JP3298957B2 - Adhesive sheet for electroless plating, method for manufacturing printed wiring board using this adhesive sheet, 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 sheet and a method for manufacturing a printed wiring board using the adhesive sheet.
And an adhesive formed in a film shape suitable for electroless plating, which is excellent in chemical resistance, heat resistance, electrical characteristics and adhesion between the substrate and the electroless plating film (that is, Adhesive sheet), a method for manufacturing a printed wiring board using the adhesive sheet, and a printed wiring board.

[0002]

2. Description of the Related Art In recent years, with the advance of the electronics industry, downsizing or speeding up of electronic equipment has been promoted. For this reason, printed wiring boards and printed wiring boards on which LSIs are mounted have high densities and high densities by fine patterns. Reliability has come to be required.

Conventionally, as a method of forming a conductive circuit in manufacturing a printed wiring board, there is known an "etched foil method" in which a conductive circuit is formed by laminating a copper foil on a substrate and then performing photoetching. Have been. 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 were problems that the process was complicated and the efficiency was not good.

For this reason, recently, as a method of forming a conductor on a substrate for a printed wiring board, an adhesive containing a diene-based synthetic rubber is applied to the surface of the substrate to form an adhesive layer. A so-called “additive method” is used, in which a conductor is formed by roughening the surface and then performing electroless plating. However, since the adhesive generally used in this method contains synthetic rubber, it has low heat resistance, for example, the adhesive strength is greatly reduced at high temperatures, or the electroless plating film is swollen during soldering. And electrical characteristics such as surface resistance are not sufficient, and the range of use is considerably 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. An adhesive for electroless plating that can be implemented relatively easily and a method for manufacturing a wiring board using the adhesive have been proposed (see Japanese Patent Application Laid-Open No. 61-276875). That is, in this prior art, a pre-cured heat-resistant resin powder that is soluble in an oxidizing agent is hardly soluble in an oxidizing agent when cured. Adhesive characterized by being dispersed in,
And after applying the adhesive to the substrate, drying and curing to form an adhesive layer, and dissolving and removing at least a part of the fine powder dispersed on the surface portion of the adhesive layer to form an adhesive layer. A method for manufacturing a wiring board, comprising roughening the surface and then performing electroless plating.

According to this prior art, 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 heat-resistant resin fine powder is uniformly dispersed in the heat-resistant resin forming the matrix. And
Because 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 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, in the above-mentioned adhesive, general-purpose and easily available as a heat-resistant resin fine powder soluble in an acid or an oxidizing agent. Epoxy resin, which is a resin with excellent hardness, was adopted and used. However, in recent years, the density of printed circuit boards has rapidly increased, and when a printed wiring board manufactured using an epoxy resin as the heat-resistant resin fine powder is left in a place where the temperature and humidity are high,
Reaction (migration) as shown in the following formula
Further, other reactions were caused, and it was found that there was a problem that the conductor circuit was melted, the surface resistance was reduced, and the pattern was short-circuited. Na ⁺ + Cl ⁻ + H ₂ O → NaOH + HCl… Cu + 2NaOH → Cu (OH) ₂ + 2Na ⁺ ... Cu + 2HCl → CuCl ₂ + 2H ⁺ ...

Therefore, the inventors have previously developed an adhesive which has overcome the above-mentioned problems. However, since this undisclosed prior art prior to the present invention takes the form of coating on a substrate mainly in the production of a printed wiring board, in the production process, such as viscosity and thixotropic properties, etc. The application conditions must be controlled, and there is a problem that it is very complicated and the productivity is low.

An object of the present invention is to improve the productivity without impairing the electroless plating property of the adhesive in order to overcome the problems of the prior art in addition to the above-mentioned problems of the prior art. An object of the present invention is to propose an adhesive sheet which is effective in doing so, a method for manufacturing a printed wiring board using the same, and a printed wiring board using the same.

[0010]

Means for Solving the Problems The inventor of the present invention has previously studied on the above-mentioned problems, and found that an epoxy resin used as a heat-resistant resin fine powder soluble in an acid or an oxidizing agent is:
In order to use an ionic compound at the time of production, Na, chloride ions and the like remain in the resin, and since the molecular weight between crosslinking points of the epoxy resin is 1000 or more, the ions easily move in the resin. Therefore, it was found to cause the above-mentioned reaction. Accordingly, the present inventors have conducted intensive studies on such resins which are not ionic compounds. As a result, when an amino resin is used as a heat-resistant resin fine powder, the above-described reaction is not caused, and the chemical resistance, heat resistance, electric characteristics, hardness, etc. are excellent. It was newly discovered that an adhesive could be obtained.

Further, as a result of studying to overcome the above problem, the inventor applied an adhesive solution on a base film as an adhesive for a wiring board, and then removed a predetermined amount of a solvent. By employing an adhesive sheet having a film-like adhesive layer obtained by making it into a state, during the printed wiring board manufacturing process, there is no need to manage application conditions such as viscosity and thixotropy,
Therefore, it was also found that quality control such as film thickness uniformity and strength was easy and an excellent adhesive layer could be obtained, and the present invention was conceived.

That is, the adhesive sheet of the present invention is made of a pre-cured melamine soluble in an acid or an oxidizing agent.
Resin fine powder and / or urea resin fine powder are dispersed in an uncured thermosetting or photosensitive heat-resistant resin matrix that exhibits a property of being hardly soluble in acids or oxidizing agents when subjected to a curing treatment. Is an adhesive sheet formed on a base film.

The method for manufacturing a printed wiring board of the present invention is a method using the above-mentioned adhesive sheet, wherein an adhesive layer for electroless plating is formed on a substrate, and the surface of the adhesive layer is roughened. Thereafter, in a method of manufacturing a printed wiring board by forming a conductor circuit by performing electroless plating, on the substrate,
Menu was previously cured soluble in the acid or oxidizing agent
Based on an adhesive layer made by dispersing a fine lamin resin powder and / or a fine urea resin powder in an uncured heat-resistant resin matrix that has the property of becoming hardly soluble in acids or oxidizing agents when subjected to curing treatment. The adhesive sheet formed on the film is overlapped such that the adhesive layer of the adhesive sheet faces the substrate, and then, after heating under pressure, the base film is peeled off to form an adhesive layer. And a method of manufacturing a printed wiring board, which comprises performing electroless plating after roughening.

