JP7030837B2 - Blue photosensitive resin composition, color filter and image display device manufactured using this - Google Patents

Description

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 film-type optical component that extracts three colors of red, green, and blue from white light and enables them in minute pixel units. The size of one pixel is about several tens to several hundreds of micrometers. Is. Such a color filter has a black matrix layer formed in a pattern defined on a transparent substrate to block the boundary portion between each pixel, and a plurality of colors (usually, a plurality of colors) to form each pixel. It has a structure in which pixel portions in which the three primary colors (red (R), green (G), and blue (B)) are arranged in a predetermined order are laminated in order.

Recently, as one of the methods for realizing a color filter, a pigment dispersion method using a pigment dispersion type photosensitive resin has been applied, but the light emitted from the light source passes through the color filter. There is a problem that a part of the light is absorbed by the color filter and the light efficiency is lowered, and the color reproduction is lowered due to the characteristics of the pigment contained in the color filter.

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

Specifically, Republic of Korea Published Patent No. 2007-0094679 discloses that color reproducibility can be enhanced by having a color filter layer formed of quantum dots (Quantum Dot), and Republic of Korea Published Patent No. 2009- No. 0036373 discloses that the emission efficiency can be improved and the display quality can be improved by replacing the existing color filter with a light emitting layer made of a quantum dot phosphor.

However, the photosensitive resin composition developed for manufacturing color filters up to now has sufficient requirements such as sufficient development speed control, fine pattern formation, excellent light efficiency and securing of viewing angle for use in the process. Did not meet.

The present invention solves the problem caused by the residue in the process, improves the problem of display failure, and secures excellent light efficiency and viewing angle by controlling the development speed and eliminating the residue of the fine pattern. It is an object of the present invention to provide a color filter, particularly a blue photosensitive resin composition capable of realizing a self-luminous color filter, and a color filter and an image display device manufactured by using the same.

The present invention is a blue photosensitive resin composition containing scattered particles, a blue colorant, a cardo-based binder resin as a binder resin, a photoinitiator, a photopolymerizable compound, a thermosetting agent, and a solvent, and the photopolymerizable. The compound provides a blue photosensitive resin composition, which comprises a photopolymerizable compound containing an alkylene oxide.

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

Further, the present invention provides an image display device including the color filter and a light source that emits blue light.

The present invention solves the problem that appears due to the residue in the process by controlling the development speed by containing the photopolymerizable compound containing the alkylene oxide in the blue photosensitive resin composition and eliminating the residue of the pattern. Provided is a color filter in which the problem of display defects is improved and the problem of undeveloped resist is improved. Further, by adjusting the taper, it is possible to provide a self-luminous color filter having an excellent viewing angle and high quality image quality.

The blue photosensitive resin composition of the present invention can contain scattered particles, a blue colorant, a cardo-based binder resin as a binder resin, a photoinitiator, a photopolymerizable compound, and a solvent, and in particular, the photopolymerizable compound. A color filter containing a blue pattern layer produced using the blue photosensitive resin composition of the present invention by containing a photopolymerizable compound containing ethylene oxide or propylene oxide controls the development rate and leaves a pattern. By eliminating the above, the problem caused by the residue in the process can be solved. Further, it is possible to provide a color filter in which the problem of display defects is improved and the problem of undeveloped resist is improved, particularly a self-luminous color filter. Further, it is possible to provide a color filter having a high quality image quality having an excellent viewing angle, particularly a self-luminous color filter, and an image display device including the self-luminous color filter.

Hereinafter, the configuration of the present invention will be described in detail.
Scattered particles
The scattered particles of the present invention may be a metal oxide having an average particle size of 10 to 1000 nm, and more preferably in the range of 30 to 500 nm. At this time, if the average particle size is less than the above range, a sufficient scattering effect of the incident light cannot be expected, and if the average particle size exceeds the above range, it is settled in the composition or is uniform. The surface of the self-luminous layer of quality cannot be obtained.

The metal oxides include 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, It may be an oxide containing one kind of metal selected from the group consisting of Nb, Ce, Ta, In, and combinations thereof. More specifically, a group consisting of Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , Bathio ₃ , TIO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ZnO, Nb ₂ O ₃ , SnO, MgO, and the like. It may be one or more selected from the above. If necessary, materials surface-treated with compounds having unsaturated bonds, such as acrylates, can also be used.

The average particle size and the content of the scattered particles in the overall composition can be appropriately adjusted as necessary so that the emission intensity of the color filter can be sufficiently improved.

Further, the scattered particles may be contained in an amount of 0.1 to 50% by weight, preferably 5 to 35% by weight, based on the total weight of the solid content in the blue photosensitive resin. When the scattered particles are within the above preferable range, the effect of increasing the emission intensity can be obtained, and the stability of the composition can be ensured.

Blue Colorant In the blue colorant of the present invention, examples of the blue pigment include compounds classified as pigments in the color index (The society of Dyers and Colorists), and more specifically, the compounds are classified as pigments. The following pigments having a color index (CI) number can be mentioned, but the pigments are not necessarily limited thereto. Specifically, the blue pigment is described in, for example, C.I. I. Pigment Blue 15: 3, 15: 4, 15: 6, 16, 21, 28, and 76, and the like, C.I. I. It is preferable to include one or more 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 contain a blue dye, and as a blue dye, a compound or a dyeing note (color dyeing company) classified as a dye in the Color Index (The Society of Dyers and Colorists). ), The known dyes described in) are mentioned.

