JPH08211608A - Resin composition, permanent resist resin composition and their cured bodies - Google Patents

Abstract

PURPOSE: To provide a resin compsn. high in resolution, excellent in solvent resistance to isopropanol, trichloroethylene, methylene chloride, acetone, etc., and plating soln. resistance at the time of electroless plating carried out for a long time under the conditions of high temp. and high alkalinity while attaining easy development with an aq. alkali soln., also having such heat resistance that the compsn. withstands about 260 deg.C temp. in a soldering process and capable of producing a printed circuit board and to obtain a permanent resist resin compsn. for a printed circuit board. CONSTITUTION: This resin compsn. consists of multifunctional epoxy resin (a) having an epoxy equiv. of 120-500, phenol novolak (b) having at least one acryloyl or methacryloyl group, a diluent (c) made of a photopolymerizable and thermoreactive monomer such as glycidyl acrylate or glycidyl methacrylate and a photopolymn. initiator (d).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition useful as a permanent resist for printed wiring boards and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, a printed wiring board has been manufactured by a subtractive method in which a copper clad laminate is used and an unnecessary portion of a circuit of a copper foil is removed by etching. This subtractive method is a fine pattern, It is difficult to form a high-density wiring board, and there are drawbacks such as small diameter through holes and via holes that cannot be uniformly formed by electroplating. It is the current situation.

On the other hand, recently, a full additive method has been attracting attention, in which an adhesive layer is formed on a laminated plate made of an insulating base material, and a circuit and a through hole are formed thereon by electroless plating. In this method, the accuracy of the conductor pattern is determined only by the transfer accuracy of the plating resist, and since the conductor part is formed only by electroless plating, even through-holes with high throwing power and even through-holes can be formed even on substrates with high aspect ratio through-holes. It is possible to perform plating. The additive method, which has been considered to be suitable for general consumers until now, has begun to be put into practical use as an industrial, high-density, high-multilayer substrate manufacturing process.

[0004]

Generally, in an additive method for manufacturing a substrate for consumer use, a plating resist pattern is transferred by a screen printing method. However, in order to manufacture a printed wiring board having high density wiring, ,
It becomes necessary to form a plating resist pattern by photolithography, that is, to adopt a photoadditive method using a photoresist. Photoresist suitable for photoadditive method has sensitivity, resolution,
In addition to the original characteristics of photoresist such as developability, the following characteristics are required. Development is limited to 1,1,1-trichloroethane organic solvent or alkaline aqueous solution. Withstands electroless plating that is performed under high temperature and high alkaline conditions for a long time, has excellent solder resist characteristics as a permanent resist after plating, 260 in the soldering process
It has heat resistance to withstand temperatures of around ℃ and solvent resistance to organic solvents that wash the flux used during soldering, and it does not reduce the thermal reliability of the entire substrate even when laminated. . At present, photoresists that can be used in this additive method are also on the market, but it is still insufficient.

Therefore, it is an object of the present invention that a resist having a high pattern accuracy can be formed by a photographic method by development using an alkaline aqueous solution, and the resist can sufficiently withstand the electroless copper plating solution of the full additive method, and A permanent resist resin composition having heat resistance that can withstand temperatures around 260 ° C during the soldering process and solvent resistance to organic solvents that wash the flux used during soldering, and that can be used without removing the final product. The present invention is to provide a cured product and a cured product thereof.

[0006]

In order to achieve the above object, a resin composition, a permanent resist resin composition for a printed wiring board and a cured product thereof according to the present invention have the following composition and are used as a permanent resist. And the ability to produce a printed wiring board using this resist resin composition.

That is, the present invention comprises the following components (a),
The present invention relates to a resin composition comprising (b), (c) and (d), a permanent resist resin composition for a printed wiring board, and a cured product thereof. (A) a polyfunctional epoxy resin having an epoxy equivalent of 120 to 500, (b) a phenol novolak having at least one acryloyl group or a methacryloyl group, (c) a diluent comprising a photopolymerization and a heat-reactive monomer, and (d) Photopolymerization initiator.

