KR20190111193A - A colored photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition which comprises an alkali-soluble resin comprising: at least one first polymer including a repeating unit derived from a 2-acryloyloxyethyl succinate monomer and including a side chain including a reaction residue of an acid group in the repeating unit and an epoxy group and a polymerizable double bond; and at least one second polymer different from the first polymer, wherein the first polymer is included in the amount of 1 to 60 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. The colored photosensitive resin composition improves both development speed and adhesiveness.

Description

Colored photosensitive resin composition, color filter and image display device manufactured using the same {A COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND IMAGE DISPLAY DEVICE PRODUCED USING THE SAME}

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

The color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light and makes them possible in fine pixel units. The size of one pixel is about tens to hundreds of micrometers. Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to shield the boundary between each pixel, and a plurality of colors (typically red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order are stacked in this order.

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

In order to solve such a problem, the Republic of Korea Patent Publication No. 2011-0065424 relates to a colored curable composition, a color filter and a method for manufacturing the same, and a solid-state image sensor, and specifically, (A) is bonded to the main chain through a linker including an ester group. A polymer comprising a structural unit having a carboxyl group, (B) a photopolymerization initiator, (C) a polymerizable compound, (D) a pigment, and a dispersing agent containing (E) a phosphate group. The contents are disclosed.

However, the colored photosensitive resin composition disclosed in the conventional literature is somewhat insufficient to satisfy both the developing speed and the adhesion.

Therefore, development of the coloring photosensitive resin composition which can improve both a development speed and adhesiveness is calculated | required.

Republic of Korea Patent Publication No. 2011-0065424 (2011.06.15)

The present invention is to provide a colored photosensitive resin composition with improved development speed and adhesion.

In addition, the present invention is to provide a color filter and an image display device having excellent adhesion and excellent performance such as durability.

The present invention includes at least one first polymer comprising a repeating unit derived from a 2-acryloyloxyethyl succinate monomer and comprising a side chain containing a reaction residue of an acid group and an epoxy group and a polymerizable double bond in the repeating unit. ; And at least one second polymer different from the first polymer; wherein the first polymer is included in an amount of 1 to 60 parts by weight based on 100 parts by weight of the total alkali-soluble resin. To provide.

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 above-described color filter.

The coloring photosensitive resin composition which concerns on this invention has the advantage that the development speed and adhesiveness 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 has an advantage in that the adhesion is improved and the durability is excellent.

1A to 1C are diagrams illustrating the water purity for the method for producing a color filter using the colored photosensitive resin composition.

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

In the present invention, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

In the present invention, when a part "includes" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

<Coloring Photosensitive Resin Composition>

One embodiment of the present invention, comprising a repeating unit derived from a 2-acryloyloxyethyl succinate monomer, comprising a side chain containing a reaction residue of an acid group and an epoxy group in the repeating unit and a polymerizable double bond The above first polymer; And at least one second polymer different from the first polymer; wherein the first polymer is included in an amount of 1 to 60 parts by weight based on 100 parts by weight of the total alkali-soluble resin. It is about.

Alkali soluble resin

The coloring photosensitive resin composition according to the present invention comprises at least one first polymer and at least one second polymer different from the first polymer, wherein the first polymer comprises repeating units derived from a 2-acryloyloxyethylsuccinate monomer. And a side chain including a reaction residue of an acid group and an epoxy group in the repeating unit and a polymerizable double bond, and the first polymer is included in an amount of 1 to 60 parts by weight based on 100 parts by weight of the alkali-soluble resin.

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

The first polymer according to the present invention includes a repeating unit derived from the 2-acryloyloxyethyl succinate monomer, and a side chain containing a reaction residue of an acid group and an epoxy group in the repeating unit and a polymerizable double bond. When included within, there is an advantage in that the developing speed does not occur while the developing speed is high, and a colored photosensitive resin composition having excellent adhesiveness can be obtained.

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, based on 100 parts by weight of the alkali-soluble resin, and in this case, the development speed is more preferable.

Specific examples of the epoxy group-containing monomer having the polymerizable double bond include glycidyl (meth) acrylate, allyl glycidyl ether, α-ethylglycidyl (meth) acrylate, and 3,4-epoxycyclohexyl Methyl acrylate (e.g., "Cychroma (registered trademark) A400" manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexyl methyl methacrylate (e.g., "Cychroma M100 manufactured by Daicel Chemical Industries, Ltd." Etc.), but are not limited thereto.

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 first polymer as a whole. More preferably, it may be included in 30 to 40 parts by weight.

