JP4611724B2 - Photosensitive composition for forming light-shielding film, and black matrix formed with the photosensitive composition for forming light-shielding film - Google Patents

Description

  The present invention relates to a photosensitive composition for forming a light-shielding film and a black matrix formed from the photosensitive composition for forming a light-shielding film, and more specifically, suitable for forming a black matrix such as a liquid crystal panel and a plasma display panel. The present invention relates to a photosensitive composition for forming a light shielding film, and a black matrix formed from the photosensitive composition for forming a light shielding film.

  A liquid crystal panel, in particular, a TN method, an STN method, and a liquid crystal panel are provided with a black matrix on a glass substrate for emphasizing image contrast, on which a transparent protective film, a transparent electrode, an alignment film, a liquid crystal, a transparent electrode, A transparent protective film, a backlight, and the like are sequentially laminated, and a seal portion is provided to maintain the airtightness of the end portion of the member. In particular, color filters are also installed in color liquid crystal panels. Further, in a liquid crystal panel using a TFT (Thin Film Transistor), it is used to shield the TFT. In order for such a liquid crystal panel to maintain a high-contrast image, the light blocking ratio of the black matrix needs to be an OD value of 1.5 or more. Moreover, the black matrix is required to be as thin as possible because of the problem of flattening the color filter and the transparent protective film. The black matrix is formed by a photolithography method after dissolving a photosensitive composition for forming a light-shielding film containing a light-shielding pigment and a photosensitive resin in a solvent or the like, applying it to a liquid crystal panel substrate, and drying it. However, in order to obtain a thin black matrix having a high OD value, it is essential to use a pigment having an excellent light shielding property, and carbon black having a large light shielding rate is usually used. (For example, see Patent Documents 1 and 2)

JP-A-9-166869 Japanese Patent Laid-Open No. 11-84125

  However, in order to obtain a sufficient light-shielding property, in the conventional photosensitive composition for forming a light-shielding film, the film thickness when the photosensitive composition for forming a light-shielding film is applied is increased or the light-shielding against the photosensitive resin is performed. It is necessary to increase the amount of the functional pigment. When such a method is used, the light transmittance in the ultraviolet region that contributes to the photosensitivity (sensitivity) of the photosensitive composition for forming a light-shielding film is lowered, and thus there is a problem that the sensitivity is remarkably deteriorated. . Furthermore, the black matrix formed from the light-shielding film-forming photosensitive composition is required to have a good shape.

  The present invention has been made in view of the above-described problems, and its object is to provide a light-sensitive film-forming photosensitive composition that has high sensitivity, can reduce the film thickness, and can form a well-shaped black matrix. Is to provide.

In order to achieve the above object, the photosensitive composition for forming a light shielding film of the present invention comprises (a) carbon black as a light shielding pigment, (b) a photopolymerizable compound, and (c) a photopolymerization initiator. and, Ri dispersed particle diameter 150~250nm der of the carbon black, Ru der transmittance than 0.25% of definitive i line when the OD value in the visible light region (780 nm from 400 nm) is 1.5 It is characterized by that.
Thereby, the transmittance | permeability of the ultraviolet-ray in the photosensitive composition for light shielding film formation can be improved, and the sensitivity of the photosensitive composition for light shielding film formation can be improved. Furthermore, a well-shaped black matrix can be formed from the photosensitive composition for forming a light-shielding film.
Moreover, the sensitivity of the photosensitive composition for light shielding film formation can be improved further by using a specific photopolymerizable compound and a photoinitiator with respect to the said carbon black.

  The photosensitive composition for forming a light-shielding film of the present invention adjusts the particle size of carbon black as a light-shielding pigment and improves the transmittance of ultraviolet rays, so that the sensitivity can be increased and the same OD value can be obtained. The film thickness can be reduced. A black matrix formed using the composition can maintain a high image contrast, and a display device such as a good liquid crystal panel or plasma display panel can be manufactured.

