JP2001242619A - Positive type photosensitive resin composition and resist pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type etching resist composition excellent in operation stability and having high sensitivity and good conductor image forming property. SOLUTION: The positive type photosensitive resin composition contains a photosensitive acrylic resin (A) having a photosensitive group of formula 1 (where X is a group of formula 2 or 3; R1 is alkyl, cycloalkyl or alkyl ether; and R2 is alkylene containing a 1-12C linear, branched or cyclic hydrocarbon) at a concentration of 0.1-1.0 mol per 1 kg resin and having a number average molecular weight of 6,000-100,000 and a water-soluble or water-dispersible acrylic resin composition (B) having a salt forming group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive etching resist composition having excellent operation stability, high sensitivity, and good conductor image formation. In particular, the present invention provides a positive photosensitive resin composition and a method for forming a resist pattern, which are suitable for a printed wiring board.

[0002]

2. Description of the Related Art Printed wiring boards used in electronic devices are mainly formed on an insulating substrate having a conductive layer on the surface by a pattern printing method using screen printing or photolithography using a photosensitive dry film. It is manufactured by the subtract method using the circuit pattern. In recent years, as printed circuit boards have become higher in density and higher in precision, circuit patterns have become finer, and there has been a demand for smaller through-hole diameters in manufacturing processes. A method using a positive photosensitive electrodeposition resist has been proposed as a manufacturing method that can meet the demand.

A copolymer resin of an ester compound of a hydroxyl group contained in an unsaturated monomer and an acid group contained in diazonaphthoquinone sulfonic acid, and another monomer (JP-A-60-207139). Composition containing resin in which quinonediazide sulfonic acid is bonded to the base resin through a sulfonic ester bond to the base resin such as resin (Japanese Patent Laid-Open No. 61-206293) Acrylic resin containing carboxyl group and phenolic A water-soluble or water-dispersible composition such as a composition containing a mixture of a sulfonate of an aromatic carboxylic acid ester having a hydroxyl group and a quinonediazide as a main component (JP-A-3-100074) has been proposed.

Since these carry a photosensitive group by a sulfonic acid ester bond, when the electrodeposition coating bath is operated for a long time, water, acid, base,
Hydrolysis is caused by alcohol or the like, and the photosensitive group is released from the resin. As a result, the sensitivity is reduced, the coating voltage at the time of electrodeposition is largely fluctuated, the coating film is hardly deposited, or the coating surface is abnormal. In addition, agglomerates are generated to cause problems such as clogging of the filter.

In order to solve these problems, a composition comprising, as a main component, a resin in which hydroxylamine and quinonediazidesulfonic acid are bonded to a base resin such as an acrylic resin having an ion-forming group via a urethane bond and a sulfonamide bond. (JP-A-64-90270, JP-A-01-121375)
, A resin composition having a carboxyl group and a water-soluble or water-dispersible resin composition having a photosensitive resin having a molecular weight of up to 6000 and a salt-forming group (JP-A-2-28860). ing. These compositions have high resistance to hydrolysis even in the state of an electrodeposition paint bath, and the electrodeposition bath is stable and easily maintains a bath state that can form a highly reliable resist film even after long-term running. In addition, it does not generate aggregates and precipitates in the running bath and does not cause clogging of the filter of the electrodeposition bath liquid circulation device, so that bath management is easy, and a highly practical positive-type photosensitive material. It is an electrodeposition coating composition. However, in the former, a carboxyl group and a photosensitive group are contained in one molecule in a single resin in the anionic electrodeposition coating composition, and the resist performance such as developability, pattern forming property, and film strength must be secured. Design is not easy.

The latter is composed of a photosensitive resin and a water-dispersible resin in order to compensate for the disadvantage. The photosensitive resin is composed of a reaction product of a hydroxyl group-containing diazide compound and a low molecular weight polyfunctional isocyanate compound. In order to obtain good resist performance, it is necessary to use a large amount of expensive photosensitive agents and to increase the photosensitive group concentration. It is desired that good resist performance can be obtained at a low photosensitive group concentration for cost reduction.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, 1, (1)

[0008]

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In the above formula, X is

[0010]

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Or

[0012]

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And R ₁ represents an alkyl group, a cycloalkyl group or an alkyl ether, and R ₂ is an alkylene group having 1 to 12 carbon atoms containing a linear, branched or cyclic hydrocarbon. A photosensitive acrylic resin having a number average molecular weight of 6,000 to 100,000 (A) having a concentration of the photosensitive group of 0.1 to 1.0 mol per kg of the resin; and (2) a water-soluble resin having a salt-forming group. Or a positive photosensitive resin composition comprising a water-dispersible acrylic resin composition (B); 2. a positive photosensitive composition as described in 1 above, wherein the salt-forming group is a carboxyl group. 3, a step of coating the substrate with the positive photosensitive resin composition according to 1 or 2 above to form a positive photosensitive film on each substrate, and applying the positive photosensitive film to a pattern mask. Through
Or a method of forming a resist pattern, wherein a step of directly exposing an image with a UV laser and a step of developing the exposed positive photosensitive film with a basic developer are sequentially performed. Coating a photosensitive resin composition of the present invention on a substrate or a metal plate having an electrically conductive coating to form a positive photosensitive coating on the substrate, exposing the positive photosensitive coating via a pattern mask, or laser. A step of directly exposing an image with light, a step of developing the exposed positive-type photosensitive film with a basic developer, a step of etching a conductive film or a metal plate surface exposed after development,
A method of forming a resist pattern, comprising sequentially performing a step of removing a photosensitive film on a pattern; 5, electrodepositing the photosensitive resin composition according to 1 or 2 on a substrate or a metal plate having a conductive film. The present invention also relates to the above-mentioned method 4 for forming a resist pattern, wherein the method is applied by a method.

According to the present invention, a photoresist having a low photosensitive group concentration and high sensitivity can be obtained by using a resin composition comprising the high molecular weight photosensitive resin and a resin having a salt-forming group without containing a photosensitive agent. Can be In addition, since the concentration of the photosensitive group can be lowered, the compatibility with the resin having a salt-forming group is also good. Further, when the resin composition has a carboxyl group, it is partially neutralized with a basic compound to obtain an anion electrodeposition photosensitive composition. Since these electrodeposition coating compositions have a photosensitive group supported on the resin by a sulfonic acid amide bond, they are not easily hydrolyzed like sulfonic acid esters, and are stable even for long-term running in an electrodeposition coating bath. Initial performance can be maintained.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (1) Photosensitive resin (A) of the present invention
Can be obtained by allowing a resin to support a quinonediazide compound containing a hydroxyl group (for example, see JP-A-64-90270) obtained by reacting quinonediazidesulfonic acid chloride with hydroxylamine by the following method or the like. .

