JPH0980748A - Aqueous photoresist composition for printed circuit board and production of printed circuit board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aq. negative type photoresist compsn. having a low org. solvent content and forming a high reliability resist pattern. SOLUTION: This aq. photoresist compsn. contains a photopolymn. initiator and an alkali-developable aq. emulsion having polymerizable unsatd. groups obtd. by adding a compd. having a polymerizable unsatd. group and a glycidyl group in one molecule to an aq. emulsion having acid groups or acid groups and amido groups. A resist pattern or a conductor pattern is formed using this compsn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based photoresist composition for printed wiring boards and a method for producing printed wiring boards using the same. More specifically, it is applied to the surface of a substrate having an electrically conductive coating or a metal. A smooth coating film is formed by drying, then the smooth coating film is cured with an actinic ray through a pattern mask, and the unexposed portion of the cured coating film is removed with an alkaline developer to form a pattern. The present invention relates to a water-based photoresist composition for printed wiring boards, which is capable of forming a film, and a method for producing a printed wiring board using the same.

[0002]

2. Description of the Related Art Conventionally, organic solvent-diluted type photoresist compositions have been known as printed wiring board photoresist compositions. When a resist film is formed using an organic solvent-diluted photoresist composition, there are problems such as odor, danger of ignition, and pollution by an organic solvent discharged during drying.

On the other hand, as an aqueous photoresist composition,
A composition has been proposed in which a resin solution having an acid group and a polymerizable unsaturated group is neutralized with a tertiary amine or the like and then made water-soluble or water-dispersible. However, there is a problem that a fine pattern cannot be obtained after development. Further, an aqueous photoresist composition in which a polymerizable unsaturated compound is mixed or dispersed in an aqueous emulsion having an acid group has been proposed, but this has a problem that the sensitivity of the resist is poor.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to find a technical means for solving the above-mentioned problems, and as a result, a specific polymerizable unsaturated group-containing aqueous emulsion and photopolymerization initiation. A novel aqueous photoresist composition containing an agent can solve the above-mentioned problems all at once.
Further, they have found that a highly reliable pattern can be formed using this composition, and completed the present invention.

Thus, according to the present invention, an alkali-developable polymerizable unsaturated group-containing aqueous solution obtained by adding a compound having a polymerizable unsaturated group and a glycidyl group in one molecule to an aqueous emulsion having an acid group. An aqueous photoresist composition for printed wiring boards, which comprises an emulsion and a photopolymerization initiator, and (a) the aqueous photoresist according to claim 1 or 2 on the surface of a substrate or a metal having a conductive coating. A step of forming a smooth coating film by coating the composition and drying; (b) a step of curing the smooth coating film with an actinic ray through a pattern mask; (c) the curing coating with an alkaline developer. A step of forming a pattern by removing an unexposed portion of the film; (d) a step of removing the exposed conductive film or metal by etching; and (e) a film on the pattern. Method for manufacturing a printed wiring board characterized by comprising the step of removed by is provided.

The aqueous emulsion having an acid group used in the present invention is prepared, for example, by various known emulsion polymerization methods of an unsaturated acid monomer and a vinyl monomer copolymerizable with the monomer. The alkali-developable polymerizable unsaturated group-containing aqueous emulsion of the present invention can be obtained by further subjecting this aqueous emulsion having an acid group to a reaction of a compound having a polymerizable unsaturated group and a glycidyl group in one molecule. The emulsion polymerization is carried out by using water as a medium to disperse and emulsify the monomer with an emulsifier, adding a water-soluble polymerization initiator and heating at 50 to 90 ° C. It is also possible to work at room temperature with a redox initiator. As the emulsifier, anion activators such as sulfates of higher alcohols and alkyl sulfonates, and nonionic activators such as various alkyl ethers, alkyl esters and alkyl allyl ethers of polyoxyethylene are used. In addition, polyvinyl alcohol may be used in combination as a stabilizer (protective colloid) for the emulsion. As the polymerization initiator, hydrogen peroxide, ammonium persulfate, cumene hydroperoxide, water-soluble redox initiator or the like is used.

