JP2018116270A - 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 composition that solves the problem of a lowered margin in a process caused by deteriorated developability and lowered exposure light transmission by black color expression.SOLUTION: The black photosensitive resin composition includes 5-12 functional groups, and is rendered black using a plurality of pigments and monomers having acid values of 10-60 mgKOH/g.SELECTED DRAWING: None

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 black photosensitive resin composition is an essential material such as a color filter, a liquid crystal display material, an organic light emitting device, and a display. As an example, the color filter of a color liquid crystal display enhances display contrast and coloring effect by forming a light shielding layer at the boundary between colored layers such as red, green, and blue. Can do.

  Recently, a technology has been developed that allows one material used in the display to perform various roles at the same time, so that the black photosensitive resin composition can be used to maintain the black matrix and cell gap on the array substrate. The role of forming the spacer is also required, and the demand for the black photosensitive resin composition is further increased.

  Korean Patent No. 2007-0094460 relates to a black photosensitive composition, which is a black photosensitive composition containing a photopolymerizable compound, a photopolymerization initiator and a black pigment, and containing an organic pigment as a shape stabilizer. The content regarding the black photosensitive composition to do is disclosed.

  Korean Patent Laid-Open No. 2012-0033893 relates to a photosensitive resin composition, and includes (A) a binder resin; (B) a polyfunctional monomer; (C) a photopolymerization initiator or a photoincreasing / decreasing agent; (D) black. A pigment; and (E) a solvent, wherein the black pigment discloses contents relating to at least one photosensitive resin composition selected from aniline black, perylene black, and metal oxide.

  However, the black photosensitive resin composition of the above document has a problem that the margin on the process is low due to the limitation of the exposure transmittance due to black expression and the disadvantage to the development process.

  Accordingly, there is a demand for the development of a black photosensitive resin composition having an improved production yield by improving the process margin.

Republic of Korea Public Patent No. 2007-0094460 (2007.2.006.) Republic of Korea Published Patent No. 2012-0033893 (2012.4.009)

  The present invention is for solving the above-described problems, and an object thereof is to provide a black photosensitive resin composition capable of increasing a process margin.

  Another object of the present invention is to provide a black matrix, a column spacer, or a black matrix integrated column spacer manufactured using the black photosensitive resin composition described above.

  In order to achieve the above object, a black photosensitive resin composition according to the present invention comprises a monomer having a functional group of 5 to 12 and an acid value of 10 to 60 mgKOH / g.

  In addition, the present invention provides a black matrix, a column spacer, or a black matrix integrated column spacer containing the cured product of the black photosensitive resin composition described above.

  The black photosensitive resin composition according to the present invention is advantageous in that it contains a specific monomer and is excellent in developability, reliability, or processability, and can improve a process margin.

  Moreover, the black matrix, column spacer, or black matrix integrated column spacer manufactured using the black photosensitive resin composition according to the present invention has an advantage of excellent reliability and easy manufacture.

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

  In the present invention, when one member is positioned “on” another member, this is not only when one member is in contact with the other member, but also when another member is 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 according to the present invention includes a monomer having 5 to 12 functional groups and an acid value of 10 to 60 mgKOH / g.

  The black photosensitive resin composition according to the present invention may further include one or more selected from the group consisting of a colorant containing a black pigment; a binder resin; a photopolymerization initiator; a solvent and an additive.

  One aspect of the present invention relates to a black photosensitive resin composition comprising a monomer having a functional group of 5 to 12 and an acid value of 10 to 60 mgKOH / g.

In the present invention, the “monomer” can be mixed with the “monomer” and can be distinguished from the “oligomer” and the “polymer”.

  The monomer according to the present invention contains 5 to 12 functional groups, preferably 5 to 9 functional groups, more preferably 6 to 8 functional groups, and the functional groups contain unsaturated groups. Alternatively, those having photosensitivity can be used.

  When the monomer according to the present invention includes a functional group within the above range, it can have a higher sensitivity, and therefore, the manufacture of a black matrix, a column spacer, or a black matrix integrated column spacer can be facilitated.

