JPS63297473A - Photosensitive electrodeposition coating polymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition, consisting essentially of a high polymer having carboxyl groups and quinone diazide groups in the molecule, capable of readily forming good resist patterns and useful for forming the resist patterns in producing printed circuit boards, etc. CONSTITUTION:The aimed composition, obtained by opening (A) an acid anhydride rings of maleic anhydride constituent units in a copolymer of a maleic anhydride compound and an unsaturated hydrocarbon compound with (B) a compound expressed by the formula H2N-R1-OH (R1 is 1-12C alkyl or aromatic group) and reacting the resultant ring opening product with (C) 1,2- naphthoquinone-2-diazido-5-sulfonyl chloride or 1,2-benzoquinone-2-azido-4-sulfonyl chloride and capable of simultaneously coating both surfaces of printed circuit boards, etc., by electrodeposition coating.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive electrodeposition paint resin composition used in forming resist patterns in the manufacture of printed wiring boards and the like.

[Conventional technology]

A photo-developable photoresist is used as a resist for forming fine patterns, and is formed by applying a solution of a resist-forming polymer in an organic solvent to a substrate and drying it. Methods for applying the solution include a roll coater method, a shower method, and a screen printing method.

[Problem that the invention seeks to solve]

In any of the above coating methods, it is not possible to coat both sides of the substrate at the same time; in other words, after coating and drying one side, the other side is coated and dried after polishing and cleaning. As a result, the resist on the first coated side is dried in Mitaka, resulting in differences in sensitivity, developability, etc. from the resist on the later coated side, which can cause problems in handling. .

On the other hand, electrodeposition coating, which is a painting method, is: ■Can be applied to both sides of the plate at the same time; ■Can form a coating film with a uniform thickness in an extremely short time; ■Since the paint is an aqueous solution, it can be used for disaster prevention and work. No environmental problems ■No need for expensive equipment
■Although it has the advantage of being able to use the paint effectively without wasting it, conventional resist-forming polymers could not be applied to electrodeposition coating.

[Means for solving problems]

As a result of various studies, the present inventors found that a specific photosensitive modified polymer can be electrocoated, and that the above-mentioned problems can be solved by coating the substrate with the polymer by electrocoating.

The present invention was made based on the above-mentioned findings, and provides a photosensitive IIT paint resin composition which is mainly composed of a polymer compound having a carboxyl group and a quinonediazide group in the molecule.

The photosensitive electrodeposition coating resin composition of the present invention will be described in detail below.

The polymer compound constituting the composition of the present invention is not particularly limited as long as it has a carboxyl group and a quinonediazide group, but preferred polymer compounds include, for example, maleic anhydride compounds and unsaturated hydrocarbon compounds. After opening the acid anhydride ring of the maleic anhydride constitutional unit of the copolymer with a compound represented by the following formula (1),
, 2-naphthoquinone-2-diazido-5-sulfonyl chloride or benzoquinone-2-diazide-4-sulfonyl chloride.

HwN R+ OH (1) (In the above formula, R represents an alkyl group or an aromatic group having 1 to 12 carbon atoms) The photosensitive modified maleic anhydride compound-containing polymer is
The ring opening rate of the acid anhydride ring is preferably 40% or more, and the addition rate of quinonediazide groups is 40% or more of the hydroxyl groups added by ring opening of the acid anhydride ring. is less than 40%, the carboxyl group concentration is low and the electrodeposition rate decreases. Moreover, if the addition rate of the quinonediazide group is less than 40%, the solubility of the polymer in an alkaline developer after irradiation with ultraviolet rays will be poor.

A preferable copolymer of a maleic anhydride compound and an unsaturated hydrocarbon compound, which is a starting material for the photosensitive modified maleic anhydride compound-containing polymer, is, for example, a maleic anhydride compound represented by the following formula (II). and the following formula (m
) with a vinyl group-containing compound represented by the following formula (rV)
Copolymers represented by:

(Rt represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or an aromatic group) formula(
Same as in II)) in the above copolymer,
The ratio of the anhydrous maleic metal oxide (referred to as A) and the vinyl foundation compound (referred to as B) is preferably A-A.

