KR102572753B1 - Gray colored photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention includes a pigment dispersion composition (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the pigment dispersion composition (A) contains red pigment, green A pigment, comprising at least one member selected from the group consisting of a blue pigment, a yellow pigment, and a purple pigment, and a black pigment, wherein the transmittance at a spectral wavelength of 460 nm to 530 nm is 30% or more and less than 75%, and at a wavelength of 580 nm to 620 nm A gray photosensitive resin composition characterized in that the transmittance at the spectral wavelength is 20% or more and less than 75%, and the transmittance at the spectral wavelength of 690 nm to 780 nm is 20% or more, a color filter manufactured using the same, and a display including the color filter It's about the little ones. The gray photosensitive resin composition of the present invention has a very excellent antireflection effect and can replace a polarizing plate in a display device, and is characterized by solving the problems of gray reproducibility and lack of fairness of the conventional gray photosensitive resin composition.

Description

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

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

Recently, a flexible display device capable of displaying an image even if it is bent like paper by forming a display unit and wiring on a flexible substrate such as plastic, which is a flexible material, has recently been in the limelight.

Flexible display devices have a wide range of applications, from computer monitors and TVs to personal portable devices. In particular, Organic Light Emitting Display (OLED), unlike Liquid Crystal Display (LCD), Since it does not require a light source and can be implemented with a relatively thin thickness, research on organic light emitting devices is being actively conducted in relation to flexible display devices.

On the other hand, in order for the flexible display element to be applied in practice, it should be able to implement full color, have low power consumption, and be easily readable even outdoors when compared to various current display products.

In this sense, the organic light emitting device has become the most useful resource as a light source for a flexible display device because it has the possibility of realizing full color, low power consumption, and fast response speed. The current organic light emitting device includes an encapsulation barrier layer to protect the organic light emitting device from oxygen and moisture, and a polarizer to maintain a high contrast ratio for outdoor readability. need.

However, when a polarizing plate having a hard property is applied, a disadvantage in that flexibility of the flexible display device is reduced may occur. On the other hand, when the polarizer is not applied, external light is transmitted into the flexible display device and then reflected back out, mixing colors with light emitted from the original organic light emitting device, and the contrast ratio under the external light source is greatly reduced.

Accordingly, research to improve this has been actively conducted recently, and as an example, Korean Patent Publication No. 10-2013-0134494 proposes an ink composition containing a colorant including a green colorant and a yellow colorant, a binder resin, and a block isocyanate group, Korean Patent Publication No. 10-2013-0134498 proposes an ink composition containing a colorant including a red colorant and a green colorant, a binder resin, and a block isocyanate group. However, in the case of the prior art, the selection range of colorants is limited in implementing high color reproducibility, and the implementation of various color gamuts is insufficient, and in addition, fairness such as tearing and undercutting is lacking in pattern formation, so that continuous Improvements are desired in the art.

Republic of Korea Patent Publication No. 10-2013-0134494 Republic of Korea Patent Publication No. 10-2013-0134498

It is an object of the present invention to solve the problem of lack of reproducibility and fairness of conventional high color (gray), and to provide a gray photosensitive resin composition that can be replaced with a polarizing plate and has a very excellent anti-reflection effect.

In addition, an object of the present invention is to provide a color filter manufactured using the gray photosensitive resin composition and a display device including the color filter.

The present invention includes a pigment dispersion composition (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the pigment dispersion composition (A) contains red pigment, green A gray photosensitive resin composition comprising at least one selected from the group consisting of a pigment, a blue pigment, a yellow pigment and a purple pigment and a black pigment is provided.

In one embodiment, the transmittance at the spectral wavelength of 460 nm to 530 nm is 30% or more and less than 75%, the transmittance at the spectral wavelength of 580 nm to 620 nm is 20% or more and less than 75%, and the transmittance at the spectral wavelength of 690 nm to 780 nm is 20% or more. % or more.

One embodiment may be that the black pigment is 0.5 to 10% by weight based on the total solid content of the colorant.

In another embodiment, a weight ratio of at least one selected from the group consisting of a red pigment, a green pigment, a blue pigment, a yellow pigment, and a purple pigment and a black pigment may be 99.5 to 90:10 to 0.5.

In another embodiment, the gray photosensitive resin composition is based on the total solid weight of the gray photosensitive resin composition, 1 to 70% by weight of the pigment dispersion composition (A), 5 to 80% by weight of the alkali-soluble resin (B), photopolymerizable 5 to 50% by weight of compound (C), 0.1 to 40% by weight based on the total solid content of alkali-soluble resin (B) and photopolymerizable compound (C), and 25 to 80% by weight of solvent based on gray photosensitive resin composition It may contain.

In another embodiment, the red pigment is C.I. Pigment Red 179, C.I. Pigment Red 177, C.I. Pigment Red 209, C.I. Pigment Red 242 and C.I. It may include one or more selected from the group consisting of Pigment Red 254.

In another embodiment, the green pigment is C.I. Pigment Green 36, C.I. Pigment Green 58 and C.I. It may include one or more selected from the group consisting of Pigment Green 59.

