WO2007114464A1

WO2007114464A1 - Resin composition for forming insulating layer

Info

Publication number: WO2007114464A1
Application number: PCT/JP2007/057521
Authority: WO
Inventors: Hirohisa Narahashi; Eiichi Hayashi
Original assignee: Ajinomoto Co., Inc.
Priority date: 2006-03-30
Filing date: 2007-03-28
Publication date: 2007-10-11
Also published as: JP2009155355A; TW200745211A

Abstract

Disclosed is a resin composition characterized by containing (A) a polymerized product of a bismaleimide compound and a diamine compound, (B) an epoxy resin having 2 or more epoxy groups in a molecule, (C) a curing agent and (D) one or more resins selected from phenoxy resins and polyvinyl acetal resins. This resin composition is suitable for forming an insulating layer of a multilayer printed wiring board or the like. This resin composition is excellent in heat resistance, mechanical strength and laminatability, while having low thermal expansion coefficient.

Description

Specification

Insulating layer forming resin composition

. Technical field

The present invention relates to a resin composition suitable for forming an insulating layer such as a multilayer printed wiring board.

Background art

In recent years, electronic devices have become smaller and have higher performance, and multilayered printed wiring boards and higher wiring density have been developed. As the number of layers increases, it is necessary to reduce the thickness of the printed wiring board while maintaining the mechanical strength (strength at break and elongation at break). In addition, in order to maintain connection reliability in increasing the density of wiring, the material forming the insulating layer is required to have high heat resistance. In addition, multilayer printed wiring boards with high-density wiring are prone to problems such as cracking due to the difference in thermal expansion coefficient between copper wiring and insulating layers, so it is required to keep the thermal expansion coefficient of insulating layers low. The

As an insulating material excellent in mechanical strength and heat resistance, for example, Japanese Patent Application Laid-Open No. 11-115828 discloses a resin composition comprising a maleimide compound, an epoxy resin, a curing agent, and a polyvinyl acetal resin. . However, when a resin composition that is generally excellent in mechanical strength and heat resistance is used as a sheet-like laminated material such as an adhesive film or a pre-preda, and the resin composition is laminated or used on an inner circuit board in a dry or semi-cured state. There is a problem that the laminar performance is low.

On the other hand, as an insulating material with a low coefficient of thermal expansion, for example, Japanese Patent Application Laid-Open No. 2 0 0 5-1 5 4 7 2 7 discloses a resin composition containing a large amount of silica. The resin composition with high silica filling has a problem that the drilling process of via holes and the like deteriorates. However, due to the progress of laser technology, etc., even when using a resin composition with high silica filling, it is accompanied by drilling. Multi-layer printed wiring boards can be produced. However, the drilling additivity is undeniably reduced compared to systems that do not contain silica or that contain a small amount. In addition, via holes tend to have smaller diameters due to higher wiring density, in which case the problem of drilling work becomes more prominent. Therefore, in order to improve the productivity of multilayer printed wiring boards or to further reduce the thermal expansion coefficient of the insulating layer, a technique for reducing the thermal expansion coefficient by a method different from the high filling of silica has been desired. Disclosure of the invention

The present invention provides a resin composition suitable for forming an insulating layer such as a multilayer printed wiring board, which is excellent in heat resistance, mechanical strength, laminate properties and low thermal expansion coefficient. The purpose is to do.

As a result of intensive studies by the present inventors, a polymer of a bismaleimide compound and a diamine compound, an epoxy resin having two or more epoxy groups in one molecule, a curing agent, and (D) a phenoxy resin and a polyvinyl acetal resin The present inventors have found that the above problems can be solved by a resin composition containing one or more kinds of resins selected from the following.

That is, the present invention includes the following contents.

[1] (A) Polymer of bismaleimide compound and diamine compound, (B) Epoxy resin having two or more epoxy groups in one molecule, (C) curing agent, and (D) phenoxy resin and polyvinyl A resin composition comprising: one or more resins selected from a settal resin.

[2] When the nonvolatile content of the resin composition is 100% by mass, the content of component (A) is 10 to 50% by mass, the content of component (B) is 15 to 45% by mass, and the component (C) The resin composition according to [1] above, wherein the content is 3 to 20% by mass and the content of component (D) is 10 to 50% by mass.

[3] An adhesive film in which the epoxy resin composition according to the above [1] or [2] is layered on a support film.

[4] An adhesive film with a copper foil, wherein the resin composition according to the above [1] or [2] is layered on the copper foil.

[5] A prepreg in which the epoxy resin composition according to the above [1] or [2] is impregnated in a sheet-like reinforcing substrate made of fibers.

[6] A multilayer printed wiring board in which an insulating layer is formed from a cured product of the epoxy resin composition according to [1] or [2].

