JP2877993B2 - Adhesive for wiring board, method for manufacturing printed wiring board using this adhesive, and printed wiring board - Google Patents

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 excellent in both electroless plating properties and coating properties, a method for manufacturing 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 method for manufacturing a printed wiring board using the adhesive, and a printed wiring board.

[0002]

2. Description of the Related Art In recent years, with the advance of the electronics industry, electronic devices have been reduced in size or increased in speed. For this reason, printed wiring boards and wiring boards on which LSIs are mounted have been improved in density and fine reliability by fine patterns. Is required.

Conventionally, as a method of forming a conductive circuit on a printed wiring board, an etched foil method of forming a conductive circuit by laminating a copper foil on a substrate and then performing photoetching has been widely used. According to this method, a conductor circuit having excellent adhesion to a substrate can be formed, but there is a major drawback that a high-precision fine pattern is difficult to be obtained by etching due to a large thickness of a copper foil. There are various problems such as complicated processes and inefficient processes.

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 after the surface of the adhesive layer is roughened, An additive method of forming a conductor by performing electroless plating is employed. However, since the adhesive generally used in this method contains a synthetic rubber, for example, the adhesive strength is greatly reduced at a high temperature, or the heat resistance is low, such as the electroless plating film bulging during soldering. There is a disadvantage that the electrical properties 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 extremely excellent heat resistance, electric characteristics and adhesion to the electroless plating film. Japanese Patent Application Laid-Open No. 61-276875 proposes an adhesive for electroless plating which can be carried out relatively easily and a method for manufacturing a wiring board using this adhesive. That is, the disclosed technology is based on a precured heat-resistant resin powder that is soluble in an oxidizing agent, and has an uncured heat-resistant resin having a property of being hardly soluble in an oxidizing agent when cured. An adhesive characterized by being dispersed in a liquid, and after applying the adhesive to a substrate, drying and curing to form an adhesive layer, and the adhesive is dispersed on a surface portion of the adhesive layer. A method for manufacturing a wiring board, comprising dissolving and removing at least a part of fine powder to roughen the surface of an adhesive layer, and then performing electroless plating.

According to this known technique, the adhesive is prepared by dispersing a heat-resistant resin fine powder which has been cured in advance in a heat-resistant resin liquid. The adhesive layer is formed in a state where the heat-resistant resin fine powder is uniformly dispersed in the heat-resistant resin forming the above. Since the heat-resistant resin fine powder and the matrix heat-resistant resin have different solubility in an oxidizing agent, by treating the adhesive layer with an oxidizing agent, the fine powder dispersed in the surface portion of the adhesive layer is treated. Is mainly dissolved and removed, an effective anchor depression is formed, and the surface of the adhesive layer can be uniformly roughened. As a result, high adhesion strength and high reliability between the substrate and the electroless plating film can be obtained.

[0007]

By the way, this heat-resistant resin fine powder has excellent heat resistance and electrical insulation, is stable to ordinary chemicals, and has a heat resistance when cured in advance. It is required that the resin be insoluble in a resin or a solvent that dissolves the resin, and furthermore, it needs to be a resin having characteristics that can be dissolved by an oxidizing agent such as chromic acid. Seed resins were listed.

However, depending on the curing means of the resin, it has not always been possible to obtain a good heat-resistant resin fine powder having all of the above characteristics. 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 above-mentioned problems of the prior art. In particular, the present invention has found a component of a heat-resistant resin fine powder capable of easily forming a clear anchor, and has disclosed an electroless plating property of an adhesive. It is an object of the present invention to propose an adhesive excellent in applicability without impairing the above, a method of manufacturing a printed wiring board using the same, and a printed wiring board.

[0010]

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

That is, first, the adhesive of the present invention is obtained by curing a heat-resistant resin fine powder which has been cured and is soluble in an acid or an oxidizing agent. In an adhesive dispersed in an uncured heat-resistant resin matrix having the property of being hardly soluble in, using an epoxy resin cured with an amine-based curing agent as the heat-resistant resin fine powder, An adhesive for a wiring board, wherein an epoxy resin cured with an imidazole-based curing agent is used as a resin matrix. This matrix may be halogenated for non-combustible treatment.

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

Second, a cured heat-resistant resin fine powder that is soluble in an acid or an oxidizing agent is hardly soluble in an acid or an oxide when cured. In an adhesive dispersed in an uncured heat-resistant resin matrix having an epoxy resin cured with an amine-based curing agent as the heat-resistant resin fine powder, an epoxy resin and an acrylic group are used as the heat-resistant resin matrix. An adhesive for a wiring board, characterized by using at least one selected from a resin and an acrylic resin. This matrix may be halogenated for non-combustible treatment.

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

The above-mentioned adhesive has a viscosity of 5.1 ± 2.0 Pa · s at a rotation speed of 6 rpm, more preferably 5.1 ± 0.7 Pa · s, when the viscosity of the adhesive is measured by a rotational viscometer.
s, 2.4 ± 1.0 Pa · s at 60 rpm, more preferably 2.4 ± 0.3 Pa · s, and the ratio of the viscosity at 6 rpm to the viscosity at 60 rpm is 2.1 ± 1.0, more preferably 2.1 ± 1.0. The solid content of the 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.

In the method for producing a printed wiring board of the present invention using the above-mentioned adhesive, the above-mentioned adhesive is applied onto a substrate by a roll coater, curtain coater, screen printing, spray coater or the like, and then dried and cured. Forming a layer, roughening the surface of the adhesive layer by dissolving and removing at least a part of the thermosetting fine powder dispersed in the surface portion of the adhesive layer, and thereafter performing electroless plating. This is a method based on an additive process.

