JP2002196485A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is excellent in sandblasting-proof, resist peelability, developer-proof and storage stability of the resist. SOLUTION: The photosensitive resin composition comprises 0.5-30 weight percent of a carboxylic acid degeneration polycaprolactone diol (B), 0.1-20 weight percent of a photoinitiator (C) and 0.1-5 weight percent of a light chromogenic dye (D) for 100 weight percent of an acrylic urethane resin including a carboxyl group (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition having excellent sandblast resistance and resist stripping properties.
In particular, the present invention relates to a photosensitive resin composition usable as a form of a dry film resist.

[0002]

2. Description of the Related Art A three-layer laminated film comprising a photosensitive resin composition applied in layers on a base film such as a polyester film, dried and laminated, and a protective film such as a polyester film, a polyethylene film, or a polyvinyl alcohol film is laminated thereon. Generally, it is called a dry film resist (hereinafter, may be abbreviated as DFR), and is widely used for manufacturing a printed wiring board, precision processing of a metal, and the like. In use, first, one of the base film or the protective film having the smaller adhesive strength is peeled off and removed from the DFR, and the photosensitive resin composition layer side is attached to the copper surface of the copper-clad substrate. Exposure is performed in a state where the pattern mask is in contact with the other film (the exposure may be performed after the other film is peeled off), and then the other film is peeled off and subjected to development. As a development method after exposure,
There are a solvent development type and a dilute alkali development type.

[0003] In addition to DFR, there is also a well-known method in which a photosensitive resin composition is applied directly onto the substrate surface, and a pattern mask is adhered through a film such as a polyester film laminated thereon to perform exposure. ing. In recent years, in addition to the use of DFR mainly for the manufacture of such printed wiring boards, DF is used for forming partition walls of plasma display panels and the like.
Sandblasting using R has been performed.

As a photosensitive resin composition for DFR that can be used for such applications, for example, it contains two or more (meth) acryloyl groups and has an acid value of 50 to 250 m.
gKOH / g, a photosensitive resin composition comprising a carboxyl group-modified urethane (meth) acrylate compound having a cured Tg of 5 to 95 ° C, an alkali-soluble polymer compound having an acid value of 50 to 250 mgKOH / g, and a photopolymerization initiator (Japanese Unexamined Patent Publication No. Hei 8-54534) has been proposed. However, the disclosed technology has a problem in developing solution resistance, and has a drawback that it is necessary to strictly control the developing solution concentration and the developing time during development. Therefore, the applicant of the present invention previously provided 0 to 20 parts by weight of an acrylic resin having an acid value of 10 to 250 and 0.5 to 10 parts by weight of a hexaarylbiimidazole based on 100 parts by weight of a carboxyl group-containing acrylic urethane resin. , A photosensitive resin composition containing 0.05 to 3 parts by weight of a leuco dye (Japanese Patent No. 3034823).

[0005]

However, in the above-mentioned disclosed technology, although the resist has a satisfactory developing solution resistance, the resist has good sand blast resistance (sometimes abbreviated as blast resistance) and after blasting. There was room for improvement in the resist strippability. In reality, it is not possible to satisfy the demand for further improvement in blast resistance and improvement in resist peelability after blasting (shorter stripping time) in the market.

[0006]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies and as a result, based on 100 parts by weight of a carboxyl group-containing acrylic urethane resin (A), a carboxylic acid-modified polycaprolactone diol. 0.5 to 30 parts by weight of the compound (B), 0.1 to 20 parts by weight of the photopolymerization initiator (C) and 0.05 of the photochromic dye (D)
It has been found that a photosensitive resin composition containing up to 5 parts by weight has excellent blast resistance, excellent resist stripping properties after blasting, and has good performance in terms of resist storage stability and developer resistance. The present invention has been completed.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The carboxyl group-containing acrylic urethane resin (A) used in the present invention comprises a carboxyl group-containing diol compound (a1) and a diisocyanate compound (a2) usually in a ratio of 1:
A compound obtained by adding a polyol (a4) to a compound (a3) obtained by reacting at a molar ratio of 2 and further adding an ethylenically unsaturated group-containing hydroxy compound (a5) is preferable, and further, such a carboxyl group The diol compound (a1) preferably has a molecular weight of 500 or less, and the diisocyanate compound (a2) preferably has a molecular weight of 300 or less.

The carboxyl group-containing diol compound (a1) having a molecular weight of 500 or less is specifically exemplified by tartaric acid, dihydroxymethylacetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) propionic acid 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-
Bis (p-hydroxyphenyl) pentanoic acid, 2,4-
Examples thereof include dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and homogentisic acid.
Bis (hydroxymethyl) butyric acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, and 2,2-bis (hydroxypropyl) propionic acid are used. If the molecular weight of the carboxyl group-containing polyol compound (a1) exceeds 500, the solubility in the reaction solvent is reduced, and the reactivity with diisocyanate is undesirably reduced.

