KR102524336B1 - Resin composition, adhesive, film type adhesive substrate, adhesive sheet, multilayer wiring board, resin attached copper foil, copper-clad laminate, printed wiring board - Google Patents

Abstract

[Problem] To provide a novel polyimide adhesive that provides an adhesive layer with good adhesiveness, heat resistance and low dielectric properties.
[Means for Solving] A monomer group containing an aromatic tetracarboxylic dianhydride (a1) and a hydrogenated dimer diamine (a2) having a free carboxylic acid content of less than 1% by weight, but not containing a diaminopolysiloxane (a3) ( 1) A resin composition containing polyimide (A1) made by reacting.

Description

Resin composition, adhesive, film type adhesive substrate, adhesive sheet, multilayer wiring board, copper foil with resin, copper clad laminate, printed wiring board CLAD LAMINATE, PRINTED WIRING BOARD}

The present invention relates to a resin composition, an adhesive, a film adhesive substrate, 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), Printed Circuit Boards (PCBs), and multi-layer wiring boards using them are mobile communication devices such as mobile phones and smartphones, their base station devices, servers and routers, etc. It is widely used as products such as network-related electronic devices and large computers.

Recently, in these products, high-frequency electrical signals are used to transmit and process large amounts of information at high speed. However, since high-frequency signals are very easily reduced, efforts to minimize transmission loss on the multilayer wiring board are required.

Means for suppressing transmission loss in a multilayer wiring board include, for example, excellent adhesion when laminated printed wiring boards or printed circuit boards, as well as low dielectric constant and low dielectric loss tangent (hereinafter also referred to as low dielectric properties). .) can be considered.

As an adhesive composition that can be used as a low dielectric material, a polyimide adhesive made by reacting aromatic tetracarboxylic dianhydride and dimer diamine, a crosslinking agent such as an epoxy resin, and an organic solvent are known (Patent Document 1 ), there were cases where the low dielectric properties were insufficient.

On the other hand, polyimide adhesives with excellent low dielectric properties are known, including polyimide made by reacting aromatic tetracarboxylic dianhydride and diamino polysiloxane, polyimide adhesives containing a crosslinking agent such as an epoxy resin, and an organic solvent (Patent Documents). 2.), but, as far as the applicants are aware, the low dielectric properties were insufficient.

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

The main object of the present invention is to provide a novel polyimide-based adhesive that provides an adhesive layer with good adhesion, heat resistance and low dielectric properties.

The present inventors conducted studies to further enhance the adhesive strength and dielectric properties of the polyimide adhesives described in Patent Documents 1 and 2.

First, it was noted that aromatic tetracarboxylic dianhydride actually contained free carboxylic acid derived from raw materials as an impurity. In addition, it was assumed that the carboxyl group of the free carboxylic acid directly increases the polarity of the polyimide, causing moisture absorption of the polyimide, and as a result, the low dielectric property of the adhesive deteriorates.

Also, attention was paid to the structure of dimer diamine. Dimer methylenediamine is generally a polymer derived from dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid (see Japanese Unexamined Patent Publication No. Hei 9-12712, etc.), contains a large amount of conjugated double bonds in the molecule, and its π electrons are polydimers. It was hypothesized that as a result of increasing the polarity of the mid, the low dielectric properties of the adhesive would be insufficient.

Furthermore, it was newly found that when diamino polysiloxane is used in combination with dimer diamine, it adversely affects the low dielectric loss tangent of polyimide. Although the reason for this is unknown, it is probably because polysiloxane has a large surface energy and repulsion with polar groups (such as imide groups) in polyimide occurs.

This invention was completed by the above examination. That is, the present invention relates to the following resin composition, adhesive agent, film adhesive base material, adhesive sheet, multilayer wiring board, copper foil with resin, copper clad laminate, and printed wiring board.

1. Monomer group (1) comprising an aromatic tetracarboxylic dianhydride (a1) and a hydrogenated dimer diamine (a2) having a free carboxylic acid content of less than 1% by weight, but not containing a diamino polysiloxane (a3) A resin composition containing polyimide (A1) formed by reacting.

2. The aromatic tetracarboxylic dianhydride constituting the component (a1) is the resin composition of item 1 represented by the following formula (1):

[Formula 1]

(Wherein, X is a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ )2-C ₆ H ₄ -O- or -COO-Y-OCO- (At this time, Y represents -(CH ₂ ) _l -(l = 1 to 20) or -H ₂ C-HC (-OC(=O)-CH ₃ )-CH ₂ -).

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

4. The resin composition according to any one of items 1 to 3, wherein the resin composition contains a polyimide (A2) other than the component (A1).

5. The component (A2) is an aromatic tetracarboxylic dianhydride (a1′) having a content of component (a1) and/or free carboxylic acid of 1% by weight or more, and component (a2) and/or unhydrogenated dimer diamine The resin composition according to item 4, characterized in that it is a polyimide resin obtained by reacting the monomer group (2) including (a2').

6. The resin composition of item 5 above, wherein the component (2) further comprises a component (a3).

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

8. The resin composition according to any one of items 1 to 7, wherein the resin composition further contains a crosslinking agent (B).

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

10. The resin composition of item 9 above, wherein the component (B1) is tetraglycidyl xylene diamine represented by the following formula (2):

[Formula 2]

(In formula, Z ^<1> represents a phenylene group or a cyclohexenyl group).

11. The polyimide resin composition of 9 or 10 above, wherein the component (B2) is a hydroxyl group-containing polyphenylene ether of the following formula (3):

[Formula 3]

(In the formula, Z ² represents an alkylene group having 1 to 3 carbon atoms or a single bond, 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, wherein the polyimide resin composition further contains an organic solvent (C).

13. The polyimide resin composition has the general formula: Q-Si(R ¹ ) _a (OR ² ) _{3 -a} (where Q is a group containing a functional group reacting with an acid anhydride group, R ¹ is hydrogen or carbon atoms) Items 1 to 12 above further contain a reactive alkoxysilyl compound (D) represented by a hydrocarbon group of 1 to 8 carbon atoms, R ² is a hydrocarbon group of 1 to 8 carbon atoms, and a represents 0, 1 or 2. Any one of the resin composition.

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

15. A film-like adhesive substrate made of a cured product of the adhesive of the above item 14.

16. An adhesive sheet comprising a cured product of the adhesive of 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 adhesive substrate of item 15, and the adhesive sheet of item 16.

18. A resin-clad copper plate obtained by using at least one selected from the group consisting of the adhesive of item 14, the film adhesive substrate of item 15, and the adhesive sheet of item 16.

