KR102300329B1 - Blue photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

[화학식 2]

[화학식 3]

The present invention includes scattering particles, a blue colorant, a cardo-based binder resin as a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent,
The photoinitiator relates to a blue photosensitive resin composition, characterized in that at least one or more selected from the compounds represented by the following Chemical Formulas 1 to 3.
[Formula 1]

[Formula 2]

[Formula 3]

Description

BLUE PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND IMAGE DISPLAY DEVICE PRODUCED USING THE SAME

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 from white light and makes it possible in fine pixel units, and the size of one pixel is tens to hundreds of micrometers. Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at a boundary between each pixel, and a plurality of colors (typically red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order have a structure in which they are sequentially stacked.

Recently, as one of the methods for implementing a color filter, a pigment dispersion method using a pigment-dispersed photosensitive resin is applied. Efficiency is lowered, and color reproduction is deteriorated due to the characteristics of the pigment included in the color filter.

In order to solve this problem, a method for manufacturing a color filter using a self-luminous photosensitive resin composition including quantum dots has been proposed.

Specifically, Korean Patent Laid-Open No. 2007-0094679 suggests that color reproducibility can be improved by having a color filter layer formed of quantum dots, and Korean Patent Laid-Open No. 2009-0036373 uses an existing color filter as a quantum dot phosphor. It is suggested that the display quality can be improved by improving the luminous efficiency by replacing it with the light emitting layer formed.

However, the photosensitive resin composition developed so far for manufacturing the color filter did not sufficiently satisfy the requirements such as development speed, excellent heat resistance and light resistance when formed into a cured film.

Republic of Korea Patent Publication No. 2007-0094679 Republic of Korea Patent Publication No. 2009-0036373

The present invention provides a blue photosensitive resin composition capable of realizing a color filter with excellent development speed, excellent processability, and excellent reliability due to excellent heat resistance and light resistance when formed into a cured film, especially a self-luminous color filter, and a color manufactured using the same An object of the present invention is to provide a filter and an image display device.

The present invention includes scattering particles, a blue colorant, a cardo-based binder resin as a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent,

The photoinitiator is a blue photosensitive resin composition, characterized in that at least one or more selected from the compounds represented by the following Chemical Formulas 1 to 3

[Formula 1]

(In Formula 1,

R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or a carbon number 1 to It is a naphthyl group unsubstituted or substituted with an alkyl group of 12.)

[Formula 2]

(In Formula 2,

이며, n은 1 내지 4인 정수이고, m은 1 내지 6인 정수이며;R ₅ is hydrogen, alkyl having 1 to 20 carbons, cycloalkyl having 3 to 8 carbons, or phenyl unsubstituted or substituted with a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxy group;

, n is an integer from 1 to 4, m is an integer from 1 to 6;

R ₆ is 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, a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxy group substituted diphenylsulfide group, a carbazole group, a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxy group, a carbazole group, a fluorene group , or a substituted fluorene group.)

[Formula 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 these are a halogen atom and/or a heterocyclic group having 2 to 20 carbon atoms. may be substituted with a ring, and among them, the alkylene portion 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, and R and R' together may form a ring there is;

Y ₁ represents an oxygen atom, a sulfur atom or a selenium atom, m represents an integer from 0 to 4, p represents an integer from 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 are a halogen atom and/or a heterocyclic group having 2 to 20 carbon atoms. may be substituted, and among them, the alkylene portion 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).

In addition, the present invention provides a color filter including a blue pattern layer made of the above-described blue photosensitive resin composition.

In addition, the present invention is the color filter; and a light source emitting blue light.

The blue photosensitive resin composition of the present invention includes at least one photoinitiator selected from the compounds represented by Chemical Formulas 1 to 3 in the blue photosensitive resin composition, and thus has excellent development speed, excellent processability, and excellent processability when formed into a cured film. It is possible to realize a color filter having excellent heat resistance and light resistance, and in particular, a self-luminous color filter having excellent reliability.

The blue photosensitive resin composition of the present invention includes a blue colorant, a cardo-based binder resin as a binder resin, at least one photopolymerizable compound selected from compounds represented by Chemical Formulas 1 to 3, a photoinitiator, and a solvent. The resin composition has excellent development speed and excellent processability, and when formed into a cured film, it has excellent heat resistance and light resistance, and thus a highly reliable color filter, especially a self-luminous color filter, may be realized.

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 it is more preferable if the average particle diameter is in the range of 30 to 300 nm. When 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 sink in the blue photosensitive composition or a problem of the non-uniform self-luminous layer surface is generated. lowers

The metal oxide is Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, It may be an oxide including one type of metal selected from the group consisting of Ce, Ta, In, and combinations thereof. More specifically, Al ₂ O ₃ , SiO ₂ , ZnO, ZrO _{2 , BaTiO 3} , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO, MgO and It may be one or more selected from the group consisting of combinations thereof. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.

