Black Photosensitive Resin Composition, Black Matrix and Display Device

Abstract

The present invention relates to a black photosensitive resin composition comprising a black coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, one or more of a cyclic siloxane compound containing an epoxy group and a silsesquioxane compound, a thiol compound, and a solvent, a black matrix formed using the same, and an image display device comprising the black matrix. The black photosensitive resin composition according to the present invention exhibits a pure taper shape even when low-temperature curing and a TMAH-based developer are applied, and can form a pattern with excellent reflectance retention rate, resolution, solvent resistance, and pencil hardness.

Description

Technology Field

[0001] The present invention relates to a black photosensitive resin composition, a black matrix, and an image display device, and more specifically, to a black photosensitive resin composition that exhibits a pure taper shape even when low-temperature curing and TMAH-based developer are applied, and has excellent reflectance retention rate, resolution, solvent resistance, and pencil hardness, and a black matrix and an image display device formed using the same. Background Technology

[0002] Black photosensitive resin compositions are essential materials for color filters, liquid crystal display materials, organic light-emitting diodes, displays, etc. For example, in the color filters of color liquid crystal displays, display contrast or color rendering effects can be enhanced by forming a light-blocking layer at the boundary between colored layers such as red, green, and blue.

[0003] Specifically, in pixels composed of red (R), green (G), and blue (B) colors, a black matrix is ​​formed at the boundary between the colored layers of each pixel to prevent mixing with other colors or to hide the electrode pattern, or a column spacer is formed at the part in contact with the liquid crystal.

[0004] Recently, there has been a focus on the development of flexible display devices that can be rolled or folded like paper. Accordingly, there is a demand for materials such as substrates used in display devices to possess flexible properties. Consequently, the available materials are limited to flexible polymer materials, and the manufacturing process is also required to be carried out under milder conditions. As a result, there is a growing need for low-temperature curing instead of the conventional high-temperature curing for photosensitive resin compositions. However, low-temperature curing presents problems such as reduced reactivity and reduced durability of the formed pattern.

[0005] In addition, the photolithography process is performed under TMAH-based conditions, but when a TMAH-based developer is applied in the development process, there is a problem in that the patternability and solvent resistance of the color filter are not secured. Therefore, during the photolithography process, a KOH-based developer, which is milder than the TMAH-based developer, was changed and applied in the development process, but this resulted in inefficiency due to the inability to maintain consistency in the process.

[0006] Korean Published Patent No. 10-2016-0056836 discloses that a black matrix photoresist composition characterized by comprising a binder resin, a polymerizable compound having ethylenically unsaturated bonds, a photopolymerization initiator comprising an oxime ester fluorene derivative compound, and a coloring agent has excellent process characteristics.

[0007] However, the above photosensitive resin composition had the problem that it was difficult to secure sufficient resolution when cured at low temperature, and processability was not secured when a TMAH-based developer was applied.

[0008] Therefore, there is a need for the development of technology for a black photosensitive resin composition that exhibits excellent resolution, solvent resistance, reflectance, and pencil hardness, as well as a pure taper shape, even when low-temperature curing and TMAH-based developers are applied. Prior art literature

[0009] Republic of Korea Published Patent No. 10-2016-0056836 The problem to be solved

[0010] One objective of the present invention is to provide a black photosensitive resin composition that exhibits a pure taper shape even when low-temperature curing and TMAH-based developer are applied, and has excellent reflectance retention, resolution, solvent resistance, and pencil hardness.

[0011] Another objective of the present invention is to provide a black matrix formed using the black photosensitive resin composition.

[0012] Another objective of the present invention is to provide an image display device comprising the black matrix. means of solving the problem

[0013] On the other hand, the present invention provides a black photosensitive resin composition comprising a black coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, one or more of a cyclic siloxane compound containing an epoxy group and a silsesquioxane compound, a thiol compound, and a solvent.

[0014] In one embodiment of the present invention, the cyclic siloxane compound may include a compound of the following chemical formula 1.

[0015] [Chemical Formula 1]

[0016]

[0017] In the above formula,

[0018] R1 to R4 are each independently a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, an epoxy group, an oxetane group, a hydroxyl group, or a silyloxy group, at least one of which is an epoxy group, and

[0019] n is an integer from 2 to 20.

[0020] In one embodiment of the present invention, the cyclic siloxane compound may include a compound of the following chemical formula 2.

[0021] [Chemical Formula 2]

[0022]

[0023] In the above formula,

[0024] R is an epoxy group.

[0025] In one embodiment of the present invention, one or more of the cyclic siloxane compound and the silsesquioxane compound containing the epoxy group may be included in an amount of 5 to 15 weight% based on 100 weight% of the total solid content of the black photosensitive resin composition.

[0026] In one embodiment of the present invention, the thiol compound may include a compound of the following chemical formula 3.

[0027] [Chemical Formula 3]

[0028]

[0029] In the above formula,

[0030] L 1 Silver carbon; substituted or unsubstituted C2-C 20 alkylene group of; substituted or unsubstituted C2-C 20 heteroalkylene group of; substituted or unsubstituted C6-C 30 arylene group of; substituted or unsubstituted C3-C 30 heteroarylene group; substituted or unsubstituted C3-C 30 cycloalkylene group of; or substituted or unsubstituted C3-C 30 It is a heterocycloalkylene group of, and

[0031] Y a to Y d are either independently non-existent; or substituted or unsubstituted C1-C 30 alkylene group of; substituted or unsubstituted C2-C 30 an alkenylene group; or at least one methylene (-CH2-) is a sulfonyl (-S(=O)2-), carbonyl (-C(=O)-), ether (-O-), sulfide (-S-), sulfoxide (-S(=O)-), ester (-C(=O)O-), amide (-C(=O)NR-) (where R is hydrogen or C1-C 10 is a straight-chain or branched-chain alkyl group), imine(-NR-)(where R is hydrogen or C1-C 10 A C1-C substituted with a straight-chain or branched-chain alkyl group) or a combination thereof. 30 The alkylene group or C2-C 30 It is an alkenylene group, and

[0032] R a to R d Each is independently hydrogen; substituted or unsubstituted C1-C 30straight-chain or branched-chain alkyl groups; substituted or unsubstituted C6-C 30 aryl group of; substituted or unsubstituted C3-C 30 heteroaryl group of; substituted or unsubstituted C3-C 30 cycloalkyl group of; substituted or unsubstituted C3-C 30 heterocycloalkyl group of; C1-C 10 alkoxy group; hydroxyl group; -NH2; substituted or unsubstituted C1-C 30 The amine group (-NRR', where R and R' are each independently hydrogen or C1-C 30 is a straight-chain or branched-chain alkyl group); isocyanate group; halogen; -ROR' (where R is a substituted or unsubstituted C1-C 20 It is an alkylene group and R' is hydrogen or C1-C 20 is a straight-chain or branched-chain alkyl group); acyl halide (-RC(=O)X, where R is a substituted or unsubstituted alkylene group and X is a halogen); -C(=O)OR' (where R' is hydrogen or C1-C 20 is a straight-chain or branched-chain alkyl group); -CN; or -C(=O)ONRR' (where R and R' are each independently hydrogen or C1-C 20 (which is a straight-chain or branched-chain alkyl group) or SH, wherein R a to R d At least two of them are SH, and

[0033] p and q are each independently integers from 1 to 2.