19. The copper clad laminated board obtained using the said copper foil with resin of 18 paragraph.

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

The resin composition of the present invention is excellent in initial adhesion and adhesion to various substrates. In addition, the cured product (adhesive layer) has low tack, does not foam when heated, hardly generates adhesive residue, and has excellent adhesive strength and low dielectric properties.

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

In addition, the multilayer wiring board, resin-clad copper foil, copper clad laminate, and printed wiring board of the present invention all have a cured product (adhesive layer) of the adhesive of the present invention, which has excellent adhesive strength and low dielectric properties, and thus has a high level of low dielectric properties. It is useful as a material for products that handle high-frequency signals such as required products, for example, mobile communication devices represented by smart phones and mobile phones, base station devices thereof, network-related electronic devices such as servers and routers, and large computers.

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

As the component (a1), various known aromatic tetracarboxylic dianhydrides are used, but the content of free carboxylic acid is less than 1% by weight, preferably 0.5% by weight or less, and most preferably 0.2% by weight or less. do. By using the component (a1), it is possible to improve the low dielectric properties of the adhesive according to the present invention while maintaining the adhesive force.

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3' , 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride Water, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 2,3,3', 4'-biphenyl tetracarboxylic dianhydride, 2,3,3', 4' -benzophenonetetracarboxylic acid dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic acid dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, 2, 2-bis(2,3-dicarboxy phenyl)propane dianhydride, 2,2-bis(3,4-dicarboxy phenyl)propane dianhydride, 4,4'[propane-2,2-diylbis(1, 4-phenyleneoxy)] diphthalic dianhydride, etc., and it is preferable even if it combines 2 or more types.

[Formula 4]

(Wherein, X is a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O- or -COO-Y-OCO- (Y represents -(CH ₂ ) _l -(l = 1 to 20) or -H ₂ C-HC (-OC(=O)-CH ₃ )-CH ₂ ).)

As the aromatic tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-[ At least one selected from the group consisting of propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride and 4,4'-hydroxy diphthalic dianhydride is preferred.

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

[Formula 5]

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

Component (a2) is a hydrogenated product of a polymer derived from a dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid (refer to Japanese Patent Laid-Open No. 9-12712, etc.), and a non-limiting structural formula of the dimer acid is shown below. In each structural formula, m + n = 6 to 17, p + q = 8 to 19, and the broken line indicates a carbon-carbon single bond or a carbon-carbon double bond. Component (a2) has at least one carbon-carbon double bond, and all of them are single bonds.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

As a commercial item of (a2) component, PRIAMINE1075 (made by Kuroda Japan Co., Ltd.) etc. are mentioned, for example. Hereinafter, an example of hydrogenated dimer diamine is shown.

[Formula 12]

The molar ratio [(a1)/(a2)] of the component (a1) and the component (a2) in the component (1) is not particularly limited, but is usually 1 to 1 from the viewpoint of the balance of adhesive strength and low dielectric properties. It is about 1.5, 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) may contain diamines (hereinafter, also referred to as component (a4)) other than component (a1) to component (a3). Specifically, for example, amino cyclohexane, diamino dicyclohexyl methane, dimethyl-diamino dicyclohexyl methane, tetramethyl-diamino dicyclohexyl methane, diamino dicyclohexyl propane, diamino bicyclo[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 - Aliphatic ring diamines such as bisaminomethylcyclohexane and isophorone diamine; bisaminophenoxyphenyl propanes such as 2,2-bis[4-(3-aminophenoxy)phenyl]propane and 2,2-bis[4-(4-aminophenoxy)phenyl]propane; diamino diphenyl ethers such as 3,3'-diamino diphenyl ether, 3,4'-diamino diphenyl ether, and 4,4'-diamino diphenyl ether; phenylene diamines such as p-phenylene diamine and m-phenylene diamine; diamino diphenyl sulfides such as 3,3'-diamino diphenyl sulfide, 3,4'-diamino diphenyl sulfide, and 4,4'-diamino diphenyl sulfide; diamino diphenyl sulfones such as 3,3'-diamino diphenyl sulfone, 3,4'-diamino diphenyl sulfone, and 4,4'-diamino diphenyl sulfone; diamino benzophenones such as 3,3'-diamino benzophenone, 4,4'-diamino benzophenone, and 3,4'-diamino benzophenone; diamino diphenyl methanes such as 3,3'-diamino diphenyl methane, 4,4'-diamino diphenyl methane, and 3,4'-diamino diphenyl methane; Diaminophenyl propane, such as 2,2-di(3-aminophenyl)propane, 2,2-di(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane Ryu; 2,2-di(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-dia(4-aminophenyl)-1,1,1,3,3 Diaminophenyl hexafluoro, such as 3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane propanes; 1,1-di(3-amino phenyl)-1-phenyl ethane, 1,1-di(4-amino phenyl)-1-phenyl ethane, 1-(3-amino phenyl)-1-(4-amino phenyl) )-1-phenyl ethane and other diamino phenylphenyl ethanes; 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4- bisaminophenoxybenzenes such as aminophenoxy)benzene; 1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(3-aminobenzoyl)benzene, 1,4-bis(4-aminobenzoyl) bisaminobenzoyl benzenes such as 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, bisamino dimethylbenzenes such as α-dimethyl benzyl)benzene and 1,4-bis(4-amino-α,α-dimethyl benzyl)benzene; 1,3-bis(3-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,4- Bisaminoditrifluoromethyl, such as bis(3-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,4-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene benzyl benzenes; 2,6-bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy)pyridine, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'- amino phenoxy biphenyls such as bis(4-amino phenoxy) biphenyl; amino phenoxyphenyl ketones such as bis[4-(3-aminophenoxy)phenyl]ketone and bis[4-(4-aminophenoxy)phenyl]ketone; aminophenoxyphenyl sulfides such as bis[4-(3-aminophenoxy)phenyl]sulfide and bis[4-(4-aminophenoxy)phenyl]sulfide; amino phenoxyphenyl sulfones such as bis[4-(3-aminophenoxy)phenyl]sulfone and bis[4-(4-aminophenoxy)phenyl]sulfone; amino phenoxyphenyl ethers such as bis[4-(3-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-hexa amino phenoxyphenyl propanes such as fluoropropane and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane; Others thereof, 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, 1,3-bis[4-(3-aminophenoxy)-α,α-dimethyl Benzyl]benzene, 1,3-bis[4-(4-aminophenoxy)-α,α-dimethyl benzyl]benzene, 1,4-bis[4-(3-aminophenoxy)-α,α-dimethyl Benzyl]benzene, 1,4-bis[4-(4-aminophenoxy)-α,α-dimethyl benzyl]benzene, 4,4'-bis[4-(4-aminophenoxy)benzoyl]diphenyl ether , 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy cy]diphenyl sulfone, 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenyl sulfone, 3,3'-diamino-4,4'-diphenoxy benzophenone, 3, 3'-diamino-4,4'-dibiphenoxy benzophenone, 3,3'-diamino-4-phenoxy benzophenone, 3,3'-diamino-4-biphenoxy benzophenone, 6, 6'-bis(3-aminophenoxy)3,3,3,'3,'-tetramethyl-1,1'-spirobiindan, 6,6'-bis(4-aminophenoxy)3,3 ,3,'3,'-tetramethyl-1,1'-spirobiindan, 1,3-bis(3-aminopropyl)tetramethyl disiloxane, 1,3-bis(4-aminobutyl)tetramethyl di Siloxane, bis(amino methyl) ether, bis(2-amino ethyl) ether, bis(3-amino propyl) ether, bis[(2-amino methoxy)ethyl] ether, bis[2-(2-amino ethoxy) ) ethyl] ether, bis [2- (3-amino protoxy) ethyl] ether, 1,2-bis (amino methoxy) ethane, 1,2-bis (2-amino ethoxy) ethane, 1,2- Bis [2- (amino methoxy) ethoxy] ethane, 1,2-bis [2- (2-amino ethoxy) ethoxy] ethane, ethylene glycol bis (3-amino propyl) ether, diethylene glycol bis ( 3-amino propyl) ether, triethylene glycol bis(3-amino propyl) ether, ethylene diamine, 1,3-diamino propane, 1,4-diamino butane, 1,5-diamino pentane, 1,6- Diamino hexane, 1,7-diamino heptane, 1,8-diamino octane, 1,9-diamino nonane, 1,10-diamino decane, 1,11-diamino undecane, 1,12-dia Minododecane etc. are mentioned, It is preferable even if it combines 2 or more types. Among these, the aliphatic ring diamine is preferable from the viewpoint of low dielectric properties. The amount of component (a4) used is not particularly limited, but is usually less than 40 mol% when all diamine components are 100 mol%.