After a hydroxyl group-containing quinonediazide compound is added to an unsaturated monomer having an isocyanate group-containing polymerizable vinyl group by a urethanation reaction, the compound is copolymerized with another unsaturated monomer.

An isocyanate group-containing quinonediazide compound obtained by adding a hydroxyl group-containing quinonediazide compound to one of the isocyanate groups of a compound containing two isocyanate groups by a urethanization reaction, and a hydroxyl group-containing vinyl monomer is converted to another unsaturated monomer Is added to the resin composition obtained by copolymerization.

The unsaturated monomer-containing quinonediazide compound obtained by reacting the isocyanate group-containing quinonediazide compound produced as described above with a hydroxyl group-containing unsaturated monomer is copolymerized with another unsaturated monomer. .
Alternatively, a hydroxyl group-containing quinonediazide compound is added to a resin composition obtained by copolymerizing an unsaturated monomer having an isocyanate group and a polymerizable vinyl group with another unsaturated monomer by a urethanation reaction.

In the above-mentioned production method, the following isocyanate group-containing vinyl monomers to be reacted with the hydroxyl group-containing diazide compound. (A) The following formula

[0020]

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In the formula, R4 represents a hydrogen atom or a methyl group, and n is an integer of 1 to 8, such as isocyanateethyl (meth) acrylate, etc. (b)

[0022]

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In the formula, R4 and n each have the same meanings as above, and R5 represents hydrogen or an alkyl group of C5 or less, for example, m-isopropenyl-
α, α-dimethylbenzyl isocyanate and the like. (C) The following formula

[0024]

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In the formula, R4 and n each represent the above-mentioned meaning, and a monomer obtained by reacting 1 mol of a hydroxyl group-containing (meth) acrylate-based monomer represented by the following formula with about 1 mol of a diisocyanate compound.

The monomers represented by the above (9) include hydroxyalkyl (meth) acrylates, especially 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. A) acrylate and the like.

As the diisocyanate compound, for example, as an aliphatic diisocyanate compound, for example,
Hexamethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate,
2,3-butylene diisocyanate, 1,3-butylene diisocyanate, etc .: As alicyclic diisocyanate compounds, for example, isophorone diisocyanate, 4,4 ′
-Methylenebis (cyclohexylisocyanate), methylcyclohexane-2,4- (or -2,6-) diisocyanate, 1,3- (or 1,4-) diisocyanatomethylcyclohexane, 1,4-cyclohexanediisocyanate, 3-cyclopentane diisocyanate, 1,2-cyclohexane diisocyanate and the like: As aromatic diisocyanate compounds, for example, xylylene diisocyanate, meta-xylylene diisocyanate, tetramethyl xylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 5-naphthalenediisocyanate, 1,4
Naphthalene diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, (m- or p-) phenylene diisocyanate, 4,4'-biphenylene diisocyanate,
3,3'-dimethyl-4,4'-biphenylenediisocyanate, bis (4-isocyanatophenyl) sulfone, isopropylidenebis (4-phenylisocyanate) and the like, among which two isocyanates having different reactivities Tolylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-
Diisocyanate, m-xylylene diisocyanate,
1,3- (or 1,4-) diisocyanatomethylcyclohexane and the like are preferred.

The above-mentioned reaction between the isocyanate-containing vinyl monomer and the hydroxyl group-containing quinonediazide compound is carried out, for example, in an inert organic solvent at a ratio of approximately 1 mol of the hydroxyl group-containing quinonediazide to 1 mol of the isocyanate-containing vinyl monomer. At room temperature to 80 ° C., preferably at about 60 ° C. for about 0.5 to 20 hours. The reaction was analyzed by infrared spectroscopy at 2250.
It can be monitored by measuring the absorption of isocyanate groups around cm ^-1 . As the solvent that can be used here, an inert organic solvent that does not react with the isocyanate group and the hydroxyl group can be used, and examples thereof include ketone, ester, aromatic, aliphatic, and ether solvents. After the reaction, these solvents can be desolvated and replaced with an alcohol-based aqueous solvent. Examples of the radical polymerizable unsaturated monomer copolymerized with the monomer obtained by reacting the isocyanate group-containing vinyl monomer with the hydroxyl group-containing quinonediazide include the following.

Examples of the radical polymerizable unsaturated monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl ( Alkyl or cycloalkyl esters of (meth) acrylic acid having 1 to 24 carbon atoms such as meth) acrylate, stearyl (meth) acrylate and decyl acrylate; glycidyl group-containing vinyl monomers such as glycidyl (meth) acrylate; Examples include vinyl monomers such as styrene, vinyl toluene, vinyl propionate, α-methylstyrene, vinyl acetate, (meth) acrylonitrile, vinyl propionate, vinyl pivalate, and beova monomer (shell chemical product).

The monomer compound obtained by reacting the isocyanate group-containing vinyl monomer with the hydroxyl group-containing quinonediazide can be copolymerized with an unsaturated monomer having a salt-forming functional group.

Specific examples of the acid group-containing unsaturated monomer include (meth) acrylic acid, crotonic acid, (anhydride) itaconic acid, (anhydride) maleic acid, fumaric acid, and 2-hydroxyethyl acrylate acid phosphate. And the like. Among them, (meth) acrylic acid is preferable. However,
When the concentration of the acidic group as the resin is increased, the ratio of the resin acid value of the exposed portion and the unexposed portion caused by exposure is reduced due to the quinonediazide group, so that a difference in solubility between the exposed portion and the unexposed portion in the developer cannot be obtained. Although it depends on the monomer composition, the acid value of the resin is preferably 0.6 mol or less per 1 kg of the resin.

In the copolymerization reaction of the above-mentioned monomers, the mixture of the above-mentioned monomers is usually reacted with a radical polymerizable initiator such as azobismethoxybutyronitrile and benzoyl peroxide in a suitable organic solvent. The reaction is carried out in the presence at about 30 to 80 ° C for about 1 to 20 hours. The suitable organic solvent is not particularly limited as long as it has good solubility (especially, when used as an electrodeposition coating material, a hydrophilic organic solvent is suitable. Examples of such an organic solvent include methanol, Alcohols such as ethanol and n-propanol, ether alcohols such as butyl zero-solve, ethyl cellosolve and propylene glycol monomethyl ether, ethers such as diethylene glycol dimethyl ether, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate And amides such as N-methylpyrrolidone.

In the above-mentioned production method, as the diisocyanate compound to be reacted with the hydroxyl group-containing quinonediazide compound, the same diisocyanate compound described in the production method can be used, and a compound having two isocyanate groups having different reactivities is preferable. The reaction between the hydroxyl group-containing quinonediazide compound and the diisocyanate compound can be carried out in the same manner as the reaction between the isocyanate group-containing vinyl monomer and the hydroxyl group-containing quinonediazide compound described in the above production method. The hydroxyl group-containing acrylic resin to be reacted with the isocyanate group-containing quinonediazide compound obtained by reacting the hydroxyl group-containing quinonediazide compound with the diisocyanate compound has a hydroxyl group concentration of 0.1 mol / Kg to 2.6 mol / Kg, preferably 0.2 mol / Kg. The range is from Kg to 1.8 mol / Kg.

