CN106909027B

CN106909027B - Colored photosensitive resin composition, color filter and method for producing the same, and image display device

Info

Publication number: CN106909027B
Application number: CN201611058903.0A
Authority: CN
Inventors: 申奎澈; 朴径嬉; 黄珍娥
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2015-12-23
Filing date: 2016-11-21
Publication date: 2021-07-16
Anticipated expiration: 2036-11-21
Also published as: CN106909027A

Abstract

The invention provides a colored photosensitive resin composition, a color filter and a manufacturing method thereof, and an image display device, wherein the colored photosensitive resin composition is characterized by comprising the following components: (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) one or more compounds selected from a polyfunctional thiol compound and an organosilicon compound, and (F) a solvent, wherein the colorant (a) contains one or more compounds selected from c.i. pigment green 59, 62, and 63, and one or more compounds selected from a pigment and a dye.

Description

Colored photosensitive resin composition, color filter and method for producing the same, and image display device

Technical Field

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

Background

Color filters are widely used in various display devices such as image sensors and Liquid Crystal Displays (LCDs), and their application range is rapidly expanding. The color filter used in the image sensor, the liquid crystal display device, and the like is formed of a colored pattern of three colors of Red (Red), Green (Green), and Blue (Blue), or a colored pattern of three colors of Yellow (Yellow), Magenta (Magenta), and Cyan (Cyan).

The colored pattern of each of the color filters is generally formed using a colored photosensitive resin composition containing a colorant such as a pigment or a dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colored pattern processing using the colored photosensitive resin composition is usually performed by a photolithography step.

In recent years, for color filters for various display devices including solid-state imaging elements such as digital cameras and liquid crystal display devices (LCDs), high luminance and high color rendering properties have been required for improving manufacturability and quality, but such requirements have not been sufficiently satisfied.

For example, korean laid-open patent No. 2013-0134494 discloses a resin composition using c.i. pigment green 7 and c.i. pigment yellow 185, but has a disadvantage that high brightness and high colorability cannot be simultaneously satisfied.

The colored photosensitive resin composition is inhibited from yellowing in a high temperature process, thereby maintaining high brightness even in a high temperature process, and also prevents development unevenness from occurring in a water washing process, which affects the taper angle of a color filter pixel coating film. Therefore, heat resistance is an important physical property required for improving the reliability of the colored photosensitive resin composition.

However, in the prior art, the heat resistance required for the colored photosensitive resin composition cannot be sufficiently satisfied in practical cases.

Prior patent literature

Patent document

Korean laid-open patent No. 2013-0134494

Disclosure of Invention

Problems to be solved

The present invention has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a colored photosensitive resin composition which has excellent heat resistance, prevents yellowing in a high-temperature step, maintains high luminance, prevents development unevenness from occurring in a water washing step, and facilitates adjustment of a taper angle of a color filter pixel coating film.

Further, an object of the present invention is to provide a colored photosensitive resin composition which has excellent adhesion, particularly prevents peeling of a coating film by maintaining adhesion between a substrate and a resist even in a low-temperature baking step, improves reliability of a panel in which a color filter and a TFT are bonded without causing residual images, and does not generate residual films or residues after development.

Another object of the present invention is to provide a colored photosensitive resin composition having excellent brightness and coloring property and high sensitivity.

Another object of the present invention is to provide a color filter comprising the colored photosensitive resin composition, and an image display device comprising the color filter.

Another object of the present invention is to provide a method for producing a color filter using the colored photosensitive resin composition.

Means for solving the problems

The present invention provides a colored photosensitive resin composition, characterized by comprising: (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) one or more compounds selected from a polyfunctional thiol compound and an organosilicon compound, and (F) a solvent, wherein the colorant (a) contains one or more compounds selected from c.i. pigment green 59, 62, and 63, and one or more compounds selected from a pigment and a dye.

In addition, the present invention provides a color filter comprising a colored pattern produced from the colored photosensitive resin composition.

Further, the present invention provides an image display device including the color filter.

Further, the present invention provides a method for manufacturing a color filter, comprising: and forming a colored pattern by using the colored photosensitive resin composition through a low-temperature firing process at 80 to 180 ℃.

Effects of the invention

The colored photosensitive resin composition of the present invention provides the following effects: the color filter has excellent heat resistance, prevents yellowing in a high temperature process, maintains high brightness, is favorable for preventing development unevenness due to a high contact angle with respect to a coating film of deionized water (DI) in a water washing process after development, facilitates adjustment of a taper angle of a color filter pixel coating film, and facilitates elimination of a difference in angular shape height (horn shape difference in height) of a color pattern.

Further, the colored photosensitive resin composition of the present invention provides the following effects: the adhesive property is excellent, especially the adhesive property between the substrate and the resist is maintained even in a low temperature sintering process to prevent the stripping of the coating, the reliability of the panel formed by the color filter and the TFT is improved under high temperature and high humidity without causing residual shadow, and no residual film or residue is generated after development.

In addition, the colored photosensitive resin composition of the present invention has excellent brightness and colorability, providing excellent sensitivity.

Further, the image display device of the present invention includes a color filter manufactured using the colored photosensitive resin composition as described above, and thus provides a high-resolution image.

Drawings

FIG. 1 is a graph showing a transmission spectrum when a colorant comprising A-1 or A-2, G58, or G7 represented by chemical formula 1 is used.

Detailed Description

The present invention relates to a colored photosensitive resin composition, which is characterized by comprising: (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) one or more compounds selected from a polyfunctional thiol compound and an organosilicon compound, and (F) a solvent, wherein the colorant (a) contains one or more compounds selected from c.i. pigment green 59, 62, and 63, and one or more compounds selected from a pigment and a dye.

Hereinafter, the colored photosensitive resin composition of the present invention will be described in detail for each component.

(A) Coloring agent

The colorant may include one or more selected from c.i. pigment green 59, 62, and 63, and one or more selected from pigments and dyes.

