JP2018084810A - Black photosensitive resin composition, black matrix for image display device produced therefrom, column spacer, and black matrix-integrated column spacer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black photosensitive resin in which the elastic recovery rate is excellent, and an angle created by a column spacer (CS-Angle) is improved, and an image display device prepared therewith.SOLUTION: A black photosensitive resin composition contains a rosin-based resin of 2-10 wt.% in the solid content 100 wt.% of the composition.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a black photosensitive resin composition, a black matrix for an image display device produced therefrom, a column spacer, and a black matrix integrated column spacer.

  The display industry has undergone rapid changes from CRT (Cathode-ray) to flat panel displays such as PDP (Plasma Display Panel), OLED (Organic Light-Emitting Diode), and LCD (Liquid-crystal display). In particular, the LCD is a main product in the flat display market, and is composed of an upper plate provided with a color filter, a lower plate provided with a thin film transistor (TFT), and a liquid crystal injected therebetween.

  The color filter is a core part for expressing colors on the LCD, and has been used in a wide range of applications such as notebook computers, PCs, monitors, and portable terminals with the spread of flat panel displays. Such a color filter implements various colors on the screen through a red (R), green (G), and blue (B) pattern on the substrate, and each red (R), green (G), and blue (B ) A black matrix that is located between patterns to prevent light leakage between pixels, an overcoat (OC) that corrects a step between pixels and improves flatness, and a cell gap between two substrates It is composed of a column spacer (CS; column spacer) that maintains (Cell-gap).

  A color filter is usually manufactured by spin coating a photosensitive resin composition containing a colorant corresponding to each color of red (R), green (G), and blue (B) on a substrate on which a black matrix is patterned. After uniformly coating, the coating film formed by heating and drying is exposed and developed, and the operation of further heating and curing as necessary is repeated for each color to form pixels of each color. At this time, the black matrix (BM) is located at a boundary portion between the colored layers of each color in order to prevent color mixture of other colors in each pixel or to conceal the electrode pattern. Formed with. Also, a black photosensitive resin composition is used to form a column spacer that maintains a cell gap between two substrates.

  Recently, a technology has been developed that allows one material used in the display to perform various roles simultaneously, and a representative example is a black matrix integrated column spacer. In addition, image display devices including a bent surface are being actively developed, and in order to secure a viewing angle, development of a technology for improving the angle (CS-angle) generated by the column spacer is required. It is the actual situation.

  Korean Patent No. 0860432 presents a black photosensitive resin composition for forming a black matrix having high shape stability against heat by including a photopolymerizable compound having a cardo structure, a photopolymerization initiator, and a black pigment. doing. However, the black matrix manufactured with the black photosensitive resin composition has a problem that a column spacer needs to be manufactured separately, and does not recognize the necessity for improving the angle generated by the column spacer.

  Korean Patent Publication No. 2012-0033893 includes one or more black pigments selected from aniline black, perylene black, and metal oxides, thereby preventing drive failure of a liquid crystal display device manufactured using the black pigment. The present invention provides a photosensitive resin composition that can function as a support spacer for maintaining a cell gap as well as a light-shielding film for improvement. However, this also does not recognize the necessity for improving the angle generated by the column spacer.

Korean Registered Patent No. 0860432 (2008.09.19) Republic of Korea Patent No. 2012-0033893 (2012.4.009)

  The present invention is for solving the above-described problems, and has an excellent elastic recovery rate and increases the angle generated by the column spacer to produce a black matrix integrated column spacer with an excellent viewing angle. Therefore, the objective is to provide the black photosensitive resin composition for this.

  Another object of the present invention is to provide a black matrix, a column spacer, or a black matrix integrated column spacer containing a cured product of the black photosensitive resin composition.

  The black photosensitive resin composition of the present invention for achieving the above object contains 2 to 10% by weight of a rosin resin based on 100% by weight of the total solid content of the black photosensitive resin composition. It contains an alkali-soluble resin.

  The black matrix, column spacer or black matrix integrated column spacer of the present invention is characterized by containing a cured product of the black photosensitive resin composition.

  The image display device of the present invention includes one or more selected from the group consisting of the black matrix, the column spacer, and the black matrix integrated column spacer.

  The black photosensitive resin composition of the present invention has an excellent elastic modulus, and can produce a black matrix, a column spacer, or a black matrix integrated column spacer that can improve the angle at which the column spacer formed on the black matrix is generated. There are advantages you can do.

