JP2001083701A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high resolution, excellent developing solution resistance and sandblast resistance by incorporating two specified carboxyl-containing urethane acrylic resins and a photopolymerization initiator. SOLUTION: The photosensitive resin composition comprises a carboxyl- containing urethane acrylic resin (A) of formula I, a carboxyl-containing urethane acrylic resin (B) obtained by reacting a urethane compound with a compound having one or more ethylenically unsaturated groups and one hydroxyl group and a photopolymerization initiator (C). In the formula I, R1 is the urethane bond residue of a compound having one or more ethylenically unsaturated groups and one hydroxyl group, R2 is the both-end urethane bond residue of a polyisocyanate compound, R3 is the both-end urethane bond residue of a carboxyl-containing polyol, X is a structure of formula II and (n) is an integer of 1-20. In the formula II, R4 is the both-end urethane bond residue of a polyol or the like.

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 resolution, developer resistance, sandblast resistance and the like, and is useful for dry film resist applications. Things.

[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. (Japanese Unexamined Patent Publication No. 8-547334), a urethane (meth) acrylate compound containing two or more (meth) acryloyl groups, an alkali-soluble polymer compound having an acid value of 50 to 250 mg / KOHg, and an alkali thiocyanate. A photosensitive resin composition comprising a polymer compound having a polyalkylene oxide segment and a photopolymerization initiator (JP-A-9-152713) is exemplified.

[0006]

However, in the sandblasting method, performance such as developer resistance (fine line adhesion performance during development), sandblast resistance (masking performance during sandblasting), and resolving power are required. In this case, although the sand blast resistance is relatively satisfied, there is a problem with the alkali resistance, the resolution is insufficient, and it is necessary to strictly control the developer concentration and the development time during development (the latitude is narrow). , Has relatively good resolution and development resistance, but lacks sand blast resistance.In the case of, the cured resist does not have flexibility and is inferior in sand blast resistance. In addition to being insufficient, there is a problem in the storage stability of the photodop (photosensitive resin composition solution) and the DFR using the same, and it is hard to say that the sandblast resistance is sufficient. It is to use the last method there is still room for improvement.

[0007]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies and as a result, have found that a carboxyl group-containing urethane acrylic resin (A) represented by the following general formula (1) and a carboxyl group-containing resin: A urethane compound obtained by reacting a diol compound and a diol compound not having an acid value with an average molecular weight of 500 or less with a polyisocyanate compound has a compound having at least one ethylenically unsaturated group and one hydroxyl group. The photosensitive resin composition comprising the carboxyl group-containing urethane resin (B) and the photopolymerization initiator (C) obtained by the reaction has high resolution, excellent developer resistance, and excellent sandblast resistance. They have found and completed the present invention.

[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.

In the present invention, the carboxyl group-containing urethane acrylic resin (B) is particularly preferably a carboxyl group-containing urethane acrylic resin represented by the following general formula (3).

[0011]

Embedded image Here, R ₅ is a urethane bond residue of a compound having at least one ethylenically unsaturated group and having one hydroxyl group, R ₆ is a urethane bond residue at both ends of the polyisocyanate compound, and Y is the following general formula: It is a bonding species represented by (4) and the general formula (5). m is an integer of 2 or more.

[0012]

Embedded image Here, R ₆ is a urethane bond residue at both ends of the polyisocyanate compound, R ₇ is a urethane bond residue at both ends of the carboxyl group-containing diol, and h is an integer of 1 to 20.

[0013]

Embedded image Here, R ₆ is a urethane-bonded residue at both ends of the polyisocyanate compound, R ₈ is a urethane-bonded residue at both ends of a diol having an average molecular weight of 500 or less and having no acid value, and i is 1 to
It is an integer of 20.

Further, in the present invention, when the composition contains a urethane acrylic resin (D) represented by the following general formula (6), the effect of the present invention is remarkably exhibited.

[0015]

Wherein R ₉ is a urethane bond residue of a compound having at least one ethylenically unsaturated group and one hydroxyl group, R ₁₀ is a urethane bond residue at both ends of the polyisocyanate compound, ₁₁ is an average molecular weight of 500 to 10,000.
The urethane-bonded residue at both ends of the high molecular polyol of 00, and k is an integer of 1 to 20.

In the present invention, an acid value of 50 to 250 mgK
It is preferable that it contains an OH / g carboxyl group-containing acrylic polymer (E) from the viewpoint of film imparting property (edge fusion suppression), and the hydroxyl group-containing monofunctional monomer is 50% by weight or more in copolymerization ratio. It is preferable to contain the acrylic polymer (F) having an acid value of 50 mgKOH / g or less from the viewpoints of film imparting property and development latitude.

