JP2000010275A - Photosensitive resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. excellent in shelf stability and useful for forming a pattern, e.g. in the formation of an electrode on a large-sized glass substrate of PDP or the like and to obtain a photoresist film of the compsn. SOLUTION: The photosensitive resin compsn. contains a base polymer (a) having a wt. average mol.wt. of 40,000-200,000, 30 to <90 pts.wt. ethylenically unsatd. compd. (b) and 0.1-30 pts.wt. photopolymn. initiator (c), based on 100 pts.wt. of the polymer (a), and a hydroxy-fatty acid or its deriv. (d).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition having extremely excellent storage stability and a photoresist film using the composition, and more particularly, to a large-sized resin such as a plasma display panel (PDP). The present invention relates to a photosensitive resin composition useful for forming a pattern on a glass substrate and a photoresist film using the composition.

[0002]

2. Description of the Related Art A three-layer laminate film obtained by applying a photosensitive resin composition in layers on a base film such as a polyester film, drying and forming a layer, and then laminating a protective film such as a polyolefin film, a polyester film or a polyvinyl alcohol film on the base film. , Generally photoresist film or dry film resist (DFR)
It is widely used for manufacturing printed wiring boards, precision processing of metals, and the like.

[0003] To use the photosensitive resin composition layer, first, the base film or the protective film having the smaller adhesive strength is peeled off from the photoresist film or the dry film resist (DFR) to remove the photosensitive resin composition layer. After attaching to the surface of the substrate on which the pattern such as the copper surface of the substrate is to be formed, exposure is performed in a state where the pattern mask is in contact with the other film (when exposing after exfoliating and removing the other film). Then, the other film is peeled off and subjected to development. As a development method after exposure, there are a solvent development type and a dilute alkali development type.

[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. With respect to the above-mentioned DFR, in recent years, a high resolution of a formed pattern has been required in accordance with the increase in density of a wiring pattern of a printed circuit, and for example, an acid value of 100 to 600 mg KO is required.
H / g, base polymer having a weight average molecular weight of 10,000 to 500,000, compound 1 having one polymerizable unsaturated group
Compound 1 having 0 to 50% by weight and two polymerizable unsaturated groups
Photopolymerizable composition containing 0 to 90% by weight of a polymerizable unsaturated compound, 2,4,5-triarylimidazolyl dimer as a photopolymerization initiator, and p-aminophenyl ketone No.-6202) and an ethylenically unsaturated compound containing p, p'-bis (dialkylamino) benzophenone, hexaarylbiimidazole and a leuco dye as a photopolymerization initiator and having two polymerizable unsaturated groups. A photosensitive resin composition containing a specific amount (Japanese Unexamined Patent Publication No.
-248621).

[0005]

However, in the photopolymerizable composition described in JP-A-3-6202, the composition (photosensitive layer) has a thickness of 50 μm and a line / space ratio of 50 μm.
The resolution is about 60 (μm) / 60 (μm). At this time, the aspect ratio represented by the value of the thickness / line width or space width of the photosensitive layer is about 0.83, which is 1 or less, and is still more. Although it is not satisfactory, there is a method of lowering the glass transition temperature of the base polymer in order to further increase the resolution, but on the contrary, it increases the fluidity of the unexposed part at room temperature, causing edge fusion, and preserving storage stability Improvement of the property is desired. Also, as described in Japanese Patent Application Laid-Open No.
Similarly, in Japanese Patent Application Laid-Open No. 1-2005, although the resolution is relatively good, the storage stability that causes edge fusion has not been sufficiently studied, and improvement is still desired in this regard.

[0006] On the other hand, recently, various flat panel displays have been actively developed, and among them, PDPs have attracted attention.
The use of such displays is expanding to various electronic bulletin boards and so-called "wall-mounted televisions". However, such a PDP display panel has electrodes formed on a glass base material. It is starting to be used.

In view of the above, the present invention provides a photosensitive resin composition having excellent storage stability and a photoresist film using the composition under such a background. It is an object of the present invention to provide a photosensitive resin composition excellent for forming an electrode and a photoresist film using the composition.