[0034] In one embodiment of the present invention, the thiol compound may include one or more of trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate).

[0035] In one embodiment of the present invention, the thiol compound may be included in an amount of 0.1 to 3 weight% based on 100 weight% of the total solid content of the black photosensitive resin composition.

[0036] In one embodiment of the present invention, the weight ratio of one or more of the cyclic siloxane compound and the silsesquioxane compound containing the epoxy group to the thiol compound may be 5:1 to 10:1.

[0037] In one embodiment of the present invention, the black photosensitive resin composition may further include an epoxy compound.

[0038] On the other hand, the present invention provides a black matrix formed using the black photosensitive resin composition.

[0039] On the other hand, the present invention provides an image display device including the black matrix. Effects of the invention

[0040] The black photosensitive resin composition according to the present invention comprises one or more of a cyclic siloxane compound containing an epoxy group and a silsesquioxane compound and a thiol compound, thereby forming a pattern that exhibits a net taper shape even after development under low-temperature curing and TMAH-based developer conditions, and has excellent reflectance retention rate, resolution, solvent resistance, and pencil hardness. Specific details for implementing the invention

[0041] The present invention will be described in more detail below.

[0042] One embodiment of the present invention relates to a black photosensitive resin composition comprising a black coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), one or more of a cyclic siloxane compound and a silsesquioxane compound containing an epoxy group (E), a thiol compound (G), and a solvent (J).

[0043] Hereinafter, a black photosensitive resin composition according to one embodiment of the present invention will be described in detail for each component.

[0045] Black coloring agent (A)

[0046] In one embodiment of the present invention, the black coloring agent (A) is used to achieve black color and can perform the role of preventing light leakage in the black matrix.

[0047] As the above black coloring agent, any black coloring agent known in the art, such as organic pigments, dyes, and inorganic pigments, may be used as long as it has light-blocking properties in visible light; however, it is preferable to use a black pigment containing an organic pigment.

[0048] As for the above black pigment, any known pigment may be used without special restrictions, but specifically, lactam black, aniline black, perylene black, etc. may be used. These may be used individually or in combination of two or more types.

[0049] Additionally, the black coloring agent may optionally include a color corrector as needed. As the color corrector, violet pigment, blue pigment, yellow pigment, green pigment, etc. may be used. Specifically, condensed polycyclic pigments such as anthraquinone-based pigments or perylene-based pigments, or organic pigments such as phthalocyanine pigments or azo pigments may be used. Anthraquinone-based pigments or phthalocyanine pigments are preferred, and phthalocyanine pigments are more preferred. Examples of phthalocyanine pigments may include CI Pigment Blue 15:6, CI Pigment Blue 15:4, and CI Pigment Blue 16, and examples of anthraquinone-based pigments may include CI Pigment Blue 60. CI Pigment Blue 15:6 may be preferred as the phthalocyanine pigment.

[0050] The above black coloring agent may consist of one or more black organic pigments selected from the group consisting of lactam black, aniline black, and perylene black.

[0051] Among black organic pigments, using lactam black (e.g., BASF’s Irgaphor® Black S 0100 CF) may be preferable in terms of optical density, dielectric constant, transmittance, etc.

[0053] The black coloring agent (A) may be included in an amount of 20 to 80 weight%, preferably 20 to 70 weight%, based on 100 weight% of the total solid content of the black photosensitive resin composition. When the black coloring agent is included within the above range, the optical density may be excellent.

[0054] In the present invention, the solid content of the black photosensitive resin composition refers to the sum of the components from which the solvent has been removed.

[0056] It is preferable to use a pigment dispersion in which the pigment particles are uniformly dispersed. Examples of methods for uniformly dispersing the pigment particles include a method of dispersion treatment containing a pigment dispersant (a1), and according to the above method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

[0058] Pigment dispersant (a1)

[0059] The pigment dispersant (a1) above is added to prevent the pigment from clumping and to maintain stability, and any commonly used in the field can be used without limitation. Commercially available dispersants include BYK’s LPN-6919, Disperbyk-101, 103, 107, 108, 110, 111, 112, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, There are 2164, etc., and Lubrizol's SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc.

[0060] These can be used alone or in a mixture of two or more types, and preferably include BYK’s LPN-6919, BYK’s Disperbyk-2000, 2001, which are dispersants having acidic functional groups, or Lubrizol’s SOLSPERSE-3000, 21000, 26000, 36600, 41000, etc., but are not limited to these.

[0062] The content of the pigment dispersant (a1) is 5 to 60 parts by weight, preferably 15 to 50 parts by weight, per 100 parts by weight of pigment. If the content of the pigment dispersant exceeds 60 parts by weight, the viscosity may increase, and if it is less than 5 parts by weight, it may be difficult to finely pulverize the pigment or cause problems such as gelation after dispersion.

[0064] Alkali-soluble resin (B)

[0065] In one embodiment of the present invention, the alkali-soluble resin (B) has reactivity and alkali solubility through the action of light or heat, acts as a dispersion medium for solids including coloring agents, and performs the function of a binding resin. Any resin known in the art can be selected and used without special limitations.

[0066] Specifically, it is preferable to use the alkali-soluble resin as a copolymer of an unsaturated carboxyl group-containing monomer and another monomer copolymerizable thereto, or a cardo-based resin.

[0067] Examples of the above unsaturated carboxyl group-containing monomers include, for instance, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, and unsaturated polycarboxylic acids having two or more carboxyl groups in the molecule.

[0068] Examples of the above unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc.

[0069] Examples of the above unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc.

[0070] The above unsaturated polycarboxylic acid may be an acid anhydride, specifically maleic anhydride, itaconic anhydride, citraconic anhydride, etc. In addition, the above unsaturated polycarboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl), phthalic acid mono(2-acryloyloxyethyl), phthalic acid mono(2-methacryloyloxyethyl), etc. The above unsaturated polycarboxylic acid may be a mono(meth)acrylate of its dicarboxypolymer, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc.

[0071] The above carboxyl group-containing monomers can each be used individually or in a mixture of two or more types.

[0073] Other monomers copolymerizable with the above carboxyl group-containing monomer include, for example, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-9-ylacrylate, 3,4-epoxytricyclo[5.2.1.0 2,6] Epoxy (meth)acrylate compounds such as decane-8-yl acrylate, glycicyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether; aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, indene;Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl 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, Unsaturated carboxylic acid esters such as methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc.;Unsaturated aminoalkyl esters of carboxylic acids such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters of glycidyl acrylate, glycidyl methacrylate, etc.; vinyl carboxylic acid esters of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc.; Unsaturated ethers such as vinylmethyl ether, vinylethyl ether, and allylglycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; Examples include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. Each of these monomers may be used individually or in a mixture of two or more.

[0074] The above cardo-based resin specifically comprises bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone and bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane and bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane and bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane and Bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane and 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether and bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, It may be obtained from 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, and 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, but is not limited thereto.

[0075] In this specification, the term "(meth)acrylate" refers to acrylate and / or methacrylate.

