KR100899410B1 - Photosensitive composition for forming light shielding pattern of plasma display - Google Patents

Abstract

The present invention provides a photosensitive resin composition for forming a light shielding pattern of a plasma display, which has a high linearity and can easily form a light shielding pattern typified by good black electrodes and black stripes without peeling or debris. The photosensitive resin composition contains a photoinitiator represented by the formula (1), a light shielding substance, a binder resin, and a photopolymerizable compound. By containing these compounds, the photosensitive resin composition becomes more sensitive to light and the shape margin of the pattern is increased. Therefore, even when the photosensitive resin composition contains a large amount of light-shielding material, it is possible to easily form a pattern having good linearity and no peeling or debris, and can easily provide a PDP with high contrast and beautiful color development.

[Formula 1]

Shading pattern, plasma display

Description

Photosensitive composition for shading pattern of plasma display {Photosensitive composition for forming light shielding pattern of plasma display}

The present invention relates to a light-shielding resin composition for forming a light-shielding pattern for use in a plasma display panel (hereinafter referred to as PDP) in a self-luminous type plasma display using gas discharge.

Plasma displays that form images by self-emitting a large number of fine cells by using discharge phenomena have excellent characteristics that cannot be realized in conventional displays such as large screens, thin films, light weights, and flatness.

In general, a PDP includes a pair of electrodes regularly arranged on two glass substrates facing each other, and a rare gas mainly containing neon, xenon, and helium is sealed between the electrodes. . When a voltage is applied between the electrodes, a discharge occurs in a small cell around the electrode, whereby each cell emits light to display. The PDP displays information by selectively discharging and emitting cells regularly arranged.

The PDP includes a direct current type (DC type) and an alternating current type (AC type), and the AC type PDP includes a PDP having a waffle structure type cell. On the front plate of the PDP, a composite electrode made of a transparent electrode and a bus electrode is formed in parallel with each other, and an address electrode is formed in parallel with each other so as to be orthogonal to the composite electrode on the back plate. As shown in Japanese Patent Laid-Open No. 2005-129319, the bus electrode may be composed of a black electrode having a high sheet resistance and a white electrode which is a metal electrode. The front plate and the back plate are arranged to face each other, and a plurality of cells are formed in a space where the composite electrode and the address electrode cross each other. Phosphor layers are provided on the inner and bottom surfaces of many cells. In the plasma display, a discharge is generated in a cell by applying a predetermined voltage from an alternating current power source between the composite electrodes of the front panel, and the phosphor layer is emitted by the generated ultraviolet rays.

In order to prevent the degradation of the contrast and the color purity of the image in the plasma display, a black matrix in which black stripes are arranged in the front plate or in the vertical direction is formed. The black stripe, like the black electrode, requires excellent light shielding properties. The black electrode and the black stripe are coated with a photosensitive resin composition containing a photosensitive resin component and a light shielding material on a substrate and dried to form a desired pattern by photolithography, as shown in Japanese Patent Application Laid-Open No. 11-84125. Produced.

However, in order to provide excellent light-shielding property to a black electrode and a black stripe, it is necessary to increase the content of the light-shielding substance in the photosensitive resin composition. In the technique disclosed in Japanese Patent Application Laid-Open No. 2005-129319 and Japanese Patent Laid-Open No. 11-84125, when the content of the light-shielding substance increases, the optical density increases, and as a result, the light is deep into the film during photocuring. There was a case where photocuring did not progress sufficiently because it did not reach. As a result, the development margin is narrowed, so that the straightness of the pattern is lowered, or the pattern peeling from the substrate and the residue on the substrate are generated, so that it is difficult to obtain a good pattern of black electrodes or black stripes.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is possible to sufficiently polymerize the photopolymerizable compound even with a very small amount of light reaching the depth of the film, so that it has a good black electrode pattern and black stripe with good straightness and no peeling or debris. An object of the present invention is to provide a photosensitive resin composition for forming a light-shielding pattern that can be easily formed.

MEANS TO SOLVE THE PROBLEM In order to solve the subject mentioned above and achieve the objective, the photosensitive resin composition for light-shielding pattern formation of the plasma display of Claim 1 of this invention is (A) light-shielding substance, (B) binder resin, and (C) It is characterized by containing a photoinitiator, (D) photopolymerizable compound, and (C) at least 1 sort (s) of the compound represented by following formula (1) as a photoinitiator.

Wherein X is the following general formula (2);

(In formula, R <_3> -R <_7> is 1 type chosen from hydrogen, a halogen, a C1-C12 alkyl group, a phenyl group, and a phenylsulfanyl group.)

