JPH0529761A - Wiring board adhesive and manufacture of printed wiring board using this adhesive and printed wiring board - Google Patents

Abstract

PURPOSE:To develop an adhesive which is capable of forming its clear anchor properties and having coating properties or proper viscosity and establish a printed wiring board manufacturing technology which uses the adhesive. CONSTITUTION:In the case of an adhesive wherein epoxy resin fine particles which are already thermoset and soluble to acid or a hardening agent is dispersed in uncured epoxy resin or acrylic resin matrixes having solution resistant properties against acid or an oxidizing agent when thermosetting treatment is carried out, this invention relates to the application of the epoxy resin cured with an amine hardening agent as the heat-resistant resin fine particles as specified above and the printed wiring board which uses the adhesive.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive for wiring boards which is excellent in both electroless plating and coating properties, a method for producing a printed wiring board using this adhesive, and a printed wiring board. The present invention relates to an adhesive suitable for electroless plating, which is excellent in heat resistance, electrical characteristics, and adhesion between a substrate and an electroless plating film, a printed wiring board manufacturing method using the adhesive, and a printed wiring board.

[0002]

2. Description of the Related Art In recent years, electronic devices have been reduced in size and increased in speed with the progress of the electronic industry. For this reason, printed wiring boards and wiring boards on which LSIs are mounted have high density and high reliability due to fine patterns. Sex is required.

Conventionally, as a method for forming a conductor circuit on a printed wiring board, an etched foil method for forming a conductor circuit by laminating a copper foil on a substrate and then photoetching has been widely used. According to this method, it is possible to form a conductor circuit having excellent adhesion to the substrate, but there is a major drawback that it is difficult to obtain a highly accurate fine pattern by etching because the copper foil is thick, and further manufacturing There are various problems that the process is complicated and the efficiency is not good.

Therefore, recently, as a method of forming a conductor on a wiring board, an adhesive containing a diene-based synthetic rubber is applied to the surface of a substrate to form an adhesive layer, and the surface of the adhesive layer is roughened. The additive method of applying electroless plating to form a conductor is adopted. However, since the adhesive that is commonly used in this method contains synthetic rubber, it has a low heat resistance, such as a large decrease in adhesion strength at high temperatures, or a blistering electroless plating film during soldering. , Has the drawback that the electrical characteristics such as surface resistance are not sufficient,
The range of use is quite limited.

On the other hand, the present inventors have solved the above-mentioned drawbacks of the adhesive for performing electroless plating, and have excellent heat resistance, electrical characteristics and adhesion to the electroless plated film. Japanese Patent Laid-Open No. 61-276875 proposes an adhesive for electroless plating which can be relatively easily carried out and a method for producing a wiring board using this adhesive. That is, the disclosed technique is that an uncured heat-resistant resin having a property that a pre-cured heat-resistant resin powder that is soluble in an oxidant is hardly soluble in an oxidant when it is hardened. An adhesive characterized by being dispersed in a liquid, and after applying the adhesive to a substrate, it is dried and cured to form an adhesive layer, and the adhesive is dispersed on the surface portion of the adhesive layer. In this method, at least a part of fine powder is dissolved and removed to roughen the surface of the adhesive layer, and then electroless plating is performed.

According to this known technique, in the above-mentioned adhesive, the heat-resistant resin fine powder which has been previously cured is dispersed in the heat-resistant resin liquid, and when this adhesive is applied to the substrate and dried and cured, the matrix is formed. The heat-resistant resin fine powder is uniformly dispersed in the heat-resistant resin forming the adhesive layer. Since the heat-resistant resin fine powder and the matrix heat-resistant resin have different solubilities with respect to the oxidizing agent, the fine powder dispersed in the surface portion of the adhesive layer by treating the adhesive layer with the oxidizing agent. Is mainly dissolved and removed, an effective anchor dent is formed, the surface of the adhesive layer can be uniformly roughened, and high adhesion strength and high reliability between the substrate and the electroless plated film can be obtained.

[0007]

By the way, this heat-resistant resin fine powder has excellent heat resistance and electrical insulation properties, is stable to ordinary chemicals, and has a heat resistance when pre-cured. Since it is required to be sparingly soluble in a resin or a solvent that dissolves this resin, and further, it is necessary to have a characteristic that it can be dissolved by an oxidizing agent such as chromic acid, the number of epoxy resins, etc. Seed resins were mentioned.

However, it is the actual situation that a good heat-resistant resin fine powder having all of the above characteristics cannot be obtained depending on the means for curing the resin. For example, depending on the selection of the curing agent, the solubility of the heat-resistant resin fine powder in the oxidizing agent becomes insufficient, a clear anchor is not formed, and as a result, the peel strength is reduced and the conductor pad is peeled off. There was a problem with reliability.

An object of the present invention is to overcome the problems of the above-mentioned prior art. In particular, the inventors have found a component of heat-resistant resin fine powder that can easily form a clear anchor, and have found out the electroless plating property of the adhesive. An object of the present invention is to provide an adhesive having excellent coating properties without impairing the properties, a method for manufacturing a printed wiring board using the same, and a printed wiring board.

[0010]

Means for Solving the Problems As a result of intensive studies for overcoming the above-mentioned problems, the inventors have found that the use of an amine-based curing agent as a curing agent for an epoxy resin makes it possible to obtain a desired heat-resistant resin composition. The inventors have found that a powder can be obtained, and have arrived at the present invention.

That is, the adhesive of the present invention is, firstly, a cured heat-resistant resin fine powder which is soluble in an acid or an oxidant, and when cured, is treated with an acid or an oxide. In an adhesive agent which is dispersed in an uncured heat-resistant resin matrix having a property of being poorly soluble to, an epoxy resin cured with an amine curing agent is used as the heat-resistant resin fine powder, and the heat resistance is An adhesive for wiring boards, characterized in that an epoxy resin cured with an imidazole-based curing agent is used as a resin matrix. Note that this matrix may be halogenated for incombustibility treatment.

Here, the heat resistant resin matrix in which the resin fine powder is dispersed is at least one selected from polyfunctional epoxy resins and difunctional epoxy resins.
Or a mixture of at least one selected from a polyfunctional epoxy resin and a bifunctional epoxy resin and an imidazole-based curing agent, and the matrix has a solid content of 20 to 100 wt% of a polyfunctional epoxy resin. -Resistant resin consisting of basic epoxy resin and 0 to 80 wt% difunctional epoxy resin, and 2 to 10 wt% based on the total solid content of the matrix
It is desirable to use the imidazole-based curing agent.

Second, the hardened heat-resistant resin fine powder which is soluble in acid or oxidant has a characteristic that it becomes hardly soluble in acid or oxide when it is hardened. In the adhesive which is dispersed in an uncured heat-resistant resin matrix, an epoxy resin cured with an amine curing agent is used as the heat-resistant resin fine powder, and an epoxy resin and an acrylic group are used as the heat-resistant resin matrix. It is an adhesive for wiring boards, characterized by using at least one selected from the above-mentioned resins and acrylic resins. Note that this matrix may be halogenated for incombustibility treatment.

The heat-resistant resin matrix in which the resin fine powder is dispersed is a polyfunctional epoxy resin,
Resin having acrylic group, at least one selected from acrylic resin, or mixed resin of at least one selected from the above-mentioned resins and at least one resin selected from bifunctional epoxy resin and acrylic resin The heat-resistant resin in the matrix is, in terms of solid content, at least one selected from a polyfunctional epoxy resin, an acrylic group-containing resin, and an acrylic resin having a polyfunctional content of 20 to 100 wt%, and 0 to 80 wt%. It is preferable that it is composed of at least one kind of bifunctional epoxy resin and acrylic resin.

