KR20180111050A - Blue photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

The present invention relates to a blue photosensitive resin composition which contains a scattering particle, a blue colorant, a cardo binder resin as a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent. The photoinitiator is at least one compound selected from compounds represented by chemical formula 1 to 3.

Description

TECHNICAL FIELD [0001] The present invention relates to a blue photosensitive resin composition, and a color filter and an image display device using the same. BACKGROUND ART [0002]

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

A color filter is a thin film type optical component that extracts three colors of red, green, and blue in white light and makes it possible in fine pixel units. The size of one pixel is several tens to several hundreds of micrometers. Such a color filter has a black matrix layer formed in a predetermined pattern on a transparent substrate so as to shield a boundary portion between each pixel and a plurality of colors (typically red (R), green (G) and Blue (B)) are arranged in a predetermined order in this order.

In recent years, as a method of implementing a color filter, a pigment dispersion method using a pigment dispersion type photosensitive resin has been applied. However, in a process in which light emitted from a light source passes through a color filter, a part of light is absorbed by a color filter, The efficiency is lowered and the color reproduction is deteriorated due to the characteristics of the pigment contained in the color filter.

To solve these problems, a method of manufacturing a color filter using a self-luminescent photosensitive resin composition containing a quantum dot has been proposed.

Specifically, Korean Patent Publication No. 2007-0094679 discloses that a color filter layer formed of quantum dots can be provided to improve color reproducibility. In Korean Patent Publication No. 2009-0036373, a conventional color filter is used as a quantum dot fluorescent material It is possible to improve the luminous efficiency and improve the display quality.

However, the photosensitive resin composition developed for producing the color filter has not satisfactorily satisfied the requirements such as the developing speed, excellent heat resistance and light resistance when formed into a cured film.

Korean Patent Publication No. 2007-0094679 Korea Patent Publication No. 2009-0036373

The present invention relates to a color filter excellent in reliability and excellent in heat resistance and light fastness when formed into a cured film with excellent developing speed and excellent processability, particularly, a blue photosensitive resin composition capable of realizing a self-emission color filter, A filter and an image display apparatus are provided.

The present invention relates to a colorant composition comprising scattering particles, a blue colorant, a cationic binder resin as a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent,

Wherein the photoinitiator is at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 3:

[Chemical Formula 1]

(In the formula 1,

R ₁ to R ₄ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, Or a naphthyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms.

(2)

(In the formula (2)

이며, n은 1 내지 4인 정수이고, m은 1 내지 6인 정수이며;R ₅ is hydrogen, My alkyl having a carbon number of 1 to 20 3 8 cycloalkyl, or unsubstituted methyl group, or a phenyl substituted by a methoxy group, a halogen, a carboxyl group and a hydroxyl group

N is an integer from 1 to 4, and m is an integer from 1 to 6;

R ₆ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a substituted phenyl group, a benzyl group or a substituted benzyl group;

R ₇ is a diphenylsulfide group substituted with a diphenylsulfide group, a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxyl group, a carbazole group, a methyl group, a methoxy group, a halogen, a carboxyl group, and a hydroxy group, , Or a substituted fluorene group.)

(3)

(3)

R ₈ , R ₉ and R ₁₀ each independently represent R, OR, COR, SR, CONRR 'or CN;

R and R 'represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, And the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, an ester bond, and R and R 'may form a ring together ;

Y ₁ represents an oxygen atom, a sulfur atom or a selenium atom; m represents an integer of 0 to 4; p represents an integer of 0 to 5;

q represents 0 or 1;

R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms;

X ₁ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, which may be substituted with a halogen atom and / or a heterocyclic group having 2 to 20 carbon atoms And the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond;

Y ₂ and Y ₃ each independently represent an oxygen atom, a sulfur atom or a selenium atom).

The present invention also provides a color filter comprising a blue pattern layer made of the above-mentioned blue photosensitive resin composition.

Further, the present invention provides a color filter comprising: the color filter; And a light source that emits blue light.

The blue photosensitive resin composition of the present invention contains a photoinitiator having at least one compound selected from the compounds represented by the formulas (1) to (3) in the blue photosensitive resin composition, It is possible to realize a color filter excellent in heat resistance and light resistance and excellent in reliability, in particular, a self-emission color filter.

The blue photosensitive resin composition of the present invention contains a blue colorant, a cadmium binder resin as a binder resin, a photopolymerizable compound having at least one or more compounds selected from the compounds represented by Chemical Formulas 1 to 3, a photoinitiator, and a solvent, The resin composition can realize a color filter excellent in reliability, particularly a self-emission color filter, because it has excellent developing speed and excellent processability, excellent heat resistance and light resistance when formed into a cured film, and excellent reliability.

Hereinafter, the configuration of the present invention will be described in detail.

Scattering particles

The scattering particles of the present invention may be a metal oxide having an average particle diameter of 10 to 1000 nm and more preferably 30 to 300 nm. If the average particle diameter of the scattering particles satisfies the above range, a sufficient scattering effect of the light emitted from the quantum dots can be expected, and there is a possibility that the scattering particles may sink or become uneven in the blue photosensitive composition, Lower.

