Blue photosensitive resin composition, color filter and image display device manufactured using the same

Abstract

The present invention provides a blue photosensitive resin composition, a color filter and an image display device manufactured using the same. The blue photosensitive resin composition comprises scattering particles, a blue colorant, a cardo-type adhesive resin as an adhesive resin, a photoinitiator, a photopolymerizable compound and a solvent, wherein the photopolymerizable compound comprises a photopolymerizable compound containing alkylene oxide.

Description

Technical Field

[0001] The present invention relates to a blue photosensitive resin composition, a color filter and an image display device manufactured using the same. Background Art

[0002] Color filters are thin-film optical components that can realize tiny pixel units by extracting three colors, red, green, and blue, from white light. The size of one pixel is about tens to hundreds of microns. This color filter has a structure in which a black matrix layer and a pixel unit are stacked in sequence, wherein the black matrix layer is formed in a predetermined pattern on a transparent substrate to shield the boundary between each pixel, and the pixel unit is formed by arranging the three primary colors of multiple colors (usually red (R), green (G), and blue (B)) in a predetermined order to form each pixel.

[0003] In recent years, as one of the methods for realizing color filters, a pigment dispersion method using a pigment-dispersed photosensitive resin has been applied. However, in the process of light irradiated from a light source passing through the color filter, part of the light is absorbed by the color filter, thereby reducing the light efficiency, and there is a problem that the color reproducibility is reduced due to the characteristics of the pigment contained in the color filter.

[0004] In order to solve such a problem, a method for producing a color filter using a self-luminous photosensitive resin composition containing quantum dots has been proposed.

[0005] Specifically, Korean Patent Publication No. 2007-0094679 proposes to improve color reproducibility by having a color filter layer formed of quantum dots, and Korean Patent Publication No. 2009-0036373 proposes to improve luminous efficiency and display quality by replacing an existing color filter with a light-emitting layer composed of quantum dot phosphors.

[0006] However, photosensitive resin compositions developed so far for the production of color filters cannot fully satisfy the requirements of sufficient development speed control, fine pattern formation, excellent light efficiency, and viewing angle when used in the process. Summary of the invention

[0007] Technical issues

[0008] The purpose of the present invention is to provide a blue photosensitive resin composition capable of realizing a color filter, especially a self-luminous color filter, a color filter and an image display device manufactured using the same, wherein the color filter can control the development speed, remove the residue of the fine pattern, thereby solving the problems caused by the residue in the process, and improve the display defects, ensuring excellent light efficiency and viewing angle.

[0009] Technical Solution

[0010] The present invention provides a blue photosensitive resin composition, comprising scattering particles, a blue colorant, a cardo-type binder resin as a binder resin, a photoinitiator, a photopolymerizable compound, a thermosetting agent and a solvent. The blue photosensitive resin composition is characterized in that the photopolymerizable compound comprises a photopolymerizable compound containing alkylene oxide.

[0011] In addition, the present invention provides a color filter including a blue pattern layer formed from the blue photosensitive resin composition.

[0012] In addition, the present invention provides an image display device, comprising: the above-mentioned color filter; and a light source emitting blue light.

[0013] Beneficial Effects

[0014] The present invention provides a color filter, which contains a photopolymerizable compound containing alkylene oxide in the above-mentioned blue photosensitive resin composition, so as to control the development speed, remove the residue of the pattern, and solve the problem caused by the residue in the process, and improve the display problem and the problem of the resist not being developed. In addition, it is possible to provide a self-luminous color filter with high quality image quality and excellent viewing angle by adjusting the taper. DETAILED DESCRIPTION

[0015] The blue photosensitive resin composition of the present invention may include scattering particles, a blue colorant, a Cardo-type binder resin as a binder resin, a photoinitiator, a photopolymerizable compound and a solvent. In particular, the photopolymerizable compound includes a photopolymerizable compound containing ethylene oxide or propylene oxide. The color filter including the blue pattern layer manufactured using the blue photosensitive resin composition of the present invention can control the development speed, remove the pattern residue and solve the problem caused by the residue in the process. In addition, a color filter, especially a self-luminous color filter, can be provided with improved display problems and improved resist undeveloped problems. In addition, a color filter, especially a self-luminous color filter, with high-quality image quality and excellent viewing angle and an image display device including the color filter can be provided.

[0016] Next, the structure of the present invention will be described in detail.

[0017] Scattering particles

[0018] The scattering particles of the present invention may be metal oxides having an average particle size of 10 to 1000 nm, more preferably 30 to 500 nm. In this case, when the average particle size is smaller than the above range, sufficient scattering effect of incident light cannot be expected, and when the average particle size is larger than the above range, the scattering particles are precipitated in the composition or a self-luminous layer surface of uniform quality cannot be obtained.

[0019] The metal oxide may be an oxide of a metal selected from the group consisting of Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, 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, Ce, Ta, In, and combinations thereof. More specifically, the metal oxide may be an oxide of a metal selected from the group consisting of Al 2 O 3 、SiO 2 、ZnO、ZrO 2 、BaTiO 3 、TiO 2 、 2 O 5 、Ti 3 O 5 , Nb 2 O 3 , SnO, MgO, etc. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.

[0020] The average particle size and the content of the scattering particles in the overall composition can be appropriately adjusted as required, thereby sufficiently improving the luminous intensity of the color filter.

[0021] In addition, the scattering particles may be contained in an amount of 0.1 to 50 wt % relative to the total weight of the solid content in the blue photosensitive resin, preferably 5 to 30 wt %. When the content of the scattering particles is within the above preferred range, the luminous intensity enhancement effect can be obtained and the stability of the composition can be ensured.

[0022] Blue colorant

[0023] In the blue colorant of the present invention, as a blue pigment, a compound classified as a pigment in the color index (published by the Society of Dyers and Colourists) can be specifically listed, and more specifically, a pigment with the following color index (CI) number can be listed, but it is not necessarily limited to this pigment. Specifically, as a blue pigment, CI Pigment Blue 15:3, 15:4, 15:6, 16, 21, 28 and 76 can be listed, preferably including one or more selected from the group consisting of CI Pigment Blue 15:3, Pigment Blue 15:6 and Pigment Blue 16.

