JPH06258832A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE: To provide a photosensitive resin compsn. which allows the execution of development processing with neutral water and is in the form of an aq. soln. or water dispersion. CONSTITUTION: This photosensitive resin compsn. contains an aq. emulsion compsn. of a polymer compd. which has an acid value of 50 to 300mg/KOH/g and a glass transition temp. of 30 to 250 deg.C, has at least one carboxyl groups in one molecule and is added with a neutralizing agent compd. at 30 to 120mol% of the carboxyl groups, a compd. having at least one ethylenic unsatd. bonds in one molecule and a photopolymn. initiator capable of generating free radicals by irradiation with active light as indispensable components.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photosensitive resin composition containing no organic solvent. For more details,
The present invention relates to a photosensitive resin composition in the form of an aqueous solution or an aqueous dispersion that can be subjected to development treatment with neutral water, a method for producing the same, and a method for producing a printed circuit board using the composition. is there.

[0002]

2. Description of the Related Art Photosensitive resin solutions and films are used as resist materials for chemical and electrochemical processing of base materials such as etching and plating in the fields of printed circuit board manufacturing, precision processing of metals and the like. It is widely used. Conventional photosensitive resin is an organic solvent solution,
Most are processed into a film from an organic solvent solution. Further, in the developing step after exposure, an organic solvent has been mainly used in the past, but in recent years, a dilute alkaline aqueous solution has come to be used as a developing solution in view of environmental problems, worker health problems and the like. However, even if the developing solution is replaced with an aqueous solution, volatilization of the organic solvent is inevitable during application of the resist, drying, or processing into a film, which causes air pollution and health problems. Further, in order to reduce the manufacturing cost, it is desirable to use neutral water that is cheaper than the alkaline aqueous solution.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems, to enable development with neutral water, and to solve the problem of organic solvent scattering in the form of an aqueous solution or water dispersion. It is to provide a photosensitive resin composition that does not occur.

[0004]

Therefore, the present invention provides (a) an acid value of 50 to 300 mg-KOH / g and 30 to 30 mg.
Aqueous emulsion of polymer compound having a glass transition temperature of 250 ° C., having at least one carboxyl group in one molecule and having 30 to 120 mol% of the neutralizing compound added to the carboxyl group. A composition; (b) a compound having at least one ethylenically unsaturated bond in one molecule; and (c) a photopolymerization initiator capable of generating a free radical upon irradiation with active light; The present invention relates to a photosensitive resin composition in the form of an aqueous solution or an aqueous dispersion which can be developed with neutral water.

The compound having at least one carboxyl group in one molecule used in the preparation of the component (a) of the composition of the present invention is solubilized, dispersed, suspended or emulsified in water to form an aqueous emulsion. It is also possible to dissolve, disperse, suspend, or emulsify a compound having at least one carboxyl group in one molecule in water using a surfactant called an emulsifier, but a more stable aqueous resin In order to obtain a composition solution, a monomer having at least one carboxyl group and at least one double bond in the molecule and a monomer copolymerizable therewith are emulsion-polymerized or suspension-polymerized. It is preferable to prepare an aqueous emulsion of a polymer compound by polymerizing it using the method described above.

A monomer having at least one carboxyl group and at least one double bond in the molecule for such purpose, that is, for preparing the component (a) in the composition of the present invention. Examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid and the like. You may use these monomers in mixture of 2 or more types. In addition, these monomers should be used in such an amount that the carboxy group content of the polymer compound having at least one carboxyl group in one molecule is 1.43 mmol to 4.46 mmol per 1 g. Is desirable.

