KR102410887B1 - Colored photosensitive resin composition, color filter, and image display apparatus comprising the same - Google Patents

Abstract

[화학식 2]

[화학식 3]

(상기 화학식 1 내지 화학식 3의 치환기는 명세서 내 정의한 바와 같다).The present invention relates to a colorant comprising a compound represented by the following formula (1); Alkali-soluble resin comprising a compound represented by the following formula (2); and an antioxidant comprising a compound represented by the following Chemical Formula 3; By including, there is no pattern peeling, and it relates to a colored photosensitive resin composition, a color filter, and an image display device having the same, which have excellent effects in heat resistance and light resistance.
[Formula 1]

[Formula 2]

[Formula 3]

(The substituents of Chemical Formulas 1 to 3 are as defined in the specification).

Description

Colored photosensitive resin composition, color filter, and image display device having the same

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

A color filter is widely used in imaging devices, liquid crystal display devices, and the like, and its application range is rapidly expanding. A color filter used in a color liquid crystal display device or an image pickup device is a color photosensitive resin composition containing a colorant corresponding to each color of red, green, and blue is applied uniformly by spin coating on a substrate on which a black matrix is patterned. , heat-drying (hereinafter, sometimes referred to as pre-firing) to expose and develop the formed coating film, and if necessary, further heat-hardening (hereinafter, referred to as post-firing) for each color. It is manufactured by forming At this time, it must go through the VD (vacuum dry) process, which is a solvent removal process of the resist immediately after application.

High color reproduction of a color filter used in an image display device is required, and accordingly, the content of a coloring material of a colored photosensitive resin composition used for manufacturing a color filter is continuously increasing.

Korean Patent Laid-Open Publication No. 10-2013-0115076 discloses a high-quality, high-quality, high-quality, high-resistance color resin with excellent resistance such as heat resistance by including a specific blue dye-based compound, a binder resin, a solvent, a curing agent, and the like, such as contrast. composition is provided.

However, the prior art has a problem in that reliability and stability such as heat resistance and light resistance are not good.

Republic of Korea Patent Publication No. 10-2013-0115076 (2013.10.21. Nippon Kayaku Co., Ltd.)

The present invention is to solve the above problems, and by including a specific colorant, a specific alkali-soluble resin and a specific antioxidant, there is no pattern peeling, and a colored photosensitive resin composition having excellent heat resistance and light resistance, a color filter, and an image display comprising the same The purpose is to provide a device.

The colored photosensitive resin composition according to the present invention for achieving the above object is a colorant comprising a compound represented by the following formula (1); Alkali-soluble resin comprising a compound represented by the following formula (2); and an antioxidant comprising a compound represented by the following formula (3).

[Formula 1]

[Formula 2]

[Formula 3]

(The substituents of Chemical Formulas 1 to 3 are as defined in the specification).

In addition, the present invention features a color filter including a cured product of the above-described colored photosensitive resin composition and an image display device including the same.

The colored photosensitive resin composition according to the present invention has no pattern peeling by including a specific colorant, a specific alkali-soluble resin, and a specific antioxidant, and has excellent heat resistance and light resistance.

A color filter made of the colored photosensitive resin composition and an image display device including the color filter have excellent reliability.

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

In the present invention, when a member is said to be located "on" another member, this includes not only a case in which a member is in 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, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

<Colored photosensitive resin composition>

The colored photosensitive resin composition of the present invention includes a colorant comprising a compound represented by the following formula (1); Alkali-soluble resin comprising a compound represented by the following formula (2); and an antioxidant comprising a compound represented by the following formula (3).

[Formula 1]

In Formula 1,

R1 to R4 are each independently an optionally substituted amino group, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, even if the methylene group contained in the alkyl group is substituted with an oxygen atom represents a group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms or a hydrogen atom which may have a substituent;

R1 and R2 may combine to form a ring together with the nitrogen atom to which they are bonded, or R3 and R4 may combine to form a ring with the nitrogen atom to which they are bonded;

R5 to R12 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group;

R6 and R10 may combine with each other to form -NH-, -O-, -S- or -SO2-,

In R1 to R4 and R5 to R12, adjacent methylene groups are not substituted with an oxygen atom at the same time, and a methylene group at the terminal of the alkyl group is not substituted with an oxygen atom;

T ₁ represents the aromatic heterocycle which may have a substituent,

[Y] ^m- represents at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and an m-valent anion containing oxygen,

m represents the integer of 2-14.

[Formula 2]

In Formula 2,

R13 is hydrogen or a methyl group, and R14 is a linear or branched alkyl group having 1 to 7 carbon atoms.

