JP2000104034A - Photosensitive additive adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive additive adhesive resin composition which can form via holes with high precision by photo-imaging by the development with the use of an alkaline aqueous solution and has a heat resistance which permits withstanding a temperature of around 260 deg.C in the soldering step and is sufficient in the bond strength to the plated copper. SOLUTION: A photosensitive additive adhesive resin composition comprises (a) a polyfunctional epoxy resin having an epoxy equivalent weight of 120-500, (b) a modified phenolic novolak obtained by reacting 20-60% phenolic hydroxyl groups with glycidyl acrylate or glycidyl methacrylate, (c) a diluent composed of a polyfunctional photopolymerizable monomer, (d) a photopolymerization initiator, and (e) a metal oxide. It is preferred to use a brominated epoxy resin as the part of the polyfunctional epoxy resin of component (a) and further to incorporate an inorganic filler into the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive additive adhesive composition suitably used for producing a multilayer printed wiring board and an adhesive film obtained by applying the composition to a carrier film.

[0002]

2. Description of the Related Art Conventionally, in a method of manufacturing a multilayer printed wiring board, a circuit is first formed on a double-sided copper-clad board by etching.
After roughening the circuit surface, one or more semi-cured prepreg sheets impregnated with epoxy resin in a glass cloth substrate are stacked on top of it, and a copper foil or single-sided copper-clad board is further stacked on top of it and heated. It was the mainstream in the process of integrating by heating with a press. In this process, a glass cloth base material must be impregnated with epoxy resin and semi-cured once to make a prepreg sheet, and press molding with a hot press requires enormous equipment and a long time. there were. In addition, since the copper foil residual ratio of the inner layer circuit board on which the circuit is formed is variously different,
In order to adjust the interlayer thickness, various types of prepregs having different amounts of resin and different melting behaviors must be prepared. Moreover, since a glass cloth substrate is used for the prepreg sheet, it is difficult to make the interlayer thickness extremely thin, which has been a factor of high cost.

[0003] In order to solve these problems, in recent years, various techniques have been reported in which a glass cloth substrate is not used for an interlayer insulating layer. For example, there is a method using a thermosetting epoxy resin coating or film, a polyimide resin coating or film, a heat-resistant film of a thermoplastic resin, or a photo-curable epoxy resin film. In recent years, in order to increase the density, reduce the size, and reduce the weight of multilayer printed wiring boards, not only fine circuit patterns but also surface via holes that provide conduction between circuit layers have been required.
When the surface via hole is machined with a mechanical drill, the diameter is limited to about 300 μm. If the diameter is less than that, problems such as hole position accuracy and drill life will arise.

[0004]

As described above, a glass cloth base material prepreg and a copper foil or a copper foil or a copper foil or a copper foil or a copper foil or a single-sided copper-clad board are formed by press-fitting with a hot press, and the surface copper foil is etched. After the circuit is formed, the method of creating a surface via hole with a mechanical drill is expensive because it uses a glass cloth, it can not be extremely thin, and also because it forms a surface via hole with a mechanical drill There are problems that cannot be refined. Further, when processing is performed with an excimer laser or a carbon dioxide laser, a hole of about 50 μm can be formed, but since the overlapping processing cannot be performed as in the case of a through-hole, the number of steps increases. To solve these problems, an insulating layer is formed on both sides or one side of the inner circuit board using a photosensitive insulating resin that does not contain glass cloth, and fine surface via holes are formed by photoimaging. Various photo build-up methods of forming a circuit by plating and etching have been studied. The photosensitive resin must have excellent developability by a photographic method and have a function as an additive adhesive.

In general, in the additive method for producing a substrate for consumer use, a thermosetting additive adhesive is often used. For example, JP-B-63-10752, JP-A-63-297571, and JP-A-63-297571. Kaisho 64-4
There are many methods of roughening an adhesive layer with an oxidizing agent as disclosed in, for example, JP-A-7095 and JP-A-3-18096. The content includes a rubber component such as acrylonitrile-butadiene rubber, and elutes the rubber component with an aqueous chromium-sulfuric acid solution as an oxidizing agent to roughen the surface of the adhesive. Also, as disclosed in Japanese Patent Publication No. 4-79160, epoxy resin,
Disperse an inorganic fine powder such as silica or calcium carbonate in a resin matrix having excellent heat resistance such as phenolic resin or melamine resin to form an adhesive, and selectively elute the inorganic fine powder with a specific chemical. Thus, as described in JP-A-1-29479, a method of roughening the adhesive layer,
There is a method in which hardened epoxy resin fine powder having different solubility to an oxidizing agent is dispersed in an epoxy resin matrix, and the epoxy resin fine powder is selectively eluted by the oxidizing agent. However, when such a thermosetting additive adhesive is used, a surface via hole cannot be formed by photoimaging.