Or in Formula 3;

(Wherein R ₃ to R ₇ are one selected from hydrogen, halogen, an alkyl group having 1 to 12 carbon atoms, and a phenyl group), and R ₁ in the general formula (1) is a phenyl group or an alkyl group having 1 to 20 carbon atoms. An alkyl group, CN, NO ₂ , a haloalkyl group having 1 to 4 carbon atoms, and R ₂ is one kind selected from an acyl group having 2 to 12 carbon atoms and an alkenyl group having 4 to 6 carbon atoms).

According to the invention according to claim 1, the photosensitive resin composition contains (A) a light-shielding substance, (B) a binder resin, (C) a photopolymerization initiator, and (D) a photopolymerizable compound, and (C) a photopolymerization initiator. It contains at least 1 type of compound represented by General formula (1). Here, the compound represented by the formula (1) is a compound having strong sensitivity to light and activating even a small amount of light irradiation. Therefore, even when the photosensitive resin composition contains black pigment as a light-shielding substance and the irradiation amount of the light which reaches the depth of the film | membrane coated on the board | substrate is very small, a photopolymerizable compound can fully be polymerized. Therefore, it is possible to provide a photosensitive resin composition having high sensitivity and large development margin of the pattern portion.

By increasing the sensitivity of the photosensitive resin composition and increasing the development margin of the pattern portion, the photosensitive resin composition irradiated with light hardens efficiently even if the content of the black pigment is high. Therefore, the light-shielding pattern represented by the favorable black electrode and black stripe excellent in light-shielding property, high linearity, and without peeling or debris can be formed on a board | substrate. This makes it possible to easily provide a PDP having high contrast and beautiful color of red, green, and blue.

In the photosensitive resin composition for forming a light-shielding pattern of the plasma display according to claim 2 of the present invention, 1,2-octanedione, 1 in which one of the compounds represented by the formula (1) contained as a photopolymerization initiator is represented by the following formula (4): -[4- (phenylthio) phenyl]-and 2- (o-benzoyloxime).

1,2-octanedione, 1- [4- (phenylthio) phenyl]-, and 2- (o-benzoyloxime) represented by the general formula (4) are particularly sensitive to light among the compounds represented by the general formula (1). Therefore, according to the invention according to claim 2, the same effects as those of the invention according to claim 1 can be obtained more reliably.

Moreover, in the photosensitive resin composition for light-shielding pattern formation of the plasma display of Claim 3 of this invention, 1 type of the compound represented by General formula (1) contained as a photoinitiator is represented by the following general formula (5): ethanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime).

Ethanan, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-and 1- (o-acetyloxime) represented by the formula (5) are represented by the formula (1). Among the compounds, the sensitivity to light is particularly high. Therefore, according to the invention according to claim 3, the same effects as those of the invention according to claim 1 can be obtained more reliably.

In addition, the photosensitive resin composition for light-shielding pattern formation of the plasma display of Claim 4 of this invention is at least 1 sort (s) of an imidazolyl compound, a triazine compound, and an amino ketone compound, in addition to the compound represented by General formula (1) as a photoinitiator. It is characterized by further containing.

According to the invention according to claim 4, since at least one of the imidazolyl compound, the amino ketone compound, and the triazine compound is further contained in addition to the compound represented by the formula (1) as the photopolymerization initiator, the light absorption concentration as the photopolymerization compound has a broad wavelength. Elevated in the area, it can be activated even with a very small dose of light. Therefore, the effect similar to invention of Claim 1 can be acquired more reliably.

Furthermore, the photosensitive resin composition for light-shielding pattern formation of the plasma display of Claim 5 of this invention contains at least 1 sort (s) of an acrylic resin and a cellulose derivative as (B) binder resin.

According to the invention according to claim 5, since the binder resin is contained in the photosensitive resin composition, developability is improved and development of development waste is prevented. Thereby, the light-shielding pattern represented by the high precision black electrode and black stripe can be formed.

Hereinafter, a photosensitive resin composition for forming a light shielding pattern of a plasma display according to the present invention will be described. In addition, this invention is not limited by this Example.

The photosensitive resin composition according to the present invention is used to form a light blocking pattern represented by a black electrode and a black stripe on a glass substrate that is a front plate of a PDP, and includes a photopolymerization initiator, a photopolymerizable compound, a light blocking material, and a binder resin. It contains. On the other hand, the photosensitive resin composition of the present invention can be similarly applied to a black matrix in which black stripes are formed vertically and horizontally, and the black stripes will be described below. In addition, the light-shielding pattern of the present invention (A) indicates a pattern containing a light-shielding material and has a light-shielding ability, and includes black stripes, but is not limited to black as long as it has a light-shielding ability. The light-shielding pattern of this invention may have electroconductivity, and although it does not specifically limit, it contains a black electrode.