The above-mentioned adhesive has a viscosity of the above adhesive measured by a rotational viscometer of 5.1 ± 2.0 Pa · s, more preferably 5.1 ± 0.7 Pa · s when the rotation speed is 6 rpm.
s at a rotation speed of 60 rpm, 2.4 ± 1.0 Pa ・ s, more preferably 2.4 ± 0.3 Pa ・ s, and the ratio of the viscosity at a rotation speed of 6 rpm to the viscosity at a rotation speed of 60 rpm is 2.1 ± 1.0, more preferably 2.1. ± 0.4, and the solid content concentration of heat-resistant resin fine powder, uncured heat-resistant resin and curing agent in the matrix is 55 to 85 wt%, and the content of heat-resistant resin fine powder Is 10 to 100 parts by weight based on 100 parts by weight of the solid content of the mixture of the heat-resistant resin matrix and the curing agent or photoinitiator, or the matrix containing the curing agent or photoinitiator.

According to the method for producing a printed wiring board of the present invention using the above-mentioned adhesive, the above-mentioned adhesive is applied onto the substrate by a roll coater, curtain coater, screen printing or spray coater, and then dried and cured to obtain the adhesive. A layer is formed, and at least a part of the thermosetting fine powder dispersed in the surface portion of the adhesive layer is dissolved and removed to roughen the surface of the adhesive layer, and then electroless plating is performed. This is a method using an additive process.

The printed wiring board of the present invention obtained by the above manufacturing method has an adhesive layer on at least one substrate surface, and a conductor circuit is formed on the adhesive layer. The cured heat-resistant resin fine powder that is soluble in the agent is placed in an uncured heat-resistant resin matrix that has the property of being hardly soluble in acids or oxides when cured. As the dispersed adhesive, the heat-resistant resin fine powder is an epoxy resin cured with an amine curing agent, the heat-resistant resin matrix is an epoxy resin cured with an imidazole curing agent, or A printed wiring board is characterized by using an epoxy resin, a resin having an acrylic group, and an acrylic resin.

[0018]

As a result of various researches on the curing agent for the resin for heat-resistant resin fine powder, the inventors have found that epoxy resin cured with an amine-based curing agent is suitable as the heat-resistant resin fine powder. Of. The reason why the epoxy resin cured with this amine-based curing agent is suitable is shown below.

That is, it has been found that the segment structure formed by the curing reaction between the epoxy group of the epoxy resin and the active hydrogen of the amino group of the amine-based curing agent is particularly soluble in an acid or an oxidizing agent. This is because, by using the amine-based curing agent, it is possible to obtain a resin fine powder that is easily soluble in the oxidizing agent and has high heat resistance. As such a segment, for example, the following structure can be considered.

Therefore, in the present invention, an effective anchor dent can be easily formed by using the epoxy resin cured with the above-mentioned amine-based curing agent as the heat-resistant resin fine powder, and therefore the coated state can be improved. It becomes possible to obtain an adhesive satisfying all the conditions of film thickness and peel strength.

The amount of the heat-resistant resin fine powder compounded is 10 to 10 parts by weight based on 100 parts by weight of the total solid content of the resin matrix.
A range of 0 parts by weight is preferred. The reason for this is that if the amount of the fine powder is less than 10 parts by weight, the anchor formed by dissolution and removal will not be clearly formed. On the other hand, if the blending amount of the fine powder is more than 100 parts by weight, the adhesive layer becomes porous and the adhesion strength (peel strength) between the adhesive layer and the electroless plating film decreases.

The particle size of the heat-resistant resin fine powder is preferably 10 μm or less, particularly 5 μm.
The following is preferable. The reason is that the average particle size is
If it is larger than 10 μm, the density of the anchor formed by dissolution and removal tends to be small and the anchor tends to be non-uniform, so that the adhesion strength and its reliability are deteriorated. Moreover, since the unevenness of the surface of the adhesive layer becomes severe, it is difficult to obtain a fine pattern of the conductor, and it is not preferable for mounting components and the like.

As such a heat-resistant resin fine powder, for example, agglomerated particles obtained by aggregating heat-resistant resin powder having an average particle size of 2 μm or less to have an average particle size of 2 to 10 μm, average particle size of 2 to 10 μm A particle mixture of the heat-resistant resin powder and the heat-resistant resin powder having an average particle diameter of 2 μm or less, or an average particle diameter of 2
It is preferable to select from pseudo particles formed by adhering at least one of a heat-resistant resin powder having an average particle size of 2 μm or less and an inorganic fine powder on the surface of the heat-resistant resin powder of ˜10 μm.

Here, the matrix heat-resistant resin used in the present invention has excellent heat resistance, electrical insulation, chemical stability and adhesiveness, and becomes hard to be dissolved in an oxidant by curing treatment. Any resin having characteristics can be used, and in particular, the heat-resistant resin matrix in which the resin fine powder is dispersed is at least one selected from polyfunctional epoxy resins, acrylic group-containing resins, and acrylic resins. Resin, or the above,
At least one selected from the above resins and at least one selected from bifunctional epoxy resins and acrylic resins
Desirably it is made of a mixed resin with the seed.

The heat resistant resin in this matrix is
In terms of solid content, at least one selected from an epoxy resin, a resin having an acrylic group, and an acrylic resin having a polyfunctionality of 20 to 100 wt% and a bifunctionality of 0 to 80 wt%,
It is preferable to use a mixed resin with at least one selected from an epoxy resin and an acrylic resin. The reason for this is that when the solid content of the polyfunctional resin is less than 20 wt%,
This is because the hardness of the adhesive decreases and the chemical resistance also decreases.

As a curing agent for this matrix resin, DICY, an amine type curing agent, an acid anhydride, an imidazole type curing agent and the like are preferable. In particular, in the case of epoxy resin, it is 2 to 10 wt% with respect to the total solid content of this matrix.
It is preferable to include the imidazole-based curing agent.
The reason for this is that if it exceeds 10 wt%, it becomes too hard and becomes brittle.
This is because if it is less than 2 wt%, the curing will be insufficient.

The hardened bifunctional epoxy resin fine powder is dispersed in at least one heat-resistant resin matrix selected from uncured polyfunctional epoxy resin and bifunctional epoxy resin. It is desirable that the mixture is stored separately from the imidazole-based curing agent, and both are mixed and used immediately before use.

As the heat-resistant resin for the matrix, a heat-resistant resin containing no solvent can be used as it is, but the heat-resistant resin obtained by dissolving the heat-resistant resin in the solvent can easily adjust the viscosity. Therefore, the fine powder can be uniformly dispersed, and since it can be easily applied to the substrate, it can be advantageously used. The solvent used for dissolving the heat resistant resin is usually a solvent such as methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate,
Butyl carbitol, butyl cellulose, tetralin,
Examples thereof include dimethylformamide and normal methylpyrrolidone. In addition, for example, an organic filler such as a fluororesin, a polyimide resin, or a benzoguanamine resin, or a filler made of an inorganic fine powder such as silica, alumina, titanium oxide, or zirconia may be appropriately mixed with the matrix heat-resistant resin. . In addition, additives such as colorants (pigments), leveling agents, defoaming agents, ultraviolet absorbers and flame retardants can be used.

