JP2000230034A - Resin composition for insulation layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin compsn. for forming an insulation layer excellent in adhesiveness with an electroless plating film in a multi-layer wiring board and has also heat resistance. SOLUTION: This resin compsn. for insulation layer is obtd. by mixing and kneading an ultraviolet curing resin (A) obtd. by reacting a reaction product of a bisphenol type epoxy compd. and an unsaturated monocarboxylic acid, and an anhydride of a saturated or unsaturated polybasic acid, a multifunctional epoxy compd.(B), an epoxy compd. having not less than 2 alicyclic epoxy groups (C), an epoxy compd. having a (meth) acrylic group and an epoxy group in a molecule (D), a photo radical polymerization initiator (E), a photo-cation polymerization initiator (F), a filler (G), and a diluent (H).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition used for forming an insulating layer of a multilayer printed wiring board. .

[0002]

2. Description of the Related Art In recent years, with the advance of electronic technology, electronic devices such as large-sized computers have been increased in density or operating functions. As a result, multilayer printed wiring boards, in which wiring layers are formed in multiple layers for the purpose of increasing the density of printed wiring boards, have been spotlighted.

Conventionally, a typical multilayer printed wiring board is, for example, a multilayer printed wiring board in which internal circuits are stacked and connected to conduct. However, in such a multilayer printed wiring board, since a plurality of internal circuits are connected and conducted through through holes, the wiring circuit becomes too complicated, and it is difficult to realize high density or high speed. Met.

As a multilayer printed wiring board capable of overcoming such a problem, recently, a multilayer printed wiring board formed by alternately building up a conductor wiring layer and an insulating layer has been developed. This multilayer printed wiring board is suitable for ultra-high density and high speed, but has a drawback in that it is difficult to form an electroless plating film on an insulating layer with high reliability.

For this reason, in such a multilayer printed wiring board, the conductor film forming the conductor wiring layer is formed by a PVD method such as evaporation or sputtering, or a combination of the PVD method and electroless plating. , Such PV
The method of forming a conductive film by the method D is inferior in productivity and high in cost.

Recently, as a method for forming an electroless plating film on such an insulating layer with high reliability, an electroless plating film is prepared by mixing and dissolving a component soluble in an insulating layer with an oxidizing agent or the like. There has been proposed a method of roughening the resin surface in contact with the resin. For example, as disclosed in JP-A-64-47095, a resin such as an epoxy resin, a bismaleimide / triazine resin, or a polyester resin, which is soluble in an oxidizing agent, and is insoluble in the oxidizing agent. A method in which an insulating layer is formed with a resin composition in which a resin or an inorganic filler is mixed to roughen the surface of the insulating layer with an oxidizing agent to enhance the anchor effect of forming an electroless plating film, and the like has been proposed. Further, as described in Japanese Patent Application Laid-Open No. 7-34505, which further enhances these effects, pseudo particles are formed from resin particles having different sizes soluble in an oxidizing agent and mixed into a heat-resistant matrix resin. And others have been proposed.

However, the insulating layer formed by these methods has poor heat resistance of a resin modifier itself such as resin particles dissolved by an oxidizing agent or the like. As a result, the heat resistance of the insulating layer may be reduced. Had been a problem.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and is intended to form an insulating layer having excellent heat resistance and excellent adhesion to an electroless plating film in a multilayer printed wiring board. An object is to provide a resin composition.

[0009]

In order to solve the above-mentioned problems, according to the present invention, first, a reaction product of a bisphenol-type epoxy compound and an unsaturated monocarboxylic acid is combined with a saturated or unsaturated polybasic anhydride. (A), a polyfunctional epoxy compound (B), an epoxy compound (C) having two or more alicyclic epoxy groups, and A) an epoxy compound having an acrylic group and an epoxy group (D), a photoradical polymerization initiator (E), and a photocationic polymerization initiator (F)
And a filler (G) and a diluent (H).

The epoxy compound (C) having two or more alicyclic epoxy groups according to the present invention.
Is a 3,4-epoxycyclohexyl group or 3,4-
The resin composition for an insulating layer according to claim 1, wherein the resin composition has an epoxycyclohexylmethyl group.

According to a third aspect of the present invention, the epoxy compound (D) having a (meth) acryl group and an epoxy group in the molecule is an acrylate or methacrylate having a 3,4-epoxycyclohexylmethyl group. A resin composition for an insulating layer according to claim 1 or 2.