[0024] The blue colorant of the present invention may further contain a blue dye. Examples of the blue dye include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) or known dyes described in the Dyeing Handbook (Dyers).

[0025] Specifically, the dyes that can be further used are listed above.

[0026] As CI solvent dye,

[0027] CI Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67, and 70 are mentioned, and it is more preferable to contain one or more of CI Solvent Blue 35, 36, 44, 45, and 70.

[0028] In addition, as a CI acid dye,

[0029] 1, 335, and 340. Among them, it is more preferable to contain one or more of CI Acid Blue 80 and 90.

[0030] In addition, as a CI direct dye,

[0031] Examples include 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, and 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, etc.

[0032] CI Mordant 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 can be mentioned.

[0033] The above blue dyes can be used independently or in combination of two or more.

[0034] The blue colorant of the present invention may further include a violet colorant as an additional colorant. The violet colorant may include one or more of a violet pigment and a violet dye, and the violet pigment may specifically include CI Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, and 38, among which CI Pigment Violet 23 is more preferably included.

[0035] Specific examples of the violet dye include CI solvent violet, CI acid violet, CI acid violet, and CI medium violet, but are not limited thereto.

[0036] Specifically, the CI solvent violet includes CI solvent violet 8, 9, 13, 14, 36, 37, 47 and 49, and more preferably includes CI solvent violet 13. CI acid violet includes CI acid violet 6B, 7, 9, 17, 19 and 66, and more preferably includes CI acid violet 66. CI direct violet includes CI direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104.

[0037] In addition, CI Medium Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, and 58 can be mentioned.

[0038] The blue colorant can be used in an amount of 0.1 to 50% by weight, preferably 0.5 to 30% by weight, relative to 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, and the color luminous intensity can be efficiently presented, and viscosity stability can be ensured.

[0039] The present invention does not include blue quantum dots but includes blue colorants and scattering particles, thereby preventing the efficiency of the blue pixels of the color filter, especially the self-luminous color filter, from decreasing.

[0040] Binder resin

[0041] The binder resin of the present invention includes a cardo-type binder resin. The cardo-type binder resin has reactivity and alkali solubility due to the action of light or heat, and acts as a dispersion medium for a coloring material. The cardo-type binder resin contained in the blue photosensitive resin composition of the present invention acts as a binder resin for scattering particles, and is not limited as long as it is a resin that can be dissolved in an alkaline developer used in a development step for manufacturing a color filter.

[0042] The cardo-based binder resin of the present invention may include one or more of the compounds represented by Chemical Formula 1-1 and Chemical Formula 1-2.

[0043] [Chemical formula 1-1]

[0044]

[0045] [Chemical formula 1-2]

[0046]

[0047] In the above Chemical Formula 1-1 or Chemical Formula 1-2,

[0048] R 1 , R 2 , R 3 and R 4 Separately

[0049] X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group;

[0050] R 5 It is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0051] In the present invention, the compound represented by the above Chemical Formula 1-1 is synthesized from the compound represented by the following Chemical Formula 2-1, and the compound represented by Chemical Formula 1-2 can be synthesized using the compound represented by Chemical Formula 2-2.

[0052] In the present invention, the compound represented by the above Chemical Formula 1-1 is synthesized from the compound represented by the following Chemical Formula 2-1, and the compound represented by Chemical Formula 1-2 can be synthesized using the compound represented by Chemical Formula 2-2.

[0053] [Chemical formula 2-1]

[0054]

[0055] [Chemical formula 2-2]

[0056]

[0057] Specifically, the compound represented by the above Chemical Formula 1-1 may be one or more of the compounds represented by Chemical Formula 1-1-1 and Chemical Formula 1-1-2, and the compound represented by the above Chemical Formula 1-2 may be one or more of the compounds represented by Chemical Formula 1-2-1 and Chemical Formula 1-2-2.

[0058] [Chemical formula 1-1-1]

[0059]

[0060] [Chemical formula 1-1-2]

[0061]

[0062] [Chemical formula 1-2-1]

[0063]

[0064] [Chemical formula 1-2-2]

[0065]

[0066] The present invention can be prepared by using a 9,9-bis(3-cinnamic diester)fluorene, 9,9-bis(3-cinnamoil,4-hydroxyphenyl)fluorene, 9,9-bis(glycidyl methacrylateether)fluorene, 9,9-bis(3,4-dihydroxyphenyl)fluorene dicinnamic ester, 3,6-diglycidyl methacrylate ether spiro(fluorene-9,9-xanthene) spiro(fluorene-9,9-xantene), 9,9-bis(3-allyl,4-hydroxyphenylfluorene), 9,9-bis(4-allyloxyphenyl)fluorene, and 9,9-bis(3,4-methacrylic acid diester)fluorene. The cardo-based binder resin is prepared by reacting at least one of the group consisting of diasterephthalic acid, fluorene, and phthalic anhydride with at least one of the group consisting of maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylenemethylenetetrahydrophthalic anhydride, chlorendic anhydride and methyltetrahydrophthalic anhydride as acid anhydride compounds, or at least one of the group consisting of aromatic polycarboxylic acid anhydrides such as pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride and diphenyl ether tetracarboxylic anhydride as acid dianhydrides, but is not limited to this.