[Formula 3]

In Formula 3,

R15 to R17 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an optionally substituted C1-C40 alkyl group, an aryl group, or an arylalkyl group;

A represents an aromatic ring or a heterocyclic ring,

X is a nitrogen, oxygen, phosphorus or sulfur atom,

d is 1 to 3,

k is 1 to 3,

n is 1 to 5;

coloring agent

The colored photosensitive resin composition according to the present invention includes a colorant, and the colorant includes a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R1 to R4 are each independently an optionally substituted amino group, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, even if the methylene group contained in the alkyl group is substituted with an oxygen atom represents a group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms or a hydrogen atom which may have a substituent;

R1 and R2 may combine to form a ring together with the nitrogen atom to which they are bonded, or R3 and R4 may combine to form a ring with the nitrogen atom to which they are bonded;

R5 to R12 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group;

R6 and R10 may combine with each other to form -NH-, -O-, -S- or -SO2-,

In R1 to R4 and R5 to R12, adjacent methylene groups are not substituted with an oxygen atom at the same time, and a methylene group at the terminal of the alkyl group is not substituted with an oxygen atom;

T ₁ represents the aromatic heterocycle which may have a substituent,

[Y] ^m- represents at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and an m-valent anion containing oxygen,

m represents the integer of 2-14.

Preferably, the alkyl group includes, for example, methyl, ethyl, propyl, and preferably, the alkyl group includes a straight-chain or branched type, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, iso butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and the like.

In addition, the arylalkyl group may include benzyl, chlorobenzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, phenylethenyl, and the like.

By including the colorant including the compound represented by Formula 1, excellent properties such as heat resistance, light resistance, and reliability (chemical resistance) may be obtained.

The colorant may be included in an amount of 5 to 50% by weight, preferably 15 to 35% by weight, based on 100% by weight of the solid content in the colored photosensitive resin composition. When the content of the colorant is within the above range, a color concentration when the color filter is manufactured is sufficient, and a pattern having sufficient mechanical strength can be formed.

Alkali-soluble resin

The colored photosensitive resin composition according to the present invention includes an alkali-soluble resin, and the alkali-soluble resin includes a compound represented by the following formula (2).

[Formula 2]

In Formula 2,

R13 is hydrogen or a methyl group, and R14 is a linear or branched alkyl group having 1 to 7 carbon atoms.

Examples of the alkyl group having 1 to 7 carbon atoms include straight or branched chains such as methyl group, ethyl group, n-propyl group, isopropyl group, sec-propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, etc. and an alkyl group having 1 to 7 carbon atoms. The alkyl group is preferably a branched chain alkyl group from the viewpoint of improving the compatibility with the dye and thus improving the reliability of the colored photosensitive resin composition.

The alkali-soluble resin including the compound represented by Formula 2 is easily decomposed by heat, and the ether bond between the oxygen atom adjacent to the (meth)acrylate and the carbon atom adjacent to the (meth)acrylate is easily broken, and (meth)acrylic acid and carbon It is decomposed into a stable compound generated on the atom side, and an ester crosslinked structure with a hydroxyl group is generated, thereby improving reliability. In addition, the pattern angle is excellent, and residue properties, film remaining rate, chemical resistance, and mechanical properties are excellent, and in particular, film wrinkles according to the amount of high material may not occur.

The amount of the alkali-soluble resin is preferably 0.1 to 20 wt%, more preferably 1 to 4 wt%, based on 100 wt% of the total colored photosensitive resin composition. When the content of the alkali-soluble resin is less than the above range, it is difficult to expect improvement in reliability and adhesion, and when it exceeds the above range, the viscosity of the composition may be increased to slightly decrease applicability, and there is a risk that developability may deteriorate.

antioxidant

The colored photosensitive resin composition according to the present invention contains an antioxidant.

The antioxidant is inactive at room temperature or normal temperature, and by baking at a high temperature of 200° C. or higher, a protecting group is released and activated to mean an additive that expresses a function, and includes a compound represented by the following formula (3).

[Formula 3]

In Formula 3,

R15 to R17 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an optionally substituted C1-C40 alkyl group, an aryl group, or an arylalkyl group;

A represents an aromatic ring or a heterocyclic ring,

X is a nitrogen, oxygen, phosphorus or sulfur atom,

d is 1 to 3,

k is 1 to 3,

n is 1 to 5;

Preferably, the alkyl group includes a straight-chain or branched type, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n- octyl, n-decyl, and the like.

In addition, the aryl group may include phenyl, biphenyl, terphenyl, stilbenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, and the like.

In addition, the arylalkyl group may include benzyl, chlorobenzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, phenylethenyl, and the like.