The unsaturated acid monomers used in the present invention include monobasic acid monomers such as acrylic acid, methacrylic acid and crotonic acid; dibasic acid monomers such as fumaric acid, citraconic acid and itaconic acid and their half-esterified products;
Half-esterified products of hydroxyl-containing (meth) acrylic acid esters such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate with dibasic acids such as succinic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic anhydride And so on. If the amount of the unsaturated acid monomer used is small, the solubility in alkaline water will be lost, and if it is too large, the water resistance will be poor. Therefore, the resin acid value is preferably 20 to 780, and more preferably 80 to 150.

The monomer copolymerizable with the unsaturated acid monomer should be selected so that the polymer emulsion has desired physical and chemical properties (for example, elasticity, rigidity, chemical resistance, etc.). For example, unsaturated amide monomers such as acrylamide, methacrylamide, diacetone acrylamide, maleic acid diamide, crotonic acid amide, itaconic acid diamide, fumaric acid diamide; styrenes, (meth) acrylonitrile, vinyl acetate, vinyl chloride; Α-Olefins such as isobutene; Dienes such as butadiene; Vinyl ethers such as ethyl vinyl ether; Acrylic esters such as butyl acrylate and hydroxypropyl acrylate; Methacrylic acid ester such as methyl methacrylate and β-hydroxyethyl methacrylate Examples thereof include nitrogen-containing monomers such as N-vinylpyridine, N-vinylcarbazole and N-vinylpyrrolidone. These may be used alone or in combination of two or more.

Among the monomers copolymerizable with the above unsaturated acid monomer, the use of an unsaturated amide monomer means that the unsaturated amide monomer is very well soluble in water, and the polymer is also soluble in water. Due to its extremely high distribution on the surface of emulsion particles, it plays a role as a so-called thickener or protective colloid for emulsion particles, and unlike conventional protective colloids, it is copolymerized with hydrophobic monomers and firmly fixed inside the particles. Therefore, it is particularly preferable. Therefore, the emulsion particles obtained by copolymerizing the unsaturated amide monomer are extremely stable, and in particular, have very high resistance to chemical and mechanical operations when the third component is added.
When the amount of the unsaturated amide monomer used is large, the amount of the water-soluble polymer portion is large, the viscosity is remarkably high, and it becomes difficult to obtain a high-concentration polymer emulsion. On the other hand, if the amount is too small, the polymer emulsion having the above characteristics cannot be obtained. Therefore, it is usually 0 to 50 in the monomer component.
It is used in the range of% by weight, preferably 2 to 40% by weight.

Next, an aqueous emulsion having an acid group is added,
Further, a compound having a polymerizable unsaturated group and a glycidyl group in one molecule (hereinafter, this compound is referred to as an "unsaturated epoxy monomer") is subjected to an addition reaction, and this reaction includes hydroquinone, hydroquinone monomethyl ether, benzoquinone, etc. In the presence of the usual polymerization inhibitor of 50 to 90 ° C. for 1 to 10 hours. The reaction can be smoothly carried out by using an epoxy ring-opening catalyst. Examples of the epoxy ring-opening catalyst include cyclic nitrogen compounds such as 2-ethylimidazole, pyridine and picoline, quaternary ammonium salts, tertiary sulfonium salts, tertiary amines, amine hydrochlorides, and the like. The amount is preferably 0.01 to 25 mol% based on the epoxy group.

The unsaturated epoxy monomer added to the aqueous emulsion having an acid group includes glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl ether, crotonyl glycidyl ether, glycidyl crotonate, and itaconic acid monoalkyl ester. Monoglycidyl ester, fumaric acid monoalkyl ester monoglycidyl ester,
Maleic acid monoalkyl ester monoglycidyl ester, Cyclomer M100 (manufactured by Daicel Chemical Industries, Ltd.), Cyclomer A200 (manufactured by Daicel Chemical Industries, Ltd.) and the like can be mentioned. These are used in the reaction either alone or in combination of two or more.

