KR20130135418A - Photosensitive resin composition and photosensitive material comprising the same - Google Patents

Abstract

The present specification relates to a photosensitive resin composition and an organic light emitting device including the same. The photosensitive resin composition including the polymer according to the present specification may be applied to various photosensitive materials.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition and a photosensitive material containing the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present specification relates to a photosensitive resin composition and a photosensitive material including the same.

Fine patterns of color filters used in display devices such as liquid crystal displays and plasma display panels are typically coated by photolithography using negative photoresist. It is formed through the process of dry-exposure-developing-firing.

In the process, to check the quality characteristics of the fine pattern of the color filter using a pattern checker between each process of the linearity of the pattern, poor pattern dropping, foreign matters, poor projections and various stains, etc. Will be detected.

Patent Application No. 10-2009-0092063 Patent Application No. 10-2009-0128708

The present specification is to provide a photosensitive resin composition and a photosensitive material comprising the same to be cured by light.

The present specification provides a photosensitive resin composition comprising a binder resin, a polymerizable compound, a photoinitiator, an adhesion promoter, and a solvent, which are at least one of the compounds represented by any one of Formulas 1 to 4 below.

[Formula 1]

(2)

(3)

[Formula 4]

In Chemical Formulas 1 and 4,

R1 to R10 are each independently represented by the following formula (5) or (8), R11 to R13 is represented by the formula (8), R14 to R17 is represented by the formula (6),

[Chemical Formula 5]

[Chemical Formula 6]

In Formulas 5 to 6, R18 and R19 are each independently hydrogen or an alkyl group of C ₁ ~ C ₁₀ , R20 is represented by the following formula (7),

[Formula 7]

In Formula 7, R21 is hydrogen or an alkyl group of C ₁ ~ C ₁₀ , R22 is represented by (CH ₂ ) _b OH or the following formula (8),

[Formula 8]

In Formula 8, R 23 is (CH ₂ ) _n O or CO (CH ₂ ) _l O, R 24 is hydrogen or an alkyl group of C ₁ ~ C ₁₀ , n and l are each independently an integer of 2 to 10, m is an integer of 1-2, o and p are integers of 1-3, and a and b are integers of 1-10.

In addition, the present specification provides a photosensitive material prepared from the photosensitive resin composition.

In addition, the present specification provides a color filter including the photosensitive material.

In addition, the present specification provides a liquid crystal display device including the color filter.

The photosensitive resin composition according to an exemplary embodiment of the present specification has an advantage of reducing a defective rate during pattern inspection during a photolithography process for forming a pattern.

The photosensitive resin composition according to the exemplary embodiment of the present specification has an advantage of reducing the generation of water stains during the photolithography process for pattern formation.

1 is a micrograph of the photosensitive material of Example 1 and Comparative Example 1 of the present specification.

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

The photosensitive resin composition according to the present specification is characterized by including a binder resin, a polymerizable compound, a photoinitiator adhesion promoter, and a solvent.

The binder resin of the present invention is a binder resin containing an ethylenically unsaturated group and an acid group, and can be synthesized through the following three steps of reactions. In the reaction of the three steps, step 1 is a step of synthesizing the basic acrylic binder resin, step 2 is the step of introducing an unsaturated group into the base acrylic binder resin, step 3 is to give an acid group to the acrylic binder resin into which the unsaturated group is introduced It's a step.

In the first step, a monomer containing an epoxy group and a monomer copolymerizable therewith are included as repeating units.

Examples of the monomer containing an epoxy group and an ethylenic unsaturated bond include allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene- At least one compound selected from the group consisting of 2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene and 1,2-epoxy-9- But is not limited thereto.

The monomer copolymerizable with the epoxy-containing monomer of step 1 may be at least one selected from the group consisting of unsaturated carboxylic acid esters, aromatic vinyl monomers, unsaturated ethers, N-vinyl tertiary amines, and unsaturated imides. However, the present invention is not limited thereto.

Specific examples of the unsaturated carboxylic acid esters include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and isobutyl ( Meta) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetra Hydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl ( Meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxy CD-ethyleneglycol (Meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate , p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1 , 1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate , Methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate and butyl α-hydroxymethyl acrylate It is, but is not limited thereto.

Specific examples of the aromatic vinyl monomers include styrene, α-methylstyrene, (o, m, p) -vinyl toluene, (o, m, p) -methoxy styrene, and (o, m, p) -chloro It may be selected from the group consisting of styrene, but is not limited thereto.

Specific examples of the unsaturated ethers may be selected from the group consisting of vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether, but are not limited thereto.