In another embodiment, the blue pigment is C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 21, C.I. Pigment Blue 28, C.I. Pigment Blue 60, C.I. Pigment Blue 64 and C.I. It may contain at least one selected from the group consisting of Pigment Blue 76.

In another embodiment, the yellow pigment is C.I. Pigment Yellow 138, C.I. Pigment Yellow 150 and C.I. It may include one or more selected from the group consisting of Pigment Yellow 185.

In another embodiment, the purple pigment is C.I. Pigment Violet 14, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 33, C.I. Pigment Violet 36, C.I. Pigment Violet 37 and C.I. It may contain at least one selected from the group consisting of Pigment Violet 38.

Another embodiment is that the black pigment is a mixture of red, blue and green pigments, C.I. Pigment Black 1, C.I. It may include at least one selected from the group consisting of pigment black 7, carbon black, organic black, and titanium black.

In addition, the present invention provides a color filter prepared using the gray photosensitive resin composition.

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

One embodiment may be that the display device is a flexible display device.

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

The gray photosensitive resin composition of the present invention is characterized in that it can replace a polarizing plate in a display device because of its excellent external light anti-reflection effect. In addition, it is also characterized by solving the problem of high-color gray reproducibility and lack of fairness of the conventional colored photosensitive resin composition. In particular, the transmittance at the spectral wavelength of 460 nm to 530 nm is 30% or more and less than 75%, the transmittance at the spectral wavelength of 580 nm to 620 nm is 20% or more and less than 75%, and the transmittance at the spectral wavelength of 690 nm to 780 nm is 20% or more. It is characterized by When the transmittance at the spectral wavelength of 460 nm to 530 nm is higher than 70%, the effect of preventing reflection of external light is not sufficient and the contrast ratio is lowered. When the transmittance is less than 30%, the color purity may be lowered. When the transmittance at the spectral wavelength of 580 nm to 620 nm is higher than 75%, the effect of preventing reflection of external light is not sufficient and the contrast ratio is lowered. When the transmittance is less than 20%, the color purity may be lowered. When the transmittance of the spectrum wavelength of 690 nm to 780 nm is less than 20%, the efficiency of the light source may be lowered due to lack of transmittance.

Figure 1 shows the transmittance according to the wavelength as a result of Experimental Example 2. In particular, FIG. 1 is a graph showing spectral transmittance in the visible light region in the range of 380 to 780 nm.

The present invention relates to a gray photosensitive resin composition, a color filter manufactured using the same, and a display device including the color filter, and can replace the use of a polarizer in a display through a gray pixel.

The present invention is a composition of a gray photosensitive resin composition, wherein the pigment dispersion composition includes at least one selected from the group consisting of a red pigment, a green pigment, a blue pigment, a yellow pigment, and a purple pigment, and a black pigment, thereby preventing external light reflection. It is very excellent and is characterized by being able to replace polarizers in display devices.

Hereinafter, the present invention will be described in detail.

pigment dispersion composition

The pigment dispersion composition may be included in an amount of 1 to 70% by weight, preferably 2 to 60% by weight, more preferably 3 to 50% by weight, based on the total weight of solids in the gray photosensitive resin composition.

The pigment (a1) included in the pigment dispersion composition essentially includes at least one pigment selected from the group consisting of a red pigment, a green pigment, a blue pigment, a yellow pigment, and a purple pigment, and a black pigment. A weight ratio of at least one pigment selected from the group consisting of the aforementioned red pigment, green pigment, blue pigment, yellow pigment, and purple pigment to the black pigment may be 99.5 to 90:10 to 0.5.

As the black pigment usable in the present invention, black pigments used in the art may be used without particular limitation, and for example, C.I Pigment Black 1 and 7, carbon black, organic black, etc. may be used alone or in combination of two or more. It can be used, and preferably one selected from carbon black and organic black can be used.

In the present invention, the black pigment may be 0.5 to 10% by weight based on the total weight of the solid content of the colorant, and the colorant refers to dyes and pigments included in the pigment dispersion composition. Based on the above, when the black pigment is less than 0.5% by weight, it is difficult to obtain the desired external light reflection effect, and when it is greater than 10% by weight, problems may occur in visibility.

pigment (a1)

The red pigment of the present invention is C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 1 species selected from the group consisting of 255 and 264 may be more than one, among which 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 is preferred.

The green pigment of the present invention is C.I. It may be one or more selected from the group consisting of Pigment Green 10, 15, 25, 36, 47, 58 and 59, among which C.I. Pigment Green 36, C.I. Pigment Green 58 and C.I. Pigment Green 59 is preferred.

The blue pigment of the present invention is C.I. It may be at least one selected from the group consisting of Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76, among which C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 21, C.I. Pigment Blue 28, C.I. Pigment Blue 60, C.I. Pigment Blue 64 and C.I. Pigment Blue 76 is preferred.

The yellow pigments of the present invention are C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 129, 137, 138, 139, 147,148, 150, 153, 154, 166, 173, 180 and 185, and among them, C.I. Pigment Yellow 138, C.I. Pigment Yellow 150 and C.I. Pigment Yellow 185 is preferred.