The dyes that can be additionally used are as follows.
C. I. As a solvent dye
C. I. Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67 and 70 and the like can be mentioned. I. It is more preferable to contain one or more of Solvent Blue 35, 36, 44, 45 and 70.

In addition, C.I. I. As an acid dye
C. I. 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 are mentioned, and among them, C.I. I. It is more preferable to contain one or more of Acid Blue 80 and 90.

Furthermore, C.I. I. As a direct dye
C. I. 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 and the like.

C. I. Modant 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 and the like.

The blue dyes can be used alone or in combination of two or more.
The blue colorant of the present invention may further contain a purple colorant as an additional colorant. The purple colorant can contain one or more of a purple pigment and a purple dye, wherein the purple pigment is specifically C.I. I. Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37 and 38, among others, C.I. I. It is more preferable to include Pigment Violet 23.

Specifically, the purple dye is C.I. I. Solvent Violet, C.I. I. Acid Violet, C.I. I. Acid Violet, C.I. I. Examples include, but are not limited to, Modant Violet.

Specifically, the above-mentioned C.I. I. Solvent Violet is C.I. I. Solvent Violet 8, 9, 13, 14, 36, 37, 47 and 49 and the like can be mentioned. I. It is more preferable to include solvent violet 13. C. I. As acid violet, C.I. I. Acid Violet 6B, 7, 9, 17, 19 and 66 and the like can be mentioned. I. It is more preferable to include acid violet 66. C. I. As direct violet, C.I. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104 and the like.

In addition, C.I. I. Modant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58 and the like.

The blue colorant can 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 content in the blue photosensitive resin. When the content of the blue colorant satisfies the above range, the reflection of external light can be suppressed, the emission intensity of the color can be effectively shown, and the stability of the viscosity can be ensured.

In the present invention, although it does not contain blue quantum dots, it is possible to prevent a decrease in the efficiency of blue pixels of a color filter, particularly a self-luminous color filter, by containing a blue colorant and scattered particles.

Binder resin The binder resin of the present invention includes a cardo-based binder resin. The cardo-based binder resin has reactivity and alkali solubility due to the action of light and heat, and acts as a dispersion medium for a coloring material. The cardo-based binder resin contained in the blue photosensitive resin composition of the present invention acts as a binder resin for scattered particles and is a resin that can be dissolved in an alkaline developer used in the developing stage for producing a color filter. If so, it is not limited.

The cardo-based binder resin of the present invention may contain one or more of the compounds represented by the chemical formulas 1-1 and 1-2.
[Chemical 1-1]

[Chemical 1-2]

In the above chemical formula 1-1 or chemical formula 1-2,
R ₁ , R ₂ , R ₃ and R ₄ are independent of each other.

And;
X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group;
R5 is a hydrogen atom or an alkyl group having 1 to ₅ carbon atoms.

In the present invention, the compound represented by the chemical formula 1-1 is synthesized by the compound represented by the following chemical formula 2-1 and the compound represented by the chemical formula 1-2 is a compound represented by the chemical formula 2-2. May be synthesized using.

In the present invention, the compound represented by the chemical formula 1-1 is synthesized by the compound represented by the following chemical formula 2-1 and the compound represented by the chemical formula 1-2 is a compound represented by the chemical formula 2-2. It may be synthesized using.
[Chemical 2-1]

[Chemical 2-2]

Specifically, the compound represented by the chemical formula 1-1 is one or more of the compounds represented by the chemical formula 1-1-1 and the chemical formula 1-1-2, and is represented by the chemical formula 1-2. The compound represented may be one or more of the compounds represented by Chemical Formula 1-2-1 and Chemical Formula 1-2-2.
[Chemical 1-1-1]

[Ka 1-1-2]

[Ka 1-2-1]

[Ka 1-2-2]

The cardo-based binder resin is 9,9-bis (3-cinnamic diester) fluorene (9,9-bis (3-cinnamic diester) fluorene), 9,9-bis (3-cinnamoil, 4-hydroxyphenyl). Fluorene (9,9-bis (3-cinnamoil, 4-hydridehydreyl) fluorene), 9,9-bis (glycidyl methacrylate ether) fluorene (9,9-bis (glycyl methyllate ether) fluorene), 9,9-bis (9,9-bis) 3,4-Dihydroxyphenyl) Full orange cinnamic ester (9,9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester), 3,6-diglycidyl methacrylate ether spiro (fluoren-9,9-xanthene) (3) , 6-dillycydyl methacryllate theer spiro (fluorene-9,9-xantene), 9,9-bis (3-allyl, 4-hydroxyphenylfluorene) (9,9-bis (3-allyl, 4-hydroxyphenylfluorene)) , 9,9-bis (4-allyloxyphenyl) fluorene (9,9-bis (4-allyloxyphenyl) fluorene), and 9,9-bis (3,4-methacrylicdiester) fluorene (9,9-bis). At least one selected from the group consisting of (3,4-methacryldiester) fluorene), and as an acid anhydride compound, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrogen anhydride. A group consisting of hydrophthalic acid, methylenedomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, or as an acid dianhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid 2 anhydride, biphenyltetracarboxylic acid 2 It can be produced by reacting with at least one selected from the group consisting of aromatic polyvalent carboxylic acid anhydrides such as anhydrides and biphenyl ether tetracarboxylic acid dianhydrides, but the present invention is not limited thereto.

