JPH0635193A - Production of resist pattern - Google Patents

Abstract

PURPOSE:To obtain a production method of high-resolution negative photosensitive electrodeposition resist pattern without irregular development. CONSTITUTION:(i) A conductive copper base body is dipped as an anode in an electrodeposition coating bath and subjected to electrodeposition coating by applying an electric current. This plating bath contains a neutralized product of a compd. (a) with a basic org. compd. (b). The compd. (a) has a carboxyl group and/or sulfonate group in the molecule and can form salt or chelate with copper. Thus, the compd. (a) is electrically deoposited on the base body. (ii) The body with electrodeposition of the compd. (a) is dipped as an anode in an electrodeposition plating bath containing a specified monomer, specified neutralized polymer, and specified photopolymn. initiator. (iii) Then, the electrodeposition coating film thus formed is exposed to active rays. (iv) And then, the electrodeposition coating film in the area not exposed is removed by development.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high resolution resist pattern without development residue.

[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 conductive substrate,
Next, an actinic ray is imagewise irradiated to develop and remove the 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 solution by means such as dip coating, roll coating or curtain coating, or a method of laminating a film (photosensitive film) of the photocurable resin composition is known. Among these methods, the method of laminating a photosensitive film is currently used as a mainstream method because it can easily form a layer of a photocurable resin composition having a uniform thickness.

Recently, as the density and precision of printed circuit boards have 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 the photosensitive film, which is the mainstream at present, with respect to such a demand. In this method, dents during manufacturing of the substrate, non-uniformity of polishing, mesh of glass cloth of the inner layer of the substrate,
It is difficult to obtain sufficient adhesion due to poor followability to irregularities on the substrate surface caused by nonuniformity of pits and the like of copper plating on the surface. This difficulty can be avoided by laminating the films under reduced pressure (see Japanese Patent Publication No. 59-3740), but this requires a special and expensive device.

For these reasons, solution coating methods such as dip 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, as a new method, a method of forming a photosensitive film by electrodeposition coating has been recently proposed (Japanese Patent Laid-Open No. 62-62160).
-235496 gazette). According to this method (1)
The adhesion 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, (4) the coating liquid is an aqueous solution The advantages are 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 kinds of electrodeposition coating methods, anion type and cation type, but the anion type is generally used because of the ease of the subsequent steps when manufacturing a printed circuit board. However, in the case of anionic type, the copper ions eluted from the copper clad laminate during electrodeposition coating form a chelate with the carboxyl groups of the resist material and form pseudo-crosslinking. There has been a problem that development cannot be performed when developing with an 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). However, as a result of investigations by the present inventors, it has not been a sufficient solution, for example, in some cases, the degree of undeveloped residue may be worsened by the addition of these compounds.

[0008]

SUMMARY OF THE INVENTION The present invention solves the above problems and provides a method for producing a high-resolution resist pattern with no development residue.

[0009]

Means for Solving the Problems As a result of intensive investigations by the present inventors, a copper clad laminate having a carboxyl group and / or a sulfonic acid group in its molecule was previously prepared before electrodeposition coating of a resist material. It has been found that treatment with an electrodeposition coating with a compound capable of forming a salt or a chelate with copper has a remarkable effect on the development residue.

The detailed reason why the undeveloped residue is remarkably eliminated by treating the copper clad laminate with the above compound by electrodeposition coating in advance is not clear, but it is probably the skeleton which forms a salt or chelate with copper. In addition, it is presumed that one of the reasons for improving the effect is to have both a carboxyl group and / or a sulfonic acid group that are easily dissolved or dispersed in an alkaline developer.

Another major effect of treating the copper clad laminate with the above compound by electrodeposition coating is to improve the electrodeposition coating property. That is, an electrodeposition coating 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 where the compound is not treated by electrodeposition coating in advance. This is advantageous for improving productivity, saving energy and improving work stability.