According to the present invention, a resin composition having excellent mechanical strength and excellent laminating performance is provided. In addition, since the resin composition of the present invention has a low coefficient of thermal expansion, It is preferably used as a resin composition for forming an insulating layer of a printed wiring board.

Brief Description of Drawings

FIG. 1 is a conceptual diagram showing the unevenness of the insulating layer formed on the circuit board.

Detailed Description of the Invention

The present invention is described in detail below.

'[Polymer of bismaleimide compound and diamine compound of component (A)]

The polymer of the component (A) bismaleimide compound and diamine compound in the present invention is obtained by Michael addition reaction of an aromatic or aliphatic primary diamine compound or secondary diamine compound to the bismaleimide compound. Can do.

The bismaleimide compound is preferably an aromatic bismaleimide compound having an aromatic ring structure from the viewpoints of heat resistance and thermal expansion coefficient. Aromatic bismaleimide compounds include N, N '-(1,3-phenylene) bismaleimide, N, N'-(1,4 monophenylene) bismaleimide, N, N, and one [ 1,3— (2-Methylphenylene)] bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, bis [4- (4-maleimidophenoxy) Phenyl] methane, bis (3-ethyl-5-methyl_4-maleimidophenyl) methane, 1,1-bis [4 (4- (3-maleimidophenoxy) phenyl] ethane, 1,1 bis [4 (4 monomaleimidophenoxy) phenyl, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (4 monomaleimidophenoxy) phenyl] Ethane, 2, 2-bis [4 1 (4 maleimide phenoxy) Felco propane, 2 2-bis [4-1- (3-maleimidophenyl) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 1,4-bis (4-maleimidophenyl) cycloto Xanthone, 1,4 bis (maleimidomethyl) benzene, 1,3-bis (3-maleimidophenoxy) benzene, 1,4 bis [4 (4-maleimidophenoxy) 1 α, α-dimethylbenzyl] Benzene, 1,3-bis [4 (4-maleimidophenoxy), a-dimethylbenzyl] benzene, 1,4bis [4 (3 maleimidephenoxy), Q! -Dimethylpen Jill] benzene, 1,3-bis [4 1- (3-maleimidophenoxy)-, (¾-dimethylbenzyl) benzene, 1,4-onebis [41- (4-maleimidophenoxy) -1,3-5-dimethyl-1-α, «-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) 1,3,5-dimethyl-1, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) 1 3 , 5-dimethyl-, a-dimethylbenzyl] benzene, 1,3-bis [4 (3- (maleimidophenoxy)] 1,3,5-dimethyl-α, (¾-dimethylbenzyl) benzene, 4, 4 ' 1-bis (3-maleimidophenoxy) p-phenyl, 4, 4, 1-bis (4-maleimidophenoxy) biphenyl, bis (4'-maleimidophenyl) cane, bis [4- (3-maleimidophenoxy) ) Phenyl] ketone, bis [4-(4-maleimidophenol) Xy) phenyl] ketone, bis (4-maleimidophenyl) sulfide, bis [4— (3-maleimidephenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [ 4-1- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenyl) phenyl] sulfoxide, bis (4-maleimidophenyl) sulfone, bis [4- (3-maleimidophenoxy) [Phenyl] sulfone, bis [4 (4-maleimidophenyl) phenyl] sulfone, bis (4maleimidophenyl) ether, bis [4 ((1-maleimidophenoxy) phenyl] ether, bis [4- (4_maleimidophenoxy) phenyl] ether and the like.

As the diamine compound, a primary diamine compound is preferable from the viewpoint of reactivity with the bismaleimide compound, and an aromatic diamine compound having an aromatic ring structure is preferable from the viewpoint of heat resistance and thermal expansion coefficient. Preferred diamine compounds include 3,

3 '— Diaminobenzophenone, 4, 4' Diaminobenzophenone, 3, 3 '— Diaminodiphenyl ether, 4, 4' Diaminodiphenyl ether, 4,