Further, according to claim 4, the polyfunctional epoxy compound (B) has a structure represented by the following chemical formula (1): The insulating layer according to any one of claims 1 to 3, And a resin composition for use.

[0013]

Embedded image

Further, in claim 5, the total amount of the ultraviolet curable resin (A), the polyfunctional epoxy compound (B), the epoxy compound (C) and the epoxy compound (D) is 100. 0.1 to 20.0 parts by weight of the photo-radical polymerization initiator (E) and 0.1 to 20.0 parts by weight of the photo-cationic polymerization initiator (F) based on parts by weight. A resin composition for an insulating layer according to any one of claims 1 to 4.

In general, a photo-radical polymerization type photosensitive resin is
Although the solvent resistance, heat resistance, and water resistance are excellent, the photosensitivity and adhesiveness are not sufficient, and the photocationic polymerization type epoxy resin has excellent photosensitivity and adhesiveness even though it is superior to the radical polymerization type. In this case, the solvent resistance, water resistance and stiffness are not sufficient.

Thus, together with the photoradical polymerization initiator,
By using the photocationic polymerization initiator in combination, efficiently react the alicyclic epoxy group contained in the epoxy compound, without reducing the heat resistance with moderate stiffness,
A cured product having excellent adhesive properties can be obtained.

By using the above resin composition for insulation, an insulation layer having high heat resistance and excellent adhesion of the electroless plating film can be formed, and a reliable multilayer printed wiring board can be obtained.

[0018]

Embodiments of the present invention will be described below. In an ultraviolet curable resin (A) obtained by reacting a reaction product of a bisphenol type epoxy compound with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride, a specific example of a bisphenol component is bis ( 4
-Hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4
-Hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-
Hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (4
-Hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-
3,5-dichlorophenyl) hexafluoropropane,
Bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, Bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2- Bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5
-Dichlorophenyl) ether and the like.

Further, specific examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid and cinnamic acid.

Further, specific examples of the saturated or unsaturated polybasic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl anhydride. Xahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride,
Dibasic acid anhydrides such as chlorendic anhydride and methyltetrahydrophthalic anhydride; aromatic polycarboxylic anhydrides such as trimellitic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride; For example, a polycarboxylic anhydride derivative such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride can be used.

Specific examples of the polyfunctional epoxy compound (B) include phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin. Resin, an epoxy resin such as an alicyclic epoxy resin, or an epoxy group such as phenylglycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate.
And the like. In addition, various derivatives of cyclohexene oxide, hydrogenated compounds of the aromatic epoxies, and alicyclic epoxies having the structure shown in Chemical Formula 1 may be used. Among these, a system using an alicyclic epoxy compound having a structure represented by Chemical Formula 1 is particularly preferable since it exhibits a high glass transition temperature and thus has excellent heat resistance.

Specific examples of the epoxy compound (C) having two or more alicyclic epoxy groups include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and caprolactone-modified products thereof.
Examples include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate modified with trimethylcaprolactone, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate modified with valerolactone. In addition, alicyclic epoxy compounds represented by the following chemical formulas 2 and 3 can also be mentioned.

[0023]

Embedded image

[0024]

Embedded image

Specific examples of the epoxy compound (D) having a (meth) acryl group and an epoxy group in the molecule include:
Glycidyl acrylate, glycidyl methacrylate,
Methyl glycidyl acrylate, methyl glycidyl methacrylate, 9,10-epoxystearyl acrylate, 9,10-epoxystearyl methacrylate,
3,4-epoxycyclohexylmethyl acrylate,
3,4-epoxycyclohexylmethylcaprolactone acrylate, 3,4-epoxycyclohexylmethylcaprolactone methacrylate, and the like.
Of these, a system having a 3,4-epoxycyclohexylmethyl group is excellent in stability when mixed with another material, and is particularly desirable.

Specific examples of the photoradical polymerization initiator (E) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert. Acetophenones such as -butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone and p, p'-bisdimethylaminobenzophenone; and benzoin such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Ethers, benzyldimethyl ketal,
Thioxanthone, 2-chlorothioxanthone, 2,4-
Diethylthioxanthone, 2-methylthioxanthone,
A sulfur compound such as 2-isopropylthioxanthone,
Anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutylnitrile, benzoyl peroxide and cumene peroxide; Mercaptobenzimidazole, 2-mercaptobenzoxazole,
Thiol compounds such as 2-mercaptobenzothiazole are exemplified. These compounds may be used in combination of two or more. In addition, a compound which does not act as a photopolymerization initiator by itself, but can be used in combination with the above compound, can increase the ability of the photopolymerization initiator. Such compounds include, for example, tertiary amines such as triethanolamine, which are effective when used in combination with benzophenone.

