JP3278143B2 - Photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition having excellent fine wire adhesion, resist peeling properties, resolution, sand blast resistance, etc., and useful for dry film resist applications. It relates to a resin composition.

[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. Hei 8-54534), 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 mgKOH / g, 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, not only the sandblasting resistance (masking performance at the time of sandblasting) but also the fine line adhesion at the time of development and the peelability of the resist are very important requirements. Required. In the above, although the sand blast resistance is relatively satisfied, there is a problem in 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. In addition, although the resolution and the development resistance are relatively good, the sandblast resistance is remarkably low, and the resist stripping property is not yet satisfactory, and further improvement is desired.

[0007]

Means for Solving the Problems Accordingly, the present inventor has conducted intensive studies in view of such circumstances, and as a result, the following general formula (1)
The present invention has been found that a photosensitive resin composition comprising a urethane acrylic compound (A), a binder polymer (B), and a photopolymerization initiator (C) represented by the formula (1) is excellent in fine wire adhesion, resist peeling properties, and sandblast resistance. Was completed.

[0008]

Embedded image Here, R ₁ is a urethane bond residue of a compound having at least one (meth) acryloyl group and one hydroxyl group and having a molecular weight of 200 or more, R ₂ is a urethane bond residue at both ends of the polyisocyanate compound, ₃ is a urethane-bonded residue at both ends of the carboxyl group-containing diol compound, and n is an integer of 1 to 20.

In the present invention, when the binder polymer (B) is a carboxyl group-containing acrylic polymer (B1) having an acid value of 50 to 250 mgKOH / g, it is preferable in terms of resolution and fine wire adhesion. Furthermore, to obtain a binder polymer (B) is, when it is represented by the following general formula (2) or the following general formula carboxyl group-containing urethanes based resin represented by (3) (B2), good resolution and sandblast resistance is Is preferred.

[0010]

Embedded image Here, R ₄ is a urethane bond residue of a polyol or a polyester polyol, R ₅ is a urethane bond residue of both ends of a polyisocyanate compound, R ₆ is a urethane bond residue of both ends of a carboxyl group-containing diol, and m is 1 or more. It is an integer.

[0011]

Embedded image Here, X is represented by the following general formula (4), R ₄ is a urethane bond residue of a polyol or a polyester polyol, R ₅ is a urethane bond residue at both ends of a polyisocyanate compound, and R ₆ is a carboxyl group-containing diol. In the urethane bond residue at both ends, R ₇ is a condensate of a saturated compound having one terminal hydroxyl group, and m is an integer of 1 or more.

[0012]

Embedded image Here, R ₅ and R ₆ are the same as above.

In the present invention, when the composition further contains a urethane acrylic compound (D) represented by the following general formula (5), the effect of the present invention is remarkably exhibited.

Embedded image Here, R ₈ is a urethane bond residue of a compound having one or more (meth) acryloyl groups and one hydroxyl group, R ₉ is a urethane bond residue at both ends of the polyisocyanate compound, and R ₁₀ is an average molecular weight. Urethane binding residues at both ends of the polyol or polyester polyol of 500 to 10,000, and l is an integer of 1 to 20.

Hereinafter, the present invention will be described in detail. The carboxyl group-containing urethane acrylic compound (A) used in the present invention may be any compound having a structure represented by the above general formula (1).

The carboxy represented by the general formula (1)
Preferably the molecular weight of the Le group-containing urethane acrylate compound (A) is 800 to 10,000, more preferably 800 to 5,000, especially preferably 800 to
3,500. When the molecular weight is less than 800, the cured resist lacks flexibility, and the sandblast resistance is reduced. When it exceeds 10,000, the reactivity is reduced, and the curing is not sufficiently obtained, so that the fine wire adhesion is poor. This is undesirably lower.

The carboxyl group-containing urethane acrylic compound (A) has an acid value of 20 to 170 mg KOH.
/ G, more preferably 30 to 15
5 mgKOH / g, particularly preferably 40 to 135 mgK
OH / g. If the acid value is less than 20 mgKOH / g, sufficient photocrosslinking cannot be obtained, and the adhesion will be reduced.
If it exceeds 170 mgKOH / g, photocrosslinking proceeds too much, and sufficient sandblast resistance cannot be obtained, which is not preferable.

The method for obtaining the above-mentioned carboxyl group-containing urethane acrylic compound (A) is not particularly limited. For example, a carboxyl group-containing diol (a1) and a polyisocyanate compound (a2) are mixed at a molar ratio of x: x + 1 (x Is an integer of 1 or more) (theoretical value), and the reaction product (a3) obtained is reacted with a compound (a4) having a molecular weight of 200 or more having one or more (meth) acryloyl groups and one hydroxyl group. A method in which the reaction is performed at a molar ratio (theoretical value) of 1: 2, and the like can be given. Such a method is preferable in terms of achieving a uniform distribution of the acid component, but is not limited thereto.