  The photosensitive composition for light-shielding film formation of this invention contains (a) carbon black as a light-shielding pigment, (b) a photopolymerizable compound, and (c) a photopolymerization initiator. And the transmittance | permeability of the ultraviolet-ray in the said photosensitive composition for light shielding film formation can be improved by making the particle diameter or dispersion | distribution particle diameter of the carbon black of said (a) component into the range of a specific value. is there. By improving the transmittance, the sensitivity of the light-sensitive film-forming photosensitive composition can be improved.

As ultraviolet rays irradiated to the photosensitive composition for forming a light-shielding film, g-line (436 nm), h-line (405 nm), i-line (365 nm), j-line (330 nm), k-line (310 nm) from the wavelength of the exposure machine. A mixture of various bright lines such as the above is used and is related to the polymerization initiation efficiency of the photopolymerization initiator. That is, the sensitivity of the photosensitive composition for forming a light shielding film is greatly related to the transmittance of various bright lines (g, h, i, j, k lines) with respect to the photosensitive composition for forming a light shielding film. However, since the OD value of the black matrix actually used is in the range of 2 to 5, the OD value in the visible light region (400 nm to 780 nm) is set to 1.5 in order to accurately measure the transmittance. By using the UV transmittance in this case, a more accurate transmittance value can be obtained. For example, as shown in FIG. 1, a transmittance result for each carbon black particle diameter can be obtained.
As described above, the light-shielding film-forming photosensitive composition has an i-line transmittance when the OD value of the light-shielding film-forming photosensitive composition is adjusted to 1.5 in order to obtain sufficient sensitivity at the wavelength. Is preferably 0.25 or more, more preferably 0.3 or more, and even more preferably 0.4 or more. If it is lower than this transmittance, the sensitivity may be lowered. Further, the j-ray is also involved in the initiation of polymerization of the photoinitiator, and its transmittance is preferably 0.15 or more, and more preferably 0.3 or more. Furthermore, k-rays are also involved in the initiation of polymerization of the photoinitiator, and the transmittance is preferably 0.05 or more, and more preferably 0.1 or more.

  Hereinafter, the photosensitive composition for forming a light-shielding film of the present invention will be described in the order of (a) carbon black as a light-shielding pigment, (b) a photopolymerizable compound, (c) a photopolymerization initiator, and other components.

In the photosensitive composition for forming a light-shielding film of the present invention, a preferable ultraviolet light transmittance can be obtained by setting the dispersed particle diameter of the carbon black used as the light-shielding pigment to be blended to 100 nm to 250 nm. . The lower limit of the dispersed particle size of the carbon black is preferably 150 nm or more, and more preferably 170 nm or more. Moreover, as an upper limit of the dispersed particle diameter of carbon black, 200 nm or less is more preferable.
In the above photosensitive composition for forming a light shielding film, when the dispersed particle size of carbon black is less than 100 nm, the transmittance of irradiated ultraviolet rays may be low and sufficient sensitivity may not be obtained. It is difficult to uniformly disperse in the forming photosensitive composition, and there is a possibility that a uniform OD value cannot be obtained. On the other hand, if the dispersed particle diameter of the carbon black is 100 nm or more, preferably 150 nm or more, sufficient ultraviolet light transmittance can be obtained, necessary sensitivity can be obtained, and dispersibility can be improved. A photosensitive composition for forming a light-shielding film capable of obtaining a uniform OD value can be obtained. Furthermore, by setting the dispersed particle diameter of carbon black to 170 nm or more, it is possible to obtain a further ultraviolet ray transmittance, improve the photosensitivity, further improve the dispersibility, and make it more uniform. The photosensitive composition for light shielding film formation which can obtain OD value can be obtained.
Further, in the photosensitive composition for forming a light shielding film, when the dispersed particle diameter of the carbon black exceeds 250 nm, sufficient ultraviolet light transmittance can be obtained, but in the photosensitive composition for forming a light shielding film, carbon black is precipitated. It becomes difficult to disperse uniformly. Furthermore, it becomes difficult to form a black matrix having a good shape from this photosensitive composition for forming a light-shielding film (the roughness increases). On the other hand, if the dispersed particle diameter of the carbon black is 250 nm or less, sufficient ultraviolet light transmittance can be obtained, necessary sensitivity can be obtained, and uniform dispersion can be achieved. Furthermore, by setting the dispersed particle diameter of carbon black to 200 nm or less, sufficient ultraviolet ray transmittance can be obtained, the necessary sensitivity can be obtained, the dispersibility can be further improved, and handling is easier. can do.