(a1) Pigment (I)

The c.i. pigment green 59 is characterized by containing a compound represented by the following chemical formula 1. The compound represented by chemical formula 1 has a structure of ZnPc (Zinc Phthalocyanine). The colorant of the present invention has an advantage of high color reproducibility when it contains the compound represented by the following chemical formula 1.

[ chemical formula 1]

In the above chemical formula 1, A¹～A¹⁶Each independently of the other being Cl, Br or H, A¹～A¹⁶1-6 of the groups are H, 0-5 are Cl, and 5-13 are Br;

more preferably, 1-6 are H, 0-5 are Cl, and 7-13 are Br;

it is further preferable that 2 to 5 of the groups are H, 0 to 3 of the groups are Cl, and 8 to 13 of the groups are Br. This case is preferable in view of maximizing the effect of the present invention.

Although c.i. pigment green 58(G58) has an advantage of high brightness, if a large amount of pigment is contained in the composition, the following problems may occur, because the content of the pigment is increased to express high coloring property: there is a risk that the developability is lowered, the pattern formed from the composition is peeled off, and the sensitivity is lowered.

However, in the present invention, by using a pigment containing the compound represented by the above chemical formula 1 as a colorant, a resist design having high color reproducibility can be realized even if the content of the pigment is small. The pigment green 59 may be the compound represented by the above chemical formula 1 itself.

The above c.i. pigment green 62 and 63 can also provide the same effect as the c.i. pigment green 59. As the above-mentioned c.i. pigment green 59, a pigment manufactured by japan DIC corporation may be used, and as the c.i. pigment green 62 and 63, a pigment manufactured by toyoyo ink corporation may be used.

On the other hand, when c.i. pigment green 7(G7) is contained in the resin composition, high coloring properties can be exhibited even if the pigment content is reduced, and the resin composition is advantageous for use, but has a problem of low brightness. However, the above pigment green 59 contained in the colored photosensitive resin composition of the present invention exhibits a transmission spectrum and color coordinates similar to those of c.i. pigment green 7 as a pigment, and exerts an effect of exhibiting excellent luminance by being contained in the colored photosensitive resin composition. As can be confirmed from fig. 1, the above pigment green 59 has a transmission spectrum at a wavelength of 400nm to 610nm similarly to c.i. pigment green 7.

In the present specification, Tmax means a wavelength at which the transmittance of the pigment is maximum, and T50% means a wavelength at which the transmittance of the pigment is 50% or more of the maximum.

In an embodiment of the present invention, the Tmax of the pigment green 59 may be 500 to 530nm, which is preferable in view of excellent coloring property.

In another embodiment of the present invention, the pigment green 59 may have a T50% of 445 to 580nm, which is preferable in view of excellent coloring property.

The above-mentioned one or more selected from c.i. pigment green 59, 62 and 63 is contained in an amount of preferably 0.05 to 30% by weight, more preferably 0.05 to 25% by weight, and still more preferably 0.05 to 20% by weight, based on the weight of the solid content in the colored photosensitive resin composition of the present invention. In the case where the compound of the above chemical formula 1 is included in the above range, it is preferable because the coloring property is excellent and a high-brightness resist can be expressed.

The colorant according to the present invention may further comprise one or more selected from pigments and dyes generally used in the art as a component capable of expressing a hue of red, yellow, blue, or the like, among the above-mentioned one or more selected from c.i. pigment green 59, 62, and 63, so that a pattern having a target hue can be manufactured and a form of mill base (Millbase) can be made.

The pigment composition preferably contains at least one selected from the group consisting of c.i. pigment green 59, 62 and 63 and at least one selected from the group consisting of pigments and dyes in a weight ratio of 1:0.050 to 1:18.0, more preferably 1:0.1 to 1:9, and still more preferably 1:0.2 to 1: 4. When the amount is contained in the above weight ratio, the color rendering property and the luminance are high, and the process margin is improved and the sensitivity is excellent, so that the method is preferable.

In this case, the colorant containing one or more selected from c.i. pigment green 59, 62, and 63 according to the present invention as a pigment may have a color coordinate of x of 0.1 to 0.35 when y is 0.6 or more in the XYZ color system.

The above pigments include organic pigments and inorganic pigments, and they may be used alone or in combination of two or more. The organic pigment is more preferably used in view of excellent heat resistance and color developability. The organic pigment may be a synthetic pigment or a natural pigment.

The organic pigment may be treated as follows as required: rosin treatment; surface treatment using a pigment derivative into which an acidic group or a basic group has been introduced; graft treatment of the surface of the pigment using a polymer compound or the like; a fine granulation treatment by a sulfuric acid fine granulation method or the like; or a cleaning treatment using an organic solvent, water or the like for removing impurities.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and inorganic salts of barium sulfate (extender pigment), and more specifically, examples of the metal compounds include metal oxides or composite metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, and the like.

Specific examples of The pigment include more preferably compounds classified as pigments in The Color Index (Color Index, publishing company: The Society of Dyers and Colourists), and more specifically, pigments exemplified by The following Color Index (c.i.) number, but are not limited thereto, and one or more pigments selected from these pigments may be co-dispersed using an alkali-soluble resin, a dispersant, or The like so as to satisfy a desired chromaticity.

Specific examples of c.i. pigment yellow include c.i. pigment yellow 1,3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194, and 214;

specific examples of c.i. pigment orange include c.i. pigment orange 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73;

specific examples of c.i. pigment red include c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265;

specific examples of c.i. pigment blue include c.i. pigment blue 15:3, 15:4, 15:6, 16, 22, 28, 60, and the like;

specific examples of the c.i. pigment violet include c.i. pigment violet 14, 19, 23, 29, 32, 177 and the like;

specific examples of c.i. pigment green include c.i. pigment green 7, 36, and 58.

Among the above-exemplified pigments, one or more selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 129, c.i. pigment yellow 150, and c.i. pigment yellow 185 may be more preferably contained.

(a2) Dye material

The dye that can be contained in the colorant of the present invention can be used without limitation as long as it has solubility in an organic solvent or can be dispersed. It is preferable to use a dye having solubility in an organic solvent and capable of ensuring reliability such as solubility in an alkaline developer, heat resistance, and solvent resistance. In the case of a dye that is not soluble in an organic solvent, it may be dispersed and used.

