KR20210073093A - Black photosensitive composition for low temperature curing, black light shielding film and display device - Google Patents

Abstract

The present application relates to a black photosensitive composition for low-temperature curing, a black light-shielding film formed using the same, and a display device including the black light-shielding film, wherein the black photosensitive composition for low-temperature curing includes a binder resin, a polyfunctional monomer, a coloring agent, a dispersant, a photoinitiator, and a solvent, the binder resin includes an alkali-soluble resin and an epoxy resin, the coloring agent includes at least one selected from a group consisting of carbon black, organic black, and a color pigment, and the dispersant has a structure represented by chemical formula 1.

Description

Black photosensitive composition for low-temperature curing, black light-shielding film, and display device {BLACK PHOTOSENSITIVE COMPOSITION FOR LOW TEMPERATURE CURING, BLACK LIGHT SHIELDING FILM AND DISPLAY DEVICE}

The present application relates to a black photosensitive composition for low-temperature curing, a black light-shielding film formed using the same, and a display device including the same.

In order to improve light leakage and contrast in the construction of an OLED device, it is a conventional technique to use a circularly polarizing plate on the device to secure the image quality. However, the use of such a circular polarizer can improve contrast and reflective luminance, but a decrease in transmittance causes a decrease in luminance and limits flexibility, which is an advantage of an OLED device, making it difficult to apply to foldable OLEDs.

Therefore, instead of using a polarizer, the function of the existing polarizer can be secured by manufacturing a black light-shielding pattern on the top of the OLED device and performing a color filter process. can be taken more widely,

However, since the previously developed photosensitive resin composition for black and color filters secured its pattern characteristics through high-temperature curing at 230°C after exposure and development, it is impossible to apply to OLED devices in which light-emitting organic materials, which are vulnerable to temperature, are adopted. Accordingly, it was necessary to develop a composition capable of patterning and curing at a temperature below 100° C. in which the pattern characteristics and organic matter are stable. It was possible to secure the formation of a black light-shielding film and fine pattern characteristics with a composition with certain characteristics. However, since curing is carried out at a low temperature of 100°C or less, the degree of crosslinking is lower than before, and this characteristic causes chemical resistance issues such as damage to the surface of the black film and chipping after the color filter or planarization process that follows the black light shielding process. did it In order to improve the chemical resistance by increasing the degree of crosslinking in the formation of the black light-shielding film, a composition containing a thermosetting epoxy resin was secured and the required characteristics were improved. However, in the case of a pigment dispersion liquid containing an amine-based dispersant essential, and a photoresist using an epoxy resin together, the chemical resistance of the formed coating film was secured, but it caused a problem in storage stability over time, making it difficult to secure uniform fairness and clean pattern characteristics without residue. has been raised

Korean Patent Application Publication No. 2011-0071965

An object of the present application is to provide a black photosensitive composition for low-temperature curing, a black light-shielding film, and a display device including the same, in which storage stability over time is secured.

An exemplary embodiment of the present application is a binder resin; polyfunctional monomers; coloring agent; dispersant; A black photosensitive composition for low-temperature curing comprising a photoinitiator and a solvent, wherein the binder resin comprises an alkali-soluble resin and an epoxy resin, and the colorant is carbon black; organic black; and at least one selected from the group consisting of color pigments, wherein the dispersant provides a black photosensitive composition for low temperature curing comprising a structure represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1,

R1 is a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; Or a substituted or unsubstituted aryl group,

R2 to R6 are the same as or different from each other, and each independently represent a substituted or unsubstituted alkyl group,

R11 to R13 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group,

L1 and L2 are the same as or different from each other, and are each independently a substituted or unsubstituted alkylene group,

X is a halogen group; sulfonic acid group; acetate group; or a phosphate group,

a, b and c are mole % of the unit in each parenthesis based on the total number of moles of the structure represented by Formula 1 above,

a is 50 to 90 mol%,

b+c is 10 to 50 mol%,

0.3b ≤ c ≤ b.

Another exemplary embodiment of the present application provides a black light-shielding film formed using the black photosensitive composition for low-temperature curing.

Another exemplary embodiment of the present application provides a display device including the above-described black light blocking film.

When a black light-shielding film is formed and applied to the embodiments described in the present specification by using the black photosensitive composition for low-temperature curing, storage stability over time is secured, so there is no change in processability, and residue properties can be kept clean without deterioration.

In addition, chemical resistance properties can be secured by preparing a black photosensitive composition for low-temperature curing by applying an oxime-based high-sensitivity initiator and thermosetting epoxy binder.

1 is a schematic diagram of a display device to which a black photosensitive composition for low-temperature curing is applied according to an exemplary embodiment of the present application.
2 is a diagram showing the transmittance spectrum at 800 nm according to the mixing of the colorant.

An exemplary embodiment of the present application is a binder resin; polyfunctional monomers; coloring agent; dispersant; A black photosensitive composition for low-temperature curing comprising a photoinitiator and a solvent, wherein the binder resin comprises an alkali-soluble resin and an epoxy resin, and the colorant is carbon black; organic black; and at least one selected from the group consisting of color pigments, wherein the dispersant provides a black photosensitive composition for low temperature curing comprising a structure represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1,

R1 is a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; Or a substituted or unsubstituted aryl group,

R2 to R6 are the same as or different from each other, and each independently represent a substituted or unsubstituted alkyl group,

R11 to R13 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group,

L1 and L2 are the same as or different from each other, and are each independently a substituted or unsubstituted alkylene group,

X is a halogen group; sulfonic acid group; acetate group; or a phosphate group,

a, b and c are mole % of the unit in each parenthesis based on the total number of moles of the structure represented by Formula 1 above,

a is 50 to 90 mol%,

b+c is 10 to 50 mol%,

0.3b ≤ c ≤ b.

The black photosensitive composition according to the present specification is a black photosensitive composition for low-temperature curing. In order to secure the lack of film strength and chemical resistance that occurs when using the existing photosensitive resin composition for LCD, the film strength and chemical resistance properties are improved when an epoxy binder that can be cured at a low temperature is added along with a high-sensitivity initiator in the existing photosensitive resin composition. can be obtained

On the other hand, the black photosensitive composition for low-temperature curing also uses a pigment dispersion, and in most pigment dispersions, an amine-based dispersant is used to achieve dispersion stability. However, when the photosensitive resin composition containing such an amine-based dispersant was prepared, there was a problem in stability over time. This may be that the amine acting as an anchor of the dispersant and the epoxy cyclic group of the epoxy binder applied to improve properties react, thereby inhibiting stability over time or storage stability. As such a characteristic of changing stability over time, a change in development time and residue may occur when storage time elapses.

