JP2019168686A - Coloring photosensitive resin composition, color filter and image display device manufactured by using the same - Google Patents

Abstract

To provide a coloring photosensitive resin composition capable of improving all of development speed and adhesion.SOLUTION: A coloring photosensitive resin composition contains an alkali soluble resin containing one or more first polymer containing a repeating unit derived from a 2-acryloyloxyethyl succinate monomer, and a repeating unit containing a reaction residue of an acid group in the repeating unit and an epoxy group, and a polymerizable double bond as side chains; and one or more second polymer different from the first polymer, in which the first polymer is contained at 1 to 60 pts.wt. based on 100 pts.wt. of whole alkali soluble resin.SELECTED DRAWING: Figure 1c

Description

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

  A color filter is a thin film optical component that enables extraction of three colors of red, green, and blue from white light and enables them in units of minute pixels. The size of one pixel is several tens to several hundreds of micrometers. Degree. Such a color filter has a plurality of colors (usually in order to form a black matrix layer formed in a predetermined pattern on a transparent substrate and each pixel in order to shield a boundary portion between each pixel. , Red (R), green (G), and blue (B)) pixel portions in which three primary colors are arranged in a predetermined order.

  Recently, a pigment dispersion method using a pigment-dispersed photosensitive resin has been applied as one of the methods for embodying a color filter, but in the process that light emitted from a light source passes through the color filter, Part of the light is absorbed by the color filter, resulting in a decrease in light efficiency, and color reproduction is reduced due to the characteristics of the pigment contained in the color filter.

  In order to solve such a problem, Patent Document 1 relates to a colored curable composition, a color filter and a method for producing the same, and a solid-state imaging device, specifically (A) via a linking group containing an ester group. A polymer containing a structural unit having a carboxyl group bonded to a chain, (B) a photopolymerization initiator, (C) a polymerizable compound, (D) a pigment, and (E) a dispersant containing a phosphate group. The content regarding the colored curable composition is disclosed.

  However, the colored photosensitive resin compositions disclosed in the conventional literature are in fact somewhat insufficient to satisfy both the development speed and the adhesion.

  Therefore, development of a colored photosensitive resin composition that can improve all the development speed and adhesion is required.

Korean Patent Publication No. 2011-0065424

  The present invention provides a colored photosensitive resin composition with improved development speed and adhesion.

  The present invention also provides a color filter and an image display device that are excellent in adhesion and excellent in performance such as durability.

  The present invention includes a repeating unit derived from 2-acryloyloxyethyl succinate monomer, and a repeating unit containing a reaction residue of a repeating unit internal acid group and an epoxy group and a polymerizable double bond as a side chain. Including one or more first polymers; and one or more second polymers different from the first polymer; and the first polymer comprises 100 parts by weight of the total alkali-soluble resin. A colored photosensitive resin composition contained in an amount of 1 to 60 parts by weight is provided.

  Moreover, this invention provides the color filter containing the hardened | cured material of the coloring photosensitive resin composition mentioned above.

  The present invention also provides an image display device including the color filter described above.

  The colored photosensitive resin composition according to the present invention has an advantage that development speed and adhesion can be improved.

  In addition, the color filter and the image display device manufactured using the colored photosensitive resin composition according to the present invention have an advantage that adhesion is improved and durability is excellent.

FIG. 1 a is a diagram illustrating a procedure for a color filter manufacturing method using a colored photosensitive resin composition. FIG. 1 b is a diagram illustrating a procedure diagram for a method of manufacturing a color filter using a colored photosensitive resin composition. FIG. 1 c is a diagram illustrating a procedure diagram for a method of manufacturing a color filter using a colored photosensitive resin composition.

  Hereinafter, the present invention will be described in more detail.

  In the present invention, when an arbitrary member is located "on" another member, this is not only when the arbitrary member is in contact with the other member, but also between the two members. Including the case where

  In the present invention, when any part “includes” a certain component, this does not exclude other components, and may further include other components unless otherwise stated to the contrary. Means.

<Colored photosensitive resin composition>
One aspect of the present invention includes a repeating unit derived from 2-acryloyloxyethyl succinate monomer, a reaction residue of an acid group and an epoxy group in the repeating unit, and a side chain including a polymerizable double bond. Including one or more first polymers; and one or more second polymers different from the first polymer; and the first polymer comprises 100 parts by weight of the total alkali-soluble resin. It is related with the coloring photosensitive resin composition contained by 1-60 weight part with respect to this.

Alkali-soluble resin The alkali-soluble resin according to the present invention comprises one or more first polymers and one or more second polymers different from the first polymer, and the first polymer comprises 2-acryloyloxyethyl succinate. A repeating unit derived from an nate monomer, and a repeating unit containing a reaction residue of an acid group and an epoxy group in the repeating unit and a polymerizable double bond as a side chain, wherein the first polymer comprises the alkali It is contained at 1 to 60 parts by weight with respect to 100 parts by weight of the whole soluble resin.

  Specifically, the first polymer includes a repeating unit derived from 2-acryloyloxyethyl succinate monomer, and the acid contained in the repeating unit derived from 2-acryloyloxyethyl succinate monomer. By reacting the group with an epoxy group-containing monomer having a polymerizable double bond, a reaction residue of an acid group and an epoxy group and a side chain containing a polymerizable double bond can be included.

