JPH10198034A - Photosensitive resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. having high adhesion to a glass substrate and excellent in removability in alkali development by using (meth)acrylic ester, (meth)acrylic acid and hydroxyl group-contg. (meth)acrylic ester as the copolymer components of a base polymer. SOLUTION: This photosensitive resin compsn. contains a base polymer, an ethylenic unsatd. compd. and a photopolymn. initiator or further contains a silane compd. Alkyl acrylate, acrylic acid and hydroxyl group-contg. alkyl acrylate are used as the copolymer components of the base polymer. Acrylic resin is used as the base polymer and (meth)acrylic ester, (meth)acrylic acid and hydroxyl group-contg. (meth)acrylic ester are used as the essential copolymer components of the acrylic resin.

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 a high adhesion to a glass substrate and excellent in the peelability by development with an alkali, and a photoresist film using the composition. The present invention relates to a photosensitive resin composition useful for forming a pattern on a large glass substrate such as a plasma display panel (PDP) and a photoresist film using the composition.

[0002]

2. Description of the Related Art A three-layer laminated film in which a photosensitive resin composition is applied in a layer form on a base film such as a polyester film, dried and laminated, and a protective film such as a polyester film or a polyvinyl alcohol film is laminated thereon, is generally a photo film. It is called a resist film or a dry film resist (DFR), and is widely used for manufacturing printed wiring boards, precision metal processing, and the like. When using the photosensitive resin composition layer, first remove the base film or the protective film having the smaller adhesive strength from the DFR to remove the photosensitive resin composition layer from the DFR. After sticking to the surface of the material, exposure is performed while the pattern mask is in contact with the other film (in some cases, exposure is performed after peeling off the other film), and then the other film is peeled off. For development. As a development method after exposure, there are a solvent development type and a dilute alkali development type.

[0003] In addition to DFR, there is also a well-known method in which a photosensitive resin composition is applied directly onto the substrate surface, and a pattern mask is adhered through a film such as a polyester film laminated thereon to perform exposure. ing. Meanwhile, recently,
Various flat panel displays are being actively developed, and PDPs are particularly attracting attention. Their use will expand from the display screen of laptop computers to various electronic bulletin boards and so-called “wall-mounted TVs” in the future. However, in such a PDP display panel, an electrode is formed on a glass substrate, and the above-mentioned DFR has begun to be used for the electrode formation.

[0004]

However, in the above-mentioned electrode formation, unlike a conventional metal such as copper, the substrate is glass, ITO film, SnO ₂ film or the like, so that the adhesion is poor and the adhesion is poor. If an adhesion aid or the like is used to increase the film thickness, the releasability at the time of alkali development is reduced, and it becomes difficult to form a good pattern.

[0005]

[Means to solve the problem] Therefore, the present inventors,
As a result of intensive studies on such a problem, it has been found that the polymer contains a base polymer (A), an ethylenically unsaturated compound (B) and a photopolymerization initiator (C), or further contains a silane compound (D). And a photosensitive resin composition using an alkyl acrylate, an acrylic acid and a hydroxyl group-containing alkyl acrylate as a main component of a copolymer of the base polymer (A), a glass substrate, an ITO film, a Sn film,
Excellent adhesion with O ₂ film, etc., and excellent peelability during alkali development, and also excellent adhesion during etching, a photoresist film obtained by laminating such a photosensitive resin composition on a base film, The present inventors have found that the present invention is useful for forming the electrodes of the above PDP, and have completed the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
An acrylic resin is used as the base polymer (A) of the present invention. In the present invention, the main feature is that (meth) acrylic acid ester, (meth) acrylic acid and hydroxyl group-containing (meth) acrylic acid ester are used as essential components as the main component of the copolymer of the acrylic resin. However, if even one of these components is missing, it is difficult to achieve the object of the present invention. Furthermore, in the present invention, the content of the hydroxyl group-containing (meth) acrylic acid ester in the above components is 5 to 50% by weight (further 5 to 20% by weight).
When the content of the hydroxyl group-containing alkyl acrylate is less than 5% by weight, the adhesion decreases, and when the content exceeds 50% by weight, the developability decreases, which is not preferable.

As the above (meth) acrylic acid ester, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl ( (Meth) acrylate, t-butyl (meth) acrylate, iso-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentanyl (meth) ) Acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc., and preferably methyl (meth) acrylate, n-
Butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are used, and more preferably, three kinds of methyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are used in combination.