Specific examples of the unsaturated imides are selected from the group consisting of N-phenyl maleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide It may be, but is not limited to these.

In the second step, as the step of introducing an unsaturated group to the basic acrylic binder resin of the first step may be obtained by reacting the acid group of the epoxy group contained in the basic acrylic binder resin of the first step and the monomer containing an acid group.

The monomer containing an acid group is at least one selected from the group consisting of (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. May be used, but is not limited thereto.

The third step is to give an acid group to the binder resin containing the unsaturated group of the second step may be obtained by reacting the hydroxy group generated by the reaction of the epoxy group of the second step with the acid group of the acid group-containing monomer with an acid anhydride.

Examples of the acid anhydride include maleic anhydride, methyl maleic anhydride, tetrahydro phthalic anhydride, and the like, but are not limited thereto.

The content of the binder resin may be 1 to 50% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

The polymerizable compound according to the present specification includes an acrylic monomer having an ethyl oxide structure.

The acrylic monomer having the ethyl oxide structure includes a compound of any one or more of the compounds represented by any one of the following Chemical Formulas 1 to 4.

[Formula 1]

(2)

(3)

[Formula 4]

In Formulas 1 and 4, R1 to R10 are each independently represented by the following Formula 5 or Formula 8, R11 to R13 are represented by the following Formula 8, and R14 to R17 are represented by the following Formula 6.

[Chemical Formula 5]

[Chemical Formula 6]

In Formulas 5 to 6, R18 and R19 are each independently hydrogen or an alkyl group of C ₁ ~ C ₁₀ , R20 is represented by the following formula (7).

[Formula 7]

In Chemical Formula 7, R21 is hydrogen or an alkyl group of C ₁ to C ₁₀ , and R22 is represented by (CH ₂ ) _b OH or the following Chemical Formula 8.

[Formula 8]

In Formula 8, R 23 is (CH ₂ ) _n O or CO (CH ₂ ) _l O, R 24 is hydrogen or an alkyl group of C ₁ ~ C ₁₀ , n and l are each independently an integer of 2 to 10, m is an integer of 1-2, o and p are integers of 1-3, and a and b are integers of 1-10.

C ₁ ~ C ₁₀ The alkyl group may be linear or branched, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, and the like, but are not limited thereto.

Formula 3 may be represented by the following Formula 9, but is not limited thereto.

[Chemical Formula 9]

Formula 4 may be represented by the following Formula 10, but is not limited thereto.

[Formula 10]

Acrylic monomers having an ethyl oxide structure include DPEA-12, RP1040, DM2015, but is not limited thereto.

In the present specification, the polymerizable compound is a compound containing an unsaturated double bond, a compound which can be polymerized by being initiated by an initiator, and particularly serves as a crosslinking agent in the photosensitive resin composition.

The polymerizable compound may further include a polymerizable compound generally used in the art.

For example, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) Compounds obtained by esterifying a polyhydric alcohol selected from the group consisting of acrylates with α, β-unsaturated carboxylic acids; A compound obtained by adding (meth) acrylic acid to a compound containing a glycidyl group such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; ester compounds of a compound having a hydroxyl group or an ethylenically unsaturated bond such as a phthalic acid diester of? -hydroxyethyl (meth) acrylate and a toluene diisocyanate adduct of? -hydroxyethyl (meth) acrylate with a polyvalent carboxylic acid , Or adducts with polyisocyanates; And (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. But it is not limited to these.

The content of the polymerizable compound may be 1 to 50% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

In the photosensitive resin composition according to the present specification, the photoinitiator is an acetophenone-based compound; Biimidazole type compounds; Triazine compounds; And oxime compounds.

Examples of the acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4 -(2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, benzoinmethyl ether, benzoinethyl ether, benzoin isobutyl ether, benzo Inbutyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butan-1-one, or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one. It is not limited only to this.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole and 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 ', 5,5'-tetraphenyl biimidazole, or 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole, etc. There is. It is not limited only to this.

Examples of the triazine compound include 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 Rhomethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p- Dimethylaminophenyl) -1,3, -butadienyl-s-triazine, or 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine. It is not limited only to this.

The oxime compounds include, but are not limited to, CGI-242, CGI-124, etc. of Shiva, Japan.

The content of the photoinitiator may be 0.1 to 20% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

In the photosensitive resin composition according to the present specification, the adhesion promoter is not particularly limited as long as it is a compound that increases adhesion to the substrate.