Next, a method of manufacturing a printed wiring board using the adhesive will be described. The production method of the present invention, the adhesive obtained by dispersing the heat-resistant resin fine powder in the heat-resistant resin as a matrix on the substrate, is applied by a roll coater or the like, dried and cured, the adhesive layer To form. The thickness of this adhesive layer is usually about 2 to 40 μm, but when this adhesive layer is also used as an interlayer insulating layer of a metal substrate or a multilayer wiring board, it can be applied thicker than that.

In this coating, when the heat-resistant resin matrix is an epoxy resin, the gap between the coating roller and the doctor bar is 0.2 to 0.6 mm, and the conveying speed is 0.1 to.
It is preferably 3.0 m / min. The reason for this is that if the above-mentioned gap is wider than 0.6 mm, the coating film tends to be uneven and
This is because if it is narrower, it is difficult to obtain an appropriate film thickness. Also, if the transport speed is lower than 0.1 mm / min, the mass productivity is poor, and if it is higher than 3.0 mm / min, the film thickness becomes non-uniform. On the other hand, the same applies when the heat-resistant resin matrix is a resin having an acrylic group or an acrylic resin.

As the substrate used in the manufacturing method of the present invention, for example, a plastic substrate, a ceramic substrate, a metal substrate, a film substrate or the like can be used. Specifically, a glass epoxy substrate, a glass polyimide substrate,
An alumina 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. Then, using these substrates, a single-sided wiring board, a double-sided through-hole wiring board, and a multilayer wiring board such as a Cu / polyimide multilayer wiring board can be manufactured. The adhesive itself may be molded into a plate-shaped or film-shaped prepreg to be used as a substrate having an adhesive property capable of performing electroless plating.

Next, at least a part of the heat resistant resin fine powder fine powder dispersed on the surface of the adhesive layer is dissolved and removed using an acid or an oxidizing agent. This method may be carried out by using the solution of the acid or the oxidant, immersing the substrate on which the adhesive layer is formed in the solution, or spraying the substrate with the acid or the oxidant solution. As a result, the surface of the adhesive layer can be roughened. In order to effectively remove the heat-resistant resin fine powder filler by dissolving, the surface portion of the adhesive layer is lightly roughened in advance by polishing or liquid honing with a fine powder abrasive, for example. Is extremely effective.

As the oxidizing agent for roughening the adhesive, chromic acid, chromate, permanganate, ozone, etc. are preferable.
As the acid, hydrochloric acid, sulfuric acid, organic acid and the like are preferable.

Then, the surface-roughened adhesive layer on the substrate is subjected to electroless plating to obtain a desired printed wiring board. Examples of the electroless plating include electroless copper plating, electroless nickel plating, electroless tin plating, electroless gold plating and electroless silver plating, and especially electroless copper plating, electroless nickel plating and It is preferable that the electroless gold plating is at least one kind. In addition, it is also possible to further perform different types of electroless plating or electroplating on the above-mentioned electroless plating, or to coat solder.

The wiring board obtained by the method of the present invention as described above can be formed with a conductor circuit by various methods which have been carried out for known printed wiring boards. For example, electroless plating is performed on a substrate. It is possible to apply a method of etching the circuit after performing the above, or a method of directly forming the circuit when performing the electroless plating.

Next, the printed wiring board of the present invention obtained as described above will be described. As the printed wiring board of the present invention, for example, as shown in FIG. 1 (f) and FIG. 3 (f), a single-sided surface is obtained by forming a plating resist 3 and a conductor circuit 4 on a substrate 1 via an adhesive layer 2. Printed wiring board, Figure 2
(f), a double-sided printed wiring board formed by forming a plating resist 3 and a conductor circuit 4 through an adhesive layer 2 and through holes 5 on both sides of a substrate 1 as shown in FIG.
As shown in 10, an interlayer insulating layer (adhesive layer) having a via hole 7 on the substrate 1'on which the first conductor layer 4 is formed
In a build-up multilayer wiring board in which conductor circuits (4, 6, 8, 10) via 2'are formed in multiple layers,

In any case, the above-mentioned adhesive is hardened heat-resistant resin fine powder which is soluble in an acid or an oxidizing agent, and when hardened, it is applied to an acid or an oxide. It is one which is dispersed in an uncured heat-resistant resin matrix having a property of becoming poorly soluble, characterized by using an epoxy resin cured with an amine curing agent as the heat-resistant resin fine powder, The resin matrix is a polyfunctional epoxy resin, at least one resin selected from an acrylic group-containing resin and an acrylic resin, or at least one resin selected from the above resins and a bifunctional epoxy resin. It is desirable to use a mixed resin with at least one selected from acrylic resins. In the case of an epoxy resin, it is advantageous to cure it with an imidazole-based curing agent.

[0038]

(Example) (Example 1) (1) Bisphenol A type epoxy resin (made by Yuka Shell)
100 parts by weight was diluted with MEK, and an aliphatic polyamine on a chain (diethylenetriamine; manufactured by Sumitomo Chemical Co., Ltd.) was used as a curing agent.
After blending parts by weight, the mixture was dried and cured at 100 ° C. for 2 hours. The hardened epoxy resin is roughly crushed, and then, while being frozen in liquid nitrogen, finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and further a wind classifier (manufactured by Donaldson Japan). Use to classify, average particle size
1.7 μm epoxy resin fine powder was obtained. (2) Dissolve 60 parts by weight of phenol novolac type epoxy resin (made by Yuka Shell), 40 parts by weight of bisphenol A type epoxy resin (made by Yuka Shell) and 5 parts by weight of imidazole type curing agent (made by Shikoku Kasei) in butyl cellosolve acetate. Then, 50 parts by weight of the fine powder prepared in (1) was mixed with 100 parts by weight of the solid content of this composition, and then the mixture was kneaded with a three-roll mill, and butyl cellosolve acetate was further added to solidify the composition. An adhesive solution having a partial concentration of 75% was prepared. According to JIS-K7117, the viscosity of this solution was measured at 20 ° C for 60 seconds using a digital viscometer manufactured by Tokyo Keiki Co., Ltd. and found to be 5.2 Pa · s at 6 rpm and 2.5 Pa · s at 60 rpm. The value (thixotropic property) was 2.0. (3) The glass epoxy resin substrate 1 is roughened by polishing, and J
After forming a rough surface of IS-B0601 R _max = 2 to 3 μm, the solution of the photosensitive resin composition prepared in the above (2) was applied using a roll coater. The coating method at this time was to use a medium-high viscosity resist coating roll (manufactured by Dainippon Screen) as the coating roll. The gap between the coating roller and the doctor bar was 0.4 mm, and the gap between the coating roller and the backup roller was 1.4 mm. And the transport speed was 400 mm / s. Then, after standing in a horizontal state for 20 minutes, it was dried at 70 ° C. to form an adhesive layer 2 having a thickness of about 50 μm (see FIGS. 1 (b) and 1 (c)). (4) Chromic acid (CrO ₃ ) 500 g / l
The surface of the adhesive layer is roughened by immersing it in an oxidizing agent consisting of an aqueous solution at 70 ° C. for 15 minutes, and then a neutralizing solution (PN, Shipley, PN) is used.
-950) and washed with water. A palladium catalyst (manufactured by Shipley Co.) was applied to the substrate 1 having the roughened adhesive to activate the surface of the adhesive layer 2 (see FIG. 1 (d)). (5) The substrate 1 is placed in a nitrogen gas atmosphere (10 ppm oxygen) 12
Heat treatment for catalyst immobilization was carried out at 0 ° C for 30 minutes, after which a photosensitive dry film was laminated, exposed, and then developed with modified chlorothane, and plating resist 3 (thickness 40 μm).
Were formed (see FIG. 1 (e)). (6) Table 1 shows the substrate 1 on which the plating resist 3 has been formed.
It was immersed in an electroless copper plating solution having the composition shown in 11 hours for 11 hours to carry out electroless copper plating with a plating film 4 having a thickness of 25 μm to obtain a printed wiring board (see FIG. 1 (f)).

