JP2001135939A - Multilayer printed wiring board and insulating resin composition used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily and inexpensively obtain a reliable multilayer printed wiring board which has a high heat resistance and a good adhesion to copper wiring or the like, can have a resin insulating layer having a high plating peel strength, and use an insulating resin composition capable of maintaining a stable material characteristic for a long period of time. SOLUTION: An insulating resin composition for a multilayer printed wiring board contains a multifunctional epoxy compound and a carboxyl compound, and an alicyclic skeleton structure is included in either of the multifunctional epoxy and carboxyl compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer printed wiring board and an insulating resin composition for a resin insulating layer used therein.

[0002]

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

Conventionally, a typical multilayer printed wiring board is, for example, a multilayer printed wiring board in which an internal circuit is connected and made conductive.

However, in such a multilayer printed wiring board, since a plurality of internal circuits are connected and connected through through holes, the wiring circuit becomes too complicated, and high density or high speed operation is required. It was difficult to realize.

As a multilayer printed wiring board capable of overcoming such problems, a multilayer printed wiring board in which conductive circuits and organic insulating films are alternately built up has recently been developed. This multilayer printed wiring board is suitable for ultra-high density and high speed, but has a drawback that it is difficult to form an electroless plating film on an organic insulating film with high reliability.

For this reason, in such a multilayer printed wiring board, a conductor circuit is formed by a PV such as evaporation or sputtering.
Although the method is formed by the combined method of the D method or the PVD method with the electroless plating and the electrolytic plating, such a method of forming a conductor circuit by the PVD method is inferior in productivity and high in cost.

Recently, as a method of forming an electroless plating film on such an organic insulating film with high reliability, a component soluble in an oxidizing agent or the like is mixed in a resin insulating layer and dissolved and removed. A method of roughening a resin surface in contact with an electrolytic plating film has been proposed. For example, Japanese Patent Application Laid-Open No. Sho 64-4709
As described in No. 5, using a heat-resistant resin insulating layer as a matrix, a resin such as an epoxy resin soluble in an oxidizing agent, a bismaleimide triazine resin, a polyester resin, and a resin insoluble in an oxidizing agent in the resin layer. There has been proposed a method in which the surface of a resin insulating layer is roughened with an oxidizing agent to enhance the anchor effect of forming an electroless plating film by mixing an inorganic filler. Further, as disclosed in Japanese Patent Application Laid-Open No. 61-276875, a method of improving the adhesiveness to an electroless plating film by incorporating a diene rubber component or the like into the heat-resistant insulating resin molecule has been proposed.

However, in these methods, since the heat resistance of the resin modifier itself such as resin particles or rubber components dissolved in the heat-resistant resin insulating layer with an oxidizing agent or the like is inferior, the resultant resin-insulating layer is formed. There has been a problem of lowering the heat resistance of the resin insulating layer.

In general, an epoxy-based material is a thermosetting resin, and the roughening treatment in the plating process progresses more slowly as the material having excellent thermophysical properties is obtained from the material after thermosetting. First, a high plating peel strength cannot be obtained, which causes a problem in the reliability of the fine wire conductor circuit. In order to sufficiently roughen such a hard-to-roughen system and obtain plating peel strength, a long roughening treatment time is required, or a very dangerous and environmental burden such as chromium mixed acid. Requires a processing solution having a large influence, which is a burden on both the cost and the environment.

Further, the epoxy material is a thermosetting resin, and is generally a hardening resin of at least two components comprising a polyfunctional epoxy compound and various amine compounds, acid anhydrides, carboxylic acids and the like. Since the thermosetting resin forms a resin by the reaction, the curing reaction after mixing the two components causes a problem of the pot life of the coating solution. That is,
After the two components are mixed, the curing reaction proceeds, and generally the coating of the insulating layer cannot be performed within several hours as the viscosity increases. Various roughening solutions have been developed to solve such material problems and increase the plating peel strength, and technology to block various reactive functional groups to extend the pot life. Is being developed. However, at present, there has been a problem that there is no material that can simultaneously solve the plating peel strength, the pot life, and the characteristics required for the interlayer insulating material, such as heat resistance.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin insulating layer having high heat resistance, good adhesion to copper wiring and the like, high plating peel strength, and stable for a long time. An object of the present invention is to provide an insulating resin composition capable of maintaining characteristics.