In another embodiment of the present invention, the repeating unit derived from the monomer containing the side chain is 50 to 95 parts by weight, preferably 60 to 80 parts by weight, more preferably 100 parts by weight of the first polymer as a whole. 60 to 70 parts by weight may be included. The repeating unit derived from the monomer containing the side chain may include a side chain including a reaction residue of an acid group and an epoxy group in the repeating unit derived from the 2-acryloyloxyethyl succinate monomer included in the first polymer and a polymerizable double bond. It can be referred to the part containing.

In another embodiment of the present invention, the first polymer is a repeating unit derived from an N-substituted maleimide monomer, a repeating unit derived from a 2-ethoxyethyl (meth) acrylate monomer, and 2-hydroxyethyl (meth). ) May further include one or more repeating units selected from the group consisting of acrylate-derived repeating units.

The N-substituted maleimide monomers are, for example, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxy Phenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, and the like. It doesn't work.

When the said 1st polymer further contains the repeating unit derived from an N-substituted maleimide-type monomer, since there exists an advantage that heat resistance improves, it is preferable.

When the said 1st polymer further contains the repeating unit derived from 2-ethoxyethyl (meth) acrylate monomer, since there exists an advantage that chemical resistance improves, it is preferable.

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

In another embodiment of the present invention, the first polymer is a repeating unit derived from an N-substituted maleimide monomer, a repeating unit derived from a 2-ethoxyethyl (meth) acrylate monomer, and 2-hydroxyethyl (meth). A repeating unit derived from an acrylate may be included.

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 repeating unit derived from a 2-ethoxyethyl (meth) acrylate monomer. And a repeating unit derived from 2-hydroxyethyl (meth) acrylate, and may include a side chain including a reaction residue of an acid group and an epoxy group and a polymerizable double bond in the repeating unit.

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

In another embodiment of the 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, more preferably based on 100 parts by weight of the first polymer as a whole. It may be included in 5 to 20 parts by weight.

In 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 30 parts by weight based on 100 parts by weight of the first polymer as a whole. Parts, more preferably 10 to 25 parts by weight.

In 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 25 parts by weight based on 100 parts by weight of the first polymer as a whole. Parts, more preferably 10 to 20 parts by weight.

When the repeating units derived from each monomer satisfy the above range, the repeating units derived from each monomer are preferable because the desired effect can be maximized.

The first polymer comprises 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 comprising at least one selected from, the repeating unit derived from the 2-acryloyloxyethyl succinate monomer is 5 to 50 parts by weight, preferably 10 to 40 parts by weight based on 100 parts by weight of the first polymer as a whole Parts, more preferably 15 to 30 parts by weight.

In addition, the repeating unit derived from the monomer containing the side chain may be included in 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 first polymer.

The first polymer may further include, but is not limited to, additional repeating units in addition to the aforementioned repeating units.

For example, the repeating unit that may be further included in the first polymer may be derived from a polymerization monomer having an unsaturated bond, and specifically, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate, and the like, and more specifically, acrylic acid, methacrylic acid, styrene, vinyltoluene, and α- Methyl styrene, p-chloro styrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-vinyl benzylmethyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl Aromatic vinyl compounds such as benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decane-8-yl (meth) acrylate, 2- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (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, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. Unsaturated oxetane compounds and the like.

When the repeating unit which may be further included includes an acid group, the repeating unit including the acid group reacts with the epoxy group-containing monomer having a polymerizable double bond to react the residue of the acid group with the epoxy group and the polymerizable double bond. It may include a side chain containing, but is not limited thereto.

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

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

The second polymer may include, but is not limited to, one or more of the additional repeating units described above, and an alkali-soluble binder resin commonly used in the art may be used without limitation.

Specifically, the second polymer may be a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with a dimer.

As said carboxyl group-containing monomer, For example, unsaturated monocarboxylic acid, unsaturated carboxylic acid, such as unsaturated polyhydric carboxylic acid which has one or more carboxyl groups in molecules, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, etc. are mentioned. Can be mentioned. Here, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, etc. are mentioned. In addition, the unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. Can be. The said carboxyl group-containing monomer can be used individually or in mixture of 2 or more types, respectively.

The carboxyl group-containing monomer may include, but is not limited to, a side chain including a reaction residue of an acid group and an epoxy group and a polymerizable double bond by reacting with an epoxy group-containing monomer having a polymerizable double bond. The epoxy group-containing monomer having the above may be applied to the above, but is not limited thereto.

