JPH05281725A - 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 formula, R1 is a hydrogen atom, alkyl group, or amino group, and A is a carboxyl group or sulfonic acid group. 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. 59-37).
This can be avoided by means of the No. 40 publication, 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)
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 in which thiazole capable of forming a chelate with copper has at least one group selected from a carboxyl group and a sulfonic acid group, and / or It has been found that the addition of a salt (component (d)) formed by the compound and the basic compound has a remarkable effect on the development residue. When mere thiazole having no carboxyl group and / or sulfonic acid group was added, no effect on the development residue was observed. Therefore, addition of a compound that forms a chelate with copper does not affect the development residue. It is clear that it is sufficient. 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 thiazole skeleton which forms a chelate with copper and a carboxyl group and / or a sulfonic acid group which are easily dissolved or dispersed in an alkaline developer. It is presumed that one of the reasons for having the effect is to have both.

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, R represents a hydrogen atom, an alkyl group or an amino group, and A is a carboxyl group, a sulfonic acid group or -X-B.
(Wherein, X represents an alkylene group which may be substituted with a carboxyl group or a sulfonic acid group, and B represents hydrogen, a carboxyl group or a sulfonic acid group)). Resin composition, electrodeposition coating bath using the same, and a conductive substrate immersed in the electrodeposition coating bath as an anode, and electrodeposition coated by energization to form an electrodeposition coating film on the conductive substrate, followed by activation The present invention relates to a method for producing a resist pattern, which comprises irradiating the electrodeposited coating film imagewise, photo-curing the exposed portions, and removing the unexposed portions 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 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 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 total amount is 100 parts by weight of 15 to 50 parts by weight, preferably 25 to 40 parts by weight.
If the amount used is less than 15 parts by weight, the sensitivity to light decreases,
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 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.

[0025]

[Chemical 3]

[0026]

[Chemical 4]

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. These are used alone or in combination of two or more. be able to. The amount of the 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 (a), (b) and (c). Is more preferable. When the amount used is less than 0.1 parts by weight, the effect of eliminating the development residue and improving the electrodeposition property due to the addition of the component (d) is small.
If it exceeds the weight part, 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.

In order to prepare an electrodeposition coating bath containing the components (a), (b), (c) and (d) described above, the components (a), (b), (c) and (d) are first 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. 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, 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. 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. 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.

Further, 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 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 in an image-wise manner, 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.

[0042]

EXAMPLES The present invention will be described below with reference to examples. Example 1 1,130 g of propylene glycol monopropyl ether was added to a flask equipped with a stirrer, a reflux condenser, a thermometer, a suitable funnel and a nitrogen gas introduction tube, and the mixture was stirred and heated to 100 ° C. while blowing nitrogen gas. Warmed. Temperature is 10
When it became constant at 0 ° C, 183 g of methacrylic acid, 600 g of methyl methacrylate, 21 of ethyl acrylate
A liquid obtained by mixing 7 g of azobisisobutyronitrile 10 g was dropped into the flask over 3 hours, and then 3.5 hours,
The mixture was kept warm at 100 ° C with stirring. After 3.5 hours, 10 g of a solution prepared by dissolving 5 g of azobisdimethylvaleronitrile in 100 g of propylene glycol monopropyl ether was used.
Drop into the flask over a period of 4 minutes, then again at 90 ° C for 4 hours.
It was kept warm with stirring.

The polymer as a precursor of the component (a) thus obtained had a weight average molecular weight of 36,000,
The acid value was 120. The solid content of the polymer solution is 4
It was 5.3% by weight.

Next, 700 g of this polymer solution was used as the component (b) as a PO-modified trimethylolpropane triacrylate (manufactured by Toagosei, trade name Aronix M-310) 1
20 g, 30 g of benzophenone as the component (c) and 1 g of N, N'-tetraethyl-4,4'-diaminobenzophenone, the above compound (1) as the component (d).
8 g and propylene glycol monomethyl ether 10
0 g was added and dissolved, and 28 g of diethylamine as a basic organic compound was further added and dissolved in this solution to neutralize the precursor polymer of the component (a) in the solution.

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 2 900 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 became constant at 90 ° C., 130 g of acrylic acid, 490 g of methyl methacrylate, 310 g of n-propyl acrylate, 70 g of methyl acrylate, and 2.5 g of azobisisobutyronitrile were mixed and dropped into the flask over 2 hours. Then, the mixture was kept warm with stirring at 90 ° C. for 3 hours. After 3 hours, a solution prepared by dissolving 1 g of azobisisobutyronitrile in 100 g of ethyl cellolube 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 61,000.
The acid value was 101. The solid content of the polymer solution is 4
It was 9.4% by weight.

Next, in 750 g of this polymer solution, 150 g of epoxy acrylate (manufactured by Osaka Organic Chemical Industry, trade name biscoat 540) as component (b) and urethane acrylate (manufactured by Shin Nakamura Chemical Co., Ltd., trade name U-108-).
A) 60 g, benzophenone as component (c) 30 g
And 1 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 5 g of the diethylamine salt of the above-mentioned compound (6) as the component (d) were added and dissolved, and 36 g of triethylamine as a basic organic compound was added to the solution.
Was added and dissolved to neutralize the polymer of the precursor of the component (a) in the solution. Next, while stirring this solution, 5,500 g of ion-exchanged water was gradually added dropwise to obtain an electrodeposition bath. This electrodeposition coating bath has a solid content of 10% by weight and a pH of 2
It was 7.4 at 5 ° C.

