KR102411686B1 - A green photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

(상기 화학식 1에서,
A₁은 1개 이상의 에테르 결합을 갖는 탄소수 2 내지 70의 탄화수소기이고,
A₂는, -C-, -CO-, -O-CO- 또는 -NHCO-이며,
A₃은 탄소수 1 내지 10의 직쇄 또는 분지쇄인 알킬렌기 또는 알킬메틸렌기이고,
n은 3 내지 10의 정수이다). The present invention relates to a thiol compound represented by the following formula (1); a colorant containing an aluminum phthalocyanine compound; alkali-soluble resin; photopolymerizable compounds; photoinitiator; and a solvent; by including, an object of the present invention is to provide a green photosensitive resin composition having excellent transmittance and excellent solvent resistance, adhesion, and pattern formation properties during pattern formation, a color filter and an image display device including the same.
[Formula 1]

(In Formula 1,
A ₁ is a hydrocarbon group having 2 to 70 carbon atoms having at least one ether bond,
A ₂ is -C-, -CO-, -O-CO- or -NHCO-,
A ₃ is a linear or branched alkylene group or alkylmethylene group having 1 to 10 carbon atoms,
n is an integer from 3 to 10).

Description

Green photosensitive resin composition, color filter and image display device including the same

The present invention relates to a green photosensitive resin composition, a color filter comprising the same, and an image display device.

A color filter is a member used for a solid-state image sensor or a liquid crystal display device, and is generally produced by forming a coloring pattern on a support body using a coloring photosensitive resin composition.

In recent years, there is a tendency for image display devices to become thinner, and color filters included in image display devices also tend to become thinner, and accordingly, the size of the coloring pattern is becoming more miniaturized. appears conspicuously.

According to the miniaturization of the coloring pattern, impreciseness at the end of the coloring pattern or the development residue in the unexposed portion is more problematic than before.

In addition, in the thin-layered color filter, the composition ratio of the colorant in the colored photosensitive resin composition increases in order to obtain spectral sensitivity equivalent to that of the conventional color filter. In this case, components other than the colorant (components contributing to photolithography performance) are relatively By decreasing, there is a problem in that durability such as solvent resistance and adhesiveness decreases.

In order to solve this problem, Korean Patent Application Laid-Open No. 10-2012-0088026 includes a colorant, an alkali-soluble resin, a photopolymerization compound, a photoinitiator and a solvent, and the resin composition further contains an azo compound, a mercapto compound, and an epoxy compound. Although it has been described with respect to the colored photosensitive resin composition comprising, this has a problem in that the color reproducibility is inferior.

Republic of Korea Patent Publication No. 10-2012-0088026 (2012.08.08.)

The present invention is to solve the above problems, and to provide a green photosensitive resin composition having excellent transmittance and excellent solvent resistance, adhesion, pattern formation, etc. during pattern formation, a color filter and an image display device including the same for that purpose

The green photosensitive resin composition of the present invention for achieving the above object is a thiol compound represented by the following formula (1); a colorant containing an aluminum phthalocyanine compound; alkali-soluble resin; photopolymerizable compounds; photoinitiator; and a solvent; characterized in that it comprises:

[Formula 1]

(In Formula 1,

A ₁ is a hydrocarbon group having 2 to 70 carbon atoms having at least one ether bond,

A ₂ is -C-, -CO-, -O-CO- or -NHCO-,

A ₃ is a linear or branched alkylene group or alkylmethylene group having 1 to 10 carbon atoms,

n is an integer from 3 to 10).

In addition, the color filter of the present invention is characterized in that it comprises a cured product of the above-described green photosensitive resin composition.

In addition, the image display apparatus of the present invention is characterized in that it includes the above-described color filter.

The green photosensitive resin composition of the present invention has advantages of excellent transmittance and excellent solvent resistance, adhesion, and pattern formation during pattern formation.

The color filter of the present invention has the same advantages as described above by including the cured product of the green photosensitive resin composition.

The image display apparatus of the present invention has the same advantages as described above by including the color filter.

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

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

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

<Green photosensitive resin composition>

A green photosensitive resin composition according to an aspect of the present invention includes a thiol compound represented by the following Chemical Formula 1; a colorant containing an aluminum phthalocyanine compound; alkali-soluble resin; photopolymerizable compounds; photoinitiator; and a solvent; by including, the transmittance is excellent and the solvent resistance, adhesion, and pattern formation properties are excellent during pattern formation.

[Formula 1]

(In Formula 1,

A ₁ is a hydrocarbon group having 2 to 70 carbon atoms having at least one ether bond,

A ₂ is -C-, -CO-, -O-CO- or -NHCO-,

A ₃ is a linear or branched alkylene group or alkylmethylene group having 1 to 10 carbon atoms,

n is an integer from 3 to 10).

thiol compound

The green photosensitive resin composition according to an embodiment of the present invention includes the thiol compound represented by Chemical Formula 1, and thus has excellent solvent resistance, adhesion, and pattern formation properties during pattern formation.

According to an embodiment of the present invention, A ₁ in Formula 1 may include one or more of the repeating units represented by Formulas 2 to 4 below.

[Formula 2]

(In Formula 2,

A ₄ is each independently an alkylene group having 1 to 6 carbon atoms,

A ₅ is each independently an alkylene group having 1 to 6 carbon atoms,

A ₆ is each independently an alkylene group having 1 to 6 carbon atoms,

"*" means a bond hand)

[Formula 3]

(In Formula 3, "*" means a bond)

[Formula 4]

(In Formula 4,

m is an integer from 0 to 2, and "*" means a bond).

