JP2935207B2 - Positive photosensitive anion electrodeposition resist composition and method for producing printed wiring board using this composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type photosensitive anion electrode which is excellent in operation stability, has good coating workability, and has high reliability for forming a conductor image, and is particularly suitable as an etching resist for manufacturing a printed wiring board. The present invention also relates to a resist composition, and to a method for producing a printed wiring board using the resist composition.

[0002]

2. Description of the Related Art Printed wiring boards used in electronic equipment and the like mainly use a circuit pattern formed by screen printing or photolithography using a photosensitive dry film on an insulating substrate having a conductor layer on the surface. Manufactured by the subtractive method used. However, recently, a method using a positive photosensitive electrodeposition resist has been proposed in order to cope with miniaturization of circuit patterns and reduction in diameter of through holes.

[0003]

As the positive photosensitive electrodeposition resist, a resin obtained by bonding quinonediazidosulfonic acid to a base resin via a sulfonate ester bond to a base resin such as an acrylic resin having an ion-forming group is mainly used. A composition as a component (see JP-A-61-206293), a photosensitive compound in which a quinonediazidosulfonic acid is bonded to a polyphenol such as polyhydroxybenzophenone via a sulfonate ester bond, and has an ion-forming group. A composition mixed with a base resin such as an acrylic resin (see JP-A-61-206293),
Composition comprising a resin in which hydroxylamine and quinonediazidesulfonic acid are bonded to a base resin such as an acrylic resin having an ion-forming group via a urethane bond and a sulfonimide bond (Japanese Patent Laid-Open No. 64-9027).
No. 0), a compound or resin having a hydroxyl group and a hydroxyamine and quinonediazidosulfonic acid bonded via a urethane bond and a sulfonimide bond, to a base resin such as an acrylic resin having an ion-forming group. Mixed composition (JP-A-2-2896)
A water-soluble or water-dispersible composition has been proposed.

[0004] However, the above-mentioned conventional composition has the following problems, and it is desired to solve them. That is,
In a resin system in which a photosensitive group is introduced via a sulfonic acid ester group, the sulfonic acid ester group is easily hydrolyzed, and there is a problem in storage stability as an electrodeposition resist solution and operation stability of a bath. Further, a composition in which a photosensitive compound having a sulfonate ester bond is mixed has a problem that the stability of the water-soluble substance or the water-dispersed substance itself is not sufficient. To solve these problems, the ion-forming group is placed at a site away from the hydrophobic polymer main chain,
Forming an aqueous dispersion in which the photosensitive compound is present in the core (core) by water dispersion, protecting the sulfonate ester from hydrolysis, and improving the stability of the aqueous dispersion itself; Specifically, a resin obtained by half-esterifying a polybasic acid anhydride with a polymer obtained by copolymerizing a long-chain (meth) acrylate-based monomer having a hydroxyl group at a terminal and introducing an ion-forming group is used as the base resin. A proposal has been made. However, even in the above proposal, when the amount of the substrate to be treated is small and the electrodeposition bath solution stays in the bath for a very long time (low turnover), the ion-forming group introduced by the half-esterification gradually undergoes hydrolysis. In addition, there is a problem that the operation stability of the bath is deteriorated and the quality of the formed electrodeposition resist film is easily deteriorated. In addition, there is a problem that a complicated and time-consuming process is required for synthesizing the base resin as compared with the case of general acrylic resin synthesis. In addition, in the method of introducing a photosensitive group through the sulfonimide bond and the urethane bond, the problem relating to hydrolysis is greatly improved, and an electrodeposition resist bath solution having excellent operation stability can be obtained. The dissolution rate of the exposed part in the developing solution is slow due to urethane bonding, and development must be performed at a high temperature.
There is a problem that the condition width for developing is slightly narrowed. In addition, there is a problem that a complicated and long process is required for introducing a photosensitive group as compared with a sulfonate type.

[0005]

Accordingly, the present inventors have found that the storage stability of the electrodeposition resist solution is excellent, the operation stability of the electrodeposition bath is high even at a low turnover speed, and the range of conditions for development is wide. In addition, intensive studies have been made to obtain a positive photosensitive electrodeposition resist composition which can be manufactured by a method which does not require a complicated and long process. Further, a method of manufacturing a printed wiring board using the electrodeposition resist composition was also studied. As a result, the present inventors have found a composition and a method for manufacturing a printed wiring board which can solve the above problems, and have completed the present invention.

