JP3152508B2 - 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, a method for manufacturing a printed wiring board using the adhesive, and a printed wiring board.
An adhesive suitable for electroless plating with excellent electrical properties and hardness, a method for manufacturing a printed wiring board using the adhesive, and a proposal for 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.

For this reason, recently, as a method for forming a conductor on a substrate, an adhesive containing a diene-based synthetic rubber is applied to the surface of the substrate to form an adhesive layer, and after the surface of the adhesive layer is roughened, An additive method of forming a conductor by plating is adopted. 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 an electroless plating film bulging during soldering, There are drawbacks such as insufficient electrical properties such as surface resistance, 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. 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 heat-resistant resin matrix have different solubility in an oxidizing agent, the adhesive layer is treated with an oxidizing agent to be dispersed on the surface of the adhesive layer. The fine powder is mainly dissolved and removed, and an effective anchor depression is formed, so that 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 been rapidly increasing, and printed wiring boards that use adhesives that use epoxy resin as heat-resistant resin fine powder in high-temperature, high-humidity environments It has been found that there is a problem that copper, which is a conductor circuit, dissolves and precipitates, lowers the surface resistance value, and causes a short circuit between patterns. The reason for this is that, when producing an epoxy resin fine powder that is soluble in an acid or an oxidizing agent, an ionic compound is used, so that sodium ions and chlorine ions remain inevitably remaining in the epoxy resin fine powder. It is presumed that this residual ion causes a reaction (migration) and other reactions as shown in the following formulas (1) and (2) (see FIG. 7). Na ⁺ + Cl ⁻ + H ₂ O → NaOH + HCl… Cu + 2NaOH → Cu (OH) ₂ + 2Na ⁺ ... Cu + 2HCl → CuCl ₂ + 2H ⁺ ...

An object of the present invention is to advantageously solve the above-mentioned problems, and in particular, to provide an adhesive excellent in chemical resistance, heat resistance, electrical properties, hardness and the like which is not affected by the use environment. An object of the present invention is to provide a printed wiring board manufacturing method and a printed wiring board using the same.

[0009]

Means for Solving the Problems The inventors of the present invention have investigated the above problems, and found that an epoxy resin for a heat-resistant resin fine powder soluble in an acid or an oxidizing agent uses an ionic compound at the time of production. In addition, Na, chloride ions, etc. remain in the resin, and the molecular weight between cross-linking points of the epoxy resin decreases.
It has been determined that, due to being above 1000, the ions are mobile in the resin and therefore cause the reaction as described above. Therefore, as a result of intensive research on a resin not using such an ionic compound, the use of amino resin fine powder as heat resistant resin fine powder does not cause the above-described reaction, and thus has high chemical resistance, heat resistance, and electrical characteristics. The present inventors newly found that an adhesive having excellent hardness can be obtained, and arrived at the present invention.

That is, the present invention provides a cured heat-resistant resin fine powder which is soluble in an acid or an oxidizing agent,
In the case of an adhesive dispersed in an uncured heat-resistant resin matrix exhibiting a property of being hardly soluble in an acid or an oxidizing agent when subjected to a curing treatment, the amino resin fine powder is used as the heat-resistant resin fine powder. An adhesive for a wiring board characterized by using a powder, wherein the amino resin fine powder is one or more resin fine powders selected from melamine resin, urea resin and guanamine resin, and heat resistant. As the conductive resin matrix, it is preferable to use one of a thermosetting heat-resistant resin and a photosensitive heat-resistant resin.

The matrix of the thermosetting heat-resistant resin is as follows:
It is composed of a mixture of a thermosetting heat-resistant resin, which is either an uncured polyfunctional epoxy resin or an uncured bifunctional epoxy resin, and an imidazole-based curing agent, and the matrix has a solid content of 20 to 100 wt. % Of an uncured polyfunctional epoxy resin and 80 to 0 wt% of an uncured bifunctional epoxy resin, and a solid content of 2 to 10 wt%
And an imidazole-based curing agent, and the amino resin fine powder is contained in this heat-resistant resin matrix in a solid content of 10%.
Disperse and mix 10 to 100 parts by weight with respect to 0 parts by weight.

On the other hand, the matrix of the photosensitive heat-resistant resin is
At least one photosensitive heat-resistant resin selected from an uncured polyfunctional epoxy resin, an uncured polyfunctional resin having an acrylic group, and an uncured polyfunctional acrylic resin, or an uncured resin and these resins A matrix comprising at least one photosensitive heat-resistant resin selected from the group consisting of a bifunctional epoxy resin and an uncured bifunctional acrylic resin, wherein the matrix has a solid content of 20 to 100 wt% of an uncured polystyrene. At least one photosensitive heat-resistant resin selected from a functional epoxy resin, an uncured polyfunctional acrylic resin, and an uncured polyfunctional acrylic resin;
80 to 0% by weight of a mixed resin with at least one photosensitive heat-resistant resin selected from uncured bifunctional epoxy resin and uncured bifunctional acrylic resin. The resin matrix is dispersed and mixed in an amount of 10 to 100 parts by weight based on 100 parts by weight of the solid content.