As the dye, at least one selected from an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of the acid dye with a nitrogen-containing compound, a sulfonamide of the acid dye, and a derivative thereof can be used. Further, it may be selected from azo-based, xanthene-based, phthalocyanine-based acid dyes and derivatives thereof.

The dye preferably includes a compound classified as a dye in color index (published by the society of dyeing chemists), or a known dye described in the dyeing text (history).

Specific examples of the dyes include c.i. Solvent Yellow No. 2, c.i. Solvent Yellow No. 14, c.i. Solvent Yellow No. 16, c.i. Solvent Yellow No. 33, c.i. Solvent Yellow No. 34, c.i. Solvent Yellow No. 44, c.i. Solvent Yellow No. 56, c.i. Solvent Yellow No. 82, c.i. Solvent Yellow No. 93, c.i. Solvent Yellow No. 94, c.i. Solvent Yellow No. 98, c.i. Solvent Yellow No. 116, and c.i. Solvent Yellow No. 135;

c.i. Solvent Orange No. 1, c.i. Solvent Orange No. 3, c.i. Solvent Orange No. 7, c.i. Solvent Orange No. 63;

c.i. Solvent Red (Solvent Red) No. 1, c.i. Solvent Red No. 2, c.i. Solvent Red No. 3, c.i. Solvent Red No. 8, c.i. Solvent Red No. 18, c.i. Solvent Red No. 23, c.i. Solvent Red No. 24, c.i. Solvent Red No. 27, c.i. Solvent Red No. 35, c.i. Solvent Red No. 43, c.i. Solvent Red No. 45, c.i. Solvent Red No. 48, c.i. Solvent Red No. 49, c.i. Solvent Red No. 1, c.i. Solvent Red No. 119, c.i. Solvent Red No. 135, c.i. Solvent Red No. 140, c.i. Solvent Red No. 196, c.i. Solvent Red No. 197;

c.i. Solvent Violet (Solvent Violet) No. 8, c.i. Solvent Violet No. 9, c.i. Solvent Violet No. 13, c.i. Solvent Violet No. 26, c.i. Solvent Violet No. 28, c.i. Solvent Violet No. 31, c.i. Solvent Violet No. 59;

c.i. Solvent Blue (Solvent Blue) No. 4, c.i. Solvent Blue No. 5, c.i. Solvent Blue No. 25, c.i. Solvent Blue No. 35, c.i. Solvent Blue No. 36, c.i. Solvent Blue No. 38, c.i. Solvent Blue No. 70;

c.i. Solvent yellow No. 3, c.i. Solvent yellow No. 5, c.i. Solvent yellow No. 7, etc., but not limited thereto.

The colorant (a) may be contained in an amount of 5 to 70 wt%, more preferably 10 to 50 wt%, based on the total weight of solid components in the colored photosensitive resin composition. If the content of the colorant is less than 5% by weight, the color separation ability of the formed pattern may be lowered, and if it exceeds 70% by weight, the lithography performance may be lowered, and problems such as residue or undeveloped residue may occur.

In the present invention, the solid content in the colored photosensitive resin composition means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition.

(B) Alkali soluble resin

The alkali-soluble resin contained in the colored photosensitive resin composition of the present invention is a component that imparts solubility to an alkali developer used in a developing step. In the present invention, the alkali-soluble resin is not particularly limited, but is preferably a copolymer of a monomer having a carboxyl group and another monomer copolymerizable with the monomer.

The monomer having a carboxyl group is not particularly limited, and specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxy polycaprolactone mono (meth) acrylate, and more preferably acrylic acid and methacrylic acid. More than one of them may be selected for use.

The other copolymerizable monomer is not particularly limited as long as it is a monomer having a carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as styrene, α -methylstyrene and vinyltoluene; unsaturated carboxylic acid ester compounds such as methacrylic acid ester, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, and benzyl methacrylate; unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl methacrylate; vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α -chloroacrylonitrile; unsaturated oxetane carboxylate compounds such as 3-methyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxyethyleneoxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyleneoxetane and 3-methyl-3-methacryloyloxyethyloxetane, and the like. These monomers may be used each alone or in combination of two or more.

According to the present invention, the molecular weight distribution of the alkali-soluble resin, that is, the weight average molecular weight (Mw)/number average molecular weight (Mn)) with respect to the number average molecular weight is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0, from the viewpoint of developability.

The acid value of the alkali-soluble resin is preferably 30 to 170mgKOH/g, more preferably 50 to 150mgKOH/g, based on the solid content. When the acid value of the alkali-soluble resin is less than 30mgKOH/g, it is difficult to secure a sufficient development speed in the colored photosensitive resin composition, and when the acid value exceeds 170mgKOH/g, the adhesion to the substrate is lowered, short-circuiting of the pattern is likely to occur, and there is a problem in compatibility with the colorant, and the colorant in the colored photosensitive resin composition precipitates, or the storage stability of the colored photosensitive resin composition is lowered, and the viscosity may increase, which is not preferable.

The alkali-soluble resin (B) is contained in an amount of 5 to 85 wt%, more preferably 10 to 70 wt%, based on the total weight of the solid content in the colored photosensitive resin composition. When the alkali-soluble resin is contained in the above content range, the solubility in the developer is sufficient, and development residue is less likely to be generated on the substrate of the non-pixel portion, and the film of the pixel portion at the exposed portion during development tends to be prevented from being reduced, and the peeling property of the non-pixel portion tends to be good, which is preferable.

(C) Photopolymerizable compound

The photopolymerizable compound contained in the colored photosensitive resin composition of the invention is a compound polymerizable by an active radical, an acid, or the like generated by irradiation with light from the (D) photopolymerization initiator described later, and is not particularly limited as long as it is a compound polymerizable by the action of the photopolymerization initiator. A polyfunctional monomer, a difunctional monomer, a polyfunctional monomer having three or more functions, or the like can be preferably used, and one or more monomers selected from these can be used.

