JP2000265073A - Resin composition for forming roughened surface and printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for forming a roughened surface which, when cured, does not separate from a conductor circuit formed thereon even under severe conditions and is excellent in crack resistance under heat cycle conditions. SOLUTION: This composition comprises (A) an uncured heat-resistant resin matrix which is hardly soluble in a roughening liquid comprising at least one compound selected from among acids, alkalis, and oxidizing agents and, dispersed in matrix A, (B) a substance which is soluble in a roughening liquid comprising at least one compound selected from among acids, alkalis, and oxidizing agents. Matrix A comprises a thermosetting resin and a poly(meth) acrylic ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for forming a roughened surface (adhesive for electroless plating) and a printed wiring board using the same, and more particularly, to the adhesion between a conductor circuit and an interlayer resin insulating layer. The present invention relates to a resin composition for forming a roughened surface capable of forming a fine pattern without lowering the cracks and suppressing the occurrence of cracks during a heat cycle, and a printed wiring board using the resin composition.

[0002]

2. Description of the Related Art In recent years, a so-called build-up multilayer wiring board has attracted attention due to a demand for higher density of the multilayer wiring board. This build-up multilayer wiring board is manufactured by a method disclosed in, for example, Japanese Patent Publication No. 4-55555. That is, an adhesive for electroless plating made of a photosensitive resin is applied onto the core substrate on which the lower conductive circuit is formed, and then dried and exposed and developed to form an interlayer resin having an opening for a via hole. An insulating layer is formed. Next, after the surface of the interlayer resin insulating layer is roughened by a treatment with an oxidizing agent or the like, the photosensitive resin layer is exposed,
A plating resist is provided by performing a development process, and thereafter, a conductive circuit pattern including via holes is formed by applying electroless plating or the like to a portion where the plating resist is not formed. By repeating such a process a plurality of times, a multilayered build-up wiring board is manufactured.

As an adhesive for electroless plating used for an interlayer resin insulating layer of such a build-up multilayer wiring board, for example, JP-A-63-158156 and JP-A-2-18892 ( US Patent No. 505
No. 5321, U.S. Pat. No. 5,519,177). Soluble resin particles composed of coarse particles having an average particle diameter of 2 to 10 μm and fine particles having an average particle diameter of 2 μm or less as described in US Pat. Examples thereof include those dispersed in a heat-resistant resin matrix.

[0004]

However, such a build-up multilayer printed wiring board is actually manufactured, and an IC is manufactured.
When a temperature change is applied after mounting the chip, peeling occurs due to the lack of adhesion between the interface between the plating resist and the conductor circuit, and due to a difference in the coefficient of thermal expansion between the plating resist and the conductor circuit, the interface between the plating resist and the conductor circuit is reduced. This causes a new problem that cracks occur in the interlayer resin insulation layer starting from the above.

Further, when a fine pattern having a width of conductor circuit / width between conductor circuits (hereinafter, referred to as L / S) of 25/25 μm is formed, a gap between the conductor circuit and the plating resist under a high temperature and high humidity condition is obtained. There was also a problem that peeling occurred.

The present invention has been made to solve the above-mentioned problems of the prior art, and its main object is to manufacture a printed wiring board by using this resin composition as an interlayer resin insulating layer. A resin composition for forming a roughened surface, which does not cause peeling between a conductor circuit and an interlayer resin insulating layer, can maintain practical peel strength, and can prevent the occurrence of cracks, and the printed wiring board. It is in.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies for realizing the above-mentioned object, and as a result, have completed the present invention having the following contents. That is, the resin composition for forming a roughened surface of the present invention contains an acid, an uncured heat-resistant resin matrix that is hardly soluble in a roughening liquid comprising at least one selected from an alkali and an oxidizing agent. In a resin composition for forming a roughened surface, in which a substance soluble in a roughening liquid comprising at least one selected from an alkali and an oxidizing agent is dispersed, the heat-resistant resin matrix comprises a thermosetting resin and a poly ( And (meth) acrylic acid esters.

[0008] In the above-mentioned resin composition for forming a roughened surface, at least one selected from the above-mentioned acids, alkalis and oxidizing agents.
Substances that are soluble in the seed roughening solution include inorganic particles,
It is preferably at least one selected from resin particles, metal particles, rubber particles, liquid phase resin and liquid phase rubber.

Further, the printed wiring board according to the first aspect of the present invention comprises:
In a hardened heat-resistant resin matrix which is hardly soluble in a roughening liquid composed of at least one selected from an acid, an alkali and an oxidizing agent, a coarse mixture composed of at least one selected from an acid, an alkali and an oxidizing agent is provided. A resin insulating layer in which a substance soluble in a chemical solution is dispersed is formed on the substrate,
A roughened surface is formed by removing the soluble substance on the surface of the resin insulating layer, and a printed circuit board in which a conductive circuit is formed on the roughened surface, wherein the heat-resistant resin matrix Is characterized by containing a thermosetting resin and a poly (meth) acrylate.

[0010] In the printed wiring board, the substance soluble in the roughening solution comprising at least one selected from the above-mentioned acids, alkalis and oxidizing agents includes inorganic particles, resin particles, metal particles, rubber particles, and liquid phase resin. And at least one selected from liquid phase rubbers.

The printed wiring board according to the second aspect of the present invention comprises:
In a printed wiring board having a resin insulating layer formed on a substrate and a conductive circuit formed on the resin insulating layer, the resin insulating layer contains a thermosetting resin and poly (meth) acrylate. It is characterized by.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for forming a roughened surface according to the present invention comprises an uncured heat-resistant resin matrix which is hardly soluble in a roughening solution comprising at least one selected from acids, alkalis and oxidizing agents. In the resin composition for forming a roughened surface, in which a substance soluble in a roughening liquid comprising at least one selected from an acid, an alkali, and an oxidizing agent is dispersed, the heat-resistant resin matrix is heat-cured. It is characterized by containing a conductive resin and a poly (meth) acrylate.

In the resin composition for forming a roughened surface according to the present invention, since the heat-resistant resin matrix contains a thermosetting resin and a poly (meth) acrylate, the cured product composed of these composites is used. The fracture toughness value is improved, cracks are less likely to occur, and peeling is less likely to occur even when a conductive circuit is formed on the cured product. Therefore, a printed wiring board in which the above-described resin composition for forming a roughened surface is used as an interlayer resin insulating layer is less likely to cause peeling between the interlayer resin insulating layer and the conductive circuit, and is resistant to cracking under heat cycle conditions. Also excellent in nature.

Examples of the poly (meth) acrylate include polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polymethyl methacrylate, polyethyl methacrylate, and polypropyl methacrylate. And polybutyl methacrylate. Of these, polymethyl methacrylate is preferred. In addition, the molecular weight is several hundred to
A few thousand is preferred.

[0015] The content of the poly (meth) acrylate is preferably 0.1 to 30% by weight based on the total solids of the resin composition for forming a roughened surface. When the content of the poly (meth) acrylate is less than 0.1% by weight, the fracture toughness of the heat-resistant resin matrix is not improved,
On the other hand, if the content exceeds 30% by weight, fragile poly (meth) acrylic acid ester crystals start to be generated, which makes it rather brittle.