Hereinafter, such a method will be described in detail. The carboxyl group-containing diol compound (a1) is not particularly limited, but preferably has a molecular weight of 500 or less, particularly preferably 300 or less. Specific examples include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, and 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; , 2-bis (hydroxymethyl) propionic acid,
2,2-bis (hydroxyethyl) propionic acid, 2,
2-bis (hydroxypropyl) propionic acid, 2,2
-Bis (hydroxyethyl) butanoic acid is used. If the molecular weight of the carboxyl group-containing diol compound (a1) exceeds 500, the solubility in the reaction solvent is reduced, and the reactivity with the isocyanate is undesirably reduced.

The polyisocyanate compound (a2) 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, 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, 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 (a2) exceeds 500, the reactivity with diols is undesirably reduced.

In reacting the carboxyl group-containing diol compound (a1) with the polyisocyanate compound (a2), known reaction means can be used. For example, a solvent (ethyl acetate) stable to the polyisocyanate compound (a2) can be used. And the like, the reaction may be carried out at a temperature lower than the boiling point of the solvent. Further, a known catalyst such as dibutyltin laurate can be added to promote the reaction.

However, in the present invention, the reaction molar ratio between the carboxyl group-containing diol compound (a1) and the polyisocyanate compound (a2) is defined as x:
It is preferable to set x + 1 (x is an integer of 1 or more) (an error of about several% is acceptable in actual preparation). If such a condition is not satisfied, isocyanate cannot be added to both terminals, and will be described later. It is difficult to obtain the desired carboxyl group-containing urethane acrylic compound in the reaction, which is not preferable.

Further, a carboxyl group-containing diol (a
The content of 1) is such that the desired acid value of the resin of the carboxyl group-containing urethane acrylic compound (A) is 20 to 17;
It is necessary to contain an amount of 0 mgKOH / g. Thus, a reaction product (a3) obtained from the carboxyl group-containing diol (a1) and the polyisocyanate compound (a2), a compound having at least one (meth) acryloyl group and one hydroxyl group and having a molecular weight of 200 or more ( The carboxyl group-containing urethane acrylic compound (A) represented by the general formula (1) is obtained by reacting a4) with a molar ratio (theoretical value) of 1: 2. In such a reaction, it is of course possible to appropriately use a catalyst.

As the compound (a4) having one or more (meth) acryloyl groups and one hydroxyl group and having a molecular weight of 200 or more, hydroxyethyl (meth) to which 3 mol or more of ethylene oxide (EO) is added Acrylate, 3 mol or more of propylene oxide (P
Hydroxyethyl (meth) acrylate to which O) was added, hydroxyethyl (meth) acrylate to which ethylene oxide (EO) and propylene oxide (PO) were added in total of 3 mol or more, and 2 mol or more of ε-caprolactone were ring-opened. Monofunctional monomers such as hydroxyethyl (meth) acrylate, polyfunctional monomers such as glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and ethylene oxide (E)
O) and / or an adduct of propylene oxide (PO). Polyethylene glycol mono (meth) acrylate (EO of n ≒ 8), polypropylene glycol mono (meth) acrylate (n of PO
# 9), glycerin di (meth) acrylate and pentaerythritol tri (meth) acrylate are used.

If the molecular weight of the compound (a4) having one or more (meth) acryloyl groups and one hydroxyl group is less than 200, the sandblast resistance is undesirably reduced. The preferred molecular weight of the compound (a4) is from 200 to 2,000, particularly preferably from 300 to 2,000.
1,000. Compound (a4) having at least one (meth) acryloyl group and at least one hydroxyl group and having a molecular weight of 200 or more reacts with an isocyanate group at a molecular terminal to form a compound having a double bond added at the terminal. A carboxyl group-containing urethane acrylic compound is prepared.

The binder polymer (B) used in the present invention is not particularly limited.
~ 250mgKOH / g, preferably 100 ~ 170m
It is preferable to use gKOH / g of a carboxyl group-containing acrylic polymer (B1) from the viewpoint of obtaining good developability and resolution, and the above general formula (2) or general formula (3)
In the carboxyl group-containing urethanes based resin represented (B2)
Is preferred from the viewpoint of obtaining high sandblast resistance. Further, if necessary, an acid value of 50% by weight or more containing a hydroxyl group-containing monofunctional monomer in a copolymerization ratio of 50% by weight or more.
It is also preferable to use an acrylic polymer (B3) of not more than 35 mgKOH / g, preferably not more than 35 mgKOH / g, from the viewpoint of obtaining a wide development latitude.

The carboxyl group-containing acrylic polymer (B1) having an acid value of 50 to 250 mgKOH / g has a weight average molecular weight of 30,000 to 200,000.
0, particularly preferably 50,000 to 150,
000, more preferably 50,000 to 120,000.
0, and if the weight average molecular weight is less than 30,000, DF
When R is formed, cold flow development occurs and causes edge fusion. Conversely, if it exceeds 200,000, developability decreases and developability decreases, which is not preferable.

The content of the carboxyl group-containing acrylic polymer (B1) is 100 to 400 parts by weight based on 100 parts by weight of the carboxyl group-containing urethane acrylic compound (A).
Parts by weight, and particularly preferably 115 to 115 parts by weight.
It is 320 parts by weight, more preferably 125 to 200 parts by weight. If the content is less than 100 parts by weight, the adhesiveness of the fine wire becomes insufficient, and if it exceeds 400 parts by weight, the cured resist becomes too hard and the sandblast resistance is lowered, which is not preferable.