In the present specification, by applying a quaternary amine-based dispersant without using a conventional tertiary amine-based dispersant as the dispersant included in the low-temperature curing black photosensitive composition, it was attempted to secure the stability over time of the low-temperature curing black photosensitive composition.

Specifically, since the binder resin contains an epoxy resin, a tertiary amine is substituted at a certain ratio or more to ensure the stability over time of the black photosensitive composition for low-temperature curing, and a pigment dispersion using a dispersant to which the quaternized amine is applied was applied.

The stability over time of the black photosensitive composition for low-temperature curing to which the dispersant to which the quaternized amine is applied is applied, compared with the photosensitive resin composition to which the tertiary amine is applied, stability over time is secured, so there is no change in fairness, and the residue properties do not deteriorate and the film can be kept clean. In addition, the low-temperature curing black photosensitive composition to which a high-sensitivity oxime-based photoinitiator and a thermosetting epoxy binder are applied can secure chemical resistance properties.

The epoxy resin included in the binder resin means a resin capable of thermosetting by having an epoxy group. Specifically, the epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, phenol novolac type epoxy resin, cresol novolac epoxy resin, DCPD (Dicyclopentadiene) novolac epoxy resin, etc. However, the present invention is not limited thereto.

In an exemplary embodiment of the present application, the epoxy resin may be a bisphenol A-type novolac epoxy resin.

In an exemplary embodiment of the present application, the epoxy group equivalent of the epoxy resin may be 150 g/eq to 250 g/eq.

The epoxy group equivalent can be calculated by dividing the average branching amount of the repeating unit by the number of epoxy groups in the repeating unit.

The epoxy group equivalent of the bisphenol A-type novolac epoxy resin may be 200 g/eq.

In an exemplary embodiment of the present application, the polyfunctional monomer includes an acrylate monomer having an acryloyl group equivalent of 80 g/eq to 110 g/eq. Preferably, the acryloyl group equivalent is 85 g/eq to 100 g/eq.

When the polyfunctional monomer satisfies the acryloyl group equivalent range, chemical resistance may be improved by maximizing the degree of crosslinking of the black matrix composition by UV curing to enhance thermosetting properties.

The acryloyl group is an acyl group derived from acrylic acid, _{and refers to the form of an enone having H 2} C=CH—C(=O)—.

In the exemplary embodiment of the present application, the multifunctional monomer may be mainly a multi-acrylate series having three or more bondable double bonds. Specifically, as the multi-functional monomer of the multi-acrylate series, glycerin triacrylate, trimethylolpropane tri acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate (pentaerythritol tetraacylate) or 2-propoxy glycerol triacrylate (2-propoxy glycerol triacrylate), dipentaerithritol penta acrylate (dipentaerithritol penta acrylate dipentaerithritol hexaacrylate) can be However, the present invention is not limited thereto.

The polyfunctional monomer may be preferably pentaerythritol triacrylate, pentaerythritol tetraacylate, or dipentaerithritol hexaacrylate.

In an exemplary embodiment of the present application, the polyfunctional monomer includes more than 70 wt% of an acrylate monomer having an acryloyl group equivalent of 80 g/eq to 110 g/eq.

Preferably, the polyfunctional monomer contains 71 wt% or more and 100 wt% or less of an acrylate monomer having an acryloyl group equivalent of 80 g/eq to 110 g/eq based on the total weight of the polyfunctional monomer.

The polyfunctional monomer includes the acrylate monomer having an acryloyl group equivalent of 80 g/eq to 110 g/eq in the above-described weight range, thereby maximizing the degree of crosslinking of the black photosensitive solution composition by UV curing to improve thermosetting properties. It can be strengthened to improve chemical resistance.

The alkali-soluble resin has an acid value of 30 KOH mg/g to 300 KOH mg/g, and preferably 50 KOH mg/g to 150 KOH mg/g. The weight average molecular weight of the alkali-soluble resin is preferably in the range of 2,000 g/mol to 200,000 g/mol, and more preferably, the weight average molecular weight is possible in the range of 2,000 g/mol to 20,000 g/mol.

When the acid value and the weight average molecular weight of the alkali-soluble resin satisfy the above ranges, it may have a wide development process margin without residue or pattern loss.

The alkali-soluble resin may be used alone or in combination of two or more, and a cardo-based binder or an acrylate or methacrylate-based copolymer may be mixed and used.

For example, the alkali-soluble resin is a copolymer of a monomer containing an acid functional group and a monomer copolymerizable with the monomer. Non-limiting examples of the monomer containing an acid group include (meth)acrylic acid. , crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2-carboxylic acid and the like. These may be used alone or may be used in combination of two or more.

Non-limiting examples of the monomer copolymerizable with the monomer containing the acid group include styrene, chlorostyrene, α-methyl styrene, vinyltoluene, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl ( meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate Acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydropuffril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylamino (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methyl Toxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, Toxytripropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, Heptadecafluorodecyl (meth)acrylate, tribromophenyl (meth)acrylate, β-(meth)acyloloxyethylhydrogen succinate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl Acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, N-phenylmaleimide, N-(4-chlorophenyl)maleimi de, etc. These may be used alone or may be used in combination of two or more.

In addition, as a non-limiting example of an ethylenically unsaturated compound containing an epoxy group capable of a polymer reaction with a copolymer of a monomer containing an acid functional group and a monomer copolymerizable with the monomer, glycidyl (meth)acrylate, vinyl benzyl glycidyl ether, vinyl glycidyl ether, allyl glycidyl ether, 4-methyl-4,5-epoxypentene, γ-glycidoxy propyl trimethoxysilane, γ-glycidyl cidoxy propyl methyldiethoxysilane, γ-glycidoxy propyl triethoxy silane, norbornyl derivatives. These may be used alone or may be used in combination of two or more.

In addition to the above monomers, a binder resin represented by the following Chemical Formula A may be used.

[Formula A]

In Formula A, Rx is a structure in which a 5-membered ring carboxylic acid anhydride or diisocyanate is addition-reacted to form an ester bond, Ry is selected from hydrogen, acryloyl, and methacryloyl, and n is 3 to 8.

Examples of the specific compound of the carboxylic acid anhydride constituting Rx include succinic anhydride, methylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, isobutenylsuccinic anhydride, 1,2-cyclohexanedicarboxylic anhydride, hexahydro- 4-methylphthalic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 1,2,3 ,4-cyclobutanetetracarboxylic dianhydride, maleic anhydride, citraconic anhydride, 2,3,-dimethylmaleic anhydride, 1-cyclopentene-1,2-dicarboxylic dianhydride, 3,4,5,6 -tetrahydrophthalic anhydride, phthalic anhydride, bisphthalic anhydride, 4-methylphthalic anhydride, 3,6-dichlorophthalic anhydride, 3-hydrophthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, 4-nitrophthalic anhydride , and at least one selected from the group consisting of diethylene glycol-1,2-bistrimelic anhydride, but is not limited thereto.