The metal oxide may be at least one selected from the group consisting of Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Sn, Zr, Nb, Sn, Zr, Ti, Sb, Ba, La, Hf, W, Ti, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Ce, Ta, In, and a combination of these metals. More specifically, _{Al 2 O 3, SiO 2,} ZnO, ZrO2, BaTiO 3, TiO 2, Ta 2 O 5, Ti 3 O 5, ITO, IZO, ATO, ZnO-Al, Nb 2 O 3, SnO, MgO , and Or a combination thereof. Materials which have been surface-treated with a compound having an unsaturated bond such as acrylate can also be used if necessary.

The scattering particles can appropriately adjust the average particle size and the content in the whole composition as needed so as to sufficiently improve the emission intensity of the color filter. The scattering particles can appropriately adjust the average particle size and the content in the whole composition as needed so as to sufficiently improve the emission intensity of the color filter.

The scattering particles may be contained in an amount of 0.1 to 50% by weight, preferably 5 to 30% by weight, based on the total weight of the solid content in the blue photosensitive resin. When the content of the scattering particles satisfies the above range, it is possible to reduce the possibility of causing a problem of lowering the stability of the blue photosensitive resin composition while achieving the desired light emission intensity.

Blue colorant

In the blue colorant of the present invention, the blue pigment is specifically a compound classified as pigment in the color index (The Society of Dyers and Colourists), and more specifically, the following color index (CI) Numbered pigments, but are not limited thereto. The blue pigments specifically include, for example, C.I. Pigment Blue 15: 3, 15: 4, 15: 6, 16, 21, 28, and 76, and C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, Pigment Blue 16, and the like.

The blue colorant of the present invention may further comprise a blue dye, and the blue dye may be a compound classified as a dye in the color index (The Society of Dyers and Colourists) or a known compound described in dyeing notes Dyes.

Specific examples of the dyes that can be used additionally include, for example,

C.I. As solvent dyes,

C.I. Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67 and 70, and C.I. More preferably at least one of Solvent Blue 35, 36, 44, 45 and 70. [

Also, C.I. As the acid dye,

CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335 and 340, and among these, CI It is more preferred to include at least one of Acid Blue 80 and 90. [ And

Also, C.I. As a direct dye,

CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293.

CI Modanito Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84, and the like.

The blue dyes may be used alone or in combination of two or more.

The blue colorant of the present invention may further include a purple coloring agent as an additional coloring agent. The purple colorant may include at least one of a purple pigment and a purple dye, and the purple pigment specifically includes C.I. Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37 and 38, among others. It is more preferable to include Pigment Violet 23.

The purple dye specifically includes C.I. But are not limited to, solvent violet, C.I. acid violet, C.I. acid violet, C.I.

Specifically, the C.I. Solvent violet is C.I. Solvent Violet 8, 9, 13, 14, 36, 37, 47 and 49, and the like. It is more preferred to include solvent violet 13. C.I. Acid violet is C.I. Acid Violet 6B, 7, 9, 17, 19 and 66, and the like. It is more preferred to include Acid Violet 66. Examples of the CI direct violet include CI direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, .

Further, CI Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58 .

The blue colorant may be used in an amount of 0.1 to 50% by weight, preferably 0.5 to 30% by weight based on the total weight of the solid matter in the blue photosensitive resin. May be contained in an amount of 0.1 to 50% by weight, preferably 0.5 to 30% by weight, and more preferably 1 to 20% by weight based on 100% by weight of the blue photosensitive resin composition.

When the content of the blue colorant is within the above range, it is advantageous for achieving the effect of suppressing the reflection of external light and is less likely to cause a problem of lowering the emission intensity or lowering the viscosity stability of the blue photosensitive resin composition.

In the present invention, the blue coloring agent and the scattering particles are included even though they do not include the blue quantum dot, thereby preventing the deterioration of the efficiency of the blue pixel of the color filter, especially the self-emission color filter.

Binder resin

The binder resin of the present invention includes a cadmium-based binder resin. The cationic binder resin has reactivity and alkali solubility due to the action of light or heat and acts as a dispersion medium of the coloring material. The cadmium binder resin contained in the blue photosensitive resin composition of the present invention is not limited as long as it functions as a binder resin for scattering particles and is soluble in the alkaline developer used in the development step for the production of color filters.

The cationic binder resin of the present invention may contain one or more of the compounds represented by Formulas (4-1) and (4-2).

[Formula 4-1]

[Formula 4-2]

Among the formulas (4-1) and (4-2)

이며;R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are, each independently,

;

X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group, and R ₁₉ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In the present invention, the compound represented by Formula 4-1 may be synthesized as a compound represented by Formula 5-1, and the compound represented by Formula 4-2 may be synthesized using a compound represented by Formula 5-2 .

[Formula 5-1]

[Formula 5-2]

The compound represented by the formula 4-1 may be any one or more of the compounds represented by the formula 6 or 7 and the compound represented by the formula 4-2 may be any one or more selected from the compounds represented by the formula 8 or 9.

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

.

.