On the other hand, as disclosed in JP-A-5-136575, a method in which an epoxy resin is used for a matrix and a cationic photoinitiator is used as a curing agent,
As disclosed in JP-A-253730, there is a method of forming surface via holes by photoimaging by using a phenol novolak type epoxy resin or an acrylate modified cresol novolak type epoxy resin as a matrix. However, an organic solvent must be used as a developer. This is not preferable in terms of working environment. Due to such requirements, as disclosed in JP-B-7-49464, a compound having a phenolic hydroxyl group and an acryloyl group or a methacryloyl group in the molecule, an epoxy compound, and a photopolymerization initiator are used. Performable curable compositions have been reported. However, the molecular weight of the compound having a phenolic hydroxyl group and an acryloyl or methacryloyl group in the molecule is small, and in alkali development using an aqueous solution of sodium hydroxide, the contrast, which is the balance between the dissolution rate and photosensitivity, is reduced. However, if the resolution is high, overexposure due to halation or surface deterioration due to a developing solution occurs.

Accordingly, it is an object of the present invention to form a via hole with high accuracy by photoimaging by developing using an alkaline aqueous solution, having excellent plating solution resistance to electroless plating, and improving the soldering process. Provide a photosensitive additive adhesive composition that has heat resistance to withstand temperatures around 260 ° C, has excellent insulation properties and flame retardancy, and has sufficient adhesive strength between the roughened surface of the adhesive and plated copper. Where you do it.

[0008]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides a photosensitive additive adhesive which is easy to form a photo via hole, has excellent flame retardancy and heat resistance, and has a large adhesive strength of plated copper. The agent is provided. That is,
The present invention provides the following components (a), (b), (c) and (d)
And (e) as essential components. (A) a polyfunctional epoxy resin having an epoxy equivalent of 120 to 500; (b) a modified phenol novolak obtained by reacting 20 to 60% of phenolic hydroxyl groups of phenol novolak with glycidyl acrylate or glycidyl methacrylate; A diluent comprising a polymerizable monomer, (d) a photopolymerization initiator, and (e) a metal oxide.

The polyfunctional epoxy resin having an epoxy equivalent of 120 to 500 as the component (a) used in the present invention is not particularly limited, such as a bisphenol A type (or F type) epoxy resin and a novolak type epoxy resin. Epoxy equivalent is 5
If it is larger than 00, it is not preferable in terms of developability using an alkaline aqueous solution. As the polyfunctional epoxy resin as the component (a), it is preferable to use a partially brominated resin for the purpose of making the adhesive composition flame-retardant. A brominated phenol novolak epoxy resin as such a brominated epoxy resin,
Brominated bisphenol A type (or F type) epoxy resin and the like can be mentioned.

The modified phenol novolak of the component (b) has a phenol novolak obtained by condensing a phenol compound having one or more phenolic hydroxyl groups in the molecule with formaldehyde under an acidic catalyst, and a glycidyl group. It is obtained by reacting with acrylate or methacrylate. In order to obtain a permanent resist having excellent alkali developability and good pattern accuracy after photopolymerization, it is necessary to use 0.2 to 0.6 equivalent of an epoxy group of an acrylate or methacrylate having a glycidyl group per 1 equivalent of a hydroxyl group of phenol novolak. Is suitably reacted. When the amount is less than 0.2 equivalent, even if photopolymerization is carried out by irradiating ultraviolet rays, since the molecular weight after polymerization is small, it is dissolved in a developing solution and resolution cannot be exhibited. Further, if it exceeds 0.6 equivalents, the phenolic hydroxyl group is small, so the alkali solubility is poor, and it does not dissolve in the developer even if it is not photopolymerized,
Similarly, resolution is lost. Therefore, in order to increase the contrast of solubility in an aqueous alkali solution by photopolymerization and to achieve good high resolution, 20 to 60% of the phenolic hydroxyl group of phenol novolak is reacted with glycidyl acrylate or glycidyl methacrylate. Is required, and more preferably 40 to 50%
It is.