[0067] The present invention may further include an acrylic alkali-soluble resin as a binder resin. Examples of the acrylic alkali-soluble resin include copolymers of carboxyl-containing monomers and other monomers copolymerizable with the monomers. Examples of carboxyl-containing monomers include unsaturated monocarboxylic acids, or unsaturated polycarboxylic acids such as unsaturated dicarboxylic acids and unsaturated tricarboxylic acids having one or more carboxyl groups in the molecule. Here, examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. The unsaturated polycarboxylic acid may be an anhydride, and specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, and the like may be mentioned. In addition, the unsaturated polycarboxylic acid can also be its mono (2-acryloxyalkyl) ester, for example, succinic acid mono (2-acryloxyethyl) ester, succinic acid mono (2-methacryloxyethyl) ester, phthalic acid mono (2-acryloxyethyl) ester, phthalic acid mono (2-methacryloxyethyl) ester, etc. can be listed. The unsaturated polycarboxylic acid can also be its mono (methyl) acrylate of dicarboxyl polymer at both ends, for example, ω-carboxyl polycaprolactone monoacrylate, ω-carboxyl polycaprolactone monomethacrylate, etc. can be listed. These carboxyl-containing monomers can be used alone or in combination of two or more. Examples of other monomers copolymerizable with the carboxyl group-containing monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene;Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-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, Isobornyl Acrylate, Isobornyl Methacrylate, Dimethoxypropane Unsaturated carboxylic acid esters such as cyclopentadienyl acrylate, dicyclopentadienyl methacrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc.; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl methacrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl methacrylate, 3-methacrylic acid Unsaturated carboxylic acid aminoalkyl esters such as dimethylaminopropyl ester; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; cyanide vinyl 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; unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide;Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; and macromonomers having a monoacryl group or a monomethacryl group at the end of the polymer molecular chain such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysiloxane. These monomers can be used alone or in combination of two or more. In particular, as other monomers copolymerizable with the above-mentioned carboxyl group-containing monomers, bulky monomers such as monomers having a norbornyl skeleton, monomers having an adamantane skeleton, and monomers having a rosin skeleton are preferred because they tend to reduce the relative dielectric constant. ;

[0068] The cardo-type binder resin and / or acrylic alkali-soluble resin of the present invention preferably has an acid value in the range of 20 to 200 (KOH mg / g). If the acid value is within the above range, the solubility in the developer is improved, the non-exposed part is easily dissolved and the sensitivity is increased, and as a result, it remains during the development of the pattern of the exposed part and can improve the residual film ratio (film remaining ratio), so it is preferred. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1g of the acrylic polymer, and can usually be obtained by titration using a potassium hydroxide aqueous solution. In addition, the cardo-type binder resin or acrylic alkali-soluble resin having a polystyrene-equivalent weight average molecular weight (hereinafter referred to as "weight average molecular weight") of 2,000 to 200,000, preferably 3,000 to 100,000 measured by gel permeation chromatography (GPC; tetrahydrofuran is used as an elution solvent) is preferred. If 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 part in the developer is excellent, and the resolution tends to be improved, so it is preferred.

[0069] The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the Cardo-type binder resin and / or the acrylic alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.5 to 6.0. If the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5 to 6.0, the developability is excellent, so it is preferred.

[0070] 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, relative to the total weight of the solid content in the blue photosensitive resin. If the content of the binder resin is within the above range, the solubility in the developer is sufficient, the non-pixel portion is unlikely to generate development residues on the substrate, and the film reduction of the pixel portion of the exposed portion is unlikely to occur during development, and the non-pixel portion has excellent leakage, so it is preferred.

[0071] Photopolymerizable compounds

[0072] 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 the photopolymerization initiator described later. Specifically, a photopolymerizable compound containing an alkylene oxide can be cited, and preferably a photopolymerizable compound containing ethylene oxide and / or propylene oxide can be cited. In the case of containing a photopolymerizable compound to which the above-mentioned ethylene oxide and / or propylene oxide is added, the development speed can be controlled, the residue of the pattern can be removed, and various problems that may occur due to the residue in the process can be solved, thereby improving the display defect, removing the undeveloped resist, and forming an excellent viewing angle by adjusting the taper, etc., and a high-quality image element can be manufactured.

[0073] Examples of the photopolymerizable compound containing the alkylene oxide include alkylene oxide-modified pentaerythritol (meth)acrylate compounds, alkylene oxide-modified dipentaerythritol (meth)acrylate compounds, alkylene oxide-modified trimethylolpropane (meth)acrylate compounds, and alkylene oxide-modified glycerol (meth)acrylate compounds. More specifically, examples include ethylene oxide-modified trimethylolpropane triacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, ethylene oxide-modified pentaerythritol tetraacrylate, propylene oxide-modified pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hexaacrylate, propoxylated pentaerythritol polyacrylate, propoxylated dipentaerythritol hexaacrylate, and ethoxylated glycerol triacrylate. More preferably, the photopolymerizable compound contains ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hexaacrylate, and propoxylated pentaerythritol polyacrylate.

[0074] The blue photosensitive resin composition of the present invention may further contain a common photopolymerizable compound that does not contain an alkylene oxide, and specifically, a photopolymerizable compound using a monofunctional monomer, a bifunctional monomer, or other polyfunctional monomer that does not contain ethylene oxide or propylene oxide.

[0075] As a specific example of a monofunctional monomer, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, etc. can be cited. As a specific example of a difunctional monomer, 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. can be cited. As a specific example of other multifunctional monomers, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. can be cited. Among them, it is preferred to use a multifunctional monomer having more than two functions. The photopolymerizable compound can be used in an amount of 5 to 5% by weight, preferably 5 to 30% by weight, relative to the total weight of the solid content in the blue photosensitive resin. When the photopolymerizable compound is within the above range, it is preferred that there is a tendency that there is no decrease in sensitivity, the film strength is sufficient, there is no pattern disappearance during development, and thus the pattern construction is excellent in the fine pattern portion, and the smoothness of the resist is excellent.

[0076] Photoinitiator

[0077] The photopolymerization initiator used in the present invention plays a role in starting the free radical reaction of the photosensitive resin composition to cause curing and improve the sensitivity, and preferably contains an acetophenone compound. As the acetophenone compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylphenylthio)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propane-1-one oligomers, etc. can be listed, and preferably 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, etc. can be listed. In addition, photopolymerization initiators other than the above-mentioned acetophenones can be used in combination. Photopolymerization initiators other than acetophenones can include active radical generators, sensitizers, acid generators, etc. that generate active radicals by irradiating light. As active radical generators, for example, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, etc. can be listed. As benzoin compounds, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. can be listed. As benzophenone compounds, for example, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. can be listed. Examples of thioxanthone compounds include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. Examples of triazine compounds 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-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)]-1,3,5-triazine. 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.As the active radical generator, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, etc. As the acid generator, for example, onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl toluenesulfonates, and benzoin toluenesulfonates can be cited. In addition, as the active radical generator, some of the above compounds generate active radicals and acids at the same time. For example, a triazine-based photopolymerization initiator can also be used as an acid generator.