As the above-mentioned heat-resistant resin matrix, for example, a thermosetting resin or a composite of a thermosetting resin (including one in which a part of the thermosetting group is sensitized) and a thermoplastic resin are used. Can be. As the thermosetting resin,
For example, an epoxy resin, a phenol resin, a polyimide resin, a thermosetting polyolefin resin, and the like can be given. When the thermosetting resin is exposed to light, a methacrylic acid, acrylic acid, or the like is used to cause the thermosetting group to undergo a (meth) acrylation reaction. Particularly, epoxy resin (meth) acrylate is most suitable. In the case of the photosensitization, it is desirable that 5 to 50% of a thermosetting group (for example, an epoxy group) is subjected to a (meth) acrylate reaction.

As the above epoxy resin, for example, novolak type epoxy resin, alicyclic epoxy resin and the like can be used. As the thermoplastic resin, for example, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like can be used.

The mixing ratio of the poly (meth) acrylate to the thermosetting resin is preferably 0.18 to 30 parts by weight based on 100 parts by weight of the thermosetting resin.

The substance soluble in the roughening liquid comprising at least one selected from the above-mentioned acids, alkalis and oxidizing agents is selected from inorganic particles, resin particles, metal particles, rubber particles, liquid resin and liquid rubber. It is desirable that it is at least one kind.

Examples of the inorganic particles include silica,
Examples include alumina, calcium carbonate, talc, and dolomite. These may be used alone or in combination of two or more. The alumina particles can be dissolved and removed with hydrofluoric acid, and the calcium carbonate can be dissolved and removed with hydrochloric acid. Further, sodium-containing silica and dolomite can be dissolved and removed with an alkaline aqueous solution.

Examples of the resin particles include amino resins (melamine resins, urea resins, guanamine resins, etc.),
Epoxy resins, bismaleimide-triazine resins and the like can be mentioned. These may be used alone or in combination of two or more. The epoxy resin can be arbitrarily manufactured by dissolving in an acid or an oxidizing agent or hardly dissolving in the acid or the oxidizing agent by selecting the type of the oligomer and the curing agent. For example, a resin obtained by curing a bisphenol A-type epoxy resin with an amine-based curing agent is very soluble in chromic acid, but a resin obtained by curing a cresol novolac-type epoxy resin with an imidazole curing agent is not easily dissolved in chromic acid. .

It is necessary that the resin particles have been previously cured. If not cured, the resin particles will dissolve in the solvent that dissolves the resin matrix, so they will be uniformly mixed, and it will not be possible to selectively dissolve and remove only the resin particles with an acid or oxidizing agent. is there.

The metal particles include, for example, gold, silver,
Examples include copper, tin, zinc, stainless steel, and aluminum. These may be used alone or in combination of two or more. Examples of the rubber particles include acrylonitrile-butadiene rubber, polychloroprene rubber,
Polyisoprene rubber, acrylic rubber, polysulfuric rigid rubber,
Fluorine rubber, urethane rubber, silicone rubber, ABS resin and the like can be mentioned. These may be used alone,
Two or more kinds may be used in combination.

As the liquid resin, an uncured solution of the thermosetting resin can be used. Specific examples of such a liquid resin include, for example, an uncured epoxy oligomer and an amine-based curing agent. And the like. As the liquid phase rubber, for example, an uncured solution of the rubber can be used.

In the case of preparing a resin composition for forming a roughened surface using the above liquid phase resin or liquid phase rubber, the heat resistant resin matrix and the soluble substance are not uniformly compatible (that is, the phase is separated so that the phase is separated). You need to choose these substances, as in By mixing a heat-resistant resin matrix and a soluble substance selected according to the above criteria, a state in which "islands" of liquid-phase resin or liquid-phase rubber are dispersed in the "sea" of the heat-resistant resin matrix Alternatively, a resin composition for forming a roughened surface in which "islands" of a heat-resistant resin matrix are dispersed in the "sea" of a liquid-phase resin or a liquid-phase rubber can be prepared.

After curing the resin composition for forming a roughened surface in such a state, the roughened surface is formed by removing the liquid resin or liquid rubber in the "sea" or "island". be able to.

Examples of the acid constituting the roughening solution include phosphoric acid, hydrochloric acid, sulfuric acid, and organic acids such as formic acid and acetic acid. Among them, it is preferable to use an organic acid. This is because when the roughening treatment is performed, the metal conductor layer exposed from the via hole is hardly corroded. As the oxidizing agent, for example, an aqueous solution of chromic acid, an alkaline permanganate (such as potassium permanganate), or the like is desirably used. As the alkali, an aqueous solution of sodium hydroxide, potassium hydroxide or the like is desirable.

In the present invention, when the above-mentioned inorganic particles, the above-mentioned metal particles and the above-mentioned resin particles are used, the average particle size is desirably 10 μm or less. Further, in particular, by using a mixture of coarse particles having a relatively large average particle diameter and fine particles having a relatively small average particle diameter having an average particle diameter of less than 2 μm, the electroless plating film Dissolved residues can be eliminated, the amount of palladium catalyst under the plating resist can be reduced, and a shallow and complicated roughened surface can be formed. By forming such a complicated roughened surface, a practical peel strength can be maintained even on a shallow roughened surface.

By combining the above coarse particles and fine particles, a shallow and complicated roughened surface can be formed because the coarse particles used are coarse particles having an average particle size of less than 2 μm. The anchor formed even when dissolved is removed becomes shallow, and the particles to be removed are formed by the mixture of coarse particles having a relatively large particle diameter and fine particles having a relatively small particle diameter. The roughened surface becomes complicated. In this case, the particle diameter used is coarse and the average particle diameter is less than 2 μm, so that roughening does not proceed too much and no voids are generated, and the formed interlayer resin insulating layer has excellent interlayer insulating properties. ing.

When an opening for a via hole is formed by exposure, development, laser processing, or the like, a residue of the insulating layer usually remains at the bottom of the opening for the via hole. Since there are components dissolved in the roughening solution such as alkali, acid and oxidizing agent in the layer, such residues can be easily removed by the roughening treatment using the roughening solution.

It is desirable that both the coarse particles and the fine particles are not crushed particles but spherical particles. For crushed particles,
The roughened surface after the roughening treatment is angular, and when the temperature of the interlayer resin insulating layer changes, stress concentration tends to occur at the tip of the angular portion, and therefore, cracks easily occur in the interlayer resin insulating layer due to a heat cycle. Because.

In the present invention, since the formed anchor is shallow, both L / S are 40 when the semi-additive method or the full-additive method is employed.
Fine patterns smaller than / 40 μm can be formed.