Further, another monomer copolymerizable with a monomer having at least one carboxyl group and at least one double bond in the molecule used in the preparation of the component (a) of the composition of the present invention. As the monomer, methyl acrylate,
Use of acrylic acid ester such as ethyl acrylate, methacrylic acid ester such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, etc., and known polymerizable monomer such as styrene, vinyltoluene, acrylamide, acrylonitrile, butadiene, etc. You can

Polymerization methods such as emulsion polymerization and suspension polymerization in the preparation of the component (a) of the present invention are carried out by known methods and conditions. That is, a monomer having at least one carboxyl group and at least one double bond in one molecule, and another monomer copolymerizable therewith are prepared as an alkyl sulfonate or an alkylbenzene sulfonate. , Anionic surfactants such as alkyl diphenyl ether disulfonate, naphthalene sulfonic acid formalin condensate, poly oxoethylene alkyl ether sulfate, etc.,
To emulsify and suspend in water using a nonionic surfactant such as polyethylene glycol ether or polyethylene sorbitan ester, and to carry out a polymerization reaction using a water-soluble polymerization initiator such as potassium persulfate, hydrogen peroxide or ammonium persulfate. You can During the reaction, known additives may be added to the reaction solution in order to enhance the stability of the solution after the reaction.
Further, in order to control the molecular weight of the polymer, it is preferable to use a known chain transfer agent such as 1-dodecanethiol or 3-dodecanethiol.

The acid value of the polymer compound having at least one carboxyl group in one molecule obtained by the above method is preferably 50 to 300 mg / g, and 80 to 2
50 mg / g is more preferable. When the acid value is less than this value, it is difficult to carry out the development process using neutralized water. Further, when the acid value is more than this value, properties such as water resistance and etching liquid resistance of the resist film are impaired.

The glass transition temperature of the polymer compound having at least one carboxyl group in one molecule obtained by the above method is preferably 30 to 250 ° C, and 50 to 200 ° C. Is more preferable. When the glass transition temperature is below this value, the resist solution remains sticky even after being applied to the substrate and dried, which is inconvenient when the negative mask is closely contacted for exposure. Further, if the glass transition temperature is above this value, it is difficult to obtain a uniform film after coating the resist solution on the substrate and drying.

In the composition of the present invention, by adding 30 to 120 mol% of the neutralizer compound to the system based on the carboxyl group of the polymer compound having at least one carboxyl group in one molecule, The carboxyl group is neutralized into a carboxylate salt form to be soluble in neutral water. Examples of the neutralizer compound used for such a purpose in the present invention include inorganic alkalis and amines. Examples of the inorganic alkali used in the present invention include sodium hydroxide, potassium hydroxide, calcium carbonate, sodium carbonate, sodium hydrogen carbonate and the like. The amines include alkylamines such as diethylamine, monoethylamine, diisopropylamine and diisobutylamine, alkanolamines such as monoethanolamine and diethanolamine, alkylalkanolamines such as dimethylaminoethanol and alicyclics such as cyclohexylamine. Examples thereof include amines having a polymerizable unsaturated bond in the molecule, such as formulaic amines, imidazoles, dimethylaminopropylacrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and allylamine.

These neutralizer compounds are added to the aqueous emulsion of the polymer compound having at least one carboxyl group in one molecule obtained by the above-mentioned step, or
Alternatively, the components (b) and (c) of the composition according to the present invention, that is, a compound having at least one ethylenically unsaturated bond in one molecule and initiation of photopolymerization capable of generating free radicals by irradiation with active light The agent may be added after mixing in the emulsion.

The boiling point of these neutralizer compounds is preferably higher than the predrying temperature of the resist coating film. If the boiling point of the neutralizing agent compound is lower than the predrying temperature, the added neutralizing agent is volatilized during the predrying and is neutralized by the neutralizing agent to become a neutral water soluble carboxylate. Disappeared,
The neutral water-insoluble carboxyl group may be regenerated.

The amount of these neutralizing agents used is 30 to 120 mol%, more preferably 50 to 90 mol% of the carboxyl groups in the polymer compound having at least one carboxyl group in one molecule. It is desirable to use. If it is below this range, the phenomenon due to neutral water or city water is difficult, and if it exceeds this range, various characteristics required for use as an etching resist are impaired.

The component (b) of the composition of the present invention, that is, the compound having at least one ethylenically unsaturated bond in one molecule is 2-hydroxyethyl acrylate, 2
-Hydroxypropyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol diacrylate, N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, melamine acrylate, or methacrylates corresponding to the above acrylates, diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate , Tripropylene glycol diacrylate, polyp Pyrene glycol diacrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, trimethylolpropane triacrylate, glycerin diglycidyl ether diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, Mention may be made of isoborneolyl acrylate, cyclopentadiene-mono or diacrylate, and the methacrylates corresponding to the above acrylates.