Further, as the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (Meth) acrylate and the like can be mentioned, and preferably, 2-hydroxyethyl (meth) acrylate is used. Further, the base polymer (A) of the present invention can also use a monomer other than the above-mentioned copolymer main component in combination, and examples of such a monomer include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, Examples include styrene, α-methylstyrene, vinyl acetate, and alkyl vinyl ether.

Further, in the case of a dilute alkali developing type, it is necessary to copolymerize an ethylenically unsaturated carboxylic acid in an amount of about 15 to 30% by weight (acid value: 100 to 200 mg KOH / g). The weight average molecular weight of the base polymer (A) is preferably from 50,000 to 100,000, and more preferably from 60,000 to 80,000.

As the ethylenically unsaturated compound (B),
Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate,
Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,
2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis- (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl ( (Meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, Examples include polyfunctional monomers such as polyethylene glycol di (meth) acrylate, and glycerin triacrylate, polyethylene glycol di (meth) acrylate (diethylene glycol di (meth) acrylate). , Tetraethylene glycol di (meth) acrylate) is suitably used, preferably in combination with bifunctional monomers and trifunctional monomers, also,
An appropriate amount of a monofunctional monomer can be used together with these polyfunctional monomers. Examples of such a monofunctional monomer include 2-hydroxyethyl (meth) acrylate,
-Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-
2-hydroxypropyl (meth) acrylate, 2-
(Meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, half of phthalic acid derivative (meta ) Acrylate, N-methylol (meth) acrylamide and the like.

The mixing ratio of the ethylenically unsaturated compound (B) to 100 parts by weight of the base polymer (A) is 10 to
It is desirable to select from the range of 200 parts by weight, particularly 40 to 100 parts by weight. An insufficient amount of the ethylenically unsaturated compound (B) causes poor curing, a decrease in flexibility and a delay in the development speed, and an excessive amount of the ethylenically unsaturated compound (B) causes an increase in tackiness, cold flow, and peeling of the cured resist. It causes a reduction in speed.

Further, 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, benzyl dimethyl ketal, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino ) Benzophenone, 4,4′-diethylaminobenzophenone, pivaloin ethyl ether, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, hexaarylimidazole dimer, 2,2 ′
-Bis (o-chlorophenyl) 4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-
Diethylthioxanthone, 2,2′-diethoxyacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, 2,2′-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibezosparone, -(4-isopropylphenyl) -2-hydroxy-2-methyl-1
-Propanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, tribromophenylsulfone, tribromomethylphenylsulfone, etc., and one or more of these are used . The content of the photopolymerization initiator (C) is 1 based on the total amount of the base polymer (A) and the ethylenically unsaturated compound (B).
It is appropriate to use about 1 to 20 parts by weight with respect to 00 parts by weight.

In the present invention, the above (A) to (C)
It is also useful to further include a silane compound (D). Examples of the silane compound (D) include γ-glycidoxypropyltrimethoxysilane and β- (3,4 epoxycyclohexyl) -ethyltrimethoxy. Silane, β- (3,
Epoxysilane such as 4 epoxycyclohexyl) -ethyltriethoxysilane, aminosilane such as N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ
Examples thereof include chloropropylsilane such as -chloropropyltrimethoxysilane and methacrylosilane such as γ-methacryloxypropyltrimethoxysilane, and it is preferable to use one or more of epoxysilane, aminosilane, and chloropropylsilane. . As the content of the silane compound (D), the total amount of the above (A) to (C) is 1
The amount is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, and particularly preferably 0.1 to 0.1 part by weight based on 100 parts by weight.
Preferably it is 3 parts by weight. Silane-based compound (D)
If the content is less than 0.01% by weight, the adhesion of the resist decreases, and if it exceeds 1% by weight, a peeling phenomenon is observed at the glass or ITO film interface, which is not preferable.

The method for incorporating the silane compound (D) is not particularly limited, and is a known method, for example, adding a predetermined amount of the silane compound (D) to the above resin compositions (A) to (C). And then thoroughly mixing and stirring. In addition to the photosensitive resin composition of the present invention, dyes (crystal violet, malachite green, malachite green lake, brilliant green, patent blue, methyl violet, Victoria blue, roseaniline, parafuchsin, ethylene violet, etc.) Additives such as agents, plasticizers, antioxidants, thermal polymerization inhibitors, solvents, surface tension modifiers, stabilizers, chain transfer agents, defoamers, and flame retardants can be added as appropriate.