[0078] The initiator may be contained in an amount of 0.1 to 30% by weight, preferably 0.3 to 20% by weight, relative to the total weight of the solid content in the blue photosensitive resin. If the content of the photopolymerization initiator is within the above range, the blue photosensitive resin composition is highly sensitive, and the strength of the pixel portion formed using the composition and the smoothness of the surface of the pixel portion tend to be excellent, so it is preferred.

[0079] In addition, the present invention can use a photopolymerization initiation aid. A photopolymerization initiation aid is sometimes used in combination with a photopolymerization initiator, and is a compound used to promote the polymerization of a photopolymerizable compound that is polymerized by the above-mentioned photopolymerization initiator. Examples of the photopolymerization initiation aid include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like.

[0080] Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, among which 4,4'-bis(diethylamino)benzophenone is preferred. Examples of alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. As thioxanthone compounds, for example, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxy thioxanthone, etc. can be cited. The photopolymerization initiator (D) can be used alone or in combination of multiple types. In addition, as a photopolymerization initiation aid, a commercially available product can also be used. As a commercially available photopolymerization initiation aid, for example, the trade name "EAB-F" (manufacturer: Hodogaya Chemical Industry Co., Ltd.) can be cited.

[0081] When using these photopolymerization initiator aids, the amount of the polymerization initiator aid used is usually 10 mol or less, preferably 0.01 to 5 mol per 1 mol of the photopolymerization initiator. If the amount of the polymerization initiator aid used is within the above range, the sensitivity of the blue photosensitive resin composition is further improved and the productivity of the color filter formed using the composition tends to be improved, so it is preferred.

[0082] Solvents

[0083] 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 blue photosensitive resin compositions 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 dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol dibutyl ether acetate; Alkylene glycol alkyl ether acetates such as alcohol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, etc.; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, etc.; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone, etc. Among the above solvents, from the viewpoint of coating properties and drying properties, preferably, among the above solvents, organic solvents having a boiling point of 100 to 200° C. are mentioned, more preferably, ester combinations such as alkylene glycol alkyl ether acetates, ketones, 3-ethoxyethyl propionate or 3-methoxymethyl propionate are mentioned, and further preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxyethyl propionate, 3-methoxymethyl propionate are mentioned. The above solvents may be used alone or in combination of two or more.

[0084] The solvent content in the blue photosensitive resin composition of the present invention may be 60 to 90% by weight, preferably 60 to 85% by weight of the solvent, relative to the total weight of the blue photosensitive resin composition. If the solvent content is within the above range, when coating is performed using a coating device such as a roll coater, a spin coater, a slit spin coater, a slit coater (sometimes referred to as a die coater), or a spray coater, there is a tendency to improve the coating properties, and therefore, it is preferred.

[0085] additive

[0086] The blue photosensitive resin composition for the blue pattern layer of the present invention may further contain fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-coagulation agents, etc. as needed.

[0087] Specific examples of the other polymer 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.

[0088] As the pigment dispersant, commercially available surfactants can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants, etc. These surfactants can be used alone or in combination of two or more.

[0089] 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, polyethyleneimines, and the like; and trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tokheimproduct Co., Ltd.), MEGAFAC (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (all manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Zeneca Corporation), EFKA (manufactured by EFKA Chemical Co., Ltd.), and PB 821 (manufactured by Ajinomoto Co., Ltd.).

[0090] Examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-chloropropyl methyl dimethoxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, and 3-mercaptopropyl trimethoxysilane. Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

[0091] Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

[0092] Specific examples of the anti-coagulation agent include sodium polyacrylate and the like.

[0093] Those skilled in the art can appropriately add the above-mentioned additives within the scope that does not hinder the effect of the present invention. For example, relative to 100 parts by weight of the above-mentioned blue photosensitive resin composition as a whole, 0.5 to 10 parts by weight of the above-mentioned additives can be used, preferably 0.1 to 10 parts by weight of the above-mentioned additives can be used, and more preferably 0.1 to 5 parts by weight of the above-mentioned additives can be used, but it is not limited thereto.

[0094] The blue photosensitive resin composition of the present invention can be prepared, for example, by the following method. The scattering particles are mixed with a solvent in advance and dispersed to an average particle size of 30 to 500 nm using a bead mill or the like. At this time, a dispersant may be further used as needed, and a part or all of the binder resin may be added. The remaining binder resin, photopolymerizable compound, photopolymerization initiator, other components used as needed, and additional solvent as needed are further added to the obtained dispersion (hereinafter sometimes referred to as mill base) at a prescribed concentration, thereby obtaining the target blue photosensitive resin composition.

[0095] <Color filter and image display device>

[0096] Another aspect of the present invention relates to a color filter including a blue pattern layer containing a cured product of the blue photosensitive resin composition for forming a blue pattern layer.

[0097] Since the color filter of the present invention is prepared by using the aforementioned blue photosensitive resin composition for forming a blue pattern layer instead of blue quantum dots, it has the advantages of being able to reduce manufacturing costs and ensure excellent viewing angles.

[0098] In addition, since the blue photosensitive resin composition of the present invention contains a photopolymerizable compound containing ethylene oxide or propylene oxide, the color filter including a blue pattern layer manufactured using the blue photosensitive resin composition of the present invention can realize a color filter, especially a self-luminous color filter: the color filter controls the development speed, removes the pattern residue and solves the problem caused by the residue in the process, and the display defect problem is improved, and the problem of non-development of the resist is improved.

[0099] The color filter includes a substrate and a blue pattern layer formed on an upper portion of the substrate.

[0100] The substrate may be the substrate of the color filter itself, or may be the part where the color filter is located in a display device, etc., without any particular limitation. 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).

[0101] The above-mentioned blue pattern layer is a layer containing the blue photosensitive resin composition of the present invention, and can be a layer formed by coating the above-mentioned blue photosensitive resin composition for forming a blue pattern layer and exposing, developing and thermally curing in a prescribed pattern. The above-mentioned pattern layer can be formed by executing a method generally known in the art.