And, it is obtained under the manufacturing method as described above.
The printed wiring board of the present invention has at least one substrate surface.
Provide an adhesive layer on the surface and form a conductive circuit on it.
In the printed wiring board, the adhesive layer is cured.
AlreadyMelamine resin fine powder and / or urea resin fine powder
Hardly soluble in acid or oxidizing agent
Uncured heat-resistant resin matrix showing properties that make it resistant
The adhesive layer dispersed in the base
Adhesive sheet formed on film
Printed wiring board characterized by being formed by
It is.

[0015]

In the known adhesive, a phenomenon that the surface resistance value is reduced by the above-described migration reaction is observed. From this, the inventor previously performed a long-term deterioration test on various resins under the conditions of a temperature of 40 ° C., a humidity of 90%, and a voltage of 24 V, and examined the change over time in the resistance value. as a result,
Polyimide resins, epoxy resins, and the like are known as resins having excellent electrical properties. Among them, resins that are soluble in acids or oxidizing agents and do not cause a so-called migration reaction with no change in resistance over time. It has been found that melamine resin fine powder and / or urea resin fine powder are resins exhibiting the most excellent properties.

Further, the inventor of the present invention adopts an adhesive sheet having an adhesive layer in a B-stage state in which quality such as film thickness uniformity and strength is guaranteed as an adhesive for a wiring board. They found that the productivity of the printed wiring board could be improved without impairing the performance.

Therefore, according to the present invention, by using a melamine resin and / or a urea resin as a pre-cured heat-resistant resin fine powder which is soluble in an acid or an oxidizing agent, it can be used in a high temperature, high humidity environment. Even when used in an atmosphere, migration does not occur, the conductor circuit does not melt, and the surface resistance value does not decrease, and sufficient adhesion strength of the conductor can be obtained. Adhesives with excellent heat resistance, electrical properties, and hardness can be obtained. Furthermore, by using an adhesive sheet having a film-like adhesive layer, application conditions such as viscosity and thixotropy can be reduced. Without management, an adhesive layer satisfying all conditions such as film thickness and peel strength can be prepared in advance.

Melamine resin for forming such an anchor
Fine powder and / or urea resin fine powder are formed on a base film having excellent releasability so as to obtain a film-like adhesive layer.
50 μm is desirable. The reason is that, when the average particle size is larger than 50 μm, the anchor formed by dissolution and removal has a low density and tends to be non-uniform, so that the adhesion strength and its reliability are reduced. In addition, since the unevenness of the surface of the adhesive layer becomes severe, the film thickness becomes non-uniform, it is difficult to obtain a fine pattern of the conductor, and it is not preferable for mounting components and the like.

Such melamine resin fine powder or urea resin
The fine powder is, for example, an agglomerated particle obtained by aggregating a resin powder having an average particle size of 2 μm or less to an average particle size of 2 to 10 μm, a resin powder having an average particle size of 2 to 10 μm and an average particle size of 2 μm
Particle mixture with the following resin powder, or average particle size 2-10
It is desirable to select from pseudo particles obtained by adhering at least one of a resin powder having an average particle diameter of 2 μm or less and an inorganic fine powder on the surface of a resin powder of μm.

In addition, melamine resin fine powder and / or urine
The compounding amount of the fine resin powder is preferably in the range of 10 to 100 parts by weight based on 100 parts by weight of the total solid content of the resin matrix. 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 melamine resin and / or urea resin employed in the present invention as a heat-resistant resin fine powder is a resin having an amino group capable of reacting with formaldehyde, and is selected from melamine resin, urea resin and guanamine resin. One or more resins. The reason is that these resins have excellent heat resistance, high surface hardness, excellent mechanical strength, excellent electrical insulation, especially excellent arc resistance, good organic solvent resistance, acid or oxidizing agent. This is because the solubility is high.

Among these resins, melamine resin is an addition condensate of melamine and formaldehyde, and forms a white and water-insoluble resin when reacted with an acid, and is transparent and soluble in water when reacted with an alkali. Produce resin. That is, as shown in (Chemical Formula 1), a melamine resin is obtained by reacting melamine with formaldehyde under neutral or alkaline conditions to obtain methylol melamine. It is obtained by forming a bond and an ether bond to form a macromolecule.

Further, the melamine resin is generally used as a molding material in a molar ratio of formaldehyde to melamine in the range of about 1: 2 to 1: 3. Suitable for making. Therefore, melamine and formaldehyde in the above molar ratio range are kept neutral or slightly alkaline with ammonia or the like, and reacted at 80 to 90 ° C., and the resulting syrup is rayon, pulp cloth strip, asbestos, A base material such as fiber is added, dried and crushed, and a pigment, a release agent, a curing agent and the like are added and finely crushed to obtain a molding material. It should be noted that curing is sufficiently performed by heating and pressing without adding a curing agent, but a curing agent such as citric acid, phthalic acid, or organic carboxylic acid ester is generally used.

[0024]

Embedded image

The urea resin is a thermosetting resin produced by the condensation polymerization of urea and formaldehyde (see Chemical Formula 2).
As a method for producing the fine powder composed of the urea resin, for example,
First, urea and formalin are mixed at a molar ratio of about 1: 2, and heated by neutral or alkaline to prepare a liquid containing 45 to 50% of an initial polymer via monomethylol urea and dimethylol urea, Thereafter, a filler such as pulp or wood flour is added to and mixed with the initial polymerized product, and the mixture is further heated to proceed with polymerization, dried and pulverized to a fine powder.

[0026]

Embedded image

[0027]

[0028]

The fine powder of epoxy resin, for example, fine powder of bisphenol A type epoxy resin (manufactured by Yuka Shell) has a concentration of sodium ions and chlorine ions remaining in the resin of about 5 ppm and dicyanic acid. Those cured by a system curing agent and made soluble in an acid or an oxidizing agent have a molecular weight between crosslinking points of 1900, and the ions easily move in the resin. Therefore, when an epoxy resin is used as the heat-resistant resin fine powder for forming an anchor, a migration reaction is caused. On the other hand, an epoxy resin insoluble in an acid or an oxidizing agent used as a heat-resistant resin matrix has a molecular weight between cross-linking points of about 600, and sodium ions and chloride ions are fixed in the resin, so that a migration reaction is hardly caused.