Specific examples of the diisocyanate constituting Rx include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1 ,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1, 4-dimethylbenzene, ω, ω'-diisocyanate-1,3-diethylbenzene, 1,4-tetramethyl xylene diisocyanate, 1,3-tetramethyl xylene diisocyanate, isophorone diisocyanate, 1,3- Cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'- at least one selected from the group consisting of methylenebisisocyanate methylcyclohexane, 2,5-isocyanatemethyl bicyclo[2,2,2]heptane, and 2,6-isocyanatemethyl bicyclo[2,2,1]heptane; , but not limited thereto.

The alkali-soluble resin may be used alone or in combination of two or more. Specifically, the alkali-soluble resin is 9,9-bisglycidyloxyphenyl fluorene (9,9-[Bis(glycidyloxy)phenyl]fluorene), 4-cyclohexene-1,2-dicarboxylic acid (4- Two or more selected from the group consisting of cyclohexen-1,2-dicarboxylic acid), acrylic acid-added bisphenol fluorene epoxy acrylate, and biphenyl-tetracarboxylic acid dianhydride may be mixed.

The mixing may be made in propylene glycol monomethyl ether acetate (PGMEA) as a solvent, but the type of the solvent is not particularly limited.

In one embodiment, the alkali-soluble resin is 9,9-bisglycidyloxyphenyl fluorene (9,9- [Bis (glycidyloxy) phenyl] fluorene) / 4-cyclohexene-1,2-dicarboxylic acid (4-cyclohexen-1,2-dicarboxylic acid) may be an alkali-soluble resin consisting of a molar ratio of 40/60, and also bisphenol fluorene epoxy acrylate/biphenyl-tetracarboxylic acid dianhydride to which acrylic acid is added ) may be an alkali-soluble resin consisting of a molar ratio of 70/30.

In an exemplary embodiment of the present application, the colorant is carbon black; organic black; and at least one selected from the group consisting of color pigments.

In an exemplary embodiment of the present application, the colorant may be organic black.

In an exemplary embodiment of the present application, the colorant is carbon black; and organic black.

In an exemplary embodiment of the present application, the colorant is carbon black; and color pigments.

In an exemplary embodiment of the present application, the colorant is carbon black; and at least one of organic black. The colorant may be carbon black; and near-infrared (IR) region transmittance by including at least one of organic black.

In the exemplary embodiment of the present application, the colorant may be included in the black photosensitive composition as a pigment dispersion together with the dispersing agent.

In the present specification, the pigment dispersion may mean a colored dispersion.

The pigment dispersion may include the colorant, the dispersant, and the solvent propylene glycol monomethyl ether acetate (PGMEA), and the colorant may be included in an amount of 10% to 25% by weight based on the total weight of the pigment dispersion. In one embodiment, the pigment dispersion may further include a binder for dispersion in addition to the dispersant. The dispersion binder is not particularly limited, and those used in the art may be appropriately employed.

In the present specification, the organic black pigment refers to a pigment that is made of an organic material and absorbs light in a visible ray wavelength band as a single species and exhibits a black color. By using the organic pigment as the organic black pigment, a desired optical density (OD) can be achieved even with a small amount compared to the conventional combination of two or more types of pigments or inorganic pigments. According to an exemplary embodiment, a lactam-based pigment or a perylene-based pigment may be used as the organic black pigment. Specifically, black S0100CF (BASF) may be applied as the organic black pigment, but is not limited thereto.

In an exemplary embodiment of the present application, the colorant has a transmittance of 15% or more and 100% or less at 800 nm of near-infrared (IR).

In the exemplary embodiment of the present application, the carbon black is 30% by weight or less based on the total weight of the colorant in the colorant.

In an exemplary embodiment of the present application, the colorant is carbon black; and organic black, or carbon black; and a color pigment, wherein the carbon black content: organic black content or carbon black content: color pigment content is 30:70 to 0.5:99.5.

For example, examples of usable carbon black include SYSTO 5HIISAF-HS, SYSTO KH, SYSTO 3HHAF-HS, SYSTO NH, SYSTO 3M, SYSTO 300HAF-LS, SYSTO 116HMMAF-HS from Donghae Carbon Co., Ltd.; cisto 116MAF, cisto 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, #9931, #9941 from Daido, EG410, EG550, EG450, EG880, EG2500G from Daido and Cabot's TPK 1099R, TPK1437R, TPK1470R, TPK1104R, TPK1227R, TPX 997, TPX 998, TPK 1104, TPX1168, TPX 1409, TPX 1410, and the like, but are not limited thereto.

Examples of organic black or color pigments that can be mixed with the carbon black include carmine 6B (C.I.12490), phthalocyanine green (C.I. 74260), phthalocyanine blue (C.I. 74160), Mitsubishi Carbon Black MA100, Black 582 (basf), C.I. Pigment BALCK 12, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, Perylene Black (BASF K0084. K0086), Cyanine Black, Lactam Black (BASF Black 582), Linole Yellow (CI21090) ), Linol Yellow GRO (CI 21090), Benzidine Yellow 4T-564D, Mitsubishi Carbon Black MA-40, Victoria Pure Blue (CI42595), CI PIGMENT RED97, 122, 149, 168, 177, 180, 192, 215, C.I. PIGMENT GREEN 7, 36, C.I. PIGMENT Blue 15:1, 15:4, 15:6, 22, 60, 64, C.I. PIGMENT yellow 83, 139, 150 C.I. Pigment VIOLET 23,29, etc., in addition, white pigment, fluorescent pigment, etc. may be used, but is not limited thereto.

In an exemplary embodiment of the present application, the dispersant includes a structure represented by the following Chemical Formula 1.

[Formula 1]

In Chemical Formula 1, specific definitions of the substituents are as described below.

In an exemplary embodiment of the present specification, R 1 is a substituted or unsubstituted C 1 to C 30 alkyl group; a substituted or unsubstituted C 3 to C 30 cycloalkyl group; or a substituted or unsubstituted C6-C30 aryl group.

In an exemplary embodiment of the present specification, R 1 is a substituted or unsubstituted C 1 to C 20 alkyl group; a substituted or unsubstituted C 3 to C 20 cycloalkyl group; or a substituted or unsubstituted C6-C20 aryl group.

In an exemplary embodiment of the present specification, R 1 is a substituted or unsubstituted C 1 to C 10 alkyl group; a substituted or unsubstituted C 3 to C 10 cycloalkyl group; or a substituted or unsubstituted C6-C12 aryl group.

In an exemplary embodiment of the present specification, R1 is a substituted or unsubstituted methyl group; a substituted or unsubstituted ethyl group; a substituted or unsubstituted propylene group; or a substituted or unsubstituted hexyl group.

