JPH03100073A - Positive photosensitive electrodeposition coating resin composition - Google Patents

Abstract

PURPOSE:To obtain an electrodeposition coating material which can form a highly photosensitive film uniform on the surface of a conductive substance by mixing a carboxylated polymer with a polymer derived by introducing a quinonediazide into a p-vinylphenol polymer. CONSTITUTION:A positive photosensitive electrodeposition coating resin composition comprising 30-99 pts.wt. per 100 pts.wt. total of (a) and (b), carboxylated polymer (a) of an acid value of 30-250 and 1-70 pts.wt., per 100 pts.wt. total of (a) and (b), polymer (b) derived by introducing a quinonediazide into a p- vinylphenol polymer. Because of their high polymerizability, acrylic acid and methacrylic acid are particularly preferable as the carboxylated polymer used. It is desirable to use a polymer formed by copolymerizing a polymerizable monomer which can give a homopolymer of a glass transition point <=0 deg.C as the polymer (a) since it can give an electrodeposition film or a resist film which is flexible and touch.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a positive photosensitive electrodeposition coating resin composition used for forming resist patterns in the manufacture of printed circuit boards, etc.

(Prior Art) Conventionally, as a method of forming a resist butter/on a substrate surface, a method is often used in which a photosensitive layer is formed on the substrate surface, and then actinic light is irradiated, followed by visual imaging. Many methods are used to form the photosensitive layer in this step.

For example, a method using a photosensitive resin composition solution (coating liquid) such as dip coating, roll coating, force-ten coating, or a method using a photosensitive layer formed on a base film (hereinafter abbreviated as photosensitive film) is used as a substrate. A method of laminating layers on the surface using a laminator or the like is known. Among these methods, the method using a photosensitive film is currently adopted as the mainstream method, particularly in the field of printed circuit board manufacturing, because it can easily form a photosensitive layer with a uniform thickness.

(Problems to be Solved by the Invention) Recently, as printed circuit boards have become denser and more precise, resist patterns of higher quality have become necessary. That is, it is desired that the resist pattern be free of pinholes and that is in close contact with the surface of the underlying substrate. It is known that the currently mainstream method of laminating photosensitive films has limitations in meeting such demands. This method eliminates dents and uneven polishing during substrate manufacturing.

It is difficult to follow irregularities on the surface of the substrate caused by non-uniform pits of copper plating on the surface of the mesh 2 of the glass cloth in the inner layer of the substrate, and it is difficult to obtain sufficient adhesion. This difficulty can be avoided to some extent by laminating photosensitive films under reduced pressure (see Japanese Patent Publication No. 59-3740), but this requires special and expensive equipment.

For these reasons, solution coating methods such as dip coating, roll coating, and curtain coating have been reconsidered in recent years.

However, these coating methods have problems such as difficulty in controlling the film thickness, insufficient uniformity of the film thickness, and occurrence of pinholes.

Recently, a new method of forming a photoresist film by electrodeposition coating has been proposed (Japanese Patent Laid-Open No. 62-23549
(See Publication No. 6). According to this method, (1) the adhesion of the resist is improved; ■Good followability to irregularities on the substrate surface,■
A photoresist film with uniform thickness can be formed in a short time. ■Because the coating liquid is an aqueous solution.

It has advantages such as preventing contamination of the working environment and causing no problems in terms of disaster prevention.

For this reason, several proposals have been made in the past regarding positive-type photosensitive electrodeposition paints that are considered to be particularly effective in manufacturing printed circuit boards having through holes. Among them, yaquinonediazide groups are introduced through ester bonds by reacting quinonediazide sulfonic acid chloride with hydroxyl groups directly bonded to benzene rings (so-called phenolic hydroxyl groups), and carboxyl groups or amino groups to enable electrodeposition coating. Polymers that simultaneously have these in the same polymer molecule have been well studied because they are relatively easy to synthesize.