  In general, in order for the black matrix formed by applying the photosensitive composition for forming a light shielding film to maintain a high-contrast image, the light shielding ratio is OD value of 1.5 or more, preferably 3.0 or more, More preferably, it is 4.0 or more.

  The (b) photopolymerizable compound is a substance that polymerizes and cures upon irradiation with light such as ultraviolet rays. As the photopolymerizable compound, a compound having an ethylenic double bond is preferable. Specifically, acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl acrylate, 2 -Hydroxyethyl 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, methacrylic acid amide, acrylonitrile, methacrylonitrile , Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl Chryrate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol Diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylo Propane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1 Monomers, oligomers such as 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardoepoxy diacrylate; polyester prepolymers obtained by condensing polyhydric alcohols with monobasic acids or polybasic acids Polyester (meth) acrylate and polyol obtained by reacting (meth) acrylic acid Polyurethane (meth) acrylate obtained by reacting a group with two isocyanate groups and then reacting with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin , Phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy Examples thereof include epoxy (meth) acrylate resins obtained by reacting epoxy resins such as resins with (meth) acrylic acid. Further, a resin obtained by reacting the epoxy (meth) acrylate resin with a polybasic acid anhydride can also be suitably used.

ここで、式（Ｉ）で示される化合物のＸは、式（II）で示される基である。

また、式（Ｉ）で示される化合物のＹは、例えば無水マレイン酸、無水コハク酸、無水イタコン酸、無水フタル酸、無水テトラヒドロフタル酸、無水ヘキサヒドロフタル酸、無水メチルエンドメチレンテトラヒドロフタル酸、無水クロレンド酸、メチルテトラヒドロ無水フタル酸、無水グルタル酸といったジカルボン酸無水物からカルボン酸無水物基（−ＣＯ−Ｏ−ＣＯ−）を除いた残基である。 また、式（Ｉ）で示される化合物のＺは、例えば無水ピロメリット酸、ベンゾフェノンテトラカルボン酸二無水物、ビフェニルテトラカルボン酸二無水物、ビフェニルエーテルテトラカルボン酸二無水物等のテトラカルボン酸二無水物から２個のカルボン酸無水物基を除いた残基である。 Further, as the photopolymerizable compound, a compound represented by the formula (I) can also be applied. The compound represented by the formula (I) itself is a preferable compound in terms of high photocurability. That is, in the photosensitive resin for forming a light shielding film containing the compound represented by the formula (I), the sensitivity can be further improved by increasing the transmittance of ultraviolet rays.

Here, X of the compound represented by the formula (I) is a group represented by the formula (II).

Y of the compound represented by the formula (I) is, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, It is a residue obtained by removing a carboxylic anhydride group (—CO—O—CO—) from a dicarboxylic anhydride such as chlorendic anhydride, methyltetrahydrophthalic anhydride, and glutaric anhydride. Z of the compound represented by the formula (I) is, for example, tetramellitic diacid such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, etc. A residue obtained by removing two carboxylic anhydride groups from an anhydride.

  The photopolymerizable compound is contained in the range of 60 to 99.9 parts by weight with respect to 100 parts by weight in total of the compound and (c) the photopolymerization initiator. If the content is less than 60 parts by weight, sufficient heat resistance and chemical resistance cannot be expected, and if it exceeds 99.9 parts by weight, the film-forming ability is inferior and photocuring failure may occur.