That is, the present invention relates to “1. (a) Carboxyl group 0.07 in 1 kg of resin
20 to 50 parts by weight of an acrylic resin having 5 to 0.55 mol and 1.5 to 5.5 mol of hydroxyl groups, (b) 1 kg of resin
Acrylic resin 25 to 70 having 1.20 to 2.50 mol of carboxyl groups and 1.5 to 5.0 mol of hydroxyl groups therein
(C) a group represented by the following formula [1], [2], or [3] in one molecule:

Embedded image Equation [2]

Embedded image Equation [3]

Embedded image Containing 7.5 to 30 parts by weight of a photosensitive agent having at least one
The total amount of the components (a), (b) and (c) is 100 parts by weight, and the content of the carboxyl group in the total of the components (a), (b) and (c) is 0.60 to 1. 25 mol / Kg, the content of the hydroxyl group is 1.2 to 3.5 mol / Kg
A positive photosensitive anion electrodeposition resist composition comprising, as a main component, a water-dispersible resin composition obtained by neutralizing and dispersing a resin mixture as described above in water with a base. 2. The components (a), (b) and (c) are each composed of 20 to 50 parts by weight of the component (a) and 25 to 25 parts by weight of the component (b) in a total of 100 parts by weight.
2. The positive photosensitive anion electrodeposition resist composition according to item 1, wherein 70 parts by weight and 7.5 to 30 parts by weight of the component (c) are used. 3. Item 1 or 2 wherein the solid content is 3 to 50%
The positive-type photosensitive anion electrodeposition resist composition described in the above item. 4. (I) On the surface of the circuit board having the conductive coating, 1
(C) electrodepositing the electrodeposition resist composition described in (1) to form a positive photosensitive film; (ii) exposing the positive photosensitive film via a pattern mask; (iii) exposing the exposed portion to light. Forming an etching pattern by removing the conductive film; (iv) removing the exposed conductive film by etching; and (v) removing the photosensitive film on the circuit pattern. A method for manufacturing a printed wiring board. 5. The electrodeposited positive photosensitive film has a dry film thickness of 2 to 5
Item 5. The method for manufacturing a printed wiring board according to Item 4, which is 0 μm. 6. Exposure to a positive photosensitive film through a pattern mask is performed by applying a light beam having a wavelength of
Irradiation of 0 to 800 mj / cm ² is performed.
13. The method for manufacturing a printed wiring board according to any one of the above items. About.

[0007]

The acrylic resin as component (a) in the resist composition of the present invention has a carboxyl group content of 0.075 to 0.55 mol, preferably 0.10 to 0.5 mol per kg of the resin.
An acrylic resin having 45 moles and 1.5 to 5.5 moles, preferably 1.75 to 4.5 moles of hydroxyl groups may be used, but generally has a number average molecular weight of 2,000 to 200,00.
About 0 is used. The acrylic resin (a) can be obtained by polymerizing by a known method.

The monomer component for obtaining the acrylic resin (a) by polymerization can be appropriately selected according to the required performance. Preferably, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) )
Alkyl (meth) acrylate having 1 to 18 carbon atoms such as acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate; 2
-Hydroxyl-containing unsaturated monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and allyl alcohol; carboxyl-containing unsaturated monomers such as (meth) acrylic acid, crotonic acid, itaconic acid and maleic acid Body; glycidyl (meth) acrylate,
Epoxy group-containing unsaturated monomers such as allyl glycidyl ether and 3,4-epoxycyclohexylmethyl (meth) acrylate; styrene, α-methylstyrene, vinyltoluene, vinyl acetate, (meth) acrylamide,
Other copolymerizable monomers such as (meth) acrylonitrile and N-methylol (meth) acrylamidobutyl ether can be exemplified. The acrylic resin (a) essentially contains the above carboxyl group-containing unsaturated monomer and hydroxyl group-containing monomer, and is blended with another monomer component, for example, by copolymerization in the presence of a polymerization catalyst and preferably an organic solvent. Can be obtained.

In the composition of the present invention, the acrylic resin as the component (b) has a carboxyl group of 1.2 kg per 1 kg of the resin.
An acrylic resin having 0 to 2.50 mol, preferably 1.25 to 2.00 mol, and 1.5 to 5.0 mol, preferably 2.0 to 4.0 mol of hydroxyl groups may be used. Those having a number average molecular weight of about 2,000 to 20,000 are used. The acrylic resin (b) is prepared in the same manner as in the synthesis of the acrylic resin (a) so that the amounts of the carboxyl group and the hydroxyl group become predetermined values.
It can be obtained by polymerization.

The component (a) is basically a water-insoluble resin and embeds a photosensitive component (c) having high hydrophobicity and being susceptible to hydrolysis. It has the effect of preventing attacking c). Component (b) is a resin that exhibits water solubility or water dispersibility upon neutralization, and component (c)
Acts as a protective colloid for the particles of the component (a) having embedded therein to form a stable dispersion. It is necessary that the component (a) and the component (b) have an appropriate affinity for each other. Therefore, the hydroxyl group content and the carboxyl group content of the component (a) and the component (b) are within predetermined ranges. Is required.