In this case, there are two methods (for example, JP-A-61-
206293). One is a nonapolymerizable monomer that already has a phenolic hydroxyl group, such as p-hydroxyphenol and a polymerizable monomer that has a carboxyl group;
For example, a method in which a polymer copolymerized with methacrylic acid is reacted with O-su7toquino/-(1°2)-diazide-(2)-sulfonic acid chloride to simultaneously provide naphthoquinone diazide and carboxyl groups in the polymer is The other method is to react quinonediazide sulfonic acid chloride with a polymerizable monomer having a phenolic hydroxyl group in advance, and introduce quinonediazide at the monomer stage.
This method involves copolymerizing a polymerizable monomer into which quinonediazide has been introduced with a polymerizable monomer having a carboxyl group, such as methacrylic acid, to simultaneously provide quinonediazide and a carboxyl group in the polymer.

However, there were major problems in these cases.

In other words, in the former method, the molecular weight of the initial polymer copolymerized with a polymerizable monomer having a phenolic hydroxyl group cannot be high and is low, so the mechanical strength of the electrodeposited film (photosensitive film) and the resist film after development is low. It has low strength and tends to cause problems such as peeling and flaking even with the slightest impact, and in the latter method, quinonediazide is likely to thermally decompose during polymerization, resulting in a decrease in the rate of quinone/diazide introduction into the polymer.Same as the former method. However, because high molecular weight polymers cannot be obtained, problems such as insufficient mechanical strength of electrodeposited coating films and resist films tend to occur.

(Means for Solving the Problems) As a result of intensive study, the present inventors separately synthesized a polymer for enabling electrodeposition coating and a polymer having positive photosensitivity. By combining these, the problems of the prior art were solved and a positive photosensitive electrodeposition coating resin composition suitable for electrodeposition coating was discovered.

In other words, one aspect of the present invention is.

(a) 30 to 99 parts by weight of a carboxyl group-containing polymer having an acid value of 30 to 250 based on 100 parts by weight of the total amount of (a) and (b), and tb) Introducing yanone diazides into a polymer containing p-vinylphenol. The present invention relates to a positive photosensitive electrodeposition resin composition containing 1 to 70 parts by weight of the polymer (al) and (b) in an amount of 1 to 70 parts by weight based on 100 parts by weight of the total amount of (al and (b)).

By using the positive-type photosensitive electrodeposition coating resin composition characterized in that the two types of polymers of the present invention are used in combination, it is possible to take advantage of the advantages of forming a photosensitive film by electrodeposition coating as described above. 1 during the subsequent exposure and development process.
By taking advantage of the high sensitivity and good resist performance that are the features of the positive photosensitive electrodeposition coating resin composition of the present invention, a resist pattern with high density and high precision can be formed.

Below, nine aspects of the present invention will be described in detail.

carboxyl group-containing yt with an acid value of 30 to 250, which is a component of fa)! ! J Mama-5 If it is a polymer having a carboxyl group in the molecule, 9 For example, alkyd resin,
There are no particular restrictions on polyester resin, etc.

Preferably acrylic acid, methacrylic acid, itaconic acid,
1 carboxyl group-containing polymerizable monomer such as maleic acid
Copolymerized * (meth)acrylic polymers can be mentioned. Among these, acrylic acid and methacrylic acid are preferred carboxyl group-containing polymerizable monomers because of their high polymerizability.

In the case of (meth)acrylic polymers, in addition to the above carboxyl group-containing polymerizable monomers, for example.

Methyl acrylate. Methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate. 2-ethylhexyl acrylate, cyclohexyl methacrylate, diacetone acrylamide, acrylonitrile, 2-hydroxyethyl acrylate.

2-hydroxyethyl methacrylate, styrene.

Copolymerization can be carried out using one or more types of radiationally polymerizable monomers such as vinyltoluene and 2,2,2-trifluoroethyl methacrylate.