Specific examples of the diisocyanate compound (a2) having a molecular weight of 300 or less include hexamethylene diisocyanate, heptane methylene diisocyanate,
2,2-dimethylpentane-1,5-diisocyanate, octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4-
Trimethylpentane-1,5-diisocyanate, nonamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, undecamethylene diisocyanate, dodecamethylene diisocyanate, tridecamethylene diisocyanate, pentadecamethylene diisocyanate, butene diisocyanate, 1 , 3-butadiene-1,4-diisocyanate, 2-butynylene diisocyanate, toluene diisocyanate, isophorone diisocyanate,
3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate, water-added products of diphenylmethane diisocyanate, etc., preferably hexamethylene diisocyanate, isophorone diisocyanate , Toluene diisocyanate is used. If the molecular weight of the diisocyanate compound (a2) exceeds 300, the reactivity with the diol compound decreases, which is not preferable.

The polyol (a) to be subjected to an addition reaction to (a3)
As 4), those having a molecular weight of 500 or more are preferred, and more preferably 500 to 10,000, particularly 500 to 4000. If the molecular weight is less than 500, the flexibility of the cured resist is lowered, which is not preferred. Specific examples include polyether-based polyols, polyester-based polyols, polycarbonate-based polyols, alkylene oxide-modified bisphenol-based diols, acrylic polyols, polybutadiene-based polyols, and polyolefin-based polyols. Further, a urethane diol obtained by reacting a low molecular weight diol such as 1,6-hexanediol and a polyisocyanate such as isophorone diisocyanate in a molar ratio of α: α-1 (α is an integer of 2 or more). Are also mentioned.

Further, as the hydroxy compound containing an ethylenically unsaturated group (a5), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- (meth) acrylate ) Acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate and the like, preferably 2-hydroxyethyl (meth) acrylate; 2-hydroxypropyl (meth) acrylate is used.

To prepare the carboxyl group-containing acrylic urethane resin (A), first, the diol compound (a)
The reaction product (a3) is obtained by reacting 1) with the diisocyanate compound (a2). The reaction can be carried out using a known reaction means, for example, in a solvent such as ethyl acetate or methyl ethyl ketone or below the boiling point of the solvent (preferably 60 to 8).
(A1) and (a2) may be reacted at a temperature of 0 ° C.). In the present invention, as described above, the diol compound (a
By making the reaction molar ratio of 1) and the diisocyanate compound (a2) about 1: 2, isocyanate can be added to both ends, and a polyol (a4) having a molecular weight of 500 or more, which will be described later, is efficiently introduced. .

Next, the reaction product (a3) has a molecular weight of 50
0 or more polyols (a4) are added and reacted at a temperature not higher than the boiling point of the solvent. At this time, it is advantageous to add a known catalyst such as dibutyltin laurate to accelerate the reaction. The catalyst is used in an amount of 0.0 to the polyol (a4).
Use about 1-0.1% by weight, and 3-10 at 60-80 ° C
Let react for about an hour. The isocyanate can be added to both terminals by setting the reaction molar ratio of the reaction product (a3) and the polyol to about β: β-1 (β is an integer of 2 or more). When (a2) is further reacted according to the above, the introduction of (a5) described later is efficiently performed. Further, an ethylenically unsaturated group-containing hydroxy compound (a5) is charged into the system and reacted. When the residual diisocyanate group content becomes about 0.1 to 0.5% by weight, the reaction is terminated, and the carboxyl group-containing acrylic compound is removed. The urethane resin (A) is obtained.

The carboxyl group-containing acrylic urethane resin (A) used in the present invention has an acid value of 10 to 150 mg.
Since KOH / g, preferably 50 to 130 mg KOH / g, is advantageous, (a1), (a2), (a4), (a
It is desirable to select the type, blending ratio, degree of condensation, and the like in 5) to make the above ranges. If the acid value is less than 10 mgKOH / g, the resolution may be poor, and if it exceeds 150 mgKOH / g, the developer resistance may be poor, which is not preferable.

In addition to adjusting the acid value within the above range, the weight ratio of the reaction product (a3) in (A) is preferably 15 to 65% by weight, and the content is 15% by weight.
If it is less than 6, sufficient strength of the cured resist cannot be obtained.
If it exceeds 5% by weight, the flexibility of the cured resist is undesirably reduced.

In the composition of the present invention, the carboxylic acid-modified polycaprolactone diol compound (B) compounded in (A) is defined as a carboxylic acid-containing diol compound having a ε-
Caprolactone can be obtained by a ring-opening addition reaction. As the carboxyl group-containing diol, (a1) disclosed in the above description of (A) is used,
Specific examples of (B) include those represented by the following general formulas (1) to (6), and in particular, those represented by general formulas (1) to (3)
Are preferred, and (1) is particularly preferred.