4, monobis (3-aminophenoxy) biphenyl, 4, 4, monobis (4-aminophenoxy) biphenyl, 3-bis (3-aminophenoxy) benzene, 4-bis (4-aminophenoxy) benzene, bis (3 — (3-Aminophenyl) phenyl) ether, bis (4- (4 monoaminophenyl) phenyl) ether, 3-bis (3- (3-aminophenoxy) phenoxy) benzene, 4-bis (41 (41-aminophenoxy) phenoxy) benzene, bis (3- (3- (3-aminophenoxy) phenoxy) phenyl) ether, bis (4 1 (4 1- (4-amino phenoxy) phenoxy) phenyl) ether, 3-bis (3— (3— (3 1-aminophenoxy) phenoxy) phenoxy) benzene, 4 1 bis (4— (4 — (4 1 Aminophenoxy) Phenoxy) Phenoxy) Benzene, 2-bis [4 1 (3-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminominophenoxy) phenyl] propane, 4, —bis (3-aminobenzyl) Biphenyl, 4, 1-bis (4-aminobenzyl) Biphenyl, 3-bis (3-aminobenzyl) benzene, 4-bis (4 -Aminobenzyl) benzene, 3-bis (<<, monodimethyl-3-aminominobenzyl) benzene, 1,4-bis (, 0! -Dimethyl-1-3-aminobenzyl) benzene, 3-bis (α, α-dimethyl-4-aminominobenzyl) ) Benzene and the like. The diamine compounds may be used alone or in combination of two or more.

The reaction between the bismaleimide compound and the diamine compound can be carried out according to a known method (see Japanese Patent Application Laid-Open No. 3-148.36). The amount of the diamine compound used is preferably 1 to 4 molar equivalents, more preferably 2 to 3.5 molar equivalents, relative to 1 mol of the bismaleimide compound. The reaction is usually carried out by reacting in the range of 100 to 2500, preferably 1700 to 2200 ° C. for several minutes to several hours. Examples of the solvent used for the reaction include polar solvents such as N, N-dimethylformamide and N-methylpyrrolidone. In order to control the reaction rate, a radical scavenger, an anion polymerization catalyst, a radical generator, a Michael addition reaction accelerator or the like can be used as a catalyst as necessary. The addition amount of the catalyst is usually from 0.001 to 5% by mass based on the total mass of the bismaleimide compound and the diamine compound.

The mass average molecular weight of the polymer of the bismaleimide compound and the diamine compound is preferably from 60 to 3500 from the viewpoint of solubility in organic solvents and mechanical strength. In the present invention, the mass average molecular weight is determined by gel permeation chromatography (G PC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method is as follows: Shimadzu Corporation (: 9/8/1 ^ 1 0-6-8 as the measuring device, Showa Denko Co., Ltd. Shode XK as the column 8 0 0 Ρ ノ Κ1 8 0 4 LZ Κ1 8 0 4 L was measured at a column temperature of 40 ° C, using Kuroguchi Form as the mobile phase, and calculated using a standard polystyrene calibration curve. The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of laminating properties.

Examples of commercially available polymers of bismaleimide compounds and diamine compounds include “Techmite E 2 0 2 0” (N, N ′ — (4,4′-diphenylmethane) bis manufactured by Printec Co., Ltd. Polymers of maleimide and 1,3-bis (α, 1-dimethyl-1,4-aminobenzyl) benzene, mass average molecular weights 15 500 to 2000, softening point 103 to L1, etc.

The content of the polymer of the bismaleimide compound and the diamine compound is preferably 10 to 50% by mass when the nonvolatile content of the resin composition of the present invention is 100% by mass. 'Polymer compound and diamine compound polymer may be used alone or in combination of two or more.

[Epoxy resin with two or more epoxy groups in one molecule of component (Β)]

The “epoxy resin having two or more epoxy groups in one molecule” of the component (の) in the present invention is an aromatic epoxy having an aromatic ring skeleton in the molecule from the viewpoint of thermal expansion coefficient and heat resistance. Resins are preferred. Preferred epoxy resins include, for example, cresol nopolac type epoxy resin, phenol nopolac type epoxy resin, tert-butyl-catechol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, Examples include bisphenol F type epoxy resin, bisphenol S type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dicyclopentene type epoxy resin, and anthracene type epoxy resin. The epoxy resins may be used alone or in combination of two or more.

The epoxy resin of component (B) preferably contains an epoxy resin that is liquid at a temperature of 20 ° C. from the viewpoint of laminating properties and mechanical strength. The content of the liquid epoxy resin is When the epoxy resin of component (B) is 100% by mass, it is preferably 20 to 100% by mass.

Examples of commercially available liquid epoxy resins include HP 4032 (Naphthalene-type epoxy resin, epoxy equivalent 149), HP 4032D (Naphthalene-type epoxy resin, epoxy equivalent 141) manufactured by Dainippon Ink and Chemicals, Japan Epoxy Epicoat 807 (Bisphenol F type epoxy resin, Epoxy equivalent 170), Epicoat 828 EL (Bisphenol A type epoxy resin, Epoxy equivalent 189)), Epicot 1 52 (Phenol nopolac type) Epoxy resin, epoxy equivalent 174) and the like.