In an exemplary embodiment of the present specification, R1 is a methyl group; an ethyl group substituted with an alkoxy group; propylene group; or a hexyl group substituted with an ethyl group.

In an exemplary embodiment of the present specification, R1 is a methyl group; an ethyl group substituted with an alkoxy group; propylene group; or a 2-ethylhexyl group.

In an exemplary embodiment of the present specification, R2 to R6 are the same as or different from each other, and each independently represents a substituted or unsubstituted C1-C30 alkyl group.

In an exemplary embodiment of the present specification, R2 to R6 are the same as or different from each other, and each independently represents a substituted or unsubstituted C 1 to C 20 alkyl group.

In an exemplary embodiment of the present specification, R2 to R6 are the same as or different from each other, and each independently represents a substituted or unsubstituted C 1 to C 10 alkyl group.

In an exemplary embodiment of the present specification, R2 to R6 are the same as or different from each other, and each independently represents a substituted or unsubstituted methyl group.

In an exemplary embodiment of the present specification, R2 to R6 are the same as or different from each other, and each independently a methyl group; or a methyl group substituted with a phenyl group.

In an exemplary embodiment of the present specification, R2 and R3 are methyl groups.

In an exemplary embodiment of the present specification, R4 to R6 are the same as or different from each other, and each independently a methyl group; or a methyl group substituted with a phenyl group.

In an exemplary embodiment of the present specification, R11 to R13 are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted C1-C30 alkyl group.

In an exemplary embodiment of the present specification, R11 to R13 are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted C 1 to C 20 alkyl group.

In an exemplary embodiment of the present specification, R11 to R13 are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted C 1 to C 10 alkyl group.

In an exemplary embodiment of the present specification, R11 to R13 are a substituted or unsubstituted methyl group.

In an exemplary embodiment of the present specification, R11 to R13 are a methyl group.

In an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted C 1 to C 30 alkylene group.

In an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted C1-C20 alkylene group.

In an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted C 1 to C 10 alkylene group.

In an exemplary embodiment of the present specification, L1 and L2 are substituted or unsubstituted ethylene groups.

In an exemplary embodiment of the present specification, L1 and L2 are ethylene groups.

In an exemplary embodiment of the present specification, X is a halogen group; sulfonic acid group; acetate group; or a phosphate group.

In an exemplary embodiment of the present specification, X is a halogen group.

In an exemplary embodiment of the present specification, X is chlorine.

In an exemplary embodiment of the present specification, a, b and c are mole % of the unit in each parenthesis based on the total number of moles of the structure represented by Formula 1, and a is 50 to 90 mol %.

In one embodiment of the present specification, b + c is 10 to 50 mol%. Preferably, b+c is 20 to 40 mol%.

In an exemplary embodiment of the present specification, a+b+c ≤ 1.

The mole % of a, b and c refers to a percentage of a value obtained by dividing the number of unit repetitions by the total sum of unit repetitions. The mole % does not mean the order of repetition or the number of repetitions.

According to an exemplary embodiment of the present specification, the dispersant may have a weight average molecular weight of 3,000 g/mol or more and 20,000 g/mol or less. Preferably, the weight average molecular weight of the dispersant may be 4,000 g/mol or more and 10,000 g/mol or less.

When the weight average molecular weight of the dispersant is less than 3,000 g/mol, even if an anchor interacting with the pigment exists, the portion capable of having affinity for the solvent becomes small, resulting in poor dispersibility and the weight average molecular weight of the dispersing agent is 20,000 g In the case of more than /mol, dispersibility may be good, but problems of increasing viscosity and impairing development fairness may occur.

로 표시되는 반복 단위는 1종의 모노머일 수 있고, 2종 내지 7종이 모노머를 포함하는 코모노머(comonomer)일 수 있다.In an exemplary embodiment of the present application, the formula (1)

The repeating unit represented by may be one type of monomer, or may be a comonomer including 2 to 7 types of monomers.

In an exemplary embodiment of the present application, the binder resin may include all repeating units represented by the structural formula, and may include only some repeating units of the structural formula.

In an exemplary embodiment of the present application, the binder resin further includes an alkali-soluble resin.

The alkali-soluble resin has an acid value of 30 KOH mg/g to 300 KOH mg/g, and preferably 50 KOH mg/g to 150 KOH mg/g. The weight average molecular weight of the alkali-soluble resin is preferably in the range of 2,000 g/mol to 200,000 g/mol, and more preferably, the weight average molecular weight is possible in the range of 2,000 g/mol to 20,000 g/mol.

The alkali-soluble resin may be used alone or in combination of two or more, specifically, the alkali-soluble resin is 9,9-bisglycidyloxyphenyl fluorene (9,9-[Bis(glycidyloxy)phenyl]fluorene) And 4-cyclohexene-1,2-dicarboxylic acid (4-cyclohexen-1,2-dicarboxylic acid) may be a mixture, styrene / FA-513 / methacrylate added with glycidyl acrylate The monomers reacted with /glycidyl-added methacrylate with tetrahydroxyphthalic anhydride may be polymerized at a ratio of 31/32/12/25 mol, respectively.

The mixing may be made in propylene glycol monomethyl ether acetate (PGMEA) as a solvent, but the type of the solvent is not particularly limited.

In an exemplary embodiment of the present application, at least one selected from the group consisting of the surfactant and the silane coupling agent is further included.

In an exemplary embodiment of the present application, the surfactant may be a fluorine-based surfactant or a silicone-based surfactant.

As the fluorine-based surfactant, DIC (DaiNippon Ink & Chemicals) F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F- 483, F-484, F-486, F-487, F-554, F-570, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. may be used, but is not limited thereto. Specifically, it may be an F-570.

As the silicone-based surfactant, products manufactured by BYK, BASF, or 3M may be mainly used, but the present invention is not limited thereto.

In an exemplary embodiment of the present application, the silane coupling agent is methacryloyloxy propyltrimethoxy silane, methacryloyloxy propyldimethoxy silane, methacryloyloxy propyltriethoxy silane, methacryloyl oxide One or more types of methacryloyl silane coupling agents such as cypropyldimethoxysilane can be selected and used, and octyltrimethoxysilane, dodecyltrimethoxysilane, and octadecyltrimethoxysilane can be used as alkyl trimethoxysilane. , vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)-silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-amino) Ethyl)-3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4 -ethoxy cyclohexyl) ethyltrimethoxysilane, 3-chloropropyl methyldimethoxysilane, 3-chloropropyl trimethoxy silane, 3-methacryloxypropyltrimethoxysilane, or 3-mercaptopropyltrimethoxy One or more types may be selected and used, such as silane. As a specific product of the silane coupling agent, Shin-Etsu's KBM or KBE series may be applied, but the present invention is not limited thereto. For example, vinyl type KBM 1003, KBE1003, epoxy type KBM303, KBM403, KBE402, KBE403, styryl type KBM1403, methacryloxy type KBM502, KBM503, KBE502, KBE503, acryloxy type KBM5103, amino type KBM602, KBM603 , KBM903, KBM573, KBM575, KBM974, KBE903, KBE9103, mercapto-type KBM 802, KBM803, other KBM 585, KBE846, KBE9007, etc., and more than one type can be selected and used.