Further, in order to increase the development contrast, a novolak obtained by condensing a bisphenol compound such as bisphenol A or F having two phenolic hydroxyl groups in the molecule with formaldehyde in the presence of phenol novolak in the presence of an acidic catalyst is used. Used, the phenolic hydroxyl groups of this bisphenol novolak 20 to 60%
Is preferred. A modified bisphenol-based novolak obtained by reacting with a glycidyl acrylate or glycidyl methacrylate is preferred. This is because even if the molecular weight is increased, the change in the dissolution rate is small, and the sensitivity can be increased. Although the reason is not clear, the structure is based on a bisphenol compound, in which a phenolic hydroxyl group showing alkali solubility is arranged at an adjacent position by hydrogen bonding and faces outward with respect to the entanglement of the molecular chain. Think to take. Other bisphenol compounds having two phenolic hydroxyl groups in the molecule include bisphenol S type. As the acrylate or methacrylate having a glycidyl group, glycidyl acrylate or glycidyl methacrylate is preferable because of its reactivity, availability, and the like.

(C) Examples of the diluent comprising a polyfunctional photopolymerizable monomer include compounds having at least two or more acryloyl groups or methacryloyl groups in one molecule. For example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4
-Butanediol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, glycerol diacrylate, neopentyl glycol diacrylate Acrylate, bisphenol A diacrylate and the like. Preferred monomers are tri- or tetrafunctional trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate having good developer resistance after photopolymerization.

These polyfunctional photopolymerizable monomers have a high photoreaction speed and can be photopolymerized to a deep portion with a small amount of energy irradiation, so that they have high resolution, are not deteriorated by a developer in the photopolymerized portion, and have a high aspect ratio. It is possible to form a good via hole instead of an undercut shape in the photo via hole. Furthermore, glycidyl acrylate or glycidyl methacrylate, which is capable of reacting with a carboxylic acid or a phenolic hydroxyl group, can be used as a polyfunctional photopolymerizable monomer to improve the chemical resistance after heat curing. These polyfunctional photopolymerizable monomers may be used alone or in combination, and the amount of the polyfunctional photopolymerizable monomer can be determined according to the balance between the development characteristics and the cured product characteristics.

(D) Examples of the photopolymerization initiator include benzophenones such as benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone and hydroxybenzophenone, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether,
Benzoin alkyl ethers such as benzoin isobutyl ether and benzyl dimethyl ketal, acetophenones such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, and diethoxyacetophenone; thioxanthone; Chlorthioxanthone, 2
Thioxanthones such as -methylthioxanthone, 2,4-dimethylthioxanthone, ethylanthraquinone,
Alkyl anthraquinones such as butyl anthraquinone and the like can be mentioned. These can be used alone or 2
Used as a mixture of more than one species. The addition amount of the photopolymerization initiator is usually used in the range of 0.1 to 10% by weight.

(E) In the present invention, the metal oxide is
It is blended for the purpose of improving plating adhesion.
Such metal oxides include zinc oxide, lead oxide, iron oxide,
There is titanium oxide and the like. Its mechanism is zinc oxide,
This is because lead oxide, titanium oxide, and the like are soluble in an acid or alkali solution, have a large surface area, and can obtain a moderately roughened shape. Although it is not clear about iron oxide and the like, iron oxide has two crystal lattice forms, one of which has a vacant lattice from which iron atoms are missing. It is considered that the part serves as an active center to adsorb the plating catalyst or the copper plating. Zinc oxide and iron oxide are preferable for improving plating adhesion. The amount of metal oxide is (a)
It is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the component, the component (b) and the component (c).

In addition to the above components, it is preferable to add an inorganic filler to improve plating adhesion. Also,
Examples of the inorganic filler include barium sulfate, silica, talc, clay, calcium carbonate, and aluminum hydroxide. Barium sulfate, which is excellent in interlayer insulation and heat resistance, is particularly preferable. The amount of the inorganic filler is preferably in the range of 20 to 50 parts by weight based on 100 parts by weight of the resin. When the amount is less than 20 parts, the effect of improving the plating adhesion by the addition of the inorganic filler is small, and when it exceeds 50 parts, the interlayer insulating property is reduced and the resolution of the photovia is reduced.