(C) [Photoinitiator]

First, a photoinitiator is demonstrated. As a photoinitiator, at least 1 sort (s) of the compound represented by General formula (1) is used.

[Formula 1]

Wherein X is the following general formula (2);

[Formula 2]

(In formula, R <_3> -R <_7> is 1 type chosen from hydrogen, a halogen, a C1-C12 alkyl group, a phenyl group, and a phenylsulfanyl group.)

Or in Formula 3;

[Formula 3]

(Wherein R ₃ to R ₇ are one selected from hydrogen, halogen, an alkyl group having 1 to 12 carbon atoms, and a phenyl group), and R ₁ in the general formula (1) is a phenyl group or an alkyl group having 1 to 20 carbon atoms. An alkyl group, CN, NO ₂ , a haloalkyl group having 1 to 4 carbon atoms, and R ₂ is one kind selected from an acyl group having 2 to 12 carbon atoms and an alkenyl group having 4 to 6 carbon atoms).

The compound represented by General formula (1) is obtained by the method of Unexamined-Japanese-Patent No. 2000-80068. Since this compound has a very high sensitivity to light as compared to other conventional photoinitiators, it can be activated efficiently by a very small dose of light to cure the photoinitiator. Thus, according to this compound, the sensitivity and image development margin of a photosensitive resin composition can be improved. Therefore, since the light-shielding pattern represented by the black electrode and the black stripe can be formed in a good shape having high linearity and no peeling or debris, it is possible to provide a PDP with high display contrast and beautiful red, green and blue colors. have.

Among o-acyl oxime compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, and 2- (o-benzoyloxime) represented by the general formula (4) can be easily obtained or sensitive to light. It is preferable at the point. The compound represented by the formula (4) is a compound of formula 1 R ₁ is n-hexyl (C ₆ H _13- ), R ₂ is a benzoyl group, X is R ₃ , R ₄ , R ₆ , R ₇ in formula (2) and is H, R ₅ is phenyl are those compounds sulfanyl group (C ₆ H ₅ S-).

[Formula 4]

In addition, in the o-acyl oxime compound, ethanone represented by the formula (5), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o -Acetyl oxime) is preferable in that it is easy to obtain sensitivity to light. The compound represented by the general formula (5) is R ₁ in formula I is methyl, R ₂ is an acetyl group, X is a group A compound and the R ₈ group is a, R ₉ in the formula (3).

[Formula 5]

In addition to the compound represented by General formula (1) as a photoinitiator, at least 1 sort (s) of compounds other than the compound represented by General formula (1) may be contained. As photoinitiators other than the compound represented by General formula (1), acetophenone, 2, 2- diethoxy acetophenone, p-dimethyl acetophenone, p-dimethylamino propiophenone, dichloro acetophenone, trichloro acetophenone, and p-tert- Acetophenones such as butyl acetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, Benzoin ethers such as benzoin isobutyl ether, benzyl dimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethyl thioxanthene, 2-methylthioxanthene, and 2-isopropylthioke Sulfur compounds such as xanthene, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone, azobisisobutyronitrile and benzoyl peroxide Organic such as cumene peroxide Thiol compounds, such as an oxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and 2- (o-chlorophenyl) -4,5-di ( imidazolyl compounds such as m-methoxyphenyl) -imidazolyl dimer, triazine compounds such as p-methoxytriazine, and 2,4,6-tris (trichloromethyl) -s-tri Azine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl ) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino -2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenol) ethenyl] -4,6-bis (trichloro) Rhomethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloro Triazine compounds having a halomethyl group such as methyl) -s-triazine can be used.

As the photopolymerization initiator other than the compound represented by the formula (1), amino ketone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1one can be used. In the present invention, triazine compounds, imidazolyl compounds and aminoketone compounds are preferably used.

As the photopolymerization initiator in which X in the general formula (1) is combined with the photopolymerization initiator represented by the general formula (2), triazine compounds are preferable among the above compounds, and the following general formulas (6), (7) and (8) (R ₁ and R ₂ are C ₁ to C _3). Particular preference is given to the triazine compound represented by the above formula. On the other hand, as a photoinitiator in which X in Formula (1) is combined with the photoinitiator represented by Formula (2), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1 temperature is effective.

Examples of the photopolymerization initiator in which X in the formula (1) is combined with the photopolymerization initiator represented by the formula (3) include the triazine compounds described above in the formula, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) -Butan-1one is preferred.