The carboxyl group-containing acrylic polymer (B1) contains (meth) acrylate as a main component, and may be copolymerized with 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,
-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.

As the ethylenically unsaturated carboxylic acid, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid are preferably used, and 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 26% by weight.

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

[0031] As the carboxyl group-containing U <br/> Etat down resin (B2) used in the present invention, may be any one having a structure represented by the general formula (2) or general formula (3) . Ca represented by the general formula (2) or general formula (3)
Carboxyl group-containing urethanes based acid value of the resin (B2) is 10
The concentration is preferably from 110 to 110 mgKOH / g, more preferably from 15 to 100 mgKOH / g, and particularly preferably from 20 to 90 mgKOH / g. Acid value is 10mgKO
If it is less than H / g, good developability cannot be obtained.
If it exceeds OH / g, the sandblast resistance is undesirably reduced.

The average molecular weight is 3,000 in terms of styrene.
~ 100,000, more preferably 5,000 ~ 70,000, particularly preferably 7000
0 to 50,000. If the average molecular weight is less than 3,000, the fluidity is high and the film imparting property is insufficient, and if it exceeds 100,000, the resolution is lowered, which is not preferable.

The carboxy represented by the general formula (2)
As a method for obtaining the Le group-containing urethanes based resin (B2), is not particularly limited, for example, polyisocyanate (b1) with the carboxyl group-containing diol (b2) 2
After reacting at a molar ratio (theoretical value) of α: α (α is an integer of 1 or more), the reaction product ( b3 ) and the polyol ( b4 )
Is the molar ratio (theoretical value) of β: β + 1 (β is an integer of 1 or more)
And a method obtained by reacting the above.

Further, the carbo represented by the general formula (3)
As a method for obtaining a cyclohexyl group-containing urethanes based resin (B2), is not particularly limited, for example, polyisocyanate (b1) with the carboxyl group-containing diol (b2)
Is reacted at a molar ratio (theoretical value) of 2γ: γ (γ is an integer of 1 or more), and then the reaction product (b3) is reacted with a polyol (b).
4) is reacted at a molar ratio (theoretical value) of δ: δ-1 (δ is an integer of 2 or more), and the reaction product (b5) is further reacted with a saturated compound (b6) having one hydroxyl group by a ratio of 1: And a method obtained by reacting at a molar ratio of 2.

First, the carbohydrate represented by the above general formula (2)
Specifically explaining a method of manufacturing a cyclohexyl group-containing urethanes based resin (B2). As the polyisocyanate (b1),
Although not particularly limited, a polyisocyanate compound having a molecular weight of 500 or less, preferably 300 or less is preferable. Specific examples thereof include hexamethylene diisocyanate, heptane methylene diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, and 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 (b1) exceeds 500, the reactivity with the diol is undesirably reduced.

The carboxyl group-containing diol (b2) is not particularly limited, but is preferably a carboxyl group-containing polyol compound having a molecular weight of 500 or less, and specific examples 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) propion 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; 2,2-
Bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, and 2,2-bis (hydroxypropyl) propionic acid are used. The carboxyl group-containing diol compound (b2) has a molecular weight of 50
If it exceeds 0, the solubility in the reaction solvent decreases, and the reactivity with the isocyanate decreases, which is not preferable.

In reacting the polyisocyanate compound (b1) with the carboxyl group-containing diol (b2), known reaction means can be used. For example, a solvent (such as ethyl acetate) which is stable in polyisocyanate
In this case, the reaction may be carried out at a temperature lower than the boiling point of the solvent. However, in the present invention, the theoretical molar ratio of the polyisocyanate compound (b1) and the carboxyl group-containing diol compound (b2) is 2α: α (α is 1
(An integer of the above) (preferably, an error of about several% is acceptable in actual preparation). If the above conditions are not satisfied, isocyanate cannot be added to both terminals, and the polyol (b4) described below will not be added. It is difficult to introduce it, which is not preferable.

Next, as described above, the polyisocyanate compound (b1) and the carboxyl group-containing diol compound (b
The polyol (b4) is further added to the reaction product (b3) obtained by reacting 2) with β: β + 1 (β is an integer of 1 or more).
The polyol (b4) is a polyether-based polyol, a polyester-based polyol, a polycarbonate-based polyol, or the like.
Acrylic polyol, polybutadiene polyol,
And polyolefin polyols. The polyol (b 4) the molecular weight is not particularly limited more than 500, preferably 500 to 10,000, it is desirable and more preferably from 500 to 4,000. Molecular weight 5
If it is less than 00, the flexibility of the cured resist is undesirably reduced.

In the above reaction, a known method can be adopted. For example, a polyol (B3) solution containing a polyisocyanate compound (b1) and a carboxyl group-containing diol compound (b2) as described above is mixed with a polyol ( b
4) may be added and the reaction may be performed at a temperature lower than the boiling point.
Further, a known catalyst such as dibutyltin laurate can be added to promote the reaction.