Regarding the above-mentioned particles, the coarse particles have an average particle size of 0.3.
The average particle diameter of the fine particles is more than 8 μm and less than 2.0 μm, and desirably 0.1 to 0.8 μm. In this range, the depth of the roughened surface is approximately Rmax = approximately 3 μm. In the semi-additive method, not only is the electroless plating film easily removed by etching, but also the P under the electroless plating film is reduced.
This is because the d catalyst can be easily removed, and a practical peel strength of 1.0 to 1.3 kg / cm can be maintained.

In addition, the full additive method can not only reduce the amount of Pd catalyst nuclei under the plating resist, but also can prevent the plating resist from remaining, and have a practical peel strength of 1 even when a shallow anchor is formed. .0
１1.3 kg / cm can be maintained.

The mixing weight ratio at this time is desirably 35/10 to 10/10. If the amount of coarse particles is too large, the depth of the anchor becomes too deep to make it difficult to remove the electroless plating film by etching. If the amount of coarse particles is too small, the adhesion strength to the plating film cannot be obtained. The amount of the coarse particles is desirably 10 to 40% by weight based on the solid content of the resin composition for forming a roughened surface. The fine particles are desirably 1 to 15% by weight based on the solid content of the resin composition for forming a roughened surface. Then, the amount of the coarse particles is adjusted so that the weight of the coarse particles is equal to or larger than that of the fine particles in the range of the weight percentage.

The resin composition for forming a roughened surface of the present invention may be a B-stage prepreg obtained by impregnating the resin composition into a fibrous substrate such as a glass cloth and drying, or formed into a film. Is also good. Further, the substrate itself may be formed of a resin composition for forming a roughened surface. As the resin composition for forming a roughened surface of the present invention, a resin obtained by halogenating a constituent resin to make it flame-retardant may be used, and a dye, a pigment, and an ultraviolet absorber may be added. Further, a fibrous filler or an inorganic filler may be filled to adjust the toughness and the coefficient of thermal expansion.

The printed wiring board according to the first aspect of the present invention comprises a hardened, heat-resistant resin matrix which is hardly soluble in a roughening solution comprising at least one selected from acids, alkalis and oxidizing agents. Forming a resin insulating layer in which a substance soluble in a roughening liquid comprising at least one selected from an alkali and an oxidizing agent is dispersed on a substrate; and removing the soluble substance on the surface of the resin insulating layer. A printed circuit board having a roughened surface formed thereon and a conductor circuit formed on the roughened surface, wherein the heat-resistant resin matrix comprises a thermosetting resin and a poly (meth) acrylate ester It is characterized by including

In the printed wiring board according to the first aspect of the present invention, since the heat-resistant resin matrix constituting the resin insulating layer (interlayer resin insulating layer) contains a thermosetting resin and poly (meth) acrylate, The fracture toughness value of the interlayer resin insulation layer is improved, the crack resistance under heat cycle conditions is excellent, and peeling between the interlayer resin insulation layer and the conductor circuit hardly occurs.

In the above printed wiring board, the acid,
The substance soluble in the roughening liquid comprising at least one selected from alkali and oxidizing agent is at least one selected from the above-mentioned inorganic particles, resin particles, metal particles, rubber particles, liquid resin and liquid rubber. It is preferred that

The depth of the roughened surface of the interlayer resin insulating layer is preferably Rmax = 1 to 5 μm. This roughening depth is
Depth Rmax of roughened surface formed with conventional adhesive =
This is about 1/2 of 10 μm, because even if the electroless plating film under the plating resist is dissolved and removed, no plating residue remains, and the amount of palladium catalyst nuclei under the plating resist can be reduced.

In the semi-additive method, since the conductor circuit is composed of a thin portion of electroless plating and a thick portion of electrolytic plating, the plating stress of electrolytic plating is small, and the plating film is peeled even if the anchor is shallow. Hard to do.

In the first printed wiring board of the present invention,
It is desirable that a conductive circuit is formed on the interlayer resin insulating layer on the substrate formed using the resin composition for forming a roughened surface, and a roughened surface is formed on the surface of the conductive circuit by etching or the like.

When the substrate is formed by the full additive method, a roughened surface is formed on the upper surface of the conductive circuit, and when the substrate is formed by the subtractive method, the roughened surface is formed on the side surface or the entire surface of the conductive circuit. It is desirable. Due to these roughened surfaces, the adhesion between the resin insulating layer and the conductor circuit is improved, and the occurrence of cracks due to the difference in thermal expansion coefficient between the conductor circuit and the resin insulating layer during a heat cycle can be suppressed. It is.

A printed wiring board according to a second aspect of the present invention is a printed wiring board in which a resin insulating layer is formed on a substrate and a conductive circuit is formed on the resin insulating layer. It is characterized by containing a conductive resin and a poly (meth) acrylate.

Therefore, in the printed wiring board according to the second aspect of the present invention as well, the fracture toughness of the resin insulating layer is improved, the crack resistance under heat cycle conditions is excellent, and the resin insulating layer and the resin insulating layer formed thereon are formed. Separation hardly occurs between the conductive circuit and the conductive circuit.

The resin insulating layer according to the second aspect of the present invention comprises an acid,
In an uncured heat-resistant resin matrix which is hardly soluble in a roughening liquid comprising at least one selected from an alkali and an oxidizing agent, a roughening liquid comprising at least one selected from an acid, an alkali and an oxidizing agent is used. It is preferable that a resin composition for forming a roughened surface, in which a soluble substance is dispersed, is applied on a substrate on which a conductive circuit is formed and cured to form an interlayer resin insulating layer.

Preferably, the conductor circuit is provided with a roughened surface or a roughened layer for ensuring adhesion with an interlayer resin insulating layer formed thereon. It is preferable that a roughened surface is formed by removing the soluble substance in order to secure adhesion to a conductor circuit formed thereon. The roughening liquid, the heat-resistant resin and the soluble substance constituting the roughened surface forming resin composition may be the same as those in the first aspect of the present invention.

Next, a method for manufacturing one type of the printed wiring board of the present invention will be described by taking a semi-additive as an example. (1) First, a wiring board having an inner copper pattern (lower conductive circuit) formed on a surface of a core board is manufactured.

When a conductor circuit is formed on the core substrate, a method of etching the copper-clad laminate into a specific pattern, a method for electroless plating on a substrate such as a glass epoxy substrate, a polyimide substrate, a ceramic substrate, and a metal substrate. A method of forming an adhesive layer, roughening the surface of the adhesive layer for electroless plating to a roughened surface, and then performing electroless plating, or performing electroless plating on the entire roughened surface, and forming a plating resist. Forming a conductive circuit consisting of an electrolytic plating film and an electroless plating film by removing the plating resist and performing an etching process after electroplating the portion where the plating resist is not formed (semi-additive method) Etc. can be used.

Further, a roughened surface or a roughened layer can be formed on the surface of the conductor circuit of the wiring board. Here, the roughened surface or the roughened layer is desirably formed by any one of a polishing process, an etching process, a blackening reduction process, and a plating process. Of these treatments, when performing the blackening reduction treatment, NaOH (20 g
/ L), NaClO ₂ (50 g / l), Na ₃ PO ₄
(Oxidation bath) consisting of an aqueous solution containing (15.0 g / l), NaOH (2.7 g / l), NaBH ₄
A method of forming a roughened surface using a reducing bath composed of an aqueous solution containing (1.0 g / l) is desirable.