[0076] The above alkali-soluble resin (B) may have an acid value of 10 to 150 (KOH mg / g). If the acid value is within the above range, solubility in the developer is improved, so the non-exposed area dissolves easily and sensitivity increases, and consequently, the pattern of the exposed area remains during development, which is desirable as it improves the film remaining ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of polymer, and can typically be obtained by titrating using an aqueous potassium hydroxide solution.

[0077] The above alkali-soluble resin (B) may have a polystyrene equivalent weight-average molecular weight (hereinafter simply referred to as "weight-average molecular weight") measured by gel permeation chromatography (GPC; using tetrahydrofuran as the elution solvent) of 3,000 to 200,000, preferably 5,000 to 100,000. It is desirable that the molecular weight is within the above range, as this improves the hardness of the coating film, increases the residual film rate, and tends to improve the solubility of the non-exposed portion in the developer solution and the resolution.

[0078] The molecular weight distribution [weight-average molecular weight (Mw) / number-average molecular weight (Mn)] of the alkali-soluble resin (B) may be 1.5 to 6.0, preferably 1.8 to 4.0. It is desirable for the molecular weight distribution to be within the above range because it provides excellent development properties.

[0080] The above alkali-soluble resin (B) may be included in an amount of 1 to 50 weight%, preferably 5 to 40 weight%, based on 100 weight% of the total solid content of the black photosensitive resin composition. When the above alkali-soluble resin is included within the above range, it is easy to obtain a black photosensitive resin composition with excellent developability and a cured film with excellent chemical resistance.

[0082] Photopolymerizable compound (C)

[0083] In one embodiment of the present invention, the photopolymerizable compound (C) is a compound capable of polymerizing by the action of light and a photopolymerization initiator to be described later, and is polymerized by an exposure process to improve the mechanical properties of a colored pattern or to complement the developability of the alkali-soluble resin.

[0084] The above photopolymerizable compounds include, for example, monofunctional monomers such as nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, or N-vinylpyrrolidone; and difunctional monomers such as 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, or 3-methylpentanediol di(meth)acrylate. Examples of polyfunctional monomers include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0085] The above photopolymerizable compound (C) may preferably include a monomer with 3 to 10 functionalities, and more preferably a monomer with 4 to 8 functionalities.

[0086] The above photopolymerizable compound (C) may be included in an amount of 1 to 30 weight%, preferably 10 to 20 weight%, based on 100 weight% of the total solid content of the black photosensitive resin composition. When the above photopolymerizable compound is included within the above range, it is desirable in terms of the intensity or smoothness of the pixel portion.

[0088] Photopolymerization initiator (D)

[0089] In one embodiment of the present invention, the photopolymerization initiator (D) can be used without special limitation on its type as long as it is capable of polymerizing the photopolymerizable compound (C). In particular, it is preferable to use one or more compounds selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, nonimidazole-based compounds, oxime-based compounds, and thioxanthone-based compounds for the photopolymerization initiator (D) in terms of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and cost.

[0090] Specific examples of the above acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc.

[0091] Examples of the above benzophenone compounds include benzophenone, 0-methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

[0092] Specific examples of the above triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine. Examples include 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0093] Specific examples of the above-mentioned nonimidazole compounds 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, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, or nonimidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted by a carboalkoxy group. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are preferably used.

[0094] Specific examples of the above-mentioned oxime compounds include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octadione,-1-(4-phenylthio)phenyl,-2-(o-benzoyloxime), ethanoone,-1-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-,1-(o-acetyloxime), and commercially available products include CGI-124 (Ciba-Geigy), CGI-224 (Ciba-Geigy), Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), Irgacure OXE-03 (BASF), N-1919 (Adeca), NCI-831 (Adeca), PBG series (TRONLY), TR-PBG-345 (TRONLY), etc. there is.

[0095] Examples of the above thioxantone compounds include 2-isopropylthioxantone, 2,4-diethylthioxantone, 2,4-dichlorothioxantone, 1-chloro-4-propoxythioxantone, etc.

[0096] In addition, other photopolymerization initiators may be additionally used within a range that does not impair the effects of the present invention. Examples include benzoin compounds or anthracene compounds, and each of these may be used alone or in combination of two or more.

[0097] Examples of the above benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzoin isobutyl ether.

[0098] Examples of the above anthracene compounds include 9,10-dimethoxycyanthracene, 2-ethyl-9,10-dimethoxycyanthracene, 9,10-diethoxycyanthracene, or 2-ethyl-9,10-diethoxycyanthracene.

[0099] In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenquinone, camphoquinone, methyl phenylchlorooxylate, or titanocene compounds may be additionally used in combination as photopolymerization initiators.

[0101] The above photopolymerization initiator (D) may be included in an amount of 0.01 to 10 weight%, preferably 0.01 to 5 weight%, based on 100 weight% of the total solid content of the black photosensitive resin composition. The above content range is determined by considering the photopolymerization rate of the photopolymerizable compound and the physical properties of the final coating film obtained. If the content is below this range, the polymerization rate is low, which may prolong the overall process time; conversely, if the content exceeds this range, the cross-linking reaction may be excessive due to an overreaction, which may actually degrade the physical properties of the coating film. Therefore, it is used appropriately within the above range.

[0103] In addition, a photopolymerization initiation aid may be used together with the photopolymerization initiator. It is desirable to use the photopolymerization initiation aid together with the photopolymerization initiator because it increases the sensitivity of the black photosensitive resin composition and improves productivity. As the photopolymerization initiation aid, one or more compounds selected from the group consisting of amines and carboxylic acid compounds may be preferably used.

[0104] It is preferable to use such photopolymerization initiation aids in an amount typically 10 moles or less, preferably in the range of 0.01 to 5 moles, per mole of photopolymerization initiator. When photopolymerization initiation aids are used within the above range, polymerization efficiency can be increased, and an improvement in productivity can be expected.

[0106] Cyclic siloxane compounds containing epoxy groups and / or silsesquioxane compounds (E)

[0107] In one embodiment of the present invention, the cyclic siloxane compound (E-1) comprises at least one epoxy group and may include a compound of the following chemical formula 1.

[0108] [Chemical Formula 1]

[0109]

[0110] In the above formula,

[0111] R1 to R4 are each independently a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, an epoxy group, an oxetane group, a hydroxyl group, or a silyloxy group, at least one of which is an epoxy group, and

[0112] n is an integer from 2 to 20.

[0114] As used in this specification, C1-C6 alkyl groups refer to straight-chain or branched monovalent hydrocarbons having 1 to 6 carbon atoms, and include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, etc.

[0115] As used in this specification, C2-C6 alkenyl groups refer to straight-chain or branched unsaturated hydrocarbons having 2 to 6 carbon atoms and having one or more carbon-carbon double bonds, and include, but are not limited to, ethyleneyl, propenyl, buteneyl, penteneyl, etc.

[0116] As used in this specification, the epoxy group refers to a hydrocarbon or heterohydrocarbon having one or more epoxy structures, and includes, but is not limited to, examples such as glycidoxyalkyl groups, epoxycyclohexylalkyl groups, and epoxyalkyl groups. Examples of the glycidoxyalkyl group include 3-glycidoxypropyl groups or 4-glycidoxybutyl groups, examples of the epoxycyclohexylalkyl groups include 2-(3,4-epoxycyclohexyl)ethyl groups, 3-(3,4-epoxycyclohexyl)propyl groups, and examples of the epoxyalkyl groups include 5,6-epoxyhexyl groups, 9,10-epoxydecyl groups.