It is preferable to use a polymerizable monomer whose homopolymer has a glass transition point of 0° C. or lower in order to make the electrodeposition coating film or resist film flexible and tougher. The amount used is the total amount of polymerizable monomers constituting the carboxyl group-containing polymer having an acid value of 30 to 250, which is the component (a).
It is preferably 10 to 70 parts by weight per 00 parts by weight. 10
If it is less than 70 parts by weight, the effect may be small, and if it exceeds 70 parts by weight, it tends to become sticky.

Ethyl acrylate is a polymerizable monomer whose homopolymer glass transition point is 0°C or lower.

n-propylacrylate] root, n-butyl acrylate,
2-ethylhexyl acrylate is preferred.

On the other hand, as a method for obtaining the (meth)acrylic carboxyl group-containing polymer which is the component (a).

It can be obtained by general solution polymerization using a polymerization initiator such as azobisisobutyronitrile or azobisdimethylvaleronitrile I peroxide in an organic solvent. In this case, the organic solvent used is preferably a hydrophilic organic solvent such as dioxane, methoxyethanol, ethoxyethanol, diethylene glycol, etc., considering that the organic solvent is used for electrodeposition coating. If toluene,
xylene.

When mainly using hydrophobic organic solvents such as benzene,
After polymer synthesis, it is necessary to distill off the solvent and replace it with the hydrophilic solvent described above.

The weight average molecular weight of the carboxyl group-containing polymer as component (a) is preferably in the range of 4,000 to 150,000. When the weight average molecular weight is less than 4.000, the mechanical strength of the coating film (photosensitive layer) after electrodeposition coating and the resist pattern after exposure and development is low; when it exceeds 150,000, the electrocoatability is poor. The appearance of the paint film tends to be poor.

The carboxyl group concentration of the carboxyl group-containing polymer, which is the component (a), that is, the acid value is in the range of 30 to 250. If the acid value is less than 30, the composition will have poor water dispersibility and water dispersion stability when a base and water are added to the positive photosensitive electrodeposition coating resin composition of the present invention and dispersed in water, as described below. Sediment. Moreover, if the acid value exceeds 250, the appearance of the coating film after electrodeposition will be poor. Therefore, when using the above-mentioned (meth)acrylic polymer as the polymer for component (a), it is necessary to combine carboxyl group-containing polymerizable monomers such as acrylic acid and methacrylic acid with other polymerizable monomers so that the acid value is within the above preferred range. The amount of monomer used may be adjusted.

The amount of the carboxyl group-containing polymer having an acid value of 30 to 250, which is a component of (a), is 9 in the present invention.
The amount is in the range of 30 to 99 parts by weight, preferably 50 to 90 parts by weight, based on 100 parts by weight of the total amount of components b). If the amount used is less than 30 parts by weight, the water dispersibility and water dispersion stability of the electrodeposition bath will be poor, and if it exceeds 99 parts by weight, the proportion of the polymer which is the component (b) will decrease, that is, the amount of chino/diazide will decrease. If the content is too low, the sensitivity to light will decrease.

A polymer in which quinonediazides are introduced into a polymer containing p-vinylphenol, which is the component (b), is a polymer in which p-vinylphenol is homopolymerized or copolymerized with other polymerizable monomers in advance, and quinonediazides are introduced into the polymer. A polymer obtained by reaction. p-vinylphenol may be homopolymerized or copolymerized with other polymerizable monomers, but the other polymerizable monomers mentioned here include (meth)acrylic polymers mentioned above for component (a). This refers to general polymerizable monomers other than the carboxyl group-containing polymerizable monomers listed above that can be used as copolymerization components with the carboxyl group-containing polymerizable monomers. ((b)
The components do not include carboxyl group-containing polymerizable monomers because they may cause the composition of the coating to be non-uniform. ) These may be used alone, or two or more types may be used in combination for copolymerization.

Further, this polymerization method may be any method, and the manufacturing method is not particularly limited.