Next, the carbohydrate represented by the above general formula (3)
Specifically explaining a method of manufacturing a cyclohexyl group-containing urethanes based resin (B2). First, the polyisocyanate (b1) and the carboxyl group-containing diol (b2) were converted into 2γ: γ (γ is 1
The reaction product (b3)
To obtain such a polyisocyanate (b
1) The carboxyl group-containing diol (b2) is the same as described above, and the reaction method is the same as described above. Next, the reaction product (b3) and the polyol (b4) were converted to δ: δ.
-1 (δ is an integer of 2 or more) in a molar ratio.
The reaction product (b5) is reacted with a saturated compound (b6) having one hydroxyl group at a molar ratio of 1: 2.

The polyol (b4) is the same as described above, and is a saturated compound having one hydroxyl group (b4).
6) As ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, alkyl monoalcohol (methanol, ethanol, n-propyl alcohol, isopropyl alcohol, hexanol, decanol, lauryl alcohol, stearyl alcohol, behenyl alcohol, etc.), Propylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, and the like. Thus by the above method or the like, and the formula (2) or carboxyl group-containing urethanes based resin represented by (3) (B2) is obtained.

Further, if necessary, an acrylic polymer 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 (B
It is also preferred to use 3) in combination, and the acrylic polymer (B3) has a weight average molecular weight of 30,000.
To 200,000, particularly preferably 50,000.
00 to 150,000, more preferably 50,000 to
120,000 and a weight average molecular weight of 30,000
If less, the film retention is insufficient, and conversely, 200,000
Exceeding the range causes development residues, which is not preferred.

The content of the acrylic polymer (B3) is determined based on the amount of the carboxyl group-containing urethane acrylic compound (A).
The amount is preferably 3 to 30 parts by weight, particularly preferably 5 to 20 parts by weight, and more preferably 5 to 15 parts by weight, per 100 parts by weight. If the content is less than 3 parts by weight, the effect of spreading the development latitude is small, and if it exceeds 30 parts by weight, the development time is undesirably too long.

The acrylic polymer (B3) is obtained by copolymerizing (meth) acrylate and a hydroxyl group-containing monofunctional monomer, and is obtained by containing the hydroxyl group-containing monofunctional monomer in an amount of 50% by weight or more.
If the content is less than 50% by weight, the compatibility is poor, and it is difficult to obtain a uniform coating film.

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, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate.

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.

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, 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 preferably acetophenone derivatives such as hexaarylbiimidazole derivatives and benzyldimethyl ketal, and P, P '
Benzophenone derivatives such as -bis (diethylamino) benzophenone, 2,4-bis (trichloromethyl) -6
Triazine derivatives such as-(4'-methoxynaphthyl) -1,3,5-triazine are used.

The content of the photopolymerization initiator (C) is preferably from 0.1 to 20 parts by weight, more preferably from 100 parts by weight of the carboxyl group-containing urethane acrylic compound (A). Is 0.1 to 15 parts by weight,
Particularly preferably, it is 0.1 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 compound (A) represented by the general formula (1), a binder polymer (B) and a photopolymerization initiator (C) is obtained. It is preferable to contain the urethane acrylic compound (D) represented by the general formula (5) from the viewpoint of obtaining higher sandblast resistance.

The content of the urethane acrylic compound (D) is determined based on the amount of the carboxyl group-containing urethane acrylic compound (A).
It is preferably from 5 to 50 parts by weight, particularly preferably from 7 to 40 parts by weight, more preferably from 10 to 35 parts by weight, per 100 parts by weight. If the content is less than 5 parts by weight, higher sandblast resistance cannot be obtained, and if it exceeds 50 parts by weight, poor compatibility or poor developability causes a decrease in developing power, which is not preferable.

The method for obtaining the urethane acrylic compound (D) is not particularly limited, but may be, for example, a molecular weight of 500 to 10,000, preferably 500 to 4,000.
Is reacted with a polyisocyanate compound (d2) at a molar ratio (theoretical value) of y: y + 1 (y is an integer of 1 or more), and then the reaction product (d3)
To a compound (d4) having one or more (meth) acryloyl groups and one hydroxyl group.

Examples of the high molecular weight polyol (d1) having a molecular weight of 500 to 10,000 include polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, polybutadiene polyols, and polyolefin polyols. Examples of the polyisocyanate compound (d2) include the same as those described above.

Having at least one (meth) acryloyl group ,
Examples of the compound (d4) having one hydroxyl group include hydroxymethyl (meth) acrylate, 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, ethylene glycol monomethyl (meth) acrylate, ethylene glycol monoethyl (meth) ) Acrylate, glycerol (meth) acrylate, dipentaerythritol monohydroxy (meth) acrylate, pentaerythritol triacrylate, and the like. Acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate is used. As for the reaction method, a known method can be employed as in the above.