[0017]

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 general formula (1). The method for obtaining the above-mentioned carboxyl group-containing urethane acrylic resin (A) is 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, which is not preferred.

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, heptamethylene 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, tridecamethylene diisocyanate , Pentadecamethylene diisocyanate, butene diisocyanate,
1,3-butadiene-1,4-diisocyanate, 2-
Examples thereof include butynylene diisocyanate, 2,4-tolylene diisocyanate, isophorone diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene diisocyanate, and preferably hexamethylene diisocyanate and isophorone diisocyanate. When the molecular weight of the polyisocyanate compound (a2) is 5
If it exceeds 00, the reactivity with the diol is undesirably reduced.

For 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). What is necessary is just to make it react at the temperature below the reflux of this 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. What is necessary is just to add the above-mentioned high molecular polyol (a4), and to make it react at the temperature below reflux. 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 carboxyl group-containing urethane acrylic resin (B) used in the present invention is a urethane compound obtained by reacting a carboxyl group-containing diol compound and a diol compound having an average molecular weight of 500 or less and having no acid value with a polyisocyanate compound. And a compound having at least one ethylenically unsaturated group and one hydroxyl group.

Particularly, a compound having a structure represented by the above general formula (3) is preferable. Of the diol compounds, the carboxyl group-containing diol preferably contains at least an amount such that the acid value of the resin (B) is 10 to 90 mgKOH / g. Such a resin acid value is 10 mgKOH
/ G causes a decrease in resolution due to a decrease in developability,
If it exceeds 90 mgKOH / g, the sandblast resistance is undesirably reduced.

The method for obtaining the above-mentioned carboxyl group-containing urethane acrylic resin (B) is not particularly limited. For example, the average molecular weight is 500 or less, preferably 70 or less.
A reaction product (b3) obtained by reacting a carboxyl group-containing diol compound (b1) having a molar ratio (theoretical value) of 1: 2 with a carboxyl group-containing diol compound (b1) of from 90 to 460, particularly preferably from 90 to 460; Average molecular weight of 500 or less, preferably 60 to 400, particularly preferably 100 to
A reaction product obtained by reacting a diol compound (b4) having no acid value of 350 with a polyisocyanate compound (b2) at a molar ratio of α: α-1 (α is an integer of 2 or more) (theoretical value) ( b5) is reacted at a molar ratio of β: β-1 (β is an integer of 2 or more) (theoretical value), and the reaction product (b6) obtained has at least one ethylenically unsaturated group and a hydroxyl group. In which a compound (b7) having one is reacted at a molar ratio (theoretical value) of 1: 2, an average molecular weight of 500 or less, preferably 70 to 500, particularly preferably 90 to 4
The carboxyl group-containing diol compound (b1) having an average molecular weight of 500 or less, preferably 60 to 400, particularly preferably 100 to 350, having no acid value (b4) and the polyisocyanate compound (b2) have a predetermined amount. After the batch charging and reaction, the reaction product (b6)
And a compound (b7) having at least one ethylenically unsaturated group and one hydroxyl group at a molar ratio (theoretical value) of 1: 2. In the present invention, the method is particularly preferable in that uniform developing property is obtained.

Hereinafter, the following method will be described in detail. As such a carboxyl group-containing diol compound (b1),
Although not particularly limited, the molecular weight is 500 or less, preferably 7
It is necessary to be 0 to 500, particularly preferably 90 to 460, and specific examples are 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, and 2,2-bis (hydroxyethyl) propionic acid. Bis (hydroxypropyl) propionic acid, 2,2-bis (hydroxymethyl)
Butanoic acid, tartaric acid, 2,2-bis (hydroxymethyl)
Butyric acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic 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) propionic acid and 2,2-bis (hydroxyethyl) Propionic acid, 2,2-bis (hydroxypropyl) propionic acid, and 2,2-bis (hydroxyethyl) butanoic acid are used. The carboxyl group-containing diol compound (b1)
If the molecular weight exceeds 500, the solubility in the reaction solvent decreases, and the reactivity with the isocyanate decreases, which is not preferred.