(A1) component can be manufactured by various well-known methods. Specifically, for example, the acid component and diamine component used respectively are usually subjected to a polyaddition reaction at a temperature of about 60 to 120°C for about 0.1 to 2 hours. Next, the obtained polyadditive may be subjected to an imidization reaction, that is, a dehydration ring closing reaction, at a temperature of about 80 to 250 ° C, preferably about 100 to 200 ° C for about 0.5 to 50 hours. In these reactions, component (C) to be described later, particularly an aprotic polar solvent can be used as the reaction solvent.

In the imidation 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, and a combination of two or more is preferable. do. Moreover, as a dehydrating agent, an aliphatic acid anhydride, such as acetic anhydride, and an aromatic acid anhydride, such as benzoic acid anhydride, etc. are mentioned, It is preferable even if it combines 2 or more types.

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

The physical properties of the component (A1) are not particularly limited, but from the viewpoint of the balance between adhesive strength and low dielectric properties, the number average molecular weight (refers to the polystyrene equivalent by gel permeation chromatography. The same applies hereafter) is about 5000 to 50000. , is preferably about 7000 to 30000, and has a glass transition temperature (JIS-K7121) of about 30 to 160°C, preferably about 40 to 140°C. In addition, the concentration of the terminal acid anhydride group of component (A1) is also not particularly limited, but is usually about 2000 to 40000 eq/g, preferably about 3000 to 20000 eq/g.

In addition, the component (A1) is preferably further modified (sealed) at its molecular ends with a low-molecular-weight primary alkyl monoamine. Specific examples thereof include ethyl amine, n-propyl amine, isopropyl amine, n-butyl amine, isobutyl amine, sec-butyl amine, tert-butyl amine, pentyl amine, isopentyl amine, tert-pentyl amine, n-octyl amine, n-decyl amine, isodecyl amine, n-tridecyl amine, n-lauryl amine, n-cetyl amine, n-stearyl amine, etc. A thing of about 4-15 is preferable. Also, the amount of primary alkyl monoamine used is not particularly limited, but is usually about 0.8 to 1.2 moles, preferably about 0.9 to 1.1 moles, per mole of the terminal acid anhydride group of component (A1).

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

As the component (A2), any polyimide other than the component (A1) may be used, but preferably, the content of the component (a1) and/or free carboxylic acid is 1% by weight or more of aromatic tetracarboxylic dianhydride. A monomer containing water (a1') (hereinafter also referred to as component (a1')) and the above-mentioned component (a2) and/or unhydrogenated dimer diamine (a2') (hereinafter also referred to as component (a2')). and polyimides (except those corresponding to the component (A1)) formed by reacting group (2) (hereinafter, also referred to as component (2)).

As the component (a1'), various known ones can be used without particular limitation, as long as the content of the free carboxylic acid in the aromatic tetracarboxylic dianhydride is 1% by weight or more. In addition, a combination of the free carboxylic acid in the component (a1) with a content of 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 enhancing the low dielectric properties of the adhesive according to the present invention while maintaining the adhesive force.

Examples of the component (a2') include those disclosed in Japanese Unexamined Patent Publication No. Hei-9-12712 and the like, and commercially available products include, for example, Barsamine 551 (manufactured by BASF Japan Co., Ltd.) and PRIAMINE1074 ( Kuroda Japan Co., Ltd. product) can be illustrated.

(2) Component may contain (a3) component. As the component (a3), there are various known diaminopolysiloxanes, for example, 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, etc. can be illustrated.

Hereinafter, representative examples of combinations of raw materials of component (2) are shown.

A. (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

H. (a1) component, (a2) component and (a4) component

I. (a1') component, (a2) component and (a4) component

J. (a1) component, (a2') component and (a4) component

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

In addition, when component (a3) is included in component (2), the amount of its amount is not particularly limited, but is usually about 0.1 to 5.0 mol% when all diamine components are 100 mol%.

Furthermore, component (2) may contain component (a4). In this case, the amount of component (a4) used is not particularly limited, but is usually less than 40 mol% when all diamine components are 100 mol%.

(A2) The manufacturing method of component conforms to (A1) component. The imide closure rate of component (A2) is also not particularly limited, but is usually 70% or more, preferably 85 to 100%.

The physical properties of component (A2) are not particularly limited, but from the viewpoint of the balance of adhesive strength and low dielectric properties, the number average molecular weight (refers to the polystyrene equivalent of gel permeation chromatography. The same applies hereinafter) is about 5000 to 50000, preferably is about 7000 to 30000, and the glass transition temperature (JIS-K7121) is about 30 to 160°C, preferably about 40 to 140°C. In addition, the concentration of the terminal acid anhydride group of component (A2) is also not particularly limited, but is usually about 2000 to 40000 eq/g, preferably about 3000 to 20000 eq/g.

