JP2000250213A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in resistance to developing solutions, sandblasting and handling properties or the like by incorporating a urethane- acrylic resin containing specific carboxyl groups, a photopolymerization initiator, an alkyl (meth)acrylate and a specific urethane-acrylic resin. SOLUTION: The composition is comprised of a urethane-acrylic resin containing specific carboxyl groups expressed by the formula I, a photopolymerization initiator, an alkyl (meth)acrylate and a urethane-acrylic resin expressed by the formula III. In the formulas I and III, R1 and R5 are each a residue of a compound having at least one or more ethylenic unsaturated group and a hydroxy group, which has a urethane bond; R2 and R6 are each a residue of a polyisocyanate having urethane bonds on its both ends; R3 is a residue of a polyol containing carboxyl groups, which has urethane bonds on its both ends; X has a structure expressed by the formula II; (m) and (n) are each an integer of 1-20; and R4 is a residue of a polyol or the like having an average molecular weight of >=500, which has urethane bonds on its both ends; R7 is a residue of a polyol or the like having an average molecular weight of 500-10,000, which has urethane bonds on its both ends.

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, and more particularly, to a photosensitive resin composition which is excellent in developer resistance, sand blast resistance, handling properties, suppression of cold flow when formed into a dry film resist, and the like. The present invention relates to a photosensitive resin composition useful for resist applications.

[0002]

2. Description of the Related Art In general, a three-layer laminated film in which a photosensitive resin composition is applied in layers on a base film such as a polyester film and dried and then a protective film such as a polyethylene film or a polyvinyl alcohol film is laminated thereon is generally used. Film photoresist (hereinafter, referred to as
DFR), which is widely used for manufacturing printed wiring boards, precision metal processing, and the like.

[0003] In use, first, a film having a smaller adhesive strength of a base film or a protective film is peeled off from the DFR to form a pattern such as a copper surface of a copper-clad substrate on the side of the photosensitive resin composition layer. After being attached to the surface of the base material to be exposed, 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 removed and subjected to development. As a development method after exposure, there are a solvent development type and a dilute alkali development type.

[0004] 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 brought into close contact with the layer through a film such as a polyester film laminated thereon to perform exposure. ing. 2. Description of the Related Art In recent years, a sandblast method using a DFR has been used for forming partition walls of a plasma display panel.

Examples of the photosensitive resin composition for DFR that can be used in such applications include, for example, a polymerizable and cross-linkable unsaturated acrylic urethane compound having an acid value of 20 to 200 mgKOH / g, and the urethane compound obtained by a specific method. Solid-state photopolymerizable resin composition comprising an alkali-soluble polymer compound and a photosensitizer compatible with
924), a photosensitive resin composition using a specific terminal carboxyl-acrylic polyurethane prepolymer (Japanese Patent Publication No. 2-10165), and an acid value of 100 to 6
00mgKOH / g and weight average molecular weight of 10,000 to 5
00000 base polymer, 10-50% by weight of a compound having one polymerizable unsaturated group and 10-90% by weight of a compound having two polymerizable unsaturated groups, and a photopolymerization initiator. Photopolymerizable composition (JP-A-3-6202) having an acid value of 100 to 200 mgK
OH / g and weight average molecular weight of 30,000 to 120,000
Base polymer, ethylenically unsaturated compound, P, P '
A specific amount of each component of bis (dialkylamino) benzophenone, hexaarylbiimidazole and leuco dye, and 95% by weight or more of an ethylenically unsaturated compound having two polymerizable unsaturated groups in the component; A photosensitive resin composition (JP-A-7-248621), a specific polymer having a carboxyl group and an amide bond,
Photosensitive polymer composition containing an unsaturated compound containing an amino group or a quaternized salt thereof, and 4,4'-diazide-3,3'-dimethoxybiphenyl (JP-A-7-21922)
No. 4), a photosensitive resin composition comprising a specific terminal (meth) acrylate group-containing urethane compound, an alkali-soluble polymer compound having an acid value of 50 to 250 mg / KOHg, and a photopolymerization initiator (JP-A-8-305017) Gazette),
It contains two or more (meth) acryloyl groups and has an acid value of 50
A photosensitive resin composition comprising a carboxyl group-modified urethane (meth) acrylate compound having a Tg of 5 to 95 ° C after curing, an alkali-soluble polymer compound having an acid value of 50 to 250 mg / KOHg, and a photopolymerization initiator. Urate (meth) containing two or more (meth) acryloyl groups
Acrylate compound, acid value 50-250mg / KOH
g of a photosensitive resin composition comprising an alkali-soluble polymer compound, a polymer compound having an alkali salt of thiocyanate and a polyalkylene oxide segment, and a photopolymerization initiator (JP-A-9-152713).