Specific examples of the polyfunctional monomer include nonylphenylcarbinol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone, and commercially available products include, but are not limited to, Aronix M-101 (Toyo Synthesis), KAYARAD TC-110S (Nippon chemical) and Viscoat 158 (Osaka organic chemical industry).

Specific examples of the above-mentioned bifunctional monomer include, but are not limited to, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, propylene glycol dimethacrylate, urethane (meth) acrylate, and commercially available products such as Aronix M-210, M-1100, 1200 (Toyo Synthesis), KAYARAD HDDA (Nippon chemical), Viscoat 260 (Osaka organic chemical industry), AH-600, AT-600, and UA-306H (Kyoho chemical Co., Ltd.).

Specific examples of the above-mentioned trifunctional or higher multifunctional photopolymerizable compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and the like, and commercially available products include Aronix M-309, TO-1382 (Toyo chemical), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPHA-40H (Japanese chemical), but is not limited thereto.

Among the photopolymerizable compounds exemplified above, polyfunctional monomers having three or more functions are more preferably used, and (meth) acrylates and (meth) urethane acrylates are more preferably used from the viewpoint of having excellent polymerizability and being capable of improving strength.

The photopolymerizable compound (C) may be contained in an amount of 5 to 45 wt%, more preferably 10 to 35 wt%, based on the total weight of the solid components in the colored photosensitive resin composition. In the case of the photopolymerizable compound in the above range, the strength and smoothness of the pixel (pixel) portion are preferable.

(D) Photopolymerization initiator

The photopolymerization initiator is not particularly limited as long as it can polymerize the photopolymerizable compound, and preferably may be one or more compounds selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, bisimidazole-based compounds, oxime-based compounds, and thioxanthone-based compounds in view of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, and mixtures thereof, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

Specific examples of the benzophenone-based compound include benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone and the like.

Specific 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-piperonyl-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) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2- Yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like.

Specific examples of the biimidazole compound include 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) biimidazole, 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetrakis (trialkoxyphenyl) biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, or an imidazole compound in which the phenyl group at the 4,4',5,5' position is substituted with an alkoxycarbonyl group, and the like.

More preferable examples thereof include 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, and 2, 2-bis (2, 6-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole.

Specific examples of the oxime compounds include o-ethoxycarbonyl- α -oxyimino-1-phenylpropan-1-one, and commercially available products thereof include OXE01 and OXE02 from basf corporation.

Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

The content of the photopolymerization initiator (D) is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight, based on the total weight of the solid components in the colored photosensitive resin composition. When the photopolymerization initiator is contained in the above range, the colored photosensitive resin composition is preferably used because the sensitivity is increased and the exposure time is shortened, thereby improving the productivity and maintaining the high resolution, and the strength of the pixel portion formed using the composition and the surface smoothness of the pixel portion are preferably improved.

(E) One or more compounds selected from the group consisting of polyfunctional thiol compounds and organosilicon compounds

The above-mentioned one or more compounds selected from the group consisting of the polyfunctional thiol compound and the organosilicon compound are preferably contained in an amount of 0.1 to 8% by weight based on the total weight of solid components contained in the composition.

When the content of the one or more compounds selected from the group consisting of the polyfunctional thiol compound and the organosilicon compound is less than 0.1% by weight, the effect of maintaining the luminance at high temperatures is not exhibited, the water repellency to DI is lowered to leave a streak, the adhesion between the substrate and the resist is lowered to cause a short circuit of a pattern, and the reliability of a panel in which a color filter and a TFT are bonded is affected to cause a residual image. If the amount exceeds 5% by weight, the tapered portion (Taper) of the colored photosensitive resin composition coating film is pulled, and it may be difficult to form a precise pattern, and a residual film or residue may be formed after development.

< polyfunctional thiol Compound >

The polyfunctional thiol compound may be a thiol compound such as the compounds exemplified below. The mercapto compound may be selected from the group consisting of 4-Mercaptohydrocinnamic Acid (4-mercaptocarnamic Acid), 4-Mercaptobenzoic Acid (4-Mercaptobenzoic Acid), Thiosalicylic Acid (Thiosalicylic Acid), 3, 4-dimethoxybenzenethiol (3, 4-dimexophenylthiol), 3-Ethoxybenzenethiol (3-Ethoxybenzenethiol), 4-hydroxyphenylthiol (4-hydroxyphenylthiol), 3-methoxyphenylthiol (3-Methoxybenzenethiol), 2-hydroxyphenylthiol (2-hydroxyphenylthiol), 4-methoxyphenylbenzenethiol (4-hydroxyphenylthiol), 3-hydroxyphenylthiol (3-hydroxyphenylthiol), 2-Methoxybenzenethiol (2-Hydroxybenzenethiol), 2-hydroxyphenylthiol (4-hydroxyphenylthiol), 3-hydroxyphenylthiol (3-hydroxyphenylthiol), 2-Methoxybenzenethiol (2-Methoxybenzenethiol), Thiosalicylic Acid Methyl ester (4-mercaptosalicylate), and 5-Mercaptobenzoic Acid (3, 4-mercaptosalicylic Acid) (3,5, 4-tetrafluorosalicylic Acid, 5-Mercaptobenzoic Acid (3, 4-Mercaptobenzoic Acid), 3-methoxybenethiol (3-hydroxybenethiol), and mixtures thereof, 2-mercaptobenzothiazole, 1, 4-bis (3-mercaptobutanoyloxy) butane, β -mercaptopropionic acid (β -Mercaptopropionic acid), Methyl 3-Mercaptopropionate (Methyl 3-Mercaptopropionate), 2-Ethylhexyl 3-Mercaptopropionate (2-Ethylhexyl 3-Mercaptopropionate), n-Octyl3-Mercaptopropionate (n-Octyl3-Mercaptopropionate), methoxybutyl 3-Mercaptopropionate (Methoxybutyl 3-Mercaptopropionate), octadecyl 3-Mercaptopropionate (Stearyl 3-Mercaptopropionate), Trimethylolpropane Tris (3-Mercaptopropionate) (trimethyl propionate), Tris [3-Mercaptopropionyloxy) -ethyl ] -isocyanurate (3-Mercaptopropionate), Pentaerythritol tetrakis (3-Mercaptopropionate) (Pentaerythritol 3-Mercaptopropionyloxy) -ethyl ] -isocyanurate (3-Pentaerythritol-Mercaptopropionate), Tetraethyleneglycol bis (3-mercaptopropionate) and Dipentaerythritol hexa (3-mercaptopropionate).