The purple pigment of the present invention is C.I. It may be one or more selected from the group consisting of Pigment Violet 14, 19, 23, 32, 33, 36 and 38, C.I. Pigment Violet 14, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 33, C.I. Pigment Violet 36, C.I. Pigment Violet 37 and C.I. Pigment Violet 38 is preferred.

The black pigment of the present invention is a mixture of red, blue and green pigments, C.I. Pigment Black 1, C.I. It may be at least one selected from the group consisting of Pigment Black 7, carbon black, organic black pigment, and titanium black pigment, and among them, Pigment Black 7 is preferred.

More specifically, the black pigment may be used by preparing a colored dispersion obtained by mixing carbon black and two or more colored pigments and milling. Usable carbon blacks include CHBK-17 from Mikuni Color Co., Ltd.; Donghae Carbon Co., Ltd.'s cisto 5HIISAFHS, cisto KH, cisto 3HHAF-HS, cisto NH, cisto 3M, cisto 300HAF-LS, cisto 116HMMAF-HS, cisto 116MAF, cisto FMFEF-HS, cisto SOFEF, cisto VGPF, cisto SVHSRF-HS, and cisto SSRF; Diagram Black, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR from Mitsubishi Chemical Corporation , #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9 , #95, #3030, #3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; 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; 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- 2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170.

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

The content of the pigment (a1) may be in the range of 1 to 70% by weight, preferably 2 to 60% by weight, in terms of weight fraction based on the total weight of the solids in the pigment dispersion composition (A). When the content of the pigment is in the range of 2 to 60% by weight based on the above, the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, so it is effective in increasing the contrast ratio, so it is preferable.

It is preferable to use a pigment dispersion in which the particle size is uniformly dispersed as the pigment. One example of a method for uniformly dispersing the particle size of the pigment is a method of dispersing treatment by containing a pigment dispersant (a2), and according to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. there is.

Pigment Dispersant (a2)

The pigment dispersant (a2) is added to maintain the deagglomeration and stability of the pigment, and those generally used in the art may be used without limitation. Preferably, it is good to contain an acrylate-based dispersant (hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N,N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by the living control method as suggested in Korean Patent Publication No. 2004-0014311, and the commercial product of the acrylate-based dispersant prepared through the living control method is DISPER BYK- 2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The above-exemplified acrylic dispersants may be used alone or in combination of two or more. As the pigment dispersant (a2), other resin type pigment dispersants may be used in addition to the above acrylic dispersants. The other resin-type pigment dispersants include known resin-type pigment dispersants, particularly polycarboxylic acid esters represented by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, and (partial) polycarboxylic acids. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) an oily dispersant such as an amide formed by reaction of a polyester having a carboxyl group with a poly(lower alkyleneimine) or a salt thereof; water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylate; adducts of ethylene oxide/propylene oxide and phosphate esters; and the like.

Commercially available cationic resin dispersants include, for example, BYK (Big) Chemie brand names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF brand names: 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 names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemical Co.: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Co., Ltd.: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 and the like. In addition to the above acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylic dispersant.

The amount of the pigment dispersant (a2) used is in the range of 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. If the content of the dispersant (a2) exceeds 60 parts by weight based on the above, the viscosity may increase, and if it is less than 5 parts by weight, it may be difficult to atomize the pigment or cause problems such as gelation after dispersion.

Dispersion aid (a3)

The dispersing aid (a3) refers to an agent that serves to prevent re-agglomeration by dispersing the pigment into fine particles. The dispersing aid is effective in constituting a colored layer having a high contrast ratio and excellent transmittance.

Dispersing aids usable in the present invention include, for example, 1,8-diamino-4,5-dihydroxyanthraquinone, 1,5-bis{[2-(diethylamino)ethyl]amino}anthra- 9,10-quinone, 1,8-bis(benzamido)anthraquinone, 1,4-bis{[2-(4-hydroxyphenyl)ethyl]amino}anthra-9,10-quinone, 1,4 -bis{[2-(dimethylamino)ethyl]amino}-5,8-dihydroxyanthra-9,10-quinone, 1,8-dihydroxy-4-[4-(2-hydroxyethyl ) Anilino] -5-nitroanthra-9,10-quinone, 1,4-dihydroxyanthraquinone, 1,4-bis (4-butylanilino) -5,8-dihydroxyanthraquinone, 4'-(4-Hydroxy-1-anthraquinonylamino)-acetanilide, 1,4-bis[(2,6-diethyl-4-methylphenyl)amino]anthraquinone, 1,4-bis( Butylamino) -9,10-anthracenedione, 1,4-bis (4-butylanilino) -5,8-dihydroxyanthraquinone, 1,5-bis [(3-methylphenyl) amino] -9 ,10-anthracenedione, 1,5-dicyclohexylaminoanthraquinone, 1,4-bis(isopropylamino)anthraquinone, 1,4-bis(methylamino)anthraquinone, 1,4-bis(2 ,6-Diethyl-4-methylanilino)anthraquinone, 2,2'-(9,10-dioxoanthracene-1,4-diyldiimino)bis(5-methylsulfonate), 1-anyl Rhino-4-hydroxyanthraquinone, 1-hydroxy-4-[(4-methylphenyl)amino]-9,10-anthracenedione, 1,4-bis(para-tolylamino)anthraquinone, 1-amino -4-Pethylaminoanthraquinone, N-[4-[(4-hydroxy-anthraquino-1-yl)amino]phenyl]acetamide, 1-(methylamino)-4-(4-methylanilino) anthracene-9,10-dione and 1,4,5,8-tetrahydroxyanthraquinone; and the like.