[0117] As used in this specification, the oxetane group refers to a hydrocarbon or heterohydrocarbon having a quaternary cyclic ether structure (1,3-epoxy structure), and includes, but is not limited to, 3-methyl-3-oxetanylalkyl group, 3-ethyl-3-oxetanylalkyl group, etc.

[0118] As used in this specification, a silyloxy group refers to an oxygen functional group single-bonded to a silyl group, and includes, but is not limited to, silyloxy groups having a C1-C4 alkyl group such as trimethylsilyloxy and triethylsilyloxy; silyloxy groups having a C1-C4 alkoxy group such as trimethoxysilyl and triethoxysilyl; and dihydroxysilyloxy groups bonded with an epoxy group.

[0119] In one embodiment of the present invention, n is an integer from 2 to 20, preferably an integer from 3 to 10, as described above.

[0121] In one embodiment of the present invention, the cyclic siloxane compound may include a compound represented by the following chemical formula 2.

[0122] [Chemical Formula 2]

[0123]

[0124] In the above formula,

[0125] R is an epoxy group.

[0126] The above-mentioned cyclic siloxane compounds may be commercially available, and examples include DSE-001 and DSE-002 (Daxin), but are not limited thereto.

[0128] In one embodiment of the present invention, the silsesquioxane compound (E-2) comprises at least one epoxy group and forms a cross-linking network within the black photosensitive resin composition to improve the degree of curing of the coating film, thereby improving durability such as chemical resistance and providing flexibility. Through this, a product with high reliability can be provided for the implementation of a black matrix requiring a low-temperature curing process.

[0129] The above silsesquioxane compound has a molecular formula (RSiO) in which the main chain backbone consists of Si-O bonds. 1.5 ) n Compounds of a structure (wherein R is hydrogen; or straight-chain, branched, or cyclic C1-C that are substituted or unsubstituted with epoxy, oxetane, or vinyl groups) 20 It means a hydrocarbon of, where n is a natural number.

[0130] Straight-chain, branched, or ring-shaped C1-C as used in this specification 20 The hydrocarbon refers to a straight-chain, branched, or cyclic hydrocarbon group composed of 1 to 20 carbon atoms, for example, C1-C 20 alkyl group of, C1-C 20 alkylene group of, C2-C 20 alkenylene group of, C2-C 20 alkynylene group of, C3-C 20 It may be a cycloalkylene group, etc.

[0131] C1-C used in this specification 20 The alkyl group refers to a straight-chain or branched monovalent hydrocarbon consisting of 1 to 20 carbon atoms, and includes, but is not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, etc.

[0132] C1-C used in this specification 20 The alkylene group refers to a straight-chain or branched divalent hydrocarbon consisting of 1 to 20 carbon atoms, and includes, but is not limited to, examples such as methylene, ethylene, propylene, butylene.

[0133] C2-C used in this specification 20The alkenyl group refers to a straight-chain or branched unsaturated hydrocarbon having 2 to 20 carbon atoms and one or more carbon-carbon double bonds, and includes, but is not limited to, examples such as ethyleneyl, propenyl, butenyl, and pentenyl.

[0134] C2-C used in this specification 20 The alkenylene group refers to a straight-chain or branched divalent unsaturated hydrocarbon having 2 to 20 carbon atoms and one or more carbon-carbon double bonds, and includes, but is not limited to, vinylene, propenylene, butenylene, pentenylene, etc.

[0135] C2-C used in this specification 20 The alkynyl group refers to a straight-chain or branched unsaturated hydrocarbon having 2 to 20 carbon atoms and one or more carbon-carbon triple bonds, including but not limited to acetyleneyl, propynyl, butyleneyl, etc.

[0136] C3-C in this specification 20 The cycloalkyl group refers to a simple or fused cyclic hydrocarbon composed of 3 to 20 carbon atoms, and includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0137] In one embodiment of the present invention, n may be an integer from 1 to 16, preferably an integer from 3 to 12. Within the above range, the structural stability of the silsesquioxane compound may be improved due to the strong bonding force of the siloxane bond.

[0138] Silsesquioxane compounds may be cage-type, ladder-type, or random-type, and among these, cage-type is preferred.

[0139] Cage-type silsesquioxane compounds are also called polyhedral oligomeric silsesquioxane (POSS) compounds, and are referred to as organic-inorganic intermediates or hybrid compounds that possess both the properties of inorganic silica (SiO2) and organic silicon (R2SiO) with a silica cage structure of 1 to 5 nm in size.

[0140] The cage-type silsesquioxane compound may be a complete cage type, or an incomplete cage-type silsesquioxane compound in which part of the cage is open.

[0141] Preferably, the silsesquioxane compound may include a cage-type silsesquioxane compound having an epoxy group, an oxetane group, or a vinyl group.

[0142] Commercially available products may be used as the above silsesquioxane compound, such as EP0409 (Hybrid Plastics), but are not limited thereto.

[0144] One or more of the cyclic siloxane compound and silsesquioxane compound containing the above epoxy group (E) may be included in an amount of 5 to 15 weight%, preferably 10 to 15 weight%, based on 100 weight% of the total solid content of the black photosensitive resin composition. When the above content range is satisfied, photocurability and pattern-forming properties are maximized so that the formed pattern can form a fine pattern with a purely tapered shape, and high solvent resistance and reflectance can be maintained.

[0146] Thiol compound (G)

[0147] In one embodiment of the present invention, the above The thiol compound (G) is a component that plays a role in improving low-temperature thermosetting ability, and is a compound having one or more thiol groups within its molecule. The above When used together with the aforementioned epoxy compound, the thiol compound can lower the thermal reaction temperature and improve low-temperature curing properties.

[0148] For example, the above Thiol compounds may be compounds represented by the following chemical formula 3, but are not limited thereto.

[0149] [Chemical Formula 3]

[0150]

[0151] L 1 Silver carbon; substituted or unsubstituted C2-C 20 alkylene group of; substituted or unsubstituted C2-C 20 heteroalkylene group of; substituted or unsubstituted C6-C 30 arylene group of; substituted or unsubstituted C3-C 30 heteroarylene group; substituted or unsubstituted C3-C 30 cycloalkylene group of; or substituted or unsubstituted C3-C 30 It is a heterocycloalkylene group of, and

[0152] Y a to Y d are either independently non-existent; or substituted or unsubstituted C1-C 30 alkylene group of; substituted or unsubstituted C2-C 30 an alkenylene group; or at least one methylene (-CH2-) is a sulfonyl (-S(=O)2-), carbonyl (-C(=O)-), ether (-O-), sulfide (-S-), sulfoxide (-S(=O)-), ester (-C(=O)O-), amide (-C(=O)NR-) (where R is hydrogen or C1-C 10 is a straight-chain or branched-chain alkyl group), imine(-NR-)(where R is hydrogen or C1-C 10 A C1-C substituted with a straight-chain or branched-chain alkyl group) or a combination thereof. 30 The alkylene group or C2-C 30 It is an alkenylene group, and