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

[0018]

The inventors of the present invention conducted various studies on the curing agent of the resin for the heat-resistant resin fine powder and found that an epoxy resin cured with an amine-based curing agent was suitable as the heat-resistant resin fine powder. It is. The reason why the epoxy resin cured with the amine-based curing agent is suitable will be described 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 has particularly high solubility in an acid or an oxidizing agent. This is because the use of an amine-based curing agent makes it possible to obtain a resin fine powder that is easily soluble in an oxidizing agent and has high heat resistance. For example, the following structure can be considered as such a segment.

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 a heat-resistant resin fine powder. It is possible to obtain an adhesive satisfying all conditions of film thickness and peel strength.

The amount of the heat-resistant resin fine powder 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 is not clearly formed. On the other hand, if the 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 average particle size of the heat-resistant resin fine powder is preferably 10 μm or less, more preferably 5 μm or less.
It is preferred that: 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 becomes small and tends to be non-uniform, so that the adhesion strength and its reliability are reduced. In addition, the irregularities on the surface of the adhesive layer become severe, so that it is difficult to obtain a fine pattern of the conductor, and it is not preferable for mounting components and the like.

Examples of such heat-resistant resin fine powder include agglomerated particles obtained by aggregating heat-resistant resin powder having an average particle diameter of 2 μm or less to have an average particle diameter of 2 to 10 μm, and an average particle diameter of 2 to 10 μm. Particle mixture of a heat-resistant resin powder having a mean particle size of 2 μm or less, or an average particle size of 2
It is desirable to select from pseudo particles obtained by adhering at least one of a heat-resistant resin powder having an average particle diameter of 2 μm or less or an inorganic fine powder to the surface of a heat-resistant resin powder of 10 μm or less.

Here, the matrix heat-resistant resin used in the present invention is excellent in heat resistance, electric insulation, chemical stability and adhesiveness, and becomes hardly soluble in an oxidizing agent by curing treatment. Any resin can be used as long as it has characteristics. In particular, the heat-resistant resin matrix in which the resin fine powder is dispersed is at least one selected from polyfunctional epoxy resins, resins having an acrylic group, and acrylic resins. Resin, or the above,
At least one selected from the group consisting of epoxy resins and acrylic resins;
Desirably, it is made of a resin mixed with a seed.

The heat resistant resin in the matrix is
A solid content of 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% by weight and a bifunctionality of 0 to 80% by weight;
It is preferable to use a mixed resin with at least one selected from an epoxy resin and an acrylic resin. The reason 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 decreases.

As the curing agent for the matrix resin, DICY, amine curing agents, acid anhydrides and imidazole curing agents are preferable. Particularly, in the case of an epoxy resin, 2 to 10% by weight based on the total solid content of the matrix.
It is preferable to include an imidazole-based curing agent.
The reason is that if it exceeds 10 wt%, it will be too hard and brittle,
If the content is less than 2% by weight, the curing is insufficient.

The cured bifunctional epoxy resin fine powder is dispersed in at least one heat-resistant resin matrix selected from an uncured polyfunctional epoxy resin and a bifunctional epoxy resin. The mixture is desirably stored separately from the imidazole-based curing agent, and the two 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. As a result, the fine powder can be uniformly dispersed, and can be advantageously used because it can be easily applied to a substrate. The solvent used to dissolve the heat-resistant resin is usually a solvent such as methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, or the like.
Butyl carbitol, butyl cellulose, tetralin,
Examples include dimethylformamide and normal methylpyrrolidone. Further, an organic filler such as a fluorine resin, a polyimide resin, or a benzoguanamine resin, or a filler composed of an inorganic fine powder such as silica, alumina, titanium oxide, or zirconia may be appropriately added to the matrix heat-resistant resin. . In addition, additives such as a coloring agent (pigment), a leveling agent, an antifoaming agent, an ultraviolet absorber, and a flame retardant 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 is a method wherein the adhesive obtained by dispersing a heat-resistant resin fine powder in a heat-resistant resin serving as a matrix on a substrate is applied by a roll coater or the like, and dried and cured to form an adhesive layer. To form The thickness of the adhesive layer is usually about 2 to 40 μm. However, when the adhesive layer is used also as an interlayer insulating layer of a metal substrate or a multilayer wiring board, it can be applied more thickly.

In this application, when the heat-resistant resin matrix is 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 0.6.
Preferably it is 3.0 m / min. The reason is that if the gap is wider than 0.6 mm, the coating film tends to be uneven,
If the thickness is smaller, it is difficult to obtain an appropriate film thickness. On the other hand, if the conveying speed is lower than 0.1 mm / min, mass productivity is lacking, and if the conveying speed is higher than 3.0 mm / min, the film thickness becomes non-uniform. On the other hand, the same applies to the case where 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 and the like can be used, and specifically, a glass epoxy substrate, a glass polyimide substrate,
Alumina substrates, low-temperature fired ceramic substrates, aluminum nitride substrates, aluminum substrates, iron substrates, polyimide film substrates, and the like can be used. By 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 can be formed into a plate-like or film-like prepreg to provide an adhesive base that can be subjected to electroless plating.

Next, at least a part of the heat-resistant resin fine powder dispersed on the surface of the adhesive layer is dissolved and removed using an acid or an oxidizing agent. As this method, it is possible to use a solution of the acid or the oxidizing agent, and immerse the substrate on which the adhesive layer is formed in the solution, or to spray the acid or the oxidizing agent solution on the substrate. As a result, the surface of the adhesive layer can be roughened. For the purpose of effectively dissolving and removing the heat-resistant resin fine powder filler, the surface portion of the adhesive layer is lightly roughened in advance by, for example, polishing with a fine abrasive or liquid honing. Is extremely effective.