The polyisocyanate compound (b2) is not particularly limited, but is preferably a polyisocyanate compound having a molecular weight of 500 or less, and specific examples thereof include hexamethylene diisocyanate, heptamethylene 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, tridecamethylene diisocyanate, pentadecamethylene diisocyanate, Butene diisocyanate, 1,3-butadiene-1,4-
Diisocyanate, 2-butynylene diisocyanate,
2,4-tolylene diisocyanate, isophorone diisocyanate, 1,3-xylylene diisocyanate,
Examples include 1,4-xylylene diisocyanate, and preferably hexamethylene diisocyanate and isophorone diisocyanate. If the molecular weight of the polyisocyanate compound (b2) exceeds 500, the reactivity with diols is undesirably reduced.

In the reaction between the carboxyl group-containing diol compound (b1) and the polyisocyanate compound (b2), known reaction means can be used. For example, a solvent (ethyl acetate) that is stable in the polyisocyanate compound (b2) can be used. And the like, the reaction may be carried out at a temperature not higher than the reflux of the solvent. However, in the present invention, the molar ratio of the reaction between the carboxyl group-containing diol compound (b1) and the polyisocyanate compound (b2) is set to 1: 2 as a theoretical value as described above (in actual charging, an error of about several% is required). If the above conditions are not satisfied, isocyanate cannot be added to both ends, and it is difficult to obtain a desired carboxyl group-containing urethane acrylic resin in a reaction described below, which is not preferable.

Further, the content of the carboxyl group-containing diol compound (b1) is adjusted so that the desired acid value of the carboxyl group-containing urethane acrylic resin (B) is 10 to 10.
It is preferable to contain an amount of 90 mgKOH / g.

Examples of the diol compound (b4) having an average molecular weight of 500 or less and having no acid value include 1,4-butanediol, 1,5-pentanediol, 1,2-pentanediol, 2,4-pentanediol, 2,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,8-octanediol, 1,9-nonanediol, alkyldiols such as 1,10-decanediol, neopentyl glycol, ethylene Glycol,
A glycol such as diethylene glycol, tetraethylene glycol, propylene glycol or dipropylene glycol, adipic acid and ethylene glycol in a ratio of 1: 1.1
And ester-based polyols obtained by caprolactone ring-opening addition.

A diol compound (b4) having an average molecular weight of 500 or less and having no acid value and a polyisocyanate compound (b
In the reaction 2), a known method is employed in the same manner as described above.
It is preferable to react the diol compound (b4) having no acid value of 00 or less with the polyisocyanate compound (b2) at a molar ratio of α: α-1 (α is an integer of 2 or more) (theoretical value).

Further, the reaction product (b3) and the reaction product (b5) obtained in the above reaction are reacted in a molar ratio of β: β-1 (β is an integer of 2 or more) (theoretical value). In such a reaction, it is preferable that the reaction product (b3) is dissolved or dispersed in a solvent such as methyl ethyl ketone or ethyl acetate, the reaction product (b5) is added thereto, and the reaction is performed at a temperature not higher than the reflux of each solvent. Further, a known catalyst such as dibutyltin laurate can be added to promote the reaction.

The reaction product (b6) thus obtained and the compound (b7) having at least one ethylenically unsaturated group and one hydroxyl group have a molar ratio of 1: 2 (theoretical value).
To obtain a carboxyl group-containing urethane acrylic resin (B).

Examples of the compound (b7) having one or more ethylenically unsaturated groups and one hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl ( (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate , Diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate and the like, and preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Data) acrylate is used.

The compound (b7) having at least one ethylenically unsaturated group and one hydroxyl group has a carboxyl group containing a double bond at the terminal by reacting with the isocyanate group at the molecular terminal. A urethane acrylic resin is prepared. The acid value of the carboxyl group-containing urethane acrylic resin (B) thus obtained is preferably from 10 to 90 mgKOH / g, more preferably from 20 to 70 mgKOH / g, as described above.

In the present invention, the mixing ratio of the carboxyl group-containing urethane acrylic resin (A) and the carboxyl group-containing urethane acrylic resin (B) is as follows: carboxyl group-containing urethane acrylic resin (A): carboxyl group-containing urethane Acrylic resin (B) = 15: 85-6
The ratio is preferably 5:35, more preferably 20:35.
80 to 60:40.

