CN107229183B

CN107229183B - Red photosensitive resin composition, color filter manufactured using the same, and display device including the color filter

Info

Publication number: CN107229183B
Application number: CN201710178183.XA
Authority: CN
Inventors: 金正植; 康德基; 金亨柱
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2016-03-23
Filing date: 2017-03-23
Publication date: 2021-03-05
Anticipated expiration: 2037-03-23
Also published as: CN107229183A; JP2017173828A; JP6778138B2

Abstract

The present invention relates to a red photosensitive resin composition, a color filter manufactured by using the same, and a display element including the color filter, wherein the composition comprises a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the colorant (A) comprises a red pigment and a black pigment, and is characterized in that the red photosensitive resin composition has a spectral transmittance of 20% or less at a wavelength of 430 to 590nm and a spectral transmittance of 70% or more and less than 90% at a wavelength of 635 to 780nm when formed into a cured film having a thickness of 3 [ mu ] m. The red photosensitive resin composition of the present invention is characterized by being capable of solving the problems of high color reproducibility and insufficient workability of the conventional red photosensitive resin composition, while replacing a polarizing plate in a display element.

Description

Red photosensitive resin composition, color filter manufactured using the same, and display device including the color filter

Technical Field

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

Background

Recently, a flexible display element in which a display portion, wiring, and the like are formed on a flexible substrate made of plastic such as a flexible material so that image display can be performed even if the flexible display element is bent like paper has recently been attracting attention.

The flexible Display element has a wide variety of applications not only to monitors and televisions of computers but also to personal carrying equipment, and particularly, an Organic Light Emitting Display device (OLED), unlike a Liquid Crystal Display device (LCD), does not require an additional Light source and thus can achieve a relatively thin thickness, and in this respect, Organic Light Emitting elements are actively studied for flexible Display elements.

On the other hand, in order to practically use the flexible display element, it is necessary to realize full color, to reduce power consumption, and to easily read even outdoors, as compared with the present various display products.

In this sense, the organic light emitting element is the most useful resource as a light source of a flexible display element because of its advantages of possibility of realizing full color, low power consumption, and fast response speed. With the present organic light emitting element, an encapsulation barrier (encapsulation barrier) layer for protecting the organic light emitting element from oxygen and moisture is required, and in order to be easily readable even outdoors, a polarizing plate (polarizer) is required to maintain a high contrast ratio (contrast ratio).

However, if a polarizing plate having hard characteristics is applied, a disadvantage that the flexibility of the flexible display element is reduced may occur. On the other hand, if no polarizing plate is used, the external light is transmitted into the flexible display element, reflected again, and emitted, and is mixed with the light originally emitted from the organic light emitting element, so that the contrast ratio under the external light source is significantly reduced.

Thus, improvement thereof has been actively studied recently, and as an example, an ink composition containing a colorant including a green colorant and a yellow colorant, a binder resin, and a blocked isocyanate group is proposed in korean laid-open patent No. 10-2013-. However, in the case of the above-mentioned prior art, there are disadvantages that the selection range of coloring materials is limited when high color reproducibility is achieved, and at the same time, realization of various color regions is insufficient, and further, there are line defects and insufficient workability such as undercut in pattern formability, and thus continuous improvement is demanded in the technical field.

Documents of the prior art

Patent document

Patent document 1: korean laid-open patent No. 10-2013-0134494

Patent document 2: korean laid-open patent No. 10-2013-0134498

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to solve the problem of insufficient workability in the prior art and to provide a red photosensitive resin composition for pixel formation which can replace a polarizing plate and can realize high color reproducibility.

Another object of the present invention is to provide a color filter produced using the red photosensitive resin composition, and a display device including the color filter.

Means for solving the problems

The present invention provides a red photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the colorant comprises a red pigment and a black pigment, and is characterized in that the red photosensitive resin composition has a spectral transmittance of 20% or less at a wavelength of 430 to 590nm and a spectral transmittance of 70% or more and less than 90% at a wavelength of 635 to 780nm when formed into a cured film having a thickness of 3 [ mu ] m.

In one embodiment, the red photosensitive resin composition may have a spectral transmittance of 20% or less at a wavelength of 430 to 590nm when formed into a cured film having a thickness of 3 μm, and the red photosensitive resin composition may have a spectral transmittance of 70% or more and less than 90% at a wavelength of 635 to 780nm when formed into a cured film having a thickness of 3 μm.

In another embodiment, when the red photosensitive resin composition is formed into a cured film having a thickness of 3 μm, the spectral transmittance at a wavelength of 635 to 780nm may be 80% or more and less than 90%.

In another embodiment, the red pigment may be 1 or more selected from c.i. pigment red 179, c.i. pigment red 177, c.i. pigment red 209, c.i. pigment red 242 and c.i. pigment red 254.

In still another embodiment, the black pigment may be 1 or more selected from the group consisting of a pigment obtained by mixing red, cyan, and green, c.i. pigment black 1, c.i. pigment black 7, carbon black, an organic black pigment, and titanium black.

In another embodiment, the black pigment may be contained in an amount of 0.5 to 10 wt% based on the total solid content of the coloring material.

In another embodiment, the weight ratio of the red pigment to the black pigment may be 99.9 to 80: 20 to 0.1.