Another object of the present invention is to provide high heat resistance, good adhesion to copper wiring and the like, and high plating peel strength.
It is to provide a highly reliable multilayer printed wiring board easily and at low cost.

[0013]

SUMMARY OF THE INVENTION The present invention firstly comprises a polyfunctional epoxy compound and a carboxyl compound,
Provided is an insulating resin composition for a multilayer printed wiring board, characterized in that either the polyfunctional epoxy compound or the carboxyl compound contains an alicyclic skeleton structure.

The present invention secondly provides a print comprising a substrate and a laminate of a resin insulating layer and a wiring layer obtained by applying the insulating resin composition for a multilayer printed wiring board described above. Provide a wiring board.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The insulating resin composition for a multilayer printed wiring board according to the present invention contains a polyfunctional epoxy compound and a carboxyl compound, and an alicyclic compound is added to either the polyfunctional epoxy compound or the carboxyl compound. It is characterized by including a formula skeleton structure.

Further, the multilayer printed wiring board of the present invention is a multilayer printed wiring board in which interlayer insulation is performed by a resin insulating layer formed of the above-described insulating resin composition,
It has a laminate of a resin insulating layer and a wiring layer formed using such a resin composition.

In the insulating resin composition of the present invention, a resin insulating layer having good heat resistance and plating peel strength can be formed by introducing an alicyclic skeleton structure into the epoxy cured product. In addition, the insulating resin composition can maintain stable material properties during the step of forming the resin insulating layer.

Examples of the method of introducing an alicyclic skeleton structure into the epoxy cured product include a method of adding a compound having a cyclohexane structure to an epoxy compound, and a method of including a compound having a cyclohexane structure as a curing agent. .

The preferred polyfunctional epoxy compound used in the present invention includes a polyfunctional epoxy compound having an aromatic ring having three or more epoxy groups in one molecule and a polyfunctional epoxy compound having a cyclohexene oxide skeleton structure. Functional alicyclic epoxy compounds.

The polyfunctional epoxy compound having a structure containing an aromatic ring having three or more epoxy groups in one molecule preferably has 3 to 50, more preferably 3 to 20 epoxy groups. The epoxy equivalent is preferably 500 or less from the viewpoint of fluidity and reactivity.

The polyfunctional alicyclic epoxy compound having a cyclohexene oxide skeleton structure preferably has 2 to 10 epoxy groups. The epoxy equivalent is also 50
0 or less is preferable.

The preferred carboxyl compound used in the present invention has a cyclohexane skeleton structure.

Further preferred carboxyl compounds for use in the present invention are curing agents obtained by reacting carboxylic acid compounds with aliphatic vinyl ether compounds.

The epoxy compound used in the present invention is a polyfunctional epoxy compound, for example, phenol novolak type epoxy resin, cresol novolak type epoxy resin, DPP novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type Epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, epoxy resin such as alicyclic epoxy resin, biphenyl type epoxy resin, diphenyl ether type epoxy resin, biphenyl novolak type epoxy resin,
Hydroquinone type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, cyclopentadienyl type epoxy resin, naphthalene type epoxy resin, isocyanurate type epoxy resin, Tris ( Glycidylphenyl) methane, phenylglycidylether, p-butylphenolglycidylether, triglycidylisocyanurate, diglycidylisocyanurate, allylglycidylether, glycidylmethacrylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, Ali Cyclic diepoxy acetal, bis- (3,4-epoxycyclohexylmethyl) adipate, vinyl cycle Hexenedioxide, epoxy compounds such as alcohol-modified vinylcyclohexene oxide, various derivatives of cyclohexene oxide and hydrogenated compounds of the aromatic epoxies, tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmethaminophenol, Various glycidylamine-type epoxy compounds such as glycidylaniline, diglycidyltoluidine, tetraglycidylmethaxylylenediamine, diglycidyltribromoaniline, and tetraglycidylbisaminomethylcyclohexane; 2,2 ', 4,4'-tetraglidoxybiphenyl And various epoxy compounds such as dimethylbisphenol C glycidyl ether and the like, and these can be used alone or by mixing some components.