The photopolymerization initiator (C) 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, dibezosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, 2-methyl- [4- (methylthio) phenyl]
-2-morpholino-1-propanone, tribromophenylsulfone, tribromomethylphenylsulfone, and further 2,4,6- [tris (trichloromethyl)]-
1,3,5-triazine, 2,4- [bis (trichloromethyl)]-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,
Triazine derivatives such as 4- [bis (trichloromethyl)]-6- (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′-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-1,1'-biimidazole, bis (2,
4,5-triphenyl) -1,1'-biimidazole and the like 1,2 'disclosed in JP-B-45-37377.
Hexaarylbiimidazole derivatives such as-, 1,4'- and 2,4'- covalently bonded tautomers, triphenylphosphine, and 2-benzoyl-2
-Dimethylamino-1- [4-morpholinophenyl]
-Butane and the like, preferably, an acetophenone derivative such as a hexaarylbiimidazole derivative, benzyldimethyl ketal, or a benzophenone derivative such as P, P'-bis (diethylamino) benzophenone;
Triazine derivatives such as 2,4-bis (trichloromethyl) -6- (4'-methoxynaphthyl) -1,3,5-triazine are used. These may be used alone or in combination of two or more.

The content of the photopolymerization initiator (C) is 100 parts by weight based on the total amount of the above-mentioned carboxyl group-containing urethane acrylic resin (A) and the above-mentioned carboxyl group-containing urethane acrylic resin (B). 0.1-20
Parts by weight, more preferably 0.5 to
15 parts by weight, particularly preferably 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.

Thus, a photosensitive resin composition comprising a carboxyl group-containing urethane acrylic resin (A), a carboxyl group-containing urethane acrylic resin (B) and a photopolymerization initiator (C) is obtained. It is preferable to contain the urethane acrylic resin (D) represented by the general formula (6) from the viewpoint of improving blast resistance.

The content of the urethane acrylic resin (D) is based on the carboxyl group-containing urethane acrylic resin (A).
And carboxyl group-containing urethane acrylic resin (B)
Is preferably 5 to 100 parts by weight, particularly preferably 5 to 80 parts by weight, and more preferably 10 to 70 parts by weight based on 100 parts by weight of the total amount of The content is 5
If the amount is less than the weight part, a remarkable effect of blast resistance cannot be obtained,
If the amount 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, but may be, for example, a molecular weight of 500 to 10,000, preferably 500 to 4,000.
Of the high molecular polyol and the polyisocyanate compound of γ:
It is obtained by reacting at a molar ratio of γ + 1 (γ is an integer of 1 or more) (theoretical value), and further reacting a compound having at least one ethylenically unsaturated group and one hydroxyl group.

Examples of the high molecular weight polyol having a molecular weight of 500 to 10,000 include polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, polybutadiene polyols, and polyolefin polyols. or,
Examples of the polyisocyanate compound and the compound having one or more ethylenically unsaturated groups and one hydroxyl group include 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.

Further, the carboxyl group-containing acrylic polymer (E) has a weight average molecular weight of 10,000 to 30.
0000 is preferable, and especially 30,000 to 200,0.
00, more preferably 40,000 to 130,000. If the weight average molecular weight is less than 10,000, DF
When R is formed, cold flow development occurs and causes edge fusion. Conversely, if it exceeds 300,000, developability decreases and the degree of development decreases, which is not preferable.

The content of the carboxyl group-containing acrylic polymer (E) is from 0 to 100 parts by weight of the total amount of the carboxyl group-containing urethane acrylic resin (A) and the carboxyl group-containing urethane acrylic resin (B). 20
Parts by weight, particularly preferably 0 to 15 parts by weight.
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, and dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and anhydrides thereof. 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, an acrylic polymer (F) having an acid value of 50 mgKOH / g or less containing a hydroxyl group-containing monofunctional monomer in a copolymerization ratio of 50% by weight or more is further provided.
Is preferred in view of the effect of expanding the development latitude.

Further, the weight average molecular weight of the acrylic polymer (F) is preferably 10,000 to 200,000, particularly preferably 30,000 to 150,000, more preferably 40,000 to 120,000. If the average molecular weight is less than 10,000, a cold flow phenomenon occurs when the DFR is formed, and conversely 200,00
If it exceeds 0, the developability and the resolving power decrease, which is not preferable.

The content of the acrylic polymer (F) is
It is preferably 3 to 20 parts by weight, particularly preferably 5 to 15 parts by weight, based on 100 parts by weight of the total amount of the carboxyl group-containing urethane acrylic resin (A) and the carboxyl group-containing urethane acrylic resin (B). is there. When the content is less than 3 parts by weight, a remarkable effect of the development latitude cannot be obtained, and when it exceeds 20 parts by weight, the developability and the resolving power decrease, which is not preferable.