  The first polymer according to the present invention includes a repeating unit derived from the 2-acryloyloxyethyl succinate monomer, a reaction residue of an acid group and an epoxy group in the repeating unit, and a side containing a polymerizable double bond. When it contains a chain and falls within the above range, there is an advantage that a colored photosensitive resin composition excellent in adhesion can be obtained without causing a development residue phenomenon although the development speed is high.

  Preferably, the first polymer may be included in an amount of 20 to 50 parts by weight, more preferably 30 to 50 parts by weight with respect to 100 parts by weight of the total alkali-soluble resin, and in this case, there is an advantage that a development speed is high. It is more preferable.

  Specific examples of the epoxy group-containing monomer having a polymerizable double bond include glycidyl (meth) acrylate, allyl glycidyl ether, α-ethylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate (for example, Daicel). "Cyclomer (registered trademark) A400" manufactured by Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, "Cyclomer M100" manufactured by Daicel Chemical Industries, Ltd.), etc. It is not something.

  In one embodiment of the present invention, the repeating unit derived from the 2-acryloyloxyethyl succinate monomer is 5 to 50 parts by weight, preferably 20 to 40 parts by weight based on 100 parts by weight of the entire first polymer. Parts, more preferably 30-40 parts by weight.

  In still another embodiment of the present invention, the repeating unit including a reaction residue of an acid group and an epoxy group in the repeating unit and a polymerizable double bond as a side chain is based on 100 parts by weight of the entire first polymer. 50 to 95 parts by weight, preferably 60 to 80 parts by weight, more preferably 60 to 70 parts by weight. The repeating unit derived from the monomer containing the side chain is a reaction residue between an acid group and an epoxy group in the repeating unit derived from the 2-acryloyloxyethyl succinate monomer contained in the first polymer. And a moiety containing a side chain containing a polymerizable double bond.

  In still another embodiment of the present invention, the first polymer includes a repeating unit derived from an N-substituted maleimide monomer, a repeating unit derived from a 2-ethoxyethyl (meth) acrylate monomer, and 2-hydroxyethyl. One or more repeating units selected from the group consisting of repeating units derived from (meth) acrylates can be further included.

  Examples of the N-substituted maleimide monomer include N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, and Np-hydroxyphenyl. Maleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, etc. However, it is not limited to these.

  It is preferable that the first polymer further includes a repeating unit derived from an N-substituted maleimide monomer because there is an advantage that heat resistance is improved.

  It is preferable that the first polymer further includes a repeating unit derived from a 2-ethoxyethyl (meth) acrylate monomer because chemical resistance is improved.

  When the said 1st polymer further contains the repeating unit derived from 2-hydroxyethyl (meth) acrylate, since there exists an advantage which developability improves, it is preferable.

  In still another embodiment of the present invention, the first polymer includes a repeating unit derived from an N-substituted maleimide monomer, a repeating unit derived from a 2-ethoxyethyl (meth) acrylate monomer, and 2-hydroxyethyl. It can contain repeating units derived from (meth) acrylates.

  Specifically, the first polymer is a repeating unit derived from a 2-acryloyloxyethyl succinate monomer, a repeating unit derived from an N-substituted maleimide monomer, and a single amount of 2-ethoxyethyl (meth) acrylate. A repeating unit derived from a body and a repeating unit derived from 2-hydroxyethyl (meth) acrylate, and a side chain including a reactive residue of an acid group and an epoxy group in the repeating unit and a polymerizable double bond. .

  When the first polymer includes all the repeating units derived from the monomer, the development speed phenomenon is high, but the development residue phenomenon does not occur, the adhesion and the reliability are maximized. Therefore, it is preferable.

  In still another embodiment of the present invention, the repeating unit derived from the N-substituted maleimide monomer is 1 to 30 parts by weight, preferably 3 to 25 parts by weight, based on 100 parts by weight of the entire first polymer. , More preferably 5 to 20 parts by weight.

  In still another embodiment of the present invention, the repeating unit derived from the 2-ethoxyethyl (meth) acrylate monomer is 1 to 35 parts by weight, preferably 5 to 100 parts by weight based on the whole first polymer. It may be included at 30 parts by weight, more preferably 10-25 parts by weight.

  In still another embodiment of the present invention, the repeating unit derived from the 2-hydroxyethyl (meth) acrylate monomer is 5 to 30 parts by weight, preferably 7 to 100 parts by weight based on 100 parts by weight of the entire first polymer. It may be contained in an amount of 25 parts by weight, more preferably 10 to 20 parts by weight.

  When the repeating unit derived from each monomer satisfies the above range, the repeating unit derived from each monomer is preferable because the intended effect can be maximized.

  The first polymer is composed of a repeating unit derived from an N-substituted maleimide monomer, a repeating unit derived from a 2-ethoxyethyl (meth) acrylate monomer, and a repeating unit derived from 2-hydroxyethyl (meth) acrylate. When further including one or more selected from the above, the repeating unit derived from the 2-acryloyloxyethyl succinate monomer is 5 to 50 parts by weight, preferably 10 to 10 parts by weight based on 100 parts by weight of the entire first polymer. It may be included at 40 parts by weight, more preferably 15-30 parts by weight.