The hydroxyl group-containing acrylic resin may be a hydroxyl group-containing monomer represented by the general formula (8) and other radically unsaturated monomers (abbreviated-(meth) acrylates, (meth) ) Acrylic acid amides, vinyl monomers, etc.).
It can also be copolymerized with an unsaturated monomer having a salt-forming functional group described in the production method.

The copolymer is prepared by converting the monomer of each of the above components into 2,2'-azobisisobutyronitrile, 2,2 in an inert organic solvent which does not react with isocyanate groups as described in the production method. In the presence of a radical polymerization initiator such as 2′-azobis-2,4-dimethylvaleronitrile, benzoyl peroxide, etc., at a temperature of about 30 to about 180 ° C., preferably about 60 ° C. to about 120 ° C. for about 1 hour to The reaction is carried out for about 20 hours.

The above-mentioned reaction between the isocyanate group-containing quinonediazide compound and the hydroxyl group-containing acrylic resin is carried out by subjecting the isocyanate group-containing quinonediazide compound and the resin to room temperature to about 80 ° C. in the presence of the inert organic solvent described in the production method. Is about 0.5-20 at room temperature to about 60 ° C
It can be performed by continuing the reaction for a time.

In the above-mentioned production method, the hydroxyl group-containing vinyl monomer which is reacted with the isocyanate group-containing quinonediazide compound as described in the production method may be any of the monomers represented by the general formula (9) described above in the production method. You can choose from. The reaction between the isocyanate group-containing quinonediazide compound and the hydroxyl group-containing acrylic monomer is carried out in the presence of the same inert organic solvent as described for the production method, with respect to 1 mol of the isocyanate group-containing quinonediazide compound and the hydroxyl group-containing acrylic monomer. About 1
The reaction can be carried out in a molar ratio from room temperature to about 80 ° C., preferably from room temperature to about 60 ° C., for about 0.5 to 20 hours. The obtained quinonediazide group and a monomer compound having an unsaturated group are obtained by a method similar to the monomer compound obtained by reacting the isocyanate group-containing vinyl monomer and the hydroxyl group-containing quinonediazide shown in the above-mentioned production method, The photosensitive group-containing resin can be obtained by copolymerization with another monomer. It can also be copolymerized with an unsaturated monomer having a salt-forming functional group described in the production method.

In the above-mentioned production method, the isocyanate group-containing acrylic copolymer which is reacted with the hydroxyl group-containing quinonediazide compound is the same as the isocyanate group-containing vinyl monomer described in the production method in the general formula described in the production method. (7) and (8) monomers and other radically unsaturated monomers (approximately-(meth)
Acrylic acid esters, (meth) acrylic acid amides,
(A vinyl monomer or the like). Further, it can be copolymerized with an unsaturated monomer having a salt-forming functional group described in the production method. When the acid group-containing unsaturated monomer is copolymerized, among the isocyanate group-containing vinyl monomers, m-isopropenyl-α, α-dimethylbenzyl isocyanate having an isocyanate group bonded to a tertiary carbon is used. When used, the isocyanate group does not react with the acid group of the unsaturated monomer containing an acid group to be copolymerized, so that there is no danger of gelling and thickening during production. This is advantageous because an isocyanate group can be surely introduced into the resin.

In the copolymerization reaction of the above-mentioned monomers, the monomer of each of the above-mentioned components is converted to 2,2 ′ in an inert organic solvent which does not react with isocyanate groups as described in the production method.
In the presence of a radical polymerization initiator such as azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, benzoyl peroxide,
The reaction is carried out at a temperature of about 180 ° C, preferably about 60 ° C to about 120 ° C for about 1 hour to about 20 hours.
The reaction between the copolymer and the hydroxyl group-containing quinonediazide compound is carried out by subjecting the copolymer and the hydroxyl group-containing quinonediazide compound to an isocyanate group of the copolymer in the presence of the same inert organic solvent as described for the production method. In a ratio of 1 mol of a hydroxyl group-containing quinonediazide compound to 1 mol,
Room temperature to about 80 ° C, preferably from room temperature to about 60 ° C for about 0.5
The reaction can be performed by continuing the reaction for up to 20 hours. Further, in this method, the isocyanate group 1 of the copolymer
When the amount of the hydroxyl group-containing quinonediazide compound is less than 1 mol per mole, an isocyanate group can be left after the addition, so that a compound having a salt-forming functional group having a hydroxyl group such as dimethylpivalic acid or hydroxyacetic acid or a large excess of ethylene glycol A salt-forming group or a hydroxyl group can be introduced by adding a polyfunctional alcohol compound such as diethylene glycol or propylene glycol.

The mixing ratio of the monomer of the quinonediazide group-containing acrylic resin obtained by the above four production methods is not strictly limited, but the quinonediazide group is compounded so as to be 0.1 to 1.0 mol per 1 kg of the resin. Is done.

The quinonediazide group-containing acrylic resin obtainable by the above production method has a number average molecular weight of about 6,000 to 100,000, preferably about 8,000 to 5,000.
It is in the range of 000.

When the composition of the present invention is used as an anionic electrodeposition coating material, examples of the salt-forming group of the resin (B) include anion-forming groups such as a carboxyl group, a sulfonyl group and a phosphate group. In particular, carboxyl groups are preferred.

The content of the salt-forming group in the resin (B) is. In general, it is preferable that the amount of the salt-forming group in the total composition of the photosensitive resin (A) and the resin (B) is adjusted to be in the range of 0.45 to 4.0 mol / kg. . If the total content of the salt-forming groups is less than 0.45 mol / kg, the solubility of the exposed portion in the developing solution in the developing step is insufficient, and an image cannot be formed. Generally, it tends to be difficult to neutralize the resin and dissolve or disperse it in water, and it may be difficult to obtain a stable electrodeposition paint bath. 4.0
When the amount exceeds mol / kg, the solubility of the exposed portion in the developing solution in the developing solution is reduced and becomes insufficient, so that an image cannot be formed. Further, the coating efficiency (coulomb yield) at the time of electrodeposition coating tends to decrease, and a coating film abnormality such as water marks easily occurs on the surface of the obtained resist film. The resin (B) generally has a number average molecular weight of 1,500 to 10,
It is preferably in the range of 000, especially 5,000 to 30,000. If the molecular weight of the resin is lower than 1,500, the film strength is not sufficient, and the resist film is liable to crack or break in the developing or cutting step.
If it exceeds 000, it tends to be difficult to obtain a smooth coated surface due to insufficient flowability of the coating film when forming a coating film.