The compound having at least one ethylenically unsaturated bond in the above-mentioned molecule has at least one carboxyl group in the above-mentioned molecule, and is a neutralizer compound of 30 to 120 mol% of said carboxyl group. Although it may be added directly to the aqueous emulsion composition of the polymer compound to which is added, it is preferable to add it after forming an aqueous emulsion in advance using a known emulsifier and a dispersant.

The above-mentioned compound having at least one ethylenically unsaturated bond in one molecule is a compound of the composition of the present invention.
Component (a), that is, an acid value of 50 to 300 mg-KOH
/ G, having a glass transition temperature of 30 to 250 ° C., having at least one carboxyl group in one molecule, and adding 30 to 120 mol% of the neutralizing compound to the carboxyl group. It is also possible to impregnate the particles of the aqueous emulsion composition of the polymer compound.
Impregnation of a polymer particle dispersed, suspended, or emulsified in water with a monomer is known as a mechanism of a seed polymerization method found in JP-B-57-24369.

The component (c) of the composition of the present invention, that is, a photopolymerization initiator capable of generating a free radical upon irradiation with actinic rays, includes 2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2. −
Quinones such as benzanthraquinone and α-such as benzoin, pivaloin and acyloin ether
Ketaldonyl alcohols, ethers, α-phenylbenzoin, α, α′-diethoxyacetophenone,
Ketones such as benzophenone and 4,4′-bisdialkylaminobenzophenone, thioxanthone derivatives,
The 2,4,5-triarylimidazolyl dimer can be mentioned. These may be used alone or in combination of two or more.

A known polymerization inhibitor may be added to the photosensitive resin composition of the present invention in order to prevent thermal polymerization during storage. Examples of these inhibitors include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tertiary butyl catechol, and phenothiazine.

In the photosensitive resin composition of the present invention, if necessary, known fillers such as barium sulfate, silicon oxide, talc, clay and calcium carbonate, phthalocyanine green, titanium oxide and carbon black are also known. Conventional colorants, leveling agents, adhesion improvers, thixotropic agents,
Fillers and the like can be added.

The photosensitive resin composition of the present invention comprises (a) 50-
Having an acid value of 300 mg-KOH / g and a glass transition temperature of 30 to 250 ° C., and having at least one carboxyl group in one molecule and having 30 relative to the carboxyl group.
To 120 mol% of the neutralizing compound is added to the aqueous emulsion composition of the polymer compound in a solid content of 10 to 5
0 parts by weight; (b) 10 to 50 parts by weight of a compound having at least one ethylenically unsaturated bond in one molecule; and (c)
It is obtained by mixing 1 to 20 parts by weight of a photopolymerization initiator capable of generating free radicals by irradiation with active light; and, if necessary, mixing with other additives. At the time of mixing, it is desirable to carry out high speed stirring using a homomixer, a disperser or the like, or ultrasonic waves, heating, etc. to complete dispersion, emulsification and impregnation into particles.

The photosensitive resin composition according to the present invention is applied onto a copper-clad laminate, which is a material for a printed wiring board, by a known method such as roll coating, dip coating or screen printing, and then dried. A resist layer can be formed by carrying out. After that, irradiation with actinic light can be performed through a negative mask, and then development processing can be performed using neutral water. By using the resist pattern thus formed, a desired wiring circuit pattern can be formed by performing an etching process by a known method.

[0023]

By using the photosensitive resin composition of the present invention, a printed wiring board can be obtained by a usual method without using an organic solvent, and the resin composition of the present invention contains an organic solvent. Since it is not contained, it has an effect that environmental and health problems due to volatilization of the organic solvent do not occur. Further, since inexpensive and safe neutral water can be used as a developing solvent, there is an effect that a printed circuit board can be manufactured at low cost without causing environmental problems.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples. The examples described below show the embodiments of the present invention, and the present invention is not limited thereto.

[0025]

Example 1 (1) Synthesis of Methyl Methacrylate / Methacrylic Acid Copolymer Aqueous Emulsion 2 g of sodium dodecylbenzenesulfonate and 2 g of Emulgen 920 (Kao Corporation nonionic surfactant) were dissolved in 300 g of deionized water. .