By incorporating two or more kinds of the above-mentioned compounds as the photopolymerization initiator into the photosensitive resin composition, it is possible to efficiently activate even a very small dose of light. This is due to the coexistence of compounds having different electron band spectra, thereby broadening a substantial wavelength region of light having a high sensitivity of the photopolymerization initiator, or at least two compounds interacting with each other.

By further increasing the sensitivity and developing phenomenon of the photosensitive resin composition, it is easier to form the light-shielding pattern represented by the black electrode and the black stripe in a good form having high linearity and no peeling or debris.

Here, the compounding ratio of the compound represented by the formula (1) and compounds other than the compound represented by the formula (1, in particular, a triazine compound, an imidazolyl compound, and an amino ketone compound) is 10:90 to 90:10 by weight. It is preferable, and it is more preferable that it is 20: 80-80: 20. When the compounding ratio of the compound represented by the formula (1) and the compound other than the compound represented by the formula (1) is within the above-mentioned range, the two compounds effectively interact, and thus the sensitivity and the development margin of the photosensitive resin composition can be further improved. .

(C) Photoinitiator contains 0.1-20 mass parts with respect to a total of 100 mass parts of (B) binder resin, (C) photoinitiator, and (D) photopolymerizable compound, Preferably it is contained in the range of 0.2-10 mass parts. It is preferable to be. When content is 0.1 mass part or more, practically suitable sclerosis | hardenability is obtained, and when it is 20 mass parts or less, the defect of bottom part hardening by excessive absorption of an initiator can be prevented.

(D) [Photopolymerizable Compound]

Next, a photopolymerizable compound is demonstrated. A photopolymerizable compound is a substance which polymerizes and hardens | cures when light, such as an ultraviolet-ray, is irradiated. As the photopolymerizable compound, a compound having an ethylenic double bond is preferable, and specifically, acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumaric acid, monoethyl fumaric acid, 2-hydroxyethyl acrylate and 2-hydride Oxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylic acid Amide, methacrylate amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylamide Latex, 2-ethylhexyl methacrylate, benzyl acrylate, ben Methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol di Methacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethyl Roll propane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate Monomers, oligomers such as dihydrate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardoepoxy diacrylate ; After the compound which has polyester (meth) acrylate obtained by making (meth) acrylic acid react with the polyester prepolymer obtained by condensation of polyhydric alcohol, monobasic acid, or polybasic acid, and a polyol group and two isocyanate groups reacts, (meth) acrylic acid Polyurethane (meth) acrylate obtained by this reaction; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycol And epoxy (meth) acrylate resins obtained by reacting (meth) acrylic acid with epoxy resins such as cylyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, and dihydroxybenzene type epoxy resins. Moreover, the resin which polybasic acid anhydride reacted with epoxy (meth) acrylate resin can also be used preferably.

(D) It is preferable that a photopolymerizable compound is contained in 50-90 mass parts with respect to a total of 100 mass parts of (B) binder resin, (C) photoinitiator, and (D) photopolymerizable compound. When the content is 50 parts by mass or more, the photopolymerization property necessary for development is obtained, and a practically sufficient image forming ability can be obtained. When it is 90 mass parts or less, the resolution of a fine image improves.

(A) [Shading Material]

Next, a light-shielding substance is demonstrated. As the light-shielding material, carbon black or titanium black can be preferably used, and in addition, Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, Inorganic pigments such as various metal oxides such as In, Sn, Sb, Hg, Pb, Bi, Si and Al, composite oxides, metal sulfides, lead metal sulfates or metal carbonates can also be used.

As carbon black, well-known carbon black, such as channel black, furnace black, thermal black, lamp black, can be used, but channel black can be used preferably because it is excellent in light-shielding property. Moreover, resin coated carbon black can also be used. Specifically, resin-coated carbon black obtained by mixing carbon black with a resin having reactivity to carboxyl group, hydroxyl group, and carbonyl group present on the surface of carbon black and heating at 50 to 380 degrees, or water-organic solvent mixture system or water- The resin coating carbon black etc. which are obtained by disperse | distributing an ethylenic monomer to surfactant mixed system and radical polymerization or radical copolymerization in presence of a polymerization initiator are mentioned. An organic pigment may also be added to the inorganic pigment as an auxiliary pigment.

(A) Light-shielding substance is contained in 10-70 mass parts with respect to a total of 100 mass parts of (A) light-shielding substance, (B) binder resin, (C) photoinitiator, and (D) photopolymerizable compound. It is preferable. When content is 10 mass parts or more, necessary light-shielding properties are obtained. When it is 70 mass parts or less, the hardening defect after exposure can be suppressed.