As another monomer copolymerizable with the said carboxyl group-containing monomer, For example, ethylenically unsaturated monomer containing a double bond, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro styrene , o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m Aromatic vinyl compounds such as vinylbenzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, 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, dicy Unsaturated carboxyl such as clopentadiethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate Acid esters; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacryl , 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3 Unsaturated carboxylic acid aminoalkyl esters such as -dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate; Unsaturated ether, such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; Acrylonitrile, methacrylonitrile, (alpha)- Vinyl cyanide compounds such as chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroarc Amides, unsaturated amides such as N-2- hydroxyethyl acrylamide, N-2- hydroxyethyl methacrylamide; maleimide, N- phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly -n- butyl methacrylate, the macromonomers which have a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polysiloxane, etc. are mentioned. These monomers can be used individually or in mixture of 2 or more types, respectively.

Content of the carboxyl group-containing monomeric unit in the said 2nd polymer is 10-50 weight part normally with respect to 100 weight part of said 2nd whole polymers, Preferably it is 10-40 weight part, More preferably, it is 13-30 weight part Can be. When content of a carboxyl group-containing monomeric unit satisfy | fills the said range, since solubility to a developing solution is favorable and there exists a tendency for the pattern at the time of image development to be formed, it is preferable.

More specifically, the second polymer is a (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 macro Monomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / Limethyl (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, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer And (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer.

Among these, acrylic acid / benzyl (meth) acrylate / styrene copolymer, acrylic acid / methyl (meth) acrylate / styrene copolymer, methyl methacrylate / benzyl methacrylate / acrylic acid copolymer and acrylic acid contained in the copolymer By reacting an acid group with an epoxy group of glycidyl (meth) acrylate, a copolymer which may include a side chain containing a reaction residue of an acid group and an epoxy group and a polymerizable double bond can be preferably used.

The second polymer may be included in an amount of 40 to 99 parts by weight, preferably 40 to 70 parts by weight, and more preferably 40 to 60 parts by weight, based on 100 parts by weight of the alkali-soluble resin in total, in which case development of development residues occurs. It is preferable because there exists an advantage which can suppress the and excellent adhesiveness.

In 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 20 to 60 parts by weight based on 100 parts by weight of the total solid of the colored photosensitive resin composition. It may be included as a negative portion, and in this case, it is preferable because the formation of a pattern is easy and the resolution and the residual film ratio tend to be improved.

As used 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 (KOH mg / g). If the acid value is in the above range, the solubility in the developing solution is improved, so that the non-exposed part is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed part remains at the time of development to improve the film remaining ratio.

The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.

Furthermore, the polystyrene reduced weight average molecular weight (hereinafter, simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as an eluting solvent) is 3,000 to 200,000, preferably 5,000 to 100,000. Alkali-soluble resins are preferred. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, solubility of the non-exposed portion in the developer is excellent and the resolution tends to be improved, which is preferable.

In another embodiment of the present invention, the colored photosensitive resin composition may further include one or more selected from the group consisting of colorants, photopolymerizable compounds, photopolymerization initiators, solvents and additives.

coloring agent

The coloring agent of this invention is not limited in color tone, It can select according to the use of the color filter obtained. The colorant may be any one of a pigment, a dye, or a natural dye, and as the pigment, a compound classified as pigment in the Color Index (Published by The Society of Dyers and Colourists) may be used. As a coloring agent of this invention, an organic pigment is preferable at the point which is excellent in heat resistance and color development property.

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

The dye of the present invention can be used by adding one or more types without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility, heat resistance and solvent resistance in an alkaline developer. The dye may be selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof, and azo, xanthene, and phthalocyanines. Acid dyes and derivatives thereof can also be selected. Examples of the dye include compounds classified as dyes in the color index (Published by The Society of Dyers and Colourists) and known dyes described in dyeing notes (color dyeing yarn).

Specific examples of the dye include C.I. As solvent dyes,

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 and 130;

C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 45, 56, 62 and the like;

C.I. Blue dyes such as solvent blue 35, 37, 45, 59, 67 and the like;

C.I. Green dyes, such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. are mentioned.

See also C.I. As an acid dye

CI 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 Yellow dyes such as, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 ;

CI 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;

Orange dyes such as C.I. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 Blue dyes such as, 335 and 340;

Violet dyes such as C.I. acid violet 6B, 7, 9, 17, 19 and the like;

Green dyes, such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. are mentioned.

Also as a C.I. direct dye

CI 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, and 141;

CI 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 and 250;

Orange dyes such as C.I.direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

CI direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 Blue dyes such as, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc .;

Violet dyes such as C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like;

Green dyes, such as C.I. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. are mentioned.

In addition, C.I. As modanto dye

Yellow dyes such as C.I. modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 and the like;

CI Modanto Orange Orange such as 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc. dyes;

CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, Blue dyes such as 43, 44, 48, 49, 53, 61, 74, 77, 83, 84 and the like;

Violet dyes such as C.I. modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and the like;

Green dyes, such as C.I. modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. are mentioned.