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

After that, 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. It is preferable that at least one of electroless gold plating is used. It should be noted that, after the electroless plating is performed, a different type of electroless plating or electroplating may be performed, or solder may be coated.

The wiring board obtained by the method of the present invention as described above can be used to form a conductor circuit by any of various methods used for known printed wiring boards. And a method of directly forming a circuit when performing 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 FIGS. 1 (f) and 3 (f), a single-sided printed circuit board is formed by forming a plating resist 3 and a conductive circuit 4 on a substrate 1 with an adhesive layer 2 interposed therebetween. Printed wiring board, Figure 2
(f), a double-sided printed wiring board formed by forming a plating resist 3 and a conductive circuit 4 through an adhesive layer 2 and a through hole 5 on both surfaces of a substrate 1 as shown in FIG.
As shown in FIG. 10, on the substrate 1 'on which the first conductor layer 4 is formed, an interlayer insulating layer having a via hole 7 (adhesive layer)
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 adhesive is a cured heat-resistant resin fine powder that is soluble in an acid or an oxidizing agent, and an acid or an oxide when cured. Dispersed in an uncured heat-resistant resin matrix having the property of becoming hardly soluble, characterized in that an epoxy resin cured with an amine-based curing agent is used as the heat-resistant resin fine powder, The functional resin matrix is a polyfunctional epoxy resin, at least one resin selected from an epoxy resin, a resin having an acrylic group, and an acrylic resin, or a bifunctional epoxy resin having at least one selected from the above resins And a resin mixture with at least one selected from acrylic resins. In the case of an epoxy resin, it is advantageous to cure with an imidazole-based curing agent.

[0038]

EXAMPLES (Example 1) (1) Bisphenol A type epoxy resin (made by Yuka Shell)
100 parts by weight were diluted with MEK, and a chain-chain aliphatic polyamine (diethylenetriamine; manufactured by Sumitomo Chemical) was added as a curing agent in 8 parts.
After mixing by weight, the mixture was dried and cured at 100 ° C. for 2 hours. The cured epoxy resin is roughly pulverized, and then finely pulverized using a supersonic jet pulverizer (manufactured by Nippon Pneumatic) while being frozen with liquid nitrogen, and further subjected to a wind classifier (manufactured by Nippon Donaldson). Use and classify the average particle size
An epoxy resin fine powder of 1.7 μm was obtained. (2) Dissolve 60 parts by weight of phenol novolak type epoxy resin (manufactured by Yuka Shell), 40 parts by weight of bisphenol A type epoxy resin (manufactured by Yuka Shell) and 5 parts by weight of imidazole-based curing agent (manufactured 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 kneaded with three rolls, and butyl cellosolve acetate was added. An adhesive solution having a concentration of 75% was prepared. The viscosity of this solution was measured using a digital viscometer manufactured by Tokyo Keiki Co., Ltd. at 20 ° C. for 60 seconds in accordance with JIS-K7117. The viscosity was 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.
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. At this time, the coating method uses a resist coating roll for medium and high viscosity resist (manufactured by Dainippon Screen) as the coating roll, the gap between the coating roller and the doctor bar is 0.4 mm, and the gap between the coating roller and the backup roller is 1.4 mm. And the transport speed was 400 mm / s. Then, after standing for 20 minutes in a horizontal state, the adhesive layer 2 was dried at 70 ° C. to form an adhesive layer 2 having a thickness of about 50 μm (see FIGS. 1B and 1C). (4) 500 g / l of chromic acid (CrO ₃ )
The surface of the adhesive layer was roughened by immersion in an oxidizing agent composed of an aqueous solution at 70 ° C. for 15 minutes, and then neutralized with a neutralizing solution (PN, manufactured by Shipley Co., Ltd.).
−950) and washed with water. The surface of the adhesive layer 2 was activated by applying a palladium catalyst (manufactured by Shipley) to the substrate 1 with the roughened adhesive (see FIG. 1 (d)). (5) The substrate 1 is placed in a nitrogen gas atmosphere (10 ppm oxygen) for 12 hours.
A heat treatment for immobilizing the catalyst is performed at 0 ° C. for 30 minutes. Then, a photosensitive dry film is laminated, exposed, developed with modified chlorocene, and plated resist 3 (40 μm thick)
Was formed (see FIG. 1 (e)). (6) The substrate 1 on which the plating resist 3 has been formed is placed in Table 1
The plating film 4 was immersed in an electroless copper plating solution having the composition shown in Table 1 for 11 hours, and subjected to electroless copper plating with 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 (manufactured by Yuka Shell)
100 parts by weight were diluted with MEK, and a cycloaliphatic polyamine (mansendiamine Rohm and Hase) was added as a curing agent to 20 parts by weight.
After mixing 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 pulverized, and then finely pulverized using a supersonic jet pulverizer (manufactured by Nippon Pneumatic) while being frozen with liquid nitrogen.
Classification was further performed using an air 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 orthocresol novolak type epoxy resin (manufactured by Yuka Shell) and 5 parts by weight of a curing agent (manufactured by Shikoku Chemicals) 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, then kneaded with three rolls, and further added with butyl cellosolve acetate to obtain a solid content of 70%. Was obtained. 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. 2B and 2C). (4) Next, the substrate 1 of (3) is drilled with a drill,
After polishing the substrate surface to expose the filler, 6
The surface of the adhesive layer 2 is roughened by dipping in an acid composed of an N hydrochloric acid aqueous solution at 70 ° C. for 15 minutes, and then a neutralizing solution (manufactured by Shipley)
And washed with water. Then, the surface of the adhesive layer 2 was activated by applying a palladium catalyst (manufactured by Shipley Co., Ltd.) to the substrate 1 on which the adhesive was roughened (see FIGS. 2 (d) and 2 (e)). (5) The substrate 1 is placed in a nitrogen gas atmosphere (10 ppm oxygen) for 12 hours.
A heat treatment for immobilizing the catalyst is performed at 0 ° C. for 30 minutes. Then, a photosensitive dry film is laminated, exposed, developed with modified chlorocene, and plated resist 3 (40 μm thick)
Was formed (see FIG. 2 (f)). (6) The substrate 1 on which the plating resist 3 has been formed is placed in Table 1
11 hours in an electroless copper plating solution having the composition shown in (1), electroless copper plating with a thickness of 30 μm of the plating film 4 was performed on both surfaces to form conductor circuits and through holes, and a double-sided printed wiring board was obtained ( FIG. 2 (f)).