Examples of the 5-membered aromatic ring represented by A include cyclopentadiene and ferrocene, and examples of the 5-membered heterocyclic ring include furan, thiophene, pyrrole, pyrrolidine, pyrazolidine, pyrazole, imidazole, and imidazole. Dazolidine, oxazole, isoxazole, isoxazolidine, thiazole, isothiazole, isothiazolidine, etc. are mentioned. Examples of the 6-membered aromatic ring include benzene, naphthalene, anthracene, fluorene, perylene, and pyrene. Examples of the 6-membered heterocyclic ring include piperidine, piperazine, morpholine, thiomorpholine, and pyridine. , pyrazine, pyrimidine, pyridazine, triazine, etc., and these rings may be condensed or substituted with other rings, for example, quinoline, isoquinoline, indole, julolidine, benzoxa Sol, benzotriazole, azulene, etc. are mentioned.

The antioxidant may be directly synthesized and used, or a commercially available form may be purchased and used. As a commercially available product of the antioxidant, GPA series (manufactured by Adeka) and the like may be used.

Conventionally, antioxidants and ultraviolet absorbers have been added to improve the heat resistance and light resistance of the colored photosensitive alkaline resin composition. However, phenolic antioxidants or HALS (Hindered Amine Light Stabilizer) are radicals that greatly affect polymer degradation or light. It acts as a radical scavenger. Therefore, since it acts as a polymerization inhibitor when antioxidant or HALS is added in the coloring photosensitive resin composition, reducing heat|fever or photocuring poses a problem. Therefore, heat resistance and light resistance may be improved by using the antioxidant including the compound represented by Formula 3 above.

The antioxidant is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on 100% by weight of the total colored photosensitive resin composition. When the content of the antioxidant is out of the above range, heat or photocuring may be reduced.

photopolymerization monomer

The colored photosensitive resin composition according to the present invention may include a photopolymerizable monomer.

The photopolymerizable monomer is a compound capable of polymerization by the action of light and a photopolymerization initiator, and includes a monofunctional monomer, a difunctional monomer, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl p Rollidone etc. are mentioned.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylic rate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, butylene glycol dimethacrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth) ) acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylate Neopentyl glycol diacrylate, propyl oxylate neopentyl glycol diacrylate, etc. are mentioned.

Specific examples of the trifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

Specific examples of the tetrafunctional monomer include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylol propane tetraacrylate, ditrimethylol propane tetramethacrylate, dipentaerythritol tetraacrylate, Tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, glycerol tetraacrylate, glycerol tetramethacrylate, etc. are mentioned.

Specific examples of the 5-functional monomer include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol monohydroxypentaacrylate, and dipentaerythritol monohydroxypentamethacrylate. can

Specific examples of the 6-functional monomer include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate.

Among them, as the photopolymerizable monomer, a polyfunctional monomer having more than difunctionality may be preferably used, and in particular, a polyfunctional monomer having more than pentafunctionality may be preferably used.

The photopolymerizable monomer may be included in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, based on 100% by weight of the solid content in the colored photosensitive resin composition. When the photopolymerizable monomer is included within the above range, the strength or smoothness of the pixel portion may be good.

photopolymerization initiator

The colored photosensitive resin composition according to the present invention may include a photopolymerization initiator.

The photopolymerization initiator preferably contains an acetophenone-based compound. Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4- (2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 -one oligomer etc. are mentioned, Preferably 2-methyl-2-morpholino-1-(4-methylthiophenyl) propan-1-one etc. are mentioned.

Each of the acetophenone-based compounds may be used alone or in combination of two or more. The photopolymerization initiator may be used in combination with other types of photoinitiators in addition to the acetophenone-based compound.

Examples of other types of photopolymerization initiators include active radical generators, sensitizers, and acid generators that generate active radicals by irradiating light.

Examples of the active radical generator include a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, and a triazine-based compound. Specific examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Specific examples of the benzophenone-based compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, methyl o-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzoyl -4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4 -Propoxythioxanthone, etc. are mentioned. 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-(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.

As the sensitizer, specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. .

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate. , 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, di Onium salts, such as phenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

Among the above compounds, there are also compounds that simultaneously generate active radicals and acids. For example, triazine-based compounds are also used as acid generators.

The photopolymerization initiator may be included in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on 100% by weight of the solid content of the alkali-soluble resin and the photopolymerizable monomer. When the content of the photopolymerization initiator is included within the above range, the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, thereby improving productivity and maintaining high resolution.

The photopolymerization initiator may be used in combination with a photopolymerization initiator adjuvant. The photopolymerization initiation adjuvant may be used to promote polymerization of a photopolymerizable monomer whose polymerization is initiated by the photopolymerization initiator.