In another embodiment, the red photosensitive resin composition may contain 10 to 80 wt% of a colorant, 5 to 80 wt% of an alkali-soluble resin, and 5 to 50 wt% of a photopolymerizable compound, based on 100 parts by weight of the total solid content of the alkali-soluble resin and the photopolymerizable compound, and may contain 0.1 to 40 parts by weight of a photopolymerization initiator, and may contain 25 to 80 wt% of a solvent, based on the total weight of the red photosensitive resin composition.

In yet another embodiment, the colorant may further comprise a yellow pigment.

In still another embodiment, the yellow pigment may be included in an amount of 3 to 30 parts by weight, based on 100 parts by weight of the total content of the red pigment and the black pigment.

In yet another embodiment, the yellow pigment may be 1 or more selected from c.i. pigment yellow 138, c.i. pigment yellow 139, and c.i. pigment yellow 150.

In another embodiment, the alkali-soluble resin may have an acid value of 30 to 150mgKOH/g and a glass transition temperature of 100 ℃ or higher.

The present invention also provides a color filter produced using the red photosensitive resin composition, wherein the color filter has high color reproducibility without using a polarizing plate.

Further, the present invention provides a display element including the color filter.

In one embodiment, a red light source may be included.

In another embodiment, the display element may be an organic light emitting element.

In yet another embodiment, the display element may be a flexible display element.

ADVANTAGEOUS EFFECTS OF INVENTION

The red photosensitive resin composition of the present invention is characterized by being capable of solving the problems of high color reproducibility and insufficient workability of the conventional red photosensitive resin composition for forming pixels while replacing a polarizing plate in a display element. Particularly, the red photosensitive resin composition has a spectral transmittance of 20% or less at a wavelength of 430 to 590nm when formed into a cured film having a thickness of 3 μm, and has a spectral transmittance of 70% or more and less than 90% at a wavelength of 635 to 780nm when formed into a cured film having a thickness of 3 μm. When the red photosensitive resin composition is formed into a cured film having a thickness of 3 μm, there is a problem that the color purity of red is lowered when the spectral transmittance at a wavelength of 430 to 590nm is more than 20%, and the external light reflection effect is good when the spectral transmittance at a wavelength of 635 to 780nm is less than 70%, but the reduction in luminance may cause poor visibility, and when the spectral transmittance is more than 90%, the external light reflection effect is small although the luminance is good. .

Drawings

Fig. 1 to 3 show spectral transmittances based on wavelengths as a result of experimental example 2. In particular, FIG. 2 is a graph showing the spectral transmittance at 430 to 590nm based on the results of Experimental example 2, and FIG. 3 is a graph showing the spectral transmittance at 635 to 775nm based on the results of Experimental example 2.

Detailed Description

The present invention relates to a red photosensitive resin composition, a color filter produced using the same, and a display element including the color filter.

The present invention is characterized in that the composition of the red photosensitive resin composition contains a red pigment and a black pigment as essential components in the pigment dispersion composition, thereby realizing color development without using a polarizing plate, and particularly, the composition can exhibit a spectral transmittance in a specific range of wavelength bands.

The present invention will be described in detail below.

Colorant (A)

The colorant may be contained in an amount of 10 to 80 wt%, preferably 20 to 60 wt%, and more preferably 30 to 50 wt% based on the total weight of the solid content in the red photosensitive resin composition.

The pigment (a1) contained in the above colorant must contain a red pigment and a black pigment. The weight ratio of the red pigment to the black pigment can be 99.9-80: 20 to 0.1, preferably 99.5 to 90: 10 to 0.5. In the case where the above range is satisfied, it may be advantageous to realize the following: the red photosensitive resin composition has a spectral transmittance of 20% or less at a wavelength of 430 to 590nm when formed into a cured film having a thickness of 3 μm, and has a spectral transmittance of 70% or more and less than 90% at a wavelength of 635 to 780nm when formed into a cured film having a thickness of 3 μm.

When the red photosensitive resin composition is formed into a cured film having a thickness of 3 μm, there is a problem that the color purity of red is lowered when the spectral transmittance at a wavelength of 430 to 590nm is more than 20%, and the visibility may be deteriorated due to the reduction of luminance although the external light reflection effect is good when the spectral transmittance at a wavelength of 635 to 780nm is less than 70%, and the external light reflection effect may be small although the luminance is good when the spectral transmittance is more than 90%.

The black pigment usable in the present invention may be any black pigment used in the art, for example, a pigment capable of mixing red, cyan and green, c.i. pigment black 1, c.i. pigment black 7, carbon black, organic black, titanium black, etc. may be used alone or 2 or more kinds may be mixed, preferably, 1 kind selected from carbon black and organic black may be used, and more preferably, carbon black may be used.

In the present invention, the black pigment may be contained in an amount of 0.5 to 10% by weight based on the total weight of the solid content of the coloring material, which means the dye and the pigment contained in the pigment dispersion composition. When the above-mentioned criteria are satisfied, the effect of preventing external light reflection and visibility can be advantageously obtained.

The colorant is described in detail below.

Pigment (a1)

The pigment (a1) must contain a red pigment and a black pigment.

