KR20210102646A - Black photosensitive resin composition, cured film and black matrix produced using the same - Google Patents

Abstract

The present invention relates to: a black photosensitive resin composition comprising a silsesquioxane compound containing a thiol group or an epoxy group; and a cured film and a black matrix manufactured by comprising the same. The black photosensitive resin composition according to the present invention has excellent adhesion, is possible to manufacture a pattern with improved sensitivity, deep hardening, and stability over time, and has excellent stability over time.

Description

Black photosensitive resin composition, cured film and black matrix prepared using the same

The present invention relates to a black photosensitive resin composition, a cured film prepared using the same, and a black matrix.

The black photosensitive resin composition is an essential material for a color filter, a liquid crystal display material, an organic light emitting device, and a display. For example, in a color filter of a color liquid crystal display, a light blocking layer is formed at a boundary between colored layers such as red, green, and blue, so that display contrast or color development effect can be improved.

Specifically, in a pixel composed of red (R), green (G), and blue (B), 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. and forming a column spacer at a portion in contact with the liquid crystal.

Recently, as various image display devices increasingly require high color purity, bright luminance, and high contrast, miniaturization of the pattern line width of the black matrix between pixels is required.

Korean Patent Application Laid-Open No. 2007-0094460 relates to a black photosensitive composition, a black photosensitive composition containing a photopolymerizable compound, a photoinitiator, and a black pigment, and discloses a black photosensitive composition containing an organic pigment as a shape stabilizer. have.

In addition, Korean Patent Publication No. 2012-0033893 relates to a photosensitive resin composition, (A) a binder resin; (B) a polyfunctional monomer; (C) a photoinitiator or a photosensitizer; (D) black pigment; and (E) a solvent, wherein the black pigment is at least one selected from aniline black, perylene black, and metal oxides.

However, the conventional documents as described above have somewhat low adhesion and stability over time, making it difficult to apply them to fine patterns.

Therefore, there is a demand for the development of a black photosensitive resin composition capable of improving the sensitivity while increasing the adhesion of the fine pattern and the degree of deep hardening using the black photosensitive resin composition.

Republic of Korea Patent Publication No. 2007-0094460 (2007.09.20.) Republic of Korea Patent Publication No. 2012-0033893 (2012.04.09.)

An object of the present invention is to provide a black photosensitive resin composition having excellent adhesion and capable of producing a fine pattern having an improved degree of deep hardening.

Another object of the present invention is to provide a black photosensitive resin composition having excellent stability over time.

In addition, an object of the present invention is to provide a cured film and a black matrix having excellent curing degree, stability over time, and improved sensitivity by being manufactured using the black photosensitive resin composition described above.

The present invention provides a black photosensitive resin composition comprising; a silsesquioxane compound containing a thiol group or an epoxy group.

Moreover, this invention provides the cured film containing the hardened|cured material of the black photosensitive resin composition mentioned above.

In addition, the present invention provides a black matrix of a color filter including the cured film described above.

The black photosensitive resin composition according to the present invention has excellent adhesion, it is possible to manufacture a pattern with improved sensitivity, depth of hardening, and stability over time, and has excellent stability over time.

In addition, the cured film and the black matrix prepared by using the black photosensitive resin composition according to the present invention have excellent deep curing degree, excellent adhesion and sensitivity, and excellent stability over time.

1 and 2 are adhesive evaluation results of Example 1 and Comparative Example 1.

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

In the present invention, when a member is said to be located "on" another member, this includes not only a case in which a member is in direct contact with another member but also a case in which another member is interposed between two members.

In the present invention, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

<Black photosensitive resin composition>

One aspect of the present invention relates to a black photosensitive resin composition comprising; a silsesquioxane compound containing a thiol group or an epoxy group.

The black photosensitive resin composition according to the present invention has the advantage of increasing the adhesion of the fine pattern and the degree of deep curing.