Preferably, in Formula 1, n is an integer of 4 or more, specifically 4 to 10, and more preferably 4, 6 or 8.

As an example, when n is 3, A ₁ may be a trivalent group represented by Formula 2 or a trivalent group represented by Formula 3, and when n is 4, 6 or 8, represented by Formula 4 It may be a tetravalent, hexavalent or octavalent group, but is not limited thereto.

The compound represented by Formula 1 may be, for example, selected from the group consisting of compounds represented by Formula 5 to Formula 12, and preferably a compound represented by Formula 5 or a compound represented by Formula 9 below. .

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

The above-mentioned thiol compounds may be used alone or in combination of two or more.

According to an embodiment of the present invention, the thiol compound may be included in an amount of 0.3 to 5% by weight, preferably 0.5 to 3% by weight, based on 100% by weight of the total solid content of the green photosensitive resin composition including the thiol compound. When the content of the thiol compound satisfies the above range, there is an advantage in that stability, odor, sensitivity, resolution, developability, and adhesion of the green photosensitive resin composition can be improved.

coloring agent

The green photosensitive resin composition according to an embodiment of the present invention has an advantage in that it has excellent transmittance by including a colorant containing an aluminum phthalocyanine compound.

aluminum phthalocyanine compound

The aluminum phthalocyanine compound is a compound having a structure in which trivalent aluminum is disposed at the center of a phthalocyanine ring, and the aluminum is bonded to a nitrogen atom in the phthalocyanine ring. In the aluminum phthalocyanine compound, an additional bond other than the bond with the nitrogen atom in the phthalocyanine ring is possible. In addition, various chemical modifications of the phthalocyanine ring of the aluminum phthalocyanine compound are possible. The aluminum phthalocyanine compound can be multimerized into a dimer, a trimer, etc. in addition to a monomer.

According to an embodiment of the present invention, the aluminum phthalocyanine compound may include a compound represented by the following Chemical Formula 13 or Chemical Formula 14.

[Formula 13]

(In Formula 13,

R ¹ to R ¹⁶ are each independently hydrogen, a halogen atom, a nitro group, a substitutable phthalimidemethyl group, a substitutable sulfamoyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, C5 to C10 of a substitutable cycloalkyl group, a heterocyclic group, a C1 to C18 substitutable alkoxy group, a C6 to C14 substitutable aryloxy group, a C1 to C18 substitutable alkylthio group, or a C6 to C14 substitutable arylthio group,

Z is -OP(=O)X ₁ X ₂ ,

wherein X ₁ and X ₂ are each independently hydrogen, a hydroxyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, a C1 to C18 substitutable alkoxy group, or a C6 to C14 substitutable aryloxy group, ,

X ₁ and X ₂ may form a heterocycle together with the bonded phosphorus atom).

In the present invention, 'substitutable' means that it may further include a substituent, and the substituents may be different or the same, and specifically, a halogen group such as fluorine, chlorine, bromine, an amino group, a hydroxyl group, a nitro group In addition to characteristic groups, such as, an alkyl group, an aryl group, a cycloalkyl group, an aryloxy group, an alkylthio group, an arylthio group, etc. may be mentioned, but are not limited thereto.

The halogen atom may include fluorine, chlorine, bromine, etc. For example, when R ¹ to R ¹⁶ in Formula 13 include hydrogen, chlorine and bromine, the number of hydrogens is 1 to 6, chlorine The number may be 3 to 9, the number of bromine may be 2 to 7, or R ¹ to R ¹⁶ may be all hydrogen, but is not limited thereto.

The alkyl group refers to a straight-chain or branched hydrocarbon group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, n -octyl group, stearyl group, 2-ethylhexyl group, etc. may be included, and the alkyl group may include a substituent, for example, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoro Ethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group group, 4-tert ptylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, and the like.

The aryl group may include, for example, a phenyl group, a naphthyl group, and an atryl group, and these may include a substituent, for example, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p- Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-trichloro-2-naphthyl group, anthraquinoryl group, 2-aminoanthraquinoryl group, etc. are mentioned.

The cycloalkyl group may include, for example, a cyclopentyl group, a cyclohexyl group, and an adamantyl group, and these may include a substituent, for example, a 2,5-dimethylcyclopentyl group, 4-tert- A phtylcyclohexyl group etc. are mentioned.

The heterocyclic group includes, for example, a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group.

The alkoxy group may be linear or branched, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, 2, 3-dimethyl-3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, etc., which may include a substituent, for example, Trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoromethyl propoxy group group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro propoxy group, benzyloxy group, etc. are mentioned.

The aryloxy group may include, for example, a phenoxy group, a naphthoxy group, an anthryloxy group, and the like, and these may include a substituent, for example, p-methylphenoxy group, p-nitrophenoxy group, p- and a methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, and a 2-methyl-4-chlorophenoxy group.

The alkylthio group is, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a phenylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, etc. and these may have a substituent, for example, a methoxyethyl thio group, an aminoethylthio group, a benzyl aminoethylthio group, a methylcarbonylamino ethylthio group, a phenylcarbonylamino ethylthio group, etc. can

The aryl thio group may include, for example, a phenyl thio group, a 1-naphthyl thio group, a 2-naphthyl thio group, a 9-anthryl thio group, etc., which may include a substituent, for example, chloro phenyl thio group, trifluoromethyl phenyl thio group, cyanophenyl thio group, nitrophenyl thio group, 2-aminophenyl thio group, 2-hydroxyphenyl thio group and the like.