That is, the present invention relates to (i) a basic organic compound (b) of a compound (a) having a carboxyl group and / or a sulfonic acid group in the molecule and capable of forming a salt or a chelate with copper. A conductive copper substrate is immersed as an anode in an electrodeposition coating bath containing a Japanese product (hereinafter referred to as the first electrodeposition coating bath), and electrodeposition coating is performed by energizing,
The compound (a) is electrodeposited on the substrate, and then (ii) (A) (a) a neutralized product of a polymer having an acid value of 20 to 300 with a basic organic compound and a photopolymerizable unsaturated bond. 2 in the molecule
Or more water-insoluble monomer and / or (b) acid value 2
Electrodeposition coating bath (hereinafter referred to as the second electrodeposition coating bath) containing 0 to 300, a neutralized product of a polymer having a photopolymerizable unsaturated bond with a basic organic compound, and (B) a water-insoluble photoinitiator
Is immersed in an electrode of a substrate on which the compound (a) is electrodeposited, and an electrodeposition coating is performed by energizing to form an electrodeposition coating film on the substrate, and then (iii) an actinic ray is applied to the electrodeposition. The present invention relates to a method for producing a resist pattern, which comprises irradiating a coating film in an image form, and then (iv) removing the electrodeposition coating film in an unexposed portion by development.

The present invention will be described in detail below. In the present invention, the first electrodeposition coating bath has a compound (a) having a carboxyl group and / or a sulfonic acid group in the molecule and capable of forming a salt or a chelate with copper, a basic organic compound (b).
And a water, and if necessary, a dye, a coloring agent such as a pigment, a surfactant, an organic solvent and the like are added.

The following compounds can be exemplified as typical examples of the compound (a), but the compound (a) is not limited thereto. Compound represented by general formula (I)

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

[0015]

[Chemical 2]

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

Compound represented by general formula (II)

[Chemical 7] (In the formula, R ₁ has the same meaning as R _{1 in} formula (I),
₄ represents a hydrogen atom, an alkyl group or a phenyl group, and n
Represents an integer of 1 to 3) Specific compounds represented by the general formula (II) are as follows.

[0021]

[Chemical 8]

Compound represented by general formula (III)

[Chemical 9] (In the formula, Y represents a carboxyl group or a sulfonic acid group, and R ₅ , R ₆ and R ₇ represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a phenyl group or —X—R ₈
(However, X represents an alkylene group which may be substituted with a carboxyl group or a sulfonic acid group, a cycloalkylene group or an alkylene ether group, and R ₈ represents a hydroxyl group, an alkoxy group, a dialkylamino group, a carboxyl group or a sulfonic acid group. And n is an integer from 1 to 3 (provided that any of R ₅ , R ₆ and R ₇ has a carboxyl group or a sulfonic acid group, it may be 0)) General formula (III) Specific compounds represented by are as follows.

[0023]

[Chemical 10]

[0024]

[Chemical 11]

[0025]

[Chemical 12]

[0026]

[Chemical 13]

Compound represented by general formula (IV)

[Chemical 14] (In the formula, Y represents a carboxyl group or a sulfonic acid group, R ₉ and R ₁₀ are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a phenyl group, or -X-R ₁₁ (where X is a carboxyl group or Represents an alkylene group which may be substituted with a sulfonic acid group, a cycloalkylene group or an alkylene ether group, R ₁₁ represents a hydroxyl group, an alkoxy group, a dialkylamino group, a carboxyl group or a sulfonic acid group), and n is The specific compound represented by the general formula (IV) is an integer of 1 to 3 (provided that either R ₉ or R ₁₁ has a carboxyl group or a sulfonic acid group, it may be 0) as follows. There is something like this.

[0028]

[Chemical 15]

[0029]

[Chemical 16]

[0030]

[Chemical 17]

[0031]

[Chemical 18]

Compound represented by general formula (V)

[Chemical 19] (In the formula, Y represents a carboxyl group or a sulfonic acid group, R ₁₂ represents a hydrogen atom, a halogen atom, a hydroxyl group,
An amino group, an alkyl group or -X ₁ -R ₁₄ (where X ₁ is
Represents an alkylene group which may be substituted with a carboxyl group or a sulfonic acid group, R ₁₄ represents a carboxyl group or a sulfonic acid group), and R ₁₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a mercapto group, an alkylthio group. group, cycloalkylthio group or -S-X ₂ -R ₁₅ (although S is a sulfur atom, X ₂ is an alkyl group, a cycloalkyl group, an alkylene group optionally substituted by carboxyl group or sulfonic acid group, a cycloalkyl An alkylene group, an alkylamino group, a cycloalkylamino group or an amino group, R ₁₅ represents 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 ₁₂ and May be 0 when any of R ₁₃ has a carboxyl group or a sulfonic acid group))
Specific compounds represented by the general formula (V) are as follows.

