JPH05281736A - Negative photosensitive electrodeposition coating resin composition, electrodeposition coating bath using that and manufacture of resist pattern - Google Patents

Abstract

PURPOSE:To provide an electrodeposition coating bath having good electrodeposition property by using a negative electrodeposition coating resin compsn. containing a specified component, and to provide a resist pattern of high resolution without incomplete development by using this bath. CONSTITUTION:This electrodeposition coating resin compsn. consists of polymers, nonwater-soluble monomers having two or more photopolymerizable unsatd. bonds in the molecule, nonwater-soluble photopolymn. initiator, and compd. expressed by formula I or II. The 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 formulae I and II, R1 is a hydrogen atom, halogen atom, hydroxyl group, alkyl group, or alkoxyl group, R2 and R4 are hydrogen atoms, hydroxyl groups, alkyl groups, phenyl groups, etc., Y is a sulfonic acid group or its salt, and (n) is an integer 1-3. An electrodeposition coating film is formed on a conductive base body in an electrodeposition coating bath made of 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 printed wiring boards have increased, it has become necessary for resist patterns to have higher quality. 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 unevenness of the substrate surface caused by dents during manufacturing of the substrate, unevenness of polishing, mesh of the glass cloth of the inner layer of the substrate, unevenness 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. 59-374).
This can be avoided by the method described in Japanese Patent Publication No. 0), but 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.
1. The adhesiveness of the resist is improved, 2. Good followability to irregularities on the substrate surface. 3. A photosensitive film having a uniform thickness can be formed in a short time. Since the coating liquid is an aqueous solution, it has the advantages that it can prevent contamination of the work environment and that 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, but anion type is generally used because of the ease of the subsequent steps when manufacturing a printed wiring 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 diligent studies by the present inventors, as a result of development, the addition of a salt of sulfonic acid or a compound having a salt thereof to benzotriazole capable of forming a chelate with copper results in residual development. It has been found that it exhibits a remarkable effect. When mere benzotriazole having no sulfonic acid or its salt was added, no effect on the residual development was observed.Therefore, addition of a compound that forms a chelate with copper is insufficient for the residual development. It is clear that there is. The detailed reason why the undeveloped residue is remarkably eliminated by the addition of the benzotriazole derivative having a sulfonic acid or a salt thereof according to the present invention is unknown, but it is dissolved or dispersed in a benzotriazole skeleton that forms a chelate with copper and an alkaline developer. It is presumed that one of the reasons for having the effect is to have both sulfonic acid and its salt which are easy to use.

Another major effect of the addition of the benzotriazole derivative having a sulfonic acid group or a salt thereof according to the present invention is an improvement in electrodeposition property. That is, when the benzotriazole derivative having a sulfonic acid group or a salt thereof in the present invention is added, as compared with the case where no addition is made, an electrodeposition film (photosensitive film) having a predetermined film thickness can be formed at a low voltage or a low current in a short time. can get. This is advantageous for improving productivity, saving energy and improving work stability.

By using a negative electrodeposition coating resin composition containing a benzotriazole derivative having a sulfonic acid group or a salt thereof as described above, an electrodeposition coating bath having excellent electrodeposition properties can be obtained, and In forming the resist pattern used, 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 (I) or general formula (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,
A hydroxyl group, an alkyl group, a phenyl group or -Z-R ₃ (although, Z is an alkylene group, a cycloalkylene group or an alkylene ether group, R ₃ represents a hydroxyl group, an alkoxy group, a sulfonic acid group or a salt thereof, or dialkylamino Group), Y represents a sulfonic acid group or a salt thereof, and n represents an integer of 1 to 3 (provided that R ₂ has a sulfonic acid group or a salt thereof may be 0).

[Chemical 4] (Wherein, Y and R ₁ is Y and same meaning as R ₁ of the general formula (I), R ₄ is the same meaning as R ₂ in the general formula (I),
(n has the same meaning as n in the general formula (I)), a negative photosensitive electrodeposition coating resin composition containing the same, an electrodeposition coating bath using the same, and a conductive substrate for the electrodeposition coating bath. A method for producing a resist pattern, which comprises: 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 may be used alone or in combination of both, and the amount used 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 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 based on 100 parts by weight of the total amount of the components (a) and (b).
˜85 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 which is the component (b) will decrease and the sensitivity to light will tend 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)
15 to 50 parts by weight based on 100 parts by weight of the total amount of the components,
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 which is the component (c) include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone and 4-methoxy-.
Aromatic ketones such as 4′-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrenequinone,
Benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and other benzoin ethers, methylbenzoin, ethylbenzoin and other benzoins, 2- (o-chlorophenyl) -4,5-diphenyltriazole dimer, 2- (o-chlorophenyl) −
Examples include 4,5-di (m-methoxyphenyl) triazole dimer and 2,4-di (p-methoxyphenyl) -5-phenyltriazole 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 preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (b). Is 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 (I) or the compound represented by the general formula (II) which is the component (d) are shown 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]