Next, the melamine resin fine powder and
Is a resin matrix constituting an adhesive solution in which urea resin fine powder is dispersed, at least one resin selected from multifunctional epoxy resin, resin having an acrylic group, acrylic resin,
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.

Among them, thermosetting resins such as bisphenol A type, bisphenol F type, cresol novolak type or phenol novolak type epoxy resin, bismaleid triazine resin, polyimide resin and phenol resin, phenol aralkyl type and phenol novolak type A photosensitive resin such as a resin obtained by converting the epoxy resin into an acrylate, an acrylic resin, and a photosensitive polyimide resin is preferably used.

This resin matrix has a solid content,
20 to 100 wt% of a multifunctional epoxy resin, a resin having an acryl group, or an acrylic resin, and at least one of a 0 to 80 wt% bifunctional epoxy resin or an acrylic resin. It is preferred to be made of a resin mixed with a seed. The reason for this is that when the polyfunctional resin is less than 20% by weight in terms of solid content, the hardness of the adhesive decreases and the chemical resistance decreases.

As the curing agent for the resin matrix, DICY, amine curing agents, acid anhydrides, imidazole curing agents and the like 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 wt%, sufficient hardness cannot be obtained due to insufficient curing.

The mixture obtained by dispersing the cured amino resin fine powder in at least one heat-resistant resin matrix selected from an uncured polyfunctional epoxy resin and a bifunctional epoxy resin is as follows: Separating and storing the imidazole-based curing agent separately from each other, and mixing and using both immediately before use is a pot life (usable time).
It is desirable in lengthening.

As the resin matrix, a heat-resistant resin containing no solvent can be used as it is.
A heat-resistant resin obtained by dissolving a heat-resistant resin in a solvent can be used advantageously because the viscosity can be easily adjusted, so that the fine powder can be uniformly dispersed, and can be easily applied on the base film. . 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 in the resin matrix and the fine amino resin powder.

When a resin matrix is used, a mixed resin of a resin having a large molecular weight (hereinafter, indicated by R) and a resin having a small molecular weight (hereinafter, indicated by r) is desirable.
Specifically, the molecular weight M of the resin R is 2000 <M ≦ 100,000,
Desirably, 2000 ≦ M ≦ 5000, and the molecular weight m of the resin r
Is 200 <m ≦ 2000, desirably 300 ≦ m ≦ 1000, and the compounding ratio is preferably 0.2 ≦ r / (r + R) ≦ 0.8 by weight ratio. Further, in order to keep the melting point of the mixed resin at room temperature or higher, the melting point of the resin R is preferably in the range of 50 to 150 ° C, and the melting point of the resin r is preferably in the range of 10 to less than 50 ° C.

The reason is that among the following properties required for film formation, resins having a small molecular weight are:
This is because a resin having a large molecular weight has an effect on the above, and if the molecular weight and the mixing ratio deviate from the above-mentioned range in which any of the effects can be exerted, the characteristics (1) to (4) are deteriorated. Tackiness (adhesive surface tackiness), flexibility (easiness to bend), cutting properties (cut or not to break when cut), edge fusion properties (adhesive layer flows when film is set up) Cause flow) and resistance to acids and oxidants.

That is, by using the above-mentioned mixed resin having a low molecular weight and a high molecular weight as a resin matrix, the peel strength of the adhesive layer can be increased to 2 kg / cm or more. Although the reason is not clear, it is considered that the resin is densely filled, so that the breaking strength of the resin increases. Thereby, the roughness of the roughened surface can be reduced, so that a finer pattern can be formed.

Next, the adhesive sheet for a wiring board of the present invention
As shown in FIG. 1 (a), melamine resin fine powder and
Urea resin powder is hardly soluble in acid or oxidizing agent when subjected to curing treatment. After application, 60 ~
It is obtained by removing a predetermined amount of the solvent by drying in a drying furnace set at 100 ° C., and bringing the state to the B stage. At this time, the thickness of the adhesive layer on the base film,
It is adjusted to 25 to 70 μm by the doctor bar gap. Since the adhesive sheet is wound into a roll, a protective film (cover film) is formed on the adhesive layer.
To protect the semi-cured adhesive layer.

Here, a film such as polyethylene terephthalate, polypropylene and polyethylene fluoride (Tedlar film) is preferably used as a base film serving as a base material of the adhesive sheet. 50 μm is desirable. In addition, in order to facilitate the peeling and removal of the base film, silicon may be applied to the contact surface with the adhesive layer as a release treatment. Further, the opposite surface may be subjected to mud processing (irregularity processing).

An adhesive solution suitable for forming an adhesive film on the base film has a kinematic viscosity at 60 rotations (JIS-K7117) measured with a rotational viscometer of 10 to 20.
00 cps Preferably those having 100 to 300 cps are used. The reason is that if the viscosity is less than 10 cps, an adhesive layer having sufficient peel strength cannot be obtained, while the viscosity is less than 20 cps.
If it exceeds 00 cps, it cannot be applied on the base film.

The solid concentration of the adhesive solution was 45%.
~ 75wt% is desirable. The reason is that if the amount is less than 45% by weight, there is a problem of residual solvent, and if the amount is more than 75% by weight, sufficient applicability (the applicability does not mean leveling property, removal of air bubbles, etc.) cannot be obtained. The ratio of the resin fine powder to the resin matrix in the solid content is 1/100 by volume ratio.
200200/100, preferably 20 / 100-50 / 100. The reason is that if it is less than 1/100, a clear anchor is not formed, and if it is more than 200/100, the anchors are too close to each other, and sufficient strength cannot be obtained.

Further, the adhesive sheet for a wiring board of the present invention can be manufactured by directly applying without using a base film.

Next, a method for manufacturing a printed wiring board of the present invention using the above-mentioned adhesive sheet will be described. First, an adhesive sheet having a semi-cured adhesive layer from which a protective film has been peeled off is placed on a substrate _whose surface is roughened to about R _mAX = 2 μm, and the adhesive layer of the adhesive sheet faces the substrate. After laminating or heating and pressing at 40 to 120 ° C. and 40 kg / cm ² , an adhesive layer for electroless plating is formed by removing the base film.