The present invention may further contain an acrylic alkali-soluble resin as the binder resin. Examples of the acrylic alkali-soluble resin include a carboxyl group-containing monomer and a copolymer of this monomer with another copolymerizable monomer. Examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, and other unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule. Carboxylic acid and the like can be mentioned. Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples thereof include maleic acid anhydride, itaconic acid anhydride, and citraconic acid anhydride. The unsaturated polyvalent carboxylic acid may be a mono (2-methacrylicyloxyalkyl) ester thereof, for example, monosuccinic acid (2-acryloyloxyethyl), monosuccinic acid (2-methacryloyloxyethyl), phthalate. Examples thereof include acid mono (2-acryloyloxyethyl) and phthalate mono (2-methacryloyloxyethyl). The unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxypolymer having both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These carboxyl group-containing monomers can be used alone or in admixture of two or more. Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o. -Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p. -Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and inden; 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-hydroxyethyl 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-methoxyethyl 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 G, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl 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, glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2 -Aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate Unsaturated carboxylic acid aminoalkyl esters such as; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; vinyl methyl ether , Vinyl ethyl ethers, unsaturated ethers such as allylglycidyl ethers; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylicamide, α-chloroacrylamide, N-2- Unsaturated amides such as hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylate; unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; 1,3-butadiene, isoprene, chloroprene and the like. Acrylic conjugated dienes; and monoacryloyl or monomethacryloyl groups at the ends of the polymer molecular chains of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane. Examples thereof include giant monomers having. These monomers can be used alone or in admixture of two or more. In particular, as other monomers copolymerizable with the carboxyl group-containing monomer, bulky monomers such as a monomer having a norbornyl skeleton, a monomer having an adamantan skeleton, and a monomer having a rosin skeleton. This is preferable because the body tends to reduce the specific dielectric constant value.

The cardo-based binder resin and / or the acrylic-based alkali-soluble resin of the present invention preferably has an acid value in the range of 20 to 200 (KOHmg / g). When the acid value is within the above range, the solubility in the developing solution is improved, the non-exposed part is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed part remains during development and the residual film ratio. It is preferable because it improves (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 is usually titrated by using an aqueous potassium hydroxide solution. Desired. Further, the polystyrene-equivalent weight average molecular weight (hereinafter, simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC; tetrahydrofuran is used as an elution solvent) is 2,000 to 200,000, preferably 3,000. A cardo-based binder resin or an acrylic-based alkali-soluble resin of up to 100,000 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 developing solution 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 alkali-soluble resin is preferably 1.0 to 6.0, preferably 1.5 to 6. The one with 0 is more preferable. When the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5 to 6.0, it is preferable because it is excellent in developability.

The binder resin of the present invention can be used 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 within the above range, the solubility in the developing solution is sufficient, the development residue is less likely to be generated on the substrate of the non-pixel portion, and the film of the pixel portion of the exposed portion is less likely to be reduced during development. , It is preferable because the missing property of the non-pixel portion tends to be good.

Photopolymerizable Compound The photopolymerizable compound contained in the blue photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and specifically contains an alkylene oxide. Examples thereof include photopolymerizable compounds, preferably photopolymerizable compounds containing ethylene oxide and / or propylene oxide. When the photopolymerizable compound to which ethylene oxide and / or propylene oxide is added is contained, various problems caused by the residue in the process can be solved by controlling the development rate and eliminating the residue of the pattern. Display defects can be improved, resist undeveloped can be eliminated, and an excellent viewing angle can be formed by adjusting the taper or the like, and an element with high quality image quality can be manufactured.

Examples of the photopolymerizable compound containing the alkylene oxide include an alkylene oxide-modified pentaerythritol (meth) acrylate compound, an alkylene oxide-modified dipentaerythritol (meth) acrylate compound, an alkylene oxide-modified trimethylolpropane (meth) acrylate compound, and an alkylene oxide. Examples thereof include modified glycerin (meth) acrylate compounds, and more specifically, ethylene oxide-modified trimethylol propantriacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, ethylene oxide-modified pentaerythritol tetraacrylate, ethylene oxide-modified pentaerythritol tetraacrylate, and propylene oxide-modified. Examples thereof include pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hexaacrylate, propoxylated pentaerythritol polyacrylate, propoxylated dipentaerythritol hexaacrylate, and ethoxylated glycerin triacrylate. More preferably, it contains ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hexaacrylate, and propoxylated pentaerythritol polyacrylate.

The blue photosensitive resin composition of the present invention may further contain ordinary photopolymerizable compounds free of alkylene oxides. Specific examples thereof include photopolymerizable compounds using monofunctional monomers and bifunctional monomers that do not contain ethylene oxide and propylene oxide, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like. 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, and bisphenol. Examples thereof include bis (acryloyloxyethyl) ether of A and 3-methylpentanediol di (meth) acrylate. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol. Hexa (meth) acrylate and the like can be mentioned. Of these, polyfunctional monomers having two or more functionalities are preferably used. The photopolymerizable compound can be used 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 photopolymerizable compound is in the above range, the light sensitivity is not reduced, the film strength is sufficient, the pattern does not disappear during development, the pattern is well constructed even in the fine pattern portion, and the resist is used. It is preferable because the smoothness tends to be good.