[0006]

However, in the sandblasting method, performances such as resistance to developing solution (adhesion performance of fine wires during development), resistance to sandblasting (masking performance during sandblasting), and resolution are required. DF
It is also required to have handling properties such as controlling the adhesion to a support film or the like at the time of R formation. In the above, although the sand blast resistance is relatively satisfied, there is a problem with the alkali resistance, and the resolution is insufficient. In addition, it is necessary to strictly control the developer concentration and the developing time during development (the latitude is narrow), but the resolution and the development resistance are relatively good, but the sandblast resistance is insufficient. ,
If the cured resist does not have flexibility and is inferior in sand blast resistance, the resolution is insufficient, and the storage stability of the photodop (photosensitive resin composition solution) and the DFR using the same is problematic. In addition, it is hard to say that the sandblast resistance is sufficient, and there is still room for improvement for use in the sandblasting method. Also, containing a urethane compound,
For,, etc., the adhesion to the support film is increased, and there is a high possibility that the handling property will be impaired.

[0007]

Means for Solving the Problems In view of such circumstances, the present inventors have made intensive studies and as a result, have found that a carboxyl group-containing urethane acrylic resin (A) represented by the following general formula (1), photopolymerization The present inventors have found that a photosensitive resin composition comprising an initiator (B) and an alkyl (meth) acrylate (C) has high resolution and excellent developer resistance, sandblast resistance, handling properties, and the like. The invention has been completed.

[0008]

Embedded image Here, R ₁ is a urethane bond residue of a compound having at least one ethylenically unsaturated group and one hydroxyl group, R ₂ is a urethane bond residue at both ends of a polyisocyanate compound, and R ₃ is a carboxyl group. X is a urethane-bonded residue at both ends of the contained polyol, and X is a structure represented by the following general formula (2), and n is an integer of 1 to 20.

[0009]

Embedded image Here, R ₄ is a urethane-bonded residue at both ends of a polyol or polyester polyol having an average molecular weight of 500 or more, and R ₂ and R ₃ are the same as described above.

Further, in the present invention, when the photosensitive resin composition contains a urethane acrylic resin (D) represented by the following general formula (3), the effect of the present invention is remarkably exhibited. .

[0011]

Embedded image Here, R ₅ is a urethane bond residue of a compound having one or more ethylenically unsaturated groups and one hydroxyl group, R ₆ is a urethane bond residue at both ends of the polyisocyanate compound, and R ₇ is an average molecular weight. Urethane-bonded residues at both ends of the polyol or polyester polyol of 500 to 10000, and m is an integer of 1 to 20.

Further, in the present invention, the acid value is 50 to 250 m.
It is preferable to contain gKOH / g of a carboxyl group-containing acrylic polymer (E) from the viewpoint of film imparting property (suppression of edge fusion).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The carboxyl group-containing urethane acrylic resin (A) used in the present invention may be a compound having a structure represented by the above formula (1). As a method for obtaining the above carboxyl group-containing urethane acrylic resin (A),
Although not particularly limited, for example, a carboxyl group-containing polyol compound (a1) and a polyisocyanate compound (a
2) was reacted at a molar ratio (theoretical value) of 1: 2, and the resulting reaction product (a3) was reacted with a polymer polyol (a4) having a molecular weight of 500 or more, and further containing a (meth) acryloyl group-containing compound. A method of reacting the hydroxy compound (a5) is exemplified.

The carboxyl group-containing polyol compound (a1) is not particularly limited, but has a molecular weight of 50.
A carboxyl group-containing polyol compound of 0 or less is preferable, and specific examples thereof include 2,2-bis (hydroxymethyl).
Butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3,5
-Dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis (4
-Hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, homogentisic acid and the like, and preferably 2,2-bis (hydroxymethyl) butyric acid and 2,2-bis (hydroxymethyl) Propionic acid,
2,2-bis (hydroxyethyl) propionic acid, 2,
2-Bis (hydroxypropyl) propionic acid is used. The carboxyl group-containing polyol compound (a1)
If the molecular weight exceeds 500, the solubility in the reaction solvent decreases, and the reactivity with the isocyanate decreases.

The polyisocyanate compound (a2) is not particularly limited, but is preferably a polyisocyanate compound having a molecular weight of 500 or less, preferably 300 or less, and specific examples thereof include hexamethylene diisocyanate, heptane methylene diisocyanate, and 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, trideca Methylene diisocyanate, pentadecamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate,
2-butynylene diisocyanate, 2,4-tolylene diisocyanate, isophorone diisocyanate, 1,3
-Xylylene diisocyanate, 1,4-xylylene diisocyanate and the like, and preferably hexamethylene diisocyanate and isophorone diisocyanate. If the molecular weight of the polyisocyanate compound (a2) exceeds 500, the reactivity with diols is undesirably reduced.