In the above, as the photopolymerizable compound, those whose molecules themselves can be polymerized are listed. However, in the present invention, a mixture of (b-1) a polymer binder and (b-2) a photopolymerizable monomer is also (b ) It is included in the photopolymerizable compound.
As the above-mentioned (b-1) polymer binder, a binder capable of alkali development is preferable because of easy development.
Specifically, monomers having a carboxyl group such as acrylic acid and methacrylic acid, and methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate N-butyl acrylate, N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, acrylamide, acrylonitrile, etc. Copolymer, and phenol novolac type epoxy acrylate polymer, phenol novolac Epoxy methacrylate polymer, cresol novolak epoxy acrylate polymer, cresol novolak epoxy methacrylate polymer, a bisphenol A type epoxy acrylate polymer, a bisphenol S type epoxy acrylate polymers include resins such as. Since the acryloyl group or the methacryloyl group is introduced into the resin, the crosslinking efficiency is improved, and the light resistance and chemical resistance of the coating film are excellent. The content of the monomer component having a carboxyl group such as acrylic acid or methacrylic acid constituting the resin is preferably in the range of 5 to 40% by weight.

  When (b) component consists of (b-1) component and (b-2) component, (b-1) component is (b-1) component, (b-2) component, and (c) light. It is preferable to blend in the range of 10 to 60 parts by weight in a total of 100 parts by weight of the polymerization initiator. If the blending amount is less than 10 parts by weight, it is difficult to form a film at the time of coating and drying, and the film strength after curing is sufficient. It cannot be increased. On the other hand, if the blending amount exceeds 60 parts by weight, the developability deteriorates.

  (B-2) Photopolymerizable monomers include methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, and triethylene. Glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, Tetramethylolpropane tetramethacrylate Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol Examples include, but are not limited to, diacrylate, benzyl acrylate, benzyl methacrylate, cardo epoxy diacrylate, acrylic acid, methacrylic acid, and the like.

  When (b) component consists of (b-1) component and (b-2) component, (b-2) component is (b-1) component, (b-2) component, and (c) light. It is preferably blended in the range of 15 to 50 parts by weight per 100 parts by weight of the polymerization initiator. If the blending amount is less than 15 parts by weight, photocuring failure can occur and sufficient heat resistance and chemical resistance can be obtained. Moreover, when it exceeds 50 weight part, the coating-film formation ability will be inferior.

（式（III）中、Ｘは、式（IV）又は式（Ｖ）で示される基であり、Ｒ_１は、フェニル基、Ｃ_１〜Ｃ_２０アルキル基、ＣＮ、ＮＯ_２又はＣ_１〜Ｃ_４ハロアルキル基であり、Ｒ_２は、Ｃ_２〜Ｃ_１２アシル基、Ｃ_４〜Ｃ_６アルケノイル基である。）

（式（IV）中、Ｒ_３〜Ｒ_７は、水素、ハロゲン、Ｃ_１〜Ｃ_１２アルキル基、フェニル基又はベンゼンスルファニル（Ｃ_６Ｈ_５Ｓ−）である。）

（式（Ｖ）中、Ｒ_８〜Ｒ_９は、水素、ハロゲン、Ｃ_１〜Ｃ_１２アルキル基又はフェニル基である。） 式（III）で示される化合物は、特開２０００−８００６８号公報に記載の方法により得られる化合物である。上記化合物は、光に対する感受性が他の既知の光重合開始剤に較べてきわめて高く、わずかな照射量の光によって効率的に活性化して光重合開始剤を硬化させることができる。さらに、上記のようなカーボンブラックを用いることによって、外線の透過率を向上させることができ、より一層遮光膜形成用感光性組成物の感度、現像マージンを向上させることができる。よって、ブラックマトリクスパターンを直線性が高く、剥がれや残さのない良好な形態にすることができるので、表示コントラストが高くてＲ、Ｇ、Ｂの発色が美しいカラーフィルタを提供することができる。 (C) As a photopolymerization initiator, at least one compound represented by the formula (III) is particularly preferable.