The acrylic polymer (F) is obtained by copolymerizing (meth) acrylate and a hydroxyl group-containing monofunctional monomer, and the hydroxyl group-containing monofunctional monomer is contained in an amount of 50% by weight or more. If the content is less than 50% by weight, poor compatibility is likely to occur when the photosensitive resin composition is doped or converted to DFR, which is not preferable.

As the (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate,
-Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, and the like. You.

Examples of the hydroxyl group-containing monofunctional monomer include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Hydroxypropyl (meth) acrylate, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, 2- (meth) acryloyloxy-
2-hydroxypropyl phthalate and the like can be mentioned.

As described above, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, alkyl vinyl ether and the like can be copolymerized as other copolymerizable monomers.

Thus, in the present invention, the photosensitive resin composition comprising (A), (B) and (C), (A), (B),
A photosensitive resin composition comprising (C) and (D), (A)
(B) a photosensitive resin composition comprising (C) and (E),
A photosensitive resin composition comprising (A), (B), (C), (D) and (E), and a photosensitive resin composition comprising (A), (B), (C) and (F) (A)
In addition to the component (F), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2
-Phenoxy-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth)
Acrylate, glycerin mono (meth) acrylate,
Monofunctional monomers such as half (meth) acrylate of phthalic acid derivatives such as 2- (meth) acryloyloxyethyl acid phosphate and 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, N-methylol (meth) acrylamide, and 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,
Bifunctional monomers such as ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, and hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate; Trimethylolpropane tri (meta)
3 such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, and glycerin polyglycidyl ether poly (meth) acrylate An ethylenically unsaturated compound such as a monomer having more than one functionality may be blended.

The amount of the ethylenically unsaturated compound to be compounded is determined according to the carboxyl group-containing urethane acrylic resin (A).
And carboxyl group-containing urethane acrylic resin (B)
Is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight, and if the amount exceeds 20 parts by weight, the cured resist becomes too hard, and the sandblast resistance decreases. Is not preferred.

In the present invention, bis (4-N, N
-Diethylamino-o-tolyl) methylenedithiophenylmethane, bis (4-N, N-diethylamino-o-
Tolyl) benzylthiophenylmethane, leuco crystal violet, leuco malachite green, leuco diamond green, and other leuco dyes, crystal violet, malachite green, brilliant green, patent blue, methyl violet, Victoria blue, rose aniline, parafuchsin, ethylene violet, etc. Colored dyes, adhesion promoters, plasticizers, antioxidants, thermal polymerization inhibitors, solvents, surface tension modifiers, stabilizers,
Additives such as a chain transfer agent, an antifoaming agent, and a flame retardant can be appropriately added.

Further, if necessary, it is preferable to further contain an alkyl (meth) acrylate from the viewpoint of improving the peel strength at the time of DFR formation, and the alkyl (meth) acrylate preferably has 12 carbon atoms. Preferred are those having an alkyl group of from 22 to 22, preferably from 15 to 22, such as stearyl (meth) acrylate, lauryl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, and behenyl (meth) acrylate. In particular, stearyl (meth) acrylate and behenyl (meth) acrylate are particularly preferably used.

The content of the alkyl (meth) acrylate is 0.1 part by weight based on 100 parts by weight of the total amount of the carboxyl group-containing urethane acrylic resin (A) and the carboxyl group-containing urethane acrylic resin (B). The amount is preferably from 7 to 7 parts by weight, more preferably from 0.5 to 5 parts by weight, particularly preferably from 1 to 3 parts by weight.

Next, the production of DFR using the photosensitive resin composition of the present invention and the sandblasting 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.

Other applications other than DFR include the use of the photosensitive resin composition of the present invention 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.

(Release of cured 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 stripper made 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 sandblasting such as dicing of a silicon wafer, PZT (piezoelectric element) processing, glass etching and ceramic processing, and further, glass metal. It can also be used for making masks and engraving gravestones.

[0072]

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.

· Carboxy group-containing urethane acrylic
Synthesis of resin (B1) In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, 236 g (2 mol) of 1,6-hexanediol and 248 g (1.5 mol) of hexamethylene diisocyanate were placed. And 280 g of ethyl acetate, and reacted under an atmosphere of nitrogen at an internal temperature of about 80 ° C. until the residual isocyanate groups became 0.3%.
I got

On the other hand, a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet was placed
2,2-bis (hydroxymethyl) propionic acid
5 g (0.6 mol), 202 g (1.2 mol) of hexamethylene diisocyanate and 200 g of ethyl acetate were charged and reacted at an internal temperature of about 80 ° C. When the residual isocyanate groups reached 10.8%, The reaction solution (a) and 80 g of ethyl acetate were added, and the remaining isocyanate groups were 1.
The reaction was carried out until it reached 0%. After that, the internal temperature is reduced to approx.
After being lowered to 2-hydroxyethyl acrylate 23.
3 g (0.2 mol) was added, and the reaction was carried out until the residual isocyanate group became 0.3% to obtain a carboxyl group-containing urethane acrylic resin (B1) solution.

