JPH07119375B2 - Positive photosensitive anion electrodeposition coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a positive photosensitive anion electrodeposition coating composition,
More specifically, an anionic electrodeposition coating composition suitable for forming a printed wiring photoresist which is electrodeposited on a copper clad laminate having a sullol part to form a smooth coating film having no tackiness and which is easily exposed to ultraviolet rays through positive. It relates to a composition.

Conventionally, a printed wiring board for an integrated circuit or the like is generally provided with a copper plating on a laminate having a through-hole portion in which a copper foil is stretched over an insulator, and a photosensitive film is laminated thereon, and a photographic negative is further added. After overlapping and exposing and developing, unnecessary copper foil other than the circuit pattern is subjected to etching treatment, and then the photosensitive film is removed to form the film. However, this photosensitive film is generally 50
Since the thickness is as thick as μm, the circuit pattern formed by exposure and development is not sharp, and it is difficult to uniformly laminate it on the copper foil surface. In particular, it is almost impossible to coat the through hole portion.

In addition, by screen-etching an etching resist ink on a copper clad laminate having a through-hole portion, then etching is performed to remove the copper in the unprinted portion, and further, the resist ink in the printed portion is removed. A method of forming a circuit pattern for printed wiring is also known.
However, since it is difficult to apply the ink to the sullol portion by this method, copper in the sullol portion is often removed by the etching treatment. For this reason, it is also possible to form a circuit board by preliminarily embedding an organic material in the suluru portion, protecting the copper of the sullol portion from being removed by etching, and finally removing the organic material. However, this method has the drawback that the cost of the circuit board finally obtained is high and the sharpness of the circuit pattern is poor.

As a method of improving these conventional drawbacks, a photosensitive resin resist film is formed on a printed wiring board having a sullol portion by electrodeposition coating, and a photographic negative is superposed on it to expose it, and then the exposed portion is exposed to alkali. There has been proposed a positive type photoresist which can obtain a printed wiring board by removing it with an aqueous solution (see JP-A-61-206293). This method is a method in which a film can be easily formed on the sullol part by electrodeposition coating and the unexposed part remains as a resist film, so that a printed wiring board having excellent resolution can be obtained.

However, a resin composition for forming a photosensitive resin resist film by electrodeposition coating is obtained by an esterification reaction between a hydroxyl group contained in an unsaturated monomer and an acid group contained in naphthoquinonediazide sulfonic acid. It is a resin obtained by copolymerizing an unsaturated monomer with another unsaturated monomer.Since the naphthoquinonediamide group is introduced into the resin through the ester group, it can be used during long-term running of electrodeposition coating. The ester groups in the resin are easily hydrolyzed by hydrolyzable substances such as water, acids, bases, alcohols, etc., often causing deterioration of the resin. As a result, the resin component aggregates in the electrodeposition coating bath or precipitates on the bath bottom, which may cause clogging of the filter, a large change in coating voltage, and abnormal electrodeposition such as plague. However, there is a problem that it becomes difficult to manage the electrodeposition coating bath. In addition, since the coating film formed from such a bath is inferior in smoothness and alkali developability, the fact remains that a printed wiring board having excellent resolution cannot be obtained.

The present invention has been made for the purpose of solving the above-mentioned problems in producing a printed wiring board, and as a result, it is excellent in ultraviolet photosensitivity, and moreover, on the surface of the copper-clad laminate and the sulfur part. The present inventors have succeeded in providing an anionic electrodeposition coating composition for forming a positive-type photoresist for printed wiring, which can form a developable coating film uniformly.

Therefore, according to the present invention, the following formula (I) Where R ₁ is R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkyl ether group, and R ₃ represents an alkylene group, a cycloalkylene group or an alkylene ether group, and the acid value of the modified quinonediazide sulfone unit is Provided is a positive photosensitive anion electrodeposition coating composition, which contains a resin in the range of 10 to 250 as a main component.

In the present specification, the “alkyl group” may be of a linear or branched type, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert. -Butyl, n-pentyl,
Isopentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl, n-heptyl, 5-methylhexyl, n-
Examples thereof include octyl, n-nonyl, n-decyl, dodecyl, tridecyl, tetradecyl, etc. Among them, in formula (I), a lower alkyl group having 1 to 10 carbon atoms is preferable. Examples of the “cycloalkyl group” include cyclopropyl, cyclobutyl, cyclohexyl, And the like, and the “alkyl ether group” includes, for example, CH
_{3 OCH 2 -, CH 3 CH} 2 -O-CH 2 CH 2 -, CH 3 CH 2 CH 2 -O-CH 2 C
H ₂ CH ₂ −, Etc. are included.

"Alkylene group" may filed in either linear or branched, for example _{-CH 2 -, - CH 2 CH} 2 -, - CH 2 CH 2 CH
_2- , −CH ₂ CH ₂ CH ₂ CH ₂ −, —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — and the like. Further, the "cycloalkylene group" includes, for example, cyclopropylene, cyclobutylene, cyclohexylene, And the like, and examples of the “alkylene ether group” include, for example, —CH ₂ CH ₂ —O—CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ CH ₂ —, And other groups.