[Formula 14]

(In Formula 14,

wherein R ¹⁷ to R ³² are each independently hydrogen, a halogen atom, a nitro group, a substitutable phthalimidemethyl group, a substitutable sulfamoyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, C5 to a C10 substitutable cycloalkyl group, a heterocyclic group, a C1 to C18 substitutable alkoxy group, a C6 to C14 substitutable aryloxy group, a C1 to C18 substitutable alkylthio group, or a C6 to C14 substitutable arylthio group; ,

또는

이며, The L is

or

is,

In this case, X ₃ to X ₇ are each independently a C1 to C18 substitutable alkyl group or a C6 to C14 substitutable aryl group).

Examples of the halogen atom include fluorine, chlorine, and bromine.

The alkyl group refers to a straight-chain or branched hydrocarbon group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, n -octyl group, stearyl group, 2-ethylhexyl group, etc. may be included, and the alkyl group may include a substituent, for example, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoro Ethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group group, 4-tert ptylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, and the like.

The aryl group may include, for example, a phenyl group, a naphthyl group, and an atryl group, and these may include a substituent, for example, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p- Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-trichloro-2-naphthyl group, anthraquinoryl group, 2-aminoanthraquinoryl group, etc. are mentioned.

The cycloalkyl group may include, for example, a cyclopentyl group, a cyclohexyl group, and an adamantyl group, and these may include a substituent, for example, a 2,5-dimethylcyclopentyl group, 4-tert- A phtylcyclohexyl group etc. are mentioned.

The heterocyclic group includes, for example, a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group.

The alkoxy group may be linear or branched, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, 2, 3-dimethyl-3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, etc., which may include a substituent, for example, Trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoromethyl propoxy group group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro propoxy group, benzyloxy group, etc. are mentioned.

The aryloxy group may include, for example, a phenoxy group, a naphthoxy group, an anthryloxy group, and the like, and these may include a substituent, for example, p-methylphenoxy group, p-nitrophenoxy group, p- and a methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, and a 2-methyl-4-chlorophenoxy group.

The alkylthio group is, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a phenylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, etc. and these may have a substituent, for example, a methoxyethyl thio group, an aminoethylthio group, a benzyl aminoethylthio group, a methylcarbonylamino ethylthio group, a phenylcarbonylamino ethylthio group, etc. can

The aryl thio group may include, for example, a phenyl thio group, a 1-naphthyl thio group, a 2-naphthyl thio group, a 9-anthryl thio group, etc., which may include a substituent, for example, chloro phenyl thio group, trifluoromethyl phenyl thio group, cyanophenyl thio group, nitrophenyl thio group, 2-aminophenyl thio group, 2-hydroxyphenyl thio group and the like.

According to one embodiment of the present invention, the aluminum phthalocyanine compound is C.I. Pigment Green 62 or C.I. Pigment Green 63 may be included.

According to an embodiment of the present invention, the aluminum phthalocyanine compound may be included in an amount of 30 to 100% by weight based on 100% by weight of the total colorant including the same. When the content of the aluminum phthalocyanine compound satisfies the above range, there is an advantage that high color reproduction is possible and coloration power and transmittance can be further improved.

According to an embodiment of the present invention, the colorant may further include one or more pigments or dyes in addition to the above-described aluminum phthalocyanine compound.

pigment

The colorant included in the green photosensitive resin composition of the present invention may further include a pigment other than the above-described aluminum phthalocyanine compound.

As the pigment, various organic or inorganic pigments commonly used in the art may be used.

As the organic pigment, various pigments used in printing inks, inkjet inks, etc. can be used, and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, Perylene pigment, perinone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinonyl pigment, anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, pravanthrone pigment, pyranthrone ) pigments, diketopyrroropyrrole pigments, and the like. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically, oxides or complexes of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. A metal oxide etc. are mentioned. In particular, as the organic and inorganic pigments, C.I. Pigment Green and C.I. Pigment yellow is preferable, and more specifically, a pigment having a color index (C.I.) number as follows, but not necessarily limited thereto.

C.I. green pigments such as Pigment Green 7, 36, 58 and 59;

C.I. yellow pigments such as Pigment Yellow 129, 138, 139, 231, 150 and 185; etc. are mentioned, These can be used individually or in mixture of 2 or more types, respectively.

According to one embodiment of the present invention, the green photosensitive resin composition of the present invention, among the above-mentioned pigments, C.I. Pigment Yellow 138 or C.I. Pigment Yellow 231 may be further included, and when they are used together with the above-mentioned aluminum phthalocyanine compound, color reproducibility and luminance characteristics can be further improved, and coloring power is also improved to prevent display defects such as visibility. And, there is an advantage that the formation of a fine pattern can be easy.

According to one embodiment of the present invention, the green photosensitive resin composition of the present invention is the above-described C.I. Pigment Yellow 138 or C.I. When Pigment Yellow 231 is further included, they may be included in an amount of 10 to 70% by weight, specifically 20 to 70% by weight, more specifically 30 to 70% by weight, based on 100% by weight of the total colorant including the same, and When the same content range is satisfied, there is an advantage that color reproducibility and luminance characteristics can be further improved.

The pigment is preferably used as a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of the method for uniformly dispersing the particle size of the pigment include a method of dispersing treatment by containing a pigment dispersant, and according to the method, a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained.

dispersant

The dispersing agent is added for deagglomeration and stability maintenance of the colorant included therewith, and those generally used in the art may be used without limitation. Commercially available dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 112, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 166, 167, 168, available from BYK. 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, and Lubrizol's SOLSPERSE-3000, 9000, 13000, 13240, 13650,13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, and the like, but is not limited thereto.

