JPH0616978A - Negative-type photosensitive electrodeposition coating resin composition, electrodeposition coating bath using the same and production of resist pattern - Google Patents

Abstract

PURPOSE:To provide a coating resin composition good in electrodeposition characteristics, capable of giving nega-type resist patterns of high degree of resolution free from portions left undeveloped, comprising a neutralized (meth) acrylic acid copolymer, water-insoluble initiator, and specific. benzotriazole derivative, etc. CONSTITUTION:The composition comprising (A) a polymer obtained by neutralizing with a basic organic compound (e.g. triethy1amine) a polymer 20-300 in acid value produced by (co)polymerizing acrylic acid and/or methacrylic acid, (B) a water-insoluble monomer having at least two photopolymerizable unsaturated bonds [e.g. trimethylolpropane di(meth)acrylate], (C) a water-insoluble photoinitiator [e.g. benzophenone] and (D) compound(s) of formula I and/or formula II (R<1> is H, halogen, etc.; R<2> is H, OH, etc.; R<4> is H, alkyl, etc.; n is 1-3). The amounts of the above components to be used are pref. as follows: (1) A: 60-75 pts.wt., B: 25-40 pts.wt., and C: 0.2-10 pts.wt., based on 100 pts.wt. of (A+B), respectively; and (2) D: 0.5-8 pts.wt. based on 100 pts.wt. of (A+B+C).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a negative type photosensitive electrodeposition coating, an electrodeposition coating bath using the same and a method for producing a resist pattern.

[0002]

2. Description of the Related Art When manufacturing a printed circuit board,
First, a layer of a photocurable resin composition is formed on a substrate, and then an actinic ray is imagewise irradiated to develop and remove an uncured portion,
A resist pattern is formed. In this process,
Various methods are adopted for forming the layer of the photocurable resin composition. For example, a method of using a photocurable resin composition solution (coating liquid) such as dip coating, roll coating, or curtain coating, or a method of laminating a film (photosensitive film) of the photocurable resin composition is known. Among these methods, the method of laminating a photosensitive film is currently used as a mainstream method because it can easily form a layer of a photocurable resin composition having a uniform thickness.

[0003]

Recently, as the density and precision of printed circuit boards have increased, higher quality resist patterns have become necessary. That is, it is desired that the resist pattern has no pinhole and is well adhered to the surface of the underlying substrate. It is known that there is a limit to the method of laminating the photosensitive film, which is the mainstream at present, with respect to such a demand. in this way,
Sufficient adherence due to poor followability to irregularities on the substrate surface caused by dents during manufacturing of the substrate, non-uniformity of polishing, mesh of glass cloth on the inner layer of the substrate, non-uniformity of copper plating bits on the surface, etc. It is difficult to get sex. This difficulty can be avoided by laminating the films under reduced pressure (see Japanese Patent Publication No. 59-3740), but this requires a special and expensive device.

For these reasons, solution coating methods such as dip code, roll coating and curtain coating have come to be reviewed again in recent years. However, these coating methods have problems that it is difficult to control the film thickness, the film thickness is not uniform, and pinholes occur.

Therefore, as a new method, a method of forming a photosensitive film by electrodeposition coating has been recently proposed (Japanese Patent Laid-Open No. 62-62160).
-235496 gazette). According to this method, the adhesiveness of the resist is improved, the conformability to irregularities on the substrate surface is good, a photosensitive film having a uniform film thickness can be formed in a short time, and the coating solution is an aqueous solution, so that the working environment is contaminated. Can be prevented and there are no problems in disaster prevention. Therefore, some proposals have recently been made regarding the composition of the electrodeposition bath suitable for this.

On the other hand, there are two kinds of electrodeposition coating methods, anion type and cation type, but the anion type is generally used because of the ease of the subsequent steps when manufacturing a printed circuit board. However, in the case of anionic type, the copper ions eluted from the copper clad laminate during electrodeposition coating form chelates with the carboxyl groups of the resist material and form a similar cross-linking. There is a problem in that it cannot be developed (hereinafter, referred to as undeveloped residue) when it is developed with an alkaline solution.