For example, the adhesion promoter may include methacryloyloxy propyltrimethoxy silane, methacryloyloxy propyldimethoxy silane, methacryloyloxy propyltriethoxy silane and methacryloyloxy propyl. Methacryloyl silane which is at least one of dimethoxysilane; And alkyl trimethoxy silane which is at least one of octyltrimethoxy silane, dodecyltrimethoxy silane, and octadecyltrimethoxy silane.

Based on the total weight of the adhesion promoter, the content of the methacryloyl-based silane may be 65 to 95% by weight, and the content of the alkyl trimethoxy silane may be 5 to 35% by weight.

The content of the alkyl trimethoxy silane may be 5 to 50% by weight of the content of the methacryloyl-based silane.

The content of the adhesion promoter may be 0.01 to 1% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

In the photosensitive resin composition according to the present specification, the solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1 , 1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol , Propanol, butanol, t-butanol, 2-ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene From the group consisting of glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether It may be one or more selected, but is not limited thereto.

The content of the solvent may be 30 to 90% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

The photosensitive resin composition according to the present specification may further include a colorant.

As the colorant, one or more pigments, dyes, or mixtures thereof may be used.

Specifically, as the black colorant, a colored dispersion containing a black pigment may be used. The carbon black which can be used includes Sisto 5HIISAF-HS, Sisto KH, Sisto 3HHAF-HS, Sisto NH, Sisto 3M, Sisto 300HAF-LS, Sisto 116HMMAF-HS, Sisto of East Sea Carbon 116MAF, cysto FMFEF-HS, cysto SOFEF, cysto VGPF, cysto SVHSRF-HS, and cysto SSRF; Mitsubishi Chemical Corporation Diagram Black?, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram 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-55, PRINTEX-55, PRINTEX-45, PRINTEX-35, PRINTEX-55, PRINTEX-85, PRINTEX-75, PRINTEX- SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A; SPECIAL BLACK-550; RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-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, RAVEN-1170, etc. may be used, but is not limited thereto.

Color pigments that can be mixed with the carbon black include carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), Mitsubishi carbon black MA100, perylene black (BASF K0084. K0086), cyanine black , Linol 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 15: 1, 15: 4, 15: 6, 22, 60, 64, C.I. PIGMENT 83, 139 C.I. PIGMENT VIOLET 23, and the like, and white pigments, fluorescent pigments and the like may also be used, but are not limited thereto.

In addition, as a blue coloring agent, it can be used individually by a blue pigment, or can mix and use a blue pigment and a violet pigment.

Examples of the blue pigment include Pig.Blue # 1 (CI42595: 2), Pig.Blue # 2 (CI44045: 2), Pig.Blue # 9 (CI42025: 1) and Pig.Blue #, which are triarylcarbonium compounds. 10 (CI44040: 2), Pig.Blue # 14 (CI42600: 1), Pig.Blue # 18 (CI42770: 1), Pig.Blue # 19 (CI42750), Pig.Blue # 56 (CI42800 ), Pig.Blue # 62 (CI44084); Cu phthalocyanine-based Pig.Blue # 15 (C.I.74160), Pig.Blue # 15: 1 (C.I.74160); Pig.Blue # 16 (C.I.74100), which is a metal phthalocyanine type; Indanthrone system Pig.Blue # 60 (C.I.69800), Pig.Blue # 64 (C.I.69825); Indigo-based Pig.Blue # 66 (C.I.73000), Pig.Blue # 63 (C.I.73015: x) and the like may be used, but is not limited thereto.

The violet pigments include Pig.Violet # 1 (CI45170: 2), Pig.Violet # 2 (CI45175: 1), Pig.Violet # 3 (CI42535: 2), Pig.Violet # 27 (CI42535: 3), Pig.Violet # 39 (CI42555: 2); Anthraquinone-based Pig.Violet # 5: 1 (C.I.58055: 1); Naphthol-based Pig.Violet # 25 (C.I.12321), Pig.Violet # 50 (C.I.12322); Pig.Violet # 19 (C.I.73900) which is a quinacridone family; Pig.Violet # 23 (C.I.51319) and Pig.Violet # 37 (C.I.51345), which are dioxazines; Perylene-based Pig.Violet # 29 (C.I.71129); Benzimidazolone-based Pig.Violet # 32 (C.I.12517) may be used, but is not limited thereto.

In addition, as a green coloring agent, it can use individually by a green pigment, or can mix and use a green pigment and a yellow pigment.