In the method of manufacturing a printed wiring board of the present invention using the above-mentioned adhesive, for example, the adhesive is applied by a roll coater, or the adhesive is laminated in a sheet form. After the adhesive layer is provided and cured, the surface of the adhesive layer is roughened with an acid or an oxidizing agent, and then electroless plating is performed. When this adhesive is applied to the substrate by a roll coater, it is desirable that the gap between the coating roller and the doctor bar is 0.2 to 0.6 mm and the transfer speed is 0.1 to 3.0 m / min. In the method of manufacturing a printed wiring board according to the present invention, a plating resist may be provided before performing the electroless plating.

Further, the printed wiring board of the present invention obtained by the above method of the present invention is obtained by subjecting at least one substrate surface to a hardening-treated heat-resistant resin fine powder which is soluble in an acid or an oxidizing agent. In a printed wiring board formed by providing an adhesive layer dispersed in a heat-resistant resin matrix exhibiting a property of being hardly soluble in an acid or an oxidizing agent, and forming a conductive circuit thereon, Characterized in that amino resin fine powder is used as heat resistant resin fine powder. Note that a plating resist may remain between the conductor circuits of the printed wiring board of the present invention.

[0015]

With the known adhesive, a phenomenon in which the surface resistance decreases due to the above-described migration reaction is observed. From this, the inventors conducted 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 an oxidizing agent and have no change with time in resistance value, that is, the above-described migration reaction can be caused. Amino resin was found to be the most effective resin.

Therefore, according to the present invention, by using a cured amino resin fine powder which is soluble in an acid or an oxidizing agent as a heat resistant resin fine powder, it can be used in a use environment, particularly in a high temperature and high humidity atmosphere. Even when used, migration does not occur, and the conductor circuit is not melted, so that the surface resistance value does not decrease, and sufficient adhesion strength of the conductor can be obtained. In addition, an adhesive having excellent chemical resistance, heat resistance, electrical properties, and hardness can be obtained.

In the adhesive of the present invention, the amino resin fine powder for forming an anchor recess by being dispersed in a heat-resistant resin matrix is used in an amount of 10 parts by weight based on 100 parts by weight of the total solid content of the heat-resistant resin matrix. Mix in the range of ~ 100 parts by weight. 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 amino resin fine powder is preferably 10 μm or less, and more preferably 5 μm
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 amino resin fine powder include aggregated particles having an average particle diameter of 2 to 10 μm by aggregating amino resin fine powder having an average particle diameter of 2 μm or less, and an average particle diameter of 2 to 10 μm. Particle mixture of amino resin powder and amino resin powder having an average particle diameter of 2 μm or less, or an average particle diameter of 2
It is preferable to select from pseudo particles obtained by adhering at least one of an amino resin powder having an average particle diameter of 2 μm or less and an inorganic fine powder on the surface of an amino resin powder of about 10 μm.

The amino resin fine powder used as the heat-resistant resin fine powder in the present invention is a resin fine powder having an amino group capable of reacting with formaldehyde, and is selected from melamine resin, urea resin and guanamine resin. One or more resin fine powders. The reason is that these resins have excellent heat resistance, high surface hardness, excellent mechanical strength, electrical insulation, especially excellent arc resistance, good organic solvent resistance, acid or oxidizing agent. This is because the solubility is high.

Among these resins, the melamine resin is an addition condensation product of melamine and formaldehyde, and produces a white and water-insoluble resin when reacted with an acid, and a transparent and water-soluble resin 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 in a neutral or alkaline manner to form methylol melamine. It is obtained by forming a bond and an ether bond to form a macromolecule. Further, the melamine resin generally has a molar ratio of formaldehyde to melamine in the range of about 1: 2 to 1: 3 as a molding material. Suitable for. 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.

[0022]

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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 made of the urea resin, for example, first, urea and formalin are mixed at a molar ratio of about 1: 2, and heated under neutral or alkaline conditions to obtain monomethylol urea, dimethylol urea, A liquid containing a prepolymer of about 50% is prepared, and then a filler such as pulp or wood flour is added to the prepolymer and mixed, and further heated to proceed with polymerization, dried and pulverized to obtain a fine powder. And

[0024]

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The guanamine resin is an addition condensate of guanamine and formaldehyde obtained in the same manner as the melamine resin and the urea resin (see chemical formula 3). It is obtained by forming a methylene bond and an ether bond to form a macromolecule.

[0026]

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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 chloride 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 that is 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 unlikely to occur.

Next, the heat-resistant resin matrix in which the amino resin fine powder is dispersed is excellent in heat resistance, electric insulation, chemical stability and adhesiveness, and is hard to resist an oxidizing agent by curing. Either thermosetting heat-resistant resin or photosensitive heat-resistant resin having the property of becoming soluble
It is preferred to use one. As the matrix composed of the thermosetting heat-resistant resin, a mixture of a thermosetting heat-resistant resin, which is either an uncured polyfunctional epoxy resin or an uncured bifunctional epoxy resin, and an imidazole-based curing agent is used. Of these, thermosetting heat-resistant resins such as bisphenol A type, bisphenol F type, cresol novolak type and phenol novolak type epoxy resin, bismaleid triazine resin, polyimide resin and phenol resin are preferable.