  Further, the black matrix, the column spacer or the black matrix integrated column spacer of the present invention has the same advantages as described above by including the above-described black photosensitive resin composition.

  In addition, the image display device of the present invention has an advantage that the viewing angle is improved by including one or more selected from the group consisting of the black matrix, the column spacer, and the black matrix integrated column spacer described above.

1 is a diagram illustrating a column spacer formed on a black matrix according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in more detail.

  In the present invention, when a certain member is positioned “on” another member, this is not only when the certain member is in contact with the other member, but also when another member is interposed between the two members. Including the case where it exists.

  In the present invention, when a part “includes” a component, this means that it does not exclude other components and can further include other components unless otherwise stated. To do.

<Black photosensitive resin composition>
The black photosensitive resin composition which concerns on 1 aspect of this invention is alkali-soluble resin containing 2-10 weight% rosin-type resin with respect to 100 weight% of whole solid content among the said black photosensitive resin composition. The black matrix, the column spacer or the black which has an excellent elastic recovery rate and can improve the angle (CS-Angle, 30) generated by the column spacer (20) formed on the black matrix (10). There is an advantage that a matrix-integrated column spacer can be manufactured. Further, an improvement in the angle (30) generated by the column spacer (20) has an advantage that an image display device with an improved viewing angle can be manufactured (see FIG. 1).

Alkali-soluble resin The black photosensitive resin composition which concerns on 1 aspect of this invention contains 2-10 weight% rosin resin with respect to 100 weight% of the whole solid content among the said black photosensitive resin composition. Black matrix, column spacer or black matrix which has an excellent elastic recovery rate and can improve the angle (30) generated by the column spacer (20) formed on the black matrix (10) by including an alkali-soluble resin There is an advantage that an integrated column spacer can be manufactured. Further, an improvement in the angle (30) generated by the column spacer has an advantage that an image display device with an improved viewing angle can be manufactured (see FIG. 1).

  The content of the rosin resin contained in the black photosensitive resin composition may be 2 to 10% by weight, preferably 5 to 8% by weight, based on the total solid content of the black photosensitive resin composition. When the rosin resin is less than the above range, the elastic modulus expected by including the rosin resin and the angle (30) generated by the column spacer (20) formed on the black matrix (10) are sufficiently improved. However, when the above range is exceeded, there is a possibility that the developability deteriorates (see FIG. 1).

  As one embodiment of the present invention, examples of the rosin resin include rosins and rosin modified resins. Examples of the rosins include gum rosin, wood rosin, tall oil rosin, disproportionated rosin, polymerized rosin, hydrogenated rosin, and derivatives thereof. The rosin is a natural substance, and there are differences in constituents depending on the place of origin, but generally it is a mixture of abietic acid, neoabietic acid, parastolic acid, levopimaric acid, tehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, etc. In particular, it may be a mixture containing a large amount of abietic acid, neoabietic acid and dihydroxylates thereof. Examples of the rosin-based modified resin include unsaturated organic acid-modified resins of the rosins that can be reactive components of Diels-Alder reaction, specifically, aliphatic unsaturated monobasic acids such as (meth) acrylic acid; fumaric acid , Aliphatic unsaturated dibasic acids such as α, β-unsaturated carboxylic acids such as maleic acid; modified resins such as unsaturated carboxylic acids having an aromatic ring such as cinnamic acid; and abietin such as these modified products One or more selected from the group consisting of acids;

  According to an embodiment of the present invention, the rosin resin may have a weight average molecular weight of 25000 to 35000, preferably 28000 to 32000. When the weight average molecular weight satisfies the above range, there are advantages in processability and pattern formation.

  The acid value of the rosin resin may be 90 to 140, preferably 100 to 120, based on the solid content. At this time, the “acid value” is a value measured by an amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and is related to solubility. When the acid value satisfies the above range, there is an advantage in the development process.

  According to an embodiment of the present invention, the black photosensitive resin composition may further include an alkali-soluble resin other than the rosin resin.

  Alkali-soluble resins other than the rosin-based resin have reactivity and alkali solubility due to the action of light and heat, and act as a dispersion medium for solids including a colorant to perform the function of a binder resin. If it is a thing, the resin well-known in this field | area can be selected and used without a restriction | limiting in particular.

  Specifically, the alkali-soluble resin may be a copolymer of an unsaturated carboxy group-containing monomer and another monomer copolymerizable therewith.

  Examples of the unsaturated carboxy group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated carboxylic acids having one or more carboxy groups in the molecule, such as unsaturated tricarboxylic acids. It is done.

  Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.

  Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

  The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples include maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as oxalic acid mono (2-acryloyloxyethyl), oxalic acid mono (2-methacryloyloxyethyl), phthalate, and the like. It may be acid mono (2-acryloyloxyethyl), phthalate mono (2-methacryloyloxyethyl), or the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.

  The carboxy group-containing monomers can be used alone or in admixture of two or more.

  Examples of other monomers copolymerizable with the carboxy group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propiyl Methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl Methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate , Allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol Acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, Sobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate Unsaturated carboxylic acid esters such as: 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl Unsaturated carboxylic acid aminoalkyl esters such as tacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate: Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate: vinyl acetate, vinyl propionate and vinyl butyrate Carboxylic acid vinyl esters such as vinyl benzoate: Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether: Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide Acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylate Unsaturated amides such as maleimide, unsaturated imides such as N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene: and polystyrene, polymethyl acrylate, Examples thereof include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, or polysiloxane. These monomers can be used alone or in admixture of two or more.

  In particular, according to an embodiment of the present invention, the alkali-soluble resin other than the rosin resin has an epoxy group in that the elastic recovery rate of the black matrix, the column spacer, or the black matrix integrated column spacer containing the resin is improved. It is preferable to use a compound containing an unsaturated bond.

  The alkali-soluble resin other than the rosin resin may have a weight average molecular weight of 3,000 to 30,000, preferably 5,000 to 20,000. When the weight average molecular weight of the alkali-soluble resin other than the rosin resin is included in the above range, not only the hardness and the remaining film ratio are improved, but also the solubility of the non-exposed portion in the developer is excellent, and the resolution There is an advantage that can be improved.

  The acid value of the alkali-soluble resin other than the rosin resin may be 50 to 200 mgKOH / g based on the solid content. When the acid value of the alkali-soluble resin other than the rosin resin is less than the above range, it is difficult to ensure a sufficient development speed. When the acid value exceeds the above range, the adhesion decreases and the pattern short circuit easily occurs. However, there is a possibility that the storage stability of the whole composition is lowered and the viscosity is increased.

  According to other embodiment of this invention, the total alkali-soluble resin contained in the black photosensitive resin composition of this invention is 5-5 with respect to the total solid content among the black photosensitive resin compositions containing this. It may be included at 85 wt%, preferably 10-80 wt%, more preferably 15-70 wt%. When the alkali-soluble resin is contained within the above range, the solubility in the developer is sufficient and pattern formation is facilitated, and the reduction of the pixel portion of the exposed portion during development is prevented, and the non-pixel portion is removed. There is an advantage that the property is good.

  The black photosensitive resin composition according to an embodiment of the present invention is one or more selected from the group consisting of a colorant, a photopolymerizable compound, a photopolymerization initiator, a solvent and an additive in addition to the alkali-soluble resin described above. Can further be included.

Colorant The black photosensitive resin composition according to an embodiment of the present invention may further include a colorant.

  The colorant provides light shielding properties to prevent light leakage from the black matrix, and the column spacer serves to prevent malfunction of the device due to light caused from the outside.

  The colorant is not particularly limited as long as it has a light-shielding property for visible light. Specifically, one or more selected from the group consisting of organic pigments, dyes, and black pigments can be used.

  Specifically, the organic pigment may be a compound classified by pigment according to a color index (published by The Society of Dyers and Colorists), and more specifically, the following color index (C.I. I.) Names can be used.

  C. I. Pigment Yellow 1, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 155, 166, 168, 173, 180, 211, etc .;

  C. I. Pigment Orange 5, 13, 14, 24, 31, 34, 36, 38, 40, 42, 43, 46, 49, 51, 55, 59, 61, 64, 65, 68, 70, 71, 72, 73 74 etc .;

  C. I. Pigment Red 1, 2, 5, 9, 17, 31, 32, 41, 97, 105, 122, 123, 144, 149, 166, 168, 170, 171, 175, 176, 177, 178, 179, 180, 185, 192, 194, 202, 206, 207, 208, 209, 214, 215, 216, 220, 221, 224, 242, 243, 254, 255, 262, 264, 265, 272, etc .;

  C. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 16, 60, 80, etc .;

  C. I. Pigment violet 1, 19, 29, 32, 36, 38, etc .;

  C. I. Pigment green 7, 36, 58, 59, 62, 63, etc .;

  C. I. Pigment brown 23, 25, etc .;

  C. I. Pigment Black 1, 7, etc.

  The pigments can be used alone or in admixture of two or more.