In the positive photosensitive anion electrodeposition coating composition of the present invention, the acidic anionic resin containing the modified quinonediazide sulfone unit represented by the general formula (I) used as the positive photosensitive component is, for example, In the formula, X represents a hydrogen atom or a halogen atom such as Cl, F, Br and I, and is represented by: quinonediazidesulfonic acid and / or quinonediazidesulfonic acid halide (hereinafter simply referred to as "quinonediazide compound") The following formula In the formula, R ₂ and R ₃ have the same meaning as described above, and the following formula produced by addition reaction with a hydroxyl group-containing amine compound represented by In the formula, R ₁ , R ₂ and R ₃ have the same meanings as described above, and using a hydroxyl group-containing quinonediazide compound represented by, for example, by reacting this hydroxyl group-containing quinonediazide compound with an isocyanate group-containing vinyl monomer The obtained monomer is subjected to a copolymerization reaction with an acid group-containing unsaturated monomer and optionally other radically unsaturated monomer; the above-mentioned hydroxyl group-containing quinonediazide compound and diisocyanate compound are reacted with 1 mole of hydroxyl group to form an isocyanate group. Isocyanate group-containing quinonediazide compound obtained by reacting at a ratio of about 2 mol is reacted with a resin containing a hydroxyl group and an acid group; Isocyanate group-containing quinonediazide compound and hydroxyl group-containing acrylic monomer produced as described above To obtain an acid group-containing unsaturated monomer and, depending on the case, Whether to other radical unsaturated monomer and copolymerization reaction; or the hydroxyl group-containing quinonediazide compound may be prepared by methods such as reacting a copolymer containing isocyanate groups and acid groups.

As the quinonediazide compound represented by the above formula (II) or (III), 1,2-benzoquinonediazidesulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride are preferable. Further, the hydroxyl group-containing amine compound of the above formula (IV) is preferably, for example, ethanolamine, neopentanolamine, 2-hydroxy-2′-aminoethyl ether, 2-hydroxy-2 ′.
-(Amine propoxy) ethyl ether, N-methyl ethanolamine, N-ethyl ethanol amine, N-propyl ethanol amine, N-methyl propanol amine, N-ethyl propanol amine, N-propyl propanol amine etc. are mentioned.

The reaction of the quinonediazide compound of the above formula (II) or (III) with the hydroxyl group-containing amine compound of the above formula (IV) is carried out by mixing the mixture of the compound of the above formula (II) or (III) with the compound of the formula (IV). In the presence of an inert organic solvent capable of being dissolved or dispersed, the reaction temperature is generally room temperature to about 80 ° C, preferably room temperature to about 60 ° C for about 10 minutes to about 60 hours, preferably about 1 to about 3 This can be done by holding the time. The progress of the reaction can be controlled by measuring the amine value.

Specific examples of the inert organic solvent that can be used in the above reaction include dioxane such as dioxane and diosolane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene and xylene. Can be mentioned. Of these, dioxane is preferable because it has excellent solubility in quinonediazide sulfonic acid halide and can be easily removed (decompression or decomposition in water).

The mixing ratio of the compound of formula (II) or (III) and the compound of formula (IV) is not particularly strictly limited,
Usually, it is suitable to mix so that the molar ratio of -SO ₂ X group and> NH group becomes almost equimolar ratio. Further, in the above reaction, the -SO ₂ X group of the quinonediazide compound and the> NH group of the hydroxyl group-containing amine compound react preferentially over the OH group, so that the main reaction product obtained by the reaction is (V)
Is a quinonediazide compound containing a hydroxyl group.

Specific preferred examples of the compound represented by the above formula (V) include:
The following are mentioned.

In the above-mentioned production method, the isocyanate group-containing vinyl monomer to be reacted with the hydroxyl group-containing diazide compound includes the following.

(A) The following general formula (VI) In the formula, R ₄ represents a hydrogen atom or a methyl group, and n is an integer of 1 to 8, for example, an isocyanate ethyl (meth) acrylate.

(B) The following general formula (VII) In the formula, R ₄ and n each have the above-mentioned meaning, and R ₅ represents a hydrogen atom or an alkyl group having ₅ or less carbon atoms, such as m-propenyl-α, α-dimethylbenzyl isocyanate.

(C) The following general formula (VIII) In the formula, R ₄ and n each have the above-mentioned meaning. A monomer obtained by reacting 1 mol of a hydroxyl group-containing (meth) acrylic acid ester-based monomer represented by and 1 mol of a diisocyanate compound.

Examples of the monomer represented by the above (VIII) include hydroxyalkyl (meth) acrylate, particularly 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and the diisocyanate compound includes For example tolylene diisocyanate,
Methylcyclohexane 2,4 (or 2,6) diisocyanate, 1,3-diisocyanate methylcyclohexane,
1,6-hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, phenylene diisocyanate,
Naphthalene diisocyanate, biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, bis (4 -Isocyanate phenyl) sulfone, isopropylidene bis (4-phenyl isocyanate), lysine isocyanate, isophorone diisocyanate and the like, among them, tolylene diisocyanate having two isocyanate groups of different reactivity, m-xylylene diisocyanate, Isophorone, methylcyclohexane 2,4-diisocyanate,
1,3-diisocyanate methylcyclohexane and the like are preferable.