In the reaction of the carboxyl group-containing polyol compound (a1) with the polyisocyanate compound (a2), known reaction means can be used, for example, in a solvent stable to polyisocyanate (such as ethyl acetate). The reaction may be performed at a temperature lower than the boiling point of the solvent. However, in the present invention, the reaction molar ratio of the carboxyl group-containing polyol compound (a1) and the polyisocyanate compound (a2) is set to 1: 2 as a theoretical value as described above. If the above conditions are not satisfied, isocyanate cannot be added to both terminals, and it is difficult to introduce an ethylenically unsaturated group described later, which is not preferable.

Next, the compound (a3) obtained by reacting the carboxyl group-containing polyol compound (a1) with the polyisocyanate compound (a2) as described above is further added with a molecular weight of 500 or more, preferably 500 to 10,000, more preferably 500 to 10,000. To 4000 polymer polyols (a
The polymer polyol (a4) is a polyether-based polyol, a polyester-based polyol, a polycarbonate-based polyol, or the like.
Acrylic polyol, polybutadiene polyol,
And polyolefin polyols. If the molecular weight is less than 500, the flexibility of the cured resist is undesirably reduced.

In the above reaction, a known method can be employed. For example, a solution having a molecular weight of 500 in a reaction product (a3) solution of a carboxyl group-containing polyol compound (a1) and a polyisocyanate compound (a2) as described above. The above polymer polyol (a4) may be added and reacted at a temperature not higher than the boiling point. Further, a known catalyst such as dibutyltin laurate can be added to promote the reaction. Further, a carboxyl group-containing urethane acrylic resin (A) is obtained by reacting the (meth) acryloyl group-containing hydroxy compound (a5) with the reaction product obtained above.

Examples of the acryloyl group-containing hydroxy compound (a5) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
-(Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, and the like. ) Acrylate and 2-hydroxypropyl (meth) acrylate are used.

The carboxyl group-containing urethane acrylic resin (A) thus obtained is particularly useful in the reaction product (a
It is preferable that the weight ratio of (3) in (A) is 15 to 65% by weight, and if the content is less than 15% by weight, sufficient strength of the cured resist cannot be obtained. Exceeding this is undesirable because the flexibility of the cured resist is reduced. In order to control the weight ratio of the reaction product (a3), the ratio of (a3) to (a5) may be controlled in the above reaction.

The photopolymerization initiator (B) is not particularly limited, and known photopolymerization initiators can be used. For example, P, P'-bis (dimethylamino) benzophenone, P, P'- Bis (diethylamino) benzophenone, P, P'-bis (dibutylamino) benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Benzoin n-butyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoyl benzoic acid, methyl benzoyl benzoate, benzyl diphenyl disulfide, benzyl dimethyl ketal, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,
3'-dimethyl-4-methoxybenzophenone, benzophenone, dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dichloro-4-phenoxyacetophenone Phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, 2-methyl- [4- (methylthio) phenyl] -2 -Morpholino-1-propanone, tribromophenylsulfone, tribromomethylphenylsulfone, furthermore 2,4,6- [tris (trichloromethyl)]-1,3,5-triazine, 2,4- [bis (trichloro Methyl)]-6- (4′- Methoxyphenyl)
-1,3,5-triazine, 2,4- [bis (trichloromethyl)]-6- (4′-methoxynaphthyl) -1,
3,5-triazine, 2,4- [bis (trichloromethyl)]-6- (piperonyl) -1,3,5-triazine, 2,4- [bis (trichloromethyl)]-6
Triazine derivatives such as (4'-methoxystyryl) -1,3,5-triazine, acridine derivatives such as acridine and 9-phenylacridine, 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'-tetra Phenyl-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-1,1'-biimidazole, bis (2,4,5-triphenyl) -1,1'-biimidazole and the like and disclosed in JP-B-45-37377. Hexaarylbiimidazole derivatives such as tautomers covalently bonded at 1,2′-, 1,4′- and 2,4′-, triphenylphosphine, and 2-
Benzoyl-2-dimethylamino-1- [4-morpholinophenyl] -butane and the like can be mentioned, and a hexaarylbiimidazole derivative is preferably used.

The content of the photopolymerization initiator (B) is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the above-mentioned carboxyl group-containing urethane acrylic resin (A). Preferably 0.5 to 15 parts by weight,
Particularly preferably, it is 1 to 12 parts by weight. If the content is less than 0.1 part by weight, the sensitivity is remarkably reduced and good workability cannot be obtained. Conversely, if the content exceeds 20 parts by weight, the storage stability when converted to DFR is undesirably reduced.