The content of p-vinylphenol in a polymer containing p-vinylphenol is as follows in the case of a homopolymer.

Of course, it is 100 mo#%, but in the case of a copolymer, it is preferably 20 mo#% or more. Content is 20mol! If the amount is less than 1, the amount of quinonediazide to be introduced thereafter will be reduced, resulting in poor solubility in the developer after irradiation with actinic rays.

In addition, the weight average molecular weight of the polymer containing p-vinylphenol is not particularly limited, but is usually 500 to so, oo.
o is a preferred range. There is no particular problem as long as the weight average molecular weight is small, but if it exceeds so or ooo, the compatibility with the polymer of component (a) tends to decrease.

The quinonediazides to be reacted with the above p-vinylphenol-containing polymer are not particularly limited as long as they have a quinonediazide group; -Naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride.

1,2-naphthoquinonediazide-4-sulfonylbromi), 1,2-be/zoquinonediazide-4-sulfonyl chloride, 1,2-benzoquinonediazide-5-sulfonyl chloride, 1,2-be/fuquinonediazide- 6-sulfonyl chloride, 1,2-benzoquinonediazide-4
-sulfonyl bromide, among which 1,2-naphthoquinonediazide-5-sulfonyl chloride is preferred.

These chino/diazides may be used alone or in combination with
More than one type may be used.

Further, the amount of the above chino/diazide to be reacted with the polymer containing p-vinylphenol is preferably 10 to 100 equivalents based on the hydroxyl group of p-vinylphenol. If the amount introduced is less than 10 equivalents, the solubility of the developer after irradiation with actinic rays tends to deteriorate.

The reaction between a polymer containing p-vinylphenol and a quinone diazide can usually be carried out in an organic solvent using a basic catalyst. Examples of organic solvents used include acetone and dioxane.

Examples include methyl ethyl ketone, selonlube acetate, butyl cellosolve acetate, acetonitrile, etc., and these can be used alone or in combination of two or more types.

Also, as a basic catalyst, sodium hydrogen carbonate is used.

Sodium carbonate, sodium hydroxide, potassium hydroxide,
Examples include ammonia, triethylamine, triethanolamine, pyridine, dimethylamine ethanol, etc.
These can be used alone or.

Two or more types can be used in combination, and the amount used is A.
Usually, 2 for the hydroΦ syl group of p-vinylphenol.
0 to 300 equivalents are used.

The reaction temperature is generally preferably in the range of 10 to 50°C.

The reaction time is usually about 30 minutes to 5 hours.

After the reaction is completed, the reaction solution is poured into water or an acidic aqueous solution, the basic catalyst is washed away, and the polymer of component (b) in the present invention can be obtained by further purification.

The amount of the polymer used as component (b) is 9 parts per 100 parts by weight of the total amount of components (a) and (b) according to the present invention.

The amount ranges from 1 to 70 parts by weight, preferably from 10 to 50 parts by weight. If the amount used is less than 1 part by weight, the solubility of the visual liquid after irradiation with actinic light will be poor, and if it exceeds 4 parts of 70i, the water dispersibility and water dispersion stability of the electrodeposition bath will be poor.

In addition to the above-mentioned (al and (bl) components, the positive-working photosensitive electrodeposition coating resin composition of the present invention may also contain quinonediazide compounds used in conventional positive-working photosensitive resin compositions.

Examples of this quinonediazide compound include 9.

&&4-trihydroxybe/siphenon-1,2-nafdoquino/diazide-4-sulfonic acid ester.