An epoxy compound having an aromatic ring-containing structure refers to a compound having an aromatic skeleton in the molecular structure. In particular, a compound having three or more functional epoxy groups in one molecule has a poor physical property at the time of curing. Excellent and more preferred.

Having three or more epoxy groups in one molecule,
Examples of the epoxy compounds having an aromatic skeleton include phenol novolak type epoxy resin, cresol novolak type epoxy resin, DPP novolak type epoxy resin, biphenyl type epoxy resin, cyclopentadienyl type epoxy resin, biphenyl novolak type epoxy resin, tris Hydroxyphenylmethane type epoxy resin,
Tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, naphthalene type epoxy resin, tris (glycidylphenyl) methane, tetraglycidyldiaminodiphenylmethane, triglycidyl paraaminophenol, triglycidyl metaaminophenol, tetraglycidyl metaxylylenediene Examples include various polyfunctional glycidylamine type epoxy compounds such as amines and tetraglycidylbisaminomethylcyclohexane, and 2,2 ′, 4,4′-tetraglycoxybiphenyl.

The polyfunctional alicyclic epoxy compound having a cyclohexene oxide skeleton used in the present invention includes 3,4-epoxycyclohexylmethyl-3,4-
Epoxy cyclohexane carboxylate, alicyclic diepoxy acetal, bis- (3,4-epoxycyclohexylmethyl) adipate, various caprolactone-modified polyfunctional cyclohexene oxide type epoxy compounds, alicyclic diepoxy acetal,
Alicyclic diepoxy adipate, vinylcyclohexene dioxide, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate And alicyclic epoxy compounds represented by the following chemical formulas (1) and (2). These may be used alone or in combination.

[0028]

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[0029]

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The curing agents used in the present invention include amine curing agents, phenolic resin curing agents, cresol resin curing agents, imidazole curing agents, various amine curing agents, carboxylic acids, carboxylic anhydrides, And various carboxyl compounds. In particular, a carboxylic acid-based curing agent is preferable because of its high reactivity and high heat resistance after curing. Also, particularly when carboxylic acids, carboxylic acid anhydrides, when cured using a skeleton structure of various carboxyl compounds having a cyclohexane skeleton, in the surface roughening step at the time of copper plating, more resin surface, A good roughened surface can be obtained.

As the curing agent comprising a carboxyl compound having a cyclohexane skeleton structure used in the present invention,
Carboxylic acids having a cyclohexane skeleton structure, carboxylic anhydrides, carboxyl compounds and the like, for example,
Hydrogenation of tetrahydrophthalic acid derivatives, hydrogenated derivatives of aromatic polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and unsaturated alicyclic polycarboxylic acids Product derivatives and the like. By using these curing agents having a cyclohexane skeleton structure, high plating peel strength can be obtained. Further, a curing agent containing a cyclohexane skeleton structure may be used alone,
It can also be used in combination with other common epoxy curing agents.

In general, a curing agent is mixed with a polyfunctional epoxy resin for thermal curing. However, since the curing reaction of the epoxy-based curing agent proceeds even at room temperature immediately after mixing, the characteristics change with time. I will. Therefore, in a preferred embodiment of the present invention, as shown in the following reaction formula (3), a carboxyl group of a hardly-soluble and highly reactive curing agent is further reacted with an aliphatic vinyl ether to form a readily soluble and chemically reactive agent. By completely blocking the reactivity of the carboxylic acid with a chemically stable hemiacetal ester, a chemically stable insulating resin composition in which the increase in viscosity after mixing was minimized was completed.