The polyfunctional thiol compound may be one or more selected from the group consisting of trimethylolpropane tris (3-mercaptopropionate) and Pentaerythritol tetrakis (3-mercaptopropionate) represented by the following chemical formulas 2 and 3.

[ chemical formula 2]

[ chemical formula 3]

The polyfunctional thiol compound may be contained in an amount of 0.1 to 5% by weight, more preferably 0.3 to 5% by weight, based on the total weight of solid components in the colored photosensitive resin composition. When the polyfunctional thiol compound is contained in the above range, the luminance maintaining effect at high temperature is excellent, the water repellency to DI is excellent in the water washing section after development without leaving unevenness, and the effect of reducing the cone angle which affects the difference in the height of the angular shape of the color pattern is provided.

If the content is less than 0.1% by weight, the effect of maintaining brightness at high temperatures may not be exhibited, and if the water repellency of DI is lowered to leave streaks, if the content exceeds 5% by weight, the tapered portion of the colored photosensitive resin composition coating film may be pulled and precise patterning may be difficult.

The colored photosensitive resin composition containing the above polyfunctional thiol compound provides the following effects: the color filter has excellent heat resistance, prevents yellowing in a high-temperature process, maintains high brightness, is favorable for preventing development stripes because a contact angle with respect to a coating film of deionized water (DI) is high in a water washing process after development, facilitates adjustment of a taper angle of a color filter pixel coating film, and facilitates elimination of differences in angular heights of color patterns.

< organosilicon Compound >

The organic silicon compound used in the present invention is added to improve the adhesion between the substrate and the resin film, and as the substrate, a glass or plastic substrate can be used, and particularly when a plastic substrate is used, the colored photosensitive resin composition of the present invention can be more preferably used.

That is, a plastic substrate such as polyethylene terephthalate is used as a substrate of a flexible display, and since the substrate stretches or shrinks during baking, there is a problem that the function as a display is hindered, and a low temperature in the baking process is required. However, in the case of the conventional colored photosensitive resin composition, if the temperature in the post-baking step is lowered in order to reduce the deformation of the substrate, sufficient curing cannot be caused, and there are problems that the adhesion between the base material and the resist is lowered and the reliability (chemical resistance) is lowered. Further, the problem of occurrence of afterimages is caused by the influence on the reliability of a panel manufactured by bonding a color filter substrate and a TFT substrate.

However, in the case of the colored photosensitive resin composition of the present invention containing the above-mentioned organosilicon compound, the composition can be used very effectively for a plastic substrate because it maintains very excellent adhesion even when it is fired at a low temperature.

The above-mentioned organosilicon compound may be represented by the following chemical formula 4:

[ chemical formula 4]

In the above formula, R¹And R²Each independently of the other, R¹Is any one organic functional group selected from the group consisting of glycidyl, (meth) acryloyl, aminopropyl, mercaptopropyl, cyanopropyl, vinyl and isocyanatopropyl, or has any one selected from the above groupsAn aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms of an organic functional group R²Is hydrogen atom, methyl, ethyl or hydroxyl, and n is an integer of 1 to 13.

Although not limited, especially R¹More preferably a (meth) acryloyl group.

The organic silicon compound represented by the above chemical formula 4 may have a cage structure or a ladder structure produced by a sol-gel process, or may be a mixture of these structures.

In particular, in the case of a form in which a cage structure and a ladder structure are mixed, a more preferable effect is provided.

The organic silicon compound can be produced by a sol-gel process using two or more of the following compounds, either alone or in combination: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 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-mercaptopropyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, a, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrichlorosilane, and the like.

Among the above compounds, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropyltrichlorosilane, methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltrichlorosilane are preferably used, and more preferably, the compound is obtained by a sol-gel process using 3-methacryloxypropyltrimethoxysilane.

The organic silicon compound is contained preferably in an amount of 0.1 to 3 wt%, more preferably 0.3 to 2 wt%, based on the total weight of solid components in the colored photosensitive resin composition. When the content of the organosilicon compound is less than 0.1 wt%, adhesion between the substrate and the resist may be reduced, short-circuiting of the pattern may occur, and the reliability of the panel in which the color filter and the TFT are bonded may be affected, thereby causing image sticking. If the amount exceeds 3% by weight, a residual film or residue may be formed after development.

The colored photosensitive resin composition containing the above-mentioned organosilicon compound provides the following effects: the adhesive property is excellent, especially the adhesive property between the substrate and the resist is maintained even in a low temperature sintering process to prevent the stripping of the coating, the reliability of the panel formed by the color filter and the TFT is improved under high temperature and high humidity without causing residual shadow, and no residual film or residue is generated after development.

(F) Solvent(s)

The solvent is used for dissolving other components of the colored photosensitive resin composition of the present invention, and any solvent used in a usual colored photosensitive resin composition can be used without any particular limitation, and ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, or the like can be preferably used.

Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; alkyl cellosolve acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl pentanone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ -butyrolactone; amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

Further, as an example thereof, ethyl 3-ethoxypropionate may be mentioned.

Among the above-exemplified solvents, in view of coatability and drying properties, organic solvents having a boiling point of 100 to 200 ℃ are preferable, and esters such as alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate are more preferable, and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate are more preferable. These solvents may be used either individually or as a mixture of two or more thereof.

The content of the solvent (F) may be 40 to 90% by weight, preferably 40 to 80% by weight, based on the total weight of the colored photosensitive resin composition. When the solvent is contained in the above range, the coating property can be improved when the coating is performed using a coating device such as a roll coater, a spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet.

