JP4245510B2 - Photosensitive resin composition and photoresist film using the same - Google Patents

Description

The present invention relates to a photosensitive resin composition and a photoresist film that are extremely excellent in sensitivity, resolution, fine line adhesion, and pattern formability, and are suitable for exposure with a blue-violet laser exposure machine. that, in particular, to useful photosensitive resin composition and a photoresist film on the transparent electrode working such as plasma display panel (PDP).

  A three-layer laminate film in which a photosensitive resin composition is applied in layers on a support film such as a polyester film and then dried and laminated, and a protective film such as a polyester film or a polyvinyl alcohol film is laminated thereon is generally referred to as a photoresist film. It is widely used for plasma display manufacturing, precision metal processing, printed wiring board manufacturing, and the like.

  In recent years, various flat panel displays have been actively developed. In particular, PDPs are attracting attention, and their use is expanding to various bulletin boards and so-called “wall-mounted TVs”. In the display panel, an electrode is formed on a glass substrate, and the above-described photoresist film is being used to form the electrode.

  When using it, first remove the support film or protective film with the lower adhesive strength from the photoresist film and attach the photosensitive resin composition layer side to the surface of the substrate on which you want to form a pattern. After that, exposure is performed with the pattern mask in contact with the other film (there may be exposure after peeling off the other film), and then the other film is peeled off for development. Provide. Development methods after exposure include a solvent development type and a rare alkali development type.

  In the exposure of the photosensitive resin composition, a laser is used in addition to ultraviolet rays and electron beams. Laser scanning exposure using such a laser has the advantage that it is possible to produce an image of a desired shape without using a pattern mask, and thus it is possible to produce a small number of products in various kinds and to shorten the production time. In general, a solid-state laser capable of reducing running costs including maintenance costs is useful as a laser used for exposure of the photosensitive resin composition, and lasers having an emission wavelength in the near ultraviolet region are particularly practical. However, an apparatus is expensive to secure a light source having a sufficient output even in a laser having an emission wavelength in the near ultraviolet region. Accordingly, a light source having a low output is usually used, and the exposure amount of the light source is inevitably low. Therefore, a photosensitive resin composition having sufficient sensitivity even at such a low exposure amount is required.

As a photosensitive resin composition excellent in such sensitivity, for example, in a composition comprising a base polymer, an ethylenically unsaturated compound and a photopolymerization initiator, a composition containing N-phenylglycine as a photopolymerization initiator is used. A photosensitive resin composition that uses a carboxylic acid having a specific pKa (see, for example, Patent Document 1), a base polymer, an ethylenically unsaturated compound containing a specific compound, and 9-phenylacridine and a specific compound The photosensitive resin composition containing the photoinitiator containing (for example, refer patent document 2 ) is proposed.
In addition, a photosensitive resin composition containing a binder polymer, an ethylenically unsaturated group-containing photopolymerizable monomer, a polycyclic aromatic hydrocarbon, a photopolymerization initiator, and a hydrogen donor has been proposed (for example, Patent Documents). 3).
JP-A-5-323589 JP-A-10-123708 JP 2003-50459 A

However, in the technique disclosed in Patent Document 1 described above, the photosensitive resin composition has good sensitivity at a normal exposure amount (about 30 to 200 mJ), but is intended for ultraviolet irradiation, thus reducing the light source cost. Is not considered for exposure using a blue-violet laser (h line: 390 to 420 nm) as a light source, and there is a possibility that pattern formation cannot be sufficiently performed by exposure with a low-power light source of such a blue-violet laser. Therefore, further improvements in this respect are required. Further, when such a photosensitive resin composition is left at a high temperature for a long time, decolorization and sensitivity of dyes such as malachite green and Victoria pure blue which are blended in the composition as a base dye to ensure the visibility. There may be problems that change.
In addition, the technique disclosed in Patent Document 2 has a problem that, although the sensitivity is excellent at a normal exposure amount, the pattern cannot be sufficiently formed by exposure with a low output light source.

  Furthermore, in the disclosed technique of Patent Document 3, it is possible to increase sensitivity to i-line (365 nm) in order to reduce development scum, and it is useful for UV-laser exposure having an oscillation frequency near 365 nm. However, the present situation is not necessarily useful for laser exposure with an emission wavelength of 390 to 420 nm. Similarly to the above, when such a photosensitive resin composition is left at a high temperature for a long time, a dye such as malachite green or Victoria pure blue blended in the composition as a base dye to ensure the visibility. There may be a problem that decolorization or sensitivity change occurs.