  The organic pigments described above are optionally rosin-treated, surface treatment using a pigment derivative having an acidic group or basic group introduced, surface graft treatment using a polymer compound, etc., fine particle formation treatment using sulfuric acid, Alternatively, it may have been washed using an organic solvent or water.

  In addition, pigments used in printing ink, ink jet, etc., and water-soluble azo, insoluble azo, phthalocyanine, quinacridone, isoindolinone, isoindoline, perylene, perinone, dioxidine, anthraquinone, dianthraquinonyl, anthrapyrimidine, Antantron, indanthrone, flavantron, and pyrantron pigments may be used.

  The black pigment may be aniline black, perylene black, titanium black, or carbon black, and any black pigment can be used without particular limitation.

  The carbon black is not particularly limited as long as it is a light-shielding pigment, and known carbon black can be used. Specific examples of the carbon black as the black pigment include channel black, furnace black, thermal black, lamp black, and the like.

  In addition, carbon black that is a black pigment may be carbon black coated with a resin. The carbon black coated with the resin has a lower conductivity than the carbon black not coated with the resin, and therefore, it is preferable because excellent electrical insulation can be imparted when forming the black matrix or the black column spacer.

  Specific examples of commercially available carbon black include CHBK-17 from Gokoku Dye Co., Ltd .; cyst 5HIISAF-HS, cyst KH, cyst 3HHAF-HS, cyst NH, cyst 3M, cyst 300HAF- from Tokai Carbon Co., Ltd. LS, cyst 116HMMAF-HS, cyst 116MAF, cyst FMFEF-HS, cyst SOFEF, cyst VGPF, cyst SVHSRF-HS, and cyst SSRF; Mitsubishi Chemical Corporation Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, # 25, # CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; Degussa Corporation's PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V , PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTE -30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; Columbia Carbon Co., Ltd. RAVEN-1100ULTRA, RAVEN-1080ULTRA , RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820V, Raven-790V -780ULTRA, RAVEN-760ULTRA RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN- 1200, RAVEN-1190ULTRA, RAVEN-1170, and the like, but are not limited thereto.

Specifically, the dye is
C. I. Solvent Yellow 2, 14, 16, 33, 34, 44, 56, 82, 93, 94, 98, 116, 135, etc .;
C. I. Solvent orange 1, 3, 7, 63, etc .;
C. I. Solvent Red 1, 2, 3, 8, 18, 23, 24, 27, 35, 43, 45, 48, 49, 91: 1, 119, 135, 140, 196, 197, etc .;
C. I. Solvent violet 8, 9, 13, 26, 28, 31, 59, etc .;
C. I. Solvent Blue 4, 5, 25, 35, 36, 38, 70 etc .;
C. I. Solvent Green 3, 5, 7, etc .; ur can be raised, but is not limited to this.

  According to an embodiment of the present invention, it is preferable to include one or more colorants selected from the group consisting of red, blue, and black among the colorants described above in order to facilitate the realization of black.

  The colorant may be contained in an amount of 25 to 55% by weight, preferably 25 to 45% by weight, based on 100% by weight of the total solid content of the black photosensitive resin composition. If the colorant is included below the range, the optical density may be low, and if it exceeds the range, the relative permittivity may be excessively high, which may cause a problem in driving when the image display apparatus is introduced. is there.

  The above-mentioned colorant can be used together with a dispersant and a dispersion aid as necessary.

  As the dispersant, for example, a suitable dispersant such as a cation system, an anion system, or a nonionic system can be used. Specifically, an acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like. Is mentioned.

  The dispersant can be used by purchasing a commercially available product. For example, as an acrylic copolymer, DisperBYK-2000, DisperBYK-2001, BYK-LPN6919, BYK-LPN21116 (manufactured by BYK Corporation), Solperse 5000 (manufactured by Lubrizol), and as a polyurethane, DisperBYK-161, DisperBYK-162, DisperBYK-163, DisperBYK-165, DisperBYK-167, DisperBYK-170, DisperBYK-182 (above, Bicchemy by SE, 76, BK Sp.) (Manufactured by Lubrizol), Solperse 24000 (Lubrizol) as polyethyleneimine Concrete), as the polyester, Ajisupo PB821, Ajisupo PB822, Ajisupo PB880 (azide under Fine-Techno Co., Ltd. production), and the like.

  Examples of the dispersion aid include pigment derivatives, specifically copper phthalocyanine, diketopyrrolopyrrole, sulfonic acid derivatives of quinophthalone, and the like, each of which is used alone or in combination of two or more. be able to.