  In one embodiment of the present invention, the monomer may further include a hydroxyl group. Although not wishing to be bound by theory, in the case of a colored photosensitive resin composition for producing a general color filter, if the monomer contains a hydroxyl group, it is advantageous for developability, but reliability and process May negatively impact margins. However, when the monomer contained in the black photosensitive composition according to the present invention contains a hydroxyl group, there is a feature that it is excellent in developability, reliability and processability. Specifically, when a hydroxyl group is contained in the monomer, there is an advantage that the degree of crosslinking can be increased by a crosslinking reaction with a photoinitiator and a binder resin, which will be described later, so that the monomer can be excellent in reliability.

  The monomer according to the present invention may have an acid value of 10 to 60 mgKOH / g, preferably 10 to 50 mgKOH / g, more preferably 20 to 40 mgKOH / g. When the acid value of the monomer is within the above range, there is an advantage that the process margin can be increased. When the acid value of the monomer is less than the above range, there is a problem that developability may be slightly lowered. When the acid value exceeds the above range, the acid value in the monomer becomes excessively high, resulting in a process margin. Therefore, it is preferable to be included within the above range.

  In the present invention, the acid value is a value measured by the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and is usually obtained by titration using an aqueous potassium hydroxide solution. Can do.

  In still another embodiment of the present invention, the functional group may include an ethylenically unsaturated double bond. When the said functional group contains the said ethylenically unsaturated double bond, it reacts with the photopolymerization alkaline resin mentioned later, a crosslinking degree becomes high, and there exists an advantage which is easy to handle on a process.

  In still another embodiment of the present invention, the monomer is 1.7 to 4.2 parts by weight, preferably 1.8 to 4.0 parts by weight, based on 100 parts by weight of the whole black photosensitive resin composition. Preferably it may be contained at 2.0 to 3.8 parts by weight.

  When the monomer is contained within the above range, it is excellent in developability, reliability, or processability, and thus there is an advantage that it is possible to provide a black photosensitive resin composition excellent in process margin. If the monomer is contained in less than the above range, it may be difficult to form a pattern because the developability may be somewhat lowered, and if it exceeds the above range, the developability and processability margin values are somewhat lowered. Since there is possibility, it is preferable that it is contained so that the said range may be satisfied.

  The monomer may be directly synthesized and used, or a commercially available product may be purchased. Examples of the commercially available monomers include, but are not limited to, Osaka Organic Chemical's Viscoat # 802-A, Viscoat # 802-B, Viscoat # 802-C, Viscoat # 802-D, and the like. Those satisfying such monomers can be used.

  In still another embodiment of the present invention, the black photosensitive resin composition may further include one or more selected from the group consisting of a black colorant; a binder resin; a photopolymerization initiator; a solvent and an additive. .

  The black photosensitive resin composition according to the present invention contains a black colorant.

  Yet another embodiment of the present invention relates to a black photosensitive resin composition, wherein the colorant comprises one or more selected from the group consisting of red, blue and black pigments.

  The black (black) pigment can be, for example, aniline black, perylene black, titanium black, or carbon black, and any black pigment can be used without particular limitation as long as it has light shielding properties.

  Carbon black that can be used includes CHBK-17 from Gokoku Dye Co., Ltd. Seest 5HISAF-HS, Seest KH, Seest 3HHAF-HS, Seest NH, Seest 3M, Seest 300HAF-LS, Seest 116HMMAF-HS from Tokai Carbon Co., Ltd. Seast 116MAF, Seast FMFEF-HS, Seast SOFEF, Seast VGPF, Seast SVHSRF-HS, and Seast SSRF; Mitsubishi Chemical Corporation's Diagram Black, 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, Da Agram 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, PR NTEX-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-820, Raven-820 RAVEN-780ULTRA, RAVEN-760U LTRA, Raven-520, Raven-500, Raven-460, Raven-450, Raven-430ULTRA, Raven-420, Raven-410, Raven-2500ULTRA, Raven-2000, Raven-1500, Raven-1255, Raven-1250, Examples include RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170.