The cadmium-based binder resin may be selected from the group consisting of 9,9-bis (3-cinnamic diester) fluorene, 9,9-bis (3-cinnamoyl, 9,9-bis (3-cinnamoyl, 4-hydroxyphenyl) fluorene, 9,9-bis (glycidyl methacrylate ether) fluorene, 9,9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester, 9,6-diglycidyl methane, (3,6-diglycidyl methacrylate ether spiro (fluorene-9,9-xantene)), 9,9-bis (3-allyl, 4-hydroxyphenyl (9,9-bis (4-allyloxyphenyl) fluorene) and 9,9-bis (4-allyloxyphenyl) And at least one selected from the group consisting of bis (3,4-methacrylic diester) fluorine (9,9-bis (3,4-methacrylic diester) fluorine) May be summed.

The present invention can be used as a binder resin together with an acrylic alkali-soluble resin together with the cationic resin. That is, the blue photosensitive resin composition may further include an acrylic alkali-soluble resin in the cationic resin.

The acrylic alkali-soluble resin includes, for example, a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer. Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having at least one carboxyl group in the molecule such as unsaturated tricarboxylic acids, have. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate . These carboxyl group-containing monomers may be used alone or in combination of two or more. Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- P-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2- Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Ally Acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, (Meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and the like Unsaturated carboxylic acid esters; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, benzyl maleimide, N-phenyl maleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, And the like. These monomers may be used alone or in combination of two or more. Particularly, as other monomers copolymerizable with the carboxyl group-containing monomer, a bulky monomer such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, or a monomer having a rosin skeleton tends to lower the dielectric constant value, which is preferable .

The cationic binder resin and / or acrylic alkali-soluble resin of the present invention preferably has an acid value in the range of 20 to 200 (KOH mg / g). When the acid value is in the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion remains during development, thereby improving the film remaining ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide. The weight average molecular weight (hereinafter, simply referred to as "weight average molecular weight") of a polymer having a weight average molecular weight of 2,000 to 200,000, preferably 3,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography (GPC: tetrahydrofuran as an elution solvent) Cadmium-based binder resin or acrylic-based resin is preferable. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution tends to be improved.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the cationic binder resin and / or acrylic resin is preferably 1.0 to 6.0, more preferably 1.5 to 6.0. When the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is 1.5 to 6.0, development is preferable.

The binder resin of the present invention may be contained in an amount of 5 to 85% by weight, preferably 5 to 60% by weight, based on the total weight of the solid content in the blue photosensitive resin. When the content of the binder resin is used within the above range, solubility in a developing solution is sufficient, so that development residue does not easily occur on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposed portion is unlikely to occur during development, It is preferable since the leakage tendency tends to be good.

Photopolymerization  compound

The photopolymerizable compound contained in the blue photosensitive resin composition of the present invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers. Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on. 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) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other multifunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) And erythritol hexa (meth) acrylate. Of these, multifunctional monomers having two or more functional groups are preferably used. The photopolymerizable compound may be contained in an amount of 5 to 50% by weight, and preferably 5 to 30% by weight based on the total weight of the solid content in the blue photosensitive resin. When the content of the photopolymerizable compound satisfies the above range, the strength and smoothness of the pixel portion tends to be favorable.

Photoinitiator

The photopolymerization initiator used in the present invention serves to improve the sensitivity of the photosensitive resin composition to improve productivity, and the photoinitiator may be at least one selected from compounds represented by the following general formulas (1) to (3).

[Chemical Formula 1]

(In the formula 1,

R ₁ to R ₄ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, Or a naphthyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms.

(2)

이며, n은 1 내지 4인 정수이고, m은 1 내지 6인 정수이며;R ₅ is hydrogen, My alkyl having a carbon number of 1 to 20 3 8 cycloalkyl, or unsubstituted methyl group, or a phenyl substituted by a methoxy group, a halogen, a carboxyl group and a hydroxyl group

N is an integer from 1 to 4, and m is an integer from 1 to 6;

R ₆ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a substituted phenyl group, a benzyl group or a substituted benzyl group;

R ₇ is a diphenylsulfide group substituted with a diphenylsulfide group, a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxyl group, a carbazole group, a methyl group, a methoxy group, a halogen, a carboxyl group, and a hydroxy group, , Or a substituted fluorene group.)

 (3)

In Formula 3,

R ₈ , R ₉ and R ₁₀ each independently represent R, OR, COR, SR, CONRR 'or CN;

R and R 'represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, And the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, an ester bond, and R and R 'may form a ring together ;

Y ₁ represents an oxygen atom, a sulfur atom or a selenium atom; m represents an integer of 0 to 4; p represents an integer of 0 to 5;

q represents 0 or 1;

R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms;

X ₁ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, which may be substituted with a halogen atom and / or a heterocyclic group having 2 to 20 carbon atoms And the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond;

Y ₂ and Y ₃ each independently represent an oxygen atom, a sulfur atom or a selenium atom.)

Preferably, the alkyl group represented by R and R 'includes an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, , Octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, aryl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, (Methoxy) ethoxy, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- Benzooxazol-2'-yl) ethenyl, and among them, an alkyl group having 1 to 8 carbon atoms is preferable.