Here, 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. , An alumina substrate, a low-temperature firing ceramic substrate, an aluminum nitride substrate, an aluminum substrate, an iron substrate, a polyimide film substrate, and the like. 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.

Next, when the resin matrix constituting the adhesive solution is a thermosetting resin, the adhesive layer in an uncured state (B stage state) is thermally cured to a cured state (C stage state). At least a portion of the thermosetting fine powder dispersed in the surface portion of the adhesive layer is dissolved and removed with an acid or an oxidizing agent to roughen the surface of the adhesive layer, and then electroless plating is performed by a conventional method. On the other hand, when the resin matrix constituting the adhesive solution is a photosensitive resin, a photomask is brought into close contact with the uncured (B-stage) adhesive layer formed on the substrate, and is cured by light curing. An additive process characterized by being in a state (C stage state), then developing unnecessary portions, forming holes for via holes, and performing electroless plating in the same manner as described above. Sa That. When a photosensitive resin is used, it is effective in manufacturing a build-up multilayer wiring board.

The oxidizing agent for roughening the adhesive layer is preferably chromic acid, chromate, permanganate, ozone or the like, and the acid is preferably hydrochloric acid, sulfuric acid, organic acid or the like.

The electroless plating includes, for example, 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 nickel plating and electroless gold plating is used.

In the manufacturing method of the present invention, after the electroless plating is performed, different types of electroless plating or electroplating may be performed, or solder may be coated.

Further, the wiring board obtained by the manufacturing 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.

[0051]

【Example】

(Example 1) (1) A mixture of 1275 parts by weight of melamine resin, 1366 parts by weight of 37% formalin and 730 parts by weight of water was mixed with 10% sodium carbonate to adjust the pH.
= 9.0 and maintained at 90 ° C. for 60 minutes, and then 109 parts by weight of methanol was added. (2) The resin liquid was dried by a spray drying method to obtain a powdery resin. (3) The resin powder, the release agent, and the curing catalyst were pulverized and mixed in a ball mill to obtain a mixed powder of the above resin. (4) Put the above mixed powder in a mold heated to 150 ° C,
A compact was obtained by applying a pressure of 250 kg / cm ² and holding for 60 minutes. During the molding, the mold was opened to release gas. (5) The above molded product is pulverized with a ball mill and the particle size is 0.5 μm
And a heat-resistant resin fine powder of 5.5 μm was obtained. (6) Next, 60 parts by weight of a phenol novolak type epoxy resin (manufactured by Nippon Kayaku: molecular weight 3600, mp = 90 ° C.) and a bisphenol A type epoxy resin (manufactured by Yuka Shell: molecular weight 900, mp
= 64 ° C) and 5 parts by weight of an imidazole-based curing agent (Shikoku Chemicals) were dissolved in butyl cellosolve acetate to obtain a resin matrix composition. Then, with respect to 100 parts by weight of the solid content of the composition, the fine powder prepared in the above (5) was ball-milled at a ratio of 15 parts by weight having a particle diameter of 0.5 μm and a particle having a particle size of 5.5 μm at a ratio of 30 parts by weight. And then add butyl cellosolve acetate to add 60% solids
Was prepared. The viscosity of this solution is JIS K711
Using a digital viscometer (DVL-B) manufactured by Tokyo Keiki Co., Ltd., measured at 20 ° C. for 60 seconds, the measured value was 0.2 Pa · s at 60 rpm.
Met. (7) This adhesive solution is applied on a PET (polyethylene terephthalate) film 14 having a silicon coat on the surface with a doctor blade 16 and dried in an IR furnace 15 at 80 ° C. for 20 minutes to obtain a B-stage state. A polyethylene cover film 11 (to protect the surface of the adhesive) was attached to form an adhesive sheet (see FIG. 1 (a)). (8) Next, the glass epoxy substrate 1 is roughened on both sides by polishing to form a rough surface of 2-3 μm, and then the adhesive sheet prepared in the above (7) is overlaid on the roughened surface of the substrate. ,
It was heated at 80 ° C under a pressure of 3 kg / cm ² (see FIGS. 1 (b) and 1 (c)). (9) The substrate 1 with the adhesive sheet after the treatment of (8) is
Chromic acid (CrO ₃ ) oxidizing agent consisting of 500 g / l aqueous solution
C. for 15 minutes to roughen the surface of the adhesive layer 2,
It was immersed in a neutralization solution (manufactured by Shipley) and washed with water. The surface of the insulating layer 2 was activated by applying a palladium catalyst (manufactured by Shipley) to the substrate 1 having the roughened adhesive layer 2 (see FIG. 1 (d)). (10) The substrate 1 is placed in a nitrogen gas atmosphere (10 ppm oxygen) for 12 minutes.
Heat treatment for immobilizing the catalyst was performed at 0 ° C. for 30 minutes. Thereafter, a photosensitive dry film was laminated, exposed, and developed with denatured chlorocene to form a plating resist 3 (40 μm in thickness) (see FIG. 1 (e)). (11) Further, the substrate 1 having been subjected to the treatment of (10) is immersed in an electroless copper plating solution having the composition shown in Table 1 for 11 hours.
The printed wiring board was manufactured by electroless copper plating having a thickness of 25 μm (see FIG. 1 (f)).

[0052]

[Table 1]