The obtained carboxyl group-containing urethane acrylic resin (A1) had a resin content of 60%, an isocyanate content of 0.3%, and an acid value of 25.7 mgKOH / g. Using the carboxyl group-containing urethane acrylic resin (A1) solution and the carboxyl group-containing urethane acrylic resin (B1) solution, the following was performed.

(Preparation of Dope) 85.1 parts of a carboxyl group-containing urethane acrylic resin (A1) solution (60 parts of the carboxyl group-containing urethane acrylic resin (A1)) • a carboxyl group-containing urethane acrylic resin (B1) Solution 66.7 parts (40 parts of the carboxyl group-containing urethane acrylic resin (B1) 40 parts) 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5.0 parts 5'-tetraphenyl- 1,2'-biimidazole (C)-N, N-tetraethyl-4,4'-diaminobenzophenone (C) 0.2 part-Leuco crystal violet 0.3 part-Malachite green 0.1 part-Methyl ethyl ketone 45 parts Was mixed and mixed well to prepare a dope of the photosensitive resin composition.

(Preparation of DFR) Next, the above dope was coated on a polyester film having a thickness of 20 μm using an applicator having a gap of 6 mil, left at room temperature for 1 minute and 30 seconds, and then heated at 60 ° C., 90 ° C., 110 ° C. 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, the 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, development is performed using a 1% aqueous solution of sodium carbonate (30 ° C.) at a spray pressure of 1.2 kg / cm ² , so that the unexposed resist of 40 μm thickness is dissolved and the substrate surface is exposed. I asked for the time to do it.

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 spray pressure 1.2 k using 1% aqueous sodium carbonate solution (30 ° C.)
g / cm ² at 1.5 times the minimum development time,
The exposure amount when the seven-step tablet remained was determined.

Resolving power The above-described 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 being 30 to 100 μm and S is exposed to light by exposure to 1%
When developing with an aqueous solution of sodium carbonate (30 ° C.) at a spray pressure of 1.2 kg / cm ² for 1.5 times the minimum developing time, the minimum slit width for resolution was measured.

Developing solution resistance The exposure amount of the above-mentioned seven-step tablet is determined separately by L
In (line width) / S (space width), S = 400
A pattern mask provided at intervals of 10 μm with L of 10 μm to 150 μm is vacuum-contacted and exposed, and 1%
Using an aqueous sodium carbonate solution (30 ° C.), development was carried out 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), sand blasting was performed until the average rib bottom width became 110 μm, and the resist state after blasting was visually observed with a microscope, and evaluated according to the following criteria. did. 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.

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.

・Carboxy group-containing urethane acrylic
Synthesis of Resin (B2) In the same manner as in Example 1, 1,5-pentanediol 260 g
(2.5 mol), isophorone diisocyanate 444.
4 g (2 mol) and 176.1 g of ethyl acetate were charged,
The reaction was carried out under a nitrogen atmosphere at an internal temperature of about 80 ° C. until the residual isocyanate groups became 0.3%, to obtain a reaction solution (b). On the other hand, 2-bis (hydroxyethyl) butanoic acid 9
9.2 g (0.67 mol), 298 g (1.34 mol) of isophorone diisocyanate and 400 g of ethyl acetate were charged and reacted at an internal temperature of about 80 ° C. When the residual isocyanate group became 7.5%, The above reaction solution (b)
And 190.4 g of ethyl acetate, and the reaction was carried out until the residual isocyanate groups became 1.1%. Then, after lowering the internal temperature to about 60 ° C., 40.6 g (0.35 mol) of 2-hydroxyethyl acrylate was added, and the reaction was carried out until the remaining isocyanate groups became 0.3%. A system resin (B2) solution was obtained.

The obtained carboxyl group-containing urethane acrylic resin (B2) has a resin content of 61.1%, an isocyanate content of 0.3%, and an acid value of 19.7 mgKOH / g.
Met. Using the carboxyl group-containing urethane acrylic resin (A2) solution and the carboxyl group-containing urethane acrylic resin (B2) solution, the following was performed.