In addition, the component (A2) is also preferably modified (sealed) at its molecular terminal with the above-mentioned primary alkyl monoamine.

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

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

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

Component (B1) includes phenol novolac type epoxy compound, cresol novolak type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, hydrogenated bisphenol A type epoxy compound, hydrogenated bisphenol F type epoxy Compounds, stilbene-type epoxy compounds, triazine skeleton-containing epoxy compounds, fluorene skeleton-containing epoxy compounds, linear aliphatic epoxy compounds, alicyclic epoxy compounds, glycidyl amine-type epoxy compounds, triphenol methane-type epoxy compounds, alkyl-modified triphenols Methane-type epoxy compounds, biphenyl-type epoxy compounds, dicyclopentadiene skeleton-containing epoxy compounds, naphthalene skeleton-containing epoxy compounds, aryl alkylene-type epoxy compounds, tetraglycidyl xylene diamine, and modifications obtained by modifying these epoxy compounds with dimer acids An epoxy compound, dimer acid diglycidyl ester, etc. are mentioned, Even if it combines 2 or more types, it is preferable. In addition, as a commercial item, "jER828", "jER834", "jER807", "jER630" by Mitsubishi Chemical Co., Ltd., "ST-3000" by Nippon-Stetsu Chemical Co., Ltd., Daicel Chemical Industries, Ltd. "Ceroxide 2021P" manufactured by Co., Ltd., "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd., and the like are exemplified.

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

[Formula 13]

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

Moreover, when using a component (B1), various well-known hardening|curing agents for epoxy compounds can be used together. Specifically, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride or 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride and mixtures, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic acid anhydride acid anhydride-based curing agents such as methylnorbornane-2,3-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 3-dodecenyl succinic anhydride, and octenyl succinic anhydride; amine-based curing agents such as dicyandiamide (DICY), aromatic diamines (trade names "LonzacureM-DEA", "LonzacureM-DETDA", etc., all manufactured by Lonza Japan Co., Ltd.), and aliphatic amines; Phenol novolac resin, cresol novolak resin, bisphenol A novolak resin, triazine-modified phenol novolak resin, phenolic hydroxyl group-containing phosphazene (manufactured by Otsuka Chemical Co., Ltd., trade name "SPH-100", etc.), etc. rosin-based crosslinking agents such as phenol-based curing agents, cyclic phosphazene-based compounds, maleic acid-modified rosin and hydrides thereof, and the like, may be used in combination of two or more. Among these, phenol-based curing agents, particularly phenolic hydroxyl group-containing phosphazene-based curing agents are preferred. The amount of these curing agents used is not particularly limited, but is usually 0.1 to 120% by weight when the solid content of the adhesive of the present invention is 100% by weight. It is about, preferably about 10 to 40% by weight.

Moreover, when using a component (B1), 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, etc. primary amines; 2-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole, 2-ethyl-4-methyl imidazole, 1-cyanoethyl-2-undecyl imidazole, 2-heptadecyl imidazole imidazoles such as dazole; organic phosphines such as tributyl phosphine, methyldiphenyl phosphine, triphenyl phosphine, diphenyl phosphine, and phenyl phosphine; tetraphenyl boron salts such as tetraphenylphosphonium tetraphenyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, and N-methylmorpholine tetraphenyl borate; organic acids such as octanoic acid, stearic acid, acetyl acetonate, naphthenic acid and salicylic acid; Organometallic salts, such as Zn, Cu, and Fe, are mentioned, and it is preferable even if it combines 2 or more types. In addition, 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 ones can be used without particular limitation. What is specifically represented by the following general formula is preferable.

[Formula 14]

(In the formula, Z ² represents an alkylene group having 1 to 3 carbon atoms or a single bond, 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 component (B2) are not particularly limited, but from the viewpoint of adhesive strength and low dielectric properties, it is generally 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 a component (B3), at least one kind selected from the group which consists of a benzoxazine compound, a bismaleimide compound, and a cyanate ester compound is mentioned, for example.

Examples of the benzoxazine compound include 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzooxazine), 6,6-(1- methyl ethylidene) bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like, and a combination of two or more is preferable. In addition, a phenyl group, a methyl group, a cyclohexyl group or the like may be bonded to the nitrogen of the oxazine ring. Furthermore, commercially available products include, for example, "benzoxazine F-a type" and "benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd., and "RLV-100" manufactured by Air Water.

Examples of the bismaleimide compound include 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, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4 '-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, etc. are mentioned, and you may combine 2 or more types. Moreover, as a commercial item, "BAF-BMI" by JFE Chemical Co., Ltd., etc. are mentioned, for example.

Examples of the cyanate ester compound include 2-arylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis(4-cyanatephenyl)-1,1,1,3,3,3-hexa Fluoropropane, bisphenol A cyanate ester, diallyl bisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris(4-cyanatephenyl)ethane, 4-cumylphenol cyanate ester, 1,1-bis(4-cyanate phenyl)ethane, 4,4'-bisphenol cyanate ester, and 2,2-bis(4-cyanate phenyl)propane; do. Moreover, as a commercial item, "PRIMASET BTP-6020S (made by Lonza Japan Co., Ltd.)", "CYTESTER TA (made by Mitsubishi Gas Chemical Co., Ltd.)", etc. are mentioned, for example.

The amount of component (B) used is not particularly limited, but is usually about 3 to 30 parts by weight with respect to 100 parts by weight of the total of component (A1) and component (A2) (hereinafter both are collectively referred to as component (A)). , 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 component (C)).

(C) As a component, various well-known solvents can be used without particular limitation. Specific examples include aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethyl formamide, dimethylacetamide, dimethyl sulfoxide, N-methyl caprolactam, methyl triglyme, and methyl diglyme; aliphatic ring solvents such as hexanone and methylcyclohexane; alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol and cresol; aromatic solvents such as toluene; Among these, aromatic solvents are particularly preferred from the viewpoint of low dielectric properties.

The amount of 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 component (A).

The resin composition of the present invention has the general formula: Q-Si(R ¹ ) _a (OR ² ) _3-a (wherein Q is a group containing a functional group reacting with an acid anhydride group, R ¹ is hydrogen or 1 to 10 carbon atoms) Reactive alkoxysilyl compound (D) represented by a hydrocarbon group of 8, R ² is a hydrocarbon group of 1 to 8 carbon atoms, and a represents 0, 1 or 2) (hereinafter also referred to as component (D).) may further include. Examples of the reactive functional group included in Q include an amino group, an epoxy group and a thiol group.