In addition, the concentration of the light-shielding substance is preferably adjusted so that the reflective optical density (OD) value per 1 μm of the film thickness of the black electrode or black matrix formed using the photosensitive resin composition of the present invention is 1.5 or more. When the reflection OD value per 1 micrometer film thickness of the photosensitive resin composition is 1.5 or more, sufficient display contrast can be obtained when this film is used for the light shielding pattern represented by the black electrode and the black stripe of the PDP.

(B) [Binder Resin]

Next, binder resin is demonstrated. In order to form the light-shielding pattern represented by a black electrode and a black stripe using the photosensitive resin composition of this invention, it is necessary to apply | coat and dry the photosensitive resin composition of this invention on a board | substrate as mentioned later. The binder resin may be appropriately selected depending on the properties to be improved such as compatibility, film formability, developability, adhesiveness, and the like.

As the binder resin, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl Acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- Hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, acryl A monomer obtained by copolymerizing a monomer selected from amide, methacrylamide, acrylonitrile, methacrylonitrile, etc. Or acidic cellulose modified products having a carboxyl group in the side chain, polyethylene oxide, polyvinylpyrrolidone, copolymers of acrylonitrile and vinyl chloride or vinylidene chloride, vinylidene chloride, chlorinated polyolefins or vinyl chloride and vinyl acetate Copolymer with polyvinyl acetate, copolymer with acrylonitrile and styrene, copolymer with acrylonitrile and styrene, butadiene, polyvinyl alkyl ether, polyvinyl alkyl ketone, polystyrene, polyamide, polyurethane, polyethylene Terephthalate isophthalate, acetyl cellulose, polyvinyl butyral, etc. are mentioned. In particular, in order to improve the developability in the alkylaqueous aqueous solution, it is preferable to use a monomer having a carboxyl group such as acrylic acid and methacrylic acid as a copolymerization component. It is preferable that content, such as acrylic acid and methacrylic acid, is 5 to 40weight% of a range in a copolymerization component. Moreover, the cellulose derivative which polybasic acid anhydride reacted with the hydroxyl group of carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can also be used preferably.

At least 1 sort (s) of acrylic resin, such as an acrylate derivative and a methacrylate derivative, and a cellulose derivative are especially preferable.

It is preferable that (B) binder resin is contained in 10-50 mass parts with respect to a total of 100 mass parts of (B) binder resin, (C) photoinitiator, and (D) photopolymerizable compound. When content is in this range, the fall of the precision which forms a required pattern can be suppressed.

[Other Additives]

The photosensitive resin composition according to the present invention further contains an additive component such as a conductive material, an ultraviolet absorber, a sensitizer, a sensitizer, a polymerization inhibitor, a plasticizer, a thickener, an organic solvent, a dispersant, an antifoaming agent, an organic or inorganic precipitation inhibitor, and the like. can do.

Although it does not specifically limit as long as it has electroconductivity as an electroconductive substance, A metal or its oxide is especially preferable. Specifically, at least one metal or oxide thereof selected from the group consisting of Ni, Zn, Pd, Ag, Au, In, Sn, Sb, Bi, Al, Ru, Cr, Fe, Co, Mn, Cu Conductive metal powder to contain is preferable. The metal powder whose surface was coat | covered with the said metal is also preferable at the point which improves cost and metal utilization efficiency. As long as it is a substance having conductivity, the inorganic powder used for the light-shielding substance can also be preferably used.

The conductive material is added in combination with (A) the light-shielding material, based on a total of 100 parts by mass of (A) the light-shielding material, (B) binder resin, (C) the photopolymerization initiator, and (D) the photopolymerizable compound. It is preferable to be contained in a negative range. When content is 10 mass parts or more, necessary light-shielding properties and electroconductivity can be obtained. When it is 70 mass parts or less, the hardening defect after exposure can be suppressed.

A sensitizer is added to improve sensitivity. Examples of the sensitizer include 2,4-diethyl thioxanthone, isopropyl thioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, and 2,6-bis (4-dimethylaminobenzal) cyclohexa Paddy, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, mihiraketone, 4,4-bis (diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone (chalcone), 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) -isonaft Thiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone, 3,3-carbonyl-bis (7-diethylaminoku Dried), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tritriethanolamine, N-phenylethanolamine, dimethylamino benzoate isoamyl, diethylamino benzoate isoamyl, 3-phenyl-5 -Benzoylthiotetrazole, 1-phenyl-5-ethoxy Viterbo carbonyl thio-tetrazole and the like, may be used singly or in combination of two or more kinds.

A polymerization inhibitor is added in order to improve the thermal stability at the time of storage. As polymerization inhibitor, hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-t-butyl-p-methylphenol , Chloranyl, pyrogallol and the like.