If the content of the carboxyl group in the acrylic resin (a) is less than 0.075 mol / Kg resin, the particle size of the dispersed particles of the obtained aqueous dispersion becomes large, and the stability of the aqueous dispersion is deteriorated. On the other hand, when the content of the carboxyl group is more than 0.55 mol / Kg resin, the ability to embed the component (c) is reduced, and the component (c) is liable to precipitate in the continuous phase during storage, and is dispersed in water. As the stability of the body deteriorates, the sulfonic acid ester group of the component (c) is easily hydrolyzed.

When the content of the carboxyl group in the acrylic resin (b) is less than 1.20 mol / Kg resin, the particle size of the dispersed particles of the obtained aqueous dispersion becomes large, and the stability of the aqueous dispersion is deteriorated. On the other hand, when the content of the carboxyl group is more than 2.50 mol / Kg resin, the water affinity becomes too high, the effect as an electrostatic and steric protective phase in the aqueous dispersion is reduced, and the stability of the aqueous dispersion is reduced. Sex is reduced.

The acrylic resin (a) has a hydroxyl group content of 1.5 to 5.5 mol / Kg resin, and the acrylic resin (b) has a hydroxyl group content of 1.5 to 5.0 mol / Kg resin. It is necessary to be. For each resin,
When the content of the hydroxyl group is lower than the lower limit value of 1.5 mol / Kg resin, the hydrophilicity of the dispersed particles of the aqueous dispersion is insufficient, and the stability is reduced. On the other hand, the content of the hydroxyl group is, When the value exceeds the upper limit, the affinity for water becomes too high, and the effect of the protective phase on the component (c) is reduced, and the stability is deteriorated.

The component (c) in the composition of the present invention is a photosensitive agent having at least one group represented by the above formula [1], [2] or [3]. This photosensitizer reacts, for example, a compound having a hydroxyl group with o-naphthoquinonediazide-5-sulfonic acid halide, o-naphthoquinonediazide-4-sulfonic acid halide and / or o-benzoquinonediazide-4-sulfonic acid halide. Can be obtained. The photosensitizer generally has a molecular weight of about 40.
0 to about 10,000, preferably in the range of about 500 to about 5,000. The photosensitive compound typically includes tri- or tetra-hydroxybenzophenone, a novolak-type phenol resin, a novolak-type cresol resin, polyhydroxystyrene, or the like, and o-naphthoquinonediazide-5-sulfonic acid chloride or o-naphthoquinonediazide-5-sulfonic acid chloride.
-Benzoquinonediazide-4-sulfonic acid chloride.

In the photosensitive agent as the component (c), the orthoquinonediazide portion becomes carboxylic acid through ketene by light irradiation, and the irradiated resist portion is removed by development. In the water-dispersible resin composition of the present invention, the compounding ratio of the components (a), (b) and (c) is such that (a), (b) and (c) ) Component 20-50 parts by weight, preferably 20
To 40 parts by weight, 25 to 70 parts by weight of component (b), preferably 35 to 70 parts by weight, 7.5 to 30 parts by weight of component (c),
Preferably it is 7.5 to 25 parts by weight.

In the water-dispersible resin composition of the present invention, if the component (a) is less than 20 parts by weight in the total of 100 parts by weight of the components (a), (b) and (c), the photosensitive agent is sufficiently encapsulated. When the component (a) exceeds 50 parts by weight, the component layer (a) having low hydrophilicity comes in contact with water as a dispersion medium. And (b), the dispersion protection effect of the component layer is reduced, and the stability of the dispersed particles is deteriorated. If the amount of the component (b) is less than 25 parts by weight, the effect of protecting the dispersion becomes insufficient and the stability of the dispersed particles is deteriorated. On the other hand, if the amount of the component (b) exceeds 70 parts by weight, the water-soluble component in the system increases. Too long, the dispersed particles are likely to be welded to each other and become unstable. When the amount of the component (c) is less than 7.5 parts by weight, the difference in solubility between the exposed portion and the unexposed portion in the developing solution after exposure of the resist is reduced, so that the developability is reduced. If the amount exceeds 30 parts by weight, the stability of the dispersed particles is deteriorated, and the sensitivity is hardly improved by adding a large amount of the photosensitizer. Therefore, it is economically disadvantageous to use a large amount of the expensive photosensitizer. is there.