Further, in the present invention, the alkyl (meth) acrylate (C) is contained, and the alkyl (meth) acrylate has an alkyl group having 12 to 22 carbon atoms, preferably 15 to 22 carbon atoms. Those are preferable, and examples thereof include lauryl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate, and among them, stearyl (meth) acrylate is particularly preferably used. Can be

The content of the alkyl (meth) acrylate (C) is preferably 0.1 to 7 parts by weight based on 100 parts by weight of the carboxyl group-containing urethane acrylic resin (A). It is preferably 0.5 to 5 parts by weight, particularly preferably 1 to 3 parts by weight. If the content is less than 0.1 part by weight, the adhesion to the support film when converted to DFR cannot be sufficiently improved, and if it exceeds 7 parts by weight, the storage stability becomes unstable, which is not preferable.

Thus, a photosensitive resin composition comprising a carboxyl group-containing urethane acrylic resin (A) represented by the general formula (1), a photopolymerization initiator (B), and an alkyl (meth) acrylate (C) is provided. Although it is obtained, in the present invention, it is more preferable to contain the urethane acrylic resin (D) represented by the formula (3) from the viewpoint of improving blast resistance.

The content of the urethane acrylic resin (D) is the same as that of the carboxyl group-containing urethane acrylic resin (A).
The amount is preferably 5 to 100 parts by weight, particularly preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, per 100 parts by weight. If the content is less than 5 parts by weight, a remarkable effect of blast resistance cannot be obtained. If the content exceeds 100 parts by weight, poor development and lowering of the resolving power are not preferred.

The method for obtaining the urethane acrylic resin (D) is not particularly limited. For example, a polyol or polyester polyol (n mol) having a molecular weight of 500 to 10,000, preferably 500 to 4000 is added to a polyisocyanate compound ( (n + 1 mol (theoretical value)), and further reacted with a (meth) acryloyl group-containing hydroxy compound. (N is an integer of 1 or more.) Examples of such a polyol or polyester polyol having a molecular weight of 500 to 10,000, a polyisocyanate compound, and a (meth) acryloyl group-containing hydroxy compound are the same as those described above. As for the reaction method, similarly to the above, a known method can be employed.

In the present invention, an acid value of 50 to 250 m
gKOH / g, preferably 95 to 180 mgKOH / g
It is preferable to contain the carboxyl group-containing acrylic polymer (E) from the viewpoint of improving the resolving power. Acid value is 50m
If the amount is less than gKOH / g, good developability of the unexposed portion cannot be obtained, and the resolution is lowered. On the other hand, if it exceeds 250 mgKOH / g, the developer resistance and sandblast resistance are undesirably reduced.

Further, the carboxyl group-containing acrylic polymer (E) has a weight average molecular weight of 10,000 to 3,000.
00 is preferable, and 30,000 to 200,000 is more preferable, and 40,000 to 130,000 is more preferable. When the weight average molecular weight is less than 10,000, cold flow development occurs at the time of DFR conversion, which causes edge fusion. And the degree of development is undesirably reduced.

The content of the carboxyl group-containing acrylic polymer (E) is preferably from 0 to 20 parts by weight, particularly preferably from 0 to 20 parts by weight, based on 100 parts by weight of the carboxyl group-containing urethane acrylic resin (A). 15 parts by weight. If the content exceeds 20 parts by weight, the cured resist becomes too hard, and the sandblast resistance is undesirably reduced.

The carboxyl group-containing acrylic polymer (E) contains (meth) acrylate as a main component, and may be obtained by copolymerizing an ethylenically unsaturated carboxylic acid or another copolymerizable monomer as required. It is an acrylic copolymer.

Here, (meth) acrylate includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples thereof include cyclohexyl (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 their anhydrides Products and half esters can also be used. Of these, acrylic acid and methacrylic acid are particularly preferred. It is desired that the ethylenically unsaturated carboxylic acid is copolymerized at about 7 to 38% by weight, preferably about 15 to 27% by weight.

Other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile,
Methacrylonitrile, styrene, α-methylstyrene,
Examples thereof include vinyl acetate and alkyl vinyl ether.

Further, in the present invention, the above (A) to (A)
(C), preferably other than (A) to (C), (D) and / or (E), 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, half (meth) of phthalic acid derivative
Acrylates, monofunctional monomers such as N-methylol (meth) acrylamide, 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, 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) acrylate, diethylene glycol diglycidyl ether di (Meth) acrylate, diglycidyl phthalate di (meth)
Acrylates, bifunctional monomers such as hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Ethylenic unsaturation such as tri- or higher functional monomers such as pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate Compounds can also be compounded. The compounding amount of the ethylenically unsaturated compound is 0 to 100 parts by weight of the carboxyl group-containing urethane acrylic resin (A).
The amount is preferably from 0 to 20 parts by weight, more preferably from 0 to 10 parts by weight, and if the compounding amount exceeds 20 parts by weight, the cured resist becomes too hard, and undesirably lowers the sandblast resistance.