When a roughened layer is formed by plating, copper sulfate (1 to 40 g / l), nickel sulfate (0.1 to 6.0 g / l), and citric acid (10 to 20 g / l) are used.
l), sodium hypophosphite (10-100 g / l),
Boric acid (10 to 40 g / l), surfactant (Surfynol 465, manufactured by Nissin Chemical Industry Co., Ltd.) (0.01 to 10 g / l)
It is preferable to form a roughened layer made of a Cu-Ni-P alloy by performing electroless plating in an electroless plating bath having a pH of 9 and containing l). This is because the crystalline structure of the film deposited in this range has a needle-like structure, and thus has an excellent anchor effect. A complexing agent or an additive may be added to the electroless plating bath in addition to the above compounds.

As the above-mentioned etching method, there is a method in which an etching solution comprising a cupric complex and an organic acid is allowed to act in the presence of oxygen to roughen the surface of a conductor circuit. In this case, the etching proceeds by the chemical reaction of the following formulas (1) and (2).

[0053]

Embedded image

As the cupric complex, a cupric complex of an azole is desirable. This cupric complex of azoles is
It acts as an oxidizing agent that oxidizes metallic copper and the like. Examples of the azoles include diazole, triazole, and tetrazole. Among these, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole and the like are desirable. The content of the cupric complex of azoles in the etching solution is desirably 1 to 15% by weight. This is because it is excellent in solubility and stability, and can also dissolve noble metals such as Pd constituting the catalyst core.

In order to dissolve copper oxide, an organic acid is added to the cupric complex of azoles. Specific examples of the organic acid include, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, crotonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, benzoic acid, Glycolic acid, lactic acid, malic acid, sulfamic acid and the like can be mentioned. These may be used alone or in combination of two or more.

The content of the organic acid in the etching solution is 0.1%.
1 to 30% by weight is desirable. This is because the solubility of the oxidized copper can be maintained and the solubility stability can be ensured. As shown in the above formula (3), the generated cuprous complex dissolves by the action of an acid and combines with oxygen to form a cupric complex, which again contributes to copper oxidation.

To assist in dissolving copper and oxidizing azoles, halogen ions, for example, fluorine ions, chlorine ions, bromine ions, etc., may be added to the above etching solution. Further, halogen ions can be supplied by adding hydrochloric acid, sodium chloride, or the like. The amount of halogen ions in the etching solution is desirably 0.01 to 20% by weight. This is because adhesion between the formed roughened surface and the interlayer resin insulating layer is excellent.

When preparing an etching solution, a cupric complex of an azole and an organic acid (if necessary, having a halogen ion) are dissolved in water. As the etching solution, a commercially available etching solution, for example, “Mech Etch Bond” manufactured by Mec Co., Ltd. is used.
The amount of etching when using the above etching solution is 1 to 1
0 μm is desirable. When the etching amount exceeds 10 μm, poor connection between the formed roughened surface and the via-hole conductor occurs. On the other hand, when the etching amount is less than 1 μm, the adhesion to the interlayer resin insulating layer formed thereon is insufficient. This is because

The roughened layer or roughened surface may be covered with a layer of a metal or a noble metal having a higher ionization tendency than copper and not more than titanium (hereinafter, referred to as a metal layer). Such metals include, for example, titanium, aluminum, zinc, iron, indium, thallium, cobalt, nickel,
Examples include tin, lead, and bismuth. Examples of the noble metal include gold, silver, platinum, and palladium. These may be used alone or in combination of two or more to form a plurality of layers.

These metal layers cover the roughened layer, and even if the interlayer resin insulating layer is roughened, the local electrode reaction is prevented and the conductor circuit is prevented from melting. The thickness of these metals is 0.1-
2 μm is desirable.

Of the metals constituting the metal layer, tin is desirable. This is because tin can form a thin layer by electroless displacement plating and can follow the roughened layer. When forming a metal layer made of tin, a solution containing tin borofluoride-thiourea, or tin chloride-
Displacement plating is performed using a solution containing thiourea. In this case, a Sn layer having a thickness of about 0.1 to 2 μm is formed by the substitution reaction of Cu—Sn. When a metal layer made of a noble metal is formed, a method such as sputtering or vapor deposition can be employed.

A through hole may be formed in the core substrate, and the wiring layers on the front and back surfaces may be electrically connected via the through hole. In addition, a low-viscosity resin such as a bisphenol F-type epoxy resin may be filled between the through hole and the conductor circuit of the core substrate to ensure smoothness.

(2) Next, an interlayer resin insulating layer is formed on the substrate prepared in the above (1). When forming the interlayer resin insulating layer, the resin composition for forming a roughened surface of the present invention can be used. In addition, the interlayer resin insulation layer is made into a plurality of layers,
The particle size of each layer may be changed. For example, the lower layer has an average particle size of 1.0 μm, and the upper layer is a mixed particle having an average particle size of 1.0 μm and an average particle size of 0.5 μm, and is composed of a cured product of a resin composition for forming a roughened surface having different particle sizes. You may. The lower layer preferably has an average particle size of 0.1 to 2.0 μm, more preferably an average particle size of 0.1 to 1.0 μm. When applying the interlayer resin insulating material, a roll coater, a curtain coater, or the like can be used.

(3) After drying the layer of the resin composition for forming a roughened surface formed in the above (2), openings for via holes are provided as necessary. In a state where the layer of the resin composition for forming a roughened surface is dried, the thickness of the resin composition layer on the conductive circuit pattern is small, and the thickness of the interlayer resin insulating layer on the plane layer having a large area is small. Thickness, and also due to irregularities in the conductor circuit and the conductor circuit non-formed part, irregularities are often generated in the interlayer resin insulating layer, so using a metal plate or a metal roll, pressing while heating, It is desirable to flatten the surface of the interlayer resin insulation layer.

When the resin matrix forming the interlayer resin insulating layer is a thermosetting resin, the via hole opening is formed by using a laser beam, oxygen plasma or the like after thermosetting. In the case where the resin matrix is a photosensitive resin, it is formed by performing a development process after exposing with an ultraviolet ray or the like. When performing exposure and development processing,
A state in which the side of the photomask (preferably a glass substrate) on which a black circle pattern is drawn in a portion corresponding to the above-described via hole opening is in close contact with the photosensitive interlayer resin insulating layer. And exposed and developed.

4) Next, the cured interlayer resin insulation layer (roughened surface forming resin composition) is roughened. When the resin composition for forming a roughened surface is used, at least one soluble substance selected from inorganic particles, resin particles, metal particles, rubber particles, liquid phase resin, and liquid phase rubber present on the surface. Is removed by using a roughening solution such as an acid, an oxidizing agent, or an alkali described above. The depth of the roughened surface is 1-5μ
m is desirable.