Example 3 (1) 100 parts by weight of a phenol novolak type epoxy resin (manufactured by Yuka Shell) was diluted with MEK, and 15 parts of a fatty aromatic amine (m-xylene diamine; manufactured by Showa Denko) was used as a curing agent.
After mixing by weight, the mixture was dried and cured at 120 ° C. for 3 hours. The cured epoxy resin is roughly pulverized, and then finely pulverized using a supersonic jet pulverizer (manufactured by Nippon Pneumatic) while being frozen with liquid nitrogen, and further subjected to a wind classifier (manufactured by Nippon Donaldson). Classify using, average particle size 1.
An epoxy resin fine powder of 8 μm was obtained. (2) Special functional epoxy resin (made by Yuka Shell) 80 parts by weight, bisphenol A type epoxy resin (made by Yuka Shell)
20 parts by weight and 7 parts by weight of a curing agent (manufactured by Shikoku Chemicals) are dissolved in xylene, and the epoxy resin fine powder prepared in the above (1) is added to 100 parts by weight of the solid content of the composition.
After mixing at a ratio of 50 parts by weight, the mixture was kneaded with a three-roll mill, and butyl cellosolve acetate was added.
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 were diluted with MEK, and 15 parts by weight of an aromatic amine (m-xylene diamine; manufactured by Sumitomo Chemical Co., Ltd.) was added as a curing agent, followed by drying and curing at 80 ° C. for 2 hours. The cured epoxy resin is roughly pulverized, and then finely pulverized using a supersonic jet pulverizer (manufactured by Nippon Pneumatic) while being frozen with liquid nitrogen, and further subjected to a wind classifier (manufactured by Nippon Donaldson). And classified to obtain a fine epoxy resin powder having an average particle size of 1.8 μm. (2) 50 parts by weight of phenol aralkyl type epoxy resin (manufactured by Yuka Shell), 50 parts by weight of novolak type polyfunctional epoxy resin (manufactured by Yuka Shell) and 5 parts by weight of a curing agent (manufactured by Shikoku Kasei) were added to butyl cellosolve acetate. Dissolved, based on 100 parts by weight of the solid content of the composition, (1)
The epoxy resin fine powder obtained in the above was mixed at a ratio of 50 parts by weight, kneaded with three rolls, and butyl cellosolve acetate was added to obtain an adhesive solution having a solid content of 80%.
The viscosity of this solution was 5.8 Pa · s at 60 rpm and 60 rpm.
Was 2.0 Pa · s, and its SVI value (thixotropic property) was 2.2. (3) Using a roll coater (manufactured by Dainippon Screen), apply the adhesive solution prepared in the above (2) to a polyethylene film on which a release agent such as silicon has been applied in advance, and apply 70 ° C.
For 1 hour to prepare a film adhesive. (4) The film-like adhesive prepared in the above (3) was applied to a glass polyimide substrate 1 (manufactured by Toshiba Chemical Co., Ltd.) to which copper foil was not adhered, with the surface on which the adhesive was applied facing the substrate,
The adhesive layer 2 was formed by pressing at 0 ° C. and 40 kg / cm ² for 200 minutes. (5) The substrate 1 obtained in the above (4) is added to the substrates 1 of the first embodiment.
A printed wiring board was prepared by performing the above steps.

Example 5 (1) Epoxy resin particles obtained by dispersing 200 g of epoxy resin particles (average particle size: 3.9 μm) prepared in the same manner as (1) of Example 1 in 5 l of acetone While stirring the suspension in a Henschel mixer (manufactured by Mitsui Miike Kakoki), an epoxy resin (manufactured by Mitsui Petrochemical) was added to 1 liter of acetone.
Example 1 was dissolved in an acetone solution dissolved at a rate of 30 g.
After dropping a suspension in which 300 g of epoxy resin particles (average particle size 0.5 μm) prepared in the same manner as (1) was dispersed, the epoxy resin powder was adhered to the surface of the epoxy resin particles, The acetone is removed and then 15
Heating to 0 ° C. produced pseudo particles. The pseudo particles had an average particle size of about 4.3 μm, and about 75% by weight was in a range of ± 2 μm around the average particle size. (2) 50 parts by weight of the pseudo particles prepared in the above (1), 60 parts by weight of a phenol novolak type epoxy resin (manufactured by Yuka Shell),
To a mixture of 40 parts by weight of a bisphenol A type epoxy resin (manufactured by Yuka Shell) and 5 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals), butyl carbitol was added, and the mixture was adjusted with a homodisper disperser. Was prepared. The viscosity of this solution was 5.8 Pa · s at 6 rpm.
, 60 Pa · s at 60 rpm, and its SVI value (thixotropic property) was 2.2. (3) A printed wiring board was prepared in the same manner as in Example 1 using this adhesive (see FIG. 3).