[0008]

Means for Solving the Problems However, as a result of intensive studies on such problems, the present inventor has found that 100 parts by weight of a base polymer (a) having a weight average molecular weight of 40,000 to 200,000 is added to an ethylenically unsaturated compound. A photosensitive resin composition comprising 30 parts by weight or more and less than 90 parts by weight of (b), 0.1 to 30 parts by weight of a photopolymerization initiator (c), and a hydroxy fatty acid or a derivative (d) thereof, The inventors have found that they have excellent storage stability and are particularly useful for forming the above-mentioned PDP electrodes, and have completed the present invention.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The base polymer (a) of the present invention is not particularly limited as long as it has a weight average molecular weight of 40,000 to 200,000, preferably 60,000 to 150,000, and may be an acrylic resin, a polyester resin, a polyurethane resin, or the like. Is used. If the weight average molecular weight is less than 40,000, the releasability of the cover film is deteriorated and the possibility of cohesive failure is increased. On the other hand, if it exceeds 200,000, the developability is reduced and the developing power is reduced. Among these,
An acrylic resin containing a carboxyl group is preferable, and an acrylic copolymer containing (meth) acrylate as a main component and optionally copolymerizing an ethylenically unsaturated carboxylic acid or another copolymerizable monomer is important. . An acetoacetyl group-containing acrylic copolymer can also be used.

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 and crotonic acid are preferably used. In addition, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and their anhydrides Products and half esters can also be used. Of these, acrylic acid and methacrylic acid are particularly preferred.

In the case of a dilute alkali developing type, about 15 to 30% by weight of an ethylenically unsaturated carboxylic acid (1
(About 200 to 200 mg KOH / g). Examples of other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, and alkyl vinyl ether. In the present invention, the base polymer (a) preferably has a softening temperature of 50 ° C. or lower, and more preferably 20 to 5 ° C.
Preferably it is 0 ° C. When the softening temperature exceeds 50 ° C., the developing power is lowered due to the lowering of the developing property, which is not preferable.

As the ethylenically unsaturated compound (b),
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol Di (meta)
Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified bisphenol A type di (meth) acrylate, propylene oxide-modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di ( (Meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid-modified neopentyl Glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth)
Acrylate, dipentaerythritol penta (meth)
Acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,
2-bis- (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate Of polyfunctional monomers.

Further, a monofunctional monomer may be used in an appropriate amount together with these polyfunctional monomers. Examples of such a monofunctional monomer include 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- ( (Meth) acryloyloxyethyl acid phosphate, phthalic acid derivative half (meth) acrylate, N-methylol (meth) acrylamide, and the like.

The amount of the ethylenically unsaturated compound (b) is 30 parts by weight based on 100 parts by weight of the base polymer (a).
It is not less than 90 parts by weight, preferably 35 to 85 parts by weight, more preferably 40 to 80 parts by weight. If the amount of the ethylenically unsaturated compound (b) is less than 30 parts by weight, crosslinking by exposure is insufficient, and the resolution and the adhesion are reduced. This leads to a decrease in the performance.

As the photopolymerization initiator (c), benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n
-Butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone,
p, p'-bis (dimethylamino) benzophenone,
p, p'-bis (diethylamino) benzophenone, pivaloin ethyl ether, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,
4-diethylthioxanthone, 2,2'-diethoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, 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, N-phenylglycine, 9-phenylacridine, triphenylbiimidazoles, especially 2- (o-
(Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-
(Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) 4,5-diphenylimidazole dimer, 2,4- ( p-methoxyphenyl) -5-phenylimidazole dimer, 2- (o-ethoxyphenyl) 4,5-diphenylimidazole dimer, 2,4-di (p-ethoxyphenyl) -5-phenylimidazole dimer And the like, which are used alone or in combination of two or more.

The content of the photopolymerization initiator (c) is 0.1 to 30 parts by weight, preferably 0.5 to 25 parts by weight, more preferably 1 to 100 parts by weight based on 100 parts by weight of the base polymer (a).
-20 parts by weight. When the content is less than 0.1 part by weight, the exposure amount until sufficient internal curing is obtained increases,
If the amount is more than 20 parts by weight, the storage stability such as recrystallization in the resist is lowered.