The scattering particles may have an average particle diameter and a content in the entire composition to be appropriately adjusted as needed so as to sufficiently improve the light emission intensity of the color filter. The scattering particles may have an average particle diameter and a content in the entire composition to be appropriately adjusted as needed so as to sufficiently improve the light emission intensity of the color filter.

The scattering particles may be included 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 a problem of stability deterioration of the blue photosensitive resin composition while achieving a desired light emission intensity.

blue colorant

In the blue colorant of the present invention, the blue pigment includes a compound classified as a pigment in the color index (published by The Society of Dyers and Colorists), and more specifically, the following color index (CI) numbered pigments, but are not necessarily limited to these. Blue pigments are specifically, for example, C.I. Pigment Blue 15:3, 15:4, 15:6, 16, 21, 28, and 76; and C.I. It is preferable to include at least one selected from the group consisting of Pigment Blue 15:3, Pigment Blue 15:6, and Pigment Blue 16.

The blue colorant of the present invention may further include a blue dye, and the blue dye is a compound classified as a dye in the Color Index (published by The Society of Dyers and Colorists) or a known compound described in the dyeing note (color dye). dyes.

Specifically, for example, the dye that can be used further

C.I. As a solvent dye,

C.I. solvent blue 5, 35, 36, 37, 44, 45, 59, 67 and 70; and C.I. More preferably, it contains at least one of solvent blue 35, 36, 44, 45 and 70.

Also, C.I. As an 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, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1 , 335 and 340, among others, CI It is more preferable 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 Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84;

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

The purple dye is specifically, C.I. Solvent Violet, C.I. Acid Violet, C.I. Acid Violet, C.I. Modanto Violet, and the like, but are not limited thereto.

Specifically, the C.I. Solvent Violet is C.I. solvent violet 8, 9, 13, 14, 36, 37, 47 and 49; and C.I. More preferably, solvent violet 13 is included. For C.I. Acid Violet, C.I. acid violet 6B, 7, 9, 17, 19 and 66; and C.I. It is more preferable to include Acid Violet 66. Examples of CI direct violet include CI direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104. .

Moreover, CI modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58 etc. are mentioned. .

The blue colorant may be included 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 content in the blue photosensitive resin. It may be included in an amount of 0.1 to 50% by weight based on 100% by weight of the blue photosensitive resin composition, preferably 0.5 to 30% by weight, and more preferably 1 to 20% by weight.

When the content of the blue colorant satisfies the above range, it is advantageous in achieving the effect of suppressing external light reflection and is less likely to cause a decrease in luminescence intensity or a decrease in viscosity stability of the blue photosensitive resin composition.

In the present invention, by including the blue colorant and the scattering particles even though the blue quantum dots are not included, it is possible to prevent a decrease in the efficiency of the blue pixel of the color filter, in particular, the self-luminous color filter.

binder resin

The binder resin of the present invention contains a cardo-based binder resin. The cardo-based binder resin has reactivity and alkali solubility under the action of light or heat, and acts as a dispersion medium for the coloring material. The cardo-based binder resin contained in the blue photosensitive resin composition of the present invention acts as a binder resin for the scattering particles, and is not limited as long as it is a resin soluble in the alkaline developer used in the developing step for manufacturing the color filter.

The cardo-based binder resin of the present invention may include one or more of the compounds represented by Chemical Formulas 4-1 and 4-2.

[Formula 4-1]

[Formula 4-2]

In Formulas 4-1 and 4-2,

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

is;

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 the compound represented by Formula 5-2. .

[Formula 5-1]

[Formula 5-2]

The compound represented by Formula 4-1 may be any one or more compounds represented by Formula 6 or Formula 7, and the compound represented by Formula 4-2 may be any one or more compounds represented by Formula 8 or Formula 9.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

.

.

The cardo-based binder resin is 9,9-bis (3-cinnamic diester) fluorene (9,9-bis (3-cinnamic diester) fluorene), 9,9-bis (3-cinnamoyl, 4-hyde Roxyphenyl)fluorene (9,9-bis(3-cinnamoil, 4-hydroxyphenyl)fluorene), 9,9-bis(glycidyl methacrylate ether)fluorene (9,9-bis(glycidyl methacrylate ether) fluorene), 9,9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester (9,9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester), 3,6-diglycidyl meta Krylate ether spiro (fluorene-9,9-xanthene) (3,6-diglycidyl methacrylate ether spiro (fluorene-9,9-xantene)), 9,9-bis (3-allyl, 4-hydroxyphenyl flu orene) (9,9-bis(3-allyl, 4-hydroxyphenlylfluorene), 9,9-bis(4-allyloxyphenyl)fluorene (`9,9-bis(4-allyloxyphenyl)fluorene) and 9,9 -bis(3,4-methacrylic diester)fluorine (9,9-bis(3,4-methacrylic diester)fluorine) may be polymerized including at least one selected from the group consisting of.