  The content of the dispersant is usually 100 parts by weight or less, preferably 1 to 70 parts by weight, and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the colorant. When the content of the dispersant exceeds the above range, problems such as deterioration in developability may occur.

Photopolymerizable Compound The black photosensitive resin composition according to an embodiment of the present invention may further include a photopolymerizable compound.

  The photopolymerizable compound is a substance that polymerizes and cures upon irradiation with light such as ultraviolet rays, and can be used without particular limitation as long as it is a compound that can be polymerized by the action of a photopolymerization initiator. The photopolymerizable compound is a component for enhancing the strength of the pattern, and a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher polyfunctional monomer can be used.

  Specific examples of the monofunctional monomer include acrylate, methacrylate, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N- Vinylpyrrolidone etc. are mentioned, As a commercial item, Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku) or Biscote 158 (Osaka organic chemical industry) etc. are mentioned.

  Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth). Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like, and commercially available products are Aronics M-210, M-1100, 1200 (Toagosei), KAYARAD HDDA ( Nippon Kayaku), Biscoat 260 (Osaka Organic Chemical Industry), AH-600, AT-600 or UA-306H (Kyoeisha Chemical Co., Ltd.).

  Specific examples of the trifunctional or higher polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylate trimethylolpropane tri (meth) acrylate, propoxylate trimethylolpropane tri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylate dipentaerythritol hexa (meth) acrylate, propoxylate dipentaerythritol hexa (meth) acrylate, Dipentaerythritol hexa (meth) acrylate and the like, and commercially available products are Aronics M-309, TO-1382 (Toagosei), KAYARAD TMPTA, AYARAD DPHA or KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) and the like.

  The photopolymerizable compounds can be used alone or in admixture of two or more. Among the photopolymerizable compounds, trifunctional or higher functional (meth) acrylates and urethane (meth) acrylates are polymerizable. Is particularly preferable in that it is excellent and the strength can be improved.

  The content of the photopolymerizable compound may be 0.1 to 40% by weight, preferably 1 to 20% by weight, based on 100% by weight of the entire black photosensitive resin composition. The content range is a range selected in consideration of the tendency to improve the strength and smoothness of black matrix, column spacer or black matrix integrated column spacer, and the content of the photopolymerizable compound If the thickness is less than the above range, strength and smoothness are insufficient, and if it exceeds the above range, there is a possibility that patterning may not be easy due to high strength.

Photopolymerization initiator The black photosensitive resin composition according to another embodiment of the present invention may further include a photopolymerization initiator.

  The photopolymerization initiator is a compound for initiating the polymerization of the photopolymerizable compound described above, and is not particularly limited in the present invention, but is not limited to acetophenone, benzophenone, triazine, thioxanthone, oxime, benzoin. It may be one or more selected from the group consisting of a series, anthracene series, anthraquinone series and non-imidazole series compounds.

  The acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2. -Methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, oligomers of 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propan-1-one, etc. are possible, of which 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) butan-1-one is preferably usable .

  Examples of the benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino). ) Benzophenone and the like are possible.

  Examples of the triazine compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (4′-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-me Xylnaphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6 Triazines are possible.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  Examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and OXE-01 and OXE-02 manufactured by Ciba are representative.

  As the benzoin compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, or the like can be used.

  Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

  Examples of the anthraquinone compound include 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone.

  Examples of the non-imidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl nonimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenyl non-imidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) non-imidazole, 2,2′-bis (2-Chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) non-imidazole, imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group, etc. Is possible.

  The photopolymerization initiator may be contained in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on 100% by weight of the entire black photosensitive resin composition. The content range is based on the photopolymerization rate of the photopolymerizable compound and the physical properties of the finally obtained coating film. If the content range is less than the above range, the overall process time can be increased because the polymerization rate is low. When the range is exceeded, an excessive reaction may cause an excessive crosslinking reaction, which may cause a problem that the physical properties of the coating film deteriorate.

  The photopolymerization initiator may be used in combination with a photopolymerization initiation auxiliary agent. If a photopolymerization initiator auxiliary agent is used in combination with the photopolymerization initiator, the black photosensitive resin composition containing them becomes even more sensitive, and is produced when a column spacer for maintaining a cell gap is formed using this composition. There is an advantage of improving the performance.

  The photopolymerization initiation auxiliary agent can be used to increase the polymerization efficiency, and specifically includes an amine compound, an alkoxyanthracene compound, and a thioxanthone compound.