In the present invention, bis (4-N, N
Leuco dyes such as -diethylamino-o-tolyl) methylenethiophenylmethane, bis (4-N, N-diethylamino-o-tolyl) benzylthiophenylmethane, leuco crystal violet, leucomalachite green, leuco diamond green, and crystal violet , Malachite Green, Brilliant Green, Patent Blue, Methyl Violet, Victoria Blue, Rose Aniline, Parafuchsin, Ethylene Violet, etc., Coloring Dyes, Adhesion Improving Agent, Plasticizer, Antioxidant, Thermal Polymerization Inhibitor, Solvent Additives such as a material, a stabilizer, a chain transfer agent, an antifoaming agent, and a flame retardant can be appropriately added.

Next, the production of DFR using the photosensitive resin composition of the present invention and the sand blasting method (formation of plasma display partition walls) using the same will be described. (Lamination method) The above-mentioned photosensitive resin composition is coated on a base film surface such as a polyester film, a polypropylene film or a polystyrene film, and then, if necessary, a polyethylene film or a polyvinyl alcohol-based film is coated on the coated surface. A DFR is formed by coating a protective film such as a film.

For applications other than DFR, the photosensitive resin composition of the present invention may be prepared by a dip coating method, a flow coating method,
The photosensitive layer having a thickness of 1 to 150 μm can be easily formed by directly coating the object to be processed by an ordinary method such as a screen printing method. At the time of coating, methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexane, methyl cellosolve, methylene chloride, 1,
A solvent such as 1,1-trichloroethane can also be added.

(Exposure) In order to form an image by DFR, the adhesive strength between the base film and the photosensitive resin composition layer and the adhesive strength between the protective film and the photosensitive resin composition layer are compared. The layer of the photosensitive resin composition layer is uniformly formed on the glass after the film is peeled off (a layer obtained by screen-printing and drying a rib paste composed of glass powder, a binder and a high boiling point solvent). Then, exposure is performed by closely attaching a pattern mask to 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. When the coating is performed directly on the surface of the rib layer, a pattern mask is brought into contact with the coating surface directly or via a polyester film or the like, and exposed.

Exposure is usually carried out by irradiation with ultraviolet rays, and 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 as a light source. After irradiation with ultraviolet rays, heating can be performed as necessary to complete the curing.

(Development) After exposure, the film on the resist is peeled off and developed. Since the photosensitive resin composition of the present invention is a rare alkali developing type, development after exposure is
This is performed using a dilute aqueous solution of about 0.01 to 2% by weight of an alkali such as sodium carbonate and potassium carbonate.

(Sand Blast) After the cured resist pattern is formed as described above, the particle diameter is 0.1 to 100.
μm of CaCO ₃ , BaSO ₄ , SiC, SiO ₂ ,
With Al ₂ O ₃ or the like, is blown in the blast pressure 0.05 to 1 MPa, performing sandblasting of the exposed rib layer by development.

(Cleaning of resist) After sandblasting,
The pattern of the remaining hardened resist is peeled off. The removal of the pattern of the cured resist is performed using sodium hydroxide,
This is performed using an alkali stripping solution composed of an aqueous alkali solution having a concentration of about 0.1 to 5% by weight such as potassium hydroxide. Instead of stripping with an aqueous alkaline solution, it is also possible to burn off the pattern of the cured resist.

Although the above description has been made on the formation of the partition walls of the plasma display, the present invention is also useful for sand blasting such as dicing of a silicon wafer, processing of a PZT (piezoelectric element), etching of glass or processing of ceramics, and furthermore, glass metal. It can also be used for making masks and engraving gravestones.

[0045]

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.

Example 1 Carboxyl group-containing urethane acrylic resin (A1)
Synthesis temperature 85.14 g (0.63 mol) of 2,2-bis (hydroxymethyl) propionic acid in a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet.
And 213.66 g of hexamethylene diisocyanate
(1.27 mol) and 450.23 g of ethyl acetate were charged and reacted at 80 ° C. under a nitrogen atmosphere. When the remaining isocyanate groups became 7.6%, 569.75 g of polyethylene glycol having an average molecular weight of 600 (09.7%) was added. .95 mol), 0.15 g of dibutyltin laurylate was added, and the mixture was further reacted for about 5 hours. When the residual isocyanate group became 0.5%, 107.40 g (0.64 mol) of hexamethylene diisocyanate was added. The reaction was continued with addition of fresh isocyanate. When the residual isocyanate groups reached 2.3%, the reaction temperature was lowered to 60 ° C., and 73.67 g (0.64 mol) of 2-hydroxyethyl acrylate was added and reacted. Is 0.3%, the reaction is terminated, and a carboxyl group-containing urethane acrylic resin (A1) solution is obtained.

The obtained carboxyl group-containing urethane acrylic resin (A1) has a resin content of 70.5%, an isocyanate content of 0.3%, and an acid value of 23.9 mgKOH / g.
Met. The following was performed using the above-mentioned carboxyl group-containing urethane acrylic resin (A1) solution.