Examples of the aryl group represented by R and R 'include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like. An aryl group having a number of 6 to 12 is preferable. Examples of the aralkyl group represented by R and R 'include an aralkyl group having 7 to 13 carbon atoms such as benzyl, chlorobenzyl,? -Methylbenzyl,?,? -Dimethylbenzyl, phenylethyl and phenylethenyl, . Examples of the heterocyclic group represented by R and R 'include a heterocyclic group having 5 to 7 carbon atoms such as pyridyl, pyrimidyl, furyl and thiophenyl. Examples of the ring formed by R and R 'together are a ring having 5 to 7 carbon atoms such as a piperidine ring and a morpholine ring. R and R 'may be substituted with a halogen element such as fluorine, chlorine, bromine or iodine, or may be substituted with a halogen atom such as pyridyl, pyrimidyl, furyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, Diazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isooxazolidyl, piperidyl, piperazinyl, pyrazolyl, Piperidyl, morpholinyl, and the like.

Preferably, the alkyl group represented by X ₁ includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, Propyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxy, ethoxy, propoxy, isopropoxy, isopropoxy, butoxy, (Methoxy) ethoxy, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- 2-yl) ethenyl, and among them, an alkyl group having 1 to 8 carbon atoms is preferable.

Examples of the aryl group represented by X ₁ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like. An aryl group of 1 to 12 carbon atoms is preferable. The aralkyl group represented by X ₁ is preferably an aralkyl group having 7 to 13 carbon atoms such as benzyl, chlorobenzyl,? -Methylbenzyl,?,? - dimethylbenzyl, phenylethyl and phenylethenyl have. Examples of the heterocyclic group represented by X ₁ include a heterocyclic group having 5 to 7 carbon atoms such as pyridyl, pyrimidyl, furyl, thiophenyl and the like.

Examples of the halogen atom represented by X < ₁ > include fluorine, chlorine, bromine and iodine. The alkyl group represented by X ₁ is preferably a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl , Isooctyl, 2-ethylhexyl, and tert-octyl.

Examples of the halogen atom represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ include fluorine, chlorine, bromine and iodine.

The alkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is preferably a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, Octyl, isooctyl, 2-ethylhexyl, and tert-octyl.

The compound represented by Formula 3 may be the following compound.

The compound represented by the general formula (1) is a compound represented by the general formula (1): 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethan- 2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 1-one, 2-ethyl-2-amino (4-morpholinophenyl) propan- , 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, and 2-methyl- 2-diethylamino (4-morpholinophenyl) propane-1-one.

The compounds represented by the formula (2) may be at least one selected from the group consisting of Irgacure OXE-01 (BASF) and TR-PBG-305 (Trontnia).

The compound represented by the formula (3) may be commercially available N-1919 (adeca).

The blue photosensitive resin composition of the present invention contains a photoinitiator having at least one compound selected from the compounds represented by the formulas (1) to (3) in the blue photosensitive resin composition, It is possible to realize a color filter excellent in heat resistance and light resistance and excellent in reliability, in particular, a self-emission color filter.

The photopolymerization initiator used in the blue photosensitive resin composition according to the present invention may be contained in an amount of 0.1 to 30% by weight, preferably 0.3 to 20% by weight based on the total weight of the solid content in the blue photosensitive resin. Within the above range, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed using the composition and the smoothness of the surface of the pixel portion tends to be favorable.

  Further, in the present invention, a photopolymerization initiator may be used. The photopolymerization initiator is sometimes used in combination with a photopolymerization initiator, and is a compound used for promoting polymerization of a photopolymerizable compound initiated by a photopolymerization initiator. Examples of the photopolymerization initiator include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylamino benzoate Ethyl (4-dimethylaminobenzoic acid), 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzphenone Amino) benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Of these, 4,4'-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene And the like. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propanedioxanthone, and the like. These photopolymerization initiators (D) may be used singly or in combination of two or more thereof. Commercially available photopolymerization initiators may be used. Examples of commercially available photopolymerization initiators include trade names " EAB-F " (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like.

When these photopolymerization initiators are used, their amount to be used is usually 10 mol or less, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. Within the above range, the sensitivity of the blue photosensitive resin composition becomes higher, and the productivity of the color filter formed using the composition tends to be improved, which is preferable.

solvent

The solvent contained in the blue photosensitive resin composition of the present invention is not particularly limited and various organic solvents used in the field of the blue photosensitive resin composition can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene Diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether, 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 monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, Ketones such as acetone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; esters such as ethyl 3-ethoxypropionate, Esters such as methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone. Among the above solvents, organic solvents having a boiling point of 100 占 폚 to 200 占 폚 in the solvent are preferably used from the viewpoint of coatability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxy Propylene glycol monomethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3-ethoxypropionate, and 3-methoxypropionate are more preferable. Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Methyl methoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent in the blue photosensitive resin composition of the present invention may be 50 to 90 mass%, preferably 55 to 85 mass%, based on 100 mass% of the blue photosensitive resin composition. When the content of the solvent is in the range of 50 to 90% by mass on the basis of the above-mentioned criteria, when the solvent is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) Is preferable because it tends to be good.

additive

The blue photosensitive resin composition according to the present invention may contain fillers, other polymer compounds, and pigment dispersants as needed. An adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and the like.