[0039]

[Table 1]

(Example 2) (1) Bisphenol F type epoxy resin (made by Yuka Shell)
Dilute 100 parts by weight with MEK and add 20% cycloaliphatic polyamine (Mensendiamine Rohm and Hase) as a curing agent.
After blending parts by weight, the mixture was dried and cured at 100 ° C. for 1 hour and at 150 ° C. for 2 hours. The cured epoxy resin is roughly crushed, and then, while being frozen with liquid nitrogen, finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Mfg. Co., Ltd.),
Further, classification was performed using a wind force classifier (manufactured by Donaldson Japan) to obtain an epoxy resin fine powder having an average particle size of 1.3 μm. (2) 100 parts by weight of an orthocresol novolac type epoxy resin (made by Yuka Shell) and 5 parts by weight of a curing agent (made by Shikoku Kasei) are dissolved in a mixed solvent of butyl cellosolve and dimethylformamide (ratio 6/4), 50 parts by weight of the fine powder prepared in (1) was mixed with 100 parts by weight of the solid content of this composition, and then the mixture was kneaded by three rolls, and butyl cellosolve acetate was further added to obtain a solid content of 70%. An adhesive solution of The viscosity of this solution was 4.2 Pa · s at 6 rpm and 2.7 Pa · s at 60 rpm, and its SVI value (thixotropic property) was 1.8. (3) Both surfaces of the glass epoxy resin substrate 1 were treated in the same manner as in Example 1 (3) to form an adhesive layer 2 having a thickness of about 45 μm (see FIGS. 2 (b) and 2 (c)). (4) Next, the substrate 1 of (3) above is drilled,
After polishing the substrate surface to expose the filler, 6
The surface of the adhesive layer 2 is roughened by immersing it in an acid consisting of an aqueous solution of N hydrochloric acid at 70 ° C. for 15 minutes, and then a neutralizing solution (made by Shipley).
And then washed with water. Then, a palladium catalyst (manufactured by Shipley Co., Ltd.) was applied to the substrate 1 having the roughened adhesive to activate the surface of the adhesive layer 2 (see FIGS. 2D and 2E). (5) The substrate 1 is placed in a nitrogen gas atmosphere (10 ppm oxygen) 12
Heat treatment for catalyst immobilization was carried out at 0 ° C for 30 minutes, after which a photosensitive dry film was laminated, exposed, and then developed with modified chlorothane, and plating resist 3 (thickness 40 μm).
Were formed (see FIG. 2 (f)). (6) Table 1 shows the substrate 1 on which the plating resist 3 has been formed.
It was immersed in an electroless copper plating solution having the composition shown in 11 hours for 11 hours, and electroless copper plating with a thickness of 30 μm of the plating film 4 was applied to both surfaces to form a conductor circuit and through holes to obtain a double-sided printed wiring board ( See Fig. 2 (f).

Example 3 (1) 100 parts by weight of a phenol novolac type epoxy resin (made by Yuka Shell) was diluted with MEK, and a fatty aromatic amine (m-xylenediamine; Showa Denko) was used as a curing agent.
After blending by weight, the mixture was dried and cured at 120 ° C. for 3 hours. This hardened epoxy resin is roughly crushed, and then while being frozen in liquid nitrogen, finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and further a wind force classifier (manufactured by Donaldson Japan). Use to classify, average particle size 1.
An epoxy resin fine powder of 8 μm was obtained. (2) 80 parts by weight of special functional epoxy resin (made by oiled shell), bisphenol A type epoxy resin (made by oiled shell)
20 parts by weight and 7 parts by weight of a curing agent (Shikoku Kasei) were dissolved in xylene, and 100 parts by weight of the solid content of this composition was mixed with the epoxy resin fine powder prepared in (1) above.
After mixing at a ratio of 50 parts by weight, kneading with a three-roll mill, and adding butyl cellosolve acetate to obtain a solid content concentration.
An 80% adhesive solution was made. The viscosity of this solution was 5.8 Pa · s at 6 rpm and 2.0 Pa · s at 60 rpm, and its SVI value was 2.2. (3) A printed wiring board was prepared in the same manner as in Example 1 using this adhesive.

(Example 4) (1) Glycidylamine type epoxy resin (made by Yuka Shell)
110 parts by weight was diluted with MEK, and 15 parts by weight of an aromatic amine (m-xylenediamine; manufactured by Sumitomo Chemical Co., Ltd.) was added as a curing agent, followed by drying and curing at 80 ° C. for 2 hours. This hardened epoxy resin is roughly crushed, and then while being frozen in liquid nitrogen, finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and further a wind force classifier (manufactured by Donaldson Japan). It was used and classified to obtain an epoxy resin fine powder having an average particle size of 1.8 μm. (2) 50 parts by weight of phenol aralkyl type epoxy resin (made by Yuka Shell), 50 parts by weight of novolac type polyfunctional epoxy resin (made by Yuka Shell) and 5 parts by weight of curing agent (made by Shikoku Kasei) to butyl cellosolve acetate. Dissolved, 100 parts by weight of the solid content of this composition, the above (1)
The epoxy resin fine powder obtained in 1 was mixed at a ratio of 50 parts by weight, then kneaded with a three-roll mill, and butyl cellosolve acetate was further added to obtain an adhesive solution having a solid content concentration of 80%.
The viscosity of this solution is 5.8 Pa · s at 60 rpm and 60 rpm.
It was 2.0 Pa · s and its SVI value (thixotropic property) was 2.2. (3) Using the roll coater (manufactured by Dainippon Screen), apply the adhesive solution prepared in (2) above to a polyethylene film that has been previously coated with a mold release agent such as silicon, and then apply 70 ° C.
And dried for 1 hour to prepare a film adhesive. (4) The film adhesive prepared in (3) above is applied to the glass polyimide substrate 1 (manufactured by Toshiba Chemical) on which the copper foil is not adhered, with the surface coated with the adhesive as the substrate side.
The pressure-sensitive adhesive layer 2 was formed by applying pressure at 0 ° C. and 40 kg / cm ² for 200 minutes. (5) (3) to (6) of Example 1 on the substrate 1 obtained in (4) above
A printed wiring board was prepared by carrying out the process of.