Photoinitiator The photoinitiator used in the present invention has a role of initiating a radical reaction of the photosensitive resin composition to cause curing and improving sensitivity, and preferably contains an acetophenone-based compound. Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]. -2-Methylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-one Examples thereof include (4-morpholinophenyl) butane-1-one, 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propan-1-one oligomers, and the like, preferably 2-benzyl-2. -Dimethylamino-1- (4-morpholinophenyl) butane-1-one and the like can be mentioned. Further, a photopolymerization initiator other than the acetophenone-based agent can be used in combination. Examples of the photopolymerization initiator other than the acetophenone-based photopolymerization initiator include active radical generators, sensitizers, and acid generators that generate active radicals when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds and the like. Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoisobutyl ether. Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (t-butylperoxy). Carbonyl) Benzophenone, 2,4,6-trimethylbenzophenone and the like can be mentioned. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-). Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -[2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl]- 1,3,5-Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (3,4 dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like can be mentioned. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2, -bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2. '-Bimidazole, 10-butyl-2-chloroacrydone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglycyloxylate, titanosen compounds and the like can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, and 4-acetoxyphenylmethylbenzylsulfonium hexa. Onium salts such as fluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylate, benzointosylate, etc. Can be mentioned. Further, as the active radical generator, some of the compounds generate an acid at the same time as the active radical. For example, a triazine-based photopolymerization initiator is also used as an acid generator.

The photoinitiator 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. If it is within the above range, the sensitivity of the blue photosensitive resin composition is increased, and the strength of the pixel portion formed by using this composition and the smoothness on the surface of the pixel portion tend to be improved. preferable.

Further, in the present invention, a photopolymerization initiation aid can be used. The photopolymerization initiator is a compound that may be used in combination with a photopolymerization initiator and is used to promote the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. Examples of the photopolymerization initiator include amine-based compounds, alkoxyanthracene-based compounds, and thioxanthone-based compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. , 2-Ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzphenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4, Examples thereof include 4'-bis (ethylmethylamino) benzophenone, and among them, 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. .. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. Such a photopolymerization initiator (D) may be used alone or in combination of two or more without any problem. Further, a commercially available photopolymerization initiator can be used, and examples of the commercially available photopolymerization initiator include the trade name "EAB-F" [manufacturer: Hodogaya Chemical Co., Ltd.]. Be done.

When these photopolymerization initiators are used, the amount used is usually 10 mol or less, preferably 0.01 to 5 mol, per 1 mol of the photopolymerization initiator. Within the above range, the sensitivity of the blue photosensitive resin composition is further increased, and the productivity of the color filter formed by using this 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 glycol dipropyl ether, and diethylene glycol di. Diethylene glycol dialkyl ethers such as butyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxy. Alkylene glycol alkyl ether acetates such as pentylacetate, aromatic hydrocarbons such as benzene, toluene, xylene, methethylene, ketones such as methylethylketone, acetone, methylamylketone, methylisobutylketone, cyclohexanone, ethanol, propanol, butanol, Examples thereof include alcohols such as hexanol, cyclohexanol, ethylene glycol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone. Among the solvents, organic solvents having a boiling point of 100 to 200 are preferable, and alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy are preferable from the viewpoint of coatability and drying property. Examples thereof include esters such as ethyl propionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and 3-methoxypropionate. Examples include methyl. These solvents can be used alone or in admixture of two or more.

The content of the solvent in the blue photosensitive resin composition of the present invention may be 60 to 90% by weight, preferably 60 to 85% by weight, based on the total amount of the blue photosensitive resin composition containing the solvent. When the solvent content is within the above range, the coatability is improved when applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an inkjet. It is preferable because it tends to be.

Additives The blue pattern layer blue photosensitive resin composition according to the present invention is, if necessary, a filler, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, antiaggregating agents. Additives such as may be additionally included.

Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastics such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and polyurethanes. Examples include resin.

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. Be done. These can be used alone or in combination of two or more.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl diethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethylene imines and the like. Yes, and other product names include KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Talkem Products Co., Ltd.), and Megafuck (MEGAFAC). (Manufactured by Dainippon Ink and Chemicals Co., Ltd.), Florad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surfron (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (Manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA Chemical Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Ltd.) and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Examples thereof include trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di- <81> t-butyl-4-methylphenol and the like. ..

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

Specific examples of the antiaggregating agent include sodium polyacrylate and the like.
The additive can be appropriately added and used by those skilled in the art as long as the effect of the present invention is not impaired. For example, the additive is 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 entire blue photosensitive resin composition. However, it is not limited to this.

The blue photosensitive resin composition according to the present invention is produced, for example, by the following method. The scattered particles are mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle size becomes 30 to 500 nm. At this time, if necessary, a dispersant may be additionally used, or a part or all of the binder resin may be blended. The obtained dispersion (hereinafter, also referred to as mil-based) contains the residue of the binder resin, a photopolymerizable compound, a photopolymerization initiator, other components used as necessary, and an additional solvent as needed. The desired blue photosensitive resin composition can be obtained by further adding the mixture so as to have a predetermined concentration.

<Color filter and image display device>
Yet another aspect of the present invention relates to a color filter containing a blue pattern layer containing a cured product of the above-mentioned blue photosensitive resin composition for forming a blue pattern layer.