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

In the above general formulas (1) to (6), R ₁
Represents any of H, CH ₃ and CH ₂ CH ₃ , and R ₂ and R ₃ represent C
H _2, CH ₂ CH _2, one of the C ₆ H _4, m is an integer of 0 to 3. Note that n in the general formulas (1) to (3) is
An integer of 1 to 50, more preferably an integer of 1 to 30, particularly preferably an integer of 2 to 20, and when such n is 0, DFR
When stored as a gel, a gel may be generated in the photosensitive resin composition or crystals may be precipitated to impair the storage stability.
If it is added in excess of 0, the resist strippability will be insufficient. Further, n in the general formulas (4) to (6) is an integer of 1 to 25, more preferably an integer of 1 to 15, and particularly preferably 1
When n is 0 or an integer exceeding 25, the same drawbacks as those in the above general formulas (1) to (3) occur.

The compound (B) has an acid value of 10 to 500.
mgKOH / g is preferred, and more preferably 10 to 250 mgK
OH / g and a hydroxyl value of 30 to 500 mg KOH /
g is preferable, and more preferably 45 to 250 mgKOH / g. If the acid value is less than 10 mgKOH / g, the resist stripping properties may be poor, and if it exceeds 500 mgKOH / g, the development resistance may be poor, which is not preferable. Hydroxyl value is 30
If the amount is less than mgKOH / g, the releasability may be poor.
If it exceeds 0 mgKOH / g, when DFR is used, storage stability may be inferior as described above, which is not preferable. Specific examples of the commercially available product (B) include “Placcel 205BA” and “Placcel 205BA” manufactured by Daicel Chemical Industries, Ltd.
210BA "and" Placcel 220BA ".

The compounding amount of the above (B) is based on 100 parts by weight of the carboxyl group-containing acrylic urethane resin (A).
0.5 to 30 parts by weight, preferably 1 to
30 parts by weight, especially 3 to 25 parts by weight. If the amount is less than 0.5 part by weight, the resist stripping property and the blast resistance become insufficient, and if it exceeds 30 parts by weight, the storage stability of the DFR deteriorates similarly to the above, which is inappropriate.

Examples of the photopolymerization initiator (C) include benzoin compounds, benzophenone compounds, acetophenone compounds, hexaarylbiimidazole compounds, thioxanthone compounds, benzotriazole compounds, triazine compounds, acridine compounds, 2-methyl- [4- (methylthiophene) ) Phenyl] -2-morpholino-1-propanone, tribromomethylphenylsulfone, N-phenylglycine, diphenyldisulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, pivaloin ethyl ether, phenylglyoxylate, α-hydroxyisobutylphenone , Dibenzosparone, 1- (4
-Isopropylphenyl) -2-hydroxy-2-methyl-1-propanone;
More than one type is used.

Examples of the benzoin compound include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether and benzoin phenyl ether.

As the benzophenone compound, 3,3 ′
-Dimethyl-4-methoxybenzophenone, benzophenone, p, p'-bis (dimethylamino) benzophenone, p, p'-bis (diethylamino) benzophenone.

As the acetophenone compound, 1,1-
Dichloroacetophenone, pt-butyldichloroacetophenone, 2,2-diethoxyacetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2,2
-Dichloro-4-phenoxyacetophenone.

The hexaarylbiimidazole compounds include 2,2'-bis (o-chlorophenyl) -4,
5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (o-chlorophenyl) -4,
5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (o-fluorophenyl)-
4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (o-methoxyphenyl)
-4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (p-methoxyphenyl) -4,5,4', 5'-tetraphenyl-1, 1 '
-Biimidazole, 2,4,2 ', 4'-bis [bi (p
-Methoxyphenyl)]-5,5'-diphenyl-1,
1'-biimidazole, 2,2'-bis (2,4-dimethoxyphenyl) -4,5,4 ', 5'-diphenyl-
1,1′-biimidazole, 2,2′-bis (p-methylthiophenyl) -4,5,4 ′, 5′-diphenyl-
Examples thereof include 1,1′-biimidazole and bis (2,4,5-triphenyl) -1,1′-biimidazole, and further include 1,1′-biimidazole and 1,1′-biimidazole disclosed in JP-B-45-37377.
Tautomers of the compounds covalently bonded at 2′-, 1,4′- and 2,4′- can also be used. Among the above, 2,2′-bis (o-chlorophenyl) -4,5
4 ', 5'-Tetraphenyl-1,2'-biimidazole is preferably used.

As the thioxanthone compound, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4
-Diethylthioxanthone.

As the benzotriazole compound, 1,
2,3-benzotriazole, 1-chloro-1,2,3
-Benzotriazole, 4-carboxy-1,2,3-
Benzotriazole, 5-carboxy-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2 ,
3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.

As the triazine compound, 2,4,6-
Tris (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n- Propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-
Chlorophenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -4'-methoxyphenyl-s-
Triazine, 2- (4-methoxy-naphth-1-yl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
[4- (2-ethoxyethyl) -naphth-1-yl]-
4,6-bis (trichloromethyl) -s-triazine,
2- (4,7-dimethoxy-naphth-1-yl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
(Acenaphth-5-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dichlorophenyl) -4,6-bis (trichloromethyl) -s
-Triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-
Trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2-p-methylstyryl-4,6-bis (trichloro Methyl) -s-
Triazine and 2-p-methoxystyryl-4,6-bis (trichloromethyl) -s-triazine.