[0033]

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The aliphatic vinyl ether compound used in the present invention includes methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, secondary butyl vinyl ether, tertiary butyl vinyl ether, and 2-ethylhexyl butyl vinyl ether. , Cyclohexyl vinyl ether, 2,3-dihydrofuran, 3,4-dihydro-2
And aliphatic vinyl ether compounds such as H-pyran.

Further, in the insulating resin composition of the present invention,
Various fillers can be added as needed. For example, an organic filler such as a fluororesin, a polyimide resin, a benzoguanamine resin, an epoxy resin, or
Silica, talc, alumina, clay, calcium carbonate,
An inorganic filler such as titanium oxide and barium sulfate can be blended.

Further, the insulating resin composition of the present invention may contain, if necessary, an epoxy group curing accelerator, a thermal polymerization inhibitor, a plasticizer, a leveling agent, an antifoaming agent, an ultraviolet absorber, and a flame retardant. It is possible to add an additive such as an agent or a coloring pigment.

Hereinafter, a multilayer printed wiring board using the resin composition of the present invention and a method for producing the same will be specifically described with reference to the drawings.

FIG. 1 is a schematic diagram showing an example of the configuration of a multilayer printed wiring board according to the present invention.

The multilayer printed wiring board 10 includes an insulating substrate 1 and a first conductive pattern 2a formed on the insulating substrate 1.
A resin insulating layer 4a having a via hole 6 provided on the first conductive pattern 2a; and a second insulating layer 4a formed on the first conductive pattern 2a and connected to the first conductive layer 2a via the via hole 6. It is composed of a conductor pattern 7a.

The multilayer printed wiring board 10 can be formed as follows.

FIGS. 2 to 6 are views for explaining the steps of manufacturing the multilayer printed wiring board of the present invention.

First, as shown in FIG. 2, a first conductor layer 2 was formed on an insulating substrate 1 by, for example, laminating a copper foil. Thereafter, as shown, the obtained first conductor layer 2
A photoresist was applied thereon, exposed in a predetermined pattern, and developed to form a resist pattern 3.

Further, as shown in FIG.
And then the resist pattern 3 was peeled off to obtain a first conductor pattern 2a.

As the substrate used in the present invention, for example, a plastic substrate, a ceramic substrate, a metal substrate, a film substrate and the like can be used, and 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 substrate, and the like.

When a conductive substrate is used, an insulating layer can be formed on both surfaces before use.

As shown in FIG. 4, the resin insulating layer coating solution according to the present invention is applied on the substrate on which the conductor pattern 2a is formed, dried, and heat-cured at 175 ° C. for 2 hours using a drying oven. Was performed to form the resin insulating layer 4.

As a method of forming the coating solution of the insulating resin composition, for example, a roller coating method, a dip coating method,
It is possible to apply a method of applying by various means such as a spray coating method, a spinner coating method, a curtain coating method, a slot coating method, a screen printing method, or a method of applying a resin film obtained by processing a coating liquid into a film. it can.

The preferable thickness of the resin insulating layer 4 is usually about 20 to 100 μm, but it can be larger when particularly high insulating property is required.

Next, as shown in FIG. 5, via hole forming holes 5 were formed in the resin insulating layer 4 by laser processing to obtain a resin insulating layer 4a.

The substrate on which the resin insulating layer 4a was formed was immersed in a swelling solution (manufactured by Shipley) at 50 ° C. for 15 minutes and in a mixed solution of potassium permanganate / sodium hydroxide at 70 ° C. for 15 minutes to obtain a resin insulating layer. The surface of 4a and the side wall of the via hole forming hole 5 are roughened, and then a neutralizing solution (manufactured by Shipley)
And further washed with water to obtain a roughened surface.

Next, as shown in FIG. 6, the via hole 6 and the second conductor layer 7 were formed by performing electroless plating and electrolytic plating on the roughened resin insulating layer 4a.