The addition amount of the photo-radical polymerization initiator (E)
0.1 to 20.0 with respect to 100 parts by weight of the total amount of the ultraviolet curable resin (A), the polyfunctional epoxy compound (B), the epoxy compound (C) and the epoxy compound (D).
It is particularly preferred to contain the parts by weight. If the amount of the photo-radical polymerization initiator (E) is less than 0.1 part by weight, sufficient curability cannot be obtained, and if it exceeds 20 parts by weight, heat resistance decreases.

Specific examples of the cationic photopolymerization initiator (F) include diazonium salts represented by the following chemical formulas 4 and 5, and sulfonium salts represented by the following chemical formulas 6, 7, 8, and 9: , An iodonium salt as shown in Chemical Formula 10, Chemical Formula 11, Chemical Formula 12
And a metal compound represented by Chemical Formula 13.

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

These compounds can be used in combination of two or more kinds.

The addition amount of the cationic photopolymerization initiator (F)
0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the ultraviolet curable resin (A), the polyfunctional epoxy compound (B), the epoxy compound (C) and the epoxy compound (D).
It is particularly preferred to contain 0 parts by weight. If the amount of the cationic photopolymerization initiator (F) is less than 0.1 part by weight, sufficient curability cannot be obtained, and if it exceeds 20 parts by weight, heat resistance decreases.

Specific examples of the filler (G) include organic fillers such as a fluorine resin, a polyimide resin, and a benzoguanamine resin, silica, talc, alumina, clay, and the like.
Inorganic fillers such as calcium carbonate, titanium oxide and barium sulfate can be blended.

Specific examples of the diluent (H) include methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, butyl carbitol, butyl cellulose, tetralin, dimethylformamide, and normal methylpyrrolidone. .

The resin composition for an insulating layer having photosensitivity may further include an epoxy group curing accelerator, if necessary.
It is possible to add additives such as a thermal polymerization inhibitor, a plasticizer, a leveling agent, an antifoaming agent, an ultraviolet absorber, a flame retardant, a coloring pigment, and the like.

Next, a method for manufacturing a multilayer printed wiring board will be specifically described. First, a coating film is formed on a substrate using the above-mentioned resin composition for an insulating layer having photosensitivity, and exposed and developed to form an insulating layer. As the substrate, for example, a plastic substrate, a ceramic substrate, a metal substrate, a film substrate, and the like can be used.Specifically, a glass epoxy substrate, a bismaleimide-triazine substrate, a low-temperature fired ceramic substrate, an aluminum nitride substrate, an aluminum substrate, An iron substrate, a polyimide film substrate, or the like can be used.

As a method of forming a coating film, the above photosensitive resin composition is coated by a roller coating method, a dip coating method, a spray coating method, a spinner coating method, a curtain coating method,
A method of applying and drying by a screen printing method or the like, a method of applying a resin film obtained by processing the above-mentioned photosensitive resin composition into a film, and forming a coating film can be applied. The thickness of the coating film is usually about 20 to 100 μm, but it is possible to increase the thickness if a particularly high insulating property is required.

Next, the coating film is exposed by irradiating it with actinic rays, and is developed using a weak alkaline aqueous solution. Also,
If necessary, heating may be performed after exposure. Examples of the aqueous alkali solution include an aqueous sodium carbonate solution, an aqueous sodium hydrogen carbonate solution, an aqueous diethanolamine solution, an aqueous triethanolamine solution, an aqueous ammonium hydroxide solution, and an aqueous sodium hydroxide solution. Among them, an aqueous solution of sodium carbonate has an appropriate alkalinity, and is safe and particularly preferable in terms of working environment unlike strong alkalis such as sodium hydroxide.

Next, after the development processing, heating and curing are performed to form an insulating layer. In the resin composition for an insulating layer of the present invention, by performing heat treatment, not only is it possible to significantly improve the durability to strong alkaline water, but also to glass, adhesion to metals such as copper, heat resistance, and surface hardness. Etc. are also improved.

Next, after the surface of the insulating layer is roughened using an acid or an oxidizing agent, a conductive wiring layer is formed by a known additive method or semi-additive method.

By repeating the above steps a predetermined number of times, a multilayer printed wiring board can be manufactured.