Silsesquioxane compound

The black photosensitive resin composition according to the present invention includes a silsesquioxane compound containing a thiol group or an epoxy group.

Since the silsesquioxane compound according to the present invention contains a thiol group or an epoxy group, it is possible to improve the adhesion of the fine pattern and the sensitivity of the depth of the pattern.

In general, in the case of a black photosensitive resin composition, the fine pattern may be somewhat lost because photocuring is not performed to the deep part in the exposure step. There is an advantage in that the adhesion of the fine pattern is improved.

In one embodiment of the present invention, the silsesquioxane compound may further contain an alkyl group.

The alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 10. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neopentyl , tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n- Octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2 -methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

Specifically, the alkyl group may be a methyl group.

Specifically, the black photosensitive resin composition according to the present invention may include a silsesquioxane compound containing a thiol group and an alkyl group.

In addition, the black photosensitive resin composition according to the present invention may include a silsesquioxane compound containing an epoxy group and an alkyl group.

In another embodiment of the present invention, the silsesquioxane compound may include a moiety represented by the following Chemical Formula 1 or 2.

[Formula 1]

[Formula 2]

In another embodiment of the present invention, the silsesquioxane compound may include a residue represented by the following formula (3).

[Formula 3]

Specifically, the silsesquioxane compound according to the present invention may include a residue represented by Formula 1 or 2, and may further include a residue represented by Formula 3 above.

More specifically, the silsesquioxane compound may include a residue represented by Chemical Formula 1 and Chemical Formula 3 above.

In addition, the silsesquioxane compound may include a residue represented by Formula 2 and Formula 3 above.

When the silsesquioxane compound according to the present invention includes a residue represented by Formula 1 or Formula 2, and further includes a residue represented by Formula 3, a micropattern having excellent adhesion and improved sensitivity for deep hardening It has the advantage of being able to manufacture.

In short, the silsesquioxane compound according to the present invention has the advantage of excellent adhesion to the inorganic material because the alkoxysilane group remains, and since it has a thiol group or an epoxy group as a substituent, the improvement of the deep curing sensitivity can be maximized. There is this.

The functional group equivalent in the silsesquioxane compound may be at least 200 g/eq or more, but is not limited thereto. However, in this case, since it is excellent in the improvement of the sensitivity of deep hardening, it is preferable.

In the present invention, the form of the silsesquioxane compound is not limited. For example, the silsesquioxane compound may be a random type, a cage type, or a ladder type.

Specifically, in the present invention, the silsesquioxane compound may be a random type silsesquioxane compound.

When the silsesquioxane compound is of the random type, it is preferable because the synthesis is simple compared to the cage type and the ladder type, and the reliability of the cured product is excellent.

In another embodiment of the present invention, the silsesquioxane compound may be included in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on 100% by weight of the total black photosensitive resin composition, in this case the It is preferable because it has the advantage of being excellent in compatibility with the other compound in a black photosensitive resin composition.

thiol silane coupling agent

In another embodiment of the present invention, the black photosensitive resin composition may further include a thiol-based silane coupling agent.

When the thiol-based silane coupling agent is further included, it is preferable because adhesion is further improved. Specifically, since the thiol-based silane coupling agent has excellent stability over time, it is possible to improve the deterioration of adhesion over time.

The thiol-based silane coupling agent is not limited as long as it has, for example, a siloxane skeleton and a thiol group, 3-MPTS ((3-Mercaptopropyl) trimethyoxysilmae), N-(2-Mercaptopropionyl) glycine, etc. may be used, and as a commercially available product, X- 41-1810 (trade name, mercapto equivalent: 450 g/mol), X-41-1805 (trade name, mercapto equivalent: 800 g/mol), X-41-1818 (trade name, mercapto equivalent: 850 g/mol) ) (all of which are manufactured by Shin-Etsu Chemical Co., Ltd.), and the like, and these may be used alone or in combination of two or more, but are also not limited thereto.