As the acridine compound, 2-methyl-
[4- (methylthio) phenyl] -2-morpholino-
1-Prolpanone acridine, 9-phenyl acridine.

The photopolymerization initiator (C) is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the carboxyl group-containing acrylic urethane resin (A). When the amount is less than 0.1 part by weight, the sensitivity is remarkably reduced and good workability cannot be obtained. Conversely, when the amount exceeds 20 parts by weight, the storage stability of the DFR deteriorates. Therefore, the object of the present invention cannot be achieved. Also, 2,2′-bis (o-chlorophenyl)
When -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole accounts for 20% by weight or more of the total amount of (C), the developer resistance and the blast resistance are more easily obtained.
If it is less than 10% by weight, the developer resistance will be reduced.

As the photochromic dye (D), bis (4-
N, N-diethylamino-o-tolyl) methylenethiophenylmethane, bis (4-N, N-diethylamino-o
-Tolyl) benzylthiophenylmethane, leuco crystal violet, leucomalachite green, leuco diamond green, and other leuco dyes, and among them, one or more of leuco crystal violet, leucomalachite green, and leuco diamond green are preferably used. The amount thereof is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the carboxyl group-containing acrylic urethane resin (A).
Parts by weight are required. If the amount is less than 0.05 part by weight, the sensitivity is remarkably reduced and good workability cannot be obtained.
Conversely, if the amount exceeds 5 parts by weight, the storage stability of the DFR decreases, and the object of the present invention cannot be achieved.

In the present invention, in addition to the above (A) to (D), by adding an acrylic resin (E) having an acid value of 50 to 250 mgKOH / g, the developer resistance can be further improved. it can. The acid value of the acrylic resin (E) is preferably from 70 to 200 mgKOH / g, and more preferably from 100 to 170 mgKOH / g. When the acid value is less than 50 mgKOH / g, sufficient addition effect cannot be obtained for imparting developability, and the resolution is lowered.
If it exceeds mgKOH / g, the developer resistance and the blast resistance may decrease.

The acid value is 50 to 250 mgKOH / g
As the acrylic resin (E), an acrylic resin containing a carboxyl group is usually used, and a (meth) acrylic ester is a main component, and an ethylenically unsaturated carboxylic acid is blended so as to satisfy the above acid value. And an acrylic copolymer obtained by copolymerizing other copolymerizable monomers as required. Here, as the (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl Examples thereof include (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and glycidyl (meth) acrylate.

As the ethylenically unsaturated carboxylic acid, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and the like are preferably used. In addition, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and anhydrides thereof are also used. Products and half esters can also be used. Of these, acrylic acid and methacrylic acid are particularly preferred. Examples of other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, and alkyl vinyl ether.

Further, the weight average molecular weight of the acrylic resin (E) is preferably 30,000 to 200,000, particularly 40,000 to 150,000, particularly 40,000 to 130.
000. If the weight average molecular weight is less than 30,000, a sufficient effect on the developer resistance cannot be obtained.
If it exceeds 0, the developing property is lowered and the resolution is lowered, which is not preferable.

The amount of the acrylic resin (E) is as follows:
The amount is required to be 1 to 50 parts by weight with respect to 100 parts by weight of the above-mentioned carboxyl group-containing acrylic urethane-based resin (A). If the compounding amount is less than 1 part by weight, the expected developer resistance cannot be obtained. If the amount exceeds 50 parts by weight, the cured resist becomes too hard, and the blast resistance is reduced, so that the object of the present invention cannot be achieved.

In the present invention, the above (A) to (A)
In addition to (D), an acrylic urethane-based resin (F) having no acid value is used in an amount of 1 to 100 parts by weight, preferably 3 to 70 parts by weight, based on 100 parts by weight of the carboxyl group-containing acrylic urethane-based resin (A). Particularly preferably, when the content is 5 to 50 parts by weight, the blast resistance can be further improved without lowering the developing property. If the amount is less than 1 part by weight, the expected effect of improving blast resistance cannot be obtained.
If the amount exceeds 0 parts by weight, the resolving power decreases due to a decrease in developability.

The acrylic urethane resin (F) having no acid value may be prepared, for example, by adding a polyol (polyester polyol or polyether polyol) having a molecular weight of 500 to 10,000, preferably 500 to 4,000, to a polyisocyanate compound. After reacting (n + 1) moles,
Further, it is a compound obtained by reacting an ethylenically unsaturated group-containing hydroxy compound (n is an integer of 1 or more). Examples of the polyol, polyisocyanate compound, and ethylenically unsaturated group-containing hydroxy compound having a molecular weight of 500 to 10,000 include those similar to those described in the description of the component (A). Regarding the reaction method (A)
The method described in the description of the components can be employed.