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

Specific examples of the other polymer compound 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. .

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylpethers, polyethylene glycol diesters, sorbitan fatty esters, fatty acid modified polyesters, tertiary amine modified polyurethanes (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), And polyethyleneimine, (Manufactured by Dainippon Ink and Chemicals, Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Sol SOLSPERSE (manufactured by Genene), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 (aminoethyl) - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Trimethoxysilane, and the like. 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 and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

The additive can be suitably added and used by those skilled in the art within a range not hindering the effect of the present invention. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the blue photosensitive resin composition.

The blue photosensitive resin composition according to the present invention can be produced, for example, by the following method. The scattering particles are mixed with the solvent in advance and dispersed using a bead mill or the like until the average particle diameter becomes 10 to 1000 nm. At this time, a dispersant may be further used if necessary, and a part or all of a binder resin (a mixture of cardade resin or cardade resin and acrylic alkali-soluble resin) may be blended. The balance of the binder resin (a mixture of cation resin or cation resin and acrylic alkali-soluble resin), the blue colorant, the photopolymerizable compound, the compound represented by the general formula (1) to (3) And other components to be used if necessary, and, if necessary, further solvents are further added to a predetermined concentration to obtain a desired blue photosensitive resin composition.

≪ Color filter and image display device >

Another aspect of the present invention relates to a color filter including a blue pattern layer including a cured product of the above-mentioned blue photosensitive resin composition for forming a blue pattern layer.

The color filter according to the present invention is advantageous in that the manufacturing cost can be lowered because the color filter is manufactured from the blue photosensitive resin composition for forming the blue pattern layer instead of the blue quantum dot. The blue light-sensitive resin composition of the present invention contains at least one photoinitiator selected from the compounds represented by Chemical Formulas (1) to (3) to provide excellent processability and excellent processability, excellent heat resistance and light resistance It is possible to realize color filters excellent in reliability and particularly in self-emission colors, in particular self-emission color filters.

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

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

The blue pattern layer may be a layer including the blue photosensitive resin composition of the present invention and may be a layer formed by applying the blue photosensitive resin composition for forming a blue pattern layer and exposing, developing and thermally curing the blue pattern composition in a predetermined pattern, May be formed by carrying out a method commonly known in the art.

In still another embodiment of the present invention, the color filter may further include at least one selected from the group consisting of a red pattern layer and a green pattern layer.

In another embodiment of the present invention, the red pattern layer or the green pattern layer may include quantum dots and / or scattering particles. In particular, the color filter according to the present invention may include a red pattern layer including an effective quantum dot or a green pattern layer including a rust quantum dot, and the red pattern layer or the green pattern layer may include scattering particles. The red pattern layer or the green pattern layer may emit red light or blue light respectively by a light source emitting blue light, which will be described later.

In another embodiment of the present invention, the scattering particles included in the red pattern layer or the green pattern layer may include a metal oxide having an average particle diameter of 10 to 1000 nm, and the content of the scattering particles and the metal oxide is The content of scattering particles and metal oxides contained in the blue photosensitive resin composition according to the invention can be applied.

In the present invention, the shape, composition and content of the quantum dots included in the red pattern layer or the green pattern layer are not limited, and quantum dots commonly used in the art can be applied.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between the respective patterns, and may further include a black matrix, but is not limited thereto.

In the present invention, the color filter may be a self-emission color filter.

Another aspect of the present invention is a color filter comprising: the color filter described above; And a light source that emits blue light. In short, the image display apparatus according to the present invention includes a color filter including a blue pattern layer including a cured product of the above-mentioned blue photosensitive resin composition, and a light source that emits blue light.

The color filter of the present invention is applicable not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

When the image display device includes the color filter including the blue pattern layer according to the present invention and the light source, there is an advantage that the image display device has excellent light emission intensity. Further, since the blue pattern layer included in the color filter according to the present invention does not include a blue quantum dot, there is an advantage that an image display apparatus with a low manufacturing cost can be manufactured.

Hereinafter, the present invention will be described in detail by way of examples to illustrate the present invention. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the above-described embodiments. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art. In the following, "% " and " part " representing the content are by weight unless otherwise specified.

Synthetic example : Synthesis of binder resin

Manufacturing example  1: Acrylic alkali-soluble resin

 A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was provided with 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were charged and stirred to prepare a charge transfer additive dropping funnel. To this was added n-dodecanethiol And 24 g of PGMEA were placed and stirred and mixed. Then, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen in air, and the temperature of the flask was elevated to 90 DEG C with stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The mixture was heated at 110 ° C. for 1 h and maintained at 90 ° C. for 1 h. The temperature was raised to 110 ° C. for 3 h. Then, a gas introduction tube was introduced to bubbling oxygen / nitrogen gas with 5/95 (v / v) . Then, 28.4 g of [(0.10 mol) of glycidyl methacrylate (33 mol% based on the carboxyl group of the acrylic acid used in the present reaction)], 2,2'-methylenebis (4-methyl-6-t- ) And 0.8 g of triethylamine were placed in a flask, and the reaction was continued at 110 캜 for 8 hours to obtain a resin A having a solid acid value of 70 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 16,000 and the molecular weight distribution (Mw / Mn) was 2.3.