The coloring agent of this invention can be used individually or in combination of 2 or more types.

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 solids of the coloring photosensitive resin composition. If it is in the said range, since the color density when it is made with a color filter is sufficient, and a composition polymer may be contained in a required amount in a composition, a pattern with sufficient mechanical strength can be formed.

Solid content of a coloring photosensitive composition in this invention means the sum total of the component remove | excluding the solvent.

Among the pigments, organic pigments may be subjected to surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, graft treatment of the surface of the pigment with a polymer compound, atomization treatment by sulfuric acid atomization, or impurities. A washing treatment with an organic solvent or water for removal, or a removal treatment by an ion exchange method of ionic impurities or the like can be performed.

It is preferable that the said colorant is uniform particle size. When the said coloring agent is a pigment, the pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in the solution can be obtained by containing a pigment dispersant and performing a dispersion process.

As said pigment dispersant, surfactant, such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine type, etc. can be mentioned, for example, These can be used individually or in combination of 2 or more types. have. When using a pigment dispersant, the usage-amount is preferably 1 weight part or less per 1 weight part of coloring agents, More preferably, it is 0.05 weight part or more and 0.7 weight part or less. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency for the pigment of a uniform dispersion state to be obtained, and it is preferable.

Photopolymerizable  compound

A photopolymerizable compound is a compound which can be polymerized by active radicals, an acid, etc. which generate | occur | produce from a photoinitiator by irradiation of light, and a monofunctional, bifunctional, trifunctional polymeric compound etc. are mentioned according to the number of functional groups.

Specific examples of the monofunctional polymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-. Vinylpyrrolidone, etc. are mentioned.

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 ( Meta) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxy The late neopentyl glycol diacrylate, the propyl oxylate neopentyl glycol diacrylate, etc. are mentioned.

Specific examples of the trifunctional polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylate trimethylolpropane tri (meth) acrylate, and propyloxylate trimethylolpropane tree (Meth) acrylate, glyceryl propyl oxylate triacrylate, isocyanurate triarylate, etc. are mentioned.

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

Further, specific examples of the 5-functional polymerizable compound include dipentaerythritol penta (meth) acrylate, and specific examples of the six-functional photopolymerizable compound include dipentaerythritol hexa (meth) acrylate.

Among these, as the photopolymerizable compound, a bifunctional or higher polyfunctional polymerizable compound may be preferably used, and in particular, a polyfunctional or higher polyfunctional polymerizable compound may be preferably used.

The photopolymerizable compounds of the present invention can be used alone or in combination of two or more kinds. The photopolymerizable compound is preferably contained in an amount of 5 to 50 parts by weight, and more preferably in an amount of 7 to 45 parts by weight, based on 100 parts by weight of the total solid in the colored photosensitive resin composition. When the said photopolymerizable compound is contained in the said range on the said reference | standard, since the intensity | strength and smoothness of a pixel part become favorable, it is preferable.

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, but is acetophenone-based in terms of polymerization characteristics, starting efficiency, absorption wavelength, availability, and price. It is preferable to contain at least one compound selected from benzoin, benzophenone, thioxanthone, triazine, oxime, onium salt, nitrobenzyltosylate or benzointosylate. can do.

Preferred acetophenone compounds for the present invention include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-. 1-phenylpropane-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl Ketones, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like, and 2-methyl-2-morpholino-1- (4- Methylthiophenyl) propan-1-one is more preferable. It is also possible to use a plurality of acetophenone compounds and other photopolymerization initiators in combination. Examples of photopolymerization initiators other than acetophenone compounds include active radical generators, sensitizers, and acid generators that generate active radicals by irradiation with light.

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

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro, for example 4-propoxy city oxanthone etc. are mentioned.

As said triazine type compound, 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 (trichloro Methyl) -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 and the like.

Examples of the oxime compound 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-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -ethyl acetate-O-benzoate, and the like.

As the sensitizer, 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, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylglyoxylate, titanocene compound and the like Can be mentioned.

As said acid generator, 4-hydroxyphenyl dimethyl sulfonium p-toluene sulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxy phenyl dimethyl sulfonium p-toluene, for example Sulfonate, 4-acetoxyphenylmethyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate And onium salts such as diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylates, benzointosylates and the like.

Among these compounds, there are also compounds which simultaneously generate active radicals and acids. For example, the triazine-based photopolymerization initiator may be used as an acid generator.

Commercially available examples of the photopolymerization initiator include, but are not limited to, OXE01 manufactured by BASF.