To solve this problem, compounds that form a chelate with copper, for example, β-diketones and acetoacetic acid esters (Japanese Patent Laid-Open No. 62-262856), and ethylenediaminetetraacetic acid or salts thereof are representative. It has been proposed to add aminopolycarboxylic acid (see JP-A-61-247090).

However, as a result of investigations by the present inventors, it has not been a sufficient solution, for example, the addition of these compounds may worsen the degree of residual development.

[0009]

Therefore, as a result of intensive studies by the present inventors, the addition of a compound having a carboxy group to benzotriazole capable of forming a chelate with copper has a remarkable effect on the residual development. I found what to show. When mere benzotriazole having no carboxyl group was added, no effect on the residual development was observed, so addition of a simple compound that forms a chelate with copper is insufficient for the residual development. Is clear. The detailed reason why the undeveloped residue is remarkably eliminated by the addition of the benzotriazole derivative having a carboxyl group according to the present invention is unknown, but it is dissolved in an alkali developer with a benzotriazole skeleton forming a chelate with copper,
Alternatively, it is presumed that one of the reasons for having the effect is to have both carboxyl groups that are easily dispersed.

Another major effect of the addition of the benzotriazole derivative having a carboxyl group according to the present invention is an improvement in electrodeposition property. That is,
When the benzotriazole derivative having a carboxyl group according to the present invention is added, the low voltage
Alternatively, a low-current, short-time electrodeposition film (photosensitive film) of a specified thickness
Is obtained. This is advantageous for improving productivity, saving energy and improving work safety.

By using the negative type photosensitive electrodeposition coating resin composition containing the benzotriazole derivative having a carboxyl group as described above, an electrodeposition coating bath having excellent electrodeposition property can be obtained and used. In forming the resist pattern, a high-resolution resist pattern with no development residue can be obtained.

That is, the present invention provides (a) a polymer obtained by neutralizing a polymer having an acid value of 20 to 300 obtained by copolymerizing acrylic acid and / or methacrylic acid with a basic organic compound,
(B) Water-insoluble monomer having two or more photopolymerizable unsaturated bonds in the molecule, (c) Water-insoluble photoinitiator, and (d)
Compounds represented by the following general formulas (I) and / or (II)

[Chemical 3] (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group, R ² represents a hydrogen atom,
Hydroxyl group, alkyl group, ester group, phenyl group or -X
-R ³ (wherein X is an alkylene group which may be substituted with a carboxyl group, a cycloalkylene group or an alkylene ether group, and R ³ is a hydroxyl group, an alkoxy group, a carboxyl group or a dialkylamino group), and n Is an integer of 1 to 3 (however, it may be 0 when R ² has a carboxyl group)

[Chemical 4] (In the formula, R ¹ has the same meaning as R ^{1 in} formula (I),
⁴ represents a hydrogen atom, an alkyl group or a phenyl group, and n
Represents an integer of 1 to 3), a negative photosensitive electrodeposition coating resin composition containing the same, an electrodeposition coating bath using the same, and an electroconductive substrate as an anode with a conductive substrate immersed in the electrodeposition coating bath. , Electrodeposition coating by energization to form an electrodeposition coating film on a conductive substrate,
Thereafter, an actinic ray is imagewise irradiated to the electrodeposition coating film, the exposed portion is photocured, the unexposed portion is removed by development, and a photocured resist pattern is formed to form a resist pattern. Regarding

The present invention will be described in detail below. The polymer as the component (a) is a polymer obtained by neutralizing a polymer having an acid value of 20 to 300 copolymerized with acrylic acid and / or methacrylic acid as an essential component with a basic organic compound.
Acrylic acid and methacrylic acid can be used alone or in combination of both, and the amount thereof is appropriately used so that the acid value of the polymer is in the range of 20 to 300. When the acid value of the polymer is less than 20, the water dispersion stability is poor when a basic organic compound is added to the photosensitive electrodeposition coating resin composition and then water is added to disperse the composition, and the composition easily precipitates. If the acid value of the polymer exceeds 300, the appearance of the electrodeposition film will be poor.