This was charged into a 1-liter four-necked flask equipped with a cooling tube, a thermometer, a nitrogen blowing port, and a stirrer, and methyl methacrylate (82.3 g) and methacrylic acid (1) were charged.
A mixture of 7.7 g and 1-dodecanethiol 0.2 g was added with stirring to emulsify. As a polymerization initiator,
A solution obtained by dissolving 0.3 g of potassium persulfate in 100 g of deionized water was added, and polymerization was carried out at 60 ° C. for 5 hours and 65 ° C. for 2 hours under a nitrogen stream to obtain an acid value of 115.5 mg in terms of solid content.
/ G, glass transition temperature calculated from the Fox equation 105.
A polymer having a solid content of 20% and having a temperature of 2 ° C. was obtained.

(2) Addition of amine to copolymer aqueous emulsion 100 g of the copolymer aqueous emulsion obtained in the above (1) was added with
2.8 g of 2-dimethylaminoethanol dissolved in 7.2 g of water was added and stirred to neutralize about 75 mol% of the carboxyl groups in the copolymer.

(3) Preparation of Photosensitive Resin Composition Solution 100 g of the neutralized polymer solution obtained in (2) above; 20 g of trimethylolpropane triacrylate; 1 g of Irgacure 651 (a photopolymerization initiator manufactured by Ciba-Geigy) Talc 15 g; Aerosil # 380 (fine powder silica manufactured by Nippon Aerosil Co., Ltd.) 1.5 g; Ethyl violet 0.2 g; High-speed stirring at 10,000 rpm or more for 5 minutes using a homomixer, and the photosensitive resin according to the present invention. A composition solution was obtained.

(4) Fabrication of printed wiring board A dry coating film thickness of 20 μm was formed on one surface of a 1.2 mm-thick copper-clad laminate made of glass epoxy with 25 μm copper foil on both sides using a roll coater. The photosensitive resin composition solution obtained above was applied so that

After drying the coating layer at 80 ° C. for 15 minutes, the resin composition according to the present invention was similarly coated on the back surface of the laminated plate,
It was dried at 0 ° C. for 20 minutes. Then, 350 mJ / cm ² of ultraviolet rays were radiated through a PET negative mask, tap water was sprayed for 1 minute for development, and an etching resist pattern was obtained. 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 desired wiring circuit pattern.

[0031]

Example 2 (1) Preparation of Acrylic Acid / Methyl Methacrylate / Ethyl Acrylate Copolymer Aqueous Emulsion 100 g of deionized water, 5 g of Emulgen 935 (Kao Corporation, nonionic surfactant), Perex SS-L 0.1 g (anionic surfactant manufactured by Kao Corporation) was dissolved. To this aqueous solution, a mixture of 25.6 g of acrylic acid, 71.6 g of methyl methacrylate, 2.8 g of ethyl acrylate and 0.2 g of 1-dodecanethiol was added with stirring.
Under a nitrogen stream, 0.05 g of potassium persulfate dissolved in 20 g of deionized water was added, and the mixture was reacted at 60 ° C. for 4 hours. After this, potassium persulfate dissolved in a small amount of water 0.0
1 g was added, and the mixture was further reacted at 60 ° C. for 2 hours to give a solid content of 43%, a solid content-based acid value of 200 mg-KOH / g, and F.
An aqueous acrylic acid / methyl methacrylate / ethyl acrylate copolymer aqueous emulsion having a glass transition temperature of 100 ° C. calculated from the equation of ox was obtained.

(2) Addition of amine to acrylic copolymer aqueous emulsion 100 g of acrylic copolymer aqueous emulsion obtained above
Then, 17 g of 2-diethylaminoethyl methacrylate dissolved in 13 g of water was added to neutralize about 60 mol% of the carboxyl groups in the acrylic copolymer.

(3) Preparation of photosensitive resin composition solution Neutralized acrylic acid copolymer aqueous emulsion obtained above
130 g; Aronix M-400 (manufactured by Toagosei Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaacrylate) 40 g; Lucirin TPO (manufactured by BASF, photopolymerization initiator) 4 g; Crystal Violet 0.5 g; At high speed to obtain a photosensitive resin composition solution.