Examples of the green pigment include Pig.Green # 1 (C.I.42040: 1), Pig.Green # 2 (C.I.42040: 1), and Pig.Green # 4 (C.I.42000: 2), which are triarylcarbonium compounds; Pig. Green # 7 (C.I.74260), Pig.Green # 36 (C.I.74265), which are Cu phthalocyanine series; Zn phthalocyanine-based Pig.Green # 58, metal complex Pig.Green # 8 (C.I.10006), Pig.Green # 10 (C.I.12775) and the like may be used, but are not limited thereto.

Examples of the yellow pigment include Pig. Yellow # 1 (CI11680), Pig. Yellow # 2 (CI11730), Pig. Yellow # 3 (CI11710), Pig. Yellow # 5 (CI11660), and Pig. Yellow # 6 (CI11670), Pig. Yellow # 10 (CI12710), Pig. Yellow # 49 (CI11765), Pig. Yellow # 65 (CI11740), Pig. Yellow # 73 (CI11738), Pig. Yellow # 74 (CI11741), Pig. Yellow # 75 (CI11770), Pig. Yellow # 97 (CI11767), Pig. Yellow # 98 (CI11727), Pig. Yellow # 111 (CI11745), Pig. Yellow # 116 (CI11790), Pig. Yellow # 167 (CI11737); Pig.Yellow # 61 (CI13880), Pig.Yellow # 62: 1 (CI13940: 1), Pig.Yellow # 100 (CI19140: 1), Pig.Yellow # 168 (CI13960) ), Pig. Yellow # 169 (CI13955), Pig. Yellow # 183 (CI18792); Pig. Yellow # 16 (C.I. 20040), which is a bisacetoacetalilide system; Pigary Yellow # 12 (CI21090), Pig. Yellow # 13 (CI21100), Pig. Yellow # 14 (CI21095), Pig. Yellow # 17 (CI21105), Pig. Yellow # 55 CI21096), Pig.Yellow # 63 (CI21091), Pig.Yellow # 81 (CI21127), Pig.Yellow # 83 (CI21108), Pig.Yellow # 87 (CI21107: 1), Pig.Yellow # 113 (CI21126), Pig.Yellow # 114 (CI21092), Pig.Yellow # 124 (CI21107), Pig.Yellow # 126 (CI21101), Pig.Yellow # 127 (21102), Pig.Yellow # 152 (CI21111), Pig. Yellow # 170 (CI21104), Pig. Yellow # 171 (CI21106), Pig. Yellow # 172 (CI21109), Pig. Yellow # 174 (CI21098); Pig.Yellow # 24 (C.I.70600), which is a flavones system; Pig.Yellow # 93 (CI20710), Pig.Yellow # 94 (CI20038), Pig.Yellow # 95 (CI20034), Pig.Yellow # 128 (CI20037), Pig.Yellow # 166 (Diazo condensate) CI20035); Anthraquinone-based Pig. Yellow # 123 (C.I.65049), Pig.Yellow # 147 (C.I.60645); Pig.Yellow # 101 (C.I.48052), which is an alginate; Pig.Yellow # 104 (C.I.15985: 1), a naphthalene sulfonic acid metal complex; Pigra Yellow # 108 (C.I.68420), which is anthrapyrimidine; Pig.Yellow # 109 (C.I.56284), Pig.Yellow # 110 (C.I.56280), Pig.Yellow # 139 (C.I.56298), Pig.Yellow # 185 (C.I.56290), which are isoindolinones; Benzimidazolone series Pig.Yellow # 123 (CI11783), Pig.Yellow # 154 (CI13980), Pig.Yellow # 175 (CI11784), Pig.Yellow # 180 (CI21290), Pig.Yellow # 181 (CI11777); Pig. Yellow # 138 (C.I. 56300), which is a quinophthalone; Pig.Yellow # 117 (CI48043), Pig.Yellow # 129 (CI48042), Pig.Yellow # 150 (CI12764), Pig.Yellow # 153 (CI48545), Pig.Yellow # 177 (CI) 48120, Pig. Yellow # 179 (CI48125), etc. may be used, but is not limited thereto.

In addition, as a red pigment, it can be used individually by a red pigment, or can mix and use a red pigment and the said yellow pigment.