(Preparation of dope) 41.8 parts of a carboxyl group-containing urethane acrylic resin (A2) solution (30 parts of the carboxyl group-containing urethane acrylic resin (A2)) • a carboxyl group-containing urethane acrylic resin (B2) Solution 114.6 parts (70 parts of the carboxyl group-containing urethane acrylic resin (B2) 70 parts) 2,2'-bis (o-chlorophenyl) -4,5,4 ', 3.0 parts 5'-tetraphenyl- 1,1′-biimidazole (C) ・ N, N-tetraethyl-4,4′-diaminobenzophenone (C) 0.1 part ・ Leuco crystal violet 0.6 part ・ Malachite green 0.1 part ・ Methyl ethyl ketone 40 parts Was mixed 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 The procedure of Example 1 was repeated, except that the dope of the photosensitive resin composition was further mixed with 20 parts of a urethane acrylic resin (D1) shown below. 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.
12/1 (molar ratio) condensate, hydroxyl value 112 mg KO
H / g) 200 g (0.2 mol), ethyl acetate 74.3
g, and reacted at 75 ° C. under a nitrogen atmosphere. When the residual isocyanate groups became 2.5%, the temperature was raised to 60%.
° C, and 2-hydroxyethyl acrylate 23.2
g (0.2 mol) was added and reacted. When the remaining isocyanate groups became 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 15 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. Further, since the acrylic polymer (E1) containing a carboxyl group was contained, the developability was improved and the resolution was good.

Example 5 In Example 1, the urethane acrylic resin (D2) as shown below was further added to the dope of the photosensitive resin composition by 15 parts.
And the same evaluation as in Example 1 was performed except that a dope of a photosensitive resin composition containing 7 parts of a carboxyl group-containing acrylic polymer (E2) as shown below was used.

Urethane acrylic resin (D2) In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 70 g (0.4 mol) of toluene-2,6-diisocyanate, average molecular weight 150
0 polyol (diethylene glycol / adipic acid =
1.12 / 1 (molar ratio) condensate, hydroxyl value 75 mgK
OH / g) 450 g (0.3 mol), ethyl acetate 234
g, and reacted at 75 ° C. under a nitrogen atmosphere. When the residual isocyanate groups became 11.5%, the temperature was increased to 6%.
0 ° C., 2-hydroxyethyl acrylate 25.
5 g (0.22 mol) was added and reacted. When the remaining isocyanate groups became 0.3%, the reaction was terminated, and a urethane acrylic resin (D2) solution was obtained. The resin content of the obtained urethane acrylic resin (D2) was 70.5%, and the isocyanate content was 0.3%.

Acrylic polymer containing carboxyl group
(E2) A copolymer of methyl methacrylate / n-butyl acrylate / methacrylic acid / styrene = 50/15/23/12, having an average molecular weight of 63,000 and an acid value of 150 mgK
OH / g, glass transition temperature was 91 ° C. Further, since the acrylic polymer (E2) containing a carboxyl group was contained, the developability was improved and the resolution was good.

Example 6 The same procedure as in Example 1 was carried out except that the dope of the photosensitive resin composition was further mixed with 7.5 parts of the acrylic polymer (F1) shown below. The same evaluation as in Example 1 was performed. Acrylic polymer (F1) Copolymer of methyl methacrylate / 2-hydroxyethyl methacrylate = 35/65 (weight ratio), average molecular weight of 90,000, acid value of 0 mgKOH / g, glass transition temperature of 71 ° C. Was. In addition, acrylic polymer (F
Because of containing (1), the development latitude was wide and the fine wire adhesion was good.

Comparative Example 1 The procedure of Example 1 was repeated except that neopentyl glycol was used in place of 2,2-bis (hydroxymethyl) propionic acid in the synthesis of the carboxyl group-containing urethane acrylic resin (A1). The same procedure was performed to obtain a urethane acrylic resin (A ′) solution. The resin content of the obtained urethane acrylic resin (A ') was 65.2%, the isocyanate content was 0.3%, and the acid value was almost 0 mgKOH / g. Next, in the same manner as in Example 1, except that the above-mentioned urethane acrylic resin (A ') was used without using the carboxyl group-containing urethane acrylic resin (A1) and the carboxyl group-containing urethane acrylic resin (B1). ,
The same evaluation as in Example 1 was performed. Table 1 shows the evaluation results of the examples and the comparative examples.