The polymer before neutralization may be, for example, methyl acrylate, in addition to acrylic acid and / or methacrylic acid.
Methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl methacrylate, cyclohexyl methacrylate, 2-
It can be obtained by copolymerizing one or more kinds of general polymerizable monomers such as hydroxyethyl acrylate, cyclohexyl methacrylate, acrylonitrile, styrene and vinyl chloride.

Among them, methyl methacrylate is preferable, and in particular, the total amount of the copolymerizable monomers constituting the polymer is 1
If it is used in an amount of 60 to 85 parts by weight relative to 00 parts by weight, the tackiness of the resist film is lost, scratches are less likely to occur, and even if the resist films are stacked, they do not stick together. Therefore, it is possible to stack substrates on which a resist film is formed. It is possible and preferable.

The synthesis of the polymer before neutralization is obtained by a general solution polymerization of the above-mentioned monomer in an organic solvent using a polymerization initiator such as azobisisobutyronitrile, azobisdimethylvaleronitrile and benzoyl peroxide. be able to. In this case, the organic solvent used is mainly a hydrophilic organic solvent such as dioxane, ethylene glycol monometal ether, propylene glycol monometal ether, ethylene glycol monoacetate, and diethylene glycol monoethyl ether acetate in consideration of being used for electrodeposition coating. It is preferable to use. If a hydrophobic organic solvent such as toluene, xylene or benzene is mainly used, it is necessary to distill off the solvent after the polymer synthesis and replace it with the hydrophilic solvent. Weight average molecular weight of the polymer before neutralization (standard polystyrene conversion) is 5,000 to 15
10,000 is preferable. If it is less than 5,000, the mechanical strength of the resist is weak, and if it exceeds 150,000, the electrocoating property tends to be poor and the appearance of the coating film tends to be poor.

The amount of the polymer used as the component (a) is 50 to 8 based on 100 parts by weight of the total amount of the components (a) and (b).
It is preferably 5 parts by weight, more preferably 60 to 75 parts by weight. If the amount used is less than 50 parts by weight, the mechanical strength of the resist is weak and the toughness is poor,
On the other hand, if it exceeds 85 parts by weight, the proportion of the photopolymerizable monomer which is the component (b) decreases, and the sensitivity to light tends to decrease.

As the water-insoluble monomer having two or more photopolymerizable unsaturated bonds in the molecule which is the component (b), for example, a polyhydric alcohol excluding polyethylene glycol condensed with one or more ethylene glycol, α, Compounds obtained by adding β-unsaturated carboxylic acid, for example, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol methahexa (meth) acrylate, etc., compounds obtained by adding α, β-unsaturated carboxylic acid to a glycidyl group-containing compound, for example, trimethylolpropane triglycidyl Ether triac Rate, bisphenol A diglycidyl ether di (meth) acrylate and the like, polycarboxylic acids such as phthalic anhydride and a substance having a hydroxyl group and an ethylenically unsaturated group, such as esterification products of β-hydroxyethyl (meth) acrylate and the like Further, a urethane diacrylate compound having a urethane skeleton and the like can also be used, and in any case, it is only required to be water-insoluble and curable by light irradiation.

In that sense, hydrophilic monomers such as (poly) ethylene glycol diacrylate are outside the scope of the present invention. These can be used alone or in combination of two or more.

The amount of the component (b) used is 15 to 50 parts by weight based on 100 parts by weight of the total amount of (a) and (b),
It is preferably in the range of 25 to 40 parts by weight. If the amount used is less than 15 parts by weight, the sensitivity to light decreases, and if it exceeds 50 parts by weight, the resist tends to become brittle.

