JPH05281723A - Negative photosensitive electrodeposition coating resin composition, electrodeposition coating bath using the same, and production of resist pattern - Google Patents

Abstract

PURPOSE:To obtain an electrodeposition coating bath having good electrodeposition property by using a negative electrodeposition coating resin compsn. containing a specified component, and to obtain a resist pattern of high resolution without incomplete development by using this bath. CONSTITUTION:This electrodeposition coating resin compsn. consists of polymers, non-water soluble monomers having two or more photopolymerizable unsatd. bonds in the molecule, non-water soluble photopolymn. initiator, and compd. expressed by formula and/or salt of this compd. with a basic compd. These polymers are prepared by neutralizing polymers having 20-300 acid value obtd. by copolymn. of acrylic acids and/or methacrylic acids with a basic org. compd. In the formula, Y is a carboxyl group or sulfonic acid group, R1 is a hydrogen atom, halogen atom, hydroxyl groups, etc., R2 is a hydrogen atom, alkyl group, cycloalkyl group, etc., and n is an integer 1-3. An electrodeposition coating film is formed on a conductive base body in an electrodeposition coating bath which uses this resin compsn. The coating film is then exposed and developed to obtain a resist pattern.

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 wiring 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 unexposed portion to form a resist pattern. In this step, various methods are adopted for forming the layer of the photocurable resin composition. For example, a method of applying a photocurable resin composition (coating liquid) by a coating method such as dip coating, roll coating, curtain coating, or a method of laminating a film (photosensitive film) of the photocurable resin composition is known. Has been. Among these methods, the method of laminating a photosensitive film is currently adopted 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 the printed circuit board have been increased, higher quality resist patterns have been required. 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 photosensitive films, which is the mainstream at present, with respect to such a demand. In this method, the followability to irregularities on the substrate surface caused by dents during manufacturing of the substrate, non-uniformity of polishing, mesh of the glass cloth of the inner layer of the substrate, non-uniformity of pits of copper plating on the surface, etc. is poor. , It is difficult to obtain sufficient adhesion. This difficulty is caused by laminating the films under reduced pressure (Japanese Patent Publication No. 59-3).
However, this requires a special and expensive device.

For these reasons, solution coating methods such as dip coating, 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, recently, as a new method, a method of forming a photosensitive film by electrodeposition coating has been proposed (JP-A-62-62).
-235496 gazette). According to this method (1)
The adhesiveness of the resist is improved, (2) the conformability to irregularities on the substrate surface is good, (3) a photosensitive film having a uniform film thickness can be formed in a short time, and (4) the coating liquid is an aqueous solution. Also, it has the advantage that it can prevent the pollution of the work environment and there is no problem 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 types of electrodeposition coating methods, anion type and cation type. Generally, the anion type is used because of the ease of the post-process 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 a chelate with the carboxyl groups of the resist material and form pseudo-crosslinking, so that the unexposed area is removed in the post-exposure step. There has been a problem that development cannot be performed when developing with alkali (hereinafter referred to as undeveloped).

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) and the like.

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

[0009]

Therefore, as a result of intensive studies by the present inventors, a compound and / or a compound in which benzothiazole capable of forming a chelate with copper has at least one of a carboxyl group and a sulfonic acid group It was found that the addition of a salt (component (d)) formed by the compound and the basic compound exerts a remarkable effect on the residual development. When mere benzothiazole or a salt thereof having no carboxyl group and / or sulfonic acid group was added, no effect on the development residue was observed, and therefore, a compound that forms a chelate with copper and / or the compound. It is clear that the addition of the salt formed with the basic compound is insufficient for the development residue. The detailed reason why the undeveloped residue is remarkably eliminated by the addition of the component (d) in the present invention is not clear, but a benzothiazole skeleton forming a chelate with copper and a carboxyl group and / or a sulfonic acid which are easily dissolved or dispersed in an alkaline developer. It is presumed that one of the reasons for having an effect is to have both groups.