(5) Next, a catalyst nucleus is applied to the wiring board in which the interlayer resin insulating layer is roughened. It is desirable to use a noble metal ion or a noble metal colloid for providing the catalyst nucleus, and generally, palladium chloride or a palladium colloid is used. Note that it is desirable to perform a heat treatment to fix the catalyst core. Palladium is preferred as such a catalyst core.

(6) Next, an electroless plating film is formed on the entire roughened surface. Electroless plating is desirably electroless copper plating. As the plating solution composition, a conventional plating solution can be used. For example, copper sulfate (29 g / l), sodium carbonate (25 g / l), tartrate (140 g / l), sodium hydroxide (40 g / l) ), An aqueous solution containing a 37% formaldehyde stock solution (5 ml / l) having a pH of 11.5 is desirable. The thickness of the electroless plating film is preferably from 0.1 to 5 μm, more preferably from 0.5 to 3 μm.

(7) Next, a photosensitive resin film (dry film) is laminated on the electroless plating film, and a photomask (preferably a glass substrate) on which a plating resist pattern is drawn is brought into close contact with the photosensitive resin film. A plating resist pattern is formed by mounting, exposing, and developing.

(8) Next, electrolytic plating is applied to the portion where the plating resist is not formed to form a conductor circuit and a via hole. Here, it is desirable to use copper plating as the electrolytic plating, and its thickness is desirably 1 to 20 μm.

(9) Further, after the plating resist is removed, the electroless plating film is formed with a mixed solution of sulfuric acid and hydrogen peroxide or an etching solution such as sodium persulfate, ammonium persulfate, ferric chloride, and cupric chloride. Dissolve and remove to form an independent conductor circuit. Further, the palladium catalyst nuclei on the exposed roughened surface are dissolved and removed with chromic acid or the like. (10) Next, a roughened layer or a roughened surface is formed on the surface of the conductor circuit. The formation of the roughened layer or the roughened surface is performed by using the method described in the above (1).

(11) Next, an interlayer resin insulating layer is formed on the substrate by using, for example, the resin composition for forming a roughened surface of the present invention. (12) Further, by repeating the steps (3) to (9), a further upper layer conductive circuit is provided, and a flat conductive pad functioning as a solder pad and a via hole are formed thereon, thereby forming a multilayer wiring. Obtain a substrate. Finally, by forming a solder resist layer and solder bumps, the manufacture of the printed wiring board is completed. Although the following method is based on the semi-additive method, a full additive method may be adopted.

Hereinafter, description will be made based on embodiments.

Example (Example 1) A. Preparation of Resin Composition for Forming Roughened Surface of Upper Layer 1) A 25% acrylate of cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 2500) is dissolved in diethylene glycol dimethyl ether (DMDG) at a concentration of 80% by weight. Resin solution 400 parts by weight, photosensitive monomer (Aronix M325, manufactured by Toagosei Co., Ltd.) 60
A mixed composition was prepared by placing parts by weight, 5 parts by weight of an antifoaming agent (S-65, manufactured by San Nopco) and 35 parts by weight of N-methylpyrrolidone (NMP) in a container and mixing with stirring.

2) Polymethyl methacrylate (PMMA) 8
0 parts by weight, 72 parts by weight of an epoxy resin particle (manufactured by Sanyo Chemical Industries, polymer pole) having an average particle size of 1.0 μm and 31 parts by weight of an epoxy resin particle having an average particle size of 0.5 μm were placed in another container and mixed with stirring. And 257 parts by weight of NMP were further added and stirred and mixed by a bead mill to prepare another mixed composition.

3) Imidazole curing agent (Shikoku Chemicals, 2
E4MZ-CN) 20 parts by weight, photopolymerization initiator (benzophenone) 20 parts by weight, photosensitizer (Ciba-Geigy, E
AB) 4 parts by weight and 16 parts by weight of NMP were placed in another container and mixed by stirring to prepare a mixed composition. Then, a resin composition for forming a roughened surface was obtained by mixing the mixed compositions prepared in 1), 2) and 3).

B. Preparation of Resin Composition for Forming Lower Surface Roughened Surface 1) A 25% acrylate of cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 2500) is dissolved in diethylene glycol dimethyl ether (DMDG) at a concentration of 80% by weight. Resin solution 400 parts by weight, photosensitive monomer (Aronix M325, manufactured by Toagosei Co., Ltd.) 60
A mixed composition was prepared by placing parts by weight, 5 parts by weight of an antifoaming agent (S-65, manufactured by San Nopco) and 35 parts by weight of N-methylpyrrolidone (NMP) in a container and mixing with stirring.

2) Polymethyl methacrylate (PMMA) 8
0 parts by weight and epoxy resin particles (manufactured by Sanyo Chemical Industries,
145 parts by weight of polymer pole) having an average particle size of 0.5 μm are placed in another container, and mixed by stirring.
285 parts by weight were added and mixed by stirring with a bead mill to prepare another mixed composition.

3) Imidazole curing agent (Shikoku Chemicals, 2
E4MZ-CN) 20 parts by weight, photopolymerization initiator (benzophenone) 20 parts by weight, photosensitizer (Ciba-Geigy, E
AB) 4 parts by weight and 16 parts by weight of NMP were placed in another container and mixed by stirring to prepare a mixed composition. Then, an adhesive for electroless plating was obtained by mixing the mixed compositions prepared in 1), 2) and 3).

C. Preparation of resin filler 1) 100 parts by weight of bisphenol F type epoxy monomer (manufactured by Yuka Shell Co., molecular weight: 310, YL983U), the average particle size of which surface is coated with a silane coupling agent is 1.6 μm, and the largest particle Having a diameter of 15 μm or less
iO ₂ spherical particles (CRS 1101- manufactured by Adtech Co., Ltd.)
CE) 170 parts by weight and 1.5 parts by weight of a leveling agent (Perenol S4 manufactured by San Nopco Co.) are placed in a container, and the mixture is stirred and mixed to have a viscosity of 4500 at 23 ± 1 ° C.
A resin filler of 0 to 49000 cps (45 to 49 Pa · s) was prepared. As a curing agent, 6.5 parts by weight of an imidazole curing agent (2E4MZ-CN, manufactured by Shikoku Chemicals Co., Ltd.) was used.

D. Manufacturing method of printed wiring board (1) 0.6 mm thick glass epoxy resin or BT
The starting material was a copper-clad laminate in which 18 μm copper foils 8 were laminated on both sides of a substrate 1 made of (bismaleimide triazine) resin (see FIG. 1A). First, the copper-clad laminate was drilled, subjected to electroless plating, and etched in a pattern to form a lower conductor circuit 4 and through holes 9 on both surfaces of the substrate 1.

(2) Through hole 9 and lower conductor circuit 4
After the substrate on which was formed was washed with water and dried, NaOH (1
0 g / l), NaClO ₂ (40 g / l), Na ₃ PO
₄ A blackening treatment using an aqueous solution containing (16 g / l) as a blackening bath (oxidizing bath), NaOH (19 g / l), NaB
A reduction treatment was performed using an aqueous solution containing H ₄ (5 g / l) as a reduction bath, and roughened surfaces 4 a and 9 a were formed on the entire surface of the lower conductor circuit 4 including the through holes 9 (see FIG. 1 (b)). ).