Example 5 (1) Epoxy resin particles prepared by dispersing 200 g of epoxy resin particles (average particle size 3.9 μm) prepared by the same method as in (1) of Example 1 in 5 l of acetone. While stirring in the suspension in a Henschel mixer (Mitsui Miike Kakoki), an epoxy resin (Mitsui Petrochemical) was added to acetone 1 liter.
Example 1 was added to an acetone solution dissolved at a rate of 30 g.
After the epoxy resin particles (average particle diameter 0.5 μm) 300 g prepared in the same manner as (1) were added dropwise to the suspension, the epoxy resin powder was attached to the surface of the epoxy resin particles. Remove the acetone, then 15
The particles were heated to 0 ° C. to prepare pseudo particles. The pseudo particles had an average particle size of about 4.3 μm, and about 75% by weight was present within a range of ± 2 μm centering on the average particle size. (2) 50 parts by weight of the pseudo particles prepared in (1) above, 60 parts by weight of phenol novolac type epoxy resin (made by Yuka Shell),
To a mixture of 40 parts by weight of a bisphenol A type epoxy resin (made by Yuka Shell) and 5 parts by weight of an imidazole type curing agent (made by Shikoku Kasei), butyl carbitol was added and adjusted with a homodisper disperser to obtain a solid content concentration of 80%. An adhesive solution was prepared. The viscosity of this solution is 5.8 Pa · s at 6 rpm.
At 60 rpm, it was 2.0 Pa · s, and its SVI value (thixotropic property) was 2.2. (3) Using this adhesive, a printed wiring board was prepared in the same manner as in Example 1 (see FIG. 3).

Example 6 (1) Epoxy resin particles (average particle size 3.9 μm) prepared by the same method as in Example 1 (1) were charged into a hot air dryer and heated at 180 ° C. for 3 hours. Heat treatment was performed to cause cohesive bonding. The agglomerated and bonded epoxy resin particles were dispersed in acetone, crushed with a ball mill for 5 hours, and then classified using an air classifier to prepare agglomerated particles. The agglomerated particles had an average particle size of about 3.5 μm, and about 68% by weight was present in the range of ± 2 μm centering on the average particle size. (2) 50 parts by weight of the agglomerated particles prepared in (1) above, 60 parts by weight of phenol novolac type epoxy resin (made by Yuka Shell),
To a mixture of 40 parts by weight of a bisphenol A type epoxy resin (made by Yuka Shell) and 4 parts by weight of an imidazole-based curing agent (made by Shikoku Kasei), butyl carbitol was added and adjusted with a homodisper disperser to obtain a solid content concentration of 80%. An adhesive solution was prepared. The viscosity of this solution is 5.8 Pa · s at 6 rpm.
At 60 rpm, it was 2.0 Pa · s, and its SVI value (thixotropic property) was 2.2. (3) Using this adhesive, a printed wiring board was prepared in the same manner as in Example 2 (see FIG. 4).

(Example 7) (1) A photosensitive dry film (manufactured by DuPont) was laminated on a glass epoxy copper clad laminate (manufactured by Toshiba Chemical) and exposed to ultraviolet light through a mask film on which a desired conductor circuit pattern was drawn. Burn the image. Then, 1,
After developing with 1,1-trichloroethane and removing the copper in the non-conductor portion using a cupric chloride etching solution, the dry film is peeled off with methylene chloride. This allows
A wiring board 1'having a first conductor layer 4 composed of a plurality of conductor patterns was formed (see FIG. 5 (a)). (2) 100 parts by weight of 50% acrylate of phenol aralkyl type epoxy resin, 15 parts by weight of diallyl terephthalate,
4-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba-Geigy) 4 parts by weight, 4 parts by weight of imidazole-based curing agent (manufactured by Shikoku Kasei) and as in Example 1 Average particle size 3.9 μm and average particle size 0.
Butyl carbitol was added to a mixture consisting of two types of 5 μm epoxy resin particles, 10 parts by weight and 25 parts by weight, respectively, to prepare with a homodisper disperser, and then kneaded with three rollers to obtain a solid content concentration of 80%. An adhesive solution was prepared. The viscosity of this solution is 6.5 Pa · s, 60 at 6 rpm.
The rpm was 2.9 Pa · s, and the SVI value (thixotropic property) was 2.2. (3) Apply the solution of the photosensitive resin composition prepared in (2) above onto the wiring board 1'prepared in (1) above using a roll coater, leave it for 20 minutes in a horizontal state, and then at 70 ° C. And dried to form a photosensitive resin insulation layer 2'having a thickness of about 50 μm (see FIG. 5).
(See (b)). (4) A photomask film having a 100 μmφ black circle printed thereon was brought into close contact with the wiring board 1 ′ that had been subjected to the treatment of (3) above, and exposed at 500 mj / cm ² by an ultra-high pressure mercury lamp. This is 1,
An ultrasonic development treatment with 1,1-trichloroethane was performed to form an opening 7 serving as a via hole of 100 μmφ on the wiring board 1 '. The wiring board 1'is exposed by an ultra-high pressure mercury lamp at about 3000 mj / cm ² and further exposed at 100 ° C. for 1 hour, then
By heat-treating at 150 ° C. for 10 hours, an interlayer insulating layer 2 ′ having an opening 7 excellent in dimensional accuracy corresponding to a photomask film was formed (see FIG. 5 (c)). (5) The wiring board 1 prepared in (4) above is treated with chromic acid (CrO).
₃ ) Immerse in an oxidizing agent consisting of 500 g / l aqueous solution at 70 ° C for 15 minutes to roughen the surface of the interlayer insulating layer 2 ', then soak in a neutralizing solution (manufactured by Shipley Co., Ltd.) and wash with water. The through hole 5 was created by the method. Then, this interlayer insulating layer 2 '
Palladium catalyst (made by Play Co.) on the roughened substrate 1 '
Was applied to activate the surface of the insulating layer, and heat treatment for fixing the palladium catalyst was performed at 120 ° C. for 30 minutes (see FIGS. 5 (d) and 5 (e)). (6) Next, a photosensitive dry film (manufactured by San Nopco) was laminated on the wiring board 1 ', and the conductor pattern was exposed and then developed (see FIG. 5 (e)). (7) Immerse in an electroless copper plating solution having the composition shown in Table 1 for 11 hours to apply electroless copper plating having a thickness of 25 μm on the plating film 6,
A multilayer printed wiring board was created (see Fig. 5 (f)).

Comparative Example 1 Basically the same as in Example 1, but a printed wiring board was prepared by using, as the heat-resistant resin fine powder, an epoxy resin cured with a dicyan hardener.

The adhesion strength between the substrate and the copper plating film of the printed wiring board obtained in Examples 1 to 7 and Comparative Example 1 was measured according to JIS-C-6481.
When the peel strength was measured by the above method, the peel strength was as shown in Table 2. As is clear from Table 2, the epoxy resin cured with the dicyan-based curing agent used in Comparative Example has low solubility in acids and oxidants, and therefore, in the case of the epoxy resin cured with the amine-based curing agent of the present invention. The peel strength was lower than that of

[0048]

[Table 2]

Example 8 (1) In the same manner as in Example 7, a wiring board 1'having a first conductor layer 4 composed of a plurality of conductor patterns was formed on a glass epoxy copper clad laminate (see FIG. 6 ( See a)). (2) In the same manner as in Example 1 (1), an epoxy resin fine powder having an average particle size of 1.7 μm was obtained. (3) 60 parts by weight of 5% acrylate of cresol novolac type epoxy resin (made by Yuka Shell), 40 parts by weight of bisphenol A type epoxy resin (made by Yuka Shell, Epicoat 1001), 15 parts by weight of diallyl terephthalate, 2-methyl -1-
[4- (Methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba Geigy) 4 parts by weight, imidazole-based curing agent (manufactured by Shikoku Kasei) 4 parts by weight, and the epoxy resin fine powder obtained in the above (2) After mixing 50 parts by weight of the powder, a butyl cellosolve was added to prepare a homodisper dispersion machine, and the mixture was kneaded with three rollers to prepare a photosensitive adhesive solution having a solid content concentration of 70%. The viscosity of this solution was 5.0 Pa · s at 6 rpm and 2.5 Pa · s at 60 rpm, and its SVI value (thixotropic property) was 2.0. (4) In the same manner as in Example 7 (3) to (7), a buildup multilayer wiring board having four wiring layers (4, 6, 8, 10) was prepared (see FIG. 6).