These can be used individually or in mixture of two or more, and preferably, BYK's Disperbyk-2000, 2001 or Lubrizol's SOLSPERSE-3000, 21000, 26000, 36600, 41000, etc., which are dispersants having an acidic functional group, can be used. However, the present invention is not limited thereto.

The content of the dispersant in the present invention is not particularly limited, but the content of the dispersant may be included in an amount of 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the total solid content of the colorant included together. If the content of the dispersant exceeds the above range, the viscosity may increase, and if it is less than the above range, it may be difficult to atomize the pigment, or it may cause problems such as gelation after dispersion.

dyes

The green photosensitive resin composition of the present invention may further include a dye as needed.

The dye may be additionally used without limitation as long as it has solubility in organic solvents or is dispersible. Preferably, it is preferable to use a dye that has solubility in organic solvents and can secure reliability such as solubility in alkali developer, heat resistance and solvent resistance. As the dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide compound of an acid dye, and derivatives thereof may be used. In addition, azo-based, xanthene-based, phthalocyanine Acid dyes and derivatives thereof can also be selected. Preferably, the dye is a compound classified as a dye in the color index (published by The Society of Dyers and Colorists), or a known dye described in a dyeing note (color dye).

Specific examples of the dye include,

C.I. As a solvent dye,

C.I. yellow dyes such as solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Green dyes, such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. are mentioned,

Also, C.I. As an acid dye, C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, yellow dyes such as 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. green dyes such as acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109;

Also, C.I. As a direct dye, C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, yellow dyes such as 136, 138, and 141;

C.I. Green dyes, such as direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. are mentioned,

Also, C.I. As a modanto dye, C.I. yellow dyes such as modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. and green dyes such as Modanto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, and the like, but are not limited thereto, and these dyes may be used alone or in combination of two or more.

According to an embodiment of the present invention, the above-described colorant may be included in an amount of 5 to 60% by weight, preferably 15 to 50% by weight, based on 100% by weight of the total solid content of the green photosensitive resin composition including the same. When the content of the colorant is included within the above range, there is an advantage in that the color concentration of the pixel is sufficient when forming the thin film, and the omission property of the non-pixel portion is not reduced during development, thereby preventing the occurrence of residues.

In the present invention, the solid content in the green photosensitive resin composition means pure solid content excluding all solvents contained in the green photosensitive resin composition.

Alkali-soluble resin

The green photosensitive resin composition according to an aspect of the present invention includes an alkali-soluble resin.

The alkali-soluble resin is added to have solubility in an alkali developer used in the developing process, and may be prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group.

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; and polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate. Among them, acrylic acid and methacrylic acid may be preferable, but the present invention is not limited thereto.

In the preparation of the alkali-soluble resin, an ethylenically unsaturated monomer having a carboxyl group and an unsaturated monomer copolymerizable may be added and polymerized. The copolymerizable unsaturated monomers are exemplified below, but are not necessarily limited thereto.

Specific examples of the polymerization monomer having a copolymerizable unsaturated bond include glycidyl methacrylate, which is an unsaturated monomer having a glycidyl group;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N -ethylenically unsaturated monomers having a hydroxyl group, such as hydroxyethyl (meth)acrylates such as hydroxyethyl acrylamide;

Styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinyl Aromatic vinyl compounds, such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds, such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate;

aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate;

3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane; 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds.

According to one embodiment of the present invention, the acid value of the above-described alkali-soluble resin may be 30 to 150 mgKOH / g, and when the acid value of the alkali-soluble resin is less than the above range, developability may be reduced, and exceeding the above range In this case, since the adhesion with the substrate may be slightly lowered and a short circuit of the pattern may occur, it may be preferable to adjust within the above range in order to secure sufficient developability.

The content of the alkali-soluble resin described above may be included in an amount of 10 to 80% by weight, specifically 10 to 70% by weight based on 100% by weight of the total solid content of the green photosensitive resin composition including the same. When the content of the alkali-soluble resin is within the above range, the solubility in the alkali developer used in the developing process is sufficient, so that the pattern formation can be easy, and the film reduction of the pixel portion of the exposed portion is prevented, thereby omission of the non-pixel portion This may be good.

photopolymerization compound

The green photosensitive resin composition according to an embodiment of the present invention includes a photopolymerizable compound.

The photopolymerizable compound is a compound that can be polymerized by the action of a photopolymerization initiator to be described later, and may be a monofunctional monomer, a bifunctional monomer, or a polyfunctional monomer, and preferably a polyfunctional monomer having a bifunctional or higher function.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, or N-vinylpi Rollidone, and the like, but is not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , bis(acryloyloxyethyl)ether of bisphenol A, or 3-methylpentanediol di(meth)acrylate, but is not limited thereto.

Specific examples of the polyfunctional monomer include trimethylol propane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth)acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) ) acrylate or dipentaerythritol hexa (meth)acrylate, but is not limited thereto.

The photopolymerizable compound may be included in an amount of 5 to 45% by weight, specifically 7 to 45% by weight, based on 100% by weight of the total solid content of the green photosensitive resin composition including the same. When the photopolymerizable compound is included within the above range, the strength or smoothness of the pixel portion may be improved, which is preferable.

light curing initiator

The green photosensitive resin composition according to an embodiment of the present invention includes a photoinitiator, and according to an embodiment of the present invention, the photoinitiator may include an oxime ester-based compound. In this case, the green photosensitive resin composition is highly sensitive Thus, there is an advantage in preventing pattern tearing and implementing a fine pattern.