[0102] In yet 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.

[0103] 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 of 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 the green pattern layer may include scattering particles. The red pattern layer or the green pattern layer may emit red light or blue light respectively by a light source emitting blue light described later.

[0104] In another embodiment of the present invention, the scattering particles contained in the above-mentioned red pattern layer or green pattern layer may include a metal oxide with an average path length of 30 to 500 nm, and the contents related to the above-mentioned scattering particles and metal oxides can be applied to the contents related to the scattering particles and metal oxides contained in the blue photosensitive resin composition of the present invention.

[0105] In the present invention, the morphology, structure 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.

[0106] The color filter including the substrate and the pattern layer as described above may further include partitions formed between the patterns, and may further include a black matrix, but is not limited thereto.

[0107] In the present invention, the color filter may be a self-luminous color filter.

[0108] Another embodiment of the present invention relates to an image display device including the color filter and a light source emitting blue light. For example, the image display device of the present invention includes a color filter including a blue pattern layer of a cured product of the blue photosensitive resin composition and a light source emitting blue light.

[0109] The color filter of the present invention can be applied not only to a general liquid crystal display device but also to various image display devices such as an electroluminescent display device, a plasma display device, and a field emission display device.

[0110] When the image display device includes a color filter containing the blue pattern layer of the present invention and the light source, there is an advantage of having excellent luminous intensity or viewing angle. In addition, since the blue pattern layer included in the color filter of the present invention does not contain blue quantum dots, there is an advantage of being able to manufacture an image display device with low manufacturing cost.

[0111] Example

[0112] Below, in order to specifically illustrate this specification, detailed description is given by taking embodiment as an example. However, the embodiment in this specification can be deformed into other various modes, and it should not be interpreted that the scope of this specification is limited to the embodiment described in detail below. The embodiment of this specification is provided to more completely illustrate this specification to those of ordinary skill in the art. In addition, below, unless otherwise mentioned, the "%" and "part" representing the content are weight basis.

[0113] Synthesis Example: Synthesis of Binder Resin

[0114] Preparation Example 1: Acrylic alkali-soluble resin

[0115] A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was prepared, and as a monomer dropping funnel, 7.8 g (0.20 mol) of benzyl maleimide, 43.2 g (0.30 mol) of acrylic acid, 118.0 g (0.50 mol) of vinyl toluene, 4 g of tert-butyl peroxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred and mixed, and as a chain transfer agent dropping tank, 6 g of n-dodecyl mercaptan and 24 g of PGMEA were added and stirred and mixed. After that, 395 g of PGMEA was introduced into the flask, and after the atmosphere in the flask was replaced from air to nitrogen, the temperature of the flask was raised to 90° C. while stirring. Then, the monomer and chain transfer agent were added dropwise from the dropping funnel. When dropping, the temperature was maintained at 90°C for 2 hours, and after 1 hour, the temperature was raised to 110°C and maintained for 3 hours, and then a gas inlet pipe was introduced to start bubbling of a mixed gas of oxygen / nitrogen=5 / 95 (v / v). Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% of the carboxyl group of the acrylic acid used in this reaction)], 0.4 g of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 0.8 g of triethylamine were added to the flask, and the reaction was continued at 110°C for 8 hours to obtain a resin A having a solid content acid value of 70 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 16,000, and the molecular weight distribution (Mw / Mn) was 2.3.

[0116] Preparation Example 2: Synthesis of the compound of Chemical Formula 1-1-1

[0117] In a 3000 ml three-necked round-bottom flask, 3', 6'-dihydroxyspiro (fluorene-9, 9'-xantene) 364.4 g and 0.4159 g of tert-butylammonium bromide were mixed, and 2359 g of epichlorohydrin was added, followed by heating to 90°C and reacting. After analysis by liquid chromatography, if 3', 6'-dihydroxyspiro (fluorene-9, 9'-xantene) was completely consumed, the mixture was cooled to 30°C and a 50% aqueous NaOH solution (3 equivalents) was slowly added. After analysis by liquid chromatography, if epichlorohydrin was completely consumed, the mixture was extracted with dichloromethane and then washed with water three times, and then the organic layer was dried with magnesium sulfate, and dichloromethane was distilled off under reduced pressure, and dichloromethane and methanol were used at a mixing ratio of 50:50 and recrystallized.

[0118] After mixing 1 equivalent of the epoxy compound synthesized in this way, 0.004 equivalent of tert-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid, 24.89 g of propylene glycol monomethyl ether acetate solvent was added for mixing. Air was blown into the reaction solution at 25 ml / min and heated to 90-100°C to dissolve it. The reaction solution was heated to 120°C in a turbid state to completely dissolve it. If the solution becomes transparent and the viscosity increases, the acid value is measured and stirred until the acid value is less than 1.0 mgKOH / g. It takes 11 hours for the acid value to reach the target (0.8). After the reaction is completed, the temperature of the reactor is lowered to room temperature to obtain a colorless and transparent compound of chemical formula 1-1-1.

[0119] [Chemical formula 1-1-1]

[0120]

[0121] Preparation Example 3: Synthesis of the compound of Chemical Formula 1-1-2

[0122] In a 3000 ml three-necked round-bottom flask, 3', 6'-dihydroxyspiro (fluorene-9, 9'-xantene) of Chemical Formula 2-1 (364.4 g) and 0.4159 g of tert-butylammonium bromide were mixed, and 2359 g of epichlorohydrin was added and heated to 90° C. to react. After analysis by liquid chromatography, if 3', 6'-dihydroxyspiro (fluorene-9, 9'-xantene) was completely consumed, the mixture was cooled to 30° C. and a 50% aqueous NaOH solution (3 equivalents) was slowly added. After analysis by liquid chromatography, if epichlorohydrin was completely consumed, the mixture was extracted with dichloromethane and washed with water three times, and then the organic layer was dried with magnesium sulfate, and dichloromethane was distilled off under reduced pressure, and dichloromethane and methanol were used at a mixing ratio of 50:50 and recrystallized.