Manufacturing example  2: Synthesis of compound of formula (6)

In a 3000 ml three-necked round flask, 364.4 g of 3 ', 6'-dihydroxyspiro (fluorene-9,9-xantene) (3', 6'-dihydroxy spiro And 2359 g of epichlorohydrin were added and reacted by heating at 90 DEG C. When the 3,6-dihydroxy spiro (fluorene-9,9-chanthylene) was completely consumed by analysis by liquid chromatography, 30 When the epichlorohydrin was completely exhausted, it was extracted with dichloromethane and then washed three times. After the organic layer was dried with magnesium sulfate The dichloromethane was distilled off under reduced pressure and recrystallized using a dichloromethane / methanol mixture ratio of 50:50.

One equivalent of the thus synthesized epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid were mixed, and 24.89 g of propylene glycol monomethyl ether acetate as a solvent was added thereto and mixed. The reaction solution was heated and dissolved at 90 to 100 ° C while air was blown at 25 ml / min. The reaction solution was completely dissolved by heating to 120 DEG C in a cloudy state. When the solution becomes transparent and the viscosity becomes high, the acid value is measured and stirred until the acid value becomes less than 1.0 mg KOH / g. It took 11 hours to reach the target price (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound of formula (6).

[Chemical Formula 6]

Manufacturing example  3: Synthesis of compound of formula (7)

In a 3000 ml three-necked round flask, 364.4 g of 3 ', 6'-dihydroxyspiro (fluorene-9,9-xantene) (3', 6'-dihydroxy spiro And 2359 g of epichlorohydrin were added and reacted by heating at 90 DEG C. When the 3,6-dihydroxy spiro (fluorene-9,9-chanthylene) was completely consumed by analysis by liquid chromatography, 30 When the epichlorohydrin was completely exhausted, it was extracted with dichloromethane and then washed three times. After the organic layer was dried with magnesium sulfate The dichloromethane was distilled off under reduced pressure and recrystallized using a dichloromethane / methanol mixture ratio of 50:50.

One equivalent of the synthesized epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of methacrylic acid were mixed, and 24.89 g of solvent propylene glycol monomethyl ether acetate was added thereto and mixed. The reaction solution was heated and dissolved at 90 to 100 ° C while air was blown at 25 ml / min. The reaction solution was completely dissolved by heating to 120 DEG C in a cloudy state. When the solution becomes transparent and the viscosity becomes high, the acid value is measured and stirred until the acid value becomes less than 1.0 mg KOH / g. It took 11 hours to reach the target price (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound of formula (7).

(7)

Manufacturing example  4: Synthesis of compound of formula (8)

A 3,000 ml three-necked round-bottomed flask was charged with 364.4 g of 4,4 '- (9H-xanthene-9,9-diyl) diphenol (4,4' And 2359 g of epichlorohydrin were charged and reacted by heating at 90 占 폚. When the 4,4 '- (9H-xanthene-9,9-diyl) diphenol (4,4' - (9Hxanthene-9,9-diyl) diphenol) was completely consumed by analysis by liquid chromatography, A 50% aqueous NaOH solution (3 eq) was slowly added. When the epichlorohydrin was completely exhausted, the reaction mixture was extracted with dichloromethane and then washed three times. The organic layer was dried over magnesium sulfate, and the dichloromethane was distilled off under reduced pressure. The dichloromethane-methanol mixture ratio was 50:50 And recrystallized. One equivalent of the thus synthesized epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid were mixed and 24.89 g of solvent propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was heated and dissolved at 90 to 100 ° C while air was blown at 25 ml / min. The reaction solution was completely dissolved by heating to 120 DEG C in a cloudy state. When the solution becomes transparent and the viscosity becomes high, the acid value is measured and stirred until the acid value becomes less than 1.0 mg KOH / g. It took 11 hours to reach the target price (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound of formula (8).

[Chemical Formula 8]

Manufacturing example  5: Synthesis of Compound (9)

A 3,000 ml three-necked round-bottomed flask was charged with 364.4 g of 4,4 '- (9H-xanthene-9,9-diyl) diphenol (4,4' And 2359 g of epichlorohydrin were charged and reacted by heating at 90 占 폚. When the 4,4 '- (9H-xanthene-9,9-diyl) diphenol (4,4' - (9Hxanthene-9,9-diyl) diphenol) was completely consumed by analysis by liquid chromatography, A 50% aqueous NaOH solution (3 eq) was slowly added. When the epichlorohydrin was completely exhausted, the reaction mixture was extracted with dichloromethane and then washed three times. The organic layer was dried over magnesium sulfate, and the dichloromethane was distilled off under reduced pressure. The dichloromethane-methanol mixture ratio was 50:50 And recrystallized. One equivalent of the synthesized epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of methacrylic acid were mixed, and 24.89 g of solvent propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was heated and dissolved at 90 to 100 ° C while air was blown at 25 ml / min. The reaction solution was completely dissolved by heating to 120 DEG C in a cloudy state. When the solution becomes transparent and the viscosity becomes high, the acid value is measured and stirred until the acid value becomes less than 1.0 mg KOH / g. It took 11 hours to reach the target price (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound of formula (9).