In the composition of the present invention, (a)
In the total of the components (b) and (c), the content of the carboxyl group is 0.60 to 1.25 mol / Kg, and the content of the hydroxyl group is 1.2 to 3.5 mol / Kg. When the content of the carboxyl group is less than 0.60 mol / Kg, the hydrophilicity of the whole system becomes insufficient and the dispersed particles become unstable.
If it exceeds 25 mol / Kg, water-soluble ones increase, so that the Coulomb efficiency during electrodeposition coating decreases, and it is necessary to lengthen the electrodeposition time to obtain a predetermined film thickness. In this case, the dispersion particles are likely to be welded to each other, and the stability of the system is lowered. When the content of the hydroxyl group is 1.2
When the amount is less than mol / Kg, the developability decreases, and it becomes necessary to increase the temperature of the developer or the development time, and the resolution of the obtained image also decreases. On the other hand, when the amount exceeds 3.5 mol / Kg, In addition, the resist film is easily swelled with a developing solution or an etching solution, and a pattern defect is easily generated, and the resolution is also reduced.

The water-dispersible resin composition as a main component of the composition of the present invention can be obtained by neutralizing a mixture of the components (a), (b) and (c) with a base and dispersing the mixture in water. Examples of the base used for neutralization include organic amines, hydroxyammonium salts, and inorganic bases such as potassium hydroxide and sodium hydroxide. Usually, the degree of neutralization is preferably such that 50 to 100% of the carboxyl groups in the mixture are neutralized.

As a method of dispersing in water, (a)
A method of adding and dispersing a mixed neutralized product of the components (b) and (c) in water, a method of adding and dispersing water to the mixed neutralized product, and a method of mixing the components (a), (b) and (c). Examples thereof include a method of adding and dispersing in water containing a base for neutralization and a method of adding and dispersing water containing a base to a mixture.

The composition of the present invention may contain, if necessary, additives such as a solvent, a surfactant, a flow control agent, and a chelating agent.
It may contain solubility control agents such as phenols, polyphenols such as novolak phenol and resol, pigments and dyes. The solid content of the resist composition of the present invention is not particularly limited, but is usually in the range of 3 to 50%.

The production of a printed wiring board using the positive photosensitive electrodeposition resist composition of the present invention can be carried out as follows. Electrodeposition coating bath (bath solid concentration: 3-30
% By weight) of a circuit board having a conductive film such as a copper foil as an anode, and applying a DC current having a maximum applied voltage of 20 to 400 V to perform electrodeposition coating. The energization time is suitably 30 seconds to 5 minutes, and the film thickness is desirably in the range of 2 to 50 μm, preferably 3 to 20 μm in dry film thickness. After the electrodeposition coating, the object to be coated is taken out of the electrodeposition bath and washed with water, and then the moisture contained in the electrodeposition coating film is removed with hot air or the like. Next, the surface of the thus formed photosensitive electrodeposition coating film is exposed to actinic rays such as ultraviolet rays through a pattern mask (photo positive). Since the orthoquinonediazide portion of the exposed portion is converted to carboxylic acid via ketene by this exposure, it is removed by a developing treatment with a developing solution such as an alkaline aqueous solution, and high resolution can be realized.

In the present invention, the actinic ray used for exposure is preferably a ray having a wavelength of 3,000 to 4,500 °.
These rays include sunlight, mercury lamps, xenon lamps, arc lamps and the like. Irradiation with actinic rays is usually 50 to 800 mj / cm ² , preferably 50 to 50 mj / cm ² .
It is performed within a range of 0 mj / cm ² .

Further, the developing treatment for removing the photosensitive film on the exposed portion to form an etching pattern can be usually carried out by spraying dilute alkaline water onto the surface of the coating to wash out the photosensitive portion of the coating. . As the dilute alkaline water, those which can be neutralized with free carboxylic acids in the coating film, such as sodium hydroxide, sodium hydroxide, sodium silicate, sodium carbonate, aqueous ammonia, etc., having a pH of 8 to 12 to give water solubility are also used. It is possible.

The exposed conductive coating (non-circuit portion), which is an etching pattern formed on the substrate by the developing process, is then applied to an acidic etching solution such as a ferric chloride solution or an ammonia / ammonium chloride system. It is removed by a normal etching process using an alkaline etching solution or the like. Thereafter, the printed wiring board can be manufactured by removing the photosensitive film which is the unexposed film on the circuit pattern. Removal of the unexposed coating film is performed using cellosolve solvents such as ethyl cellosolve and ethyl cellosolve acetate; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl kentone; acetic acid such as ethyl acetate and butyl acetate. Ester solvent: It is removed with a chlorinated solvent such as trichloroethylene, or with caustic soda having a pH of 10 or more, aqueous caustic solution, amine aqueous solution, or the like.

As described above, the positive photosensitive anion electrodeposition resist composition of the present invention can be easily electrodeposited on the surface of a circuit board, and the deposited coating film is dried to form a uniform photosensitive film. Form. When this photosensitive film is irradiated with light through a pattern mask, the exposed portions change as described above and are developed with dilute alkaline water, and the unexposed portions are dissolved and removed with a solvent or alkali in the step of removing the photosensitive film after etching. Can be done. The present invention can also be suitably used for a resist for punching by etching for producing a lead frame or the like.