[0123] After mixing 1 equivalent of the epoxy compound synthesized in this way, 0.004 equivalent of tert-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of methacrylic acid, 24.89 g of propylene glycol monomethyl ether acetate solvent was added for mixing. Air was blown into the reaction solution at 25 ml / min and heated to 90-100°C to dissolve it. The reaction solution was heated to 120°C in a turbid state to completely dissolve it. If the solution becomes transparent and the viscosity increases, the acid value is measured and stirred until the acid value is less than 1.0 mgKOH / g. It takes 11 hours for the acid value to reach the target (0.8). After the reaction is completed, the temperature of the reactor is lowered to room temperature to obtain a colorless and transparent compound of chemical formula 1-1-2.

[0124] [Chemical formula 1-1-2]

[0125]

[0126] Preparation Example 4: Synthesis of the compound of Chemical Formula 1-2-1

[0127] 364.4 g of 4,4'-(9H-xanthene-9,9-diyl)diphenol and 0.4159 g of tert-butylammonium bromide were mixed in a 3000 ml three-necked round-bottom flask, and 2359 g of epichlorohydrin was added, and then heated to 90°C and reacted. After analysis by liquid chromatography, if 4,4'-(9H-xanthene-9,9-diyl)diphenol was completely consumed, the mixture was cooled to 30°C and a 50% aqueous solution of NaOH (3 equivalents) was slowly added. After analysis by liquid chromatography, if epichlorohydrin was completely consumed, the mixture was extracted with dichloromethane and washed with water three times, and then the organic layer was dried with magnesium sulfate, and dichloromethane was distilled under reduced pressure, and dichloromethane and methanol were used at a mixing ratio of 50:50 and recrystallized. After mixing 1 equivalent of the epoxy compound synthesized in this way, 0.004 equivalent of tert-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid, 24.89 g of propylene glycol monomethyl ether acetate solvent was added for mixing. Air was blown into the reaction solution at 25 ml / min and heated to 90-100°C to dissolve it. The reaction solution was heated to 120°C in a turbid state to completely dissolve it. If the solution becomes transparent and the viscosity increases, the acid value is measured and stirred until the acid value is less than 1.0 mgKOH / g. It takes 11 hours for the acid value to reach the target (0.8). After the reaction is completed, the temperature of the reactor is lowered to room temperature to obtain a colorless and transparent compound of chemical formula 1-2-1.

[0128] [Chemical formula 1-2-1]

[0129]

[0130] Preparation Example 5: Synthesis of the compound of Chemical Formula 1-2-2

[0131] 364.4 g of 4,4'-(9H-xanthene-9,9-diyl)diphenol and 0.4159 g of tert-butylammonium bromide were mixed in a 3000 ml three-necked round-bottom flask, and 2359 g of epichlorohydrin was added, and then heated to 90°C and reacted. After analysis by liquid chromatography, if 4,4'-(9H-xanthene-9,9-diyl)diphenol was completely consumed, the mixture was cooled to 30°C and a 50% aqueous solution of NaOH (3 equivalents) was slowly added. After analysis by liquid chromatography, if epichlorohydrin was completely consumed, the mixture was extracted with dichloromethane and washed with water three times, and then the organic layer was dried with magnesium sulfate, and dichloromethane was distilled under reduced pressure, and dichloromethane and methanol were used at a mixing ratio of 50:50 and recrystallized. After mixing 1 equivalent of the epoxy compound synthesized in this way, 0.004 equivalent of tert-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of methacrylic acid, 24.89 g of propylene glycol monomethyl ether acetate solvent was added for mixing. Air was blown into the reaction solution at 25 ml / min and heated to 90-100°C to dissolve it. The reaction solution was heated to 120°C in a turbid state to completely dissolve it. If the solution becomes transparent and the viscosity increases, the acid value is measured and stirred until the acid value is less than 1.0 mgKOH / g. It takes 11 hours for the acid value to reach the target (0.8). After the reaction is completed, the temperature of the reactor is lowered to room temperature to obtain a colorless and transparent compound of chemical formula 1-2-2.

[0132] [Chemical formula 1-2-2]

[0133]

[0134] Preparation Example 6: Synthesis of Cardo-based Binder Resin (A-1)

[0135] After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of chemical formula 1-1-1 in Preparation Example 2 and dissolving it, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was slowly raised and reacted at 110-115°C for 4 hours. After confirming that the anhydride group disappeared, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90°C for 6 hours to polymerize into a Cardo-based binder resin. The disappearance of the anhydrous substance was confirmed by IR spectrum. The weight average molecular weight was 3500.

[0136] Preparation Example 7: Synthesis of Cardo-based Binder Resin (A-2)

[0137] After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of chemical formula 1-1-2 in Preparation Example 3 and dissolving it, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was slowly raised and reacted at 110-115°C for 4 hours. After confirming that the anhydride group disappeared, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90°C for 6 hours to polymerize into a Cardo-based binder resin. The disappearance of the anhydrous substance was confirmed by IR spectrum. The weight average molecular weight was 3800.

[0138] Preparation Example 8: Synthesis of Cardo-based Binder Resin (A-3)

[0139] After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of chemical formula 1-2-1 in Preparation Example 4 and dissolving it, 78 g of benzene tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was slowly raised and reacted at 110-115°C for 4 hours. After confirming that the anhydride group disappeared, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90°C for 6 hours to polymerize into a Cardo-based binder resin. The disappearance of the anhydrous substance was confirmed by IR spectrum. The weight average molecular weight was 4500.

[0140] Preparation Example 9: Synthesis of Cardo-based binder resin (A-9):

[0141] After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of chemical formula 1-2-2 in Preparation Example 5 and dissolving it, 78 g of benzene tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was slowly raised and reacted at 110-115°C for 4 hours. After confirming that the anhydride group disappeared, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90°C for 6 hours to polymerize into a Cardo-based binder resin. The disappearance of the anhydrous substance was confirmed by IR spectrum. The weight average molecular weight was 4900.