Specifically, the silane coupling agent may be KBM-503 (Shin-Etsu Corporation), but is not limited thereto.

In an exemplary embodiment of the present application, the black matrix composition has a thickness retention of 85% or more after forming a coating film having a thickness of 0.5 μm to 2 μm and performing chemical resistance evaluation.

Specifically, the coating film may be 0.7 μm to 1.3 μm.

The thickness retention may be 85% or more and 100% or less.

The said thickness retention can progress and measure chemical resistance (solvent resistance evaluation) with respect to the coating film which the black photosensitive composition hardened|cured. A coating-pressure drying-prebake-development-postbake process is performed using the red photosensitive resin composition for low-temperature curing on the black light-shielding film pattern substrate. This process is called the red process. As an experiment to check the chemical resistance of the black matrix used as a substrate, the pattern process through ultraviolet (UV) curing is not carried out, but the development is carried out with an alkali developer immediately, the coated red film is peeled off, and after curing at a low temperature, the black light-shielding film Check the properties of the surface. In this way, after measuring the thickness before and after the red process, the thickness retention can be measured using the following formula.

[formula]

The fact that the black photosensitive composition for low-temperature curing satisfies the thickness retention range indicates excellent chemical resistance.

The thickness of the black light-shielding film may be measured using an optical microscope.

In an exemplary embodiment of the present application, the low-temperature curing black photosensitive composition has an optical density (OD) of 0.4/μm to 2.5/μm when a coating film having a thickness of 0.5 μm to 2 μm is formed. Specifically, the coating film may be 0.7 μm to 1.3 μm. More specifically, the coating film may be 1.2 μm to 1.3 μm.

The optical density (OD) may be measured using a Densitometer 3411C equipment of X-rite as a method of measuring the manufactured black light-shielding substrate. The wavelength for measuring the optical density may be 380 nm to 780 nm of white light.

When the optical density (OD) of the above range is satisfied when forming the coating film of the black photosensitive composition for low temperature curing, an excellent effect on light leakage and external light reflection blocking may be exhibited, but the effective value may vary depending on the laminate structure and design of the device. have.

In an exemplary embodiment of the present application, the low-temperature curing black photosensitive composition is based on the total solids weight of the low-temperature curing black photosensitive composition, the alkali-soluble resin is 10 to 40 wt%, the epoxy resin is 5 to 20 % by weight, the polyfunctional monomer is 10 to 30% by weight, the colorant is 10 to 50% by weight, the dispersant is 2 to 15% by weight, the photoinitiator comprises 0.5 to 10% by weight.

When the alkali-soluble resin included in the low-temperature curing black photosensitive composition is less than the above-mentioned weight range, developability is insufficient and undeveloped residues may be generated. When the above-mentioned weight range is exceeded, the polymer film matrix is strong and the development time is shortened. It becomes longer, impairing fairness, and may reduce the mobility of radicals in the film and reduce sensitivity.

If the epoxy resin included in the low-temperature curing black photosensitive composition is less than the above-mentioned weight range, the degree of crosslinking due to thermal curing may decrease and chemical resistance problems may occur, and if the above-mentioned weight range is exceeded, the stability over time of the composition is deteriorated. can do it

When the content of the polyfunctional monomer included in the black photosensitive composition for low-temperature curing is less than the above-mentioned weight range, the degree of crosslinking may decrease and film scraping may occur. (stickiness) increases, which can easily cause surface contamination and cause residues.

When the colorant included in the low-temperature curing black photosensitive composition is less than the above-mentioned weight range, the light-shielding power is lowered. can cause

If the dispersant included in the low-temperature curing black photosensitive composition is less than the above-mentioned weight range, the dispersibility may be poor because it does not sufficiently cover the surface of the colorant, which may cause a poor dispersion state, and the dispersant may exceed the above-mentioned weight range. In this case, the amount of the free dispersant remaining after covering the surface of the colorant may be excessive to impair fairness, and the amine functional groups acting as anchors of the free dispersant may react with other components of the photosensitive composition. This increases, and stability with time may be reduced.

When the photoinitiator included in the low-temperature curing black photosensitive composition is less than the above-mentioned weight range, the sensitivity may decrease and pattern dropout may be induced. It can be hard.

In another exemplary embodiment of the present application, the photoinitiator is a material serving to generate radicals by light, and is selected from the group consisting of acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, and oxime-based compounds. It is preferable to use 1 type or a mixture of 2 or more types of compounds to be used.

Examples of the acetophenone-based compounds usable as the photoinitiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1 -one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, benzoinmethyl ether, benzoinethyl ether, benzoiniso Butyl ether, benzoinbutyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-(4-methylthio)phenyl-2-morpholino-1-propan-1-one, 2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(4-bromo-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane those selected from the group consisting of -1-one and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one may be used.

Examples of the biimidazole-based compound include 2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl biimidazole, 2,2'-bis(o-chlorophenyl)-4, 4',5,5'-tetrakis(3,4,5-trimethoxyphenyl)-1,2'-biimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4 group consisting of ',5,5'-tetraphenyl biimidazole, and 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole One selected from may be used.

As a triazine-based compound, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 1,1,1,3,3,3- Hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionate, ethyl-2-{4-[2,4 -bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 2-epoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6 -yl]phenylthio}acetate, cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, benzyl-2-{4-[ 2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazine-6 -yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionamide, 2,4-bis(trichloro methyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3,-butadienyl-s One selected from the group consisting of -triazine, and 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine can be used.

Oxime compounds include OXE-01 (BASF), OXE-02 (BASF), OXE-03 (BASF), OXE-04 (BASF), PBG-304 (Tronni), PBG-305 (Tronni), PBG -3059 (Tronni), PI-102 (LGC), PI 103 (LGC), ZS-928 (FFEM), OXE-01-Me, PBG-3057 (Tronni), PBG-3053 (Tronni), NCI -930 (Adecas), TPM-P07 (Takoma), PBG-3056 (Tronni), PBG-3037, SPI-03 (Samyang), DFI-306 (Gyeongin), PBG-3055 (Tronni), DFI- 301 (Gyeongin), SPI-02 (Samyang), DFI-020 (Gyeongin), PBG-3044 (Tronni), N-1919 (Adecas), MCC-OXE (MCC), HPP2 (Takoma), HPP3 (Takoma) ), TPM-P12 (Takoma), PBG-314 (Tronly), PBG-3142 (Tronly), ZS-539 (FFEM), PBG-309 (Tronly), and PBG-304 (Tronly).