Examples of the method of electroless plating include, for example, electroless copper plating, electroless nickel plating, electroless gold plating, electroless silver plating, electroless tin plating, and electrolytic plating. , Gold plating, silver plating, tin plating and the like. Preferred are electroless copper plating and electrolytic copper plating.

Thereafter, a photoresist was applied on the second conductor layer 7, and a second conductor pattern 7a was formed by a photo-patterning process to obtain a multilayer printed wiring board 10 shown in FIG.

As a method of forming the second conductor pattern 7a, an additive method, a semi-additive method, and the like can be applied in addition to the subtractive method.

By forming an insulating layer using the resin composition of the present invention, a multilayer printed wiring board having an electroless plated film formed with high reliability can be easily and inexpensively provided.

[0056]

The present invention will be described below in detail with reference to examples.

Example 1 First, the following compositions were mixed and stirred to prepare a resin insulating layer coating solution.

Photosensitive resin insulating layer coating solution 1 Trimellitic anhydride 100 parts by weight Polyfunctional aromatic epoxy resin E157S70 (manufactured by Yuka Shell Co.) represented by the following chemical formula (4) 180 parts by weight In the following chemical formula (5) Represented Polyfunctional alicyclic epoxy resin having a cyclohexene oxide skeleton structure GT403 (manufactured by Daicel Chemical) 200 parts by weight Spherical amorphous silica average particle size 3 μm (FB-3S, manufactured by Denki Kagaku Kogyo) 120 parts by weight Leveling agent ( 3.6 parts by weight of cyclohexanone solvent remaining The viscosity of the obtained coating solution was measured.

Next, the coating solution of the photosensitive resin insulating layer was applied to a degreased and washed copper-clad glass epoxy substrate to a thickness of about 50 μm using a slot coater and dried to obtain a resin insulating layer.

Thereafter, using a drying oven at 175 ° C.
For 90 minutes to form a resin insulating layer.
The substrate on which the resin insulating layer was formed was provided with a copper plating layer having a thickness of about 18 μm in a normal copper plating step of a printed wiring board.

The adhesion strength of the obtained copper plating layer was determined according to JIS-
It was examined by a 90-degree peel test of a 1 cm wide pattern based on C6481.

Thereafter, a circuit pattern having a width of about 50 μm was formed by a usual photolithographic etching method to obtain a printed wiring board. The pattern shape of the obtained printed wiring board was observed.

Further, the prepared coating solution was stored, and after 3 days,
And measuring the viscosity of the coating solution after 20 days,
Coating was performed in the same manner using these to form a resin insulating layer, and a printed wiring board was obtained.

Table 1 below shows the results obtained for the viscosity of the coating solution, the peel strength by a 90-degree peel test, and the pattern shape.

Example 2 First, the following compositions were mixed and stirred to prepare a resin insulating layer coating solution.

Coating Solution 2 for Photosensitive Resin Insulating Layer Varnish obtained by reacting n-propyl vinyl ether with polycarboxylic acid having an acid value of 496 (mg KOH / g) obtained by reacting pentaerythritol with trimellitic anhydride 100 parts by weight of a cured resin having an equivalent amount of 302 (g / mol) 100 parts by weight of polyfunctional aromatic epoxy resin E157S70 (manufactured by Yuka Shell Co., Ltd.) represented by the following chemical formula (4) 70 parts by weight represented by the following chemical formula (5) Polyfunctional alicyclic epoxy resin having a cyclohexene oxide skeleton structure GT401 (manufactured by Daicel Chemical Industries, Ltd.) 75 parts by weight Spherical amorphous silica average particle diameter 3 μm (FB-3S, manufactured by Denki Kagaku Kogyo) 30 parts by weight Leveling agent (BIC Chemie) 0.8 weight part cyclohexanone solvent balance The viscosity of the obtained coating liquid was the same as in Example 1. Constant, and also, the copper plating layer in the same manner, to create a printed wiring board, the peel strength, the pattern shape measuring was observed. The results are shown in Table 1 below.