2λ4,4'-tetrahydroxypensiphenone-1゜1,2-naphthoquinonediazide-4-sulfonic acid esters of polyhydroxybenzophenol such as 2-naphthoquinonediazide-4-sulfonic acid ester, 15-dihydroxybenzoic acid Polyhydroxybenzoic acid alkyl esters such as lauryl-1゜2-su7toquinonediazide 4-sulfo/acid ester, Z3.4-)lyhydroxybenzoic acid phenyl-1,2-naphthoquinonediazide-5-sulfonic acid ester, etc. Examples include 1,2-naphthoquino/diazide sulfonic acid ester of polyhydroxybenzoic acid aryl ester. The amount of these chino/diazide compounds used is the total amount of components (a) and [b) 1
The amount is preferably 50 parts by weight or less relative to 00 parts by weight. If it exceeds 50 parts by weight, the compatibility with the polymer of component (a) tends to decrease, and the water dispersion stability tends to decrease.

Furthermore, a sensitizer can also be blended into the positive photosensitive electrodeposition coating resin composition of the present invention.

Examples of the sensitizer include pyrrole, imidazole,
Nitrogen-containing compounds having active hydrogen such as triazole, indole, benzimidazole, oxazolidone, piperidone, hydantoin, glycine, barbylic acid and derivatives thereof can be mentioned. The amount of these sensitizers used is preferably 30 parts by weight or less based on 100 parts by weight of the total amount of components (a) and (b). If it exceeds 30 parts by weight, the solubility of the resist increases during development and the residual film rate tends to decrease.

The positive photosensitive electrodeposition coating resin composition of the present invention further contains a dye, a pigment, a plasticizer, and an adhesion promoter.

Inorganic fillers can also be used as appropriate.

In order to convert the positive photosensitive electrodeposition paint resin composition of the present invention into an electrodeposition paint, components (a) and (b) are first prepared.

Further, although it is desirable that the various components mentioned above, which are used as necessary, are uniformly dissolved in the hydrophilic organic solvent, it is not necessary to be particular about this. The hydrophilic organic solvent mentioned here includes dioxa/, methoxyethanol, ethoxyethanol, diethylene glycol, and the like. These solvents may be used alone or in combination of two or more, and the amount used is 300 parts by weight per 100 parts by weight of total solids.
It is preferably in a range of parts by weight or less.

Next, a base is added to this solution to neutralize the carboxyl groups contained in the polymer, which is the component (a).
Facilitates water solubilization or water dispersion of the composition. The base used here is not particularly limited, but examples include triethylamine, monoethanolamine, jetanolamine,
Diisopropylamine, dimethylaminoethanol, morpholine.

Examples include ammonia, sodium hydroxide, sodium hydroxide, and the like, and these can be used alone or in a mixture of two or more. The amount of these bases used is preferably 0.4 to 1.0 equivalents per equivalent of carboxyl group in the polymer as component (a). If the amount is less than 0.4 equivalent, the water dispersion stability of the electrodeposition coating bath will decrease, and if it exceeds 1.0 equivalent, the thickness of the coating film (photosensitive layer) after electrodeposition will become thinner, and storage stability will tend to decrease. be.

Next, water is added to dissolve or disperse the positive photosensitive electrodeposition coating resin composition in water to prepare an electrodeposition coating bath. The solid content of the electrodeposition coating bath is usually 5 to 20% by weight, and the pH is 7.
．． A range of 0 to 9.0 is preferred. If the pH is less than 7.0, dispersion may deteriorate and electrophoresis may become difficult. On the other hand, if the pH exceeds 9.0, the ants once electrodeposited may be redissolved, resulting in no film being formed. In order to adjust the pH to the above-mentioned preferred range, the above-mentioned base may be added later to adjust the pH.

Further, in order to improve the water dispersibility and dispersion stability of the positive photosensitive electrodeposition coating resin composition, surfactants such as nonionic, cationic, and subionic surfactants may be added as appropriate.

Furthermore, a hydrophobic solvent such as toluene, xylene, 2-ethylhexyl alcohol, etc. can be added as appropriate to increase the coating amount during electrodeposition coating.

The electrodeposition coating bath thus obtained was used to coat the substrate surface (
In this case, the substrate surface is iron or aluminum.