In view of this, the present invention provides a photosensitive resin composition and a photoresist film that are extremely excellent in sensitivity, resolving power, fine line adhesion, and pattern formability under the irradiation conditions of an exposure wavelength of 390 to 420 nm. In particular, an object of the present invention is to provide a photosensitive resin composition and a photoresist film that are useful for forming electrodes such as glass substrates in the production of PDP display panels.

However, the present inventors have result of extensive research in view of such circumstances, mosquitoes carboxyl group-containing polymer (A), the ethylenically unsaturated compound (B), the photopolymerization initiator (C) and, perylene, naphtho [2 , 3-a] pyrene, benzopyrene, dibenzo [b, def] chrysene, 9,10-diphenyl least one compound selected from anthracene (D) Ri greens contain carboxyl group-containing polymer (a) is, An acrylic copolymer comprising at least an alkyl (meth) acrylate having 8 or more carbon atoms in the alkyl group, a hydroxyl group-containing (meth) acrylate, (meth) acrylic acid and an aromatic vinyl monomer as a copolymerization component. The present invention was completed by finding that the photosensitive resin composition satisfying the above purpose.

The photosensitive resin composition of the present invention is a photosensitive resin composition for exposure in a laser exposure machine having an exposure wavelength of 390 to 420 nm, and includes a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), Photopolymerization initiator (C) and at least one compound selected from perylene, naphtho [2,3-a] pyrene, 3,4-benzopyrene, dibenzo [b, def] chrysene, and 9,10-diphenylanthracene ( D), the carboxyl group-containing polymer (A) is an alkyl (meth) acrylate having at least 8 carbon atoms in the alkyl group, a hydroxyl group-containing (meth) acrylate, (meth) acrylic acid and aromatic vinyl A laser exposure machine having an exposure wavelength of 390 to 420 nm because it is an acrylic copolymer containing a monomer as a copolymerization component. Even under low exposure conditions, it has excellent effects on sensitivity, resolving power, fine line adhesion, and pattern formability, and is particularly useful for forming electrodes such as glass substrates in the manufacture of PDP display panels. It is.

The present invention is described in detail below.
The carboxyl group-containing polymer (A) used in the present invention is an alkyl (meth) acrylate having at least 8 carbon atoms in the alkyl group, a hydroxyl group-containing (meth) acrylate, (meth) acrylic acid and an aromatic vinyl-based monomer. It is an acrylic copolymer comprising a body as a copolymerization component.

Examples of the alkyl (meth) acrylate having 8 or more carbon atoms in the alkyl group include 2-ethylhexyl (meth) acrylate, and examples of the hydroxyl group-containing (meth) acrylate include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. Etc., and examples of the aromatic vinyl monomer include styrene and α-methylstyrene .

The acrylic copolymer as the carboxyl group-containing polymer (A) may contain other monomer components. Examples of the other monomer component, include ethylenically unsaturated carboxylic acids, except for acrylic acid and methacrylic acid, other monocarboxylic acids such as crotonic acid, Ma maleic acid, fumaric acid, dicarboxylic acids such as itaconic acid, Alternatively, anhydrides and half esters thereof can also be used. Other monomer components include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth). acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetic acid, alkyl vinyl ether and the like.

  Although it does not restrict | limit especially about the acid value of a carboxyl group-containing polymer (A), 100-300 mgKOH / g is preferable, More preferably, it is 110-200 mgKOH / g, Most preferably, it is 115-170 mgKOH / g. When the acid value is less than 100 mgKOH / g, the developability is lowered and the resolution is lowered, and when it exceeds 300 mgKOH / g, the developing solution resistance of the cured resist is lowered and the fine line adhesion is lowered.

  Furthermore, the weight average molecular weight of the carboxyl group-containing polymer (A) is 30,000 to 200,000, preferably 40,000 to 150,000, particularly preferably 45,000 to 130,000, and the weight average molecular weight. If it is less than 30,000, the resin becomes too soft and edge fusion occurs when the resin film is processed into a roll form. On the other hand, if it exceeds 200,000, the resolution is lowered, which is not preferable.