The red pigment of the present invention may be, for example, 1 or more selected from the group consisting of c.i. pigment red 177, c.i. pigment red 179, c.i. pigment red 202, c.i. pigment red 206, c.i. pigment red 207, c.i. pigment red 208, c.i. pigment red 209, c.i. pigment red 215, c.i. pigment red 216, c.i. pigment red 220, c.i. pigment red 224, c.i. pigment red 226, c.i. pigment red 242, c.i. pigment red 243, c.i. pigment red 245, c.i. pigment red 254, c.i. pigment red 255, c.i. pigment red 264, and c.i. pigment red 265, wherein c.i. pigment red 179, c.i. pigment red 177, pigment red 209, c.i. pigment red 242, and c.i. pigment red 254 are preferable. The red pigment is more preferably c.i. pigment red 177, c.i. pigment red 179, and pigment red 254.

The black pigment of the present invention can use carbon black; an organic black pigment; titanium black; and a pigment dispersion liquid in which red, cyan, and green are mixed, c.i. pigment black 1, c.i. pigment black 7, and the like.

More specifically, the black pigment can be used by mixing carbon black with 2 or more coloring pigments to produce a mixed coloring dispersion liquid.

Examples of the carbon black that can be used include CHBK-17 available from Yuanhong corporation; seast 5HIISAFHS, Seast KH, Seast 3HHAF-HS, Seast NH, Seast 3M, Seast 300HAF-LS, Seast 116HMMAF-HS, Seast 116MAF, Seast FMFEF-HS, Seast SOFF, Seast VGPF, Seast SVHSRF-HS, and Seast SSRF of east China sea carbon; ダイヤグラムブラック II, ダイヤグラムブラック N339, ダイヤグラムブラック SH, ダイヤグラムブラック H, ダイヤグラム LH, ダイヤグラム HA, ダイヤグラム SF, ダイヤグラム N550M, ダイヤグラム M, ダイヤグラム E, ダイヤグラム G, ダイヤグラム R, ダイヤグラム N760M, ダイヤグラム LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45L, #25, # CF9, #95, #3030, #3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B of Mitsubishi chemical; デグサ (strain) PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; コロンビアカーボン (strain) RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190-STRA, and RAVEN 1170-1170.

Examples of the coloring pigment that can be used in combination with the carbon black include magenta 6B (c.i.12490), phthalocyanine green (c.i.74260), phthalocyanine blue (c.i.74160), mitsubishi carbon black MA100, perylene black (BASF k0084.k0086), cyanine black, lithol (リオノール) yellow (c.i.21090), lithol yellow GRO (c.i.21090), benzidine yellow 4T-564D, mitsubishi carbon black MA-40, victoria pure blue (c.i.42595), c.i. pigment red 97, 122, 149, 168, 177, 180, 192, 215, c.i. pigment green 7, 36, c.i. pigment 15: 1. 15: 4. 15: 6. 22, 60, 64, c.i. pigments 83, 139, c.i. pigment violet 23, etc., and further, white pigments, fluorescent pigments, etc. can be used.

The carbon black is not particularly limited as long as it is a pigment having light-shielding properties, and known carbon blacks can be used. Specific examples of the carbon black as the black pigment include channel black, furnace black, thermal black, and lamp black.

In addition, a yellow pigment may be optionally contained.

The yellow pigment may be 1 or more selected from c.i. pigment yellow 138, c.i. pigment yellow 139 and c.i. pigment yellow 150, preferably, c.i. pigment yellow 139 and c.i. pigment yellow 150, more preferably, c.i. pigment yellow 139.

The yellow pigment may be included in an amount of 3 to 30 parts by weight, based on 100 parts by weight of the total amount of the red pigment and the black pigment. When the yellow pigment is contained in the above content range, the content of the pigment in the resist based on the solid content can be reduced, and the composition is advantageous in terms of pattern adhesion and straightness in workability, and thus is preferable.

The content of the pigment (a1) may be 10 to 90% by weight, preferably 20 to 50% by weight, based on the total weight of the solid content in the colorant (a). The content of the pigment is preferably in the range of 10 to 90% by weight based on the above, because the viscosity is low, the storage stability is excellent, the dispersion efficiency is high, and the increase of the contrast ratio is effective. The pigment is preferably a pigment dispersion liquid in which the particle diameter is uniformly dispersed. As an example of a method for uniformly dispersing the particle diameter of the pigment, a method of dispersing the pigment dispersion liquid containing the pigment dispersant (a2) can be mentioned, and according to this method, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

Pigment dispersant (a2)

The pigment dispersant (a2) is added for deagglomeration of the pigment and maintenance of stability, and any pigment dispersant generally used in this field can be used without limitation. It is preferable to contain an acrylate-based dispersant (hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). In this case, it is preferable to use an acrylic dispersant manufactured by the activity control method described in Korean laid-open patent No. 2004-0014311, and examples of commercially available acrylic dispersants manufactured by the activity control method include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The above-exemplified acrylic dispersants can be used each alone or in combination of 2 or more. The dispersant (a2) may be a resin type pigment dispersant other than the acrylic dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, and particularly, oil-based dispersants such as polyurethanes, polycarboxylates typified by 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 phosphates, esters of hydroxyl-containing polycarboxylic acids, and modified products thereof, or amides or salts thereof formed by reaction of polyesters having free (free) carboxyl groups with poly (lower alkylene imines); water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinyl pyrrolidone; a polyester; a modified polyacrylate; ethylene oxide/propylene oxide addition products, phosphoric esters, and the like. As a commercial product of the resin type dispersant, a cationic resin dispersant includes, for example, a trade name of BYK 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 name 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 Chuanmo Fine chemicals: ヒノアクト (HINACT) T-6000, ヒノアクト T-7000, ヒノアクト T-8000; trade name of Aomoto Co., Ltd: アジスパー (AJISPUR) PB-821, アジスパー PB-822, アジスパー PB-823; trade name of Kyoeisha chemical Co., Ltd: フローレン (FLORENE) DOPA-17HF, フローレン DOPA-15BHF, フローレン DOPA-33, フローレン DOPA-44, etc. In addition to the above-mentioned acrylic dispersants, other resin-type pigment dispersants may be used alone or in combination of 2 or more kinds, and may be used in combination with the acrylic dispersant.