The mixing ratio of the photosensitive resin (A) and the resin (B) is not strictly limited, and may vary widely depending on the type of the photosensitive resin (A) and / or the resin (B) used. However, from the viewpoint of photosensitivity, developability, coating workability, cost, etc., the content of the quinonediazide sulfone unit per 1 kg of the solid content of the composition is in the range of 0.1 to 0.5 mol. It is preferable to mix as follows. When the content of the photosensitive group is less than 0.1 mol, the difference in solubility between the exposed part and the unexposed part in the developing solution is reduced, and the development condition range is easily narrowed. On the other hand, there is a tendency that the light transmittance of the resist film decreases and the photosensitivity decreases. In addition, since the quinonediazide-containing compound is expensive, it is not economically preferable to use it more than necessary.

When used as an electrodeposition paint, the ratio of the photosensitive resin (A) is 10 parts by weight in the total of 100 parts by weight of the photosensitive resin (A) and the resin (B) from the viewpoint of the photosensitivity and the stability of the electrodeposition paint bath.
It is preferably from 80 to 80 parts by weight. If the amount is less than 10 parts by weight, the photosensitivity is poor. If the amount is more than 80 parts by weight, the photosensitive resin (A)
The resin (B) which disperses the resin has insufficient dispersion stabilizing action, and tends to cause aggregation and sedimentation. Further, it is preferable to mix them so that the content of the salt-forming group is in the range of 0.45 to 4.0 mol. Further, when the content of the salt-forming group is less than 0.45 mol, it becomes difficult to neutralize the resin and dissolve or disperse it in water, and it is difficult to obtain a stable electrodeposition paint bath. If it exceeds 4.0 moles, the coating efficiency (coulomb yield) during electrodeposition coating tends to be low, and the resulting resist film surface is liable to cause coating film abnormalities such as water marks.

Further, as the photosensitive acrylic resin (A), one kind or two or more kinds can be used as a mixture with the resin (B).

The neutralizing agent which can be used in the composition of the invention comprising the photosensitive resin (A) and the resin (B) includes, for example, alkylamines such as triethylamine, diethylamine, monoethylamine, diisobutylylamine, trimethylamine and diisobutylamine; Alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkylalkanolamines such as dimethylaminoethanol; finger-ring amines such as cyclohexylamine; alkali metal hydroxides such as sodium hydroxide and sodium hydroxide; ammonia; These can be used alone or as a mixture.

In the present invention, a hydrophilic solvent such as isopropanol, n-butanol, t-butanol, methoxyethanol, ethoxyethanol, butoxyethanol may be used to further improve the flowability of the water-soluble or water-dispersed electrodeposition paint. Ethylene glycol dimethyl ether, diethylene glycol, methyl ether, dioxane, tetrahydrofuran and the like can be added.

These hydrophilic solvents can be used within a range of usually 100 parts by weight or less based on 100 parts by weight of the solid content of the electrodeposition coating composition. Further, in order to increase the amount of coating on the object to be coated, a hydrophobic solvent such as a petroleum solvent such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; Hydrophobic alcohols such as ethylhexyl alcohol and benzyl alcohol; and hydrophobic ethers such as ethylene glycol dibutyl ether, diethylene glycol dibutyl ether and propylene glycol phenyl ether can also be added. It is desirable that the amount of the hydrophobic solvent used is usually 30 parts by weight or less based on 100 parts by weight of the solid content of the electrodeposition coating composition.

The composition of the present invention may contain, if necessary, a resin other than those described above to adjust the resist performance and the performance of the electrodeposition coating film appropriately, such as phenols, polyphenols such as novolak phenol and resol, and the like. Resins having no salt-forming group such as resins may be blended in an amount of less than 50 parts by weight based on 100 parts by weight of the total composition. Further, additives such as a surfactant, a complexing agent, and a chelating agent, a dye, a pigment, and the like can be added.

The production of a printed wiring board using the composition of the present invention can be carried out, for example, as follows. The photosensitive resin composition described above is adjusted to an appropriate viscosity with an organic solvent in a liquid resist, and then roll-coated, spray-coated, curtain-flow coated on a surface having a conductive film such as a copper-clad laminate or a gold layer. Apply by painting, dip painting, etc. The film thickness at this time is 1 to 100 μm in dry film thickness.
m, preferably in the range of 5 to 20 μm. Next, the coating film is dried with hot air or the like to remove the solvent. Next, the surface of the thus formed photosensitive electrodeposition coating film is exposed to actinic rays such as ultraviolet rays through a pattern mask (photo positive). Since the portion of the orthoquinonediazide compound exposed by this exposure becomes carboxylic acid via ketene, it is removed by a developing treatment with a developing solution such as an aqueous alkali solution, and a high-resolution pattern can be formed.

The electrodeposition resist is prepared by immersing the printed circuit board as an anode in an electrodeposition coating bath (bath solid concentration: 3 to 30% by weight) and applying a DC current having a maximum applied voltage of 20 to 400 V. It is. The energization time is suitably about 10 seconds to 5 minutes, and the film thickness is 2 to 100 in dry film thickness.
μm, preferably in the range of 3 to 20 μm. After the electrodeposition coating, the object to be coated is taken out of the electrodeposition bath and washed with water, and then the moisture contained in the electrodeposition coating film is removed with hot air or the like. Thereafter, exposure and development are performed in the same manner to form a high-resolution pattern.

In the present invention, active rays used for exposure preferably have a wavelength of 3000 to 4500 °. These light sources include sunlight, mercury lamps, xenon lamps,
Arc lamps and the like. It is also possible to directly draw a pattern with UV laser light. Irradiation with actinic rays is usually from 100 to 800 mJ / cm ² , but in the present invention, the concentration of the photosensitive group can be reduced.
It is performed within the range of 0 mJ / cm ² . Further, the developing treatment can be usually carried out by spraying dilute alkaline water onto the coating film surface to wash out the photosensitive portion of the coating film. As the dilute alkaline water, those which can be neutralized with a free carboxylic acid contained in a coating film, such as caustic soda, caustic potash, sodium silicate, sodium carbonate, and ammonia water having a pH of 8 to 12 to give water solubility are used. It is possible.
The copper foil portion (non-circuit portion) exposed on the substrate by the developing process is then removed by a normal etching process using, for example, a ferric chloride solution or the like. Thereafter, the final exposed coating on the circuit pattern is also a cellosolve solvent such as ethyl cellosolve and ethyl cellosolve acetate; an aromatic hydrocarbon solvent such as toluene and xylene; a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone: ethyl acetate; An acetate ester solvent such as butyl acetate; a chlorine solvent such as trichloroethylene; or dissolved and removed using a caustic soda solution or a caustic potash solution having a pH of 11 or more to form a printed circuit on the substrate.