This thermosetting heat-resistant resin matrix is composed of a thermosetting thermosetting resin composed of 20 to 100% by weight of an uncured polyfunctional epoxy resin and 80 to 0% by weight of an uncured bifunctional epoxy resin. A mixture of a heat-resistant resin and an imidazole-based curing agent having a solid content of 2 to 10% by weight is preferable. The reason is that when the solid content of the polyfunctional epoxy resin is less than 20% by weight, the hardness of the adhesive decreases and the chemical resistance decreases. In addition, the solid content of the imidazole-based curing agent is 10%.
If the content is more than 2% by weight, the composition is too hard to be brittle, and if the content is less than 2% by weight, the curing is insufficient and sufficient hardness cannot be obtained.

The mixture obtained by dispersing the cured amino resin fine powder in a heat-resistant resin matrix of either an uncured polyfunctional epoxy resin or an uncured bifunctional epoxy resin is an imidazole-based resin. It is desirable to separately store the curing agent and store them, and to mix and use the two immediately before use in order to prolong the pot life (usable time).

On the other hand, the matrix made of the photosensitive heat-resistant resin is at least one resin selected from the group consisting of an uncured polyfunctional epoxy resin, an uncured polyfunctional acrylic group-containing resin and an uncured acrylic resin. Alternatively, a mixed resin of these resins and at least one photosensitive heat-resistant resin selected from an uncured bifunctional epoxy resin and an uncured bifunctional acrylic resin is used. Among them, a photosensitive heat-resistant resin such as a phenol aralkyl-type or phenol novolak-type epoxy resin acrylated resin, an acrylic resin, and a photosensitive polyimide resin are preferable.

The photosensitive heat-resistant resin matrix has a solid content of 20 to 100% by weight of an uncured polyfunctional epoxy resin,
At least one photosensitive heat-resistant resin selected from an uncured polyfunctional acrylic resin and an uncured polyfunctional acrylic resin; 80 to 0 wt% of uncured bifunctional epoxy resin and uncured A mixed resin with at least one photosensitive heat-resistant resin selected from the above bifunctional acrylic resins is preferred. The reason is that the solid content of polyfunctional resin is 20wt%
If the amount is smaller, the hardness of the adhesive decreases and the chemical resistance decreases. A photoinitiator, a photosensitizer, a reactive diluent, and the like may be further added to the photosensitive heat-resistant resin matrix.

The heat-resistant resin matrix and the amino resin fine powder may be subjected to non-combustibility treatment such as halogenation.

Next, a method for manufacturing a printed wiring board using the adhesive for wiring boards of the present invention will be described in detail.
In producing a printed wiring board using the wiring board adhesive of the present invention, first, a cured amino resin fine powder that is soluble in an acid or an oxidizing agent is cured on a substrate. In the case of an adhesive or an uncured heat-resistant resin matrix that exhibits the property of being hardly soluble in an acid or oxidizing agent, an adhesive is applied by a roll coater or the like, 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 an epoxy resin, the gap between the coating roller and the doctor bar is 0.2 to 0.6 mm, and the transport 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.
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.

The fine amino resin powder soluble in the above-mentioned acid or oxidizing agent is composed of a cured heat-resistant resin. The amino resin fine powder is limited to the cured resin. When the uncured resin is used, the heat resistant resin liquid for forming the heat resistant resin matrix or the heat resistant resin for forming the heat resistant resin matrix is used. When added to a solution dissolved using a solvent, this amino resin fine powder also dissolves in the heat-resistant resin liquid or solution, making it impossible to exhibit the function as the amino resin fine powder. Because.

The amino resin fine powder is, for example, heat-cured amino resin and then pulverized using a jet mill or a freeze pulverizer, or spray-dried the amino resin solution before curing, and then cured. Particles obtained by adding an aqueous curing agent to an uncured amino resin emulsion and stirring the resulting mixture are classified by an air classifier or the like. Further, the amino resin may be cured by heating with a foaming agent and then pulverized to obtain amino resin fine powder having closed cells.

As a method for curing the heat-resistant resin constituting the amino resin fine powder, there is a method of curing by heating or a method of curing by adding a catalyst. Among them, the method of curing by heating is practical. It is.

Among the amino resin fine powders, as a method for forming pseudo particles obtained by adhering at least one of amino resin fine powder and inorganic fine powder to the surface of the amino resin powder, for example, amino resin particles It is advantageous to apply a method in which an amino resin fine powder or an inorganic fine powder is coated on the surface and then heated and fused or bonded via a binder.

Among the amino resin fine powders, as a method of forming aggregated particles obtained by aggregating the amino resin powder, for example, the amino resin powder is simply heated by a hot air drier or the like, or various binders are added and mixed. And agglomerated by drying. Then, it is advantageous that the product is crushed using a ball mill, an ultrasonic disperser, or the like, and further classified by an air classifier or the like to produce the product.