The unsaturated epoxy monomer is preferably added in an amount of 0.1 to 2.0 equivalents based on the acid groups. When the amount of the unsaturated epoxy monomer added is 0.1 equivalent or less, the curability of the emulsion is extremely lowered. On the other hand, addition of 2.0 equivalents or more has no advantage and causes a problem in storage stability and the like.

In the alkali-developable polymerizable unsaturated group-containing aqueous emulsion of the present invention, a polymerizable unsaturated group-containing compound may be dispersed or dissolved in order to increase the crosslink density and improve the physical properties. it can. Since the alkali-developable polymerizable unsaturated group-containing aqueous emulsion of the present invention has a very high stability, when dispersing or dissolving the polymerizable unsaturated group-containing compound, a surfactant or a water-soluble resin is used. It is not always necessary to add a protective colloid.

Examples of the polymerizable unsaturated group-containing compound include the following.

Aliphatic, alicyclic and araliphatic mono- and poly (meth) acrylates of alcohols and polyalkylene glycols having 1 to 6 valences; aliphatic, alicyclic and araliphatic 2
To mono- and poly (meth) acrylates of polyhydric alcohols obtained by adding alkylene oxides to hexavalent polyhydric alcohols; polyester poly (meth) acrylates; polyester poly (meth) acrylates are usually poly (meth) acrylic acid and poly (meth) acrylate. It is synthesized by esterifying a polyhydric alcohol and a polycarboxylic acid.

Epoxy poly (meth) acrylate; (epoxy resin having two or more epoxy groups in the molecule), (meth) acrylic acid in an amount approximately equivalent to the epoxy groups, (meth) acrylate having a carboxyl group, or (meth)
It is synthesized by reacting a mixture of acrylic acid or a (meth) acrylate having a carboxyl group with a polybasic acid. Alternatively, there is a method of reacting an epoxy group-containing (meth) acrylate with a polycarboxylic acid.

Polyurethane poly (meth) acrylate;
It has a (meth) acrylate structure of a polyhydric alcohol having a polyurethane bond unit in the main chain, and is usually synthesized by a method of reacting a hydroxyl group-containing (meth) acrylate with a polyisocyanate and optionally a polyhydric alcohol. To be done.

Polyamide poly (meth) acrylate; having a (meth) acrylate structure of a polyhydric alcohol having a polyamide bond unit in the main chain, and usually a polyamide-type polyvalent carboxylic acid containing a hydroxy group-containing (meth) acrylate or epoxy. It is synthesized by a method such as reacting a group-containing (meth) acrylate or reacting a polyamide type polyhydric alcohol with (meth) acrylic acid.

A vinyl or diene low polymer having a (meth) acryloyloxy group on the side chain and / or the terminal;
On the side chain or terminal of vinyl-based or diene-based low polymer,
It has a structure in which a (meth) acryloyloxy group is bonded via an ester bond, a urethane bond, an amide bond, an ether bond, or the like. Usually, a low polymer having a hydroxyl group, a carboxyl group, an epoxy group or the like in a side chain or a terminal, is reacted with these groups (meth) acrylic acid, a carboxyl group-containing (meth) acrylate, a hydroxyl group-containing (meth) Acrylate, containing epoxy group (meth)
It is synthesized by reacting an acrylate, an isocyanate group-containing (meth) acrylate, an amino group-containing (meth) acrylate and the like.

Examples of the photopolymerization initiator used in the present invention include benzoin, benzoin methyl ether, benzoin ethyl ether, benzyl, diphenyl disulfide, tetramethyl thiuram monosulfide, eosin, thionine, diacetyl, Michler's ketone, anthraquinone, chloranthraquinone, Methyl anthraquinone, α-hydroxyisobutylphenone, p-isopropyl-α-hydroxyisobutylphenone, α, α'-
Dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, methylbenzoyl formate, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholino-propanone-
1, thioxanthone, diethylthioxanthone, benzophenone, 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butanone 1,2,4,6
-Trimethylphosphyl oxide or the like can be used.