As component (D), the melt viscosity can be adjusted while maintaining the low dielectric properties of the cured layer of the adhesive according to the present invention. As a result, it is possible to increase the interfacial adhesion between the cured layer and the substrate (so-called anchor effect), and to suppress the outflow of the cured layer from the edge of the substrate (hereinafter, this operation is referred to as flow control).

Examples of compounds in which the functional group of Q is an amino group include N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, and 3-ureido propyl trialkoxy silane; and the like.

Examples of the compound in which the functional group of Q is an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltrimethyx. Toxy silane, 3-glycidoxypropyl methyldiethoxy silane, 3-glycidoxypropyl triethoxy silane, etc. are mentioned.

Examples of compounds in which the functional group of Q is a thiol group include 3-mercaptopropyl trimethoxy silane, 3-mercaptopropyl triethoxy silane, 3-mercaptopropyl methyldimethoxy silane and 3-mercaptopropyl methyl. Diethoxy silane etc. are mentioned.

As component (D), it reacts quickly with the terminal acid anhydride group of component (A), and since the said flow control effect is good, it is preferable that the functional group of Q is a compound of an amino group.

The amount of 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 component (A).

The adhesive of the present invention is made of a resin composition, and the resin composition may be used as it is. If necessary, the ring-opening esterification reaction catalyst, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, and a bleaching agent , Additives such as a colorant, a conductive agent, a release agent, a surface treatment agent, a viscosity modifier, a phosphorus-based flame retardant, a flame retardant filler, a silica filler, a fluorine filler, or a diluting solvent may be incorporated.

The film-type adhesive substrate 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 component (C), and then peeled from the support, and this can be used as a film-type adhesive substrate. In addition, the coating means is not specifically limited, A curtain coater, a roll coater, a laminator, etc. are mentioned. Furthermore, 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 using the cured product as an adhesive layer. Specifically, it is composed of the cured product and various known sheet substrates, such as polyester polyimide, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, and polymethacrylic acid. Aromatic polyester resins obtained from methyl resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene or styrene resin, ethylene terephthalate or phenol, phthalic acid, hydroxy naphthoic acid, and para-hydroxy benzoic acid (so-called liquid crystal polymers) ; Plastic films such as Kuraray Co., Ltd., &quot;Bax Star&quot;, etc.) are exemplified. 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 adhesive, the film-like adhesive substrate, and the adhesive sheet. Specifically, it can be obtained by forming an adhesive layer on at least one surface of a printed wiring board as a core substrate using these, laminating another printed wiring board or printed circuit board thereon, and then pressing it under heat and pressure. The heating temperature, pressure 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 resin-coated copper foil of the present invention is an article obtained by forming an adhesive layer on copper foil using at least one selected from the group consisting of the polyimide adhesive, the film-like adhesive substrate, and the adhesive sheet. Examples of the copper foil include rolled copper foil and electrodeposited copper foil, which are preferably treated with various surface treatments (igniting, waterproofing, etc.). In addition, 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-coated copper foil may be uncured or partially cured or completely cured under heating. The partially cured adhesive layer is in a so-called B stage. Also, the thickness of the adhesive layer is not particularly limited, and is usually about 0.5 to 30 μm. Furthermore, it can be set as copper foil with double-sided resin by sticking copper foil further to the adhesive surface of the obtained copper foil with resin.

The copper clad laminate of the present invention is also called CCL (Copper Clad Laminate), which is an article formed by attaching and adding the copper foil with resin of the present invention and the copper foil or insulating sheet. Specifically, the resin-coated copper foil of the present invention is pressed under heating on at least one side or both sides of various known insulating sheets. In addition, in the case of one surface, you may crimp a copper foil different from the copper foil with resin of this invention to the other surface. In addition, the copper foil with resin of the said copper clad laminated board and the number of sheets of an insulating sheet are not specifically limited. Further, the insulating sheet is preferably a prepreg. Prepreg refers to a layered material made by improving a resin on a reinforcing material such as glass fabric and curing it to the B stage (JIS C 5603), and the resin is usually polyimide, phenol resin, epoxy resin, polyester resin, liquid crystal polymer , insulating resins such as aramid resins are used. In addition, the thickness of the prepreg is not particularly limited and is usually about 20 to 500 μm. Further, heating and pressure conditions are not particularly limited, and are usually about 150 to 280° C. and about 0.5 to 20 MPa.

In the printed wiring board of the present invention, a circuit pattern is 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. As a semi-additive method, for example, after patterning the copper foil surface of the copper clad laminate of the present invention with a resist film, electrolytic copper plating is performed, the resist is removed, and the method of etching with an alkali solution is exemplified. In addition, the thickness of the circuit pattern layer of the said printed wiring board is not specifically limited. Furthermore, a multilayer board can also be obtained by using this printed wiring board as a core base material and laminating the same printed wiring board and another known printed wiring board or printed circuit board thereon. During lamination, not only the polyimide adhesive of the present invention but also other known polyimide adhesives may be used. Also, the number of stacked layers of the multi-layer board is not particularly limited. Furthermore, a via hole may be inserted for each lamination and the inside may be plated.

[ Example ]

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples, but the scope of the present invention is not limited thereby. In addition, in each case, unless otherwise specified, parts and % are based on weight.

Preparation Example 1

A commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-UP", manufactured by Evonik Japan Co., Ltd.; 3,3', 4, 210.0 g of 4'-benzophenone tetracarboxylic dianhydride content of 99.9% or more), 1008.0 g of cyclohexanone, and 201.6 g of methylcyclohexane were added, and the solution was heated to 60°C. Next, 341.7 g of hydrogenated dimer diamine (trade name "PRIAMINE 1075" manufactured by Kuroda Japan Co., Ltd.) was gradually added, followed by an imidization reaction at 140°C for 10 hours to obtain a polyimide having a softening point of about 80°C and a weight average molecular weight of about 35,000. Resin (A1-1) solution (30.0% of non-volatile content) was obtained. Moreover, the molar ratio of acid component/amine component was 1.03.

Preparation Example 2

Commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA2000", manufactured by SABIC Japan Corporation; 4,4'[propane-2,2-diylbis(1,4-phenyleneoxy) was added to the same reaction vessel as in Production Example 1. )] 60.0 g of diphthalic dianhydride content of 99.5% or more), 165.0 g of cyclohexanone, and 27.5 g of methylcyclohexane were added, and the solution was heated to 60°C. Next, 59.3 g of PRIAMINE 1075 was gradually added, followed by an imidization reaction at 140° C. for 10 hours to obtain a polyimide resin (A1-2) solution (31.9% non-volatile matter) having a softening point of about 90° C. and a weight average molecular weight of about 30,000. Got it. In addition, the molar ratio of the acid component/amine component was 1.05.