As the oxime ester compound, 1,2-Octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), 1-[9-Ethyl-6-(2-methylbenzoyl)-9H- carbazol-3-yl]ethanone 1-(O-acetyloxime), etc., and commercially available oxime ester-based photopolymerization initiators include BASF's Irgacure® OXE 01, Irgacure® OXE 02, and Irgacure® OXE 03. Since the radical species to be used are various, it is preferable to use two or more types in combination.

In addition, the green photosensitive resin composition of this invention can also use photoinitiators other than the above-mentioned oxime ester type|system|group photoinitiator. Typically, it is preferable to use at least one compound selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, and a thioxanthone-based compound.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyl) oxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one; 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 -one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra( tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone.

Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -(4-Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4, 4',5,5'-tetraphenyl-1,2'-biimidazole or the imidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group, etc. are mentioned. Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is preferably used

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. There is this.

In addition, the photopolymerization initiator may further include a photopolymerization initiation adjuvant in order to further improve the sensitivity of the green photosensitive resin composition of the present invention. The green photosensitive resin composition according to the present invention may further include a photopolymerization initiation auxiliary as described above, thereby further increasing the sensitivity and improving productivity.

The photopolymerization initiation adjuvant may be, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and a polyfunctional thiol compound.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler ketone) ), 4,4'-bis(diethylamino)benzophenone, etc. can be used.

The carboxylic acid compound is preferably aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

Examples of the polyfunctional thiol compound include Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, Trimethylolpropane tris-3-mercaptopropionate), Pentaerythritol tetrakis-3-mercaptopropionate), and Dipentaerythritol hexa-3-mercaptopropionate).

The total content of the above-described photopolymerization initiator may be 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total solid content of the alkali-soluble resin and the photopolymerizable compound included together. When the photopolymerization initiator is included within the above range, the green photosensitive resin composition is highly sensitive and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. In addition, the strength of the pixel portion formed by using the composition under the above conditions and the smoothness on the surface of the pixel portion may be improved.

In addition, the oxime ester-based compound may be included in an amount of 10 to 100% by weight, preferably 20 to 100% by weight, based on 100% by weight of the total photopolymerization initiator including the oxime ester compound. When the content of the oxime ester-based compound in the total photopolymerization initiator is less than 10% by weight, there is a problem that the decrease in sensitivity due to the colorant cannot be overcome and a short circuit of the pattern may occur during the developing process.

When the photopolymerization initiation adjuvant is further included, 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, may be included with respect to 100 parts by weight of the total of the alkali-soluble resin and the photopolymerizable compound based on the solid content. When the amount of the photopolymerization initiation adjuvant is within the range of 0.1 to 40 parts by weight described above, the sensitivity of the colored photosensitive resin composition may be higher, and productivity of a color filter formed using the composition may be further improved.

solvent

The green photosensitive resin composition according to an embodiment of the present invention includes a solvent.

The solvent is preferably propylene glycol monomethyl ether acetate, but as long as it dissolves the above-described green photosensitive resin composition, it can be used without particular limitation. In particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are preferable.

Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol di Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether and dipropylene glycol ethers such as dibutyl ether; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; 3-ethyl 3-ethoxypropionate, 3-methoxymethyl propionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methyl Toxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Esters such as monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate and γ-butyrolactone, etc. may be mentioned, but is not limited thereto, and these may be used alone or in combination of two or more.

The solvent may be included in an amount of 60 to 90% by weight, preferably 70 to 87% by weight, based on 100% by weight of the total green photosensitive resin composition including the solvent. When the solvent is included within the above range, the coating property may be improved when applied with an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet.

additive

The green photosensitive resin composition of the present invention may contain additives such as fillers, other high molecular compounds, curing agents, adhesion promoters, ultraviolet absorbers, and anti-aggregation agents in addition to the above-mentioned components according to the needs of those skilled in the art within the scope not impairing the object of the present invention. may include

Specifically, the filler may be glass, silica, alumina, or the like, but is not limited thereto.

Specific examples of the other high molecular compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. However, the present invention is not limited thereto.

The curing agent is used for deep curing and increasing mechanical strength, and specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. may be used, but the present invention is not limited thereto. Specifically, the epoxy compound is a bisphenol A-based epoxy resin, a hydrogenated bisphenol A-based epoxy resin, a bisphenol F-based epoxy resin, a hydrogenated bisphenol F-based epoxy resin, a novolak-type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, gly Cydyl ester-based resins, glycidylamine-based resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxide, isoprene (co) Polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like may be used, but is not limited thereto. Specifically, the oxetane compound may include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like, but is limited thereto. it is not

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. Specifically, as the curing auxiliary compound, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, acid generators, and the like may be used. As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. The commercially available epoxy resin curing agent includes, for example, a trade name (Adecahadona EH-700) (manufactured by Adeka Industrial Co., Ltd.), a trade name (Rikasiddo HH) (manufactured by Shin-Nippon Ewha Co., Ltd.), trade name (MH-700) (manufactured by Nippon Ewha Co., Ltd.) and the like.

The curing agent and curing auxiliary compound exemplified above may be used alone or in combination of two or more.

The adhesion promoter is specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri One or a mixture thereof selected from the group consisting of methoxysilane, 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane may be used.