The shape of the amino resin fine powder obtained in this way has not only a spherical shape but also various complicated shapes, so that the shape of the anchor formed thereby becomes complicated accordingly. It works effectively to improve the adhesion strength of the plating film such as the peel strength and the pull strength.

The amino resin fine powder produced as described above is mixed with a heat-resistant resin solution forming a heat-resistant resin matrix or a solution obtained by dissolving a heat-resistant resin forming the heat-resistant resin matrix using a solvent. Add and uniformly disperse.

As the heat-resistant resin liquid to which the amino resin fine powder is added, a heat-resistant resin containing no solvent can be used as it is. Particularly, a heat-resistant resin liquid obtained by dissolving a heat-resistant resin in a solvent is preferable. Since the viscosity can be easily adjusted, the resin fine powder can be uniformly dispersed, and can be advantageously used because it can be easily applied to a substrate. Examples of the solvent used for dissolving the heat-resistant resin include, for example, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, butyl carbitol, butyl cellulose, and the like.
Tetralin, dimethylformamide, normal methylpyrrolidone and the like can be used.

An organic filler such as a fluororesin, a polyimide resin or a benzoguanamine resin, or a filler composed of an inorganic fine powder such as silica, alumina, titanium oxide, or zirconia is appropriately blended into the heat-resistant resin liquid. You may. 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.

The next step is a treatment for roughening the surface of the adhesive layer provided on the substrate. In this step, when the heat-resistant resin matrix is a thermosetting resin, an uncured or semi-cured state formed on the substrate (B-stage state)
Is thermally cured to a cured state (C stage state), and then at least a part of the amino resin fine powder dispersed on the surface of the adhesive layer is dissolved and removed with an acid or an oxidizing agent. To roughen the surface of the adhesive layer.

On the other hand, when the heat-resistant resin matrix of the adhesive layer is a photosensitive resin, a photomask is brought into close contact with the uncured or semi-cured (B-stage) adhesive layer formed on the substrate. Light curing is performed to obtain a cured state (C-stage state), and thereafter, unnecessary portions are developed to obtain a roughened surface.

The amino resin fine powder dispersed on the surface of the adhesive layer can be dissolved and removed by immersing the substrate on which the adhesive layer has been formed in the solution using the acid or oxidizing agent solution, Alternatively, it can be carried out by means such as spraying an acid or oxidant solution onto the substrate, and as a result, the surface of the adhesive layer can be roughened. For the purpose of effectively dissolving and removing the amino resin fine powder, the surface portion of the adhesive layer may be lightly roughened in advance by, for example, polishing with a fine abrasive or liquid honing. Extremely effective.

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 next step is a process of forming a required conductor pattern by applying electroless plating to the surface of the roughened adhesive layer on the substrate. This treatment includes, for example, electroless copper plating, electroless nickel plating, electroless tin plating, electroless gold plating, and electroless silver plating, and particularly, electroless copper plating, electroless nickel plating, and electroless gold plating. It is preferable to use at least one method of plating.

In the manufacturing method of the present invention, after performing the above-described electroless plating, different types of electroless plating or electroplating may be further performed, or solder may be coated.

Further, in the method of the present invention, the above-mentioned conductive circuit can be formed by other methods used for a known printed wiring board. For example, a method of performing electroless plating on a substrate and then etching the circuit. For example, a method of directly forming a circuit when performing electroless plating or the like may be applied.

Further, in the case of manufacturing a multilayer printed wiring board by the method of the present invention, an additive process characterized by forming holes for via holes and performing electroless plating in the same manner as described above. Applied.
The use of a photosensitive resin is particularly effective for manufacturing a build-up multilayer wiring board.

The printed wiring board of the present invention obtained by applying the above-described manufacturing method of the present invention is, for example, shown in FIG.
As shown in FIGS. 2 (f) and 6 (g), a single-sided printed wiring board having a plating resist 3 and a conductive circuit 4 formed on a substrate 1 via an adhesive layer 2, as shown in FIG. 3 (f). A double-sided through-hole printed wiring board in which a plating resist 3 and a conductive circuit 4 are formed via an adhesive layer 2 on both sides of a substrate 1 and a through-hole 5, and a first conductive layer as shown in FIG. 4 is formed on a substrate 1 on which a conductive circuit (4, 6, 8, 1) is interposed via an interlayer insulating layer (adhesive layer) 2 having a via hole 7.
0), in a build-up multilayer wiring board formed by multilayering, the adhesive is hardened by curing a heat-resistant resin fine powder which is soluble in any case with an acid or an oxidizing agent. It is dispersed in a heat-resistant resin matrix exhibiting a property of being hardly soluble in an acid or an oxidizing agent, and furthermore, an amino resin fine powder is used as the heat-resistant resin fine powder. At least one resin selected from the group consisting of epoxy resin, resin having an acrylic group, and acrylic resin is used.