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

The acrylic alkali-soluble resin includes, for example, a carboxyl group-containing monomer and a copolymer of this monomer and another monomer copolymerizable therewith. Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule such as unsaturated tricarboxylic acids. have. Here, as an unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, a crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl) ), mono(2-acryloyloxyethyl phthalate), mono(2-methacryloyloxyethyl) phthalate, etc. are mentioned. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer at both terminals, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively. Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methyl Toxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p- aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy 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, Allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxy Ethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol Methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopenta Dienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy- unsaturated carboxylic acid esters such as 3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-Aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl groups such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. unsaturated imides such as N-cyclohexyl maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; and a monoacryloyl group or a 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 polysiloxane. and macromonomers having These monomers can be used individually or in mixture of 2 or more types, respectively. In particular, as another monomer copolymerizable with the carboxyl group-containing monomer, bulky monomers such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton are preferable because they tend to lower the relative dielectric constant. .

As the cardo-based binder resin and/or acrylic alkali-soluble resin of the present invention, the acid value is preferably 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, so that the non-exposed portion is easily dissolved and the sensitivity is increased, so that the pattern of the exposed portion remains at the time of development, which is preferable, thereby improving the film remaining ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be usually obtained by titration using an aqueous potassium hydroxide solution. In addition, the polystyrene reduced weight average molecular weight (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; tetrahydrofuran is used as the elution solvent) is 2,000 to 200,000, preferably 3,000 to 100,000. Cardo-based binder resin or acrylic resin is preferred. When the molecular weight is in the above range, the hardness of the coating film is improved, the film remaining rate is high, the solubility of the non-exposed part in the developer is excellent, and the resolution tends to be improved, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the cardo-based binder resin and/or the acrylic resin is preferably 1.0 to 6.0, and more preferably 1.5 to 6.0. A molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because developability is excellent.

The binder resin of the present invention may be included 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 in the above range, the solubility in the developer is sufficient, so that it is difficult to generate a developing residue on the substrate of the non-pixel portion, and it is difficult to reduce the film of the pixel portion of the exposed portion during development. Since omission property tends to be favorable, it is preferable.

photopolymerization compound

The photopolymerizable compound contained in the blue photosensitive resin composition of the present invention is a compound capable of polymerization by the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, difunctional monomers, 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-vinylpyrrol money, etc. 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) acrylate, Bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned. Specific examples of the other polyfunctional monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate, dipenta Erythritol hexa(meth)acrylate etc. are mentioned. Among these, the polyfunctional monomer more than bifunctional is used preferably. The photopolymerizable compound may be included in an amount of 5 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 photopolymerizable compound satisfies the above range, it is preferable because the intensity or smoothness of the pixel portion tends to be good.

photoinitiator

The photoinitiator used in the present invention serves to increase the productivity by improving the sensitivity of the photosensitive resin composition, and the photoinitiator may be at least one selected from compounds represented by Chemical Formulas 1 to 3 below.

[Formula 1]

(In Formula 1,

R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or a carbon number 1 to It is a naphthyl group unsubstituted or substituted with an alkyl group of 12.)

[Formula 2]

이며, n은 1 내지 4인 정수이고, m은 1 내지 6인 정수이며;R ₅ is hydrogen, alkyl having 1 to 20 carbons, cycloalkyl having 3 to 8 carbons, or phenyl unsubstituted or substituted with a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxy group;

, n is an integer from 1 to 4, m is an integer from 1 to 6;

R ₆ is 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, a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxy group substituted diphenylsulfide group, a carbazole group, a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxy group, a carbazole group, a fluorene group , or a substituted fluorene group.)

[Formula 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 these are a halogen atom and/or a heterocyclic group having 2 to 20 carbon atoms. may be substituted with a ring, and among them, the alkylene portion 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, and R and R' together may form a ring there is;

Y ₁ represents an oxygen atom, a sulfur atom or a selenium atom, m represents an integer from 0 to 4, p represents an integer from 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 are a halogen atom and/or a heterocyclic group having 2 to 20 carbon atoms. may be substituted, and among them, the alkylene portion 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' is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl. , octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, aryl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyoxyethyl, Methoxyethoxyethyl, ethoxyethoxyethyl, propyoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-( Benzoxazol-2'-yl)ethenyl etc. are mentioned, Especially, a C1-C8 alkyl group is preferable.

Examples of the aryl group represented by R and R' include phenyl, toryl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, and the like. Among them, a carbon atom The number 6-12 aryl group is preferable. As the aralkyl group represented by R and R', for example, an aralkyl group having 7 to 13 carbon atoms, such as benzyl, chlorobenzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and phenylethenyl, is preferable. can be heard As the heterocyclic group represented by R and R', for example, a heterocyclic group having 5 to 7 carbon atoms such as pyridyl, pyrimidyl, furyl, and thiophenyl is preferably mentioned. Moreover, as a ring which R and R' can form together, a C5-C7 ring, such as a piperidine ring and a morpholine ring, is mentioned preferably, for example. In addition, R and R' are substituted with a halogen element such as fluorine, chlorine, bromine, iodine, or pyridyl, pyrimidyl, furyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidyl Dazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, pipera It may be substituted with a heterocyclic group having 5 to 7 carbon atoms, such as diyl (piperadyl) or morpholinyl.