The thiol-based silane coupling agent may be included in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on 100% by weight of the total black photosensitive resin composition, and in this case, the advantage of improving adhesion while having stability over time It is preferable to have

In another embodiment of the present invention, the black photosensitive resin composition may further include one or more selected from the group consisting of a binder resin, a photopolymerizable compound, a photoinitiator, a colorant including a black pigment, a solvent, and an additive. .

binder resin

The binder resin makes the unexposed part of the black photosensitive resin layer formed by using the photosensitive resin composition alkali-soluble, and can also act as a dispersion medium for the pigment. The binder resin may be selected from a variety of polymers used in the applicable technical field, and an alkali-soluble resin including an epoxy group is preferable because it may be effective in improving reliability.

Examples of the binder resin include a monomer containing an epoxy group, and a copolymer of the monomer and other copolymerizable monomers.

The 　 monomer containing an epoxy group is specifically, for example, 3,4-epoxytricyclo[5.2.1.0,2,6]decan-9-ylacrylate, 3,4-epoxytricyclo[5.2.1.0,2 and ,6]decan-8-yl acrylate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether.

Examples of the other monomer copolymerizable with the monomer containing an epoxy group include unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, and vinyl cyanide compounds. , unsaturated amides, unsaturated imides, aliphatic conjugated dienes, and macromonomers having a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polysiloxane, and these monomers are each alone or two types The above can be mixed and used.

In addition, the 　 binder resin having an acid value of 20 to 200 (KOH mg/g) may be preferably used. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer and is related to the solubility of the resin. When the acid value of the resin falls within the above range, the solubility in the developer is improved, so that the non-exposed portion is easily dissolved and the sensitivity is increased. As a result, the pattern of the exposed portion remains at the time of development, thereby improving the film remaining ratio.

In addition, the binder resin may consider limitation of molecular weight and molecular weight distribution (MW/MN) in order to improve surface hardness, and in the case of a weight average molecular weight, 3,000 to 200,000, preferably 5,000 to 100,000, more preferably 5,000 to 30,000 can be used. In the case of molecular weight distribution, a range of 1.5 to 6.0, preferably 1.8 to 4.0, may be used. When the binder resin has a molecular weight and molecular weight distribution within the above ranges, it is preferable because hardness is improved, a residual film prevention effect is excellent, and solubility of non-exposed parts in a developer is excellent and resolution can be improved.

The binder resin may be included in an amount of 5 to 50% by weight, preferably 5 to 30% by weight, based on 100% by weight of the total black photosensitive resin composition.

The content range of the 　 binder resin was selected in consideration of solubility in the developer and pattern formation, etc., and when used within the content range, the solubility in the developer is sufficient to facilitate pattern formation, It can be prevented from peeling off and falling off.

photopolymerization compound

The photopolymerizable compound contained in the black photosensitive resin composition of the present invention is a compound capable of polymerization by the action of light and a photopolymerization initiator to be described later, and includes monofunctional monomers, difunctional monomers, and other polyfunctional monomers.

The type of the monofunctional monomer is not particularly limited, and for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and 2-hydroxyethyl acryl Late, N-vinylpyrrolidone, etc. are mentioned.

The type of the bifunctional monomer is not particularly limited, and for example, 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, 3-methylpentanediol di(meth)acrylate, etc. are mentioned.

The type of the polyfunctional monomer is not particularly limited, and for example, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth) ) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octaacrylate, etc. are mentioned.

Commercially available examples of the photopolymerizable compound include Miramer M600 of Miwon Corporation, V#802 of Osaka Organic Chemical, and the like, but are not limited thereto.

The photopolymerizable compound may be included in an amount of 5 to 30% by weight, preferably 5 to 15% by weight, based on 100% by weight of the total amount of the black photosensitive resin composition, and when included within the above range, a desirable advantage in terms of strength or smoothness of the pixel portion have.

