JP2000122281A - Photosensitive resin composition and photoresist ink for production of printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition which can reduce such problems of labor safety and hygiene, environmental pollution, fire prevention or the like due to the volatilization of an organic solvent in the formation of a pre-dried coating film after application to a substrate while having high resolution, is useful as a photoresist ink or the like for the production of a printed circuit board, can be made aqueous and is developable with water or an aqueous dilute alkali solution. SOLUTION: The photosensitive resin composition contains (A) a water-soluble photosensitive resin obtained by adding an N-alkylol (meth)acrylamide to a polyvinyl alcohol polymer, (B) a binder polymer which has carboxyl groups, is swollen, dispersed or dissolved in the aqueous dilute alkali solution and does not have an ethylenically unsaturated group capable of photoreaction, (C) a photopolymerization initiator, (D) a photopolymerizable ethylenically unsaturated monomer and (E) water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition which can be made water-soluble, and more particularly to a photosensitive resin composition which can be developed with water or a dilute aqueous alkaline solution, particularly for the production of printed wiring boards. The present invention relates to a photoresist ink useful as a photoresist ink and a photoresist ink for producing a printed wiring board, comprising the photosensitive resin composition.

[0002]

2. Description of the Related Art A photoresist ink which can be developed with a dilute alkaline aqueous solution does not require the use of a solvent at the time of development. Because of its superiority, in recent years, it has been used in the fields of inks for manufacturing printed wiring boards, inks for etching gravure rolls, inks for manufacturing color filter pixels, photosensitive compositions for manufacturing screen printing plates, and inks for manufacturing color filter protective films. It is actively used. Conventionally, a photoresist ink that can be developed with a dilute aqueous alkaline solution is disclosed in, for example, JP-A-5-22
A photosensitive resin composition as disclosed in JP-A-4413 and JP-A-5-241340 has been used.

[0003]

However, a photoresist ink which can be developed with a dilute alkaline aqueous solution as described above generally has a composition in which the ink component is uniformly applied to the surface of the base material and the subsequent exposure and development process. The components are dissolved or dispersed in various organic solvents so that the organic solvents can be used for exposure to light. For this reason, it is necessary to volatilize these organic solvents by preliminary drying before exposure. Therefore, in the process from the application to the formation of the pre-dried coating film, problems such as occupational safety and health, environmental pollution, and fire prevention caused by the organic solvent have not been solved.

[0004] The present invention has been made in view of the above points, and has high resolution, but is caused by volatilization of an organic solvent in a process of forming a pre-dried coating film after being applied to a substrate. It can reduce problems such as occupational safety and health, environmental pollution and fire prevention. Photoresist ink for manufacturing printed wiring boards such as etching resist ink, plating resist ink, solder resist ink, and marking ink, and photo for gravure roll etching It is useful as a resist ink, an ink for producing a color filter pixel, a photosensitive composition for producing a screen printing plate, an ink for producing a color filter protective film, etc., and can be made aqueous, and can be developed with water or a dilute aqueous alkaline solution. Provided are a photosensitive resin composition and a photoresist ink for manufacturing a printed wiring board comprising the photosensitive resin composition. It is an object of the present invention.

[0005]

Means for Solving the Problems The photosensitive resin composition according to the first aspect of the present invention comprises a water-soluble photosensitive resin obtained by adding (A) N-alkylol (meth) acrylamide to a polyvinyl alcohol-based polymer. Resin, (B) a binder polymer having a carboxyl group and swelling, dispersing or dissolving in a dilute alkaline aqueous solution, having no photoreactive ethylenically unsaturated group, (C) a photopolymerization initiator , (D) a photopolymerizable ethylenically unsaturated monomer, and (E) water or a dilute aqueous alkali solution containing water.

The photosensitive resin composition according to claim 2 of the present application further comprises, in addition to the constitution of claim 1, (d1) molecules as the photopolymerizable ethylenically unsaturated monomer (D). A material comprising a compound containing at least one carboxyl group and at least one photoreactive ethylenically unsaturated group.

The photosensitive resin composition according to claim 3 of the present invention may further comprise, as the compound (d), one hydroxyl group in the molecule (d1), in addition to the constitution of claim 1 or 2. And a partially esterified product of a compound having one photoreactive ethylenically unsaturated group and a polyvalent carboxylic acid.

Further, the photoresist ink for manufacturing a printed wiring board according to claim 4 of the present invention is characterized in that:
The photosensitive resin composition according to any one of the above.

[0009]

Embodiments of the present invention will be described below. In this specification, "(meth) acryl-"
Means acryl- and / or methacryl-, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and (meth) acrylamide means acrylamide and / or methacrylamide. <(A) Water-soluble photosensitive resin obtained by adding N-alkylol (meth) acrylamide to a polyvinyl alcohol-based polymer> The photosensitive resin composition of the present invention comprises polyvinyl alcohol as a water-soluble photosensitive resin. It contains a water-soluble photosensitive resin (A) obtained by adding N-alkylol (meth) acrylamide to a system polymer.

The polyvinyl alcohol-based polymer used in the production of the photosensitive resin (A) includes, for example, polyvinyl alcohol obtained by completely or partially saponifying polyvinyl acetate, and completely or partially saponified polyvinyl. A water-soluble polyvinyl alcohol derivative obtained by reacting various compounds such as an acid anhydride-containing compound, a carboxy-containing compound, an epoxy group-containing compound or an aldehyde group-containing compound with an -OH group or -OCOCH ₃ group in an alcohol, A vinyl alcohol-based copolymer having a vinyl alcohol unit obtained by partially or completely saponifying vinyl acetate. Examples of the vinyl acetate copolymer component include (meth) acrylic acid, (meth) acrylamide, N- Methylol (meth) acrylamide, styrene, ethylene, Propylene, maleic anhydride, (meth) acrylonitrile, etc., those using a (meth) acrylic acid esters and the like.

Here, the polyvinyl alcohol polymer desirably contains at least 60 mol% of a vinyl alcohol unit in the polymerized unit.
When the content is 80 mol% or more or a completely saponified polyvinyl acetate, the water-soluble photosensitive resin composition is particularly excellent in water solubility, and an optimum result is obtained. If the content of the vinyl alcohol unit is less than 60 mol%, the polyvinyl alcohol-based polymer is hardly soluble in water, and it is difficult to make the photosensitive resin composition of the present invention a good aqueous one.

A method for producing a water-soluble photosensitive resin (A) obtained by adding N-alkylol (meth) acrylamide to a polyvinyl alcohol-based polymer is known. For example, JP-B-49-5923, 62-267302
Can be synthesized by a method disclosed in Japanese Unexamined Patent Application Publication No. H10-133, etc.

Specifically, the inorganic acid or sulfonic acid derivative is dissolved in a solution of a polyvinyl alcohol-based polymer in a good solvent such as N-methylpyrrolidone or water or in a suspension of a polyvinyl alcohol-based polymer in a poor solvent. The photosensitive resin (A) is obtained by an etherification reaction between a polyvinyl alcohol-based polymer and N-alkylol (meth) acrylamide in the presence of an acid catalyst such as

Examples of N-alkylol (meth) acrylamide include N-methylol (meth) acrylamide, N-ethylol (meth) acrylamide, N-propylol (meth) acrylamide, N-butyrol (meth) acrylamide and the like. Can be mentioned. When these N-alkylol (meth) acrylamide-based compounds are added to a polyvinyl alcohol-based polymer, only one kind can be added, or a combination of two or more kinds can be added.