The reaction between the above-mentioned isocyanate group-containing vinyl monomer and hydroxyl group-containing quinonediazide compound is carried out by reacting the isocyanate group-containing vinyl monomer and hydroxyl group-containing quinonediazide compound in an inert organic solvent in an amount of approximately 1 mol of the hydroxyl group with respect to 1 mol of the isocyanate. Room temperature to 80
C., preferably room temperature to about 60.degree. C., for about 0.5 to about 20 hours. The reaction can be monitored by measuring the isocyanate groups near 2250 cm ^{-1 by} infrared spectroscopy. As the inert organic solvent that can be used here, an inert organic solvent that does not react with an isocyanate group and a hydroxyl group can be used, and examples thereof include ketone-based, ester-based, aromatic-based, aliphatic-based, and ether-based solvents. These solvents are preferably desolvated after the reaction and replaced with an alcohol-based aqueous solvent.

Further, as an acid group-containing unsaturated monomer and other radically unsaturated monomer copolymerized with the monomer obtained by reacting the isocyanate group-containing vinyl monomer and the hydroxyl group-containing quinonediazide compound The following examples can be used.

First, as the acid group-containing unsaturated monomer, specifically, for example, (meth) acrylic acid, crotonic acid, itaconic acid,
(Anhydrous) maleic acid, fumaric acid, 2-hydroxyethyl acrylate acid phosphate, etc. may be mentioned, among which (meth) acrylic acid is preferred. Further, other radically unsaturated monomers used as necessary include, for example, hydroxyl group-containing (meth) acrylic acid esters represented by the general formula (VIII); methyl (meth) acrylate, ethyl (meth). ) Acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate,
tert- butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) alkyl C ₁ ~ ₂₄ pieces of such acrylic acid or methacrylic acid acrylate or Cycloalkyl esters; acryl or methacrylamide such as (meth) acrylamide, N-methyl (meth) acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl acrylamide;
Styrene, vinyltoluene, vinyl propionate, α-
Examples thereof include vinyl monomers such as methylstyrene, vinyl acetate, (meth) acrylonitrile, vinyl propionate, vinyl pivalate, and Veova monomer (Ciel Chemicals).

The copolymerization reaction of the above-mentioned monomers is usually carried out by mixing the above-mentioned monomers in a suitable organic solvent in the presence of a radical polymerizable initiator such as azobismethoxybutyronitrile or benzoyl peroxide. It is carried out by reacting at about 30 to about 80 ° C. for about 1 to 20 hours. As a suitable organic solvent, a water-soluble organic solvent (particularly alcohol-based or ether-based solvent) used for electrodeposition coating is suitable. Examples of such a solvent include methanol, ethanol, n-propanol, isopropanol, butanol, ethylene glycol, butyl cellosolve, ethyl cellosolve, diethylene glycol, methyl carbitol, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. The mixing ratio of the monomers described above is not strictly limited, but in general,
5 to 98% by weight, preferably 20 to 70% by weight of a monomer obtained by reacting an isocyanate group-containing vinyl monomer and a hydroxyl group-containing quinonediazide compound; 2 to 60% by weight of an acid group-containing unsaturated monomer, It is preferably 3 to 40% by weight; other radical unsaturated monomer is 0 to 90% by weight, preferably 10 to 70% by weight.

In the above-mentioned production method, as the diisocyanate compound to be reacted with the hydroxyl group-containing quinonediazide compound, the same diisocyanate compound as described in the production method can be used, and preferably a compound having two or more different reactive isocyanate groups.

The reaction between the hydroxyl group-containing quinonediazide compound and the diisocyanate compound can be carried out in the same manner as the reaction between the isocyanate group-containing vinyl monomer and the hydroxyl group-containing quinonediazide compound described in the above production method.

As a resin containing a hydroxyl group and an acid group that is reacted with an isocyanate group-containing quinonediazide compound obtained by reacting a hydroxyl group-containing quinonediazide compound and a diisocyanate compound, a hydroxyl value is 10 to 100, preferably 3
Resins having an acid value of 0 to 80 and an acid value of 10 to 300, preferably 20 to 250 are advantageously used, but such resins are those commonly used in the coating field. You can
For example, alkyd resin polyester, acrylic resin,
Examples thereof include acid-modified epoxy resin.

The reaction between the above-mentioned isocyanate group-containing quinonediazide compound and the resin is generally carried out in the presence or absence of an inert organic solvent similar to that described for the production method,
The isocyanate group-containing quinonediazide compound and the resin are mixed at room temperature to about 80 ° C., preferably at room temperature to about 60 ° C.
It can be performed by holding for 5 to 20 hours.