  The glass transition temperature (Tg) of the acrylic resin is preferably in the range of 30 to 150 ° C, more preferably 40 to 130 ° C. When the glass transition temperature is less than 30 ° C., the resin becomes too soft, and edge fusion occurs when the resin exudes when processed into a roll form as a photoresist film, while when it exceeds 150 ° C., it is used as a photoresist film. The followability to the unevenness of the substrate surface at the time may decrease, which is not preferable.

Particularly in the present invention, the content ratio of each monomer component of the carboxyl group-containing polymer (A) is an alkyl (meth) acrylate having 8 or more carbon atoms in the alkyl group with respect to the total of the monomer components. 5 to 15 wt% (preferably 7 to 13 wt%), hydroxyl group-containing (meth) acrylate is 5 to 20 wt% (preferably 10 to 15 wt%), (meth) acrylic acid is 10 to 40 wt% ( Preferably 15 to 38% by weight), the aromatic vinyl monomer is preferably 1 to 15% by weight (preferably 5 to 13% by weight), and the remainder contains other monomer components.

The ethylenically unsaturated compound (B) used in the present invention is not particularly limited, and is a monomer having one polymerizable unsaturated group, a monomer having two polymerizable unsaturated groups, a polymerizable unsaturated group. Examples thereof include monomers having 3 or more saturated groups, and these are used alone or in combination as appropriate.
Examples of the monomer having one polymerizable unsaturated group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 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 Examples thereof include phosphate, phthalic acid derivative half (meth) acrylate, N-methylol (meth) acrylamide, and the like, which are used alone or in combination.

  Examples of the monomer having two polymerizable unsaturated groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 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, ethylene oxide / 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, Examples thereof include hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, and are used alone or in combination. Among these, tetraethylene glycol di (meth) acrylate, ethylene oxide-modified bisphenol A type di (meth) acrylate, and ethylene oxide / propylene oxide modified bisphenol A type di (meth) acrylate are preferably used.

  Examples of the monomer having three polymerizable unsaturated groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxy. Examples include trimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, and the like. These may be used alone or in combination.

Particularly in the present invention, the ethylenically unsaturated compound (B) has two polymerizable unsaturated groups and has a weight average molecular weight of 1,200 or less, preferably 300 to 1,000, particularly preferably 320 to 900. The ethylenically unsaturated compounds are preferably ethylene oxide-modified bisphenol A di (meth) acrylate and ethylene oxide / propylene oxide-modified bisphenol A di (meth) acrylate. If the weight average molecular weight exceeds 1,200, the distance between crosslinks becomes long, and sufficient curing cannot be obtained, resulting in a decrease in resolution and a decrease in fine line adhesion.
The content of the ethylenically unsaturated compound having two such polymerizable unsaturated groups and having a weight average molecular weight of 1,200 or less is not particularly limited, but is 70% in the ethylenically unsaturated compound (B) component. It is preferably at least wt%, particularly preferably at least 80 wt%.
If the content is less than 70% by weight, it is not preferable because the resolution, the fine line adhesion, and the pattern formation are liable to occur.

  The content of the ethylenically unsaturated compound (B) is desirably selected from the range of 10 to 200 parts by weight, particularly 40 to 100 parts by weight, with respect to 100 parts by weight of the carboxyl group-containing polymer (A). Too little ethylenically unsaturated compound (B) leads to poor curing, poor flexibility and slow development, too much ethylenically unsaturated compound (B) increases tackiness, cold flow, peels off cured resist This is not preferable because it causes a reduction in speed.

  The photopolymerization initiator (C) used in the present invention is not particularly limited, and a known photopolymerization initiator 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, benzoylbenzoic acid, benzoyl Methyl benzoate, benzyl diphenyl disulfide, benzyl dimethyl ketal, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, dichloroacetate Phenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzo Spalon, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, tribromophenylsulfone, tri Bromomethylphenylsulfone, 2,4,6- [tris (trichloromethyl)]-1,3,5-triazine, 2,4- [bis (trichloromethyl)]-6- (4'-methoxyphenyl) -1,3,5-triazine, 2,4- [bis (trichloro Methyl)]-6- (4'-methoxynaphthyl) -1,3,5-triazine, 2,4- [bis (trichloromethyl)]-6- (piperonyl) -1,3,5-triazine, 2, Triazine derivatives such as 4- [bis (trichloromethyl)]-6- (4'-methoxystyryl) -1,3,5-triazine, acridine derivatives such as acridine and 9-phenylacridine, 2,2'-bis ( o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl -1,1'-biimidazole, 2,2'-bis (o-fluorophenyl) -4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis ( o-methoxyphenyl) -4 5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (p-methoxyphenyl) -4,5,4', 5'-tetraphenyl-1,1'- Biimidazole, 2,4,2 ', 4'-bis [bi (p-methoxyphenyl)]-5,5'-diphenyl-1,1'-biimidazole, 2,2'-bis (2,4- Dimethoxyphenyl) -4,5,4 ', 5'-diphenyl-1,1'-biimidazole, 2,2'-bis (p-methylthiophenyl) -4,5,4', 5'-diphenyl-1 1,1′-biimidazole, bis (2,4,5-triphenyl) -1,1′-biimidazole, etc., and 1,2′-, 1,4′-disclosed in JP-B-45-37377 , Hexaarylbiimidazoles such as tautomers covalently bonded at 2,4′- Conductor, triphenylphosphine, Besides 2-benzoyl-2-dimethylamino-1- [4-morpholinophenyl] - Although butane and the like, preferably hexaarylbiimidazole derivative is used.