Preferably _{, the alkyl group represented by X 1} is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, and octyl. , isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, aryl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyoxyethyl, methoxy Ethoxyethyl, ethoxyethoxyethyl, propyoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxa Zol-2'-yl)ethenyl etc. are mentioned, Especially, a C1-C8 alkyl group is preferable.

Further _{, examples of the aryl group represented by X 1} include phenyl, toryl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, and the like. Among them, 6 carbon atoms An aryl group of ˜12 is preferred. Further, _{as the aralkyl group represented by X 1} , for example, an aralkyl group having 7 to 13 carbon atoms, such as benzyl, chlorobenzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, phenylethenyl, is preferably mentioned. have. As the _{heterocyclic group represented by X 1} , for example, a heterocyclic group having 5 to 7 carbon atoms, such as pyridyl, pyrimidyl, furyl, and thiophenyl, is preferably mentioned.

Examples _{of the halogen atom represented by X 1} include fluorine, chlorine, bromine and iodine. In addition _{, the alkyl group represented by X 1} is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, or octyl substituted or unsubstituted with a halogen atom. , 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 methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, and tert-octyl.

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

The compound represented by Formula 1 is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-methyl-2-amino(4-morpholinophenyl)ethane- 1-one, 2-ethyl-2-amino(4-morpholinophenyl)ethan-1-one, 2-propyl-2-amino(4-morpholinophenyl)ethan-1-one, 2-butyl- 2-amino (4-morpholinophenyl)ethan-1-one, 2-methyl-2-amino (4-morpholinophenyl) propan-1-one, 2-methyl-2-amino (4-morphol Nophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one , 2-methyl-2-methylamino(4-morpholinophenyl)propan-1-one, 2-methyl-2-dimethylamino(4-morpholinophenyl)propan-1-one, and 2-methyl- It may be at least one selected from the group consisting of 2-diethylamino(4-morpholinophenyl)propan-1-one.

The compound represented by Formula 2 may be at least one selected from the group consisting of Irgacure OXE-01 (BASF) and TR-PBG-305 (Tronni) as a commercially available product.

The compound represented by the formula (3) may be N-1919 (Adecas) as a commercially available product.

The blue photosensitive resin composition of the present invention includes at least one photoinitiator selected from the compounds represented by Chemical Formulas 1 to 3 in the blue photosensitive resin composition, and thus has excellent development speed, excellent processability, and excellent processability when formed into a cured film. It is possible to realize a color filter having excellent heat resistance and light resistance, and in particular, a self-luminous color filter having excellent reliability.

The photopolymerization initiator used in the blue photosensitive resin composition according to the present invention may be included in an amount of 0.1 to 30 wt%, preferably 0.3 to 20 wt%, based on the total weight of the solid content in the blue photosensitive resin. When it exists in said range, since there exists a tendency for a coloring photosensitive resin composition to become highly sensitive, the intensity|strength of the pixel part formed using this composition, and the smoothness in the surface of this pixel part, it is preferable.

Furthermore, in this invention, a photoinitiation adjuvant can be used. A photopolymerization initiation adjuvant may be used in combination with a photoinitiator, and is a compound used for accelerating|stimulating the polymerization of the photopolymerizable compound whose polymerization was initiated by the photoinitiator. As a photopolymerization initiation adjuvant, an amine compound, an alkoxyanthracene type compound, a thioxanthone type compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis(diethyl Amino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. and the like. As the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone etc. are mentioned. Such a photoinitiator (D) does not interfere even if it uses individually or in combination of plurality. Moreover, a commercially available thing can be used as a photoinitiation adjuvant, As a commercially available photoinitiation adjuvant, the brand name "EAB-F" [manufacturer: Hodogaya Chemical Industry Co., Ltd.] etc. are mentioned, for example.

When using these photoinitiator adjuvants, the usage-amount is 10 mol or less normally per 1 mol of photoinitiator, Preferably 0.01-5 mol is preferable. When it exists in said range, since the sensitivity of a blue photosensitive resin composition becomes higher and there exists a tendency for productivity of the color filter formed using this composition to improve, it is preferable.

solvent

The solvent in particular contained in the blue photosensitive resin composition of this invention is not restrict|limited, Various organic solvents used in the field|area of a 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, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene Diethylene glycol dialkyl ethers such as 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, and propylene glycol 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, 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, ethyl 3-ethoxypropionate, 3-methoxy Esters, such as methyl propionate, Cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned. Among the above solvents, organic solvents having a boiling point of 100°C to 200°C in the above solvents are preferable from the viewpoint of applicability and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxy and esters such as ethyl propionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethyl propionate, 3- and methyl methoxypropionate. These solvents can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent in the blue photosensitive resin composition of the present invention may be 50 to 90% by mass, preferably 55 to 85% by mass based on 100% by weight of the blue photosensitive resin composition. If the content of the solvent is in the range of 50 to 90% by mass based on the above criteria, the applicability when applied with an application device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet, etc. Since this tends to become favorable, it is preferable.

additive

The blue photosensitive resin composition according to the present invention may contain, if necessary, a filler, another polymer compound, and a pigment dispersant. Additives such as adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors may be further included.