Examples of the water-insoluble photoinitiator or photoinitiator system as the component (c) include, for example, benzophenone, N,
Aromatic ketones such as N'-tetramethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrenequinone, benzoin methyl ether, benzoin ethyl ether, benzoinphenyl Benzoin ether such as ether, benzoin such as methylbenzoin and ethylbenzoin, 2- (o-chlorophenyl)-
4,5-Diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl)
Examples thereof include imidazole dimer and 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer. These can be used alone or in combination of two or more.

The amounts of components (c) used are (a) and (b)
Is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight. If the amount used is less than 0.1 parts by weight, the sensitivity to light tends to decrease, and if it exceeds 15 parts by weight, the light absorption on the surface of the composition increases during exposure, resulting in insufficient internal photocuring. Tends to become.

The components (b) and (c) must be water insoluble. If it is water-soluble, it becomes difficult to perform electrodeposition coating in a state of being uniformly mixed with other components.

The general formulas (I) and (I) which are components of (d)
The compounds represented by I) are exemplified below.

[0025]

[Chemical 5]

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

One or more of these compounds may be mixed and used. The amount of the component (d) used is (a), (b)
The total amount of (c) and (c) is preferably 0.1 to 15 parts by weight, and more preferably 0.5 to 8 parts by weight. If the amount used is less than 0.1 part by weight (d)
The effect of eliminating the development residue and improving the electrodeposition property due to the addition of the components is small, and if it exceeds 15 parts by weight, the stability of the electrodeposition bath tends to decrease.

The photosensitive electrodeposition coating resin composition of the present invention may contain a coloring agent such as a dye or a pigment. Examples of the colorant include fuchsin, auramine base, crystal violet, Victoria pure blue, malachite green, methyl orange, acid violet R.
RH or the like is used.

Further, the photosensitive resin composition of the present invention comprises
You may add a thermal-polymerization inhibitor, a plasticizer, an adhesion promoter, an inorganic filler, etc.

To prepare the electrodeposition coating bath containing the components (a), (b), (c) and (d) described above, first, the components (a), (b), (c) and (d) are prepared. Is preferably a solution in which the above-mentioned hydrophilic organic solvent is uniformly dissolved. In this case, the hydrophilic organic solvent used when synthesizing the polymer (polymer precursor of the component (a)) before neutralization may be used as it is, and once the synthesis solvent is distilled off, another hydrophilic organic solvent is used. May be added. Moreover, two or more kinds of hydrophilic organic solvents may be used. The amount of the hydrophilic organic solvent used is the solid content 1 including the components (a), (b), (c) and (d).
The amount is preferably 300 parts by weight or less with respect to 00 parts by weight. Next, a basic organic compound is added to the above solution to neutralize the carboxyl groups contained in the polymer before neutralization, thereby preparing a polymer that is easily water-solubilized or dispersed. be able to.

The basic organic compound used here is not particularly limited, but examples thereof include triethylamine, monoethanolamine, diethanolamine, diisopropylamine, dimethylaminoethanol, and morpholine. These may be used alone or in combination of two or more. Can be used.

The amount of the basic organic compound used is 0. 1 with respect to 1 equivalent of the carboxyl group in the polymer before neutralization.
3 to 1.0 equivalent is preferable, and 0.4 to 1.0
It is more preferable that the amount is equivalent. If it is less than 0.3 equivalent, the water dispersion stability of the electrodeposition coating bath tends to decrease, and 1.0
If it exceeds the equivalent weight, the thickness of the coating film after electrodeposition coating tends to be thin, and the appearance tends to deteriorate.

Further, basic inorganic compounds such as sodium hydroxide and potassium hydroxide are liable to be hydrolyzed in the negative photosensitive electrodeposition coating resin composition, and therefore it is preferable not to use them.

The electrodeposition coating bath can be usually prepared by adding water to a negative photosensitive electrodeposition coating resin composition and dissolving or dispersing it in water. The solid content of the electrodeposition coating bath is 5 to 20% by weight, and the pH is 6.0 to 9.
The range of 0 is preferable from the viewpoint of bath management, electrodeposition property, and the like. In order to adjust the pH to the above preferred range, the basic organic compound may be added later to adjust the pH.