The epoxy resin of the component (a) used in the present invention is preferably a bisphenol A type (or F type) epoxy resin, and when the average molecular weight is more than 1000, it is preferable in terms of developability using an alkaline aqueous solution. Absent.

The phenol novolak having at least one acryloyl group or methacryloyl group of the component (b) is usually obtained by reacting a phenol novolak having two or more nuclei with an acrylate or methacrylate having a glycidyl group. 3-5 for phenol novolac
The range of the nucleus is preferable from the viewpoint of easy handling. In order to obtain a photosensitive additive having a high degree of accuracy by photopolymerization and having excellent alkali developability, an epoxy group of acrylate or methacrylate having a glycidyl group is contained in an amount of 0.2 to 0.6 with respect to 1 equivalent of hydroxyl group of phenol novolac. Equivalent weight is appropriate. At this time, when the number of remaining phenolic hydroxyl groups is small, the alkali water solubility is deteriorated, and when it is too large, it becomes a factor of deteriorating the properties as a resist such as chemical resistance during curing and electrical properties.

As the acrylate or methacrylate having a glycidyl group, for example, glycidyl acrylate and glycidyl methacrylate are preferable because of their reactivity and availability. When alkylphenol novolac is used, the alkyl group preferably has about 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-butyl group,
It is a sec-butyl group, a tert-butyl group, an allyl group, or the like. When the number of carbon atoms is more than that, lipophilicity increases and alkali developability is not preferable.

(C) Examples of the diluent composed of a photopolymerizable and thermoreactive monomer include acrylate or methacrylate compounds having at least one hydroxyl group in one molecule. For example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, butanediol monoacrylate glycerol methacrylate, phenoxy hydroxypropyl acrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, or glycerol dimethacrylate. Etc. Alternatively, a photopolymerizable monomer such as glycidyl acrylate or glycidyl methacrylate having a glycidyl group is used. Preferred monomers are glycidyl acrylate and glycidyl methacrylate, which can react with carboxylic acid and phenolic hydroxyl group for chemical resistance after thermosetting. Generally, the amount of the diluent as the component (c) is 1 to 1 of the residual phenolic hydroxyl groups after the thermosetting reaction of the epoxy resin as the component (a).
Five times equivalents are preferred.

(D) As the photopolymerization initiator, benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, benzophenones such as hydroxybenzophenone, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether,
Benzoin alkyl ethers such as benzoin isobutyl ether, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t
-Butyl-trichloroacetophenone, acetophenones such as diethoxyacetophenone, thioxanthone,
2-chlorothioxanthone, 2-methylthioxanthone,
Examples thereof include thioxanthones such as 2,4-dimethylthioxanthone and alkylanthraquinones such as ethylanthraquinone and butylanthraquinone. These may be used alone or as a mixture of two or more kinds. The addition amount of this photopolymerization initiator is usually 0.1 to
Used in the range of 10% by weight.

In addition, an ultraviolet ray inhibitor, a thermal polymerization inhibitor, a plasticizer, etc. may be added to the permanent resist of the present invention, if necessary, for storage stability. Further, an acrylate monomer, a methacrylate monomer, a vinyl monomer or the like may be added for adjusting the viscosity, and further a photosensitizer or the like may be added.

The permanent resist resin 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 aqueous alkaline solution is due to the phenolic hydroxyl group of the phenol novolac having at least one acryloyl group or methacryloyl group of the component (b). And, as described above, the photocured product in which the phenolic hydroxyl group remains is a resist having poor alkali resistance, chemical resistance, electrical characteristics, etc., but the permanent resist resin composition of the present invention is photocured and after development. This is a resin composition whose main component is the thermosetting reaction, and the post-heat treatment causes the epoxy resin of (a) component and the glycidyl group in (c) component to thermally react with the phenolic hydroxyl group in (b) component, resulting in demand. It forms the main skeleton with excellent properties. Therefore, it becomes a permanent resist cured product that can withstand electroless plating performed for a long time under high temperature and highly alkaline conditions.