The actual addition rate of N-alkylol (meth) acrylamide in the photosensitive resin (A) is 0.05 to 25 mol% per vinyl alcohol polymerized unit constituting the photosensitive resin (A). Is preferred. 0.
When the amount is less than 05 mol%, the polymerizability of the photosensitive resin decreases, while when it exceeds 25 mol%, the water solubility becomes poor. When the content is 0.05 to 15 mol%, an optimal result is obtained in which the balance between photocurability and water solubility is optimal.

The photosensitive resin (A) thus obtained
Is dissolved, emulsified, or dispersed in water (E) or a mixed solvent such as water (E) and an aqueous organic solvent together with other components to prepare the photosensitive resin composition of the present invention. Thus, the photosensitive resin composition of the present invention can be made aqueous. Also, in the process of forming a pre-dried film after applying the photosensitive resin composition to the base material, the volatilization of the organic solvent is compared with that in which the components of the photosensitive resin composition are dissolved or dispersed in various organic solvents. It can suppress and reduce problems such as occupational safety and health, environmental pollution and fire prevention caused by organic solvents. The method of dissolving, emulsifying, and dispersing is not particularly limited. For example, the dissolving, emulsifying, and dispersing may be performed by adding an aqueous solution of the photosensitive resin (A) to other components. The solution (A) may be dissolved, emulsified, or dispersed by adding other components to the aqueous solution. For dissolution, emulsification, and dispersion, various types of agitators and kneaders such as a homomixer, a pipeline homomixer, a bead mill, a roll mill, and a ball mill can be used.

The mixing ratio of the photosensitive resin (A) is 0.1 to 50 in the total amount of all components excluding water (E) and the organic solvent used in the photosensitive resin composition of the present invention. %, More preferably 1% by weight.
３０30% by weight. When the compounding ratio is less than 0.1% by weight, it is difficult to make the photosensitive resin composition of the present invention aqueous, and when it exceeds 50% by weight, the photosensitive resin composition of the present invention is subjected to a photopolymerization reaction. The water resistance of the cured film after curing is apt to be insufficient, and the cured film is easily peeled off when the cured film is formed. When the content is 0.5% by weight or more, development with water becomes particularly easy. <(B) a binder polymer having a carboxyl group and swelling, dispersing or dissolving in a dilute alkali aqueous solution and having no photoreactive ethylenically unsaturated group> The photosensitive resin composition of the present invention And a binder polymer having a carboxyl group and swelling, dispersing or dissolving in a dilute alkaline aqueous solution and containing no photoreactive ethylenically unsaturated group (B).

Since the binder polymer (B) has a sufficient carboxyl group in the molecule, it can swell, disperse or dissolve in a dilute aqueous alkali solution.

For this reason, the photosensitive resin composition of the present invention containing the binder polymer (B) is combined with the water-soluble photosensitive resin component (A) to form a film formed thereby. However, before exposure, it swells with water or dilute alkaline aqueous solution,
Can be dispersed or dissolved. Therefore, this photosensitive resin composition, after performing selective exposure of the formed film, by performing development with water or a dilute alkaline aqueous solution, while washing away the non-exposed portion of the photosensitive resin composition, the exposed portion By leaving it, image formation can be made possible.

Further, as described above, the photosensitive resin composition of the present invention contains a polyvinyl alcohol-based water-soluble photosensitive resin (A) together with the component (B). The cured product formed by waking up can be peeled off with either an aqueous solution such as an alkali metal hydroxide or a peeling agent for a polyvinyl alcohol-based photosensitive agent such as sodium periodate.

The binder polymer (B) does not have a photoreactive ethylenically unsaturated group. Here, it does not contain a photoreactive ethylenically unsaturated group,
This means that a photoreactive ethylenically unsaturated group is not actively introduced when synthesizing the binder polymer (B). The presence of slight ethylenically unsaturated bonds unavoidably caused by leveling and other factors is acceptable. Therefore, when the photosensitive resin composition of the present invention is used as a photoresist ink for manufacturing a printed wiring board, when exposing and curing the photosensitive resin composition of the present invention applied to a substrate for manufacturing a printed wiring board, a binder is used. It prevents a high molecular weight component such as the polymer (B) from causing a photoreaction by a slight exposure to cause a rapid increase in the molecular weight, and a slight exposure at a boundary surface between an exposed portion and an unexposed portion during selective exposure. By preventing curing due to light leakage, it is possible to improve solubility, swelling property, and the like in a dilute alkali solution at the interface between the exposed portion and the unexposed portion. Therefore, a sharp pattern faithful to the artwork can be formed, and the resolution can be improved.

It is desirable that the binder polymer (B) itself be capable of forming a film. The photosensitive resin of the present invention comprising such a binder polymer (B) and the above-mentioned photosensitive resin (A) is combined. By using the resin composition, the pre-dried film of the photosensitive resin composition loses surface tackiness, and even when the photo tool artwork or the like is directly applied, the photosensitive resin composition adheres to the photo tool artwork or the like. It does not get dirty.

Here, in order to make the photosensitive resin composition of the present invention developable with a dilute alkaline aqueous solution, and to make the cured product of the photosensitive resin composition of the present invention peelable with an alkaline aqueous solution, The acid value of the binder polymer (B) is 2
When the acid value is less than 20 mgKOH / g, it becomes difficult to develop in a short time with a dilute alkali solution.
If it exceeds H / g, the resistance of the cured product to a dilute alkali solution may be too low, making it difficult to form a good pattern. More preferably, the acid value of the binder polymer (B) is from 40 to 250 mgKOH / g. In this case, short-term development is possible and particularly favorable pattern formation is possible. The binder polymer (B) is easily emulsified and dispersed in the photosensitive resin composition of (1), and an optimum result is obtained.

The weight average molecular weight of the binder polymer (B) is preferably 4,000 to 500,000, and if it is less than 4,000, the film tends to remain tacky after predrying, and the phototool artwork is not easily prepared. When exposed directly to the dry film, exposure may result in the traces of the phototool artwork remaining on the cured film, and when it exceeds 500,000, the developability tends to decrease. When the weight average molecular weight of the binder polymer (B) is from 4,000 to 300,000, there is no problem that the adhesion of the film after the preliminary drying is increased, and good sensitivity and developability can be obtained. Further, when the ratio is 20,000 to 300,000, particularly high sensitivity and resolution are obtained, and an optimum result is obtained.

These properties are particularly suitable when the ink of the present invention is used as a photo-etching resist ink for producing a printed wiring board, a plating resist ink capable of forming an image, and the like.

The amount of the binder polymer (B) is preferably at least 5% by weight based on the total weight of the photosensitive resin composition of the present invention except for the water (E) and the organic solvent. When the compounding amount of the binder polymer (B) is less than 5% by weight in all the components excluding water and the organic solvent from the photosensitive resin composition of the present invention, tackiness tends to remain in the film after predrying, When the phototool artwork is directly attached to the preliminary dried film and exposed, there is a possibility that a mark of the phototool artwork remains on the cured film.

Examples of the binder polymer (B) include those obtained by introducing a sufficient amount of a carboxyl group into a polymer or copolymer of an ethylenically unsaturated monomer by any method. Specifically, the following (B1) to (B3) can be shown. <(B1) an ethylenically unsaturated monomer (a) having one or more carboxyl groups, and an ethylenically unsaturated monomer component (b) copolymerizable with the ethylenically unsaturated monomer (a) A) a copolymer obtained by polymerizing a copolymer component comprising
Here, the ethylenically unsaturated monomer (a) having one or more carboxyl groups is mainly obtained by introducing a sufficient carboxyl group into the binder polymer (B), which is a copolymer product, to form a binder. It is used to make the polymer (B) swell, disperse or dissolve in a dilute aqueous alkaline solution.