As the red pigment, Pig.Red # 1 (CI12070), Pig.Red # 2 (CI12310), Pig.Red # 3 (CI12120), Pig.Red # 4 (CI12085), which are naphthol-based red pigments, Pig.Red # 5 (CI12490), Pig.Red # 6 (CI12090), Pig.Red # 7 (CI12420), Pig.Red # 8 (CI12355), Pig.Red # 9 (CI12460), Pig.Red # 10 (CI12440), Pig.Red # 11 (CI12430), Pig.Red # 12 (CI12385), Pig.Red # 13 (CI12395), Pig.Red # 14 (CI12380), Pig.Red # 15 (CI12465), Pig.Red # 16 (12500), Pig.Red # 17 (CI12390), Pig.Red # 18 (CI12350), Pig.Red # 21 (CI12300), Pig .Red # 22 (CI12315), Pig.Red # 23 (CI12355), Pig.Red # 31 (12360), Pig.Red # 32 (12320), Pig.Red # 95 (CI15897), Pig.Red # 112 (CI12370), Pig.Red # 114 (CI12351), Pig.Red # 119 (CI12469), Pig.Red # 146 (CI12485), Pig.Red # 147 (CI12433), Pig.Red # 148 (CI12369), Pig.Red # 150 (CI12290), Pig.Red # 151 (CI15890), Pig.Red # 184 (CI12487), Pig.Red # 187 (CI12486), Pig.Red # 188 (CI12467), Pig.Red # 210 (CI12474), Pig.Red # 245 (CI12317), Pig.Red # 253 (CI12375), Pig.Red # 258 (CI12318), Pig .Red # 261 (C.I.12468); Pig.Red # 49 (CI15630), Pig.Red # 49: 1 (CI15630: 1), Pig.Red # 49: 2 (CI15630: 2), Pig.Red # 49: naphthol-based and metal complexes 3 (CI15630: 3), Pig.Red # 50: 1 (CI15500: 1), Pig.Red # 51: 1 (CI15580: 1), Pig.Red # 53 (CI15585), Pig.Red # 53: 1 (CI15585: 1), Pig.Red # 68 (CI15525), Pig.Red # 243 (CI15910), Pig.Red # 247 (CI15915); Disazopyrazolone Pig.Red # 37 (C.I.21205), Pig.Red # 38 (C.I.21210), Pig.Red # 41 (C.I.21200); Disazo-based condensates Pig.Red # 144 (CI20735), Pig.Red # 166 (CI20035), Pig.Red # 220 (CI20055), Pig.Red # 221 (CI20065), Pig.Red # 242 (CI20067); Pig.Red # 48: 1 (CI15865: 1), Pig.Red # 48: 2 (CI15865: 2), Pig.Red # 48: 3 (CI, 2-hydroxy-3-naphthoic acid-based metal complexes 15865: 3), Pig.Red # 48: 4 (CI15865: 4), Pig.Red # 48: 5 (CI15865: 5), Pig.Red # 52: 1 (CI15860: 1), Pig.Red # 52: 2 (CI15860: 2), Pig.Red # 57: 1 (CI15850: 1), Pig.Red # 58: 2 (CI15825: 2), Pig.Red # 58: 4 (CI15825: 4), Pig.Red # 63: 1 (CI15880: 1), Pig.Red # 63: 2 (CI15880: 2), Pig.Red # 64 (CI15800), Pig.Red # 64: 1 (CI 15800: 1), Pig. Red # 200 (CI15867); Pig.Red # 60: 1 (C.I.16105: 1), Pig.Red # 66 (C.I.18000: 1), Pig.Red # 67 (C.I.18025: 1), naphthalenesulfonic acid metal complexes; Triarylcarbonium-based Pig.Red # 81: 1 (C.I.45160: 1), Pig.Red # 81: 3 (C.I.45160: 3), Pig.Red # 169 (C.I.45160: 2); Pig.Red # 89 (C.I. 60745), Pig.Red # 177 (65300), which are anthraquinones; Pig.Red # 88 (C.I.73312), Pig.Red # 181 (C.I.73360), which are ciiodigo-based; The quinacridone family Pig.Red # 122 (C.I.73915), Pig.Red # 207 (C.I.73900), Pig.Red # 209 (C.I.73905); Perylene-based Pig.Red # 123 (CI71145), Pig.Red # 149 (CI71137), Pig.Red # 178 (CI71155), Pig.Red # 179 (CI71130), Pig.Red # 190 (CI 71140), Pig. Red # 194 (CI71100), Pig. Red # 224 (CI71127); Van. Imidazolone-based Pig.Red # 171 (CI12512), Pig.Red # 175 (CI12513), Pig.Red # 176 (CI12515), Pig.Red # 185 (CI12516), Pig.Red # 208 (CI12514); Pyranthrone Pig.Red # 216 (C.I.59710); Pig.Red # 254 (C.I.56110), a diketopyrrolopyrrole system; And Pig.Red # 260 (C.I.56295), which is isoindolin-based, and the like.