(3) By applying the resin filler 10 to one surface of the substrate using a roll coater, the lower conductive circuit 4
After filling in the space or through hole 9 and heating and drying at 70 ° C. for 20 minutes, the resin filler 10 is similarly filled between the conductor circuits 4 or in the through hole 9 on the other surface. It was dried by heating for minutes (see FIG. 1 (c)).

(4) One surface of the substrate after the treatment of the above (3) is subjected to belt sander polishing using # 600 belt polishing paper (manufactured by Sankyo Rikagaku Co., Ltd.) to form the surface of the inner layer copper pattern 4 and the through holes 9. Polishing was performed so that the resin filler 10 did not remain on the land surface, and then buffing was performed to remove scratches caused by the belt sander polishing. Such a series of polishing was similarly performed on the other surface of the substrate. Then, at 100 ° C for 1 hour, at 120 ° C for 3 hours, at 150 ° C
For 1 hour and a heat treatment at 180 ° C. for 7 hours to cure the resin filler 10.

In this way, the surface layer of the resin filler 10 and the surface of the lower conductor circuit 4 formed in the through holes 9 and the portions where the conductor circuit is not formed are flattened, and the resin filler 10 and the side surfaces of the lower conductor circuit 4 are flattened. 4a is firmly adhered through the roughened surface, and the inner wall surface 9a of the through hole 9 and the resin filler 10
Was obtained, thereby obtaining an insulating substrate firmly adhered through the roughened surface (see FIG. 1D). By this step, the resin filler 10
And the surface of the lower conductor circuit 4 are flush with each other. Here, the filled resin had a Tg point of 155.6 ° C. and a linear thermal expansion coefficient of 44.5 × 10 ⁻⁶ / ° C.

(5) On the upper surface of the land of the inner layer conductor circuit 4 and the through hole 9 exposed by the processing of the above (4), a thickness of 2.5
Roughened layer (concavo-convex layer) 1 made of μm Cu-Ni-P alloy
1 on the surface of the roughened layer 11.
A 3 μm Sn layer was provided (see FIG. 2A, except that Sn
The layers are not shown). The formation method is as follows. That is, copper sulfate (8 g / l), nickel sulfate (0.6 g / l), citric acid (15 g / l), sodium hypophosphite (29 g / l), boric acid (31 g / l),
Surfactant (Surfinol 46, manufactured by Nissin Chemical Industry Co., Ltd.)
5) The substrate was immersed in an electroless copper plating bath at pH = 9 consisting of an aqueous solution containing (0.1 g / l), and after 1 minute of immersion, vibrated vertically and horizontally at a rate of once every 4 seconds. The surface of the land of the lower conductor circuit and the through hole is
A roughened layer 11 of a needle-like alloy made of -Ni-P was provided. Furthermore, a temperature of 50 ° C. containing tin borofluoride (0.1 mol / l) and thiourea (1.0 mol / l), pH = 1.2
Cu-Sn substitution reaction was performed using the plating bath of No. 1, and a Sn layer having a thickness of 0.3 μm was provided on the surface of the roughened layer.

(6) The adhesive for electroless plating (viscosity: 1.5 Pa · s) described in B was applied to both surfaces of the substrate by a roll coater, and left in a horizontal state for 20 minutes. 3
Drying was performed for 0 minutes to form an adhesive layer 2a for electroless plating. Further, A is placed on the adhesive layer 2a for electroless plating.
The adhesive for electroless plating (viscosity: 7 Pa · s) described in 1 above was applied using a roll coater, left in a horizontal state for 20 minutes, and then dried at 60 ° C. for 30 minutes to obtain an adhesive layer 2b.
Was formed to form an adhesive layer 2 for electroless plating having a thickness of 35 μm (see FIG. 2B).

(7) The adhesive layer 2 for electroless plating according to the above (6)
A photomask film on which a black circle having a diameter of 85 μm is printed is brought into close contact with both surfaces of the substrate 1 on which is formed, and is exposed at an intensity of 500 mJ / cm ² by an ultra-high pressure mercury lamp, and then DMDG
Spray developed with the solution. Thereafter, the substrate is further exposed to an ultrahigh pressure mercury lamp at an intensity of 3000 mJ / cm ² , and subjected to a heat treatment at 100 ° C. for 1 hour and at 150 ° C. for 5 hours to obtain a diameter excellent in dimensional accuracy equivalent to a photomask film. Thickness 3 having 85 μm via hole opening 6
An interlayer resin insulation layer 2 having a thickness of 5 μm was formed (see FIG. 2C). Note that the tin plating layer was partially exposed in the opening serving as the via hole.

(8) The substrate on which the via hole opening 6 was formed was placed in a solution containing 800 g / l of chromic acid at 70 ° C. for 19 hours.
The surface of the interlayer resin insulation layer 2 is roughened (depth: 3 μm) by dissolving and removing the epoxy resin particles present on the surface of the interlayer resin insulation layer 2, and then neutralizing solution (manufactured by Shipley Co., Ltd.) ) And washed with water (Fig. 2)
(D)). Further, by applying a palladium catalyst (manufactured by Atotech) to the surface of the substrate subjected to the surface roughening treatment, catalyst nuclei were attached to the surface of the interlayer resin insulating layer 2 and the inner wall surface of the via hole opening 6.

(9) Next, the substrate was immersed in an electroless copper plating aqueous solution having the following composition to form an electroless copper plating film 12 having a thickness of 0.8 μm on the entire rough surface (FIG. 3 (a)). )reference).
At this time, since the plating film was thin, irregularities were observed on the surface of the electroless plating film. [Electroless plating aqueous solution] EDTA 150 g / l Copper sulfate 20 g / l HCHO 30 ml / l NaOH 40 g / l α, α'-bipyridyl 80 mg / l Polyethylene glycol (PEG) 0.1 g / l Electroplating conditions] 30 minutes at a liquid temperature of 70 ° C

(10) A commercially available photosensitive dry film is adhered to the electroless copper plating film 12, a mask is placed thereon, and
Exposure at mJ / cm ² and development with a 0.8% aqueous sodium carbonate solution provided a plating resist 3 (see FIG. 3B).