In the present invention, the above (A) to (F)
In addition, an ethylenically unsaturated compound may be added for imparting development resistance. Examples of the ethylenically unsaturated compound include a monofunctional monomer, a difunctional monomer, and a trifunctional or higher monomer.

As monofunctional monomers, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth)
Acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2 -(Meth) acryloyloxyethyl acid phosphate, phthalic acid derivative half (meth) acrylate, and N-methylol (meth) acrylamide.

Examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene. Glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Ethylene oxide modified bisphenol A type di (meth)
Acrylate, propylene oxide-modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Examples include acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, and hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate.

The trifunctional or higher functional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane and glycerin poly Glycidyl ether poly (meth) acrylate is exemplified.

The ethylenically unsaturated compound can be added in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the acrylic urethane-based resin (A) having a carboxyl group. If the amount is less than 30 parts by weight, sufficient developer resistance cannot be obtained, and if the amount is more than 30 parts by weight, the plasticizing effect is large and the storage stability when DFR is used is impaired.

In the present invention, crystal violet, malachite green, brilliant green, patent blue, methyl violet, Victoria blue,
Colored dyes such as roseaniline, parafuchsin, ethylene violet, etc., adhesion promoters, plasticizers, antioxidants, thermal polymerization inhibitors, solvents, surface tension modifiers, stabilizers, chain transfer agents, defoamers, flame retardants Such additives as can be added as appropriate.

The photosensitive resin composition of the present invention is applied to a base film surface such as a polyester film, a polypropylene film, and a polystyrene film, and then protected from above the coated surface with a polyethylene film, a polyvinyl alcohol-based film, a polyester film, and the like. It is often put to practical use by manufacturing a DFR by coating a film. In addition, dip coating, flow coating,
It can also be applied directly on the object to be processed by a conventional method such as a screen printing method.

Next, a method of forming a resist pattern for manufacturing a printed wiring board using the above-mentioned DFR will be described. In order to form a resist pattern by DFR, the adhesive strength between the base film and the protective film and the photosensitive resin composition layer is compared, the film having the lower adhesive strength is peeled off, and the photosensitive resin composition layer is formed on a copper plate or the like. Glass surface, ITO
After being attached to a substrate such as a film, exposure is performed by bringing a pattern mask into close contact with the other film. When the photosensitive resin composition does not have adhesiveness, the other film may be peeled off, and then the pattern mask may be brought into direct contact with the photosensitive resin composition layer for exposure. Exposure is usually performed by ultraviolet irradiation, and as a light source at that time, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, or the like is used. After irradiation with ultraviolet rays, heating can be performed as necessary to complete the curing. After the exposure, development is performed after the film on the resist is removed. Since the photosensitive resin composition of the present invention is of a dilute alkali developing type, development after exposure is carried out at 0.1 to 2% by weight of alkali such as sodium carbonate and potassium carbonate.
A dilute aqueous solution of a certain degree may be used.

The photosensitive resin composition of the present invention is useful for forming a partition wall by a sandblasting method in addition to the above-mentioned applications, and such a method will be described below. First, a resist pattern is formed in the same manner as described above except that a glass substrate for forming a rib is used as a substrate. After the resist pattern is formed as described above, SiC, SiO ₂ , Al ₂ O ₃ , calcium carbonate, etc., having a particle size of about 1 to 100 μm,
Sandblasting is performed by spraying onto the substrate at a blast pressure of 0.05 to 1 MPa. After the sandblasting, the remaining pattern of the cured resist is peeled off to form a desired partition wall. The removal of the pattern of the cured resist is performed by using 0.1 to 5% by weight of sodium hydroxide, potassium hydroxide, or the like.
This is performed using an alkaline stripping solution composed of an alkaline aqueous solution having a moderate concentration. Instead of stripping with an aqueous alkaline solution, it is also possible to burn off the pattern of the cured resist.

The composition of the present invention is also useful for the above-mentioned sand blasting methods such as glass engraving and ceramic processing, and can also be used for producing glass metal masks and engraving gravestones.

[0054]

The present invention will be specifically described below with reference to examples. In the examples, “%” and “part” mean on a weight basis unless otherwise specified. [Carboxyl group-containing acrylic urethane resin (A1)
Production of 104 g of 2,2-bis (hydroxymethyl) propionic acid (a1) in a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet.
(0.78 mol), 261 g (1.55 mol) of hexamethylene diisocyanate (a2), and ethyl acetate 45
After charging 0 g, the two were reacted under a nitrogen atmosphere at 70 ° C. until the residual isocyanate groups became 8.2% to obtain a reaction product (a3). Next, 700 g (1.16 mol) of polyethylene glycol (a4) having an average molecular weight of 600,
0.15 g of dibutyltin laurate was added and further reacted. When the residual isocyanate group became 0.3%, 131.2 g of hexamethylene diisocyanate (a2) was obtained.
(0.78 mol) was added, and the reaction was continued. When the remaining isocyanate groups became 2.3%, 90.0 g (0.76 mol) of 2-hydroxyethyl acrylate (a5) was added.
mol), and the mixture was reacted.
The reaction was terminated when the concentration reached 3%, and the carboxyl group-containing acrylic urethane-based resin (A1) [acid value of 28.7 mgK
OH / g, (a3) content 31%, solid content 74%].