When the adhesion promoter is included, its content may be 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on 100% by weight of the total solid content in the composition.

Specifically, the ultraviolet absorber may include, but is not limited to, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyrazole, alkoxybenzophenone, and the like.

The aggregation inhibitor may be specifically sodium polyacrylate, but is not limited thereto.

The method for producing the above-described green photosensitive resin composition may be used without limitation, a method used in the art, but an example is as follows.

First, the pigment among the colorants is mixed with a solvent or a dispersing agent and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, if necessary, a pigment dispersant, part or all of the alkali-soluble resin, or a dye may be mixed with a solvent to be dissolved or dispersed.

A green photosensitive resin composition according to the present invention may be prepared by further adding a dye, the remainder of the alkali-soluble resin, a photopolymerizable compound and a photoinitiator, and, if necessary, additives and solvents to a predetermined concentration in the mixed dispersion.

<Color filter>

A color filter according to another aspect of the present invention includes a cured product of the above-described green photosensitive resin composition. Specifically, the cured product of the green photosensitive resin composition may mean a colored pattern prepared from the green photosensitive resin composition of the present invention on a substrate. The substrate is a transparent material, and a material having sufficient strength and support for the stability of the color filter may be used. Preferably, a glass having excellent chemical stability and high strength may be used. In addition, the color filter may further include a blue light source as a light source.

A specific configuration and manufacturing method of the color filter may use a conventional configuration and method well known in the art, but typically a coating step; light guiding step; and a removing step; may be manufactured through a process comprising a.

Specifically, the green photosensitive resin composition is applied to an uncoated glass substrate and a glass substrate coated with SiNx (protective film) to a thickness of 500 to 1,500 Å using an appropriate method such as spin coating or slit coating, from 2.0 to It is applied to a thickness of 3.4 μm. After application, light is irradiated to form a pattern required for the color filter. After irradiating the light, if the coating layer is treated with an alkali developer, the unirradiated portion of the coating layer is dissolved and a pattern required for the color filter is formed. By repeating this process according to the required number of R, G, and B colors, a color filter having a desired pattern can be obtained. Further, in the above process, crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing it by irradiation with actinic rays or the like.

<Image display device>

An image display apparatus according to another aspect of the present invention includes the color filter described above.

Specifically, the image display device may include other components that can be typically included in an image display device, such as a light emitting device such as a light source, a light guide plate, and a liquid crystal display including a color filter according to the present invention. It does not limit this.

In addition, the image display device of the present invention includes a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles in addition to the color filter described above. It may be additionally provided. In such a case, the emitted light of the light source applied to the image display apparatus is not particularly limited, but a light source emitting blue light may be preferably used in terms of superior color reproducibility.

The image display device of the present invention may further include a color filter including only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer in addition to the above-described color filter. In such a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles. When only two types of color pattern layers are provided, a light source emitting light having a wavelength representing the remaining colors that is not included may be used. For example, when only the red pattern layer and the green pattern layer are included, a light source emitting blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits the blue light as it is to display blue color.

The image display device includes a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, a display device for a digital camera, and a car display device. A display device such as a display device for navigation may be included, but the present invention is not limited thereto.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. , it is natural that such variations and modifications fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "part" indicating the content are by weight unless otherwise specified.

production example 1: Preparation of pigment dispersion composition

production example 1-1: Preparation of pigment dispersion composition M1

As a pigment, C.I. Pigment Green 62 10.0 parts by weight, 5.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion composition M1 did

production example 1-2: pigment dispersion composition M2

As a pigment, C.I. Pigment Green 63 10.0 parts by weight, 5.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion composition M2 did

production example 1-3: pigment dispersion composition M3

As a pigment, C.I. Pigment Green 7 10.0 parts by weight, 5.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion composition M3 did

production example 1-4: pigment dispersion composition M4

As a pigment, C.I. Pigment Green 58 10.0 parts by weight, 5.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion composition M4 did

production example 1-5: pigment dispersion composition M5

As a pigment, C.I. Pigment Green 59 10.0 parts by weight, 5.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion composition M5 did

production example 1-6: pigment dispersion composition M6

As a pigment, C.I. Pigment Yellow 138 10.0 parts by weight, 5.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion composition M6 did

Synthesis example : Synthesis of alkali-soluble resin

In a flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel and nitrogen inlet tube, 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 13.0 parts of acrylic acid, 10 parts of benzyl methacrylate , 57.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate, 3 parts of n-dodecyl mercapto were introduced and nitrogen substituted. After that, the temperature of the reaction solution was raised to 110° C. with stirring, and the reaction was carried out for 6 hours. The alkali-soluble resin thus synthesized had a solid content acid value of 100.2 mgKOH/g, and a weight average molecular weight Mw measured by GPC of about 15110.

Example and comparative example : Preparation of green photosensitive resin composition

A green photosensitive resin composition was prepared by mixing each component according to the composition and content shown in Table 1 below.