[0026]

The present invention will be described more specifically with reference to the following examples.

Production of component (a) acrylic resin

Preparation Example 1 Styrene 300 parts by weight n-butyl methacrylate 663 parts by weight 2-hydroxyethyl acrylate 350 parts by weight Acrylic acid 13 parts by weight 2,2'-azobisisobutyronitrile 15 parts by weight 1341 parts by weight of the above mixture 750 heated to 110 ° C
It was added dropwise to 3 parts by weight of ethoxyethanol over 3 hours. After completion of dropping, the mixture was kept at 110 ° C. for 1 hour, and
-3 parts by weight of azobisisobutyronitrile was added, and the mixture was further kept at 110 ° C for 2 hours.
As a result, a resin solution (a-1) in a weight% was obtained. The obtained resin (solid content) had a number average molecular weight (by gel permeation chromatography, the same applies hereinafter) of about 35,000, a carboxyl group concentration of 0.18 mol / Kg resin, and a hydroxyl group concentration of 3.0 mol / Kg resin. Met.

Production Example 2 n-butyl methacrylate 300 parts by weight n-butyl acrylate 440 parts by weight 2-hydroxyethyl methacrylate 240 parts by weight acrylic acid 20 parts by weight t-butyl peroxybenzoate 50 parts by weight 1050 parts by weight of the above mixture at 125 ° C. 600 heated to
The solution was added dropwise to 3 parts by weight of butoxyethanol over 3 hours. After completion of the dropwise addition, the mixture was maintained at 125 ° C. for 3 hours and then cooled to obtain a resin solution (a-2) having a solid content of about 62.5% by weight. The obtained resin (solid content) has a number average molecular weight of about 12,
000, carboxyl group concentration 0.28 mol / Kg resin,
The hydroxyl group concentration was 1.9 mol / Kg resin.

Production Example 3 200 parts by weight of styrene 300 parts by weight of n-butyl methacrylate 231 parts by weight of n-butyl methacrylate 240 parts by weight of 2-hydroxyethyl acrylate 29 parts by weight of acrylic acid 2,2'-azobisisobutyronitrile 70 Parts by weight 1070 parts by weight of the above mixture was heated to 105 ° C. 600
It was added dropwise to 3 parts by weight of methoxypropanol over 3 hours. After completion of the dropwise addition, the mixture was maintained at 105 ° C. for 2 hours and then cooled to obtain a resin solution (a-3) having a solid content of about 62.5% by weight. The obtained resin (solid content) has a number average molecular weight of about 8.1.
The carboxyl group concentration was 0.40 mol / Kg resin and the hydroxyl group concentration was 2.1 mol / Kg resin.

Production Example 4 10 parts by weight of methacrylic acid 522 parts by weight of 2-hydroxyethyl acrylate 300 parts by weight of methyl methacrylate 168 parts by weight of n-butyl acrylate 45 parts by weight of t-butyl peroxybenzoate 1045 parts by weight of the above mixture was heated to 125 ° C. 600
The solution was added dropwise to 3 parts by weight of butoxyethanol over 3 hours. After completion of the dropwise addition, the mixture was kept at 125 ° C. for 3 hours and then cooled to obtain a resin solution (a-4) having a solid content of about 62.5% by weight. The obtained resin (solid content) had a number average molecular weight of about 13,
000, carboxyl group concentration 0.12 mol / Kg resin,
The hydroxyl group concentration was 4.5 mol / Kg resin.

(B) Production of component acrylic resin

Production Example 5 240 parts by weight of styrene 310 parts by weight of n-butyl acrylate 290 parts by weight of methacrylic acid 160 parts by weight 65 parts by weight of benzoyl peroxide 1065 parts by weight of the above mixture was heated to 100 ° C. 550
It was added dropwise to 3 parts by weight of methoxypropanol over 3 hours. After completion of the dropwise addition, the mixture was maintained at 100 ° C. for 1 hour, 60 parts by weight of a solution obtained by dissolving 10 parts by weight of benzoyl peroxide in 50 parts by weight of methoxypropanol was added, and the mixture was further maintained at 100 ° C. for 2 hours, cooled, and solidified. About 62.5% by weight of a resin solution (b-1) was obtained. Obtained resin (solid content)
Has a number average molecular weight of about 9,600, a carboxyl group concentration of 1.86 mol / Kg resin, and a hydroxyl group concentration of 2.5 mol / Kg
It was a resin.

Production Example 6 Styrene 100 parts by weight N-butyl acrylate 190 parts by weight Methyl methacrylate 100 parts by weight 2-hydroxyethyl methacrylate 520 parts by weight Acrylic acid 90 parts by weight t-butyl peroxyoctoate 50 parts by weight 1050 parts by weight of the above mixture 600 heated to 125 ° C.
The solution was added dropwise to 3 parts by weight of butoxyethanol over 3 hours. After completion of the dropwise addition, the mixture was kept at 125 ° C. for 2 hours and then cooled to obtain a resin solution (b-2) having a solid content of about 62.5% by weight. The obtained resin (solid content) has a number average molecular weight of about 10,
500, carboxyl group concentration 1.25 mol / Kg resin,
The hydroxyl group concentration was 4.0 mol / Kg resin.

