was obtained.

Comparative Example 7
A resin composition having a non-volatile content of 30.0% (adhesion) by mixing 100.00 g of a solution of the component (A2-5), 1.66 g of Tetrad-X and 1.66 g of SA90, 7.26 g of toluene, and 0.07 g of KBM603. Agent) was obtained.

<Making an adhesive sheet>
The adhesive of Example 1 is applied to a support sheet (trade name "Kapton 100EN", manufactured by Toray Industries, Inc .; film thickness 25 μm; coefficient of thermal expansion; 15 ppm / ° C.) so that the thickness after drying is 10 μm. After coating with a coater, an adhesive sheet was obtained by drying at 180 ° C. for 3 minutes. Adhesive sheets of other examples and comparative examples were obtained in the same manner.

Next, the mirror surface side of an 18 μm thick electrolytic copper foil (trade name “F2-WS”, manufactured by Furukawa Circuit Foil Co., Ltd.) was superposed on the adhesive surface of each adhesive sheet, and the conditions were pressure 1 MPa, 180 ° C. and 30 minutes. A laminate was produced by heating and pressing with. A laminate was obtained in the same manner for the adhesive of Comparative Example 1.

<Measurement of relative permittivity and dielectric loss tangent of adhesive layer>
Approximately 7 g of the adhesives of Examples and Comparative Examples were poured into a fluororesin PFA flat plate (diameter 75 mm, manufactured by Mutual Rikagaku Glass Mfg. Co., Ltd.), and 30 ° C. × 10 hours, 70 ° C. × 10 hours, 100 ° C. × 6 hours, respectively. , 120 ° C. × 6 hours, 150 ° C. × 6 hours, 180 ° C. × 12 hours, to obtain a cured product sheet having a thickness of about 300 &micro; m. Next, with respect to the cured product sheet, the relative permittivity (Dk) and the dielectric loss tangent (Df) at 10 GHz are measured using a commercially available permittivity measuring device (cavity resonator type, manufactured by AET) according to JIS C2565. did.

<Adhesion test>
The peeling strength (N / cm) of each of the laminates of Examples and Comparative Examples was measured according to JIS C-6488 (copper-clad laminate test method for flexible printed wiring boards).

<Solder heat resistance test>
After curing, each of the laminates of Examples and Comparative Examples was floated in a solder bath at 288 ° C. with the copper foil side down for 30 seconds, and the presence or absence of a change in appearance was confirmed. No change was marked with ◯, and foaming or swelling was marked with x.

<Making a bonding sheet>
The adhesive of Example 1 is applied to a release film (trade name "WH52-P25CM (white)", manufactured by Sun A. Kaken Co., Ltd.) with a gap coater so that the thickness after drying is about 25 &micro; m. After the work, a bonding sheet was obtained by drying at 150 ° C. for 5 minutes. Bonding sheets were obtained in the same manner for the adhesives of the other examples and comparative examples.

<Manufacturing of printed wiring board>
A copper foil having a line / space = 0.2 / 0.2 (mm) resist pattern formed on the copper foils on both sides of the copper-clad laminate according to Example 1 was immersed in a ferric chloride aqueous solution having a concentration of 40%. Etching was performed by forming a copper circuit. In this way, a printed wiring board was obtained.

<Manufacturing of multilayer wiring board>
The obtained printed wiring board was used as a core material, and the copper foil with resin according to Example 1 was laminated on both sides thereof and crimped under the conditions of a pressure of 4.5 MPa, 200 ° C. and 30 minutes, and the untreated copper foil of the outer layer was formed. A resist pattern of line / space = 0.2 / 0.2 (mm) was formed in the above. Then, the obtained substrate was etched by immersing it in a ferric chloride aqueous solution having a concentration of 40% to form a copper circuit. The adhesive sheet was laminated on the surface layer on which the copper circuit was formed, and was laminated by heating and pressing under the conditions of a pressure of 1 MPa, 180 ° C. and 30 minutes. In this way, a multilayer wiring board having four circuit pattern layers was obtained.