Example 6 (1) Epoxy resin particles (average particle size: 3.9 μm) prepared in the same manner as in (1) of Example 1 were charged into a hot-air dryer, and were heated at 180 ° C. for 3 hours. Heat treatment was performed to cause cohesion. The cohesively bonded epoxy resin particles were dispersed in acetone, crushed in a ball mill for 5 hours, and then classified using an air classifier to prepare coagulated particles. The aggregated particles had an average particle size of about 3.5 μm, and about 68% by weight existed in a range of ± 2 μm around the average particle size. (2) 50 parts by weight of the aggregated particles prepared in the above (1), 60 parts by weight of a phenol novolak type epoxy resin (manufactured by Yuka Shell),
To a mixture of 40 parts by weight of a bisphenol A type epoxy resin (manufactured by Yuka Shell) and 4 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals), butyl carbitol was added, and the mixture was adjusted with a homodisper disperser. Was prepared. The viscosity of this solution was 5.8 Pa · s at 6 rpm.
, 60 Pa · s at 60 rpm, and its SVI value (thixotropic property) was 2.2. (3) A printed wiring board was prepared using this adhesive in the same manner as in Example 2 (see FIG. 4).

(Example 7) (1) A photosensitive dry film (manufactured by DuPont) is laminated on a glass epoxy copper-clad laminate (manufactured by Toshiba Chemical), and is exposed to ultraviolet light through a mask film on which a desired conductive circuit pattern is drawn. Burn the image. Then, 1,
After developing with 1,1-trichloroethane and removing 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. 5A). (2) 100 parts by weight of a 50% acrylate of a 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, imidazole-based curing agent (manufactured by Shikoku Chemicals) 4 parts by weight and the same as in Example 1. Average particle size of 3.9 μm and average particle size of 0.
Butyl carbitol was added to a mixture consisting of 10 parts by weight and 25 parts by weight of each of two types of epoxy resin particles of 5 μm, and the mixture was prepared with a homodisper disperser. Was prepared. The viscosity of this solution is 6.5 Pa · s at 60 rpm, 60
The rpm was 2.9 Pa · s, and its SVI value (thixotropic property) was 2.2. (3) The solution of the photosensitive resin composition prepared in the above (2) is applied on the wiring board 1 'prepared in the above (1) using a roll coater, and left in a horizontal state for 20 minutes. 5 to form a photosensitive resin insulating layer 2 'having a thickness of about 50 .mu.m.
(b)). (4) A photomask film on which a black circle having a diameter of 100 μm was printed was brought into close contact with the wiring board 1 ′ that had been subjected to the treatment of (3), and was exposed at 500 mj / cm ² using an ultrahigh pressure mercury lamp. This is
An opening 7 serving as a 100 μmφ via hole was formed on the wiring board 1 ′ by ultrasonic development with 1,1-trichloroethane. The wiring board 1 'is exposed at about 3000 mj / cm ² by an ultra-high pressure mercury lamp, and further exposed at 100 ° C. for 1 hour.
By performing a heat treatment at 150 ° C. for 10 hours, an interlayer insulating layer 2 ′ having an opening 7 having excellent dimensional accuracy corresponding to a photomask film was formed (see FIG. 5C). (5) The wiring board 1 prepared in (4) is replaced with chromic acid (CrO
₃ ) The surface of the interlayer insulating layer 2 'is roughened by immersion in an oxidizing agent composed of a 500 g / l aqueous solution at 70 ° C for 15 minutes, then immersed in a neutralizing solution (manufactured by Shipley Co., Ltd.), washed with water, and then constantly washed. Through holes 5 were formed by the method. Then, the interlayer insulating layer 2 '
Palladium catalyst (made by Prey) on the roughened substrate 1 '
Was applied to activate the surface of the insulating layer, and heat treatment was performed for fixing the palladium catalyst 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 developed (see FIG. 5 (e)). (7) Immersion 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 having a thickness of 25 μm,
A multilayer printed wiring board was prepared (see FIG. 5 (f)).

(Comparative Example 1) A printed wiring board was prepared in the same manner as in Example 1, except that an epoxy resin cured with a dicyanic curing agent was used as a heat-resistant resin fine powder.

The adhesion strength between the substrate of the printed wiring board obtained in Examples 1 to 7 and Comparative Example 1 and the copper plating film was measured according to JIS-C-6481.
As a result, the peel strength was as shown in Table 2. As is clear from Table 2, the epoxy resin cured with the dicyan curing agent used in the comparative example has low solubility in acids and oxidizing agents. Showed a lower peel strength as compared with.

[0048]

[Table 2]

(Embodiment 8) (1) In the same manner as in Embodiment 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 (FIG. 6 ( 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 novolak type epoxy resin (manufactured by Yuka Shell), 40 parts by weight of bisphenol A type epoxy resin (manufactured by Yuka Shell, Epicoat 1001), 15 parts by weight of diallyl terephthalate, 2-methyl -1-
4 parts by weight of [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba-Geigy), 4 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals), and the fine epoxy resin obtained in the above (2) After mixing 50 parts by weight of the powder, the mixture was prepared with a homodisper disperser while adding butyl cellosolve, and then kneaded with three rollers to prepare a photosensitive adhesive solution having a solid 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 Examples 7 (3) to (7), a build-up multilayer wiring board having four wiring layers (4, 6, 8, 10) was produced (see FIG. 6).