Examples of the ethylenically unsaturated monomer (a) include (meth) acrylic acid and cinnamic acid. Further, examples of the component (a) include fumaric acid, itaconic acid, crotonic acid, maleic acid, anhydrides thereof, and partial esters of these with saturated alcohols. These can be used alone or in combination of two or more.

The ethylenically unsaturated monomer component (b) copolymerizable with the ethylenically unsaturated monomer component (a) includes:
For example, as (meth) acrylate unsaturated monomers, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate,
t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, Cetyl (meta)
Linear, branched or alicyclic (meth) such as acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate
Acrylic esters, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, methoxydiethylene glycol mono (meth) acrylate, etc. Of aromatic glycols such as ethylene glycol ester (meth) acrylate and similar propylene glycol (meth) acrylate, butylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, and benzyl (meth) acrylate (Meth) acrylate and (meth) acrylamide unsaturated monomer (meth)
Acrylamide, N-methyl (meth) acrylamide,
N-propyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, diacetone (meth) acrylamide, etc.
And styrene, α-methylstyrene, vinyl ether and the like.

Further, as the ethylenically unsaturated monomer component (b) copolymerizable with the component (a), other than the above, N-substituted monomers such as N-phenylmaleimide and N-cyclohexylmaleimide can be used. Examples include maleimides, vinylpyrrolidone, (meth) acrylonitrile, vinyl acetate, and the like. These can be used alone or in combination of two or more.

As the unsaturated monomers (a) and (b) as described above, if only those which are liquid or solid at room temperature are selected and used, the unsaturated monomers (a) and (b) Are mixed and reacted, and can be easily performed to improve the handleability.In addition, the polymer can be easily polymerized under normal pressure and with a free copolymer composition. , Is what you like.

As the binder polymer (B1),
Particularly preferred are a copolymer component containing a (meth) acrylate unsaturated monomer and (meth) acrylic acid as main components, and a (meth) acrylate unsaturated monomer and (meth) acrylate. ) The mixing ratio with acrylic acid is adjusted so that the acid value of the binder polymer (B1) becomes a desired value, or a (meth) acrylamide unsaturated monomer as a copolymer component and (meth) ) Acrylic acid as the main component, and the mixing ratio of the (meth) acrylamide-based unsaturated monomer and (meth) acrylic acid is adjusted so that the acid value of the binder polymer (B1) becomes a desired value. In this case, it is possible to easily synthesize a binder polymer (B1) having a desired degree of oxidation or polymerization.

Further, a copolymer containing maleic acid or a derivative thereof and styrene as main components as the copolymer component is also particularly preferable as the binder polymer (B1). It is possible to easily synthesize a binder polymer (B1) having the following formula:

The method for obtaining the copolymer using these monomer components is not particularly limited, and a general polymerization method such as solution polymerization, emulsion polymerization, dispersion polymerization and the like can be used. In the case of solution polymerization, emulsion polymerization, or the like, the copolymer or resin may be blended for the composition of the present invention in the form of a solution or emulsion without removing the copolymer resin.

The copolymer containing a maleic acid partial ester and styrene as copolymer components can be directly obtained by polymerizing these copolymer components or these copolymer components and other copolymer components. It is possible to obtain a binder polymer (B1) having a desired oxidation by obtaining a polymer containing styrene and maleic anhydride as copolymerization components in advance, and then adding a saturated alcohol, particularly a saturated monoalcohol. Is also good.

Specific examples of a polymer or copolymer of an ethylenically unsaturated monomer having a sufficient amount of carboxyl groups introduced therein by the following method include the following (B2). <(B2) Polymer or copolymer containing a hydroxyl group-containing ethylenically unsaturated monomer as a polymerization component and a polybasic acid anhydride added> Ethylically unsaturated monomer having a hydroxyl group Examples of the body include hydroxyethyl (meth) acrylate, ethoxyethyl (meth)
Ethylene glycol ester (meth) acrylates such as acrylate, diethylene glycol mono (meth) acrylate and triethylene glycol mono (meth) acrylate, and similar propylene glycol (meth) acrylates, butylene glycol mono (meth) acrylates, glycerol mono ( And meth) acrylates, and these can be used alone or in combination of two or more. Further, together with these ethylenically unsaturated monomers having a hydroxyl group, other ethylenically unsaturated monomers copolymerizable therewith may be copolymerized.

Here, the polymerization method is not particularly limited, and general polymerization methods such as solution polymerization, emulsion polymerization and dispersion polymerization can be used.

As the polybasic anhydride, for example, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and the like used in the synthesis of (d1) described later can be used. These can be used alone or in combination of two or more. Also,
The addition of the polymer or copolymer to the polybasic acid anhydride can be performed by a known method.

Specific examples of those obtained by introducing a sufficient amount of a carboxyl group into a polymer or copolymer of an ethylenically unsaturated monomer by any method include the following (B)
3) can be mentioned. <(B3) Obtained by reacting a polymer or copolymer containing an ethylenically unsaturated monomer having an epoxy group as a polymerization unit with a saturated monocarboxylic acid and a polybasic anhydride> Examples of the ethylenically unsaturated monomer include glycidyl (meth) acrylates such as glycidyl (meth) acrylate and 2-methylglycidyl (meth) acrylate, and (3,4-epoxycyclohexyl) methyl (meth) acrylate and the like. And epoxycyclohexyl derivatives of (meth) acrylic acid. These can be used alone or in an appropriate combination of two or more. Further, together with these ethylenically unsaturated monomers having an epoxy group, other ethylenically unsaturated monomers copolymerizable therewith may be copolymerized.

Here, the polymerization method is not particularly limited, and general polymerization methods such as solution polymerization, emulsion polymerization and dispersion polymerization can be used.

Examples of the saturated monocarboxylic acid include formic acid, acetic acid, propionic acid, glycolic acid, lactic acid and the like, and these can be used alone or in an appropriate combination of two or more.

As the polybasic anhydride, for example, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and the like used in the synthesis of (d1) described later can be used. These can be used alone or in combination of two or more.

Further, addition of a saturated monocarboxylic acid and a polybasic anhydride can be performed by a known method.

The above-mentioned various binder polymers (B) have some or all of the carboxyl groups.
It may be neutralized with an organic basic compound such as alkanolamine, ammonia or the like. <(C) Photopolymerization initiator> The photosensitive resin composition of the present invention comprises:
It contains a photopolymerization initiator (C). As the photopolymerization initiator (C), either a polar solvent-soluble or a non-soluble solvent can be used. For example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and its alkyl ethers, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, Acetophenones such as 1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and anthraquinones such as 2-methylanthraquinone and 2-amylanthraquinone. , 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4
Thioxanthones such as diisopropylthioxanthone and 1-chloro-4-propoxythioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone and 3,3-dimethyl-
Benzophenones such as 4-methoxybenzophenone, 3,3 ′, 4,4′-tetra- (tert-butylperoxylcarbonyl) benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and xanthones;
-Methyl-1- [4- (methylthio) phenyl] -2-
Morpholino-propan-1-one, 2-benzoyl-2
-Dimethylamino-1- (4-morpholinophenyl)-
Those containing a nitrogen atom such as butanone-1,4,4'-bis-diethylaminobenzophenone, and 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide and the like, and for direct drawing by laser, for example, bis (η ⁵ -2,4-cyclopentadien-1-yl)-
Bis (2,6-difluoro-3- (1H-pyrrole-1
And metallocenes such as -yl) -phenyl) titanium. These photopolymerization initiators (C) may be used alone or in combination of two or more as appropriate. These photopolymerization initiators (C) include known benzoic acid-based or tertiary amine-based compounds such as p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester and 2-dimethylaminoethylbenzoate. And a photopolymerization accelerator and a sensitizer.