Examples of the photopolymerization initiation adjuvant include amine-based compounds and alkoxyanthracene-based compounds. Specific examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. , 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name, Michler's ketone), 4,4'-bis(diethylamino) ) benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. are mentioned, Among these, 4,4'-bis(diethylamino)benzophenone is preferable. Specific examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. can be heard The photopolymerization initiation adjuvant may be used alone or in combination of two or more. In addition, as the photopolymerization initiation aid, a commercially available product under the trade name EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Specific examples of a preferred combination of the photopolymerization initiator and the photopolymerization initiation aid include: diethoxyacetophenone and 4,4'-bis(diethylamino)benzophenone; 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and 4,4′-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-phenylpropan-1-one and 4,4′-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one and 4,4′-bis(diethylamino)benzophenone; 1-hydroxycyclohexylphenylketone and 4,4'-bis(diethylamino)benzophenone; an oligomer of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one and 4,4′-bis(diethylamino)benzophenone; a combination of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 4,4'-bis(diethylamino)benzophenone, preferably 2 The combination of -methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and 4,4'-bis(diethylamino)benzophenone, etc. are mentioned. When the photopolymerization initiator and the photopolymerization initiation adjuvant are used together, the amount of the photopolymerization initiation adjuvant is preferably 0.01 to 5 moles based on 1 mole of the photopolymerization initiator. When the photopolymerization initiation auxiliary agent is included within the above range, the sensitivity of the colored photosensitive resin composition may be increased, and productivity of a color filter formed using the composition may be improved.

thermal crosslinking agent

The colored photosensitive resin composition according to the present invention may include a thermal crosslinking agent.

Specific examples of the thermal crosslinking agent 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. can

The thermal crosslinking agent is used to harden the deep part and increase mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the thermal crosslinking agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins Resins, glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene (co)polymer epoxidized product, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the thermal crosslinking agent include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The thermal crosslinking agent may use 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. The curing auxiliary compound includes, for example, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, and acid generators. As the polyhydric carboxylic acid anhydrides, commercially available epoxy resin curing agents may be used. Specific examples of the epoxy resin curing agent include a trade name (Adekahadona EH-700) (manufactured by Adeka Industries, Ltd.), a trade name (Rikasiddo HH) (manufactured by Shin Nippon Ewha Co., Ltd.), a trade name (MH-700) (Shin Nippon Ewha Co., Ltd.) manufactured by Nippon Ewha Co., Ltd.) and the like. The curing agents exemplified above may be used alone or in combination of two or more.

The thermal crosslinking agent may be included in an amount of 0.5 to 5.0% by weight, preferably 1.0 to 3.0% by weight based on 100% by weight of the colored photosensitive resin composition. When the content of the thermal crosslinking agent is included within the above range, the curing density and reliability can be improved by maximizing thermosetting properties.

solvent

The colored photosensitive resin composition according to the present invention may contain a solvent.

As long as the solvent is effective in dissolving other components included in the colored photosensitive resin composition, the solvent used in the conventional colored photosensitive resin composition may be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters and amides are preferred.

The solvent is specifically ethylene glycol monoalkyl ethers such as 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 dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl ketone , acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 3-ethyl ethoxypropionate, 3- Esters, such as methyl methoxypropionate, and cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned.

The solvent is preferably an organic solvent having a boiling point of 100 to 200° C. in terms of coatability and drying properties, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalactate. , 3-ethoxy ethyl propionate, 3-methoxy methyl propionate, etc. can be used.

Each of the solvents exemplified above may be used alone or in mixture of two or more, and may be included in an amount of 60 to 90 wt%, preferably 70 to 85 wt%, based on the total weight% of the colored photosensitive resin composition of the present invention. When the solvent is included within the above range, the applicability 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 colored photosensitive resin composition according to the present invention may include an additive.

The additive may be selectively added as needed, and for example, other high molecular compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors may be mentioned.

Specific examples of the other high molecular compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. can be heard

The curing agent is used to enhance deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound. Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins , glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene ( A co)polymer epoxidized product, a glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned. Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. The curing auxiliary compound includes, for example, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, and acid generators. As the polyhydric carboxylic acid anhydrides, commercially available epoxy resin curing agents may be used. Specific examples of the epoxy resin curing agent include a trade name (Adekahadona EH-700) (manufactured by Adeka Industries, Ltd.), a trade name (Rikasiddo HH) (manufactured by Shin Nippon Ewha Co., Ltd.), a trade name (MH-700) (Shin Nippon Ewha Co., Ltd.) manufactured by Nippon Ewha Co., Ltd.) and the like. The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film-forming property of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicone as commercially available products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, and TSF- from GE Toshiba Silicone. 4460 and TSF-4452. The fluorine-based surfactants include, for example, Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink Chemical Co., Ltd. as a commercially available product. Each of the surfactants exemplified above may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(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-mercaptopropyltrimethyl Toxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on 100% by weight of the solid content of the colored photosensitive resin composition.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzothiazole, alkoxybenzophenone, and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate.