Production Example 7 200 parts by weight of styrene 100 parts by weight of methyl methacrylate 362 parts by weight of n-butyl acrylate 209 parts by weight of methacrylic acid 129 parts by weight of methacrylic acid 60 parts by weight of 2,2'-azobisisobutyronitrile 1060 parts by weight of the mixture was heated to 105 ° C. 600
It was added dropwise to 3 parts by weight of methoxypropanol over 3 hours. After completion of the dropwise addition, the mixture was maintained at 105 ° C. for 2 hours and then cooled to obtain a resin solution (b-3) having a solid content of about 62.5% by weight. The obtained resin (solid content) has a number average molecular weight of about 9,6.
The carboxyl group concentration was 1.50 mol / Kg resin, and the hydroxyl group concentration was 1.8 mol / Kg resin.

Production Example 8 126 parts by weight of acrylic acid 390 parts by weight of 2-hydroxyethyl methacrylate 250 parts by weight of styrene 234 parts by weight of n-butyl acrylate 45 parts by weight of t-butyl peroxyoctoate 45 parts by weight of the above mixture 1045 parts by weight was heated to 125 ° C. 600
The solution was added dropwise to 3 parts by weight of butoxyethanol over 3 hours. After completion of the dropwise addition, the mixture was maintained at 125 ° C. for 2 hours and then cooled to obtain a resin solution (b-4) having a solid content of about 62.5% by weight. The obtained resin (solid content) has a number average molecular weight of about 12,
000, carboxyl group concentration 1.75 mol / Kg resin,
The hydroxyl group concentration was 3.0 mol / Kg resin.

Production Example 9 (for comparison) Styrene 200 parts by weight Methyl methacrylate 100 parts by weight n-butyl acrylate 230 parts by weight 2-hydroxyethyl acrylate 290 parts by weight Acrylic acid 180 parts by weight 2,2'-azobisisobutyronitrile 60 parts by weight In the same manner as in Production Example 7, except that 1060 parts by weight of the mixture of the above monomer and polymerization initiator is used instead of 1060 parts by weight of the mixture, the solid content was about 62.5 parts by weight.
A resin solution (d-1) of 5% by weight was obtained. The obtained resin (solid content) had a number average molecular weight of about 9,800, a carboxyl group concentration of 2.50 mol / Kg resin, and a hydroxyl group concentration of 2.5 mol / Kg resin.

Production Example 10 (for comparison) Styrene 235 parts by weight n-butyl acrylate 400 parts by weight 2-hydroxyethyl acrylate 300 parts by weight Acrylic acid 65 parts by weight 2,2'-azobisisobutyronitrile 10 parts by weight The above mixture 700 obtained by heating 1010 parts by weight to 105 ° C.
It was added dropwise to 3 parts by weight of ethoxyethanol over 3 hours. After the completion of the dropwise addition, the temperature was maintained at 105 ° C. for 1 hour,
3 'parts by weight of 2'-azobisisobutyronitrile were added,
After further keeping at 105 ° C. for 2 hours, the mixture was cooled to obtain a resin solution (d-2) having a solid content of about 59% by weight. The obtained resin (solid content) had a number average molecular weight of about 35,000, a carboxyl group concentration of 0.90 mol / Kg resin, and a hydroxyl group concentration of 2.3.
Mol / Kg resin.

(C) Production of component photosensitizer

Preparation Example 11 1,2-Naphthoquinonediazide-5-sulfonyl chloride 535 in 10,000 parts by weight of tetrahydrofuran
Parts by weight and 230 parts by weight of 2,3,4-trihydroxybenzophenone are mixed and dissolved, and then cooled to 0 ° C., and a mixed solution 610 of 210 parts by weight of triethylamine and 400 parts by weight of tetrahydrofuran is stirred therein. Parts by weight were gradually added dropwise over 1 hour. The temperature of the system was raised to 30 ° C. by this dropping. After the completion of dropping, 2
After holding for a time, this reaction solution was poured into a large amount of a 0.1% by weight aqueous hydrochloric acid solution to form a precipitate. The precipitate was filtered off, washed with a washing solution (methanol / deionized water = 1/1 mixture) until the washing solution became neutral, and the resulting solid was dried at room temperature under reduced pressure. Photosensitive agent A was obtained. The obtained photosensitive agent A had an average of about two photosensitive groups represented by the above formula [1] in one molecule.