[0055]

EXAMPLES (Example 1) (1) 1275 parts by weight of melamine resin
Mix 1366 parts by weight of 37% formalin and 730 parts by weight of water,
The mixture was adjusted to pH = 9.0 with sodium carbonate, and kept 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 obtained in the above (2), a release agent, and a curing catalyst were pulverized and mixed in a ball mill. (4) Put the mixed powder in a mold heated to 150 ° C,
It was kept at a pressure of 0 kg / cm ² for 60 minutes. In this molding,
The mold was opened and degassing was performed. (5) The molded product obtained in the above (2) was pulverized with a ball mill and pulverized to obtain powders having particle diameters of 0.5 μm and 5.5 μm. (6) 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 The solid content of 100 parts by weight of the composition, (5)
15 parts by weight of the fine powder prepared in
A mixture having a particle size of 5.5 μm was mixed at a ratio of 30 parts by weight, and then kneaded with three rolls, and butyl cellosolve acetate was further added to prepare an adhesive solution having a solid concentration of 75%. 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 2.6 Pa · s at 60 rpm. The value (thixotropic property) was 2.0. (7) The glass epoxy substrate 1 is roughened by polishing,
After forming a rough surface of B0601 R _max = 2 to 3 μm, the adhesive solution of the photosensitive resin composition prepared in the above (6) was applied to the substrate using a roll coater. At this time, the coating method used a coating roll for resist for medium and high viscosity (manufactured by Dainippon Screen) as a coating roll, and the gap between the coating roller and the doctor bar was 0.4 m.
m, the gap between the coating roller and the backup roller was 1.4 mm, and the transport speed was 400 mm / s. afterwards,
After standing for 20 minutes in a horizontal state, dry at 70 ° C to a thickness of about 50
An adhesive layer 2 having a thickness of μm was formed (see FIGS. 1B and 1C). (8) The substrate 1 on which the adhesive layer 2 is formed is immersed in an oxidizing agent consisting of a 500 g / l chromic acid (CrO ₃ ) aqueous solution at 70 ° 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 adhesive layer 2 was activated by applying a palladium catalyst (manufactured by Shipley) to the substrate 1 having the roughened adhesive (see FIG. 1 (d)). (9) Next, this substrate 1 is placed in a nitrogen gas atmosphere (10 ppm oxygen).
Heat treatment at 120 ° C. for 30 minutes in the catalyst, then laminating a photosensitive dry film, exposing, developing with modified chlorocene, and plating resist 3 (thickness
40 μm) (see FIG. 1 (e)). (10) The substrate 1 on which the plating resist 3 has been formed is immersed 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 4 having a thickness of 25 μm. A wiring board was obtained (see FIG. 1 (f)).

[0056]

[Table 1]

Example 2 (1) 200 g of melamine resin particles (average particle size: 3.9 μm) prepared in the same manner as in (1) to (5) of Example 1 were dispersed in 5 l of acetone. While stirring the suspension in a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.), melamine resin fine powder (average particle size) prepared in the same manner as in (1) to (5) of Example 1 in 10 liters of acetone. 0.
5 μm) The suspension in which 300 g was dispersed was dropped and mixed, whereby the melamine resin fine powder was adhered to the surface of the melamine resin particles, acetone was removed, and then 150 ° C.
To produce 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 consisting 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. An 80% adhesive solution was made. The viscosity of this solution was 5.
It was 2.0 Pa · s at 8 Pa · s and 60 rpm, and its SVI value (thixotropic property) was 2.9. (3) A printed wiring board was manufactured using this adhesive in the same manner as in Example 1 (see FIG. 2).

Example 3 (1) Melamine resin particles (average particle size: 3.9 μm) prepared in the same manner as in Example 1 were charged into a hot air drier and heat-treated at 180 ° C. for 3 hours to form cohesive bonds. I let it. The coagulated melamine resin particles are dispersed in acetone and crushed in a ball mill for 5 hours.
The particles were classified using an air classifier to produce aggregated particles. The aggregated particles had an average particle size of about 3.5 μm, and about 68% by weight was 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),
Butyl carbitol was added 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) to prepare an adhesive solution having a solid concentration of 80%. The viscosity of this solution is
It was 5.4 Pa · s at 6 rpm and 2.0 Pa · s at 60 rpm, and its SVI value (thixotropic property) was 2.2. (3) Both surfaces of the glass epoxy substrate 1 are roughened by polishing,
After forming a rough surface of JIS B0601 R _max = 2 to 3 μm, the adhesive solution of the photosensitive resin composition prepared in the above (2) is applied on the substrate 1 by using a roll coater, and then placed in a horizontal state. After drying at 70 ° C for about 45μ
m of the adhesive layer 2 was formed (see FIGS. 3B and 3C). (4) Next, the surface of the adhesive layer 2 was cut by drilling, and the substrate 1 was lightly buffed to expose the filler surface, and then immersed in an acid composed of a 6N hydrochloric acid aqueous solution at 70 ° C. for 15 minutes. Was roughened and then immersed in a neutralizing solution (manufactured by Shipley) 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 having the roughened adhesive (see FIGS. 3 (d) and 3 (e)). (5) Next, the substrate 1 was subjected to a heat treatment for immobilizing the catalyst at 120 ° C. for 30 minutes in a nitrogen gas atmosphere (10 ppm oxygen), and then a photosensitive dry film was laminated, exposed, and then denatured. By developing with chlorocene, a plating resist 3 (thickness: 40 μm) was formed (see FIG. 3 (f)). (6) The substrate 1 on which the plating resist 3 has been formed is immersed in an electroless copper plating solution having the composition shown in Table 1 for 11 hours, and both surfaces are plated with a 30 μm thick electroless copper plating film 4. ,
Conductor circuits and through holes 5 were formed to obtain a double-sided printed wiring board (see FIG. 3 (f)).