(Example 9) (1) In the same manner as in Example 7, a wiring board 1'having a first conductor layer 4 consisting of a plurality of conductor patterns was formed on a glass epoxy copper clad laminate (see FIG. 7 ( See a)). (2) Bisphenol F type epoxy resin (made by Yuka Shell)
110 parts by weight was diluted with MEK, 5 parts by weight of a cycloaliphatic polyamine (mensendiamine; manufactured by Sumitomo Chemical Co., Ltd.) was added as a curing agent, and the mixture was dried and cured at 120 ° C. for 3 hours. This hardened epoxy resin is roughly crushed, frozen with liquid nitrogen, finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and a wind classifier (manufactured by Donaldson Japan) is used. Then, the particles were classified, and the average particle size was 3.9 μm and was 0.1.
An epoxy resin fine powder of 5 μm was obtained. (3) Resin particles prepared by the method of (2) (average particle size 3.9 μ
m) 200 g of an epoxy resin particle suspension dispersed in 5 l of acetone was dissolved in an acetone solution in which a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) was dissolved at a rate of 30 g,
Resin particles prepared in the same way as (1) (average particle size 0.5 μm) 3
By dropping a suspension in which 00g is dispersed, to adhere the epoxy resin powder to the surface of the epoxy resin particles, remove the acetone, and then heat to 150 ℃,
Pseudo particles were created. The pseudo particles have an average particle size of about 4.
3 μm, about 75% by weight is centered on the average particle size ±
It was present in the range of 2 μm. (4) 75 parts by weight of 75% acrylate of cresol novolac type epoxy resin (manufactured by Nippon Kayaku), 50 parts by weight of bisphenol A type epoxy resin (manufactured by Dow Chemical), 25 parts by weight of dipentaerythritol hexaacrate, benzyl acrylic ketal (Ciba Geigy) 5 parts by weight, imidazole-based curing agent (Shikoku Kasei) 6 parts by weight, and epoxy resin fine powder 50 parts by weight prepared in (2) above are mixed, and then homodisper stirrer is added while adding butyl cellosolve. And then kneading with 3 rollers to obtain solid content
A 70% photosensitive adhesive solution was prepared. The viscosity of this solution was 5.2 Pa · s at 6 rpm and 2.6 Pa · s at 60 rpm, and its SVI value (thixotropic property) was 2.0. (5) Apply the solution of the photosensitive resin composition prepared in (4) above onto the wiring board 1'prepared in (1) above using a roll coater and leave it in a horizontal state for 20 minutes, then at 70 ° C. It was dried to form a photosensitive resin layer 2'having a thickness of about 45 μm. (6) A build-up multilayer wiring board having four wiring layers (4, 6, 8, 10) was prepared in the same manner as in Example 7 (4) to (6) (see FIG. 7).

(Example 10) (1) In the same manner as in Example 7, a wiring board 1'having a first conductor layer 4 composed of a plurality of conductor patterns was formed on a glass epoxy copper clad laminate (see FIG. 8 ( See a)). (2) Glycidylamine type epoxy resin (made by Yuka Shell)
110 parts by weight was diluted with MEK, 5 parts by weight of an aromatic amine (m-xylenediamine; manufactured by Sumitomo Chemical Co., Ltd.) was added as a curing agent, and the mixture was dried and cured at 120 ° C. for 3 hours. This hardened epoxy resin is roughly crushed, frozen with liquid nitrogen, finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and a wind classifier (manufactured by Donaldson Japan) is used. The powder was classified to obtain an epoxy resin fine powder having an average particle diameter of 3.9 μm. (3) Resin particles (average particle size 3.
9 μm) was placed in a hot-air dryer and heat-treated at 180 ° C. for 3 hours to aggregate and bond. The coagulated and bonded epoxy resin particles are dispersed in acetone, and the mixture is mixed with a ball mill to form 5
After crushing for a period of time, classification was performed using an air classifier to create agglomerated particles. The aggregated particles have an average particle size of about 3.5 μm.
And about 68% by weight is ± 2 μm centered on the average particle size.
Existed in the range. (4) Cresol novolac type epoxy resin (manufactured by Nippon Kayaku) 40% by weight acrylate, bisphenol A type epoxy resin (manufactured by Yuka Shell) 60 parts by weight, diacrylic terephthalate 15 parts by weight, 2-hydroxy-1 After mixing 30 parts by weight of 3,3-bis (hydrazinocarboethyl) -5-isopropylhydrontoin (manufactured by Ajinomoto) and 60 parts by weight of the epoxy resin fine powder prepared in (3) above, butyl cellosolve was added while homogenizing. The mixture was stirred with a Disper stirrer and then kneaded with three rollers to prepare a photosensitive adhesive solution having a solid content concentration of 60%. (5) Apply the solution of the photosensitive resin composition prepared in (4) above onto the wiring board 1'prepared in (1) above using a roll coater and leave it in a horizontal state for 20 minutes, then at 70 ° C. It was dried to form a photosensitive resin layer 2'having a thickness of about 45 μm. (6) In the same manner as in Example 7 (4) to (6), a build-up multilayer wiring board having four wiring layers (4, 6, 8, 10) was prepared (see FIG. 8).

(Example 11) (1) In the same manner as in Example 7, a wiring board 1'having a first conductor layer 4 consisting of a plurality of conductor patterns was formed on a glass epoxy copper clad laminate (Fig. 9 ( See a) and (b). (2) Glycidylamine type epoxy resin (made by Yuka Shell)
110 parts by weight was diluted with MEK, 5 parts by weight of an aromatic amine (m-xylenediamine; manufactured by Sumitomo Chemical Co., Ltd.) was added as a curing agent, and the mixture was dried and cured at 120 ° C. for 3 hours. This hardened epoxy resin is roughly crushed, frozen with liquid nitrogen, finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and a wind classifier (manufactured by Donaldson Japan) is used. And classify, average particle size 3.9 μm, 0.5
A fine powder of epoxy resin having a size of μm was obtained. (3) 100 parts by weight of 80% acrylate of phenol aralkyl type epoxy resin, 15 parts by weight of diallyl terephthalate,
2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba Geigy) 4 parts by weight, imidazole-based curing agent (manufactured by Shikoku Kasei) and 4 parts by weight and the above
Prepared with a homodisper disperser while adding butyl carbitol after mixing 10 parts by weight and 25 parts by weight of the two kinds of fine epoxy resin powders having an average particle size of 3.9 μm and 0.5 μm obtained in (2) respectively. Then, the mixture was kneaded with three rollers to prepare a photosensitive adhesive solution having a solid content concentration of 80%. The viscosity of this solution is 5.8 Pa · s at 6 rpm and 2. at 60 rpm.
5 Pa · s and its SVI value (thixotropic property)
Was 2.1. (4) A photosensitive adhesive solution was applied on the substrate 1'of the above (1), heated at 120 ° C. for 30 minutes and dried. Further, a photomask film having a 100 μmφ black circle printed thereon was brought into close contact with the substrate 1 ′ and exposed at 500 mj / cm ² by an ultra-high pressure mercury lamp. This was ultrasonically developed with 1,1,1-trichloroethane to form an opening 7 serving as a via hole of 100 μmφ on the wiring board. The wiring board is exposed at about 3000 mj / cm ² by an ultra-high pressure mercury lamp and further heat-treated at 100 ° C. for 1 hour, and then at 150 ° C. for 10 hours to form an opening 7 with excellent dimensional accuracy equivalent to a photomask film.
Were formed (see FIGS. 9 (c) and 9 (d)). (5) Apply the solution of the photosensitive resin composition prepared in (3) above onto the wiring board 1'prepared in (1) above using a roll coater, leave it for 20 minutes in a horizontal state, and then at 70 ° C. It was dried to form a photosensitive resin layer 2'having a thickness of about 50 µm. Then the above
By the same processing as (4) (however, the diameter of the black circle is 85 μm)
A via hole opening 7 was formed (see FIGS. 9 (e) and 9 (f)). (6) The wiring board 1 ′ prepared in (5) above is immersed in an acid consisting of 6N hydrochloric acid at 70 ° C. for 15 minutes to roughen the surface of the interlayer insulating layer 2 ′, and then a neutralizing solution (made by Shipley Co., Ltd. ) And washed with water. Palladium catalyst (manufactured by Shipley Co.) is applied to the substrate 1'having the roughened interlayer insulating layer 2'to activate the surface of the insulating layer 2'and heating for fixing the palladium catalyst at 120 ° C for 30 minutes. Treatment, and then immersing in an electroless copper plating solution having the composition shown in Table 1 for 11 hours to obtain a plating film 6 having a thickness of 25
Electroless copper plating of μm was applied (see FIGS. 9 (g) and 9 (h)).
(7) By repeating the steps (4) to (6) twice, a build-up multilayer wiring board having four wiring layers was prepared (see FIG. 9).