Example 2 (1) 200 g of melamine resin fine powder (average particle size: 3.9 μm) obtained in the same manner as in (1) to (5) of Example 1 was dispersed in 5 l of acetone. While stirring into the melamine resin particle suspension in a Henschel mixer (Mitsui Miike Kakoki),
300 g of melamine resin fine powder (average particle size: 0.5 μm) obtained in the same manner as in (1) to (5) of Example 1 was dispersed in an acetone solution at a ratio of 30 g of melamine resin to 1 liter of acetone. By dropping the suspension, the melamine resin fine powder was adhered to the surface of the melamine resin particles, the acetone was removed, and then heated to 150 ° C. to produce pseudo particles. This pseudo particle has an average particle size of about 4.3 μ
m, and about 75% by weight is ± 2 μm around the average particle size.
m. (2) 50 parts by weight of the pseudo particles prepared in the above (1), cresol novolak type epoxy resin (manufactured by Nippon Kayaku, molecular weight 2500
30 parts by weight, phenol novolak type epoxy resin (manufactured by Yuka Shell, molecular weight 700, mp = 40 ° C) 40 parts by weight, bisphenol A type epoxy resin (manufactured by Yuka Shell,
Butyl carbitol was added to a mixture consisting of 30 parts by weight of a molecular weight of 500, mp = 25 ° C.) and 5 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals), and adjusted with a ball mill so that the solid content concentration became 50%. An adhesive solution was prepared. The viscosity of this solution was measured using a digital viscometer (DVL-B) manufactured by Tokyo Keiki in accordance with JIS K7117 at 20 ° C for 60 seconds.
0.1 Pa · s at 60 rpm. (3) Apply this adhesive solution to the surface of Tedlar film 12 (manufactured by DuPont) with a doctor blade 16, and
After drying at 5 ° C. for 5 minutes to obtain a B-stage state, a polyethylene cover film 11 (to protect the surface of the adhesive) was attached to form an adhesive sheet (see FIG. 2 (a)). (4) A printed wiring board was manufactured in the same manner as in Examples 1 (8) to (11) (see FIG. 2).

(Example 3) (1) The melamine resin fine powder (average particle size: 3.9 μm) obtained in the same manner as (1) of Example 1 was charged into a hot air drier, and
Heat treatment was carried out at 80 ° C. for 3 hours for cohesive bonding. The coagulated and bonded melamine resin fine powder was dispersed in acetone, crushed with a ball mill for 5 hours, and then classified using an air classifier to prepare coagulated particles. The aggregated particles are
The average particle size was about 3.5 μm, and about 68% by weight was in the range of ± 2 μm around the average particle size. (2) 50 parts by weight of the agglomerated particles prepared in the above (1), special functional epoxy resin (manufactured by Nippon Kayaku, molecular weight 3200, mp = 60 ° C.) 80
20 parts by weight of bisphenol A type epoxy resin (manufactured by Yuka Shell, molecular weight 500, mp = 25 ° C.) and 7 parts by weight of a azole curing agent (manufactured by Shikoku Chemicals) are dissolved in butyl carbitol, and the solid content concentration is 65%. Was prepared. The viscosity of this solution was measured at 20 ° C. for 60 seconds using a digital viscometer (DVL-B) manufactured by Tokyo Keiki according to JIS 7117, and it was 0.3 Pa · s at 60 rpm. (3) The adhesive solution prepared in the above (2) was applied onto a commercially available prepreg 13 using a doctor blade 16 and then heated to 100 ° C.
5 minutes in the B-stage state, a polyethylene cover film 11 (to protect the surface of the adhesive) is adhered, and a PET for protecting the adhesive layer 2
(Polyethylene terephthalate) film 14 was bonded to form an adhesive sheet (see FIG. 3 (a)). (4) While peeling off the cover film 11, five commercially available prepregs and the above-mentioned adhesive sheet are superimposed on each other so as to be in contact with the adhesive layer 2, and pressurized at 150 ° C., 50 kg / cm ² for 200 minutes, and thereafter Then, the PET (polyethylene terephthalate) film 14 was peeled off to obtain an insulating substrate 1 having an adhesive layer 2 formed on both sides (see FIGS. 3B and 3C). (5) Next, the substrate 1 with the adhesive sheet after the treatment of the above (4) is drilled and immersed in an acid composed of a 6N hydrochloric acid aqueous solution at 70 ° C. for 15 minutes to form a surface of the adhesive layer 2. Was roughened and then immersed in 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) to the substrate 1 having the roughened adhesive layer 2 (see FIGS. 3D and 3E). . (6) The substrate 1 is placed in a nitrogen gas atmosphere (10 ppm oxygen) for 12 minutes.
Heat treatment for immobilizing the catalyst was performed at 0 ° C. for 30 minutes. Thereafter, a photosensitive dry film was laminated, exposed, and developed with denatured chlorocene to form a plating resist 3 (40 μm in thickness) (see FIG. 3 (f)). (7) Further, the substrate 1 after the treatment of (6) was immersed in an electroless copper plating solution having the composition shown in Table 1 for 11 hours, and electroless copper plating with a thickness of 30 μm of the plating film 4 was performed on both surfaces. Then, a conductor circuit and a through hole were formed to produce a double-sided printed wiring board (see FIG. 3 (f)).

Example 4 (1) This example is basically the same as Example 1, except that 50 parts by weight of a special trifunctional epoxy resin (molecular weight 3000, mp = 80 ° C.) Functional epoxy resin (molecular weight 500,
(mp = 35 ° C.) 50 parts by weight and 7 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals) were dissolved in butyl cellosolve acetate to obtain a resin matrix composition. To 100 parts by weight of the solid content of this composition, 15 parts by weight of a fine powder having a particle diameter of 0.5 μm prepared in the same manner as in Examples 1 (1) to (5),
One having a particle size of 5.5 μm was mixed in a ball mill at a ratio of 30 parts by weight, and butylcellosolve acetate was further added to prepare an adhesive solution having a solid concentration of 45%. The viscosity of this solution was measured using a digital viscometer (DVL-B) manufactured by Tokyo Keiki in accordance with JIS K7117 at 20 ° C. for 60 seconds.
m was 0.1 Pa · s. (2) Using this adhesive solution, a printed wiring board was manufactured in the same manner as in Example 1 (see FIG. 1).