[0100]

[Table 1] Minimum development time Sensitivity Resolution power Developing solution resistance Lasting resistance (seconds) (mj / cm ² ) (μm) Example 1 35 160 70 ◎ 〃 240 224 70 ◎ ３ 3 32 112 60 ◎ 〃 4 30 112 40 ○ ○ 〃 5 28 80 40 ○ ◎ 〃 6 47 160 80 ◎ ○ Comparative example 1 --- --- - - - Note) Comparative example 1 is developing shortage due to insufficient acid value Therefore, measurement was impossible.

[0101]

The photosensitive resin composition of the present invention comprises a specific carboxyl group-containing urethane acrylic resin (A) and a specific carboxyl group-containing urethane acrylic resin (B).
And a photopolymerization initiator (C), and more preferably a urethane acrylic resin (D) and / or a carboxyl group-containing acrylic polymer (E) represented by the general formula (6):
Also, since it contains an acrylic polymer (F), it is excellent in resolution, developer resistance, sandblast resistance, etc., and is useful for various sandblasting applications, and is particularly useful for sandblasting applications for forming partition walls of plasma displays. .

Claims (10)

[Claims] 1. A carboxyl group-containing urethane acrylic resin (A) represented by the following general formula (1), a carboxyl group-containing diol compound, and a diol compound having an average molecular weight of 500 or less and having no acid value are reacted with a polyisocyanate compound. Group-containing urethane acrylic resin (B) obtained by reacting a urethane compound obtained by reacting a compound having at least one ethylenically unsaturated group and one hydroxyl group with a photopolymerization initiator (C) A) 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) obtained by the above reaction is reacted with a high molecular 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 acrylic compound. 2. The photosensitive resin composition according to claim 1, which 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, wherein the carboxyl group-containing urethane acrylic resin (B) is a carboxyl group-containing urethane acrylic resin represented by the following general formula (3). Embedded image Here, R ₅ is a urethane bond residue of a compound having at least one ethylenically unsaturated group and having one hydroxyl group, R ₆ is a urethane bond residue at both ends of the polyisocyanate compound, and Y is the following general formula: It is a bonding species represented by (4) and the general formula (5). m is an integer of 2 or more. Embedded image Here, R ₆ is a urethane bond residue at both ends of the polyisocyanate compound, R ₇ is a urethane bond residue at both ends of the carboxyl group-containing diol, and h is an integer of 1 to 20. Embedded image Here, R ₆ is a urethane-bonded residue at both ends of the polyisocyanate compound, R ₈ is a urethane-bonded residue at both ends of a diol having an average molecular weight of 500 or less and having no acid value, and i is 1 to
It is an integer of 20. 5. A carboxyl group-containing urethane acrylic resin (B) reacts a carboxyl group-containing diol compound (b1) having an average molecular weight of 500 or less with a polyisocyanate compound (b2) at a molar ratio (theoretical value) of 1: 2. The reaction product (b3) obtained by the reaction, the diol (b4) having an average molecular weight of 500 or less and having no acid value and the polyisocyanate compound (b2) are mixed at a molar ratio of α: α-1 (α is an integer of 2 or more). (Theoretical value), the reaction product (b)
5) is reacted at a molar ratio of β: β-1 (β is an integer of 2 or more) (theoretical value), and the reaction product (b6) obtained has one or more ethylenically unsaturated groups and a hydroxyl group. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a carboxyl group-containing urethane acrylic resin obtained by reacting a compound (b7) having one compound at a molar ratio (theoretical value) of 1: 2. . 6. The photosensitive resin composition according to claim 1, further comprising a urethane acrylic resin (D) represented by the following general formula (6). Embedded image Here, R ₉ is a urethane bond residue of a compound having at least one ethylenically unsaturated group and one hydroxyl group, R ₁₀ is a urethane bond residue at both ends of a polyisocyanate compound, and R ₁₁ is an average molecular weight. Urethane binding residues at both ends of the high molecular polyol of 500 to 10,000, and k is an integer of 1 to 20. 7. An acid value of 50 to 250 mg KOH / g.
The photosensitive resin composition according to any one of claims 1 to 6, comprising a carboxyl group-containing acrylic polymer (E). 8. An acid value of 50 mgK containing a hydroxyl group-containing monofunctional monomer in a copolymerization ratio of 50% by weight or more.
The photosensitive resin composition according to any one of claims 1 to 5, further comprising an OH / g or less acrylic polymer (F). 9. The photosensitive resin composition according to claim 1, which is used for a dry film resist. 10. The photosensitive resin composition according to claim 1, which is used for forming a partition of a plasma display panel.