Since the color filter according to the present invention is manufactured by the above-mentioned blue photosensitive resin composition for forming a blue pattern layer instead of the blue quantum dots, there is an advantage that the manufacturing cost can be reduced and an excellent viewing angle can be secured. be.

Further, a color filter containing a blue pattern layer produced by using the blue photosensitive resin composition of the present invention by containing a photopolymerizable compound containing ethylene oxide or propylene oxide in the blue photosensitive resin composition of the present invention can be used. By controlling the development speed and eliminating the residue of the pattern, the problem caused by the residue in the process is solved, the problem of display failure is improved, and the problem of undeveloped resist is improved. Color filters, especially self-luminous color. It is possible to realize a filter.

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

The substrate may be the color filter itself or a portion where the color filter is located in 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, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC). And so on.

The blue pattern layer is a layer containing the blue photosensitive resin composition of the present invention, and is formed by applying the blue photosensitive resin composition for forming the blue pattern layer and exposing, developing, and heat-curing the predetermined pattern. The pattern layer may be formed by a method generally known in the art.

In yet another embodiment of the invention, the color filter may further comprise one or more selected from the group consisting of a red pattern layer and a green pattern layer.

In yet another embodiment of the invention, the red or green pattern layer may include quantum dots and / or scattered particles. Specifically, the color filter according to the present invention can include a red pattern layer containing red quantum dots or a green pattern layer containing green quantum dots, and the red pattern layer or green pattern layer contains scattered particles. be able to. The red pattern layer or the green pattern layer can emit red light or blue light, respectively, by a light source that emits blue light, which will be described later.

In still another embodiment of the present invention, the scattered particles contained in the red pattern layer or the green pattern layer can contain a metal oxide having an average particle size of 30 to 500 nm, and the scattered particles and the metal oxide can be contained. As the content, the content relating to the scattered 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 form, configuration, and content of the quantum dots contained in the red pattern layer or the green pattern layer are not limited, and quantum dots commonly used in the art can be applied.

A color filter including a substrate and a pattern layer as described above may further include, but is not limited to, a partition wall formed between each pattern and may further include a black matrix.

In the present invention, the color filter may be a self-luminous color filter.
Yet another aspect of the present invention relates to an image display device including the color filter described above and a light source that emits blue light. In short, the image display device according to the present invention includes a color filter including a blue pattern layer containing 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 can be applied not only to a normal liquid crystal display device but also to various image display devices such as a field emission 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 emission intensity or viewing angle. Further, since the blue pattern layer included in the color filter according to the present invention does not contain blue quantum dots, there is an advantage that an image display device having a low manufacturing cost can be manufactured.

Hereinafter, in order to specifically explain the present specification, examples will be given and described in detail. However, the embodiments according to the present specification can be transformed into various different forms, and the scope of the present specification is not construed to be limited to the examples detailed below. The examples herein are provided to provide a more complete description of the specification to those with average knowledge in the art. Further, hereinafter, “%” and “part” indicating the content are based on weight unless otherwise specified.

Synthesis example: Synthesis of binder resin Production example 1: Acrylic-based alkali-soluble resin A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen introduction tube is prepared, while benzylmaleimide 74. As a monomer dropping funnel. 8 g (0.20 mol), acrylic acid 43.2 g (0.30 mol), vinyl toluene 118.0 g (0.50 mol), t-butylperoxy-2-ethylhexanoate 4 g, propylene glycol monomethyl ether After adding 40 g of acetate (PGMEA), the mixture was stirred and mixed to prepare, and as a chain transfer agent dropping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were added and mixed by stirring. After that, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and then the temperature of the flask was raised to 90 ° C. while stirring. Next, the monomer and the chain transfer agent were started to be added dropwise from the dropping funnel. The dropping was carried out for 2 hours while maintaining 90 ° C., and after 1 h, the temperature was raised to 110 ° C. and maintained for 3 hours, and then a gas introduction tube was introduced to oxygen / nitrogen = 5/95 (v / v). Bubbling of the mixed gas was started. Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% with respect to the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis (4-methyl-6-t). -Butylphenol) 0.4 g and triethylamine 0.8 g were put into a flask and the reaction was continued at 110 ° C. for 8 hours to obtain a resin A having a solid acid value of 70 mgKOH / g. The polystyrene-equivalent weight average molecular weight measured by GPC was 16,000, and the molecular weight distribution (Mw / Mn) was 2.3.

Production Example 2: Synthesis of Compound of Chemical Formula 1-1-1 In a 3000 ml three-necked round-bottom flask, 3', 6'-dihydroxyspiro (fluorene-9,9-xanthene) (3', 6'-dihydroxyspiro (fluorene) -9,9-xanthene)) 364.4 g and 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added, and the mixture was heated to 90 ° C. for reaction. When 3,6-dihydroxyspiro (fluorene-9,9-xanthene) was completely exhausted by analysis by liquid chromatography, the temperature was cooled to 30 ° C. and a 50% aqueous NaOH solution (3 equivalents) was slowly added. After analysis by liquid chromatography and complete exhaustion of epichlorohydrin, extraction with dichloromethane, washing with water three times, drying the organic layer with magnesium sulfate, distillation of dichloromethane under reduced pressure, dichloromethane and methanol are performed. It was recrystallized using a mixing ratio of 50:50 with.