  As content of this photoinitiator (C), it is 0.01-10 weight part with respect to a total of 100 weight part of the said carboxyl group-containing polymer (A) and ethylenically unsaturated compound (B). Is preferable, more preferably 0.1 to 8 parts by weight, and particularly preferably 1 to 6 parts by weight. When the content is less than 0.01 parts by weight, the sensitivity is remarkably lowered and good workability cannot be obtained. On the other hand, when the content exceeds 10 parts by weight, the storage stability of the photoresist film is lowered, which is not preferable. .

In the photosensitive resin composition of the present invention, in addition to the carboxyl group-containing polymer (A), the ethylenically unsaturated compound (B), and the photopolymerization initiator (C), perylene, naphtho [2,3- a) pyrene, 3,4-benzopyrene, dibenzo [b, def] chrysene, and 9,10-diphenylanthracene are required to be contained, and such compound (D) is required to be contained. By containing, a photosensitive resin composition having excellent sensitivity, resolution, fine line adhesion, and pattern formability can be obtained even when exposure is performed with a laser exposure machine having an exposure wavelength of 390 to 420 nm.
Among these compounds (D), perylene is particularly preferable in terms of sensitivity.

  In this invention, content of the said compound (D) is 0.01-3.0 weight part with respect to a total of 100 weight part of the said carboxyl group-containing polymer (A) and an ethylenically unsaturated compound (B). The amount is preferably 0.05 to 2.0 parts by weight, more preferably 0.05 to 1.0 part by weight. If the content is less than 0.01 parts by weight, the sensitivity is low, and the resolution and adhesion are lowered due to poor curing. Conversely, if the content exceeds 3.0 parts by weight, the top portion of the cured resist is thickened or transmitted. Curing of the deep portion of the cured resist due to insufficient light becomes insufficient, resulting in lower resolution and lower adhesion.

  Furthermore, in this invention, it is also preferable to contain the alkylamine compound (E) from the point of improvement of edge fusion as needed. The alkylamine compound (E) is not particularly limited, but is preferably a trialkylamine having 4 or more carbon atoms, specifically, tri-n-butylamine, triisobutylamine, tri-tert-butylamine, tri- n-pentylamine, tri-n-octylamine, tris (2-ethylhexyl) amine, triisooctylamine, tri-n-decylamine, tridodecylamine, tri-n-hexylamine, etc., among which tri-n -Butylamine and tri-n-pentylamine are preferably used.

  The content of the alkylamine compound (E) is preferably 0.05 to 7 parts by weight with respect to a total of 100 parts by weight of the carboxyl group-containing polymer (A) and the ethylenically unsaturated compound (B). In particular, it is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3 parts by weight. If the content is less than 0.05 parts by weight, the expected thickening effect cannot be obtained, and if it exceeds 7 parts by weight, the developability is lowered, which is not preferable.

  In addition, the photosensitive resin composition of the present invention includes colored dyes such as crystal violet, malachite green, malachite green lake, brilliant green, patent blue, methyl violet, victoria blue, rose aniline, parafuxin, ethylene violet, and the like. Additives such as additives, plasticizers, antioxidants, thermal polymerization inhibitors, solvents, surface tension modifiers, stabilizers, chain transfer agents, antifoaming agents, flame retardants, and the like can be appropriately added.

  Next, production of a photoresist film using the photosensitive resin composition of the present invention obtained above and a method of forming an electrode (pattern formation) on a PDP substrate using the same will be described. However, it is not limited to these.