(4) Manufacture of printed wiring board A dry film thickness of 30 μm was formed on one surface of a 1.6 mm-thick glass-epoxy copper-clad laminate having copper foil of 25 μm stretched on both sides using a doctor knife. The photosensitive resin composition solution obtained above was applied so that

After the coated layer was dried at 80 ° C. for 15 minutes, the resin composition was similarly coated on the back surface of the laminated plate and dried at 90 ° C. for 20 minutes. Then 250 through a PET negative mask
Ultraviolet rays of mJ / cm ² were irradiated and tap water was sprayed for 90 seconds for development 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 desired wiring circuit pattern.

[0036]

Example 3 (1) Synthesis of Aqueous Emulsion of Styrene / Methacrylic Acid Copolymer 1 g of Emulgen 920 (Kao Corporation nonionic surfactant) and 1 g of sodium dodecylbenzenesulfonate were dissolved in 150 g of deionized water. A mixture of 40.8 g of styrene, 9.2 g of methacrylic acid and 0.1 g of 1-dodecanethiol was added to this solution with stirring. Then
Under a stream of nitrogen, 0.15 g of potassium persulfate was added to deionized water 5
What was dissolved in 0 g was added, and after reacting at 60 ° C. for 5 hours and at 65 ° C. for 2 hours, the nitrogen stream was stopped, 0.1 g of L-ascorbic acid was added, and further reacted at 70 ° C. for 2 hours,
A styrene / methacrylic acid copolymer aqueous emulsion having a solid content of 19.1% was obtained. The styrene / methacrylic acid copolymer emulsified and dispersed in this solution had an acid value of 120 mg-KOH / g in terms of solid content, a glass transition temperature of 105.2 ° C. calculated by the Fox equation, and a diameter of 0. It had a spherical shape of 5 μm.

(2) Preparation of Photosensitive Resin Composition Solution 0.2 g of sodium laurylsulfonate was dissolved in 70 ml of deionized water, and 12 g of trimethylolpropane triacrylate and Irgacure 907 were stirred with high speed.
0.6 g (a photopolymerization initiator manufactured by Ciba-Geigy) was added and emulsified. To this solution was added 35 g of the styrene / methacrylic acid copolymer aqueous emulsion obtained in (1) above, 30 ml of acetone was added, and the mixture was stirred at 40 ° C. for 5 hours to allow the aqueous emulsion particles to contain the monomer and trimethylolpropane. Impregnated with triacrylate. After the acetone was distilled off, the particle size of the aqueous emulsion was 0.5 μm to 2.
It was increased to 8 μm.

(3) Addition of amine to copolymer aqueous emulsion 100 g of the resin composition solution obtained in (2) above was dissolved in 10 g of water DMAPPA (manufactured by Kojinsha, N, N-dimethylaminopropylacrylamide). ) 10.5 g was added to neutralize about 90 mol% of the carboxyl groups.

(4) Preparation of printed wiring board A glass epoxy plate having a thickness of 1.4 mm and having a thickness of 25 on both sides.
0.7mm to 0.3m on a laminated plate with copper foil of μm
m, followed by electroless plating activation treatment, thin electroless copper plating, and electrolytic copper plating to deposit copper having a thickness of 25 μm in the through holes. Above this board
The photosensitive resin composition solution obtained in (2) is dip-coated and dried, exposed, developed, etched, and resist stripped in the same manner as in Examples 1 and 2 to obtain a printed wiring board having a desired pattern. It was

[0040]

Example 4 (1) Synthesis of Methyl Methacrylate / Methacrylic Acid Copolymer Aqueous Emulsion 2 g of Emulgen 920 and 2 g of sodium dodecylbenzenesulfonate were dissolved in 300 g of deionized water.
Methyl methacrylate 81.
A mixture of 6 g, 18.4 g of methacrylic acid and 0.2 g of 1-dodecanethiol was added and emulsified. As a polymerization initiator, 0.3 g of potassium persulfate dissolved in 100 g of deionized water was added, and the mixture was reacted at 60 ° C. for 5 hours and at 65 ° C. for 2 hours under a nitrogen stream. 0.2 g of 1 L-ascorbic acid was added, the nitrogen stream was stopped, and the temperature was further increased to 70 ° C.
The reaction was carried out for 2 hours to remove residual radicals. The solid content concentration of the obtained methyl methacrylate / methacrylic acid copolymer aqueous emulsion was 19.8%, the acid value in terms of solid content was 120 mg-KOH / g, and the glass transition temperature calculated from the Fox equation was It was 109.4 ° C.