<Color filter>

When the color filter of the present invention is applied to an image display device, since it emits light by the light of the light source of the display device, superior light efficiency can be realized. In addition, since light having a color is emitted, color reproducibility is more excellent, and since light is emitted in all directions by photoluminescence, a viewing angle can be improved.

The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be a color filter itself substrate, or may be a region where the color filter is positioned on a display device, etc., and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer is a layer including the blue curable resin composition of the present invention, and may be a layer formed by applying the blue curable resin composition and exposing, developing and thermosetting the blue curable resin composition in a predetermined pattern.

The color filter including the substrate and the pattern layer as described above may further include a barrier rib formed between each pattern, and may further include a black matrix. In addition, a passivation layer formed on the pattern layer of the color filter may be further included.

<Image display device>

The present invention provides an image display device including the color filter.

The color filter of the present invention can be applied to various image display devices, such as an electroluminescence display device, a plasma display device, and a field emission display device, as well as a general liquid crystal display device.

The image display device of the present invention may include 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 such a case, when applied to an image display device, the emission light of the light source is not particularly limited, but a light source emitting blue light may be preferably used in terms of superior color reproducibility.

According to another embodiment of the present invention, the image display device of the present invention may 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 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 of a wavelength representing the remaining colors that is not included may be used. For example, when a red pattern layer and a 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.

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

Synthesis example 1: Compound of colorant (A-1)

The following reaction was performed in nitrogen atmosphere. After putting 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide to a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After adding 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) little by little over 30 minutes under ice cooling, the mixture was stirred for 1 hour while the temperature was raised to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added to the reaction solution, followed by stirring at room temperature for 24 hours. After adding the reaction liquid little by little to 200 parts of ice water, it left still at room temperature for 15 hours, and when water was removed by decantation, a viscous solid was obtained as a residue. After adding methanol 60 parts to this viscous solid, it stirred at room temperature for 15 hours. The precipitated solid was separated by filtration and purified by column chromatography. The purified pale yellow solid was dried at 60°C under reduced pressure to obtain 9.8 parts of a compound represented by the following formula (A'-1).

[Formula (A'-1)]

In a flask equipped with a cooling tube and a stirring device, 8.2 parts of a compound represented by the following formula (A'-2), 10 parts of a compound represented by the formula (A'-1), and 20 parts of toluene were introduced, and then 12.2 phosphorus oxychloride parts were added, and the mixture was stirred at 95°C for 3 hours. Next, the reaction mixture was cooled to room temperature and then diluted with 170 parts of isopropanol. Next, after pouring the diluted reaction solution into 300 parts of saturated saline, 100 parts of toluene was added and it stirred for 30 minutes. Next, stirring was stopped, and when it left still for 30 minutes, it wasolate|separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by liquid separation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer, stirred for 30 minutes, and filtered to obtain a dried organic layer. The obtained organic layer was solvent-distilled by the evaporator, and the blue-violet solid was obtained. Furthermore, the blue-violet solid was dried at 60 degreeC under reduced pressure, and 18.4 parts of compounds represented by a following formula (A'-3) were obtained.

[Formula (A'-2)]

[Formula (A'-3)]

To a flask equipped with a cooling tube and a stirring device, 8 parts of the compound represented by the formula (A'-3) and 396 parts of methanol were charged, followed by stirring at room temperature for 30 minutes to prepare a blue solution. Next, after injecting|throwing-in 396 parts of water to the blue solution, it stirred at room temperature for 30 minutes, and obtained the reaction solution. It was put into 53 parts of water in a beaker, and 11.8 parts of Kegin type tungstic acid (manufactured by Aldrich) and 53 parts of methanol were put into the water, and mixed at room temperature in an air atmosphere to prepare a phosphotungstic acid solution. The obtained phosphotungstic acid solution was dripped over 1 hour in the reaction solution prepared previously. Furthermore, after stirring at room temperature for 30 minutes, it filtered and obtained blue solid. After putting the obtained blue solid in 200 parts of methanol and disperse|distributing it for 1 hour, operation of filtering was repeated twice. The blue solid obtained by this operation was poured into 200 parts of water and dispersed for 1 hour, and then the operation of filtration was repeated twice. The blue solid obtained by the said operation was dried at 60 degreeC under reduced pressure, and 17.1 parts of compounds represented by a following formula (A'-4) were obtained.