(11) Next, the substrate was washed with water at 50 ° C., degreased, rinsed with water at 25 ° C., further washed with sulfuric acid, and then subjected to electrolytic copper plating under the following conditions to a thickness of 15 μm. (See FIG. 3C). [Electrolytic plating aqueous solution] Sulfuric acid 180 g / l Copper sulfate 80 g / l Additive 1 ml / l (Capparaside GL, manufactured by Atotech Japan) [Electroplating conditions] Current density 1 A / dm ² hours 30 minutes Temperature Room temperature

(12) After the plating resist 3 is stripped and removed with 5% KOH, the electroless plating film 12 under the plating resist 3 is dissolved and removed by etching with a mixed solution of sulfuric acid and hydrogen peroxide. Copper plating film 12 and electrolytic copper plating film 1
A conductor circuit (including the via hole 7) 5 made of 3 and having a thickness of 18 μm was formed. Further, the surface of the interlayer resin insulating layer 2 between the conductor circuits located at the part where the conductor circuits are not formed is immersed in a 70 ° C. solution containing 800 g / l of chromic acid for 3 minutes, and the surface of the interlayer resin insulation layer 2 is etched by 1 μm. The resulting palladium catalyst was removed (see FIG. 3 (d)).

(13) The substrate on which the conductor circuit 5 was formed was coated with copper sulfate (8 g / l), nickel sulfate (0.6 g / l), citric acid (15 g / l), and sodium hypophosphite (29 g / l).
l), an aqueous solution containing boric acid (31 g / l) and a surfactant (Surfynol 465, manufactured by Nissin Chemical Industry Co., Ltd.) (0.1 g / l). After immersion, one minute after immersion, vibrating in the vertical and horizontal directions at a rate of once every 4 seconds, the surface of the land of the lower conductor circuit and the through-hole was roughened with a needle-like alloy made of Cu-Ni-P. An oxide layer 11 was provided (see FIG. 4A). At this time, the formed roughened layer 11 is converted to an EPMA (X-ray fluorescence analyzer).
As a result, the composition ratio of Cu was 98 mol%, Ni was 1.5 mol%, and P was 0.5 mol%. Further, tin borofluoride (0.1 mol / l), thiourea (1.0 mol / l)
(mol / l) using a plating bath at a temperature of 50 ° C. and a pH of 1.2, and a Cu—Sn substitution reaction was performed to provide a 0.3 μm thick Sn layer on the surface of the roughened layer. However, the Sn layer is not shown.

(14) By repeating the above steps (6) to (13), a conductor circuit of an upper layer was further formed to obtain a multilayer wiring board. However, Sn substitution was not performed (see FIGS. 4B to 5B).

(15) Next, a cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) dissolved in diethylene glycol dimethyl ether (DMDG) so as to have a concentration of 60% by weight was used. 46.67 parts by weight of an oligomer for imparting properties (molecular weight: 4000), 6.67 parts by weight of a bisphenol A type epoxy resin (trade name: Epicoat 1001 manufactured by Yuka Shell Co., Ltd.) dissolved in methyl ethyl ketone, and also bisphenol 6.67 parts by weight of an A-type epoxy resin (manufactured by Yuka Shell Co., trade name: Epicoat E-1001-B80), imidazole curing agent (manufactured by Shikoku Chemicals, trade name: 2E)
4MZ-CN) 1.6 parts by weight, photosensitive monomer 2
Functional acrylic monomer (trade name: R60, manufactured by Nippon Kayaku Co., Ltd.)
4) 4.5 parts by weight, a polyvalent acrylic monomer (manufactured by Kyoei Chemical Co., trade name: DPE6A) 1.5 parts by weight, and a leveling agent composed of an acrylate polymer (manufactured by Kyoei Chemical Co., trade name: Polyflow No.) .75) 0.36 parts by weight was placed in a container, stirred and mixed to prepare a mixed composition, and Irgacure I was used as a photopolymerization initiator for the mixed composition.
-907 (manufactured by Ciba-Geigy) 2.0 parts by weight, 0.2 parts by weight of DETX-S (manufactured by Nippon Kayaku) as a photosensitizer,
By adding 0.6 parts by weight of DMDG, the viscosity was increased to 25.
A solder resist composition adjusted to 1.4 ± 0.3 Pa · s at ℃ was obtained. The viscosity was measured with a B-type viscometer (DVL-B type, manufactured by Tokyo Keiki Co., Ltd.) when the rotor No. was 60 rpm. In the case of 4, 6 rpm, the rotor No. According to 3.

(16) Next, the above-mentioned solder resist composition is applied to both sides of the multilayer wiring board in a thickness of 20 μm,
After performing a drying process under the conditions of 20 ° C. for 20 minutes and 70 ° C. for 30 minutes, a 5 mm-thick photomask on which a pattern of the opening of the solder resist is drawn is brought into close contact with the solder resist layer, and an ultraviolet ray of 1000 mJ / cm ² is applied. Exposure with DM
Development was performed with a TG solution to form an opening having a diameter of 200 μm. Then, at 80 ° C. for 1 hour, and at 100 ° C. for 1 hour.
The solder resist layer was cured by performing heat treatment under the conditions of 120 ° C. for 1 hour and 150 ° C. for 3 hours to form a solder resist pattern layer 14 having an opening and a thickness of 20 μm.

(19) Next, the substrate on which the solder resist layer 14 was formed was coated with nickel chloride (30 g / l), sodium hypophosphite (10 g / l), and sodium citrate (10 g / l).
g / l) in the electroless nickel plating solution with pH = 5.
This was immersed for 0 minutes to form a nickel plating layer 15 having a thickness of 5 μm in the opening. Further, the substrate was subjected to potassium gold cyanide (2 g / l), ammonium chloride (75 g / l),
It was immersed in an electroless plating solution containing sodium citrate (50 g / l) and sodium hypophosphite (10 g / l) at a temperature of 93 ° C. for 23 seconds to form a 0.03 μm thick nickel plating layer 15 on the nickel plating layer 15. A gold plating layer 16 was formed.

(20) Thereafter, a solder paste is printed on the opening of the solder resist layer 14 and reflowed at 200 ° C. to form a solder bump (solder body) 17.
A multilayer wiring printed board having the solder bumps 17 was manufactured (see FIG. 5C).

(Comparative Example 1) A two-layer roughened surface forming resin composition layer was formed using the following roughened surface forming resin composition, and then cured to form an interlayer resin insulation. A printed wiring board having solder bumps was manufactured in the same manner as in Example 1 except that the layer was formed. A. Preparation of Resin Composition for Forming Roughened Surface of Upper Layer 1) A 25% acrylate of cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 2500) is dissolved in diethylene glycol dimethyl ether (DMDG) at a concentration of 80% by weight. Resin solution 400 parts by weight, photosensitive monomer (Aronix M325, manufactured by Toagosei Co., Ltd.) 30
A mixed composition was prepared by placing parts by weight, 5 parts by weight of an antifoaming agent (S-65, manufactured by San Nopco) and 35 parts by weight of N-methylpyrrolidone (NMP) in a container and mixing with stirring.

2) Polyether sulfone (PES) 80
Parts by weight, 72 parts by weight of an epoxy resin particle (manufactured by Sanyo Chemical Co., polymer pole) having an average particle size of 1.0 μm and 31 parts by weight of an epoxy resin particle having an average particle size of 0.5 μm were placed in another container.
After stirring and mixing, 257 parts by weight of NMP were further added,
Another mixed composition was prepared by stirring and mixing with a bead mill.