The amount of these photopolymerization initiators used is generally 0.1 to 10 relative to 100 parts by weight of the resin (solid content).
Within the range of parts by weight is preferable. If the amount used is less than 0.1 parts by weight, the curability tends to decrease, and if it is more than 10 parts by weight, the mechanical strength of the cured coating tends to decrease.

A paint or a pigment may be added to the aqueous photoresist composition for a printed wiring board of the present invention, if necessary.

Production of a printed wiring board using the composition of the present invention can be carried out, for example, as follows.

The above-mentioned aqueous photoresist composition for printed wiring boards is applied to the surface of a substrate having an electrically conductive coating such as a copper clad laminate or a metal surface by roll coating, spray coating, curtain flow coating, dip coating or the like.
The film thickness at this time is preferably 1 to 100 μm, and more preferably 5 to 20 μm in terms of dry film thickness. Next, the coating film is dried with hot air or the like to remove water. Then, apply a pattern mask on the uncured photocurable coating film formed on the substrate,
Exposing with active light, an unexposed portion other than a portion to be a conductor circuit is removed by a developing process.

The actinic ray used for exposure in the present invention varies depending on the kind of the photopolymerization initiator used, but is generally a ray having a wavelength of 3000 to 4500 angstroms. As a light source that emits these rays,
For example, sunlight, a mercury lamp, a xenon lamp, an arc lamp, etc. are mentioned. Curing of the coating film by irradiation of actinic rays,
It is completed within a few minutes, usually within 1 second to 20 minutes.

The development treatment can be carried out by spraying weak alkaline water on the coating film to wash away the uncured portion of the coating film. As the weak alkaline water, water such as caustic soda, sodium carbonate, caustic potash, and ammonia water which can neutralize the free carboxylic acid contained in the coating film to make the coating film water-soluble can be used.

Then, the copper foil portion (non-circuit portion) exposed on the substrate by the developing treatment is removed by a usual etching treatment using ferric chloride, cupric chloride or the like. Thereafter, the photo-cured coating film on the circuit pattern is dissolved and removed by a strong alkali such as caustic soda to form a printed circuit on the substrate.

[0028]

EXAMPLES The present invention will be described below with reference to production examples of the aqueous photoresist composition for a printed wiring board of the present invention and specific examples of a method for producing a printed wiring board using the same. However, the present invention is not limited to this example. In addition, all "parts" and "%" used below are based on weight.

Example 1 (1) Preparation of Polymerizable Unsaturated Group-Containing Aqueous Emulsion In a 2 L four-necked flask, 600 parts of water was dissolved in 1 part of sodium dodecylbenzenesulfonate, and the mixture was stirred well to form a foam. , Styrene 75 parts, butyl acrylate 3
00 parts, methyl methacrylate 75 parts, acrylic acid 50
Part and a monomer mixed solution of 1 part of dodecyl mercaptan were added and emulsified to obtain an emulsion. This emulsion was heated to 70 ° C., and 100 parts of a 3% ammonium persulfate aqueous solution was added dropwise from a dropping funnel under a nitrogen stream over 2 hours to carry out emulsion polymerization. Then, the temperature was raised to 90 ° C. and held for 4 hours in order to crush the remaining polymerization initiator. Then, when 50 parts of glycidyl methacrylate and 5 parts of tetramethylammonium chloride in which 0.1 part of di-t-butylmethylphenol was dissolved were added and held at the same temperature for about 3 hours, the epoxy groups disappeared completely. The final acid value is 46 mg-KOH / g, which is about 7 of the epoxy group.
0% was reacting. The solid content concentration of this product was 44%, and the particle diameter was about 0.2 μm.

(2) Production of Water-based Photoresist Composition for Printed Wiring Boards 250 parts (solid content 110 parts) of the polymerizable unsaturated group-containing water-based emulsion obtained in (1) is stirred with a disper to photopolymerization initiator. 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 which is
(Ciba Geigy Co., product name Irgacure 907) 5
Part and 2 parts of diethyl thioxanthone dissolved in 10 parts of propylene glycol monomethyl ether were added to produce an aqueous photoresist composition for printed wiring boards. The organic solvent content of this product was 3.7%.