Example 3 First, the following compositions were mixed and stirred to prepare a resin insulating layer coating solution.

Photosensitive Resin Insulating Layer Coating Solution 3 Varnish obtained by reacting n-propyl vinyl ether with polycarboxylic acid having an acid value of 496 (mg KOH / g) obtained by reacting pentaerythritol with trimellitic anhydride. 100 parts by weight of cured resin having an equivalent amount of 302 (g / mol) 100 parts by weight of pentaerythritol and hexahydrophthalic acid were reacted with polycarboxylic acid having an acid value of 302 (mg KOH / g) to react with n-propyl vinyl ether. 87 parts by weight of the obtained cured resin Polyfunctional aromatic epoxy resin E157S70 (manufactured by Yuka Shell Co., Ltd.) represented by the following chemical formula (4) 240 parts by weight Spherical amorphous silica average particle size 3 μm (FB-3S, Denki Kagaku Kogyo Co., Ltd.) 60 parts by weight Leveling agent (manufactured by BYK-Chemie) 1.8 parts by weight Cyclohexanone solvent balance Is the viscosity was measured in the same manner for the coating solution as in Example 1, also, the copper plating layer in the same manner, to create a printed wiring board, the peel strength, the pattern shape measuring was observed. The results are shown in Table 1 below.

Example 4 First, the following compositions were mixed and stirred to prepare a resin insulating layer coating solution.

Photosensitive resin insulating layer coating solution 4 Varnish obtained by reacting n-propyl vinyl ether with polycarboxylic acid having an acid value of 496 (mg KOH / g) obtained by reacting pentaerythritol with trimellitic anhydride. Cured resin having an equivalent weight of 302 (g / mol) 100 parts by weight Reaction of pentanediol and hexahydrophthalic acid to obtain a polycarboxylic acid having an acid value of 275 (mg KOH / g), which is reacted with n-propyl vinyl ether. Cured resin having a varnish equivalent of 348 (g / mol) 87 parts by weight Polyfunctional aromatic epoxy resin E157S70 (manufactured by Yuka Shell Co.) represented by the following chemical formula (4) 240 parts by weight Spherical amorphous silica average particle diameter 3 μm (FB-3S, manufactured by Denki Kagaku Kogyo) 60 parts by weight Leveling agent (manufactured by Big Chemie) 1.8 parts by weight Cyclohexanone solvent Remainder The viscosity of the obtained coating solution was measured in the same manner as in Example 1, and a copper plating layer and a printed wiring board were prepared in the same manner, and the peel strength and pattern shape were measured and observed. The results are shown in Table 1 below.

Example 5 The following compositions were mixed and stirred to prepare a resin insulating layer coating solution.

Photosensitive Resin Insulating Layer Coating Solution 5 Varnish obtained by reacting n-propyl vinyl ether with polycarboxylic acid having an acid value of 496 (mg KOH / g) obtained by reacting pentaerythritol with trimellitic anhydride. Cured resin having an equivalent weight of 302 (g / mol) 100 parts by weight Polyfunctional aromatic epoxy resin E157S70 (manufactured by Yuka Shell Co., Ltd.) represented by the following chemical formula (4) 70 parts by weight Represented by the following chemical formula (6) 70 parts by weight of a polyfunctional alicyclic epoxy resin having a cyclohexene oxide skeleton structure (manufactured by Daicel Chemical Industries, Ltd.) 70 parts by weight Average particle diameter of spherical amorphous silica 3 μm (FB-3S, manufactured by Denki Kagaku Kogyo Co., Ltd.) 30 parts by weight Leveling agent (BIC Chemie) 0.8 parts by weight Cyclohexanone solvent Remainder The obtained coating solution is the same as in Example 1. The viscosity was measured, also the copper plating layer in the same manner, to create a printed wiring board, the peel strength, the pattern shape measuring was observed. The results are shown in Table 1 below.

Example 6 The following compositions were mixed and stirred to prepare a resin insulating layer coating solution.