In the present invention, an organic solvent is added as required. Organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cell sorbs such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; methyl carbitol and butyl carbitol Such as carbitols, propylene glycol monomethyl ether, propylene glycol dimethyl ether,
Glycol ethers such as dipropylene glycol monoethyl ether and triethylene glycol monoethyl ether; and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, and the like. Even if these are used alone, 2
You may use in combination of 2 or more types. The purpose of use of these organic solvents is to dissolve and liquefy the solid modified phenol novolak of the component (b), and to evaporate the solvent by heating and drying the liquid resin composition applied on the inner layer substrate. This is because the resin can be made free and the resin is dissolved to adjust the viscosity of the adhesive to an appropriate level in order to apply it to the carrier film and volatilize the solvent to form a dry film.

In these resin compositions, radicals are generated from the photopolymerization initiator of the component (d) by irradiation with ultraviolet rays,
Polymerization occurs between the acryloyl group or the methacryloyl group of the component (b) and the component (c). Next, by heating, the glycidyl group of the component (a) and the phenolic hydroxyl group of the component (b) are polymerized and thermally cured. At this time,
If (c) has a hydroxyl group or a glycidyl group,
It polymerizes with the glycidyl group of component (a). In addition, the photosensitive additive adhesive composition of the present invention, if necessary,
An ultraviolet absorber, a thermal polymerization inhibitor, or a plasticizer for storage stability can be added.

The photosensitive additive adhesive composition of the present invention comprising these components has high resolution and excellent developability with an aqueous alkaline solution. In particular, the solubility in an alkaline aqueous solution is mainly the phenolic hydroxyl group of a modified phenol novolak in which an acryloyl group or a methacryloyl group is introduced into 20 to 60% of the phenolic hydroxyl group of the component (b). And, as described above, the photopolymer in which these functional groups remain is a polymer having insufficient alkali resistance, chemical resistance, and electrical properties, but the photosensitive additive adhesive composition of the present invention is The resin composition is mainly composed of a resin composition mainly subjected to a thermosetting reaction after photopolymerization and development. In this heat treatment, the epoxy resin of the component (a) is converted into the phenolic hydroxyl group in the component (b) and the epoxy resin in the component (c). And a thermosetting reaction with the hydroxyl group or glycidyl group to form a main skeleton excellent in various properties required as an interlayer insulating material of a multilayer printed wiring board. Therefore, it is an additive adhesive cured product that withstands electroless plating performed for a long time under high temperature and high alkalinity conditions and has excellent adhesion to plated copper.

Next, a process for producing a multilayer printed wiring board using the photosensitive additive adhesive composition of the present invention will be described. The photosensitive additive adhesive composition is applied on the inner circuit board and dried. Alternatively, the photosensitive additive adhesive composition is applied to a carrier film and dried to form a film, which is roll-laminated on an inner circuit board. On the inner circuit board provided with the additive adhesive layer in this manner, a via hole pattern is placed and exposed using a high-pressure mercury lamp exposure device or the like, and then
Develop with an aqueous alkali solution such as sodium hydroxide.
After washing with water and drying, the adhesive in which the via holes are formed is sufficiently cured by heating. After the cured adhesive surface is polished, it is further immersed in a heated aqueous solution of peroxide such as potassium permanganate, and then neutralized to roughen the adhesive surface. Next, after passing through the steps of degreasing, catalyst application, and activation,
Immerse in an electroless copper plating solution to form an electroless copper plating film. Thereafter, heat treatment is performed to produce an additive-plated multilayer printed wiring board.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments.

Synthesis Example 1: Methacryloyl-modified phenol
Synthetic Novolak Phenolite TD-20 as phenol novolak
90-60M (manufactured by Dainippon Ink and Chemicals, Inc .: nonvolatile content 6)
700 g (about 4 equivalents of OH, 0%, MEK solution) was charged into a 2 liter flask, 1 g of tributylamine and 0.2 g of hydroquinone were added, and the mixture was heated to 110 ° C. 284 g (2 mol) of glycidyl methacrylate was added to the mixture for 30 minutes.
After dropping over a period of 1 minute, the mixture was stirred and reacted at 110 ° C. for 5 hours.

