KR102300331B1 - Blue photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

The present invention is a blue photosensitive resin composition comprising scattering particles, a blue colorant, a cardo-based binder resin as a binder resin, a photoinitiator, a photopolymerizable compound, and a solvent, wherein the photopolymerizable compound is a photopolymerizable compound containing an alkylene oxide It relates to a blue photosensitive resin composition comprising, a color filter and an image display device manufactured using the same.

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 sufficient development speed control, fine pattern formation, and excellent light efficiency and viewing angle for use in the process.

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

The present invention controls the development speed, eliminates the residue of the fine pattern, solves the problem caused by the residue in the process, improves the display defect, and implements a color filter, especially a self-luminous color filter, capable of securing excellent light efficiency and viewing angle An object of the present invention is to provide a possible blue photosensitive resin composition, a color filter and an image display device manufactured using the same.

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

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 present invention includes a photopolymerizable compound containing an alkylene oxide in the blue photosensitive resin composition to control the development speed, remove pattern residues, solve problems caused by residues in the process, and improve display problems, To provide a color filter in which the problem of undeveloped resist is improved. In addition, it is possible to provide a self-luminous color filter of high quality having an excellent viewing angle by adjusting the taper.

The blue photosensitive resin composition of the present invention may include a cardo-based binder resin, a photoinitiator, a photopolymerizable compound and a solvent as scattering particles, a blue colorant, and a binder resin, and in particular, the photopolymerizable compound includes ethylene oxide or propylene oxide. By including the photopolymerizable compound, the color filter including the blue pattern layer prepared by using the blue photosensitive resin composition of the present invention controls the development speed and eliminates the residue of the pattern to solve the problem that appears due to the residue in the process, It is possible to provide a color filter, in particular a self-luminous color filter, in which the display defect problem is improved and the problem of undeveloped resist is improved. In addition, it is possible to provide a high-quality color filter having an excellent viewing angle, particularly a self-luminous color filter, and an image display device including the same.

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 500 nm. At this time, when the average particle diameter is less than the above range, sufficient scattering effect of incident light cannot be expected, and when the average particle diameter is above the above range, it is not possible to sink in the composition or obtain a surface of the self-luminous layer of uniform quality.

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 , ZnO, Nb ₂ O ₃ , SnO, and MgO selected from the group consisting of There may be more than one type. 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.

In addition, the scattering particles may be included 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 scattering particles are within the above preferred range, it is possible to obtain an effect of increasing the luminescence intensity and ensure the stability of the composition.

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.

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 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, external light reflection can be suppressed, the luminous intensity of the color can be effectively displayed, and the stability of the viscosity can be secured.

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 1-1 and 1-2.

[Formula 1-1]

[Formula 1-2]

In Formula 1-1 or Formula 1-2,

이며; R ₁ , R ₂ , R ₃ and R ₄ are each independently,

is;

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

R ₅ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

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

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

[Formula 2-1]

[Formula 2-2]

Specifically, the compound represented by Formula 1-1 is at least one of the compounds represented by Formula 1-1-1 and Formula 1-1-2, and the compound represented by Formula 1-2 is Formula 1-2- 1 and may be at least one of compounds represented by Formula 1-2-2.

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-2-1]

[Formula 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-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) fluorene (9,9-bis (3,4-methacrylic diester) fluorene) as an acid anhydride compound with at least one selected from the group consisting of maleic anhydride, succinic anhydride, Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylene anhydride, pyromellitic anhydride, benzophenone as an acid dianhydride It may be prepared by reacting with at least one selected from the group consisting of aromatic polyhydric carboxylic acid anhydrides such as tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and bitenyl ether tetracarboxylic dianhydride, but is not limited thereto.