Production Example 12 1,2-Naphthoquinonediazide-4-sulfonyl chloride 80 in 15,000 parts by weight of tetrahydrofuran
After mixing and dissolving 2.5 parts by weight and 246 parts by weight of 2,3,4,4'-tetrahydroxybenzophenone,
° C and stirred therein while stirring triethylamine 2
610 parts by weight of a mixed solution of 10 parts by weight and 400 parts by weight of tetrahydrofuran was gradually dropped over 1 hour. After completion of the dropwise addition, the mixture was maintained at 30 ° C. for 2 hours, and the reaction solution was precipitated, filtered and dried in the same manner as in Production Example 11 to obtain Photosensitive Agent B. The obtained photosensitive agent B had an average of about 3 photosensitive groups represented by the formula [2] in one molecule.

Production Example 13 100 parts by weight of poly (parahydroxyvinylbenzene) having a number average molecular weight of about 3,000 was added to tetrahydrofuran 100
1,100 parts by weight of a solution obtained by dissolving 100 parts by weight of o-naphthoquinonediazide-5-sulfonic acid chloride in 1,000 parts by weight of tetrahydrofuran were added to the solution dissolved in parts by weight. While maintaining the temperature at 20 ° C., 50 parts by weight of triethylamine was added dropwise over 30 minutes, further maintained at 20 ° C. for 2 hours, and then the contents were poured into a large amount of a 0.5% by weight aqueous hydrochloric acid solution, and the precipitate was filtered. Separately, the resultant was washed with a large amount of deionized water and dried under reduced pressure at normal temperature to obtain a photosensitive agent C. The obtained photosensitive agent C had an average of about 11 photosensitive groups represented by the formula [1] in one molecule.

Production Example 14 Into 5,000 parts by weight of tetrahydrofuran, 546 parts by weight of 1,2-benzoquinonediazide-4-sulfonyl chloride and 230 parts by weight of 2,3,4-trihydroxybenzophenone were mixed and dissolved. 570 parts by weight of a mixed solution of 270 parts by weight of triethylamine and 300 parts by weight of tetrahydrofuran were gradually added dropwise thereto over 1 hour under stirring. After completion of the dropwise addition, the mixture was kept at 30 ° C. for 2 hours, and the reaction solution was precipitated, filtered and dried in the same manner as in Production Example 11 to obtain Photosensitive Agent D. The obtained photosensitive agent D has an average of about 2.5 per formula [3] in one molecule.
And a photosensitive group represented by

Example 1 526 parts by weight of the resin solution (a-1) obtained in Production Example 1 800 parts by weight of the resin solution (b-2) obtained in Production Example 6 200 parts by weight of the photosensitive agent A obtained in Production Example 11 Activator E (nonionic surfactant of HLB14) 10 parts by weight 400 parts by weight of benzyl alcohol 74.5 parts by weight of triethylamine (an amount corresponding to a degree of neutralization of 75% by weight) was added to the above mixture, and the mixture was neutralized with stirring. 847 parts by weight of deionized water was gradually added while stirring the mixture with a stirrer at 1,500 gpm to obtain an electrodeposited resist composition having a nonvolatile content of about 35% by weight, which was a stable emulsion liquid.

Examples 2 to 5 and Comparative Examples 1 to 4 The same procedures as in Example 1 were carried out except for using the formulations shown in Table 1 below to obtain each electrodeposition resist composition. Table 1 shows the property values of the electrodeposition resist compositions obtained in each example.

[0046]

[Table 1] (Note) in Table 1 is as follows. ( ^* 1) ^* Activator F: Nonionic surfactant of HLB16 ( ^* 2) Each symbol in the table is an abbreviation for the following compound. TEA: triethylamine, DMAE: dimethylaminoethanol, BA: benzyl alcohol, DMG: dimethylglyme

Each of the electrodeposition resist compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was diluted with deionized water so that the non-volatile content was 10% by weight to prepare each electrodeposition bath. A test was conducted on the stability of each electrodeposition resist composition applied solution (stock solution) and each electrodeposition bath solution. Table 2 shows the test results. The test method is as follows.