Coating solution 6 for photosensitive resin insulating layer Varnish obtained by reacting i-propyl vinyl ether with polycarboxylic acid having an acid value of 496 (mg KOH / g) obtained by reacting pentaerythritol with trimellitic anhydride. 100 parts by weight of a cured resin having an equivalent amount of 305 (g / mol) 100 parts by weight Polyfunctional aromatic epoxy resin E157S70 (manufactured by Yuka Shell) represented by the following chemical formula (4) 70 parts by weight represented by the following chemical formula (6) Polyfunctional alicyclic epoxy resin having a cyclohexene oxide skeleton structure Celloxide 2081 (manufactured by Daicel Chemical Industries, Ltd.) 70 parts by weight Spherical amorphous silica average particle diameter 3 μm (FB-3S, manufactured by Denki Kagaku Kogyo) 30 parts by weight Leveling agent (BIC Chemie) 0.8 parts by weight cyclohexanone solvent remainder The same as in Example 1 for the obtained coating liquid The copper plating layer and the printed wiring board were prepared in the same manner, and the peel strength and the pattern shape were measured and observed. The results are shown in Table 1 below.

Example 7 The following compositions were mixed and stirred to prepare a resin insulating layer coating solution.

Coating solution 7 for photosensitive resin insulating layer Varnish obtained by reacting n-propyl vinyl ether with polycarboxylic acid having an acid value of 496 (mg KOH / g) obtained by reacting pentaerythritol with trimellitic anhydride. Cured resin having an equivalent weight of 302 (g / mol) 100 parts by weight Polyfunctional aromatic epoxy resin E157S70 (manufactured by Yuka Shell Co., Ltd.) 60 parts by weight Polyfunctional having a cyclohexene oxide skeleton structure represented by the following chemical formula (7) Alicyclic epoxy resin Epode GT302 (manufactured by Daicel Chemical Co., Ltd.) 90 parts by weight Spherical amorphous silica average particle diameter 3 μm (FB-3S, manufactured by Denki Kagaku Kogyo) 30 parts by weight Leveling agent (manufactured by Big Chemie) 0.8 part by weight Cyclohexanone Solvent Remainder The viscosity of the obtained coating solution was measured in the same manner as in Example 1, and the same Copper plating layer is to create a printed wiring board, the peel strength, the pattern shape measuring was observed. The results are shown in Table 1 below.

Comparative Example 1 The following compositions were mixed and stirred to prepare a resin insulating layer coating solution.

Coating solution for photosensitive resin insulating layer 8 Trimellitic anhydride 100 parts by weight Polyfunctional aromatic epoxy resin E157S70 (manufactured by Yuka Shell Co., Ltd.) 400 parts by weight Spherical amorphous silica Average particle size 3 μm (FB-3S, electrochemical 120 parts by weight Leveling agent (manufactured by BYK-Chemie) 3.6 parts by weight Cyclohexanone solvent balance The viscosity of the obtained coating solution was measured in the same manner as in Example 1, and the copper plating layer and the printed wiring were similarly formed. A plate was prepared, and its peel strength and pattern shape were measured and observed. The results are shown in Table 1 below.

Comparative Example 2 Photosensitive Resin Insulating Layer Coating Solution 9 n-propyl vinyl ether was reacted with polycarboxylic acid having an acid value of 496 (mg KOH / g) obtained by reacting pentaerythritol with trimellitic anhydride. Cured resin having an equivalent varnish of 302 (g / mol) 100 parts by weight Polyfunctional aromatic epoxy resin E157S70 (manufactured by Yuka Shell Co., Ltd.) 150 parts by weight Spherical amorphous silica average particle diameter 3 μm (FB-3S, electrochemical (Manufactured by Kogyo Co., Ltd.) 30 parts by weight Leveling agent (manufactured by BYK-Chemie) 0.8 parts by weight Cyclohexanone solvent Remainder The viscosity of the obtained coating solution was measured in the same manner as in Example 1, and the copper plating layer and the printed wiring were similarly formed. A plate was prepared, and its peel strength and pattern shape were measured and observed. The results are shown in Table 1 below.