The photoinitiator may further include 0.01 to 5% by weight of a photocrosslinking sensitizer for accelerating the generation of radicals as an auxiliary component, or 0.01 to 5% by weight of a curing accelerator for accelerating curing, based on the total weight of the resin composition.

The photocrosslinking sensitizer includes benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoyl benzophenone compounds such as benzoate, 3,3-dimethyl-4-methoxybenzophenone, and 3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone; fluorenone compounds such as 9-fluorenone, 2-chloro-9-prorenone, and 2-methyl-9-fluorenone; Thioxanthone type, such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone, diisopropyl thioxanthone compound; xanthone-based compounds such as xanthone and 2-methylxanthone; anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3-bis(9-acridinyl)propane, etc. acridine-based compounds; dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-dione, and 9,10-phenanthrenequinone; phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide; benzophenone compounds such as methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, and 2-n-butoxyethyl-4-(dimethylamino)benzoate; 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzal)cyclohexanone, 2,6-bis(4-diethylaminobenzal)-4- amino synergists such as methyl-cyclopentanone; 3,3-carbonylvinyl-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3 -benzoyl-7-methoxy-coumarin, 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]-benzo coumarin-based compounds such as pyrano[6,7,8-ij]-quinolizin-11-one; chalcone compounds such as 4-diethylamino chalcone and 4-azidebenzalacetophenone; 2-benzoylmethylene or 3-methyl-b-naphthothiazoline may be used.

In addition, the curing accelerator is 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2- Mercapto-4,6-dimethylaminopyridine, pentaerythritol-tetrakis (3-mercaptopropionate), pentaerythritol-tris (3-mercaptopropionate), pentaerythritol-tetrakis (2-mercapto) acetate), pentaerythritol-tris(2-mercaptoacetate), trimethylolpropane-tris(2-mercaptoacetate), or trimethylolpropane-tris(3-mercaptopropionate) can be used.

In another exemplary embodiment of the present application, the solvent is propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, in consideration of solubility, pigment dispersibility, applicability, etc. Ethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 2-hydroxyethylpropionate, 3-methyl-3-methoxybutylpropionate, ethyl-3- Methoxypropionate, methyl-3-ethoxypropionate, ethyl-3-ethoxypropionate, butyl acetate, amyl permate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, ethyl pyruvate, or γ-butyrol acetate may be used. The said solvent may be used independently and may be used in mixture of 2 or more types.

The black photosensitive composition according to the above-described embodiment may further include additives as long as it does not adversely affect the object of the present invention. For example, one or more additives selected from the group consisting of dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, thermal polymerization inhibitors, and leveling agents may be additionally used.

Non-limiting examples of the antioxidant include 2,2-thiobis(4-methyl-6-t-butylphenol), or 2,6-g,t-butylphenol, and the non-limiting examples of the ultraviolet absorber Examples include 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chloro-benzotriazole, or alkoxy benzophenone. In addition, non-limiting examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis(3 -methyl-6-t-butylphenol), 2,2-methylenebis(4-methyl-6-t-butylphenol), or 2-mercaptoimidazole.

The ultraviolet absorber, the thermal polymerization inhibitor and the leveling agent may be appropriately employed in the art, and are not particularly limited.

In addition, the black photosensitive composition may further include at least one additive selected from the group consisting of the pigment mixture dispersion, a functional resin binder, a monomer, a radiation-sensitive compound, and other additives.

The black photosensitive composition according to the above-described embodiments may be prepared by mixing the above-mentioned components. According to one example, a pigment dispersion is first prepared. By using a commercially available pigment in the state of a dispersion, it can be substituted for the preparation of a pigment dispersion. A black photosensitive composition may be prepared by mixing the binder resin with the pigment dispersion, adding a polyfunctional monomer, a photoinitiator, and a solvent and stirring.

An exemplary embodiment of the present application provides a black light-shielding film formed using the above-described black photosensitive composition.

An exemplary embodiment of the present application provides a display device including the aforementioned black light blocking film.

An example of a method of forming the black light-shielding layer is as follows.

Specifically, a) applying the black photosensitive composition for low-temperature curing on a substrate, b) drying and prebaking the applied black photosensitive composition under reduced pressure, c) exposing the applied black photosensitive composition to exposure and developing, d) post-baking the applied black photosensitive composition.

In the method of manufacturing a black light-shielding film according to an exemplary embodiment of the present invention, step a) is a step of applying a low-temperature curing black photosensitive composition, for example, it may be applied on a substrate using a method known in the art. . More specifically, a method of applying the composition may use a spray method, a roll coating method, a spin coating method, a bar coating method, a slit coating method, etc., However, the present invention is not limited thereto.

In this case, as the substrate, metal, glass, plastic, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. may be used, and these substrates may be chemically treated with a silane coupling agent according to the purpose; Appropriate pretreatment such as plasma treatment, ion plating, sputtering, vapor phase reaction method, and vacuum deposition can be performed. In addition, the substrate may optionally have a driving thin film transistor on it, a silicon nitride film may be sputtered, and an organic film coating such as a planarization film may be applied to the substrate.

In the method of manufacturing a black light-shielding film according to an exemplary embodiment of the present application, step b) is a step of drying and prebaking the applied black photosensitive composition under reduced pressure. Vacuum drying is preferably performed until reaching 65 Pa in a step of vacuum drying from 30 Pa to 150 Pa under reduced pressure conditions. Thereafter, as a pre-bake step, a pre-bake is performed using a contact hot plate or an oven, and the temperature applied at this time is 80° C. to 100° C., and preferably, a temperature applied at the time of post-baking is selected. The pre-bake time may be performed in 60 seconds to 5 minutes.

Step c) is a step of exposing and developing the applied composition. For exposure, if exposure is performed using a UV light source and the mask dimension fidelity is considered as exposure equipment, it is preferable to use a projection type, but the present invention is not limited thereto. As a developing method, a dipping method, a puddle method, a shower method, etc. can be applied without limitation. The development time can be easily determined by those skilled in the art, and is, for example, usually about 30 seconds to 180 seconds.

Examples of the developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, sodium methsilicate, and ammonia as an aqueous alkali solution; primary amines such as ethylamine and N-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as trimenylamine, methyldiethylamine and dimethylethylamine; tertiary alcohol amines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine; pyrrole, piperidine, n-methylpiperidine, n-methylpyrrolidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0] cyclic tertiary amines such as -5-nonene; aromatic tertiary amines such as pyridine, corizine, lutidine and quinoline; The aqueous solution of quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, etc. can be used.