In order to improve the water dispersibility and dispersion stability of the electrodeposition coating bath containing the negative photosensitive electrodeposition coating resin composition, a nonionic surfactant, a cationic surfactant, and an anionic surfactant are used. Agents and the like can be added as appropriate.

Hydrophobic solvents such as toluene, xylene, and 2-ethylhexyl alcohol can be appropriately added to increase the coating amount during electrodeposition coating.

In order to carry out electrodeposition coating on a conductive substrate using the electrodeposition coating bath thus obtained, the conductive substrate is immersed as an anode in the electrodeposition coating bath, and usually 50 to 400 V is applied.
Is applied for 10 seconds to 5 minutes. The film thickness of the obtained coating film is preferably 5 to 50 μm.
At this time, it is desirable to control the temperature of the electrodeposition coating bath to 15 to 30 ° C.

After electrodeposition coating, the article to be coated is pulled out from the electrodeposition coating bath, washed with water, drained, and then dried with hot air or the like. At this time, if the drying temperature is high, the coating film is heat-cured, and a part of the film remains undeveloped in the developing step after exposure. Therefore, it is usually desirable to dry at 110 ° C. or lower.

On the electrodeposition coating film thus obtained, a film of a water-soluble polymer such as polyvinyl alcohol is used in an amount of about 1 in order to protect the film and prevent the inhibition of curing by oxygen during the next exposure. You may form with a film thickness of about 10 micrometers.

Then, the coated film is irradiated with an actinic ray in an image-wise manner, the exposed portion of the coated film is photocured, and the unexposed portion is removed by development to obtain a photocured resist pattern. As a light source of actinic rays, a wavelength of 300 to 450n
Those that emit m rays, such as mercury vapor arc, carbon arc, and xenon arc are preferably used.

The development can be carried out by spraying an alkaline water such as sodium hydroxide, sodium carbonate or potassium hydroxide, or by immersing the alkaline water.

[0050]

The present invention will be described with reference to the following examples. Example 1 1130 g of dioxane was added to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introducing tube, and the mixture was heated to a temperature of 90 ° C. while blowing nitrogen gas while stirring. When the temperature became constant at 90 ° C, 169 g of methacrylic acid, 250 g of methyl methacrylate, 381 g of n-butyl acrylate, 20 of ethyl methacrylate.
A liquid obtained by mixing 0 g and 10 g of azobisisobutyronitrile was dropped into the flask over 2.5 hours, and then the temperature was kept stirring at 90 ° C. for 3 hours. After 3 hours, a solution prepared by dissolving 3 g of azobisisobutyronitrile in 100 g of dioxane was dropped into the flask over 10 minutes, and then, the temperature was kept stirring again at 90 ° C. for 4 hours.

The polymer as a precursor of the component (a) thus obtained has a weight average molecular weight of 55,000.
The acid value was 0 and 109. The solid content of the polymer solution was 45.1% by weight.

Next, 650 g of this polymer solution was added with EO-modified bisphenol A dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK ester BPE-20) as component (b).
0) 150 g and hexanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK ester HD) 25
g, 30 g of benzophenone as the component (c) and N,
1 g of N'-tetraethyl-4,4'-diaminobenzophenone, the above-mentioned compound (I-1) as component (d)
5 g was added and dissolved.

To this solution, 31.8 g of dimethylaminoethanol as a basic organic compound was added and dissolved to neutralize the precursor polymer of the component (a) in the solution. Then,
While stirring this solution, 4,200 g of ion-exchanged water was gradually added dropwise to obtain an electrodeposition coating bath. The solid content of the electrodeposition coating bath was 10% by weight, and the pH was 7.85 at 25 ° C.