[0033]

[Chemical 20]

[0034]

[Chemical 21]

[0035]

[Chemical formula 22]

[0036]

[Chemical formula 23]

Compound represented by general formula (VI)

[Chemical formula 24] (In the formula, Y represents a carboxyl group or a sulfonic acid group, R ₁₆ represents a hydrogen atom, an alkyl group or a mercapto group, and R ₁₇ represents an alkylene group or a phenylene group which may be substituted with a carboxyl group or a sulfonic acid group. The specific compounds represented by the general formula (VI) are as follows.

[0038]

[Chemical 25]

[0039]

[Chemical formula 26]

Compound represented by general formula (VII)

[Chemical 27] (In the formula, R ₁₈ represents a hydrogen atom, an alkyl group or an amino group, and A is a carboxyl group, a sulfonic acid group or -X ₃ -B.
(However, X ₃ represents an alkylene group which may be substituted with a carboxyl group or a sulfone group, and B represents a carboxyl group or a sulfonic acid group.) As a specific compound represented by the general formula (VII), There are the following.

[0041]

[Chemical 28]

[0042]

[Chemical 29]

Compound represented by general formula (VIII)

[Chemical 30] (In the formula, R ₁₉ represents a hydrogen atom, an alkyl group, an amino group, an alkylthio group or a mercapto group, and R ₂₀ represents an alkylene group, an alkyleneamino group or an alkylenethio group which may be substituted with a carboxyl group or a sulfonic acid group. (Wherein Y represents a carboxyl group or a sulfonic acid group). Specific compounds represented by the general formula (VIII) are as follows.

[0044]

[Chemical 31]

[0045]

[Chemical 32]

Compound represented by general formula (IX)

[Chemical 33] (In the formula, R ₂₁ and R ₂₂ represent a hydrogen atom or an alkyl group, R ₂₃ represents an alkylene group, and Y represents a carboxyl group or a sulfonic acid group)

[0047]

[Chemical 34]

Compound represented by formula (X)

[Chemical 35] (In the formula, Y represents a carboxyl group or a sulfonic acid group, R ₂₄ represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group or —X—R ₃ (where X represents a carboxyl group or a sulfonic acid group. Represents an alkylene group which may be substituted with, a cycloalkylene group or an alkylene ether group, and R ₃ represents a hydroxyl group, an alkoxy group, a carboxyl group, a sulfonic acid group or a dialkylamino group)
Are shown, R ₂ is a hydrogen atom, a hydroxyl group, an alkyl group, a phenyl group or a -Z-R ₄ (except Z is a carboxylic hexyl group or sulfonic acid alkylene group which may be substituted with a group, a cycloalkylene group or an alkylene ether represents a group, R ₄ represents a hydroxyl group, an alkoxy group, a carboxyl group,
Represents a sulfonic acid group or a dialkylamino group),
n represents an integer of 1 to 3 (provided that either R ₁ or R ₂ has a carboxyl group, a sulfonic acid group, or a salt thereof), and may be 0. Specific examples represented by the general formula (X) The compounds include the following.

[0049]

[Chemical 36]

[0050]

[Chemical 37]

[0051]

[Chemical 38]

Compound represented by formula (XI)

[Chemical Formula 39] (In the formula, Y represents a sulfonic acid group, R ₂₆ represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group, and R ₂₇ represents a hydrogen atom, a hydroxyl group, an alkyl group, a phenyl group or -Z. -R ₂₈ (wherein Z represents an alkylene group which may be substituted with a sulfonic acid group, a cycloalkylene group or an alkylene ether group, and R ₂₈ represents a hydroxyl group, an alkoxy group, a sulfonic acid group or a dialkylamino group) And n is an integer of 1 to 3 (provided that R ₂₇ may be 0 when it has a sulfonic acid group therein). Specific compounds represented by the general formula (XI) include the following. .

[0053]

[Chemical 40]

[0054]

[Chemical 41]

[0055]

[Chemical 42]

[0056]

[Chemical 43]

Compound represented by general formula (XII)

[Chemical 44] (In the formula, Y and R ₂₉ have the same meanings as Y and R ₂₆ in the general formula (XI), R ₃₀ has the same meaning as R _{27 in the} general formula (XI), and n represents the general formula ( Specific compounds represented by the general formula (XII), which have the same meaning as n in XI), are as follows.