[0050]

The present invention will be described below in detail with reference to examples. <Example 1> An acid value of about 158 (mgKOH / mg) obtained by reacting bisphenol A type epoxy acrylate (Ripoxy VR-90, manufactured by Showa Kogyo Co., Ltd.) with phthalic anhydride
g) 50 parts by weight of ultraviolet resin, epoxy resin EHPE3
150 (manufactured by Daicel Chemical) 12 parts by weight, alicyclic epoxy resin celloxide 2021 (manufactured by Daicel Chemical) 5 parts by weight, 3,4-epoxycyclohexylmethyl methacrylate (trade name M100; manufactured by Daicel Chemical) 13 parts by weight, 15 parts by weight of a silica fine powder, 1 part by weight of a leveling agent (manufactured by BYK-Chemie), TPO (B
ASF) 2 parts by weight, photocationic polymerization initiator FX51
2 (manufactured by Three M) and propylene glycol monomethyl ether acetate solvent were added and stirred, and then kneaded with three rolls to prepare a photosensitive resin solution A.

Next, the above resin solution A was applied to a degreased and washed glass epoxy substrate using a slot coater and dried, and then passed through a photomask to 150 mJ / cm ^2.
Exposure with organic amine-based alkaline developer for 30 minutes
C., development was performed for 1 minute to remove unexposed portions. Thereafter, the resultant was heated and cured at 100 ° C. for 1 hour and further at 200 ° C. for 1 hour using a drying oven to form an insulating layer having a thickness of 40 μm.

25 μm on the insulating layer by the semi-additive method.
An m-thick conductor wiring layer was formed.

The steps of forming the insulating layer and the conductor wiring layer were repeated a predetermined number of times to obtain a multilayer printed wiring board.

<Example 2> Bisphenol A type epoxy acrylate (Lipoxy VR-90, manufactured by Showa Polymer Co., Ltd.)
Value obtained by reacting phthalic anhydride with phthalic anhydride
(MgKOH / g) 50 parts by weight of an ultraviolet resin, 11 parts by weight of an epoxy resin EHPE3150 (manufactured by Daicel Chemical), 7 parts by weight of an alicyclic epoxy resin celloxide 2081 (manufactured by Daicel Chemical), 3,4-epoxycyclohexylmethyl 12 parts by weight of methacrylate (trade name: M100; manufactured by Daicel Chemical Co., Ltd.), 15 parts by weight of silica fine powder, 1 part by weight of a leveling agent (manufactured by BYK Chemie), 2 parts by weight of photo-radical polymerization initiator TPO (manufactured by BASF), photocation 2 parts by weight of a polymerization initiator FX512 (manufactured by Three M Co.) was added with a propylene glycol monomethyl ether acetate solvent, stirred, and kneaded with three rolls to obtain a photosensitive resin solution B.

Next, using the degreasing solution B, an insulating layer and a conductor wiring layer were formed in the same manner as in Example 1, and this process was repeated a predetermined number of times to obtain a multilayer printed wiring board.

<Example 3> Bisphenol A type epoxy acrylate (Lipoxy VR-90, manufactured by Showa Polymer Co., Ltd.)
Value obtained by reacting phthalic anhydride with phthalic anhydride
(Mg KOH / g) 50 parts by weight of an ultraviolet resin, 10 parts by weight of an epoxy resin EHPE3150 (manufactured by Daicel Chemical), 10 parts by weight of an alicyclic epoxy resin celloxide 2083 (manufactured by Daicel Chemical), 3,4-epoxycyclohexylmethyl methacrylate 10 parts by weight (trade name: M100, manufactured by Daicel Chemical Co., Ltd.), 15 parts by weight of silica fine powder, 1 part by weight of a leveling agent (manufactured by Big Chemie), 2 parts by weight of a photoradical polymerization initiator TPO (manufactured by BASF), photocationic polymerization 2 parts by weight of an initiator FX512 (manufactured by Three M) was added with a propylene glycol monomethyl ether acetate solvent and stirred, and then kneaded with three rolls to obtain a photosensitive resin solution C.

Next, using the resin solution C, an insulating layer and a conductor wiring layer were formed in the same manner as in Example 1, and this process was repeated a predetermined number of times to obtain a multilayer printed wiring board.