(3) Production of Printed Wiring Board A glass epoxy copper clad laminate was coated with the aqueous photoresist composition for a printed wiring board obtained above using a roll coater so that the dry film thickness was 10 μm. did.

After the coated layer was dried at 80 ° C. for 20 minutes, a negative film for a printed circuit board was brought into close contact with this coated plate with a vacuum device and 100 mJ / cm ² using a 3 KW ultra-high pressure mercury lamp.
Of the ultraviolet rays.

Next, the unexposed area was washed out with a 1% sodium carbonate aqueous solution at 30 ° C. for 30 seconds and developed to obtain an etching resist pattern. Using this pattern, etching was performed with a ferric chloride / hydrochloric acid etching solution, and then the resist was peeled off with a 1% sodium hydroxide aqueous solution to obtain a printed wiring board having a sharp pattern.

Example 2 (1) Preparation of Polymerizable Unsaturated Group-Containing Aqueous Emulsion In a 2 L four-necked flask, 600 parts of water was dissolved in 1 part of sodium dodecylbenzenesulfonate, and the mixture was thoroughly stirred to form a foam. , Styrene 75 parts, butyl acrylate 3
00 parts, methyl methacrylate 25 parts, acrylic acid 10
A monomer mixed solution of 0 part and 1 part of dodecyl mercaptan was added and emulsified to obtain an emulsion. This emulsion was heated to 70 ° C., and 100 parts of a 3% ammonium persulfate aqueous solution was added dropwise from a dropping funnel under a nitrogen stream over 2 hours to carry out emulsion polymerization. Then, the temperature was raised to 90 ° C. and held for 4 hours in order to crush the remaining polymerization initiator. After that, 150 parts of glycidyl methacrylate in which 0.1 part of di-t-butylmethylphenol was dissolved and 5 parts of tetramethylammonium chloride were added, and the mixture was kept at the same temperature for about 3 hours, and the epoxy group disappeared completely. The final acid value was 56 mg-KOH / g, and about 70% of the epoxy groups had reacted. The solid content of this product is 48%
And the particle size was about 0.2 μm.

(2) Production of aqueous photoresist composition for printed wiring board 270 parts (solid content 120 parts) of the polymerizable unsaturated group-containing aqueous emulsion obtained in (1) was stirred with a disper and polyethylene glycol 20 parts of an average molecular weight of 200) diacrylate was added, followed by photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2.
-Morpholino-propanone-1 (manufactured by Ciba-Geigy, trade name Irgacure 907) and a solution of 2 parts of diethylthioxanthone dissolved in 10 parts of propylene glycol monomethyl ether were added to produce an aqueous photoresist composition for printed wiring boards. did. The organic solvent content of this product was 3.3%.

(3) Production of Printed Wiring Board A glass epoxy copper-clad laminate was coated with the aqueous photoresist composition for printed wiring board obtained above using a curtain coater so that the dry film thickness was 10 μm. did.

After the coated layer was dried at 80 ° C. for 20 minutes, a negative film for a printed circuit board was brought into close contact with this coated plate with a vacuum device and irradiated with ultraviolet rays of 50 mJ / cm ² using a 3 KW ultra-high pressure mercury lamp.

Next, the unexposed area was washed out with a 1% sodium carbonate aqueous solution at 30 ° C. for 30 seconds and developed to obtain an etching resist pattern. Using this pattern, etching was performed with a ferric chloride / hydrochloric acid etching solution, and then the resist was peeled off with a 1% sodium hydroxide aqueous solution to obtain a printed wiring board having a sharp pattern.