Thus, in the present invention, the photosensitive resin composition comprising (A), (B) and (C), preferably (A),
A photosensitive resin composition comprising (B1) and (C),
A photosensitive resin composition comprising (A), (B2) and (C), and further a photosensitive resin composition comprising (A), (B1), (C) and (D) are obtained. A) ~
In addition to the component (D), 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,
Monofunctional monomers such as glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, half (meth) acrylate of phthalic acid derivative, 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 A) 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) acrylate, bifunctional monomers such as hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acryl An ethylenically unsaturated compound such as a trifunctional or higher-functional monomer such as a salt may be blended. The blending amount of the ethylenically unsaturated compound is based on 100 parts by weight of the carboxyl group-containing urethane acrylic compound (A). The amount is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight, and when the compounding amount exceeds 20 parts by weight, the cured resist becomes too hard,
It is not preferable because sandblast resistance is reduced.

Further, in the present invention, other screws (PN, N
Leuco dyes such as -diethylamino-o-tolyl) methylenethiophenylmethane, bis (PN, 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. Additives such as a material, a stabilizer, 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 methacrylate from the viewpoint of improving the stability of the dope of the photosensitive resin composition and the storage stability of the DFR. And those having an alkyl group having 12 to 22 carbon atoms, preferably 14 to 22 carbon atoms, such as lauryl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate,
Examples include behenyl (meth) acrylate, and among them, stearyl (meth) acrylate is particularly preferably used.

The content of the methacrylic acid alkyl ester is based on the carboxyl group-containing urethane acrylic compound (A)
The amount is preferably 0.5 to 10 parts by weight, more preferably 1 to 7 parts by weight, particularly preferably 1 to 5 parts by weight with respect to 100 parts by weight.

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.

As a use other than the DFR, the photosensitive resin composition of the present invention is 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. At this time, as a light source, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp or the like is used. After irradiation with ultraviolet rays, heating can be performed as necessary to complete the curing.

(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 pattern of the cured resist is formed as described above, the particle diameter is 0.1 to 100.
μm of CaCO ₃ , BaSO ₄ , SiC, SiO ₂ ,
The blast pressure is 0.5 to 10 kg / c using Al ₂ O ₃ or the like.
blowing m ^2, and the performing sandblasting of the exposed rib layer by development.

(Removal of cured resist) After sand blasting,
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 wall of the plasma display, the present invention is also useful for a sand blasting method such as dicing of a silicon wafer, processing of a PZT (piezoelectric element), etching of a glass or processing of a ceramic, and further, a glass metal. It can also be used for making masks and engraving gravestones.

[0067]

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 compound (A1)
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 444.4 g (2 mol) of isophorone diisocyanate and 148 g (1 mol) of 2,2-bis (hydroxymethyl) butanoic acid , Ethyl acetate 8
42 g was charged and reacted at 80 ° C. under a nitrogen atmosphere. When the residual isocyanate groups became 6.2%, the internal temperature was lowered to 60 ° C., and 710 g of a tetrahydrofuran-polyethylene glycol-modified acrylate having an average molecular weight of 350 was obtained.
(2 mol) was added, and the reaction was continued. When the remaining isocyanate group became 0.3%, the reaction was terminated to obtain a carboxyl group-containing urethane acrylic compound (A1) solution.

The obtained carboxyl group-containing urethane acrylic compound (A1) has a resin content of 60.7%, an isocyanate content of 0.3%, and an acid value of 26.0 mgKOH / g.
Met. The following was performed using the above-mentioned carboxyl group-containing urethane acrylic compound (A1) solution.

(Preparation of Dope) 164.7 parts of the above-mentioned carboxyl group-containing urethane acrylic compound (A1) solution (100 parts of the carboxyl group-containing urethane acrylic compound (A1)) ・ A carboxyl group-containing acrylic polymer as shown below ( B1-1) 375 parts of a solution (150 parts of the carboxyl group-containing acrylic polymer (B1-1) 150 parts) • 2,4-bis (trichloromethyl) -6- (4′-methoxysinaphthyl) -1,3,5- Triazine (C) 0.7 part ・ Leuco crystal violet 0.3 part ・ Malachite green 0.1 part The above composition is dissolved in methyl ethyl ketone and mixed well.
A dope of a photosensitive resin composition having a resin content of 50% was prepared.

[0071]Acrylic polymer containing carboxyl group
(B1-1) Methyl methacrylate / n-butyl methacrylate / 2
-Ethylhexyl acrylate / methacrylic acid = 32 /
30/15/23 (weight ratio) copolymer, weight average
The molecular weight is 73,000, the acid value is 150 mg KOH / g,
The lath transition temperature is 48.4 ° C and the resin content is 40% (solvent:
Tyl ethyl ketone / isopropyl alcohol = 8/2
(Weight ratio).

(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 7 mm, allowed to stand at room temperature for 1 minute and 30 seconds, and then dried 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 3 kg / cm ² , lamination speed 1.5 m /
min.

(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. Hereinafter, the sensitivity, the fine wire adhesion, the resist stripping property, and the sandblast resistance were evaluated.

[0075] Sensitivity in exposure above, using Sutofa 21-step tablet, from 50 mj / cm ² to 1000 mj / cm ^2, was exposed for each ^{50mj / cm 2, 0.3% Na} 2 CO 3 aqueous solution ( (30 ° C.) using a spray pressure of 1.5 kg / cm ² for 1.5 times the minimum developing time, and the exposure amount when the seven-step tablet remains was determined as the sensitivity. .