When the photopolymerizable compound is included in less than the above range, the intensity of the pixel portion may be slightly lowered, and if the photopolymerizable compound is included in excess of the above range, smoothness may be slightly reduced, so it is preferable to be included in the above range. .

light curing initiator

The black photosensitive resin composition according to the present invention may include a photoinitiator.

As the photopolymerization initiator, a photopolymerization initiator generally used in the black photosensitive resin composition may be used. For example, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, biimidazole-based compounds and the like may be used.

The photopolymerization initiator including the acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, and biimidazole-based compound is used in the art as long as it does not impair the purpose of the present invention A photoinitiator can be used without limitation.

For example, as the oxime-based compound, o-ethoxycarbonyl- α -oxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1, 2-dione e-2-(o-acetyloxime) etc. are mentioned.

Commercially available products of the photopolymerization initiator include TR-PBG-327 (manufactured by Tronley), NCI-831E (manufactured by ADEKA), N-1919 (manufactured by ADEKA), OXE-01, and OXE-02 (manufactured by Ciba). However, the present invention is not limited thereto.

The photopolymerization initiator may be used in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on 100% by weight of the total black photosensitive resin composition. This content range is in consideration of the photopolymerization rate of the photopolymerizable compound and the physical properties of the finally obtained coating film. If the content is less than the above range, the polymerization rate is low and the overall process time may be prolonged. Since the physical properties of the coating film may be rather deteriorated over time, it is appropriately used within the above range.

In addition, a photopolymerization initiation auxiliary may be used together with the photopolymerization initiator. When the photopolymerization initiation auxiliary is used together with the photopolymerization initiator, the photosensitive resin composition becomes more sensitive and productivity is improved. At least one compound selected from the group consisting of amines and carboxylic acid compounds may be preferably used as the photopolymerization initiation adjuvant.

Such a photopolymerization initiation adjuvant is usually 10 mol or less per 1 mol of the photopolymerization initiator, and preferably used within the range of 0.01 to 5 mol. When the photopolymerization initiation auxiliary agent is used within the above range, the effect of improving the productivity can be expected by increasing the polymerization efficiency.

coloring agent

The black photosensitive resin composition according to the present invention includes a colorant including a black pigment.

The black pigment may be used as an organic black pigment, carbon black, or a mixture of organic black and carbon black.

The organic black may be, for example, lactam black, aniline black, or perylene black, and may be used without particular limitation as long as it has light-shielding properties. Preferably, it may contain lactam black.

When the organic black pigment is included, the optical density may be improved while not affecting the infrared region, and the dielectric constant and transmittance may be improved.

When the carbon black is included, the optical density may be improved, which is preferable.

Available carbon blacks include CHBK-17 from Mikuni Saxo Co.; Donghae Carbon Co., Ltd. SYSTO 5HIISAF-HS, SYSTO KH, SYSTO 3HHAF-HS, SYSTO NH, SYSTO 3M, SYSTO 300HAF-LS, SYSTO 116HMMAF-HS, SYSTO 116MAF, SYSTO FMFEF- HS, cisto SOFEF, cisto VGPF, cisto SVHSRF-HS, and cisto SSRF; Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram of Mitsubishi Chemical Corporation LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, # CF9, #95, #3030, #3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; 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 BLACK-101; RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA of Columbia Carbon Co., Ltd. RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN- 2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170 etc. are mentioned.

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

In addition, as the carbon black which is the said black pigment, resin-coated carbon black may be used. Since the resin-coated carbon black has lower conductivity than the resin-coated carbon black, excellent electrical insulation properties can be provided when forming a black matrix or black column spacer.

The colorant may further include at least one selected from the group consisting of organic pigments and dyes.

Specifically, the colorant may include an organic pigment and dye having a light blocking property to visible light alone or two or more types.

The organic pigment is, for example, a compound classified as a pigment in the color index (CI; published by The Society of Dyers and Colorists), specifically, a color commonly used in the art. For example, those with index (CI) names are given,

In some cases, rosin treatment, surface treatment using a pigment derivative having an acidic or basic group introduced therein, surface graft treatment using a polymer compound, etc., fine particle treatment using sulfuric acid, or washing treatment using an organic solvent or water may have been performed. For example, the colorant may further include a blue pigment.