[0153] R ato R d Each is independently hydrogen; substituted or unsubstituted C1-C 30 straight-chain or branched-chain alkyl groups; substituted or unsubstituted C6-C 30 aryl group of; substituted or unsubstituted C3-C 30 heteroaryl group of; substituted or unsubstituted C3-C 30 cycloalkyl group of; substituted or unsubstituted C3-C 30 heterocycloalkyl group of; C1-C 10 alkoxy group; hydroxyl group; -NH2; substituted or unsubstituted C1-C 30 The amine group (-NRR', where R and R' are each independently hydrogen or C1-C 30 is a straight-chain or branched-chain alkyl group); isocyanate group; halogen; -ROR' (where R is a substituted or unsubstituted C1-C 20 It is an alkylene group and R' is hydrogen or C1-C 20 is a straight-chain or branched-chain alkyl group); acyl halide (-RC(=O)X, where R is a substituted or unsubstituted alkylene group and X is a halogen); -C(=O)OR' (where R' is hydrogen or C1-C 20 is a straight-chain or branched-chain alkyl group); -CN; or -C(=O)ONRR' (where R and R' are each independently hydrogen or C1-C 20 (which is a straight-chain or branched-chain alkyl group) or SH, wherein R a to R d At least two of them are SH, and

[0154] p and q are each independently integers from 1 to 2.

[0156] Unless otherwise defined below, "substitution" means that hydrogen in a compound is C1-C 30 alkyl group of, C2-C 30 alkynyl group of, C6-C 30 aryl group of, C7-C 30 alkylaryl group of, C1-C 30 alkoxy group, C1-C 30heteroalkyl group of, C3-C 30 heteroalkylaryl group of, C3-C 30 cycloalkyl group of, C3-C 15 cycloalkenyl group of, C6-C 30 cycloalkynyl group of, C2-C 30 heterocycloalkyl group, halogen (-F, -Cl, -Br, or -I), hydroxyl group (-OH), nitro group (-NO2), cyano group (-CN), amino group (-NRR', where R and R' are independently hydrogen or C1-C6 alkyl groups), azido group (-N3), amido group (-C(=NH)NH2), hydrazino group (-NHNH2), hydrazono group (=N(NH2)), aldehyde group (-C(=O)H), carbamoyl group (-C(O)NH2), thiol group (-SH), ester group (-C(=O)OR, where R is a C1-C6 alkyl group or C6-C 12 It means substituted with a substituent selected from an aryl group, a carboxyl group (-COOH) or its salt (-C(=O)OM, where M is an organic or inorganic cation), a sulfonic acid group (-SO3H) or its salt (-SO3M, where M is an organic or inorganic cation), a phosphate group (-PO3H2) or its salt (-PO3MH or -PO3M2, where M is an organic or inorganic cation), and combinations thereof.

[0157] Also, unless otherwise defined below, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S, Si, and P.

[0158] In this specification, "alkylene group" is a straight-chain or branched-chain saturated aliphatic hydrocarbon group having two or more valences.

[0159] In this specification, "heteroalkylene group" is a straight-chain or branched-chain saturated aliphatic hydrocarbon group having two or more valences and one or more of the chain carbons being substituted with a heteroatom.

[0160] In this specification, "arylene group" means a functional group having two or more valencies formed by the removal of at least two hydrogens from one or more aromatic rings.

[0161] In this specification, "heteroarylene group" means a functional group having two or more valencies formed by the removal of at least two hydrogens from one or more aromatic rings, and having one or more ring carbons substituted with a heteroatom.

[0162] In this specification, "cycloalkylene group" means a functional group having two or more valence formed by the removal of at least two hydrogens from one or more saturated aliphatic rings.

[0163] In this specification, "heterocycloalkylene group" means a functional group having two or more valence formed by the removal of at least two hydrogens from one or more saturated aliphatic rings, wherein one or more of the ring carbons are substituted with a heteroatom.

[0164] In this specification, "alkenylene group" is a straight-chain or branched-chain unsaturated aliphatic hydrocarbon group having two or more valences and one or more carbon-carbon double bonds.

[0165] In this specification, "alkyl group" is a straight-chain or branched-chain saturated aliphatic hydrocarbon group having 1 valence.

[0166] In this specification, "aryl group" means a functional group having one valence formed by the removal of one hydrogen from one or more aromatic rings.

[0167] In this specification, "heteroaryl group" means a functional group having one valence formed by the removal of one hydrogen from one or more aromatic rings, and in which one or more of the ring carbons are substituted with a heteroatom.

[0168] In this specification, "cycloalkyl group" means a functional group having one valence formed by the removal of one hydrogen from one or more saturated aliphatic rings.

[0169] In this specification, "heterocycloalkyl group" means a functional group having one valence formed by the removal of one hydrogen from one or more saturated aliphatic rings, in which one or more of the ring carbons are substituted with a heteroatom.

[0171] Specifically, the above Thiol compounds (G) are 2-ethylhexyl-3-mercaptopropionate, butane-1,4-diyl bis(mercaptoacetate), ethoxylated pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), trimethylolpropane tri(3-mercaptoacetate), glycol di-(3-mercaptopropionate), polypropylene glycol 3-mercaptopropionate, ethoxylated trimethylolpropane tri(3-mercaptopropionate), glycol dimercaptoacetate, ethoxylated glycol dimercaptoacetate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, It may be 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(2-mercaptoacetate), dipentaerythritol hexakis(3-mercaptopropionate), 1,6-hexanedithol, 1,3-propanedithiol, 1,2-ethanedithol, polyethylene glycol dithiol containing 1 to 10 repeating ethylene glycol units, or a combination thereof. In particular, the above The thiol compound may include one or more of trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate).

[0173] In one embodiment of the present invention, the content of the thiol compound may be 0.1 to 3 weight%, preferably 0.5 to 2.5 weight%, based on 100 weight% of the total solid content of the black photosensitive resin composition. If the thiol compound is included in an amount of less than 0.1 weight% based on 100 weight% of the total solid content of the black photosensitive resin composition, it may be difficult to form a fine pattern during low-temperature curing, and if it is included in an amount of more than 3 weight%, it may be difficult to expect the pattern to become purely tapered during low-temperature curing and it may be difficult to form a fine pattern.

[0175] In one embodiment of the present invention, the weight ratio of one or more of the cyclic siloxane compound and silsesquioxane compound containing the epoxy group to the thiol compound is 5:1 to 10:1. When the above weight ratio condition is satisfied, the pattern can exhibit a purely tapered shape even when the black photosensitive resin composition is cured at a low temperature, and a fine pattern with high resolution can be formed, and the cured film can exhibit excellent solvent resistance, reflectance retention rate, and pencil hardness.

[0177] Epoxy compound (H)

[0178] The black photosensitive resin composition of the present invention may further include other epoxy compounds as needed, in addition to the cyclic siloxane compound and silsesquioxane compound containing the epoxy group.

[0179] The above epoxy compound (H) is a component that improves the degree of curing and is a compound having an epoxy group within its molecule.