After mixing 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid, the solvent propylene glycol monomethyl ether acetate 24 .89 g was added and mixed. The reaction solution was heated and dissolved at a temperature of 90 to 100 ° C. while blowing air at 25 ml / min. The reaction solution was heated to 120 ° C. in a cloudy state to completely dissolve it. When the solution became transparent and the viscosity became high, 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 1-1-1.
[Chemical 1-1-1]

Production Example 3: Synthesis of Compound of Chemical Formula 1-1-2 In a 3000 ml three-necked round-bottom flask, 3', 6'-dihydroxyspiro (fluorene-9,9-xanthene) (3', 6) of Chemical Formula 2-1 364.4 g of'-dihydroxyspiro (fluorene-9,9-xanthene)) and 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added, and the mixture was heated to 90 ° C. for reaction. When 3,6-dihydroxyspiro (fluorene-9,9-xanthene) was completely exhausted by analysis by liquid chromatography, the temperature was cooled to 30 ° C. and a 50% aqueous NaOH solution (3 equivalents) was slowly added. When the epichlorohydrin is completely exhausted by analysis by liquid chromatography, it is extracted with dichloromethane, washed with water three times, the organic layer is dried with magnesium sulfate, and dichloromethane is distilled under reduced pressure. It was recrystallized using a mixing ratio of 50:50.

After mixing 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of methacrylic acid, the solvent propylene glycol monomethyl ether acetate is used. 24.89 g was added and mixed. The reaction solution was heated and dissolved at a temperature of 90 to 100 ° C. while blowing air at 25 ml / min. The reaction solution was heated to 120 ° C. in a cloudy state to completely dissolve it. When the solution became transparent and the viscosity became high, 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 1-1-2.
[Ka 1-1-2]

Production Example 4: Synthesis of Compound of Chemical Formula 1-2-1 In a 3000 ml three-necked round-bottom flask, 4,4'-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9H-) 364.4 g of xanthene-9,9-diyl) diphenyl) and 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added, and the mixture was heated at 90 for reaction. When analyzed by liquid chromatography and the 4,4'-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9Hxanthene-9,9-diyl) diphenyl) is completely exhausted, the temperature is 30 ° C. A 50% aqueous NaOH solution (3 equivalents) was slowly added. When the epichlorohydrin is completely exhausted by analysis by liquid chromatography, it is extracted with dichloromethane, washed with water three times, the organic layer is dried with magnesium sulfate, and dichloromethane is distilled under reduced pressure. It was recrystallized using a mixing ratio of 50:50. After mixing 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid, the solvent propylene glycol monomethyl ether acetate 24 .89 g was added and mixed. The reaction solution was heated and dissolved at a temperature of 90 to 100 ° C. while blowing air at 25 ml / min. The reaction solution was heated to 120 ° C. in a cloudy state to completely dissolve it. When the solution became transparent and the viscosity became high, 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 1-2-1.
[Ka 1-2-1]

Production Example 5: Synthesis of Compound of Chemical Formula 1-2-2 In a 3000 ml three-necked round-bottom flask, 4,4'-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9H-) 364.4 g of xanthene-9,9-diyl) diphenyl) and 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added, and the mixture was heated to 90 ° C. for reaction. When analyzed by liquid chromatography and the 4,4'-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9Hxanthene-9,9-diyl) diphenyl) is completely exhausted, the temperature is 30 ° C. A 50% aqueous NaOH solution (3 equivalents) was slowly added. When the epichlorohydrin is completely exhausted by analysis by liquid chromatography, it is extracted with dichloromethane, washed with water three times, the organic layer is dried with magnesium sulfate, and dichloromethane is distilled under reduced pressure. It was recrystallized using a mixing ratio of 50:50. After mixing 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of methacrylic acid, the solvent propylene glycol monomethyl ether acetate is used. 24.89 g was added and mixed. The reaction solution was heated and dissolved at a temperature of 90 to 100 ° C. while blowing air at 25 ml / min. The reaction solution was heated to 120 ° C. in a cloudy state to completely dissolve it. When the solution became transparent and the viscosity became high, 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 1-2-2.
[Ka 1-2-2]

Production Example 6: Synthesis of cardo-based binder resin (A-1)
After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Chemical Formula 1-1-1 of Production Example 2 and dissolving it, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually. The temperature was raised and the reaction was carried out at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize on a cardo-based binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 3500
Production Example 7: Synthesis of cardo-based binder resin (A-2)
After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Chemical Formula 1-1-2 of Production Example 3 and dissolving it, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually. The temperature was raised and the reaction was carried out at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize on a cardo-based binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 3800
Production Example 8: Synthesis of cardo-based binder resin (A-3)
After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Chemical Formula 1-2-1 of Production Example 4 and dissolving it, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually. The temperature was raised and the reaction was carried out at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize on a cardo-based binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 4500
Production Example 9: Synthesis of cardo-based binder resin (A-4)
After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Chemical Formula 1-2-2 of Production Example 5 and dissolving it, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually. The temperature was raised and the reaction was carried out at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize on a cardo-based binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 4900
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° 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)
Calibration standard material: 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 and the number average molecular weight obtained above was defined as the molecular weight distribution (Mw / Mn).