[Fine Line Adhesion] In the exposure amount of the above-described seven-step tablet, L (line width) / S (space width) is S = 400 μm, and L is 10 to 15
At 0 μm, a pattern mask provided every 5 μm is brought into close contact with a vacuum to perform exposure, and a 0.3% sodium carbonate aqueous solution (30 ° C.) is used to spray pressure: 1.5 kg / cm.
After developing for 1.5 times the minimum developing time in ² , the sample was observed with a microscope and evaluated 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.

[Resistability of resist] Further, 50 mm × 50
2% after performing solid exposure (exposure amount becomes 7 with a 21-step Stofa tablet)
40 ° C with sodium hydroxide aqueous solution, spray pressure 1.5
Peeling was performed at kg / cm ² , the peeling time was measured, and evaluated as follows. ○ ・ ・ ・ peeled within 2 minutes △ ・ ・ ・ peeled within 2-3 minutes × ・ ・ ・ peeled within 3 minutes or more

[Sand Blast Resistance] Exposure was performed using the above-described exposure dose of the 7-step tablet, and a spray pressure of 1.5% was applied using a 0.3% aqueous sodium carbonate solution (30 ° C.).
By performing development at 1.5 times the minimum development time at kg / cm ² , line / space = 60 μm / 160 μm
After forming a resist pattern through a mask of m, "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 120 μm, and the resist state after blasting was visually observed with a microscope. evaluated. A: The resist was good without any damage.・ ・ ・: The resist tip seemed to be slightly floating, but the resist was not damaged. Δ: Chipping occurred at a part or the tip of the resist. X: Part or all of the resist disappeared. Further, a carboxyl group-containing acrylic polymer (B1-
Since it contained 1), the resolution was very good.

Example 2 Carboxyl group-containing urethane acrylic compound (A2)
Synthesis of hexamethylene diisocyanate 5
04.6 g (3 mol), 268 g (2 mol) of 2,2-bis (hydroxymethyl) propionic acid, ethyl acetate 40
3 g, and reacted at 80 ° C. under a nitrogen atmosphere. When the residual isocyanate groups became 7.5%, the internal temperature was lowered to 6%.
The temperature was lowered to 0 ° C., 850 g (2 mol) of polypropylene glycol monoacrylate having an average molecular weight of 420 was added, and the reaction was continued. When the residual isocyanate group became 0.3%, the reaction was terminated, and the carboxyl group-containing urethane acrylic compound (A2 ) A solution was obtained.

The carboxyl group-containing urethane acrylic compound (A2) had a resin content of 80%, an isocyanate content of 0.3%, and an acid value of 54 mgKOH / g. Using the carboxyl group-containing urethane acrylic compound (A2) solution, the following was performed.

(Preparation of dope) 125 parts of the above-mentioned carboxyl group-containing urethane acrylic compound (A2) solution (100 parts of the carboxyl group-containing urethane acrylic compound (A2)) 100 parts of the carboxyl group-containing acrylic polymer (B1- 2) 375 parts of a solution (150 parts of the carboxyl group-containing acrylic polymer (B1-2) 150 parts) 2,4-bis (trichloromethyl) -6- (4'-methoxysinaphthyl) -1,3,5-triazine ( C) 0.7 parts ・ Leuco crystal violet 0.3 parts ・ Malachite green 0.1 parts The above composition is dissolved in methyl ethyl ketone and mixed well.
A dope of a photosensitive resin composition having a resin content of 50% was prepared.

[0082]Acrylic polymer containing carboxyl group
(B1-2) Methyl methacrylate / n-butyl acrylate / meth
Crylic acid is a copolymer of 55/22/23 (weight ratio),
Weight average molecular weight is 65,000, acid value is 150 mg KO
H / g, glass transition temperature 71.7 ° C, resin content 40%
(Solvent: methyl ethyl ketone / methyl cellosolve = 6 /
4). After that, a DFR is manufactured in the same manner as in the first embodiment.
Then, the same evaluation as in Example 1 was performed. Also, carboxyl
Contains a group-containing acrylic polymer (B1-2)
Therefore, the resolution was very good.

[0083] Example 3 In Example 1, the carboxyl group-containing acrylic polymer (B1-1) a carboxyl group-containing <br/> as shown below urethanes based resin (B 2 - 1) 0.99 parts (as resin solution 198 Part), and the same evaluation as in Example 1 was performed. Also, urethane containing carboxyl group
Since the resin (B2-1) was contained, the sandblast resistance was very good.

Carboxyl group-containing urethane resin ( B2-1) 504.6 g (3.0 mol) of hexamethylene diisocyanate was placed in a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet. 201 g of 1,2-bis (hydroxymethyl) propionic acid (1.50
Mol) and 617 g of ethyl acetate, and charged under a nitrogen atmosphere.
When the reaction was carried out at 80 ° C. and the remaining isocyanate groups became 10%, 1200 g (2.0 mol) of polyethylene glycol having an average molecular weight of 600 was added, 0.15 g of dibutyltin laurylate was added, and the mixture was further reacted for about 5 hours. residual isocyanate groups is complete the reaction upon reaching 0.3%, carboxyl group-containing urethanes based resin (B2-
1) A solution was obtained.