[0180] For example, the above epoxy compound (H) may be an epoxy compound obtained by epoxidizing a condensate of phenol or alkyl phenols with hydroxybenzaldehyde; a biphenyl-type epoxy compound; a bisphenol-type epoxy compound such as a bisphenol A / F-type epoxy compound or a tetramethylbisphenol F-type epoxy compound; a stilbene-type epoxy compound; a novolak-type epoxy compound such as a phenol novolak-type epoxy compound or a cresol novolak-type epoxy compound; a polyfunctional epoxy compound such as a triphenolmethane-type epoxy compound or an alkyl-modified triphenolmethane-type epoxy compound; a phenolaryl-type epoxy compound such as a phenolaryl-type epoxy compound having a phenylene backbone or a phenolaryl-type epoxy compound having a biphenylene backbone; a naphthol-type epoxy compound such as a dihydroxynaphthalene-type epoxy compound or an epoxy compound obtained by glycidyl etherifying a dimer of dihydroxynaphthalene; Triazine core-containing epoxy compounds such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; carboxylic acid cyclic hydrocarbon modified phenolic epoxy compounds such as dicyclopentadiene-modified phenolic epoxy compounds, etc., may be used, and these may be used alone or in combination of two or more types.

[0181] In one embodiment of the present invention, the content of the epoxy compound may be 0.1 to 15 weight% with respect to 100 weight% of the total solid content of the black photosensitive resin composition. When the above content range is satisfied, a good cured film can be formed at low temperatures and high surface flatness can be maintained.

[0183] Additives (I)

[0184] A black photosensitive resin composition according to one embodiment of the present invention may further include an additive (I) as needed in addition to the above-mentioned components.

[0185] The above additive may specifically be one or more selected from the group consisting of leveling agents, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, UV absorbers, and anti-coagulation agents.

[0186] As the leveling agent, commercially available surfactants may be used to further improve the film-forming ability of the black photosensitive resin composition, and examples include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, amphoteric surfactants, etc., and each of these may be used individually or in combination of two or more types.

[0187] The above additive may be appropriately added and used by those skilled in the art within a range that does not impede the effects of the present invention. For example, the above additive may be used in an amount of 0.01 to 10 weight%, preferably 0.01 to 9 weight%, with respect to the total solid content of the black photosensitive resin composition, but is not limited thereto.

[0189] Solvent (J)

[0190] In one embodiment of the present invention, the solvent is not particularly limited as long as it is effective in dissolving other components included in the black photosensitive resin composition of the present invention, and various organic solvents used in photosensitive resin compositions may be used.

[0191] Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; methyl ethyl ketone, acetone, methyl amyl ketone, and methyl isobutyl ketone. Examples include ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

[0192] Among the above solvents, in terms of coating properties and drying properties, an organic solvent having a boiling point of 100°C to 200°C may be used, and more preferably, alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate or methyl 3-methoxypropionate may be used, and even more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate may be used. Each of these solvents may be used individually or in a mixture of two or more types.

[0193] The above solvent (J) may be included in the remainder so that the total weight of the black photosensitive resin composition is 100% by weight.

[0195] A black photosensitive resin composition according to one embodiment of the present invention has the advantage of being able to be cured at a low temperature, which is advantageous when applied to a flexible substrate.

[0196] Specifically, the black photosensitive resin composition can be cured at 100°C or lower, for example, at 80°C to 100°C. After immersing the cured film obtained by curing the black photosensitive resin composition at 80°C to 100°C in propylene glycol monomethyl ether acetate (PGMEA) at 90°C for 10 minutes, the residual film rate may be 90% or higher.

[0198] The method for manufacturing the black photosensitive resin composition of the present invention is not particularly limited and follows the method for manufacturing a black photosensitive resin composition known in the art.

[0199] For example, a coloring agent can be added to a solvent, and then the remaining composition and other additives are added and stirred. In this case, the coloring agent may be added in the form of a mill base in which pigments, etc., are pre-dissolved or dispersed in a solvent or an alkali-soluble resin. If the additives are in solution form, they may be pre-added to the solvent along with the coloring agent.

[0200] The black photosensitive resin composition produced in this way can be preferably used in the manufacture of a black matrix for an image display device.

[0202] Accordingly, one embodiment of the present invention relates to a black matrix formed using the black photosensitive resin composition described above.

[0204] A conventional patterning process for forming a black matrix according to a photolithography method is

[0205] a) a step of applying a black photosensitive resin composition to a substrate;

[0206] b) a pre-bake step for drying the solvent;

[0207] c) a step of placing a photomask over the obtained film and irradiating it with an active light to cure the exposed area;

[0208] d) a step of performing a developing process to dissolve the unexposed area using an alkaline aqueous solution; and

[0209] e) It is performed by including drying and post-baking steps.

[0210] The above substrate is a glass substrate or a polymer plate. As a glass substrate, soda-lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, or quartz may be preferably used. In addition, as a polymer plate, polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, or polysulfone may be used.

[0211] At this time, the coating can be performed by a wet coating method using a coating device such as a roll coater, spin coater, slit-and-spin coater, slit coater (sometimes called a die coater), or inkjet to obtain a desired thickness.

[0212] Pre-baking is performed by heating with an oven, a hot plate, etc. At this time, the heating temperature and heating time for pre-baking are appropriately selected depending on the solvent used, for example, at a temperature of 80 to 150°C for 1 to 30 minutes.

[0213] In addition, the exposure performed after prebaking is carried out by an exposure machine and sensitizes only the parts corresponding to the pattern by exposing through a photomask. The light irradiated at this time can be, for example, visible light, ultraviolet light, X-rays, and electron beams.

[0214] Alkali development after exposure is performed for the purpose of removing the black photosensitive resin composition from the unexposed portion, and a desired pattern is formed by this development. This is performed using a developer or an ultrasonic cleaner, etc., within a temperature of 10 to 50°C, preferably 20 to 40°C, using a 0.02 to 0.06 wt% KOH alkaline aqueous solution or a 1 to 3% TMAH developer.

[0215] Post-baking is performed to increase the curing degree of the patterned film and to increase the reflow of the pattern's taper angle, and is carried out through heat treatment at 80 to 100°C for 10 to 120 minutes. Post-baking is performed using an oven, a hot plate, etc., just like pre-baking.

[0217] One embodiment of the present invention relates to an image display device comprising the black matrix described above.

[0218] Except for having the black matrix described above, the image display device of the present invention includes configurations known in the art. That is, any image display device capable of applying the black matrix of the present invention is included in the present invention. For example, a transmissive liquid crystal display device may be provided in which a counter electrode substrate having a thin film transistor (TFT element), a pixel electrode, and an alignment layer is oriented facing each other at a predetermined distance, and a liquid crystal material is injected into this gap to form a liquid crystal layer. Additionally, there is a reflective liquid crystal display device in which a reflective layer is installed between a substrate of a color filter and a coloring layer. As another example, a liquid crystal display device may be provided in which a thin film transistor (TFT) substrate is combined on the transparent electrode of a color filter and a backlight is fixed at a position where the TFT substrate overlaps with the color filter.

[0220] The present invention will be explained more specifically below through examples, comparative examples, and experimental examples. These examples, comparative examples, and experimental examples are intended solely to illustrate the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.