(Embodiment 9) (1) In the same manner as in Embodiment 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 (FIG. 7 ( a)). (2) Bisphenol F type epoxy resin (made by Yuka Shell)
110 parts by weight were diluted with MEK, and 5 parts by weight of a cycloaliphatic polyamine (mensendiamine; manufactured by Sumitomo Chemical Co., Ltd.) was added as a curing agent, followed by drying and curing at 120 ° C. for 3 hours. The cured epoxy resin is coarsely crushed and finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Industries) while being frozen with liquid nitrogen, and then an air classifier (manufactured by Nippon Donaldson) is used. And classify it into an average particle size of 3.9 μm.
An epoxy resin fine powder of 5 μm was obtained. (3) Resin particles (average particle size 3.9 μm) prepared by the method of (2)
m) 200 g of an epoxy resin particle suspension dispersed in 5 l of acetone, and an acetone solution in which a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) was dissolved at a ratio of 30 g,
Resin particles prepared as in (1) (average particle size 0.5 μm) 3
After dropping the suspension in which 00 g was dispersed, the epoxy resin powder was adhered to the surface of the epoxy resin particles, the acetone was removed, and then heated to 150 ° C.
A pseudo particle was created. These pseudo particles have an average particle size of about 4.
3 μm, and about 75% by weight is ±
It was in the range of 2 μm. (4) 50% by weight of 75% acrylate of cresol novolak type epoxy resin (Nippon Kayaku), 50 parts by weight of bisphenol A type epoxy resin (Dow Chemical), 25 parts by weight of dipentaerythritol hexaacrylate, benzyl acryl ketal After mixing 5 parts by weight (manufactured by Ciba-Geigy), 6 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals) and 50 parts by weight of the epoxy resin fine powder prepared in the above (2), a homodisper stirrer is added while adding butyl cellosolve. And then knead with three rollers to obtain a solid content
A 70% photosensitive adhesive solution was made. 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) The solution of the photosensitive resin composition prepared in the above (4) is applied on the wiring board 1 'prepared in the above (1) using a roll coater and left in a horizontal state for 20 minutes. It was dried to form a photosensitive resin layer 2 'having a thickness of about 45 .mu.m. (6) Example 7 A build-up multilayer wiring board having four wiring layers (4, 6, 8, and 10) was prepared in the same manner as in (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 (FIG. 8 ( a)). (2) Glycidylamine type epoxy resin (made by Yuka Shell)
110 parts by weight were diluted with MEK, and 5 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 120 ° C. for 3 hours. The cured epoxy resin is coarsely crushed and finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Industries) while being frozen with liquid nitrogen, and then an air classifier (manufactured by Nippon Donaldson) is used. And classified to obtain an epoxy resin fine powder having an average particle size of 3.9 μm. (3) The resin particles (average particle size of 3.
9 μm) was placed in a hot-air drier and subjected to heat treatment at 180 ° C. for 3 hours for cohesive bonding. The cohesively bonded epoxy resin particles are dispersed in acetone, and are dispersed in a ball mill.
After pulverizing for an hour, the particles were classified using an air classifier to produce aggregated particles. The aggregated particles have an average particle size of about 3.5 μm
And about 68% by weight is ± 2 μm around the average particle size.
Existed in the range. (4) 40 parts by weight of a 50% acrylate of cresol novolak type epoxy resin (manufactured by Nippon Kayaku), 60 parts by weight of bisphenol A type epoxy resin (manufactured by Yuka Shell), 15 parts by weight of diacryl terephthalate, 2-hydroxy-1 After mixing 30 parts by weight of 3,3-bis (hydrazinocarboethyl) -5-isopropylhydontoin (manufactured by Ajinomoto) and 60 parts by weight of the epoxy resin fine powder prepared in the above (3), homogenization was conducted while adding butyl cellosolve. The mixture was stirred by a disper stirrer and kneaded with three rollers to prepare a photosensitive adhesive solution having a solid content of 60%. (5) The solution of the photosensitive resin composition prepared in the above (4) is applied on the wiring board 1 'prepared in the above (1) using a roll coater and left in a horizontal state for 20 minutes. It was dried to form a photosensitive resin layer 2 'having a thickness of about 45 .mu.m. (6) Example 7 In the same manner as in (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 composed of a plurality of conductor patterns was formed on a glass epoxy copper clad laminate (FIG. 9 ( a) and (b)). (2) Glycidylamine type epoxy resin (made by Yuka Shell)
110 parts by weight were diluted with MEK, and 5 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 120 ° C. for 3 hours. The cured epoxy resin is coarsely crushed and finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Industries) while being frozen with liquid nitrogen, and then an air classifier (manufactured by Nippon Donaldson) is used. And classified, average particle size 3.9 μm, 0.5
A μm epoxy resin fine powder 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, an imidazole-based curing agent (manufactured by Shikoku Chemicals) 4 parts by weight and the aforementioned
After mixing 10 parts by weight and 25 parts by weight of the two types of epoxy resin fine powder having an average particle size of 3.9 μm and 0.5 μm obtained in (2), respectively, the mixture is prepared with a homodisper disperser while adding butyl carbitol. 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 was 5.8 Pa · s at 6 rpm and 2.60 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 (1), and heated and dried at 120 ° C. for 30 minutes. Further, a photomask film on which a black circle having a diameter of 100 μm was printed was brought into close contact with the substrate 1 ′, and the substrate 1 ′ was exposed to light at 500 mj / cm ² using an ultrahigh pressure mercury lamp. This was subjected to ultrasonic development with 1,1,1-trichloroethane to form an opening 7 serving as a 100 μmφ via hole on the wiring board. The above-mentioned wiring board is exposed at about 3000 mj / cm ² by an ultra-high pressure mercury lamp, and is further subjected to a heat treatment at 100 ° C. for 1 hour and then at 150 ° C. for 10 hours.
(See FIGS. 9 (c) and 9 (d)). (5) The solution of the photosensitive resin composition prepared in (3) is applied on the wiring board 1 'prepared in (1) using a roll coater and left in a horizontal state for 20 minutes. It was dried to form a photosensitive resin layer 2 'having a thickness of about 50 μm. Then,
By the same process as (4) (however, the diameter of the black circle is 85 μm)
Via hole openings 7 were formed (see FIGS. 9 (e) and 9 (f)). (6) The wiring board 1 'prepared in (5) 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 neutralized with a neutralizing solution (manufactured by Shipley Co., Ltd.). ) And washed with water. The surface of the insulating layer 2 'is activated by applying a palladium catalyst (manufactured by Shipley Co., Ltd.) to the substrate 1' having the interlayer insulating layer 2 'roughened, and heating for fixing the palladium catalyst at 120 ° C. for 30 minutes. Treatment, and then immersed 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) The steps (4) to (6) were repeated twice to produce a build-up multilayer wiring board having four wiring layers (see FIG. 9).