The amount of the dispersant (a2) used is 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1) used. When the content of the dispersant (a2) satisfies the above criteria, the viscosity and the micronization of the pigment are advantageous, and the possibility of occurrence of problems such as gelation after dispersion can be reduced.

Dye (a3)

The above dye (a3) may be optionally contained in the colorant. The dye (a3) may be additionally used without limitation as long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and capable of ensuring solubility in an alkali developing solution and reliability in heat resistance, solvent resistance, and the like is preferably used. As the dye, a dye selected from an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye with a nitrogen-containing compound, a sulfonamide of an acid dye, and derivatives thereof can be used, and an azo-based, xanthene-based, phthalocyanine-based acid dye, and derivatives thereof can be selected. Preferably, The dye includes a compound classified as a dye in The color index (published by The Society of Dyers and Colourists) and a known dye described in notes on dyeing (color dyeing Co.).

Specific examples of the above-mentioned dye include c.i. solvent dyes

C.i. yellow dyes such as solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163, etc.;

among the c.i. solvent dyes, c.i.

solvent yellows

14, 16, 21, 56, 151, 79, 93 having excellent solubility in organic solvents are preferable, and among them, c.i. solvent yellows 21, 79 are more preferable.

Further, as the c.i. acid dye, yellow dyes such as c.i. acid yellow 1,3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and the like can be cited.

Among the acid dyes, c.i. acid yellow having excellent solubility in organic solvents is preferable.

Examples of the c.i. direct dye include yellow dyes such as c.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, and 141.

Further, as the c.i. mordant dyes, yellow dyes such as c.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 and the like can be cited.

These dyes can be used each alone, or 2 or more kinds thereof can be used in combination.

Dispersion solvent (a4)

The colorant may optionally contain the above-mentioned dispersion solvent (a4), and the kind thereof is not particularly limited, and various organic solvents used in this field can be used.

Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, aromatic hydrocarbons such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, alkylene glycol alkyl ether acetates such as benzene, toluene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, ketones such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerol, alcohols such as ethanol, butanol, cyclohexanol, ethylene glycol and glycerol, Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ -butyrolactone. Preferably, esters such as alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate can be used, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate can be used.

The dispersion solvents can be used individually or in combination of 2 or more.

Alkali soluble resin (B)

The alkali-soluble resin (B) must be soluble in the solvent of the present invention and reactive to the action of light or heat. The colorant is not particularly limited as long as it functions as a binder resin and is soluble in an alkaline developer.

The alkali-soluble resin may be a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the above monomer. The carboxyl group-containing monomer may be, for example, an unsaturated carboxylic acid such as an unsaturated polycarboxylic acid having 1 or more carboxyl groups in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid. The unsaturated monocarboxylic acid may be, for example, acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid, or the like. The unsaturated dicarboxylic acid may be, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, or the like. The unsaturated polycarboxylic acid may be an acid anhydride, specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, or the like. The unsaturated polycarboxylic acid may be a mono (2-methacryloxyalkyl) ester, and examples thereof include a mono (2-acryloyloxyethyl) succinate, a mono (2-methacryloyloxyethyl) succinate, a mono (2-acryloyloxyethyl) phthalate, and a mono (2-methacryloyloxyethyl) phthalate. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends, and examples thereof include ω -carboxy polycaprolactone monoacrylate and ω -carboxy polycaprolactone monomethacrylate. The carboxyl group-containing monomers may be used in a single amount of 1 kind or in a mixture of 2 or more kinds. Specific examples of the other monomer copolymerizable with the above carboxyl group-containing monomer include aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, isopropyl acrylate, isobutyl acrylate, butyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiglycol acrylate, methoxydiglycol methacrylate, methoxytriglycol acrylate, methoxytriglycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, allyl acrylate, allyl methacrylate, Unsaturated carboxylic acid esters such as 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate; aminoalkyl esters of unsaturated carboxylic acids such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethyl acrylamide, and N-2-hydroxyethyl methacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; giant monomers having a monoacrylyl group or a monomethacrylyl group at the end of a polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, and the like. The above monomers may be used in a single kind or in a mixture of 2 or more kinds.