In addition to the above dispersing aids, a commercially available dispersing aid may be further included as needed. Specifically, Lubrizol's SOLSPERSE-5000, SOLSPERSE-12000, SOLSPERSE-22000, BYK's BYK-SYNERGIST 2100, BYK-SINERGIST 2105, BASF's EFKA-6745 or EFKA-6750, and the like.

The dispersion aid includes 1 to 30 parts by weight based on 100 parts by weight of the pigment in the colorant. If the amount of the dispersing aid exceeds 30 parts by weight, the color inherent to the pigment dispersion composition (A) may be altered, and discoloration may be caused by hard baking during the manufacturing process of the colored layer.

Dispersion solvent (a4)

The dispersion solvent (a4) is not particularly limited, and various organic solvents used in the art may be used.

Specifically, for example, 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, and diethylene glycol diethyl ether Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate , alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl Ketones such as ketones, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, ethyl 3-ethoxypropionate, 3 - Cyclic esters, such as esters, such as methoxy methyl propionate, and (gamma)-butyrolactone, etc. are mentioned. Preferably, esters such as alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate or methyl 3-methoxypropionate may be used, more preferably propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate or methyl 3-methoxypropionate can be used.

The dispersion solvents may be used alone or in combination of two or more.

The dispersion solvent may be included in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the pigment dispersion composition. Outside of the above range, a disadvantage in that the storage stability of the pigment dispersion composition is poor may occur.

Dispersion resin (a5)

The dispersion resin (a5) serves as a dispersion medium of the pigment dispersion composition (A) and can be optionally added, and when the dispersion resin (a5) is mixed and used rather than the dispersant (a2) alone, a more excellent pigment dispersion composition can be obtained. manufacturing is possible In the case of a dispersion resin, it can be used without limitation as long as it can act as a dispersion medium, but it is preferable to have an acid value in order to have solubility in an alkali developer in consideration of the developability of the gray photosensitive resin composition prepared as a pigment dispersion composition.

The acid value here is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titrating using an aqueous potassium hydroxide solution. In the case of a dispersion resin having an acid value, it can be prepared by copolymerizing a compound (b1) having a carboxyl group and an unsaturated bond and a compound (b2) having an unsaturated bond copolymerizable with the compound (b1).

Specific examples of the compound (b1) having a carboxylic acid group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of the above dicarboxylic acids; Examples include mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, and acrylic acid and methacrylic acid are preferable. In the present invention, (meth)acrylate refers to acrylate, methacrylate, or both.

The compounds exemplified as the above compound (b1) may be used alone or in combination of two or more. The compound (b2) having an unsaturated bond copolymerizable with the compound (b1) is, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p -methoxy styrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycidyl Aromatic vinyl compounds, such as dil ether; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate or t-butyl (meth)acrylate; Cyclopentyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-methylcyclohexyl(meth)acrylate, tricyclo[5.2.1.0 2,6]decan-8-yl(meth)acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate or isobornyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate or benzyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide; unsaturated amide compounds such as (meth)acrylamide and N,N-dimethyl (meth)acrylamide; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane or 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. unsaturated oxetane compounds of, and the like, but are not limited thereto.

The compounds exemplified as the compound (b2) can be used individually or in combination of two or more.

The dispersion resin is included in an amount of 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the pigment solid content in the colorant. If the dispersion resin exceeds 60 parts by weight, the viscosity may increase due to the dispersion resin, and if it is less than 5 parts by weight, the amount of the dispersion resin may be insufficient to obtain an atomized pigment dispersion composition.

Dye (a6)

A dye may be optionally included in the pigment dispersion composition, and the dye may be used without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye capable of securing reliability such as solubility in an alkaline developing solution, heat resistance, and solvent resistance while having solubility in organic solvents. As the dye, acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof may be used. Acid dyes of the system and their derivatives can also be selected.

Preferably, the dye may be a compound classified as a dye in the color index (published by The Society of Dyers and Colourists) or a known dye described in a dyeing note (color dyeing yarn).

Specific examples of the dye include,

C.I. As a solvent dye,

C.I. Solvent Yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162;

C.I. Solvent Red 8, 45, 49, 122, 125 and 130;

C.I. Solvent Orange 2, 7, 11, 15, 26 and 56;

C.I. Solvent Blue 35, 37, 59 and 67;

C.I. and green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

Also C.I. as an acid dye

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 ; 184 ;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 ,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346, 349 , 382, 383, 394, 401, 412, 417, 418, 422 and 426;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173;

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

C.I. Acid Violet 6B, 7, 9, 17 and 19;

dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

Also as a C.I. direct dye

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;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;

C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107;

C.I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 ; 189 ,190,192,193,194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;

C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;

dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.