For electrocoating (coated with metals such as copper, zinc, and other metals and alloys), the substrate is immersed in an electrocoat bath as an anode, and a DC voltage of usually 50 to 400 V is applied for 10 minutes. The application is carried out for a period of seconds to 5 minutes. At this time, it is desirable to control the temperature of the electrodeposition coating bath at 15 to 30°C.

After electrodeposition coating, the object to be coated is taken out of the electrodeposition coating bath, washed with water, drained, and then dried with hot air. At this time, if the drying temperature is high, there is a risk that the quinone diazide in the positive type photosensitive electrodeposition coating resin composition will decompose, so it is usually preferable to dry at 110° C. or lower.

The thickness of the coating film (photosensitive layer) obtained in this way is 2 to 50 μm.
is preferred. If the film thickness is less than 2 μm, developer resistance is low;
Furthermore, when used in the manufacture of printed circuit boards, for example, when a resist pattern is formed and then etched, the resistance to etching liquid and etch factor tend to be poor, and if the film thickness exceeds 50 μm, the resolution of the resist pattern decreases. There are things to do.

Next, the coating film is imagewise irradiated with actinic rays to photodecompose the exposed areas, and then the exposed areas are removed by development to obtain a resist pattern.

Examples of active light sources include those that emit light with a wavelength of 300 to 450 nm9, such as a mercury vapor arc.

Carbon arc, xenon arc, etc. are preferably used.

Development is usually carried out by spraying alkaline water such as sodium hydroxide, sodium carbonate, or potassium hydroxide, or by immersing the film in alkaline water.

(Example) The present invention will be explained below with reference to Examples.

First, a method for synthesizing the polymers of component (a) and component (b) used in the examples will be described.

(a) Polymer synthesis of components (a-1) Dioxane 11309 was added to a flask equipped with a stirrer, a reflux condenser, a thermometer, two dropping funnels, and a nitrogen gas introduction tube, and the mixture was heated to 90°C while stirring and blowing nitrogen gas. Warmed to temperature. When the temperature became constant at 90°C, methacrylic acid 1699. Methyl methacrylate asog, n-
Liquid f, which was a mixture of 481 g of butyl acrylate and 5 g of azobisin butyronitrile, was added dropwise into the flask over 2 hours, and then kept at 90° C. with stirring for 3 hours.

After 3 hours, a solution prepared by dissolving 2.59 g of azobisisobutyronitrile in 100 g of dioxane was added dropwise into the flask over 10 minutes, and then kept at 90'C for 4 hours with stirring.

The weight average component weight of the polymer thus obtained was 8
3,000. The acid value was 112. The solids content of the polymer solution was 45.7% by weight.

(a-2) 900 g of etel cellosolve was added to a flask equipped with the same surface as in (a-1), nitrogen gas was blown into the flask while stirring, and the flask was heated to 90°C. At the point where the temperature is constant at 90℃, acrylic acid 649 and methyl methacrylate 4
189.2-Ethylhexyl acrylate 4689.2
A mixture of 50 g of -hydroxyethyl acrylate and 109 g of azobisisobutyronitrile was added dropwise into the flask over 25 hours, and then kept at 90° C. with stirring for 3 hours. After 3 hours, azobisisobutyronitrile 5
A solution obtained by dissolving 100 g of dioxane in 100 g of dioxane was added dropwise into the flask over 10 minutes, and then kept at 90° C. for 4 hours while stirring.

The weight average molecular weight of the polymer thus obtained was 6.
5,000. The acid value was 49.5. The solids content of the polymer solution was 49.8 wt.

(b) Polymer synthesis of components (b-1) Poly(p-vinylphenol)! Product name Nilinker M9
Weight average molecular weight 1,600. Maruzen Petrochemical) 1209
, 1.160 g of 2-naphthoquinonediazide-5-sulfonic acid chloride and dioxane a, ooog were added to a flask and dissolved, kept at 40°C, and after 9 hours, without stirring, 1
650 g of an aqueous solution of 0.0% sodium carbonate was added dropwise over 1 hour. After dripping.