The permanent resist resin composition according to the present invention comprises
It is applied to the adhesive for full additive in a thickness of 20 to 60 μm, and is subjected to heat treatment at 60 to 100 ° C. for about 5 to 10 minutes to be solvent-removed and solidified or prepolymerized to form a resist layer. Alternatively, a film-like material which is previously applied onto a carrier film and prepolymerized under the same conditions as above may be laminated on the adhesive layer.

[0016]

EXAMPLES The present invention will be described below based on examples. (Synthesis Example 1) Synthesis of methacryloyl group-containing phenol novolac Phenolite TD-20 as phenol novolac
90-60M (manufactured by Dainippon Ink and Chemicals, Inc.) 700 g of methyl ethyl ketone solution having a nonvolatile content of 60% (about 4 equivalents of OH) was charged into a 2 l flask, and tributylamine 1 was added.
g and hydroquinone 0.2 g were added, and the mixture was heated to 110 ° C. 284 g of glycidyl methacrylate (2
(Mol) was added dropwise over 30 minutes, and the mixture was reacted with stirring at 110 ° C. for 5 hours.

(Synthesis example 2) Synthesis of methacryloyl group-containing alkylphenol novolac 1080 g (10 mol) of cresol, formalin (37)
%) 1220 g (15 mol) and 10 g of oxalic acid were charged into a pressure reaction vessel and reacted at 120 ° C. (pressure 2.5 kg / cm ² ) for 4 hours. After completion of the reaction, dehydration was performed under reduced pressure and the resin temperature was 1%.
Heated to 40 ° C. After cooling, the mixture was pulverized, and the resin content was adjusted to 60% with a methyl ethyl ketone solvent to obtain an alkylphenol novolak. 800 g of the above-mentioned alkylphenol novolac (about 4 equivalents of OH) was put into a 2 l flask, 1 g of tributylamine and 0.2 g of hydroquinone were added, and the mixture was heated to 110 ° C. After 284 g (2 mol) of glycidyl methacrylate was dropped therein, the mixture was stirred and reacted at 110 ° C. for 5 hours.

Example 1 15 g of Epicoat 828,
45 g of the methacryloyl group-containing phenol novolac of Synthesis Example 1 and 15 g of glycidyl methacrylate were mixed, and 2.5 g of Irgacure 651 (manufactured by Ciba Geigy) as a photoinitiator and 0.2 g of triphenylphosphine as a thermosetting accelerator were added. Then, a permanent resist resin composition was obtained. Example 2 15 g of Epicoat 828, 45 g of the methacryloyl group-containing phenol novolac of Synthesis Example 1 and 15 g of glycidyl methacrylate were mixed to prepare a photoinitiator.
2.5 g of Irgacure 651 was added to obtain a permanent resist resin composition.

Example 3 15 g of Epicoat 828,
45 g of methacryloyl group-containing phenol novolac of Synthesis Example 1, 15 g of epoxy acrylate V-5510 (manufactured by Dainippon Ink and Chemicals, Inc.) and 15 g of glycidyl methacrylate were mixed, and Irgacure 65 as a photoinitiator.
13 g was added to obtain a permanent resist resin composition. << Example 4 >> 10 g of Epicoat 828, 45 g of methacryloyl group-containing phenol novolak of Synthesis Example 1, 10 g of epoxy acrylate V-5510 and 15 g of glycidyl methacrylate were mixed, and 3 g of Irgacure 651 as a photoinitiator was added to the permanent resist resin. It was a composition.

Example 5 15 g of Epicoat 828,
45 g of methacryloyl group-containing phenol novolac of Synthesis Example 1, 15 g of epoxy acrylate SP-4010 (manufactured by Showa High Polymer Co., Ltd.) and 15 g of glycidyl methacrylate were mixed, and 3 g of Irgacure 651 was added as a photoinitiator to obtain a permanent resist resin composition. did. Example 6 10 g of Epicoat 828, 45 g of methacryloyl group-containing phenol novolac of Synthesis Example 1, 10 g of epoxy acrylate SP-4010 and 15 g of glycidyl methacrylate were mixed, and 3 g of Irgacure 651 as a photoinitiator was added, and a permanent resist resin was added. It was a composition.