Example 3 (1) Preparation of Polymerizable Unsaturated Group-Containing Aqueous Emulsion In a 2 L four-necked flask, 600 parts of water was dissolved in 1 part of sodium dodecylbenzenesulfonate, and the mixture was well stirred to foam. , Styrene 75 parts, butyl acrylate 3
00 parts, methyl methacrylate 25 parts, acrylic acid 50
Part and a monomer mixed solution of 1 part of dodecyl mercaptan were added and emulsified to obtain an emulsion. This emulsion was heated to 70 ° C., and 100 parts of a 3% ammonium persulfate aqueous solution was added dropwise from a dropping funnel under a nitrogen stream over 2 hours to carry out emulsion polymerization. Then, the temperature was raised to 90 ° C. and held for 4 hours in order to crush the remaining polymerization initiator. After that, 150 parts of glycidyl methacrylate in which 0.1 part of di-t-butylmethylphenol was dissolved and 5 parts of tetramethylammonium chloride were added, and the mixture was kept at the same temperature for about 3 hours, and the epoxy group disappeared completely. The final acid value was 46 mg-KOH / g, and about 70% of the epoxy groups had reacted. The solid content of this product is 44%
And the particle size was about 0.2 μm.

(2) Production of aqueous photoresist composition for printed wiring board 250 parts (solid content 110 parts) of the polymerizable unsaturated group-containing aqueous emulsion obtained in (1) was stirred with a disper and polyethylene glycol 20 parts of an average molecular weight of 200) diacrylate was added, followed by photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2.
-Morpholino-propanone-1 (manufactured by Ciba-Geigy, trade name Irgacure 907) and a solution of 2 parts of diethylthioxanthone dissolved in 10 parts of propylene glycol monomethyl ether were added to produce an aqueous photoresist composition for printed wiring boards. did. The organic solvent content of this product was 3.5%.

(3) Production of Printed Wiring Board A glass epoxy copper-clad laminate was coated with the aqueous photoresist composition for printed wiring board obtained above using a spray coater so that the dry film thickness was 10 μm. did.

After the coated layer was dried at 80 ° C. for 20 minutes, a negative film for a printed circuit board was brought into close contact with this coated plate with a vacuum device and irradiated with 70 mJ / cm ² of ultraviolet rays using a 3 KW ultra-high pressure mercury lamp.

Next, the unexposed area was washed with a 1% sodium carbonate aqueous solution at 30 ° C. for 30 seconds and developed to obtain an etching resist pattern. Using this pattern, etching was performed with a ferric chloride / hydrochloric acid etching solution, and then the resist was peeled off with a 1% sodium hydroxide aqueous solution to obtain a printed wiring board having a sharp pattern.

Comparative Example 1 (1) Production of photocurable resin 40 parts of methyl methacrylate, 40 parts of butyl acrylate
Part, 20 parts of acrylic acid and 2 parts of azobisisobutyronitrile were mixed in a nitrogen gas atmosphere at a temperature of 11 parts.
It was added dropwise to 90 parts of propylene glycol monomethyl ether (hydrophilic solvent) kept at 0 ° C. over 3 hours.
After the dropping, the mixture was aged for 1 hour, a mixed solution containing 1 part of azobisdimethylvaleronitrile and 10 parts of propylene glycol monomethyl ether was added dropwise over 1 hour, and the mixture was aged for 5 hours to obtain a high acid value acrylic resin (acid value 155 ) A solution was obtained. Next, 24 parts of glycidyl methacrylate, 0.12 part of hydroquinone and 0.6 part of tetraethylammonium bromide were added to this solution, and the mixture was reacted at 110 ° C. for 5 hours while blowing air to obtain a photocurable resin (acid value: about 50, Saturation 1.35 mol / kg, Tg point 20
A solution having a number average molecular weight of about 20,000) was obtained.

(2) Manufacture of aqueous photoresist composition for printed wiring board: After 6.7 parts of triethylamine was added to 227 parts of the photocurable resin solution of (1) to sufficiently neutralize, it was a photopolymerization initiator. 6 parts of α-hydroxyisobutylphenone was added, and deionized water was added so that the solid content was 20% to obtain an aqueous photoresist composition for printed wiring boards. The organic solvent content of this product was 16.1%.

(3) Production of Printed Wiring Board A glass epoxy copper-clad laminate was coated with the aqueous photoresist composition for a printed wiring board obtained above using a spray coater so that the dry film thickness was 10 μm. did.