The content of the colorant may be 5 to 60% by weight based on the total weight of the photosensitive resin composition.

The photosensitive resin composition according to the present disclosure may further include at least one additive selected from the group consisting of photocrosslinking sensitizers, curing accelerators, dispersants, antioxidants, ultraviolet absorbers, thermal polymerization inhibitors, surfactants and leveling agents.

Examples of the photocrosslinking sensitizer include benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4bis (diethylamino) benzophenone, 2,4,5-trimethylaminobenzophenone, and methyl-o-. Benzophenone compounds such as benzoylbenzoate, 3,3-dimethyl-4-methoxybenzophenone or 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone; Fluorene-based compounds such as 9-fluorenone, 2-chloro-9-proprenone and 2-methyl-9-fluorenone; Thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone or diisopropyl thioxanthone compound; Xanthone compounds such as xanthone or 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butylanthraquinone or 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinylpentane) or 1,3-bis (9-acridinyl) propane 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 or bis (2,6dimethoxybenzoyl) -2,4,4-trimethylphenyl phosphine oxide; Benzophenone compounds such as methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate or 2-n-butoxyethyl-4- (dimethylamino) benzoate; 2,5-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-ethylaminobenzal) cyclohexanone or 2,6-bis (4-diethylaminobenzal) -4-methyl Amino synergists such as cyclopentanone; 3,3-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3 -Benzoyl-7-methoxy-coumarin or 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] -quinolizine-11-one; Chalcone compounds such as 4-diethylaminokalone and 4-azidobenzalacetophenone; 2-benzoylmethylene, or 3-methyl-b-naphthothiazoline.

Examples of the curing accelerator include 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-mercaptoacetate), Pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), and Trimethylolethane tris (3-mercaptopropionate) may include one or more selected from the group consisting of, but is not limited to these, and may include those generally known in the art.

The dispersant may be used as a method of internally adding to the pigment in the form of surface treatment of the pigment in advance or externally adding to the pigment. The dispersant may be a polymeric, nonionic, anionic, or cationic dispersant, and examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohols, ester alkylene oxide adducts, and alcohol alkylenes. At least one selected from the group consisting of oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, and alkylamines, but is not limited thereto.

The antioxidant may be 2,2-thiobis (4-methyl-6-t-butylphenol), or 2,6-g, t-butylphenol, -Butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, or alkoxybenzophenone.

The ultraviolet absorber may use 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole or alkoxy benzophenone, but is not limited thereto.

The thermal polymerization inhibitor is hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogarol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t -Butylphenol), 2,2-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptoimidazole and the like can be used, but is not limited thereto.

Specifically, the silicone surfactant is BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307 , BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-370, BYK-370, BYK-380, and BYK-390 may be used as the fluorine-based surfactant, and DIC F-444, F-444, F-441, F-450, F-493, F-494, F-443, F-444, F-445 and F-446 of Dai Nippon Ink & , F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F- TF-1116SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1025SF, TF- , TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, and the like.

The dispersant, antioxidant, ultraviolet absorbent, thermal polymerization inhibitor, and leveling agent may include those generally known in the art.

The amount of the additive may be independently 0.01 to 5% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

The photosensitive resin composition according to the exemplary embodiment of the present specification includes a polymerizable compound having a functional group that absorbs water such as ethylene oxide, whereby water exposed during the process of generating a fine pattern is absorbed by the fine pattern and is generated by water. There is an advantage that stains are reduced.

If water stains or the like are generated during the process of generating the fine pattern, the pattern inspector recognizes the defect as a defect and the defect rate is relatively high. As a result, the yield of producing the related products is also lowered.

There is provided a photosensitive material produced using the photosensitive resin composition according to the present specification.

In more detail, the photosensitive resin composition of this specification is apply | coated on a base material by an appropriate method, and the photosensitive material of a thin film or a pattern form is formed.

Although it does not restrict | limit especially as said coating method, A spray method, a roll coating method, a spin coating method, etc. can be used, and spin coating method is generally used widely. In addition, after forming a coating film, some residual solvent can be removed in some cases under reduced pressure.

As a light source for curing the photosensitive resin composition according to the present specification, for example, mercury vapor arc (arc), carbon arc, Xe arc, etc., which emit light having a wavelength of 250 to 450 nm, but is not limited thereto.