(G) Additive agent

The colored photosensitive resin composition of the present invention may further contain additives such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, anti-gelling agents, pigment dispersants, and the like, as required.

Specific examples of the other polymer compounds include thermosetting resins such as epoxy resins and maleimide resins; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The curing agent is used for achieving deep curing and improving mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, and the like.

Of the above curing agents, specific examples of the epoxy compound include bisphenol a type epoxy resins, hydrogenated bisphenol a type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol F type epoxy resins, novolac type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester type resins, glycidyl amine type resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, epoxides of butadiene (co) polymers, epoxides of isoprene (co) polymers, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate, and the like;

specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, and the like.

The above curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerizing an epoxy group of the epoxy compound or an oxetane skeleton of the oxetane compound together with the curing agent. Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators. The polycarboxylic acid anhydride may be a commercially available epoxy resin curing agent. Specific examples of the epoxy resin curing agent include ADEKA HARDENER EH-700 (trade name, manufactured by ADEKA industries, Ltd.), RIKACID HH (trade name, manufactured by Nissian Chemicals Co., Ltd.), MH-700 (trade name, manufactured by Nissian Chemicals Co., Ltd.), and the like. The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used for further improving the film formability of the photosensitive resin composition, and a fluorine-based surfactant, a silicone-based surfactant, or the like may be preferably used.

Examples of the silicone surfactants include commercially available silicone surfactants such as DC3PA, DC7PA, SH11PA, SH21PA and SH8400 available from Dow Corning Tokyo Silicones, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 available from GE Toshiba Silicones. Examples of the fluorine-based surfactant include Megafac F-470, F-471, F-475, F-482 and F-489, which are commercially available from Dainippon ink chemical industries. The above-exemplified surfactants may be used alone or in combination of two or more.

The surfactant may be contained in an amount of usually 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of solid components in the colored photosensitive resin composition.

The adhesion promoter is preferably a silane compound, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 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, and the like, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like. The adhesion promoters exemplified above may 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.

Specific examples of the above-mentioned antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3, 5-di-tert-pentylphenyl) ethyl ] -4, 6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8, 10-tetra-tert-butyldibenzo [ d, f ] [1,3,2] dioxaphosphine, 3, 9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy } -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane, 2' -methylenebis (6-tert-butyl-4-methylphenol), 4' -butylidenebis (6-tert-butyl-3-methylphenol), 4' -thiobis (2-tert-butyl-5-methylphenol), 2' -thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3' -thiodipropionate, dimyristyl 3,3' -thiodipropionate, distearyl 3,3' -thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 3', 5,5' -hexa-tert-butyl-a, a '- (mesitylene-2, 4, 6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2, 6-di-tert-butyl-4-methylphenol, 2' -thiobis (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butyl-4-methylphenol and the like.

Specific examples of the anti-gelling agent include sodium polyacrylate and the like.

The pigment dispersant is added to the pigment for the purpose of disaggregating the pigment and maintaining stability, and any one commonly used in the art may be used without limitation. An acrylate-based dispersant (hereinafter also referred to as "acrylic dispersant") containing Butyl Methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) can be preferably used. As the above acrylic ester based dispersant, commercially available products such as DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and DISPER BYK LPN-6919 can be used, and the above exemplified acrylic dispersants can be used singly or in combination of two or more.

The above pigment dispersant may use other resin type pigment dispersants in addition to the above acrylic dispersant.

Examples of the other resin type pigment dispersants include, in particular, emulsion dispersants such as polycarboxylates represented by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids, and modified products thereof, or amides or salts thereof formed by reaction of polyesters having free carboxyl groups with poly (lower alkylene imine); water-soluble resins or water-soluble polymers such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, or polyvinyl pyrrolidone; a polyester; a modified polyacrylate; ethylene oxide/propylene oxide addition products and phosphoric acid esters, and the like.

As for commercially available products of the above-mentioned other resin type pigment dispersants, examples of the cationic resin dispersant include trade names of dick chemical: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, and DISPER BYK-184; trade names of basf corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; trade name of Lubirzol corporation: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanjian fine chemical company: HINACT T-6000, HINACT T-7000, HINACT T-8000; trade name of ajinomoto corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; trade name of Kyoeisha chemical Co: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc.

The pigment dispersant may be contained in an amount of preferably 5 to 60 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the solid content of the (a1) pigment used. When the content of the pigment dispersant is less than 5 parts by weight, the pigment is difficult to be finely pulverized or there is a possibility that gelation or the like occurs after dispersion. If it exceeds 60 parts by weight, the viscosity may become high, which is not preferable.

In addition, the present invention provides a color filter produced from the colored photosensitive resin composition and an image display device comprising the same.

The image display device of the present invention includes the color filter of the present invention formed including a substrate and a color layer. The image display device described above includes a configuration known to those skilled in the art of the present invention in addition to the color filter described above.

Further, the present invention provides a method of manufacturing a color filter, comprising: forming a colored pattern by using the colored photosensitive resin composition of the present invention through a low temperature firing process at 80 to 180 ℃.

The above-mentioned manufacturing method can prevent the peeling of the coating film by maintaining the adhesion between the substrate and the resist even in the low-temperature baking step, and can improve the reliability of the panel in which the color filter and the TFT are bonded under high temperature and high humidity without causing residual image.

For example, the method for producing the photosensitive resin composition of the present invention is described below.

First, in the colorant (A), the pigment (a1) and the solvent (F) are mixed and dispersed by a bead mill or the like until the average particle diameter of the pigment becomes 0.2 μm or less. In this case, if necessary, a part or the whole of the alkali-soluble resin (B) and a part or the whole of the solvent (F) may be mixed together and dissolved or dispersed.

In the above mixture, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) one or more of a polyfunctional thiol compound and an organosilicon compound, and (F) a solvent may be further added so as to achieve a predetermined concentration, to produce the colored photosensitive resin composition according to the present invention.

The present invention will be described in more detail below with reference to examples, but the embodiments of the present invention disclosed below are merely examples, and the scope of the present invention is not limited to these embodiments.