The present invention may further include an acrylic alkali-soluble resin as a binder resin. The acrylic alkali-soluble resin includes, for example, a carboxyl group-containing monomer and a copolymer of the monomer and other copolymerizable monomers. 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 alkali-soluble resin is preferable. 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 alkali-soluble 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 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 developer is sufficient, so that the development residue is hardly generated on the substrate of the non-pixel portion, and the film reduction of the pixel portion of the exposed portion is difficult to occur during development, so that the non-pixel portion is missing. This is preferable because it tends to be favorable.

photopolymerization 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 to be described later, specifically, a photopolymerizable compound including an alkylene oxide, preferably ethylene oxide and/or propylene oxide. and photopolymerizable compounds containing When the ethylene oxide and/or propylene oxide is included in the added photopolymerizable compound, it is possible to control the development rate and remove the pattern residue, thereby solving various problems that may appear due to the residue in the process, thereby improving display defects. It is possible to eliminate undeveloped resist, and to form an excellent viewing angle through taper control, etc., so that a high-quality device 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, and an alkylene oxide-modified trimethylolpropane ( meth) acrylate compounds, and alkylene oxide-modified glycerin (meth) acrylate compounds, and more specifically, ethylene oxide-modified trimethylolpropane triacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, ethylene oxide Modified pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hexaacrylate, pro and oxylated pentaerythritol polyacrylate, propoxylated dipentaerythritol hexaacrylate, and ethoxylated glycerin triacrylate. It is more preferable to include ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hexaacrylate, and propoxylated pentaerythritol polyacrylate.

The blue photosensitive resin composition of the present invention may further include a conventional photopolymerizable compound that does not include an alkylene oxide. Specific examples include photopolymerizable compounds using monofunctional monomers, difunctional monomers, and other polyfunctional monomers that do not contain ethylene oxide and propylene oxide.

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 other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and di Pentaerythritol hexa(meth)acrylate etc. are mentioned. Among these, the polyfunctional monomer more than bifunctional is used preferably. The photopolymerizable compound may 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. If the photopolymerizable compound is within the above range, there is no reduction in photosensitivity, sufficient film strength, no pattern loss during development, good pattern construction even in micropatterned portions, and good resist smoothness. desirable.

photoinitiator

The photopolymerization initiator used in the present invention initiates a radical reaction of the photosensitive resin composition, causes curing, and serves to improve sensitivity, and preferably contains an acetophenone-based compound. Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 2-hydroxy-1-[4-(2). -Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- One, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propane-1- an oligomer of one, preferably 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one. Moreover, it can be used combining photoinitiators other than the said acetophenone type. Examples of the photopolymerization initiator other than acetophenone include active radical generators, sensitizers, and acid generators that generate active radicals by irradiating light. Examples of the active radical generator include a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, and a triazine-based compound. As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzo isobutyl ether, etc. are mentioned, for example. Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra( t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone etc. are mentioned. Examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) -6-(4-Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-methylphenyl)ethenyl]-1,3,5-triazine,2,4-bis(trichloromethyl)-6-[2-(3,4 dimethoxyphenyl)ethenyl]-1,3,5 -triazine, etc. are mentioned. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like can be used. The acid generator includes, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfo nate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned. Moreover, as an active radical generating agent, there are also compounds which generate|occur|produce an acid simultaneously with an active radical among the said compound, For example, a triazine-type photoinitiator is used also as an acid generator.

The photoinitiator may be included 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. When it exists in said range, since the blue photosensitive resin composition becomes highly sensitive, the intensity|strength of the pixel part formed using this composition, and the smoothness in the surface of this pixel part tend to become favorable, 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 -butyrolactone, etc. are mentioned. Among the above solvents, organic solvents having a boiling point of 100 to 200 in the above solvents are preferable in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionate ethyl and esters such as methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethyl propionate, 3-methoxy Methyl propionate, etc. are mentioned. These solvents can be used individually or in mixture of 2 or more types, respectively.

Content of the solvent in the blue photosensitive resin composition of this invention is 60-90 mass % with respect to the blue photosensitive resin composition whole quantity containing it, Preferably it can contain 60-85 mass %. If the content of the solvent is within the above range, it is preferable because the coating property tends to be good when applied with a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet or other coating device. .

additive

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

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 becomes 30 to 500 nm. In this case, a dispersing agent may be additionally used as necessary, and some or all of the binder resin may be blended. The remainder of the binder resin, a photopolymerizable compound, a photoinitiator, other components used as necessary, and an additional solvent if necessary are further added to the obtained dispersion (hereinafter, sometimes referred to as mill base) to a predetermined concentration. A target blue photosensitive resin composition can be obtained.