After further reaction at 40° C. for 2 hours while stirring.

Pour the liquid into a 7% by weight aqueous hydrochloric acid solution to obtain a precipitate. After redissolving this precipitate in dioxane, the solution was poured into ion-exchanged water again, and the resulting precipitate was vacuum-dried at 220 °C.
g (b-1) was obtained. The naphthoquinonediazide in (b-1) is 4s, 6 to the hydroxyl group in the polymer.
Mff1% has been introduced to my friend.

(b-2) p-vinylphenol/n-butyl acrylate) = 36
/64 (mo!! ratio) copolymer (trade name Nilinker CBA, weight average molecular weight 16,000, manufactured by Maruzen Petrochemical) 1259, 116 g of 1.2-naphthoquinonediazide-5-sulfonic acid chloride and dioxane 1.2009 Add to the flask and dissolve.

After keeping the temperature at 40℃, add triethylamine 4 while stirring.
49 was added dropwise over 1 hour. After the dropwise addition, the reaction was continued at 40° C. for 2 hours while stirring, and then purified and dried in the same manner as in (b-1) to obtain 1969 (b-2).

The naphthoquinone diazide in (b-2) has a 98% relative to the hydroxyl group in the polymer. OM Keichi had been introduced.

Example 1 Solution 8759 (polymer solid content 400G) of (a-X)
, (b-1) Dissolve 1009 in dioxane and make a solution of 30
After mixing 09 and triethylamine 48.59,
While stirring the solution, 3.780 g of ion-exchanged water was gradually added dropwise to obtain an electrodeposition coating bath. The actual solid content of this electrodeposition coating bath was 10.1% by weight, and the pH was 25°C.
It was 7.8.

A stainless steel plate (SU8304) (shape 200mm x 75mm+
x 1mm) as a cathode, and immersed it at a temperature of 25°C.
A DC voltage of 50 V fr was applied for 2 minutes to form an electrodeposition coating film on the surface of the steel clad laminate. Thereafter, it was washed with water, drained, and dried at 80° C. for 10 minutes (film thickness after drying: 6 μm).

A 3kW ultra-high pressure mercury lamp was applied to this item through a mask for 400 minutes.
After image-wise exposure to a light intensity of "mJ/am" and visual imaging with a 1-inch sodium carbonate aqueous solution, a good resist pattern with a 5-step photosensitivity of a step tablet was obtained and a high resolution of 50 μm was formed. I was able to. Also,
After forming this resist pattern, the steel-clad laminate was made to a length of 75 cm.
After dropping the resist pattern vertically onto the floor from a height of 1, the appearance of the resist pattern was inspected and no abnormalities such as resist flaking, peeling, or cracking were observed.

Example 2 Solution 7039 of (a-2) (polymer solid content 3509)
, (b-2) 300 g of a solution prepared by dissolving 15 og in ethyl cellosolve and 26.69 g of triethylamine were mixed, and the solution was stirred.

Ion exchange water4. OO09 was gradually added dropwise to obtain an electrodeposition coating bath. The actual solid content of this electrodeposition coating bath was 10.2% by weight, and the pH was 8.6 at 25°C.

An electrodeposition coating film was formed on the surface of a copper-clad laminate using the above electrodeposition coating bath under the same conditions as in Example 1.

Thereafter, it was washed with water, drained, and dried at 80° C. for 10 minutes (film thickness after drying: 8 μm).

As a result of exposing and developing this material through a mask in the same manner as in Example 1, it was possible to obtain a photosensitivity of 5 steps of a step tablet and form a good resist pattern with a high resolution of 50 μm. . In addition, after vertically dropping the copper-clad laminate on which this resist pattern was formed onto the floor from a height of 75 cm, the appearance of the resist pattern was inspected, but no abnormalities such as resist flaking, peeling, or cracking were observed. There wasn't.