Examples of the unsaturated hydrocarbon compound include styrene, α-methylstyrene, vinylnaphthalene, isobutylene, 3-methylbutene-1, hexene-1, vinylcyclohexene, and the like.

Furthermore, the copolymer of the above maleic anhydride compound and unsaturated hydrocarbon compound has a number average molecular weight (Mn) of 1.
．． 000 to 500.000 is preferred.

In addition, examples of the compound represented by the old formula (1) used for opening the acid anhydride ring in the photosensitive modified maleic anhydride compound-containing polymer include 2-amino-1 to ethanol, l-amino-2- propatool, 3-amino-
1-propatol, 1-amino-2-butanol, 2-
Amino-1~butanol, 4-amino-1~butanol, 2-amino-2-methyl-1~propertool, 3-amino-2,2-dimethyl-1~propertool, 5-amino-1~propertool , 6-amino-1-hexanol, 0-1m-1p-aminophenol, 6-amino-1
-naphthol, 5-amino-1-naphthol, and the like.

Further, preferable quinonediazides to be reacted with the ring-opened product include, for example, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-8-sulfonyl chloride, 1.2-naphthoquinone-2-diazide-8-sulfonyl chloride, -benzoquinone-2-diazide-4-sulfonyl chloride and the like.

The polymer compound used in the composition of the present invention only needs to have a carboxyl group and a quinonediazide group, and in addition to the above-mentioned photosensitive modified maleic anhydride compound-containing polymer,
Polyester resins, polyesterimide resins, alkyd resins, having carboxyl groups and quinonediazide groups,
Maleated oils and the like can be mentioned.

The photosensitive electrodeposition coating resin composition of the present invention is mainly composed of the above-mentioned polymer compound, and may be composed only of the polymer compound, but if necessary, one or more of the polymer compound may be added to the resin composition of the present invention.
Alternatively, a plurality of additives can also be blended. Therefore, in the present invention, even a composition consisting only of the polymer compound is referred to as a composition.

Examples of the above-mentioned additives include melamine resins, inorganic fillers, etc., and these additives are added to the above-mentioned polymer compound in appropriate amounts (usually 50 parts by weight or less of the additive per 100 parts by weight of the polymer compound). By blending, the physical properties of the film after electrodeposition can be improved.

Therefore, when applying the photosensitive electrodeposition coating resin composition of the present invention to electrodeposition coating, first, the above-mentioned polymer compound, for example, a photosensitive modified maleic anhydride compound-containing polymer, or the polymer compound A composition containing the above-mentioned additives, such as melamine resin and inorganic filler, is dissolved and dispersed in water to prepare an electrodeposition solution.

Dispersion of the above polymer or composition in water involves dissolving and dispersing the above polymer or composition in the above solvent using 10 to 300 parts by weight of a solvent such as butyl cellosolve or dioxane per 100 parts by weight of the polymer or composition. After that, it is preferable to add water to the mixture.

At this time, it is preferable that the polymer concentration of the electrodeposition solution is 5 to 20% by weight, and if necessary, a neutralizing base is added to the electrodeposition solution to adjust the pH of the electrodeposition solution. The above-mentioned neutralizing base, which is preferably adjusted to 8 to 9 suitable for coating, is not particularly limited, but includes, for example, potassium hydroxide, ammonia, triethylamine, diethylamine, diethyltriamine, monoethanolamine, jetanolamine, Triethanolamine, diisopropanolamine, dimethylethanolamine, morpholine and the like can be mentioned.

Next, the electrodeposition solution prepared as described above is used to perform electrodeposition coating on a substrate having a conductive metal layer, so that the surface of the substrate is coated with the polymer dissolved and dispersed in the electrodeposition solution. to form a photo-developable photoresist.