<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, the manufacturing cost can be lowered and an excellent viewing angle can be secured.

In addition, by including a photopolymerizable compound including ethylene oxide or propylene oxide in the blue photosensitive resin composition of the present invention, the color filter comprising a blue pattern layer prepared using the blue photosensitive resin composition of the present invention controls the development speed In addition, it is possible to realize a color filter, particularly a self-luminous color filter, in which the pattern residue is removed to solve the problem caused by the process residue, the display defect problem is improved, and the problem of the undeveloped resist is improved.

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 30 to 500 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 light source and the color filter including the blue pattern layer according to the present invention, there is an advantage in having excellent light emission intensity or viewing angle. In addition, 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 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 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 1-1-1

364.4 g of 3',6'-dihydroxyspiro(fluorene-9,9-xantene) and t-butylammonium in a 3000ml three-necked round flask 0.4159 g of bromide 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, After cooling to 30° C., a 50% aqueous NaOH solution (3 equivalents) was slowly added, and when epichlorohydrin was completely consumed as analyzed by liquid chromatography, the mixture was extracted with dichloromethane, washed with water 3 times, and the organic layer was dried over magnesium sulfate. Then, 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. The reaction solution was completely dissolved by heating the temperature to 120 in a cloudy state. 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 1-1-1.

[Formula 1-1-1]

manufacturing example 3: Synthesis of the compound of Formula 1-1-2

364.4 g of 3',6'-dihydroxyspiro(fluorene-9,9-xantene) of Formula 2-1 in a 3000ml three-necked round flask and 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added, and the reaction was heated to 90° C. 3,6-dihydroxyspiro (fluorene-9,9-xanthene) analyzed by liquid chromatography ) was completely consumed, it was cooled to 30° C., and a 50% aqueous NaOH solution (3 equivalents) was slowly added thereto. When epichlorohydrin was completely consumed by liquid chromatography analysis, the organic layer was washed with water 3 times after extraction with dichloromethane. After drying over magnesium sulfate, dichloromethane was distilled under reduced pressure, and recrystallized using a mixture ratio of dichloromethane and methanol 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 Formula 1-1-2.

[Formula 1-1-2]

manufacturing example 4: Synthesis of the compound of Formula 1-2-1

364.4 g of 4,4'-(9H-xanthene-9,9-diyl)diphenol) 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 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 1-2-1.

[Formula 1-2-1]

manufacturing example 5: Synthesis of the compound of Formula 1-2-2

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 1-2-2.

[Formula 1-2-2]

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 1-1-1 of Preparation Example 2, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide were mixed and the temperature was gradually raised to 110 The reaction was carried out at ~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, reacted at 90° C. for 6 hours, and polymerized into a cardo-based binder resin. Disappearance of anhydride was confirmed by 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 1-1-2 of Preparation Example 3, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide were mixed, and the temperature was gradually raised to 110 The reaction was carried out at ~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, reacted at 90° C. for 6 hours, and polymerized into a cardo-based binder resin. Disappearance of anhydride was confirmed by 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 1-2-1 of Preparation Example 4, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide were mixed, and the temperature was gradually increased to 110 ~ The reaction was carried out at 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, reacted at 90° C. for 6 hours, and polymerized into a cardo-based binder resin. Disappearance of anhydride was confirmed by 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 1-2-2 of Preparation Example 5, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide were mixed, and the temperature was gradually raised to 110 ~ The reaction was carried out at 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, reacted at 90° C. for 6 hours, and polymerized into a cardo-based binder resin. Disappearance of anhydride was confirmed by 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°C

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 9 comparative example 1 to 7: Preparation of blue photosensitive resin composition

According to the compositions of Tables 1 to 3, Examples 1 to 9 Blue photosensitive resin compositions of Comparative Examples 1 to 3 were prepared. (Table 1 shows the scattering particles, and Table 2 shows the composition and content of the compositions of Examples and Comparative Examples.)