<Making a printed wiring board 2>
A copper foil of a single-sided copper-clad laminate according to Example 1 having a resist pattern of line / space = 0.2 / 0.2 (mm) formed therein is immersed in a ferric chloride aqueous solution having a concentration of 40%. By etching, a copper circuit was formed. The same material was prepared, the bonding sheets were sandwiched between the base materials without a copper circuit, and heat-pressed under the conditions of a pressure of 1 MPa, 180 ° C., and 30 minutes for laminating. Then, the adhesive sheet was superposed on the surface layer on which the copper circuit of the laminated body was formed, and was laminated by heating and pressing under the conditions of a pressure of 1 MPa, 180 ° C. and 30 minutes. In this way, a multilayer wiring board having four circuit pattern layers was obtained.

For the adhesives of other examples, a printed wiring board and a multilayer wiring board were obtained by the same method.

Claims (16)

Free aromatic content is less than 1 wt% of a carboxylic acid dianhydride (a1) and hydrogenated dimer include diamine (a2), and diamino polysiloxane (a3) an included no monomer groups (1) polyimide obtained by reacting (A1), wherein the (A1) a polyimide other than the component (A2), as well as the cross-linking agent (B),
(A2) component, (a1) component and / or the content of free carboxylic acid is 1 wt% or more aromatic tetracarboxylic acid dianhydride (a1 '), (a2) component and / or non-hydrogenated dimer diamine (a2 ') and Ri polyimide resin der obtained by reacting a monomer unit (2) including,
The solid content weight ratio [(A1) / (A2)] of the component (A1) and the component (A2) is 40/60 to 99/1.
A resin composition in which the amount of the component (B) used is 3 to 30 parts by weight based on 100 parts by weight of the total of the components (A1) and (A2) . (A1) an aromatic tetracarboxylic acid dianhydride constituting a component is represented by the following structure, the resin composition according to claim 1.
(In the formula, X is a single bond, -SO _2- , -CO-, -O-, -O-C ₆ H _4- C (CH ₃ ) _2- C ₆ H _4- O- or -COO-Y- It represents OCO- (Y indicates − (CH ₂ ) _l − (l = 1 to 20) or −H ₂ C—HC (−OC (= O) −CH ₃ ) −CH ₂₋ ). ) The resin composition according to claim 1 or 2, wherein the molar ratio [(a1) / [(a2)] of the component (a1) and the component (a2) in the component (1) is 1 to 1.5. The resin composition according to any one of claims 1 to 3, wherein the component (2) further contains the component (a3). The resin composition according to any one of claims 1 to 4, wherein the component (B) is a polyepoxy compound (B1) and / or a polyphenylene ether compound (B2). The resin composition according to claim 5 , wherein the component (B1) is tetraglycidyl xylene diamine having the following structure.
(In the formula, Z ¹ represents a phenylene group or a cyclohexylene group.) The resin composition according to claim 5 or 6 , wherein the component (B2) is a hydroxyl group-containing polyphenylene ether having the following structure.
(In the formula, Z ² represents an alkylene group or a single bond having 1 to 3 carbon atoms, m represents 0 to 20, n represents 0 to 20, and the sum of m and n represents 1 to 30. ) The polyimide resin composition according to any one of claims 1 to 7 , further containing an organic solvent (C). Further general formula: Q-Si (R ¹ ) _a (OR ² ) _3-a (In the formula, Q is a group containing a functional group that reacts with an acid anhydride group, and R ¹ is hydrogen or 1 to 8 carbon atoms. Claims 1 to 1, wherein R ² contains a hydrocarbon group having 1 to 8 carbon atoms, and a contains a reactive alkoxysilyl compound (D) represented by 0, 1 or 2). The polyimide resin composition according to any one of 8 . An adhesive comprising the resin composition according to any one of claims 1 to 9 . A film-like adhesive made of a cured product of the adhesive according to claim 10 . An adhesive sheet using the cured product of the adhesive according to claim 10 as an adhesive layer. A multilayer wiring board obtained by using at least one selected from the group consisting of the adhesive according to claim 10 , the film-like adhesive according to claim 11 , and the adhesive sheet according to claim 12 . A copper foil with a resin obtained by using at least one selected from the group consisting of the adhesive according to claim 10 , the film-like adhesive according to claim 11 , and the adhesive sheet according to claim 12 . A copper-clad laminate obtained by using the resin-attached copper foil of claim 14 . A printed wiring board obtained by using the copper-clad laminate according to claim 15 .