[Production of carboxyl group-containing acrylic urethane resin (A2)] In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet,
2,2-bis (hydroxymethyl) propionic acid (a
1) 119.5 g (0.89 mol) and 396.2 g (1.78 mol) of isophorone diisocyanate (a2)
l), 435 g of ethyl acetate was charged, and the mixture was charged under a nitrogen atmosphere to 60 g.
The mixture was reacted at 8.2 ° C. until the residual isocyanate groups became 8.2% to obtain a reaction product (a3). Then average molecular weight 10
445.6 g of polyethylene glycol (a4) of 00
(0.45 mol), dibutyltin laurate 0.1
5 g was added and the reaction was further continued for about 5 hours. When the remaining isocyanate group became 3.0%, 61.4 g (0.46 mol) of 2-hydroxyethyl acrylate (a5) was added and reacted, and the remaining isocyanate group became 0%. The reaction was terminated at the time of 0.3%, and the carboxyl group-containing acrylic urethane resin (A2) [acid value 30.5 mgKOH / g,
(A3) content: 50%, solid content: 70%].

[Production of acrylic urethane resin (F1) having no acid value] Thermometer, stirrer, water-cooled condenser,
In a four-necked flask equipped with a nitrogen gas inlet, 222 g (1.0 mol) of isophorone diisocyanate and 670 g of polypropylene glycol having an average molecular weight of 1,000
(0.67 mol) and reacted at 80 ° C. under a nitrogen atmosphere. When the remaining isocyanate groups became 3.4%, 79.0 g of 2-hydroxyethyl acrylate was used.
(0.67 mol) and allowed to react. When the remaining isocyanate groups became 0.3%, methyl ethyl ketone 24 was added.
By adding 3 g, an acrylic urethane-based resin (F1) [acid value: 0 mgKOH / g, solid content: 80%] was obtained.

Example 1 The above carboxyl group-containing acrylic urethane resin (A
1) 135.1 parts of a solution (the acrylic urethane resin (A
1) 100 parts in terms of conversion), carboxylic acid-modified polycaprolactone diol [Placcel manufactured by Daicel Chemical Industries, Ltd.
205BA ": Ring-opening addition reaction product of 2,2-bis (hydroxymethyl) butyric acid and ε-caprolactone, hydroxyl value 223 mgKOH / g, acid value 110 mgKOH / g]
(B1) 10 parts, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2 ′
-Biimidazole (C1) 4.0 parts, P, P'-bis (diethylamino) benzophenone (C2) 0.2 parts,
1.0 part of leuco crystal violet (D1), 0.05 part of malachite green (D2) and 95 parts of methyl ethyl ketone were blended and mixed well to prepare a photosensitive resin composition. A DFR was prepared using the composition prior to the evaluation for evaluating the blast resistance, the resist stripping property, the developer resistance, and the storage stability of the resist by the following method.

The above composition was coated on a 25 μm-thick polyester film using an applicator having a gap of 8 mils, left at room temperature for 1 minute 30 seconds, and then dried at 60 ° C., 90 ° C.
The resultant was dried in an oven at 110 ° C. and an oven at 110 ° C. for 3 minutes to obtain a DFR having a resist thickness of 40 μm (provided that no protective film was provided). [Blasting resistance] The above DFR was preheated to 60 ° C. in an oven on a glass substrate for rib formation (a glass substrate coated with a 200 μm thick rib-forming composition “White Rib DLS-3551” manufactured by NEC Corporation). Laminating was performed at a laminating roll temperature of 100 ° C., a laminating roll pressure of 0.3 MPa, and a laminating speed of 1 m / min. After lamination, heat is removed by leaving the laminate at room temperature for 10 minutes, and a mask having a negative pattern of line / space = 80/200 is brought into close contact with it, and a parallel exposure machine “EXM” manufactured by Oak Manufacturing Co., Ltd.
-1201 ”, Stouffer Step Tablet 7
Exposure was performed in an amount equivalent to a step. Then, using a 0.3% aqueous sodium carbonate solution (30 ° C.), a spray pressure of 0.10 M
After performing development for 1.5 times the minimum development time with Pa to form a resist pattern, “PNEU” manufactured by Fuji Manufacturing Co., Ltd.
MA BLASTER "(Hyper nozzle, compressed air pressure: 0.3 MPa, cutting agent: calcium carbonate powder S4
# 600, powder supply amount: 220 g / min)
Sand blasting was performed until the rib bottom width became 110 μm, and the resist state after blasting was visually observed with a microscope, and evaluated as follows. A: The resist was not damaged and the ribs were well formed. −-- A part of the resist (end) was slightly damaged, but the rib formation was good. C: All the resist was damaged, and the ribs were also damaged.