The compounding amount of the photopolymerization initiator (C) is desirably 0.1 to 20% by weight in all components excluding water and the organic solvent from the photosensitive resin composition of the present invention.
If the amount is less than 0.1% by weight, it is difficult to impart sufficient photocurability to the photosensitive resin composition of the present invention.
Even if it is more than 0% by weight, it does not contribute to further improving the photocurability. <(D) Photopolymerizable ethylenically unsaturated monomer> The photopolymerizable ethylenically unsaturated monomer (D) is blended with the photosensitive resin composition of the present invention.

The photopolymerizable ethylenically unsaturated monomer (D) imparts sufficient photoreactivity to the photosensitive resin composition of the present invention so that an image can be formed by selective exposure. is there.

Examples of the photopolymerizable ethylenically unsaturated monomer (D) include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Tripropylene glycol di (meth) acrylate,
2,2-bis [4-((meth) acryloxyethoxy)
Phenyl] propane, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 2-hydroxy-1,3-di (meth) acryloxypropane,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1-methoxycyclododecadienenyl (meth) acrylate, β- (meth) acryloyloxyethyl hydrogen phthalate, β- (meth) acryloyloxyethyl hydrogen succinate Nate, 3
-Chloro-2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, bisphenol A-diepoxyacrylic acid adduct, (meth) acrylamide, N-methoxymethyl ( (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acryloylmorpholine, N-methylol (meth)
Acrylamide, hydroxypropyl (meth) acrylate, polyethylene glycol di (meth) acrylate, methylenebis (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2,2-bis [4-
[Methacryloyloxy-polyethoxyphenyl] propane. These compounds can be used alone or in combination of two or more.

As the photopolymerizable ethylenically unsaturated monomer (D), those containing the following (d) can be used. <(D) Compound having at least one carboxyl group and at least one photoreactive ethylenically unsaturated group in the molecule> Photopolymerizable ethylenically unsaturated monomer (D)
When a compound containing at least one carboxyl group and at least one photoreactive ethylenically unsaturated group (d) in the molecule is used,
By appropriately adjusting the compounding ratio of the compound (d) having a carboxyl group in the molecule in the photosensitive resin composition of the present invention, the solubility of the photosensitive resin composition of the present invention in a dilute alkaline aqueous solution can be adjusted. It will be easier. When this compound (d) is used, it is preferable that the compound (d) is blended in an amount of preferably 1 to 50% by weight based on the total amount of the photopolymerizable ethylenically unsaturated monomer (D).

The compound (d) is not particularly restricted but includes, for example, one hydroxyl group and one hydroxyl group in the molecule.
Compounds (d) which are partially esterified compounds of a compound having a photoreactive ethylenically unsaturated group and a polyvalent carboxylic acid
1) and a partially esterified compound (d2) of a compound having only one epoxy group and one ethylenically unsaturated group with a polyvalent carboxylic acid. <(D1) Partially esterified compound of a compound having one hydroxyl group and one photoreactive ethylenically unsaturated group in the molecule with a polycarboxylic acid> As the compound (d), a partially esterified compound (d1) ) Is known in the art, for example, it has an anhydride such as a dibasic acid or a tribasic acid and one hydroxyl group and one photoreactive ethylenically unsaturated group in the molecule. It can be obtained by subjecting a compound to a heat reaction using a catalyst as necessary. This reaction is desirably stopped by monoesterification.

The above-mentioned anhydrides such as dibasic acid and tribasic acid include, for example, succinic acid, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, nadic acid, methylnadic acid, dotesylsuccinic acid, chlorendic Acid, benzophenonetetracarboxylic acid, ethylene glycol bis (anhydrotrimate), polyazeleic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid,
-Methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, 3-propyltetrahydrophthalic acid, 4-propyltetrahydrophthalic acid, 3-butyltetrahydrophthalic acid, 4-butyltetrahydrophthalic acid, hexahydro Phthalic acid, 3
-Methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, 3-propylhexahydrophthalic acid, 4-propylhexahydrophthalic acid, 3-butyl Examples thereof include anhydrides corresponding to polyvalent carboxylic acids such as hexahydrophthalic acid and 4-butylhexahydrophthalic acid. These acid anhydrides can be used alone or in appropriate combination of two or more kinds.

Further, one hydroxyl group and one
Examples of the compound having a photoreactive ethylenically unsaturated group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, a reaction product with polybutylene glycol mono (meth) acrylate, and the like, and polycaprolactone mono (meth) acrylate and the like. it can. These can be used alone or in an appropriate combination of two or more. <(D2) Partially esterified compound of compound having only one epoxy group and one ethylenically unsaturated group and polycarboxylic acid> When partially esterified compound (d2) is used as compound (d), production of this compound The method is known, for example, by heating an ethylenically unsaturated compound having only one each of an epoxy group and an ethylenically unsaturated group and an acid anhydride such as dibasic acid and tribasic acid, using a catalyst as necessary, It is obtained by reacting. This reaction is desirably stopped by monoesterification.

Examples of the ethylenically unsaturated compound having only one epoxy group include glycidyl (meth) acrylates such as glycidyl (meth) acrylate and 2-methylglycidyl (meth) acrylate;
Epoxycyclohexyl derivatives of (meth) acrylic acid such as (epoxycyclohexyl) methyl (meth) acrylate. These can be used alone or in an appropriate combination of two or more. Further, as the polyvalent carboxylic acid, those corresponding to the above-mentioned acid anhydride used for producing compound (d1) can be used.

The photo-polymerizable ethylenically unsaturated monomer (D) as described above is used together with the above-mentioned photosensitive resin (A) to form the photo-reactive resin of the present invention. Can be increased.

The mixing ratio of the photopolymerizable ethylenically unsaturated monomer (D) is 0.05 to 7 based on all components excluding water and the organic solvent from the photosensitive resin composition of the present invention.
Desirably, it is 5% by weight. If it is less than 0.05, the strength of the cured film may not be sufficient. If it exceeds 75% by weight, the surface adhesiveness of the film after pre-drying of the photosensitive resin composition of the present invention becomes strong. When a photo tool artwork or the like is directly attached, dirt easily occurs. Particularly, when the content is 1.0 to 50% by weight, the cured film strength is good and the surface tackiness is low, so that it is more preferable. <(E) Water> The photosensitive resin composition of the present invention uses water (E) as an essential medium. The compounding ratio is desirably 10 to 97% by weight based on all components of the photosensitive resin composition of the present invention. If the compounding ratio is less than 10% by weight, the fluidity of the ink becomes insufficient, and it is difficult to improve the coating properties and the like. If the compounding ratio exceeds 97% by weight, the photosensitive resin composition of the present invention cannot be used. When applied to the substrate surface, the coating film becomes too thin, and it is not preferable because it cannot exhibit sufficient performance as an etching resist ink, a plating resist ink, a solder resist ink, or the like.