<Example 4> Bisphenol A type epoxy acrylate (Lipoxy VR-90, manufactured by Showa Polymer Co., Ltd.)
Value obtained by reacting phthalic anhydride with phthalic anhydride
(MgKOH / g) 50 parts by weight of an ultraviolet resin, 12 parts by weight of an epoxy resin EHPE3150 (manufactured by Daicel Chemical Co., Ltd.), 6 parts by weight of an alicyclic epoxy resin Epode GT301 (manufactured by Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (Trade name: M100; Daicel Chemical Co., Ltd.) 12 parts by weight, silica fine powder 15 parts by weight, leveling agent (by Big Chemie) 1 part by weight, photoradical polymerization initiator TPO (by BASF) 2 parts by weight, photocationic polymerization 2 parts by weight of an initiator FX512 (manufactured by Three M) were added with a propylene glycol monomethyl ether acetate solvent and stirred, and then kneaded with a three-roll mill to obtain a photosensitive resin solution D.

Next, using the resin solution D, an insulating layer and a conductor wiring layer were formed in the same manner as in Example 1, and this process was repeated a predetermined number of times to obtain a multilayer printed wiring board.

<Example 5> Bisphenol A type epoxy acrylate (Lipoxy VR-90, manufactured by Showa Polymer Co., Ltd.)
Value obtained by reacting phthalic anhydride with phthalic anhydride
(MgKOH / g) 50 parts by weight of an ultraviolet resin, 11 parts by weight of an epoxy resin EHPE3150 (manufactured by Daicel Chemical Co., Ltd.), 7 parts by weight of an alicyclic epoxy resin Epode GT401 (manufactured by Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (Trade name: M100; Daicel Chemical Co., Ltd.) 12 parts by weight, silica fine powder 15 parts by weight, leveling agent (by Big Chemie) 1 part by weight, photoradical polymerization initiator TPO (by BASF) 2 parts by weight, photocationic polymerization 2 parts by weight of an initiator FX512 (manufactured by Three M Co.) was added to a propylene glycol monomethyl ether acetate solvent and stirred, and then kneaded with three rolls to obtain a photosensitive resin solution E.

Next, using this resin solution E, an insulating layer and a conductor wiring layer were formed in the same manner as in Example 1, and this process was repeated a predetermined number of times to obtain a multilayer printed wiring board.

<Comparative Example 1> Bisphenol A type epoxy acrylate (Ripoxy VR-90, manufactured by Showa Polymer Co., Ltd.)
Value obtained by reacting phthalic anhydride with phthalic anhydride
(MgKOH / g) 50 parts by weight of an ultraviolet resin, 15 parts by weight of an epoxy resin EHPE3150 (manufactured by Daicel Chemical), 15 parts by weight of 3,4-epoxycyclohexylcycyclohexylmethyl methacrylate (trade name: M100; manufactured by Daicel Chemical), silica 15 parts by weight of a fine powder, 1 part by weight of a leveling agent (manufactured by BIC Chemie), and 4 parts by weight of a photo-radical polymerization initiator TPO (manufactured by BASF) are mixed with a propylene glycol monomethyl ether acetate solvent, and then kneaded with a three-roll mill. Then, a photosensitive resin solution F was obtained.

Next, using this resin solution F, an insulating layer and a conductive wiring layer were formed in the same manner as in Example 1, and this process was repeated a predetermined number of times to obtain a multilayer printed wiring board.

<Comparative Example 2> Bisphenol A type epoxy acrylate (Lipoxy VR-90, manufactured by Showa Polymer Co., Ltd.)
Value obtained by reacting phthalic anhydride with phthalic anhydride
(Mg KOH / g) 50 parts by weight of an ultraviolet resin, 10 parts by weight of an epoxy resin EHPE3150 (manufactured by Daicel Chemical), 10 parts by weight of an alicyclic epoxy resin celloxide 2083 (manufactured by Daicel Chemical), 3,4-epoxycyclohexylmethyl methacrylate 10 parts by weight (trade name: M100, manufactured by Daicel Chemical Co., Ltd.), 15 parts by weight of silica fine powder, 1 part by weight of a leveling agent (manufactured by BYK Chemie), 4 parts by weight of a photo-radical polymerization initiator TPO (manufactured by BASF), and propylene glycol monomethyl After adding and stirring an ether acetate solvent, the mixture was kneaded with three rolls to obtain a photosensitive resin solution G.

Next, using this resin solution G, an insulating layer and a conductor wiring layer were formed in the same manner as in Example 1, and this process was repeated a predetermined number of times to obtain a multilayer printed wiring board.