(In formula (III), X is a group represented by formula (IV) or formula (V), and R ₁ is a phenyl group, a C _{1 to} C ₂₀ alkyl group, CN, NO _2, or C ₁ to C. _{4 is a} haloalkyl group, and R ₂ is a C _{2 to} C ₁₂ acyl group or a C _{4 to} C ₆ alkenoyl group.)

(In formula (IV), R _{3 to} R ₇ are hydrogen, halogen, C _{1 to} C ₁₂ alkyl group, phenyl group or benzenesulfanyl (C ₆ H ₅ S—).)

(In the formula (V), R _{8 to} R ₉ are hydrogen, halogen, a C _{1 to} C ₁₂ alkyl group or a phenyl group.) The compound represented by the formula (III) is disclosed in JP-A No. 2000-80068. It is a compound obtained by the described method. The above compounds are extremely sensitive to light compared to other known photopolymerization initiators, and can be efficiently activated by a small amount of light to cure the photopolymerization initiator. Furthermore, by using carbon black as described above, the transmittance of external lines can be improved, and the sensitivity and the development margin of the photosensitive composition for forming a light-shielding film can be further improved. Therefore, since the black matrix pattern can have a high linearity and a good form with no peeling or residue, a color filter with high display contrast and beautiful R, G, and B color can be provided.

  Photopolymerization initiators other than the compound represented by formula (III) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxy Ethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) ) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -buta -1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate Butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2 -Propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thio Xanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobis Isobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) ) -Imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4 Methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethyl Aminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, gibe Zosberon, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9- Acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 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-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -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 (trichloromethyl) -s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo -4-methoxy) styrylphenyl-s-triazine and the like.

  In the present invention, among these, triazines such as p-methoxytriazine; 2,4,6-tris (trichloromethyl) -s-triazine, 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-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-to Azine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, etc. Triazines having the following halomethyl groups; Triazine compounds such as 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer; Imidazolyl compounds such as 2-benzyl-2- An amino ketone compound such as dimethylamino-1- (4-morpholinophenyl) -butan-1-one; is preferably used.

  Furthermore, the photosensitive composition for forming a light shielding film of the present invention preferably contains a compound represented by the formula (III) and at least one other compound as a photopolymerization initiator. The photosensitive composition for forming a light-shielding film is efficiently activated by a very small amount of light by containing at least two kinds of compounds as a photopolymerization initiator. This is because the compounds having different electron band spectra coexist in the photosensitive composition for forming a light-shielding film, so that the photopolymerization initiator broadens the net wavelength range of light having high sensitivity, or at least two kinds of compounds are present. By interacting. Thus, since the photosensitive composition for forming a light-shielding film of the present invention can further increase sensitivity and development margin, a black matrix pattern can be more easily formed in a good form with high linearity and no peeling or residue. be able to. Preferred examples (i) to (iii) of the combination of the compound represented by the formula (III) and at least one other compound are shown below.

  (I) at least one photopolymerization initiator of the O-acyloxime compound represented by the formula (III) and a compound other than the O-acyloxime compound (a photopolymerization initiator other than the compound represented by the formula (III) ) In combination.

Among the O-acyloxime compounds, in formula (III), R ₁ is n-hexyl (C ₆ H ₁₃ —), R ₂ is a benzoyl group, X is represented by formula (IV), and R ₃ , R ₄ , R ₆ , R ₇ are H, R ₅ is a phenylsulfanyl group (C ₆ H ₅ S—), 1,2-octanedione represented by formula (VI), 1- [4- ( Phenylthio) phenyl]-, 2- (O-benzoyloxime) is preferable in terms of sensitivity to light and availability.

Further, among the O-acyloxime compounds, in formula (III), R ₁ is methyl, R ₂ is an acetyl group, X is represented by formula (V), R ₈ is an ethyl group, R Ethanone represented by formula (VII), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), wherein ₉ is a methyl group However, the sensitivity to light is further higher, which is more preferable.

  (Ii) A combination of a photopolymerization initiator represented by the formula (III) and X represented by the formula (IV) and a triazine compound.