After development, the pattern can be formed by rinsing with DI water and then drying with air (air or nitrogen). A finished pattern can be obtained through post-bake using a heating device such as a hot plate or an oven on the patterned coating film. At this time, it is preferable that the conditions of the post-baking are heated at 80°C to 100°C for 3 minutes to 120 minutes.

In the present specification, the completed black light-shielding film may be formed of a coating film having a thickness of 0.7 μm to 1.3 μm, a thickness retention ratio of 85% or more, and an optical density (OD) of 0.4/μm to 2.0/μm.

A method of manufacturing a display device including an organic light emitting device according to an exemplary embodiment of the present application is not particularly limited, but may be manufactured, for example, as follows.

After the TFT film is manufactured through the TFT process, an anode is patterned thereon, an insulating film (pixel define layer) is patterned by aligning it thereon, and then an organic material is deposited and laminated. The organic material includes a light emitting layer, and may further include other charge transport or charge blocking layers, such as an electron injection layer, an electron transport layer, a hole blocking layer, a hole transport layer, a hole injection layer and/or an electron blocking layer, if necessary. have.

Then, the metal electrode layer is formed and then encapsulated with an encapsulant (sealant) to prepare a sealed encap layer. On the sealed encap layer, silicon nitride may be deposited or a touch center layer may be laminated as needed. A black light-shielding layer may be patterned on the encap layer using the black photosensitive composition for low-temperature curing, and a low-temperature color filter layer may be manufactured thereon as needed. The subsequent process is a manufacturing process including a conventional organic light emitting device Thus, a display device including an organic light emitting diode can be manufactured.

1 shows a simplified schematic diagram of a display device to which a black photosensitive composition for low-temperature curing is applied according to an exemplary embodiment of the present application. When the black photosensitive composition for low-temperature curing according to the present specification is applied, stability over time is secured, so there is no change in processability, no residue is generated, and a display device having excellent chemical resistance can be manufactured.

2 is a diagram showing the transmittance spectrum at 800 nm according to the mixing of the colorant. “C.B 30%” in FIG. 2 indicates that 30% by weight of carbon black and 70% by weight of organic lactam black were used based on the total weight of the colorant, and “C.B. “100%” means 100% by weight of carbon black based on the total weight of the colorant, and “O.B. 100%” means 100% by weight of organic black (lactam-based) based on the total weight of the colorant. The transmittance spectrum is measured by forming a coating film having a thickness of 1.4 μm in the low-temperature curing black photosensitive composition, and each of the colorants is 40 wt% based on the total solid weight of the low-temperature curing black photosensitive composition.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited thereto.

manufacturing example

(Preparation of colored dispersion)

700 g of organic black pigment (Black S0100CF, BASF Corporation) and 300 g of high-resistance carbon black (TPK1227R, Cabot Corporation) were used as a colorant, and each of Dispersants 1 to 3 included the monomer types and contents shown in Table 1 below. After using 250 g, using zirconia beads with 5,000 g of solvent propylene glycol monomethyl ether acrylate and dispersing for 5 hours using a dispersing equipment, each of the colored dispersions 1 to 3 (16% by weight of the colorant based on the total weight of the colored dispersion) was prepared. Data for each dispersant ratio are as follows.

Monomer (mol %) Molecular Weight (g/mol) MMA BMA EHMA BzMA ETEGMA DMAEMA DAEMA-BC Coloring Dispersion 1 Dispersant 1 40 13.5 8 5 3.5 30 0 6,100 Coloring Dispersion 2 dispersant 2 40 13.5 8 5 3.5 18 12 5,460 Coloring Dispersion 3 dispersant 3 40 13.5 8 5 3.5 0 30 5,510

MMA: Methyl Methacrylate,

BMA: Butyl Methacrylate,

EHMA: Ethylhexyl Methacrylate,

BzMA: Benzyl Methacrylate,

ETEGMA: Ethyl tri(ethyleneoxide)-yl-methacrylate,

DMAEMA: Dimethylaminoethyl methacrylate,

DAEMA-BC:Dimethylaminoethyl methacrylate-benzyl chloride

(Preparation of black photosensitive composition for low temperature curing)

Black photosensitive compositions of Examples and Comparative Examples were prepared by mixing with the mass (g) of Table 2 below .

Comparative Example 1 Example 1 Example 2 Comparative Example 2 Coloring Dispersion 1 (colorant 16% by weight in PGMEA) 325 325 Coloring Dispersion 2 (colorant 16% by weight in PGMEA) 325 Coloring Dispersion 3 (colorant 16% by weight in PGMEA) 325 Alkali Soluble Resin 1 40 40 40 40 Alkali Soluble Resin 2 38.5 38.5 38.5 45.5 Epoxy resin (KBPN_Kukdo Chemical) 15 15 15 0 pentaerythritol tetraacrylate, 19.45 19.45 19.45 27.45 Oxime initiator (OXE-02_BASF) 3 3 3 3 Photoinitiator (HABI 101) 1.5 1.5 1.5 1.5 Surfactant (F-570) 0.375 0.375 0.375 0.375 Silane coupling agent (KBM 503) 4 4 4 4 Solvent (propylene glycol monomethyl ether acetate) 191 191 191 191 Solvent (methyl-3-methoxy propionate) 124 124 124 124

Coloring dispersion: 16% by weight of organic black pigment and carbon black as colorant (based on the total weight of the coloring dispersion), dispersion solvent propylene glycol monomethyl ether acrylate (PGMEA)

Alkali-soluble resin 1: 9,9-bisglycidyloxyphenyl fluorene (9,9-[Bis(glycidyloxy)phenyl]fluorene)/4-cyclohexene-1,2-dicarboxylic acid (4-cyclohexen- Alkali-soluble binder resin having a weight average molecular weight of 2,300 g/mol, an acid value of 86 KOH mg/g, a solid content of 30%, and a solvent PGMEA consisting of 1,2-dicarboxylic acid) in a molar ratio of 40/60

Alkali-soluble resin 2: styrene/FA513/methacrylate with glycidyl acrylate/monomer (31/32/12/25 mol %) in which tetrahydroxyphthalic anhydride is reacted with methacrylate added with glycidyl ) polymerization-soluble alkali-soluble resin 2 (weight average molecular weight 10,000 g/mol, acid value 66 KOH mg/g, solid content 35%, solvent PGMEA)

Epoxy resin: Bisphenol A type novolac epoxy resin (epoxy equivalent 200 g/eq)

Polyfunctional monomer: pentaerythritol tetraacrylate

Oxime initiator: OXE-02 (BASF)

Photoinitiator: HABI 101 (Tronly)

Surfactant: F 570 (DIC)

Silane coupling agent: KBM 503 (Shin-Etsu)

Solvent: PGMEA: propylene glycol monomethyl ether acetate, MMP: methyl-3-methoxy propionate

After coating the black photosensitive composition prepared above on a silicon nitride (SiNx) substrate (370 mm X 470 mm), a vacuum drying process was performed until reaching 65 Pa. Subsequently, pre-bake was performed on a digital hot plate at 85° C. for 2 minutes. After the pre-baked coated substrate was cooled to room temperature, a crosslinking reaction was performed through ultraviolet (UV) irradiation. In this case, the exposure machine used was a projection type with good mask fidelity (Ushio Corporation), and the irradiated exposure amount was used in the range of 40mJ/cm2 to 80mJ/cm2, and the reference exposure amount was 50mJ/cm2.