In addition to this, pigments used in printing inks, inkjets, etc. and water-soluble azo, insoluble azo, phthalocyanine, quinacritone, isoindolinone, isoindoline, perylene, perinone, dioxyzine, anthraquinone, dianone Traquinonyl, anthrapyrimidine, ananthrone, indanthrone, pravantron, and pyranthrone pigments may be used, but the present invention is not limited thereto.

The dye can be used without limitation as long as it is commonly used in the art in a range that does not impair the purpose of the present invention.

The colorant according to the present invention may be included in an amount of 2 to 40 wt%, preferably 2 to 30 wt%, based on 100 wt% of the total black photosensitive resin composition. When the content of the colorant is less than the above range, the optical density (Optical Density, OD) may be somewhat lowered, and if the content of the colorant exceeds the above range, the relative permittivity is slightly increased, which may cause some problems in driving the display device. it is preferable

The black pigment may be included in an amount of 40 to 100% by weight, more preferably 45 to 100% by weight, based on 100% by weight of the total colorant. When the black pigment satisfies the above range, O.D/㎛ has an advantage of satisfying 1.33 or more. When the black pigment is included below the above range, there may be a problem in that the OD is lowered and light leakage occurs at short and long wavelengths, and when the black pigment exceeds the above range, there may be a problem in that the dielectric constant increases. It is preferably included within the above range.

The colorant may be used in the form of a dispersion in which the particle size of the pigment is uniformly dispersed, but is not limited thereto. Examples of a method for uniformly dispersing the particle size of the pigment include a method of dispersing the pigment by containing a dispersing agent, and according to the method, a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained.

Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants, and these may be used alone or in combination of two or more.

In addition, it is preferable to include an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Commercial products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 or DISPER BYK-2150, and the acrylate-based dispersant may be used alone or in combination of two or more. can

The pigment dispersant may use a pigment dispersant other than the acrylic dispersant, but is not limited thereto.

The content of the pigment dispersant may be included in an amount of 5 to 60% by weight, preferably 5 to 50% by weight, based on 100% by weight of the solid content of the colorant, in which case it is easy to atomize the pigment, and problems such as gelation after dispersion can be suppressed, which is preferable.

solvent

The solvent in particular contained in the black photosensitive resin composition of this invention is not restrict|limited, Various organic solvents used in the field|area of the black photosensitive resin composition can be used.

Specific examples thereof 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 dimethyl ether, diethylene glycol diethyl ether, diethylene Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol Alkylene glycol alkyl ether acetates such as 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, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-methoxy Esters, such as methyl propionate, Cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned.

Among the above solvents, organic solvents having a boiling point of 100°C to 200°C in the above solvents are preferable from the viewpoint of applicability and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxy Esters, such as ethyl propionate and 3-methoxy methyl propionate, are mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethyl propionate, 3- and methyl methoxypropionate. These solvents can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent is usually 60 to 90% by weight, preferably 60 to 85% by weight based on 100% by weight of the total black photosensitive resin composition including it. When the content of the solvent satisfies the above range, the coating property tends to be good when applied with an application device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet, etc. It is preferable because there is

additive

The black photosensitive resin composition according to the present invention may further include additives such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, and the like, if necessary.

Specific examples of the filler include glass, silica, alumina, and the like.

Specific examples of the other high molecular compound include thermosetting resins such as epoxy resins and maleimide resins; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The curing agent is used for deep curing and increasing mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound. Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, Glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxide, isoprene (co) ) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like. Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent.