[0142] Device: HLC-8120GPC (manufactured by Tosoh Corporation)

[0143] Column: TSK-GELG4000HXL + TSK-GELG2000HXL (connected in series)

[0144] Column temperature: 40°C

[0145] Mobile phase solvent: tetrahydrofuran

[0146] Flow rate: 1.0mL / min

[0147] Injection volume: 50μL

[0148] Detector: RI

[0149] Measurement sample concentration: 0.6 wt% (solvent = tetrahydrofuran)

[0150] Calibration standard substances: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

[0151] The ratio of the weight average molecular weight and the number average molecular weight obtained above is defined as molecular weight distribution (Mw / Mn).

[0152] Examples 1 to 9 and Comparative Examples 1 to 7: Preparation of blue photosensitive resin composition

[0153] According to the compositions of Tables 1 to 3 below, blue photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared (Table 1 shows the scattering particles, and Table 2 shows the composition constitution and content of the Examples and Comparative Examples).

[0154] [Table 1]

[0155] type Average particle size Product Name Manufacturing Company E-1 <![CDATA[TiO 2 ]]> 130nm PT-401L ishihara co., ltd. E-2 <![CDATA[TiO 2 ]]> 210nm CR-63 ishihara co., ltd. E-3 <![CDATA[Al 2 THE 3 ]]> 50nm 0.05um Alumina Powder Joint Company E-4 <![CDATA[Al 2 THE 3 ]]> 300nm 0.3um alumina powder Joint Company

[0156] [Table 2]

[0157]

[0158] 0) Colorant: CI Pigment Blue 15:6

[0159] 1) Binder resin: A-1 to A-5

[0160] A-1: Preparation Example A-1, A-2: Preparation Example A-2, A-3: Preparation Example A-3,

[0161] A-4: Preparation Example A-4, A-5: Mono(2-methacryloyloxyalkyl) ester

[0162] 2) Photopolymerizable compound (C):

[0163] C-1: Ethoxylated pentaerythritol tetraacrylate,

[0164] C-2: Ethoxylated dipentaerythritol hexaacrylate,

[0165] C-3: propoxylated pentaerythritol polyacrylate,

[0166] C-4: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

[0167] 3) Initiator (D): Irgaqure-907 (manufactured by BASF)

[0168] 4) Solvent (E): Propylene glycol monomethyl ether acetate

[0169] Color filter manufacturing

[0170] Color filters were manufactured using the metal oxide photosensitive resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 7. That is, each of the photosensitive resin compositions was applied onto a glass substrate by spin coating, and then placed on a hot plate and maintained at 100° C. for 3 minutes to form a thin film.

[0171] Next, a test photomask having a square transmission pattern of 20 mm in width and 20 mm in height and a line / space pattern of 1 to 100 μm was placed on the film, and ultraviolet rays were irradiated with a distance of 100 μm from the test photomask.

[0172] At this time, the ultraviolet light source was an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Electric Co., Ltd., and the ultraviolet light was emitted at 200 mJ / cm 2 The light was irradiated with an exposure dose of 100 nm (365 nm) without using any special optical filter.

[0173] The film irradiated with ultraviolet light was immersed in a KOH aqueous solution developer solution of pH 10.5 for 80 seconds for development. The glass plate covered with the 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.

[0174] Experimental Example 1: Development Speed, Sensitivity, Pattern Stability, Taper Line Width and Morphology of Color Filters The color filters produced from the blue photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated as shown in Table 3. The evaluation criteria for each experiment are as follows.

[0175] Development speed (sec): Development <Spray Developer (HPMJ method)> The time required for the non-exposed area to begin to dissolve in the developer.

[0176] Sensitivity: The degree to which a fine pattern of a sensitivity mask (1 to 60) is formed without a thin film peeling off (the lower the value, the better the sensitivity)

[0177] Pattern stability: The error of the pattern mask after exposure at low exposure (20-100 mJ)

[0178] ○: No error in the pattern

[0179] ×: There are more than 3 pattern errors

[0180] ○ and × are the results of confirmation using an optical microscope of a three-dimensional surface shape measuring device.

[0181] Taper line width (μm): The line width of the 100μm pattern of the pattern mask after exposure

[0182] [Table 3]

[0183]

[0184] In the case where the development speed exceeds 60 seconds, it is impossible to manufacture within the specified process time. In the case where the development speed exceeds 30 seconds, the surface roughness of the pattern is uneven, and the uniformity may be reduced. With regard to Examples 1 to 5 of the present invention, it is confirmed that the development speed is less than 30 seconds and the sensitivity is less than 60, which is excellent, and has excellent effects of pattern stability and taper line width. On the contrary, in the case of Comparative Example 1, the pattern stability is unstable due to the absence of scattering particles, causing pattern imbalance. In the case of Comparative Example 2, if only acrylic resin is used for bonding, the scattering particles and the blue colorant cannot be firmly supported like the Cardo-type adhesive resin, and peeling occurs. In the case of Comparative Example 3, it is confirmed that the development speed is significantly reduced in the case of a photopolymerizable compound that does not contain ethylene oxide and propylene oxide, and the pattern stability is poor and the pattern is uneven due to the longer development speed.

[0185] Experimental Example 2: Fine Pattern Measurement

[0186] In the color filters manufactured using the metal oxide photosensitive resins prepared in Examples 1 to 5 and Comparative Examples 1 to 3, the size of the pattern obtained using the line / space pattern mask designed at 100 μm was measured using an OM device (ECLIPSE LV100POL, Nikon Corporation). The measurement results are described in Table 4.

[0187] [Table 4]

[0188] Division Micro pattern Example 1 18 Example 2 15 Example 3 19 Example 4 17 Example 5 15 Comparative Example 1 Bad pattern Comparative Example 2 Stripping Comparative Example 3 Bad pattern

[0189] 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 is difficult to realize fine pixels.

[0190] Thus, 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 contrary, in the case of Comparative Examples 1 to 3, it was confirmed that a defective fine pattern was formed or peeling occurred, and it was not possible to confirm whether a pattern was formed.