Comparative Preparation Example 1

Commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA-1000", manufactured by SABIC Japan Corporation; 4,4'[propane-2,2-diylbis(1,4-phenyl) was added to the same reaction vessel as in Production Example 1. 65.0 g of rene oxy)] diphthalic dianhydride (98.0%), 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane were added, and the solution was heated to 60°C. Next, 43.7 g of PRIAMINE 1075 and 5.4 g of 1,3-bisaminomethylcyclohexane were gradually added, followed by an imidization reaction at 140°C for 10 hours to obtain a polyimide resin having a softening point of about 100°C and a weight average molecular weight of about 30,000. (A2-1) A solution (29.2% of non-volatile content) was obtained. In addition, the molar ratio of the acid component/amine component was 1.05.

Comparative Preparation Example 2

Commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-PF", manufactured by Evonik Japan Co., Ltd.; 3,3',4,4'-benzophenone tetracarboxylic dianhydride) was placed in the same reaction vessel as in Production Example 1. 200.0 g of water (98%), 960.0 g of cyclohexanone, and 192.0 g of methylcyclohexane were added, and the solution was heated to 60°C. Next, 319.2 g of PRIAMINE 1075 was gradually added, followed by an imidization reaction at 140 ° C for 10 hours to obtain a polyimide resin (A2-2) solution (29.8% of non-volatile matter) having a softening point of about 80 ° C and a weight average molecular weight of about 25,000. got it In addition, the molar ratio of the acid component/amine component was 1.05.

Comparative Preparation Example 3

190.0 g of BTDA-PF, 277.5 g of cyclohexanone, and 182.4 g of methylcyclohexane were placed in the same reaction vessel as in Preparation Example 1, and the solution was heated to 60°C. Next, after gradually adding 277.5 g of PRIAMINE 1075 and 23.8 g of commercially available polydimethylsiloxane (trade name "KF-8010", manufactured by Shin-Etsu Chemical Industry Co., Ltd.), an imidization reaction was performed at 140 ° C. for 10 hours to obtain a softening point A polyimide resin (A2-3) solution (29.8% of non-volatile matter) at about 70°C and having a weight average molecular weight of about 15,000 was obtained. In addition, the molar ratio of the acid component/amine component was 1.09.

Comparative Preparation Example 4

190.0 g of BTDA-UP, 912.0 g of cyclohexanone, and 182.4 g of methylcyclohexane were placed in the same reaction vessel as in Preparation Example 1, and the solution was heated to 60°C. Next, 476.0 g of KF-8010 was gradually added, followed by an imidization reaction at 140°C for 10 hours, resulting in a polyimide resin (A2-4) solution having a softening point of about 20°C and a weight average molecular weight of about 35,000 (non-volatile content: 36.7%). got In addition, the molar ratio of the acid component/amine component was 1.09.

Comparative Preparation Example 5

200.0 g of BTDA-UP, 960.0 g of cyclohexanone, and 192.0 g of methylcyclohexane were placed in the same reaction vessel as in Preparation Example 1, and the solution was heated to 60°C. Next, 319.2 g of commercially available non-hydrogenated dimer diamine (trade name "PRIAMINE 1074" manufactured by Kuroda Japan Co., Ltd.) was gradually added, followed by an imidation reaction at 140°C for 10 hours to obtain a softening point of about 70°C and a weight average molecular weight of about 25,000. A polyimide (A2-5) solution (29.8% of non-volatile content) was obtained. In addition, the molar ratio of the acid component/amine component was 1.05.

Comparative Preparation Example 6

200.0 g of BisDA-1000, 700.0 g of cyclohexanone, and 175.0 g of methylcyclohexane were placed in the same reaction vessel as in Preparation Example 1, and the solution was heated to 60°C. Next, 190.5 g of commercially available hydrogenated dimer diamine (trade name "PRIAMINE 1075" manufactured by Kuroda Japan Co., Ltd.) was gradually added, followed by an imidization reaction at 140°C for 10 hours, resulting in a softening point of about 80°C and a weight average molecular weight of about 35,000. A polyimide (A2-6) solution (29.9% of non-volatile content) was obtained. In addition, the molar ratio of the acid component/amine component was 1.09.

<Measurement of dielectric constant and dielectric loss tangent of polyimide resin film>

Each of the polyimide solutions of Production Example and Comparative Production Example was coated on naphron PTFE tape TOMBO No.9001 (Nichiasu Co., Ltd.), dried at room temperature for 12 hours, and then cured at 200°C for 1 hour, resulting in a cured product having a thickness of 50 μm. got a sheet Next, relative permittivity (Dk) and dielectric loss tangent (Df) at 10 GHz were measured for the cured sheet according to JIS C2565 using a commercially available permittivity measuring device (cavity resonator type, manufactured by AT). The results are shown in Table 1.

(a1) (a2) (a3)
type (a4)
type Dk Df type impurities
% type number Preparation Example 1 (A1-1) BTDA-UP 0.1 P1075 you - - 2.40 0.0016 Preparation Example 2 (A1-2) BisDA-2000 0.5 P1075 you - - 2.45 0.0018 Comparative Manufacturing Example 1 (A2-1) BisDA-1000 2.0 P1075 you 1,3BAC - 2.60 0.0030 Comparative Manufacturing Example 2 (A2-2) BTDA-PF 2.0 P1074 radish - - 2.50 0.0030 Comparative Preparation Example 3 (A2-3) BTDA-PF P1075 - KF-8010 2.55 0.0028 Comparative Preparation Example 4 (A2-4) BTDA-UP - - KF-8010 2.40 0.0080 Comparative Manufacturing Example 5 (A2-5) BTDA-UP P1074 - - 2.40 0.0026 Comparative Preparation Example 6 (A2-6) BisDA-1000 P1075 - - 2.45 0.0024

Example 1

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

Example 2

(A1-2) 100.00 g of the solution of the component, 1.78 g of Tetrad-X, 1.78 g of SA90, 14.78 g of toluene, and 0.07 g of KBM603 were mixed to obtain a resin composition (adhesive) having a non-volatile content of 30.0%.

Example 3

100.00 g of the solution of component (A1-1) and 25.17 g of solution of 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 to obtain a resin composition with a non-volatile content of 30.0% ( adhesive) was obtained.

Example 4

100.00 g of the solution of component (A1-1) and 25.17 g of solution of 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 to obtain a resin composition having a non-volatile content of 30.0% ( adhesive) was obtained.