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

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

As said pigment dispersant, commercially available surfactant can be used, For example, surfactant, such as silicone type, fluorine type, ester type, cationic type, anionic type, nonionic type, amphoteric type, etc. are mentioned. These may be used individually or in combination of 2 or more types, respectively.

As said surfactant, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, polyethylene glycol diesters, sorbitan fatty esters, fatty acid modified polyesters, tertiary amine modified polyurethanes , polyethyleneimines, etc. In addition, as trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink Chemical Co., Ltd.), Flourad (manufactured by Sumitomo 3M), Asahi guard, Surflon (above, manufactured by Asahi Glass), brush SOLSPERSE (manufactured by Zeneca Corporation), EFKA (manufactured by EFKA Chemicals Corporation), PB 821 (manufactured by Ajinomoto Corporation), and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned. 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-chlorobenzotyriazole and alkoxybenzophenone.

Specific examples of the aggregation inhibitor include sodium polyacrylate.

The additive may be appropriately added and used by those skilled in the art in a range that does not impair the effects 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 blue photosensitive resin composition, but is not limited thereto.

The blue photosensitive resin composition according to the present invention may be prepared, for example, by the following method. The scattering particles are mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle diameter is 10 to 1000 nm. In this case, a dispersing agent may be additionally used if necessary, and some or all of the binder resin (cardo-based resin or a mixture of cardo-based resin and acrylic alkali-soluble resin) may be blended. The remainder of the binder resin (cardo-based resin or a mixture of cardo-based resin and acrylic alkali-soluble resin) in the obtained dispersion (hereinafter sometimes referred to as mill base), a blue colorant, a photopolymerizable compound, At least one or more selected from the compounds, other components used as necessary, and additional solvents may be 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-described blue photosensitive resin composition for forming a blue pattern layer.

Since the color filter according to the present invention is made of the above-described blue photosensitive resin composition for forming a blue pattern layer instead of blue quantum dots, there is an advantage in that the manufacturing cost can be lowered. In addition, by including at least one photoinitiator selected from the compounds represented by Chemical Formulas 1 to 3 in the blue photosensitive resin composition of the present invention, it has excellent development speed and excellent processability, and excellent heat resistance and light resistance when formed into a cured film It is possible to realize a color filter with excellent reliability, especially a self-luminous color, especially a self-luminous color filter.

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

The substrate may be a substrate of the color filter itself, or may be a region in which a color filter is positioned on a display device, and the like, 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 blue pattern layer is a layer comprising the blue photosensitive resin composition of the present invention, and may be a layer formed by applying the blue photosensitive resin composition for forming the blue pattern layer and exposing, developing and thermosetting the pattern layer in a predetermined pattern. can be formed by performing a method commonly known in the art.

In 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. Specifically, the color filter according to the present invention may include a red pattern layer including red quantum dots or a green pattern layer including green quantum dots, and the red pattern layer or 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. The content regarding the scattering particles and the metal oxide contained in the blue photosensitive resin composition according to the present invention can be applied.

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

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, but is not limited thereto.

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

Another aspect of the present invention, the above-described color filter; and a light source emitting blue light. In short, the image display device according to the present invention includes a color filter including a blue pattern layer including a cured product of the above-described blue photosensitive resin composition and a light source emitting blue light.

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

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 in having excellent light emission intensity. In addition, since the blue pattern layer included in the color filter according to the present invention does not include blue quantum dots, there is an advantage in that an image display device having a low manufacturing cost can be manufactured.

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 : Synthesis of binder resin

manufacturing example 1: Acrylic alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping funnel and a nitrogen introduction tube was prepared, and as a monomer dropping funnel, 74.8 g (0.20 mole) of benzylmaleimide, 43.2 g (0.30 mole) of acrylic acid, and 118.0 of vinyltoluene were prepared. g (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added and prepared by stirring and mixing, and as a chain transfer agent dropping tank, n-dodecanthiol 6g, PGMEA 24g was put, and what stirred and mixed was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Then, the monomer and the chain transfer agent were started dripping from the dropping lot. Dropping proceeds for 2 h while maintaining 90 ° C. After 1 h, the temperature is raised to 110 ° C. and maintained for 3 h. Then, a gas introduction tube is introduced to bubbling the oxygen/nitrogen = 5/95 (v/v) mixed gas. started Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% based on the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis(4-methyl-6-t-butylphenol ) 0.4 g and 0.8 g of triethylamine were put into the flask, and the reaction was continued at 110° C. for 8 hours to obtain Resin A having a solid content acid value of 70 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3.

manufacturing example 2: Synthesis of the compound of formula (6)

364.4 g of 3',6'-dihydroxyspiro(fluorene-9,9-xantene) and t-butylammonium bromide in a 3000ml three-necked round flask 0.4159 g was mixed, 2359 g of epichlorohydrin was added, and the reaction was heated to 90° C. When 3,6-dihydroxyspiro (fluorene-9,9-xanthene) is completely consumed by liquid chromatography analysis, 30 After cooling to ° C, a 50% aqueous NaOH solution (3 equivalents) was slowly added, and when epichlorohydrin was completely consumed by analysis by liquid chromatography, extraction was performed with dichloromethane, washed with water 3 times, and the organic layer was dried over magnesium sulfate. Dichloromethane was distilled under reduced pressure and recrystallized using a dichloromethane and methanol mixing ratio of 50:50.