Furtherance pigment dispersion composition thiol
compound alkali
soluble resin photopolymerization
compound photopolymerization initiator solvent M1 M2 M3 M4 M5 M6 B1 B2 C1 D1 E1 F1 Example 1 25.15 - - - - 27.35 0.06 - 9.47 3.36 0.34 34.27 Example 2 25.15 - - - - 27.35 0.38 - 9.04 3.21 0.32 34.55 Example 3 25.15 - - - - 27.35 0.75 - 8.54 3.04 0.30 34.87 Example 4 25.15 - - - - 27.35 - 0.75 8.54 3.04 0.30 34.87 Example 5 - 26.14 - - - 26.36 0.06 - 9.47 3.36 0.34 34.27 Example 6 - 26.14 - - - 26.36 0.38 - 9.04 3.21 0.32 34.55 Example 7 - 26.14 - - - 26.36 0.75 - 8.54 3.04 0.30 34.87 Example 8 - 26.14 - - - 26.36 - 0.75 8.54 3.04 0.30 34.87 Comparative Example 1 25.15 - - - - 27.35 - - 9.55 3.39 0.34 34.22 Comparative Example 2 - 26.14 - - - 26.36 - - 9.55 3.39 0.34 34.22 Comparative Example 3 - - 30.40 - - 22.10 0.38 - 9.04 3.21 0.32 34.55 Comparative Example 4 - - 30.40 - - 22.10 - - 9.55 3.39 0.34 34.22 Comparative Example 5 - - - 42.42 - 10.08 0.38 - 9.04 3.21 0.32 34.55 Comparative Example 6 - - - 42.42 - 10.08 - - 9.55 3.39 0.34 34.22 Comparative Example 7 - - - - 19.95 32.55 0.38 - 9.04 3.21 0.32 34.55 Comparative Example 8 - - - - 19.95 32.55 - - 9.55 3.39 0.34 34.22 M1: Pigment dispersion composition of Preparation Example 1-1
M2: Pigment dispersion composition of Preparation Example 1-2
M3: Pigment dispersion composition of Preparation Example 1-3
M4: Pigment dispersion composition of Preparation Example 1-4
M5: Pigment dispersion composition of Preparation Example 1-5
M6: pigment dispersion composition of Preparation Example 1-6
B1: Trimethylolpropane tris (3-mercaptopropionate); TMMP-20P; Formula 5)
B2: Pentaerythritoltetrakis (3-mercaptopropionate); PEMP; Formula 9)
C1: Alkali-soluble resin of synthesis example
D1: KAYARAD DPHA (manufactured by Nippon Kayaku Corporation)
E1: Irgacure®OXE02 (manufactured by BASF)
F1: propylene glycol monomethyl ether acetate

Preparation Example 2: Preparation of color filters

Each of the green photosensitive resin compositions prepared in Examples and Comparative Examples was coated on a glass substrate (“EAGLE XG”, manufactured by Corning, Inc.) of 2 inches in width and length by spin coating method, and then placed on a heating plate at a temperature of 100° C. was maintained for 3 minutes to form a thin film. Then, a test photomask having a line/space pattern of 1 µm to 100 µm was placed on the thin film, and ultraviolet rays were irradiated with an interval of 200 µm from the test photomask. At this time, the ultraviolet light source was irradiated at 60 mJ/cm 2 using a 1KW high-pressure mercury lamp containing all of the g, h, and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet light was developed by immersing it in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230° C. for 20 minutes to prepare a color filter.

Experimental example One: color coordinates and transmittance measurement

A color filter was manufactured in the same configuration and method except that the test photomask was not used in Preparation Example 2, and transmittance was measured using a colorimeter (manufactured by Olympus, OSP-200), and the results are shown in Table 2 below. described in.

At this time, the color coordinates (Gx, Gy) of each color filter were prepared in the same manner as Gx=0.260 and Gy=0.550, and were evaluated according to the following transmittance (GY) criterion. In order to make the evaluation conditions of transmittance the same, the color coordinates were also adjusted in the same manner as above. Despite the use of different green pigments, C.I. Pigment Yellow 138 (Preparation Example 1-6: Pigment dispersion composition M6) was additionally added, and the color coordinates could be adjusted equally by adjusting the content differently as shown in Table 1 above.

<Judgment Criteria>

◎: increase in transmittance by 2% or more compared to the reference transmittance (GY) of 60

○: Increase in transmittance by less than 1% compared to 60, which is the standard transmittance (GY)

△: A decrease in transmittance of less than 1% compared to the reference transmittance (GY) of 60

×: Reduced transmittance by 2% or more compared to 60, the standard transmittance (GY)

Experimental example 2: solvent resistance Experiment

Each color filter prepared in Preparation Example 2 was immersed in N-methylpyrrolidone solvent for 30 minutes, and color change before and after evaluation was compared and evaluated.

Specifically, the solvent resistance is measured by measuring the chromaticity and transmittance of the substrate manufactured in the color filter manufacturing using a colorimeter (OSP-200, manufactured by Olympus) and immersing the substrate on which the color coordinate measurement is completed in N-methylpyrrolidone solvent for 30 minutes. Chromaticity and transmittance were measured with a colorimeter (manufactured by Olympus, OSP-200). △Eab is the value required by the following formula for saturation according to the CIE 1976 (L*, a*, b*) spatial colorimetric system.

The formula used at this time is calculated by the following Equation 1 representing the color change in the three-dimensional colorimeter defined by L*, a*, and b*, and the smaller the color change value, the more reliable the color filter can be manufactured. Evaluation was carried out based on the same evaluation criteria. The results are shown in Table 2 below.

[Equation 1]

ΔEab* = [(ΔL*) ² + (Δa*) ² +(Δb*) ² ] ^{1 /2}

<Evaluation criteria>

○: The numerical value of ΔE*ab is 3 or less

×: The numerical value of ΔE*ab exceeds 3

Experimental example 3: Adhesion evaluation

Each color filter prepared in Preparation Example 2 was evaluated using the following evaluation criteria through an optical microscope, and the results are shown in Table 2 below.