[0080]

[Table 1]

As shown in Table 1, the multilayer printed wiring board using the insulating resin compositions according to Examples 1 to 7 was
It was found that peel strength, viscosity and pattern shape were all good. In contrast, the multilayer printed wiring boards using the insulating resin compositions according to Comparative Examples 1 and 2 were not practical because the peel strength was low and the copper plating was easily peeled off.

[0082]

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[0083]

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[0084]

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[0085]

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[0086]

According to the present invention, it is possible to form a resin insulating layer having high heat resistance, good adhesion to copper wiring and the like, high plating peel strength, and maintain stable material properties for a long time. The resulting insulating resin composition is obtained.

Further, according to the present invention, by using the above-mentioned insulating resin composition, a highly reliable multilayer having high heat resistance, good adhesion to copper wiring and the like, high plating peel strength, and the like. A printed wiring board can be easily and inexpensively obtained.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view illustrating an example of a multilayer printed wiring board according to the present invention.

FIG. 2 is a diagram for explaining a manufacturing process of an example of a multilayer printed wiring board according to the present invention.

FIG. 3 is a diagram for explaining a manufacturing process of an example of the multilayer printed wiring board according to the present invention.

FIG. 4 is a diagram for explaining a manufacturing process of an example of the multilayer printed wiring board according to the present invention.

FIG. 5 is a diagram for explaining a manufacturing process of an example of the multilayer printed wiring board according to the present invention.

FIG. 6 is a diagram for explaining a manufacturing process of an example of the multilayer printed wiring board according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Insulating board 2 ... 1st conductor layer 2a ... 1st conductor pattern 3 ... Resist pattern 4, 4a ... Resin insulation layer 5 ... Via hole formation hole 6 ... Via hole 7 ... 2nd conductor layer 7a ... 2nd conductor pattern 10 ... Multilayer printed wiring boards

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kenji Kawamoto 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. (72) Inventor Hiroshi Sato 630 Totsukacho, Totsuka-ku, Yokohama-shi, Kanagawa-ken (72) Inventor Atsushi Sato 447-1 Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa F-term (reference) 5E346 AA02 AA43 CC08 CC09 CC33 CC37 CC38 CC39 DD02 DD03 DD12 DD23 DD32 EE43 FF15 GG15

Claims (6)

[Claims] An insulation for a multilayer printed wiring board, comprising a polyfunctional epoxy compound and a carboxyl compound, wherein either the polyfunctional epoxy compound or the carboxyl compound contains an alicyclic skeleton structure. Resin composition. 2. The polyfunctional epoxy compound includes a polyfunctional epoxy compound having an aromatic ring having at least three epoxy groups in one molecule, and a polyfunctional alicyclic ring having a cyclohexene oxide skeleton structure. The insulating resin composition for a multilayer printed wiring board according to claim 1, comprising a compound of the formula epoxy. 3. The insulating resin composition for a multilayer printed wiring board according to claim 1, wherein the carboxyl compound has a cyclohexane skeleton structure. 4. The multilayer printed wiring according to claim 1, wherein the carboxyl compound contains a curing agent obtained by reacting a carboxylic acid compound with an aliphatic vinyl ether compound. Insulating resin composition for boards. 5. The aliphatic vinyl ether compound includes methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether and n
-Butyl vinyl ether, isobutyl vinyl ether,
Secondary butyl vinyl ether, tertiary butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, and at least one selected from the group consisting of 2,3-dihydrofuran and 3,4-dihydro-2H-pyran. The insulating resin composition for a multilayer printed wiring board according to claim 4, wherein 6. A substrate, and a laminate of a resin insulating layer and a wiring layer obtained by applying the insulating resin composition for a multilayer printed wiring board according to any one of claims 1 to 5. A multilayer printed wiring board characterized by the following.