(Manufacture of photoresist film)
The photosensitive resin composition obtained above is applied to a support film surface such as a polyester film, a polypropylene film, or a polystyrene film, and dried to obtain a photoresist film. If necessary, it is also preferable to cover the coated surface with a protective film such as a polyethylene film or a polyvinyl alcohol film to form a photoresist film.

  For applications other than photoresist film, the photosensitive resin composition of the present invention is processed on a substrate (glass, metal, etc.) to be processed by conventional methods such as dip coating, flow coating, and screen printing. It is also possible to add a solvent such as methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexane, methyl cellosolve, methylene chloride, 1,1,1-trichloroethane.

(Pattern formation)
In order to form an image with the above-mentioned photoresist film, the adhesive strength between the support film and the photosensitive resin composition layer and the adhesive strength between the protective film and the photosensitive resin composition layer are compared. After peeling off the film, the photosensitive resin composition layer side is attached to a glass surface or an ITO film, and then exposed with a laser exposure machine having an exposure wavelength of 390 to 420 nm. At this time, the exposure pattern is supplied as a digital file. When the photosensitive resin composition is not subjected to oxygen inhibition, it can be exposed after peeling the other film.

After the exposure, the film on the resist is peeled off and then developed.
Since the photosensitive resin composition of the present invention is a dilute alkali development type, development after exposure is performed using a dilute aqueous solution of about 0.1 to 3% by weight of an alkali such as sodium carbonate or potassium carbonate.

Etching is performed after development.
For etching, an acidic etching solution such as cupric chloride-hydrochloric acid or ferric chloride-hydrochloric acid is usually used, but an ammonia-based alkaline etching solution is rarely used.

After the etching process, the remaining cured resist is peeled off.
The cured resist is stripped and removed using an alkali stripping solution made of an aqueous alkali solution having a concentration of about 0.1 to 10% by weight such as sodium hydroxide or potassium hydroxide.
Then, after sufficiently washing with water, it is dried.
Thus, an electrode is formed on the front substrate for PDP, and after that, gas is sealed between the substrate and the back substrate, and then joined and put into practical use as a PDP.

The photosensitive resin composition of the present invention, mosquitoes carboxyl group-containing polymer (A), the ethylenically unsaturated compound (B), the photopolymerization initiator (C) and, perylene, naphtho [2,3-a] pyrene, 3 , 4-benzopyrene, dibenzo [b, def] chrysene, 9,10-diphenyl least one compound selected from anthracene (D) Ri greens contain carboxyl group-containing polymer (a) is, at least an alkyl group alkyl number of 8 or more carbon atoms (meth) acrylate, hydroxyl group-containing (meth) acrylate, (meth) acrylic copolymer der because comprising as a copolymerization component acrylic acid and an aromatic vinyl monomer , even in low exposure conditions where the exposure wavelength using a laser exposure apparatus 390 to 420 nm, sensitivity, resolution, fine line adhesion, very excellent in pattern formability It is very useful for applications that require high resolution and high fine line adhesion, such as processing of transparent conductive films such as glass, ITO or NESA film (tin oxide film) and chemical rings such as 42 alloy and SUS. In particular, it is highly expected for electrode formation of PDP.

Hereinafter, the present invention will be specifically described with reference to examples.
In the examples, “%” and “part” mean weight basis unless otherwise specified.

Example 1
(Dope adjustment)
The following carboxyl group-containing polymer (A) 58.0 parts, ethylenically unsaturated compound (B) 42.0 parts, photopolymerization initiator (C) 4.2 parts, perylene (D) 0.3 part, dye 0.8 parts was mixed, and 105 parts of methyl ethyl ketone was further mixed as a solvent to prepare a dope.

[Carboxyl group-containing polymer (A)]
Copolymer (acid) in which the copolymerization ratio of methyl methacrylate / n-butyl methacrylate / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / styrene / methacrylic acid is 40/10/10/10/8/22 on a weight basis 143 mg KOH / g, glass transition point 71.1 ° C., weight average molecular weight 60,000, dispersity (weight average molecular weight / number average molecular weight) 1.9)
[Ethylenically unsaturated compound (B)]
・ Ethylene oxide modified bisphenol A dimethacrylate (modified amount 10 mol%, weight average molecular weight 804)
[Photopolymerization initiator (C)]
・ 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole [dye]
・ Malachite Green 0.04 part ・ Leuco Crystal Violet 0.76 part

(Preparation of photoresist film)
The dope was coated on a 19 μm thick polyester film using a gap 3 mil applicator, left at room temperature for 1 minute 30 seconds, and then dried in an oven at 60 ° C., 95 ° C., and 110 ° C. for 2 minutes. Further, a protective film (polyethylene film, thickness 22.5 μm) was provided on the photosensitive resin composition layer to obtain a photoresist film having a resist thickness of 20 μm.