As said hardening auxiliary compound, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, an acid generator etc. are mentioned, for example. As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. Examples of the epoxy resin curing agent include a brand name (adecahadona EH-700) (manufactured by Adeka Industrial Co., Ltd.), a trade name (Rikasiddo HH) (manufactured by Shin-Nippon Ewha Corporation), a trade name (MH-700) ( Manufactured by New Nippon Ewha Co., Ltd.) and the like. The curing agents exemplified above may be used alone or in combination of two or more.

As the leveling agent, commercially available surfactants can be used, and for example, surfactants such as silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants may be mentioned, and these may be used alone. You may use it in combination of 2 or more type. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, In addition to polyethyleneimines, trade names include KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), FTOP (manufactured by Tochem Products), and Megapac (Dainippon Ink Chemical Industry Co., Ltd.). (manufactured by Co., Ltd.), Florad (manufactured by Sumitomo 3M Co., Ltd.), Asahigard, Saffron (above, manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKACHEMICALS) , PB821 (manufactured by Ajinomoto Co., Ltd.); and the like.

As the adhesion promoter, in addition to the above-described thiol-based silane coupling agent, a silane coupling agent having a reactive substituent selected from the group consisting of a methacryloyl group, an isocyanate group, an epoxy group, and combinations thereof may be further included. Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxy silane, vinyltriacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, r-glycidoxy and propyl trimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, which can be used alone or in combination of two or more. Commercially available products of the adhesion promoter include, but are not limited to, Shin-Etsu's KBM-403, KBM-503, BM-603, KBM-573, and KBM-5083.

When the adhesion promoter is further included, it is preferable because better adhesion can be imparted.

The additive may be appropriately added in a range that does not impair the purpose of the present invention, for example, 0.01 to 10% by weight, preferably 0.01 to 5% by weight, more preferably based on 100% by weight of the total black photosensitive resin composition may be included in 0.01 to 3% by weight, but is not limited thereto.

The black photosensitive resin composition according to the present invention includes a specific silsesquioxane compound, thereby improving sensitivity for deep curing, and improving adhesion and stability over time of the prepared micropattern.

< cured film and Black Matrix>

Another aspect of this invention relates to the cured film containing the hardened|cured material of the black photosensitive resin composition mentioned above.

Since the cured film contains a specific silsesquioxane compound, there is an advantage in excellent adhesion and curing degree.

Another aspect of this invention relates to the black matrix of the color filter containing the cured film mentioned above.

The introduction of the black matrix may be formed by patterning through a photolithography method after forming a cured film.

The photolithography method is not particularly limited in the present invention, and any known method using the photosensitive resin composition is applicable. An example may include the following steps:

a) applying a black photosensitive resin composition to the substrate;

b) a pre-baking step of drying the solvent;

c) applying a photomask on the obtained cured film and irradiating actinic light to cure the exposed portion;

d) performing a developing process by dissolving the unexposed part using an aqueous alkali solution; and

e) Drying and post-baking steps

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

In this case, the coating may be performed by a wet coating method using an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet so as to obtain a desired thickness.

The said prebaking is performed by heating with an oven, a hot plate, etc. At this time, the heating temperature and heating time in the prebaking are appropriately selected according to the solvent to be used, and are performed at a temperature of, for example, 80 to 150° C. for 1 to 30 minutes.

Moreover, exposure performed after a prebaking is performed by an exposure machine, and only the part corresponding to a pattern is exposed by exposing through a photomask. In this case, the irradiated light may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

Alkali development after exposure It is performed for the purpose of removing the photosensitive resin composition of the part which is not removed of a non-exposed part, and a desired pattern is formed by this development. As a developing solution suitable for this alkali development, the aqueous solution of the carbonate of an alkali metal or alkaline-earth metal, etc. can be used, for example. In particular, using an aqueous alkali solution containing less than 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate, a developer or ultrasonic cleaner is used at a temperature of 10 to 50° C., preferably 20 to 40° C. to do it

The post-baking is performed to increase adhesion between the patterned film and the substrate, and is performed through heat treatment at 100 to 250° C. for 10 to 120 minutes. Post-bake As with pre-bake, it is performed using an oven, a hot plate, or the like.