<Comparative Example 3> Bisphenol A type epoxy acrylate (Lipoxy VR-90, manufactured by Showa Polymer Co., Ltd.)
Value obtained by reacting phthalic anhydride with phthalic anhydride
(Mg KOH / g) 50 parts by weight of an ultraviolet resin, 10 parts by weight of an epoxy resin EHPE3150 (manufactured by Daicel Chemical), 10 parts by weight of an alicyclic epoxy resin celloxide 2083 (manufactured by Daicel Chemical), 3,4-epoxycyclohexylmethyl methacrylate 10 parts by weight (trade name: M100, manufactured by Daicel Chemical Co., Ltd.), 15 parts by weight of silica fine powder, 1 part by weight of a leveling agent (manufactured by Big Chemie), and 4 parts by weight of photocationic polymerization initiator FX512 (manufactured by Three M) are propylene glycol. After adding and stirring a monomethyl ether acetate solvent, the mixture was kneaded with three rolls to obtain a photosensitive resin solution H.

Next, using this resin solution H, an insulating layer and a conductor wiring layer were formed in the same manner as in Example 1, and this process was repeated a predetermined number of times to obtain a multilayer printed wiring board.

The results of measuring the adhesion strength between the insulating layer of the multilayer printed wiring board obtained in the above Examples and Comparative Examples and the electroless plating film forming the conductor wiring layer by the method of JIS-C-6481. Are shown in Table 1. The measurement of the glass transition temperature by a dynamic viscoelasticity measuring device was also performed at the same time.

[0069]

[Table 1]

As is clear from the results in Table 1, Example 1
In Comparative Examples 1 and 2, the peel strength was sufficient, but the peel strength was low, and it was difficult to form the conductor wiring layer with high reliability. there were. In Comparative Example 3, the peel strength was sufficient, but the heat resistance was low and the material lacked reliability.

From the above results, it was confirmed that by using the resin composition for an insulating layer of the present invention, an insulating layer having excellent adhesion to an electroless plating film and having heat resistance can be formed.

[0072]

EFFECT OF THE INVENTION By using the resin composition for an insulating layer of the present invention, an insulating layer having excellent adhesion to an electroless plating film and heat resistance can be formed, and a reliable multilayer printed wiring board can be formed. Can be easily and inexpensively provided.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takuzo Watanabe 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. F-term (reference) 2H025 AA00 AA10 AA14 AA20 AB15 AC01 AD01 BC64 BC74 BC83 BE00 BE07 CA01 CA18 CA31 CC03 CC08 CC20 FA17 FA29 4J036 AA01 AA02 AA06 AB17 AC18 AD01 AD07 AD08 AD21 AF06 AF08 AJ02 AJ03 AJ08 AJ09 AK19 CA20 CA21 CB08 CB15 EA04 FA01 FA02 FA04 FA05 FA06 FA11 FB02 FB09 GA03 GA03 GA03 GA24 GA03 GA24 DD22 DD33 EE31 GG02 GG17 GG19 HH11 HH18

Claims (5)

[Claims] An ultraviolet curable resin (A) obtained by reacting a reaction product of a bisphenol type epoxy compound with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride.
, A polyfunctional epoxy compound (B), an epoxy compound (C) having two or more alicyclic epoxy groups, and an epoxy compound (D) having a (meth) acryl group and an epoxy group in a molecule. And a photoradical polymerization initiator (E), a photocationic polymerization initiator (F), a filler (G), and a diluent (H). 2. The epoxy compound (C) having two or more alicyclic epoxy groups has a 3,4-epoxycyclohexyl group or a 3,4-epoxycyclohexylmethyl group. The resin composition for an insulating layer according to the above. 3. The epoxy compound (D) having a (meth) acryl group and an epoxy group in the molecule is an acrylate or methacrylate having a 3,4-epoxycyclohexylmethyl group. Or the resin composition for an insulating layer according to 2. 4. The polyfunctional epoxy compound (B) has a structure represented by the following chemical formula 1.
The resin composition for an insulating layer according to any one of the above. Embedded image 5. The ultraviolet-curable resin (A), the polyfunctional epoxy compound (B), and the epoxy compound (C)
And the photo-radical polymerization initiator (E) is 0.1 to 2 parts by weight based on 100 parts by weight of the total amount of the epoxy compound (D).
5. The insulating layer according to claim 1, wherein the photocationic polymerization initiator (F) is included in an amount of 0.1 to 20.0 parts by weight. 6. Resin composition.