Plasticizers are added to improve the followability to the substrate. Examples of the plasticizer include dibutyl phthalate (DBP), dioctyl phthalate (DOP), dicyclohexyl phthalate, polyethylene glycol, glycerin, dibutyl stannate and the like.

Defoamers are added to reduce the bubbles in the paste or film to reduce the pores after firing. Examples of the antifoaming agent include antifoaming agents of alkylene glycols such as polyethylene glycol (molecular weights 400 to 800), silicones, and higher alcohols.

The photocurable resin composition of this invention may further contain glass powder as a binder. The glass powder is not particularly limited as long as it has the necessary transparency with respect to the exposure light source. For example, PbO-SiO ₂ , PbO-B ₂ O ₃ -SiO ₂ , ZnO-SiO ₂ , ZnO-B ₂ O _And glass powders such as lead borosilicate glass, zinc borosilicate glass and bismuth borosilicate glass of ₃ -SiO ₂ -based, BiO-SiO ₂ -based, BiO-B ₂ O ₃ -SiO ₂ -based.

Although depending on the shape of the pattern to be produced, it is preferable that it is 0.5-10 micrometers, and, as for the average particle diameter of glass powder, it is more preferable that it is 1-8 micrometers. If the average particle diameter exceeds 10 mu m, curvature occurs on the surface when forming a pattern with high precision, and if the average particle diameter is less than 1 mu m, fine voids are formed during firing, and this cavity causes the occurrence of poor insulation. Cause. Examples of the shape of the glass powder include spherical shape, block shape, flake shape, and dendrite shape. One type of glass powder may be used alone, or two or more types of glass powder may be used. It may be used in combination.

The photocurable resin composition of this invention is prepared by melt | dissolving or disperse | distributing in a solvent. The solvent to be used is not particularly limited as long as it has excellent affinity with the inorganic component and solubility of the organic component, can impart proper viscosity to the resin composition, and can be easily evaporated and removed by drying. As such a solvent, ketones, such as diethyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol and diacetone alcohol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Ether alcohols such as diethylene glycol diethyl ether; Saturated aliphatic monocarboxylic acid alkyl esters such as n-butyl acetate and amyl acetate; Lactic acid esters such as ethyl lactate and lactic acid-n-butyl; Methyl vertical solution acetate, ethyl vertical solution acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl-3- ethoxy propionate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4- Methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxy butyl acetate, 4-ethoxybutyl Ether esters such as acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate and the like. These may be used individually or in combination of 2 or more types.

The content ratio of the solvent is preferably 300 parts by mass or less, more preferably 10-70 parts by mass, most preferably 25, in order to maintain the viscosity of the photosensitive resin composition in a preferred range. It contains -35 mass parts.

[Formation method of light shielding pattern]

Next, the formation method of the light-shielding pattern represented by the black electrode and black stripe using the photosensitive resin composition of this invention is demonstrated. First, image exposure is performed by irradiating actinic rays, such as ultraviolet rays, excimer lasers, X-rays, and electron beams, onto a photosensitive resin composition layer applied or transferred onto a substrate through a mask. Subsequently, developing is carried out using an alkaline solution or water, and a pattern is formed on the substrate by dissolving and removing the unilluminated portion, and then firing again. By baking the pattern in the presence of oxygen and making it black, a light shielding pattern represented by a black electrode and a black stripe is formed.

When forming a pattern of higher precision, a photosensitive film is used. For the photosensitive film, a photosensitive paste film is formed by forming (coating and drying) a photosensitive resin composition on a supporting film such that the dry film thickness is 10 to 50 µm, for example, to stably secure the photosensitive paste film when not in use. It is produced by adhering the protective film. First, the protective film is removed from the photosensitive film, the photosensitive paste film is transferred onto the substrate, and the image is exposed to light, and then the supporting film is removed. Subsequently, development treatment and baking in the presence of oxygen form a light shielding pattern represented by a black electrode and a black stripe.

As a board | substrate, the board | substrate with which electrodes, such as a bus electrode, was installed on the glass substrate, a glass substrate, a ceramic substrate, etc. are mentioned, for example. For example, a black electrode can be formed by stacking on a bus electrode on which a white electrode is formed. As a radiation irradiation apparatus used for exposure, the ultraviolet irradiation apparatus generally used by the photolithographic method, the exposure apparatus used when manufacturing a semiconductor, and a liquid crystal display device, etc. can be used.

The light-shielding pattern represented by the black electrode and black stripe obtained by the said method is an optical density (reflective OD value) per 1 micrometer of film thickness of the photosensitive resin composition, 1.5 or more.