The black photosensitive resin composition according to the present invention can be applied to a column spacer or a black matrix-integrated column spacer, if necessary, in addition to the black matrix.

Specifically, the cured film and the black matrix prepared by using the black photosensitive resin composition according to the present invention can be usefully applied to various image display devices such as liquid crystal displays and OLDEs.

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art. In addition, "%" and "part" indicating the content hereinafter are based on weight unless otherwise specified.

Synthesis example : Binder resin

270 g of methoxybutyl acetate was put into a 1 liter separable flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube, and the temperature was raised to 80° C., and then 3,4-epoxytricyclo[5.2.1.0 ²⁹⁴ g of a mixture of 2,6 ]decan-9-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate [50:50 (molar ratio)], dicyclopentenyl A mixed solution obtained by dissolving 14 g of acrylate, 42 g of acrylic acid, and 30 g of azobisdimethylvaleronitrile in 350 g of methoxybutyl acetate was added dropwise over 5 hours, and further aged for 3 hours to obtain a copolymer solution [solid content (NV) 35.8 wt%] got The obtained copolymer had an acid value (dry) of 90.5 KOH mg/g, a weight average molecular weight (Mw) of 9500, and a degree of dispersion (Mw/Mn) of 1.8.

manufacturing example : Preparation of colored dispersion

A colored dispersion was prepared according to the composition and composition of Table 1 below. Specifically, OBP (lactam black) was used as the colorant, the binder resin according to the above synthesis example was used as the dispersion resin, the polymer dispersant (DisperBYK-2000) was used as the dispersant, and propylene glycol monomethyl ether acetate (PGMEA) was used as the solvent. was used. The mixture was dispersed for 8 hours at room temperature with a paint shaker. Dispersion was carried out using 0.1 mm zirconia beads, and after the dispersion was completed, it was filtered.

Component content (wt%) coloring agent dispersion resin dispersant menstruum total content 15 2.26 4.20 78.54 100.0

Example and comparative example : Preparation of black photosensitive resin composition

Black photosensitive resin compositions according to Examples and Comparative Examples were prepared according to the configuration and composition of Table 2 below.

(weight%) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 colored dispersion 20 20 20 20 20 20 20 20 binder resin 6.66 6.66 6.66 6.66 6.66 6.66 6.66 6.66 photopolymerizable compound 6.66 6.66 6.66 6.66 6.66 6.66 6.66 6.66 photopolymerization initiator 0.54 0.54 0.54 0.54 0.54 0.54 0.54 0.54 Silsesquioxane compound a+c a+c b+c b+c - c - c 0.4 0.4 0.4 0.4 - 0.4 - 0.4 Thiol-based Silane Coupling Agent - 0.4 - 0.4 - - 0.4 0.4 additive 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22 solvent 65.52 65.12 65.52 65.12 65.92 65.52 65.52 65.12 Colored dispersion: Colored dispersion according to Preparation Example
Dispersant: DisperBYK-2000
Binder resin: Binder resin according to Synthesis Example
Photopolymerizable compound: tripentaerythritol octaacrylate (8-functional group, #V802, Osaka Organic Chemical Co., Ltd.)
Photoinitiator: TR-PBG-327 (Tronley)
Silsesquioxane compound a + c: including the residues represented by formulas 1 and 3, functional group equivalent 250 g / eq
Silsesquioxane compound b+c: including residues represented by formulas 2 and 3, functional group equivalent 280 g/eq
Silsesquioxane compound c: including a residue represented by Formula 3, functional group equivalent 0
Thiol-based silane coupling agent: 3-MPTS (3-Mercaptopropyl) trimethyoxysilmae)
Additive: KBM-503 (Shin-Etsu)
Solvent: PGMEA (propylene glycol monomethyl ether acetate)

Experimental example

(1) Adhesion evaluation

A 5 cm × 5 cm glass substrate (Corning) was washed with a neutral detergent and water, and then dried. Each of the black photosensitive resin compositions prepared in Examples and Comparative Examples was spin-coated on the glass substrate to have a final film thickness of 5.0 μm, pre-baked at 100° C., and dried for 2 minutes to remove the solvent. Then, it was exposed to an exposure dose of 150 mJ/cm ² with a mask including a line pattern, developed for 400% of the time to start development, and then post-fired at 200° C. for 20 minutes to form a line pattern.