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, or a polystyrene film, and then protected from above the coated surface with a polyethylene film, a polyvinyl alcohol-based film, or the like. DFR by coating the film
And In addition, the photosensitive resin composition of the present invention can be used for applications other than DFR, such as the use of the photosensitive resin composition of the present invention, a dip coating method,
It is applied directly onto a substrate (such as glass) to be processed by a conventional method such as a flow coating method or a screen printing method, and has a thickness of 1 to
A photosensitive layer having a thickness of 150 μm can be easily formed. At the time of coating, methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexane,
Solvents such as methylcellosolve, methylene chloride, 1,1,1-trichloroethane can also be added.

(Exposure) 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 the glass surface or ITO film,
Exposure is performed by bringing a pattern mask into close contact with the other film. When the photosensitive resin composition does not have adhesiveness, the other film may be peeled off, and then the pattern mask may be brought into direct contact with the photosensitive resin composition layer for exposure.
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, 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 diluted aqueous solution of about 0.5 to 3% by weight of an alkali such as sodium carbonate and potassium carbonate. (Etching) After development, etching is performed. For etching, an acidic etching solution such as cupric chloride-hydrochloric acid or ferric chloride-hydrochloric acid is usually used. (Removal of cured resist) After the etching step, the remaining cured resist is removed. Removal and removal of the cured resist
0.5 to 10 such as sodium hydroxide and potassium hydroxide
This is performed using an alkali stripper composed of an aqueous alkali solution having a concentration of about weight%. Then, after thoroughly washing with water,
Dried.

Thus, the electrodes are formed on the front substrate for PDP, and after that, the gas is sealed between the front substrate and the back substrate, and then joined to be put to practical use as a PDP.

[0019]

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) 59 parts of the following base polymer (A)
A photosensitive resin composition was prepared by mixing 25 parts of the following ethylenically unsaturated compound (B) and 5 parts of a photoweight initiator (C) having the following formulation. The copolymerization ratio of the base polymer (A) methyl (meth) acrylate / n-butyl acrylate / 2-ethylhexyl acrylate / methacrylic acid / hydroxyethyl (meth) acrylate is 15/30/15/20/20 (acid value) on a weight basis. 143.
3, glass transition point 66.3 ° C, weight average molecular weight 80,000) ethylenically unsaturated compound (B) tetraethylene glycol di (meth) acrylate photopolymerization initiator (C) benzophenone / 4,4'-diethylaminobenzophenone / 2 , 2-bis (o-chlorophenyl) 4,5
Mixture of 4 ', 5'-tetraphenyl-1,2'-biimidazole in a weight ratio of 8 / 0.15 / 1

(Preparation of Dry Film) The above dope was applied to a thickness of 20 mm using an applicator having a gap of 3 mils.
3 μm at room temperature for 1 min.
After leaving it for 0 seconds, it was dried in an oven at 60 ° C., 90 ° C., and 110 ° C. for 3 minutes each to obtain a dry film having a resist thickness of 20 μm (however, no protective film was provided). (Lamination on PDP glass substrate) This dry film was laminated on a glass substrate with ITO (200 mm × 200 mm × 2 mm) preheated to 60 ° C. in an oven, at a laminating roll temperature of 100 ° C. and a roll pressure of 3 kg / cm ² , and laminated. Lamination was performed at a speed of 1.5 m / sec. (Exposure, development) After lamination, a line pattern is placed on the polyester film so that L / S (line / space) = 100 μm / 100 μm over the entire surface of the ITO.
Exposure was performed to 100 mj with a 3 kW ultra-high pressure mercury lamp using an exposure machine HMW-532D manufactured by Oak Manufacturing Co., Ltd. After taking a hold time of 15 minutes after exposure, 1% Na ₂ CO ₃ aqueous solution, 3
Develop at 0 ° C. for 1.5 times the minimum development time, then wash and dry to obtain L / S = 100 μm / 100
A pattern of a μm resist layer was formed. (Etching, peeling of cured resist) The above pattern was etched with ferric chloride (45 ° C., 42 ° Be), and then a 3% NaOH aqueous solution was sprayed on the resist pattern at 50 ° C. under a pressure of 2 kg to form a resist. The layer was peeled off to form an ITO pattern (L / S = 100 μm / 100 μm).
m) was formed on a PDP substrate.