The photosensitive resin composition according to the present disclosure is preferably used for pigment dispersion type photosensitive material for manufacturing TFT LCD color filter, photosensitive material for forming black matrix of TFT LCD or organic light emitting diode, photosensitive material for forming overcoat layer, column spacer photosensitive material, It can also be used in photocurable paints, photocurable inks, photocurable adhesives, printing plates, photosensitive materials for printed wiring boards, other transparent photosensitive materials, PDP production, and the like, and the use thereof is not particularly limited.

The present specification provides a color filter including the photosensitive material.

Currently, the liquid crystal display device and the liquid crystal display device using the LED BLU, which occupy the largest portion in the display market, use color filters to realize high quality color characteristics. The pattern of the color filter is formed using a photolithography process, which typically consists of a process of coating, vacuum drying, electrothermal treatment, exposure, development and post-heat treatment to a glass substrate.

The photolithography process may be configured by coating, vacuum drying, exposing, developing, and post-heating the glass substrate by omitting the electrothermal treatment process.

On the other hand, in the photolithography process, in order to check the quality characteristics of the pattern, before the post-heat treatment after the development and cleaning process, the pattern inspector is used for pattern straightness defects, pattern dropout defects, foreign matter defects, protrusion defects, and various stains. Due to the detection of defects.

In the photosensitive resin composition according to the present disclosure, when the electrothermal treatment step is omitted in the photolithography process, when the pattern inspection is performed before the post-heat treatment is performed, there is no defect detection due to water staining or there is little advantage.

Since the acryl crab monomer having a structure of ethyl oxide is included as the polymerizable compound in the photosensitive resin composition, water used during the developing process and the cleaning process is absorbed by the pattern formed by the photosensitive resin composition to prevent water staining. Can be reduced.

The photosensitive material may be included in any one or more of three color patterns of red, green, and blue color, overcoat, black matrix, column spacer, and printed wiring board.

The present specification provides a liquid crystal display including the color filter.

Hereinafter, an embodiment according to the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present specification, whereby the scope of the present specification is not limited.

<Examples>

<Synthesis Example>

Synthesis of Binder Resin

(1) step 1: basic acrylic binder resin polymerization step

10.3 g of each monomer, benzyl methacrylate, 23.8 g of N-phenyl maleimide, and 14.0 g of styrene are mixed so that the molar ratio of benzyl methacrylate, N-phenyl maleimide and styrene is 1: 2: 2, 71.9 g of glycidyl methacrylate, 4 g of 1-dodecanethiol as a chain transfer agent, and 480 g of propylene glycol monomethyl ether acetate as a solvent were mixed with a mechanical stirrer under a nitrogen atmosphere for 30 minutes. When the temperature of the reactor was increased to 60 ° C. under a nitrogen atmosphere and the mixture temperature reached 60 ° C., 5 g of a thermal polymerization initiator V-65 was added thereto and stirred for 15 hours. (Mw 6,000, Av 0)

(2) Step 2: Introduction of unsaturated group

The reactor was polymerized to a temperature of 80 ° C., 0.5 g of tetraethylammonium bromide and 0.1 g of 4-methoxy phenol, a thermal polymerization inhibitor, were stirred under an air atmosphere for 3 hours, followed by 26.1 g of methacrylic acid. Put the reactor temperature to 100 ℃ and stirred for 24 hours. (Mw 8,000, Av 5)

(3) Stage 3: Give birth

The temperature of the polymer solution prepared in step 2 was lowered to 70 ° C., and 30.8 g of tetrahydro phthalic anhydride was added thereto, followed by further stirring at 80 ° C. for 24 hours to synthesize a desired binder resin. (Mw 10,100, Av 75)

&Lt; Example 1 >

Pigment Green 58, which is 5.04 parts by weight, Pigment yellow 150, which is 0.15 parts by weight, 0.30 part by weight of the binder resin prepared in the synthesis example, 0.55 part by weight of DPEA-12 as the polymerizable compound, 0.12 part by weight of I-369 as the photoinitiator, 0.023 part by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, 0.060 part by weight of F-475 (DaiNippon Ink & Chemicals) as a surfactant, and 3.80 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed. Stirring for 5 hours to prepare a photosensitive resin composition.

<Example 2>

A photosensitive resin composition was prepared in the same manner as in Example 1, except that RP1040 was used instead of DPEA-12 as the polymerizable compound in Example 1.

&Lt; Comparative Example 1 &

A photosensitive resin composition was prepared in the same manner as in Example 1 except that dipentaerythritol hexa (meth) acrylate (DPHA) was used instead of DPEA-12 as the polymerizable compound in Example 1.