(Preparation of dope) 141.8 parts of the above carboxyl group-containing urethane acrylic resin (A1) solution (the carboxyl group-containing urethane acrylic resin (A1) 1
00 parts), 2,2'-bis (o-chlorophenyl)-
4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (B) 4.0 parts, stearyl methacrylate (C) 3 parts, leuco crystal violet 1.0 part,
P, P'-bis (diethylamino) benzophenone
2 parts, 0.05 part of malachite green and 40 parts of methyl ethyl ketone were blended and mixed well to prepare a dope of the photosensitive resin composition.

(Preparation of DFR) Next, the above-mentioned dope was coated on a polyester film having a thickness of 20 μm using an applicator having a gap of 6 mil and left at room temperature for 1 minute and 30 seconds. Each was dried in an oven at 3 ° C. for 3 minutes to produce a DFR having a resist thickness of 40 μm (however, no protective film was provided).

(Lamination on glass substrate for forming ribs)
The above-mentioned DFR was preheated to 60 ° C. in an oven, and a glass substrate for rib formation (a glass substrate coated with a 200 μm thick rib-forming composition “White Rib DLS-3551” manufactured by Nippon Electric Glass Co., Ltd.) with a laminating roll temperature of 100 μm. ℃,
Roll pressure 3kg / cm ² , lamination speed 2m / mi
n.

(Exposure) After lamination, heat was removed by leaving the laminate at room temperature for 10 minutes, and a parallel exposure machine manufactured by Oak Manufacturing Co., Ltd .:
Exposure was performed with EXM-1201.

Minimum development time After the above exposure, 0.3% aqueous solution of sodium carbonate (30 ° C.)
Was used to develop the film at a spray pressure of 1.2 kg / cm ² , and the time until the unexposed 40 μm-thick resist was dissolved and the substrate surface was exposed was determined.

Sensitivity In the above exposure, a 21-step Stofa step tablet was used, and 50 mj / cm ² to 1000 mj / cm ^2.
Exposure every 50 mj / cm ² until the spray pressure is increased to 1% using a 0.3% aqueous sodium carbonate solution (30 ° C.).
When development was performed at 2 kg / cm ² for 1.5 times the minimum development time, the exposure amount when the seven-step tablet remained was determined.

Resolving power The above-mentioned exposure amount of the seven-step tablet is used to separately determine L
In (line width) / S (space width), L = 400
A pattern mask provided every 10 μm with S of 30 to 100 μm and S is vacuum-contacted to perform exposure.
When a 3% aqueous solution of sodium carbonate (30 ° C.) was used for development at a spray pressure of 1.2 kg / cm ² for 1.5 times the minimum development time, the minimum slit width for resolution was measured.

Developing solution resistance At the exposure amount of the above-mentioned seven-step tablet, L
In (line width) / S (space width), S = 400
A pattern mask provided every 10 μm with L of 10 μm to 150 μm is brought into close contact with a vacuum to perform exposure.
Using a 3% aqueous solution of sodium carbonate (30 ° C.), development was performed at a spray pressure of 1.2 kg / cm ² for 120 seconds, and observed by a microscope to evaluate as follows. A: When L is 80 μm, no poor adhesion due to swelling or lifting of the resist is observed.・ ・ ・: When L is 80 μm, the leading end of the line appears to be slightly floating, but no defective portion is observed. Δ: When L is 80 μm, poor adhesion is clearly observed at a part or the end of the line. ×: When L is 80 μm, it is recognized that part or all of the line is missing or missing.

Sandblast resistance By the above exposure and development, line / space = 60/16
After forming a resist pattern using a mask of No. 0, “PNEUMA BLASTER” (Hyper Nozzle, air pressure: 0.3 MPa, cutting material: BaS) manufactured by Fuji Seisakusho
(O ₄ # 600, powder supply amount: 220 g / min) was subjected to sand blasting for 2 minutes, and the resist state after blasting was visually observed with a microscope, and evaluated according to the following criteria. A: A good pattern is obtained.・ ・ ・: A pattern with a slightly irregular line end is obtained. Δ: A pattern with a chip at a part or the end of the line is obtained. ×: A pattern in which part or all of the line has disappeared is obtained.