Example 12 (1) Glycidylamine type epoxy resin (manufactured by Yuka Shell)
110 parts by weight were diluted with MEK, and 5 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 120 ° C. for 3 hours. The cured epoxy resin is coarsely crushed and finely crushed using a supersonic jet crusher (manufactured by Nippon Pneumatic Industries) while being frozen with liquid nitrogen, and then an air classifier (manufactured by Nippon Donaldson) is used. And classified, average particle size 3.9 μm, 0.5
A μm epoxy resin fine powder was obtained. (2) 100 parts by weight of a 50% acrylate of a 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, an imidazole-based curing agent (manufactured by Shikoku Chemicals) 4 parts by weight and the aforementioned
After mixing 10 parts by weight and 25 parts by weight of the two types of epoxy resin fine powder having an average particle size of 3.9 μm and 0.5 μm obtained in (2), respectively, the mixture is prepared with a homodisper disperser while adding butyl carbitol. 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 was 5.8 Pa · s at 6 rpm and 2.60 at 60 rpm.
5 Pa · s and its SVI value (thixotropic property)
Was 2.1. (3) Next, the adhesive solution prepared in the above (3) is entirely coated with a roll coater 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. After coating at 100 ° C for 1 hour,
After drying and curing for an hour, an insulating layer 2 'was formed (FIGS. 5A and 5B).
reference). (4) A photomask film on which a black circle of 100 μmφ is printed is brought into close contact with the substrate 1 ′, and the photomask film is 500 m long using an ultra-high pressure mercury lamp.
Exposure was at j / cm ² . This is subjected to ultrasonic development with 1,1,1-trichloroethane, so that 100
An opening 7 serving as a μmφ via hole was formed. The wiring board 1 'is exposed to light of about 3000 mj / cm ² by an ultra-high pressure mercury lamp, and is further subjected to heat treatment at 100 ° C. for 1 hour and then at 150 ° C. for 10 hours. Was formed (see FIG. 5 (c)). (5) Next, the resin surface was immersed in sulfuric acid for 10 minutes to roughen the surface, neutralized and washed with water (see FIG. 5 (d)). (6) Through-hole 5 was prepared by an ordinary method. (7) A palladium catalyst (manufactured by Shipley Co., Ltd.) 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 developed (see FIG. 5 (e)). (9) Immersion 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 having a thickness of 25 μm,
A multilayer printed wiring board was prepared (see FIG. 5 (f)).

Example 13 (1) The same treatment as (1) and (2) in Example 1 was performed to obtain an adhesive solution A. However, an imidazole-based curing agent (manufactured by Shikoku Chemicals) was not mixed. (2) An adhesive solution B was obtained by mixing 5 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals) with an appropriate amount of butyl cellosolve acetate. (3) The adhesive solution A and the 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) The same treatment as in Example 1 was performed using this adhesive,
A printed wiring board was manufactured. The adhesive solutions A and B are
Long-term storage is possible.

Example 14 (1) This example is basically the same as Example 1, except that 100 parts by weight of a special polyfunctional epoxy resin (manufactured by Yuka Shell) and an imidazole-based curing agent (Shikoku) 5 parts by weight) were dissolved in butyl cellosolve acetate, and the solid content of this composition was 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, and then kneaded with three rolls, and butyl cellosolve acetate was added to prepare an adhesive solution having a solid content of 75% by weight. 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% by weight of 70% acrylate of ortho-cresol type epoxy resin (manufactured by Nippon Kayaku), diallyl terephthalate 15 parts by weight, 2 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba-Geigy), 2 parts by weight of imidazole-based curing agent (manufactured by Shikoku Chemicals) 5 parts by weight of an initiator (manufactured by Ciba-Geigy) and of Example 8
After mixing 50 parts by weight of the epoxy resin fine powder obtained in (2), the mixture is prepared with a homodisper disperser while adding butyl cellosolve, and then kneaded with three rollers to obtain a photosensitive adhesive having a solid concentration 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.
The 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, except that an epoxy resin cured with a dicyanic curing agent was used as a heat-resistant resin fine powder to produce a printed wiring board.