Example 3 1,130 g of ethyl cellosolve was added to a flask equipped with the same apparatus as in Example 1 and stirred, and the mixture was heated to a temperature of 90 ° C. while blowing nitrogen gas. When the temperature became constant at 90 ° C., a mixture of 215 g of methacrylic acid, 343 g of methyl methacrylate, 249 g of ethyl acrylate, 193 g of ethyl methacrylate and 9 g of azobisisobutyronitrile 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, 2 g of azobisisovaleronitrile 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 43,000.
The acid value was 140. The solid content of the polymer solution is 4
It was 6.1% by weight.

Next, (b) was added to 557 g of this polymer solution.
Pentaerythritol tetraacrylate as a component (manufactured by Sartomer Company, trade name SR-295) 10
0 g and 25 g of trisacryloxyethyl isocyanate (manufactured by Hitachi Chemical Co., Ltd., trade name FA-731A),
33 g of benzophenone and N, N 'as component (c)
-Tetraethyl-4,4'-diaminobenzophenone 0.8 g, the above-mentioned compound (6) 1 as component (d)
5 g was added and dissolved, and 39 g of morpholine as a basic organic compound was added to the solution to neutralize the precursor polymer of the component (a) in the solution, and n-butanol 100 was added.
g was added and dissolved.

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 10% by weight, pH
Was 7.5 at 25 ° C. Example 4 To a flask equipped with the same apparatus as in Example 1 was added 1130 g of propylene glycol monoprepyl ether, and the mixture was heated to 90 ° C. while blowing nitrogen gas while stirring. Methacrylic acid 1 at a constant temperature of 90 ° C
A liquid prepared by mixing 76 g, 248 g of methyl methacrylate, 379 g of n-butyl acrylate, 197 g of ethyl methacrylate and 10 g of azobisisobutyronitrile was dropped into the flask over 2.5 hours, and then 9 hours for 3 hours.
The mixture was kept warm with stirring at 0 ° C. 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 54,000.
The acid value was 115. The solid content of the polymer solution is 4
It was 5.1% by weight.

Next, 650 g of this polymer solution was added to (b)
200 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 component (c)
-Tetraethyl-4,4'-diaminobenzophenone 1
g, and 5 g of the compound (1) described above as the component (d) were added and dissolved.

To this solution, 31.8 g of diethanolamine 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, 4,700 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 7.5 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 (1) which was the component (d) was not added.

Comparative Example 2 5 g of thiazole was used instead of the component (d) in Example 1.
An electrodeposition coating bath was obtained with the same materials and method except for the addition.

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 the same material and method as in Example 1 except that 5 g of ethylenediaminetetraacetic acid was added instead of the component (d).

A glass epoxy copper clad laminate (Hitachi Chemical Co., Ltd.) was added to 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 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.

[0062]

[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 4 containing the component (d) in the present invention, as compared with Comparative Example 1 not containing it, all of them had a low voltage and a film thickness equal to or more than that 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
In the case of ˜4, the electrodeposition property is equivalent to that of 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 4 is This can be said to be one of the major features of the addition of the component (d) in the invention.

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 Example 2 in which simple thiazole and acetylacetone were added
In the cases of Nos. 3 and 3, almost no etching was performed and the development residue was rather deteriorated as compared with Comparative Example 1 in which no additive was added.

On the other hand, in the case of Examples 1 to 4 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 4 obtained after development
Had a good resist shape with a resolution of 50 μm.

The adhesiveness of the electrodeposition 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, they did not adhere to each other and scratched easily. It was

[0069]

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 / 00 310 13/06 B G03F 7/004 501 7/028 7/038 7/30 7124-2H H01L 21/027 H05K 3/00 F 6921-4E (72) Inventor Hideaki Uehara 4-13, Higashimachi, Hitachi City, Ibaraki Prefecture No. 1 Hitachi Chemical Co., Ltd. in Ibaraki Research Center (72) Inventor Shigeo Tachiki 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. in Ibaraki Research Center (72) Inventor Takuro Kato Hitachi City, Ibaraki Prefecture 4-13-1 Higashimachi Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Inventor Katsushige Tsukada 4-13-1 Higashimachi Hitachi City, Ibaraki Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Akiya Yamazaki 1382-12 Shimoishigami, Otawara-shi, Tochigi Dainippon Paint Co., Ltd.Nasu Plant (72) Inventor Toshiya Takahashi 1382-12 Shimoishigami, Otawara-shi, Tochigi Dainippon Paint Co., Ltd. Nasu Plant (72) Inventor Toshihiko Shiotani 1382-12 Shimoishigami, Otawara-shi, Tochigi Dainippon Paint Co., Ltd. Nasu factory (72) Yoshihisa Nagashima 1382-12 Shimoishigami, Otawara-shi, Tochigi Dainippon Paint Co., Ltd. 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 and / or a salt formed by the compound and a basic compound: (In the formula, R represents a hydrogen atom, an alkyl group or an amino group, and A is a carboxyl group, a sulfonic acid group or -X-B.
(However, X represents an alkylene group which may be substituted with a carboxyl group or a sulfone group, and B represents a hydrogen atom, a carboxyl group or a sulfonic acid group)). 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.