In the above-mentioned production method, the hydroxyl group-containing acrylic monomer that is reacted with the same isocyanate group-containing quinonediazide compound as described in the production method is selected from the monomers of the general formula (VIII) described above in the production method. You can

The reaction of the isocyanate group-containing quinonediazide compound and the hydroxyl group-containing acrylic monomer, in the presence or absence of the same inert organic solvent as described in the production method, the isocyanate group-containing quinonediazide compound and the hydroxyl group-containing acrylic system Isocyanate group 1 with monomer
About 1 mole of hydroxyl group per mole, room temperature to about 80
It can be carried out by continuing the reaction at 0 ° C, preferably room temperature to about 60 ° C for about 0.5 to 20 hours.

In the production method, as the copolymer containing an isocyanate group and an acid group that is reacted with a hydroxyl group-containing quinonediazide compound, the same isocyanate group-containing vinyl monomer as described above for the production method, and the same as used in the production method. acid group-containing unsaturated monomer and optionally other radical unsaturated monomer [C ₁ ~ ₂₄ alkyl or cycloalkyl esters of acrylic acid or methacrylic acid, acrylic or methacrylic amides;
Vinyl monomers and the like] are preferable. As the isocyanate group-containing vinyl monomer, when m-propenyl-α, α-dimethylbenzylisocyanate having an isocyanate group bonded to a tertiary carbon is used, an acid group-containing unsaturated monomer which is copolymerized by the isocyanate group is used. Since it does not react with the acid group of the body, there is no fear that the resin will gel or thicken during the production, and the isocyanate group can be reliably introduced into the resin, which is advantageous.

The copolymerization reaction of the above-mentioned monomers is carried out in the same manner as described in the production method in an inert organic solvent which does not react with an isocyanate group, the monomers of the above respective components are 2,2′-azobisisobutyronitrile. , 2,2'-azobis (2,4-dimethylvaleronitrile), in the presence of a radical polymerizable initiator such as benzoyl peroxide, at a temperature of about 30 to about 180 ℃, preferably about 60 to about 120 ℃ It is carried out by reacting for about 1 to about 20 hours.

The reaction between the copolymer and the hydroxyl group-containing quinonediazide compound is carried out by reacting the copolymer and the hydroxyl group-containing quinonediazide compound usually at room temperature to about 80 ° C., preferably at room temperature to about 60 ° C. for about 0.5 to about 20 hours. It can be done by A solvent solution of the copolymer thus obtained with a hydroxyl group-containing quinonediazide compound can be desolvated to replace the water-soluble organic solvent as described above used in the electrodeposition coating composition.

The acidic resin produced as described above has the following formula (I) derived from a reaction product of a hydroxyl group-containing quinonediazide compound and an isocyanate group-containing compound or resin. Where R ₁ is R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkyl ester group, and R ₃ represents an alkylene group, a cycloalkylene group or an alkylene ether group, and a modified quinonediazide sulfone unit and an acid group represented by .

The acidic resin in the present invention contains the modified quinonediazide sulfone unit of the above formula (I) in an amount of 5 to 5 based on the acidic resin.
It may be contained in an amount of 60% by weight, preferably 10 to 50% by weight. The modified quinonediazide sulfone unit is 5
If the amount is less than wt%, the amount of ketene in the exposed portion of the formed coating film is small and thus the amount of carboxylic acid is small, so that development with weak alkali becomes difficult. On the other hand, when it is more than 60% by weight, the glass transition temperature (Tg) of the resin becomes high and the formed electrodeposition coating film becomes hard, so that cracking is likely to occur.

The acidic resin in the present invention has an acid value of 10 to 250, preferably in the range of 10 to 80, and when the acid value is less than 10, it becomes difficult to make it water-soluble or water-dispersible.
If it exceeds, it becomes difficult to coat the electrodeposition paint on the substrate and there is a tendency that a large amount of electric power is required to increase the coating amount.

The acidic resin also differs depending on the type of resin,
Generally, the number average molecular weight is 3,000 to 100,000, preferably
It can be in the range of 5,000 to 30,000. If the number average molecular weight is less than 3,000, the coating film applied during electrodeposition coating tends to be destroyed and often a uniform coating film cannot be obtained. The other 10
If it is more than 000, the smoothness of the electrodeposition coating film tends to be low and the coated surface tends to be uneven, and the resolution of the image lines tends to be poor.

The positive photosensitive anion electrodeposition coating composition of the present invention is obtained by neutralizing the above acidic resin containing a modified orthoquinonediazide group and an acid group with an amine or an alkaline compound, and dispersing or dissolving it in water. Examples of the neutralizing agent used at that time include monoethanolamine,
Alkanolamines such as diethanolamine and triethanolamine; Alkanolamines such as triethylamine; triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine,
Alkylamines such as diisobutylamine; alkylalkanolamines such as dimethylaminoethanol; alicyclic amines such as microhexylamine; alkali metal hydroxides such as caustic soda and caustica; ammonia and the like, which may be used alone or It can be used as a mixture.