As described above, the positive photosensitive composition of the present invention can be easily applied on a circuit board, and the coating film is dried to form a uniform photosensitive film. In particular, the electrodeposition coating composition of the present invention is most suitable for manufacturing a printed circuit board having through holes, and eliminates the need for a soldering process when a photosensitive negative type dry film is used, thereby shortening the printed circuit board manufacturing process. Can be. Further, it is difficult to form a cured film in a small-diameter through-hole with a negative etching resist, but the composition of the present invention produces a printed board having a small diameter because an unexposed portion remains as a resist film. Also suitable for.

The present invention will be described more specifically with reference to the following examples.

Parts and% in Examples are parts by weight and% by weight, respectively.

Production Example of Photosensitive Compound 1 (Hydroxy-Containing Orthonaphthoquinonediazide Compound) (See JP-A-64-90270) Orthonaphthoquinonediazide-5 was placed in a four-necked flask equipped with a stirrer, a condenser and a thermometer. 269 parts of sulfonic acid chloride and 1345 parts of dioxane were added, and the mixture was stirred at room temperature, and 150 parts of N-methylethanolamine was added dropwise over about 1 hour while blowing nitrogen gas into the gas phase. After the completion of the dropwise addition, stirring was continued for about 3 hours to obtain an IR spectrum of 330
After confirming that the absorption of the amino group near 0 cm ^-1 disappeared, the reaction was terminated. The solution was then placed in deionized water to trap the hydrochloric acid generated during the reaction and remove the amine salt formed. Next, after extracting the product with isobutyl acetate, the solvent was distilled off, and the residue was placed in a reduced-pressure drier and dried to obtain photosensitive compound 1.

Production Example of Photosensitive Compound 2 (Isocyanate Group-Containing Orthonaphthoquinone Diazide Compound) A four-necked flask equipped with a stirrer, a condenser, and a thermometer was charged with 489 parts of diethylene glycol dimethyl ether.
Photosensitive compound 1 (307 parts) and isophorone diisocyanate (202 parts) were added, and the mixture was stirred and heated to 60 ° C. for 30 minutes while blowing nitrogen into the gas phase. Thereafter, 0.03 parts of dibutyltin dilaurate was added every 30 minutes. The mixture was added three times, and the stirring was further continued. After about 4 hours, the reaction was completed to obtain photosensitive compound 2. Example of Synthesis of Unsaturated Compound 1 with Solid Content of 51% In a four-necked flask equipped with a stirrer, a condenser, and a thermometer, 1535 parts of methyl isobutyl ketone, photosensitive compound 1
307 parts and 0.2 part of hydroquinone monomethyl ether were added, and the temperature was raised to 50 ° C. while blowing dry air into the liquid phase and stirring. Then, 155 parts of 2-isocyanatoethyl methacrylate was added dropwise over 2 hours, and the mixture was allowed to stand for 8 hours. Keeping this gave unsaturated compound 1. Solids concentration is 23.1%
Met.

Synthesis Example of Unsaturated Compound 2 230 parts of isophorone diisocyanate and 0.2 parts of hydroquinone monomethyl ether were placed in a four-necked flask equipped with a stirrer, a condenser, a gas inlet and a thermometer, and heated to 70 ° C. After warming, 116 parts of hydroxyethyl acrylate was added dropwise over 2 hours while blowing dry air into the liquid phase and stirring. After the dropwise addition, the temperature was raised to 80 ° C., and the reaction was further performed for 4 hours. The concentration of the isocyanate group was 3.1 mmol / Kg.
At that time, 330 parts of photosensitive compound 1 and 997 parts of diethylene glycol dimethyl ether were added. When the temperature was maintained at 60 ° C., dibutyltin dilaurate was added to 5 parts.
After about 2 hours, it was confirmed that the absorption of the isocyanate group near 2250 cm ^{-1 in the} IR spectrum disappeared, whereby unsaturated compound 2 was obtained. The solids concentration was 40.4%.

Synthesis Example of Unsaturated Compound 3 In a four-necked flask equipped with a gas inlet tube and a thermometer, 1535 parts of mesobutyl ketone, 307 parts of photosensitive compound 1 and 0.2 parts of hydroquinone monomethyl ether were charged. After the temperature was raised to 50 ° C. while stirring by blowing dry air into the mixture, 201 parts of m-isopropenyl-α, α-dimethylbenzyl isocyanate was added dropwise over 2 hours, and the mixture was kept for 8 hours to obtain unsaturated compound 3. Solids concentration is 2
It was 4.9%.

Synthesis Example of Photosensitive Resin A-1 Diethylene glycol dimethyl ether 3 was placed in a four-necked flask equipped with a stirrer, a cooling pipe, a gas blowing pipe and a thermometer.
80 parts are charged and nitrogen gas is blown into the gas phase while stirring.
After the temperature was raised to 0 ° C., a mixture of 300 parts of methyl methacrylate, 300 parts of n-butyl acrylate, 140 parts of ethyl acrylate, 180 parts of hydroxyethyl acrylate, 1,040 parts of unsaturated photosensitive compound 1 and 50 parts of azobismethoxydimethylvaleronitrile was taken for 4 hours. And dripped evenly. After further holding at 60 ° C. for 1 hour, a mixed solution composed of 10 parts of azobismethoxydimethylvaleronitrile and 40 parts of diethylene glycol dimethyl ether was added dropwise over 30 minutes, and the mixture was further kept at 60 ° C. for 2 hours. 1 was obtained. Solid content Photosensitive group concentration / 0.43 mol / kg of solid content Hydroxyl value 72, number average molecular weight 8,000
Met.

Synthesis Example of Photosensitive Resin A-2 Diethylene glycol dimethyl ether 4 was placed in a four-necked flask equipped with a stirrer, a cooling pipe, a gas blowing pipe and a thermometer.
Add 00 parts, and blow nitrogen gas into the gas phase while stirring.
After the temperature was raised to 0 ° C., a mixture of methyl methacrylate 300 parts n-butyl acrylate 300 parts ethyl acrylate 80 parts acrylic acid 30 parts hydroxyethyl acrylate 170 parts unsaturated compound 1 1560 parts azobismethoxydimethyl valeronitrile 40 parts It was dropped evenly over time. After further holding at 60 ° C. for 1 hour, a mixed solution composed of 10 parts of azobismethoxydimethylvaleronitrile and 40 parts of diethylene glycol dimethyl ether was added dropwise over 30 minutes,
By further maintaining the temperature at 60 ° C. for 2 hours, the photosensitive resin A-
2 was obtained. Solid content 44%, photosensitive group concentration / 0.61 mol / kg solid content, hydroxyl value 64, number average molecular weight 10,
000.