[0085] resin component 75.8% of the resulting carboxyl group-containing urethanes based resin <br/> fat (B 2 - 1), an isocyanate content of 0.3%, an acid value of 33.1mgKOH / g, The average molecular weight was 12,700.

[0086] In Example 4 Example 2, the carboxyl group-containing acrylic polymer (B1-2) a carboxyl group-containing <br/> as shown below urethanes based resin (B2-2) 240 parts (as resin solution 348 Part), and the same evaluation as in Example 1 was performed. Also, urethane containing carboxyl group
Since the resin (B2-2) was contained, the sandblast resistance was very good.

Carboxyl group-containing urethane resin (B2-2) 504.6 g (3.0 mol) of hexamethylene diisocyanate was placed in a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet. 201 g of 1,2-bis (hydroxymethyl) propionic acid (1.50
Mol) and 617 g of ethyl acetate, and charged under a nitrogen atmosphere.
The reaction was carried out at 80 ° C., and when the remaining isocyanate groups became 10%, 450 g (0.75 mol) of polyethylene glycol having an average molecular weight of 600 was added, 0.15 g of dibutyltin laurylate was added, and the mixture was further reacted for about 5 hours. When the residual isocyanate groups became 0.3%, 202 g of diethylene glycol monoethyl ether was further added.
(1.5 mol) was added and the reaction continued, residual isocyanate groups is complete the reaction when it becomes 0.3%, carboxy
Le group-containing urethanes based resin (B2-2) to obtain a solution.

[0088] resin component 69% of the resulting carboxyl group-containing urethanes based resin <br/> fat (B2-2), an isocyanate content of 0.3%, an acid value of 42.5mgKOH / g, average molecular weight Was 8,300.

Example 5 The same evaluation as in Example 1 was performed except that 10 parts (25 parts as a resin solution) of an acrylic polymer (B3-1) as shown below was further added. went. Acrylic polymer (B3-1) is a copolymer of methyl methacrylate / 2-hydroxyethyl methacrylate = 40/60 (weight ratio), having an average molecular weight of 58,000, an acid value of 0 mgKOH / g, and a glass transition temperature of 73. At 3 ° C., the resin content was 40% (solvent: methyl ethyl ketone). In addition, acrylic polymer (B3
-1), the development latitude was wide and good.

Example 6 In Example 1, the urethane acrylic compound (D1) shown below was further added to the dope of the photosensitive resin composition.
Part (75.4 parts as a resin solution) of the photosensitive resin composition, except that a dope was used, and the same evaluation as in Example 1 was performed. Further, since the acrylic polymer (B1-1) containing a carboxyl group was contained, the developability was very good.

Urethane acrylic compound (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, 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.
When the reaction was carried out at 75 ° C. and the remaining isocyanate groups became 2.9%, the temperature was lowered to 60 ° C., and 23.2 g (0.2 mol) of 2-hydroxyethyl acrylate was added to react. At 0.3%, the reaction was terminated to obtain a urethane acrylic compound (D1) solution. The resin content of the obtained urethane acrylic compound (D1) was 79.6%, and the isocyanate content was 0.3%.

Example 7 In Example 2, a urethane acrylic compound (D2) as shown below was further added to the dope of the photosensitive resin composition for 30 minutes.
And the same evaluation as in Example 1 was performed except that a dope of the photosensitive resin composition blended with the photosensitive resin composition was used. In addition, since it contained a carboxyl group-containing acrylic polymer (B1-2), the developability was very good.

Urethane acrylic compound (D2) In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 33.6 g (0.2 mol) of hexamethylene diisocyanate, an average molecular weight of 150
0 polyol (diethylene glycol / adipic acid =
150 g (0.1 mol) of a condensate (1.12 / 1 (molar ratio)) and 70 g of ethyl acetate were charged, and charged under a nitrogen atmosphere at 75 g.
° C, when the residual isocyanate groups reached 3.7%, the temperature was lowered to 60 ° C, and 24 g (0.2 mol) of hydroxyethyl acrylate was added and reacted. The reaction was terminated at the point when it became, and a urethane acrylic compound (D2) solution was obtained. The resin content of the obtained urethane acrylic compound (D2) is 75
% And the isocyanate content was 0.3%.

Comparative Example 1 In Example 1, 2,2-bis (hydroxymethyl)
Neopentyl glycol 1 instead of 148 g of butanoic acid
A urethane acrylic compound (A ') solution was obtained in the same manner except that 04 g was used. The resin content of the obtained urethane acrylic compound (A ') was 60%, 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 164.7 parts of the carboxyl group-containing urethane acrylic compound (A1) was changed to 166.7 parts of the urethane acrylic compound (A '), the same evaluation as in Example 1 was performed. Was done.