Thus, the alkali-soluble resin may be, for example, a (meth) acrylic acid/methyl (meth) acrylate copolymer, a (meth) acrylic acid/benzyl (meth) acrylate copolymer, a (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate copolymer, a (meth) acrylic acid/methyl (meth) acrylate/polystyrene macromonomer copolymer, a (meth) acrylic acid/methyl (meth) acrylate/polymethyl (meth) acrylate macromonomer copolymer, a (meth) acrylic acid/benzyl (meth) acrylate/polystyrene macromonomer copolymer, a (meth) acrylic acid/benzyl (meth) acrylate/polymethyl (meth) acrylate macromonomer copolymer, a (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate Ester/polystyrene macromonomer copolymer, (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate/polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid/styrene/(meth) benzyl (acrylate/N-phenylmaleimide copolymer, (meth) acrylic acid/mono (2-acryloyloxy) succinate/styrene/(meth) benzyl (acrylate/N-phenylmaleimide copolymer, (meth) acrylic acid/mono (2-acryloyloxyethyl) succinate/styrene/(meth) allyl (acrylate/N-phenylmaleimide copolymer, and (meth) acrylic acid/benzyl (meth) acrylate/N-phenylmaleimide/styrene/glycerol Mono (meth) acrylate copolymers, and the like. The above (meth) acrylate means acrylate or methacrylate.

Among the alkali-soluble resins, preferred are (meth) acrylic acid/benzyl (meth) acrylate copolymers, (meth) acrylic acid/benzyl (meth) acrylate/styrene copolymers, (meth) acrylic acid/methyl (meth) acrylate copolymers, and (meth) acrylic acid/methyl (meth) acrylate/styrene copolymers.

The alkali-soluble resin has a weight average molecular weight as measured by Gel Permeation Chromatography (GPC) using tetrahydrofuran as an elution solvent, as measured in terms of polystyrene, of 5000 to 50000, preferably 8000 to 40000, and more preferably 10000 to 30000. When the weight average molecular weight of the alkali-soluble resin falls within the range of 5000 to 50000, the coating film hardness is improved, an excellent film residue rate is exhibited, and good solubility of an unexposed portion in a developer and improved resolution can be exhibited. The acid value is 50 to 150(mgKOH/g), preferably 60 to 140, and more preferably 80 to 130. Within the above acid value range, the solubility of the alkali-soluble resin in a developer is improved, unexposed portions are easily dissolved and highly sensitive, and a pattern of exposed portions is left during development, whereby the residual film ratio can be improved.

The alkali-soluble resin is contained in an amount of 5 to 80 wt%, preferably 10 to 60 wt%, based on the total weight of the solid content in the red photosensitive resin composition. When the above range is satisfied, the possibility of occurrence of problems of a decrease in the residual film ratio and a decrease in reliability is reduced, and pattern formation is easy.

Photopolymerizable compound (C)

The photopolymerizable compound is a polymerizable compound such as an active radical or an acid generated from a photopolymerization initiator by irradiation with light, and may be a 1-functional or polyfunctional polymerizable compound depending on the number of functional groups. The 1-functional polymerizable compound may be nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, or the like. Examples of the 2-functional polymerizable compound include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, 3-methylpentanediol di (meth) acrylate, butanediol dimethacrylate, hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate and propoxylated neopentyl glycol diacrylate. Examples of the 3-functional polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated glycerol triacrylate, and isocyanurate triacrylate. The 4-functional polymerizable compound may be pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, or the like. The 5-functional polymerizable compound may be dipentaerythritol penta (meth) acrylate, and the 6-functional photopolymerizable compound may be dipentaerythritol hexa (meth) acrylate. Among these, as the photopolymerizable compound, a polyfunctional polymerizable compound having 2 or more functions can be preferably used, and particularly, a polyfunctional polymerizable compound having 5 or more functions can be preferably used.

The photopolymerizable compound is preferably contained in an amount of 5 to 50 wt%, more preferably 7 to 45 wt%, based on the total weight of the solid content in the red photosensitive resin composition. When the photopolymerizable compound is contained within this range, the strength and smoothness of the pixel portion can be improved.

Photopolymerization initiator (D)

The photopolymerization initiator in the present invention is a compound that generates radicals capable of initiating polymerization of the polyfunctional monomer of the photopolymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. Such photopolymerization initiators include, typically, acetophenone compounds, benzophenone compounds, bisimidazole compounds, triazine compounds, oxime ester compounds, thioxanthone compounds, and the like. In the present invention, the photopolymerization initiator may be used alone or in combination of 2 or more, and preferably 1 or more oxime ester compounds are used.

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.

Examples of the benzophenone-based compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone.

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. Of these, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl biimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole are preferably used.

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.

Examples of the oxime ester compounds include 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -, 2- (O-benzoyloxime), and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime).

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

In order to improve the sensitivity of the red photosensitive resin composition of the present invention, the photopolymerization initiator (D) may further contain a photopolymerization initiation auxiliary (D1). The red photosensitive resin composition according to the present invention contains the photopolymerization initiation auxiliary (d1), so that the sensitivity is further improved and the productivity can be improved.

As the photopolymerization initiation auxiliary (d1), for example, 1 or more compounds selected from amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group can be preferably used.

As the amine compound, an aromatic amine compound is preferably used, and specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine and the like, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4 ' -bis (dimethylamino) benzophenone (known as michler's ketone), 4 ' -bis (diethylamino) benzophenone and the like can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), and the like.

The red photosensitive resin composition of the present invention may contain the photopolymerization initiator (D) in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total weight of solid components of the red photosensitive resin composition, relative to the contents of the alkali-soluble resin (B) and the photopolymerizable compound (C). That is, the photopolymerization initiator may be contained in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the total solid content of the alkali-soluble resin and the photopolymerizable compound. When the photopolymerization initiator (D) is in the range of 0.1 to 40% by weight, the red photosensitive resin composition is preferably made highly sensitive and the exposure time is shortened, so that the productivity is improved and the high resolution can be maintained. In addition, the strength of the pixel portion formed using the composition under the above conditions and the smoothness of the surface of the pixel portion can be improved.