Example 5

100.00 g of the solution of component (A1-2) and 26.76 g of solution of 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 to obtain a resin composition of 30.0% non-volatile content ( adhesive) was obtained.

Example 6

(A1-1) component solution 30.00 g, (A2-1) component solution 30.82 g and (A2-3) component solution 15.10 g, commercially available polyfunctional epoxy resin (trade name "jER630", Mitsubishi Chemical Corporation) ) agent: 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, methyl ethyl 1.30 g of 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, methyl ethyl ketone 0.62 g and 0.05 g of KBM603 were mixed to obtain a resin composition (adhesive) containing 30.0% of non-volatile content.

Example 8

(A1-1) 100.00 g of the solution of the component, 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, methyl ethyl ketone 0.62 g and 0.05 g of KBM603 were mixed to obtain a resin composition (adhesive) containing 30.0% of non-volatile content.

Example 10

(A1-1) component solution 30.00 g, (A2-1) component solution 30.82 g and (A2-6) component solution 15.05 g, jER630 3.30 g and Bis-A type cyanate ester (trade name "CYTESTER TA" , Mitsubishi Gas Chemical Co., Ltd.) 2.34 g, toluene 8.96 g, methyl ethyl ketone 3.51 g, and KBM603 0.05 g were mixed to obtain a resin composition (adhesive) with a non-volatile content of 30.0%.

Example 11

30.00 g of solution of component (A1-1), 30.82 g of solution of component (A2-1) and 15.05 g of solution of component (A2-6), 0.70 g of jER630 and 0.49 g of CYTESTER TA, 1.39 g of toluene, 0.74 methyl ethyl ketone g 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 component (A1-1) and 25.17 g of solution of 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 to obtain a resin composition with a non-volatile content of 30.0% ( adhesive) was obtained.

Comparative Example 1

(A2-2) 100.00 g of the solution of the component, 1.65 g of Tetrad-X, 1.65 g of SA90, 7.05 g of toluene, and 0.07 g of KBM603 were mixed to obtain a resin composition (adhesive) with a non-volatile content of 30.0%.

Comparative Example 2

(A2-3) 100.00 g of the solution of the component, 1.65 g of Tetrad-X, 1.65 g of SA90, 7.05 g of toluene, and 0.07 g of KBM603 were mixed to obtain a resin composition (adhesive) having a non-volatile content of 30.0%.

Comparative Example 3

20.00 g of the solution of component (A1-1), 80.54 g of component (A2-3), 1.67 g of Tetrad-X, 1.67 g of SA90, 7.47 g of toluene, and 0.07 g of KBM603 were mixed to form a resin composition (adhesive) containing 30.0% non-volatile matter. got

Comparative Example 4

100.00 g of the solution of component (A1-1), 25.17 g of 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 were mixed to form a resin composition (adhesive) containing 30.0% non-volatile content. got

Comparative Example 5

100.00 g of the solution of component (A1-1), 25.17 g of component (A2-3), 0.19 g of Tetrad-X, 0.19 g of SA90, 0.71 g of toluene, and 0.08 g of KBM603 were mixed to form a resin composition (adhesive) containing 30.0% non-volatile content. got

Comparative Example 6

(A2-4) 100.00 g of the solution of the component, 2.04 g of Tetrad-X, 2.04 g of SA90, 32.04 g of toluene, and 0.08 g of KBM603 were mixed to obtain a resin composition (adhesive) having a non-volatile content of 30.0%.

Comparative Example 7

100.00 g of the solution of component (A2-5), 1.66 g of Tetrad-X, 1.66 g of SA90, 7.26 g of toluene, and 0.07 g of KBM603 were mixed to obtain a resin composition (adhesive) containing 30.0% of non-volatile content.

<Production of adhesive sheet>

The adhesive of Example 1 was applied to a support sheet (trade name "Kapton 100EN", manufactured by Toray DuPont Co., Ltd.; thickness: 25 μm; coefficient of thermal expansion: 15 ppm/° C.) with a gap coater so that the thickness after drying was 10 μm. Then, it was dried at 180° C. for 3 minutes to obtain an adhesive sheet. Adhesive sheets were obtained in the same way for the adhesives of other Examples and Comparative Examples.

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

<Measurement of dielectric constant and dielectric loss tangent of adhesive layer>

About 7 g of the adhesives of Examples and Comparative Examples were placed on a fluororesin PFA flat dish (diameter 75 mm, manufactured by Sangho Chemical Glass Manufacturing Co., Ltd.), 30 ° C × 10 hours, 70 ° C × 10 hours, 100 ° C × 6 time, 120°C×6 hours, 150°C×6 hours, and 180°C×12 hours were cured to obtain a cured product sheet having a thickness of about 300 μm. Next, relative permittivity (Dk) and dielectric loss tangent (Df) at 10 GHz were measured for the cured sheet according to JIS C2565 using a commercially available permittivity measuring device (cavity resonator type manufactured by AT).

<Adhesion test>

About each laminated body of an Example and a comparative example, it was peeled off and the strength (N/cm) was measured according to JIS C-6481 (Copper-clad laminated board test method for flexible printed wiring boards).

<Solder heat resistance test>

About each laminated body of an Example and a comparative example, after hardening, it floated with the copper foil side down in a 288 degreeC solder bath for 30 seconds, and the presence or absence of a change in appearance was confirmed. No change was evaluated as ○, and the case of foaming or swelling was evaluated as ×.