  The repeating unit derived from a monomer containing a side chain is 10 to 50 parts by weight, preferably 20 to 40 parts by weight, more preferably 25 to 35 parts by weight, based on 100 parts by weight of the entire first polymer. Can be included.

  The first polymer may further include additional repeating units in addition to the above-described repeating units, but is not limited thereto.

For example, the repeating unit that may be further included in the first polymer may be derived from a polymerized monomer having an unsaturated bond, and specifically, monolithic monomers such as acrylic acid, methacrylic acid, and crotonic acid. Carboxylic acids; Dicarboxylic acids such as fumaric acid, mesaconic acid, itaconic acid; and anhydrides of these dicarboxylic acids; mono (meta) of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate ) Acrylates, etc., more specifically acrylic acid, methacrylic acid, styrene, vinyl toluene, α-methyl styrene, p-chlorostyrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene O-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl vinyl Aromatic vinyl compounds such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) Alkyl (meth) acrylates such as acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-dicyclopentanyl Oki Alicyclic (meth) acrylates such as ethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) oxetane 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane And unsaturated oxetane compounds such as 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane.

  When the repeating unit that can be further contained contains an acid group, the repeating unit containing the acid group reacts with an epoxy group-containing monomer having a polymerizable double bond to thereby react the acid group and the epoxy group. It can also include, but is not limited to, side groups including reactive residues with groups and polymerizable double bonds.

  The above-mentioned content can be applied to the epoxy group-containing monomer.

  The second polymer is derived from the 2-acryloyloxyethyl succinate monomer repeating unit and the 2-acryloyloxyethyl succinate monomer among the repeating units constituting the first polymer. By reacting an acid group contained in the repeating unit with an epoxy group-containing monomer having a polymerizable double bond, a reaction residue of the acid group and the epoxy group and a side chain containing a polymerizable double bond are formed. It means a polymer that does not contain.

  The second polymer may include one or more of the above-described additional repeating units, but is not limited thereto, and the binder resin having alkali solubility usually used in the industry is not limited. Can be used.

  Specific examples of the second polymer include a carboxyl group-containing monomer and a copolymer with another monomer copolymerizable with the monomer.

  Examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, and other unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule. A carboxylic acid etc. are mentioned. Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, phthalate, and the like. Examples include acid mono (2-acryloyloxyethyl) and phthalate mono (2-methacryloyloxyethyl). The unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. The carboxyl group-containing monomers can be used alone or in admixture of two or more.

  The carboxyl group-containing monomer includes a reaction residue of an acid group and an epoxy group and a side chain including a polymerizable double bond by reacting with an epoxy group-containing monomer having a polymerizable double bond. However, the present invention is not limited to this, and the above-mentioned content can be applied to the epoxy group-containing monomer having a polymerizable double bond, but it is not limited thereto.

  Examples of other monomers copolymerizable with the carboxyl group-containing monomer include ethylenically unsaturated monomers containing double bonds, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p. -Vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl Aromatic vinyl compounds such as ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 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-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-hydro Xylbutyl 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 methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol Monoacrylate, glycerol Unsaturated carboxylic acid esters such as methacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylic acid aminoalkyl esters such as dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate; glycidyl acrylate Glycidyl esters of unsaturated carboxylic acids such as glycidyl methacrylate; vinyl acetate, vinyl propionate, vinyl butyrate, benzoate Carboxylic acid vinyl esters such as vinyl acid; 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; acrylamide Unsaturated amides such as methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethyl methacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl meta Relate, giant monomers having Monoakuriroiru group or mono-methacryloyl group at the terminal of the polymer molecular chain of the polysiloxane, and the like. These monomers can be used alone or in admixture of two or more.

  The content of the carboxyl group-containing monomer unit in the second polymer is usually 10 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the whole second polymer. More preferably, it may be 13 to 30 parts by weight. When the content of the carboxyl group-containing monomer unit satisfies the above range, it is preferable because the solubility in a developer is good and the pattern tends to be formed accurately during development.

  More specifically, the second polymer includes (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2- Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (Meth) acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate Giant monomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate Benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, ( (Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxy) / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer Polymer, (meth) acrylic acid / mono (2-acryloyloxyethyl) succinate / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / benzyl (meth) acrylate / N- Phenylmaleimide / styrene / glycerol Roh (meth) acrylate copolymer, and the like.

  Among these, acrylic acid / benzyl (meth) acrylate / styrene copolymer, acrylic acid / methyl (meth) acrylate / styrene copolymer, methyl methacrylate / benzyl methacrylate / acrylic acid copolymer and the above-mentioned copolymer are included. A copolymer that can contain a side chain containing a reactive residue of an acid group and an epoxy group and a polymerizable double bond by reacting an acid group of acrylic acid with an epoxy group of glycidyl (meth) acrylate is preferable. Can be used.