In the present invention, in order to improve the fluidity of the water-soluble or water-dispersed electrodeposition coating composition, a hydrophilic solvent (eg, isopropanol, n-butanol, t-butanol,
Methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol, methyl ether, dioxane, tetrahydrofuran etc.) can be added. Generally, the amount of the hydrophilic solvent used is preferably 300 parts by weight or less with respect to 100 parts by weight of the acidic resin.

Further, in order to increase the coating amount on the article to be coated, a hydrophobic solvent (for example, a petroleum solvent such as toluene or xylene; a ketone such as methyl ethyl ketone or methyl isobutyl ketone);
Esters such as ethyl acetate and butyl acetate; alcohols such as 2-ethylhexyl alcohol) can also be added. Generally, the amount of the hydrophobic solvent used is preferably 200 parts by weight or less with respect to 100 parts by weight of the acidic resin.

Furthermore, if necessary, the performance of the electrodeposition coating film can be appropriately adjusted by blending a resin other than the above acidic resin, and a dye, a pigment or the like can be added.

Production of a printed wiring board using the positive photosensitive anion electrodeposition coating composition of the present invention is carried out as follows.

An anion electrodeposition coating bath containing a neutralized product of the above acidic resin as a main component has a pH of 5 to 10, a bath concentration (solid content concentration) of 3 to 30% by weight, preferably 5 to 15% by weight, and a bath temperature of 15 to 40 ° C. Preferably 15 to
Control at 30 ℃. Then, the electrodeposited coating bath is dipped as a positive electrode in a printed wiring board made by plating an insulating plate with a copper foil on it, and a direct current of 20 to 400 V is applied. It is appropriate that the energizing time is 30 seconds to 5 minutes, and the film thickness is 2 to 100 μm, preferably 3 to 20 μm in dry film thickness.
It is desirable that it is m.

After the electrodeposition coating, the object to be coated is lifted from the electrodeposition bath and washed with water, and then the water contained in the electrodeposition coating film is removed by hot air or the like.

Then, a pattern mask (photo positive) is superposed on the surface of the thus-formed photosensitive electrodeposition coating film, and only unnecessary parts other than the conductor circuit (circuit pattern) are exposed to actinic rays such as ultraviolet rays. Since the orthoquinonediazide compound in this exposed portion becomes a carboxylic acid via ketene, it is removed by the developing treatment of a developing solution such as an alkaline aqueous solution, and high resolution can be realized.

The actinic ray used for exposure in the present invention is 3000 to 4500Å
A light beam having a wavelength of These light sources include sunlight, mercury lamps, xenon lamps, arc lamps and the like. Irradiation with actinic rays is usually performed for 1 second to 20 minutes.

Further, the developing treatment is carried out by spraying a weak alkaline water on the surface of the coating film to wash away the photosensitive portion of the coating film. As weak alkaline water, caustic soda, sodium carbonate, caustic potash, aqueous ammonia having a pH of 8 to 10, which can neutralize the free carboxylic acid contained in the coating film to give water solubility, can be used.

Then, the copper foil portion (non-circuit portion) exposed on the substrate by the developing treatment is removed by a normal etching treatment using, for example, ferric chloride solution. Thereafter, the unexposed coating film on the circuit pattern is also a cellosolve solvent such as ethyl cellosolve or ethyl cellosolve acetate; an aromatic hydrocarbon solvent such as toluene or xylene; a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone; ethyl acetate, Acetate solvent such as butyl acetate; Chlorine solvent such as trichloroethylene or pH 12
The printed circuit is formed on the substrate by dissolving and removing with the above caustic soda, caustic potash, or the like.

The positive photosensitive anion electrodeposition coating composition of the present invention can be easily anion electrodeposition coated on a copper foil, and the deposited coating film is dried to form a uniform photosensitive film. When the photosensitive film is irradiated with light through a positive film, the exposed area changes as described above and is developed with weak alkaline water, and the unexposed area can be dissolved and removed with a solvent or strong alkali. It can be replaced with the photosensitive film of.

In particular, the electrodeposition coating composition of the present invention is most suitable for the production of a printed circuit board having a through hole, and the soldering process and the like are eliminated as compared with the case where a photosensitive dry film is used, and the printed circuit board production process can be shortened. Further, although it is difficult to form a cured film in a small diameter through-hole with a photocurable electrodeposition coating, the present invention is suitable for the production of a printed circuit board having a small diameter because the unexposed portion remains as a resist film. ing.

Further, in the positive-type photosensitive electrodeposition coating composition of the present invention, since the resin in which the quinonediazide group is introduced through the sulfonamide bond and the urethane bond is used as the main vehicle component of the electrodeposition coating, the resin is Management of the electrodeposition coating bath is easy because there is no agglomeration or precipitation at the bath bottom during the electrodeposition coating over a long period of time, or a large change in coating voltage.

Next, examples of the present invention will be described. Parts and% in the examples are parts by weight and% by weight, respectively.