[0058]

[Chemical formula 45]

[0059]

[Chemical formula 46]

Compound represented by formula (XIII)

[Chemical 47] (In the formula, Y represents a carboxyl group or a sulfonic acid group, and R ₃₁ is —X—Y (where X is an alkylene group, a cycloalkylene group, or an alkylene ether group which may be substituted with a carboxyl group or a sulfonic acid group. R ₃₂ represents a hydrogen atom, a hydroxyl group, an alkyl group, an ester group, a phenyl group or —Z—R ₃₃ (wherein Z represents an alkylene group which may be substituted with a carboxyl group or a sulfonic acid group, cyclo An alkylene group or an alkylene ether group, R ₃₃ represents a hydroxyl group, an alkoxy group, a carboxyl group, a sulfonic acid group or a dialkylamino group), and n represents an integer of 0 to 3) in the general formula (XIII). Specific compounds represented include the following.

[0061]

[Chemical 48]

Compound represented by formula (XIV)

[Chemical 49] (In the formula, Y and R ₃₄ have the same meanings as Y and R ₃₁ in the general formula (XIII), R ₃₅ has the same meaning as R _{32 in the} general formula (XIII), and n represents the general formula ( The following are specific compounds represented by the general formula (XIV), which have the same meaning as n in XIII).

[0063]

[Chemical 50]

Compound represented by formula (XV)

[Chemical 51] (In the formula, X ₄ represents a carboxyl group or a sulfonic acid group, R ₃₆ represents a hydrogen atom, an alkyl group or a phenyl group, and R ₃₇ represents a hydrogen atom or a methyl group.) General formula (XV)
Specific compounds represented by are as follows.

[0065]

[Chemical 52]

Compound represented by general formula (XVI)

[Chemical 53] (In the formula, Y ₂ is a carboxyl group, a sulfonic acid group, or —X ₅
-R ₃₉ (wherein X ₅ represents an alkylene group which may be substituted with a carboxyl group or a sulfonic acid group or a phenylene group, R ₃₉ represents a carboxyl group or a sulfonic acid group), and R ₃₈ represents a hydrogen atom or Specific compounds represented by the general formula (XVI) (which represent an alkyl group) are as follows.

[0067]

[Chemical 54]

Other Compounds In addition to the above compounds, the following compounds can be exemplified.

[0069]

[Chemical 55]

[0070]

[Chemical 56]

These compounds (a) can be used alone or in combination of two or more kinds. As the basic organic compound (b), compounds conventionally known as neutralizing agents for acid compounds can be used without particular limitation, but organic amines are preferable. Specific examples of organic amines include monoethanolamine, diethanolamine,
Diisopropylamine, dimethylaminoethanol, diethylamine, triethylamine, butylamine, tri-n-butylamine, tri-n-octylamine, triphenylamine, triethanolamine, dimethylethanolamine, propylamine, t-butylamine, pyridine, morpholine, piperidine , Pyrrolidine monoethanolamine and the like, and these can be used alone or in combination of two or more kinds.

The first electrodeposition coating bath contains 0.01 part by weight or more, preferably 0.05 to 5 parts by weight of the compound (a) based on 100 parts by weight of the first electrodeposition coating bath. Is suitable, and in this range, the effect of residual development and the effect of improving the electrocoating property can be remarkably obtained. The compound (b) is
It is suitable to add 0.4 to 2.0 equivalents to 1 equivalent of the carboxyl group and the sulfonic acid group in the compound (a).

In the present invention, the second electrodeposition coating bath is

Consists of the above components (A) and (B) and water, and if necessary, coloring agents such as dyes and pigments, fillers, plasticizers, solvent for materials, other thermal polymerization inhibitors, surfactants, etc. And various additives and the like are added.

The component (a) comprises a neutralized product of a polymer having an acid value of 20 to 300 with a basic organic compound and a water-insoluble monomer having two or more photopolymerizable unsaturated bonds in the molecule. is there.

As the polymer having an acid value of 20 to 300, acrylic acid and / or methacrylic acid are used as essential constituent monomers, and, for example, methyl acrylate, 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-hydroxyethyl acrylate, cyclohexyl methacrylate, acrylonitrile, styrene, vinyl chloride and other polymerizable monomers A copolymer having a weight average molecular weight of about 5,000 to 150,000, which is obtained by copolymerizing one or more of

However, the resin is not limited to the above-mentioned polymer, and any resin that has been conventionally used for electrodeposition coating can be used without particular limitation as long as it is a polymer having the mechanical strength of resist, the electrical insulating property and the like. is there. If the acid value of the polymer is less than 20, precipitation or the like is likely to occur and the stability of the electrodeposition coating bath is deteriorated, whereas if it exceeds 300, the appearance of the electrodeposition coating film obtained is not preferable, which is not preferable.