  The second polymer may be included in an amount of 40 to 99 parts by weight, preferably 40 to 70 parts by weight, more preferably 40 to 60 parts by weight, based on 100 parts by weight of the total alkali-soluble resin. It is preferable because the occurrence of the phenomenon can be suppressed and there is an advantage of excellent adhesion.

  In still another embodiment of the present invention, the alkali-soluble resin is 10 to 80 parts by weight, preferably 20 to 70 parts by weight, more preferably 100 parts by weight based on the total solid content of the colored photosensitive resin composition. It can be contained in an amount of 20 to 60 parts by weight. In this case, it is preferable because the pattern can be easily formed and the resolution and the remaining film ratio tend to be improved.

  As recorded herein, (meth) acrylate means acrylate and / or methacrylate.

  The alkali-soluble resin of the present invention may have an acid value in the range of 20 to 200 (mgKOH / g). If the acid value is in the above range, the solubility in the developer is improved, the non-exposed part is easily dissolved, the sensitivity is increased, and as a result, the pattern of the exposed part remains during development, This is preferable because it improves the film remaining ratio.

  Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and is usually titrated using an aqueous potassium hydroxide solution. It can ask for.

  The weight average molecular weight in terms of polystyrene (hereinafter simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) is 3,000 to 200,000, preferably 5,000. Alkali-soluble resins that are ~ 100,000 are 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 unexposed portion in the developer is excellent, and the resolution tends to be improved, which is preferable.

  In still another embodiment of the present invention, the colored photosensitive resin composition may further include one or more selected from the group consisting of a colorant, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive. .

Colorant The colorant of the present invention is not limited in color tone, and can be selected according to the use of the obtained color filter. The colorant may be any one of a pigment, a dye, and a natural pigment, and the pigment is a compound classified as a pigment by a color index (published by The Society of Dyers and Colorists). Can be used. The colorant of the present invention is preferably an organic pigment from the viewpoint of excellent heat resistance and color developability.

  Specific examples of preferable pigments that can be used in the present invention include C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 53, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 173, C.I. I. Pigment yellow 194, C.I. I. Yellow pigments such as CI Pigment Yellow 214; I. Pigment orange 13, C.I. I. Pigment orange 31, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 42, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 55, C.I. I. Pigment orange 59, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 65, C.I. I. Pigment orange 71, C.I. I. Orange pigments such as CI Pigment Orange 73; I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 105, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 264, C.I. I. Red pigments such as CI Pigment Red 265; I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Blue pigments such as CI Pigment Blue 60; I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Violet color pigments such as CI Pigment Violet 38; I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Green pigments such as CI Pigment Green 58; I. Pigment brown 23, C.I. I. A brown pigment such as CI Pigment Brown 25; I. Pigment black 1, C.I. I. And black pigments such as CI Pigment Black 7. Among these, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 209, C.I. I. Pigment red 254, C.I. I. Pigment violet 23, C.I. I. Pigment blue 15: 6 and C.I. I. It is preferable to include one or more pigments selected from among CI Pigment Green 36. The organic pigment and the inorganic pigment can be used alone or in combination of two or more. For example, in order to form a red pixel, C.I. I. Pigment red 254 and C.I. I. Pigment Yellow 139 is contained, and in order to form a green pixel, C.I. I. Pigment green 58, C.I. I. Pigment yellow 150 or C.I. I. Pigment Yellow 138 is contained, and in order to form a blue pixel, C.I. I. Pigment Blue 15: 6 is preferably contained.

  As long as the dye of the present invention has solubility in an organic solvent, one or more kinds can be additionally used without limitation. Preferably, it is preferable to use a dye that has a solubility in an organic solvent and can ensure the solubility in an alkali developer, heat resistance, solvent resistance, and the like. As the dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or a derivative thereof can be used. In addition, azo, xanthene, and phthalocyanine acid dyes and derivatives thereof can be selected. Examples of the dye include compounds classified as dyes in the color index (published by The Society of Dyers and Colorists), and known dyes described in dyeing notes (color dyeing company).

Specific examples of the dye include C.I. I. As solvent dye,
C. I. Yellow dyes such as solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C. I. Red dyes such as Solvent Red 8, 45, 49, 122, 125, 130;
C. I. Orange dyes such as Solvent Orange 2, 7, 11, 15, 26, 45, 56, 62;
C. I. Blue dyes such as Solvent Blue 35, 37, 45, 59, 67;
C. I. Examples thereof include green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.

In addition, C.I. I. As an acid dye, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251, etc .;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;
C. I. Orange dyes such as Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 Blue dyes such as 335, 340;
C. I. Violet dyes such as Acid Violet 6B, 7, 9, 17, 19;
C. I. And green dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109.

In addition, C.I. I. C. as a direct dye I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, Yellow dyes such as 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, Red dyes such as 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Orange dyes such as Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, Blue of 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc. Dyes;
C. I. Violet color dyes such as direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.

In addition, C.I. I. As a modern dye, C.I. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, etc. yellow dyes;
C. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95, etc. red dyes;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc. dye;
C. I. Modern 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, 84, etc .;
C. I. Modern violet dyes such as 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern green 1,3,4,5,10,15,19,26,29,33,34,35,41,43,53 etc. are mentioned.