In particular, as the triazine compound, a triazine compound represented by the formula (VIII), the formula (IX), or the formula (X) (R ₁ and R ₂ represent a C ₁ -C ₃ alkyl group) is particularly preferable. 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one can also be used in the same manner as the triazine compound.

  (Iii) a photopolymerization initiator represented by the formula (III) and X being represented by the formula (V), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1one, Combination. Moreover, the above-mentioned triazine compound can be similarly combined instead of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

  Here, the compounding ratio of the compound represented by the compound represented by the formula (III) and the compound other than the compound represented by the formula (III) (particularly triazine compound, imidazolyl compound and aminoketone compound) is 10: It is preferably 90 to 90:10, and particularly preferably 20:80 to 80:20. Since the compounding ratio of the compound represented by the formula (III) and the compound other than the compound represented by the formula (III) is within the above-mentioned range, both compounds effectively interact to form a light shielding film. The sensitivity and development margin of the photosensitive composition can be further improved.

  The blending amount of the component (c) can be blended in the range of 0.1 to 30 parts by weight in a total of 100 parts by weight of the photopolymerizable compound (polymer binder, photopolymerizable monomer and photopolymerization initiator).

  Since the proportional relationship of FIG. 1 is established between the amount of carbon black added to the total amount of 100 parts by weight of the photosensitive composition for forming a light shielding film comprising the components (a) to (c) and the OD value, the black matrix In order to make the shading rate of 1.5 or more in terms of OD value, the amount of carbon black needs to be blended at least 20 parts by weight with respect to 100 parts by weight of the total amount of components (a) to (c).

In the photosensitive composition for forming a light-shielding film of the present invention, in addition to the carbon black of component (a), other pigments are added within the range where the color tone is adjusted and the light-shielding performance is not lowered to further increase the resistance value. can do. Such a pigment is a color index (CI) number,
Yellow pigment: C.I. I. 20, 24, 83, 86, 93, 109, 110, 117, 125, 137, 138, 139, 147, 148, 153, 154, 166, 168
Orange pigment: C.I. I. 36, 43, 51, 55, 59, 61
Red pigment: C.I. I. 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, or 217, 220, 223, 224, 226, 227, 228, 240
Purple pigment: C.I. I. 19, 23, 29, 30, 37, 40, 50
Blue pigment: C.I. I. 15, 16, 22, 60, 64
Green pigment: C.I. I. 7, 36
Brown pigment: C.I. I. 23, 25, 26
Can be suitably used.

  The amount of pigment (including the amount of carbon black) added to the photosensitive composition for forming a light-shielding film of the present invention includes (b) a photopolymerizable compound (or a polymer binder and a photopolymerizable monomer), and (c ) 20 to 150 parts by weight, preferably 25 to 100 parts by weight, and more preferably 30 to 80 parts by weight with respect to 100 parts by weight of the photopolymerization initiator. If the range is less than 20 parts by weight, the black matrix cannot have sufficient light-shielding properties, and if it exceeds 150 parts by weight, the amount of the photosensitive resin component decreases, causing poor curing and forming a good black matrix. Can not do it.

  Furthermore, the carbon black as the component (a) and the pigment to be added can be mixed with other components as a solution dispersed at an appropriate concentration (for example, 10 to 20%) using a dispersant. The dispersant is not particularly limited. For example, a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant is preferably used.

  In addition to the above, an organic solvent can be added to the photosensitive composition for forming a light-shielding film of the present invention in order to improve coatability and adjust viscosity. Examples of the organic solvent include benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol Roh ether propionate, propylene glycol monoethyl ether propionate, methyl carbonate, ethyl carbonate, propyl carbonate and carbonate butyl. Among these, 3-methoxybutyl acetate is preferable because it not only exhibits excellent solubility for the soluble component in the photosensitive composition for forming a light-shielding film but also improves dispersibility of insoluble components such as pigments. . The organic additive can be used in an amount of 50 to 500 parts by weight based on 100 parts by weight of the total of carbon black as a polymer binder, a photopolymerizable monomer, a photopolymerization initiator, and a light shielding pigment.