[Chemical Formula 9]

.

.

Manufacturing example  6: Carometer  Synthesis of binder resin (A-1)

After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of formula (6) in Preparation Example 2, 78 g of biphenyltetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed and slowly heated to 110 to 115 캜 And reacted for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to polymerize with a cationic binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 3500

Manufacturing example  7: Carometer  Synthesis of binder resin (A-2)

78 g of biphenyltetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were added to 307.0 g of the compound of Formula 7 in Preparation Example 3 and 600 g of propyleneglycol monomethylether acetate was added and dissolved. After gradually heating the mixture, the mixture was heated at 110 to 115 캜 And reacted for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to polymerize with a cationic binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 3800

Manufacturing example  8 : Carometer  Synthesis of binder resin (A-3)

78 g of phenyl tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were added to 307.0 g of the compound of Formula 8 in Preparation Example 4 and 600 g of propyleneglycol monomethyl ether acetate was added and dissolved. After gradually heating the mixture, the mixture was heated to 110 Lt; / RTI > After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to polymerize with a cationic binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 4500

Manufacturing example  9: Carometer  Synthesis of binder resin (A-4)

78 g of phenyltetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were added to 307.0 g of the compound of Formula 9 of Production Example 5 and 600 g of propyleneglycol monomethyl ether acetate was added and dissolved. After slowly heating the mixture, the mixture was heated to 110 Lt; / RTI > After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to polymerize with a cationic binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 4900

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)

The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

Example  1 to 7 and Comparative Example  1 to 2: Preparation of blue photosensitive resin composition

The blue photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were prepared according to the composition shown in Table 1 below.

[Table 1] (unit:% by weight)

1) blue colorant

B-1: Fastogen Blue EP-7S (DCI): C.I. Pigment Blue 15: 6

B-2: Fastogen Blue 5424 (DCI): C.I. Pigment Blue 15: 4

V-1: Fastogen Super Violet 140V (DIC): C.I. Pigment Violet 23

2) Scattering particles (E-1): Tioxide® TR88 (Huntsman)

3) Binder resin:

A-1: Cadordinate resin of Production Example 6,

A-2: Cadochemical resin of Production Example 7,

Acrylic resin: Acrylic alkali-soluble resin of Production Example 1

4) Photopolymerization  compound: Dipentaerythritol hexaacrylate ( KAYARAD DPHA ; Nippon Kaya Ltd.)

5) Photoinitiator

C-1: Compound of Chemical Formula 1: IRGACURE 占 369 (BASF)

C-2: Compound of formula (2): TR-PBG-305 (Tronney)

C-3: Compound of Formula 3: N-1919 (Adeka)

6) Solvent: Propylene glycol monomethyl ether acetate

Manufacture of color filters

A color filter was prepared using the blue photosensitive resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 and 2. That is, the respective blue photosensitive resin compositions were coated on a glass substrate by spin coating, and then placed on a heating plate and held at a temperature of 100 ° C for 3 minutes to form a thin film.

Then, a test photomask having a transmittance of 20 mm × 20 mm square and a line / space pattern of 1 to 100 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 μm from the test photomask.

At this time, the ultraviolet light source was irradiated with light at an exposure dose of 200 mJ / cm 2 (365 nm) using an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI Co., Ltd., and no special optical filter was used.

The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 80 seconds to develop. 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 150 캜 for 10 minutes to prepare a color filter pattern. The film thickness of the color pattern prepared above was 5.0 mu m.

Test Example  1: Evaluation of heat resistance

The light resistance was measured by measuring the chromaticity and transmittance of the substrate manufactured in the color filter using a colorimeter (OSP-200, manufactured by Olympus Corporation) and heating the substrate with the color coordinates measured at 230 캜 for 120 minutes The chromaticity and transmittance were re-measured with a colorimeter (OSP-200, manufactured by Olympus). The heat resistance was evaluated by measuring the color change value (ΔEab) after heating at 230 ° C. for 120 minutes. △ Eab is the value required by the following saturation formula by the CIE 1976 (L *, a *, b *) spatial colorimetric system. (New Color Science Handbook by the Japanese Association of Colorists (1986) p.266).

^{△ Eab * = [(△ L} *) 2 + (△ a *) 2 + (△ b *) 2] 1/2

 [Criteria for evaluation of heat resistance]

?:? Eab * value: 3 or less

DELTA: Eab * Value: 3 to 10 or less

X: DELTA Eab * value: exceed 10

Test Example  2: Light resistance  evaluation

The light resistance was measured by measuring the chromaticity and transmittance of the substrate manufactured in the above color filter with a colorimeter (OSP-200 manufactured by Olympus Corporation) and irradiating the substrate having the color coordinate measured for 200 hours with light resistance equipment (ATLAS Co., CPS + equipment) And then re-measured with a colorimeter (OSP-200, manufactured by Olympus).

△ Eab is the value required by the following saturation formula by the CIE 1976 (L *, a *, b *) spatial colorimetric system. (New Color Science Handbook by the Japanese Association of Colorists (1986) p.266).