The colorant of the present invention can be used alone or in combination of two or more.
The colorant may be included in an amount of 10 to 70 parts by weight, preferably 18 to 60 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. If it is within the above range, the color density when produced in the color filter is sufficient, and the composition polymer can be included in the composition in a necessary amount, so that a pattern with sufficient mechanical strength can be formed. .

  In the present invention, the solid content of the colored photosensitive composition means the total of components from which the solvent has been removed.

  Among the above-mentioned pigments, organic pigments include surface treatment using a pigment derivative or the like into which an acidic group or basic group has been introduced, a pigment surface graft treatment with a polymer compound, or the like, a sulfuric acid atomization method (refinement method). ) And the like, cleaning treatment with an organic solvent or water for removing impurities, or removal treatment of ionic impurities by an ion exchange method or the like.

  The colorant preferably has a uniform particle diameter, and when the colorant is a pigment, the pigment is dispersed uniformly in the solution by adding a pigment dispersant and performing a dispersion treatment. A pigment dispersion can be obtained.

  Examples of the pigment dispersant may include surfactants such as cationic, anionic, nonionic, amphoteric, polyester and polyamine, and these may be used alone or in combination of two or more. Can be used in combination. When a pigment dispersant is used, the amount used is preferably 1 part by weight or less, more preferably 0.05 part by weight or more and 0.7 part by weight or less per 1 part by weight of the colorant. If the amount of the pigment dispersant used is in the above range, it is preferable because a pigment in a uniform dispersion state tends to be obtained.

Photopolymerizable compound A photopolymerizable compound is a compound that can be polymerized by an active radical, acid, etc. generated from a photopolymerization initiator upon irradiation of light, and is monofunctional, bifunctional, or trifunctional polymerization depending on the number of functional groups. Compound.

  Specific examples of the monofunctional polymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. It is done.

  Specific examples of the bifunctional polymerizable compound include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth). Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, butylene glycol dimethacrylate, hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di ( (Meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate Rate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, and the like.

  Specific examples of the trifunctional polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylate trimethylolpropane tri (meth) acrylate, propoxylate trimethylolpropane tri (meth) ) Acrylate, glyceryl propoxylate triacrylate, isocyanurate triarylate and the like.

  Specific examples of the tetrafunctional polymerizable compound include pentaerythritol tetra (meth) acrylate and dimethylolpropane tetra (methyl) acrylate.

  Further, specific examples of the pentafunctional polymerizable compound include dipentaerythritol penta (meth) acrylate, and specific examples of the hexafunctional photopolymerizable compound include dipentaerythritol hexa (meth) acrylate. Is mentioned.

  Among these, as the photopolymerizable compound, a bifunctional or higher polyfunctional polymerizable compound can be preferably used, and a pentafunctional or higher polyfunctional polymerizable compound can be preferably used.

  The photopolymerizable compound of the present invention can be used alone or in combination of two or more. The photopolymerizable compound is preferably contained in an amount of 5 to 50 parts by weight, more preferably 7 to 45 parts by weight, based on 100 parts by weight of the total solid content in the colored photosensitive resin composition. It is preferable that the photopolymerizable compound is contained in the above-described range based on the above criteria because the strength and smoothness of the pixel portion are improved.

Photopolymerizable initiator The photopolymerizable initiator of the present invention is not particularly limited as long as it can polymerize the above-described photopolymerizable compound and the alkali-soluble resin. However, polymerization characteristics, initiation efficiency, absorption From the viewpoint of wavelength, availability, price, etc., at least one selected from acetophenone, benzoin, benzophenone, thioxanthone, triazine, oxime, onium salt, nitrobenzyl tosylate, or benzoin tosylate It is preferable to contain a seed compound, and a light stabilizer can be used in combination.

  Preferred acetophenone compounds for the present invention include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- There is an oligomer of 1- [4- (1-methylvinyl) phenyl] propan-1-one, and 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one is more preferable. A plurality of acetophenone compounds and other photopolymerization initiators can also be used in combination. Examples of the photopolymerization initiator other than the acetophenone-based compound include an active radical generator, an increase / decrease agent, an acid generator, and the like that generate an active radical when irradiated with light.

  Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxy). Carbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (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.

  Examples of the oxime compounds include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl-phenyl) -butane-1,2. -Butane-2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O- Examples include acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate, and the like.

  Examples of the increase / decrease agent include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biphenyl. Examples include imidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexanium. Onium salts such as fluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, etc. Can be mentioned.

  Some of the compounds generate active radicals and acids at the same time. For example, the triazine photopolymerization initiator can also be used as an acid generator.

  Examples of commercially available photopolymerization initiators include OXE01 manufactured by BASF, but are not limited thereto.

  The photopolymerization initiator of the present invention is preferably contained in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the entire solid content of the colored photosensitive resin composition. Is more preferable. When the photopolymerization initiator is included in the above range, the sensitivity is increased and the exposure time is shortened, which is preferable because productivity can be improved and high resolution can be maintained.

  The colored photosensitive resin composition of the present invention can further contain a photopolymerization initiation auxiliary agent. The photopolymerization initiation auxiliary agent may be used in combination with a photopolymerization initiator, and is used to promote polymerization of a photopolymerizable compound that has been polymerized by the photopolymerization initiator.