[Formula (A'-4)]

Synthesis example 1-1: Resin (B) using colored dispersion

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L/min to make a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added and stirred while 70 heated to &lt;RTI ID=0.0&gt;C.&lt;/RTI&gt; Next, 60 parts of methacrylic acid, 240 parts of 3,4-epoxytricyclo [5.2.1.02,6] decyl acrylate and 140 parts of 3-methoxybutyl acetate are melt|dissolved, the solution is prepared, the said solution is It was dripped in the flask kept at 70 degreeC over 4 hours using the dropping funnel. On the other hand, a solution obtained by dissolving 30 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was added dropwise into the flask over 4 hours using another dropping funnel. . After the dropwise addition of the polymerization initiator solution was completed, it was maintained at 70° C. for 4 hours, then cooled to room temperature, and a resin (B-1) solution having a solid content of 32.6% and an acid value of 110 mg-KOH/g (in terms of solid content) got it The weight average molecular weight Mw of the obtained resin (B) was 13,400, and molecular weight distribution was 2.50.

Preparation of colored dispersion

10 parts of the compound represented by the said formula (A'-4), 2 parts of dispersing agent (BYK (trademark)-LPN6919 (made by Big Chemie Japan)), 4 parts of resin B (in terms of solid content), propylene glycol monomethyl ether acetate A colored dispersion (1) was prepared by mixing 84 parts and 300 parts of 0.2 mm zirconium oxide beads, shaking with a paint conditioner (manufactured by Red Deil) for 6 hours, and then removing the zirconia beads by filtration.

Synthesis example 2: Compound of colorant (A-2)

By the method described in Synthesis Example 1, a phosphomolybdic acid solution was added to obtain a compound represented by the following formula (A'-5).

[Formula (A'-5)]

Synthesis example 3: Alkali-soluble resin containing the compound of formula (2) (B-1)

800 g of propylene glycol monomethyl ether acetate was poured into a reaction tank equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube and a dripping tank inlet, and after nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as the dropping tank (A), 50 g of N-benzylmaleimide, 100 g of glycidyl methacrylate, 120 g of methacrylic acid, and 100 g of methacrylate acid methyl ester were stirred and mixed in a beaker and mixed, and the dropping tank ( To B), 21 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition|polymerization was performed. After completion of the dropwise addition, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C and maintained for 90 minutes.

As a result of analyzing the obtained alkali-soluble resin solution, the weight average molecular weight was 11200, the acid value was 100 mgKOH/g, and resin solid content was 38.2 mass %.

Synthesis example 4: Alkali-soluble resin containing the compound of Formula 2 (B-2)

800 g of propylene glycol monomethyl ether acetate was poured into a reaction tank equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube and a dripping tank inlet, and after nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as the dropping tank (A), 50 g of N-benzylmaleimide, 100 g of glycidyl methacrylate, 120 g of methacrylic acid, and 100 g of isopropyl methacrylate were stirred and mixed in a beaker, and the dropping tank (B) ), 21 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank reached 90° C., while maintaining the same temperature, dropping was started over 3 hours from the dropping tank, and polymerization was carried out. After completion of the dropwise addition, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C and maintained for 90 minutes.

As a result of analyzing the obtained alkali-soluble resin solution, the weight average molecular weight was 11800, the acid value was 105 mgKOH/g, and resin solid content was 38.4 mass %.

Synthesis example 5: Alkali-soluble resin containing the compound of Formula 2 (B-3)

800 g of propylene glycol monomethyl ether acetate was poured into a reaction tank equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube and a dripping tank inlet, and after nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as the dropping tank (A), 50 g of N-benzyl maleimide, 100 g of glycidyl methacrylate, 120 g of methacrylic acid, and 100 g of t-butyl methacrylate were stirred and mixed in a beaker and mixed, and a dropping tank was prepared. In (B), 21 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate were prepared by stirring and mixing. After the temperature of the reaction tank reached 90° C., while maintaining the same temperature, dropping was started over 3 hours from the dropping tank, and polymerization was carried out. After completion of the dropwise addition, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C and maintained for 90 minutes.

As a result of analyzing the obtained alkali-soluble resin solution, the weight average molecular weight was 12200, the acid value was 112 mgKOH/g, and resin solid content was 38.5 mass %.

Synthesis example 6: Alkali-soluble resin containing the compound of Formula 2 (B-4)

800 g of propylene glycol monomethyl ether acetate was poured into a reaction tank equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube and a dripping tank inlet, and after nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as the dropping tank (A), 50 g of N-benzylmaleimide, 100 g of glycidyl methacrylate, 120 g of methacrylic acid, and 100 g of 1-methylpropyl methacrylate were stirred and mixed in a beaker and mixed, and a dropping tank was prepared. To (B), 21 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank reached 90° C., while maintaining the same temperature, dropping was started over 3 hours from the dropping tank, and polymerization was carried out. After completion of the dropwise addition, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C and maintained for 90 minutes.

As a result of analyzing the obtained alkali-soluble resin solution, 11500 and an acid value of the weight average molecular weight were 115 mgKOH/g, and resin solid content was 38.5 mass %.