Comparative Example 2 A urethane acrylic compound (A ″) solution was obtained in the same manner as in Example 1 except that 232 g of hydroxyethyl acrylate (molecular weight: 116) was used instead of 710 g of tetrahydrofuran-polyethylene glycol-modified acrylate. . The resin content of the obtained urethane acrylic compound (A '') was 50%, the isocyanate content was 0.3%, and the acid value was 34 mgKOH / g. Next, the same evaluation as in Example 1 was performed except that the carboxyl group-containing urethane acrylic compound (A1) was changed to the urethane acrylic compound (A ″) in Example 1. Table 1 shows the evaluation results of Examples and Comparative Examples.
Shown in

[0096]

[Table 1] Sensitivity (mj / cm ² ) Fine wire adhesion Resist stripping resistance Sandblast resistance Example 1 224 ○ 〃 〃 〃 2160 ○ ○ 〃 3 320 ３２０ ◎ ◎ 〃 4 450 ◎ 〃 5 300 ◎ ○ 〃 ６ 6200 ○ 〃 ２５０ 7250 ○ ◎ 比較 Comparative Example 1 * * * * 〃 2160 × × 注 Note) * cannot be evaluated because the developability is extremely poor.

[0097]

The photosensitive resin composition of the present invention contains a carboxyl group-containing urethane acrylic compound (A) represented by the above general formula (1), a binder polymer (B), and a photopolymerization initiator (C). Sensitivity, fine wire adhesion,
It is excellent in resist stripping properties, sandblast resistance, etc., and is useful for various sandblasting applications, and is particularly useful for sandblasting applications for forming partition walls of plasma displays.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ identification code FI G03F 7/035 G03F 7/035 (58) Investigated field (Int.Cl. ⁷ , DB name) G03F 7/027 513

Claims (9)

(57) [Claims] 1. A photosensitive resin composition comprising a carboxyl group-containing urethane acrylic compound (A) represented by the following general formula (1), a binder polymer (B), and a photopolymerization initiator (C). Embedded image Here, R ₁ is a urethane bond residue of a compound having at least one (meth) acryloyl group and one hydroxyl group and having a molecular weight of 200 or more, R ₂ is a urethane bond residue at both ends of the polyisocyanate compound, ₃ is a urethane-bonded residue at both ends of the carboxyl group-containing diol compound, and n is an integer of 1 to 20. 2. The binder polymer (B) having an acid value of 50
2. The photosensitive resin composition according to claim 1, which is a carboxyl group-containing acrylic polymer (B1) in an amount of from 250 to 250 mgKOH / g. Wherein the binder polymer (B) is represented by the following general formula (2) or the following general formula according to claim 1, characterized in that the (3) a carboxyl group-containing urethanes based resin represented by (B2) Photosensitive resin composition. Embedded image Here, R ₄ is a urethane bond residue of a polyol or a polyester polyol, R ₅ is a urethane bond residue of both ends of a polyisocyanate compound, R ₆ is a urethane bond residue of both ends of a carboxyl group-containing diol, and m is 1 or more. It is an integer. Embedded image Here, X is represented by the following general formula (4), R ₄ is a urethane bond residue of a polyol or a polyester polyol, R ₅ is a urethane bond residue at both ends of a polyisocyanate compound, and R ₆ is a carboxyl group-containing diol. In the urethane bond residue at both ends, R ₇ is a condensate of a saturated compound having one terminal hydroxyl group, and m is an integer of 1 or more. Embedded image Wherein general formula (2) or 3,000 acid value 10~110mgKOH / g of the general formula (3) a carboxyl group-containing urethanes based resin represented by (B2), the weight average molecular weight of styrene terms The photosensitive resin composition according to claim 3, wherein the composition is 100,000. 5. A carboxyl group represented by the general formula (2)
Containing urethanes based resin (B2) is a polyisocyanate (b1) with the carboxyl group-containing diol (b2) 2
After reacting at a molar ratio of α: α (α is an integer of 1 or more),
The reaction product (b3) and the polyol (b4) are converted to β: β +
1 (beta is an integer of 1 or more) according to claim 3 or 4, characterized in that a <br/> urethanes based resin obtained by reacting in a molar ratio of
The photosensitive resin composition as described in the above. 6. A carboxyl group represented by the general formula (3)
Containing urethanes based resin (B2) is a polyisocyanate (b1) with the carboxyl group-containing diol (b2) 2
After reacting at a molar ratio of γ: γ (γ is an integer of 1 or more),
The reaction product (b3) and the polyol (b4) are converted to δ: δ-
The reaction product (b5) is reacted in a molar ratio of 1: 2 (δ is an integer of 2 or more), and the reaction product (b5) is reacted with a saturated compound (b6) having one hydroxyl group in a molar ratio of 1: 2. <br/> lettuce emissions based photosensitive resin composition according to claim 3 or 4, wherein it is a resin. 7. The photosensitive resin composition according to claim 1, further comprising a urethane acrylic compound (D) represented by the following general formula (5). Embedded image Here, R ₈ is a urethane bond residue of a compound having one or more (meth) acryloyl groups and one hydroxyl group, R ₉ is a urethane bond residue at both ends of the polyisocyanate compound, and R ₁₀ is an average molecular weight. Urethane binding residues at both ends of the polyol or polyester polyol of 500 to 10,000, and l is an integer of 1 to 20. 8. claims 1-7 photosensitive resin composition according to any one, which comprises using a dry film resist. 9. The photosensitive resin composition according to claim 1, which is used for forming a partition of a plasma display panel.