The above-mentioned electrodeposition coating can be performed by a known method, but it is particularly preferable to perform the electrodeposition under conditions where the applied voltage is 50 to 0.0V.

Further, the photo-developable photoresist formed on the surface of the substrate is preferably post-treated at a temperature of about 60 to 120° C. for 1 to 30 minutes after washing and draining.

The photo-developable photoresist thus formed is photodecomposed by exposure using an ultra-high pressure mercury lamp, etc., and developed with an aqueous solvent such as an aqueous sodium carbonate solution (
The exposed areas dissolve and the unexposed areas remain as a film).

〔Example〕

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples.

Example 1 Isopan-600 (manufactured by Clareisobrene Chemical Co., Ltd.) 154, a copolymer of maleic anhydride and isobutylene
After dissolving 109 g of N,N-dimethylformamide and 109 g of p-aminophenol and reacting at 90°C for 5 hours, 97 g of triethylamine was added to the reaction solution.
2 g of N,N-
Dimethylformamide 2.0OOadi solution was gradually added dropwise to the reaction solution at room temperature while stirring, and after the dropwise addition was completed, stirring was continued for 2 hours.

Next, this reaction solution was dropped into 6,000 ml of water while being stirred to precipitate a polymer. This polymer had an acid anhydride ring opening rate of 95% and a quinonediazide group addition rate of 78%.

Next, after drying the polymer under reduced pressure, the polymer 10
After dissolving and dispersing 0 g in 100 g of dioxane, 7.5 g of triethylamine was added to this solution to neutralize it, and then 4 g of water was added.
60g was added and dissolved and dispersed to obtain a polymer aqueous solution having a concentration of 15% by weight. This polymer aqueous solution has a pH of 8,
Triethylamine was added in an amount of 2 to obtain an electrodeposition solution.

While stirring the electrodeposition solution, a glass epoxy double-sided copper-clad laminate and a stainless steel plate are immersed in the electrodeposition solution, and energized at 70 V DC for 1 minute with the copper-clad laminate as an anode and the stainless steel plate as a cathode, Electrodeposition coatings were formed on both sides of the copper-clad laminate.

The copper-clad laminate on which the electrodeposited coating was formed was washed with water, drained, and then treated at 70°C for 10 minutes to remove the solvent remaining in the coating, so that both sides of the copper-clad laminate were free of stickiness. A photo-developable photoresist was formed.

The photo-development type photoresist formed on both sides of the copper-clad laminate was irradiated with light using an ultra-high pressure mercury lamp through a mask, and then developed with a 1% sodium carbonate aqueous solution.
A pattern was obtained on both sides of the copper-clad laminate in which the exposed areas of the resist were dissolved and the unexposed areas remained as a film.

Example 2 154 g of Isopan-04 (manufactured by Clarei Sobrene Chemical Co., Ltd.), which is a copolymer of maleic anhydride and isobutylene
After dissolving 109 g of p-aminophenol in 1,000 ad of N,N-dimethylformamide and reacting at 90°C for 5 hours, 97.2 g of triethylamine was added to the reaction solution.
g, and then add 1゜2naphthoquinone-2-diazide-
A solution of 214.8 g of 5-sulfonyl chloride in 2.000 g of N,N-dimethylformamide was gradually added dropwise to the reaction solution at room temperature while stirring, and after the addition was completed, stirring was continued for 2 hours.

Next, this reaction solution was dropped into 6,000 ml of water while being stirred to precipitate a polymer. This polymer had an acid anhydride ring opening rate of 90% and a quinonediazide group addition rate of 75%.