(Example 5) (1) A photosensitive dry film (manufactured by DuPont) is 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 conductive circuit pattern is drawn. Burn the image. Then 1,1,
After developing with 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. Thereby, wiring board 1 ′ having the first conductor layer composed of a plurality of conductor patterns
Was obtained (see FIG. 4 (a)). (2) 80% by weight of a 50% acrylate of a cresol novolak type epoxy resin, 20 parts by weight of a bisphenol A type epoxy resin, 2-methyl-4- [4- (methylthio) phenyl] -2-
4 parts by weight of Morifolinopropanone-1 (manufactured by Ciba Baigye), 15 parts by weight of diallyl terephthalate, 4 parts by weight of an imidazole-based curing agent (Shikoku Chemicals) and 50 parts by weight of fine powder of hollow melamine resin (manufactured by Honen: particle size 2 μm) After mixing, a leveling agent was added, and the mixture was stirred with a homodisper stirrer while further adding butyl cellosolve, and then kneaded with a ball mill to prepare a photosensitive adhesive solution having a solids concentration of 50%. The viscosity of this solution was measured using a digital viscometer (DVL-B) manufactured by Tokyo Keiki in accordance with JIS 7117.
When measured at 60 ° C. for 60 seconds, it was 0.5 Pa · s at 60 rpm. (3) The adhesive solution was applied on a silicone-coated polypropylene film 12 in the same manner as in Example 1 to prepare a photosensitive adhesive sheet. (4) Next, on the wiring board 1 'prepared in (1) above,
Lay the photosensitive adhesive sheet created in (3), and
Heating was carried out at a pressure of 3 kg / cm ² at a temperature of 3 ° C. (see FIGS. 4B and 4C). (5) Wiring board 1 'with an adhesive sheet after the treatment of (4) above
Then, a photomask film on which a black circle of 100 μmφ was printed was brought into close contact with the photomask film, and exposed at 500 mj / cm ² using an ultra-high pressure mercury lamp. This is subjected to ultrasonic development and development with a chlorocene solution to form an opening that becomes a 100 μmφ via hole on the wiring board.
/ exposed with cm ^2, 1 hour at 100 ° C., after which an interlayer insulating layer 2 'having an opening 7 having excellent dimensional accuracy corresponding to the photomask film by 10 hours of heat treatment at 0.99 ° C. (FIG. 4 (d)). (6) Crude the surface of the (5) process circuit board 1 having been subjected to the 'a, chromic acid (CrO ₃₎ was immersed for 15 minutes at 70 ° C. in an oxidizing agent consisting of 500 g / l aqueous solution of the interlayer insulating layer 2' After immersion, it was immersed in a neutralization solution (manufactured by Shipley) and washed with water. The surface of the insulating layer 2 'was activated by applying a palladium catalyst (manufactured by Shipley) to the wiring board 1' having the roughened interlayer insulating layer 2 '(see FIG. 4 (d)). (7) The wiring board 1 'was subjected to a heat treatment for fixing the catalyst in a nitrogen gas atmosphere (10 ppm oxygen) at 120 DEG C. for 30 minutes. Then, laminating a photosensitive dry film,
After the exposure, the resist was developed with denatured chlorocene to form a plating resist 3 (thickness: 40 μm) (see FIG. 4E). (8) Further, the wiring board 1 'having been subjected to the treatment of (7) is immersed in an electroless copper plating solution having the composition shown in Table 1 for 11 hours, so that the plating film 6 has a thickness of 25 μm. Was given. (9) The plating resist 3 was dissolved and removed with methylene chloride (see FIG. 4 (f)). (10) The above (4) to (8) were repeated to produce a four-layer (4, 6, 8, 10) build-up multilayer printed wiring board (see FIG. 4 (g)).

Example 6 (1) 60% by weight of 50% acrylate of cresol novolac type epoxy resin (manufactured by Yuka Shell), 40 parts by weight of bisphenol A type epoxy resin (manufactured by Yuka Shell), 2-methyl-
4 parts by weight of 4- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba Vigie) and 4 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals) are dissolved in butyl cellosolve acetate, and this composition is dissolved. Solid content of 100
15 parts by weight of a melamine resin fine powder (made by Honen) having a particle diameter of 0.5 μm,
One having a particle size of 5.5 μm was mixed in a ball mill at a ratio of 30 parts by weight, and butylcellosolve acetate was further added to prepare an adhesive solution having a solid concentration of 45%. The viscosity of this solution was measured using a digital viscometer (DVL-B) manufactured by Tokyo Keiki in accordance with JIS K7117 at 20 ° C. for 60 seconds.
m was 0.1 Pa · s. (2) This adhesive solution was used as a photosensitive adhesive sheet in the same manner as in Example 5 to produce a build-up multilayer printed wiring board (see FIG. 4).

Example 7 (1) 50 parts by weight of a 75% acrylated cresol novolac epoxy resin (manufactured by Yuka Shell), 50 parts by weight of a bisphenol A type epoxy resin (Dow Chemical) and an imidazole-based curing agent (Shikoku) 5 parts by weight of a chemical compound (made by Kasei) were dissolved in butyl cellosolve acetate, and 15 parts by weight of a melamine resin fine powder (manufactured by Honen) having a particle size of 0.5 μm, which was pulverized with a ball mill, was added to 100 parts by weight of a solid content of the composition. Particle size
The mixture having a thickness of 5.5 μm was mixed in a ball mill at a ratio of 30 parts by weight, and butylcellosolve acetate was added to prepare an adhesive solution having a solid content of 50%. The viscosity of this solution was measured in accordance with JIS K7117, using a digital viscometer (DV
LB) and measured at 20 ° C for 60 seconds.
0.3 Pa · s. (2) Next, this adhesive solution is applied on a Tedlar film 12 coated with silicon by a roll coater,
It was dried by heating at 80 ° C. for 30 minutes to prepare a photosensitive adhesive sheet. (3) Using this adhesive sheet, a build-up multilayer printed wiring board was manufactured in the same manner as in Example 5 (FIG. 4).
reference).

(Eighth Embodiment) (1) This embodiment is basically the same as the fifth embodiment.
60 parts by weight of 50% acrylate of ortho-cresol novolak type epoxy resin (manufactured by Nippon Kayaku), 40 parts by weight of bisphenol F type epoxy resin, 15 parts by weight of diallyl terephthalate, 2-methyl-1- [4- (methylthio) phenyl]
4 parts by weight of 2-morpholinopropanone-1 (manufactured by Ciba-Geigy), 4 parts by weight of imidazole-based curing agent (manufactured by Shikoku Chemicals), photoinitiator (manufactured by Ciba-Geigy), and fine powder of hollow melamine resin (manufactured by Honen: particle diameter 2 μm) ) After mixing 50 parts by weight, the mixture was stirred with a homodisper stirrer while adding butyl cellosolve, and kneaded with a ball mill to obtain a solid concentration.
A 50% photosensitive adhesive solution was prepared. The viscosity of this solution was measured in accordance with JIS K7117, using a digital viscometer (DV
LB) and measured at 20 ° C for 60 seconds.
It was 0.2 Pa · s. (2) Using this adhesive solution, in the same manner as in Example 5,
An adhesive sheet and a multilayer printed wiring board were manufactured (see FIG. 4).