After exposure, development was performed for 60 to 80 seconds with a 0.043% (aq) KOH developer to obtain a pattern. Thereafter, a black light-shielding film was prepared by post-bake at 85° C. for 60 minutes.

A spin coater was used for the coating, and the coating conditions were as follows.

Coating RPM: 430 rpm, coating time 9sec (ramping 2sec)

Target thickness: 1.3㎛

The prepared black light-shielding film was evaluated under the following conditions, and is shown in Table 3 below.

Chemical resistance (solvent resistance evaluation) was performed on the cured coating film of the black light-shielding film that had undergone all processes. The coating-reduced pressure drying-prebake-development-post-bake process was performed using the red photosensitive resin composition for low-temperature curing on the black light-shielding film pattern substrate.

As an experiment to check the chemical resistance of the black light-shielding film used as a substrate, the pattern process through uv curing is not carried out, but the development with an alkali developer is immediately performed, the coated red film is peeled off, and then the black light-shielding film surface characteristics are subjected to post-make. was confirmed.

Evaluation of chemical resistance: The image of the black light-shielding film subjected to the red process was confirmed through an optical microscope.

Stability evaluation over time: After the fairness evaluation of the prepared black photosensitive composition was performed, the black photosensitive composition was left at room temperature for 5 days, and then the fairness evaluation was performed again after 5 days elapsed. It was confirmed whether there was a change in the fairness from the initial evaluation. . In the case of the black photosensitive composition having poor stability over time, it was confirmed that there was a change in the development time and the residue properties deteriorated.

[Evaluation standard]

When the following conditions are satisfied, ok (◎, ○), insufficient (▲), no evaluation (*)

The no evaluation refers to a case in which accurate thickness measurement is impossible due to severe surface abrasion and defects when observed through an optical image.

1. Fairness: ok when there is no development residue and the straightness of the pattern is good

2. Surface properties after chemical resistance evaluation: ok when there are no surface defects after chemical resistance evaluation

3. Residual film rate (thickness retention) after chemical resistance evaluation: After chemical resistance evaluation, when the remaining film rate (thickness retention) is maintained at 90% or more (◎), when the remaining film rate (thickness retention) is maintained at 5% or more and less than 90% (○)

4. Stability-Development time change over time: When the change in development time differs by 3 seconds or less by observing the change in characteristics after leaving it at room temperature for 5 days

4. Stability over time-residues and protrusions: ok when no residues or protrusions occur on the anode substrate during fairness evaluation after 5 days of standing at room temperature

Comparative Example 1 Example 1 Example 2 Comparative Example 2 Fairness (developable patternability) ◎ ◎ ◎ ◎ Surface properties after chemical resistance evaluation ◎ ◎ ◎ ▲ Remaining film rate after chemical resistance evaluation ◎ ◎ ○ * Stability over time - development time change ▲ ◎ ◎ ◎ Stability over time - residue ▲ ◎ ◎ ◎

According to Table 3, it was confirmed that the surface properties, residual film rate, and stability with time after evaluation of fairness and chemical resistance of Examples 1 and 2 were all superior to those of Comparative Examples 1 and 2.

Claims (12)

binder resin; polyfunctional monomers; coloring agent; dispersant; A black photosensitive composition for low-temperature curing comprising a photoinitiator and a solvent, the black photosensitive composition comprising:
The binder resin includes an alkali-soluble resin and an epoxy resin,
The colorant may be carbon black; organic black; and at least one selected from the group consisting of color pigments,
The dispersant is a black photosensitive composition for low-temperature curing comprising a structure represented by the following Chemical Formula 1:
[Formula 1]

In Formula 1,
R1 is a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; Or a substituted or unsubstituted aryl group,
R2 to R6 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group,
R11 to R13 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group,
L1 and L2 are the same as or different from each other, and are each independently a substituted or unsubstituted alkylene group,
X is a halogen group; sulfonic acid group; acetate group; or a phosphate group,
a, b and c are mole % of the unit in each parenthesis based on the total number of moles of the structure represented by Formula 1 above,
a is 50 to 90 mol%,
b+c is 10 to 50 mol%,
0.3b ≤ c ≤ b. The black photosensitive composition for low-temperature curing according to claim 1, wherein the colorant has a transmittance of 15% or more and 100% or less in near infrared (IR) 800 nm. The black photosensitive composition for low temperature curing according to claim 1, wherein the colorant contains 30 wt% or less of the carbon black based on the total weight of the colorant. The black photosensitive composition for low temperature curing according to claim 1, further comprising at least one selected from the group consisting of a surfactant and a silane coupling agent. The black photosensitive composition of claim 1, wherein L1 and L2 are the same as or different from each other and each independently represent a substituted or unsubstituted ethylene group. The black photosensitive composition for low temperature curing according to claim 1, wherein R2 to R6 are the same as or different from each other and each independently represent a substituted or unsubstituted methyl group. The black photosensitive composition for low-temperature curing according to claim 1, wherein the low-temperature curing black photosensitive composition has a thickness retention of 85% or more for evaluation of chemical resistance when a coating film having a thickness of 0.5 μm to 2 μm is formed. The black photosensitive composition for low-temperature curing according to claim 1, wherein the low-temperature curing black photosensitive composition has an optical density (OD) of 0.4/μm to 2.5/μm when a coating film having a thickness of 0.5 μm to 2 μm is formed. The method according to claim 1, Based on the total weight of solids in the black photosensitive composition for low-temperature curing,
The alkali-soluble resin is 10 to 40% by weight,
The epoxy resin is 5 to 20% by weight,
The polyfunctional monomer is 10 to 30% by weight,
The colorant is 10 to 50% by weight,
The dispersant is 2 to 15% by weight,
The photoinitiator is a black photosensitive composition for low temperature curing comprising 0.5 to 10% by weight. The black photosensitive composition for low-temperature curing according to claim 1, wherein the polyfunctional monomer includes an acrylate monomer having an acryloyl group equivalent of 80 g/eq to 110 g/eq. A black light-shielding film formed using the black photosensitive composition for low-temperature curing according to any one of claims 1 to 10. A display device comprising the black light blocking film according to claim 11 .

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