[Resistability of Resist] The resist on the rib formed in the evaluation of the blast resistance was immersed in a 1% aqueous solution of sodium hydroxide at 35 ° C., and the time required for complete removal of the resist was measured. ◎ −−− less than 30 seconds ○ −−− 30−60 seconds × −−− more than 60 seconds

[Developer resistance] The above DFR was heated in an oven at 6
A glass substrate for rib formation preheated to 0 ° C. (manufactured by NEC Corporation, a composition for rib formation “white rib DLS-3551” was 2
On a glass substrate coated with a thickness of 00 μm), a laminating roll temperature of 100 ° C., a roll pressure of 0.3 MPa,
Lamination was performed at a lamination speed of 1 m / min. After lamination, heat is removed by leaving at room temperature for 10 minutes,
With a parallel exposure machine “EXM-1201” manufactured by Oak Manufacturing Co., Ltd., a mask for forming a positive pattern in which a space width can be obtained every 10 μm within a range of 30 to 200 μm, and a line width equal to 300 μm and a constant width. A mask for forming a negative pattern which can be obtained every 10 μm in a range of 30 to 200 μm was brought into close contact with the mask, and exposure was performed in an amount equivalent to 7 steps of a Stouffer step tablet. Then, using a 0.3% aqueous sodium carbonate solution (30 ° C.) and a spray pressure of 0.10 MPa, a minimum development time of 1.5
The development was performed for twice as long and evaluated as follows. ◎ −−− 80 μm positive pattern was resolved and 60
The μm negative pattern was not damaged. ○ −−−− 80 μm or more positive pattern was resolved and 60 μm negative pattern was damaged, but 8
The 0 μm negative pattern was not damaged. C: Even if the positive pattern of 80 μm or more has poor resolution / resolution, the negative pattern of 80 μm is damaged.

[Preservation Stability of Resist] The above composition was coated on a polyester film with a width of 500 mm so as to have a dry film thickness of 40 μm, dried and then sandwiched between polyethylene films as a cover film to form a three-layer structure. It is wound around a branch pipe having a diameter of 82.2 mm so as to have a diameter of 300 mm and a total length of the film of 150 m, and is slit.
It was left for 2 days in a thermo-hygrostat set at 40 ° C. and 40 RH% under black poly light shielding. The storage stability was examined by observing the state of the DFR after standing. −: Crystal generation and unevenness did not occur in DFR. C: Generation of crystals in DFR was observed. Or unevenness has occurred.

Example 2 “Placcel 2” of Example 1 manufactured by Daicel Chemical Industries, Ltd.
05BA ”(B1) instead of“ P ”manufactured by Daicel Chemical Industries, Ltd.
lacel 220BA "(Ring-opening addition reaction product of 2,2-bis (hydroxymethyl) butyric acid and ε-caprolactone, hydroxyl value 56 mgKOH / g, acid value 28 mgKO
H / g), except that H / g) was used.

Example 3 "Placcel 2" manufactured by Daicel Chemical Industries, Ltd.
05BA ”(B1), and a ring-opened adduct of 2,2-bis (hydroxymethyl) propionic acid and ε-caprolactone (hydroxyl value 60 mg KOH / g, acid value 30 mg KO)
H / g), except that H / g) was used.

Example 4 The photosensitive resin composition of Example 1 was further added to a copolymer of methyl methacrylate / n-butyl acrylate / styrene / methacrylic acid (copolymer weight ratio was 40/25/12/2).
3, acid value 149.8mgKOH / g, glass transition temperature 5
6.2 [deg.] C., average molecular weight 42,000] (E1) 10 parts were added, and an experiment was conducted in the same manner as in Example 1 to evaluate the same.

Example 5 An experiment was carried out in the same manner as in Example 1 except that 12.5 parts of an acrylic urethane resin (F1) having no acid value was further added to the composition in Example 1, and the same evaluation was conducted.

Example 6 10 parts of (E1) used in Example 4 and (F1) used in Example 5 were added to the composition in Example 1
Five parts were added, the experiment was performed in the same manner as in Example 1, and the evaluation was performed in the same manner.

Example 7 An experiment was performed in the same manner as in Example 1 except that the same amount of (A2) was added instead of (A1), and the same evaluation was performed.

Example 8 An experiment was conducted in the same manner as in Example 1 except that the addition amount of (B1) was changed to 20 parts, and the same evaluation was performed.

Example 9 An experiment was conducted in the same manner as in Example 1 except that the addition amount of (C1) was changed to 8.0 parts, and the same evaluation was performed.

Example 10 An experiment was carried out in the same manner as in Example 1 except that leukomalachite green (D3) was used instead of (D1), and the same evaluation was performed.

Comparative Example 1 A composition was prepared in the same manner as in Example 1 except that the addition amount of (B1) was changed to 0.3 part, and the same experiment and experiment as in Example 1 were performed.