  Moreover, you may add a thermal-polymerization inhibitor, an antifoamer, surfactant, etc. to the said photosensitive composition for light shielding film formation. The thermal polymerization inhibitor may be a conventionally known one, and examples thereof include hydroquinone and hydroquinone monoethyl ether. The antifoaming agent may be a conventionally known surfactant, and includes silicone-based and fluorine-based compounds. Furthermore, it may be a conventionally known compound, and examples thereof include anionic, cationic, and nonionic compounds.

Hereinafter, (1) a method for adjusting a photosensitive composition for forming a light shielding film, and (2) a method for forming a light shielding film will be described.
(1) Method for preparing photosensitive composition for forming light-shielding film (a) Carbon black as a light-shielding pigment, (b) a photopolymerizable compound, (c) a photopolymerization initiator, and organic additives as required And mixing (dispersing / kneading) with a stirrer such as a three-roll mill, ball mill, or sand mill, and filtering with a 5 μm membrane filter to prepare a photosensitive composition for forming a light-shielding film.

(2) Method for forming black matrix (light-shielding film) A roll coater, a reverse coater, and a bar coater are prepared on a glass substrate having a clean surface with a thickness of 0.5 to 1.1 mm. The coating is performed using a contact transfer type coating device such as a spinner (rotary coating device) or a non-contact type coating device such as a curtain flow coater.
In the above preparation and application, a silane coupling agent can be blended or applied to the substrate in order to improve the adhesion between the glass substrate and the photosensitive composition for forming a light-shielding film.
After the above coating, it is dried on a hot plate at a temperature of 80 ° C. to 120 ° C., preferably 90 ° C. to 100 ° C. for 60 seconds to 120 seconds, or left at room temperature for several hours to several days, or warm air After removing the solvent by placing it in a heater or infrared heater for several tens of minutes to several hours, adjust the coating film thickness to the range of 0.5 to 5 μm, and then activate the UV, excimer laser light, etc. through the negative mask An energy beam is exposed in an irradiation energy dose range of 30 to 2000 mJ / cm ² . The irradiation energy dose may vary slightly depending on the type of light-shielding film photosensitive composition used. The light shielding film obtained by exposure is developed with a developer by a dipping method, a spray method, or the like to form a black matrix pattern. Examples of the developer used for development include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.
The black matrix obtained by the above manufacturing method is useful for various display devices such as liquid crystal panels and plasma display panels.

  Examples of the present invention will be described below, but the present invention is not limited thereby.

(Resin synthesis example)
According to JP 2001-354735 A, a 500 mL four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tertbutyl-4-methylphenol and acrylic acid 72.0 g was charged and dissolved by heating at 90 to 100 ° C. while blowing air at a rate of 25 mL / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. The solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mg KOH / g. It took 12 hours for the acid value to reach the target. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the colorless and transparent solid-form formula [3]. Next, after adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate obtained in this way and dissolving, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed. The temperature was gradually raised and the reaction was carried out at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to give compound 1 (Y / Z molar ratio in the formula = 50.0 / 50.0) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

(Transmittance measurement)
In Examples 1 to 4 and Comparative Examples 1 and 2 below, the photosensitive composition for forming a light-shielding film is spin coated (1H-360s: Mikasa Co., Ltd.) so that the optical density of the quartz plate is 1.5. Applied). The coated light-sensitive film-forming photosensitive composition was dried on a hot plate at 90 ° C. for 2 minutes to form a light-shielding film-forming photosensitive composition film.
Subsequently, the transmittance | permeability of the ultraviolet-ray of the formed film | membrane was measured with the UV measuring device.

About Examples 1-4 and Comparative Examples 1 and 2, the sample of the composition for light shielding film formation was prepared with the composition shown in the following Table 1, and evaluated. In Examples and Comparative Examples, UV measurement was performed without adding a polymerization initiator.