Synthesis Example 2: Methacryloyl-modified bispheno
Synthesis of phenol A novolak Phenolite LF as bisphenol A novolak
-4871 (manufactured by Dainippon Ink and Chemicals, Inc .: nonvolatile content 60
%, MEK solution) 800 g (about 4 equivalents of OH) was charged into a 2 liter flask, and 0.2 g of hydroquinone and 284 g (2 mol) of glycidyl methacrylate were added.
Was heated. After 1 g of tributylamine was added thereto, the mixture was stirred and reacted at 110 ° C. for 5 hours.

Example 1 10 g of Epicoat 828 (bisphenol-type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd .: epoxy equivalent: 190), BREN-S (Nippon Kayaku Co., Ltd.)
Brominated novolak epoxy resin: Epoxy equivalent 27
5, bromination ratio 36%) 15 g, 50 g of the methacryloyl-modified phenol novolak obtained in Synthesis Example 1, 1,4-
15 g of butanediol diacrylate, 0.3 of zinc oxide
g, and 30 g of barium sulfate were mixed and kneaded with a three-roll mill, and 3 g of Irgacure 651 (manufactured by Ciba-Geigy) as a photoinitiator and 0.2 g of triphenylphosphine as a thermosetting accelerator were added. An additive adhesive composition was obtained.

Example 2 10 g of Epicoat 828,
15 g of BREN-S, 50 g of methacryloyl-modified bisphenol A novolak obtained in Synthesis Example 2, 1,4-
Butanediol diacrylate 15 g, iron oxide 0.5
g, and 30 g of barium sulfate are mixed and kneaded with a three-roll mill, and Irgacure 651 (Ciba.
Geigy Co., Ltd.) (3 g) and triphenylphosphine (0.2 g) as a thermosetting accelerator were added to obtain a photosensitive additive adhesive composition.

Example 3 10 g of Epicoat 828,
15 g of Epicoat 5050 (manufactured by Yuka Shell Epoxy Co., Ltd .: epoxy equivalent: 395, bromination ratio: 49%), methacryloyl-modified phenol novolak 50 obtained in Synthesis Example 1
g, 15 g of 1,4-butanediol diacrylate, 0.3 g of iron oxide, and 30 g of barium sulfate, and kneaded with a three-roll mill. Irgacure 65 was used as a photoinitiator.
1 (manufactured by Ciba-Geigy) and 0.2 g of triphenylphosphine as a thermosetting accelerator were added to obtain a photosensitive additive adhesive composition.

Examples 4 to 6 The photosensitive additive adhesive compositions obtained in Examples 1 to 3 were dried on a carrier film composed of a PET film (glass transition temperature: 80 ° C.) to a thickness of 70 μm. The film was coated with a roller coater and dried at 80 ° C. for 20 minutes to produce a film with an additive adhesive.

<< Comparative Example 1 >> 10 g of Epicoat 828
15 g of BREN-S, 50 g of methacryloyl-modified phenol novolak obtained in Synthesis Example 1, 15 g of 1,4-butanediol diacrylate, and 30 g of barium sulfate
g, and kneaded with a three-roll mill. 3 g of Irgacure 651 (manufactured by Ciba-Geigy) as a photoinitiator and 0.2 g of triphenylphosphine as a thermosetting accelerator were added, and a photosensitive additive adhesive composition was added. I got something.

<< Comparative Example 2 >> 10 g of Epicoat 828
15 g of BREN-S, 50 g of methacryloyl-modified bisphenol A novolak obtained in Synthesis Example 2, 1,4-
15 g of butanediol diacrylate, 0.5 g of calcium carbonate and 30 g of barium sulfate were mixed and kneaded with a three-roll mill, and Irgacure 651 was used as a photoinitiator.
3 g of Ciba-Geigy and 0.2 g of triphenylphosphine as a thermosetting accelerator were added to obtain a photosensitive additive adhesive composition.

Comparative Examples 3 and 4 The photosensitive additive adhesive composition obtained in Comparative Examples 1 and 2 was dried on a carrier film composed of a PET film (glass transition temperature: 80 ° C.) to a thickness of 70 μm. The film was coated with a roller coater and dried at 80 ° C. for 20 minutes to produce a film with an additive adhesive.