Example 2 To a flask equipped with the same apparatus as in Example 1, 1,130 g of ethyl cellosolve was added and stirred, and the temperature was raised to 90 ° C. while blowing nitrogen gas. When the temperature became constant at 90 ° C, 230 g of methacrylic acid, 367 g of methyl methacrylate, 250 g of ethyl acrylate, 153 g of methyl acrylate and 10 of azobisisobutyronitrile
The liquid in which g was mixed was dropped into the flask over 2 hours.
Then, the mixture was kept warm at 90 ° C. for 3 hours with stirring. After 3 hours, a liquid obtained by mixing 5 g of azobisisovaleronitrile with 100 g of ethyl cellosolve was added dropwise into the flask over 10 minutes, and then the temperature was maintained again at 90 ° C. for 4 hours with stirring.

The weight average molecular weight of the polymer as the precursor of the component (a) thus obtained was 4100.
The acid value was 0 and the acid value was 157. The solid content of the polymer solution was 45.3% by weight.

Next, (b) was added to 557 g of this polymer solution.
As components, 150 g of epoxy acrylate (manufactured by Osaka Organic Chemical Industry, trade name VISCOAT 540) and urethane acrylate (manufactured by Shin-Nakamura Chemical Industry, trade name U-108-
A) 60 g, benzophenone 33 g as component (c)
And 0.8 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 15 g of the compound (I-26) as the component (d) were added and dissolved, and morpholine as a basic organic compound was added to the solution. 39 g was added to neutralize the polymer as the precursor of the component (a) in the solution, and 100 g of n-butanol was further added and dissolved.

Then, while stirring this solution, 4,100 g of ion-exchanged water was gradually added dropwise to obtain an electrodeposition coating bath. The solid content of this electrodeposition coating bath is 10% by weight, pH
Was 7.48 at 25 ° C.

Example 3 900 g of ethyl cellosolve was added to a flask equipped with the same apparatus as in Example 1, stirred, and heated to a temperature of 90 ° C. while blowing nitrogen gas. When the temperature remained constant at 90 ° C, 141 g of acrylic acid and 5 of methyl methacrylate
1.10 g, n-propyl acrylate 320 g, methyl acrylate 29 g and azobisisobutyronitrile 2.
A liquid obtained by mixing 5 g was dropped into the flask over 2 hours,
After that, the temperature was kept stirring for 3 hours at 90 ° C. After 3 hours, a solution prepared by dissolving 1.0 g of azobisisobutyronitrile in 100 g of ethyl cellosolve was added dropwise into the flask over 10 minutes, and then the temperature was again maintained at 90 ° C. for 4 hours while stirring.

The polymer as a precursor of the component (a) thus obtained had a weight average molecular weight of 62,000.
The acid value was 107. The solid content of the polymer solution is 5
It was 0.3% by weight.

Next, 750 g of this polymer solution was mixed with 10 parts of pentaerythritol tetraacrylate (manufactured by Sartomer Company, trade name SR-295) as the component (b).
0 g and trisacryloxyethyl isocyanurate (manufactured by Hitachi Chemical Co., Ltd., trade name FA-731A) 25
g, 30 g of benzophenone as the component (c) and N,
N′-tetraethyl-4,4′-diaminobenzophenone 1 g, the compound (I-1) described above as the component (d)
2.5 g was added and dissolved, and 16 g of triethylamine as a basic organic compound was added and dissolved in this solution to neutralize the polymer as the precursor of the component (a) in the solution. Then, while stirring this solution, 4,400 deionized water was added.
g was gradually added dropwise to obtain an electrodeposition coating bath. This electrodeposition coating bath has a solid content of 10% by weight and a pH of 25 ° C. of 7.
It was 75.

Example 4 1,130 g of propylene glycol monopropyl ether was added to a flask equipped with the same apparatus as in Example 1 and stirred, and the temperature was raised to 100 ° C. while blowing nitrogen gas. When the temperature became constant at 100 ° C., 192 g of methacrylic acid, 780 g of methyl methacrylate, 28 g of ethyl acrylate and 10 of azobisisobutyronitrile
The liquid in which g was mixed was dropped into the flask over 3 hours, and then the temperature was kept for 3.5 hours with stirring at 100 ° C.
After 3.5 hours, a solution prepared by dissolving 5 g of azobisdimethylvaleronitrile in 100 g of propylene glycol monopropyl ether was added dropwise into the flask over 10 minutes, and then the temperature was again maintained at 100 ° C. for 4 hours while stirring.