Example 4 (1) A photosensitive dry film (manufactured by DuPont) was laminated on a glass epoxy copper-clad laminate (manufactured by Toshiba Chemical), and exposed to ultraviolet light through a mask film on which a desired conductive circuit pattern was drawn. Burn the image. Then, development is performed with 1,1,1-trichloroethane, copper in the non-conductor portion is removed using a cupric chloride etching solution, and the dry film is peeled off with methylene chloride. Thus, the wiring board 1 having the first conductor layer 4 including a plurality of conductor patterns was formed (see FIG. 4A). (2) 60 parts by weight of a 50% acrylate of a cresol novolak type epoxy resin (manufactured by Nippon Kayaku), 40 parts by weight of a bisphenol A type epoxy resin (manufactured by Yuka Shell), 15 parts by weight of diallyl terephthalate, 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropanone-1
After mixing 4 parts by weight (manufactured by Ciba-Geigy), 4 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals) and 50 parts by weight of fine powder of hollow melamine resin (manufactured by Honen Corporation: particle size 2 μm), while adding butyl cellosolve The mixture was stirred with a homodisper stirrer. Thereafter, the mixture was kneaded with three rollers to prepare a photosensitive adhesive solution having a solid content of 70%.
The viscosity of this solution was 5.0 Pa · s at 60 rpm and 60 rpm.
Was 2.5 Pa · s, and its SVI value was 2.0. (3) The adhesive solution of the photosensitive resin composition prepared in (2) is applied to the wiring board 1 prepared in (1) above using a roll coater, and then left horizontally for 20 minutes. , 70
The photosensitive resin insulating layer 2 having a thickness of about 50 .mu.m was formed by drying at .degree. C. (see FIGS. 4 (b) and 4 (c)). (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 ultra-high pressure mercury lamp. This is
By performing ultrasonic development treatment with 1,1-trichloroethane, an opening serving as a 100 μmφ via hole was formed on the wiring board 1, and further, about 3000 mj / cm ² by an ultra-high pressure mercury lamp.
Then, heat treatment was performed at 100 ° C. for 1 hour and then at 150 ° C. for 10 hours to form an interlayer insulating layer 2 having openings 7 having excellent dimensional accuracy corresponding to a photomask film (see FIG. 4D). ). (5) The wiring board 1 prepared in (4) is replaced with chromic acid (CrO
₃ ) The surface of the interlayer insulating layer 2 was roughened by immersing it in an oxidizing agent consisting of a 500 g / l aqueous solution at 70 ° C. for 15 minutes, and then immersed in a neutralizing solution (manufactured by Shipley) and washed with water. A surface of the insulating layer 2 was activated by applying a palladium catalyst (manufactured by Shipley) to the substrate having the roughened interlayer insulating layer 2 and immersed in an electroless copper plating solution having the composition shown in Table 1 for 11 hours. , Thickness of plating film 6 25
A μm electroless copper plating was applied (see FIGS. 4 (d) and 4 (e)). (6) By repeating the steps (3) to (5) two more times, a build-up multilayer wiring board having four wiring layers (4, 6, 8, 10) was prepared (FIG. f)).

Example 5 (1) 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 an imidazole-based curing agent (manufactured by Shikoku Chemicals) 5 parts by weight were dissolved in methyl ethyl ketone, and 15 parts by weight of a melamine resin fine powder (manufactured by Honen Corporation) having a particle size of 0.5 μm and a particle size of 5.5 μm were added to 100 parts by weight of the solid content of the composition. Are mixed in a proportion of 30 parts by weight,
After kneading with a ball mill, methyl ethyl ketone was further added to prepare an adhesive solution having a solid content concentration of 55%. The viscosity of this solution is 0.6 Pa · s at a rotation speed of 6 rpm and 0.5 at 60 rpm.
Pa · s and its SVI value (thixotropic property)
Was 1.2. (2) This adhesive solution was impregnated in a glass cloth and dried to prepare a prepreg 11 (see FIG. 5 (a)). (3) Glass epoxy substrate 1 on which conductive circuit 4 is formed
, Prepreg 11 is overlaid, hot pressed, and adhesive layer 2
Was formed (see FIG. 5 (b)). (4) Next, a hole is drilled by a drill, and the substrate 1 is
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. 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 (see FIG. 5 (c)). (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. 5 (d)). (6) The substrate 1 on which the plating resist has been formed is placed in Table 1
11 hours, immersed in an electroless copper plating solution having the composition shown in (1) for 11 hours, applied electroless copper plating having a thickness of 30 μm to the plating film 4 on both sides to form a conductor circuit and a through hole 5, thereby obtaining a double-sided printed wiring board. (See FIG. 5 (e)).