(Example 12) (1) Glycidylamine type epoxy resin (made by Yuka Shell)
110 parts by weight was diluted with MEK, 5 parts by weight of an aromatic amine (m-xylenediamine; manufactured by Sumitomo Chemical Co., Ltd.) was added as a curing agent, and the mixture was dried and cured at 120 ° C. for 3 hours. This hardened epoxy resin is roughly crushed, frozen with liquid nitrogen, finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and a wind classifier (manufactured by Donaldson Japan) is used. And classify, average particle size 3.9 μm, 0.5
A fine powder of epoxy resin having a size of μm was obtained. (2) 100 parts by weight of 50% acrylate of phenol aralkyl type epoxy resin, 15 parts by weight of diallyl terephthalate,
2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba Geigy) 4 parts by weight, imidazole-based curing agent (manufactured by Shikoku Kasei) and 4 parts by weight and the above
Prepared with a homodisper disperser while adding butyl carbitol after mixing 10 parts by weight and 25 parts by weight of the two kinds of fine epoxy resin powders having an average particle size of 3.9 μm and 0.5 μm obtained in (2) respectively. Then, the mixture was kneaded with three rollers to prepare a photosensitive adhesive solution having a solid content concentration of 80%. The viscosity of this solution is 5.8 Pa · s at 6 rpm and 2. at 60 rpm.
5 Pa · s and its SVI value (thixotropic property)
Was 2.1. (3) Next, on the wiring board 1'obtained by photoetching the surface copper foil of the glass-epoxy double-sided copper-clad laminate by a conventional method, the adhesive solution prepared in (3) above was entirely coated with a roll coater. After applying it to 100 ° C for 1 hour, then at 150 ° C for 5 hours
Insulating layer 2'is formed by drying and curing for an hour (Figs. 5 (a) and 5 (b)).
reference). (4) A photomask film on which a 100 μmφ black circle is printed is brought into close contact with this substrate 1 ', and it is exposed to 500 m with an ultra-high pressure mercury lamp.
It was exposed at j / cm ² . By ultrasonically developing this with 1,1,1-trichloroethane, 100
An opening 7 was formed to be a μmφ via hole. The wiring board 1'is exposed by an ultra-high pressure mercury lamp at about 3000 mj / cm ² and further heat-treated at 100 ° C. for 1 hour and then at 150 ° C. for 10 hours to obtain an opening 7 having excellent dimensional accuracy equivalent to a photomask film. Was formed (see FIG. 5 (c)). (5) Next, the resin surface was roughened by immersing it in sulfuric acid for 10 minutes, neutralized and washed with water (see FIG. 5 (d)). (6) Through holes 5 were prepared by a conventional method. (7) A palladium catalyst (manufactured by Shipley) was applied to the substrate 1'to activate the surface of the insulating layer 2 ', and the catalyst was fixed by heating at 120 ° C for 30 minutes in a nitrogen gas atmosphere. (8) Next, a photosensitive dry film (manufactured by San Nopco) was laminated on the wiring board 1 ', and the conductor pattern was exposed and then developed (see FIG. 5 (e)). (9) Immerse in an electroless copper plating solution having the composition shown in Table 1 for 11 hours to perform electroless copper plating with a plating film 6 thickness of 25 μm.
A multilayer printed wiring board was created (see Fig. 5 (f)).

Example 13 (1) An adhesive solution A was obtained by performing the same treatments as in (1) and (2) of Example 1. However, the imidazole type curing agent (manufactured by Shikoku Kasei) was not mixed. (2) 5 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Kasei) was mixed with an appropriate amount of butyl cellosolve acetate to obtain an adhesive solution B. (3) Adhesive solution A and adhesive solution B were mixed and mixed with a homogenizer stirrer. The properties of the obtained adhesive were the same as in Example 1. (4) Using this adhesive, perform the same treatment as in Example 1,
A printed wiring board was manufactured. The adhesive solutions A and B are
Can be stored for a long period of time.

Example 14 (1) This example is basically the same as Example 1, except that 100 parts by weight of a special polyfunctional epoxy resin (made by Yuka Shell) and an imidazole type curing agent (Shikoku 5 parts by weight) was dissolved in butyl cellosolve acetate to obtain a solid content of 10%.
0 parts by weight of the fine powder prepared in (1) of Example 1
The mixture was mixed at a ratio of 50 parts by weight, then kneaded with a three-roll mill, and butyl cellosolve acetate was further added to prepare an adhesive solution having a solid content concentration of 75 wt%. The viscosity of this solution was 5.3 Pa · s at 6 rpm and 2.4 Pa · s at 60 rpm, and its SVI value (thixotropic property) was 2.2. (2) Using this adhesive, a printed wiring board was prepared in the same manner as in Example 1.

Example 15 (1) This example is basically the same as Example 8, except that 100 parts by weight of 70% acrylate of ortho-cresol type epoxy resin (Nippon Kayaku) and diallyl terephthalate are used. 15 parts by weight, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba Geigy) 4 parts by weight, imidazole-based curing agent (manufactured by Shikoku Kasei) 2 parts by weight, light 5 parts by weight of an initiator (manufactured by Ciba Geigy) and that of Example 8
After mixing 50 parts by weight of the epoxy resin fine powder obtained in (2), prepare with a homodisper disperser while adding butyl cellosolve, and then knead with 3 rollers to obtain a photosensitive adhesive with a solid content of 70%. An agent solution was prepared. The viscosity of this solution is 5.1 Pa · s at 6 rpm and 2.4 Pa · s at 60 rpm.
And its SVI value (thixotropic property) was 2.1. (2) Using this adhesive, a multilayer printed wiring board was prepared in the same manner as in Example 8.