The polymer as a precursor of the component (a) thus obtained had a weight average molecular weight of 35,000.
The acid value was 125. The solid content of the polymer solution was 45.3% by weight.

Next, to 700 g of this polymer solution, 80 g of dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku) as the component (b), 30 g of benzophenone as the component (c) and N, N'-tetraethyl-4. , 4'-diaminobenzophenone 1 g, the compound (I-1) 8 g as the component (d) and propylene glycol monomethyl ether 100 g were added and dissolved, and triethylamine 22 g was added as a basic organic compound to the solution and further dissolved. Then, the polymer as the precursor of the component (a) in the solution was neutralized.

Next, while stirring this solution, 3,700 g of ion-exchanged water was gradually added dropwise to obtain an electrodeposition coating bath. The solid content of this electrodeposition coating bath is 9.5% by weight,
The pH was 7.52 at 25 ° C.

Comparative Example 1 An electrodeposition coating bath was obtained by using the same material and method as in Example 1 except that the compound (I-1) as the component (d) was not added.

Comparative Example 2 An electrodeposition coating bath was obtained by using the same material and method as in Example 1 except that 5 g of benzotriazole was added instead of the component (d).

Comparative Example 3 An electrodeposition coating bath was obtained by using the same material and method as in Example 1 except that 5 g of acetylacetone was added instead of the component (d).

Comparative Example 4 An electrodeposition coating bath was obtained by using the same material and method as in Example 1 except that 5 g of ethylenediaminetetraacetic acid was added instead of the component (d).

Glass epoxy copper clad laminates (Hitachi Chemical Co., Ltd.) were used in each of the electrodeposition coating baths of Examples 1 to 4 and Comparative Examples 1 to 4.
Made MCL-E-61) (200 mm x 75 mm) as an anode, stainless steel plate (SUS304) (shape 200 mm x 7)
5 mm × 1 mm) was immersed as a cathode, and a DC voltage was applied at a temperature of 25 ° C. for 3 minutes to form an electrodeposition coating film (photosensitive film) on the surface of the copper clad laminate. The applied voltage and the film thickness of the electrodeposition coating film at this time are shown in Table 1. After that, it was washed with water, drained and dried at 80 ° C. for 15 minutes.

This product was imagewise exposed to a light amount of 60 mJ / cm ² with a 3 kW ultrahigh pressure mercury lamp through a negative mask, and then developed with a 1 wt% sodium carbonate aqueous solution. At this time, for the purpose of confirming the presence or absence of residual development, the developed substrate was immersed in a 1 wt% copper chloride aqueous solution for 1 minute, and the degree of etching of the unexposed portion of the substrate was visually observed. The results are shown in Table 1.

[0071]

[Table 1]

From Table 1, Examples 1 to 4 containing the benzotriazole derivative having a carboxyl group according to the present invention are shown.
It can be seen that, in comparison with Comparative Example 1 which does not contain it, a film thickness equal to or higher than that of Comparative Example 1 was obtained at a low voltage, and the electrodeposition property was improved.

On the other hand, Comparative Example 2 in which another chelating agent was added
In the case of Nos. 4 to 4, the electrodeposition property was equivalent to that of Comparative Example 1, and the addition of the chelating agent did not necessarily lead to the improvement of the electrodeposition property. It can be said that this is one of the major features of the addition of the benzotriazole derivative having a carboxyl group.

Further, in the case of Comparative Example 1, the etching property of the unexposed portion is not completely etched and there is a development residue.
Comparative Examples 2 and 3 to which mere benzotriazole and acetylacetone were added showed that etching was scarcely performed and development residue was rather deteriorated as compared with Comparative Example 1 in which no benzotriazole or acetylacetone was added.