[Table 1]

[Table 2]

Manufacture of color filters

Color filters were prepared using the metal oxide photosensitive resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 7 above. That is, each of the 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.

Experimental example 1: Color filter development speed, sensitivity, pattern stability, taper line width and morphology experiments

The color filters prepared from the blue photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated as shown in Table 3 below. The evaluation criteria for each experiment are as follows.

Development speed (sec): The time it takes for the unexposed part to dissolve in the developer for the first time during development <Spray Developer HPMJ method>

Sensitivity: The degree to which a thin film without tearing of the sensitivity mask micropatterns (1 to 60) is formed (the lower the number, the better the sensitivity)

Pattern stability: the degree of error in the pattern after exposure of the pattern mask at a low exposure dose (20-100 mJ).

○: No error in pattern

X: 3 or more errors in the pattern

○, X are the results of confirmation through the optical microscope of the three-dimensional surface shaper.

Tapered line width (μm): Post-exposure line width of a 100 μm pattern of a pattern mask.

[Table 3]

If the development speed exceeds 60 seconds, manufacturing is impossible within a given process time, and if it exceeds 30 seconds, the roughness of the pattern surface becomes non-uniform, and uniformity may also be reduced. In Examples 1 to 5 of the present invention, the developing speed was less than 30 seconds, the sensitivity was excellent at 60 or less, and it was confirmed that both the pattern stability and the tapered line width had excellent effects. On the other hand, in the case of Comparative Example 1, scattering particles were not included, so the pattern stability was unstable, causing a pattern imbalance. In the case of Comparative Example 2, when combined with only acrylic resin, the scattering particles and the blue colorant could not be supported as strongly as the cardo-based binder resin, resulting in peeling, and in Comparative Example 3, photopolymerizable without ethylene oxide and propylene oxide In the case of the compound, the development speed was significantly lowered, and it was confirmed that the pattern stability and pattern imbalance occurred due to the long development speed.

Experimental example 2: Measurement of fine patterns

The size of the pattern obtained through a line/space pattern mask designed to be 100 μm among the color filters manufactured using the metal oxide photosensitive resin prepared in Examples 1 to 5 and Comparative Examples 1 to 3 was measured using OM equipment (ECLIPSE LV100POL Nikon). G) was used to measure the pattern size, and the results are shown in Table 4 below.

[Table 4]

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

Accordingly, as can be seen in Table 4, it was confirmed that in the case of Examples 1 to 4 including the photopolymerizable compound to which ethylene oxide and propylene oxide were added, a fine pattern of less than 20 μm was formed. On the other hand, in Comparative Examples 1 to 3, it was confirmed that the fine pattern was poorly formed or peeled, so that it was impossible to confirm whether the pattern was formed.

Experimental example 3: Measurement of luminescence intensity

Among the color filters manufactured using the metal oxide photosensitive resin prepared in Examples 1 to 5 and Comparative Examples 1 to 3, a 365 nm tube type 4 W UV irradiator (VL-4LC) was applied to the portion formed in a 20 x 20 mm square pattern. , VILBER LOURMAT) was used to measure the light-converted region, and in Examples 1 to 5 and Comparative Examples 1 to 3, the emission intensity in the 450 nm region was measured using a Spectrum meter (Ocean Optics). The results are shown in Table 5 below.

[Table 5]

The higher the measured light emission intensity, the higher the light efficiency. Thus, looking at Table 6, in the case of Examples 1 to 5 including the photopolymerizable compound to which ethylene oxide and propylene oxide were added, it was confirmed that the luminescence intensity was excellently improved to 3 or more. On the other hand, in Comparative Examples 1 to 3, it was confirmed that the light efficiency was lowered to 2 or less.