[0222] Preparation Example 1: Preparation of coloring agent dispersion (A-1)

[0223] A coloring agent dispersion (A-1) was prepared by mixing a composition consisting of 15.0 wt% organic black pigment (Basf IrgaphorS100CF) as the pigment, 3 wt% alkali-soluble resin (benzyl methacrylate / N-phenylmaleimide / styrene / methacrylic acid copolymer, molar ratio 55 / 9 / 11 / 25, Mw=20,000, acid value 100 mgKOH / g) as the dispersion resin, 2.5 wt% acrylic polymer dispersant (DISPERBYK-2000, NV=40.0%) as the dispersant, and 79.5 wt% propylene glycol monomethyl ether acetate as the solvent with a rigid milling medium (zirconia beads) having an average particle size of 0.1 mm in a weight ratio of 50:50 and then dispersing the pigment using a bead mill for 4 to 6 hours.

[0225] Examples 1 to 4 and Comparative Examples 1 to 8: Preparation of black photosensitive resin compositions

[0226] A black photosensitive resin composition was prepared by mixing each component according to the compositions of Tables 1 and 2 below (Unit: weight%).

[0228] Experimental Example 1: Evaluation of Physical Properties of Colored Substrate

[0229] A 5cm × 5cm glass substrate (Corning) was cleaned with a neutral detergent and water, and then dried. Each of the black photosensitive resin compositions prepared in the above examples and comparative examples was spin-coated onto the glass substrate to a final film thickness of 2.0 μm, and pre-fired at 85°C for 2 minutes and 30 seconds. Then, using a mask engraved with a pattern width of 3 to 50 μm, 100 mJ / cm² 2 A pattern was formed by exposure to light, and the unexposed area was removed by immersion in a 2.38% tetramethylammonium hydroxide (TMAH) developer for 100 seconds and then washed with water. Subsequently, a line pattern was formed by post-firing at 85°C for 1 hour.

[0230] The reflectance retention rate, solvent resistance, pencil hardness, pattern resolution, and taper shape of the fabricated substrate were measured in the following manner, and the results are shown in Tables 1 and 2 below.

[0232] (1) Evaluation of reflectance retention rate

[0233] When fabricating the above substrate, the front substrate was fabricated by proceeding with exposure without using a photomask, and then the SCI (specular component included) reflectance (Y1) of the PR surface was measured using an integrating sphere reflectance meter (Konica Minolta, Spectrophotometer CM-3700A). Subsequently, a post-process PR (Color PR) was spin-coated onto the fabricated front substrate to a final film thickness of 2.9 μm and pre-fired at 85°C for 2 minutes and 30 seconds. Then, the substrate was fabricated by developing in an aqueous KOH solution. When the reflectance of the obtained cured film was set to Y2, the value of Y2 / Y1 was calculated to evaluate the reflectance retention rate before and after the post-process.

[0234] [Equation 1]

[0235] Reflectance Retention Rate (%) = SCI Value After Post-processing (Y2) / SCI Value Before Post-processing (Y1) * 100

[0237] <Evaluation Criteria for Reflectance Retention Rate>

[0238] ◎: 90% or more

[0239] ○: 80% or more and less than 90%

[0240] △: 70% or more and less than 80%

[0241] ×: Less than 70%

[0243] (2) Measurement of the minimum size of the fine pattern (resolution evaluation)

[0244] The pattern of the substrate manufactured as described above was analyzed using an optical microscope (Nikon, LV100POL) to measure the size of the minimum pattern that can be formed without loss of the pattern.

[0246] (3) Evaluation of tapered shape

[0247] A cross-section of a 20㎛ pattern was cut from the line pattern of the substrate prepared by the above method, and the tapered shape was observed using an SEM (HITACHI, SU-8100).

[0248] <Taper Shape Evaluation Criteria>

[0249] ○: Net taper

[0250] ×: Undercut

[0252] (4) Evaluation of content

[0253] The substrate prepared by the above method was immersed in a PGMEA / PGME=7 / 3 mixed solution at 65°C for 5 minutes and then dried, and the rate of change in film thickness of a 100㎛ pattern before and after immersion was measured.

[0254] Residual film percentage (%) = [Film thickness of 100㎛ pattern after immersion / Film thickness of 100㎛ pattern before immersion] × 100

[0255] <Content Evaluation Criteria>

[0256] ◎: Residue rate 90% or higher

[0257] ○: Residue rate 70% or more and less than 90%

[0258] △: Residue rate less than 70%

[0259] ×: Surface anomalies and pattern loss

[0261] (5) Pencil hardness evaluation

[0262] The surface hardness of the cured film obtained using the above substrate fabrication method was measured. Surface hardness was measured by using a Pencil Hardness Tester to contact a Mitsubishi Pencil with the substrate, placing a 500g weight on it to increase the load, and then scraping the surface of the substrate at a speed of 50 mm / sec while observing the surface. The measurement standard was evaluated based on the point where no wear, peeling, tearing, or scratching was observed on the surface at a level corresponding to pencil hardness.

[0264] Unit: Weight (%) Solids (%) Examples Comparative example 1 2 3 4 1 2 Black coloring agent (A) A-1 20.8 27.5 27.5 27.5 27.5 27.5 27.5 Alkali-soluble resin (B) B 50.6 9.83 9.83 8.76 9.83 13.63 13.09 Photopolymerizable compound (C) C 100 1.83 1.83 1.83 1.83 1.83 1.83 Photopolymerization initiator (D) D-1 100 0.27 0.27 0.27 0.27 0.27 0.27 D-2 100 0.27 0.27 0.27 0.27 0.27 0.27 Cyclic siloxane compound (E-1) E-1 50.1 3.31 3.31 3.31 0 0 0 Silsesquioxane compound (E-2) E-2 100 0 0 0 1.66 0 0 Thiol compound (G) G-1 100 0.27 0 0.27 0.27 0 0.27 G-2 100 0 0.27 0 0 0 0 Epoxy compound (H) H 51 0 0 1.09 0 0 0 Additives (I) I-1 10 0.15 0.15 0.15 0.15 0.15 0.15 I-2 100 0 0 0 0 0 0 Solvent (J) J 0 56.57 56.57 56.55 58.22 56.35 56.62 E:G (based on solid content) 6:1 6:1 6:1 6:1 0:0 0:1 Rate of change in reflectance (%) ◎ ◎ ◎ ◎ × △ Micro-pattern (㎛) 3 3 3 3 12 10 Taper ○ ○ ○ ○ × × Content ◎ ◎ ◎ ◎ × △ Pencil hardness 3H 3H 4H 3H H H

[0265] Unit: Weight (%) Solids (%) Comparative example 3 4 5 6 7 8 black coloring agent (A) A-1 20.8 27.5 27.5 27.5 27.5 27.5 27.5 Alkali-soluble resin (B) B 50.6 10.51 10.35 7.23 10.35 9.13 7.37 Photopolymerizable compound (C) C 100 1.83 1.83 1.83 1.83 1.83 1.83 Photopolymerization initiator (D) D-1 100 0.27 0.27 0.27 0.27 0.27 0.27 D-2 100 0.27 0.27 0.27 0.27 0.27 0.27 Cyclic siloxane compound (E-1) E-1 50.1 0 0 0 3.31 3.31 5.79 Silsesquioxane compound (E-2) E-2 100 0 0 0 0 0 0 Thiol compound (G) G-1 100 0 0 0 0 0.62 0.27 G-2 100 0 0 0 0 0 0 Epoxy compound (H) H 51 3.09 0 3.09 0 0 0 Additives (I) I-1 10 0.15 0.15 0.15 0.15 0.15 0.15 I-2 100 0 1.66 1.66 0 0 0 Solvent (J) J 0 56.38 57.97 58 56.32 56.92 56.55 E:G (based on solid content) 0:0 0:0 0:0 1:0 3:1 11:1 Rate of change in reflectance (%) ○ △ ○ ○ ○ ◎ Micro-pattern (㎛) 10 9 8 6 8 8 Taper × ○ × ○ × × Content ○ △ ○ ○ ◎ ◎ Pencil hardness 2H 2H 3H 2H 3H 3H

[0267] A-1: Colorant dispersion of Preparation Example 1

[0268] B: Alkali-soluble resin (copolymer of benzyl methacrylate / N-phenylmaleimide / styrene / methacrylic acid, molar ratio 55 / 9 / 11 / 25, Mw=20,000, acid value 100 mgKOH / g)

[0269] C: Dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.)