Also, C.I. as modanto dye

C.I. Modanto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65;

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

C.I. Modanto Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48;

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

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

dyes such as C.I. Modanto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

Alkali-soluble resin (B)

The alkali-soluble resin (B) must be soluble in the solvent of the present invention and have reactivity to the action of light or heat. In addition, any acrylic copolymer that functions as a binder resin for the colorant and is soluble in an alkaline developer may be used without particular limitation.

The alkali-soluble resin may be a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer. The carboxyl group-containing monomer may be, for example, an unsaturated carboxylic acid such as an unsaturated polycarboxylic acid having at least one carboxyl group in a 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, and cinnamic acid. The unsaturated dicarboxylic acid may be, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid. The unsaturated polyhydric carboxylic acid may be an acid anhydride, specifically maleic anhydride, itaconic acid anhydride and citraconic acid anhydride. In addition, the unsaturated polyvalent carboxylic acid may be a mono(2-methacryloyloxyalkyl) ester, for example, mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate ), phthalic acid mono(2-acryloyloxyethyl) and phthalic acid mono(2-methacryloyloxyethyl). In addition, the unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of a dicarboxylic polymer at both ends, for example, ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. there is. The carboxyl group-containing monomers may be used alone or in combination of two or more. Specific examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and m-methoxystyrene. Toxy styrene, p-methoxy styrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl meth acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Rate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl Acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate, etc. unsaturated carboxylic acid esters of; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane having a monoacryloyl group or monomethacryloyl group at the end of the molecular chain of the polymer. Macromonomers etc. are mentioned. These monomers may be used alone or in combination of two or more.

Therefore, the alkali-soluble resin, for example, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl ( meth)acrylate/benzyl(meth)acrylate copolymer, (meth)acrylic acid/methyl(meth)acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/methyl(meth)acrylate/polymethyl(meth)acryl Late macromonomer copolymer, (meth)acrylic acid/benzyl (meth)acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/benzyl (meth)acrylate/polymethyl (meth)acrylate macromonomer copolymer, (meth)acrylic acid/benzyl (meth)acrylate macromonomer copolymer, ) Acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / Polymethyl (meth)acrylate macromonomer copolymer, (meth)acrylic acid/styrene/benzyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono(2-acryloyloxy)/ Styrene/benzyl(meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/mono(2-acryloyloxyethyl) succinate/styrene/allyl(meth)acrylate/N-phenylmaleimide copolymer and (meth)acrylic acid/benzyl(meth)acrylate/N-phenylmaleimide/styrene/glycerol mono(meth)acrylate copolymers. The (meth)acrylate means acrylate or methacrylate.

Among the alkali-soluble resins, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer and ( A meth)acrylic acid/methyl (meth)acrylate/styrene copolymer is preferably used.

In addition, the alkali-soluble resin should have a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluting solvent of 5,000 to 50,000, preferably 8,000 to 40,000, and more preferably 10,000 to 30,000. When the weight average molecular weight of the alkali-soluble resin is in the range of 5,000 to 50,000, the coating film hardness is improved, exhibits an excellent film remaining rate, and exhibits good solubility in the developing solution and improved resolution of the unexposed area. In addition, the acid value should be 50 to 150 (mgKOH/g), preferably 60 to 140, more preferably 80 to 130. Within the above acid value range, the solubility of the alkali-soluble resin in the developing solution is improved, so that the unexposed portion is easily dissolved and highly sensitive, so that a pattern of the exposed portion remains during development to improve the remaining film rate.

The alkali-soluble resin may be included in an amount of 5 to 80% by weight, preferably 10 to 60% by weight, based on the total weight of the solid content in the gray photosensitive resin composition. If it is out of the above range, the remaining film rate and reliability may be deteriorated, and it may not be easy to form a pattern.

photopolymerization Compound (C)

The photopolymerizable compound is a compound that can be polymerized by active radicals, acids, etc. generated from a photopolymerization initiator by irradiation of light, and may be a monofunctional or multifunctional polymerizable compound depending on the number of functional groups. Examples of the monofunctional polymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylphy. Rolidone or the like. Examples of the bifunctional polymerizable compound include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. , bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, butylene glycol dimethacrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth) Acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylate neo pentyl glycol diacrylate and propyloxylate neopentyl glycol diacrylate. As the trifunctional polymerizable compound, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylate trimethylolpropane tri(meth)acrylate, propyloxylate trimethylolpropane tri(meth) ) acrylate, glycerylpropyloxylate triacrylate, and isocyanurate triarylate. Examples of the tetrafunctional polymerizable compound include pentaerythritol tetra(meth)acrylate and dimethylolpropane tetra(methyl)acrylate. Further, the 5-functional polymerizable compound may be dipentaerythritol penta(meth)acrylate, and the 6-functional photopolymerizable compound may be dipentaerythritol hexa(meth)acrylate. Among them, as the photopolymerizable compound, a difunctional or higher functional polymerizable compound may be preferably used, and a pentafunctional or higher functional polymerizable compound may be preferably used.