The following evaluations were made in the above-described ITO pattern forming process. [Resist Adhesion] In the above-mentioned development step, the adhesion of the resist when developed separately for three times the minimum development time was visually observed and evaluated as follows. ◎ −−− No lift is observed in the resist at all ○ −−− Lift is recognized at the tip of the resist × −−− Lift of the resist is recognized as a whole [etching adhesion] In the above etching process,
The line width (100 μm) of the formed pattern was actually measured, and the measured value was used to evaluate as follows. Although the line pattern is set to 100 μm, if the adhesion at the time of etching is reduced, the formed line width becomes thin, which is not preferable. ◎ −−− The formed line width is 95 μm or more ○ −−− The formed line width is 90 μm or more, 95
Less than μm × −−− The formed line width is less than 90 μm [Removability] In the resist removal step after the above etching, the removal state of the linear resist was visually observed and evaluated as follows. ◎ −−− The resist is dispersed (subdivided) and peeled ○ −−− The resist is divided into two and peeled × −−− The resist is peeled in a line

Example 2 Photosensitivity was obtained in the same manner as in Example 1, except that 0.2 part of γ-glycidoxypropyltrimethoxysilane, which is a silane compound (D), was further added as a compounding component of the dope. A resin composition was obtained and similarly evaluated. Example 3 In Example 2, tetraethylene glycol di (meth) acrylate / glycerin triacrylate = 10/25 (weight ratio) as the ethylenically unsaturated compound (B).
The photosensitive resin composition was obtained in the same manner except that a mixture of the above was used, and was similarly evaluated. Example 4 In Example 2, the copolymerization ratio of methyl (meth) acrylate / n-butyl acrylate / 2-ethylhexyl acrylate / methacrylic acid / hydroxyethyl (meth) acrylate of the base polymer (A) was 3 based on the weight.
A photosensitive resin composition was obtained in the same manner except that 0/30/15/20/5 was used, and the evaluation was performed in the same manner.

Comparative Example 1 In Example 1, the base polymer (A) was changed to methyl (meth) acrylate / n-butyl acrylate / 2-ethylhexyl acrylate / methacrylic acid = 40/30 /
A photosensitive resin composition was obtained in the same manner except that a 15/15 (weight ratio) copolymer was used, and the same evaluation was performed. Table 1 shows the evaluation results of the examples and the comparative examples.

[0024]

[Table 1] Resist adhesion Etching adhesion Peeling Example 1 ○ ○ ◎ 〃 2 ◎ ◎ ◎ 〃 3 ◎ ◎ ◎ 〃 4 ○ ○ ○ Comparative Example 1 × × ×

[0025]

The photosensitive resin composition of the present invention uses a base polymer having a specific copolymer component and contains a silane compound, so that a glass substrate, an ITO film,
Excellent adhesion with SnO ₂ film, etc., excellent peeling property by development with alkali, and also excellent adhesion during etching, pattern formation such as forming electrodes on large glass base material such as PDP Very useful for applications.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI H01J 9/02 H01J 9/02 F

Claims (9)

[Claims] 1. A composition comprising a base polymer (A), an ethylenically unsaturated compound (B) and a photopolymerization initiator (C), and (meth) acryl as a main component of a copolymer of the base polymer (A). A photosensitive resin composition using an acid ester, (meth) acrylic acid and a hydroxyl group-containing (meth) acrylate. 2. A copolymer of a base polymer (A) comprising a base polymer (A), an ethylenically unsaturated compound (B), a photopolymerization initiator (C) and a silane compound (D). (Meth) acrylic acid ester as the main component,
A photosensitive resin composition using (meth) acrylic acid and a hydroxyl group-containing (meth) acrylate. 3. Hydroxyl group-containing (meth) in the main component of the copolymer
3. The photosensitive resin composition according to claim 1, wherein the content of the acrylate is 5 to 50% by weight. 4. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the base polymer (A) is 50,000 to 100,000. 5. The silane compound (D) is one of epoxy silane, amino silane and chloropropyl silane.
The photosensitive resin composition according to claim 2, wherein the composition is at least one kind. 6. The content of the silane-based compound (D) is 0.1 part by weight based on 100 parts by weight of the total amount of the base polymer (A), the ethylenically unsaturated compound (B) and the photopolymerization initiator (C).
The photosensitive resin composition according to any one of claims 2 to 5, wherein the amount is from 01 to 5 parts by weight. 7. The mixing ratio of the ethylenically unsaturated compound (B) to 100 parts by weight of the base polymer (A) is 10
The photosensitive resin composition according to any one of claims 1 to 6, wherein the amount is from 200 to 200 parts by weight. 8. A photoresist film obtained by laminating the photosensitive resin composition according to claim 1 on a base film. 9. The photosensitive resin composition according to claim 1, which is used for forming a pattern when forming an electrode on a substrate for forming a plasma display panel, or the photoresist film according to claim 8. .