(2) Preparation of Photosensitive Resin Composition Solution To 100 g of the methyl methacrylate / methacrylic acid copolymer aqueous emulsion obtained above, DMAPPA (N, N-dimethylaminopropylacrylamide manufactured by Kojin Co., Ltd.) was added.
A solution prepared by dissolving 6.0 g in 4.0 g of deionized water was added to neutralize 90 mol% of the carboxyl groups contained in the methyl methacrylate / methacrylic acid copolymer. In this solution, 20 g of Kayarad DPCA-20 (manufactured by Nippon Kayaku Co., caprolactone-modified dipentaerythritol hexaacrylate), Darocur-4265 (manufactured by Merck, photopolymerization initiator, 2-hydroxy-2-methyl-1-phenyl-). 0.2 g of 1-propanone-1) and 0.2 g of ethyl violet were added to prepare a photosensitive resin composition solution. Carboxyl group-neutralized methyl methacrylate /
Since the methacrylic acid copolymer acts as a surfactant, it was not necessary to add further surfactant to neutralize the monomer.

(3) Preparation of Printed Wiring Board A printed wiring board was prepared in the same manner as in Examples 1 and 2 by using the photosensitive resin composition solution obtained in (2) above.

[0043]

Example 5 (1) Styrene / acrylic acid / n-butyl acrylate /
Synthesis of Methyl Methacrylate Copolymer Aqueous Emulsion 0.1 g of sodium lauryl sulfonate and 8.8 g of sodium hydrogen carbonate were dissolved in 150 g of deionized water. To this solution, 3/4 of an aqueous solution in which 2.64 g of potassium persulfate was dissolved in 50 g of deionized water was added under a nitrogen stream. After the temperature was raised at 70 ° C, styrene 1 was added to the reaction solution.
A mixture of 8.2 g and 10 g of acrylic acid was added dropwise over 2 hours. After adding the remaining potassium persulfate aqueous solution,
Methyl methacrylate 50 g, n-butyl acrylate 20
g was added dropwise over 3 hours and reacted at 70 ° C. for 3 hours,
An aqueous emulsion of styrene / acrylic acid / n-butyl acrylate / methyl methacrylate copolymer having a solid content of 29.4% was obtained. The acid value of the solid content of this copolymer is 80
The glass transition temperature calculated from the formula of mg / g, Fox is 5
It was 0 ° C.

(2) Addition of amine to copolymer aqueous emulsion Styrene / acrylic acid / acrylic acid n-obtained above
To 100 g of a butyl / methyl methacrylate copolymer aqueous emulsion, 5 g of DMAPPA dissolved in 5 g of water was added to neutralize 80 mol% of carboxyl groups.

(3) Preparation of photosensitive resin composition solution 12 g of trimethylolpropane triacrylate, G1
5 g of 01P (glycerin dimethacrylate manufactured by Kyoeisha Yushi Co., Ltd.) and 2.4 g of Irgacure 651 were mixed.
While stirring this at high speed, neutralized styrene obtained in (2) above /
A photosensitive resin composition solution was prepared by adding 110 g of acrylic acid / n-butyl acrylate / methyl methacrylate copolymer aqueous emulsion.

(4) Preparation of printed wiring board A printed wiring board was prepared in the same manner as in Examples 1 and 2 using the photosensitive resin composition solution obtained in (3) above.