Production Example of Hydroxyl-Containing Orthoquinonediazide Compound 1 A four-neck flask was charged with 269 parts of orthonaphthoxone diazide sulfonic acid chloride and 1345 parts of dioxane, and 1 part of 150 parts of N-methylethanolamine was stirred at room temperature.
Dropped over time. After the dropping, continue stirring for about 3 hours,
After confirming that absorption of amino group around 3300 cm ^{-1 in} IR spectrum disappeared, the reaction was terminated.

This solution was then placed in deionized water to remove hydrochloric acid trapped quaternary amine generated during the reaction. Next, the product was extracted with isobutyl acetate, the solvent was distilled off, and the product was placed in a vacuum dryer and dried to obtain a hydroxyl group-containing orthoquinonediazide compound 1.

Production Example of Hydroxyl-Containing Orthoquinonediazide Compound 2 A four-necked flask was charged with 269 parts of orthonaphthoquinonediazidesulfonic acid chloride and 1345 parts of dioxane, and 122 parts of monoethanolamine was added dropwise over 1 hour while stirring at room temperature. After completion of the dropwise addition, stirring was continued for about 3 hours, and it was confirmed that the absorption of amino groups near 3300 cm ^-1 in the IR spectrum disappeared, and then the reaction was terminated.

This solution was then placed in deionized water to remove the hydrochloric acid trapped quaternary amine generated during the reaction. After the product was extracted with isobutyl acetate, the solvent was distilled off,
It was put in a vacuum dryer and dried to obtain a hydroxyl group-containing orthoquinonediazide compound 2.

Production Example of Unsaturated Compound 1 After adding 489 parts of isophorone diisocyanate to a four-necked flask and heating to 80 ° C., hydroxyethyl acrylate
232 parts was added dropwise over 2 hours and kept as such for 6 hours to obtain unsaturated compound 1.

Production Example of Unsaturated Compound 2 370 parts of tolylene diisocyanate was placed in a four-necked flask, heated to 80 ° C., 232 parts of 2-hydroxyethyl acrylate was added dropwise over 2 hours, and the mixture was kept as it was for 6 hours to be unsaturated. Compound 2 was obtained.

Production Example of Unsaturated Compound 3 In a four-necked flask, 1535 parts of methyl isobutyl ketone and 307 parts of hydroxyl group-containing orthoquinonediazide compound 1 were put, and 50
After the temperature was raised to 0 ° C., 201 parts of m-isopropenyl-α, α-dimethylbenzylisocyanate was added dropwise over 2 hours and kept as such for 8 hours to obtain unsaturated compound 3.

Production Example of Unsaturated Compound 4 529 parts of the following isocyanate group-containing compound, 130 parts of hydroxyethyl acrylate and 0.07 part of dibutyltin diacetate were placed in a four-necked flask and stirred for 3 hours, and the isocyanate group around 2250 cm ^-1 in IR spectrum Was confirmed to have disappeared, and unsaturated compound 4 was obtained.

Production Example of Isocyanate Group-Containing Compound A four-necked flask was charged with 307 parts of hydroxyl group-containing orthoquinonediazide compound 1 and 222 parts of isophorone diisocyanate and stirred at 50 ° C. for 5 hours to obtain an isocyanate group-containing compound.

Example 1 290 parts of diethylene glycol dimethyl ether was placed in a four-necked flask, the temperature was raised to 110 ° C. with stirring, and then n
-Butyl methacrylate 202 parts, acrylic acid 24 parts, m
A mixed solution of 92 parts of isopropenyl-α, α-dimethylbenzoyl isocyanate and 20 parts of azobisbutyrovaleronitrile was added dropwise over 3 hours, and after maintaining for 1 hour, 14 parts of methyl isobutyl ketone and 14 parts of azobisbutyrovalero A mixed solution of 3 parts of nitrile was added dropwise over 1 hour and kept for another 2 hours. After that, the temperature was lowered to 50 ° C, 142 parts of hydroxyl group-containing orthoquinonediazide compound 1 and 4.6 parts of dibutyltin diacetate were added, and the mixture was kept for 3 hours.
It was confirmed that the absorption of isocyanate groups around 250 cm ^-1 had disappeared, and a positive photosensitive resin (acid value 40.7) was obtained. Viscosity E, molecular weight 7,000. Then, 33 parts of triethylamine was added to the photosensitive resin solution to sufficiently neutralize it, and then the solid content was 10%.
Deionized water is added so that the amount becomes 100%, and an electrodeposition coating bath (pH 8.0)
And

Example 2 290 parts of diethylene glycol dimethyl ether was placed in a four-necked flask, the temperature was raised to 110 ° C. with stirring, and then n-
Butyl methacrylate 185 parts, acrylic acid 41 parts, m-
A mixed solution of 92 parts of isopropenyl α, α-dimethylbenzyl isocyanate and 20 parts of azobisbutyrovaleronitrile was added dropwise over 3 hours and kept for 1 hour, and then 15 parts of methyl isobutyl ketone and 3 parts of azobisbutyrovaleronitrile. The mixed solution of was added dropwise over 1 hour and kept for 2 hours. After that, the temperature was lowered to 50 ° C., 142 parts of hydroxyl group-containing orthoquinonediazide compound 1 and 4.6 parts of dibutyltin diacetate were added, and the mixture was kept for 3 hours, after which absorption of isocyanate groups around 2250 cm ^{−1 in} the infrared spectrum disappeared. Check the
A positive photosensitive resin (acid value 69.4) was obtained. Viscosity N, molecular weight
7,600. Then add triethylamine 5 to this photosensitive resin solution.
After 7 parts were added and the mixture was sufficiently neutralized, deionized water was added so that the solid content became 10% to prepare an electrodeposition coating bath (pH 8.2).