Another major effect of the addition of the component (d) in the present invention is an improvement in electrodeposition property. That is, when the component (d) in the present invention is added, an electrodeposition film (photosensitive film) having a predetermined film thickness can be obtained in a short time at a low voltage or a low current, as compared with the case of no addition. This is advantageous for improving productivity, saving energy and improving work stability.

As described above, by using the negative electrodeposition coating resin composition containing the component (d) in the present invention, an electrodeposition coating bath having excellent electrodeposition can be obtained, and a resist pattern using the same. In the formation of, it is possible to obtain a high-resolution resist pattern with no development residue.

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)
A compound represented by the following general formula and / or a salt formed with the compound and a basic compound

[Chemical 2] (In the formula, Y represents a carboxyl group or a sulfonic acid group,
R ₁ is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkyl group or -X ₁ -R ₃ (wherein X ₁ is a carboxyl group or an alkylene group which may be substituted with a sulfonic acid group, and R ₃ is a carboxyl group. Or a sulfonic acid group), R ₂ is a hydrogen atom, an alkyl group, a cycloalkyl group, a mercapto group, an alkylthio group, a cycloalkylthio group or —S—X ₂ —R ₄ (where S is a sulfur atom) , X ₂ is an alkyl group, a cycloalkyl group, an alkylene group which may be substituted with a carboxyl group or a sulfonic acid group, a cycloalkylene group, an alkylamino group, a silloalkylamino group or an amino group, and R ₄ is an alkyl group , A cycloalkyl group, a carboxyl group or a sulfonic acid group) and n is an integer of 1 to 3 (provided that R ₁ or R ₂ is carboxy). A negative-type photosensitive electrodeposition coating resin composition, which contains 0) in the case of having a hydroxyl group or a sulfonic acid group), an electrodeposition coating bath using the same, and an electroconductivity in the electrodeposition coating bath. The electroconductive substrate is immersed as an anode, and the electrodeposition coating is performed by energizing to form an electrodeposition coating film on the electroconductive substrate.After that, the actinic ray is imagewise irradiated to the electrodeposition coating film, and the exposed portion is photocured. , A method for producing a resist pattern, which comprises removing the unexposed portion by development.

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 used is
It is appropriately used so that the acid value of the polymer is in the range of 20 to 300. If 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 tends to settle. If the acid value of the polymer exceeds 300, the appearance of the electrodeposited 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
When 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 to each other. 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 to be used should be a hydrophilic organic solvent such as dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoacetate, and diethylene glycol monoethyl ether acetate, considering that it will be used for electrodeposition coating. Is preferred. 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. The 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 will be weak, and if it exceeds 85 parts by weight, the proportion of the photopolymerizable monomer as the component (b) tends to decrease 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, α and β are added to polyhydric alcohols except polyethylene glycol condensed with one or more ethylene glycol. Compounds obtained by addition of unsaturated carboxylic acids, such as trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, Compounds obtained by adding α, β-unsaturated carboxylic acid to a glycidyl group-containing compound, such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, for example, trimethylolpropane triglycidyl ether triacryl , Bisphenol A diglycidyl ether di (meth) acrylate and the like, polycarboxylic acids such as phthalic anhydride and substances having a hydroxyl group and an ethylenically unsaturated group, for example ester compounds such as β-hydroxyethyl (meth) acrylate And the like, and further, a urethane diacrylate compound having a urethane skeleton and the like can be used, and in any case, a water-insoluble and curable by irradiation with light may be used.

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

The amount of the component (b) used is (a) and (b)
It is preferable that the amount is 15 to 50 parts by weight, preferably 25 to 40 parts by weight, based on 100 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 which is the component (c) include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone and 4-methoxy-.
Aromatic ketones such as 4′-dimethylaminobenzophenone, 2-ethylanthraquinone and phenanthrenequinone,
Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzoin such as methylbenzoin and ethylbenzoin, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) −
Examples include 4,5-di (m-methoxyphenyl) imidazole dimer and 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer. These may be used alone or in combination of two or more.

The amount of the component (c) used is preferably 0.1 to 15 parts by weight, and more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the total amount of (a) and (b). More preferable. 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. Tend to be.

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.

Specific examples of the compound represented by the general formula which is the component (d) are shown below.