In addition, the photopolymerizable compound is included in an amount of 5 to 50% by weight, more preferably 7 to 45% by weight, based on the total weight of solids in the gray photosensitive resin composition. When the photopolymerizable compound is included in the above range, strength or smoothness of the pixel portion may be improved.

light polymerization 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, deep ultraviolet light, electron beam, and X-ray. Examples of such photopolymerization initiators include acetophenone-based compounds, benzophenone-based compounds, biimidazole-based compounds, triazine-based compounds, oxime ester-based compounds, and thioxanthone-based compounds. In this invention, a photoinitiator can be used individually or in mixture of 2 or more types, and it is preferable to use 1 or more types of oxime ester type compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyl) Roxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 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, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra ( tert-butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro). Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-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 a carboalkoxy group; and the like. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferably used do.

Specific examples of the triazine-based 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) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine; and the like.

The oxime ester compounds include 1,2-Octanedione, 1-[4-(phenylthio) phenyl]-,2-(O-benzoyloxime), 1-[9-Ethyl-6-(2-methylbenzoyl)-9H- carbazol-3-yl]ethanone 1-(O-acetyloxime) and the like.

Examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. there is

In addition, the photopolymerization initiator (D) may further include a photopolymerization initiator (d1) to improve the sensitivity of the gray photosensitive resin composition of the present invention. The gray photosensitive resin composition according to the present invention contains the photopolymerization initiation auxiliary agent (d1), so that the sensitivity is further increased and productivity can be improved.

As the photopolymerization initiation aid (d1), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group may be preferably used.

As the amine compound, it is preferable to use an aromatic amine compound, specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone) ), 4,4'-bis (diethylamino) benzophenone, etc. can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

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-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptobutyl rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. can

The photopolymerization initiator (D) is 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total solid weight of the gray photosensitive resin composition of the present invention, based on the content of the alkali-soluble resin (B) and the photopolymerizable compound (C). weight percent may be included. When the amount of the photopolymerization initiator (D) is within the range of 0.1 to 40% by weight, the gray photosensitive resin composition is highly sensitive and the exposure time is shortened, thereby improving productivity and maintaining high resolution. In addition, the strength of the pixel portion formed using the composition under the above-described conditions and the smoothness of the surface of the pixel portion may be improved.

In addition, in the case of the photopolymerization initiation aid (d1), 10 to 100% by weight, preferably 20 to 100% by weight, of the total photopolymerization initiator may be included. When the ratio of the photopolymerization initiation aid (d1) in the total photopolymerization initiator is less than 10% by weight, the decrease in sensitivity due to the dye cannot be overcome and the short circuit of the pattern is likely to occur during the developing process.

In addition, when the photopolymerization initiation auxiliary agent (d1) is further used, the photopolymerization initiation auxiliary agent (d1) is an alkali-soluble resin (B) and a photopolymerizable compound (C) based on the total solid weight of the gray photosensitive resin composition of the present invention With respect to the content of 0.1 to 40% by weight, preferably 1 to 30% by weight may be included. When the amount of the photopolymerization initiation aid (d1) is within the range of 0.1 to 40% by weight, the sensitivity of the gray photosensitive resin composition is further increased, 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 gray photosensitive resin composition, and ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are particularly preferred. Specifically, 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 di Butyl 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 ethers such as 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; Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methyl Toxybutyl 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-buty Ester, such as rolactone, etc. are mentioned. The solvent may be used by mixing one or two or more selected from the group consisting of the exemplified solvents. In addition, the boiling point should be 100 to 200 ° C in terms of coating and drying properties, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate are preferred.

The solvent may be included in an amount of 25 to 80% by weight, preferably 30 to 70% by weight, based on the total weight of the gray photosensitive resin composition. In the above range, when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (or a die coater), and a Cjet, good coating properties may be exhibited.

Additive (F)

In the gray photosensitive resin composition of the present invention, in addition to the above components, additives (F) such as fillers, other polymer compounds, curing agents, adhesion promoters, ultraviolet absorbers, and aggregation inhibitors are used in combination according to the needs of those skilled in the art within the range not impairing the object of the present invention. It is also possible to do

Specifically, glass, silica, alumina, etc. may be used as the filler, but is not limited thereto.

Examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and polyurethanes. It may, but is not limited thereto.

The curing agent is used to increase deep curing and mechanical strength, and specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. may be used, but is not limited thereto. The epoxy compound is specifically, bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, noblock type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycol Cidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxides, isoprene (void) Polymer epoxides, glycidyl (meth)acrylate (co)polymers, triglycidyl isocyanurate, and the like may be used, but are not limited thereto. Specifically, the oxetane compound may be carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, etc., but are limited thereto It is not.

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with the curing agent. Specifically, polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, acid generators, and the like may be used as the curing auxiliary compound. The carboxylic acid anhydrides may be commercially available as epoxy resin curing agents. Examples of the commercially available epoxy resin curing agent include a trade name (Adeka Hadona EH-700) (manufactured by Adeka Kogyo Co., Ltd.), a trade name (Rika Siddo HH) (manufactured by Shinnippon Ewha Co., Ltd.), and a trade name (MH-700). (manufactured by Shin Nippon Ewha Co., Ltd.); and the like.