Examples of commercially available solid epoxy resins include HP 4700 (Naphthalene type epoxy resin, epoxy equivalent 163), N-690 (Cresol nopolac type epoxy resin, epoxy equivalent) manufactured by Dainippon Ink and Chemicals, Inc. 208), N-695 (cresol nopolac type epoxy resin, epoxy equivalent 208), Nippon Kayaku's EPPN-502H (trisphenol epoxy resin, epoxy equivalent 168), NC 7000 L (naphthol nopolac type epoxy) Resin, Epoxy equivalent 228), NC 3000H (Biphenyl type epoxy resin, Epoxy equivalent 290), ESN185 (Naphthol nopolac type epoxy resin, Epoxy equivalent) manufactured by Tohto Kasei Co., Ltd.

27 5), ESN47 5 (Naf) ^ One-Lunopolak type epoxy resin, epoxy equivalent

350).

The content of the epoxy resin is preferably 15 to 45% by mass, more preferably 20 to 20%, when the nonvolatile content of the resin composition in the present invention is 100% by mass.

It is 40% by mass, particularly preferably 25 to 35% by mass.

[Curing agent for component (C)]

As the curing agent of component (C) in the present invention, an amine curing agent, a guanidine curing agent, an imidazole curing agent, a phenol curing agent, an acid anhydride curing agent, a hydrazide curing agent, a carboxylic acid Examples thereof include a system-based curing agent, a thiol-based curing agent, or those epoxy-encapsulated microcapsules. As the curing agent, a phenolic curing agent is particularly preferable. Examples of phenolic curing agents include: W Enol nopolac resin, Alkyl phenol nopolac resin, Triazine structure-containing phenol nopolac resin, Bisphenol A nopolac resin, Dicyclopentane structure-containing phenol resin, Xylok (X y 1 ok) type phenol resin, Terpene modified phenol resin And polyvinylphenols, naphthalene structure-containing phenolic curing agents, fluorene structure-containing phenolic curing agents, and the like. Specific examples of commercially available phenolic curing agents include Dainippon Ink & Chemicals, Inc., “Phenolite LA 700 4”, “Phenolite EXB 9 8 9”, and the like. The curing agents may be used alone or in combination of two or more.

The content of the curing agent of component (C) is preferably 3 to 20% by mass, and 6 to 15% by mass, where the nonvolatile content of the resin composition of the present invention is 100% by mass. More preferably. When the content of the curing agent is outside this range, the thermal expansion coefficient tends to increase or the mechanical strength tends to decrease.

If necessary, an organic phosphine compound such as triphenylphosphine, an imidazole compound such as 2-ethyl 4-methylimidazole, or the like is added to the resin composition of the present invention as a curing accelerator. Also good. When a curing accelerator is used, the blending amount is preferably in the range of 0.5 to 2% by weight when the blending amount of the curing agent is 100% by weight.

[Phenoxy resin or polyvinylacetal resin of component (D)]

Examples of the phenoxy resin in the present invention include bisphenol type phenoxy resin (phenoxy resin having a bisphenol skeleton in the molecule), nopolac type phenoxy resin (phenoxy resin having a nopolak skeleton in the molecule), naphthalene type phenoxy. Examples thereof include phenoxy resins such as resins (phenoxy resins having a naphthalene skeleton in the molecule) and biphenyl-type phenoxy resins (phenoxy resins having a biphenyl skeleton in the molecule). The phenoxy resin can be obtained by reacting a bifunctional epoxy resin with a bisphenol compound. The phenoxy resins may be used alone or in combination of two or more. As the phenoxy resin, a biphenyl type phenoxy resin is particularly preferable from the viewpoint of heat resistance and moisture resistance. Heat The weight average molecular weight of the plastic resin is not particularly limited, but is preferably 500,000 to 100,000.

Commercially available phenoxy resins include Phenototo YP 50 (Bisphenol A type phenoxy resin) manufactured by Toto Kasei Co., Ltd. E-1256 (Bisphenol A type phenoxy resin) manufactured by Japan Epoxy Resin Co., Ltd. Toto Kasei Co., Ltd. FX280, FX293 (fluorene type phenoxy resin) manufactured by Japan Epoxy Resins Co., Ltd. YX8100, YL695, YL6974 (biphenyl type phenoxy resin), etc. are mentioned.

Examples of the polypinyl acetal resin in the present invention include a polyvinyl formal resin and a polyvinyl acetal resin. Polyvinyl acetal resin can be obtained by condensation of polyvinyl alcohol and aldehyde, and has acetal bond in the molecule. When formaldehyde is used as the aldehyde, a polyvinyl formal resin can be obtained, and when butyraldehyde is used as the aldehyde, a polyvinyl petital resin can be obtained. Each of the polyacetal resins may be used alone or in combination of two or more.

Specific examples of the polyvinyl acetal resin include Denki Petitral 4000-2, 5000--, 6000-C, 6000-EP, manufactured by Denki Kagaku Kogyo Co., Ltd., and Sekisui Chemical Co., Ltd.