  Examples of the amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. 2-dimethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4 Examples include '-bis (ethylmethylamino) benzophenone, and among these, 4,4'-bis (diethylamino) benzophenone is preferable.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. It is done.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  The photopolymerization initiation auxiliary agent can be produced directly or purchased commercially, and as an example, EAB-F series (Hodogaya Chemical Co., Ltd.) or the like can be used.

  The photopolymerization initiation auxiliary agent is usually used in an amount of usually 10 mol or less, preferably 0.01 to 5 mol per mol of the photopolymerization initiator. When the photopolymerization initiation auxiliary is used within the above range, there is an advantage that the polymerization efficiency is increased and the productivity is improved.

Solvent The black photosensitive resin composition according to an embodiment of the present invention may further contain a solvent.

  The said solvent will not be specifically limited if the other component contained in the black photosensitive resin composition mentioned above can be melt | dissolved or disperse | distributed.

  Specific examples include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters. More specifically, as the solvent, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Diethylene glycol dialkyl ethers such as ether and diethylene glycol dibutyl ether: methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate And alkylene glycol alkyl ether acetates such as methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone: ethanol, propanol, Examples include alcohols such as butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate: cyclic esters such as γ-butyrolactone, and the like.

  Of the above solvents, organic solvents having a boiling point of 100 to 200 ° C. can be preferably used in terms of coating properties and drying properties, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropion. And esters such as ethyl acrylate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. Is mentioned.

  These solvents can be used alone or in admixture of two or more.

  The content of the solvent is not particularly limited, but may be 20 to 85% by weight, preferably 30 to 80% by weight with respect to 100% by weight of the entire black photosensitive resin composition. When the content of the solvent is within the above range, there is an advantage that the coating property is good.

Additives The black photosensitive resin composition according to an embodiment of the present invention includes an adhesion promoter, a surfactant, a dispersant, an antioxidant, an ultraviolet absorber, and thermal polymerization prevention as necessary in addition to the components described above. One or more additives selected from the group consisting of an agent and a leveling agent may be further included.

  The adhesion promoter is selected from the group consisting of methacryloylsilane coupling agents such as methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyldimethoxysilane, methacryloyloxypropyltriethoxysilane, and methacryloyloxypropyldimethoxysilane. One or more selected from the group consisting of octyltrimethoxysilane, dodecyltrimethoxysilane, and octadecyltrimethoxysilane can also be used as the alkyltrimethoxysilane.

  As the surfactant, MCF 350SF, F-475, F-488, F-552 (manufactured by DIC) and the like can be used, but are not limited to these, and the range thereof may be further increased depending on circumstances. Can be enlarged.

  As the dispersant and leveling agent, all those commonly used in the industry can be used.

  As the antioxidant, 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-g, t-butylphenol and the like can be used, and as the ultraviolet absorber, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benztriazole, alkoxybenzophenone, and the like can be used. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol). 2,2-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptoimidazole, and the like can be used.

<Black matrix, column spacer, black matrix integrated column spacer>
Another aspect of the present invention is a black matrix, a column spacer or a black matrix integrated column spacer containing a cured product of the black photosensitive resin composition of the present invention.

  The black photosensitive resin composition of the present invention has an advantage that a black matrix, a column spacer, or a black matrix integrated column spacer can be manufactured by basically having an optical density, a light shielding property and an insulating property.

  In particular, a black matrix, a column spacer, or a black matrix-integrated column spacer containing a cured product of the black photosensitive resin composition of the present invention has an excellent elastic recovery rate, and therefore has little deformation due to external pressure and has flexibility. Since the angle (30) generated when forming the column spacer (20) on the black matrix (10) is improved, there is an advantage that the viewing angle is improved when this is applied to an image display device (FIG. 1). reference).

  At this time, the black matrix-integrated column spacer means that the black matrix and the column spacer are not formed separately, but can perform all the functions of the black matrix and the column spacer in one pattern.

  The elastic recovery rate of the black matrix, the column spacer, or the black matrix integrated column spacer according to an embodiment of the present invention may be 85% or more. At this time, the elastic recovery rate is for minimizing deformation due to external pressure, and a larger value is preferable.

  The black matrix (10), the column spacer (20), or the black matrix-integrated column spacer according to an embodiment of the present invention has an angle (30) generated when the column spacer (20) is formed on the black matrix (10). ) May be 20 ° or more. The angle (30) generated by the column spacer (20) formed on the black matrix (10) is for improving the viewing angle of the image display device including the column spacer (20), and the larger the angle, the better (see FIG. 1).