Further, in the case of the photopolymerization initiation auxiliary (d1), the photopolymerization initiator may be contained in an amount of 10 to 100% by weight, preferably 20 to 100% by weight, based on the total amount of the photopolymerization initiator. When the content of the photopolymerization initiation auxiliary (d1) in the entire photopolymerization initiator satisfies the above range, the decrease in sensitivity to the dye can be reduced, and the possibility of pattern short-circuiting in the developing step can be reduced.

When the photopolymerization initiation auxiliary (d1) is used, the photopolymerization initiation auxiliary (d1) may be contained in an amount of 0.1 to 40 wt%, preferably 1 to 30 wt%, based on the total weight of the solid content of the red photosensitive resin composition of the present invention, relative to the contents of the alkali-soluble resin (B) and the photopolymerizable compound (C). When the photopolymerization initiation auxiliary (d1) is used in an amount within the range of 0.1 to 40 wt%, the following effects are provided: the sensitivity of the red photosensitive resin composition is further improved, and the productivity of a color filter formed using the composition is improved.

Solvent (E)

The solvent is not particularly limited as long as it dissolves the red photosensitive resin composition, and ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, or the like are particularly preferable. Specific examples thereof include ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, and dipropylene glycol dibutyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and γ -butyrolactone. The solvent can be selected from the solvent of 1 or more than 2 mixed use. In addition, in terms of coatability and drying property, the boiling point must be 100 to 200 ℃, and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate are preferable.

The solvent may be contained in an amount of 25 to 80 wt%, preferably 30 to 70 wt%, based on the total weight of the red photosensitive resin composition. Within the above range, when the coating is performed by using a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (or die coater), or an inkjet, good coatability can be exhibited.

Additive (F)

The red photosensitive resin composition of the present invention may contain, in addition to the above components, additives (F) such as a filler, other polymer compound, a curing agent, an adhesion promoter, an ultraviolet absorber, and an anti-coagulant, as required by those skilled in the art, within a range not to impair the object of the present invention.

As the filler, glass, silica, alumina, and the like can be used, but the filler is not limited thereto.

Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane, but are not limited thereto.

The curing agent is used for improving the deep-section curing and mechanical strength, and specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like can be used, but the curing agent is not limited thereto. Specifically, the epoxy compound may be a bisphenol a epoxy resin, a hydrogenated bisphenol a epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a novolac epoxy resin, another aromatic epoxy resin, an alicyclic epoxy resin, a glycidyl ester resin, a glycidyl amine resin, or a brominated derivative of such an epoxy resin, an aliphatic, alicyclic or aromatic epoxy compound other than the epoxy resin and the brominated derivative thereof, a butadiene (co) polymer epoxy, an isoprene (co) polymer epoxy, a glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, or the like, but is not limited thereto. Specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, but the compound is not limited thereto.

The curing agent may be used together 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. Specifically, polycarboxylic acids, polycarboxylic anhydrides, acid generators, and the like can be used as the curing auxiliary compound. The carboxylic acid anhydrides can be commercially available as curing agents for epoxy resins. Examples of the commercially available epoxy resin curing agent include a trade name (Adeka Harden EH-700) (manufactured by Adeka industries, Ltd.), a trade name (Rikacid HH) (manufactured by Nissian Chemicals, Ltd.), and a trade name (MH-700) (manufactured by Nissian Chemicals, Ltd.).

The curing agents and curing auxiliary compounds exemplified above may be used each alone or 2 or more kinds may be mixed and used.

Specifically, the adhesion promoter may be selected from the group consisting of 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, 3-mercaptopropyltrimethoxysilane, and, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane, alone or in combination.

The adhesion promoter may be contained in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, based on the solid content of the composition.

Specific examples of the ultraviolet absorber include, but are not limited to, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

The above-mentioned anti-agglomerating agent can be specifically sodium polyacrylate or the like, but is not limited thereto.

The present invention provides a color filter produced by using the red photosensitive resin composition. The red photosensitive resin composition can be applied to a substrate, and photocured and developed to form a pattern.

First, the red photosensitive resin composition is applied to a substrate or a layer composed of a solid component of the photosensitive resin composition, and then heated and dried to remove volatile components such as a solvent, thereby obtaining a smooth coating film.

The coating method is performed by spin coating, cast coating, roll coating, slit and spin coating, slit coating, or the like. After the coating, the coating is dried by heating (prebaking), or dried under reduced pressure and then heated to volatilize volatile components such as a solvent. The heating temperature is 70-200 ℃, preferably 80-130 ℃. The thickness of the coating after heating and drying is about 1 to 8 μm. In order to form a target pattern on the coating film, ultraviolet rays are irradiated through a mask. In this case, it is necessary to uniformly irradiate the entire exposure portion with parallel light beams and to accurately align the mask and the substrate, and it is preferable to use a device such as a mask aligner or a stepper. When ultraviolet rays are irradiated, the ultraviolet-irradiated portion is cured. As the ultraviolet ray, g-line (wavelength: 436nm), h-line, i-line (wavelength: 365nm), and the like can be used. The dose of the ultraviolet ray irradiation may be appropriately selected as needed, and is not limited in the present invention. The cured coating film is brought into contact with a developer to dissolve and develop the unexposed portion, whereby a cured product having a desired pattern shape can be obtained.