After the coated layer was dried at 80 ° C. for 20 minutes, a negative film for a printed circuit board was brought into close contact with this coated plate with a vacuum device and 1000 mJ / cm using a 3 KW ultra-high pressure mercury lamp.
Irradiated with ² ultraviolet rays.

Next, the unexposed area was washed with a 1% sodium carbonate aqueous solution at 30 ° C. for 30 seconds and developed.
The water resistance of the exposed area was poor, and an etching resist pattern could not be obtained.

Comparative Example 2 (1) Production of High Acid Value Aqueous Emulsion In a 2 L four-necked flask, 1 part of sodium dodecylbenzene sulfonate was dissolved in 600 parts of water, and the mixture was well stirred to foam styrene 75 therein. Part, butyl acrylate 3
00 parts, methyl methacrylate 75 parts, acrylic acid 50
Part and a monomer mixed solution of 1 part of dodecyl mercaptan were added and emulsified to obtain an emulsion. This emulsion was heated to 70 ° C., and 100 parts of a 3% ammonium persulfate aqueous solution was added dropwise from a dropping funnel under a nitrogen stream over 2 hours to carry out emulsion polymerization. Then, the temperature was raised to 90 ° C. and held for 4 hours in order to crush the remaining polymerization initiator. The acid value of this product was 46 mg-KOH / g, the solid content concentration was 42%, and the particle diameter was about 0.2 μm.

(2) Production of aqueous photoresist composition for printed wiring board 240 parts of high acid value aqueous emulsion obtained in (1) (100 parts of solid content) was stirred with a disper and polyethylene glycol (number average molecular weight of 200) was used. ) Diacrylate 4
0 part was added, followed by photopolymerization initiator 2-methyl-
A solution prepared by dissolving 5 parts of 1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 (manufactured by Ciba-Geigy, trade name Irgacure 907) and 2 parts of diethylthioxanthone in 10 parts of propylene glycol monomethyl ether was added. To produce an aqueous photoresist composition for a printed wiring board. The organic solvent content of this product is 3.
4%.

(3) Production of Printed Wiring Board A glass epoxy copper-clad laminate was coated with the aqueous photoresist composition for a printed wiring board obtained above using a spray coater so that the dry film thickness was 10 μm. did.

After the coated layer was dried at 80 ° C. for 20 minutes, a negative film for a printed circuit board was brought into close contact with this coated plate with a vacuum device and 400 mJ / cm ² using a 3 KW ultra-high pressure mercury lamp.
Of the ultraviolet rays.

Next, the unexposed area was washed out with a 1% aqueous sodium carbonate solution at 30 ° C. for 30 seconds and developed to obtain an etching resist pattern. Using this pattern, etching was performed with a ferric chloride / hydrochloric acid etching solution, and then the resist was peeled off with a 1% sodium hydroxide aqueous solution to obtain a printed wiring board having a sharp pattern.

Organic solvent content of Examples 1 to 3 and Comparative Examples 1 and 2, peeling degree of negative film after exposure to negative film, exposure amount, wash-out development of unexposed area with weak alkali, chlorination after water washing Etching removal of copper foil with ferric iron,
The peeling of the cured coating film after exposure was examined. Table 1 shows the results. In Table 1, the exposure amount: line / space = 20/20 μm
The minimum exposure that gives a solid cured film after development.

Development: A state after washing out an unexposed area after spraying a 1% sodium carbonate solution at 30 ° C. for 2 minutes.

Etching treatment: After exposure, development and washing with water, 5
Line / space = 50/50 μm image line after spraying ferric chloride / hydrochloric acid etching solution at 0 ° C. for 3 minutes.

Peeling of the cured film: The peeled state of the cured film after spraying 1% NaOH solution at 50 ° C. for 3 minutes.