Example 3 290 parts of diethylene glycol dimethyl ether was placed in a four-necked flask, the temperature was raised to 110 ° C. with stirring, and then n-
Butyl methacrylate 185 parts, acrylic acid 41 parts, m-
A mixed solution of 92 parts of isopropenyl-α, α-dimethylbenzyl isocyanate and 20 parts of azobisbutyrovaleronitrile was added dropwise over 3 hours, and the mixture was kept for 1 hour. Then, 15 parts of diethylene glycol dimethyl ether and 3 parts of azobisbutyrovaleronitrile were used. Part of the mixed solution was added dropwise over 1 hour and kept for another 2 hours. Thereafter, the temperature was lowered to 50 ° C., 136 parts of hydroxyl group-containing orthoquinonediazide compound 2 and 4.6 parts of dibutyltin diacetate were added, and after maintaining for 3 hours, absorption of isocyanate group around 2250 cm ⁻¹ in infrared spectrum disappeared. Was confirmed, and a positive photosensitive resin (acid value 69.4) was obtained. Viscosity M, molecular weight 7,300. Next, 57 parts of triethylamine was added to this photosensitive resin solution to sufficiently neutralize it, and deionized water was added so that the solid content became 10% to prepare an electrodeposition coating bath (pH 8.2).

Example 4 290 parts of diethylene glycol dimethyl ether was placed in a four-necked flask and the temperature was raised to 110 ° C. with stirring. Then, 185 parts of n-butyl acrylate, 41 parts of acrylic acid, 155 parts of unsaturated compound 1, azobisbutyro valero. After a mixed solution of 20 parts of nitrile was added dropwise over 3 hours and kept for 1 hour, a mixed solution of 15 parts of methyl isobutyl ketone and 3 parts of azobisbutyrovaleronitrile was added dropwise over 1 hour and maintained for 2 hours. . Then, the temperature was lowered to 50 ° C., 142 parts of hydroxyl group-containing orthoquinonediazide compound 1 and 4.6 parts of dibutyltin diacetate were added, and the mixture was kept for 3 hours.
It was confirmed that the absorption of the isocyanate group around 250 cm ^-1 had disappeared, and a positive photosensitive resin (acid value 61.1) was obtained. Viscosity X, molecular weight 7,300. Next, 57 parts of triethylamine was added to this photosensitive resin solution to sufficiently neutralize
Deionized water was added to 10%, and an electrodeposition coating bath (pH 8.
2) got.

Example 5 After adding 290 parts of diethylene glycol dimethyl ether to a four-necked flask and heating to 110 ° C. with stirring, n-butyl methacrylate 185 parts, acrylic acid 41 parts, unsaturated compound 2 130 parts, azobisbutyro valero After a mixed solution of 20 parts of nitrile was added dropwise over 3 hours and kept for 1 hour, a mixed solution of 15 parts of methyl isobutyl ketone and 3 parts of azobisbutyrovaleronitrile was added dropwise over 1 hour and maintained for 2 hours. . After that, the temperature was lowered to 50 ° C., 142 parts of hydroxyl group-containing orthoquinonediazide compound 1 and 4.6 parts of dibutyltin diacetate were added, and the mixture was kept for 3 hours.
It was confirmed that the absorption of isocyanate groups around 250 cm ^-1 had disappeared, and a positive photosensitive resin (acid value 64.1) was obtained. Viscosity Z, molecular weight 6,800. Then, 57 parts of triethylamine was added to this photosensitive resin solution to sufficiently neutralize the solid content.
Deionized water was added to 10%, and an electrodeposition coating bath (pH 8.
2)

Example 6 After adding 290 parts of diethylene glycol dimethyl ether to a four-necked flask and heating to 60 ° C. with stirring, n-butyl methacrylate 185 parts, acrylic acid 41 parts, unsaturated compound 3 233 parts, azobismethoxydimethyl valero After adding a mixed solution of 28 parts of nitrile over 3 hours and keeping it for 1 hour, a mixed solution of 15 parts of diethylene glycol dimethyl ether and 3 parts of azobismethoxydimethylvaleronitrile was added dropwise over 1 hour and kept for 2 hours. A photosensitive resin (acid value 69.6) was obtained. Viscosity N, molecular weight 7,000.

Then, 57 parts of triethylamine was added to this photosensitive resin solution to sufficiently neutralize it, and then deionized water was added so that the solid content became 10% to obtain an electrodeposition coating bath (pH 8.2).