  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.

  Further, carbon black that is a black pigment may be carbon black coated with a resin. Since the carbon black coated with the resin has lower conductivity than the carbon black not coated with the resin, excellent electrical insulation can be imparted when forming the black matrix or the black column spacer.

  The colorant may further include one or more selected from the group consisting of organic pigments and dyes. Specifically, the colorant may contain one or more organic pigments and dyes having a light-shielding property for visible light.

  The organic pigment is, for example, a compound classified as a pigment by a color index (CI; issued by The Society of Dyers and Colorists), and specifically, a color index (CI) name as shown below. However, it is not limited to this.

Specifically, the organic pigment is C.I. I. Pigment Yellow No. 1, C.I. I. Pigment Yellow No. 12, C.I. I. Pigment Yellow No. 13, C.I. I. Pigment Yellow No. 14, C.I. I. Pigment Yellow No. 15, C.I. I. Pigment Yellow No. 16, C.I. I. Pigment Yellow No. 17, C.I. I. Pigment Yellow No. 20, C.I. I. Pigment Yellow No. 24, C.I. I. Pigment Yellow No. 31, C.I. I. Pigment Yellow No. 53, C.I. I. Pigment Yellow No. 55, C.I. I. Pigment Yellow No. 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow No. 93, C.I. I. Pigment Yellow No. 94, C.I. I. Pigment Yellow No. 109, C.I. I. Pigment Yellow No. 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow No. 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 137, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow No. 150, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 173, C.I. I. Pigment Yellow No. 180, C.I. I. Pigment Yellow No. 211;
C. I. Pigment Orange No. 5, C.I. I. Pigment Orange No. 13, C.I. I. Pigment Orange No. 14, C.I. I. Pigment Orange 24, C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 40, C.I. I. Pigment Orange 42, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 46, C.I. I. Pigment Orange 49, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 65, C.I. I. Pigment Orange 68, C.I. I. Pigment Orange 70, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 72, C.I. I. Pigment Orange 73, C.I. I. Pigment Orange 74
C. I. Pigment Red No. 1, C.I. I. Pigment Red No. 2, C.I. I. Pigment Red No. 5, C.I. I. Pigment Red No. 9, C.I. I. Pigment Red No. 17, C.I. I. Pigment Red No. 31, C.I. I. Pigment Red No. 32, C.I. I. Pigment Red No. 41, C.I. I. Pigment Red No. 97, C.I. I. Pigment Red No. 105, C.I. I. Pigment Red No. 122, C.I. I. Pigment Red No. 123, C.I. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I. Pigment Red No. 170, C.I. I. Pigment Red 171 C.I. I. Pigment Red 175, C.I. I. Pigment Red 176, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red No. 180, C.I. I. Pigment Red 185, C.I. I. Pigment Red 192, C.I. I. Pigment Red 194, C.I. I. Pigment Red No. 202, C.I. I. Pigment Red 206, C.I. I. Pigment Red 207, C.I. I. Pigment Red No. 208, C.I. I. Pigment Red 209, C.I. I. Pigment Red No. 214, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221; C.I. I. Pigment Red 224, C.I. I. Pigment Red No. 242, C.I. I. Pigment Red 243, C.I. I. Pigment Red 254, C.I. I. Pigment Red No. 255, C.I. I. Pigment Red 262, C.I. I. Pigment Red 264, C.I. I. Pigment Red 265, C.I. I. Pigment Red No. 272;
C. I. Pigment Blue No. 15, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue No. 16, C.I. I. Pigment Blue No. 60, C.I. I. Pigment Blue No. 80;
C. I. Pigment Purple No. 1, C.I. I. Pigment Purple No. 19, C.I. I. Pigment Purple 23, C.I. I pigment purple 29, C.I. I pigment purple No. 32, C.I. I pigment purple No. 36, C.I. I pigment purple 38
C. I. Pigment Green No. 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green No. 58, C.I. I. Pigment Green No. 59, C.I. I. Pigment Green No. 62, C.I. I. Pigment Green No. 63;
C. I. Pigment Brown No. 23, C.I. I. Pigment Brown No. 25;
C. I. Pigment Black No. 1, C.I. I. Pigment Black No. 7 can be used. In some cases, rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, surface graft treatment using a polymer compound, sulfuric acid, etc. It may be one that has been subjected to a fine particle treatment or a cleaning treatment using an organic solvent or water.