  As can be seen from Table 1 above, it can be seen that the transmittance of the i-line varies depending on the particle size of the carbon black, and the transmittance is good when the dispersed particle size is 100 nm or more, particularly when the dispersed particle size is 150 nm or more. Further, it can be seen that the surface roughness is poor when the dispersed particle size is 300 nm or more, and good when the dispersed particle size is 250 nm or less, particularly 200 nm or less.

In the following Examples 5 to 8 and Comparative Examples 3 and 4, a light-shielding film-forming photosensitive composition actually adjusted to an OD value of 3.5 for a black matrix was prepared with the composition shown in Table 2, Evaluation was performed.
This light-shielding film-forming photosensitive composition was applied to a glass substrate so as to have a film thickness of 1.4 μm using a spin coater (1H-360s: manufactured by Mikasa Co., Ltd.). The photosensitive composition for drying was dried on a hot plate at 90 ° C. for 2 minutes to form a film of the photosensitive composition for forming a light shielding film.
Then, exposure machine: was exposed at an irradiation energy dose 50 to 300 mJ / cm ² to 10 mJ / cm ² intervals at (EXM-1066-E01 oak). The light-shielding film obtained by exposure was developed with a potassium hydroxide 0.04% developer by a spray method for 100 seconds.
In the obtained black matrix, the line width of the 20 μm line at each exposure dose is measured, and the exposure sensitivity at which the same 20 μm line is formed with respect to the mask line width of 20 μm is shown. Furthermore, the line shape was observed, and evaluated as good: ◯, unusable (large roughness): x.

  As can be seen from Table 2 above, the exposure sensitivity and line shape change depending on the dispersed particle size of carbon black, and the dispersed particle size is particularly 100 to 250 nm, and both the exposure sensitivity and line shape can withstand use. The diameter was 150 to 200 nm and the exposure sensitivity and line shape were both good.

It is a figure which shows the relationship between carbon black amount and OD value.

Claims (6)

In a photosensitive composition for forming a light shielding film, comprising (a) carbon black as a light shielding pigment, (b) a photopolymerizable compound, and (c) a photopolymerization initiator,
The carbon black has a dispersed particle diameter of 150 to 250 nm and an i-line transmittance of 0.25% or more when the OD value in a visible light region (400 nm to 780 nm) is 1.5. A photosensitive composition for forming a light shielding film.   The photosensitive composition for forming a light-shielding film according to claim 1, wherein the carbon black has a dispersed particle diameter of 150 to 200 nm. 3. The photosensitive composition for forming a light-shielding film according to claim 1 , wherein an OD value in a visible light region (400 nm to 780 nm) is 3.0 or more. The said (b) photopolymerizable compound contains the compound represented by Formula (I), The photosensitive composition for light shielding film formation of any one of Claims 1-3 characterized by the above-mentioned.

(In the formula (I), X represents the formula (II)

Y represents a dicarboxylic acid anhydride to a carboxylic acid anhydride group (—CO—O
It is a residue excluding -CO-).
Z is a residue obtained by removing two carboxylic anhydride groups from tetracarboxylic dianhydride. ) Wherein (c) photopolymerization initiator, at least comprise one characterized by claim 1 forming a light-shielding film for photosensitive composition according to any one of 4 of the compound represented by the formula (III).

(In formula (III), X is a group represented by formula (IV) or formula (V), and R ₁ is a phenyl group, a C ₁ -C ₂₀ alkyl group, CN, NO ₂ or C ₁ -C. _{4 is a} haloalkyl group, and R ₂ is a C ₂ -C ₁₂ acyl group or a C ₄ -C ₆ alkenoyl group.)

(In formula (IV), R ₃ -R ₇ is hydrogen, halogen, C ₁ -C ₁₂ alkyl group, phenyl group or benzenesulfanyl (C ₆ H ₅ S—).)

(In formula (V), R ₈ -R ₉ is hydrogen, halogen, a C ₁ -C ₁₂ alkyl group or a phenyl group.) The black matrix formed with the photosensitive composition for light shielding film formation of any one of Claims 1-5 .

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