[0058]

[Table 1]

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[Procedure amendment]

[Submission date] November 28, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction contents]

(2) Production of aqueous photoresist composition for printed wiring board 270 parts (solid content 130 parts) of the polymerizable unsaturated group-containing aqueous emulsion obtained in (1) was stirred with a disper and polyethylene glycol 20 parts of an average molecular weight of 200) diacrylate was added, followed by photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2.
-Morpholino-propanone-1 (manufactured by Ciba-Geigy, trade name Irgacure 907) and a solution of 2 parts of diethylthioxanthone dissolved in 10 parts of propylene glycol monomethyl ether were added to produce an aqueous photoresist composition for printed wiring boards. did. The organic solvent content of this product was 3.3%.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction contents]

Example 3 (1) Preparation of Polymerizable Unsaturated Group-Containing Aqueous Emulsion In a 2 L four-necked flask, 600 parts of water was dissolved in 1 part of sodium dodecylbenzenesulfonate, and then 50 parts of acrylamide may be added. The mixture was stirred and foamed, and a monomer mixed solution of 75 parts of styrene, 300 parts of butyl acrylate, 25 parts of methyl methacrylate, 50 parts of acrylic acid and 1 part of dodecyl mercaptan was added and emulsified to obtain an emulsion. Heat this emulsion to 70 ° C,
Under nitrogen stream, 100 parts of 3% ammonium persulfate aqueous solution was added dropwise from a dropping funnel over 2 hours to carry out emulsion polymerization. Then, the temperature is adjusted to 90 to crush the remaining polymerization initiator.
It was kept at 4 ° C for 4 hours. Then, 50 parts of glycidyl methacrylate and 0.1 parts of tetramethylammonium chloride in which 0.1 part of di-t-butylmethylphenol was dissolved.
When parts were added and the mixture was kept at the same temperature for about 3 hours, the epoxy groups disappeared completely. Final acid value is 46 mg-KOH
/ G, and about 70% of the epoxy groups had reacted. The solid content concentration of this product was 44%, and the particle size was about 0.2.
μm.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction contents]

Comparative Example 2 (1) Production of High Acid Value Aqueous Emulsion In a 2 L four-necked flask, 1 part of sodium dodecylbenzene sulfonate was dissolved in 600 parts of water, and the mixture was well stirred to foam styrene 75 therein. Part, butyl acrylate 3
00 parts, methyl methacrylate 75 parts, acrylic acid 50
Part and a monomer mixed solution of 1 part of dodecyl mercaptan were added and emulsified to obtain an emulsion. This emulsion was heated to 70 ° C., and 100 parts of a 3% ammonium persulfate aqueous solution was added dropwise from a dropping funnel under a nitrogen stream over 2 hours to carry out emulsion polymerization. Then, the temperature was raised to 90 ° C. and held for 4 hours in order to crush the remaining polymerization initiator. The acid value of this product was 78 mg-KOH / g, the solid content concentration was 42%, and the particle diameter was about 0.2 μm.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Yoshikawa 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd.

Claims (4)

[Claims] 1. An alkali-developable polymerizable unsaturated group-containing aqueous emulsion obtained by adding a compound having a polymerizable unsaturated group and a glycidyl group in one molecule to an aqueous emulsion having an acid group, and a photopolymerization initiator. An aqueous photoresist composition for a printed wiring board, comprising: 2. An alkali-developable polymerizable unsaturated group-containing aqueous emulsion obtained by adding a compound having a polymerizable unsaturated group and a glycidyl group in one molecule to an aqueous emulsion having an acid group and an amide group, and an optical emulsion. A water-based photoresist composition for a printed wiring board, which comprises a polymerization initiator. 3. A compound having a polymerizable unsaturated group-containing compound dispersed or dissolved therein.
The water-based photoresist composition for a printed wiring board as described above. 4. (a) A step of forming a smooth coating film by coating the aqueous photoresist composition according to any one of claims 1 to 3 on a surface of a substrate or a metal having a conductive coating film and drying the same. b) a step of curing the smooth coating film with an actinic ray through a pattern mask; (c) a step of removing an unexposed portion of the cured coating film with an alkaline developer to form a pattern; (d) exposing A method for producing a printed wiring board, comprising: a step of removing the conductive coating film or metal by etching; and (e) a step of removing the coating film on the pattern.