Example 9 This example is basically the same as Example 5, except that 60 parts by weight of a phenol novolak type epoxy resin (manufactured by Yuka Shell) was used as an adhesive solution.
40 parts by weight of a functional acrylic resin (manufactured by Yuka Shell) and 5 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals) are dissolved in butyl cellosolve acetate, and the solid content of the composition is 10%.
0 parts by weight of melamine resin fine powder with a particle size of 0.5 μm
15 parts by weight, and 30 parts by weight of a particle having a particle size of 5.5 μm, kneaded with a three-roll mill, and further adjusted to a solids concentration of 60% by adding butyl cellosolve acetate. It was used.

Example 10 This example is basically the same as Example 5, except that a 60% acrylate of a phenol novolak type epoxy resin (manufactured by Yuka Shell) was used as an adhesive solution. Dissolve 40 parts by weight of a bifunctional acrylic resin (manufactured by Yuka Shell) and 5 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals) in butyl cellosolve acetate,
With respect to 100 parts by weight of the solid content of this composition, 15 parts by weight of a melamine resin fine powder having a particle size of 0.5 μm and a particle size of 5.5 μm were used.
Were mixed at a ratio of 30 parts by weight, kneaded with a three-roll mill, and further, butylcellosolve acetate was added to adjust the solid content to 65%.

Example 11 This example is basically the same as Example 5, except that 60 parts by weight of an acrylic resin (manufactured by Yuka Shell) and a bisphenol A type epoxy resin (oil 40 parts by weight) and 5 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals) are dissolved in butyl cellosolve acetate, and a melamine resin fine powder having a particle diameter of 0.5 μm is added to 100 parts by weight of the solid content of this composition. 15 parts by weight and a particle size of 5.5 μm are mixed at a ratio of 50 parts by weight,
After kneading with three rolls, butylcellosolve acetate was further added to adjust the solid content to 65%.

Example 12 This example is basically the same as Example 5, except that 60 parts by weight of an acrylic resin (manufactured by Yuka Shell) was used as an adhesive solution. 40 parts by weight of Yuka Shell) and 5 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals) are dissolved in butyl cellosolve acetate, and a fine powder of melamine resin having a particle size of 0.5 μm is added to 100 parts by weight of the solid content of this composition. 15 parts by weight and 30 parts by weight of a particle having a particle size of 5.5 μm were mixed and kneaded with three rolls, and then butyl cellosolve acetate was added to adjust the solid content to 55%. It was used.

Example 13 This example is basically the same as Example 5, except that 100 parts by weight of an acrylic resin (manufactured by Shin-Nakamura Chemical) and an imidazole-based curing agent (Shikoku) were used as the adhesive solution. 5 parts by weight of a chemical compound) were dissolved in butyl cellosolve acetate, and 15 parts by weight of melamine resin fine powder having a particle size of 0.5 μm and 30 parts by weight of 5.5 μm Mix in parts by weight and mix
After kneading with this roll, butyl cellosolve acetate was further added to adjust the solid content to 55%.

[0065]

Example 14 (1) Urea, isothiourea and formalin were used in a ratio of 1: 1: 2
The mixture was heated at 80 ° C. and co-condensed to obtain a urea-thiourea co-condensed resin fine powder. (2) This embodiment is basically the same as the seventh embodiment,
As the amino resin fine powder, the urea-thiourea co-condensation resin fine powder obtained in the above (1) was used. Also, 100 parts by weight of a 75% acrylated cresol novolak type epoxy resin was used, and no bisphenol A type epoxy resin was used. Note that the viscosity of the adhesive solution in this example is J
According to IS-K7117, using a digital viscometer manufactured by Tokyo Keiki Co., Ltd., it was measured at 20 ° C. for 60 seconds.
s.

Comparative Example 1 Basically the same as Example 1, except that an epoxy resin cured with pyromellitic anhydride was used as the heat-resistant resin fine powder.

Comparative Example 2 (1) A melamine resin fine powder was obtained in the same manner as in (1) to (5) of Example 1. (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, based on 100 parts by weight of the solid content of the composition, (1)
15 parts by weight of the fine powder obtained in the step of 0.5 μm in particle size and 30 parts by weight of the fine powder in a particle size of 5.5 μm are kneaded with three rolls, and then butylcellosolve acetate is added. Thus, an adhesive solution having a solid concentration of 75% was prepared. The viscosity of this solution was measured using a digital viscometer (DVL-B) manufactured by Tokyo Keiki Co., Ltd. at 20 ° C. for 60 seconds in accordance with JIS K7117, and it was 5.2 Pa · s at 6 rpm and 2.5 Pa · s at 60 rpm. . The SVI value was 2. (3) Roughen the glass epoxy substrate by polishing, 2-3μ
After forming the rough surface of m, the solution of the photosensitive resin composition prepared in the above (2) was applied using a roll coater. The coating method used at this time was to use a coating roll for resist for medium and high viscosity (manufactured by Dainippon Screen) as a coating roll, and set the gap between the coating roller and doctor bar to 0.
4mm, between coating roller and backup roller 1.
4 mm, and the transport speed was 400 mm / s. After being left for 20 minutes in a horizontal state, it was dried at 70 ° C. to form an adhesive layer having a thickness of about 50 μm. (4) The substrate of (3) was immersed in an oxidizing agent consisting of a 500 g / l aqueous solution of chromic acid (CrO ₃ ) at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer. (Manufactured by Sharp Corporation). A surface of the insulating layer was activated by applying a palladium catalyst (manufactured by Shipley) to the substrate having the roughened adhesive layer. (5) Place the substrate in a nitrogen gas atmosphere (10 ppm oxygen) for 120 minutes.
A heat treatment for immobilizing the catalyst was performed at 30 ° C. for 30 minutes. Thereafter, a photosensitive dry film is laminated, exposed, developed with denatured chlorocene, and plated with a resist (thickness: 40 mm).
μm). (6) Further, the substrate after the treatment of (5) is 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 plating film thickness of 25 μm, followed by printing. A wiring board was manufactured.