<Evaluation criteria>

○: No tearing in pattern

△: 1 to 3 torn patterns

×: 4 or more torn in the pattern

Experimental example 4: Measurement of fine patterns

When each color filter manufactured in Preparation Example 2 was measured through OM equipment (ECLIPSE LV100POL Nikon Corporation), the size of the pattern obtained through a line/space pattern mask designed to be 100 μm was measured, and the results are as follows Table 2 shows. At this time, the evaluation criteria are as follows.

<Evaluation criteria>

If the difference between the design value of the line/space pattern mask and the measured value of the obtained fine pattern is 20 μm or more, it becomes difficult to implement the fine pixel, and if it has a negative value, it means a critical value that causes process defects.

Furtherance transmittance solvent resistance adhesion Fine pattern (㎛) Example 1 ◎ ○ △ 2 Example 2 ◎ ○ ○ 11 Example 3 ◎ ○ ○ 18 Example 4 ◎ ○ ○ 19 Example 5 ◎ ○ △ One Example 6 ◎ ○ ○ 10 Example 7 ◎ ○ ○ 18 Example 8 ◎ ○ ○ 18 Comparative Example 1 ◎ × × -6 Comparative Example 2 ◎ × × -6 Comparative Example 3 × ○ ○ 10 Comparative Example 4 × × × -9 Comparative Example 5 ○ ○ ○ 11 Comparative Example 6 ○ × × -10 Comparative Example 7 △ ○ ○ 7 Comparative Example 8 △ × × -15

Referring to Table 2, in the case of Examples 1 to 8, which satisfy all of the conditions of the present invention, transmittance, solvent resistance, adhesiveness, It was confirmed that all of the fine pattern formation effects were excellent.

Specifically, when the thiol compound presented in the present invention is not included (Comparative Examples 1, 2, 4, 6 and 8), it was confirmed that the solvent resistance, adhesion and the effect of forming a fine pattern were not good, and the When the colorant was not included (Comparative Examples 3 to 8), it was confirmed that the transmittance was not good.

Claims (13)

at least one of the thiol compounds represented by the following Chemical Formulas 5 to 12;
a colorant containing an aluminum phthalocyanine compound;
alkali-soluble resins containing n-dodecyl mercaptan;
photopolymerizable compounds;
photoinitiator; and
A green photosensitive resin composition comprising a solvent:
[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

delete The method of claim 1,
The aluminum phthalocyanine compound is a green photosensitive resin composition comprising a compound represented by the following Chemical Formula 13 or Chemical Formula 14:
[Formula 13]

(In Formula 13,
R ¹ to R ¹⁶ are each independently hydrogen, a halogen atom, a nitro group, a substitutable phthalimidemethyl group, a substitutable sulfamoyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, C5 to C10 of a substitutable cycloalkyl group, a heterocyclic group, a C1 to C18 substitutable alkoxy group, a C6 to C14 substitutable aryloxy group, a C1 to C18 substitutable alkylthio group, or a C6 to C14 substitutable arylthio group,
Z is -OP(=O)X ₁ X ₂ ,
wherein X ₁ and X ₂ are each independently hydrogen, a hydroxyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, a C1 to C18 substitutable alkoxy group, or a C6 to C14 substitutable aryloxy group, ,
The X ₁ and X ₂ may form a heterocycle together with the bonded phosphorus atom)
[Formula 14]

(In Formula 14,
wherein R ¹⁷ to R ³² are each independently hydrogen, a halogen atom, a nitro group, a substitutable phthalimidemethyl group, a substitutable sulfamoyl group, a C1 to C18 substitutable alkyl group, a C6 to C14 substitutable aryl group, C5 to a C10 substitutable cycloalkyl group, a heterocyclic group, a C1 to C18 substitutable alkoxy group, a C6 to C14 substitutable aryloxy group, a C1 to C18 substitutable alkylthio group, or a C6 to C14 substitutable arylthio group; ,
The L is

or

is,
In this case, X ₃ to X ₇ are each independently a C1 to C18 substitutable alkyl group or a C6 to C14 substitutable aryl group). The method of claim 1,
The aluminum phthalocyanine compound is a green photosensitive resin composition comprising CI pigment green 62 or CI pigment green 63. The method of claim 1,
The aluminum phthalocyanine compound is a green photosensitive resin composition, characterized in that it is included in an amount of 30 to 100% by weight based on 100% by weight of the total colorant. The method of claim 1,
The thiol compound is a green photosensitive resin composition, characterized in that contained in 0.3 to 5% by weight based on 100% by weight of the total solid content of the green photosensitive resin composition. The method of claim 1,
The colorant is a green photosensitive resin composition, characterized in that it further comprises CI Pigment Yellow 138 or CI Pigment Yellow 231. 8. The method of claim 7,
The CI Pigment Yellow 138 or CI Pigment Yellow 231 is a green photosensitive resin composition, characterized in that it is included in an amount of 10 to 70% by weight based on 100% by weight of the total colorant. The method of claim 1,
The colorant is a green photosensitive resin composition, characterized in that it is contained in an amount of 5 to 60% by weight based on 100% by weight of the total solid content of the green photosensitive resin composition. The method of claim 1,
The alkali-soluble resin is a green photosensitive resin composition, characterized in that the acid value of 30 to 150 mgKOH / g. The method of claim 1,
The photopolymerization initiator is a green photosensitive resin composition comprising an oxime ester compound. A color filter comprising a cured product of the green photosensitive resin composition according to any one of claims 1 to 11. An image display device comprising the color filter of claim 12 .