The manufactured substrate was confirmed with the pattern of the minimum size remaining on the substrate using an optical microscope, and the results according to Example 1 and Comparative Example 1 are shown in FIGS. 1 and 2 .

In addition, it was evaluated using the following evaluation criteria, and the results are shown in Table 3 below.

[Evaluation standard]

◎: Maintain pattern less than 5㎛

○: Maintain pattern of 5㎛ or more and less than 8㎛

△: Maintaining a pattern of 8 μm or more and less than 9 μm

×: pattern loss of 9 μm or more

(2) residual feeling evaluation

Among the line patterns of the substrate fabricated in the same way as in (1), the film thickness of the line having a line width of 10 µm and the film thickness of the line having a line width of 30 µm were compared.

By comparing the film thicknesses of these two line widths, it can be confirmed whether the height of the pattern is maintained in the fine pattern (10um). In general, when the sensitivity is lowered to form a fine pattern, the upper portion of the fine pattern is scraped off, resulting in a problem that the height of the pattern is lowered.

The residual film sensitivity was evaluated using the following evaluation criteria, and the results are shown in Table 3 below.

[Evaluation standard]

○: 10㎛ pattern height / 30㎛ pattern height (%) is 90% or more

△: 10 µm pattern height/30 µm pattern height (%) is 80% or more and less than 90%

×: 10 µm pattern height/30 µm pattern height (%) is less than 80%

(3) Stability over time

The black photosensitive resin compositions according to Examples and Comparative Examples were left at room temperature, and the adhesion was evaluated on the 0th and 15th days in the same manner as (1), and the results were compared using the following evaluation criteria and the results are shown in the table below. 3 is shown.

[Evaluation standard]

◎: Equivalent to Day 0 result

○: difference of 3㎛ or less

△: difference greater than 3 μm and less than or equal to 5 μm

×: more than 5 μm

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 adhesion ○ ◎ ○ ◎ × △ △ △ residual feeling ○ ○ ○ ○ × × × △ Stability over time ○ ◎ ○ ◎ × △ ○ ○

As can be seen from Table 3, FIGS. 1 and 2 , when the black photosensitive resin composition according to the present invention is used, it can be seen that all of the adhesiveness, the residual film sensitivity and the stability over time are excellent.

Claims (9)

A black photosensitive resin composition comprising; a silsesquioxane compound containing a thiol group or an epoxy group. According to claim 1,
The silsesquioxane compound is a black photosensitive resin composition that further contains an alkyl group. According to claim 1,
The silsesquioxane compound is a black photosensitive resin composition comprising a residue represented by the following Chemical Formula 1 or 2:
[Formula 1]

[Formula 2]

. 3. The method of claim 2,
The silsesquioxane compound is a black photosensitive resin composition comprising a residue represented by the following Chemical Formula 3:
[Formula 3]

. According to claim 1,
The silsesquioxane compound is included in an amount of 0.1 to 10% by weight based on 100% by weight of the total black photosensitive resin composition. According to claim 1,
The black photosensitive resin composition further comprising a thiol-based silane coupling agent. According to claim 1,
A black photosensitive resin composition further comprising at least one selected from the group consisting of a binder resin, a photopolymerizable compound, a photoinitiator, a colorant including a black pigment, a solvent, and an additive. The cured film containing the hardened|cured material of the black photosensitive resin composition in any one of Claims 1-7. A black matrix of a color filter comprising the cured film according to claim 8 .

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