Peel strength The DFR was evaluated to have a length of 125 to evaluate the handleability in peeling and removing the polyester film after the exposure.
A glass substrate of 5 mm in width, 50.8 mm in width, and 2.8 mm in thickness was laminated under the above lamination conditions, and unexposed, and peeled 180 degrees in the length direction using an Autograph AG-100 manufactured by Shimadzu Corporation. And the peel strength were measured and evaluated according to the following criteria. ○ ・ ・ ・ less than 20g / 2inch △ ・ ・ ・ 20g / 2inch or more and less than 40g / 2inch × ・ ・ ・ 40g / 2inch or more

Example 2 Carboxyl group-containing urethane acrylic resin (A2)
In the same manner as in Synthesis Example 1, 2,2-bis (hydroxymethyl)
119.5 g (0.89 mol) of propionic acid, 396.2 g (1.78 mol) of isophorone diisocyanate, and 435 g of ethyl acetate were charged and reacted at 80 ° C. under a nitrogen atmosphere to reduce residual isocyanate groups to 8.3%. At the time, polyethylene glycol 44 having an average molecular weight of 1000
5.6 g (0.45 mol) was added, and 0.15 g of dibutyltin laurylate was added and reacted for about 5 hours. When the remaining isocyanate groups became 1.8%, the reaction temperature was lowered to 60 ° C. 2-hydroxyethyl acrylate 1
03.0 g (0.88 mol) was added and reacted, and the reaction was terminated when the remaining isocyanate groups became 0.3%.
A carboxyl group-containing urethane acrylic resin (A2) solution was obtained.

The obtained carboxyl group-containing urethane acrylic resin (A2) has a resin content of 71.7%, an isocyanate content of 0.3% and an acid value of 34.3 mg KOH / g.
Met. The following was performed using the above-mentioned carboxyl group-containing urethane acrylic resin (A2) solution.

(Preparation of dope) 139.5 parts of the above carboxyl group-containing urethane acrylic resin (A2) solution (the carboxyl group-containing urethane acrylic resin (A1) 1
00 parts), 2,2'-bis (o-chlorophenyl)-
7.0 parts of 4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (B), 3 parts of stearyl methacrylate (C), 0.3 parts of leuco diamond green,
P, P'-bis (diethylamino) benzophenone
2 parts, malachite green 0.03 parts, 2,2-dimethoxy-2-benzylacetophenone 3 parts and methyl ethyl ketone 55.0 parts were blended and mixed well to prepare a dope of the photosensitive resin composition. Thereafter, a DFR was prepared in the same manner as in Example 1, laminated on a glass substrate for forming a rib, exposed and developed, and evaluated in the same manner as in Example 1.

Example 3 In the same manner as in Example 1, except that a dope of a photosensitive resin composition in which 20 parts of a urethane acrylic resin (D1) shown below was further added to the dope of the photosensitive resin composition was used. The same evaluation as in Example 1 was performed.

Urethane acrylic resin (D1) In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 66.6 g (0.3 mol) of isophorone diisocyanate and a polyol having an average molecular weight of 1,000 (Diethylene glycol / adipic acid = 1.
200 g (0.2 mol) of a condensate of 12/1 (molar ratio) and 74.3 g of ethyl acetate were charged under nitrogen atmosphere.
The reaction was carried out at 75 ° C., and when the residual isocyanate groups became 2.5%, the temperature was lowered to 60 ° C., and 23.2 g (0.2 mol) of 2-hydroxyethyl acrylate was added and reacted. At 0.3%, the reaction was terminated, and a urethane acrylic resin (D1) solution was obtained. The resin content of the obtained urethane acrylic resin (D1) was 79.6%, and the isocyanate content was 0.3%.

Example 4 In Example 1, the dope of the photosensitive resin composition was replaced with a carboxyl group-containing acrylic polymer (E
The same evaluation as in Example 1 was performed except that a dope of the photosensitive resin composition containing 10 parts of 1) was used. ・ Carboxyl group-containing acrylic polymer (E1) methyl methacrylate / n-butyl methacrylate / 2
-Ethylhexyl acrylate / methacrylic acid = 32 /
It was a copolymer of 30/15/23 (weight ratio), the average molecular weight was 73,000, the acid value was 150 mgKOH / g, and the glass transition temperature was 48.4 ° C.

Example 5 In Example 1, the urethane acrylic resin (D1) used in Example 3 was further added to the dope of the photosensitive resin composition.
The same evaluation as in Example 1 was performed except that a dope of the photosensitive resin composition containing 0 part and 10 parts of the carboxyl group-containing acrylic polymer (E1) used in Example 4 was used.

Comparative Example 1 In Example 1, 2,2-bis (hydroxymethyl)
Using neopentyl glycol instead of propionic acid, 65.79 g (0.63 mol) of neopentyl glycol and 213.66 g of hexamethylene diisocyanate
(1.27 mol) and 450.23 g of ethyl acetate were charged and reacted at 80 ° C. under a nitrogen atmosphere. When the remaining isocyanate groups became 7.7%, 569.75 g of polyethylene glycol having an average molecular weight of 600 (09.7 g) was added. .95 mol), 0.15 g of dibutyltin laurylate was added, and the mixture was further reacted for about 5 hours. When the residual isocyanate group became 0.5%, 107.40 g (0.64 mol) of hexamethylene diisocyanate was added. The reaction was newly added and the reaction was continued. When the remaining isocyanate groups became 2.3%, 73.67 g of 2-hydroxyethyl acrylate was used.
(0.64 mol), and the reaction was terminated when the remaining isocyanate groups became 0.3%, to obtain a urethane acrylic resin (A ') solution.