These compounds can be used alone or in combination of two or more kinds. Further, salts formed from these compounds and basic compounds can be used as well.

The basic compound for forming a salt is not particularly limited, but organic amines are preferable, for example,
Diethylamine, triethylamine, monoethanolamine, diethanolamine, diisopropylamine, dimethylaminoethanol, butylamine, tree n-butylamine, tree n-octylamine, triphenylamine, triethanolamine, dimethylethanolamine, propylamine, t-butylamine, pyridine,
Examples thereof include morpholine, piperidine, and pyrrolidine, and these can be used alone or in combination of two or more.

The amount of component (d) used is preferably 0.1 to 15 parts by weight, and 0.5 to 8 parts by weight, based on 100 parts by weight of the total amount of components (a), (b) and (c). More preferably, it is a part. 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. is there.

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, and examples thereof include triethylamine, monoethanolamine, diethanolamine, diisopropylamine, dimethylaminoethanol, morpholine, etc., which 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 the carboxyl group 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 should not be used.

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
In terms of bath control and electrodeposition property, it is preferable that the content of the resin is 0.5% by weight and PH is 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.

Further, in order to improve the water dispersibility and dispersion stability of the electrodeposition coating bath containing the negative type 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 perform 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.
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 to photo-cur the exposed portion of the coating film, and the unexposed portion is removed by development to obtain a photo-cured 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.

[0051]

EXAMPLES The present invention will be described below with reference to examples. Example 1 1150 g of dioxane was added to a flask equipped with a stirrer, a reflux condenser, a thermometer, a suitable 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, 200 g of methacrylic acid, 300 g of methyl methacrylate, n-
Butyl acrylate 300g, ethyl methacrylate 1
A liquid obtained by mixing 80 g and 9 g of azobisisobutyronitrile was dropped into the flask over 2.5 hours, and then the mixture was kept warm with 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 had a weight average molecular weight of 55,000 and an acid value of 133. The solid content of the polymer solution is 4
It was 4.2% by weight.

Next, 600 g of this polymer solution was added to (b)
Pentaerythritol tetraacrylate as a component (manufactured by Sartomer Company, trade name SR-295) 17
0 g, 30 g of benzophenone as the component (c) and 1 g of N, N'-tetraethyl-4,4'-diaminobenzophenone, and the compound (I- as described above as the component (d).
1) 5 g was added and dissolved.

To this solution, 25 g of monoethanolamine as a basic organic compound was added and dissolved to obtain (a) in the solution.
The component precursor polymer 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 the electrodeposition coating bath was 9.4% by weight, and the pH was 7.8 at 25 ° C.

Example 2 A flask similar to that used in Example 1 was charged with methyl cellosolve 1000.
90 g while blowing nitrogen gas while adding g and stirring
Warmed to the temperature of. When the temperature became constant at 90 ℃, 140 g of methacrylic acid and 270 of methyl methacrylate
g, n-butyl acrylate 380 g, ethyl methacrylate 210 g and azobisisobutyronitrile 10 g
Was added dropwise to the flask over 2.5 hours,
After that, the temperature was maintained for 3 hours with stirring at 90 ° C. After 3 hours, a solution obtained by dissolving 3 g of azobisisobutyronitrile in 100 g of butyl cellosolve was added dropwise 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 45,000 and an acid value of 91. The solid content of the polymer solution is 45.
It was 8% by weight.

Next, 700 g of this polymer solution was added to (b)
120 g of aliphatic triacrylate (manufactured by Sartomer Company, trade name C-9003) and urethane acrylate (manufactured by Shin-Nakamura Chemical Co., trade name U-108-) as components
A) 40 g, benzophenone as component (c) 30 g
And 1 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 5 g of the butylamine salt of the compound (I-1) as the component (d) were added and dissolved.