Examples of the water-insoluble monomer having two or more photopolymerizable unsaturated bonds in the molecule include, for example, polyhydric alcohols other than polyethylene glycol condensed with one or more ethylene glycol, and α, β-unsaturated carboxylic acid. A compound obtained by adding trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta ( Compounds obtained by adding α, β-unsaturated carboxylic acid to a glycidyl group-containing compound, such as (meth) acrylate and dipentaerythritol hexa (meth) acrylate,
For example, trimethylolpropane triglycidyl ether triacrylate, bisphenol A glycidyl ether di (meth) acrylate and the like, polyvalent carboxylic acids such as phthalic anhydride and a substance having a hydroxyl group and an ethylenically unsaturated group such as β-hydroxyethyl ( An ester compound such as (meth) acrylate may be used, and a urethane diacrylate compound having a urethane skeleton may also be used. In any case, a water-insoluble compound that is cured by irradiation with light may be used.

The ratio of the polymer to the monomer constituting the component (a) is preferably (50 to 85:50 to 15) (weight basis). Incidentally, when the amount of the polymer is less than the above range, the mechanical strength of the resist tends to be decreased, and when the amount of the polymer is too large, the proportion of the monomer is relatively decreased and the sensitivity to light is decreased, and similarly the mechanical strength of the resist is decreased. Tends to decline.

The polymer is neutralized with a basic organic compound to be water-soluble or water-dispersed. As the basic organic compound, the same basic organic compound (b) as described above can be used, and the amount thereof is 1 acid group in the polymer.
It is suitable to use 0.4 to 1.0 equivalent with respect to the equivalent.

The component (b) has an acid value of 20 to 300,
It is a neutralized product of a basic organic compound of a polymer having a photopolymerizable unsaturated bond. The polymer has an acid value of 20 to 300, and has a photopolymerizable unsaturated bond that is photocured by irradiation with actinic rays described below, and is a polymer having mechanical strength of resist, electrical insulation, etc. Conventionally used photocurable coating resin can be used without particular limitation.

Specifically, for example, a high acid value acrylic resin, glycidyl acrylate, glycidyl methacrylate,
A polymer having an acid value of 20 to 300 to which a glycidyl group-containing unsaturated compound such as aryl glycidyl ether is added; an acrylic resin having an acid value of 20 to 300 and having a hydroxyl group, and an excess amount of polyisocyanate and a hydroxyl group-containing unsaturated compound. A polymer having an acid value of 20 to 300 reacted with a reaction product having a free isocyanate group; a polymer having an acid value of 20 to 300 obtained by reacting a polybasic acid anhydride with an addition reaction product of an epoxy resin and an unsaturated carboxylic acid; Acid value of 20 to 300 obtained by reacting an addition reaction product of a conjugated diene (co) polymer and an unsaturated dicarboxylic acid anhydride with a polymerizable monomer having a hydroxyl group.
Polymers and the like are mentioned as typical ones.

The polymer has a degree of unsaturation of 0.2 to 4.0.
A polymer having a mol / kg and a number average molecular weight of about 500 to 50,000 is suitable, and the polymer is neutralized with a basic organic compound in the same manner as the polymer in the component (a) to be water-soluble or water-dispersed. ing.

The component (b) polymer may be used alone, but the component (a) polymer and / or a water-insoluble monomer having two or more photopolymerizable unsaturated bonds in the molecule may be used in combination. You can also

As the water-insoluble photoinitiator (B), photoinitiators for photocurable coatings that have been conventionally used are
Any water-insoluble substance can be used without particular limitation. Specifically, for example, benzophenone, N, N'-tetramethyl-
4,4'-diaminobenzophenone, 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. When the photoinitiator is water-soluble, it becomes difficult to carry out electrodeposition coating in a state of being uniformly mixed with other components, which is not preferable.

The amount of the photoinitiator used is 100 parts of the component (a).
0.1 to 15 parts by weight, preferably 0.2 to
10 parts by weight is suitable. The second electrodeposition coating bath composed of such components has a solid content of 5 to 20% by weight and a pH of 6.0.
From the viewpoint of bath management, electrodeposition property and the like, it is preferable to set the temperature within the range of to 9.0 (25 ° C.).