The curing agent and curing auxiliary compound exemplified above may be used alone or in combination of two or more.

The adhesion promoter is specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (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-mercapto propyltri Methoxysilane, 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane may be used alone or in mixtures thereof.

The adhesion promoter may be included 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.

Specifically, the ultraviolet absorber may be 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyriazole, alkoxybenzophenone, etc., but is not limited thereto.

The aggregation inhibitor may specifically use sodium polyacrylate, etc., but is not limited thereto.

The present invention provides a color filter made of the gray photosensitive resin composition. A pattern may be formed by applying the gray photosensitive resin composition on a substrate, photocuring, and developing.

First, the gray photosensitive resin composition is applied onto a substrate or a layer made of a solid content of the photosensitive resin composition, and then heated and dried to remove volatile components such as a solvent to obtain a smooth coating film.

The coating method may be carried out by spin coating, casting coating, roll coating, slit and spin coating, or slit coating. After coating, heat drying (prebaking) or vacuum drying is followed by heating to volatilize volatile components such as solvents. The heating temperature is 70 to 200°C, preferably 80 to 130°C. The coating film thickness after heating and drying is about 1 to 8 μm. The coating film is irradiated with ultraviolet rays through a mask in order to form a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel light rays must be uniformly irradiated to the entire exposure area, and to accurately align the mask and the substrate. When irradiated with ultraviolet rays, the portion irradiated with ultraviolet rays is cured. As the ultraviolet rays, g-rays (wavelength: 436 nm), h-rays, and i-rays (wavelength: 365 nm) may be used. The irradiation amount of ultraviolet rays may be appropriately selected as needed, but is not limited thereto in the present invention. When the cured coating film is brought into contact with a developing solution to dissolve the unexposed portion and developed, a cured product having a desired pattern shape can be obtained.

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

Hereinafter, preferred examples, comparative examples, and experimental examples are presented to aid understanding of the present invention, but these examples, comparative examples, and experimental examples are only illustrative of the present invention and do not limit the scope of the appended claims, It is obvious to those skilled in the art that various changes and modifications to the Examples, Comparative Examples, and Experimental Examples are possible within the scope and spirit of the present invention, and it is natural that such changes and modifications fall within the scope of the appended claims.

<Preparation of Pigment Dispersion Composition>

manufacturing example 1. Pigment Dispersion Composition M1

As a pigment, C.I. 12.0 parts by weight of Pigment Red 254, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 13.0 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, propylene glycol methyl ether acetate 70.0 parts by weight were mixed/dispersed by a bead mill for 12 hours to prepare a pigment dispersion composition M1.

manufacturing example 2. Pigment Dispersion Composition M2

As a pigment, C.I. 12.0 parts by weight of Pigment Red 177, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 13.0 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, 70.0 parts by weight of propylene glycol methyl ether acetate The pigment dispersion composition M2 was prepared by mixing/dispersing for 12 hours by a bead mill.

manufacturing example 3. Pigment Dispersion Composition M3

As a pigment, C.I. 12.0 parts by weight of Pigment Green 36, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 13.0 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, 70.0 parts by weight of propylene glycol methyl ether acetate The pigment dispersion composition M3 was prepared by mixing/dispersing for 12 hours by a bead mill.

manufacturing example 4. Pigment Dispersion Composition M4

As a pigment, C.I. 12.0 parts by weight of Pigment Yellow 138, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 13.0 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, 70.0 parts by weight of propylene glycol methyl ether acetate The pigment dispersion composition M4 was prepared by mixing/dispersing for 12 hours by a bead mill.

manufacturing example 5. Pigment Dispersion Composition M5

As a pigment, C.I. 12.0 parts by weight of Pigment Blue 15:6, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by weight of propylene glycol methyl ether acetate and 40 parts by weight of propylene glycol methyl ether as solvents for 12 hours by a bead mill A pigment dispersion composition M5 was prepared by mixing/dispersing.

manufacturing example 6. Pigment Dispersion Composition M6

As a pigment, C.I. Pigment Blue 15:6 8.4 parts by weight, C.I. 3.6 parts by weight of pigment violet23, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by weight of propylene glycol methyl ether acetate and 40 parts by weight of propylene glycol methyl ether as a solvent were mixed/dispersed for 12 hours by a bead mill. Thus, a pigment dispersion composition M6 was prepared.

manufacturing example 7. Pigment Dispersion Composition M7

20.0 parts by weight of carbon black, 6 parts by weight of Ajispa PB821 (Ajinomoto Fine Techno Co., Ltd.) as a dispersing agent, and 74 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed/dispersed with a bead mill for 12 hours to obtain a pigment dispersion composition M7 manufactured.

synthesis example 1. Synthesis of alkali soluble resin

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet pipe, 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, and benzyl methacrylic acid were added. 10 parts by weight of latex, 57.0 parts by weight of styrene, 20 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecylmercapto were added and replaced with nitrogen. Thereafter, while stirring, the temperature of the reaction solution was raised to 110° C. and reacted for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 100.2 mgKOH/g and the weight average molecular weight Mw measured by GPC was about 15110.