To this solution, 20 g of monoethanolamine as a basic organic compound was added and dissolved to obtain (a) in the solution.
The component precursor polymer was neutralized. Next, while stirring this solution, 4,100 g of ion-exchanged water was gradually added dropwise to obtain an electrodeposition coating bath. The electrodeposition coating bath had a solid content of 10.7% by weight and a pH of 7.2 at 25 ° C.

Example 3 A flask similar to that of Example 1 was charged with ethyl cellosolve 1200.
90 g while blowing nitrogen gas while adding g and stirring
Warmed to the temperature of. When the temperature became constant at 90 ℃, 140 g of methacrylic acid and 450 of methyl methacrylate
g, 200 g of n-butyl acrylate, 150 g of ethyl methacrylate and 10 g of azobisisobutyronitrile
Was added dropwise to 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 100% dioxane.
The solution dissolved in g was dropped into the flask over 10 minutes,
After that, the temperature was maintained again while stirring at 90 ° C. for 4 hours.

The polymer as a precursor of the component (a) thus obtained has a weight average molecular weight of 50,000,
The acid value was 97. The solid content of the polymer solution is 4
It was 2.3% by weight.

Next, 650 g of this polymer solution was added to (b)
170 g of epoxy acrylate (trade name: Biscoat 540, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a component, 30 g of benzophenone and 1 g of N, N′-tetraethyl-4,4′-diaminobenzophenone as a component (c), and (d) as a component 5 g of the compound (II-1) described above was added and dissolved.

To this solution, 27 g of dimethylaminoethanol as a basic organic compound was added and dissolved to neutralize the precursor polymer of the component (a) in the solution. 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 was 9.9% by weight, and the pH was 7.6 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) which was 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 2 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 3 except that 5 g of acetylacetone was added instead of the component (d).

Glass epoxy copper clad laminates (Hitachi Chemical Industry Co., Ltd.) were used in 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 70 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.

[0068]

[Table 1] Note 1) Etching of unexposed area ○: Good (no development residue) ×: Poor (development residue)

From Table 1, in Examples 1 to 3 containing the component (d) of the present invention, as compared with Comparative Examples 1 to 3 not containing it, all of them have a low voltage and an equivalent or more film thickness, It can be seen that the electrodeposition property is improved.

On the other hand, Comparative Example 2 in which another chelating agent was added
In the case of No. 3 to No. 3, 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. 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 the comparative example, the etching property of the unexposed portion is not completely etched and there is a development residue.

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 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 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.

[0074]

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 number Internal reference number FI Technical display location G03F 7/027 502 7/028 H01L 21/027 H05K 3/00 F 6921-4E (72) Inventor Hitoshi Amanokura 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Shigeo Tachiki 4-13-1, Higashi Town, Hitachi City, Ibaraki Hitachi Chemical Co., Ltd. (72) Inventor Takuro Kato 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Factory (72) Inventor Katsushige Tsukada 4-13-1, Higashimachi, Hitachi City, Ibaraki Hitachi Chemical Co., Ltd. Company Yamazaki Factory (72) Inventor Yuji Yamazaki 1382-12 Shimoishigami, Otawara-shi, Tochigi Dainippon Paint Co., Ltd.Nasu Factory (72) Inventor Toshiya Takahashi Otawara, Tochigi Prefecture 1382-12 Shimoishi On the Nasu Plant of Dainippon Paint Co., Ltd. (72) Inventor Toshihiko Shiotani 1382-12 Shimoishi on the Nasu Plant of Odawara, Tochigi Prefecture (72) Inventor of Hisashi Nagashima Yoshihisa Otawara, Tochigi 1382-12 Shimoishi On the Nasu Plant of Dainippon Paint Co., Ltd.

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) the following general formula (I)
Alternatively, a compound represented by the general formula (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,
A hydroxyl group, an alkyl group, a phenyl group or -Z-R ₃ (although, Z is an alkylene group, a cycloalkylene group or an alkylene ether group, R ₃ represents a hydroxyl group, an alkoxy group, a sulfonic acid group or a salt thereof, or dialkylamino Group), Y represents a sulfonic acid group or a salt thereof, and n represents an integer of 1 to 3 (provided that R ₂ has a sulfonic acid group or a salt thereof may be 0). [Chemical 2] (Wherein, Y and R ₁ is Y and same meaning as R ₁ of the general formula (I), R ₄ is the same meaning as R ₂ in the general formula (I),
n is the same meaning as n in the general formula (I)), and is a negative photosensitive electrodeposition coating resin composition. 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.