Also, a medium such as an organic solvent can be blended as an optional component. Specifically, not only a solvent which is easily soluble in water but also a hardly soluble or insoluble organic solvent can be used. Examples of these organic solvents include ethanol, propanol, 2-propanol, butanol, 2-butanol, hexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol,
Linear, branched, secondary or polyhydric alcohols such as trimethylolpropane, neopentyl glycol, glycerin, 1,2,4-butanetriol, 1,2-butanediol, 1,4-butanediol, diacetone alcohol , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol alkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,
Polyethylene glycol alkyl ethers such as diethylene glycol monoethyl ether and triethylene glycol monomethyl ether; propylene glycol alkyl ethers such as propylene glycol monomethyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether; ethylene glycol monomethyl ether acetate; diethylene glycol Acetates such as monomethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, glycerin monoacetate and glycerin diacetate; lactate esters such as ethyl lactate and butyl lactate; and dialkyl glycols such as diethylene glycol diethyl ether Ether compounds, methyl ethyl ketone, cyclohexanone, ketones such as isophorone, toluene,
Aromatic hydrocarbons such as xylene, petroleum aromatic mixed solvents such as Swazole series (manufactured by Maruzen Petrochemical) and Solvesso series (manufactured by Exxon Chemical), or n-hexane, cyclohexane, tetrahydrofuran, etc. No. These media may be used alone or in combination of two or more.

In the photoresist ink of the present invention, as a polymer compound into which a photoreactive group has been introduced, for example, a (meth) acrylate copolymer having an ethylenically unsaturated group introduced therein, ) Acrylate-
(Meth) acrylic acid copolymer, styrene-acrylic acid ester copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, polymers such as styrene-maleic acid resin, and (meth) ) Acrylic acid-added bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin and alicyclic type epoxy resin, or those obtained by further adding a saturated or unsaturated polybasic acid anhydride Etc., or these emulsions can be added.

The photosensitive resin composition of the present invention, which can be developed with water or a dilute aqueous alkali solution, may contain a silicone, a (meth) acrylate copolymer, a fluorine Leveling agents such as surfactants, thixotropic agents such as Aerosil, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine, antihalation agents, flame retardants, plating resistance improvers, and defoamers. Agents, antioxidants, pigment wetting agents, organic or inorganic pigments and dyes, various additives such as natural or synthetic rubber powder, and surfactants and polymer dispersants for improving dispersion stability. May be added.

The method for preparing the photosensitive resin composition of the present invention is not particularly limited, and each component can be mixed using a known method. For example, mixing and dispersion may be performed by adding an aqueous solution of the photosensitive resin (A) to another compounding component, or mixing and dispersion may be performed by adding the other compounding component to the aqueous solution of the photosensitive resin (A). They may be dispersed. For the dispersion and mixing, various types of agitators and kneaders such as a homomixer, a pipeline homomixer, a bead mill, a roll mill, and a ball mill can be used.

As described above, the photosensitive resin composition of the present invention is obtained by dissolving, emulsifying or dispersing other components in water or a mixed solvent of water and an aqueous organic solvent using the photosensitive resin (A). Can be made water-soluble, and the non-exposed portion can be removed with water or a dilute alkaline aqueous solution after exposure and curing of the photosensitive resin composition, and an organic solvent is used during development. It is not necessary, and in the process of forming a pre-dried film after applying the photosensitive resin composition to the base material, the volatilization of the organic solvent from the photosensitive resin composition can be suppressed, and labor caused by the organic solvent can be suppressed. Problems such as safety, environmental pollution, and fire can be reduced. The cured film produced by the photopolymerization reaction of the photosensitive resin composition has a high film hardness, good adhesion to a substrate, and excellent etching resistance, water resistance and heat resistance to a plating solution and the like. can do. The cured product of the photosensitive resin composition can be peeled off by using either an aqueous solution of sodium periodate or the like or an alkali metal hydroxide. Accordingly, the photosensitive resin composition of the present invention can be used as a photoresist ink for manufacturing a printed wiring board such as an etching resist ink, a plating resist ink, a solder resist ink, and a marking ink, a photoresist ink for gravure roll etching, and a screen printing plate. It is most suitable as a photosensitive composition, an ink for producing a color filter pixel, an ink for producing a color filter protective film, and the like.

As a method for forming a pattern on a substrate using the photosensitive resin composition of the present invention, a developing method can be used. The method for forming a pattern on a substrate by a development method using the photosensitive resin composition of the present invention is not particularly limited, and for example, the following method can be employed. -Coating process The photosensitive resin composition is coated on the substrate by dipping, spray coating, spin coating, roll coating, curtain flow coating, screen printing, or the like. Here, when the photosensitive resin composition of the present invention is used as an ink for manufacturing a printed wiring board, a substrate for manufacturing a printed wiring board such as a copper-clad laminate is used as a base material. Preliminary drying step The above photosensitive resin composition, hot air heating, electromagnetic induction heating,
Dry using hot press or far infrared drying etc.
Form a pre-dried film. -Exposure process The phototool artwork is applied directly or indirectly to the surface of the pre-dried photosensitive resin composition coating film, and a tungsten lamp, a chemical lamp, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, and an ultra-high-pressure mercury lamp are used. , Xenon lamp,
Ultraviolet rays are irradiated using a metal halide lamp or the like to selectively expose the coating film surface. Alternatively, exposure may be performed by a laser direct writing method using a helium cadmium laser, an argon laser, a YAG laser, or the like. Development Step After the exposure step, the photosensitive resin composition of the present invention can be developed by washing and removing the non-exposed area with water or a dilute alkaline solution.

Here, when using water, the temperature is not particularly limited, but it is preferable to use room temperature water or hot water.

When development is carried out with a dilute alkaline solution, for example, an aqueous solution of an alkali hydroxide such as sodium, potassium or lithium, or an alkali carbonate such as sodium carbonate or potassium carbonate can be used.

As the water or dilute alkaline solution,
As the solvent, not only water alone but also a mixture of water and a hydrophilic organic solvent such as an alcohol can be used.・ Etching, plating stepWhen the photosensitive resin composition of the present invention is used as an etching resist or a plating resist of a printed wiring board,
For example, there is a method in which the exposed surface of the substrate is treated by a known method such as etching or plating using the resist pattern formed on the substrate for manufacturing a printed wiring board by the above-described developing method as a mask.

When etching is performed, an etching agent selected according to the type of the conductive layer on the substrate can be used. For example, the etching can be performed using an acidic etching solution such as cupric chloride, an ammonia-based etching solution, or the like.

In the case of plating, for example, copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high throw solder plating, nickel plating such as nickel sulfamate plating, soft gold plating, and hard gold plating Etc. can be performed. -Peeling step The photosensitive resin composition of the present invention may be used as a solder resist or a marking ink, and the cured product thereof may be used, but when used as an etching resist or a plating resist, the cured product may be used. Can be finally peeled off. Here, the cured product can be peeled off by decomposing a portion derived from the photosensitive resin (A) in the cured product with sodium periodate, sodium hypochlorite, or the like.

In addition, it is also possible to peel off with an alkali solution used in the developing step. In this case, it is preferable to use a stronger alkali solution than that used for the development.