[0047]

Example 6 (1) Preparation of Photosensitive Resin Composition Solution 100 g of the methyl methacrylate / methacrylic acid copolymer aqueous emulsion obtained in the step (1) of Example 4 was deionized with 1.4 g of potassium hydroxide. What was dissolved in 10.0 g of water was added to neutralize 60 mol% of the carboxyl groups contained in the methyl methacrylate / methacrylic acid copolymer.
Kayarad DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.,
12 g of caprolactone-modified dipentaerythritol hexaacrylate, 0.5 g of Irgacure 651,
0.2 g of ethyl violet was added to prepare a photosensitive resin composition solution.

(2) Preparation of Printed Wiring Board A printed wiring board was prepared in the same manner as in Examples 1 and 2 by using the photosensitive resin composition solution obtained in (1) above. The development processing was performed with city water.

[0049]

Comparative Example 1 (1) Synthesis of Styrene / Acrylic Acid / n-Butyl Acrylate Copolymer Aqueous Emulsion 0.1 g of sodium lauryl sulfonate and 9.32 g of sodium hydrogen carbonate were dissolved in 150 g of deionized water.
To this, 2.64 g of ammonium persulfate dissolved in 50 g of deionized water was added under a nitrogen stream and the temperature was raised to 70 ° C. A mixture of 18.2 g of styrene and 10 g of acrylic acid was added dropwise over 2 hours, and then n-butyl acrylate 81.
8 g was added dropwise over 7 hours to obtain a styrene / acrylic acid / n-butyl acrylate copolymer aqueous emulsion having a solid content of 37.2%. The acid value of the solid equivalent of the copolymer is 7
The glass transition temperature calculated from the formula of 1 mg / g Fox was −28 ° C.

(2) Preparation of Photosensitive Resin Composition Solution 75 mol% of the carboxyl groups of the aqueous emulsion obtained above was neutralized with DMAPPA in the same manner as in Example 3, and then the same composition and method as in Example 5 were used. Then, a photosensitive resin composition solution was prepared.

(3) Preparation of Printed Wiring Board Using the photosensitive resin composition solution obtained above, Example 1,
The photosensitive resin composition solution was applied onto the copper-clad laminate in the same manner as in 2. After drying at 80 ° C. for 30 minutes, a uniform film was formed, but the surface was so sticky that the negative mask could not be adhered and exposed. Even after being dried at high temperature or for a long time, stickiness did not disappear.

[0052]

Comparative Example 2 (1) Synthesis of Styrene / Acrylic Acid Copolymer Aqueous Emulsion 4 g of Perex SS-L (manufactured by Kao Corporation, anionic surfactant, sodium alkyldiphenyl ether disulfonate) was dissolved in 250 g of deionized water. Styrene 9
A mixture of 4.9 g, acrylic acid 5.1 g, and 1-dodecanethiol 0.1 g was added with stirring under a nitrogen stream,
After adding 0.25 g of potassium persulfate dissolved in 50 g of deionized water, the mixture was reacted at 85 ° C. for 7 hours to give a styrene / acryl having a solid content of 25.3% and an acid value of 40 mg / g in terms of solid content. An aqueous acid copolymer emulsion was obtained. The glass transition temperature of this copolymer was 100.4 ° C. according to the Fox equation.

(2) Preparation of Photosensitive Resin Composition Solution To 100 g of the aqueous emulsion obtained above, 3.3 g of 2-diethylaminoethyl methacrylate dissolved in 7.0 g of water was added to obtain 80 mol% of carboxyl groups. 25 g of DPCA-20 and Darocur 4265 1 after neutralizing
g and 0.2 g of ethyl violet were added, and the mixture was stirred at high speed with a homomixer to obtain a photosensitive resin composition solution.

This photosensitive resin composition solution was used in Example 1,
The substrate was coated and dried in the same manner as in 2. The photosensitive resin after drying has a uniform film shape and is 200 m
After irradiation with UV light of J / cm ² , a latent image was observed, but spray development using 1% sodium carbonate was impossible.

[0055]

Comparative Example 3 By the same method as in Example 1, the monomer composition ratio was 53.8 g of methyl methacrylate and 46.
As 2 g, a methyl methacrylate / methacrylic acid copolymer aqueous emulsion having an acid value of 301.7 mg / g and a glass transition temperature of 105.5 ° C. calculated by the Fox equation was synthesized. To 100 g of the obtained methyl methacrylate / methacrylic acid copolymer aqueous emulsion, 7.7 g of 2-dimethylaminoethanol dissolved in 12.3 g of water was added to neutralize about 80% of the carboxyl groups.