S-Lec B H series, BX series, KS series, B L series, B M series, etc. manufactured by Co., Ltd. are listed.

The polyvinyl acetal resin preferably has a glass transition temperature of 80 ° C or higher. The “glass transition temperature” here is determined according to the method described in JISK 71 97. In addition, when the glass transition temperature is higher than the decomposition temperature and the glass transition temperature is not actually observed, the decomposition temperature can be regarded as the glass transition temperature in the present invention. The decomposition temperature is defined as the temperature at which the mass reduction rate is 5% when measured according to the method described in JISK 7120.

In the resin composition of the present invention, the content ratio of the phenoxy resin or polyvinylacetal resin of component (D) is preferably 10 to 50% by mass when the nonvolatile content of the resin composition is 100% by mass, It is more preferable to be 15-35% by mass ^ If the content of component (c) is too small, the coefficient of thermal expansion tends to increase and the mechanical strength tends to decrease. If the content is too large, the laminating performance tends to decrease. A mixture of phenoxy resin and polyvinyl acetal resin may be used. The resin composition of the present invention may contain components other than those described above as long as the effects of the present invention are exhibited. For example, a radical polymerization initiator such as dicumyl peroxide or an aromatic sulfonic acid such as benzoic acid may be added as a curing catalyst. In this case, the addition amount is preferably in the range of 0.001 to 5% by mass with respect to 100% by mass of the polymer of the bismaleimide compound and the diamine compound. Further, for example, an inorganic filler such as silica may be contained for the purpose of further reducing the coefficient of thermal expansion. In the case of containing an inorganic filler, the blending amount may be appropriately adjusted within a range where there is no inconvenience in drilling workability such as via holes. Further, for example, other resin components such as thermoplastic resins such as phenoxy resin and polyvinyl acetal may be contained. Further, for example, for the purpose of imparting flame retardancy, it may have a flame retardant such as an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, or a metal hydroxide. . Also, for example, organic fillers such as silicon powder, nylon powder, fluorine powder, thickeners such as olven and benton, silicone-based, fluorine-based, polymer-based antifoaming agent or leveling agent, imidazole-based , Thiazol-based, Triazole-based, Adhesion imparting agents such as silane coupling agents, Resin such as phthalocyanine blue, phthalocyanine secondary green, Iodine 'green, disazo yellow, force one pump rack, etc. It may contain additives.

The total content of components (A) to (D) in the resin composition of the present invention is not particularly limited, but is usually based on the resin composition (non-volatile content: 100% by mass). It is in the range of 50 to 100 mass%.

The resin composition of the present invention is, for example, applied on a support film to form a resin composition layer to form an adhesive film, applied on a copper foil to form a resin composition layer, and an adhesive film with copper foil. Alternatively, the resin composition can be impregnated in a sheet-like reinforcing substrate made of fibers to prepare a pre-preda. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer. 2007/057521 It is preferably used for forming an insulating layer in the form of an adhesive film, an adhesive film with copper foil, or a pre-preda.

Although the resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, it is generally industrially generally used as an adhesive film, an adhesive film with a copper foil, a sheet-like laminate such as a prepreg, etc. It is preferably used in the form of a material.

The adhesive film and the adhesive film with copper foil of the present invention are prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and using the support film or the copper foil as a support. It can be produced by applying a varnish and further drying the organic solvent by ripening or blowing hot air to form a resin composition layer.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and ester acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. And carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like. Two or more organic solvents may be used in combination.

The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a varnish containing 30 to 60% by mass of an organic solvent is dried at 50 to 150 ° C for about 3 to 10 minutes. It is prepared by. Those skilled in the art can appropriately set suitable drying conditions by simple experiments.

The thickness of the resin composition layer formed in the adhesive film and the adhesive film with copper foil is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70, the thickness of the resin composition layer preferably has a thickness of 10 to 100 m. The resin composition layer may be protected by a protective film described later. By protecting with a protective film, dust etc. adheres to the surface of the resin composition layer 7 057521 and scratches can be prevented.

As the support film and protective film in the present invention, polyethylene, polypropylene, polyvinyl chloride and other polyolefins, polyethylene terephthalate

(Hereinafter, it may be abbreviated as “PET”.) Polyester such as polyethylene naphthalate, polycarbonate, polyimide, and metal foil such as release paper, copper foil, aluminum foil, and the like. The support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

The thickness of the support film is not particularly limited, but is usually from 10 to 15 50, and preferably from 25 to 50 m. The thickness of the protective film is not particularly limited, but is usually in the range of 1 to 40 m, preferably 10 to 30 / im.