[0067]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition,
All “parts” and “%” used below are by weight unless otherwise indicated. Also, "weight average molecular weight"
Is a value measured by GPC (gel permeation chromatography) under the following measurement conditions. [GPC measurement method] Each sample was 10 mg / m
A THF (tetrahydrofuran) solution was prepared so as to be 1 l, and each was measured at an injection volume of 100 μl.・ Measurement conditions GPC measurement device: Showa Denko KK, trade name “SHOdex”
"SYSTEM 11" Column: "SHOdex" manufactured by Showa Denko KK
KF-800P "," SHOdex KF-80
5 "," SHOdex KF-803 "and" SHOD
EX KF-801 ”in series Moving bed: THF flow rate: 1 ml / min Column temperature: 45 ° C. Detector: RI conversion: polystyrene [Synthesis Example 1] partially saponified polyvinyl acetate (polymerization degree 170
0, saponification degree 88 mol%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
200 g of water (trade name "Gohsenol GH-17")
00g. 40 g of N-methylolacrylamide was dissolved in this aqueous solution, 2 g of a 0.1% methoxyhydroquinone aqueous solution and 3 g of 85% phosphoric acid were added, and the mixture was reacted at 60 ° C. for 20 hours. After completion of the reaction, the mixture was neutralized with 5% caustic soda, and further adjusted with water so that the total amount of the solution became 1500 g. An N-methylolacrylamide adduct of a polyvinyl alcohol polymer (corresponding to the photosensitive resin (A)) )) Was obtained. [Synthesis Example 2] Vinyl acetate polymer-unsaturated carboxylic acid Na
Partially saponified copolymer (degree of polymerization 1800, degree of saponification 88
Mol%, manufactured by Kuraray Co., Ltd., trade name "Poval KL31
8 ") was dissolved in 1000 g of water. Dissolve 60 g of N-methylolacrylamide in this aqueous solution,
After adding 2 g of a 0.1% methoxyhydroquinone aqueous solution and 3 g of 85% phosphoric acid, the mixture was reacted at 80 ° C. for 5 hours. After completion of the reaction, the mixture was neutralized with 5% caustic soda, and further adjusted with water so that the total amount of the solution became 1625 g. The N-methylolacrylamide adduct of a polyvinyl alcohol polymer (corresponding to the photosensitive resin (A)) )) Was obtained. [Synthesis Example 3] In a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for purging nitrogen, and a stirrer, 20 parts of methacrylic acid, 80 parts of methyl methacrylate, 100 parts of methyl ethyl ketone, and azobisisobutyronitrile 1 Then, the mixture was heated under a nitrogen stream and polymerized at 75 ° C. for 5 hours, and a 50% binder polymer solution (P-1) (a solution of an acrylate copolymer corresponding to the binder polymer (B1)) was added. Obtained. The weight average molecular weight of the obtained binder polymer is 110,000, and the acid value is 130 m.
gKOH / g. [Synthesis Example 4] Styrene-maleic anhydride copolymer (trade name "SMA-1000A", manufactured by Elphatochem) 15
0 parts was heated and dissolved in 152 parts of methyl ethyl ketone, and while blowing air, 56 parts of n-butyl alcohol, 0.1 part of hydroquinone and 3.0 parts of dimethylbenzylamine were added with stirring, and the mixture was heated at 80 ° C. by a conventional method. The reaction was carried out for 24 hours to obtain a 57% solution (P-2) (a solution of a styrene-maleic ester copolymer corresponding to the binder polymer (B1)). The weight average molecular weight of the obtained binder polymer was 7400, and the acid value was 203 mgKOH /
g. [Synthesis Example 5] A four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for purging nitrogen and a stirrer was charged with 25 parts of hydroxyethyl methacrylate and 7 parts of methyl methacrylate.
5 parts, 100 parts of methyl ethyl ketone, 0.5 parts of lauryl mercaptan, and 3 parts of azobisisobutyronitrile were added, and the mixture was heated under a nitrogen stream and polymerized at 75 ° C. for 5 hours to obtain a 50% copolymer solution. .

To the above 50% copolymer solution, 0.05 part of hydroquinone, 25 parts of methyl ethyl ketone, 20 parts of tetrahydrophthalic anhydride, 2.0 parts of dimethylbenzylamine
Part, and an addition reaction is performed for 10 hours while blowing air at 80 ° C., and a 50% binder polymer solution (P-3)
(Corresponding to a solution of the binder polymer (B2)) was obtained.

The weight average molecular weight of the obtained binder polymer was 20,000, and the acid value was 61 mgKOH / g. [Synthesis Example 6] In a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen replacement, and a stirrer, 70 parts of glycidyl methacrylate, 10 parts of methyl methacrylate,
20 parts of tert-butyl methacrylate, 100 parts of methyl ethyl ketone, 0.5 parts of lauryl mercaptan and 3 parts of azobisisobutyronitrile were added, and the mixture was heated under a nitrogen stream, polymerized at 75 ° C. for 5 hours, and subjected to a 50% copolymer. A solution was obtained.

To the above 50% copolymer solution were added 0.05 parts of hydroquinone, 39 parts of propionic acid, and 2.0 parts of dimethylbenzylamine, and the mixture was subjected to an addition reaction at 80 ° C. for 24 hours while blowing air thereinto. Add 38 parts of phthalic anhydride and 77 parts of methyl ethyl ketone and add 80 parts.
The mixture was reacted at 10 ° C. for 10 hours to obtain a 50% binder polymer solution (P-4) (corresponding to a solution of the binder polymer (B3)).

The obtained photosensitive prepolymer had a weight average molecular weight of 21,000 and an acid value of 79 mgKOH / g. [Synthesis Example 7] In a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for purging nitrogen, and a stirrer, 20 parts of methacrylic acid, 80 parts of methyl methacrylate, 100 parts of carbitol acetate, and azobisisobutyro were used. One part of nitrile was added, and the mixture was heated under a nitrogen stream, and polymerized at 80 ° C. for 5 hours, and a 50% binder polymer solution (P-5)
(Acrylic ester-based copolymer solution corresponding to binder polymer (B1)) was obtained. The weight average molecular weight of the obtained binder polymer is 95,000, and the acid value is 130.
mg KOH / g. [Synthesis Example 8] Styrene-maleic anhydride copolymer (trade name "SMA-1000A", manufactured by Elphatochem) 15
Of n-butyl alcohol, 0.1 part of hydroquinone and 3.0 parts of dimethylbenzylamine were added to a solution prepared by heating and dissolving 0 parts in 152 parts of carbitol acetate while blowing air, and 80 parts were added thereto by a conventional method. 24 at ° C
The reaction was carried out for an hour to obtain a 57% solution (P-6) (a solution of a styrene-maleic acid ester-based copolymer corresponding to the binder polymer (B1)). The weight average molecular weight of the obtained binder polymer is 7400, and the acid value is 203 mg KO.
H / g. Synthesis Example 9 70 parts of glycidyl methacrylate, 30 parts of tert-butyl methacrylate, 100 parts of carbitol acetate, 100 parts of lauryl mercaptan were placed in a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for purging nitrogen, and a stirrer. .3 parts, azobisisobutyronitrile 3
The polymerization was carried out at 80 ° C. for 5 hours to obtain a 50% copolymer solution.

To the above 50% copolymer solution were added 0.05 part of hydroquinone, 37 parts of acrylic acid and 0.4 part of dimethylbenzylamine, and an addition reaction was carried out at 105 ° C. for 24 hours, followed by tetrahydrophthalic anhydride 31 And 68 parts of carbitol acetate were added and reacted at 100 ° C. for 3 hours to obtain a 50% photosensitive prepolymer solution (P′-1).