Synthesis Example of Photosensitive Resin A-3 Diethylene glycol dimethyl ether 5 was placed in a four-necked flask equipped with a stirrer, a cooling pipe, a gas injection pipe and a thermometer.
90 parts were charged and nitrogen gas was blown into the gas phase while stirring.
After the temperature was raised to 0 ° C, a mixture consisting of 300 parts of methyl methacrylate, 400 parts of n-butyl acrylate, 30 parts of acrylic acid, 110 parts of hydroxyethyl acrylate, 1616 parts of unsaturated compounds, and 50 parts of azobismethoxydimethylvaleronitrile was uniformly added over 4 hours. Was dropped. After further holding at 60 ° C. for 1 hour, a mixed solution composed of 10 parts of azobismethoxydimethylvaleronitrile and 40 parts of diethylene glycol dimethyl ether was added dropwise over 30 minutes,
By further maintaining the temperature at 60 ° C. for 2 hours, the photosensitive resin A-
3 was obtained. Solid content 50% Photosensitive group concentration / 0.51 mol / kg solid content, hydroxyl value 34, number average molecular weight 8,0
00.

Example of Synthesis of Photosensitive Resin A-4 Diethylene glycol dimethyl ether 7 was placed in a four-necked flask equipped with a stirrer, cooling tube, gas blowing tube and thermometer.
Add 20 parts, and blow nitrogen gas into the gas phase while stirring.
After the temperature was raised to 05 ° C., a mixture consisting of 350 parts of methyl methacrylate, 350 parts of n-butyl acrylate, 300 parts of hydroxyethyl acrylate, and 50 parts of azobisisobutyronitrile was dropped uniformly over 4 hours. After further holding at 105 ° C. for 1 hour, 6 parts of azobisisobutyronitrile and 40 parts of diethylene glycol dimethyl ether 40
Part of the mixed solution over 30 minutes,
The polymer was obtained by keeping at 05 ° C. Next, the temperature was lowered to 60 ° C., and 400 parts of photosensitive compound 2, 300 parts of diethylene glycol dimethyl ether and 1 part of dibutyltin dilaurate were added to this polymer, and after stirring and holding for 3 hours, the isocyanate group near 2250 cm ^{−1 in} the IR spectrum was removed. After confirming that the absorption disappeared, photosensitive resin A-4 was obtained. Solid content 50% Photosensitive group concentration / 0.32 mol / kg solid content, hydroxyl value 101, number average molecular weight 9,0
00.

Synthesis Example of Photosensitive Resin A-5 Diethylene glycol dimethyl ether 7 was placed in a four-necked flask equipped with a stirrer, a cooling pipe, a gas blowing pipe and a thermometer.
30 parts were charged, and nitrogen gas was blown into the gas phase while stirring.
After the temperature was raised to 05 ° C., a mixture of 350 parts of methyl methacrylate, 350 parts of n-butyl acrylate, 30 parts of acrylic acid, 270 parts of hydroxyethyl acrylate, and 50 parts of azobisisobutyronitrile was dropped evenly over 4 hours. After further holding at 105 ° C. for 1 hour, 6 parts of azobisisobutyronitrile and 40 parts of diethylene glycol dimethyl ether 40
Part of the mixed solution over 30 minutes,
The polymer was obtained by keeping at 05 ° C. Next, the temperature was lowered to 60 ° C., 800 parts of photosensitive compound 2, 320 parts of diethylene glycol dimethyl ether and 1 part of dibutyltin dilaurate were added to the polymer, and after stirring and holding for 3 hours, the isocyanate group near 2250 cm ^{−1 in} the IR spectrum was removed. It was confirmed that the absorption disappeared, and photosensitive resin A-5 was obtained. Solid content 50% Photosensitive group concentration / 0.55 mol / kg solid content, hydroxyl value 62, number average molecular weight 11.0
00.

Synthesis Example of Photosensitive Resin A-6 Diethylene glycol dimethyl ether 5 was placed in a four-necked flask equipped with a stirrer, a cooling pipe, a gas injection pipe and a thermometer.
Add 40 parts, add nitrogen gas into the gas phase and stir while stirring.
The temperature was raised to 05 ° C., then 100 parts of styrene 250 parts of methyl methacrylate 300 parts of n-butyl acrylate 75 parts of ethyl acrylate 30 parts of hydroxyethyl acrylate 180 parts of unsaturated photosensitive compound 2 900 parts of azobisisobutyronitrile 50 parts Was dripped evenly over 4 hours. Next, the mixture was kept at 105 ° C. for 30 minutes, and then 6 parts of azobisisobutyronitrile and 40 parts of diethylene glycol dimethyl ether 40
Part of the mixture was added dropwise over 30 minutes, and the mixture was maintained at 105 ° C. for 1 hour to obtain photosensitive resin A-6. Solid content 40% Photosensitive group concentration / 0.1 kg / kg solid content
The molecular weight was 57 mol, the hydroxyl value was 88, and the molecular weight was 10,000.

Synthesis Example of Photosensitive Resin A-7 590 parts of xylene was placed in a four-necked flask equipped with a stirrer, a cooling tube, a gas blowing tube and a thermometer, and nitrogen gas was blown into the gas phase to 105 ° C. while stirring. The temperature was raised, and then a mixture of 300 parts of methyl methacrylate, 300 parts of n-butyl acrylate, 180 parts of n-butyl methacrylate, 130 parts of ethyl acrylate, 90 parts of isocyanate ethyl methacrylate, and 30 parts of azobisisobutyronitrile was dropped uniformly over 4 hours. did. Next, the mixture was kept at 105 ° C. for 30 minutes, and then a mixed solution consisting of 6 parts of azobisisobutyronitrile and 40 parts of xylene was added dropwise over 30 minutes, and further kept at 105 ° C. for 1 hour to obtain a polymer. Was. Next, 550 parts of diethylene glycol dimethyl ether was added, the xylene solvent was distilled off with a vacuum pump while maintaining the temperature at 60 ° C. to 70 ° C., and 550 parts of diethylene glycol dimethyl ether was further added. After the temperature was raised to 60 ° C, the photosensitive compound 1 was added to the polymer solution.
178 parts and 1 part of dibutyltin dilaurate, and 3
After stirring and holding for a time, it was confirmed that the absorption of the isocyanate group near 2250 cm ^-1 in the IR spectrum disappeared, and photosensitive resin A-7 was obtained. Solid content 50% Photosensitive group concentration / 0.48 mol / kg solid content, and molecular weight 8,000.