The copper foil in the adhesive film with a copper foil of the present invention includes an electrolytic copper foil, a rolled copper foil, etc., an ultrathin copper foil with a carrier, a release film such as polyethylene terephthalate subjected to a release treatment, and the like. What formed the vapor deposition layer etc. can be used. The thickness of the copper foil is usually preferably 9 to 3 5. In the case of ultra-thin copper foil with a carrier:! ~ 5 im copper foil is preferably used. In the case of a copper vapor-deposited film in which a copper vapor-deposited layer is formed on a peelable film, the thickness of the vapor-deposited layer is usually from 100 A to 500 A.

In order that the copper foil used for this invention may improve the adhesive strength by a throwing effect, it is preferable that the surface in which the curable resin composition of this invention is layered is roughened. The method of the roughening treatment is not particularly limited. For example, a method of roughening by etching, a copper foil immersed in an aqueous copper sulfate solution, and copper is precipitated by electrolysis, so that fine copper particles are deposited on the surface of the copper foil. It can carry out by well-known methods, such as the method of forming. In addition, after the surface roughening treatment, an anti-bacterial treatment may be applied, or a treatment for improving the adhesiveness with the resin such as a chromate treatment or a blackening treatment may be applied. From the viewpoint of suppressing transmission loss, the surface roughness (R z) of the copper foil is preferably 6.0 m or less, more preferably 4. O ^ m or less, and even more preferably 3.0 m or less. In addition, the surface roughness in the present invention is defined by the ten-point average roughness of “Definition of Surface Roughness” of JIS Β 06 6 1-1 9 94. Commercially available copper foils include: JTC—LP foil, JTC 1 AM foil (all manufactured by Nikko Materials), GTS—MP foil, F 2—WS foil (all Furukawa Circuit Oil Co., Ltd.) Manufactured).

Next, a method for producing the multilayer printed wiring board of the present invention using the adhesive film of the present invention will be described. When the resin composition layer is protected with a protective film, after peeling off, the resin composition layer is laminated on one or both sides of the circuit board so that the resin composition layer is in direct contact with the circuit board. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. The laminar method may be a batch method or a continuous method using a roll. In addition, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

As the substrate used for the circuit board, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or the like can be used. In the present invention, the circuit board refers to one having a conductor layer (circuit) patterned on one or both sides of the board as described above. The circuit board referred to in the present invention includes a conductor layer (circuit) in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned. The conductor layer surface may be subjected to roughening treatment in advance by blackening treatment or the like.

The laminating conditions are preferably a crimping temperature (laminating temperature) of 70 to 140 ° C and a crimping pressure of preferably 1 to: L 1 kg iZcm ² (9.8 x 10 ^{4 to} 107.9 x 10 N / m ² ) and laminating under reduced pressure of air pressure 20mmHg (26.7 hPa) or less. Vacuum lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminates include, for example, vacuum applique Ichiichi made by Nichigo Morton Co., Ltd., vacuum pressurization type laminator made by Meiki Seisakusho, and roll made by Hitachi Industries, Ltd. And the like, and the vacuum laminar manufactured by Hitachi Ishii Corporation.

After laminating the adhesive film on the circuit board, the support film is peeled off. When using a support film that has been demolded, the support film may be peeled off after curing. Good. An insulating layer can be formed on the circuit board by thermosetting. The conditions for thermosetting are selected in the range of 20 ° C. to 2 20 ° C. and 20 minutes to 180 ° C., more preferably 160 ° C. to 20 ° C. 30 to 30 for C; L 20 minutes.

If the support film is not peeled off after the insulating layer is formed, it is peeled off here. If necessary, drill holes in the insulating layer formed on the circuit board to form via holes and through holes. For example, the drilling can be performed by a known method such as drilling, laser, or plasma, or a combination of these methods if necessary. However, drilling by a laser such as a carbon dioxide laser or a YAG laser is possible. This is the more general method.

Next, a conductor layer is formed by plating. As the plating, for example, dry plating such as vapor deposition, sputtering, or ion plating can be used. As a subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

The roughness of the roughened surface obtained by roughening the surface of the insulating layer (surface roughness Ra value) is preferably 0.5 μππι or less in forming a fine wiring, and 0.35 m More preferably, it is as follows.

The Ra value is a kind of numerical value representing the surface roughness, and is called arithmetic average roughness. Specifically, the absolute value of the height that changes in the measurement region is expressed as an average line. Measured from a certain surface and arithmetically averaged. For example, using WY KO NT 3 3 0 0 manufactured by Beecoin Sturmen Co., Ltd., the VSI contact mode and 50 × lens can be used to obtain the measurement range as 1 2 1 um X 9 2 m. wear.