The black matrix obtained by the above method is used as a material for producing various displays such as PDP, organic EL, inorganic EL, and field emission display, and can be preferably used particularly for PDP. In addition, the black electrode obtained by the said method can be used suitably as a bus electrode of a PDP.

Next, the photosensitive resin composition for light-shielding pattern formation of the plasma display which concerns on this invention is demonstrated further more concretely based on an Example. In addition, in a sentence, "part" shows a "mass part" unless there is particular limitation.

(Example 1)

(B) 100 mass parts of n-lauryl methacrylate / n-butyl methacrylate / methacrylic acid = 20/60/20 (mass%) copolymer (Mw = 150,000) as binder resin, (C) photopolymerization Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) as an initiator (CGI 242, manufactured by Chiba Specialty Chemicals, Japan) 10 mass parts, (D) 20 mass parts of pentaerythritol tetraacrylate as a photopolymerizable compound, and 20 mass parts of EO modified trimethylolpropane triacrylate (M-350 by Toagosei Co., Ltd.), and (A ) 150 parts by mass of Ni powder (average particle diameter: 0.02 µm) as light-shielding material and 50 parts by mass of Ag powder (average particle diameter: 0.05 µm) as conductive material were kneaded with three-roll to combine the photosensitive resin composition. . The photosensitive resin composition was uniformly coated on a PET film (38 μm thick) and dried for about 5 minutes with a hot air convection dryer at 70 ° C., followed by laminating a protective film (25 μm thick PET film) to obtain a photosensitive dry film. On the other hand, the photosensitive film thickness of the photosensitive resin composition was 15 micrometers.

Subsequently, while removing the protective film on the substrate obtained by washing and drying the glass plate (PD 200) manufactured by Asahi Glass Co., Ltd. in Japan, the photosensitive dry film at a roll temperature of 105 ° C., a roll pressure of 2.9 × 10 ⁻³ Pa, and a roll speed of 1 m / min. Was laminated. Subsequently, after exposing at 200mJ / cm <^2> using a 3.5 kw ultrahigh pressure mercury lamp (made by Hakuto Corporation, Japan), the pattern was formed by spray-developing for 45 second with 0.3 mass% sodium-carbonate aqueous solution. After pattern formation, it baked for 30 minutes at 580 degreeC, and burned resin, and the light-shielding pattern which has the function of a favorable black stripe and a black electrode was obtained. The obtained light-shielding pattern was a favorable pattern with a good linearity and without peeling or debris. The reflection OD value was 1.7.

(Example 2)

(C) 10 parts by mass of 1,2-octanedione, 1- [4- (phenylthio) phenyl]-and 2- (o-benzoyloxime) (CGI 124, manufactured by Chiba Specialty Chemical Co., Ltd.) as photopolymerization initiators A photosensitive dry film was obtained in the same manner as in Example 1 except that the photosensitive resin composition was combined.

Subsequently, while removing the protective film on the substrate obtained by washing and drying the glass plate (PD 200) manufactured by Asahi Glass Co., Ltd. in Japan, the photosensitive dry film at a roll temperature of 105 ° C., a roll pressure of 2.9 × 10 ⁻³ Pa, and a roll speed of 1 m / min. Was laminated. Subsequently, after exposing at 300mJ / cm <^2> using a 3.5 kw ultrahigh pressure mercury lamp (made by Hakuto Japan), the pattern was formed by spray-developing for 45 second with 0.3 mass% sodium-carbonate aqueous solution. After pattern formation, it baked for 30 minutes at 580 degreeC, and burned resin, and the light-shielding pattern which has the function of a favorable black stripe and a black electrode was obtained. The obtained light-shielding pattern was a favorable pattern with a good linearity and without peeling or debris. The reflection OD value was 1.7.

(Example 3)

(C) In addition to the photoinitiator of Example 1 as a photoinitiator, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer which is an imidazolyl compound (B-CIM by Hodogaya Kagaku Co., Ltd., Japan) Except having used 5 mass parts), it carried out similarly to Example 1, and combined the photosensitive resin composition and obtained the photosensitive dry film.

Subsequently, the glass plate (PD 200) manufactured by Asahi Glass Co., Ltd., Japan, was washed with water and dried to remove the protective film from the substrate, and the photosensitive dry film at a roll temperature of 105 ° C., a roll pressure of 2.9 × 10 ⁻³ Pa and a roll speed of 1 m / min. Was laminated. Subsequently, after exposing at 150 mJ / cm <^2> using a 3.5 kw ultrahigh pressure mercury lamp (made by Hakuto Japan), the pattern was formed by spray-developing for 45 second with 0.3 mass% sodium-carbonate aqueous solution. After pattern formation, it baked for 30 minutes at 580 degreeC, and burned resin, and the light-shielding pattern which has the function of a favorable black stripe and a black electrode was obtained. The obtained light-shielding pattern was a favorable pattern with a good linearity and without peeling or debris. The reflection OD value was 1.7.