(Lamination on PDP glass substrate)
The photoresist film was peeled off from the protective film and then preheated to 60 ° C. in an oven on a glass substrate with ITO (200 mm × 200 mm × 2 mm), laminating roll temperature 100 ° C., roll pressure 0.3 MPa , Lamination was performed at a laminating speed of 1.5 m / min.

  Made by Ball Semiconductor to form patterns of L (μm) / S (μm) (line / space) = 10/10, 15/15, 20/20, 25/25, and 30/30 after lamination. Laser exposure machine “LAB-A2” (specific wavelength: 405 ± 5 nm), exposure energy is 0.3 W, substrate feed rate is 4 mm / sec, mirror on-time is 200 μsec, 180 μsec, 160 μsec, 140 μsec, Exposure was performed under conditions of 120 μsec, 100 μsec, 80 μsec, and 60 μsec. After taking a hold time of 15 minutes after exposure, the support film was peeled off, developed with a 0.7% sodium carbonate aqueous solution at 25 ° C. for 1.7 times the minimum development time, and then washed with water. After drying, the minimum L / S value that was resolved and adhered and the conditions (mirror on time) that gave it were determined by observation with a scanning electron microscope. The pattern shape was also evaluated.

Reference example 1
In Example 1, it carried out similarly except having changed the dope composition as follows, the photosensitive resin composition was obtained, and evaluation similar to Example 1 was performed.

(Dope adjustment)
The following carboxyl group-containing polymer (A) 55 parts, ethylenically unsaturated compound (B) 45 parts, photopolymerization initiator (C) 6.0 parts, perylene (D) 0.2 parts, dye 1.03 parts And 105 parts of methyl ethyl ketone as a solvent were mixed to prepare a dope.

[Carboxyl group-containing polymer (A)]
A copolymer having a copolymerization ratio of methyl methacrylate / n-butyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid of 34/30/15/21 on a weight basis (acid value 137 mgKOH / g, glass transition point 78 ° C., Weight average molecular weight 60,000, dispersity (weight average molecular weight / number average molecular weight) 2.4)
[Ethylenically unsaturated compound (B)]
・ Ethylene oxide modified bisphenol A dimethacrylate (modified amount 10 mol%, weight average molecular weight 804)
[Photopolymerization initiator (C)]
・ 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole [dye]
・ Crystal Violet 0.03 part ・ Loico Crystal Violet 1.00 part

Example 2
In Example 1, it carried out similarly except having further mixed 1.0 part of tri-n-butylamine (E), the photosensitive resin composition was obtained, and evaluation similar to Example 1 was performed.

Example 3
In the same manner as in Example 1, except that 0.3 part of perylene (D) was changed to 0.35 part of naphtho [2,3-a] pyrene (D), a photosensitive resin composition was obtained. Evaluation similar to 1 was performed.

Example 4
In Example 1, it carried out similarly except having changed 0.3 part of perylene (D) into 0.3 part of 3, 4- benzopyrene (D), and obtained the photosensitive resin composition, and was the same as that of Example 1 Evaluation was performed.

Example 5
In the same manner as in Example 1, except that 0.3 part of perylene (D) was changed to 0.35 part of dibenzo [b, def] chrysene (D), a photosensitive resin composition was obtained. Similar evaluations were made.

Example 6
The same procedure as in Example 1 was performed except that 0.3 part of perylene (D) was changed to 0.4 part of 9,10-diphenylanthracene (D) in Example 1, and a photosensitive resin composition was obtained. Was evaluated.

Comparative Example 1
In Example 1, it carried out similarly except not having mix | blended perylene (D) 0.3 part, the photosensitive resin composition was obtained, and evaluation similar to Example 1 was performed.

Comparative Example 2
In Example 1, it carried out similarly except having changed 0.3 part of perylene (D) into 0.3 part of anthracene, the photosensitive resin composition was obtained, and evaluation similar to Example 1 was performed.