  In addition to this, pigments used in printing inks, ink jets and the like, water-soluble azo-based, insoluble azo-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, isoindoline, perylene, perinone, dioxidine, anthraquinone, dianthraquinonyl, Anthrapyrimidine, ansanthrone, indanthrone, flavantron, and pyranthrone pigments may be used, but are not limited thereto.

  Examples of the dye include C.I. I. Solvent Yellow No. 2, C.I. I. Solvent Yellow No. 14, C.I. I. Solvent Yellow 16, C.I. I. Solvent Yellow 33, C.I. I. Solvent Yellow 34, C.I. I. Solvent Yellow 44, C.I. I. Solvent Yellow 56, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow No. 93, C.I. I. Solvent Yellow 94, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow No. 116, C.I. I. Solvent Yellow 135; C.I. I. Solvent Orange No. 1, C.I. I. Solvent Orange No. 3, C.I. I. Solvent Orange No. 7, C.I. I. Solvent Orange No. 63; C.I. I. Solvent Red No. 1, C.I. I. Solvent Red No. 2, C.I. I. Solvent Red No. 3, C.I. I. Solvent Red No. 8, C.I. I. Solvent Red No. 18, C.I. I. Solvent Red No. 23, C.I. I. Solvent Red No. 24, C.I. I. Solvent Red No. 27, C.I. I. Solvent Red No. 35, C.I. I. Solvent Red No. 43, C.I. I. Solvent Red 45, C.I. I. Solvent Red 48, C.I. I. Solvent Red 49, C.I. I. Solvent Red 91: 1, C.I. I. Solvent Red 119, C.I. I. Solvent Red 135, C.I. I. Solvent Red 140, C.I. I. Solvent Red 196, C.I. I. Solvent Red 197; C.I. I. Solvent Purple No. 8, C.I. I. Solvent Purple No. 9, C.I. I. Solvent Purple No. 13, C.I. I. Solvent Purple 26, C.I. I. Solvent Purple 28, C.I. I. Solvent Purple No. 31, C.I. I. Solvent Purple No. 59; C.I. I. Solvent Blue No. 4, C.I. I. Solvent Blue No. 5, C.I. I. Solvent Blue No. 25, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 38, C.I. I. Solvent blue 70; C.I. I. Solvent Green No. 3, C.I. I. Solvent Green No. 5, C.I. I. Solvent green No. 7 etc. are mentioned.

  In still another embodiment of the present invention, the black photosensitive resin composition according to the present invention is selected from the group consisting of red, blue, and black among the colorants described above in order to facilitate black realization. Contains the above colorants.

  In still another embodiment of the present invention, the colorant may include a blue pigment. Specifically, in the present invention, the organic pigment may be a blue pigment.

  When the colorant further contains a blue pigment, the effect on the exposure process can be improved as the transmittance in the near infrared region becomes excellent, and the reliability can be improved by improving the chemical resistance to the organic solvent. .

  The colorant according to the present invention is contained, for example, in an amount of 25 to 55 parts by weight, preferably 27 to 40 parts by weight, more preferably 28 to 33 parts by weight, based on 100 parts by weight of the total solid content of the black photosensitive resin composition. However, it is not limited to this. When the content of the colorant is less than the above range, the optical density (OD) may be somewhat low. When the content exceeds the above range, the relative dielectric constant is slightly high, which may cause a problem in driving the display device. Is likely to occur to some extent, and is preferably included within the above range.