When an adhesive film with copper foil is used, circuit formation can be performed by patterning the copper foil, which is a conductor layer, by a subtractive method using etching. In addition, in the case of the above-mentioned ultrathin copper foil with a carrier or an adhesive film with copper foil using a copper vapor-deposited film as a support, a circuit can be formed by a semi-additive method. In addition, after removing the copper foil by etching, a conductor layer can be formed on the surface of the insulating layer by plating according to the method described above. The pre-preda of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing substrate made of fibers by a hot melt method or a solvent method and semi-curing by heating. That is, it can be set as the pre-preda which will be in the state which the resin composition of this invention impregnated the sheet-like reinforcement base material which consists of fibers. As the sheet-like reinforcing substrate made of fibers, for example, those commonly used as fibers for pre-predators such as glass cloth garamide fibers can be used.

In the hot melt method, without dissolving the resin in an organic solvent, the resin is once coated on the resin and a coated paper having good releasability, and then laminated to a sheet-like reinforcing substrate, or by DAIKO This is a method of manufacturing a pre-preda by direct coating. Similarly to the adhesive film, the solvent method is a method in which a sheet-like reinforcing base material is immersed in a resin varnish obtained by dissolving a resin in an organic solvent, and the sheet-like reinforcing base material is impregnated and then dried.

Next, a method for producing the multilayer printed wiring board of the present invention using the pre-preder of the present invention will be described. One or a plurality of the pre-preders of the present invention are stacked on a circuit board, and a metal plate is sandwiched through a release film, and press lamination is performed under pressure and heating conditions. The pressure is preferably 5 to 40 kgf / cm ² (49 × 10 ^{4 to} 392 × 10 ⁴ N / m ² ), the temperature is preferably 120 to 200, and the molding is preferably performed in the range of 20 to 100 minutes. It can also be manufactured by laminating to a circuit board by vacuum laminating as in the case of an adhesive film, followed by heat curing. Thereafter, in the same manner as described above, the surface of the hardened pre-preda is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.

The present invention will be described in more detail with reference to the following examples and comparative examples, which are not intended to limit the present invention in any way.

Example 1

Bisphenol F-type epoxy resin (Japan Epoxy Resin Co., Ltd. “Epi Coat 807”, epoxy equivalent of about 170) 15 parts by mass, triazine ring-containing phenolic nopolac resin (Dainippon Ink Chemical Co., Ltd.) "Phenolite EX98 89", phenol equivalent approximately 120) 8 parts by mass, Phenenyl-containing phenoxy resin (di 33 parts by mass of “Xa 8 100” (non-volatile content 30% by weight) manufactured by Rapane Epoxy Resin Co., Ltd., a polymer of bismaleimide compound and diamine compound (“Tec 20 20” manufactured by Printec Co., Ltd.) )) 20 parts by mass, radical polymerization initiator (Nippon Yushi Co., Ltd. “Park Mill D”) 0.1 6 parts by mass, N, N-dimethylacetamide 6 parts by mass are mixed, dissolved, and high-speed rotating mixer A thermosetting resin composition resin varnish was prepared by uniformly dispersing at. Next, the resin varnish is uniformly applied on a polyethylene terephthalate (thickness 38 ^ m, hereinafter abbreviated as PET) with a die coater so that the resin thickness after drying becomes 40 μηι. 1 Dried at 20 ° C (average 100) for 6 minutes (residual solvent amount of about 4% by mass). Next, a 15 m thick polypropylene film was bonded to the surface of the resin composition and wound into a roll. The roll-like adhesive film was slit to a width of 507 mm, and a sheet-like adhesive film having a size of 507 X 3 36 mm was obtained.

Example 2

Pisphenol F-type epoxy resin of Example 1 was replaced with naphthalene-type epoxy resin (“HP 403 2” manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent of about 149), and 33 parts of biphenyl-containing phenoxy resin containing fluorene skeleton An adhesive film was obtained in exactly the same manner except that the non-volatile content of 40 wt% methyl ethyl ketone solution of phenoxy resin (“FX 293” manufactured by Tohto Kasei Co., Ltd.) was changed to 28 parts.

Example 3

Example 3 Biphenyl-containing phenoxy resin 3 3 parts of polyvinylacetal resin (“; BX-5” manufactured by Sekisui Chemical Co., Ltd.) 15% by weight ethanol / toluene 1: 1 mixed solution 40% An adhesive film was obtained by exactly the same method except that the part was changed to the part.