Synthesis example 7: Alkali-soluble resin (B-5) not containing the compound of formula (2)

800 g of propylene glycol monomethyl ether acetate was poured into a reaction tank equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube and a dripping tank inlet, and after nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as the dropping tank (A), 50 g of N-benzyl maleimide, 100 g of glycidyl methacrylate, 120 g of methacrylic acid, and 100 g of cyclohexyl methacrylate were stirred and mixed in a beaker, and the dropping tank (B) ), 21 g of n-dodecyl mercaptan and 84 g of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank reached 90° C., while maintaining the same temperature, dropping was started over 3 hours from the dropping tank, and polymerization was carried out. After completion of the dropwise addition, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C and maintained for 90 minutes.

As a result of analyzing the obtained alkali-soluble resin solution, the weight average molecular weight was 12000, the acid value was 100 mgKOH/g, and resin solid content was 38.8 mass %.

Example 1 to 5 and comparative example 1 to 4: Preparation of colored photosensitive resin composition

Colored photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 4 were prepared with the components and contents shown in Table 1 below.

Example comparative example One 2 3 4 5 One 2 3 4 Colorant (A) (A-1) 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 (A-2) 3.69 3.69 3.69 3.69 3.69 3.69 3.69 - 3.69 (A-3) - - - - - - - 3.69 - alkali-soluble resin
(B) (B-1) 3.4 - - - - - - 3.4 - (B-2) - 3.4 - - - - - - - (B-3) - - 3.4 - 0.9 - 3.4 - 3.4 (B-4) - - - 3.4 - - - - - (B-5) - - - - - 3.4 - - - Photopolymerizable compound (C) (C-1) 4.33 4.33 4.33 4.33 6.73 4.33 4.33 4.33 4.33 Photopolymerization Initiator (D) (D-1) 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 solvent
(E) (E-1) 76.6 76.6 76.6 76.6 76.6 76.6 76.6 76.6 76.6 (E-2) 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 Additive (F) (F-1) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 (F-2) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 (F-3) 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 antioxidant
(G) (G-1) 0.43 0.43 0.43 0.43 0.43 0.43 - 0.43 - (G-2) - - - - - - 0.43 - - (G-3) - - - - - - - - 0.43 Thermal crosslinking agent (H) (H-1) 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 (A-1) Synthesis Example 1
(A-2) Synthesis Example 2
(A-3) CI Pigment Violet 23
(B-1) Synthesis Example 3
(B-2) Synthesis Example 4
(B-3) Synthesis Example 5
(B-4) Synthesis Example 6
(B-5) Synthesis Example 7
(C-1) dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
(D-1) N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) manufactured by BASF; O-acyloxime compound)
(E-1) Propylene glycol monomethyl ether acetate
(E-2) propylene glycol monomethyl ether
(F-1) Polyether-modified silicone oil (SH8400; manufactured by Toray Dow Corning Co., Ltd.)
(F-2) Megafax (registered trademark) F554 (manufactured by Dainippon Ink Chemical Co., Ltd.)
(F-3) 3-methacryloxypropyltrimethoxysilane
(G-1) GPA series (manufactured by Adeka)
(G-2) Tinuvin series (manufactured by Basf)
(G-3) AO series (manufactured by Adeka)
(H-1) Adeka Hadona EH-700 (manufactured by Adeka Industrial Co., Ltd.)

Experimental example

A color filter was prepared as follows by using the colored photosensitive resin composition prepared in Examples and Comparative Examples, and the sensitivity, development speed, adhesion, heat resistance, light resistance and NMP solvent resistance at this time were measured in the following manner, and the The results are shown in Table 2 below.

(1) Manufacture of color filter

The colored photosensitive resin composition prepared in Examples and Comparative Examples was coated on a glass substrate (#1737, manufactured by Corning) by spin coating, then placed on a heating plate and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Next, a test photomask having a pattern that changes in a stepwise manner in the range of transmittance of 1 to 100% is placed on the thin film, the distance from the test photomask is set to 1000 μm, and an ultra-high pressure mercury lamp (USH-250D, Ushio Denki (USH-250D, Ushio Denki) Note) was used to irradiate the light with an exposure dose (365 nm) of 40 mJ/cm 2 in an atmospheric atmosphere. The thin film irradiated with ultraviolet light was developed for 70 seconds in a developing solution of a KOH aqueous solution having a pH of 12.5 using a spray developer. The glass substrate 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. The pattern shape (thin film) thickness of the manufactured color filter was 2.3 μm.

(2) Sensitivity and development speed

The development speed was measured by measuring the time for which peeling of the non-exposed thin film part appears during development during the manufacturing process of the color filter. In addition, the sensitivity, which is the minimum exposure dose (mJ/cm 2 ) required to form a thin film without tearing of the pattern after development during the manufacturing process of the color filter, was measured, and the results are shown in Table 2 below.