The present invention is characterized by further containing a hydroxy fatty acid or a derivative (d) thereof. In particular, it is preferable to use a hydroxy fatty acid having 6 or more carbon atoms or a derivative (d) thereof. As the hydroxy fatty acid or its derivative (d), 2-oxy-2-
Methylpentanoic acid, 2-oxy-5-methylhexanoic acid, 3-oxy-2-methylpentanoic acid, 8-oxytetradecanoic acid, 11-oxytetradecanoic acid, 10-oxyhexadecanoic acid, 11-oxyhexadecanoic acid, 1
4-oxyhexadecanoic acid, 12-oxidedecanoic acid,
Examples thereof include 16-oxyhexadecanoic acid, 12-oxyoctadecanoic acid, 9-oxyoctadecanoic acid, 22-oxidesuccinic acid, and alkali salts and esterified products thereof. Among them, 8-oxytetradecanoic acid, 10-oxyhexadecanoic acid and 12-oxyoctadecanoic acid are preferable, and 12-oxyoctadecanoic acid is particularly practical.
Hydroxy fatty acids having 5 or less carbon atoms or derivatives thereof cannot form a sufficient physical gel, increase the fluidity during dry film formation, and cannot remarkably obtain the effects of the present invention.

The content of the hydroxy fatty acid or its derivative (d) is preferably 0.5 to 25 parts by weight, more preferably 1 to 20 parts by weight, particularly preferably 100 parts by weight based on 100 parts by weight of the base polymer (A). Preferably it is 2 to 15 parts by weight. If the content is less than 0.5 part by weight, a sufficient physical gel state may not be formed, resulting in insufficient storage stability. If the content exceeds 25 parts by weight, the dissolving operation becomes complicated, and the adhesion due to insufficient tackiness of the resist. Is undesirably reduced.

The photosensitive resin composition of the present invention comprises the above base polymer (a), ethylenically unsaturated compound (b), photopolymerization initiator (c), hydroxy fatty acid or its derivative (d) as essential components. However, if necessary, a thermal polymerization inhibitor, a plasticizer, a dye (colorant, discoloring agent), an adhesion promoter, an antioxidant, a solvent, a surface tension modifier, a stabilizer, a chain transfer agent,
Additives such as an antifoaming agent and a flame retardant can be appropriately added.

For example, a thermal polymerization inhibitor is added to prevent thermal polymerization or polymerization with time of the photosensitive resin composition, and includes p-methoxyphenol, hydroquinone, t
-Butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-p-cresol, nitrobenzene , Picric acid, p
-Toluidine and the like.

The plasticizer is added to control the physical properties of the film. Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate and diallyl phthalate; triethylene glycol diacetate, tetraethylene glycol diacetate and the like. Glycol esters; phosphate esters such as tricresyl phosphate and triphenyl phosphate;
Amides such as p-toluenesulfonamide, benzenesulfonamide, Nn-butylacetamide; aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dioctyl azelate, dibutyl malate; citric acid Triethyl, tributyl citrate, glycerin triacetyl ester,
Glycols such as butyl laurate, dioctyl 4,5-diepoxycyclohexane-1,2-dicarboxylate, polyethylene glycol and polypropylene glycol are exemplified.

Examples of the dye include leuco such as tris (4-dimethylaminophenyl) methane [leucocrystal violet], tris (4-diethylamino-2-methylphenyl) methane, leucomalachite green, leucoaniline and leucomethyl violet. In addition to compounds, brilliant green, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red , Rose Bengal, Methanil Yellow,
Thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone,
2,7-dichlorofluorescein, paramethyl red,
Congo Red, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue A, Phenacetaline, Methyl Violet, Malachite Green, Parafuchsin, Oil Blue # 603, Victoria Pure Blue BOH, Spiron Blue GN, Rhodamine 6G and the like.

The discoloring agent is added to the photosensitive resin composition so that a visible image can be given by exposure, and specific examples thereof include diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, Diphenyl-p-phenylenediamine, p-toluidine,
4,4'-biphenyldiamine, o-chloroaniline,
And the like.

Examples of the adhesion promoter include benzimidazole, benzthiazole, benzoxozole, benztriazole, 2-mercaptobenzthiazole,
-Mercaptobenzimidazole and the like.

DFR using the photosensitive resin composition of the present invention
The method of forming an electrode (pattern formation) on a PDP substrate using the same and a method for manufacturing the same will be specifically described. (Lamination method) The above-mentioned photosensitive resin composition is coated on a base film surface such as a polyester film, a polypropylene film, and a polystyrene film, and then protected on the coated surface with a polyethylene film, a polyvinyl alcohol-based film, and the like. Cover the film to make DFR.