Examples 1 to 9 and Comparative Examples 1 to 7: Production of blue photosensitive resin compositions The blue photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were produced according to the compositions of Tables 1 to 3 below. .. (Table 1 shows the scattered particles, and Table 2 shows the composition and content of the compositions of Examples and Comparative Examples.)

Production of Color Filter A color filter was produced using the metal oxide photosensitive resin compositions produced in the above Examples and Comparative Examples. That is, each of the photosensitive resin compositions was applied onto a glass substrate by a spin coating method, then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film.

Next, a test photomask having a horizontal × vertical 20 mm × 20 mm square transmission pattern and a line / space pattern of 1 to 100 μm is placed on the thin film, and the space between the test photomask and the test photomask is set to 100 μm to irradiate ultraviolet rays. did.

At this time, the ultraviolet light source is an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio, Inc., which is irradiated with light at an exposure amount (365 nm) of 200 mJ / cm ² under an atmospheric atmosphere, and special optics is used. No filter was used.

The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds for development. The glass plate covered 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 produce a color filter pattern. The film thickness of the color pattern produced above was 5.0 μm.

Experimental Example 1: Development speed, sensitivity, pattern stability, taper line width and morphological experiment of a color filter For a color filter produced from the blue photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3. The evaluation was made as shown in Table 3 below. The evaluation criteria for each experiment are as follows.

Development speed (sec): Time required for the unexposed area to first dissolve in the developer during development <Spray Developer HPMJ method> Sensitivity: Degree of forming a thin film without biting into the sensitivity mask fine pattern (1 to 60). (The lower the value, the better the sensitivity)
Pattern stability: Degree of pattern error after exposure of the pattern mask at low exposure (20 to 100 mJ) ○: No error on the pattern X: 3 or more errors on the pattern ○, X are three-dimensional surface shapes Confirmation result by the optical microscope of the vessel.

Taper line width (μm): The line width after exposure of the 100 μm pattern of the pattern mask.

If the development speed exceeds 60 seconds, production is impossible within a given process time, and if it exceeds 30 seconds, the roughness of the pattern surface becomes uneven and the uniformity may decrease. It was confirmed that Examples 1 to 5 of the present invention had excellent development speeds of less than 30 seconds and sensitivity of 60 or less, and had excellent effects in both pattern stability and taper line width. On the other hand, in the case of Comparative Example 1, scattered particles were not included, the pattern stability was unstable, and the pattern was imbalanced. In the case of Comparative Example 2, if the scattering particles and the blue colorant cannot be strongly supported only by the cardo-based binder resin if they are bonded only with the acrylic resin, they are peeled off, and in the case of Comparative Example 3, ethylene oxide and propylene oxide are not contained. In the case of the photopolymerizable compound, it was confirmed that the development speed was significantly reduced, and that the long development speed caused an imbalance between the pattern stability and the pattern.

Experimental Example 2: Measurement of fine pattern Among the color filters manufactured using the metal oxide photosensitive resins manufactured in Examples 1 to 5 and Comparative Examples 1 to 3, the line / space pattern designed to be 100 μm. The size of the pattern obtained through the mask was measured by OM equipment (ECLIPSE LV100POL Nikon Co., Ltd.), and the results are shown in Table 4 below.

If the difference between the design value of the line / space pattern mask and the measured value of the obtained fine pattern is 20 μm or more, it becomes difficult to realize fine pixels.

Therefore, as can be confirmed from Table 4, in the case of Examples 1 to 4 containing the photopolymerizable compound to which ethylene oxide and propylene oxide were added, it was confirmed that a fine pattern of less than 20 μm was formed. On the other hand, in the cases of Comparative Examples 1 to 3, it was confirmed that the fine pattern was poorly formed or peeled off and the presence or absence of pattern formation could not be confirmed.

Experimental Example 3: Measurement of light emission intensity Among the color filters manufactured using the metal oxide photosensitive resins manufactured in Examples 1 to 5 and Comparative Examples 1 to 3, the color filters were formed into a 20 × 20 mm square pattern. The region light-converted by a 365 nm Tube type 4W UV irradiator (VL-4LC, VILBER LOURMAT) was measured in the portion, and Examples 1 to 5 and Comparative Examples 1 to 3 showed emission intensity in the region of 450 nm. Was measured using a Spectrum meter (Ocean Optics). The results are shown in Table 5 below.

The higher the measured emission intensity, the higher the light efficiency. Therefore, looking at the table, it was confirmed that in the cases of Examples 1 to 5 containing the photopolymerizable compound to which ethylene oxide and propylene oxide were added, the emission intensity was excellently improved to 3 or more. On the other hand, in the cases of Comparative Examples 1 to 3, it was confirmed that the light efficiency was reduced to 2 or less.

Experimental Example 4: Measurement of viewing angle Among the color filters manufactured using the metal oxide photosensitive resins manufactured in Examples 1 to 5 and Comparative Examples 1 to 3, they were formed into a square pattern of 20 × 20 mm. The light intensity due to the viewing angle under the light transmission condition was measured using a variable angle photometric meter (GC-5000L, Nippon Denshoku), and the diffusion rate was calculated using the following formula 1.
[Equation 1]

Diffusion rate = (B ₇₀ + B ₂₀ ) / 2 x B ₅ x 100
(B _θ = I _θ / cos θ)
I means the optical intensity measured at each angle, and B ₇₀ , B ₂₀ and B ₅ mean that the light was measured at 70 degrees, 20 degrees and 5 degrees.