3) Imidazole curing agent (Shikoku Chemicals, 2
E4MZ-CN) 20 parts by weight, photopolymerization initiator (benzophenone) 20 parts by weight, photosensitizer (Ciba-Geigy, E
AB) 4 parts by weight and 16 parts by weight of NMP were placed in another container and mixed by stirring to prepare a mixed composition. Then, a resin composition for forming a roughened surface was obtained by mixing the mixed compositions prepared in 1), 2) and 3).

B. Preparation of Resin Composition for Forming Lower Surface Roughened Surface 1) A 25% acrylate of cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 2500) is dissolved in diethylene glycol dimethyl ether (DMDG) at a concentration of 80% by weight. Resin solution 400 parts by weight, photosensitive monomer (Aronix M325, manufactured by Toagosei Co., Ltd.) 30
A mixed composition was prepared by placing parts by weight, 5 parts by weight of an antifoaming agent (S-65, manufactured by San Nopco) and 35 parts by weight of N-methylpyrrolidone (NMP) in a container and mixing with stirring.

2) Polyether sulfone (PES) 80
Parts, and 145 parts by weight of epoxy resin particles (manufactured by Sanyo Kasei Co., Ltd., polymer pole) having an average particle size of 0.5 μm are placed in another container, mixed with stirring, and further mixed with NMP28.
5 parts by weight were added and stirred and mixed by a bead mill to prepare another mixed composition.

3) Imidazole curing agent (Shikoku Chemicals, 2
E4MZ-CN) 20 parts by weight, photopolymerization initiator (benzophenone) 20 parts by weight, photosensitizer (Ciba-Geigy, E
AB) 4 parts by weight and 16 parts by weight of NMP were placed in another container and mixed by stirring to prepare a mixed composition. Then, an adhesive for electroless plating was obtained by mixing the mixed compositions prepared in 1), 2) and 3).

The printed wiring boards of Example 1 and Comparative Example 1 thus manufactured were subjected to a heat cycle test in which a heat cycle of holding at −55 ° C. for 30 minutes and then holding at 125 ° C. for 30 minutes was repeated 1,000 times. Then, the occurrence of cracks in the interlayer resin insulating layer was observed with an optical microscope. In addition, temperature 121 ° C., relative humidity 100
%, At a pressure of 2 atm for 168 hours, and the interlayer resin insulation layer was observed with an optical microscope to confirm the presence or absence of peeling. The results are shown in Table 1 below.

[0106]

[Table 1]

As is clear from the results shown in Table 1 above,
In the printed wiring board (Example 1) using the resin composition for forming a roughened surface of the present invention, peeling of the interlayer resin insulating layer did not occur, and cracking under heat cycle conditions was suppressed. it can.

[0108]

As described above, according to the resin composition for forming a roughened surface of the present invention, even under severe conditions, the resin composition does not peel off from the conductor circuit formed on the cured body, and the heat cycle does not occur. It is possible to provide a resin composition for forming a roughened surface which is excellent in crack resistance under conditions.

Further, according to the printed wiring boards of the first and second aspects of the present invention, peeling does not occur between the interlayer resin insulating layer and the conductor circuit even under severe conditions, and the heat cycle conditions In the above, it is possible to provide a printed wiring board excellent in crack resistance in which cracks are not generated even when stress due to a difference in thermal expansion coefficient between the conductor circuit and the interlayer resin insulating layer occurs.

[Brief description of the drawings]

FIGS. 1A to 1D are cross-sectional views showing a part of a manufacturing process of a printed wiring board according to the present invention.

FIGS. 2A to 2D are cross-sectional views illustrating a part of a manufacturing process of a printed wiring board according to the present invention.

FIGS. 3A to 3D are cross-sectional views illustrating a part of the manufacturing process of the printed wiring board according to the present invention.

FIGS. 4A to 4C are cross-sectional views showing a part of the manufacturing process of the printed wiring board according to the present invention.

FIGS. 5A to 5C are cross-sectional views showing a part of the manufacturing process of the printed wiring board according to the present invention.

[Explanation of symbols]

 Reference Signs List 1 substrate 2 interlayer resin insulating layer (roughened surface forming resin composition layer) 2a roughened surface forming resin composition layer 2b roughened surface forming resin composition layer 3 plating resist 4 lower conductor circuit (inner copper pattern) 5 Upper Conductor Circuit 6 Via Hole Opening 7 Via Hole 8 Copper Foil 9 Through Hole 10 Filling Resin (Resin Filler) 11 Roughening Layer 12 Electroless Plating Film 13 Electrolytic Plating Film 14 Solder Resist Layer 15 Nickel Plating Layer 16 Gold Plating Layer 17 Solder bump

Continued on the front page F-term (reference) 4F100 AG00 AK01A AK25A AK53 AR00A AS00C AT00B BA02 BA03 BA07 BA10C CA02 CA30 DD07A DG01 GB43 JB13A JG04A JJ03A JK06 JK14 4J002 AC073 AC093 BB001 BD123 CC03 CC03 CD03 CC03 CD03 CC03 CD01 DA097 DA117 DD016 DE056 DE147 DE176 DE237 DG046 DH026 DJ005

Claims (5)

[Claims] 1. An uncured heat-resistant resin matrix which is hardly soluble in a roughening solution comprising at least one selected from an acid, an alkali and an oxidizing agent, and comprises at least one selected from an acid, an alkali and an oxidizing agent. In a resin composition for forming a roughened surface, wherein a substance soluble in a roughening liquid is dispersed, the heat-resistant resin matrix contains a thermosetting resin and a poly (meth) acrylate. A resin composition for forming a roughened surface. 2. A substance soluble in a roughening liquid comprising at least one selected from the group consisting of an acid, an alkali and an oxidizing agent, comprising inorganic particles, resin particles, metal particles, rubber particles, liquid resin and liquid rubber. The resin composition for forming a roughened surface according to claim 1, which is at least one member selected from the group consisting of: 3. A hardened, heat-resistant resin matrix which is hardly soluble in a roughening liquid comprising at least one selected from an acid, an alkali and an oxidizing agent, and comprises at least one selected from an acid, an alkali and an oxidizing agent. A resin insulating layer in which a substance soluble in one kind of roughening liquid is dispersed is formed on a substrate, and a roughened surface is formed on the surface of the resin insulating layer by removing the soluble substance. A printed wiring board comprising a conductive circuit formed on the roughened surface, wherein the heat-resistant resin matrix contains a thermosetting resin and a poly (meth) acrylate. Wiring board. 4. The substance soluble in a roughening liquid comprising at least one selected from the group consisting of an acid, an alkali and an oxidizing agent includes inorganic particles, resin particles, metal particles, rubber particles, liquid resin and liquid rubber. The printed wiring board according to claim 3, wherein the printed wiring board is at least one member selected from the group consisting of: 5. In a printed wiring board having a resin insulating layer formed on a substrate and a conductor circuit formed on the resin insulating layer, the resin insulating layer is formed of a thermosetting resin and poly (meth)
A printed wiring board comprising an acrylic ester.