A photosensitive resin solution was prepared in the same manner as in Example 1, coated on a substrate, dried and exposed. When tap water was sprayed, the image area also swelled and peeled off, and an etching resist pattern could not be formed.

[0057]

Comparative Example 4 90 mol% of the carboxyl groups in the polymer aqueous emulsion obtained in Example 4 were neutralized by using ammonia instead of DMAPPA. A photosensitive resin composition was prepared by the same composition and method as in Example 4, and the substrate was coated, dried and exposed in the same manner as in Example 4. Although development was carried out by spraying tap water, ammonia volatilized during drying and the carboxyl groups were not neutralized, and development with water was impossible.

Table 1 shows the composition of the aqueous emulsions obtained in Examples 1 to 6 and Comparative Examples 1 to 4, the glass transition temperature, the acid value, and the characteristics of the photosensitive resin compositions.

[0059]

[Table 1]

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Claims (8)

[Claims] 1. (a) having at least one carboxyl group in a molecule and having an acid value of 50 to 300 mg-KOH / g and a glass transition temperature of 30 to 250 ° C., relative to the carboxyl group. An aqueous emulsion composition of a polymer compound to which 30 to 120 mol% of a neutralizer compound is added; (b) a compound having at least one ethylenically unsaturated bond in one molecule; and (c) active light. A photosensitive resin composition in the form of an aqueous solution or aqueous dispersion developable with neutral water, which comprises as an essential component a photopolymerization initiator capable of generating free radicals upon irradiation. 2. A particle of a polymer compound having at least one carboxyl group in one molecule is impregnated with a compound having at least one ethylenically unsaturated bond in one molecule. 1. The photosensitive resin composition according to 1. 3. A water-based emulsion in which the compound having at least one ethylenically unsaturated bond in one molecule is solubilized in water or dispersed, suspended or emulsified by the action of an emulsifier. 1. The photosensitive resin composition according to 1. 4. The photosensitive resin composition according to claim 1, wherein the neutralizing agent compound added to the aqueous emulsion of the polymer compound having at least one carboxyl group in one molecule is an inorganic alkali or an amine. 5. The photosensitive resin composition according to claim 4, wherein the neutralizer compound is an amine having a boiling point higher than the predrying temperature of the resist coating film or an amine having an unsaturated bond. 6. A method such as emulsion polymerization or suspension polymerization of a monomer having at least one carboxyl group and at least one double bond in the molecule and a monomer copolymerizable therewith, By using and polymerizing, 50-300 m
An aqueous emulsion of a polymer compound having an acid value of g-KOH / g and a glass transition temperature of 30 to 250 ° C. and having at least one carboxyl group in one molecule is produced, and a carboxyl group of the polymer compound is obtained. 30 to 1
After adding 20 mol% of a neutralizer compound, a compound having at least one ethylenically unsaturated bond in one molecule and a photopolymerization initiator capable of generating a free radical upon irradiation with active light are mixed. The method for producing a photosensitive resin composition in the form of an aqueous solution or aqueous dispersion developable with neutral water according to claim 1. 7. A method such as emulsion polymerization or suspension polymerization of a monomer having at least one carboxyl group and at least one double bond in the molecule and a monomer copolymerizable therewith, By using and polymerizing, 50-300 m
An aqueous emulsion of a polymer compound having an acid value of g-KOH / g and a glass transition temperature of 30 to 250 ° C. and having at least one carboxyl group in one molecule is produced, and such emulsion is formed into one molecule. After mixing a compound having at least one ethylenically unsaturated bond and a photopolymerization initiator capable of generating a free radical upon irradiation with actinic light, 30% of the carboxyl group of the polymer compound is mixed.
The method for producing a photosensitive resin composition in the form of an aqueous solution or aqueous dispersion developable with neutral water according to claim 1, characterized in that the neutralizer compound is added in an amount of 120 mol%. 8. A method for producing a printed circuit board, wherein the composition according to claim 1 is used as an aqueous resist solution, and the irradiation resist layer is developed with neutralized water.