(A1)
(A2) usage
(wt%) (D) Dk Df adhesion
robbery
(N/m) pewter
heat resistance Example 1 (A1-1) - - 100 Tetrad-X SA90 10 KBM603 2.50 0.0029 1.0 ○ Example 2 (A1-2) - - 100 Tetrad-X SA90 10 KBM603 2.50 0.0027 1.0 ○ Example 3 (A1-1) (A2-3) - 80 Tetrad-X SA90 10 KBM603 2.60 0.0028 0.9 ○ Example 4 (A1-1) (A2-3) - 80 Tetrad-X SA90 15 KBM603 2.70 0.0031 1.0 ○ Example 5 (A1-2) (A2-3) - 80 Tetrad-X SA90 10 KBM603 2.55 0.0026 1.0 ○ Example 6 (A1-1) (A2-1) (A2-3) 40 jEr630 T759 10 KBM603 2.50 0.0025 1.0 ○ Example 7 (A1-1) (A2-1) (A2-3) 40 jEr630 T759 5 KBM603 2.50 0.0023 1.1 ○ Example 8 (A1-1) - - 100 Tetrad-X - 5 - 2.50 0.0031 1.0 ○ Example 9 (A1-1) (A2-1) (A2-6) 40 jEr630 T759 5 KBM603 2.50 0.0021 1.1 ○ Example 10 (A1-1) (A2-1) (A2-6) 40 jEr630 TA 20 KBM603 2.50 0.0022 1.1 ○ Example 11 (A1-1) (A2-1) (A2-6) 40 jEr630 TA 5 KBM603 2.50 0.0018 1.1 ○ Example 12 (A1-1) (A2-3) - 80 Tetrad-X SA90 3 KBM603 2.50 0.0025 0.9 ○ Comparative Example 1 - (A2-2) - 0 Tetrad-X SA90 10 KBM603 2.65 0.0045 1.0 ○ Comparative Example 2 - (A2-3) - 0 Tetrad-X SA90 10 KBM603 2.65 0.0038 0.2 ○ Comparative Example 3 (A1-1) (A2-3) - 20 Tetrad-X SA90 10 KBM603 2.70 0.0050 0.4 ○ Comparative Example 4 (A1-1) (A2-3) - 80 Tetrad-X SA90 25 KBM603 2.70 0.0050 1.0 ○ Comparative Example 5 (A1-1) (A2-3) - 80 Tetrad-X SA90 One - 2.60 0.0025 0.9 ○ Comparative Example 6 - (A2-4) - 0 Tetrad-X SA90 10 KBM603 2.50 0.0090 1.0 ○ Comparative Example 7 - (A2-5) - 0 Tetrad-X SA90 10 KBM603 2.60 0.0038 0.8 ○

<Production of bonding sheet>

The adhesive of Example 1 was coated on a release film (trade name "WH52-P25CM (white)", manufactured by San-Ai Kayon Co., Ltd.) with a gap coater so that the thickness after drying was about 25 μm, and then dried at 150 ° C. for 5 minutes to obtain a bonding sheet. Bonding sheets were obtained in the same manner for the adhesives of other Examples and Comparative Examples.

<Production of printed wiring board>

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

<Manufacture of multilayer wiring board>

Using the obtained printed wiring board as a core substrate, the resin-coated copper foil according to Example 1 was superimposed on both sides thereof, and pressure was 4.5 MPa, 200° C., and 30 minutes. A resist pattern of 0.2 (mm) was formed. Next, the obtained substrate was immersed in a 40% concentration ferric chloride aqueous solution and etched to form a copper circuit. On the surface layer on which the copper circuit was formed, the adhesive sheet was overlaid and laminated by hot pressing under 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.

<Production of printed wiring board 2>

A resist pattern of line/space = 0.2/0.2 (mm) was formed on the copper foil of the single-sided copper-clad laminate according to Example 1, and immersed in a 40% concentration ferric chloride aqueous solution for etching to form a copper circuit. The same was prepared, and the same bonding sheet was overlapped on the side of the base material without the copper circuit, and laminated by hot pressing under conditions of a pressure of 1 MPa, 180 ° C., and 30 minutes. Thereafter, the adhesive sheet was overlaid on the surface layer of the laminate where the copper circuit was formed, and laminated while heating and pressing under 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.

Printed wiring boards and multilayer wiring boards were obtained in the same manner for the adhesives of other Examples.

Claims (20)

A monomer group (1) containing an aromatic tetracarboxylic dianhydride (a1) having a content of free carboxylic acid of less than 1% by weight and a hydrogenated dimer diamine (a2) but not containing a diaminopolysiloxane (a3) is reacted. polyimide (A1) made of;
(A1) Polyimide (A2) other than a component; and
a cross-linking agent (B);
The component (A2) comprises an aromatic tetracarboxylic dianhydride (a1') having a content of component (a1) and/or free carboxylic acid of 1% by weight or more, and component (a2) and/or unhydrogenated dimer diamine (a2). It is a polyimide resin made by reacting the monomer group (2) containing '),
The solid content weight ratio [(A1)/(A2)] of component (A1) and component (A2) is 40/60 to 99/1,
The resin composition whose usage-amount of component (B) is 3-30 parts by weight with respect to 100 parts by weight of the total of the component (A1) and the component (A2).
According to claim 1,
The aromatic tetracarboxylic dianhydride constituting the component (a1) is a resin composition represented by the following formula (1):
[Formula 1]

(Wherein, X is a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ )2-C ₆ H ₄ -O- or -COO-Y-OCO- (At this time, Y represents -(CH ₂ ) _l -(l = 1 to 20) or -H ₂ C-HC (-OC(=O)-CH ₃ )-CH ₂ -).
According to claim 1 or 2,
The resin composition wherein the molar ratio [(a1)/[(a2)] of the component (a1) and the component (a2) in the monomer group (1) is 1 to 1.5.
delete delete According to claim 1 or 2,
The monomer group (2) is a resin composition further comprising a component (a3).
delete delete According to claim 1 or 2,
The resin composition wherein the component (B) is a polyepoxy compound (B1) and/or a polyphenylene ether compound (B2).
According to claim 9,
The component (B1) is a resin composition in which tetraglycidyl xylene diamine represented by the following formula (2):
[Formula 2]

(In formula, Z ^<1> represents a phenylene group or a cyclohexylene group).
According to claim 9,
The resin composition in which the component (B2) is a hydroxyl group-containing polyphenylene ether of the following formula (3):
[Formula 3]

(In the formula, Z ² represents an alkylene group having 1 to 3 carbon atoms or a single bond, m represents 0 to 20, n represents 0 to 20, and the sum of m and n represents 1 to 30).
According to claim 1 or 2,
The polyimide resin composition further contains an organic solvent (C).
According to claim 1 or 2,
The polyimide resin composition has the general formula: Q-Si(R ¹ ) _a (OR ² ) _3-a (wherein Q is a group containing a functional group reacting with an acid anhydride group, R ¹ is hydrogen or 1 to 10 carbon atoms) A polyimide resin composition further containing a reactive alkoxysilyl compound (D) represented by a hydrocarbon group of 8, R ² is a hydrocarbon group of 1 to 8 carbon atoms, and a represents 0, 1 or 2.
An adhesive made of the resin composition according to claim 1.
A film-type adhesive substrate made from a cured product of the adhesive of claim 14.
An adhesive sheet comprising a cured product of the adhesive according to claim 14 as an adhesive layer.
A multilayer wiring board obtained by using at least one selected from the group consisting of the adhesive of claim 14, the film-like adhesive substrate of claim 15, and the adhesive sheet of claim 16.
A resin-clad copper plate obtained by using at least one selected from the group consisting of the adhesive of claim 14, the film-like adhesive substrate of claim 15, and the adhesive sheet of claim 16.
The copper clad laminated board obtained using the copper foil with resin of Claim 18.
A printed wiring board obtained by using the copper-clad laminate according to claim 19.