It is preferable that the photoinitiator of this invention is contained in 0.1-30 weight part with respect to 100 weight part of total solids of a coloring photosensitive resin composition, and it is more preferable that it is contained in 0.5-20 weight part. In the case where the photopolymerization initiator is included in the above range, since the sensitivity is reduced and the exposure time is shortened, productivity is improved and high resolution can be maintained.

The coloring photosensitive resin composition of this invention may further contain a photoinitiation start adjuvant. The photopolymerization start adjuvant may be used in combination with a photopolymerization initiator, and is used to promote polymerization of the photopolymerizable compound in which polymerization is initiated by the photopolymerization initiator.

Examples of the photopolymerization initiation aid include an amine compound, an alkoxy anthracene compound, a thioxanthone compound, and the like. Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, 4- Methyl dimethylaminobenzoate, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2-dimethylaminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4 ' -Bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (Diethylamino) benzophenone is preferable. Examples of the alkoxy anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10- diethoxy anthracene etc. are mentioned. As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-, for example 4-propoxy city oxanthone etc. are mentioned. The said photoinitiator can be used individually or in combination of 2 or more types.

In addition, a commercially available product may be used as the photopolymerization start adjuvant, and commercially available photopolymerization start adjuvant includes, for example, EAB-F (product of Hodoga Yagaku Kogyo Co., Ltd.).

As a combination of the photoinitiator and photoinitiator adjuvant which are preferable for the coloring photosensitive resin composition of this invention, diethoxy acetophenone / 4,4'-bis (diethylamino) benzophenone, 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) benzo Phenone, 1-hydroxycyclohexylphenylketone / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 Oligomer / 4,4'-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'-bis Combinations of (diethylamino) benzophenone and the like, and more preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4'-ratio. (Diethylamino) there is a combination of benzophenone.

When the photopolymerization initiator and the photopolymerization initiation aid are used together as described above, the photopolymerization initiation assistant is preferably used in an amount of 10 mol or less per mole of the photopolymerization initiator, and more preferably in a range of 0.01 to 5 mol.

solvent

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

As said ether, For example, tetrahydrofuran, tetrahydropyran, 1, 4- dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, di Ethylene 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 glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate Methoxybutyl Rim

As said aromatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

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

Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol or glycerin.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoam acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate and alkyl esters. Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxyacetate, methoxyacetate, ethoxyacetic acid methyl, 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, 2-oxy Propyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl lopionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate or γ-butyro Lactone, etc. are mentioned.

As said amides, N, N-dimethylformamide, N, N-dimethylacetamide, etc. are mentioned, for example.

As another solvent, N-methylpyrrolidone, dimethyl sulfoxide, etc. are mentioned, for example.

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

The said solvent is 10-90 weight part with respect to 100 weight part of said coloring photosensitive resin compositions, Preferably it is 20-85 weight part, More preferably, within the range of 30-85 weight part individually or in combination of 2 or more types Can be used. When content of the said solvent is the said range, since flatness at the time of application | coating is favorable, and a color filter is sufficient when a color filter is formed, display property is favorable, and it is preferable.

additive

The additive may be optionally added as needed, and may include, for example, one or more selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-agglomerating agents. have.

Moreover, it is most preferable to contain surfactant among the said additives.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters and polyurethanes, and the like. Can be mentioned.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin , Aliphatic, cycloaliphatic or aromatic epoxy compounds other than glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene ( Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.

Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane and cyclohexane dicarboxylic acid bis oxetane.

The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent.

Examples of the curing aid compound include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, and acid generators. As said polyhydric carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. Examples of the commercially available products include Adeka Hado and EH-700 (manufactured by Adeka Industry Co., Ltd.), Rikashitdo HH (manufactured by Nippon Ewha Co., Ltd.) and MH-700 (manufactured by Nippon Ewha Co., Ltd.). The hardeners illustrated above can be used individually or in mixture of 2 or more types.

The surfactant may be used to further improve the film formation of the colored photosensitive resin composition, and silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric surfactants and the like may be preferably used.

The silicone surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicone Co., Ltd., and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF, manufactured by GE Toshiba Silicon, Inc. -4460 and TSF-4452.

Examples of the fluorine-based surfactants include Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink & Chemicals Co., Ltd. as commercially available products.

Other commercially available products include KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products), Mega Pack (MEGAFAC). (Dainitbon Ink Kagaku Kogyo Co., Ltd.), Florad (Sumitomo 3M Co., Ltd.), Asahi guard, Suflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) , EFKA (EFKA Chemicals Co., Ltd.), PB 821 (Ajinomoto Co., Ltd.) and Disperbyk-series (BYK-chemi).

The cationic surfactants include, for example, amine salts and quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.