In the following examples and comparative examples, "%" and "part(s)" as indicated by weight are given unless otherwise specified.

Synthesis example 1: synthesis of organosilicon Compounds

80ml of 3-methacryloxypropyltrimethoxysilane (MTMS: A-174, manufactured by GE-Toshiba) was put into a reaction vessel equipped with a stirrer, a thermometer and a pH meter, and 20ml of a mixed solution prepared by mixing 15ml of methanol with 5ml of an aqueous solution of malonic acid having a pH of 2.5 was put into a dropping funnel, and the aqueous solution mixed solution of methanol and malonic acid was dropped into the reaction vessel at room temperature over 30 minutes while stirring the reaction vessel. After the completion of the dropwise addition, the mixture was stirred for 2 hours while maintaining the ordinary temperature. After stirring for 2 hours, the solvent was removed under reduced pressure. The distilled water remaining as anhydrous magnesium sulfate was dehydrated, and the anhydrous magnesium sulfate was filtered and classified. In the above process, the finally obtained organosilicon compound is present in the form of a colorless viscous liquid silica sol exhibiting the best performance in increasing the adhesiveness. One specific example of the hydrolysis and polycondensation reaction can be represented by the following reaction formula.

[ reaction formula 1]

Hydrolysis

Polycondensation

Sol-gel

Synthesis example 2: synthesis of organosilicon Compounds

An organic silicon compound was synthesized in the same manner as in Synthesis example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to 3-glycidoxypropyltrimethoxysilane (GPTMS: A-187, manufactured by GE Toshiba).

Synthesis example 3: synthesis of organosilicon Compounds

An organosilicon compound was synthesized in the same manner as in Synthesis example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to vinyltrimethoxysilane (VTMS: GE-Toshiba, A-171) in Synthesis example 1.

Examples 1 to 13 and comparative examples 1 to 13: production of colored photosensitive resin composition

The components described in the following tables 1 to 3 were mixed in the corresponding composition ratios to produce colored photosensitive resin compositions.

[ Table 1]

(unit: wt%)

[ Table 2]

(unit: wt%)

[ Table 3]

(unit: wt%)

The ingredients used in tables 1 to 3 above are as follows:

a-1: in the structure of chemical formula 1, Cl: 2, Br: 9, H: 5 pieces (Tmax: 515nm, T50%: 450 to 575nm) (DIC Co., Ltd.)

A-2: in the structure of chemical formula 1, Cl: 3, Br: 8, H: 5 (Tmax: 510nm, T50%: 445 to 570nm) (DIC Co., Ltd.)

A-3: g58 (in the structure of chemical formula 1, the central atom is Zn, A1-A16 is a mixture of 0-1H, 0-1 Cl and 14-16 Br)

A-4: g7 (in the structure of chemical formula 1, the central atom is Cu, A1-A16 is a mixture of 0-2H and 14-16 Cl)

A-5: y129 (manufacturing company: DIC company)

A-6: y138 (manufacturing company: BASF corporation)

A-7: y185 (manufacturing company: BS company)

B-1: methacrylic acid benzyl methacrylate copolymer of 31:69 (molar ratio), weight average molecular weight of 30,000, acid value of 105mgKOH/g

C-1: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufacturing Co., Japan chemical Co., Ltd.)

D-1: OXE-01 (manufacturing company: Ciba Co., Ltd.)

E-1: TMMP [ trimethylolpropane tris (3-mercaptopropionate) ] (product of Jiugi chemical Co., Ltd.)

E-2: PEMP [ pentaerythritol tetra 3-mercaptopropionate ] (product of Jiuging chemical Co., Ltd.)

E-3: synthesis example 1

E-4: synthesis example 2

E-5: synthesis example 3

E-6: 3-methacryloxypropyltrimethoxysilane

E-7: 3-glycidoxypropyltrimethoxysilane

E-8: vinyl trimethoxy silane

F-1: propylene glycol monomethyl ether acetate

F-2: 3-Ethoxypropionic acid ethyl ester

G-1: organosilicon surfactant (SH-8400)

G-2: acrylic pigment dispersant (DISPER BYK-2001, manufactured by BYK corporation)

G-3: sealing promoter (3-methacryloxypropyltrimethoxysilane)

Test example 1: evaluation of physical Properties of colored photosensitive resin composition

Color filters were produced from the colored photosensitive resin compositions produced in examples 1 to 13 and comparative examples 1 to 13.

The colored photosensitive resin compositions were applied to a glass substrate by spin coating, and then placed on a hot plate and maintained at a temperature of 100 ℃ for 3 minutes to form a thin film. Then, a test photomask having a pattern in which the transmittance is changed stepwise in the range of 1 to 100% and a line/space pattern of 1 to 50 μm is placed on the film, and the test photomask is irradiated with ultraviolet rays with a distance of 100 μm from the test photomask. In this case, the ultraviolet light source uses a high voltage of 1KW including the g, h and i raysMercury lamp at 100mJ/cm²The illumination of (2) is performed without using a special optical filter. The film irradiated with the ultraviolet ray was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes to be developed. After the glass plate coated with the film was washed with distilled water, it was dried by blowing nitrogen gas and heated in a heating oven at 220 ℃ for 1 hour to produce a color filter. The film thickness of the color filter produced above was 2.0. mu.m.

The spectral (brightness), reliability (heat resistance and chemical resistance), development mottle, cone angle, residue TEST, and PCT TEST (PCT TEST) of the above color filter were measured and evaluated as follows, and the results thereof are shown in tables 4 and 5 below.

< measurement of spectral (Brightness) >

The brightness and color coordinates were determined using a microspectrophotometer (Microcopic Spectrophotometer; model No. OSP-SP2000, Olympus).

Evaluation criterion of brightness

-: 47.0 or more is suitable

-X: less than 47.0 is not suitable

< reliability-Heat resistance >

The substrate produced by the above experimental method was left in an oven at 230 ℃ for 2 hours, and then the color change (Δ E ab) was measured. At this time, the color characteristics before and after the heat resistance evaluation were confirmed by a microspectrophotometer (model No. OSP-SP2000, Olympus).