  Examples of the photopolymerization initiation auxiliary agent include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds. Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethyl) Methylamino) benzophenone and the like, and among these, 4,4′-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like. . Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. The photopolymerization initiators can be used alone or in combination of two or more.

  In addition, as the photopolymerization initiation auxiliary agent, a commercially available product can be used, and examples of the commercially available photopolymerization initiation auxiliary agent include EAB-F (Hodogaya Chemical Co., Ltd. product).

  Preferred combinations of a photopolymerization initiator and a photopolymerization initiation auxiliary agent for the colored photosensitive resin composition of the present invention include diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone and 2-methyl-2-morpholino-1. -(4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-phenylpropan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4 ′ -Bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- 1-methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / And combinations of 4,4′-bis (diethylamino) benzophenone and the like, more preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) ) There is a combination of benzophenone.

  When the photopolymerization initiator and the photopolymerization initiation auxiliary are used together as described above, the photopolymerization initiation auxiliary is preferably used at 10 mol or less per 1 mol of the photopolymerization initiator, More preferably, it is used in an amount of 0.01 to 5 mol.

Solvent The solvent of the present invention can be used as long as it is effective for dispersing or dissolving other components, and ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are particularly preferable. .

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Recall monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, heptyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, and the like.

  Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.

  Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone.

  Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexaneol, ethylene glycol, and glycerin.

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and oxyacetic acid. Methyl, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxypropionic acid Chill, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methylpropionic acid Ethyl, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, Examples include ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.

  Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.

  Examples of other solvents include N-methylpyrrolidone and dimethyl sulfoxide.

  Among the solvents, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate or propylene glycol methyl ether is preferable.

  The solvent is 10 to 90 parts by weight, preferably 20 to 85 parts by weight, more preferably 30 to 85 parts by weight, based on 100 parts by weight of the whole colored photosensitive resin composition, or two or more kinds. Can be used in combination. If the content of the solvent is within the above range, the flatness at the time of coating is good, and when a color filter is formed, the color density is sufficient and the display characteristics are good, which is preferable.

Additives The additives can be selectively added as necessary, and include, for example, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation preventing agents. 1 or more types chosen from the group which consists of an agent can be included.

  Moreover, it is most preferable that a surfactant is included among the additives.

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

  The curing agent is used to enhance deep curing and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

  Specific examples of the epoxy compound in the curing agent include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, and other aromatics. Epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of the above epoxy resins, aliphatic resins other than epoxy resins and brominated derivatives thereof, alicyclic or aromatic epoxy compounds Butadiene (co) polymer epoxidized product, isoprene (co) polymer epoxidized product, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate and the like.

  Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent.

  Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. What is marketed as an epoxy resin hardening | curing agent can be utilized for the said polyhydric carboxylic acid anhydrides. Examples of the commercially available products include ADEKA HARDNER EH-700 (manufactured by ADEKA INDUSTRY CO., LTD.), RIKACID HH (manufactured by Shin Nippon Rika Co., Ltd.) and MH-700 (manufactured by Nippon Nippon Rika Co., Ltd.). The curing agents exemplified above can be used alone or in admixture of two or more.

  The surfactant can be used to further improve the film formation of the colored photosensitive resin composition, and is a silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, amphoteric surfactant. Etc. can be preferably used.

  Examples of the silicone-based surfactant include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Toray Dow Corning Silicone as commercially available products, and TSF-4440, TSF-4300, TSF-4445, and GE Toshiba Silicone. There are TSF-4446, TSF-4460, TSF-4442, and the like.

  Examples of the fluorosurfactant include Megaface F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals, Inc. as commercially available products.

  As other commercially available products, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (POLYFLOW) (manufactured by Kyoeisha Chemical Co., Ltd.), FTOP (EFTOP) (manufactured by Tochem Products), MegaFac (MEGAFAC) (Dainippon Ink & Chemicals), Florad (Sumitomo 3M), Asahi guard, Surflon (above, Asahi Glass), SOLSPERSE (Lubrisol), EFKA ( EFKA Chemicals), PB 821 (Ajinomoto Co.), Disperbyk-series (BYK-chemi), and the like.

  Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts.

  Examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and dodecylnaphthalenesulfone. And alkyl aryl sulfonates such as sodium acid.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, and sorbitan fatty acid esters. And polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester and polyoxyethylene alkylamine.

  The exemplified surfactants can be used alone or in combination of two or more.

  The kind of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Mercaptopropyltrimethoxy Run, 3-isocyanate propyl trimethoxysilane and 3-isocyanate propyl triethoxysilane, and the like.

  The adhesion promoters exemplified above can be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

  The type of the antioxidant is not particularly limited, and examples thereof include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol and the like.

  The type of the ultraviolet absorber is not particularly limited, and specific examples that can be used include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone. Etc.

  The type of the anti-aggregation agent is not particularly limited, and specific examples that can be used include sodium polyacrylate.

  The additive can be used in addition to an appropriate content as long as the object of the present invention is not impaired. For example, the additive is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the whole colored photosensitive resin composition. It can be included, but is not limited to this.