1 equivalent of the thus synthesized epoxy compound, 0.004 equivalents of t-butylammonium bromide, 0.001 equivalents of 2,6-diisobutylphenol, and 2.2 equivalents of acrylic acid were mixed, and then 24.89 g of propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was dissolved by heating at a temperature of 90 to 100°C while blowing air at a rate of 25 ml/min. In a state in which the reaction solution was cloudy, the temperature was heated to 120° C. to completely dissolve it. When the solution became transparent and the viscosity increased, the acid value was measured and stirred until the acid value became less than 1.0 mgKOH/g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of Formula 6.

[Formula 6]

manufacturing example 3: Synthesis of the compound of formula 7

364.4 g of 3',6'-dihydroxyspiro(fluorene-9,9-xantene) and t-butylammonium bromide in a 3000ml three-necked round flask 0.4159 g was mixed, 2359 g of epichlorohydrin was added, and the reaction was heated to 90° C. When 3,6-dihydroxyspiro (fluorene-9,9-xanthene) is completely consumed by liquid chromatography analysis, 30 After cooling to ° C, a 50% aqueous NaOH solution (3 equivalents) was slowly added, and when epichlorohydrin was completely consumed by analysis by liquid chromatography, extraction was performed with dichloromethane, washed with water 3 times, and the organic layer was dried over magnesium sulfate. Dichloromethane was distilled under reduced pressure and recrystallized using a dichloromethane and methanol mixing ratio of 50:50.

1 equivalent of the thus synthesized epoxy compound, 0.004 equivalents of t-butylammonium bromide, 0.001 equivalents of 2,6-diisobutylphenol, and 2.2 equivalents of methacrylic acid were mixed, and then 24.89 g of propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was dissolved by heating at a temperature of 90 to 100°C while blowing air at a rate of 25 ml/min. In a state in which the reaction solution was cloudy, the temperature was heated to 120° C. to completely dissolve it. When the solution became transparent and the viscosity increased, the acid value was measured and stirred until the acid value became less than 1.0 mgKOH/g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of Chemical Formula 7.

[Formula 7]

manufacturing example 4: Synthesis of the compound of Formula 8

In a 3000ml three-necked round flask, 364.4 g of 4,4'-(9H-xanthene-9,9-diyl)diphenol (4,4'-(9H-xanthene-9,9-diyl)diphenol) and t-butylammonium bromide 0.4159 g was mixed, 2359 g of epichlorohydrin was added, and the reaction was heated to 90 °C. When 4,4'-(9H-xanthene-9,9-diyl)diphenol (4,4'-(9Hxanthene-9,9-diyl)diphenol) is completely consumed by analysis by liquid chromatography, it is cooled to 30℃ 50% aqueous NaOH solution (3 eq) was added slowly. When epichlorohydrin is completely consumed by analysis by liquid chromatography, extraction with dichloromethane is performed, washing with water three times, drying the organic layer over magnesium sulfate, dichloromethane is distilled under reduced pressure, and dichloromethane and methanol mixing ratio is 50:50. was recrystallized. 1 equivalent of the thus synthesized epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid were mixed, and then 24.89 g of propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was dissolved by heating at a temperature of 90 to 100°C while blowing air at a rate of 25 ml/min. In a state in which the reaction solution was cloudy, the temperature was heated to 120° C. to completely dissolve it. When the solution became transparent and the viscosity increased, the acid value was measured and stirred until the acid value became less than 1.0 mgKOH/g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of Formula 8.

[Formula 8]

manufacturing example 5: Synthesis of the compound of formula 9

In a 3000ml three-necked round flask, 364.4 g of 4,4'-(9H-xanthene-9,9-diyl)diphenol (4,4'-(9H-xanthene-9,9-diyl)diphenol) and t-butylammonium bromide 0.4159 g was mixed, 2359 g of epichlorohydrin was added, and the reaction was heated to 90 °C. When 4,4'-(9H-xanthene-9,9-diyl)diphenol (4,4'-(9Hxanthene-9,9-diyl)diphenol) is completely consumed by analysis by liquid chromatography, it is cooled to 30℃ 50% aqueous NaOH solution (3 eq) was added slowly. When epichlorohydrin is completely consumed by analysis by liquid chromatography, extraction with dichloromethane is performed, washing with water three times, drying the organic layer over magnesium sulfate, dichloromethane is distilled under reduced pressure, and dichloromethane and methanol mixing ratio is 50:50. was recrystallized. 1 equivalent of the thus synthesized epoxy compound, 0.004 equivalents of t-butylammonium bromide, 0.001 equivalents of 2,6-diisobutylphenol, and 2.2 equivalents of methacrylic acid were mixed, and then 24.89 g of a solvent propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was dissolved by heating at a temperature of 90 to 100°C while blowing air at a rate of 25 ml/min. In a state in which the reaction solution was cloudy, the temperature was heated to 120° C. to completely dissolve it. When the solution became transparent and the viscosity increased, the acid value was measured and stirred until the acid value became less than 1.0 mgKOH/g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of Formula 9.