Experimental example 4: Measuring the viewing angle

A variable angle photometer was used to measure the light intensity according to the viewing angle under the light transmission condition in the portion formed in a 20 x 20 mm square pattern among the color filters manufactured using the metal oxide photosensitive resin prepared in Examples 1 to 5 and Comparative Examples 1 to 3 (GC-5000L, Nippon Denshoku) was used, and the diffusion rate was calculated using Equation 1 below.

[Equation 1]

Diffusion = (B ₇₀ + B ₂₀ ) / 2 x B ₅ x 100

(B _θ =I _θ /cosθ)

I means the light intensity measured at each angle, and means measured at B _70, B _20, B ₅ 70 degrees, 20 degrees, and 5 degrees.

[Table 6]

The higher the measured diffusion, the better the viewing angle. Thus, looking at Table 7, Examples 1 to 5 including the photopolymerizable compound to which ethylene oxide and propylene oxide were added had a diffusion rate of 85 or more, and it was confirmed that the viewing angle was very excellently improved. On the other hand, in Comparative Examples 1 and 3, the diffusion rate was significantly lower than that of Examples 1 to 5, and it was confirmed that the viewing angle was lowered or the diffusion rate could not be measured due to peeling.

Claims (16)

It contains a photopolymerizable compound including scattering particles, a blue colorant, a photoinitiator, a cardo-based binder resin as a binder resin, and an alkylene oxide as a photopolymerizable compound,
A blue photosensitive resin composition that does not contain quantum dots,
The photopolymerizable compound containing the alkylene oxide is ethylene oxide modified trimethylol propane triacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, ethylene oxide modified pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol tetra Acrylate, propylene oxide modified pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hexaacrylate, propoxylated pentaerythritol polyacrylate, propoxylated dipenta The blue photosensitive resin composition of at least one selected from the group consisting of erythritol hexaacrylate and ethoxylated glycerin triacrylate. The method according to claim 1,
The scattering particles include a metal oxide having an average particle diameter of 10 to 1000 nm, a blue photosensitive resin composition. 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 1 selected from the group consisting of The blue photosensitive resin composition comprising more than one species. The method according to claim 1,
The blue photosensitive resin composition further comprises a purple colorant, the blue photosensitive resin composition. The method according to claim 1,
The blue photosensitive resin composition will further include a photopolymerizable compound that does not contain an alkylene oxide, the blue photosensitive resin composition. The method according to claim 1,
The blue colorant comprises at least one of a blue pigment and a blue dye, a blue photosensitive resin composition. The method according to claim 1,
The cardo-based binder resin is a blue photosensitive resin composition comprising at least one of the compounds represented by the following Chemical Formulas 1-1 and 1-2.
[Formula 1-1]

[Formula 1-2]

(In Formula 1-1 or Formula 1-2,
R ₁ , R ₂ , R ₃ and R ₄ are each independently,

is;
X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group;
R ₅ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) The method according to claim 1,
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 acrylate 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) fluorene (9,9-bis (3,4-methacrylic diester) fluorene) will include at least one selected from the group consisting of, the blue photosensitive resin composition. The method according to claim 1,
The blue photosensitive resin composition further comprises an acrylic alkali-soluble resin as a binder resin, the blue photosensitive resin composition. delete The method according to claim 1,
0.1 to 50% by weight of scattering particles based on the total weight of solids in the blue photosensitive resin; 0.1 to 50% by weight of a blue colorant; 5 to 85% by weight of a binder resin; 5 to 50% by weight of a photopolymerizable compound; and 0.1 to 30% by weight of a photoinitiator, and 60 to 90% by weight of a solvent based on the total weight of the blue photosensitive resin composition, the blue photosensitive resin composition. A color filter comprising a blue pattern layer made of the blue photosensitive resin composition of any one of claims 1 to 9 and 11 . 13. The method of claim 12,
The color filter further comprises at least one selected from the group consisting of a red pattern layer and a green pattern layer. 14. The method of claim 13,
The red pattern layer or the green pattern layer is a color filter comprising quantum dots. 15. The method of claim 14,
The color filter is a color filter, characterized in that it is a self-luminous color filter. The color filter according to claim 12; and
a light source emitting blue light; An image display device comprising a.