  The colored photosensitive resin composition of the present invention can be produced, for example, by the following method. The colorant is mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle size of the coloring material is about 0.2 μm or less. At this time, a pigment dispersant is used as necessary, and some or all of the alkali-soluble resin may be blended. Residue of alkali-soluble resin, additive such as photopolymerizable compound and photopolymerization initiator, antioxidant, other components used as necessary in the obtained dispersion (hereinafter sometimes referred to as mill base) Further, if necessary, a further solvent may be further added so as to have a predetermined concentration to obtain a target colored photosensitive resin composition.

<Color filter>
The other aspect of this invention is related with the color filter containing the hardened | cured material of the colored photosensitive resin composition mentioned above.

  Specifically, the present invention provides a color filter comprising a color layer formed by applying a colored photosensitive resin composition on an upper portion of a substrate, and exposing and developing in a predetermined pattern. There is provided a color filter using the above-described colored photosensitive resin composition as a product.

  A partition wall may be further formed between the colored patterns, and a black matrix may be added. Further, a protective film may be further formed on the color filter shown in the drawing. 1a to 1c are procedural diagrams for a method for producing a color filter using the above-described colored photosensitive resin composition.

  In order to form a colored pattern, for example, the colored photosensitive resin composition of the present invention is subjected to pattern treatment. Specifically, a color layer 11 made of a colored photosensitive resin composition is formed on the top of the substrate 10 (FIG. 1a), and the formed color layer 11 is irradiated with light in a predetermined pattern (FIG. 1b). And developing (FIG. 1c).

The substrate 10 is not limited and may be a color filter substrate itself, or may be a part where the color filter is located in a display device or the like. The substrate may be a glass plate, a silicon wafer, and a plastic plate such as PES (Poly Ether Sulfone) and PC (Poly Carbonate). That is, the substrate may be silicon (Si), silicon oxide (SiO _x ), a glass substrate, or a polymer substrate.

  In order to form the color layer 11 made of the colored photosensitive resin composition on the substrate 10, for example, the colored photosensitive resin composition diluted with a solvent is spun, spin after slitting, slit, roll, spray, ink jet method, etc. After coating on the substrate by the coating method, a volatile component such as a solvent is volatilized. As a result, a color layer 11 made of a colored photosensitive resin composition is formed. The color layer is formed by solid formation of the colored photosensitive resin composition and contains almost no volatile component.

  The thickness of the film surface is determined by coating conditions such as the viscosity of the composition, the solid content concentration, the coating speed, and the like. When the composition of the present invention is used, the color layer 11 having a thickness of 0.5 to 5 μm. Can be obtained.

  Next, the color layer 11 made of the colored photosensitive resin composition is exposed to light. In order to expose, for example, the color layer is irradiated with light in a predetermined pattern through the photomask 20. As light, ultraviolet g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm) and the like are usually used. The light passes through the pattern of the photomask. The photomask provides a light shielding layer that shields light rays in a predetermined pattern on the surface of a glass plate. The light 30 is shielded by the light shielding layer. The portion of the glass plate that is not provided with the light shielding layer is a light transmitting portion that transmits light. The color layer 11 is exposed by such a pattern of the light transmitting portion. The amount of light irradiation is appropriately selected depending on the colored photosensitive resin composition used. The portion irradiated with the light beam has a much lower solubility than the portion not irradiated with the light beam, and the difference in solubility between the two is maximized.

  Development is performed after exposure. For the development, for example, the colored photosensitive resin composition layer after exposure is immersed in a developer.

  As the developer, an aqueous solution of an alkali compound such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, tetramethylammonium hydroxide is used. By the development, the light non-irradiated region that is not irradiated with the light of the colored photosensitive resin composition layer is removed. On the contrary, the light irradiation area irradiated with the light remains to form a colored pattern.

  After development, the layer is usually washed with water and dried to obtain a predetermined colored pattern. In addition, heat treatment can be performed after drying. The colored pattern formed by the heat treatment is cured, and the mechanical strength is improved. Thus, since the mechanical strength of a coloring pattern can be improved by heat treatment, it is preferable to use a colored photosensitive composition containing a curing agent. The heating temperature is usually 180 ° C. or higher, preferably 200 to 250 ° C.

<Image display device>
Another aspect of the present invention relates to an image display device including the color filter described above.

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

  The image display device may include other configurations that can be included in a normal image display device, such as a light emitting device such as a light source, a light guide plate, and an image display unit including a color filter according to the present invention. This is not limited in the invention.

  The colored photosensitive resin composition according to the present invention has an advantage that it has a high development speed, can prevent development residue, and has excellent adhesion. Thereby, the color filter and image display apparatus manufactured with the colored photosensitive resin composition by this invention have the advantage that it is excellent in performances, such as durability.

  Hereinafter, in order to explain this specification concretely, an example is taken and explained in detail. However, the examples according to the present specification can be modified in various other forms, and the scope of the present specification is not construed to be limited to the examples described in detail below. The examples herein are provided to more fully explain the present specification to those skilled in the art. In addition, “%” and “parts” indicating the content are based on weight unless otherwise specified.