Further, the photosensitive resin composition of the present invention comprises a DFR
It can also be used for other applications, such as the photosensitive resin composition of the present invention, a dip coating method,
The photosensitive layer having a thickness of 1 to 150 μm can be easily formed by directly coating the substrate to be processed by an ordinary method such as a flow coating method or a screen printing method. At the time of coating, a solvent such as methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexane, methyl cellosolve, methylene chloride, 1,1,1-trichloroethane and the like can 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. After the film is peeled off, the photosensitive resin composition layer side is attached to a substrate such as a copper plate, a glass surface, or an ITO film, and then the other film is exposed to light with a pattern mask adhered thereto. 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 a conductive material such as an ITO film is applied directly, a pattern mask is brought into contact with the coated surface directly or via a polyester film or the like and exposed. Exposure is usually performed by ultraviolet irradiation, and as a light source at that time,
A high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp and the like are 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 diluted aqueous solution of about 0.5 to 3% by weight of an alkali such as sodium carbonate and potassium carbonate. A surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed in the alkaline aqueous solution.

(Etching) The etching is usually performed by an ordinary method using an acidic etching solution such as an aqueous solution of cupric chloride-hydrochloric acid or an aqueous solution of ferric chloride-hydrochloric acid. Rarely, an ammonia-based alkali etching solution is also used.

(Removal of Hardened Resist) After the etching step, the remaining hardened resist is removed. Stripping and removal of the cured resist is performed using an alkali stripping solution composed of an aqueous solution of an alkali having a concentration of about 0.5 to 5% by weight such as sodium hydroxide or potassium hydroxide. Then, after sufficiently washing with water, it is dried.

Thus, it is possible to manufacture a printed wiring board, perform precision metal processing, and form a lead frame.
For PDP, an electrode is formed on the front substrate for PDP,
Then, after filling the gas with the back substrate, it is joined to PD
It is practically used as P.

The photosensitive resin composition of the present invention and a photoresist film using the composition can be used for producing printed wiring boards,
It is very useful as an etching resist used for precision processing of metal, lead frame manufacturing, etc., or a resist for forming electrodes of PDP. As described above, base polymer (a), ethylenically unsaturated compound (b), photopolymerization Since it contains an initiator (c), a hydroxy fatty acid or a derivative (d) thereof, it exhibits a very excellent effect on storage stability.

[0035]

The present invention will be specifically described below with reference to examples. In the examples, "parts" means on a weight basis unless otherwise specified. Example 1 (Adjustment of dope) Photosensitive by mixing a base polymer (a), an ethylenically unsaturated compound (b), a photopolymerization initiator (c), a hydroxy fatty acid (d) and other additives as described below. A resin composition was prepared.

Base Polymer (a) Copolymer having a copolymerization ratio of methyl methacrylate / n-butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid of 40/10/25/25 by weight (weight average molecular weight 70,000) , Softening temperature 42 ° C, acid value 168mgKOH / g) 100 parts

[0037]Ethylenically unsaturated compound (b)  ・ Ethylene oxide-modified bisphenol A type dimethacrylate 60 parts ・ 2-Acryloyloxyethyl-2-hydroxyethylphthalic acid 20 parts

Photopolymerization initiator (c) 0.25 parts of p, p'-bis (diethylamino) benzophenone 5.5 parts of 2- (o-chlorophenyl) -4,5-diphenyl imidazole dimer hydroxy fatty acid ( d). 10 parts of 12-oxyoctadecanoic acid Other additives 0.55 parts of leuco crystal violet 0.1 part of malachite green 200 parts of methyl ethyl ketone

(Preparation of Photoresist Film) The above-mentioned dope was applied on a polyester film having a thickness of 20 μm using an applicator having a gap of 4 mil, left at room temperature for 1 minute 30 seconds, and then heated at 60 ° C. and 90 ° C. Each was dried for 2 minutes in an oven at 110 ° C., and a polyethylene film was further laminated thereon as a protective film to obtain a photoresist film having a resist thickness of 20 μm.