Example 7 15 g of Epicoat 828,
45 g of the methacryloyl group-containing alkylphenol novolac of Synthesis Example 2 and 15 g of glycidyl methacrylate were mixed, and 2.6 g of Irgacure 651 (manufactured by Ciba Geigy) as a photoinitiator and 0.2 g of triphenylphosphine as a thermosetting accelerator were added. Then, a permanent resist resin composition was obtained. << Example 8 >> 15 g of Epicoat 828, methacryloyl group-containing alkylphenol novolac 45 of Synthesis Example 2
g and glycidyl methacrylate 15 g were mixed, and Irgacure 651 2.6 g was added as a photoinitiator to obtain a permanent resist resin composition.

Example 9 15 g of Epicoat 828,
45 g of a methacryloyl group-containing alkylphenol novolak of Synthesis Example 2 and epoxy acrylate V-5510
15 g and 15 g of glycidyl methacrylate were mixed, and 3 g of Irgacure 651 as a photoinitiator was added to obtain a permanent resist resin composition. <Example 10> 10 g of Epicoat 828, methacryloyl group-containing alkylphenol novolak 4 of Synthesis Example 2
5 g, 10 g of epoxy acrylate V-5510 and 15 g of glycidyl methacrylate were mixed, and 3 g of Irgacure 651 as a photoinitiator was added to obtain a permanent resist resin composition.

Example 11 Epicoat 828 15
g, methacryloyl group-containing alkylphenol novolak of Synthesis Example 2 45 g, epoxy acrylate SP-4
010 15 g and glycidyl methacrylate 15 g were mixed, and Irgacure 651 3 g was added as a photoinitiator to obtain a permanent resist resin composition. Example 12 10 g of Epicoat 828, methacryloyl group-containing alkylphenol novolak 4 of Synthesis Example 2
5 g, 10 g of epoxy acrylate SP-4010 and 15 g of glycidyl methacrylate were mixed, and 3 g of Irgacure 651 was added as a photoinitiator to obtain a permanent resist resin composition.

Comparative Example 1 Epoxy acrylate SP
-4010 45 g and glycidyl methacrylate 15 g were mixed, and Irgacure 651 3 g was added as a photoinitiator to obtain a resist resin composition. << Comparative Example 2 >> Epoxy acrylate V-5510 45
g and glycidyl methacrylate 15 g were mixed, and Irgacure 651 3 g was added as a photoinitiator to obtain a resist resin composition.

[Preparation of Additive Process Multilayer Printed Wiring Board] The resin compositions obtained in Examples 1 to 12 and Comparative Example were applied to a catalyst-activated adhesive-coated laminate with a thickness of 30 μm. And heat treated at 80 ° C. for 15 minutes. However, in the comparative example, since the liquid was tacky even after the heat treatment, the cover film was brought into contact with the resist. A predetermined pattern was placed on this laminated plate and exposed with a high-pressure mercury lamp exposure device at an irradiation dose of 350 mJ / cm ² .
Then, it was developed with an aqueous sodium hydroxide solution at a spray pressure of ² kg / m ² . After washing with water and drying, the entire surface was post-exposed to 1 J / cm ² and heat-treated at 150 ° C. for 60 minutes. Immerse this in electroless copper plating solution at 70 ℃ for 10 hours,
m electroless copper plating film was formed to produce an additive method multilayer printed wiring board.

Table 1 shows the results of evaluation of resist characteristics in the process of obtaining the additive-type multilayer printed wiring board in this manner.