[0191] Experimental Example 3: Luminous Intensity Measurement

[0192] In the color filters manufactured using the metal oxide photosensitive resins prepared in Examples 1 to 5 and Comparative Examples 1 to 3, the area after light conversion was measured by a 365 nm tube-type 4W UV irradiator (VL-4LC, VILBER LOURMAT) at a portion formed in a 20 mm×20 mm square pattern, and the luminous intensity in the 450 nm area was measured by a spectrometer (Spectrum meter, Ocean Optics) for Examples 1 to 5 and Comparative Examples 1 to 3. The measurement results are recorded in Table 5 below.

[0193] [Table 5]

[0194] Division Luminous intensity Example 1 3.46 Example 2 3.65 Example 3 3.23 Example 4 3.53 Example 5 3.67 Comparative Example 1 1.53 Comparative Example 2 Stripping Comparative Example 3 1.22

[0195] The higher the measured luminous intensity, the higher the light efficiency. In this regard, referring to Table 6, it can be confirmed that in the case of Examples 1 to 5 containing photopolymerizable compounds added with ethylene oxide and propylene oxide, the luminous intensity is 3 or more and significantly improved. On the contrary, it can be confirmed that in the case of Comparative Examples 1 to 3, the light efficiency is 2 or less and decreased.

[0196] Experimental Example 4: Measurement of viewing angle

[0197] In the color filter manufactured using the metal oxide photosensitive resin prepared by the above-mentioned Examples 1 to 5 and Comparative Examples 1 to 3, a goniophotometer (GC-5000L, Nippon Denshoku) was used to measure the intensity (Intensity) of light generated by the viewing angle under light transmission conditions in a portion formed by a 20×20 mm square pattern, and the diffusion coefficient was calculated using the following formula 1.

[0198] [Formula 1]

[0199] Diffusion rate = (B 70 +B 20 ) / 2×B 5 ×100

[0200] (B θ =I θ / cosθ)

[0201] I refers to the light intensity measured at each angle, B 70 , B20 and B 5 Refers to the values ​​measured at 70 degrees, 20 degrees and 5 degrees.

[0202] [Table 6]

[0203] Diffusion rate Example 1 88.3 Example 2 91.3 Example 3 85.7 Example 4 89.1 Example 5 90.6 Comparative Example 1 20.6 Comparative Example 2 Stripping Comparative Example 3 30.7

[0204] This means that the higher the measured diffusivity, the better the viewing angle. With reference to Table 7, it can be confirmed that the diffusivities of Examples 1 to 5 containing photopolymerizable compounds added with ethylene oxide and propylene oxide are 85 or more, and the viewing angle is significantly improved. On the contrary, in the case of Comparative Examples 1 and 3, it can be confirmed that the diffusivities are significantly lower than those of Examples 1 to 5, and the viewing angle is lowered or peeled off, and the diffusivities cannot be measured.

[0205] Industrial Applicability

[0206] The present invention provides a color filter, which contains a photopolymerizable compound containing alkylene oxide in the above-mentioned blue photosensitive resin composition, so as to control the development speed, remove the residue of the pattern, and solve the problem caused by the residue in the process, and improve the display problem and the problem of the resist not being developed. In addition, it is possible to provide a self-luminous color filter with high quality image quality and excellent viewing angle by adjusting the taper.

Claims

1. A blue photosensitive resin composition comprising scattering particles, a blue colorant, a photoinitiator, a Cardo-type binder resin as a binder resin, and a photopolymerizable compound, wherein: The average particle size of the scattering particles is 10 nm to 1000 nm. The scattering particles include one or more selected from the group consisting of Al2O3, SiO2, ZnO, ZrO2, BaTiO3, TiO2, Ta2O5, Ti3O5, Nb2O3, SnO and MgO, The cardo-based binder resin is synthesized from the following compounds: one of the compounds represented by the following chemical formulas 1-1-1 to 1-2-2, one of biphenyltetracarboxylic dianhydride and benzenetetracarboxylic dianhydride, and 1,2,3,6-tetrahydrophthalic anhydride. The photopolymerizable compound is one or more selected from the group consisting of ethylene oxide-modified trimethylolpropane triacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, ethylene oxide-modified pentaerythritol tetraacrylate, propylene oxide-modified pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hexaacrylate, propoxylated pentaerythritol polyacrylate, propoxylated dipentaerythritol hexaacrylate, and ethoxylated glycerol triacrylate, [Chemical formula 1-1-1] [Chemical formula 1-1-2] [Chemical formula 1-2-1] [Chemical formula 1-2-2] 2. The blue photosensitive resin composition according to claim 1, wherein The blue photosensitive resin composition further includes a purple colorant.

3. The blue photosensitive resin composition according to claim 1, wherein The blue photosensitive resin composition further includes a photopolymerizable compound that does not contain an alkylene oxide.

4. The blue photosensitive resin composition according to claim 1, wherein The blue colorant includes one or more of a blue pigment and a blue dye.

5. The blue photosensitive resin composition according to claim 1, wherein The blue photosensitive resin composition further includes an acrylic alkali-soluble resin as a binder resin.

6. The blue photosensitive resin composition according to claim 1, wherein The blue photosensitive resin comprises, relative to the total weight of the solid components, 0.1 wt % to 50 wt % of scattering particles; 0.1 wt % to 50 wt % of a blue colorant; 5 wt % to 85 wt % of a binder resin; and 5 wt % to 50 wt % of a photopolymerizable compound. 0.1 wt % to 30 wt % of a photoinitiator; and 0.001 wt % to 10 wt % of a UV absorber, wherein the UV absorber comprises one or more of benzotriazoles, triazines and benzophenones, and relative to the total weight of the blue photosensitive resin composition, comprises 60 wt % to 90 wt % of a solvent. 7 . A color filter comprising a blue pattern layer formed from the blue photosensitive resin composition according to claim 1 .

8. The color filter according to claim 7, wherein: The color filter further includes one or more selected from the group consisting of a red pattern layer and a green pattern layer.

9. The color filter according to claim 8, wherein The red pattern layer or the green pattern layer includes quantum dots.

10. The color filter according to claim 9, wherein The color filter is a self-luminous color filter.

11. An image display device, comprising: The color filter according to claim 7; as well as A light source that emits blue light.

Images