(Comparative Example)

(C) Photosensitive resin compositions were combined and obtained in the same manner as in Example 1 except that 10 parts by mass of 2,2-dimethoxy-1,2-diphenylethan-1-one was used as the photopolymerization initiator. In 200 mJ / cm <^2> of exposure amount, an exposure amount was inadequate and it could not expose to the bottom, and the favorable pattern at the time of image development was not obtained. Then, although the exposure amount was raised to 1000 mJ / cm <^2> , the favorable light-shielding pattern which was good in linearity and did not have peeling or dregs was not obtained.

As described above, the photosensitive resin composition for forming the light-shielding pattern of the plasma display according to the present invention can sufficiently polymerize the photopolymerizable compound even when there is very little light reaching the depth of the film, so that the linearity is good and there is no peeling or residue. A light shielding pattern represented by a good black electrode pattern and a black stripe can be easily formed on a substrate. Therefore, it is useful for plasma displays having high contrast and beautiful red, green, and blue colors.

According to the present invention, by applying a photopolymerization initiator having excellent sensitivity to light to a photosensitive resin composition, a light shielding pattern represented by a good black electrode pattern and black stripe having excellent linearity, no peeling or debris and excellent display contrast It can be easily formed on the stomach. Thereby, a plasma display with high contrast and beautiful color of red, green, and blue can be provided.

Claims (9)

As a photosensitive resin composition for forming a black electrode pattern of a plasma display having light shielding properties, (A) light-shielding substance, (B) binder resin, (C) photoinitiator, (D) photopolymerizable compound, and electroconductive substance, (C) Photosensitive resin composition for black electrode pattern formation of the plasma display with light-shielding property which contains at least 1 sort (s) of the compound represented by following formula (1) as a photoinitiator: [Formula 1]

Wherein X is the following general formula (2); [Formula 2]

(In formula, R <_3> -R <_7> is 1 type chosen from hydrogen, a halogen, a C1-C12 alkyl group, a phenyl group, and a phenylsulfanyl group.) Or in Formula 3; [Formula 3]

(In formula, R <_8> -R <_9> is 1 type chosen from hydrogen, a halogen, a C1-C12 alkyl group, and a phenyl group.), R <_1> in the said General formula ( ₁₎ is a phenyl group, C1-C20 An alkyl group, CN, NO ₂ , a haloalkyl group having 1 to 4 carbon atoms, and R ₂ is one kind selected from an acyl group having 2 to 12 carbon atoms and an alkenyl group having 4 to 6 carbon atoms). The method of claim 1, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-), represented by the following general formula (4), is one of the compounds represented by the general formula (1) contained as the (C) photopolymerization initiator. Benzoyl oxime), the photosensitive resin composition for forming a black electrode pattern of a plasma display with light shielding property: [Formula 4]

. The method of claim 1, 1 type of the compound represented by the said Formula (1) contained as said (C) photoinitiator is ethanone represented by following formula (5), and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 A photosensitive resin composition for forming a black electrode pattern of a plasma display with light shielding, characterized in that -yl]-and 1- (o-acetyloxime): [Formula 5]

. The method of claim 1, In addition to the compound represented by the formula (1) as the photopolymerization initiator (C), at least one of an imidazolyl compound, a triazine compound, and an amino ketone compound is further contained. Photosensitive resin composition for forming a black electrode pattern. The method of claim 1, The photosensitive resin composition for black electrode pattern formation of the plasma display with light-shielding property which contains at least 1 sort (s) of acryl-type resin and a cellulose derivative as said (B) binder resin. The method of claim 1, As said (B) binder resin, the copolymer which contains 5-40 weight% of monomers which have a carboxyl group in a copolymerization component, and carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, or A photosensitive resin composition for forming a black electrode pattern of a plasma display with light shielding, comprising at least one selected from cellulose derivatives in which a polybasic acid anhydride is reacted with a hydroxyl group of hydroxypropyl cellulose. The method of claim 1, A photosensitive resin composition for forming a black electrode pattern of a plasma display with light shielding, wherein the conductive material is a metal or an oxide thereof. The method of claim 1, The photosensitive resin composition for black electrode pattern formation of the plasma display with light shielding characterized by the said (A) light-shielding substance is a substance with electroconductivity. The photosensitive film which has a photosensitive paste film which consists of a photosensitive resin composition for black electrode pattern formation of the plasma display provided with the light-shielding property of any one of Claims 1-8 on a support film.