The second electrodeposition coating bath is preferably prepared as follows. A solution in which the component (A) and the component (B) before being neutralized are uniformly dissolved in a hydrophilic organic solvent. Typical examples of the hydrophilic organic solvent include dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoacetate, and diethylene glycol monoethyl ether acetate. When the hydrophilic organic solvent is used when synthesizing the polymer, it may be used as it is.

The amount of the hydrophilic organic solvent used is 30 with respect to 100 parts by weight of the solid content containing the components (A) and (B).
It is desirable that the amount be 0 parts by weight or less. Next, a basic organic compound is added to the solution to neutralize it, and then water is added to dissolve or disperse in water to prepare a second electrodeposition coating bath. A hydrophobic solvent such as toluene, xylene or 2-ethylhexyl alcohol may be appropriately added to the electrodeposition coating bath in order to increase the coating amount during electrodeposition coating.

Next, a method of manufacturing a resist pattern will be described. First, in step (i), a conductive copper substrate, for example, a copper-clad laminate is used as an anode and immersed in a first electrodeposition coating bath adjusted to a bath temperature of 10 to 30 ° C., preferably a voltage of about 4 to 10
V, current density of about 10 to 70 mA / dm ² DC voltage of 1
The compound (a) is electrodeposited on the substrate by applying for 0 seconds to 5 minutes.

The substrate is washed with water, drained, dried by blowing gas or the like, or in the state without being washed with water, in step (ii), the substrate to which the compound (a) is attached is used as an anode. Second temperature adjusted to 10-30 ℃
Immerse in the electrodeposition coating bath. The electrodeposition coating is preferably a DC voltage of about 50 to 400 V or 30 mA / dm ² to 4
A direct current of 00 mA / dm ² is applied for 10 seconds to 5 minutes. The obtained electrodeposition coating film is preferably about 5 to 50 μm.

After electrodeposition coating, the substrate is taken out from the electrodeposition coating bath, washed with water, drained and then dried with hot air or the like. At this time, if the drying temperature is high, the coating film is thermally cured, and a part of the film remains undeveloped in the developing step after exposure.

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 curing inhibition by oxygen during the next exposure. You may form with a film thickness of about 10 micrometers.

Next, in the step (iii), the electrodeposition coating film is imagewise irradiated with an actinic ray to photo-cur the electrodeposition coating film in the exposed portion. In addition, as a light source of the active ray,
Those which emit a light beam of up to 450 nm, for example, mercury vapor arc, carbon arc, xenon arc and the like are preferably used.

Next, in the step (iv), development treatment, that is, spraying an alkaline water such as sodium hydroxide, sodium carbonate, calcium hydroxide or the like on the surface of the electrodeposition coating film, or immersing it in an alkaline water, unexposed Part of the electrodeposition coating film is removed, and a resist pattern having a cured electrodeposition coating film corresponding to the image on the surface of the substrate is manufactured.

[0095]

[Composition of the first electrodeposition coating bath (A)]

 Compound (a) of the general formula (I-1) 5 g Triethylamine 3 g Water 4992 g [Composition of the first electrodeposition coating bath (B)] Compound (a) of the general formula (I-1) 25 g Dimethylaminoethanol 11 g Water 4964 g [Composition of first electrodeposition coating bath (C)] Compound (a) of the general formula (II-1) 5 g Triethylamine 2 g Water 4993 g [Composition of first electrodeposition coating bath (D)] The general formula (III -1) Compound (a) 5 g Triethylamine 3 g Water 4992 g

[Composition of First Electrodeposition Coating Bath (E)] Compound (a) of General Formula (IV-2) 10 g Diethylamine 3 g Water 4987 g [Composition of First Electrodeposition Coating Bath (F)] General Formula Compound (I) of (V-1) 15 g Triethylamine 8 g Water 4977 g [Composition of first electrodeposition coating bath (G)] Compound (I) of the general formula (VI-1) 10 g Triethylamine 7 g water 4983 g [Dai-Iden] Composition of coating bath (H)] Compound (a) of the general formula (VII-6) 5 g Triethylamine 3 g Water 4992 g [Composition of first electrodeposition coating bath (I)] Compound of the general formula (VIII-1) (A) 5 g triethylamine 3 g water 4992 g