The photosensitive additive adhesive compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were applied on an inner layer circuit board having a roughened copper foil, and then heated at 80 ° C. for 20 minutes. Dried. However, the resin thickness after all drying was 70 μm. The photosensitive additive adhesive films obtained in Examples 4 to 6 and Comparative Examples 3 and 4 were roll-laminated on a laminate. A via hole pattern of 100 μmφ was placed on the inner layer circuit board provided with these additive adhesive layers, and the irradiation amount was 200 using a high pressure mercury lamp exposure apparatus.
Exposure was performed at mJ / cm ² . Thereafter, in the case of Examples 4 to 6 and Comparative Examples 3 and 4, the carrier film was peeled off. Subsequently, development was performed with a 1.5% aqueous sodium hydroxide solution at 25 ° C. at a spray pressure of ² kg / m ² . After washing and drying, 1
Heat treatment was performed at 50 ° C. for 60 minutes. The cured adhesive surface was polished with a buff, immersed in a 4% aqueous sulfuric acid solution for 3 minutes, further immersed in an aqueous solution of potassium permanganate at 80 ° C. for 10 minutes, and then neutralized to roughen the adhesive surface. . Degreasing this,
Through the steps of catalyst application and activation, immersion in an electroless copper plating solution (KC-500 manufactured by Japan Energy) at 70 ° C. for 5 hours to form an electroless copper plating film of about 25 μm, and then at 150 ° C. for 60 minutes Heat treatment was performed to produce an additive-plated multilayer printed wiring board.

In the process of obtaining an additive-processed multilayer printed wiring board in this manner, via-formability plating adhesion,
Table 1 shows the results of evaluating the solder heat resistance.

Table 1 Via Formability Plating Adhesion Strength Solder Heat Resistance (Via Diameter 100 μm) kgf / cm Example 1 ○ 1.2 ○ Example 2 ○ 1.3 ○ Example 3 ○ 1.2 ○ Comparative Example 1 ○ 0.6 ○ Comparative Example 2 × 0.7 ○ Example 4 ○ 1.4 ○ Example 5 ○ 1.3 ○ Example 6 ○ 1.3 ○ Comparative Example 3 ○ 0.8 ○ Comparative Example 4 × 0.0. 8 ○

(Measurement method) Via Formability The via hole formed by the above method was observed with a microscope. ：: Normal via was formed, ×: Via was not formed 2. Plating adhesion strength (peel strength) According to JIS standards Solder heat resistance The multilayer printed wiring board obtained above was tested at n = 5. When the sample was immersed in a 260 ° C. solder bath for 20 seconds, all five samples showed no change and were evaluated as ○.

[0041]

As described above, the photosensitive additive adhesive composition of the present invention and the film adhesive applied to the carrier film have high resolution after photopolymerization, are easily developed with an aqueous alkali solution, and are heat-cured. Later, it has heat resistance to withstand a temperature of around 260 ° C. in the soldering step, and also has excellent plating copper adhesion. Therefore, when used as an interlayer insulating material of a multilayer printed wiring board, it is possible to manufacture a multilayer printed wiring board having excellent characteristics.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08J 5/18 C08J 5/18 F term (Reference) 4F071 AA41 AA42 AB18 AH13 BA02 BB02 BB12 BC02 4J002 CC07X CD05W CD06W CD19X DE108 DE118 DE148 DE158 ED017 EE037 EE057 EF046 4J040 EB071 EB072 EC061 EC062 EC071 EC072 EC341 EC342 GA02 GA03 HA136 HB16 HB18 HB21 HB27 HB31 HB34 HD19 JA09 JB02 JB08 KA13 LA30 CC12 LA10 HH18

Claims (3)

[Claims] 1. The following components (a), (b), (c),
(D) and (e) as essential components, a photosensitive additive adhesive composition, (a) an epoxy equivalent of 1
(B) a modified phenol novolak obtained by reacting 20 to 60% of the phenolic hydroxyl groups of phenol novolak with glycidyl acrylate or glycidyl methacrylate;
A diluent comprising a polyfunctional photopolymerizable monomer, (d) a photopolymerization initiator, and (e) a metal oxide. 2. A modified phenol novolak of the following (c) reacts 20 to 60% of phenolic hydroxyl groups of a bisphenol phenol novolak obtained by condensing a bisphenol compound with formaldehyde under an acidic catalyst with glycidyl acrylate or glycidyl methacrylate. The photosensitive additive adhesive composition according to claim 1, which is a modified bisphenol novolak obtained by the above method. 3. A photosensitive additive adhesive film formed by applying the photosensitive additive adhesive composition according to claim 1 or 2 to a carrier film and forming a film.