[0026]

[Chemical 3]

[0026]

[Chemical 4]

[0027]

[Chemical 5]

[0028]

[Chemical 6]

[0029]

[Chemical 7]

[0030]

[Chemical 8]

These compounds may be used alone or in combination of two or more. In addition, salts formed from a carboxyl compound and / or a sulfonic acid group in these compounds and a basic compound can be similarly used. The basic compound for forming a salt is not particularly limited, but organic amines are preferable, for example, monoethanolamine, diethanolamine, diisopropylamine, dimethylaminoethanol, diethylamine, triethylamine, butylamine, tri-n-butylamine, Tri-n-octylamine, triphenylamine,
Examples include triethanolamine, dimethylethanolamine, propylamine, t-butylamine, pyridine, morpholine, piperidine, pyrrolidine monoethanolamine, diethanolamine, diisopropylamine, dimethylaminoethanol, etc., which may be used alone or in combination with 2
A mixture of more than one type can be used. The amount of the component (d) used is preferably 0.1 to 15 parts by weight based on 100 parts by weight of the total amount of (a), (b) and (c),
More preferably, it is 0.5 to 8 parts by weight. If the amount used is less than 0.1 part by weight, the effect of eliminating the undeveloped residue and improving the electrodeposition property due to the addition of component (d) is small, and if it exceeds 15 parts by weight, the stability of the electrodeposition coating 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 colorants 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
A thermal polymerization inhibitor, a plasticizer, an adhesion promoter, an inorganic filler, etc. may be added.

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. A solvent may be added. 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 to prepare 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. It can be used in combination.

The amount of these basic organic compounds used is 0.3 with respect to 1 equivalent of carboxyl groups in the polymer before neutralization.
It is preferable to set to 1.0 equivalent, and it is more preferable to set to 0.4 to 1.0 equivalent. If it is less than 0.3 equivalent, the water dispersion stability of the electrodeposition coating bath tends to decrease, and if it exceeds 1.0 equivalent, the coating film thickness 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. Solid content of electrodeposition coating bath is 5-20
From the viewpoints of bath management, electrodeposition properties, etc., it is preferable that the weight% and the pH are in the range of 6.0 to 9.0 at 25 ° C. 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 in the electrodeposition coating bath as an anode, and usually 50 to 400 V is applied.
Or a direct current of 30 to 400 mA / dm ² is applied for 10 seconds to 5 minutes. The film thickness of the obtained coating film is preferably 5 to 50 μm. The temperature of the electrodeposition coating bath at this time is preferably controlled to 15 to 30 ° C.

After the electrodeposition coating, the article to be coated is lifted 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 thermally cured, and a part of the film remains undeveloped in the developing step after exposure. Therefore, it is usually desirable to dry at 120 ° 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 coating film is irradiated with an actinic ray imagewise, the exposed portion of the coating 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 it in an alkaline water.

[0046]

EXAMPLES The present invention will be described below with reference to examples. Example 1 Ethyl cellosolve 1,130 was added to a flask equipped with a stirrer, a reflux condenser, a thermometer, an appropriate lower funnel and a nitrogen gas introducing tube.
g was added and stirred, and heated to a temperature of 90 ° C. while blowing nitrogen gas. When the temperature became constant at 90 ° C, 230 g of methacrylic acid, 240 g of methyl methacrylate,
A liquid in which 320 g of n-butyl acrylate, 210 g of methyl methacrylate and 10 g of azobisisobutyronitrile were 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 solution prepared by dissolving 3 g of azobisisovaleronitrile in 100 g of dioxane 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 has a weight average molecular weight of 40,000,
The acid value was 151. The solid content of the polymer solution is 4
It was 5.1% by weight.

Next, (b) was added to 680 g of this polymer solution.
As components, 100 g of urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name U-108-A) and epoxy acrylate (manufactured by Osaka Organic Chemical Industry, trade name Viscoat 54)
0) 25 g, benzophenone as component (c) 33 g
And 0.8 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 15 g of the compound (12) as the component (d) were added and dissolved, and 39 g of diethanolamine as a basic organic compound was added to the solution. In addition, the polymer of the precursor of the component (a) in the solution was neutralized, and 100 g of n-butanol was further added and dissolved.