[0270] D-1: Irgacure OXE-03 (Basf)

[0271] D-2: TR-PBG-345 (Tronly)

[0272] E-1: DSE-002 (Cyclosiloxane Compound, Daxin)

[0273] E-2: EP0409 (Epoxysilsesquioxane Compound, Hybrid Plastics)

[0274] G-1: Trimethylolpropane tris(3-mercaptopropionate) (TMMP, Sakai Kagaku Co.)

[0275] G-2: Pentaerythritol tetrakis(3-mercaptopropionate) (PEMP, Sakai Kagaku Co.)

[0276] H: EHPE-3150 (Epoxy compound, Daicel)

[0277] I-1: F-554 (DIC)

[0278] I-2: SO1458 (Silsesquioxane compound, Hybrid Plastics)

[0279] J: Propylene glycol monomethyl ether acetate (PGMEA)

[0281] As shown in Tables 1 and 2 above, the black photosensitive resin compositions of Examples 1 to 4, comprising a cyclic siloxane compound or a silsesquioxane compound containing an epoxy group and a thiol compound, were confirmed to exhibit a pure taper shape even when fired at a low temperature of 100°C or lower, and to have excellent reflectance retention, resolution, solvent resistance, and pencil hardness.

[0282] On the other hand, it was confirmed that the black photosensitive resin compositions of Comparative Examples 1 to 6, which do not contain one or more of cyclic siloxane compounds and silsesquioxane compounds containing epoxy groups or thiol compounds, exhibited a reverse taper shape when fired at low temperature, or had poor reflectance retention, resolution, solvent resistance, or pencil hardness.

[0283] In addition, it was confirmed that the black photosensitive resin compositions of Comparative Examples 7 and 8, in which the weight ratio of one or more of the cyclic siloxane compound and silsesquioxane compound containing the epoxy group and the thiol compound deviates from the range of 5:1 to 10:1, exhibited a reverse taper shape or poor resolution when fired at low temperature.

[0285] As specific parts of the present invention have been described in detail above, it is evident to those skilled in the art that such specific descriptions are merely preferred embodiments and do not limit the scope of the present invention. Those skilled in the art will be able to make various applications and modifications within the scope of the present invention based on the above description.

[0286] Accordingly, the substantial scope of the present invention shall be defined by the appended claims and their equivalents.

Claims

Claim 1 A black photosensitive resin composition comprising a black coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, one or more of a cyclic siloxane compound containing an epoxy group and a silsesquioxane compound, a thiol compound, and a solvent, wherein the cyclic siloxane compound containing an epoxy group comprises a compound of the following Chemical Formula 2: [Chemical Formula 2] In the above formula, R is an epoxy group. Claim 2 delete Claim 3 delete Claim 4 A black photosensitive resin composition according to claim 1, wherein one or more of the cyclic siloxane compound containing an epoxy group and the silsesquioxane compound are included in an amount of 5 to 15 weight% based on 100 weight% of the total solid content of the black photosensitive resin composition. Claim 5 In claim 1, the thiol compound comprises a black photosensitive resin composition of the following chemical formula 3: [Chemical Formula 3] In the above equation, L 1 Silver carbon; substituted or unsubstituted C2-C 20 alkylene group of; substituted or unsubstituted C2-C 20 heteroalkylene group of; substituted or unsubstituted C6-C 30 arylene group of; substituted or unsubstituted C3-C 30 heteroarylene group; substituted or unsubstituted C3-C 30 cycloalkylene group of; or substituted or unsubstituted C3-C 30 It is a heterocycloalkylene group of, and Y a to Y d are either independently non-existent; or substituted or unsubstituted C1-C 30 alkylene group of; substituted or unsubstituted C2-C 30 an alkenylene group; or at least one methylene (-CH2-) is a sulfonyl (-S(=O)2-), carbonyl (-C(=O)-), ether (-O-), sulfide (-S-), sulfoxide (-S(=O)-), ester (-C(=O)O-), amide (-C(=O)NR-) (where R is hydrogen or C1-C 10 is a straight-chain or branched-chain alkyl group), imine(-NR-)(where R is hydrogen or C1-C 10 A C1-C substituted with a straight-chain or branched-chain alkyl group) or a combination thereof. 30 The alkylene group or C2-C 30 It is an alkenylene group of, and R a to R d Each is independently hydrogen; substituted or unsubstituted C1-C 30 straight-chain or branched-chain alkyl groups; substituted or unsubstituted C6-C 30 aryl group of; substituted or unsubstituted C3-C 30 heteroaryl group of; substituted or unsubstituted C3-C 30 cycloalkyl group of; substituted or unsubstituted C3-C 30 heterocycloalkyl group of; C1-C 10 alkoxy group; hydroxyl group; -NH2; substituted or unsubstituted C1-C 30 The amine group (-NRR', where R and R' are each independently hydrogen or C1-C 30 is a straight-chain or branched-chain alkyl group); isocyanate group; halogen; -ROR' (where R is a substituted or unsubstituted C1-C 20 It is an alkylene group and R' is hydrogen or C1-C 20 is a straight-chain or branched-chain alkyl group); acyl halide (-RC(=O)X, where R is a substituted or unsubstituted alkylene group and X is a halogen); -C(=O)OR' (where R' is hydrogen or C1-C 20 is a straight-chain or branched-chain alkyl group); -CN; or -C(=O)ONRR' (where R and R' are each independently hydrogen or C1-C 20 (which is a straight-chain or branched-chain alkyl group) or SH, wherein R a to R d At least two of them are SH, and p and q are each independently integers from 1 to 2. Claim 6 In claim 5, the thiol compound comprises one or more of trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate), a black photosensitive resin composition. Claim 7 A black photosensitive resin composition according to claim 1, wherein the thiol compound is included in an amount of 0.1 to 3 weight% based on 100 weight% of the total solid content of the black photosensitive resin composition. Claim 8 A black photosensitive resin composition according to claim 1, wherein the weight ratio of one or more of the cyclic siloxane compound and silsesquioxane compound containing the epoxy group to the thiol compound is 5:1 to 10:

1. Claim 9 A black photosensitive resin composition comprising an epoxy compound further comprising the 1st aspect. Claim 10 A black matrix formed using a black photosensitive resin composition according to any one of claims 1 and 4 to 9. Claim 11 An image display device including a black matrix according to paragraph 10.

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