The obtained urethane acrylic resin (A ')
Has a resin content of 70.3% and an isocyanate content of 0.3
%, The acid value was almost 0 mgKOH / g. Next, the same evaluation as in Example 1 was performed except that the carboxyl group-containing urethane acrylic resin (A1) was changed to the urethane acrylic resin (A ′) in Example 1.

Comparative Example 2 The procedure of Example 1 was repeated except that stearyl methacrylate (C) was not used, and the evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results of the examples and the comparative examples.

[0068]

[Table 1] Minimum development sensitivity Resolution power Development resistance Anti-ghosting resistance Time Liquid property Last strength Intensity (sec) (mj / cm ² ) (μm) Example 1 35 1160 31 80 60 ○ ◎ ○ 〃 4 37 80 40 ◎ ○ ○ 〃 535 80 50 ○ ◎ ○ Comparative Example 1 −− −− −− −− −− −− 〃 235 60 60 ○ ○ × *) Was not measurable due to insufficient developability due to insufficient acid value.

[0069]

The photosensitive resin composition of the present invention comprises a specific carboxyl group-containing urethane acrylic resin (A), a photopolymerization initiator (B), and an alkyl (meth) acrylate (C), preferably Since it contains a specific urethane acrylic resin (D) and / or a carboxyl group-containing acrylic polymer (E) having an acid value of 50 to 250 mgKOH / g, resolution, developer resistance, sandblast resistance,
It is excellent in handling properties and the like, and is useful for various sandblasting applications, and is particularly useful for sandblasting applications for forming partition walls of plasma displays.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) H01J 17/04 H01J 17/04 F term (Reference) 2H025 AA00 AA04 AB11 AB20 AC01 AD01 BC13 BC31 BC67 BC83 BC86 CA00 CB13 CB42 CB51 FA42 4J011 QA03 QB24 RA03 RA12 SA21 SA25 SA31 SA36 SA83 UA01 WA01 4J027 AG01 AG03 AG04 AG09 AG12 AG23 AG24 AG27 AJ01 AJ02 BA07 BA12 CA03 CA09 CB10 CC05 CD10 5C040 GF18 JA09 JA15 JA17 KA16 KB02 KB28 MA23

Claims (7)

[Claims] 1. A carboxyl group-containing urethane acrylic resin (A) represented by the following general formula (1), a photopolymerization initiator (B), and an alkyl (meth) acrylate (C)
A photosensitive resin composition comprising: Embedded image Here, R ₁ is a urethane bond residue of a compound having at least one ethylenically unsaturated group and one hydroxyl group, R ₂ is a urethane bond residue at both ends of a polyisocyanate compound, and R ₃ is a carboxyl group. X is a urethane-bonded residue at both ends of the contained polyol, and X is a structure represented by the following general formula (2), and n is an integer of 1 to 20. Embedded image Here, R ₄ is a urethane-bonded residue at both ends of a polyol or polyester polyol having an average molecular weight of 500 or more, and R ₂ and R ₃ are the same as described above. 2. The carboxyl group-containing urethane acrylic resin (A) represented by the general formula (1) has a carboxyl group-containing polyol compound (a1) and a polyisocyanate compound (a2) in a molar ratio of 1: 2 (theoretical). Value), the reaction product (a3) is reacted with a polymer polyol (a4) having a molecular weight of 500 or more, and further reacted with a (meth) acryloyl group-containing hydroxy compound (a5) to obtain a urethane acryl. 2. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a resin and has one or more ethylenically unsaturated groups in one molecule. 3. A carboxyl group-containing polyol compound (a1) having a molecular weight of 500 or less, a polyisocyanate compound (a2) having a molecular weight of 500 or less, and a carboxyl group-containing urethane acrylic resin of a reaction product (a3). 3. The photosensitive resin composition according to claim 2, wherein the weight ratio in A) is 15 to 65% by weight. 4. The photosensitive resin composition according to claim 1, further comprising a urethane acrylic resin (D) represented by the following general formula (3). Embedded image Here, R ₅ is a urethane bond residue of a compound having one or more ethylenically unsaturated groups and one hydroxyl group, R ₆ is a urethane bond residue at both ends of the polyisocyanate compound, and R ₇ is an average molecular weight. Urethane-bonded residues at both ends of the polyol or polyester polyol of 500 to 10000, and m is an integer of 1 to 20. 5. Further, the acid value is 50 to 250 mgKOH / g.
The photosensitive resin composition according to any one of claims 1 to 4, comprising a carboxyl group-containing acrylic polymer (E). 6. The photosensitive resin composition according to claim 1, which is used for a dry film resist. 7. The photosensitive resin composition according to claim 1, which is used for forming a partition of a plasma display panel.