The adhesion strength between the substrate of the printed wiring board obtained in Examples 8 to 12 and Comparative Example 2 and the copper plating film was measured according to JIS-C-6481.
As a result, the peel strength was as shown in Table 3. As is clear from Table 3, the epoxy resin cured with the dicyan curing agent used in the comparative example has low solubility in acids and oxidizing agents. Showed a lower peel strength as compared with. Furthermore, it was found that the adhesive of the present invention has a large fracture toughness value and is excellent in drill workability and punching workability.

[0059]

[Table 3]

[0060]

As described above, according to the wiring board adhesive of the present invention and the method of manufacturing a wiring board using this adhesive, the adhesive has good electroless plating properties, heat resistance, electrical properties, An adhesive for a wiring board which is extremely excellent in adhesion, workability and applicability between a substrate and an electroless plating film and a printed wiring board using this adhesive can be easily obtained.

[Brief description of the drawings]

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

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

FIG. 3 is another manufacturing process drawing showing one embodiment of the printed wiring board of the present invention.

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

FIG. 5 is another manufacturing process drawing showing one embodiment of the printed wiring board of the present invention.

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

FIG. 7 is another manufacturing process drawing showing one embodiment of the printed wiring board of the present invention.

FIG. 8 is another manufacturing process drawing showing one embodiment of the printed wiring board of the present invention.

FIG. 9 is another manufacturing process diagram showing one embodiment of the printed wiring board of 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 hole 7 via hole opening

Claims (15)

(57) [Claims] 1. A cured heat-resistant resin fine powder which is soluble in an acid or an oxidizing agent, and which is hardly soluble in an acid or an oxide when cured. An adhesive for a wiring board, wherein an epoxy resin cured with an amine-based curing agent is used as heat-resistant resin fine powder in an adhesive dispersed in a cured heat-resistant resin matrix. 2. A cured heat-resistant resin fine powder which is soluble in an acid or an oxidizing agent, and which is hardly soluble in an acid or an oxide when cured. In an adhesive dispersed in a cured heat-resistant resin matrix, using an epoxy resin cured with an amine-based curing agent as the heat-resistant resin fine powder, and 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. A cured heat-resistant resin fine powder which is soluble in an acid or an oxidizing agent, and an uncured heat-resistant resin matrix having a property that a cured product is hardly soluble in an acid or an oxide. In the adhesive dispersed therein, an epoxy resin cured with an amine-based curing agent is used as the heat-resistant resin fine powder, and the heat-resistant resin matrix is selected from an epoxy resin, a resin having an acrylic group, and an acrylic resin. An adhesive for a wiring board, wherein at least one kind is used. 4. The viscosity of the adhesive measured by a rotational viscometer at a rotational speed of 6 rpm is 5.1 ± 2.0 Pa · s,
It shows 2.4 ± 1.0 Pa · s at a rotation speed of 60 rpm, and the ratio of the viscosity at a rotation speed of 6 rpm to the viscosity at a 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 according to claim 1, wherein the solid content is 20%.
100 wt% of a multifunctional epoxy resin and 0 to 80 wt% of a bifunctional epoxy resin, and the content of the bifunctional epoxy resin fine powder is 10 to 10 parts by weight based on 100 parts by weight of the total solid content of the matrix. The adhesive according to claim 5, wherein the amount is 100 parts by weight. 7. The cured bifunctional epoxy resin comprises a mixture of at least one resin selected from an uncured polyfunctional epoxy resin and a bifunctional epoxy resin, and an imidazole-based curing agent. The adhesive according to claim 2, which is dispersed in a matrix. 8. The matrix according to claim 1, wherein the matrix is a solid content,
A heat-resistant resin comprising 0 wt% of a multifunctional 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 to 100 based on 100 parts by weight of solid content of the matrix
The adhesive according to claim 7, which is in parts by weight. 9. The cured bifunctional epoxy resin may be an uncured polyfunctional epoxy resin, at least one resin selected from a polyfunctional acrylic group-containing resin and a polyfunctional acrylic resin, or 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 Claim 3 which is dispersed
The adhesive according to item 1. 10. The heat-resistant resin matrix comprises at least one selected from a polyfunctional epoxy resin having a solid content of 20 to 100% by weight, a resin having a polyfunctional acrylic group, and a polyfunctional acrylic resin. , A bifunctional epoxy resin of 0 to 80% by weight or less, and a bifunctional acrylic resin, and the content of the bifunctional epoxy resin fine powder is adjusted to 100 parts by weight of the total solid content of the matrix. The adhesive according to claim 9, wherein the adhesive is used in an amount of 10 to 100 parts by weight. 11. A heat-resistant resin fine powder in a matrix,
The solid content concentration of the uncured heat-resistant resin and curing agent is 55 to
The adhesive according to claim 1, which is 85 wt%. 12. A cured heat-resistant resin which is soluble in acid or oxidizing agent in a printed wiring board having an adhesive layer provided on at least one substrate surface and a conductive circuit formed thereon. The heat-resistant resin fine powder, as an adhesive dispersed in an uncured heat-resistant resin matrix having the property of being hardly soluble in an acid or oxide when subjected to a curing treatment, Wherein the resin is an epoxy resin cured with an amine-based curing agent. 13. The printed wiring board according to claim 12, wherein the heat-resistant resin matrix is an epoxy resin cured with an imidazole-based curing agent. 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. 15. An adhesive according to claim 1, which is applied on a substrate, and then dried and cured to form an adhesive layer, and then the surface of the adhesive layer is formed. The surface of the adhesive layer is roughened by dissolving and removing at least a part of the thermosetting fine powder dispersed in the part, and thereafter, electroless plating is performed on the roughened adhesive layer. Manufacturing method of a printed wiring board.