  For example, the black pigment may be included in an amount of 1 to 17 parts by weight, and more preferably 2 to 17 parts by weight, with respect to 100 parts by weight of the entire colorant, but is not limited thereto. When the black pigment satisfies the above range, there is an advantage that the optical density can be excellent. When the black pigment is included below the above range, there may be a problem that the optical density may be slightly reduced. When the black pigment exceeds the above range, the transmittance in the near infrared region is slightly reduced. Since there may be a possible problem, it is preferable that the black pigment is included within the range.

  The black photosensitive resin composition according to the present invention contains a binder resin. The binder resin normally makes the non-exposed portion of the black photosensitive resin layer formed using the black photosensitive resin composition alkali-soluble and acts as a dispersion medium for the pigment. The binder resin is not particularly limited in the present invention, and can be selected from various polymers used in the applicable technical field.

  The weight average molecular weight of the binder resin is preferably 3000 to 30000, more preferably 5000 to 20000, and the acid value of the binder resin has a range of 50 to 200 mgKOH / g based on solid content. It is preferable.

  When the acid value satisfies the above range, developability with respect to alkali development is excellent, generation of residues is suppressed, and pattern adhesion can be improved.

  The binder resin may be included in an amount of 5 to 85 parts by weight, preferably 10 to 80 parts by weight, and more preferably 15 to 75 parts by weight with respect to 100 parts by weight of the total solid content of the black photosensitive resin composition. When the binder resin is included within the above range, the non-pixel portion is difficult to generate a residue on the substrate because the developer is sufficiently soluble, and the pixel portion of the exposed portion is less likely to be reduced during development. For this reason, there is a tendency that the non-pixel portion has a good dropout property.

  As the photopolymerization initiator included in the present invention, those generally used in photosensitive resin compositions can be applied. For example, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, non-imidazole System compounds can be used.

  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, among which 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) butan-1-one can be preferably used.

  Examples of 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 triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 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-methoxy Naphth-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 oxime compounds 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 biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5 ″ -tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4, 4 ', 5,5 "-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5" -tetra (alkoxyphenyl) biimidazole, 2,2'-bis ( 2-chlorophenyl) -4,4 ′, 5,5 ″ -tetra (trialkoxyphenyl) biimidazole, imidazole compounds in which the phenyl group at the 4,4 ′, 5,5 ″ position is substituted with a carboalkoxy group, and the like Is possible.

  The photopolymerization initiator may be used in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the black photosensitive resin composition. Such a content range takes into consideration the photopolymerization rate of the monomer and the physical properties of the finally obtained coating film, and if it is less than the above range, the polymerization rate is low, so the entire process time can be extended, On the other hand, when the above range is exceeded, the crosslinking reaction may occur excessively due to an excessive reaction, and the physical properties of the coating film may be deteriorated.

  In addition, a photopolymerization initiator auxiliary agent can be used together with a photopolymerization initiator. However, when a photopolymerization initiator auxiliary agent is used together with the photopolymerization initiator, the photosensitive resin composition becomes more sensitive and the productivity is improved. Therefore, it is preferable. As the photopolymerization initiation auxiliary agent, one or more compounds selected from the group consisting of amines and carboxylic acid compounds can be preferably used.

  Such a 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, it is possible to increase the polymerization efficiency and expect an improvement in productivity.

  Although the said solvent has compatibility with each structure mentioned above, if it does not react, it can be used without limitation. Various commonly used organic solvents can be used, and the solvent is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C. in terms of coating properties and drying properties.

  For example, the solvent includes alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl. Examples include ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate. These solvents can be used alone or in admixture of two or more.

  The content of the solvent in the black photosensitive resin composition of the present invention is preferably 60 to 90 parts by weight, and 65 to 85 parts by weight with respect to 100 parts by weight of the entire black photosensitive resin composition. It is more preferable. When the content of the solvent is within the above range, the coatability can be improved when coated with a coating apparatus such as a roll coater, spin coater, slit and spin coater, slit coater (also referred to as a die coater), or an ink jet. .

  The black photosensitive resin composition according to the present invention may further include an additive commonly used in the art for enhancing dispersibility, coating property, adhesion, and the like.

  As the dispersant, for example, an appropriate dispersant such as a cation system, an anion system, or a nonionic system can be used, and a polymer dispersant is preferable. Specific examples include acrylic copolymers, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like. Such a dispersant can be obtained commercially. For example, as an acrylic copolymer, DisperBYK-2000, DisperBYK-2001, BYK-LPN6919, BYK-LPN21116 (manufactured by BYK Corporation (BYK)), Solsperse 5000 (manufactured by Lubrizol), polyurethane as DisperBYK-161, DisperBYK-162, DisperBYK-163, DisperBYK-165, DisperBYK-167, DisperBYK-170, DisperBYK-182 (se) 76500 (manufactured by Lubrizol), as polyethyleneimine, Solsperse 24000 (Lubrizo) Company production), as polyester, Ajisupo PB821, Ajisupo PB822, Ajisupo PB880 (Ajinomoto Fine-Techno Co., Ltd. production), and the like.

  The additive may be, for example, a silane coupling agent having a reactive substituent selected from the group consisting of a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof in order to improve adhesion to the substrate. It can include, but is not limited to this. Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycidoxypropyl. Examples include trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. These can be used alone or in combination of two or more, but are not limited thereto.

  In order to improve the coating property, a surfactant can be further added. For example, fluorine-based surfactants such as M-1000, BM-1100 (BM Chemie), Florard FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.) can be used. Without limitation, a surfactant usually used in the art can be used.

  In the present invention, the content of the additive is not limited, and can be appropriately added as long as the object of the present invention is not impaired. For example, the additive may be included in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the entire black photosensitive resin composition, but is not limited thereto.

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

  The black photosensitive resin composition according to the present invention has an advantage of excellent production yield of a black matrix, a column spacer, or a black matrix-integrated column spacer as the margin of the development process and the exposure process increases.

  In the present invention, the black matrix-integrated column spacer means that the black matrix and the column spacer are not formed respectively, but can function as both the black matrix and the column spacer in one pattern.

The black matrix, the column spacer, or the black matrix integrated column spacer can be formed by patterning through a photolithography method after coating, but is not limited thereto. 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 with active light to cure the exposed portion;
d) performing a development process by dissolving an unexposed portion using an aqueous alkali 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, it 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. At this time, the irradiated light can be, for example, visible light, ultraviolet light, X-rays, and electron beams.

  After the exposure, the alkali development is performed for the purpose of removing the photosensitive resin composition in the unexposed portion of the non-exposed portion, and a desired pattern is formed by this development. As a developer suitable for this alkali development, for example, an alkali metal or alkaline earth metal carbonate aqueous solution can be used.

  The post-bake 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.

  The black matrix, column spacer, and black matrix integrated column spacer manufactured using the black photosensitive resin composition according to the present invention can be applied to various image display devices such as liquid crystal displays, OLEDs, and flexible displays. It is.

  Hereinafter, the present specification will be described in detail by way of examples in order to specifically describe the present specification. However, the examples according to the present specification may be modified in various different forms, and the scope of the present specification is not construed to be limited to the examples detailed below. The examples herein are provided in order to more fully describe the present specification to those skilled in the art. In the following, “%” and “parts” representing the contents are based on weight unless otherwise specified.

Synthesis Example: A flask equipped with a binder resin synthesis stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was 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 to change the atmosphere in the flask from air to nitrogen, and then the temperature of the flask was raised to 90 ° C. with stirring. Thereafter, the monomer and the chain transfer agent were dropped from the dropping funnel. The dropping was continued for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature was raised to 110 ° C. and maintained for 5 hours to obtain a resin having a solid content acid value of 100 mgKOH / g.

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

  An HLC-8120GPC (manufactured by Tosoh Corporation) apparatus was used. TSK-GELG4000HXL and TSK-GELG2000HXL columns were used in series, and the column temperature was 40 ° C. Tetrahydrofuran was used as a solvent for the mobile phase, 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, F-1, A-2500, A-500 (manufactured by Tosoh Corp.) was used as a calibration standard, and the alkali-soluble resin obtained under the above conditions was used. The weight average molecular weight and number average molecular weight were measured.

  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.

Production of black photosensitive resin composition: Examples 1-4 and Comparative Examples 1-4
The black photosensitive resin composition which concerns on an Example and a comparative example with the structure and composition by following Table 1 was manufactured.

Experimental example

(1) Fabrication of pattern substrate A 5 cm × 5 cm glass substrate (Corning) was washed with a 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 as to have a final film thickness of 3.0 μm, and pre-baked at 80 to 120 ° C. to 1 to 2 The solvent was removed by drying for a minute. 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, post-baking was performed at 200 to 250 ° C. for 10 to 30 minutes to produce a patterned substrate.

(2) Exposure margin The substrate is manufactured with -10 mJ from the reference exposure, and the substrate is manufactured with +10 mJ from the reference exposure, and the three types of substrates (reference exposure, reference exposure -10 mJ, reference exposure +10 mJ) are used. Table 2 shows the margin results. The line widths of the patterns formed on the three types of manufactured substrates were measured and compared, and the results for the exposure margin in the process margin were confirmed.

  The line width was evaluated after production of the substrate using a line pattern mask. The evaluation proceeded with pattern measurement using SNU SIS-2000.

  Therefore, of the process margins, the exposure margin is evaluated by using the numerical value on the result within the exposure range of 20 mJ. As a result of the evaluation, the range is as follows.

  Excellent ◎ = ± 0.5 or less, Good ○ = ± 1.0 or less, Insufficient △ = ± 1.0 Exceeded

(3) Development margin A substrate was manufactured 10 seconds shorter than the reference development time, and a substrate was manufactured 10 seconds longer than the reference development time, and the characteristics of the three types of substrates were evaluated.

  The line width of the formed pattern was measured, the process margin (exposure margin) was measured, and the line width was evaluated after the substrate was manufactured using a line pattern mask. The evaluation proceeded with pattern measurement using SNU SIS-2000.

  The development margin is evaluated by using the numerical value on the result in the 20-second development process. As a result of the evaluation, the range is as follows.

  Excellent ◎ = ± 1.0 or less, Good ○ = ± 1.5 or less, Insufficiency △ = Over ± 1.5

  Referring to Table 2, the pattern substrate formed using the black photosensitive resin composition according to the present invention has an excellent exposure margin or development margin, but the black photosensitive resin composition according to the comparative example is used. It can be seen that the patterned substrate formed in this manner is not excellent in both exposure margin and development margin.

Claims (10)

Containing 5 to 12 functional groups,
A black photosensitive resin composition comprising: a monomer having an acid value of 10 to 60 mgKOH / g.   The black photosensitive resin composition according to claim 1, wherein the monomer further contains a hydroxyl group.   The black photosensitive resin composition according to claim 1, wherein the monomer contains 6 to 8 functional groups.   The black photosensitive resin composition according to claim 1, wherein the monomer has an acid value of 20 to 40 mg KOH / g.   The black photosensitive resin composition according to claim 1, wherein the functional group contains an ethylenically unsaturated double bond.   The black photosensitive resin composition according to claim 1, wherein the monomer is contained in an amount of 1.7 to 4.2 parts by weight with respect to 100 parts by weight of the entire black photosensitive resin composition.   The black photosensitive resin composition according to claim 1, further comprising at least one selected from the group consisting of a black colorant; a binder resin; a photopolymerization initiator; a solvent and an additive.   The black photosensitive resin composition according to claim 7, wherein the colorant further contains one or more selected from the group consisting of red, blue, and black pigments.   The black photosensitive resin composition according to claim 8, wherein the colorant contains a blue pigment.   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 9.