(Lamination on PDP glass substrate) After the protective film of this photoresist film was peeled off,
Glass substrate with ITO preheated to 60 ° C in oven (2
(200 mm × 200 mm × 2 mm), the laminate was rolled at a lamination roll temperature of 100 ° C., a roll pressure of 3 kg / cm ² , and a lamination speed of 1.5 m / sec.

(Exposure, development) After lamination, L / S (line / space) = 100 μm / 100 μ
In order to form m, a line pattern mask was vacuum-adhered on the polyester film, and the exposure was performed using a 3 kW ultra-high pressure mercury lamp with an exposure machine HMW-532D manufactured by Oak Manufacturing Co., Ltd.
Exposure was performed so as to be mj / cm ² . After a hold time of 15 minutes after the exposure, the polyester film was peeled off, and developed with a 1% aqueous solution of Na ₂ CO ₃ at 30 ° C. for 1.5 times the minimum developing time, followed by washing and drying. As a result, a pattern of a resist layer of L / S = 100 μm / 100 μm was formed.

[0042] (etching, curing the resist stripping) above pattern ferric (45 ° C., 42 ° Be) chloride etching with, then warmed to 50 ° C. in the resist pattern 3% NaOH aqueous solution 2 kg / cm ² The resist pattern is removed by spraying at a pressure of
S = 100 μm / 100 μm) was formed on a PDP substrate.

The following evaluations were made in the above-described ITO pattern forming process. [Storage Stability] When a slit roll (outer diameter of branch tube: 8.24 cm) having a width of 300 mm and a length of 100 m was stored horizontally in a dryer at 32 ° C., the state of exudation at the end was visually observed. . The evaluation criteria are as follows. ◎ ・ ・ ・ No exudation even if stored for 5 days or more.・ ・ ・: No exudation in 3 days or more and less than 5 days. ×: Bleeding is observed at the end portion in less than 3 days, or a recrystallized product of the additive is deposited in the resist. [Sensitivity] The sensitivity was measured by measuring the exposure amount (mj / cm ² ) when the number of steps on the 21-step Stofa tablet was 7.

[Resolution] After laminating on a glass substrate with ITO, a line / space = 1/1, a pattern mask designed every 5 μm at 5 to 100 μm is adhered in vacuum,
Exposure is performed at an exposure amount equivalent to 7 steps of a 21-step stofer step tablet, and after development, the minimum line width (μm) at which the resist image is resolved is examined. The aspect ratio (resist thickness / minimum line width) at that time is also determined. Calculated. The development conditions are as described above.

Example 2 A photosensitive polymer was prepared by mixing a base polymer (a), an ethylenically unsaturated compound (b), a photoweight initiator (c), a hydroxy fatty acid (d), and other additives as described below. Except having prepared the composition, it carried out similarly to Example 1 and performed the same evaluation as Example 1.

Base Polymer (a) A copolymer having a copolymerization ratio of n-butyl methacrylate / 2-ethylhexyl acrylate / methyl acrylate / methacrylic acid of 42/10/25/23 by weight (weight average) Molecular weight 100,000, softening temperature 29 ° C., acid value 150 mg KO H / g) 100 parts ethylenically unsaturated compound (b) · ethylene oxide-modified bisphenol A type dimethacrylate 50 parts • 2-acryloyloxyethyl-2-hydroxyethyl phthalate 15 parts of acid

Photopolymerization initiator (c) 0.15 parts of p, p'-bis (diethylamino) benzophenone 3.5 parts of 2- (o-chlorophenyl) -4,5-diphenyl imidazole dimer hydroxy fatty acid ( d). 5 parts of 12-oxyoctadecanoic acid Other additives 0.35 parts of leuco crystal violet 0.1 part of malachite green 175 parts of methyl ethyl ketone

Example 3 A photosensitive resin composition was obtained in the same manner as in Example 1 except that 7 parts of 12-oxyoctadecanoic acid was used, and the evaluation was performed in the same manner as in Example 1.

Comparative Example 1 An evaluation was performed in the same manner as in Example 1 except that 12-oxyoctadecanoic acid was omitted.