Table 1 ------------------------------------- Development developability solvent resistance plating solution resistance solder heat resistance-- −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 1 ○ ○ ○ ○ Example 2 ○ ○ ○ ○ Example 3 Δ ○ △ △ Example 4 ○ ○ △ △ Example 5 △ ○ ○ ○ Example 6 ○ ○ ○ ○ Example 7 ○ ○ ○ ○ Example 8 ○ ○ ○ ○ Example 9 △ ○ △ △ Example 10 ○ ○ △ △ Implementation Example 11 △ ○ ○ ○ Example 12 ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Comparative Example 1 × Peeling × × Comparative Example 2 × △ △ ○ ○ －－－－－－－－－－－－－－－－－－－－－－――――――

(Measurement method) 1. Developability: ◯: What was developed, Δ: There is some development residue x: There is development residue 2. Solvent resistance: ◯ means that no change was observed after 20 minutes of immersion in acetone. 3. Resistance to plating solution: The one that showed no change in the electroless plating process was marked with "O". 4. Solder heat resistance: n = 5, 260 ° C. for all test pieces
The case where no change was observed in 20 seconds was marked with “◯”.

[0029]

As described above, the permanent resist resin composition for a printed wiring board of the present invention and the cured product thereof have high resolution and are easy to develop with an aqueous alkaline solution, but they are isopropyl alcohol and trichloroethylene. Resistance to methylene chloride, acetone, etc.,
We also manufacture printed wiring boards with excellent resistance to electroless plating that is performed under high temperature and high alkaline conditions for a long time, as well as heat resistance that can withstand temperatures around 260 ° C during the soldering process. Made possible

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03F 7/032 501 H05K 3/18 D 7511-4E 3/28 D

Claims (7)

[Claims] 1. A resin composition comprising the following components (a), (b), (c) and (d): (A) a polyfunctional epoxy resin having an epoxy equivalent of 120 to 500, (b) a phenol novolak having at least one acryloyl group or a methacryloyl group, (c) a diluent comprising a photopolymerization and a heat-reactive monomer, and (d) Photopolymerization initiator. 2. A permanent resist resin composition for a printed wiring board, which comprises the following components (a), (b), (c) and (d): (A) a polyfunctional epoxy resin having an epoxy equivalent of 120 to 500, (b) a phenol novolak having at least one acryloyl group or a methacryloyl group, (c) a diluent comprising a photopolymerization and a heat-reactive monomer, and (d) Photopolymerization initiator. 3. The component (b) is obtained by reacting a binuclear or more phenol novolac with an acrylate or methacrylate having a glycidyl group, and is obtained in one molecule by one or more acryloyl group or methacryloyl group and one or more The permanent resist resin composition for printed wiring boards according to claim 2, which is a phenol novolac having a phenolic hydroxyl group. 4. The component (b) is obtained by reacting an alkylphenol novolac with an acrylate or methacrylate having a glycidyl group, and has one or more acryloyl group or methacryloyl group and one or more phenolic hydroxyl group in one molecule. The permanent resist resin composition for a printed wiring board according to claim 2, which is an alkylphenol novolac. 5. The component (a) is a liquid bisphenol A type epoxy resin or a liquid bisphenol F type epoxy resin, and the component (b) is prepared by reacting a phenol novolac having two or more nuclides with an acrylate or methacrylate having a glycidyl group. A phenol novolac having one or more acryloyl group or methacryloyl group and one or more phenolic hydroxyl group obtained in one molecule, wherein component (c) is one or more acryloyl group or methacryloyl group in one molecule. The permanent resist resin composition for a printed wiring board according to claim 2, which is a diluent comprising a photopolymerizable and heat-reactive monomer having one or more glycidyl groups. 6. The component (a) is a liquid bisphenol A type epoxy resin or a liquid bisphenol F type epoxy resin, and the component (b) is obtained by reacting an alkylphenol novolac with an acrylate or methacrylate having a glycidyl group, and one molecule is obtained. An alkylphenol novolak having at least one acryloyl group or methacryloyl group and at least one phenolic hydroxyl group, wherein the component (c) has at least one acryloyl group or methacryloyl group and at least one per molecule. The permanent resist resin composition for a printed wiring board according to claim 2, which is a diluent comprising a photopolymerizable and heat-reactive monomer having a glycidyl group. 7. A cured product of the resin composition according to claim 1, 2, 3, 4, 5 or 6.