The obtained photosensitive prepolymer had a weight average molecular weight of 18,000 and an acid value of 67 mgKOH / g. [Examples 1-4, 7-10, 13-16, 19-22]
After stirring and mixing the components prepared in the compositions shown in Tables 1 and 2, the mixture was thoroughly dispersed with a homomixer, and further distilled under reduced pressure to remove the organic solvent component while blowing air, thereby obtaining an aqueous solution. A photoresist ink was prepared. [Examples 5, 6, 11, 12, 17, 18, 23, 2
4) The components prepared as shown in Tables 1 and 2 were stirred and mixed, and then thoroughly dispersed with a homomixer to prepare an aqueous photoresist ink. [Comparative Examples 1 and 2] The components prepared as shown in Table 2 were sufficiently kneaded with three rolls to prepare a photoresist ink.

[0074]

[Table 1]

[0075]

[Table 2] Here, in the table, (* 1) "Aronix M-309" is a trade name of trimethylolpropane triacrylate (ethylenically unsaturated monomer (D)) manufactured by Toagosei Chemical Industry Co., Ltd.

(* 2) "Aronix M-101"
It is a trade name of phenol-modified monofunctional acrylate (ethylenically unsaturated monomer (D)) manufactured by Toagosei Chemical Industry Co., Ltd.

(* 3) "Light acrylate HOA-H"
"H" is a trade name of 2-acryloyloxyethyl hexahydrophthalic acid (partially esterified product (d1)) manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.

(* 4) "Irgacure 907" is a trade name of a photopolymerization initiator manufactured by Ciba Geigy Corporation.

(* 5) "Kayacure DETX" is a trade name of a photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd.

(* 6) "Victoria Pure Blue BO"
"H" is a trade name of an organic dye manufactured by Hodogaya Chemical Industry Co., Ltd.

The aqueous photoresist inks of Examples 1 to 24 and the photoresist inks of Comparative Examples 1 and 2 were subjected to the following evaluation tests. [Evaluation Test] <Coating Step> [1] Measurement of Preliminary Dry Film Thickness FR-4 double-sided copper-clad laminate of the photoresist inks of all Examples and Comparative Examples having a base material thickness of 1.6 mm and a copper foil thickness of 35 μm. Plate (manufactured by Sumitomo Bakelite Co., Ltd., trade name "ELC
4762 ”) using a vertical roll coater (manufactured by Furness Co., Ltd.), and applying a hot air convection drier to both sides.
After drying at 0 ° C. for 15 minutes, it was cooled to room temperature. The thickness of the preliminary dried film obtained at this time was measured. <Exposure / Development Step> [2] Surface Adhesion of Pre-Dried Film Following the operation of [1], for all Examples and Comparative Examples, a photo showing a wiring pattern drawn on the laminated board with the pre-dried film formed Tool artwork is directly attached from both sides and exposed using a double-sided simultaneous exposure machine (Oak HMW-201GX, manufactured by Oak Manufacturing Co., Ltd.) having an ultra-high pressure mercury lamp so that the integrated light amount becomes 200 mJ / cm ^2. After exposure, observe the presence or absence of traces on the pre-dried film when removing the photo tool artwork from the pre-dried film, and check the ease of peeling of the photo tool artwork from the pre-dried film. The pre-dried film was evaluated as “good” if the photo-tool artwork could be easily peeled off because of the small adhesiveness of the pre-dried film and no peeling marks. [3] Developability Following the operation of [2], the developability of all Examples and Comparative Examples was evaluated using the following two conditions (i) and (ii), respectively.

(I) A 1% by weight aqueous solution of sodium carbonate was sprayed at a spray pressure of 1.5 kg / cm ² for 1 minute at 30 ° C. to remove unexposed portions and developed.

(Ii) 30 ° C. water spray pressure 1.5 kg
/ Cm ² for 3 minutes to remove unexposed portions and develop.

Regarding the above (i) and (ii), the developability was visually observed, and the unexposed portion where the exposed portion where the cured film was formed remained and the unexposed portion was removed, and the case where there was no undeveloped portion was evaluated as “◎”. It was determined. In addition, those in which a slight indentation was observed at the line between the unexposed portion and the exposed portion were evaluated as “と し て”. Further, a sample in which both the exposed part and the unexposed part could not be removed was evaluated as “x”. [4] Evaluation of Adhesiveness by Adhesive Tape Peeling Test In order to confirm the adhesiveness of the obtained resist to the substrate, the cured film was subjected to JISD 0202-1988.
Perform cellophane adhesive tape peeling test by cross cut according to No. 15, the number of grids formed on the effective surface in the denominator,
The molecule was evaluated in terms of the number of grids remaining without completely peeling it off. <Etching process> [5] Resistance to etching solution (water resistance to acidic aqueous solution)
Etching was performed at 5 ° C. for 240 seconds, the presence or absence of peeling of the cured film was observed, and those without peeling were evaluated as “good”. [6] Peelability of cured film Following the operation of [5], (i) Examples 1 to 6, 13 to 18, and Comparative Example 1
Regarding the samples Nos. 2 and 3, peeling of the cured film was observed when the resist was peeled off by spraying a 3% aqueous solution of sodium hydroxide at 45 ° C. at a spray pressure of 2 kg / cm ² .

(Ii) Embodiments 7 to 12, 19 to 24,
In addition, for Comparative Examples 1 and 2, after immersion in a 3% periodic acid aqueous solution at 20 ° C. for 2 minutes, the resist was peeled off by spraying at a spray pressure of 2 kg / cm ² , and peeling of the cured film was observed.

With respect to the above (i) and (ii), the time required for completely removing the cured film was measured. Those that could not be peeled were evaluated as "impossible". [7] Evaluation of etching property The conductor pattern formed on the laminated board from which the cured film was peeled off according to [6] showed breaks, missing wires, thin lines, pinholes, and the like.
Those which did not have line scratches (poor linearity of the linear pattern of the conductor) and etching were not rated. <Plating step> [8] Plating solution resistance After development treatment of [3],-Degreasing (trade name "PC-45" manufactured by Meltex Co., Ltd.)
5 immersed in a 25% by weight aqueous solution of the agent at 30 ° C. for 5 minutes) ・ Washing ・ Soft etching (ammonium persulfate type soft etching agent (Mitsubishi Gas Chemical Co., Ltd., trade name “NP
E-300 ") immersed in a 20% by weight aqueous solution at room temperature for 2 minutes)-Washed with water-Sulfuric acid washed (immersed in 10% by weight sulfuric acid at room temperature for 1 minute), and then subjected to a nickel plating bath (nickel sulfate 3)
00 g, nickel chloride 40 g, boric acid 40 g, water 620
g), nickel plating at 45 ° C, 1.5 A / dm
² for 10 minutes. Immediately after the completion of the nickel plating, the plate was washed with water, and subsequently, a gold plating bath (trade name “Aurobright HS-2” manufactured by Nippon Kojundo Chemical Co., Ltd.) was used to obtain a liquid temperature of 40.
Gold plating was performed at 1.0 A / dm ² for 10 minutes.

During the above steps, the presence or absence of peeling of the cured film was observed, and those without peeling were evaluated as “good”. [9] Peeling test of the adhesive tape of the cured film after plating is completed. After the operation of [8], washing and drying are performed, and the cured film after drying is described in 4.15 of JISD0202-1988.
A cellophane pressure-sensitive adhesive tape peeling test was carried out by cross-cutting in accordance with the standards described above, and the number of grids formed on the effective surface of the denominator and the number of grids remaining without completely peeling off the molecule were evaluated. [10] Evaluation of Plating Property Subsequently, for Examples 1 to 30 and Comparative Examples 1 and 2,
A 3% aqueous solution of sodium hydroxide at 45 ° C. was sprayed at a spray pressure of 2
After removing the resist by spraying with kg / cm ² ,
It was visually observed with a magnifying glass, and those having good plating properties and no plating were evaluated as “good”. [11] Evaluation of Gold Conductor Pattern After Alkali Etching Subsequently, line etching (poor linearity of the linear pattern of gold) after copper was peeled off by alkali etching was confirmed with an optical microscope. Was measured.