Example 7 Next, 315 parts of diethylene glycol dimethyl ether was placed in a four-necked flask and heated to 80 ° C. with stirring,
122 parts of n-butyl methacrylate, 36 parts of acrylic acid,
A mixed solution of 305 parts of the unsaturated compound 4 and 14 parts of azobismethoxybutyrovaleronitrile was added dropwise over 3 hours, and the mixture was kept for 1 hour. Then, 15 parts of diethylene glycol dimethyl ether and 2 of azobismethoxybutyrovaleronitrile were used.
Part of the mixed solution was added dropwise over 1 hour and kept for 2 hours to obtain a positive photosensitive resin (acid value 60.0). Viscosity W, molecular weight 7,800. Then, 38 parts of triethylamine was added to the photosensitive resin solution to sufficiently neutralize it, and deionized water was added so that the solid content became 10% to prepare an electrodeposition coating bath (pH 8.2).

Example 8 Next, 315 parts of diethylene glycol dimethyl ether was placed in a four-necked flask, the temperature was raised to 110 ° C. with stirring, and then 122 parts of n-butyl methacrylate and 36 parts of acrylic acid.
Part, hydroxyethyl methacrylate 60 parts, azobisbutyrovaleronitrile 14 parts mixed solution was added dropwise over 3 hours and kept for 1 hour. Then, a mixed solution of 15 parts diethylene glycol dimethyl ether and 2 parts azobisbutyro valeronitrile was added. After maintaining for 1 hour and 2 hours, then at room temperature, 245 parts of isocyanate group-containing compound and 0.04 part of dibutyltin diacetate were added, and after maintaining for 3 hours, absorption of isocyanate group around 2250 cm ^-1 in IR spectrum Was confirmed to have disappeared, and a positive photosensitive resin (acid value 60.0) was obtained. Viscosity Z, molecular weight 7,400. Next, 38 parts of triethylamine was added to the photosensitive resin solution to sufficiently neutralize it, and deionized water was added so that the solid content became 10% to prepare an electrodeposition coating bath (pH 8.0).

A copper clad laminate for printed wiring (240 × 170 × 1.5 mm) having through holes was immersed as an anode in each of the electrodeposition coating baths obtained in Examples 1 to 8 and a DC current of 100 V was applied at a bath temperature of 25 ° C. It was energized for a minute and was electrodeposited. The coating film was washed with water and dried at 50 ° C. for 5 minutes to form a sticky, smooth photosensitive film having a thickness of 5 μm.
Then, a positive film was attached to this electrodeposition coated surface with a vacuum device, and 150 mJ / cm ^{2 on} both sides using a 3 KW ultra-high pressure mercury lamp.
Irradiate each. Next, the exposed area is washed out with a 0.1% sodium carbonate aqueous solution and developed. After washing with water (ferric chloride solution), the copper foil is etched to remove it, and then the unexposed area is removed with ethylene glycol monoethylene ether solvent. As a result, a printed circuit board with a clear and sharp pattern in which copper foil was attached to the through holes was obtained.

Further, each of the electrodeposition coating baths obtained in Examples 1 to 8 was heated at 30 ° C. for 3 hours.
After conducting a storage promotion test for a month, the appearance change of the coating bath was examined. As a result, the coating bath was good without any abnormality such as sedimentation and aggregation of the resin component. Further, a printed circuit board was prepared by the same method as described above using the coating bath which was subjected to the storage acceleration test. As a result, it was possible to obtain a printed circuit board having a clean sharp pattern in which the copper foil was also attached to the through holes, which was excellent.

Comparative Example In Example 1, the unsaturated monomer 1 was replaced with a quinone diazide sulfonic acid ester (1 mol of naphthoquinone diazide sulfonyl chloride was esterified with 1 mol of an equivalent addition product of glycidyl methacrylate and hydroxybenzoic acid). A positive type photosensitive resin (acid value 48, average molecular weight 12,000) solution was obtained by the same formulation and production method as in Example 1 except that the same amount was used. Then, the positive photosensitive resin solution was used to carry out the same formulation and manufacturing method as in Example 1 to prepare a 15% solids electrodeposition coating bath (pH 7.2). After conducting a storage acceleration test for 3 months at the electrodeposition coating bath at 30 ° C., the appearance change of the coating bath was examined. As a result, the resin component was settled and agglomerated at the bottom of the coating bath, and even if the resin component was stirred, it did not return to the original state. Further, a printed circuit board was prepared in the same manner as in Example 1 using the coating bath which was subjected to the storage acceleration test. As a result, a printed circuit board having a sharp pattern could not be obtained because the exposed area was not washed with an aqueous solution of sodium carbonate and the developability was poor.

Claims (1)

[Claims] 1. A compound represented by the following formula (I) in the molecule: Where R ₁ is R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkyl ether group, and R ₃ represents an alkylene group, a cycloalkylene group or an alkylene ether group, and the acid value of the modified quinonediazide sulfone unit is A positive photosensitive anion electrodeposition coating composition, which contains a resin in the range of 10 to 250 as a main component.