[Formula 9]

.

.

manufacturing example 6: cardio Synthesis of binder resin (A-1)

After adding and dissolving 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Formula 6 of Preparation Example 2, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide were mixed, and the temperature was gradually increased at 110 to 115 ° C. The reaction was carried out for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, reacted at 90° C. for 6 hours, and polymerized into a cardo-based binder resin. The disappearance of the anhydride was confirmed by the IR spectrum. Weight average molecular weight: 3500

manufacturing example 7: cardio Synthesis of binder resin (A-2)

After adding and dissolving 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Formula 7 in Preparation Example 3, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide were mixed, and the temperature was gradually increased at 110 to 115 ° C. The reaction was carried out for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, reacted at 90° C. for 6 hours, and polymerized into a cardo-based binder resin. The disappearance of the anhydride was confirmed by the IR spectrum. Weight average molecular weight: 3800

manufacturing example 8 : cardio Synthesis of binder resin (A-3)

After adding and dissolving 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Formula 8 of Preparation Example 4, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide were mixed, and the temperature was gradually increased at 110 to 115 ° C. reacted for an hour. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, reacted at 90° C. for 6 hours, and polymerized into a cardo-based binder resin. The disappearance of the anhydride was confirmed by the IR spectrum. Weight average molecular weight: 4500

manufacturing example 9: cardio Synthesis of binder resin (A-4)

After adding and dissolving 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Formula 9 of Preparation Example 5, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide were mixed, and the temperature was gradually increased at 110 to 115 ° C. reacted for an hour. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, reacted at 90° C. for 6 hours, and polymerized into a cardo-based binder resin. The disappearance of the anhydride was confirmed by the IR spectrum. Weight average molecular weight: 4900

Device: HLC-8120GPC (manufactured by Toso Co., Ltd.)

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

Column temperature: 40℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 μl

Detector: RI

Measurement sample concentration: 0.6 wt% (solvent = tetrahydrofuran)

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

Ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw/Mn).

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

According to the composition of Table 1 below, the blue photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 2 were prepared.

[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 (Huntzmann)

3) Binder resin:

A-1: Cardo-based resin of Preparation Example 6,

A-2: Cardo-based resin of Preparation Example 7,

Acrylic resin: acrylic alkali-soluble resin of Preparation Example 1

4) photopolymerization compound: Dipentaerythritol Hexaacrylate ( KAYARAD DPHA ; Nippon Kaya Co., Ltd.)

5) photoinitiator

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

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

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

6) Solvent: Propylene glycol monomethyl ether acetate

Manufacture of color filters

Color filters were prepared using the blue photosensitive resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 2 above. That is, each of the blue photosensitive resin compositions was applied on a glass substrate by spin coating, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film.

Then, a test photomask having a transmission pattern of 20 mm x 20 mm square and a line/space pattern of 1 to 100 μm was placed on the thin film, and ultraviolet rays were irradiated with an interval of 100 μm with the test photomask.

In this case, the ultraviolet light source was irradiated with an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd. at an exposure dose (365 nm) of 200 mJ/cm 2 in an atmospheric atmosphere, and no special optical filter was used.

The thin film irradiated with ultraviolet light was developed by immersing it in a developing solution of a KOH aqueous solution having a pH of 10.5 for 80 seconds. The glass plate coated with this thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150° C. for 10 minutes to prepare a color filter pattern. The film thickness of the color pattern prepared above was 5.0 μm.

test example 1: Heat resistance evaluation

The light resistance was measured by measuring the chromaticity and transmittance of the substrate manufactured in the color filter manufacturing using a colorimeter (OSP-200, manufactured by Olympus). Chromaticity and transmittance were measured again with a colorimeter (manufactured by Olympus, OSP-200). The heat resistance was evaluated by measuring the color change value (ΔEab) after heating at 230°C for 120 minutes. ΔEab is a value required by the following saturation formula according to the CIE 1976 (L*, a*, b*) spatial colorimetric system. (New edition of the Color Science Handbook (Showa 60) p.266, edited by the Japan Color Society).