The anionic surfactants include, for example, higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and sodium dodecylbenzenesulfonate. And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

The nonionic surfactant is, for example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester and polyoxyethylene alkylamine.

Surfactant illustrated above can be used individually or in combination of 2 or more types, respectively.

The type 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-methacryloxy Propyl trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like.

The adhesion promoter illustrated above can be used individually or in combination of 2 or more types, respectively. The adhesion promoter may be included in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of solids in the red photosensitive resin composition.

Although the kind of said antioxidant is not specifically limited, 2,2'- thiobis (4-methyl-6-t- butylphenol), 2, 6- di- t- butyl- 4-methyl phenol, etc. are mentioned. .

The type of the ultraviolet absorber is not particularly limited, but specific examples of usable ultraviolet rays include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like. .

Although the kind of the said aggregation inhibitor is not specifically limited, Sodium polyacrylate etc. are mentioned as a specific example which can be used.

The additive may be used in addition to an appropriate content in a range that does not inhibit the object of the present invention. For example, the additive may be included in an amount of 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 total color photosensitive resin composition, but is not limited thereto.

The coloring photosensitive resin composition of this invention can be manufactured by the following methods, for example. The coloring agent is previously mixed with the solvent and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. At this time, a pigment dispersant is used as needed, and some or all of alkali-soluble resin may be mix | blended. The remainder of alkali-soluble resin, the photopolymerizable compound, the photoinitiator, the additives, such as antioxidant, the other components used as needed, and the additional solvent as needed are prescribed | regulated to the obtained dispersion liquid (henceforth a mill base). It can further add so that it may become the density | concentration of, and can obtain the target coloring photosensitive resin composition.

<Color filter>

Another aspect of this invention relates to the color filter containing the hardened | cured material of the coloring photosensitive resin composition mentioned above.

Specifically, the present invention is a color filter comprising a colored layer formed by coating a colored photosensitive resin composition on a substrate and exposed and developed in a predetermined pattern, wherein the colored photosensitive resin composition is used as the colored photosensitive resin composition. It provides a color filter characterized in that the use.

A partition may be further formed between each colored pattern, and a black matrix may be added. In addition, a protective film may be further formed on the illustrated color filter. 1A to 1C are flowcharts illustrating a method of manufacturing a color filter using the above-mentioned colored photosensitive resin composition.

In order to form a coloring pattern, the coloring photosensitive resin composition of this invention is pattern-processed, for example. Specifically, a color layer 11 made of a colored photosensitive resin composition is formed on the substrate 10 (FIG. 1A), and the formed color layer 11 is irradiated with a predetermined pattern (FIG. 1B). (FIG. 1C).

The substrate 10 is not limited and may be a substrate of a color filter itself, or may be a portion where the color filter is positioned in a display device or the like. The substrate may be a glass plate, a silicon wafer, and a plastic plate such as poly ether sulfate (PES), poly carbonate (PC), or the like. That is, the substrate may be silicon (Si), silicon oxide (SiO _x ), a glass substrate, or a polymer substrate.

In order to form the layer 11 made of the colored photosensitive resin composition on the substrate 10, for example, the colored photosensitive resin composition diluted with a solvent may be spin, slit backspin, slit, roll, spray, inkjet method, or the like. After coating on the substrate by the coating method, volatile components such as solvents and the like are volatilized. Thereby, the color layer 11 which consists of a coloring photosensitive resin composition is formed, Comprising: The said color layer consists of solid components of a coloring photosensitive resin composition, and contains few volatile components.

The thickness of the film surface is determined by the coating conditions such as the viscosity of the composition, the concentration of solids, the coating speed, and the like, and when using the composition of the present invention, a colored layer 11 having a thickness of 0.5 to 5 μm can be obtained.

Next, the color layer 11 which consists of colored photosensitive resin composition is exposed to light. In order to expose, for example, the color layer is irradiated with a predetermined pattern through the photomask 20. As light, ultraviolet rays g line (wavelength: 436 nm), h line, i line (wavelength: 365 nm) and the like are usually used. The light beam is passed according to the pattern of the photomask. The photomask provides a light shielding layer for shielding light rays in a predetermined pattern on the surface of the glass plate. Light ray 30 is shielded by the light shielding layer. The part of the glass plate 20 in which this light shielding layer is not provided is a light transmission part through which light rays pass. According to the pattern of the light transmitting portion, the color layer 11 is exposed. The irradiation amount of light ray is suitably selected according to the coloring photosensitive resin composition used. The portion irradiated with the light rays is much smaller in solubility than the portion not irradiated with light, thereby maximizing the difference in solubility between them.