In addition, the present invention provides a display element including the color filter.

Hereinafter, preferred examples, comparative examples and experimental examples are given for understanding the present invention, but such examples, comparative examples and experimental examples are merely illustrative of the present invention and should not limit the appended patent claims, and various changes and modifications of examples, comparative examples and experimental examples may be made within the scope of the scope and technical idea of the present invention, which will be apparent to those skilled in the art, and such changes and modifications naturally fall within the appended patent claims.

< production of pigment Dispersion composition >

Production example 1 pigment Dispersion composition A-1

Pigment dispersion composition a-1 was prepared by mixing and dispersing c.i. pigment red 17712.0 parts by weight as a pigment, DISPER BYK-2001(BYK corporation) 5.0 parts by weight as a pigment dispersant, 4-hydroxy-4-methyl-2-pentanone 13.0 parts by weight as a solvent, and propylene glycol methyl ether acetate 70.0 parts by weight for 12 hours using a bead mill.

Production example 2 pigment Dispersion composition A-2

Pigment dispersion composition a-2 was prepared by mixing and dispersing c.i. pigment red 17912.0 parts by weight as a pigment, DISPER BYK-2001(BYK corporation) 5.0 parts by weight as a pigment dispersant, 4-hydroxy-4-methyl-2-pentanone 13.0 parts by weight as a solvent, and propylene glycol methyl ether acetate 70.0 parts by weight for 12 hours using a bead mill.

Production example 3 pigment Dispersion composition A-3

Pigment dispersion composition a-3 was prepared by mixing and dispersing c.i. pigment red 25412.0 parts by weight as a pigment, DISPER BYK-2001(BYK corporation) 5.0 parts by weight as a pigment dispersant, 4-hydroxy-4-methyl-2-pentanone 13.0 parts by weight as a solvent, and propylene glycol methyl ether acetate 70.0 parts by weight for 12 hours using a bead mill.

Production example 4 pigment Dispersion composition A-4

Carbon black pbk 720.0 parts by weight, AJISPUR PB821(Ajinomoto Fine-Techno co., Inc.)6 parts by weight as a dispersant, and propylene glycol monomethyl ether acetate 74 parts by weight as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare a pigment-dispersed composition a-4.

Production example 5 pigment Dispersion composition A-5

Pigment dispersion composition a-5 was prepared by mixing and dispersing c.i. pigment yellow 13912.0 parts by weight as a pigment, DISPER BYK-2001(BYK corporation) 5.0 parts by weight as a pigment dispersant, propylene glycol methyl ether acetate 70 parts by weight as a solvent, and propylene glycol methyl ether 13 parts by weight for 12 hours using a bead mill.

Synthesis example 1 Synthesis of alkali-soluble resin

Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 13.0 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 57.0 parts by weight of styrene, 20 parts by weight of methyl methacrylate and 3 parts by weight of n-dodecylmercaptan were charged and nitrogen substitution was carried out. Then, the temperature of the reaction mixture was raised to 110 ℃ by stirring, and the reaction was carried out for 6 hours. The alkali-soluble resin thus synthesized had an acid value of the solid content of 100.2mgKOH/g and a weight-average molecular weight Mw of about 15110 as measured by GPC.

Examples 1 to 3 and comparative examples 1 to 4 preparation of Red photosensitive resin composition

A red photosensitive resin composition was produced with the composition and content (unit: parts by weight) shown in Table 1 below.

[ TABLE 1 ]

Alkali-soluble resin (B): synthesis example 1

Photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARD DPHA; manufactured by Nippon Kagaku Co., Ltd.)

Photopolymerization initiator (D): 2-O-benzoyloxime-1- [4- (phenylthio) phenyl ] -1, 2-octanedione (OXE-01; manufactured by BASF)

Solvent (E): propylene glycol monomethyl ether acetate

Experimental example 1 production of color Filter

Color filters were produced using the red photosensitive resin compositions produced in examples 1 to 3 and comparative examples 1 to 4.

Specifically, each of the red photosensitive resin compositions was applied onto a 2-inch square glass substrate (available XG, manufactured by corning corporation) by a spin coating method, 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 within a range of 1 to 100% and an exposed portion pattern of 3cm × 3cm was placed on the film, and the film was irradiated with ultraviolet rays with a distance of 100 μm from the test photomask. In this case, a 1KW high-pressure mercury lamp containing all g, h and i lines was used as the ultraviolet light source at a concentration of 100mJ/cm²The illumination of (2) is performed without using a special optical filter. To be irradiated with the above ultraviolet raysThe film was immersed in a developing solution of KOH aqueous solution having a pH of 10.5 for 2 minutes to develop the film. The glass plate coated with the thin film was washed with distilled water, then dried by spraying nitrogen gas, and heated in a heating oven at 200 ℃ for 25 minutes to produce a color filter. The thickness of the film obtained was 3 μm. The thickness of the film was measured by using a film thickness measuring apparatus (DEKTAK 6M; manufactured by Veeco).

Experimental example 2 spectroscopic measurement

Spectral transmittance was measured in the visible light region in the range of 380nm to 780nm using a colorimeter (OSP-200, manufactured by olympus corporation) after manufacturing a color filter in the same manner as in experimental example 1, except that a test photomask was not used, and the results are shown in table 2 and table 3, and fig. 1 to fig. 3.