Next, after drying the polymer under reduced pressure, the polymer 70
g, water-soluble melamine resin [manufactured by Sanwa Chemical Co., Ltd., Nikaratsuku MX-706 (solid content 70% by weight)] lOg, 20 g of inorganic filler (talc) was dissolved and dispersed in 100 g of dioxane, and then this solution was dissolved in triethylamine. Then, 460 g of water was added to this solution for dissolution and dispersion to obtain a polymer aqueous solution having a concentration of 11% by weight. Triethylamine was added to this polymer aqueous solution to adjust the pH to 8.2 to obtain an electrodeposition solution.

Electrodeposition coating was carried out in the same manner as in Example 1 using the above electrodeposition solution to form a non-adhesive photo-developable photoresist on both sides of a glass epoxy double-sided steel clad laminate.

When the photo-developable photoresist formed on both sides of the copper-clad laminate was exposed and developed in the same manner as in Example 1, the exposed areas of the resist were dissolved and the unexposed areas remained as a film. The above copper clad N was obtained on both sides.

Example 3 154 g of isopane-04 was dissolved in 1.00 (ld) of N,N-dimethylformamide, and 61 g of monoethanolamine was gradually added dropwise to this solution while stirring at room temperature.
After the addition, stirring was continued for 2 hours, 97.2 g of triethylamine was added, and 1.2-benzoquinone-2-
174.8 g of diazide-4-sulfonyl chloride,
A solution of 2,000 m of N-dimethylformamide was gradually added dropwise while stirring the solution at room temperature.
Stirring was continued for an hour.

Next, this reaction solution was dropped into 6,000 ml of water while being stirred to precipitate a polymer. This polymer had an acid anhydride ring opening rate of 96% and a quinonediazide group addition rate of 78%.

Next, after drying the polymer under reduced pressure, the polymer 10
After dissolving and dispersing 0 g in 100 g of dioxane, 7.5 g of triethylamine was added to the solution to neutralize it, and 460 g of water was further added thereto for dissolution and dispersion to obtain a polymer aqueous solution having a concentration of 15% by weight.

Triethylamine was added to this polymer aqueous solution to adjust the pH to 8.2 to obtain an electrodeposition solution.

Electrodeposition was carried out in the same manner as in Example 1 using the above electrodeposition solution to form a non-adhesive photo-developable photoresist on both sides of a glass-epoxy double-sided copper-clad laminate.

When the photo-developable photoresist formed on both sides of the copper-clad laminate was exposed and developed in the same manner as in Example 1, the exposed areas of the resist were dissolved and the unexposed areas remained as a film. This was obtained on both sides of the above copper clad laminate.

〔Effect of the invention〕

The photosensitive electrodeposition paint resin composition of the present invention is a photosensitive composition that can be applied to electrodeposition coating, and can be applied simultaneously to both sides of a printed wiring board, etc. by electrodeposition coating, making it easy to form a good resist pattern. This has the effect that it can be formed into

Claims (3)

[Claims] (1) A photosensitive electrodeposition coating resin composition mainly consisting of a polymer compound having a carboxyl group and a quinonediazide group in the molecule. (2) The above polymer compound opens the acid anhydride ring of the maleic anhydride constituent unit of the copolymer of a maleic anhydride compound and an unsaturated hydrocarbon compound with a compound represented by the following general formula (I). After that, 1,2-naphthoquinone-2 was added to the ring-opened product.
Claim 1, which is a photosensitive modified maleic anhydride compound-containing polymer obtained by reacting -diazide-5-sulfonyl chloride or 1,2-benzoquinone-2-diazide-4-sulfonyl chloride. Photosensitive electrodeposition paint resin composition. H_2N-R_1-OH (I) (In the above formula, R_1 represents an alkyl group or an aromatic group having 1 to 12 carbon atoms.) (3) The photosensitive modified maleic anhydride compound-containing polymer has an acid anhydride ring opening rate of 40% or more, and an addition rate of quinonediazide groups of 40% of the hydroxyl groups added by the opening of the acid anhydride ring. Claim No. (
2) The photosensitive electrodeposition coating resin composition described in item 2).