Comparative Example 2 A photosensitive resin composition was obtained in the same manner as in Example 1 except that the base polymer (a) having the following composition was used, and the evaluation was performed in the same manner. Base polymer (a) methyl methacrylate / n-butyl methacrylate /
Copolymer having a copolymerization ratio of 2-ethylhexyl acrylate / methacrylic acid of 40/10/25/25 on a weight basis (weight average molecular weight: 330,000, softening temperature: 41.8 ° C., acid value: 162.8 mg KOH / g)

Comparative Example 3 A photosensitive resin composition was obtained in the same manner as in Example 1, except that the ethylenically unsaturated compound (b) was changed to only 20 parts of ethylene oxide-modified bisphenol A type dimethacrylate. An evaluation was performed.

Comparative Example 4 A photosensitive resin composition was obtained in the same manner as in Example 1, except that only 175 parts of the ethylene oxide-modified bisphenol A type dimethacrylate was used as the ethylenically unsaturated compound (b). An evaluation was performed.

Comparative Example 5 Photosensitization was carried out in the same manner as in Example 1 except that the photopolymerization initiator (c) was changed to 0.05 part of 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer alone. A conductive resin composition was obtained and similarly evaluated.

Comparative Example 6 A photosensitive resin was prepared in the same manner as in Example 1 except that the photopolymerization initiator (c) was changed to only 32 parts of 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer. The composition was obtained and evaluated similarly. Table 1 shows the evaluation results of the examples and the comparative examples.

[0055]

Table 1 Storage stability Sensitivity resolution (mj / cm ² ) Minimum line width (μm) Aspect ratio Example 1 125 20 1.0 〃 2 〃 160 20 1.0 1.0 １．０ 3 125 20 1.0 Comparative example 1 × 125 20 1.0 〃 2 125 30 0.67 ３ 3 900 35 0.57 ４ 4 × 250 20 1.0 〃 5 ＞> 1000 Could not be evaluated due to poor sensitivity. ６ 6 × 8 35 0.57

[0056]

As described above, the photosensitive resin composition of the present invention and the photoresist film using the composition are composed of a base polymer (a), an ethylenically unsaturated compound (b) and a photopolymerization initiator (c). , A hydroxy fatty acid or a derivative thereof (d), which is very excellent in storage stability, and is an etching resist used in the production of printed wiring boards, precision metal processing, lead frame production and the like, or PD.
It is very useful for pattern forming applications such as forming electrodes on large glass substrates such as P.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 101/00 C08L 101/00 F term (reference) 2H025 AA02 AA11 AB16 BC32 BC42 CA01 CA13 CB55 CC20 DA11 4J002 BG041 BG051 BG061 CH052 EE037 EE047 EE057 EF058 EH037 EH076 EN097 EN117 EU037 EU117 EV067 EV087 EV217 EV307 FD020 FD030 FD090 FD142 FD146 FD157 FD200 GP03 GQ00 4J011 QA12 QA13 QA15 QA22 QA23 QA23 QA23 QA23 QA23 QA23 QA22 SA25 SA26 SA28 SA29 SA32 SA34 SA43 SA48 SA61 SA62 SA63 SA64 SA77 SA78 SA83 TA08 TA10 UA01 VA01 WA01 5C027 AA01 5C040 DD03

Claims (6)

[Claims] An ethylenically unsaturated compound (b) is used in an amount of 30 to less than 90 parts by weight, based on 100 parts by weight of a base polymer (a) having a weight average molecular weight of 40,000 to 200,000, and a photopolymerization initiator (c A) a photosensitive resin composition comprising 0.1 to 30 parts by weight of a) and hydroxy fatty acid or a derivative (d) thereof. 2. The softening temperature of the base polymer (a) is 50.
The photosensitive resin composition according to claim 1, wherein the temperature is lower than or equal to ° C. 3. Hydroxy fatty acid or its derivative (d)
With respect to 100 parts by weight of the base polymer (a).
The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises from 25 to 25 parts by weight. 4. A hydroxy fatty acid or a derivative thereof (d)
4. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is at least one of 8-oxytetradecanoic acid, 10-oxyhexadecanoic acid, and 12-oxyoctadecanoic acid. 5. A photoresist film obtained by laminating the photosensitive resin composition according to claim 1 on a base film. 6. The photosensitive resin composition according to claim 1, which is used for forming a pattern when an electrode is formed on a substrate for forming a plasma display panel, or the photoresist according to claim 5. the film.