Example 3 Solution 711G of (a-1) (polymer solid content 325g)
, (b-2) 175g dissolved in dioxane 30
After mixing 0 g of triethylamine and 409 g of triethylamine, 3.950 g of ion-exchanged water was gradually added dropwise while stirring the liquid to obtain an electrodeposition coating bath. The actual solid content of this electrodeposition coating bath was 10.1% by weight, and the pH was 7.7 at 25°C.
Met.

An electrodeposition coating film was formed on the surface of a copper-clad laminate using the above electrodeposition coating bath under the same conditions as in Example 1.

Thereafter, it was washed with water, drained, and dried at 80° C. for 10 minutes (film thickness after drying: 8 μm).

As a result of exposing and developing this material through a mask in the same manner as in Example 1, it was possible to obtain a photosensitivity of 6 steps of a step tablet and form a good resist pattern with a high resolution of 50 μm. . In addition, after vertically dropping the copper-clad laminate on which this resist pattern was formed onto the floor from a height of 75 cm, the appearance of the resist pattern was inspected, but no abnormalities such as resist flaking, peeling, or cracking were observed. There wasn't.

Example 4 Solution 904G of (a-2) (polymer solid content 450g
), (b-1) 50g solution dissolved in dioxane 30
After mixing 09 and dimethylamine ethanol 2129, ion exchange water 3.7759 was gradually added dropwise while stirring the solution to obtain an electrodeposition coating bath. The actual solid content of this electrodeposition coating bath was 10.3% by weight, and the pH was 25°C.
It was 8.3.

An electrodeposition coating film was formed on the surface of a copper-clad laminate using the above electrodeposition coating bath under the same conditions as in Example 1.

Thereafter, it was washed with water, drained, and dried at 80° C. for 10 minutes (film thickness after drying: 5 μm).

As a result of exposing and developing this material through a mask in the same manner as in Example 1, a good resist pattern with a photosensitivity of 4 steps of a step tablet and a high resolution of 50 μm could be formed.

In addition, the copper clad laminate e7 on which this resist pattern was formed
After dropping vertically to the floor from a height of 5 cm.

The appearance of the resist pattern was inspected, but no abnormalities such as resist flaking, peeling, or cracking were observed.

(Effect of the invention) The positive photosensitive electrodeposition coating resin composition of the present invention is:

A highly sensitive photosensitive film can be uniformly formed on the surface of a conductive substrate by electrodeposition coating, and a resist pattern with high resolution can be obtained by exposure and development. The photosensitive film and resist have good mechanical strength and are excellent in impact resistance.

Claims (1)

[Claims] 1. (a) 30 to 99 parts by weight of a carboxyl group-containing polymer having an acid value of 30 to 250 based on 100 parts by weight of the total amount of (a) and (b) (b) p-vinylphenol A positive photosensitive electrodeposition coating resin composition, characterized in that it contains 1 to 70 parts by weight of a polymer in which a quinonediazide is introduced, based on 100 parts by weight of the total amount of (a) and (b). . 2. The positive-working photosensitive electrodeposition coating resin composition according to claim 1, wherein the carboxyl group-containing polymer is a (meth)acrylic polymer copolymerized with acrylic acid and/or methacrylic acid. 3. The carboxyl group-containing polymer is copolymerized with 10 to 70 parts by weight of a polymerizable monomer having a homopolymer glass transition point of 0°C or less per 100 parts by weight of the total amount of polymerizable monomers constituting the polymer. The positive photosensitive electrodeposition coating resin composition according to claim 1 or 2, which is a composition comprising: 4. The positive-working photosensitive electrodeposition paint according to claim 3, wherein the polymerizable monomer having a homopolymer glass transition point of 0° C. or lower is 2-ethylhexyl acrylate, n-propyl acrylate, n-butyl acrylate and/or ethyl acrylate. Resin composition.