Liquid stability: Each stock solution and the electrodeposition bath solution were sealed, and the liquid state was checked at 30 ° C. every other month for up to 6 months. The state of the liquid one day after storage was also examined. Further, the particle size of the dispersed emulsion particles before storage and after 6 months of storage for each of the electrodeposition bath solutions was determined by Coulter M.
model N4SD (Coulter Electro
nics Inc. Manufactured). Regarding the liquid state, those having no abnormalities such as solidification, remarkable thickening, sedimentation, and separation were indicated by ○.に お け る in long-term storage indicates that there is no abnormality after storage for 6 months. In addition, the above-mentioned electrodeposition bath solutions before storage and after storage for 6 months were kept in a bath kept at 28 ° C.
A copper-clad laminate (substrate) having a through-hole with a copper plating of 0.3 mmφ is used as an anode, and 60 mA / d between counter electrodes.
After applying a direct current of m ² for 3 minutes, the laminate (substrate) was taken out of the bath, washed with water, and then drained and dried at 80 ° C. for 10 minutes to obtain a resist film. Table 2 below shows the thickness and the appearance of the coated surface of the obtained resist film. A sample in which no abnormality was observed in appearance was marked with “○”. Further, the through-hole portion of the obtained resist film is shielded from light, and a line space of 30 μm / 3 is provided in other portions.
A polyester pattern mask having a black and white pattern of 0 μm was brought into close contact, and exposure was performed at 150 mj / cm ² using an ultra-high pressure mercury lamp. Further, the exposed substrate is placed at 20 ° C., 25 ° C., 30 ° C., 35 ° C., 40 ° C., 45 ° C., respectively.
Was sprayed with a 1% aqueous solution of sodium carbonate maintained for 1 minute for development. Next, after the copper exposed by cupric chloride was removed by etching, the remaining resist film was removed with a 1% aqueous sodium hydroxide solution at 50 ° C. to obtain an etching pattern.
The state of the obtained etching pattern was examined for the line / space portion and the through-hole portion. In the line / space portion, those having no pattern peeling loss or copper residue were indicated by ○, and those in the through hole portion where plating remained in a complete state were indicated by ○. Further, the practical temperature range of the developing solution that can be developed was also examined. The test results are shown in Table 2 below.

[0049]

[Table 2] (Note) HC in the table is an abbreviation for hard caking.

[0050]

The resist composition of the present invention has excellent operational stability during coating, good coating workability, and can provide a resist having high reliability in forming a conductive image. The resist composition of the present invention is particularly suitable for an etching resist for manufacturing a printed wiring board, and according to the method for manufacturing a printed wiring board of the present invention using the resist composition of the present invention, operating conditions with a long residence time of a bath solution. Even below, a highly reliable printed wiring board can be manufactured.

Continuation of the front page (72) Inventor Naozumi Iwasawa 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Pref. Kansai Paint Co., Ltd. (56) References JP-A-2-289660 (JP, A) JP-A-4-53877 ( JP, A) JP-A-4-100870 (JP, A) JP-A-63-141048 (JP, A) JP-A-3-100073 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , (DB name) G03F 7/023 501 C08L 33/00 C09D 133/00 G03F 7/022 H05K 3/06

Claims (6)

(57) [Claims] 1. (a) 0.075 to 0.55 mol of carboxyl groups and 1.5 to 5.5 hydroxyl groups per 1 kg of resin.
20 to 50 parts by weight of an acrylic resin having a molar amount of (b) an acrylic resin 2 having a carboxylic acid group of 1.20 to 2.50 mol and a hydroxyl group of 1.5 to 5.0 mol in 1 kg of the resin
5 to 70 parts by weight and (c) the following formula [1] in one molecule:
A group represented by the formula [1] represented by [2] or [3]: Formula [2] Formula [3] Containing 7.5 to 30 parts by weight of a photosensitive agent having at least one
The total amount of the components (a), (b) and (c) is 100 parts by weight, and the content of the carboxyl group in the total of the components (a), (b) and (c) is 0.60 to 1. 25 mol / Kg, the content of the hydroxyl group is 1.2 to 3.5 mol / Kg
A positive photosensitive anion electrodeposition resist composition comprising, as a main component, a water-dispersible resin composition obtained by neutralizing and dispersing a resin mixture as described above in water with a base. 2. Components (a), (b) and (c) each comprising 100 to 50 parts by weight of component (a), 20 to 50 parts by weight, component (b) 25 to 70 parts by weight, and component (c) 7 The positive photosensitive anion electrodeposition resist composition according to claim 1, wherein the amount is from 0.5 to 30 parts by weight. 3. The positive photosensitive anion electrodeposition resist composition according to claim 1, wherein the proportion of the solid content is 3 to 50%. 4. A step of (i) electrodepositing the electrodeposition resist composition according to claim 1 on a surface of a circuit substrate having an electrically conductive film to form a positive photosensitive film; Exposing the photosensitive film through a pattern mask; (iii) removing the photosensitive film in the exposed area to form an etching pattern; (iv) removing the exposed conductive film by etching; and (V) A method for manufacturing a printed wiring board, comprising a step of removing a photosensitive film on a circuit pattern. 5. The method according to claim 4, wherein the electrodeposited positive photosensitive film has a dry film thickness of 2 to 50 μm. 6. The exposure according to claim 4, wherein the exposure of the positive photosensitive film through the pattern mask is performed by irradiating a light beam having a wavelength of 3,000 to 4,500 ° with 50 to 800 mj / cm ^2. Of manufacturing a printed circuit board.