(2) Adhesion

After the colored substrate prepared according to (1) production of the colored substrate is cut into 100 matrix structures within an area of 10×10 mm, a tape is attached thereon and the number of matrices that have fallen off while strongly releasing vertically is marked ( The number of dropped /100), and the results are shown in Table 2 below.

(3) heat resistance

Finally, after forming the pattern, color change (heat resistance) around 230°C/2hr was comparatively evaluated. The formula used at this time is calculated by the following Equation (1) representing the color change in a three-dimensional colorimeter defined by L*, a*, b*, and the smaller the color change value, the more reliable the color filter can be manufactured. . The results are shown in Table 2 below.

Equation 1

△Eab* =(△L*)2+(△a*)2+(△b*)2]1/2

(4) light resistance

Finally, after forming the pattern, the color change (light resistance) before and after Xe Lamp 300W/200hr was comparatively evaluated. The equation used at this time is calculated by the above Equation (1) representing the color change in the three-dimensional colorimeter defined by L*, a*, b*, and the smaller the color change value, the more reliable the color filter can be manufactured. . The results are shown in Table 2 below.

(5) NMP solvent resistance

The colored substrate prepared according to (1) Preparation of Colored Substrate was cut into 3x3 cm, and then immersed in 14.6 ml of NMP solution at 80° C. for 40 minutes. Thereafter, the absorbance of the solution was evaluated with a UV-Vis spectrometer, and the results are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Sensitivity
(mJ/cm ² ) 25 25 20 20 30 35 20 40 50 development speed 10 8 7 9 18 25 8 32 8 adhesion 100/100 100/100 100/100 100/100 95/100 80/100 90/100 80/100 70/100 heat resistance 1.45 1.58 1.22 1.28 1.95 3.35 1.36 3.14 1.44 light fastness 2.11 2.45 1.88 1.97 2.58 3.14 3.97 3.58 2.52 NMP solvent resistance 0.48 0.43 0.34 0.44 0.62 1.56 2.56 3.05 1.64

Referring to Table 2, it can be seen that the colored photosensitive resin composition of Examples exhibits excellent sensitivity and development speed compared to the colored photosensitive resin composition of Comparative Examples and has excellent adhesion, and has excellent reliability such as heat resistance, light resistance and NMP solvent resistance. can

Claims (7)

a colorant comprising a compound represented by the following formula (1);
Alkali-soluble resin comprising a compound represented by the following formula (2); and
An antioxidant comprising a compound represented by the following formula (3); Colored photosensitive resin composition comprising:
[Formula 1]

(In Formula 1,
R1 to R4 are each independently an optionally substituted amino group, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, even if the methylene group contained in the alkyl group is substituted with an oxygen atom represents a group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms or a hydrogen atom which may have a substituent;
R1 and R2 may combine to form a ring together with the nitrogen atom to which they are bonded, or R3 and R4 may combine to form a ring with the nitrogen atom to which they are bonded;
R5 to R12 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group;
R6 and R10 may combine with each other to form -NH-, -O-, -S- or -SO2-,
In R1 to R4 and R5 to R12, adjacent methylene groups are not substituted with an oxygen atom at the same time, and a methylene group at the terminal of the alkyl group is not substituted with an oxygen atom;
T ₁ represents the aromatic heterocycle which may have a substituent,
[Y] ^m- represents at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and an m-valent anion containing oxygen,
m represents an integer of 2 to 14)
[Formula 2]

(In Formula 2,
R13 is hydrogen or a methyl group, and R14 is a linear or branched alkyl group having 1 to 7 carbon atoms)
[Formula 3]

(In Formula 3,
R15 to R17 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an optionally substituted C1-C40 alkyl group, an aryl group, or an arylalkyl group;
A represents an aromatic ring or a heterocyclic ring,
X is a nitrogen, oxygen, phosphorus or sulfur atom,
d is 1 to 3,
k is 1 to 3,
n is 1 to 5). According to claim 1,
The colored photosensitive resin composition is a colored photosensitive resin composition, characterized in that it further comprises at least one selected from the group consisting of a photopolymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, an additive and a solvent. According to claim 1,
The colorant is a colored photosensitive resin composition, characterized in that it is contained in an amount of 5 to 50% by weight based on 100% by weight of the total solid content of the colored photosensitive resin composition. According to claim 1,
The alkali-soluble resin is colored photosensitive resin composition, characterized in that contained in 0.1 to 20% by weight based on 100% by weight of the colored photosensitive resin composition. According to claim 1,
The antioxidant is a colored photosensitive resin composition, characterized in that it is contained in an amount of 0.1 to 10% by weight based on 100% by weight of the colored photosensitive resin composition. A color filter comprising the cured product of the colored photosensitive resin composition according to any one of claims 1 to 5. An image display device comprising the color filter of claim 6 .