The above results are shown in Tables 3 to 5.

[0089]

[Table 3]

[0090]

[Table 4]

[0091]

[Table 5] As is clear from Tables 1 to 5, in Comparative Examples 1 and 2, which were not water-soluble, development was possible with a dilute aqueous alkaline solution, but not with water. All could be developed with both water and dilute aqueous alkaline solution. In all of the examples, the developability in a dilute aqueous alkaline solution was improved as compared with those of Comparative Examples 1 and 2. Particularly, as the binder polymer (B), the number average molecular weight is 20,000 to 2,000.
Examples 1 to 5, 7 to 11 using 300,000,
In 13 to 17 and 19 to 23, the developability was particularly improved.

In Comparative Examples 1 and 2, the cured film could not be peeled off by the sodium periodate solution, whereas in the Examples, the cured film could be peeled off by the alkali solution and the periodic acid solution was removed. It was confirmed that peeling was possible even with a sodium solution.

In all of the examples, the tackiness of the pre-dried film was small, and the adhesion of the cured film to the substrate was high. In addition, the etchant resistance is high, the cured film can be peeled off with an alkaline solution, and when used as an etching resist, the fuselage pattern formed on the laminated board from which the cured film has been peeled has broken lines, broken lines, There was no line thinning, no pinhole, no line crease and no etching, and the etching property was good. In addition, when used as a plating resist, it was confirmed that there was no plating, the plating property was good, and the line crease of the gold circuit pattern after alkali etching was small. These evaluation results were equal to or higher than those of Comparative Examples 1 and 2, which were not water-soluble.

Therefore, it was confirmed that all of the examples were suitable as etching resist inks, plating resist inks, solder resist inks, marking inks and the like using the developing method.

[0095]

As described above, the photosensitive resin composition according to the first aspect of the present invention comprises a water-soluble resin (A) obtained by adding N-alkylol (meth) acrylamide to a polyvinyl alcohol-based polymer. Photosensitive resin, (B) a binder polymer having a carboxyl group and swelling, dispersing or dissolving in a dilute aqueous alkali solution and having no photoreactive ethylenically unsaturated group, (C) photopolymerization initiation Agent, (D) a photopolymerizable ethylenically unsaturated monomer, and (E) water, which can be developed with water or a dilute alkaline aqueous solution.
Using the photosensitive resin (A), other components can be dissolved, emulsified or dispersed in water or a mixed solvent of water and an aqueous organic solvent, and the binder polymer (B)
Sufficient carboxyl groups in the molecule can swell, disperse or dissolve in a dilute aqueous alkaline solution, and the film formed by the photosensitive resin composition of the present invention swells with water or a dilute aqueous alkaline solution before exposure. , Can be dispersed or dissolved, therefore, the photosensitive resin composition, after performing selective exposure of the formed film, by performing development with water or a dilute alkaline aqueous solution, the photosensitive resin composition By washing away the non-exposed portions and leaving the exposed portions, image formation can be performed. In addition, there is no need to use an organic solvent during the development, and in the process of forming a pre-dried film after applying the photosensitive resin composition to the substrate, it is possible to suppress volatilization of the organic solvent from the photosensitive resin composition. Work safety due to organic solvents,
Problems such as environmental pollution and fire can be reduced.

The cured film formed by the photopolymerization reaction of the photosensitive resin composition has a high film hardness and can have good adhesion to the substrate.

A cured product formed by causing a photoreaction by exposing the photosensitive resin composition of the present invention to light is used for an aqueous solution of an alkali metal hydroxide or the like or a polyvinyl alcohol-based photosensitive agent such as sodium periodate. It can be peeled off by any of release agents.

In the case where the photosensitive resin composition of the present invention is used as a photoresist ink for manufacturing a printed wiring board, when the photosensitive resin composition of the present invention applied to a substrate for manufacturing a printed wiring board is cured by exposure. Further, it is possible to prevent a high molecular weight component such as the binder polymer (B) from causing a photoreaction due to a slight exposure to rapidly increase the molecular weight. Can prevent hardening due to slight light leakage and improve the solubility and swelling of dilute alkali solution at the boundary between exposed and unexposed areas. Can be formed, and the resolution can be improved.

Further, the photoreactivity of the photosensitive resin composition of the present invention can be enhanced by the photopolymerizable ethylenically unsaturated monomer (D).

The photosensitive resin composition according to claim 2 of the present invention further comprises, in addition to the constitution of claim 1, the photopolymerizable ethylenically unsaturated monomer (D) as (d) Since a compound containing at least one carboxyl group and at least one photoreactive ethylenically unsaturated group in the molecule is used, the compound (d) having a carboxyl group in the molecule as described above By appropriately adjusting the mixing ratio in the photosensitive resin composition of the present invention, the solubility of the photosensitive resin composition of the present invention in a dilute alkaline aqueous solution can be easily adjusted.

The photosensitive resin composition according to claim 3 of the present invention may further comprise, in addition to the constitution of claim 1 or 2, as the photopolymerizable ethylenically unsaturated monomer (D): d)
Since a compound containing a partial esterified product of a compound having one hydroxyl group and one photoreactive ethylenically unsaturated group in the molecule and a polyvalent carboxylic acid is used, a compound having a carboxyl group in the molecule ( By appropriately adjusting the mixing ratio of d) in the photosensitive resin composition of the present invention, the solubility of the photosensitive resin composition of the present invention in a dilute alkaline aqueous solution can be easily adjusted.

The photoresist ink for manufacturing a printed wiring board according to the fourth aspect of the present invention comprises the photosensitive resin composition according to any one of the first to third aspects. It is suitable as a marking ink or the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2H025 AA00 AB15 AC01 AC08 AD01 BC31 BC85 BC86 CA00 CB07 CB43 CB52 CB53 CC03 FA15 4J027 AA05 AB10 AB28 AC02 AC03 AC04 AC06 AE02 AJ08 BA02 BA03 BA07 BA08 BA09 BA12 BA23 BA26 BA27 CA02 CA03 CB10 CC05 CC07 CD10 5E339 BE13 CC01 CC02 CD01 CE19 CF16 CF17 CG04 DD02

Claims (4)

[Claims] 1. A (A) water-soluble photosensitive resin obtained by adding N-alkylol (meth) acrylamide to a polyvinyl alcohol-based polymer, (B) a carboxyl group,
A binder polymer which swells, disperses or dissolves in a dilute aqueous alkali solution and does not have a photoreactive ethylenically unsaturated group, (C) a photopolymerization initiator, (D) a photopolymerizable ethylenically unsaturated A photosensitive resin composition which is developable with water or a dilute aqueous alkaline solution comprising a monomer and (E) water. 2. The photopolymerizable ethylenically unsaturated monomer (D) comprises (d) at least one carboxyl group and at least one photoreactive ethylenically unsaturated group in the molecule. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises a compound having a compound having the same. 3. A partially esterified product of the compound (d), wherein (d1) a compound having one hydroxyl group and one photoreactive ethylenically unsaturated group in the molecule, and a polycarboxylic acid. 3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises: 4. A photoresist ink for producing a printed wiring board, comprising the photosensitive resin composition according to claim 1.