Comparative Example 2 An experiment was conducted in the same manner as in Example 1 except that the blending amount of (B1) was changed to 50 parts, and the same evaluation was conducted.

Comparative Example 3 The same evaluation was performed as in Example 1 except that the amount of (C1) was changed to 0.05 part.

Comparative Example 4 Evaluation was made in the same manner as in Example 1 except that the blending amount of (C1) was changed to 25 parts.

Comparative Example 5 Evaluation was made in the same manner as in Example 1, except that the amount of (D1) was changed to 0.03 part.

Comparative Example 6 Evaluation was made in the same manner as in Example 1 except that the blending amount of (D1) was changed to 8 parts. Table 1 shows the evaluation results of the examples and the comparative examples.

[Table 1] Blast resistance Resist stripping resistance Developer resistance Storage stability Example 1 ○ ○ ○ ○ 〃 2 ○ ○ ○ ○ 〃 3 ○ ○ ○ ○ 4 ○ ◎ ◎ ○ ５ 5 ◎ ○ ○ ○ 〃 6 ◎ ◎ ◎ ○ 〃 7 ○ ○ ○ ○ ８ 8 ○ ○ ○ ○ ９ 9 ○ ○ ○ ○ 〃 10 ○ ○ ○ ○ Comparative Example 1 ○ × ○ ○ 〃 2 × ○ × × ３ 3 (Resist pattern formation Impossible) ○ ４ 4 ○ ○ ○ × ５ 5 (resist pattern cannot be formed) ○ ６ 6 ○ ○ ○ ×

[0078]

According to the photosensitive resin composition of the present invention, the carboxylic acid-modified polycaprolactone diol compound (B) is used in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the carboxyl group-containing acrylic urethane resin (A). Contains 0.1 to 20 parts by weight of a photopolymerization initiator (C) and 0.05 to 5 parts by weight of a photochromic dye (D), so that blast resistance, resist peeling property, developer resistance, It has excellent storage stability of the resist and is useful for various sandblasting applications, and is particularly useful for sandblasting applications for forming partition walls of plasma displays.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 507 G03F 7/004 507 512 512 7/028 7/028 F term (reference) 2H025 AA00 AB11 AB15 AB17 AC01 AD01 BC66 BC85 CA01 CA14 CA28 CC15 CC20 FA03 FA17 4J011 PA88 PB40 PC02 PC08 QB24 RA07 SA06 SA07 SA22 SA25 SA26 SA36 SA64 SA78 SA88 UA01 VA01 WA01 4J027 AG03 AG04 AG05 AG09 AG23 AG24 AG27 AG33 CA09 CB10 CC05 CD10

Claims (9)

[Claims] 1. A carboxylic acid-modified polycaprolactone diol compound (B) of 0.5 to 30 parts by weight and a photopolymerization initiator (C) of 0 to 100 parts by weight of a carboxyl group-containing acrylic urethane resin (A). A photosensitive resin composition comprising 1 to 20 parts by weight and 0.05 to 5 parts by weight of a photochromic dye (D). 2. The method according to claim 1, wherein the carboxyl group-containing acrylic urethane resin (A) is a carboxyl group-containing diol compound (a)
The reaction product (a3) obtained by reacting 1) with the diisocyanate compound (a2) is subjected to an addition reaction with a polyol (a4), followed by an addition reaction with an ethylenically unsaturated group-containing hydroxy compound (a5). The photosensitive resin composition according to claim 1, wherein the compound is obtained and contains one or more ethylenically unsaturated groups in one molecule. 3. A carboxyl group-containing diol compound (a)
The molecular weight of 1) is 500 or less, the molecular weight of the diisocyanate compound (a2) is 300 or less, and the content of the reaction product (a3) in (A) is 15 to 65% by weight. The photosensitive resin composition according to claim 2, wherein 4. The carboxylic acid-modified polycaprolactone diol compound (B) is a compound obtained by subjecting a carboxyl group-containing diol compound to a ring-opening addition reaction of ε-caprolactone.
The photosensitive resin composition according to any one of the above. 5. A photopolymerization initiator (C) containing at least 20% by weight of 2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole. The photosensitive resin composition according to any one of claims 1 to 4, wherein 6. The photochromic dye (D) comprises one or more of leuco crystal violet, leucomalachite green, and leuco diamond green. Photosensitive resin composition. 7. An acid value of 50 to 2 with respect to 100 parts by weight of the carboxyl group-containing acrylic urethane resin (A).
50 mg KOH / g of acrylic resin (E) is
The photosensitive resin composition according to any one of claims 1 to 6, wherein the photosensitive resin composition comprises parts by weight. 8. An acrylic urethane-based resin (F) having no acid value is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the carboxyl group-containing acrylic urethane-based resin (A). The photosensitive resin composition according to claim 1. 9. The photosensitive resin composition according to claim 1, which is used for a dry film resist.