Production Example: Production of Colored Dispersion C.I. I. Pigment Blue 15: 6 Pigment 11.89% by weight, EFKA 4300 (manufactured by BASF) 7.73% by weight, propylene glycol monomethyl ether acetate (PGMAC) 80.38% by weight was mixed and stirred uniformly. Then, using zirconia beads having a diameter of 0.5 mm, the mixture was dispersed for 3 hours with Eiger Meal (“Mini Model M-250 MKII” manufactured by Eiger Japan). Thereafter, the obtained mixture was filtered through a filter having a pore diameter of 5.0 μm to produce a colored dispersion having a nonvolatile component of 19.62% by weight.

Examples and Comparative Examples: Production of colored photosensitive resin compositions Colored photosensitive resin compositions (unit: parts by weight) according to Examples and Comparative Examples were produced according to the constitution and composition shown in Table 1 below.

[Chemical Formula 1]

[Chemical formula 2]

[Chemical formula 3]

Manufacture of color filter After each colored photosensitive resin composition solution is applied onto a glass substrate by spin coating, it is placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. did. Next, a test photomask having a line / space pattern of 1 μm to 50 μm was placed on the thin film, and an ultraviolet ray was irradiated at an interval of 100 μm from the test photomask. At this time, the ultraviolet light source was irradiated at an illuminance of 100 mJ / cm ² using a 1 kW high-pressure mercury lamp containing all g, h, and i rays, and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed by immersing in a KOH aqueous solution developing solution having a pH of 10.5 for 1 minute. The glass plate provided with this thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C. for 30 hours to produce a color filter. The film thickness of the color filter manufactured above was 2.0 μm.

Experimental Example The development speed, development residue, and pattern adhesion of the color filter were measured and evaluated as shown in Table 2 below.

(1) Development speed When a thin film irradiated with ultraviolet rays in the production of a color filter was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 1 minute and developed, the time required until a pattern was formed was shown. .

(2) Development residue A thin film irradiated with ultraviolet rays in the production of a color filter is developed by immersing it in a KOH aqueous solution developing solution having a pH of 10.5 for 1 minute, and the glass plate on which this thin film has been applied is obtained using distilled water. After cleaning, blown with nitrogen gas, dried and then checked with an optical microscope (model name: ECLIPSE LV100POL, manufacturer: Nikon). If there is no development residue on the substrate, it is indicated by “◯”. When a development residue is generated above, it is indicated by “x”.

(3) Pattern adhesion As a result of checking the pattern formed by the color filter manufacturing method presented above with an optical microscope, a pattern with a size of 50 μm remains without omission. In the case where a loss occurs, it is indicated by “x”.

  Referring to Table 2, when the colored photosensitive resin composition according to the example is used, a color filter having no development residue, excellent pattern adhesion, and no pattern defect is produced even though the development speed is high. I can see that In particular, in the case of the comparative example, compared to the case where the excellent development speed, the development residue, and the pattern adhesion are not satisfied, the examples are excellent in the development residue and the pattern adhesion, and exhibit an excellent development speed. I understand.

10 substrate 11 color layer 11R formed color layer 20 photomask 30 light

Claims (9)

Repeating units derived from 2-acryloyloxyethyl succinate monomer;
One or more first polymers comprising a reaction residue of an acid group and an epoxy group in the repeating unit and a repeating unit containing a polymerizable double bond as a side chain; and one or more different from the first polymer A second polymer of
An alkali-soluble resin containing,
The said 1st polymer is a coloring photosensitive resin composition contained by 1-60 weight part with respect to 100 weight part of said alkali-soluble resin whole.   The first polymer includes a repeating unit derived from an N-substituted maleimide monomer, a repeating unit derived from 2-ethoxyethyl (meth) acrylate monomer, and a repeating unit derived from 2-hydroxyethyl (meth) acrylate. The colored photosensitive resin composition according to claim 1, further comprising one or more repeating units selected from the group.   The first polymer includes a repeating unit derived from an N-substituted maleimide monomer, a repeating unit derived from a 2-ethoxyethyl (meth) acrylate monomer, and a repeating unit derived from 2-hydroxyethyl (meth) acrylate. The colored photosensitive resin composition according to claim 2, which is a waste product.   2. The colored photosensitive composition according to claim 1, wherein the repeating unit derived from the 2-acryloyloxyethyl succinate monomer is contained in an amount of 5 to 50 parts by weight with respect to 100 parts by weight of the entire first polymer. Resin composition.   The repeating unit containing a reaction residue of an acid group and an epoxy group in the repeating unit and a polymerizable double bond as a side chain is contained in an amount of 50 to 95 parts by weight with respect to 100 parts by weight of the entire first polymer. The colored photosensitive resin composition according to claim 1, wherein   The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is contained in an amount of 10 to 80 parts by weight with respect to 100 parts by weight as a whole of the solid content of the colored photosensitive resin composition.   The colored photosensitive resin composition according to claim 1, further comprising one or more selected from the group consisting of a colorant, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive.   A color filter comprising a cured product of the colored photosensitive resin composition according to claim 1. An image display device comprising the color filter according to claim 8.