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

As a developer, aqueous solutions, such as an alkali compound, such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, tetramethylammonium hydroxide, are used. By the image development, the light non-irradiated area | region which was not irradiated by the light ray of a coloring photosensitive resin composition layer is removed. On the contrary, the light irradiation area irradiated by the light rays remains to form a coloring pattern.

After development, the layer is usually washed with water and dried to obtain the desired colored pattern. Moreover, you may heat-process after drying. The colored pattern formed by the heat treatment is cured, and the mechanical strength thereof is improved. Thus, since the mechanical strength of a coloring pattern can be improved by heat processing, it is preferable to use the coloring photosensitive composition containing a hardening | curing agent. Heating temperature is usually 180 degreeC or more, Preferably it is 200-250 degreeC.

<Image display device>

Further, another aspect of the present invention relates to an image display apparatus including the color filter described above.

The color filter of the present invention can be applied to various image display devices such as electroluminescent display devices, plasma display devices, field emission display devices, as well as ordinary liquid crystal display devices.

The image display apparatus may include other components that may be normally included in the image display apparatus, such as a light emitting device such as a light source, a light guide plate, an image display unit including a color filter according to the present invention, and the like. Do not.

The coloring photosensitive resin composition which concerns on this invention has the advantage that a developing speed is fast, it can prevent the development residue, and it is excellent in adhesiveness. For this reason, the color filter and the image display apparatus made of the colored photosensitive resin composition according to the present invention have an advantage of excellent performance such as durability.

Hereinafter, the present specification In order to demonstrate, an Example is given and it demonstrates in detail. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not to be interpreted as being limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art. In addition, "%" and "part" which show content below are a basis of weight unless there is particular notice.

Production Example : Preparation of Colored Dispersion

C.I. Pigment Blue 15: 6 Pigment 11.89 parts by weight, EFKA 4300 (manufactured by BASF) 7.73% by weight, propylene glycol monomethyl ether acetate (PGMAC) 80.38% by weight of the mixture was stirred and mixed to uniformity, 0.5 mm in diameter Using zirconia beads, it was dispersed for 3 hours in iGamil ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.). Thereafter, the obtained mixture was filtered through a filter having a pore diameter of 5.0 µm to prepare a colored dispersion having a nonvolatile content of 19.62 wt%.

Example  And Comparative example : Preparation of Colored Photosensitive Resin Composition

The coloring photosensitive resin composition (unit: weight part) according to the Example and the comparative example was manufactured according to the structure and composition of the following Table 1.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Coloring dispersion (A) 25.2 (A) 25.2 (A) 25.2 (A) 25.2 (A) 25.2 (A) 25.2 (A) 25.2 (A) 25.2 (A) 25.2 Alkali soluble resin (B-1) 2.1
(B-3) 9.0 (B-1) 3.2
(B-3) 7.9 (B-1) 5.5
(B-3) 5.7 (B-2) 2.1
(B-3) 9.0 (B-2) 3.2
(B-3) 7.9 (B-2) 5.5
(B-3) 5.7 (B-1) 7.7
(B-3) 3.5 (B-2) 7.7
(B-3) 3.5 (B-3) 11.2 Photopolymerizable compound (C) 5.1 (C) 5.1 (C) 5.1 (C) 5.1 (C) 5.1 (C) 5.1 (C) 5.1 (C) 5.1 (C) 5.1 Photopolymerization initiator (D) 1.0 (D) 1.0 (D) 1.0 (D) 1.0 (D) 1.0 (D) 1.0 (D) 1.0 (D) 1.0 (D) 1.0 additive (E) 0.2 (E) 0.2 (E) 0.2 (E) 0.2 (E) 0.2 (E) 0.2 (E) 0.2 (E) 0.2 (E) 0.2 solvent (F) 57.3 (F) 57.3 (F) 57.3 (F) 57.3 (F) 57.3 (F) 57.3 (F) 57.3 (F) 57.3 (F) 57.3 (A) Colored dispersion liquid according to the preparation example
(B) alkali soluble resin
(B-1) Formula 1, monomer weight ratio (a): (b) = 30: 70, acid value is 90, polystyrene reduced weight average molecular weight is 13,000, solid content: 35%, solvent: propylene glycol monomethyl ether acetate
(B-2) the following formula (2), monomer weight ratio (a) :( b) :( c) :( d) :( e) = 15: 20: 15: 20: 30, acid value is 70, polystyrene conversion weight average molecular weight Silver 12,000, solid content: 35%, solvent: propylene glycol monomethyl ether acetate
(B-3) Formula 3, monomer weight ratio (a) :( b) :( c) :( d) = 10: 50: 15: 25, acid value is 100, polystyrene reduced weight average molecular weight is 11,000, solid content: 35% , Solvent: propylene glycol monomethyl ether acetate
(C) Photopolymerizable Compound: Dipentaerythritol hexaacrylate (DPHA, Nippon Gunpowder)
(D) Photoinitiator: OXE01 (BASF Corporation)
(E) Additive: SH8400 from Dow Corning Toray Silicone Co., Ltd.
(F) Solvent: Propylene Glycol Monomethyl Ether Acetate