<Experimental Example 1>

Evaluation method of water stain

The photosensitive resin compositions of Examples and Comparative Examples were spin-coated on glass, left at room temperature for 30 minutes, exposed to light using a photomask at 40 mJ / cm ^2, and then developed at 26 ° C. in a Na ₂ CO ₃ developer, followed by 26 Spin linsing is carried out in a developer using distilled water for 40 seconds. Thereafter, blowing is performed for 20 seconds at 1000 rpm in a spin coater. The board | substrate with which the said photosensitive resin composition was apply | coated was observed with the optical microscope, and the general tone of the pattern and the grade and number of water stains were visually observed.

Polymerizable compound Water staining Water stain Example 1 DPEA-12 Good (improved) 0 Example 2 RP1040 Good (improved) 0 Comparative Example 1 DPHA Strong level 10

As can be seen from the results of Table 1, the present invention has the effect of greatly reducing the number of water stains (Example 1 and Example 2) compared to Comparative Example 1 according to the content of the polymerizable compound having an ethylene oxide structure It was observed that the tone of the overall pattern was also brightened and uniform so that the water stain was improved.

Claims (13)

A photosensitive resin composition comprising a binder resin, a polymerizable compound, a photoinitiator, an adhesion promoter, and a solvent, any one or more of compounds represented by any one of the following Chemical Formulas 1 to 4:
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In Chemical Formulas 1 and 4,
R1 to R10 are each independently represented by the following formula (5) or (8),
R11 to R13 are represented by the following formula (8),
R14 to R17 are represented by the following formula (6),
[Chemical Formula 5]

[Chemical Formula 6]

In Chemical Formulas 5 to 6,
R18 and R19 are each independently hydrogen or an alkyl group of C ₁ to C ₁₀ ,
R20 is represented by the following formula (7),
(7)

In Formula 7,
R21 is hydrogen or an alkyl group of C ₁ to C ₁₀ ,
R22 is represented by (CH ₂ ) _b OH or the following formula (8),
[Chemical Formula 8]

In Formula 8,
R 23 is (CH ₂ ) _n O or CO (CH ₂ ) _l O,
R24 is hydrogen or an alkyl group of C ₁ to C ₁₀ ,
n and l are each independently an integer of 2 to 10,
m is an integer of 1 to 2,
o and p are integers from 1 to 3,
a and b are integers from 1 to 10. The photosensitive resin composition of claim 1, wherein Formula 3 is represented by Formula 9 below:
[Chemical Formula 9]

The photosensitive resin composition of claim 1, wherein Formula 4 is represented by Formula 10:
[Formula 10]

The method of claim 1, wherein the binder resin is unsaturated carboxylic esters; Aromatic vinyls; Unsaturated ethers; Unsaturated imides; And a copolymerized resin of at least one monomer selected from the group consisting of acid anhydrides and monomers containing an acid group. The method of claim 1, wherein the adhesion promoter is methacryloyloxy propyltrimethoxy silane, methacryloyloxy propyldimethoxy silane, methacryloyloxy propyltriethoxy silane and methacryloyloxy propyldimethoxysilane Methacryloyl silane which is at least one of; And an alkyl trimethoxy silane which is at least one of octyltrimethoxy silane, dodecyltrimethoxy silane, and octadecyltrimethoxy silane. The method of claim 1, wherein the content of the binder resin is 1 to 50% by weight, the content of the polymerizable compound is 1 to 50% by weight, and the content of the photoinitiator is 0.1 to 20% by weight based on the total weight of the photosensitive resin composition. The content of the adhesion promoter is 0.01 to 1% by weight and the content of the solvent is a photosensitive resin composition, characterized in that 30 to 90% by weight. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises a colorant. The photosensitive resin composition of claim 7, wherein the content of the colorant is 5 to 60 wt% based on the total weight of the photosensitive resin composition. The method of claim 1, wherein the photosensitive resin composition further comprises at least one additive selected from the group consisting of photocrosslinking sensitizers, curing accelerators, dispersants, antioxidants, ultraviolet absorbers, thermal polymerization inhibitors, surfactants and leveling agents. Photosensitive resin composition to be. The photosensitive material manufactured from the photosensitive resin composition of any one of Claims 1-9. The method of claim 10, wherein the photosensitive material is selected from the group consisting of a pigment dispersion type photosensitive material for producing a color filter, a photosensitive material for forming a black matrix, a photosensitive material for forming an overcoat layer, a column spacer photosensitive material and a photosensitive material for a printed wiring board. Photosensitive material. A color filter comprising the photosensitive material of claim 10. A liquid crystal display device comprising the color filter of claim 12.

Images