Synthesis Example of Photosensitive Resin A-8 Diethylene glycol dimethyl ether 7 was placed in a four-necked flask equipped with a stirrer, cooling tube, gas blowing tube and thermometer.
Add 20 parts, add nitrogen gas into the gas phase and stir while stirring.
The temperature was raised to 10 ° C., followed by methyl methacrylate 300 parts n-butyl acrylate 470 parts n-butyl methacrylate 80 parts acrylic acid 30 parts m-isopropenyl-α, α-dimethylhexyl isocyanate 120 parts t-butyl peroxyoctoate 50 Part of the mixture was added dropwise over 4 hours. Next, the mixture was kept at 110 ° C. for 30 minutes, then a mixed solution composed of 6 parts of t-butyl peroxyoctoate and 50 parts of diethylene glycol dimethyl ether was added dropwise over 30 minutes. A mixture of 6 parts and 50 parts of diethylene glycol dimethyl ether was added dropwise over 30 minutes, and the mixture was further maintained at 110 ° C. for 1 hour to obtain a polymer. This ethylene glycol dimethyl ether was added, after a temperature of 60 ° C., after the polymer solution to photosensitive compound 1 183 parts of 1 part of dibutyltin dilaurate was added 3 hours stirring holding, in the vicinity of 2250 cm ^-1 of the IR spectrum It was confirmed that the absorption of isocyanate groups disappeared, and photosensitive resin A-8 was obtained. Solid content 50% Photosensitive group concentration / 0.48 mol / kg of solid content, acid value 18, number average molecular weight 8,000.

Synthesis Example of Photosensitive Resin A-9 Diethylene glycol dimethyl ether 4 was placed in a four-necked flask equipped with a stirrer, cooling tube, gas injection tube and thermometer.
Introduce 00 parts and introduce nitrogen gas into the gas phase while stirring.
After the temperature was raised to 10 ° C., methyl methacrylate 300 parts n-butyl acrylate 500 parts m-isopropenyl-α, α-dimethylbenzene isocyanate 200
A mixture consisting of 50 parts of t-butyl peroxyoctoate was added dropwise over 4 hours. After further maintaining at 110 ° C. for 1 hour, a mixed solution consisting of 6 parts of t-butyl peroxyoctoate and 50 parts of diethylene glycol dimethyl ether was added dropwise over 30 minutes, and again 6 parts of t-butyl peroxyoctoate and 50 parts of diethylene glycol dimethyl ether were added. 3 parts of the mixture
The polymer was obtained by dropping over 0 minutes and further maintaining at 110 ° C. for 1 hour. After 440 parts of ethylene glycol dimethyl ether was added thereto and the temperature was brought to 60 ° C., 178 parts of photosensitive compound 1 and 1 part of dibutyltin dilaurate were added to the polymer solution, and after stirring and holding for 3 hours,
49 parts of hydroxypivalic acid was added, and the mixture was further stirred at 60 ° C. for 3 hours. It was confirmed that the absorption of the isocyanate group near 2250 cm ^{-1 in the} IR spectrum disappeared, and photosensitive resin A-9 was obtained. Solid content 50% Photosensitive group concentration / 0.45 mol / kg solid content, molecular weight 8,000.

Synthesis Example of Photosensitive Resin A-10 Diethylene glycol dimethyl ether 4 was placed in a four-necked flask equipped with a stirrer, cooling tube, gas blowing tube and thermometer.
50 parts are charged and nitrogen gas is blown into the gas phase while stirring.
After the temperature was raised to 0 ° C., a mixture consisting of 300 parts of methyl methacrylate, 300 parts of n-butyl acrylate, 140 parts of ethyl acrylate, 180 parts of hydroxyethyl acrylate, 1040 parts of an unsaturated photosensitive compound, and 150 parts of azobismethoxydimethylvaleronitrile was applied over 4 hours. Drip evenly. After further holding at 60 ° C. for 1 hour, a mixed solution composed of 10 parts of azobismethoxydimethylvaleronitrile and 40 parts of diethylene glycol dimethyl ether was added dropwise over 30 minutes,
Once again, a mixed solution consisting of 6 parts of azobismethoxydimethylvaleronitrile and 50 parts of diethylene glycol dimethyl ether was added dropwise over 30 minutes, and further kept at 60 ° C. for 1 hour to obtain photosensitive resin A-10. Solid content 48%, Photosensitive group concentration / 0.40mo per 1kg solid content
1, the hydroxyl value was 66, and the number average molecular weight was 4,000.

Synthesis Example of Photosensitive Resin A-11 700 parts of xylene was placed in a four-necked flask equipped with a stirrer, a cooling tube, a gas injection tube and a thermometer, and nitrogen gas was blown into the gas phase to 110 ° C. while stirring. The temperature was raised, followed by 300 parts of methyl methacrylate, 500 parts of n-butyl acrylate, 100 parts of n-butyl methacrylate, 100 parts of m-isopropenyl-α, α-dimethylbenzene isocyanate, 100 parts of t-butyl peroxyoctoate, 100 parts of dodecyl mercaptan. The mixture was evenly dropped over 4 hours. Next, after maintaining at 110 ° C. for 30 minutes, a mixed solution composed of 6 parts of t-butyl peroxyoctoate and 50 parts of diethylene glycol dimethyl ether was added dropwise over 30 minutes, maintained for 30 minutes, and then again with t-butyl peroxyoctoate. A mixture of 6 parts and 50 parts of diethylene glycol dimethyl ether was added dropwise over 30 minutes, and the mixture was maintained at 110 ° C. for 2 hours to obtain a polymer. 450 parts of diethylene glycol dimethyl ether was added to this,
After the temperature was reduced to 0 ° C., 1 part of photosensitive compound 1 was added to the polymer solution.
After adding 83 parts and 1 part of dibutyltin dilaurate with stirring and maintaining for 3 hours, it was confirmed that the absorption of isocyanate groups near 2250 cm ^{-1 in} the IR spectrum disappeared, and photosensitive resin A-11 was obtained. Solid content 50% Photosensitive group concentration / Solid content 1k
It was 0.40 mol / g and the number average molecular weight was 3,000.

Example of Synthesis of Resin B-1 In a four-necked flask equipped with a stirrer, a cooling pipe, a gas injection pipe and a thermometer, 6 parts of propylene glycol methyl ether was added.
Put 35 parts, add nitrogen gas into the gas phase and stir while stirring.
The temperature was raised to 10 ° C., and a mixture of 233 parts of styrene, 358 parts of n-butyl acrylate, 207 parts of n-butyl methacrylate, 122 parts of acrylic acid, 80 parts of hydroxyethyl acrylate, and 20 parts of azobisisobutyronitrile was dropped over 4 hours. Further 110
After holding at 30 ° C for 30 minutes, azobisisobutyronitrile
A mixed solution composed of 5 parts and 40 parts of diethylene glycol dimethyl ether was added dropwise over 30 minutes, and the mixture was further added for 110 hours.
The resin B-1 was obtained by keeping at ℃. Number average molecular weight 16,000, resin acid value 93, hydroxyl value 36, solid content 6
It was 0%.