[Formula 1]

[Formula 2]

[Formula 3]

Manufacture of color filter

Each colored photosensitive resin composition solution was coated on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a line / space pattern of 1 μm to 50 μm was placed on the thin film, and ultraviolet rays were irradiated with a distance of 100 μm from the test photomask. In this case, the ultraviolet light source was irradiated with luminous intensity of 100mJ / cm 2 using a 1KW high-pressure mercury lamp containing g, h, and i rays, and no special optical filter was used. The UV-irradiated thin film was immersed in a KOH aqueous solution developing solution of pH 10.5 for 1 minute and developed. The thin film coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C. for 30 hours to prepare a color filter. The film thickness of the color filter prepared above was 2.0 μm.

Experimental Example

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

(1) Developing speed

In the preparation of the color filter, the thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution of pH 10.5 for 1 minute to show the time required to form a pattern when developing.

(2) Development residue

In the preparation of the color filter, a thin film irradiated with UV light was immersed in a developing solution of KOH aqueous solution of pH 10.5 for 1 minute and developed. Model name: ECLIPSE LV100POL (manufacturer: Nikon) indicates that there is no developing residue on the substrate, and '×' when developing residue on the substrate.

(3) pattern adhesion

When the pattern formed by the method of manufacturing a color filter described above was confirmed by an optical microscope, a pattern having a size of 50 μm remained without a dropout was indicated as '○', and a dropping occurred as '×'.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Alkali-soluble resin
ratio (B-1): (B-3)
= 19%: 81% (B-1): (B-3)
= 29%: 71% (B-1): (B-3)
= 49%: 51% (B-2): (B-3)
= 19%: 81% (B-2): (B-3)
= 29%: 71% (B-2): (B-3)
= 49%: 51% (B-1): (B-3)
= 69%: 31% (B-2): (B-3)
= 69%: 31% (B-3) = 100% Developing speed 27sec 17sec 12sec 30sec 19sec 14sec 8sec 6sec 43 sec Status residue ○ ○ ○ ○ ○ ○ × × × Pattern adhesion ○ ○ ○ ○ ○ ○ × × ○

As can be seen from Table 2, in the case of using the colored photosensitive resin composition according to the embodiment, although the developing speed is fast, there is no developing residue, and the pattern adhesiveness is excellent, so that a color filter which does not generate a pattern defect can be produced. Able to know. In particular, in the case of the comparative example, it can be seen that the embodiment shows excellent development speed while excellent development residue and pattern adhesion, while not satisfactory excellent development speed, development residue, and pattern adhesion.

10: Substrate
11: color layer
11R: formed color layer
20: photomask
30: light

Claims (9)

A repeating unit derived from a 2-acryloyloxyethyl succinate monomer,
At least one first polymer comprising a reaction chain of an acid group and an epoxy group in the repeating unit and a side chain including a polymerizable double bond; And
At least one second polymer, different from the first polymer;
Including an alkali-soluble resin comprising,
The said 1st polymer is 1-60 weight part with respect to 100 weight part of said alkali-soluble resins, The coloring photosensitive resin composition. The method of claim 1,
The first polymer is a group consisting of repeating units derived from N-substituted maleimide monomers, repeating units derived from 2-ethoxyethyl (meth) acrylate monomers, and repeating units derived from 2-hydroxyethyl (meth) acrylate The coloring photosensitive resin composition which further contains 1 or more repeating units chosen from. The method of claim 2,
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. Colored photosensitive resin composition. The method of claim 1,
The repeating unit derived from the said 2-acryloyloxyethyl succinate monomer is 5-50 weight part with respect to 100 weight part of said 1st whole polymers, The coloring photosensitive resin composition. The method of claim 1,
The repeating unit derived from the monomer containing the said side chain is 50-95 weight part with respect to 100 weight part of whole said 1st polymers. The method of claim 1,
The said alkali-soluble resin is 10-80 weight part with respect to 100 weight part of whole colored solid photosensitive resin composition solid coloring photosensitive resin composition. The method of claim 1,
The coloring photosensitive resin composition which further contains 1 or more selected from the group which consists of a coloring agent, a photopolymerizable compound, a photoinitiator, a solvent, and an additive. The color filter containing the hardened | cured material of the coloring photosensitive resin composition of any one of Claims 1-7. An image display device comprising the color filter according to claim 8.

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