Comparative Example 3
In Example 1, it carried out similarly except having changed 0.3 part of perylene (D) into 0.3 part of pyrene, the photosensitive resin composition was obtained, and evaluation similar to Example 1 was performed.
The results of Examples and Comparative Examples are shown in Table 1.

注）比較例１〜３についてはいずれも感度が得られず評価不能であった。

Note) For Comparative Examples 1 to 3, no sensitivity was obtained and evaluation was impossible.

The photosensitive resin composition of the present invention is a photosensitive resin composition for exposure in a laser exposure machine having an exposure wavelength of 390 to 420 nm, and includes a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), Photopolymerization initiator (C) and at least one compound selected from perylene, naphtho [2,3-a] pyrene, 3,4-benzopyrene, dibenzo [b, def] chrysene, and 9,10-diphenylanthracene ( D), the carboxyl group-containing polymer (A) is an alkyl (meth) acrylate having at least 8 carbon atoms in the alkyl group, a hydroxyl group-containing (meth) acrylate, (meth) acrylic acid and aromatic vinyl A laser exposure machine having an exposure wavelength of 390 to 420 nm because it is an acrylic copolymer containing a monomer as a copolymerization component. Even under low exposure conditions, it has a very excellent effect on sensitivity, resolving power, fine line adhesion, and pattern formability, processing of transparent conductive films such as glass, ITO or NESA film (tin oxide film) and 42 alloy, It is very useful for applications requiring high resolution and high fine wire adhesion, such as chemical rings such as SUS, and is expected to be frequently used for electrode formation of PDPs.

Claims (10)

A photosensitive resin composition for exposure in a laser exposure machine having an exposure wavelength of 390 to 420 nm, comprising a carboxyl group-containing polymer (A), an ethylenically unsaturated compound (B), a photopolymerization initiator (C), and perylene , Naphtho [2,3-a] pyrene, benzopyrene, dibenzo [b, def] chrysene, 9,10-diphenylanthracene, and a carboxyl group-containing polymer (A ) Is an acrylic system comprising at least an alkyl (meth) acrylate having an alkyl group having 8 or more carbon atoms, a hydroxyl group-containing (meth) acrylate, (meth) acrylic acid and an aromatic vinyl monomer as a copolymerization component. A photosensitive resin composition, which is a copolymer.
  The photosensitive resin composition according to claim 1, wherein the acid value of the carboxyl group-containing polymer (A) is 100 to 300 mgKOH / g. As the carboxyl group-containing polymer (A), the alkyl (meth) acrylate having 8 or more carbon atoms in the alkyl group is 5 to 15% by weight and the hydroxyl group-containing (meth) acrylate is 5 to 5% with respect to the total of the monomer components. The photosensitive resin composition according to claim 1 or 2 , wherein 20% by weight, 10% to 40% by weight of (meth) acrylic acid, and 1% to 15% by weight of an aromatic vinyl monomer. As the ethylenically unsaturated compound (B), having two polymerizable unsaturated groups and a weight average molecular weight, characterized in that it comprises an ethylenically unsaturated compound is 1200 or less claim 1-3, wherein either Photosensitive resin composition. An ethylenically unsaturated compound having two polymerizable unsaturated groups and having a weight average molecular weight of 1200 or less is an ethylene oxide-modified bisphenol A type di (meth) acrylate, an ethylene oxide / propylene oxide modified bisphenol A type di ( The photosensitive resin composition according to claim 4, which is at least one of (meth) acrylate. Photopolymerization initiator as (C), the photosensitive resin composition according to any one of claims 1-5, characterized in that it comprises a hexaarylbiimidazole derivatives. The photopolymerization initiator (C) is 0.01 to 10 parts by weight, perylene, naphtho [2,3-a, based on 100 parts by weight of the total of the carboxyl group-containing polymer (A) and the ethylenically unsaturated compound (B). 2) At least one compound (D) selected from pyrene, benzopyrene, dibenzo [b, def] chrysene, and 9,10-diphenylanthracene is 0.01 to 3.0 parts by weight. 1-6 photosensitive resin composition according to any one. Furthermore, according to claim 1-7 photosensitive resin composition according to any one which is characterized by containing a leuco dye and / or malachite green. Photoresist film, characterized in that formed by laminating the claims 1-8 photosensitive resin composition according to any one of the support film. The photoresist film according to claim 9 , further comprising a protective film laminated on the photosensitive resin composition side.