Next, 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 7.5 at 25 ° C.

Example 2 1,130 g of dioxane was added to a flask equipped with the same apparatus as in Example 1 and heated to 90 ° C. while blowing nitrogen gas while stirring. When the temperature became constant at 90 ° C., a mixture of 226 g of methacrylic acid, 225 g of methyl methacrylate, 234 g of methyl acrylate, 315 g of ethyl methacrylate and 5 g of azobisisobutyronitrile was dropped into the flask over 2.5 hours, After that, the temperature was maintained for 3 hours with stirring at 90 ° C. After 3 hours, 3 g of azobisisobutyronitrile was added to 1 of dioxane.
The solution dissolved in 00 g was added dropwise into the flask over 10 minutes, and then the temperature was maintained again while stirring at 90 ° C. for 4 hours.

The polymer as a precursor of the component (a) thus obtained had a weight average molecular weight of 42,000.
The acid value was 145. The solid content of the polymer solution is 4
It was 5.1% by weight.

Next, 800 g of this polymer solution was added to (b)
150 g of hexanediol dimethacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., trade name NK ester HD) as a component,
30 g of benzophenone and N, N 'as the component (c)
-Tetraethyl-4,4'-diaminobenzophenone 1
g, 5 g of the triethylamine salt of the above-mentioned compound (7) as the component (d) was added and dissolved.

To this solution, 31.8 g of diethylamine 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, 4,800 g of ion-exchanged water was gradually added dropwise to obtain an electrodeposition coating bath. The solid content of this electrodeposition coating bath was 10% by weight, and the pH was 7.4 at 25 ° C.

Example 3 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. Acrylic acid 1 when the temperature becomes constant at 100 ℃
A liquid in which 80 g, 430 g of methyl methacrylate, 390 g of ethyl acrylate, and 10 g of azobisisobutyronitrile were mixed was dropped into the flask over 3 hours, and then the temperature was kept for 3.5 hours while stirring at 100 ° C. 3.5
After a lapse of time, a solution prepared by dissolving 5 g of azobisdimethylvaleronitrile in 100 g of propylene glycol monopropyl ether was dropped into the flask over 10 minutes, and then the temperature was again maintained at 90 ° C. for 4 hours with 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 is 4
It was 5.3% by weight.

Next, in 700 g of this polymer solution, as component (b), 120 g of dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku), 30 g of benzophenone as component (c) and N, N'-tetraethyl-4. , 4'-diaminobenzophenone 1 g, (d)
8 g of the above-mentioned compound (1) as a component and 100 g of propylene glycol monomethyl ether were added and dissolved, and 40 g of triethylamine as a basic organic compound was further dissolved in this solution to further dissolve the precursor of the component (a) in the solution. Was neutralized.

Next, 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 this electrodeposition coating bath is 10% by weight, pH
Was 7.4 at 25 ° C.

Comparative Example 1 In Example 1, the above-mentioned compound (1) as the component (d) was used.
An electrodeposition coating bath was obtained with the same materials and method except that 2) 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 benzothiazole was added instead of the component (d).

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

Glass epoxy copper clad laminates (Hitachi Chemical Co., Ltd.) were applied to the electrodeposition coating baths of Examples 1 to 3 and Comparative Examples 1 to 3.
Made MCL-E-61) (200 mm x 75 mm) as an anode, stainless steel plate (SUS304) (shape 200 m)
m × 75 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 ultra-high 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.

[0063]

[Table 1] Note 1) Etching of unexposed area ○: Good (no development residual) ×: Poor (developed residual) XX: Very poor (large development residual)

From Table 1, in Examples 1 to 3 containing the component (d) of the present invention, as compared with Comparative Example 1 not containing it, all of the films had a low voltage and a film thickness equal to or more than the above was obtained. It can be seen that the property has improved.

On the other hand, Comparative Example 2 in which another chelating agent was added
And 3 have the same electrodeposition property as in Comparative Example 1, and the addition of the chelating agent does not necessarily lead to the improvement of the electrodeposition property, and the improvement of the electrodeposition property seen in Examples 1 to 3 is This can be said to be one of the major features of the addition of the component (d) in the invention.