Synthetic Examples of Resins B-2 to B-4 Except for the following composition, the same procedure was carried out as for the dispersion resin B-1, except that the monomer composition in the resin and the amount of the initiator were changed. All the same. Table 1 shows the monomer composition and resin special values.

[0073]

[Table 1] Table 1

Example 1 109 parts of photosensitive resin A-1 83 parts of resin B-2 58 parts of propylene glycol methyl ether 58 parts of the above mixture was mixed with a copper-clad laminate (100 mm) for a printed wiring board.
X 150 mm x 1 mm) on a bar coater, 10
Heating was performed at 0 ° C. for 10 minutes to obtain a resist film having a thickness of about 8 μm. Next, a polyester positive pattern film having a black-and-white pattern with a line / space of 30 μm / 30 μm to 150 μm / 150 μm is adhered under vacuum,
Exposure was performed at 150 mJ / cm ² using a 3 KW high-pressure mercury lamp. Next, the film was immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1.5 times as long as the time for dissolving the exposed portion, washed with water, and developed. Then, after the copper exposed by cupric chloride was removed by etching, the remaining resist film was removed with a 4% aqueous sodium hydroxide solution at 50 ° C. to obtain an etching pattern. In the tested test substrate, a good etching pattern was obtained at 30 μm / 30 μm or more without any pattern peeling defects or copper residue. After the paint was stored at 30 ° C. for 2 months, the resist performance was confirmed. The performance was the same as the initial performance and was good.

Examples 2 to 5 The formation, exposure, development and etching of a liquid resist film were carried out in the same manner as in Example 1 based on the formulations shown in Table 2 below. Table 2 shows the results of the performance evaluation. Example 6 87 parts of photosensitive resin A-1 100 parts of resin B-1 0.2 parts of benzotriazole 2.7 parts of triethylamine was added to the above mixture while stirring to neutralize the mixture, and then the mixture was stirred for 2000 to 30 using a stirrer.
Deionized water was slowly added dropwise while stirring at 00 rpm to obtain a stable emulsion solution having a solid content of 10%. Examples 7 to 8 and 10 to 11 and Comparative Examples 1 and 2 Stable emulsion solutions having a solid content of 10% were obtained in the formulations shown in Table 2 by the same method as in Example 6.

Example 9 87 parts of photosensitive resin A-1 100 parts of resin B-1 0.2 parts of benzotriazole Polyvinyl phenol having a number average molecular weight of about 5,000 dissolved in the above mixture in 15 parts of ethylene glycol monobutyl ether ( After adding 4 parts of Marullinker M) (manufactured by Maruzen Petrochemical Co., Ltd.) and adding 2.7 parts of triethylamine with stirring to neutralize the mixture, the mixture was stirred with a stirrer at 1500 to 3000 r.
Deionized water was slowly added dropwise while stirring at pm to obtain a stable emulsion solution having a solid content of 10%.

The emulsion solution obtained in Example 6 was
In a room maintained at 5 ° C, a copper-clad laminate having a copper-plated through hole of 0.3 mm mΦ ((100 mm x 150 m
After applying a direct current of 60 mA / dm ² between the counter electrodes for 60 seconds, the laminate (substrate) was taken out of the bath, washed with water, drained at 90 ° C. for 10 minutes, and dried. 8μm
Was obtained. The coating appearance was good. Next, the line / space is increased from 30 μm / 30 μm to 150 μm.
A polyester positive pattern film having a black / white pattern of μm / 150 μm was adhered under vacuum and exposed to 150 mJ / cm ² using a 3 KW high-pressure mercury lamp. Next, the film was immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1.5 times as long as the time for dissolving the exposed portion, washed with water, and developed. Then, after the copper exposed by cupric chloride was removed by etching, the remaining resist film was removed with a 4% aqueous sodium hydroxide solution at 50 ° C. to obtain an etching pattern.

The test substrate tested had a good etching pattern of 30 μm / 30 μm or more with no peeling defect or copper residue and complete plating in the through hole. After the paint was stored at 30 ° C. for 2 months, the resist performance was confirmed, and the performance was equivalent to the initial performance.
It was good.

In Examples 7 to 11 and Comparative Examples 1 and 2, the same test as in Example 6 was performed, and the results shown in Table 3 were obtained. In Examples 7 to 11, as in Example 6, a good etching pattern was obtained with 30 μm / 30 μm or more, no peeling defects or copper residue, and complete plating in the through holes.
After the paint was stored at 30 ° C. for 2 months, the resist performance was confirmed. The performance was the same as the initial performance and was good. In Comparative Examples 1 and 2, peeling defects and the like were produced in the etching pattern of 50 μm / 50 μm or less, and plating in the through holes was partially defective. After the paint was stored at 30 ° C. for 2 months, the resist performance showed the same performance as the initial performance. Table 2

[0080]

[Table 2]

Table 3

[0082]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/42 G03F 7/42 F term (Reference) 2H025 AA00 AA01 AB15 AC01 AC08 AD03 BE02 CB13 CB14 CB42 CB43 FA03 FA10 FA17 FA40 FA48 2H096 AA26 BA10 BA20 CA05 CA12 CA20 EA02 GA08 HA17 JA04 LA02

Claims (5)

[Claims] (1) The following formula: In the above formula, X is Or And R ₁ represents an alkyl group, a cycloalkyl group or an alkyl ether; and R ₂ represents a linear, branched or cyclic hydrocarbon-containing alkylene group having 1 to 12 carbon atoms. And the concentration of the photosensitive group is 1K
Number average molecular weight 6,000 to 0.1 to 1.0 mol per g
A positive-type photosensitive resin composition comprising 100,000 photosensitive acrylic resin (A) and (2) a water-soluble or water-dispersible acrylic resin composition (B) having a salt-forming group. 2. The positive photosensitive resin composition according to claim 1, wherein the salt-forming group is a carboxyl group. 3. A step of applying the positive photosensitive resin composition according to claim 1 or 2 to a substrate to form a positive photosensitive film on each substrate, and applying a pattern mask to the positive photosensitive film. A step of exposing an image directly or through a UV laser, and a step of developing the exposed positive photosensitive film with a basic developer in order. 4. A step of coating the photosensitive resin composition according to claim 1 or 2 on a substrate or a metal plate having an electrically conductive film to form a positive photosensitive film on the substrate. Exposing a conductive film through a pattern mask, or exposing an image directly with a laser beam, developing the exposed positive-type photosensitive film with a basic developer, a conductive film or metal plate exposed after development A method of forming a resist pattern, comprising sequentially performing a step of etching a surface and a step of removing a photosensitive film on a pattern. 5. A method for forming a resist pattern according to claim 4, wherein the photosensitive resin composition according to claim 1 or 2 is coated on a substrate or a metal plate having a conductive film by an electrodeposition method.