The CIE color coordinate values before and after the evaluation were measured, calculated by the following equation 1, and evaluated according to the following evaluation criteria.

[ mathematical formula 1]

△E*ab＝[(△L*)²+(△a*)²+(△b*)²]×1/2

In the above formula 1, Δ E × ab represents a color change, Δ L represents a luminance difference, Δ a represents a color difference between red and green, and Δ b represents a color difference between yellow and blue.

-: delta E ab < 2.0

-. DELTA: delta E ab is 2.0 or more and less than 3.0

-X: Δ Ε ab exceeds 3.0.

< reliability-chemical resistance >

The substrate produced by the above experimental method was immersed in a NMP (N-methyl-2-pyrrolidone) solution for 30 minutes, and then the color change (Δ E ab) was measured.

At this time, the color characteristics before and after NMP impregnation were confirmed by a microspectrophotometer (model No. OSP-SP2000, Olympus).

The CIE color coordinate values before and after the evaluation were measured, calculated by the following equation 2, and evaluated based on the following evaluation criteria.

[ mathematical formula 2]

△E*ab＝[(△L*)²+(△a*)²+(△b*)²]×1/2

In the above formula 2, Δ E × ab represents a color change, Δ L represents a luminance difference, Δ a represents a color difference between red and green, and Δ b represents a color difference between yellow and blue.

Evaluation criteria

O: delta E ab < 2.0

And (delta): delta E ab is 2.0 or more and less than 3.0

X: Δ Ε ab exceeds 3.0.

< development Rib >

DI was dropped on the substrate developed by the above experimental method, and the contact angle was measured using a contact angle measuring instrument (Kyoeish Co., Ltd.: DSA-100).

O: the contact angle is more than 70 DEG

And (delta): the contact angle is 60 degrees or more and less than 70 degrees

X: the contact angle is less than 60 degrees.

< evaluation of taper Angle >

For the substrate manufactured by the experimental method described above, the pattern gradient of the cross-sectional portion of the coating film was measured by SEM.

O: the cone angle being less than 40 degrees

And (delta): the taper angle is 40-60 deg

X: the cone angle is more than 60 degrees

< residue test >

The periphery of the coating film of the pattern formed by the above method was observed with an ultra-deep 3D shape measuring microscope (VK-9500, keyence corporation) to confirm the presence or absence of development residue on the substrate.

Evaluation criteria

O: no development residue on the substrate

X: development residue on the substrate

< PCT Test (Pressure Cooker Test >

After the substrate produced by the above method was left to stand for 24 hours under the following conditions, 100 checkerboard squares of 1mm × 1mm were cut on the substrate on which the coating film was formed, and the peeled state after the peeling test using the adhesive tape was determined using an ultra-deep 3D shape measuring microscope (VK-9500, kirnshi).

Evaluation conditions

High temperature (120 deg.C)/high humidity (100% humidity)/barometric pressure (2atm)

Evaluation criteria

O: 100/100 (number of squares peeled/total number of squares) -no peeling at all

△：80/100～99/100

×：0/100～79/100

[ Table 4]

[ Table 5]

While certain aspects of the present invention have been described in detail, it will be apparent to those skilled in the art that such specific techniques are merely preferred embodiments, and the scope of the present invention is not limited thereto. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above-described matters.

Accordingly, the actual scope of the invention is to be determined by the appended claims and their equivalents.

Claims

1. A colored photosensitive resin composition, comprising: (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) at least one compound selected from a polyfunctional thiol compound and an organosilicon compound, and (F) a solvent,

the colorant (A) contains one or more selected from C.I. pigment green 59, 62 and 63 and one or more selected from pigments and dyes,

mixing the raw materials in a ratio of 1:0.050 to 1:18.0 weight ratio comprising one or more selected from the group consisting of the C.I. pigment greens 59, 62 and 63 and one or more selected from the group consisting of pigments and dyes,

the polyfunctional thiol compound of (E) is one or more selected from the group consisting of trimethylolpropane tri (3-mercaptopropionate) and pentaerythritol tetra (3-mercaptopropionate),

the organosilicon compound of (E) comprises a compound represented by the following chemical formula 4,

the colored photosensitive resin composition comprises, relative to the total weight of solid components contained in the composition: (A) 5 to 70 wt% of a colorant, (B) 5 to 85 wt% of an alkali-soluble resin, (C) 5 to 45 wt% of a photopolymerizable compound, (D) 0.1 to 40 wt% of a photopolymerization initiator, and (E) 0.1 to 8 wt% of one or more compounds selected from a polyfunctional thiol compound and an organosilicon compound, wherein the colored photosensitive resin composition comprises (F) 40 to 90 wt% of a solvent based on the total weight of the colored photosensitive resin composition,

chemical formula 4

In the chemical formula 4, the first and second organic solvents,

R¹and R²Each independently of the other, R¹Is selected from the group consisting of glycidylAny one organic functional group selected from the group consisting of a glyceryl group, a (meth) acryloyl group, an aminopropyl group, a mercaptopropyl group, a cyanopropyl group, a vinyl group and an isocyanatopropyl group, or an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms having any one organic functional group selected from the group, R²Is a hydrogen atom, a methyl group, an ethyl group or a hydroxyl group,

n is an integer of 1 to 13.

2. The colored photosensitive resin composition according to claim 1, further comprising one or more additives selected from the group consisting of other high molecular compounds, curing agents, surfactants, adhesion promoters, anti-gelling agents and pigment dispersants.

3. The colored photosensitive resin composition according to claim 1, wherein the firing temperature of the colored photosensitive resin composition is 80 to 180 ℃.

4. A color filter comprising a colored pattern produced from the colored photosensitive resin composition according to any one of claims 1 to 3.

5. An image display device comprising the color filter of claim 4.

6. A method of manufacturing a color filter, comprising: a step of forming a colored pattern by using the colored photosensitive resin composition according to any one of claims 1 to 3 and a low-temperature firing step at 80 to 180 ℃.