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.
In the cases of Comparative Examples 2 and 3 in which benzothiazole or acetylacetone was simply added, it was shown that etching was scarcely performed and the development residue was rather deteriorated as compared with Comparative Example 1 in which no benzothiazole or acetylacetone was added.

On the other hand, in the case of Examples 1 to 3 in which the component (d) in the present invention was added, it was found that the unexposed portion 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 component (d) in the present invention has a great feature.

Of course, Examples 1 to 3 obtained after development
Had a good resist shape with a resolution of 50 μm.

The adhesiveness of the electrodeposited film after electrodeposition coating was the smallest in the resist of Example 2 among Examples 1 to 3, and even if the resists were superposed on each other, they did not adhere to each other and scratched easily. It was

[0070]

The method for producing a resist pattern using an electrodeposition coating bath containing the negative-type photosensitive electrodeposition coating resin composition of the present invention improves the electrodeposition property as compared with the conventional method, and the 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 using a copper clad laminate as a substrate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09D 4/00 PDS 7921-4J 5/44 PRS 7211-4J 133/02 PGC 7921-4J C25D 13 / 06 B G03F 7/004 501 7/028 7/038 7/30 7124-2H H01L 21/027 H05K 3/00 F 6921-4E // C25D 13/00 310 (72) Inventor Hideaki Uehara Higashi Town, Hitachi City, Ibaraki Prefecture 4-13-1 Hitachi Chemical Co., Ltd. Ibaraki Research Laboratory (72) Inventor Shigeo Tachiki 4-13-1 Higashimachi, Hitachi City, Ibaraki Hitachi Chemical Co., Ltd. Ibaraki Research Laboratory (72) Inventor Takuro Kato Ibaraki 4-13-1 Higashimachi, Hitachi, Ltd. Yamazaki Plant, Hitachi Chemical Co., Ltd. (72) Inventor Katsushige Tsukada 4-13-1 Higashimachi, Hitachi City, Ibaraki Hitachi Chemical Co., Ltd. Yama (72) Inventor Yuji Yamazaki 1382-12 Shimoishikami, Otawara-shi, Tochigi Dainippon Paint Co., Ltd.Nasu Plant (72) Inventor Toshiya Takahashi 1382-12 Shimoishi, Otawara-shi, Tochigi Dainippon Paint Co., Ltd. Nasu (72) Inventor Toshihiko Shiotani 1382-12 Shimoishigami, Otawara-shi, Tochigi Dainippon Paint Co., Ltd.Nasu Factory (72) Inventor Yoshihisa Nagashima 1382-12 Shimoishi, Otawara-shi, Tochigi Dainippon Paint Co., Ltd. Nasu in the factory

Claims (3)

[Claims] 1. 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, and (b) having a photopolymerizable unsaturated bond in the molecule. A water-insoluble monomer having two or more in (c)
A water-insoluble photoinitiator and (d) a compound represented by the following general formula and / or a salt formed from the compound and a basic compound (In the formula, Y represents a carboxyl group or a sulfonic acid group,
R ₁ is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkyl group or -X ₁ -R ₃ (wherein X ₁ is a carboxyl group or an alkylene group which may be substituted with a sulfonic acid group, and R ₃ is a carboxyl group. Or a sulfonic acid group), R ₂ is a hydrogen atom, an alkyl group, a cycloalkyl group, a mercapto group, an alkylthio group, a cycloalkylthio group, or —S—X ₂ —R ₄ (where S is a sulfur atom). X ₂ is an alkyl group, a cycloalkyl group, a alkylene group which may be substituted with a carboxyl group or a sulfonic acid group, a cycloalkylene group, an alkylamino group, a siloalkylamino group or an amino group, and R ₄ is an alkyl group. Group, a cycloalkyl group, a carboxyl group or a sulfonic acid group) and n is an integer of 1 to 3 (provided that R ₁ or R ₂ is a carboxyl group). (It may be 0 when it has a silyl group or a sulfonic acid group)). 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.