[Composition of First Electrodeposition Coating Bath (J)] Compound (a) of the General Formula (IX-1) 10 g Triethylamine 4 g Water 4986 g [Composition of First Electrodeposition Coating Bath (K)] The General Formula Compound (I) of (X-1) 5 g Triethylamine 3 g Water 4992 g [Composition of first electrodeposition coating bath (L)] Compound (I) of the general formula (XI-1) 5 g Triethylamine 3 g water 4992 g [Dai-Iden] Composition of coating bath (M)] Compound (a) of the general formula (XII-1) 20 g Triethylamine 12 g Water 4968 g [Composition of first electrodeposition coating bath (N)] Compound of the general formula (XIII-1) (A) 5 g triethylamine 3 g water 4992 g [composition of the first electrodeposition coating bath (O)] benzotriazole 5 g triethylamine 4 g water 4991 g

<Preparation of Second Electrodeposition Coating Bath> [Preparation of Second Electrodeposition Coating Bath (A)] Stirrer, reflux condenser,
1130 g of dioxane was added to a flask equipped with a thermometer, a dropping funnel and a nitrogen gas introducing tube, and the mixture was heated to 90 ° C. while blowing nitrogen gas while stirring. When the temperature became constant at 90 ° C., 169 g of methacrylic acid, 250 g of methyl methacrylate, n-butyl acrylate 381
g, 200 g of ethyl methacrylate and 10 g of azobisisobutyronitrile were added dropwise to the flask over 2.5 hours, and then the mixture was kept warm at 90 ° C. for 3 hours with stirring. After 3 hours, 3 g of azobisisobutyronitrile
A solution of 100 g of dioxane was added dropwise into the flask over 10 minutes, and then the temperature was maintained again at 90 ° C. for 4 hours with stirring.

The polymer thus obtained had a weight average molecular weight of 55,000 and an acid value of 109. The solid content of the polymer solution was 45.1% by weight. Next, 650 g of this polymer solution was added to EO-modified bisphenol A.
150 g of dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK ester BPE-200) and 25 g of hexanediol dimethacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., trade name NK ester HD), 30 g of benzophenone and N, N'-
Tetraethyl-4,4'-diaminobenzophenone 1 g
Was added and dissolved.

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

[Preparation of Second Electrodeposition Coating Bath (B)] A phenol novolac type epoxy resin (trade name: Epicoat 152; epoxy equivalent 175, manufactured by Shell Co.) was placed in the flask.
175 g and 50 g of dioxane were added, and it heated up at 100 degreeC. A liquid obtained by mixing 70 g of acrylic acid, 0.1 g of p-quinone and 0.3 g of benzyltriethylammonium chloride was added dropwise over 1 hour, and the mixture was further stirred at the same temperature for 10 hours, and the acid value of the reaction system was 1 or less. And then cooled to 60 ° C. Next, 120 g of tetrahydrophthalic anhydride and 170 g of dioxane were added, and the mixture was added again for 10 hours over 10 hours.
The temperature was raised to 0 ° C., and the temperature was kept for 10 hours while stirring.

The polymer thus obtained had a number average molecular weight of about 800 and an acid value of 100. The solid content of the polymer solution was 63% by weight. Next, 27 g of benzophenone, 1 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 180 g of dioxane were added and dissolved in 400 g of this polymer solution. To this solution, 35 g of triethylamine as a basic organic compound was added and dissolved to neutralize the polymer in the solution. Next, 2500 g of ion-exchanged water was gradually added dropwise with stirring to this solution to obtain a second electrodeposition coating bath (B). The solid content of the electrodeposition bath (B) was 9% by weight, and the pH was 7.6 at 25 ° C.

Examples 1 to 14 and Comparative Example 1 A glass epoxy copper clad laminate (200 mm × 75 mm) was immersed in the first electrodeposition coating baths (A) to (O) as an anode, and was immersed at 25 ° C. for 5 V. A direct current was applied for 5 minutes to perform electrodeposition coating. Then, it was similarly immersed in the second electrodeposition coating bath (A), and a direct current of 120 V was applied at 25 ° C. for 2 minutes to carry out electrodeposition coating. After that, it was washed with water, drained and dried at 80 ° C. for 15 minutes. The electrodeposition coating film (photosensitive film) thus formed on the copper clad laminate was imagewise exposed to a light amount of 60 mJ / cm ² with a 3 kW high pressure mercury lamp through a negative mask, and then 1% by weight of sodium carbonate was used. Develop with an aqueous solution,
A resist pattern was manufactured.