COMPARATIVE EXAMPLE 2 Basically the same as in Example 1, but a printed wiring board was prepared by using, as the heat resistant resin fine powder, an epoxy resin cured with a dicyan hardener.

The adhesion strength between the substrate and the copper plating film of the printed wiring board obtained in Examples 8 to 12 and Comparative Example 2 was measured according to JIS-C-6481.
When the peel strength was measured by the above method, the results are shown in Table 3. As is clear from Table 3, since the epoxy resin cured with the dicyan-based curing agent used in Comparative Example has low solubility in an acid and an oxidizing agent, the epoxy resin cured with the amine-based curing agent of the present invention The peel strength was lower than that of Further, it was found that the adhesive of the present invention has a large fracture toughness value and excellent drilling workability and punching workability.

[0059]

[Table 3]

[0060]

As described above, according to the adhesive for wiring boards of the present invention and the method for producing a wiring board using this adhesive, the adhesive resistance to electroless plating, heat resistance, electrical characteristics, It is possible to easily obtain an adhesive for wiring boards, which has extremely excellent adhesion, workability, and coatability between the substrate and the electroless plating film, and a printed wiring board using this adhesive.

[Brief description of drawings]

FIG. 1 is a manufacturing process diagram showing an embodiment of a printed wiring board of the present invention.

FIG. 2 is another manufacturing process drawing showing an embodiment of the printed wiring board of the present invention.

FIG. 3 is another manufacturing process diagram showing the embodiment of the printed wiring board according to the present invention.

FIG. 4 is another manufacturing process diagram showing the embodiment of the printed wiring board according to the present invention.

FIG. 5 is another manufacturing process diagram showing the embodiment of the printed wiring board according to the present invention.

FIG. 6 is another manufacturing process drawing showing the embodiment of the printed wiring board according to the present invention.

FIG. 7 is another manufacturing process diagram showing the embodiment of the printed wiring board according to the present invention.

FIG. 8 is another manufacturing process diagram showing the embodiment of the printed wiring board according to the present invention.

FIG. 9 is another manufacturing process drawing showing the embodiment of the printed wiring board according to the present invention.

[Explanation of symbols]

1,1 'substrate (wiring board) 2,2 'Adhesive layer (insulating layer) 3 plating resist 4, 6, 8, 10 Wiring board (plating film, conductor layer) 5 Through hole 7 Via hole openings

[Procedure amendment]

[Submission date] October 31, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Added

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

[0048]

[Table 2]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

[0059]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C23C 18/18 8414-4K 18/20 Z 8414-4K // H05K 3/18 A 6736-4E

Claims (14)

[Claims] 1. A cured heat-resistant resin fine powder which is soluble in an acid or an oxidant, has a characteristic of being hardly soluble in an acid or an oxide when subjected to a curing treatment. An adhesive for wiring boards, characterized in that an epoxy resin cured with an amine-based curing agent is used as the heat-resistant resin fine powder in an adhesive dispersed in a curing heat-resistant resin matrix. 2. A cured heat-resistant resin fine powder which is soluble in an acid or an oxidant, has a characteristic of being hardly soluble in an acid or an oxide when subjected to a curing treatment. In an adhesive that is dispersed in a heat-resistant resin matrix for curing, an epoxy resin cured with an amine-based curing agent is used as the heat-resistant resin fine powder, and is cured with an imidazole-based curing agent as the heat-resistant resin matrix. An adhesive for wiring boards, characterized by using an epoxy resin. 3. An uncured heat-resistant resin matrix having a characteristic that a cured heat-resistant resin fine powder that is soluble in an acid or an oxidizing agent is hard to be dissolved in an acid or an oxide. In an adhesive dispersed therein, an epoxy resin cured with an amine curing agent is used as the heat resistant resin fine powder, and an epoxy resin, a resin having an acrylic group and an acrylic resin is selected as the heat resistant resin matrix. At least one adhesive is used for a wiring board. 4. The viscosity of the adhesive measured by a rotational viscometer is 5.1 ± 2.0 Pa · s when the rotational speed is 6 rpm,
When the rotation speed is 60 rpm, it shows 2.4 ± 1.0 Pa · s, and the ratio of the viscosity at the rotation speed of 6 rpm and the viscosity at the rotation speed of 60 rpm is
The adhesive according to any one of claims 1 to 3, which exhibits 2.1 ± 1.0. 5. A cured bifunctional epoxy resin fine powder is dispersed in a matrix resin comprising at least one selected from an uncured polyfunctional epoxy resin and a bifunctional epoxy resin. The adhesive according to claim 2, comprising a mixture and an imidazole-based curing agent. 6. The resin matrix has a solid content of 20
Consisting of 〜100 wt% polyfunctional epoxy resin and 0-80 wt% difunctional epoxy resin, the content of bifunctional epoxy resin fine powder is 10〜100% by weight of the total solid content of the matrix. The adhesive according to claim 5, which is 100 parts by weight. 7. A mixture of a cured bifunctional epoxy resin, at least one resin selected from an uncured polyfunctional epoxy resin and a bifunctional epoxy resin, and an imidazole curing agent. The adhesive according to claim 2, which is dispersed in a matrix. 8. The matrix has a solid content of 20 to 10
A heat-resistant resin composed of 0 wt% of a polyfunctional epoxy resin and 0 to 80 wt% of a bifunctional epoxy resin, and 2 to 10 wt% of an imidazole-based curing agent based on the total solid content of the matrix, The content of the bifunctional epoxy resin fine powder is
10-100 based on 100 parts by weight of solids in the above matrix
The adhesive according to claim 7, which is defined as parts by weight. 9. A cured bifunctional epoxy resin, at least one resin selected from an uncured polyfunctional epoxy resin, a resin having a polyfunctional acrylic group, and a polyfunctional acrylic resin, or In a mixed resin of at least one selected from a polyfunctional epoxy resin, a resin having a polyfunctional acrylic group, and a polyfunctional acrylic resin, and at least one selected from a bifunctional epoxy resin and a bifunctional acrylic resin. 4. The dispersion according to claim 3
The adhesive according to. 10. The heat-resistant resin matrix comprises at least one selected from a polyfunctional epoxy resin having a solid content of 20 to 100 wt%, a resin having a polyfunctional acrylic group, and a polyfunctional acrylic resin. , At least one selected from a bifunctional epoxy resin of 0 to 80 wt% and a bifunctional acrylic resin, and the content of the bifunctional epoxy resin fine powder is based on 100 parts by weight of the total solid content of the matrix. The adhesive according to claim 9, wherein the total amount is 10 to 100 parts by weight. 11. The solid content concentration of the heat-resistant resin fine powder, the uncured heat-resistant resin and the curing agent in the matrix is 55 to 85.
The adhesive according to claim 1, which is wt%. 12. In a printed wiring board having an adhesive layer on at least one substrate surface and a conductor circuit formed thereon, a cured heat-resistant resin soluble in an acid or an oxidant. The heat-resistant resin fine powder as an adhesive obtained by dispersing the fine powder in an uncured heat-resistant resin matrix having a property of being hardly soluble in an acid or an oxide when subjected to a curing treatment. A printed wiring board characterized by using an epoxy resin cured with an amine-based curing agent. 13. The heat-resistant resin matrix is an epoxy resin that is cured with an imidazole-based curing agent.
The printed wiring board described in 12. 14. The printed wiring board according to claim 12, wherein the heat-resistant resin matrix is at least one resin selected from an epoxy resin, a resin having an acrylic group, and an acrylic resin.