[ TABLE 2 ]

[ TABLE 3 ]

Wavelength (nm)

Example 1

Example 2

Example 3

Comparative example 1

Comparative example 2

Comparative example 3

Comparative example 4

635

82.6％

77.1％

77.5％

94.4％

85.8％

92.8％

17.9％

645

83.9％

79.3％

79.6％

95.8％

88.1％

93.7％

18.2％

655

84.3％

80.1％

80.6％

96.1％

88.9％

93.2％

18.5％

665

82.9％

83.0％

83.3％

94.2％

91.9％

92.1％

18.9％

675

82.8％

84.4％

84.5％

93.9％

93.2％

92.5％

19.5％

685

85.7％

83.9％

84.3％

97.0％

92.6％

94.5％

20.3％

695

87.8％

83.7％

84.2％

99.3％

92.3％

95.7％

20.9％

705

86.8％

84.2％

84.6％

97.9％

92.7％

94.8％

21.2％

715

84.6％

84.8％

85.0％

95.4％

93.3％

93.5％

21.4％

725

84.3％

86.1％

94.8％

94.5％

93.5％

21.9％

735

85.6％

87.3％

87.4％

96.2％

95.8％

94.5％

22.5％

745

87.1％

87.7％

87.9％

97.6％

96.0％

95.3％

23.3％

755

87.6％

86.7％

87.1％

98.0％

94.7％

95.3％

23.9％

765

87.8％

85.5％

86.0％

97.9％

93.2％

94.8％

24.7％

775

88.0％

85.4％

86.0％

98.0％

93.0％

94.7％

25.4％

780

88.2％

85.9％

86.5％

98.0％

93.5％

94.8％

25.6％

Table 2 and table 3, and fig. 1 to fig. 3 show spectral transmittances according to wavelengths based on the results of the above experiments.

As shown in Table 2 and Table 3, and FIGS. 1 to 3, in the examples of the present invention, when the red photosensitive resin composition was formed into a cured film having a thickness of 3 μm, the spectral transmittance was 20% or less at a wavelength of 430 to 590nm, and the spectral transmittance was 70% or more and less than 90% at a wavelength of 635 to 780 nm.

As shown in fig. 1, in comparative examples 1 and 2 containing no black pigment, when the red photosensitive resin composition was formed into a cured film having a thickness of 3 μm, the spectral transmittance was 90% or more at a wavelength of 635nm or more, but in the example containing the black pigment, the spectral transmittance was 70% or more and less than 90% at a wavelength of 635nm or more.

In addition, the examples containing the black pigment showed a transmittance of 20% or less at a wavelength of 430nm to 590nm when the red photosensitive resin composition was formed into a cured film having a thickness of 3 μm.

On the other hand, comparative examples 3 and 4, in which the black pigment was less than 0.5% by weight or more than 10% by weight based on the solid content of the coloring material, were insufficient in the effect of preventing reflection of external light and visibility.

Claims

1. A red photosensitive resin composition for a display device not including a polarizing plate, comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant comprises a red pigment and a black pigment, and is characterized in that the red photosensitive resin composition, when formed into a cured film having a thickness of 3 [ mu ] m, has a spectral transmittance of 20% or less at a wavelength of 430 to 590nm and a spectral transmittance of 70% or more and less than 90% at a wavelength of 635 to 780nm, and the black pigment is 0.5 to 10% by weight based on the solid content of the colorant.

2. The red photosensitive resin composition according to claim 1, wherein the weight ratio of the red pigment to the black pigment is 99.9 to 80: 20 to 0.1.

3. The red photosensitive resin composition according to claim 1, which comprises 10 to 80% by weight of a colorant, 5 to 80% by weight of an alkali-soluble resin, and 5 to 50% by weight of a photopolymerizable compound, based on 100 parts by weight of the total solid content of the alkali-soluble resin and the photopolymerizable compound, and which comprises 0.1 to 40 parts by weight of a photopolymerization initiator, and 25 to 80% by weight of a solvent, based on the total weight of the red photosensitive resin composition.

4. The red photosensitive resin composition according to claim 1, wherein the colorant further comprises a yellow pigment.

5. The red photosensitive resin composition according to claim 4, wherein the yellow pigment is contained in an amount of 3 to 30 parts by weight based on 100 parts by weight of the total content of the red pigment and the black pigment.

6. The red photosensitive resin composition according to claim 1, wherein the red pigment contains 1 or more selected from the group consisting of c.i. pigment red 179, c.i. pigment red 177, c.i. pigment red 209, c.i. pigment red 242, and c.i. pigment red 254.

7. The red photosensitive resin composition according to claim 1, wherein the black pigment contains 1 or more selected from the group consisting of a pigment obtained by mixing red, cyan, and green, c.i. pigment black 1, c.i. pigment black 7, carbon black, organic black, and titanium black.

8. The red photosensitive resin composition according to claim 4, wherein the yellow pigment contains 1 or more selected from the group consisting of C.I. pigment yellow 138, C.I. pigment yellow 139, and C.I. pigment yellow 150.

9. A color filter produced using the red photosensitive resin composition according to any one of claims 1 to 8.

10. A display element comprising the color filter according to claim 9.

11. A display element according to claim 10, characterised in that the display element is a flexible display element.

12. The display element according to claim 10, wherein the display element is an organic light-emitting element.