Example 6 (1) 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 an imidazole-based curing agent (manufactured by Shikoku Chemicals) 5 parts by weight were dissolved in butyl cellosolve, and 15 parts by weight of a melamine resin fine powder (manufactured by Honen Corporation) having a particle size of 0.5 μm and a particle size of 5.5 μm were added to 100 parts by weight of the solid content of the composition. Are mixed in a proportion of 30 parts by weight,
After kneading with this roll, butyl cellosolve was further added to prepare an adhesive solution having a solid content concentration of 55%. The viscosity of this solution was 2.6 Pa · s at 6 rpm and 1.0 Pa at 60 rpm.
S and its SVI value (thixotropic property) is 2.
6 (2) Apply this adhesive to a polyethylene film 12 coated with silicon using a roll coater,
For 30 minutes to obtain an adhesive film (FIG. 6 (a),
(b)). (3) This film was overlaid on an insulating plate (substrate 1), and the polyethylene film 12 was peeled off, and then heated and pressed to obtain an adhesive layer 2 (see FIGS. 6C and 6D). (4) A printed wiring board was obtained in the same manner as in Example 1 (FIG. 6).
reference).

(Example 7) (1) An adhesive solution A was prepared by performing the same processes as in (1) to (6) of Example 1 (excluding the curing agent). (2) 5 parts by weight of an imidazole-based curing agent was dissolved in butyl cellosolve to prepare an adhesive solution B. (3) The adhesive solution A and the adhesive solution B were stored at room temperature for one month, and then mixed to obtain an adhesive solution. The characteristics were the same as in Example 1. (4) A printed wiring board was manufactured using this adhesive solution. When the characteristics were evaluated, the same results as those of the printed wiring board obtained in Example 1 were obtained.

Example 8 (1) This example is basically the same as Example 1, except that 100 parts by weight of a flame-retardant novolak epoxy resin (manufactured by Nippon Kayaku) and an imidazole-based curing agent (Shikoku) 7 parts by weight of a chemical compound (manufactured by Kasei Chemical Co., Ltd.) were dissolved in butyl cellosolve acetate, and 15 parts by weight of the fine powder prepared in (5) of Example 1 was added to 15 parts by weight based on 100 parts by weight of the solid content of the composition. A mixture having a particle size of 5.5 μm was mixed at a ratio of 30 parts by weight, and then kneaded with three rolls, and butyl cellosolve acetate was further added to prepare an adhesive solution having a solid content of 75%. The viscosity of this solution was 5.2 at 6 rpm.
Pa · s and 2.5 Pa · s at 60 rpm, and its SVI value (thixotropic property) was 2.0. (2) Using this adhesive, a printed wiring board was prepared in the same manner as in Example 1.

Example 9 (1) This Example is basically the same as Example 4, except that 100 parts by weight of a 50% acrylate of ortho-cresol novolak type epoxy resin (manufactured by Nippon Kayaku), diallyl terephthalate 15 parts by weight, 2-methyl-
4 parts by weight of 1- [4- (methylthio) phenyl] -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) After mixing 50 parts by weight of hollow melamine resin fine powder (made by Honen Corporation: particle size: 2 μm), the mixture was stirred with a homodisper stirrer while adding butyl cellosolve. Thereafter, the mixture was kneaded with three rollers to prepare a photosensitive adhesive solution having a solid content of 70%.
The viscosity of this solution was 5.1 Pa · s at 60 rpm and 60 rpm.
Was 2.6 Pa · s, and its SVI value was 2.0. (2) Using this adhesive, a multilayer printed wiring board was prepared in the same manner as in Example 4.

Example 10 (1) 1 to 1 mol of guanamine was mixed with 1.2 to 1.6 mol of formalin, the pH was adjusted to 6.5, and the mixture was reacted at 60 ° C. to obtain a transparent resin solution. (2) After drying this resin solution, it was roughly pulverized, put into a ball mill together with phosphoric acid and a plasticizer, and finely pulverized simultaneously with curing to obtain a fine guanamine resin powder. (3) This embodiment is basically the same as the first embodiment,
The guanamine resin fine powder obtained in the above (1) and (2) was used as the amino resin fine powder. Also, 100 parts by weight of a phenol novolak type epoxy resin was used, and no bisphenol A type epoxy resin was used. The viscosity of the adhesive solution in this example was measured at 20 ° C. for 60 seconds using a digital viscometer manufactured by Tokyo Keiki according to JIS-K7117, and it was 5.0 Pa · s at 6 rpm.

Example 11 (1) Urea, isothiourea and formalin were mixed at a molar ratio of 1: 1: 2, and this mixture was heated at 80 ° C. and co-condensed to form a urea-thiourea co-condensation. A resin fine powder was obtained. (2) This embodiment is basically the same as the fourth 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 phenol novolak type epoxy resin was used, and no bisphenol A type epoxy resin was used. The viscosity of the adhesive solution in this example was measured at 20 ° C. for 60 seconds using a digital viscometer manufactured by Tokyo Keiki according to JIS-K7117, and it was 0.05 Pa · s at 6 rpm.