On the other hand, in Examples 1 to 4 in which the benzotriazole derivative having a carboxyl group was added, it was found that the unexposed area was completely etched and there was no development residue. Also in this case, addition of the chelating agent does not always lead to elimination of the development residue as in the case of improving the electrodeposition property described above, and it can be said that the benzotriazole derivative having a carboxyl group according to the present invention has a great feature.

Of course, Examples 1 to 4 obtained after development
Had a good resist shape with a resolution of 50 μm.

The adhesiveness of the electrodeposition coating film after electrodeposition coating was the smallest in the resist of Example 4 among Examples 1 to 4, and even if the resists were superposed on each other, they did not adhere and were scratched. It was difficult.

[0078]

EFFECT OF THE INVENTION By the method for producing a resist pattern using an electrodeposition coating bath containing the negative photosensitive electrodeposition coating resin composition of the present invention, the electrodeposition property is improved as compared with the conventional one, and exposure,
By development, a high-resolution resist pattern having no development residue can be obtained.

The resist obtained by the method for producing a resist pattern of the present invention can be used as a relief, or can be applied to the formation of a photoresist for etching or plating by using a copper clad laminate as a substrate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication location G03F 7/085 H05K 3/00 F 6921-4E (72) Inventor Masahiko Hiroshi Higashimachi, Hitachi, Ibaraki Prefecture 13-13-1 Hitachi Chemical Co., Ltd. in Ibaraki Research Institute (72) Inventor Satoshi Akahori 4-13-1 Higashimachi, Hitachi City, Ibaraki Hitachi 72, Ltd. In Ibaraki Research Center (72) Inventor Takuro Kato Ibaraki Prefecture Hitachi City Higashimachi 4-chome 13-1 Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Inventor Hajime Kakumaru Hitachi City Ibaraki Prefecture Higashimachi 4-chome 13-1 Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Invention Yoshitaka Minami 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Inventor Yuji Yamazaki 1382-12 Shimoishigami, Otawara City, Tochigi Prefecture Dainippon Paint Inside the Nasu Factory (72) Inventor Toshiya Takahashi 1382-12 Shimoishigami, Otawara-shi, Tochigi Dainippon Paint Co., Ltd.Nasu Factory (72) Inventor Toshihiko Shioya 1382-12 Shimoishi, Otawara-shi, Tochigi Dainippon Paint Inside Nasu Factory (72) Inventor Yoshihisa Nagashima 1382-12 Shimoishigami, Otawara City, Tochigi Prefecture Dainippon Paint Co., Ltd. Inside Nasu Factory

Claims (3)

[Claims] 1. A polymer obtained by neutralizing (a) a polymer having an acid value of 20 to 300 obtained by copolymerizing acrylic acid and / or methacrylic acid with a basic organic compound, and (b) an intramolecular photopolymerizable unsaturated bond. A water-insoluble monomer having two or more in
(C) a water-insoluble photoinitiator, and (d) a compound represented by the following general formula (I) and / or (II): (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group, R ² represents a hydrogen atom,
Hydroxyl group, alkyl group, ester group, phenyl group or -X
-R ³ (where X is an alkylene group, cycloalkylene group or alkylene ether group which may be substituted with a carboxyl group, and R ³ is a hydroxyl group, an alkoxy group, a carboxyl group or a dialkylamino group), and n is ,
It represents an integer of 1 to 3 (however, it may be 0 when R ² has a carboxyl group). (In the formula, R ¹ has the same meaning as R ^{1 in} formula (I),
⁴ represents a hydrogen atom, an alkyl group or a phenyl group, and n
Represents an integer of 1 to 3). A negative photosensitive electrodeposition coating resin composition containing 2. An electrodeposition coating bath containing the negative photosensitive electrodeposition coating resin composition according to claim 1. 3. A conductive substrate as an anode is immersed in the electrodeposition coating bath according to claim 2, and electrodeposition coating is carried out by energization to form an electrodeposition coating film on the conductive substrate. A method for producing a resist pattern, which comprises irradiating an image on a coating film for coating, photo-curing the exposed part, and removing the unexposed part by development.