^{△ Eab * = [(△ L} *) 2 + (△ a *) 2 + (△ b *) 2] 1/2

[Criteria for evaluating light resistance]

?:? Eab * value: 3 or less

DELTA: Eab * Value: 3 to 10 or less

X: DELTA Eab * value: exceed 10

Experimental Example  3: Development speed

Each of the blue photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 was coated on a glass substrate by spin coating and then placed on a heating plate and held at a temperature of 100 ° C for 3 minutes to form a thin film. After irradiating ultraviolet rays of 50 mJ / cm ^{2 with} the front exposure, the film thickness of the pattern was measured using a film thickness measuring apparatus (DEKTAK 6M; Veeco). After the thickness measurement was completed, the substrate was again immersed in a KOH aqueous solution of pH 10.5 for 80 seconds, and then the remaining portion of the blue photosensitive resin composition was observed on the unexposed portion.

[Development rate evaluation criteria]

The time taken for the unexposed area to completely dissolve in the developing solution was measured and shown. And the case where the development can not be performed is represented by 'x'.

It can be seen that Examples 1 to 7 are excellent in heat resistance and light resistance, and have a high developing speed. On the other hand, in the case of Comparative Examples 1 and 2, the development speed is slow, and the heat resistance and the light resistance are not excellent.

Claims (14)

A scattering particle, a blue colorant, a cadmium binder resin as a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent,
Wherein the photoinitiator is at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 3:
[Chemical Formula 1]

(In the formula 1,
R ₁ to R ₄ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, Or a naphthyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms.
(2)

(In the formula (2)
R ₅ is hydrogen, My alkyl having a carbon number of 1 to 20 3 8 cycloalkyl, or unsubstituted methyl group, or a phenyl substituted by a methoxy group, a halogen, a carboxyl group and a hydroxyl group

N is an integer from 1 to 4, and m is an integer from 1 to 6;
R ₆ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a substituted phenyl group, a benzyl group or a substituted benzyl group;
R ₇ is a diphenylsulfide group substituted with a diphenylsulfide group, a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxyl group, a carbazole group, a methyl group, a methoxy group, a halogen, a carboxyl group, and a hydroxy group, , Or a substituted fluorene group.)
(3)

(3)
R ₈ , R ₉ and R ₁₀ each independently represent R, OR, COR, SR, CONRR 'or CN;
R and R 'represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, And the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, an ester bond, and R and R 'may form a ring together ;
Y ₁ represents an oxygen atom, a sulfur atom or a selenium atom; m represents an integer of 0 to 4; p represents an integer of 0 to 5;
q represents 0 or 1;
R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms;
X ₁ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, which may be substituted with a halogen atom and / or a heterocyclic group having 2 to 20 carbon atoms And the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond;
Y ₂ and Y ₃ each independently represent an oxygen atom, a sulfur atom or a selenium atom.)
2. The compound according to claim 1, wherein the compound represented by Formula 1 is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) (4-morpholinophenyl) ethane-1-one, 2-ethyl-2- 1-one, 2-methyl-2-amino (4-morpholinophenyl) propan- Amino (4-morpholinophenyl) propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) propan-1-one, 2-methyl-2-dimethylamino , And 2-methyl-2-diethylamino (4-morpholinophenyl) propane-1-one. The blue photosensitive resin composition according to claim 1, wherein the scattering particles comprise a metal oxide having an average particle diameter of 10 to 1000 nm. The method according to claim 1, wherein the scattering particles are made of _{Al 2 O 3, SiO 2,} ZnO, ZrO 2, BaTiO 3, TiO 2, Ta 2 O 5, Ti 3 O 5, ZnO, Nb 2 O 3, SnO and MgO And at least one member selected from the group consisting of the compounds represented by the general formula (1). The blue photosensitive resin composition according to claim 1, wherein the scattering particle-containing blue photosensitive resin composition further comprises a purple coloring agent. The blue photosensitive resin composition according to claim 1, wherein the blue colorant comprises at least one of a blue pigment and a blue dye. The blue photosensitive resin composition according to claim 1, wherein the cationic binder resin comprises at least one of compounds represented by the following Chemical Formulas (4-1) and (4-2).
[Formula 4-1]

[Formula 4-2]

Among the formulas (4-1) and (4-2)
R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are, each independently,

;
X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group, and R ₁₉ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The compound represented by the formula (4-1) is any one or more of the compounds represented by the formula (6) or (7), and the compound represented by the formula (4-2) Or more, blue photosensitive resin composition:
[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

. The blue photosensitive resin composition according to claim 1, wherein the blue photosensitive resin composition further comprises an acrylic alkali-soluble resin as a binder resin. A color filter comprising a blue pattern layer made of the blue photosensitive resin composition according to any one of claims 1 to 9. The method of claim 10,
Wherein the color filter further comprises at least one selected from the group consisting of a red pattern layer and a green pattern layer. The method of claim 11,
Wherein the red pattern layer or green pattern layer comprises a quantum dot. 11. The color filter according to claim 10, wherein the color filter is a self-emission color filter. A color filter according to claim 10; And
And a light source for emitting blue light.