The higher the measured diffusion rate, the better the viewing angle. Therefore, looking at the above table, it is confirmed that Examples 1 to 5 containing the photopolymerizable compound to which ethylene oxide and propylene oxide are added have a diffusion rate of 85 or more and a very excellent improvement in viewing angle. Was made. On the other hand, in the cases of Comparative Examples 1 and 3, it was confirmed that the diffusivity was remarkably lowered as compared with Examples 1 to 5, the viewing angle was lowered, or the diffusivity could not be measured due to peeling.

The present invention solves the problem that appears due to the residue in the process by controlling the development speed by containing the photopolymerizable compound containing the alkylene oxide in the blue photosensitive resin composition and eliminating the residue of the pattern. Provided is a color filter in which the problem of display defects is improved and the problem of undeveloped resist is improved. Further, by adjusting the taper, it is possible to provide a self-luminous color filter having an excellent viewing angle and high quality image quality.

Claims (15)

A blue photosensitive resin composition comprising scattered particles, a blue colorant, a photoinitiator, a cardo-based binder resin as a binder resin, and a photopolymerizable compound containing an alkylene oxide as a photopolymerizable compound.
The blue photosensitive resin composition, wherein the cardo-based binder resin contains one or more of the compounds represented by the following chemical formulas 1-1 and 1-2.
[Chemical 1-1]

[Chemical 1-2]

(In the above chemical formula 1-1 or chemical formula 1-2, R ₁ , R ₂ , R ₃ and R ₄ are independently, respectively.

And;
X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group;
R5 is a hydrogen atom or an alkyl group having 1 to ₅ carbon atoms. ) The blue photosensitive resin composition according to claim 1, wherein the scattered particles contain a metal oxide having an average particle size of 10 to 1000 nm. The scattered particles are selected from the group consisting of Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , Bathio ₃ , TIO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ZnO, Nb ₂ O ₃ , SnO, and MgO. The blue photosensitive resin composition according to claim 1, wherein the blue photosensitive resin composition comprises one or more of them. The blue photosensitive resin composition according to claim 1, wherein the blue photosensitive resin composition further contains a purple colorant. The blue photosensitive resin composition according to claim 1, wherein the blue photosensitive resin composition further contains a photopolymerizable compound containing no alkylene oxide. The blue photosensitive resin composition according to claim 1, wherein the blue colorant contains one or more of a blue pigment and a blue dye. The cardo-based binder resin includes 9,9-bis (3-cinnamic diester) fluorene (9,9-bis (3-cinnamic diester) fluorene) and 9,9-bis (3-cinnamoyle, 4-hydroxyphenyl). Fluorene (9,9-bis (3-cinnamoil, 4-hydroxyphenyl) fluorene), 9,9-bis (glycidyl methacrylate ether) fluorene (9,9-bis (glycydl methyllate ether) fluorene), 9,9-bis (9,9-bis) 3,4-Dihydroxyphenyl) Fluorene cinnamic ester (9,9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester), 3', 6'-diglycidyl methacrylate ether spiro (fluorene-9,9'-xanthene) ) (3', 6'-diglicydyl methacrylate theer spiro (fluorene-9,9'-xanthene)), 9,9-bis (3-allyl, 4-hydroxyphenylfluorene) (9,9-bis (3-allyl) , 4-hydroxyphenylfluorene)), and 9,9-bis (4-allyloxyphenyl) fluorene (9,9-bis (4-allyloxyphenyl) fluorene) produced by reacting one or more of them. The blue photosensitive resin composition according to claim 1, wherein the fluorene photosensitive resin composition is characterized by the above. The blue photosensitive resin composition according to claim 1, wherein the blue photosensitive resin composition further contains an acrylic alkali-soluble resin as a binder resin. The photopolymerizable compound containing the alkylene oxide includes ethylene oxide-modified trimethylolpropane triacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, ethylene oxide-modified pentaerythritol tetraacrylate, propylene oxide-modified pentaerythritol tetraacrylate, and ethoxylated dipentaerythritol hexaacrylate. The blue photosensitive resin composition according to claim 1, which is one or more selected from the group consisting of acrylate, propoxylated pentaerythritol polyacrylate, propoxylated dipentaerythritol hexaacrylate, and ethoxylated glycerin triacrylate. Scattered particles 0.1 to 50% by weight; blue colorant 0.1 to 50% by weight; binder resin 5 to 85% by weight; photopolymerizable compound 5 to 5 to 50% by weight based on the total solid content in the blue photosensitive resin. 50% by weight; 0.1 to 30% by weight of photoinitiator; and 0.001 to 10% by weight of UV absorber containing one or more of benzotriazole, triazine, and benzophenone, said blue photosensitive. The blue photosensitive resin composition according to claim 1, which contains 60 to 90% by weight of a solvent with respect to the total weight of the sex resin composition. A color filter including a blue pattern layer made of the blue photosensitive resin composition according to any one of claims 1 to 10. The color filter according to claim 11, wherein the color filter further includes one or more selected from the group consisting of a red pattern layer and a green pattern layer. The color filter according to claim 12, wherein the red pattern layer or the green pattern layer includes quantum dots. The color filter according to claim 13, wherein the color filter is a self-luminous color filter. The color filter according to claim 11 and
An image display device including a light source that emits blue light.