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

[Heat resistance evaluation criteria]

○: △Eab* value: 3 or less

Δ: ΔEab* value: 3 to 10 or less

X: ΔEab* value: greater than 10

test example 2: light fastness evaluation

For light resistance, the chromaticity and transmittance of the substrate manufactured in the above color filter manufacturing were measured with a colorimeter (OSP-200 manufactured by Olympus). It was measured again with a colorimeter (manufactured by Olympus, OSP-200).

ΔEab is a value required by the following saturation formula according to the CIE 1976 (L*, a*, b*) spatial colorimetric system. (New edition of the Color Science Handbook (Showa 60) p.266, edited by the Japan Color Society).

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

[Light resistance evaluation criteria]

○: △Eab* value: 3 or less

Δ: ΔEab* value: 3 to 10 or less

X: △Eab* value: greater than 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, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film. After irradiating an ultraviolet ray of 50 mJ/cm ² with full exposure, the film thickness of the pattern was measured using a film thickness measuring device (DEKTAK 6M; manufactured by Veeco). After the thickness measurement was completed, the substrate was developed by immersing it in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds, and then, it was checked whether the blue photosensitive resin composition remained in the non-exposed part.

[Development Speed Evaluation Criteria]

The time taken for the unexposed part to completely dissolve in the developer during development was measured and shown. The case where the development did not occur is indicated by 'x'.

It can be seen that Examples 1 to 7 are excellent in heat resistance and light resistance, and the development speed is also fast. On the other hand, in the case of Comparative Examples 1 and 2, the development speed is also slow, and it can be seen that both heat resistance and light resistance are not excellent.

Claims (14)

Scattering particles, a blue colorant, and a cardo-based binder resin as a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent,
does not contain quantum dots,
The photoinitiator is at least one or more selected from the compounds represented by the following Chemical Formulas 1 to 3,
The cardo-based binder resin is a blue photosensitive resin composition comprising at least one of the compounds represented by the following Chemical Formulas 4-1 and 4-2.

[Formula 1]

(In Formula 1,
R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or a carbon number 1 to It is a naphthyl group unsubstituted or substituted with an alkyl group of 12.)
[Formula 2]

(In Formula 2,
R ₅ is hydrogen, alkyl having 1 to 20 carbons, cycloalkyl having 3 to 8 carbons, or phenyl unsubstituted or substituted with a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxy group;

, n is an integer from 1 to 4, m is an integer from 1 to 6;
R ₆ is 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, a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxy group substituted diphenylsulfide group, a carbazole group, a methyl group, a methoxy group, a halogen, a carboxyl group and a hydroxy group, a carbazole group, a fluorene group , or a substituted fluorene group.)
[Formula 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 these are a halogen atom and/or a heterocyclic group having 2 to 20 carbon atoms. may be substituted with a ring, and among them, the alkylene portion 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, and R and R' together may form a ring there is;
Y ₁ represents an oxygen atom, a sulfur atom or a selenium atom, 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 are a halogen atom and/or a heterocyclic group having 2 to 20 carbon atoms. may be substituted, and among them, 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.)
[Formula 4-1]

[Formula 4-2]

(In Formulas 4-1 and 4-2,
R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each independently,

is;
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 method according to claim 1, wherein the compound represented by Formula 1 is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-methyl-2-amino (4-morph Polynophenyl)ethan-1-one, 2-ethyl-2-amino(4-morpholinophenyl)ethan-1-one, 2-propyl-2-amino(4-morpholinophenyl)ethan-1-one One, 2-Butyl-2-amino(4-morpholinophenyl)ethan-1-one, 2-methyl-2-amino(4-morpholinophenyl)propan-1-one, 2-methyl-2- Amino(4-morpholinophenyl)butan-1-one, 2-ethyl-2-amino(4-morpholinophenyl)propan-1-one, 2-ethyl-2-amino(4-morpholinophenyl) ) Butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one , And 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one at least one selected from the group consisting of a blue photosensitive resin composition. The blue photosensitive resin composition of claim 1, wherein the scattering particles include a metal oxide having an average particle diameter of 10 to 1000 nm. The method according to claim 1, The scattering particles are 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 consisting of A blue photosensitive resin composition comprising at least one selected from the group. The method according to claim 1, The blue photosensitive resin composition containing scattering particles will further include a purple colorant, the blue photosensitive resin composition. The blue photosensitive resin composition of claim 1 , wherein the blue colorant comprises at least one of a blue pigment and a blue dye. delete The method according to claim 1, wherein the compound represented by Formula 4-1 is any one or more of the compounds represented by Formula 6 or Formula 7, and the compound represented by Formula 4-2 is any one of the compounds represented by Formula 17 or Formula 18 Above, the blue photosensitive resin composition:
[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

. The blue photosensitive resin composition of 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 of any one of claims 1 to 6, 8 and 9. 11. The method of claim 10,
The color filter further comprises at least one selected from the group consisting of a red pattern layer and a green pattern layer. 12. The method of claim 11,
The red pattern layer or the green pattern layer is a color filter comprising quantum dots. The color filter according to claim 10, wherein the color filter is a self-luminous color filter. The color filter according to claim 10; and
An image display device comprising a; a light source emitting blue light.