Example 15 and Comparative Example 2 Electrodeposition coating was performed in the first electrodeposition coating baths (A) and (O), and then the second electrodeposition coating bath (A) was used instead of the second electrodeposition coating bath. A resist pattern was produced in the same manner as in Example 1 except that the electrodeposition coating was performed in the bath (B).

Comparative Examples 3 to 4 In Example 1, the glass epoxy copper clad laminate was not directly electrodeposited in the first electrodeposition coating bath, but directly in the second electrodeposition coating baths (A) and (B). A resist pattern was produced in the same manner as in Example 1 and Example 15 except that electrodeposition coating was performed.

For the purpose of confirming the film thickness of the electrodeposition coating film (photosensitive film) of the test plates obtained in Examples 1 to 15 and Comparative Examples 1 to 4 and the presence or absence of undeveloped film, 1 weight of the developed substrate was used. % 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.
As is clear from Table 1, the resist pattern obtained by the method of the present invention had a practical film thickness, good etching properties, and no development residue. On the other hand, a chelate can be formed in the first electrodeposition coating bath, but a carboxyl group and / or
Alternatively, in Comparative Examples 1 and 2 in which the compound having no sulfonic acid group was electrodeposited, the etching was scarcely performed and the development residue was left. The film thickness was also reduced. Similarly, Comparative Examples 3 and 4, which did not take the step of electrodeposition coating the compound (a), which is a conventional method, also had a development residue and the film thickness was reduced.

[0107]

[Table 1]

[0108]

According to the method for producing a resist pattern of the present invention, it is possible to obtain a high-resolution resist pattern with no development residue as compared with a conventional method (for example, a method in which the step (i) is omitted). This is a method of high practical value because an electrodeposition coating film having a predetermined film thickness can be obtained in a short time with a voltage or a low current, and thus productivity, energy saving, and work stability can be improved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hitoshi Amanokura 13-13-1, Higashimachi, Hitachi City, Ibaraki Hitachi Chemical Co., Ltd. Ibaraki Research Institute (72) Inventor Shigeo Tachiki 4, 13 Higashimachi, Hitachi City, Ibaraki Prefecture No. 1 Hitachi Chemical Co., Ltd. in Ibaraki Research Laboratory (72) Inventor Takuro Kato 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. in Yamazaki Factory (72) Inventor Katsushige Tsukada Hitachi City, Ibaraki Prefecture 4-13-1, Higashimachi Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Inventor Yuji Yamazaki 1382-12 Shimoishigami, Otawara-shi, Tochigi Dainippon Paint Co., Ltd. Nasu Plant (72) Inventor Masaharu Yamada Tochigi Prefecture 1382-12 Shimoishigami, Otawara City Dainippon Paint Co., Ltd.Nasu Plant (72) Inventor Toshihiko Shiotani 1382-12 Shimoishigami, Otawara City, Tochigi Prefecture Dainippon Paint Co., Ltd. Company Nasu in the factory (72) inventor Yoshihisa Nagashima Tochigi Prefecture Otawara Shimoishigami 1382 No. No. 12 Dai Nippon Paint Co., Ltd. Nasu in the factory

Claims (1)

[Claims] 1. A neutralized product of a compound (a) having a carboxyl group and / or a sulfonic acid group in the molecule and capable of forming a salt or a chelate with copper, by a basic organic compound (b). In a contained electrodeposition coating bath, a conductive copper substrate is immersed as an anode, and electrodeposition coating is performed by energization, and on the substrate,
The compound (a) is electrodeposited, and then (ii) (A) (a) a neutralized product of a polymer having an acid value of 20 to 300 with a basic organic compound and a photopolymerizable unsaturated bond are incorporated into the molecule.
Or more water-insoluble monomer and / or (b) acid value 2
The compound (a) is electrodeposited in an electrodeposition coating bath containing 0 to 300, a neutralized product of a polymer having a photopolymerizable unsaturated bond with a basic organic compound and (B) a water-insoluble photoinitiator. The substrate thus prepared is immersed as an anode, and electrodeposition coating is carried out by energizing to form an electrodeposition coating film on the substrate, and then (iii) actinic rays are imagewise irradiated onto the electrodeposition coating film,
Then, (iv) a method for producing a resist pattern, characterized in that the unexposed portion of the electrodeposition coating film is removed by development.