Comparative Example 1

Polymer of aromatic bismaleimide and aromatic diamine described in Example 1 is mixed with bis (3-ethyl-5-methyl-4-monomaleimidophenyl) methane (KEI Kasei Co., Ltd. “BMI-7 0”) 20 parts by mass An adhesive film was obtained in exactly the same manner except that it was changed to. Comparative Example 2

Polymer of aromatic bismaleimide and aromatic diamine described in Example 2 was added to 20 parts by mass of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (Kay Kasei Co., Ltd., ΓΒΜΙ-70 ”). The adhesive-film was obtained in exactly the same manner except that it was changed.

評価 Evaluation of Tg (glass transition temperature) and thermal expansion coefficient by TMA method>

From the adhesive films obtained in the Examples and Comparative Examples, the polypropylene film was peeled off and laminated to a copper foil (“JTC One LP Foil” manufactured by Nikko Materials Co., Ltd.) using a vacuum laminator. Subsequently, PET was peeled off and heated at 190 ° C. for 90 minutes to obtain a cured product of the resin composition with copper foil. Thereafter, the copper foil was removed with ferric chloride (manufactured by Tsurumi Soda Co., Ltd.), washed with water and dried at 130 ° C for 15 minutes to obtain a cured product of the resin composition. The obtained cured product was cut into a test piece with a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed using the Rigaku thermomechanical analyzer (ThermoPlus TM A8310) by the tensile load method. Went. After mounting the test piece on the apparatus, the measurement was performed twice continuously under the measurement conditions of a load l g and a heating rate of 5 ° C./min. The average coefficient of linear expansion from 25 ° C to 150 ° C in the second measurement was calculated and used as the value of the coefficient of thermal expansion. The second value of Tg was used.

Evaluation of strength at break and elongation at break>

Remove the polypropylene film from the adhesive films obtained in the examples and comparative examples, and use a vacuum laminating film to make a copper foil ("JTC one LP foil" manufactured by Nikko Materials Co., Ltd.) Laminated. Subsequently, the PET was peeled off and heated at 190 for 90 minutes to obtain a cured product of the resin composition with copper foil. Thereafter, the copper foil was removed with ferric chloride (manufactured by Tsurumi Soda Co., Ltd.), washed with water and dried at 130 ° C for 15 minutes to obtain a cured product of the resin composition. According to JIS K7 172, dumbbell specimens were cut out and a tensile test was performed using these specimens. From the results, the strength at break and elongation at break of the cured product were calculated.

On a glass epoxy board with a thickness of 0.4 mm, conductor thickness 35 m, L / S = 1 A double-sided wiring board on which 60 zm / 160 m comb-teeth wiring was formed was prepared, and roughening was performed using “CZ 8100” manufactured by Mec Co., Ltd. so that the copper surface roughness was 2 im. The adhesive films produced in the examples and comparative examples on the substrate were subjected to a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., ML P-500, with a degree of vacuum of 0.75 mmHg, a pressure bonding temperature of 130 ° C, The resin composition layer was laminated by pressing for 30 seconds under a pressure of 58.8 × 10 ⁴ N // m ² . After lamination, the PET was peeled off, and this was heat cured at 190 ° C for 60 minutes to form an insulating layer. The comb wiring portion of the printed wiring board on which the insulating layer was formed was cut. Using a KEYENCE microscope, VK8510, cross-sectional observation was performed to determine the unevenness difference of the insulating layer. As shown in Fig. 1, the unevenness difference was obtained from the difference between the resin thickness (a) on the copper wiring and the resin thickness (b) at the portion without the copper wiring, and was evaluated based on the value with the largest unevenness.

Table 1 shows the results of each test for the samples of Examples and Comparative Examples. It can be seen that the example samples are excellent in heat resistance (Tg) and mechanical strength (strength at break, elongation at break) and at the same time laminate properties. Also, the coefficient of thermal expansion shows a low value.

Industrial Applicability 'The resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board.

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Claims

The scope of the claims

1. (A) polymer of bismaleimide compound and diamine compound, (B) epoxy resin having two or more epoxy groups in one molecule, (C) curing agent, and (D) phenoxy resin and polyvinylaceta A resin composition comprising one or more resins selected from a single resin.

2. When the nonvolatile content of the resin composition is 100% by mass, the content of component (A) is 10 to 50% by mass, the content of component (B) is 15 to 45% by mass, The resin composition according to claim 1, wherein the content of the component (C) is 3 to 20% by mass and the content of the component (D) is 10 to 50% by mass.

3. An adhesive film in which the epoxy resin composition according to claim 1 or 2 is layered on a support film.

4. A copper foil-attached film in which the resin composition according to claim 1 or 2 is layered on a copper foil.

5. A pre-preda in which the epoxy resin composition according to claim 1 or 2 is impregnated in a sheet-like reinforcing base material comprising fibers.

6. A multilayer printed wiring board in which an insulating layer is formed of a cured product of the epoxy resin composition according to claim 1 or 2.