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

[0068]

[Table 2]

The adhesion, chemical resistance, heat resistance, electrical characteristics, hardness and the effect of impurities (migration resistance) of the electroless plating film of the wiring board manufactured as described above were measured. The results were as shown.

As is clear from Table 2, in the case of the present invention, not only high adhesion strength of conductors can be obtained, but also insulation reliability between conductors is excellent, and high-density printed wiring boards can be manufactured. It is particularly advantageous in doing so. In addition, since it has a high surface hardness, it has excellent wire bonding properties, and can be advantageously used as a bare chip mounting substrate.

Next, as a result of examining the change in the surface resistance of the adhesive layer by immersing it in boiling water at 100 ° C. for 2 hours, no change occurred as compared with the initial value. Furthermore, in the present invention example,
No abnormality was found even after a heat resistance test in which the surface of the wiring board was brought into close contact with a hot plate maintained at a surface temperature of 300 ° C. and heated for 10 minutes.

Each test method for the adhesion strength (peel strength), electric insulation, hardness and influence of impurities (migration resistance) of the electroless plating film will be described. (1) Adhesion strength (peel strength) of electroless plating film JIS-C-6481 (2) Electrical insulation L / S = 100/100 μ formed on printed wiring board
A DC voltage or a sine-wave AC peak voltage at a frequency of 50 Hz or 60 Hz is applied to the comb pattern of m, and 500 V is applied. The voltage is gradually applied to the specified voltage in about 5 seconds, and the battery is charged for 1 minute to check 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. After 1000 hours, the presence or absence of migration between patterns is checked.

[0073]

As described above, according to the adhesive for wiring boards of the present invention and the wiring board using this adhesive, chemical resistance, heat resistance and electric resistance which are not affected by the use environment. An adhesive excellent in characteristics and hardness, a method for manufacturing a printed wiring board using the same, and a printed wiring board can be stably provided.

[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 an explanatory diagram showing a migration reaction of a printed wiring board.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate (wiring board) 2 Adhesive layer (insulating layer) 3 Plating resist 4,6,8,10 Wiring layer (plating layer, conductor layer) 5 Through hole hole 7 Via hole opening 11 Prepreg 12 Polyethylene film

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) H05K 3/10-3/38 C09J 161/20-161/32

Claims (8)

(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 oxidizing agent when cured. An adhesive for wiring boards, wherein an amino resin fine powder is used as the heat resistant resin fine powder in an adhesive dispersed in a cured heat resistant resin matrix. 2. The adhesive according to claim 1, wherein the amino resin fine powder is one or more resin fine powders selected from melamine resin, urea resin and guanamine resin. 3. The heat-resistant resin matrix is a mixture of a thermosetting heat-resistant resin, which is either an uncured polyfunctional epoxy resin or an uncured bifunctional epoxy resin, and an imidazole-based curing agent. 2. The adhesive according to 1. 4. The heat-resistant resin matrix has a solid content,
20-100 wt% of uncured polyfunctional epoxy resin and 80-0 wt%
A thermosetting heat-resistant resin composed of wt% of an uncured bifunctional epoxy resin and an imidazole-based curing agent having a solid content of 2 to 10% by weight. Inside, for 100 parts by weight of its solids content
4. The composition according to claim 3, wherein 10 to 100 parts by weight are dispersed and mixed.
The adhesive according to item 1. 5. The heat-resistant resin matrix is at least one photosensitive material selected from an uncured polyfunctional epoxy resin, an uncured polyfunctional acrylic group-containing resin, and an uncured polyfunctional acrylic resin. The adhesive according to claim 1, wherein the adhesive is a heat-resistant resin or a mixed resin of these resins and at least one photosensitive heat-resistant resin selected from an uncured bifunctional epoxy resin and an uncured bifunctional acrylic resin. Agent. 6. The heat-resistant resin matrix has a solid content,
20 to 100% by weight of at least one photosensitive heat-resistant resin selected from an uncured polyfunctional epoxy resin, an uncured polyfunctional resin having an acrylic group, and an uncured polyfunctional acrylic resin; In minutes, a resin mixture of at least one photosensitive heat-resistant resin selected from an uncured bifunctional epoxy resin and an uncured bifunctional acrylic resin in an amount of 80 to 0% by weight; In this heat-resistant resin matrix, 10 to 10 parts by weight of the solid content thereof
The adhesive according to claim 5, wherein 100 parts by weight of the adhesive are dispersed and mixed. 7. After providing the adhesive layer according to any one of claims 1 to 6 on a substrate and curing, the surface of the adhesive layer is roughened with an acid or an oxidizing agent. A method for manufacturing a printed wiring board, comprising performing electroless plating. 8. A printed wiring board having an adhesive layer provided on at least one substrate surface and a conductive circuit formed thereon, wherein a cured heat-resistant resin soluble in acid or oxidizing agent is provided. An amino resin fine powder was used as the heat-resistant resin fine powder of the adhesive obtained by dispersing the fine powder in a heat-resistant resin matrix which is cured and hardly soluble in an acid or an oxidizing agent. A printed wiring board, characterized in that: