Photosensitive resin composition for black light spacer

Abstract

The photosensitive resin composition for a black light spacer includes: a binder resin including a cardo-based polymer resin and a (meth) acrylic polymer resin, the cardo-based polymer resin including a repeating unit; an acrylic polyfunctional monomer having different acrylics having two or more functional groups; a colorant; a photoinitiator which is at least one type selected from the group consisting of an O-acyl oxime-based photoinitiator, an acetophenone-based photoinitiator, and a benzophenone-based photoinitiator; the additive comprises at least one of a silane coupling agent, a leveling agent, a thermal polymerization inhibitor and a sensitizer; and a solvent.

Description

Technical Field

[0001] Embodiments of the present invention relate to a photosensitive resin composition for a black photo spacer. More specifically, embodiments of the present invention relate to a photosensitive resin composition for a black photo spacer having improved light shielding property, straightness, surface state, and relatively excellent curing degree. Background Art

[0002] A liquid crystal display apparatus (LCD) generally has a COT (Color Filter on TFT Array) structure.

[0003] The COT structure includes a thin film transistor substrate (TFT substrate), a color filter film arranged on the TFT substrate, and an upper plate covering the color filter film.

[0004] A black photo spacer (hereinafter referred to as "BPS") is formed between the upper plate and the color filter film to suppress light leakage from the outer frame or the frame portion equivalent to the edge surrounding the display screen and maintain the gap between the upper and lower substrates, thereby improving the aperture ratio.

[0005] The BPS simultaneously performs the functions of a black matrix (BM) isolating adjacent pixels from each other and a photo spacer (PS) maintaining a gap between upper and lower substrates. Therefore, the BPS must simultaneously satisfy the functions of the BM and the PS.

[0006] That is, BPS needs to satisfy not only the optical density (OD) characteristic as the required characteristic value of the black matrix (BM), but also the step difference achieved by the characteristic value Dual PS of the photo spacer (PS). Therefore, compared with the gap photo spacer (Gap PS) formed by the full tone (Full Tone) in the past, the film characteristics of the touch photo spacer (PS) formed by the half tone (Half Tone) may be reduced. Therefore, there is usually a problem of reduced adhesion to the substrate such as pattern loss and PS cracking.

[0007] Therefore, it is necessary to develop a new photosensitive material that satisfies both BM and PS characteristics and can suppress pattern bleeding and PS fragmentation phenomena when forming black photo spacers (BPS). Summary of the invention

[0008] Technical issues

[0009] Embodiments of the present invention provide a photosensitive resin composition for black photo-spacers, which has excellent development adhesion to a substrate and can suppress pattern cracking.

[0010] Technical Solution

[0011] The photosensitive resin composition for black photo spacers according to an embodiment of the present invention comprises: a binder resin including a cardo polymer resin and a (meth) acrylic polymer resin, wherein the cardo polymer resin comprises a repeating unit of the following chemical formula 1; an acrylic multifunctional monomer having different difunctional or higher acrylic acid esters; a colorant; a photoinitiator selected from at least one of a photoinitiator group including an O-acyl oxime photoinitiator, an acetophenone photoinitiator and a benzophenone photoinitiator; an additive including at least one of a silane coupling agent, a leveler, a thermal polymerization inhibitor and a sensitizer; and a solvent.

[0012] [Chemical formula 1]

[0013]

[0014] wherein n is an integer from 1 to 1000, * is a bonding point, R1 to R8 are hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms, and R9 to R 14 are hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms, respectively, and X is a substituent represented by the following Chemical Formula 1-1.

[0015] [Chemical formula 1-1]

[0016]

[0017] In one embodiment of the present invention, the cardo-based polymer resin may be in the range of 10 to 100 wt % with respect to 100 parts by weight of the (meth)acrylic copolymer resin.

[0018] In one embodiment of the present invention, the (meth)acrylic copolymer resin may include a copolymer represented by the following Chemical Formula 2.

[0019] [Chemical formula 2]

[0020]

[0021] In the chemical formula 2, j, k, l, m, and n are integers of 1 to 90, R1, R2, R3, R4, R5, and R7 are hydrogen or selected from the group consisting of methyl and hydroxymethyl, R6 is hydrogen or a group forming a carboxylic anhydride or amide structure, X is methyl or cyclohexyl, Y is selected from the group consisting of an alkyl ester having 1 to 12 carbon atoms, an alkyl ester having 2 to 6 carbon atoms substituted with 1 to 2 hydroxyl groups, an alkoxy polyalkylene having 1 to 3 carbon atoms, a glycol ester having 2 to 3 carbon atoms, and an alkyl ester group having 1 to 6 carbon atoms substituted with a phenyl group, and the symbol * is a bonding point.

[0022] In one embodiment of the present invention, the cardo-based polymer resin may have a weight average molecular weight (Mw) ranging from 1,000 to 50,000 g / mol.

[0023] In one embodiment of the present invention, the (meth)acrylic copolymer resin may have a weight average molecular weight (Mw) ranging from 1,000 to 100,000 g / mol.

[0024] In one embodiment of the present invention, the acrylic multifunctional monomer may be in the range of 50 to 150 wt % with respect to 100 parts by weight of the (meth)acrylic polymer resin.

[0025] In one embodiment of the present invention, for 100 parts by weight of the (meth)acrylic polymer resin, the photoinitiator may include 0.1 to 5.0 weight % of an O-acyl oxime photoinitiator and 0.1 to 10 weight % of at least one of an acetophenone photoinitiator and a benzophenone photoinitiator.

[0026] In one embodiment of the present invention, the colorant may include a coloring dispersion in which a black pigment and a coloring pigment are mixed and dispersed.

[0027] In one embodiment of the present invention, the (meth)acrylic polymer resin may further include 0.1 to 10% by weight of an epoxy curing agent based on 100 parts by weight of the (meth)acrylic polymer resin.

[0028] In one embodiment of the present invention, 0.1 to 10 wt % of a curing accelerator may be further included with respect to 100 parts by weight of the (meth)acrylic polymer resin.

[0029] Technical Effects

[0030] The photosensitive resin composition for black photo-spacers according to an embodiment of the present invention has relatively high development adhesion to a substrate and can prevent a pattern fragmentation phenomenon. DETAILED DESCRIPTION

[0031] The embodiments of the present invention are described in detail below. However, the present invention is not necessarily constituted as defined in the embodiments described below, but can be embodied in various different ways. The following embodiments are not provided to fully complete the present invention, but are provided to fully convey the scope of the present invention to ordinary technicians in the technical field to which the present invention belongs.

[0032] In embodiments of the present invention, when describing that an element is configured or connected to another element, the element may be directly configured or connected to the other element, and other elements may be arranged between them. In contrast, when describing that an element is directly configured or connected to another element, other elements may not exist between them. Terms such as first, second, and third may be used to describe various items such as various elements, components, fields, layers, and / or parts, but the items are not limited to these terms.

[0033] The professional terms used in the embodiments of the present invention are only used to illustrate specific embodiments, and are not used to limit the present invention. In addition, unless otherwise specified, all terms, including technical and scientific terms, have the same meaning as those understood by ordinary technicians in the technical field to which the present invention belongs. Regarding terms such as those defined in common dictionaries, they should be interpreted as meanings consistent with the meanings in the context of the description of the relevant technology and the present invention, and unless clearly defined, they will not be interpreted with ideal or excessive appearance intuition.

[0034] [A] Cardo polymer resin

[0035] The cardo-based polymer resin may be represented by the following Chemical Formula 1.

[0036] [Chemical formula 1]

[0037]

[0038] Where n is an integer from 1 to 1000, * is the binding point,

[0039] R1 to R8 are independently hydrogen, halogen, alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms, or cycloalkyl having 4 to 10 carbon atoms,

[0040] R9 to R 14 are respectively hydrogen, halogen, alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or cycloalkyl having 4 to 10 carbon atoms,

[0041] X is a substituent represented by the following Chemical Formula 1-1.

[0042] [Chemical formula 1-1]

[0043]

[0044] The cardo-based adhesive such as Chemical Formula 1 includes a urethane group and thus has a relatively hard and rigid structure, so that it can play a role in maintaining a pattern during development.

[0045] The cardo-based polymer resin may have a weight average molecular weight (Mw) of about 1,000 to about 50,000 g / mol.

[0046] When the weight average molecular weight (Mw) of the cardo polymer resin is less than 1000 g / mol, the development speed of the black photo spacer photosensitive resin composition may be excessively increased, which may cause pattern shedding or reduced heat resistance. On the contrary, when the weight average molecular weight of the cardo polymer resin exceeds 50000 g / mol, the development of the black photo spacer photosensitive resin composition is delayed, so that pattern formation may not occur.

[0047] [B] (Meth) acrylic polymer resin

[0048] The (meth) acrylic polymer resin may be a polymer or copolymer formed from one or more (meth) acrylic monomers or oligomers. Specifically, the (meth) acrylic polymer resin may include a copolymer comprising a vinyl repeating unit substituted or unsubstituted with an aromatic functional group and one or more (meth) acrylic repeating units. As a specific example of the (meth) acrylic polymer resin, a copolymer represented by the following chemical formula 2 may be cited.

[0049] [Chemical formula 2]

[0050]

[0051] In the chemical formula 2,

[0052] j, k, l, m, and n are integers from 1 to 1000, respectively.

[0053] R1, R2, R3, R4, R5 and R7 are each hydrogen or selected from the group consisting of methyl and hydroxymethyl.

[0054] R6 is hydrogen or a group forming a carboxylic anhydride or amide structure,

[0055] X is methyl or cyclohexyl,

[0056] Y is selected from the group consisting of alkyl esters having 1 to 12 carbon atoms, alkyl esters having 2 to 6 carbon atoms substituted with 1 to 2 hydroxy groups, alkoxy polyalkylene groups having 1 to 3 carbon atoms, ethylene glycol esters having 2 to 3 carbon atoms, and alkyl ester groups having 1 to 6 carbon atoms substituted with phenyl groups,

[0057] The symbol * is a joining point.

[0058] The (meth)acrylic polymer resin is used in the preparation of the photosensitive resin composition as a solution, and can also be separated from the solution for the preparation of the photosensitive resin composition. According to the type, content and molecular weight of the monomers used, many kinds of (meth)acrylic polymer resins can be obtained, each having different physical properties, and the advantages and disadvantages obtained when used in the final photosensitive resin composition may also be different. Therefore, mixing two or more (meth)acrylic polymer resins for use in the preparation of the photosensitive resin composition will be more conducive to complementing the characteristics of each copolymer.

[0059] On the other hand, the (meth)acrylic polymer resin may be a polymer or a copolymer formed from more than one (meth)acrylic monomer or oligomer.

[0060] Specifically, the (meth)acrylic polymer resin may include a copolymer including a vinyl repeating unit substituted or unsubstituted with an aromatic functional group and one or more (meth)acrylic repeating units.

[0061] The (meth)acrylic copolymer resin may have a weight average molecular weight (Mw) of about 1,000 to about 100,000 g / mol.

[0062] When the weight average molecular weight of the (meth)acrylic polymer resin is 1000 g / mol or more, the adhesive function is excellent, the physical external force can be withstood during development, so the pattern does not disappear, and basic physical properties such as heat resistance and chemical resistance can be satisfied. In addition, when the weight average molecular weight is 100000 g / mol or less, the problem of being unable to develop due to low developability to an alkali developer can be prevented, and the problem of difficulty in controlling the coating thickness or ensuring thickness uniformity due to poor fluidity can be prevented.

[0063] On the other hand, the content of the (meth)acrylic copolymer resin can be appropriately adjusted according to specific physical properties, for example, for 100 parts by weight of the (meth)acrylic copolymer resin, the cardo-based polymer resin of Chemical Formula 1 can be in the range of 10 to 100 weight %.

[0064] [C] Acrylic multifunctional monomer

[0065] The acrylic multifunctional monomer is not particularly limited, but difunctional or trifunctional or higher-functional (meth)acrylic monomers are preferred because of their good polymerizability and improved strength of the resulting insulating film. In particular, trifunctional or higher-functional (meth)acrylic monomers are preferred.

[0066] Examples of the difunctional (meth)acrylic monomer include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanolfluorenedimethacrylate, and the like.

[0067] In addition, examples of the trifunctional or higher-functional (meth) acrylic monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tris(2-acryloyloxyethyl)phosphate, tris(2-methacryloyloxyethyl)phosphate, and the like.

[0068] Furthermore, monofunctional, difunctional, or trifunctional or higher-functional (meth)acrylic acids may be used alone or in combination of two or more.

[0069] For every 100 parts by weight of the (meth)acrylic polymer resin, the acrylic multifunctional monomer is 50 to 150 parts by weight, preferably 50 to 120 parts by weight, and most preferably 70 to 100 parts by weight. When the amount is within this range, it is possible to prepare a photosensitive resin composition having high elasticity and high sensitivity, which is easy to control the film thickness of the obtained photosensitive resin and provides a photosensitive resin with excellent strength and adhesion.

[0070] [D] Colorant

[0071] The colorant may include a black pigment or a black pigment and a color pigment, and any known colorant in the art may be used.

[0072] The black pigment may be carbon black having a surface resistance value of 1011Ω·cm or more obtained by subjecting carbon black to high resistance treatment, or may be a mixture of the carbon black and an organic black pigment. When the organic black pigment is mixed, not only the average optical density is increased, but also the average optical density (OD) per unit wavelength is uniformly adjusted, thereby having a high light-shielding effect. The colorant may include a coloring dispersion obtained by mixing and grinding a black pigment and a coloring pigment. As the carbon black, there can be used SEAST 5HIISAF-HS, SEAST KH, SEAST 3HHAF-HS, SEAST NH, SEAST 3M, SEAST 300HAF-LS, SEAST 116HMMAF-HS, SEAST 116MAF, SEAST FMFEF-HS, SEASTSOFEF, SEAST VGPF, SEAST SVHSRF-HS and SEAST SSRF manufactured by Tokai Carbon Co., Ltd.; BK-5075 or BK-8132 manufactured by Tokushiki Co., Ltd.; DIAGRAM BLACKⅡ, 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, DIAGRAMLR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, #3030, #3050, MA 7. MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B;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, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLA CK-101 manufactured by Degussa Co., Ltd.; RAVEN manufactured by Columbia Co., Ltd. 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-790ULTRA, RAVEN-780UL TRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVE N-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTR A. RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA and RAVEN-1170 can be used alone or in combination. The color pigments that can be mixed with the black pigment include carmine 6B (CI12490), phthalocyanine green (CI74260), phthalocyanine blue (CI74160), flax yellow (CI21090), flax yellow GRO (CI21090), benzidine yellow 4T 564D, Victoria pure blue (CI42595), CIPIGMENT RED97, 122, 149, 168, 177, 180, 192, 215, CIPIGMENT GREEN7, 36, CIPIGMENT 15:1, 15:4, 15:6, 22, 60, 64, CIPIGMENT 83, 139C.I.PIGMENT VIOLET 23, etc. In addition, white pigments, fluorescent pigments, etc. can also be used. ;

[0073] In the photosensitive resin composition for black photo-spacers, the content of the colorant is not greatly limited, but may be 10 to 300 wt % with respect to 100 parts by weight of the binder resin including the cardo-based polymer resin and the (meth)acrylic polymer resin.

[0074] [E] Photoinitiator

[0075] O-acyl oxime compounds as examples of photoinitiators include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetoxime), 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl]-9.H.-carbazole-3-yl]ethanone-1-(O-acetoxime), 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-1,2-nonane-2-oxime-O-benzoate, 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-1,2-nonane-2-oxime-O-acetate, 1-[ 9-ethyl-6-benzoyl-9.H.-carbazol-3-yl]-1,2-pentane-2-oxime-O-acetate, 1-[9-ethyl-6-benzoyl-9.H.-carbazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazol-3-yl]-ethane-1-one oxime-O-acetate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9.H.-carbazol-3-yl]-ethane-1-one oxime-O-benzoate, and the like.

[0076] For the O-acyl oxime photoinitiator, other photoinitiators can be added in the range of 50 to 250 weight % of the total weight of the photoinitiator for use. For example, acyloins, acyloin ethers, acetophenones, benzophenones, quinones, halogen compounds, acylphosphine oxides and peroxides can be added for use.

[0077] As for other photoinitiators, specifically, there are benzyl group, diacetyl, benzoin, o-toluene, p-toluene, anisole, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenone, p-dimethylaminoacetophenone, α,α'-dimethoxyacetoxybenzophenone, 4,4-bis-(diethylamino)-benzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl 1-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, anthraquinone, 1,4-naphthoquinone, phenacyl chloride, tribromomethylphenyl sulfone, tris(trichloromethyl)-s-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, benzoyl peroxide, di-tert-butyl peroxide, etc.

[0078] In one embodiment of the present invention, for 100 parts by weight of the (meth)acrylic polymer resin, 0.1 to 5.0 weight % of an O-acyl oxime photoinitiator, 1 to 10 weight % of at least one of an acetophenone photoinitiator and a benzophenone photoinitiator may be included.

[0079] When used within this range, a photosensitive resin composition having a good balance between the heat resistance and solvent resistance of the photosensitive resin and the controllability of the pattern shape after development is provided.

[0080] [F] Additives [silane coupling agent (F-1), leveling agent (F-2), thermal polymerization inhibitor and sensitizer, etc.]

[0081] The photosensitive resin composition of the present invention may contain 0.1 to 5% by weight of additives other than the above-mentioned components [A] to [E] as needed, within a range not impairing the desired effects of the present invention.

[0082] As the additive, a silane coupling agent (F-1) can be used to improve adhesion to the substrate. As examples of the silane coupling agent, silane coupling agents with reactive functional groups such as carboxyl, methacryloyl, isocyanate, and epoxy groups can be cited, and more specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2-(3',4'-epoxycyclohexyl)ethyltrimethoxysilane, etc. can be cited. The silane coupling agent can be used alone or in combination of two or more. Regarding the amount of the (meth) acrylic polymer resin, 0.1 to 5.0% by weight can be used, preferably 0.1 to 3.0% by weight.

[0083] Another example of the additive is a leveling agent (F-2) for improving coating properties. Examples of commercially available leveling agents include R-08, R-475, and R-30 (manufactured by DIC Corporation), BM-1000, and BM-1100 (manufactured by BM Chemie Corporation), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, and FLUORAD FC-431 (manufactured by Sumitomo 3M Co., Ltd.), SAFLON S-112, SAFLON S-113, SAFLON S-131, SAFLON S-141, SAFLON S-145, SAFLON S-382, SAFLON SC-101, SAFLON SC-102, SAFLON SC-103, SAFLON SC-104, SAFLON SC-105, and SAFLON Fluorine-based or silicon-based surfactants such as SC-106 (manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, and DC190 (manufactured by TORAY SILICON Co., Ltd.). These leveling agents may be used alone or in combination of two or more. The amount thereof may be 0.1 to 5.0% by weight, preferably 0.1 to 3.0% by weight, based on 100 parts by weight of the (meth)acrylic polymer resin.

[0084] In addition, other additives such as a thermal polymerization inhibitor and a sensitizer may be used. The amount of the thermal polymerization inhibitor and the sensitizer is in the range of 0.1 to 3.0 wt % based on 100 parts by weight of the (meth)acrylic polymer resin.

[0085] [G] Epoxy curing agent

[0086] As the epoxy curing agent, amines, anhydrides, imidazoles, isocyanines, thiol compounds, etc. can be used, more specifically, amine compounds such as diethylenetriamine (DETA), triethylenetetramine (TETA), triethylenepentamine (TEPA), diaminodiphenylmethane (DDM), diaminodiphenyl sulfone (DDS), polyamide amine, dicyandiamide, etc.; anhydride compounds such as polyamide resin, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhydrophthalic anhydride, etc.; imidazole compounds such as 2MZ and 2E4MZ; isocyanine compounds; and thiol compounds such as polythiol, etc. These can be used alone or in combination of two or more.

[0087] Regarding the content of the epoxy curing agent, in order to further improve the heat resistance and adhesion strength and prevent the curing of the insulating layer from causing a decrease in forming characteristics such as bendability (bending processability) and stamping processability, it is preferably in the range of 0.1 to 10 weight % for 100 parts by weight of the (meth) acrylic polymer.

[0088] [H] Curing accelerator

[0089] Examples of the curing accelerator include amine complexes of boron trifluoride, imidazole derivatives, organic acids such as phthalic anhydride and trimellitic anhydride, but are not limited thereto. Preferably, examples of the curing accelerator include imidazole derivative curing accelerators, specifically 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and derivatives thereof. Examples of the derivatives include cyanoethyl derivatives, carboxylic acid derivatives, hydroxymethyl derivatives, but are not limited thereto. Such curing accelerators can be used alone or in combination of two or more.

[0090] Regarding the content of the curing accelerator, it is preferably in the range of 0.1 to 10 wt % with respect to 100 parts by weight of the (meth)acrylic polymer resin.

[0091] [I] Solvent

[0092] The photosensitive resin composition for black light spacers may further include a solvent. When the photosensitive resin composition for black light spacers of the implementation example includes a solvent as described above, the solid content in the composition may be 10 to 80% by weight. Although the examples of the solvent are not too limited, for example, the solvent may include 3-methoxypropionic acid methyl ester, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol diethyl ether, dibutyl ether, propylene glycol methyl ether ethyl pyruvate propylene glycol methyl ether, propylene glycol methyl ether acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butyl propionate, isoamyl propionate, ethyl butyrate, propyl butyrate, 3-methoxyisobutyric acid methyl ester, methyl hydroxyacetate (Methyl glycolate), methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, ethyl ethoxylate, ethyl 2-methoxylate, ethylene glycol methyl ether acetate, 2-ethoxyethyl acetate, dibutyl ether, cyclopentanone, cyclohexanone, 2-hexanone, 3-hexanone, 5-methyl-2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 1-methoxy-2-propanol, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, 2-methoxyethyl ether, butyl 3-methoxyacetate, 2-ethoxy ethyl ether, 2-butoxyethanol, 3-ethoxypropanol, diethylene glycol dodecyl ether, dipropylene glycol methyl ether, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 3-nonanone, 5-nonanone, 4-hydroxy-4-methyl-2-pentanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, hexyl acetate, amyl butyrate, isopropyl lactate, butyl lactate, ethyl 3-hydroxybutyrate, ethyl 3-ethoxypropionate, 3 -Ethyl hydroxybutyrate, 2-hydroxypropyl propionate, propylene glycol diacetate, propylene glycol butyl ether, propylene glycol methyl ether propionate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl isopropyl ether, diethylene glycol diethyl ether, butyl butyrate, ethyl 3-ethoxypropionate, diethylene glycol monomethyl ether, 4-ethylcyclohexanone, ethyl 2-butoxyacetate, diethylene glycol monoethyl ether, butyrolactone, hexyl butyrate, diethylene glycol methyl ether acetate, diethylene glycol Butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, 3-epoxy-1,2-propylene glycol, ethyl 4-acetylbutyrate, diethylene glycol monobutyl ether, tripropylene glycol methyl ether, diethylene glycol, ethyl 2-(2-butoxyethoxy)acetate, catechol, triethylene glycol methyl ether, diethylene glycol dibutyl ether, triethylene glycol ethyl ether, diethylene glycol monohexyl ether, triethylene glycol butyl methyl ether, triethylene glycol butyl ethyl ether, tripropylene glycol, tetraethylene glycol dimethyl ether or a mixture of two or more thereof.

[0093] [Synthesis Example 1: Synthesis of cardo polymer resin]

[0094] After preparing a flask with a mechanical stirrer, a thermometer, and a cooling jacket, 240 g of propylene glycol monomethyl ether and 100 g of bisphenol (Fluorenbisphenol) were added under a nitrogen stream and heated to 40°C for stirring. 0.288 g of dibutyltin dilaurate was added as a catalyst for the reaction and the temperature of the reactor was raised to 65°C. Then, while continuing to stir the reaction solution, 36.98 g of 4,4'-diphenylmethane diisocyanate was slowly added in portions, and the absorption spectrum of the isocyanate group (2280 cm -1 ) disappeared. Subsequently, 315.2 g of epichlorohydrin was added to the reaction solution, heated to 100°C and stirred for 1 hour. Thereafter, 33.8 g of methacrylic acid was added, and the temperature was raised to 110°C for reaction for 3 hours. The reactant was then dissolved in a THF solution, the precipitate was captured with water and dissolved in a chloromethane (Methylene Chloride, Dichloromethane, MC) solvent, and then the precipitate was captured in hexane to obtain 20 g of a light yellow polymer resin of [Chemical Formula 3]. Here, it was confirmed that the solid content of the polymer resin of [Chemical Formula 3] was 20% and the weight average molecular weight was 6500 g / mol.

[0095] [Chemical formula 3]

[0096]

[0097] Wherein, X is chemical formula 3-1.

[0098] [Chemical formula 3-1]

[0099]

[0100] Next, the polymer resin of Chemical Formula 3 and the compound of the following Chemical Formula 4 were mixed at a molar ratio of 66:32 to synthesize a cardo-based polymer resin.

[0101] [Chemical formula 4]

[0102]

[0103] Here, the synthesized cardo-based polymer resin has a weight average molecular weight of 8800 g / mol and can be represented by the following Chemical Formula 5.

[0104] [Chemical formula 5]

[0105]

[0106] Here, X is a substituent represented by the following Chemical Formula 3-1.

[0107] [Chemical formula 3-1]

[0108]

[0109] [Synthesis Example 2: Synthesis of (meth)acrylic polymer resin]

[0110] In a flask equipped with a cooling tube with a drying tube and a stirrer, 2 parts by weight of octane mercaptan, 2 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 25 parts by weight of 2-carboxyethyl acrylate, 20 parts by weight of acrylic acid, 25 parts by weight of dicyclopentyl methacrylate, 10 parts by weight of styrene monomer, and 20 parts by weight of 2-methyl-acrylic acid 4-(2-methyl-acryloyloxymethyl)-cyclohexyl ester were added, and the air in the flask was replaced with nitrogen. The temperature of the solution was raised to 60° C. while slowly stirring, and the temperature was maintained for 6 hours to allow polymerization to obtain a solution of a copolymer [A-1] represented by the following [Chemical Formula 6]. The weight average molecular weight of the copolymer resin [A-1] was 7000 g / mol.

[0111] [Chemical formula 6]

[0112]

[0113] In the chemical formula 6,

[0114] j, k, l, m, n are integers from 1 to 1000,

[0115] In the chemical formula 6, * is a binding point.

[0116] [Example 1-12 and Comparative Example 1-4: Preparation of Photosensitive Resin Composition for Black Photo Spacer and Black Photo Spacer]

[0117] The components listed in Table 1 below were mixed and stirred for 5 hours to prepare the photosensitive resin composition for black photo-spacers of each example and comparative example.

[0118]

Table 1

[0119]

[0120] in,

[0121] [C]: Dipentaerythritol pentaacrylate (product name: SR-399NS, SARTOMER Co., Ltd.)

[0122] [D]: Organic black dispersion (product name: Black WS-IM-001, Sakata Inx Corp.)

[0123] [E-1]: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyl oxime) (Product name: OXE-02, BASF Corporation)

[0124] [E-2]: 4,4-Bis-(diethylamino)-benzophenone (Product name: HI CURE EMK, CHEMAX Corporation)

[0125] [F-1]: Silane coupling agent (γ-glycidoxypropyltrimethoxysilane, product name: XIAMETER TM OFS-6040 Silane, DOW)

[0126] [F-2]: Leveling agent (Product name: BYK-333, BYK CHEMIE Co., Ltd.)

[0127] [G]: Epoxy curing agent (product name: diethylenetriamine, Sigma-Aldrich)

[0128] [H]: Curing accelerator (product name: 2-methylimidazole, Sigma-Aldrich)

[0129] [Evaluation of photosensitive resin composition for black photo-spacers]

[0130] After coating the photosensitive resin composition solutions according to Examples 1 to 12 and Comparative Examples 1 to 4 on one side of a glass substrate, a thin film was formed by heating (prebaking) the coated surface.

[0131] A glass substrate was used as a transparent substrate for forming a pattern. The composition was applied to a glass substrate to form an organic film with a thickness of 3 μm, and then pre-baked at 80° C. for 90 seconds. The formed film was then irradiated with a high-pressure mercury lamp at 40 mJ / cm 2 After exposure, the film was developed with a 0.042 wt % aqueous solution of potassium hydroxide at 25° C. for 60 seconds, washed with pure water for 1 minute, and heated in an oven at 230° C. for 20 minutes to form a pattern.

[0132] Next, various evaluations on the following items were performed on the photosensitive resin compositions prepared in Examples and Comparative Examples.

[0133] (Evaluation Item 1) Pattern

[0134] The photosensitive resin composition solutions according to Examples 1 to 12 and Comparative Examples 1 to 4 were coated on one side of a glass substrate to form an organic film with a thickness of 3 μm, and then pre-baked at 80° C. for 90 seconds. The formed thin film was then irradiated under a high pressure mercury lamp at 40 mJ / cm 2 Energy exposure. Here, the exposure was adjusted to 10% and 100% respectively, and after exposure, it was developed with a 0.042 wt% aqueous solution of potassium hydroxide at 25°C for 60 seconds, then washed with pure water for 1 minute, and heated in an oven at 230°C for 20 minutes to form a pattern. When the residual film rate is 5B, it can be considered good. The benchmark table is shown in Table 2 below.

[0135]

Table 2

[0136] project Residual film thickness / μm 2.00 and above 1.25 and above 1.00 and above Less than 1.00 Residual film rate / % 66.67 and above More than 5000 33.33 and above Less than 33.33 grade 5B 4B 3B 2B

[0137] ◎=5B, ○=4B, △=3B, X≤2B

[0138] (Evaluation Item 2) Adhesion

[0139] After coating the photosensitive resin composition solution of Examples 1 to 12 and Comparative Examples 1 to 4 on one side of the glass substrate to form an organic film of 3 μm, a photomask is not used, and the other processes are the same as above to form a cured film and place it at room temperature (25°C) for 10 minutes, and then PCT (121°C, 2atm, 100% Rh water, 2hr) is performed. Then, according to the method of ATSM-D3359, 100 chessboard scales are formed on the cured film with a cutter according to the chessboard scale tape method and then peeled off with tape. At this time, the number of chessboard patterns peeled off among the 100 was measured. Adhesion is considered good when it is 4B. The benchmark table is shown in Table 3 below.

[0140]

Table 3

[0141] Residual rate 100％ More than 80% More than 60% More than 40% More than 20% 0％ Classification 5B 4B 3B 2B 1B 0B

[0142] 5B=◎,○=4B,△=3B,X≤2B

[0143] (Evaluation Item 3) Resolution

[0144] The photosensitive resin composition solutions according to Examples 1 to 12 and Comparative Examples 1 to 4 were coated on one side of a glass substrate to form an organic film with a thickness of 3 μm, and then pre-baked at 80° C. for 90 seconds. The formed thin film was then irradiated under a high pressure mercury lamp at 40 mJ / cm 2Energy exposure. Here, exposure was performed at exposure amounts of 10% and 100%, and after exposure, a 0.042w% aqueous solution of potassium hydroxide was used for development at 25°C for 60 seconds, and then washed with pure water for 1 minute, and heated in an oven at 230°C for 20 minutes to form a pattern. Here, a pattern of less than 25um was formed, which can be considered good. The criteria are as follows.

[0145] 20>◎,20≤○<25,25≤△<30,X≥30

[0146] The comprehensive evaluation results of Examples 1 to 12 and Comparative Examples 1 to 4 are shown in Table 4.

[0147]

Table 4

[0148]

[0149] ◎: very good, ○: good, △: fair, ×: poor.

Claims

1. A photosensitive resin composition for black photo spacers, comprising: The binder resin comprises a cardo polymer resin and a (meth) acrylic polymer resin, wherein the cardo polymer resin comprises a repeating unit of the following chemical formula 1; Acrylic multifunctional monomers, with different acrylates with two or more functional groups; Colorants; The photoinitiator is at least one selected from the group consisting of O-acyl oxime photoinitiators, acetophenone photoinitiators and benzophenone photoinitiators; An additive comprising at least one of a silane coupling agent, a leveling agent, a thermal polymerization inhibitor and a sensitizer; and Solvents, [Chemical formula 1] in, n is an integer from 1 to 1000, * is the binding point, R1 to R8 are independently hydrogen, halogen, alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms, or cycloalkyl having 4 to 10 carbon atoms, R9 to R 14 are respectively hydrogen, halogen, alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or cycloalkyl having 4 to 10 carbon atoms, X is a substituent represented by the following chemical formula 1-1, [Chemical formula 1-1] 2. The photosensitive resin composition for black photo-spacers according to claim 1, wherein: The cardo-based polymer resin is in the range of 10 to 100 wt % with respect to 100 parts by weight of the (meth)acrylic-based copolymer resin.

3. The photosensitive resin composition for black photo-spacers according to claim 1, wherein: The (meth)acrylic copolymer resin includes a copolymer represented by the following Chemical Formula 2, [Chemical formula 2] In the chemical formula 2, j, k, l, m, n are integers from 1 to 90, R1, R2, R3, R4, R5 and R7 are each hydrogen or selected from the group consisting of methyl and hydroxymethyl, R6 is hydrogen or a group forming a carboxylic anhydride or amide structure, X is methyl or cyclohexyl, Y is selected from the group consisting of alkyl esters having 1 to 12 carbon atoms, alkyl esters having 2 to 6 carbon atoms substituted with 1 to 2 hydroxyl groups, alkoxy polyalkylene groups having 1 to 3 carbon atoms, ethylene glycol esters having 2 to 3 carbon atoms, and alkyl ester groups having 1 to 6 carbon atoms substituted with phenyl groups, The symbol * is a joining point.

4. The photosensitive resin composition for black photo-spacers according to claim 1, wherein: The cardo-based polymer resin has a weight average molecular weight (Mw) ranging from 1,000 to 50,000 g / mol.

5. The photosensitive resin composition for black photo-spacers according to claim 1, wherein: The (meth)acrylic copolymer resin has a weight average molecular weight (Mw) ranging from 1,000 to 100,000 g / mol.

6. The photosensitive resin composition for black photo-spacers according to claim 1, wherein: The acrylic multifunctional monomer is in the range of 50 to 150 wt % with respect to 100 parts by weight of the (meth)acrylic polymer resin.

7. The photosensitive resin composition for black photo-spacers according to claim 1, wherein: For 100 parts by weight of the (meth)acrylic polymer resin, the photoinitiator includes: 0.1 to 5.0 wt % of an O-acyl oxime photoinitiator; and 0.1 to 10 wt% of at least one of acetophenone and benzophenone-based photoinitiators.

8. The photosensitive resin composition for black photo-spacers according to claim 1, wherein: The colorant includes a coloring dispersion in which a black pigment and a coloring pigment are mixed and dispersed.

9. The photosensitive resin composition for black photo-spacers according to claim 1, wherein: For 100 parts by weight of the (meth)acrylic polymer resin, 0.1 to 10% of an epoxy curing agent is further included.

10. The photosensitive resin composition for black photo-spacers according to claim 1, wherein: For 100 parts by weight of the (meth)acrylic polymer resin, 0.1 to 10% of a curing accelerator is further included.

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