The black matrix can be introduced by patterning through a photolithography method after coating. The photolithography method is not particularly limited in the present invention, and any known method using a photosensitive resin composition can be applied. An example can include the following steps:
a) applying a black photosensitive resin composition to the substrate;
b) a pre-bake step of drying the solvent;
c) A step of applying a photomask on the obtained film and irradiating actinic rays to cure the exposed portion;
d) performing a development process by dissolving an unexposed portion using an alkaline aqueous solution; and e) performing a drying and post-baking process.

  As the substrate, a glass substrate or a polymer plate is used. As the glass substrate, soda lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, or quartz can be preferably used. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

  At this time, the coating can be performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), and an ink jet so as to obtain a desired thickness. .

  The pre-baking is performed by heating with an oven, a hot plate or the like. At this time, the heating temperature and heating time in the pre-baking are appropriately selected depending on the solvent used, and for example, the heating is performed at a temperature of 80 to 150 ° C. for 1 to 30 minutes.

  In addition, the exposure performed after pre-baking is performed by an exposure machine and exposed through a photomask so that only a portion corresponding to the pattern is exposed. The light irradiated at this time can be, for example, visible light, ultraviolet light, X-rays, and electron beams.

  This is performed for the purpose of removing the photosensitive resin composition in the unexposed portion of the alkali-development non-exposed portion after exposure, and a desired pattern is formed by this development. As the developer suitable for the alkali development, for example, an alkali metal or alkaline earth metal carbonate aqueous solution can be used. In particular, using an aqueous alkaline solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate, or lithium carbonate, a developing machine or ultrasonic cleaning at a temperature of 10 to 50 ° C., preferably 20 to 40 ° C. We perform using machine.

  The post-baking is performed to improve the adhesion between the patterned film and the substrate, and is performed through heat treatment at 80 to 220 ° C. for 10 to 120 minutes. Post bake is performed using an oven, a hot plate, and the like in the same manner as pre-bake.

<Image display device>
Still another aspect of the present invention is an image display device including one or more selected from the group consisting of the above-described black matrix, column spacer, and black matrix integrated column spacer, specifically a liquid crystal display, OLED And flexible displays.

  An image comprising at least one selected from the group consisting of a black matrix (10), a column spacer (20), and a black matrix integrated column spacer manufactured using a cured product of the black photosensitive resin composition of the present invention. The display device has an advantage that the viewing angle is improved by improving the angle (30) generated by the column spacer (20) formed on the black matrix (10). In particular, there is a favorable advantage when applied to an image display device including a bent surface that requires an improved viewing angle as compared to a flat image display device (see FIG. 1).

  Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described later. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. In the following, “%” and “parts” representing the contents are based on weight unless otherwise specified.

Production Example: An alkali-soluble resin (A2) synthesis stirrer, a thermometer reflux condenser, a dropping funnel, and a flask equipped with a nitrogen inlet were prepared. 40 weight of a mixture prepared by mixing 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meth) acrylate at a molar ratio of 50:50 as a monomer dropping funnel Parts, methyl methacrylate 50 parts by weight, acrylic acid 40 parts by weight, vinyl toluene 70 parts by weight, t-butylperoxy-2-ethylhexanoate 4 parts by weight, propylene glycol monomethyl ether acetate (PGMEA) 40 parts by weight Was added to prepare stirring. As a chain transfer agent dropping tank, 6 parts by weight of n-todecanethiol and 24 parts by weight of PGMEA were added to prepare stirring. Thereafter, 395 parts by weight of PGMEA was added to the flask, and the atmosphere in the flask was changed from air to nitrogen, followed by stirring to raise the temperature of the flask to 90 ° C. Thereafter, dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dropwise addition is maintained at 90 ° C., and proceeds for 2 hours each. After 1 hour, the temperature is increased to 110 ° C. and maintained for 5 hours, and the acid value of the solid content is 100 mg KOH / g (A2) Got.

  The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alkali-soluble resin (A2) were measured by the GPC method under the following conditions.

  An HLC-8120GPC (manufactured by Tosoh Corporation) apparatus was used. TSK-GELG4000HXL and TSK-GEL2000HXL columns were used in series, and the column temperature was 40 ° C. Tetrahydrofuran was used as a solvent for the moving bed, and measurement was performed while flowing at a flow rate of 1.0 mL / min. The concentration of the measurement sample was 0.6% by weight, the injection volume was 50 μL, and analysis was performed using an RI detector. TSK STANDARD POLYSTYRENE F-40, F-4, A-2500, A-500 (manufactured by Tosoh Corporation) was used as the calibration standard substance, and the weight-average molecular weight of the alkali-soluble resin (A2) and The number average molecular weight was measured. At this time, the weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw / Mn) was 2.3.