The adhesion, electrical characteristics, hardness, influence of impurities (migration resistance), etc. of the electroless plating film of the wiring board manufactured as described above were measured. The results are shown in Table 2.

As is clear from Table 2, the epoxy resin cured with trimet anhydride used in Comparative Example 1 has low solubility in acids and oxidizing agents. The peel strength was lower than in the case. Furthermore, in the case of the present invention, no migration reaction was observed.

Next, comparing the adhesive formation time as an index of the productivity of the printed wiring board, it is clear from Table 2 that the method of applying the adhesive of Comparative Example 2 shows that the viscosity of the adhesive Since it was necessary to control application conditions such as thixotropy, it was found that productivity was significantly inferior to the method using the adhesive sheet of the present invention.

[0072]

[Table 2]

Each test method for the adhesion strength (peel strength) of the electroless plating film, the electrical insulation, the hardness, and the influence of impurities (migration resistance) will be described. (1) Adhesion strength (peel strength) of electroless plating film JIS-C-6481 (2) Electrical insulation DC voltage or frequency 50Hz or L / S = 25 / 25μm comb pattern formed on printed wiring board 60
Apply 500V using the peak voltage of sine wave AC at Hz.
The voltage is gradually increased to the specified voltage in about 5 seconds, charged for 1 minute, and checked for abnormalities such as mechanical damage, flashover, and dielectric breakdown (when a current of 0.5 mA or more is applied). . (3) Hardness (Barcol hardness) Device: Type A Indicated value of aluminum alloy reference piece 85-87 (hard), 43-48
(Soft) Model: GYZJ934-1 Adjustment: Using a glass plate, adjust so as to have an indicated value of 100 ± 1, then use an aluminum alloy reference piece to adjust so as to be the indicated value of the reference piece. Operation: Press the indenter of the hardness tester so as to be perpendicular to the sample surface, and read the indicated value of the maximum value. The measurement position should be a smooth surface at least 3 mm inside from the sample end.
When measuring with the same sample, it must be at least 3 mm away from the pit defined by the regulations. Measurement: The substrate is heated to 150 ° C., kept for 5 minutes, and the hardness is measured. (4) Influence of impurities (migration resistance) Specimen: Printed wiring board with L / S = 50/50 μm comb-shaped Measurement: Temperature and humidity of 85 ± 1 ° C, 85-90% relative humidity And leave it with a bias of 30V. Migration between patterns after 1000hr

[0074]

As described above, according to the adhesive sheet of the present invention and the method of manufacturing a wiring board using the adhesive sheet, the migration reaction is achieved by using the amino resin as the heat-resistant resin fine powder. And a printed wiring board which is not affected by the use environment can be easily manufactured. Further, by employing an adhesive sheet having a film-like adhesive layer as the adhesive for a wiring board, the productivity of the printed wiring board can be improved without impairing the electroless plating property.

[Brief description of the drawings]

FIG. 1 is a process chart showing one embodiment of the present invention.

FIG. 2 is a process chart showing another embodiment of the present invention.

FIG. 3 is a process chart showing another embodiment of the present invention.

FIG. 4 is a process chart showing another embodiment of the present invention.

[Explanation of symbols]

 1, 1 'board (wiring board) 2, 2' adhesive layer 3 plating resist 4, 6, 8, 10 plating film (conductor layer) 5 through hole hole 7 via hole opening 11 polyethylene film 12 polypropylene film, te Dryer film 13 Pre-preg 14 PET film 15 Drying furnace (IR furnace) 16 Doctor blade

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C23C 18 / 18,18 / 20 C09J 7/02 H05K 3 / 18,3 / 38

Claims (5)

(57) [Claims] 1. A pre-cured melamine resin fine powder and / or urea resin soluble in an acid or an oxidizing agent.
No a fat powder, when subjected to curing acid or formed by dispersing the resin matrix in the uncured state indicating the characteristics to be hardly soluble in oxidizing agent adhesive layer is formed on a base film Adhesive sheet for electrolytic plating . 2. The adhesive sheet for electroless plating according to claim 1, wherein the resin matrix is one of a thermosetting heat-resistant resin and a photosensitive heat-resistant resin. 3. A printed wiring board is manufactured by forming an adhesive layer for electroless plating on a substrate, roughening the surface of the adhesive layer, and applying electroless plating to form a conductor circuit. In the method, on the substrate, a pre-cured melamine resin fine powder soluble in an acid or an oxidizing agent, and
Alternatively, an adhesive layer formed by dispersing a urea resin fine powder in an uncured thermosetting heat-resistant resin matrix exhibiting a property of being hardly soluble in an acid or an oxidizing agent when subjected to a curing treatment is formed on a base film. Electroless plating formed on
The adhesive sheet for the adhesive is laminated such that the adhesive layer of the adhesive sheet faces the substrate, and then heated under pressure, and then the base film is peeled off to form an adhesive layer for electroless plating. A method for producing a printed wiring board, comprising subjecting the printed wiring board to electroless plating. 4. A photosensitive adhesive layer for electroless plating is formed on a substrate, and after exposing the adhesive layer, the surface thereof is roughened and subjected to electroless plating to form a conductor circuit and print. In a method of manufacturing a wiring board, a pre-cured melamine soluble on an acid or an oxidizing agent is provided on the substrate.
Electroless plating by dispersing fine resin powder and / or urea resin fine powder in an uncured photosensitive heat-resistant resin matrix that exhibits a property of becoming hardly soluble in acids or oxidizing agents when subjected to curing treatment. An adhesive sheet for electroless plating formed by forming an adhesive layer for a base film on a base film, such that the adhesive layer of the adhesive sheet faces the substrate, and then heated under pressure, and then the base film Is peeled off to form an adhesive layer, and then, after being exposed and cured,
A method for manufacturing a printed wiring board, comprising performing electroless plating after roughening. 5. A printed wiring board comprising an adhesive layer provided on at least one substrate surface and a conductive circuit formed thereon, wherein said adhesive layer is a cured melamine resin.
An adhesive layer formed by dispersing a fine resin powder and / or a fine urea resin powder in an uncured heat-resistant resin matrix that exhibits a property of being hardly soluble in an acid or an oxidizing agent when subjected to a curing treatment is peeled off. A printed wiring board formed by sticking an adhesive sheet for electroless plating formed on a base film to be removed.