Examples 1-3 and Comparative Examples 1-4
A black photosensitive resin composition was produced with the composition shown in Table 1 below.

Experimental Examples 1-2

Experimental Example 1: Measurement of angle (CS-Angle) generated by column spacer 5 × 5 cm glass substrate (manufactured by Corning) was washed with neutral detergent and water and then dried. Each of the black photosensitive resin compositions produced in the examples and comparative examples was spin-coated on the glass substrate so that the final film thickness was 3.0 μm, and pre-baked at 80 to 120 ° C. Dry for ~ 2 minutes to remove solvent. Then, it exposed with the exposure amount of 40-100 mJ / cm < ² >, the pattern was formed, and the non-exposed part was removed using alkaline aqueous solution. Subsequently, main baking was carried out at 200 to 250 ° C. for 10 to 30 minutes to produce a black matrix integrated column spacer pattern.

  The angle (CS-Angle, 30) which a column spacer produces | generates using the SNU (SIS-1200, manufacture by SNU precision company) for the pattern on the produced said board | substrate was measured. The measurement site is shown in FIG. 1, and the results are shown in Table 2 below.

Experimental Example 2: Elastic Modulus Measurement A black matrix integrated column spacer pattern was manufactured in the same manner as in Experimental Example 1.

  Using the Fisher hardness meter (Fischerscope H100C, manufactured by Helmut-Fisher), press the manufactured pattern to 50 mN at a speed of 3.3 mN / sec, then check the amount of displacement to recover and calculate the elastic modulus. The results are shown in Table 2 below.

  Referring to Table 2, in the case of a black matrix-integrated column spacer manufactured using the black photosensitive resin composition containing the rosin resin of the present invention (Examples 1 to 3), the column spacer is generated. When using the black photosensitive resin composition which has an angle (CS-angle) of 20 ° or more and an elastic modulus of 85% or more and does not contain the rosin resin of the present invention (Comparative Examples 1 and 2) Even if it contains, it can confirm that it is more excellent than the case where the content remove | deviates from the content range shown by this invention (Comparative Examples 3-4).

10: Black matrix 20: Column spacer 30: Angle generated by the column spacer (CS-Angle)

Claims (12)

In the black photosensitive resin composition containing the alkali-soluble resin,
The alkali-soluble resin contains 2 to 10% by weight of a rosin resin based on 100% by weight of the total solid content of the black photosensitive resin composition containing the alkali-soluble resin. .   The black photosensitive resin composition further includes one or more selected from the group consisting of alkali-soluble resins other than the rosin resin, colorants, photopolymerizable compounds, photopolymerization initiators, solvents, and additives. The black photosensitive resin composition according to claim 1, wherein:   The black photosensitive resin composition according to claim 2, wherein the alkali-soluble resin other than the rosin resin contains an epoxy group and has no unsaturated bond.   The black photosensitive resin composition according to claim 1, wherein the rosin resin is a rosin or a rosin modified resin.   2. The black photosensitive resin composition according to claim 1, wherein the rosin resin has a weight average molecular weight of 25,000 to 35,000.   2. The black photosensitive resin composition according to claim 1, wherein the rosin resin has an acid value of 90 to 140 mg KOH / g based on a solid content.   The total alkali-soluble resin contained in the black photosensitive resin composition is contained in an amount of 5 to 85% by weight based on the total solid content of the black photosensitive resin composition. Black photosensitive resin composition.   The black photosensitive resin composition according to claim 2, wherein the colorant includes one or more selected from the group consisting of red, blue, and black.   A black matrix, a column spacer, or a black matrix-integrated column spacer, comprising a cured product of the black photosensitive resin composition according to any one of claims 1 to 8.   The black matrix, column spacer, or black matrix integrated column spacer according to claim 9, wherein the black matrix, column spacer, or black matrix integrated column spacer has an elastic recovery rate of 85% or more.   The black matrix, the column spacer, or the black matrix-integrated column spacer according to claim 9, wherein an angle (CS-Angle) generated by the column spacer formed on the black matrix is 20 ° or more.   An image display device comprising at least one selected from the group consisting of a black matrix, a column spacer and a black matrix integrated column spacer according to claim 9.