Example 1-8 and comparative example 1-3. Preparation of gray photosensitive resin composition

A gray photosensitive resin composition was prepared with the composition and content (unit: weight%) shown in Table 1 below (Comparative Example 3 is 25% by weight of the black pigment based on the total weight of the solid content of the colorant).

[Table 1]

(A) Pigment Dispersion Composition:

(A1) Synthesis Example 1 (Pigment Dispersion Composition M1, C.I. Pigment Red 254)

(A2) Synthesis Example 2 (Pigment Dispersion Composition M2, C.I. Pigment Red 177)

(A3) Synthesis Example 3 (Pigment Dispersion Composition M3, C.I. Pigment Green 36)

(A4) Synthesis Example 4 (Pigment Dispersion Composition M4, C.I. Pigment Yellow 138)

(A5) Synthesis Example 5 (Pigment Dispersion Composition M5, C.I. Pigment Blue B15:6)

(A6) Synthesis Example 6 (Pigment Dispersion Composition M6, C.I. Pigment Blue B15:6 / C.I. Pigment Violet 23 = 7/3)

(A7) Synthesis Example 7 (Pigment Dispersion Composition M7, C.I. Pigment Black 7)

(B) alkali-soluble resin (alkali-soluble resin of Synthesis Example 1)

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

(D) photopolymerization initiator:

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

(D-2) 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one (Irgacure 907 (manufactured by Ciba Specialty Chemical))

(E) solvent (propylene glycol monomethyl ether acetate)

Experimental example 1. Manufacture of color filters

A color filter was prepared using the gray photosensitive resin composition prepared in Examples 1 to 8 and Comparative Examples 1 to 3.

Specifically, each of the gray photosensitive resin compositions was coated on a 2-inch square glass substrate ("EAGLE XG" manufactured by Corning) by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. made it Subsequently, a test photomask having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a 3 x 3 cm exposed part pattern was placed on the thin film, and ultraviolet rays were irradiated at a distance of 100 μm from the test photomask. . At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ/cm 2 using a 1KW high-pressure mercury lamp containing all of the g, h, and i lines, and no special optical filter was used. The UV-irradiated thin film was developed by immersing it in a KOH aqueous solution of pH 10.5 for 2 minutes. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200° C. for 25 minutes to prepare a color filter. The film thickness was measured using a film thickness measuring device (DEKTAK 6M; manufactured by Veeco), and the measured film thickness was 2.5 μm.

Experimental example 2. Characterization

2.1 Spectroscopic measurements

For spectroscopy, a color filter was prepared in the same manner as in Experimental Example 1 except that the test photomask was not used, and transmittance was measured using a colorimeter (OSP-200, manufactured by Olympus), and the results are shown in Table 2 below. shown in In addition, spectral transmittance was measured in the visible light region in the range of 380 nm to 780 nm using a colorimeter (OSP-200, manufactured by Olympus), and the results are shown in Tables 4 and 5, and FIGS. 1 and 2.

2.2 Reflectance measurement

After preparing the color filter in the same manner as in Experimental Example 1 except that the test photomask was not used, the 2 degree specular reflectance on the coated surface was measured using an integrating sphere reflectance meter (Konica Minolta Co., Ltd., Spectrophotometer CM-3700d), The results are shown in Table 2 below.

[Table 2]

Table 3 shows the evaluation criteria.

[Table 3]

As shown in Table 2, Examples 1 to 8 were confirmed to be superior in external light reflection effect compared to Comparative Examples 1 to 3.

[Table 4]

Table 4 and FIG. 1 show the transmittance according to the wavelength according to the above experimental results.

1 is a graph showing spectral transmittance in the visible light region in the range of 380 to 780 nm. Table 4 shows the transmittance of some wavelengths in the visible light region in the range of 460 nm to 730 nm.

As shown in FIG. 1, Comparative Examples 1 and 2, which did not contain black pigment, showed a transmittance of less than 30% or 75% or more at a wavelength of 460 nm to 530 nm, and a transmittance of 20% or more and less than 75% at a wavelength of 580 nm to 620 nm. In the embodiment including the black pigment, transmittance of 30% or more and less than 75% at a wavelength of 460 nm to 530 nm, transmittance of 20% or more and less than 75% at a wavelength of 580 nm to 620 nm, and transmittance of 20% or more at a wavelength of 690 nm to 780 nm to reflect external light As an effect, it showed a lacking aspect.

On the other hand, in Comparative Example 3 in which the black pigment is less than 0.5% by weight or more than 10% by weight based on the solid content of the colorant, the external light reflection prevention effect and visibility are insufficient.

Claims (14)

A pigment dispersion composition (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E),
The pigment dispersion composition (A) includes at least one selected from the group consisting of a red pigment, a green pigment, a blue pigment, a yellow pigment, and a purple pigment, and a black pigment;
The black pigment is a gray photosensitive resin composition of 0.5 to 10% by weight based on the total weight of the solid content of the colorant,
When the gray photosensitive resin composition is formed into a cured film having a thickness of 2.5 μm, the transmittance at a spectral wavelength of 460 nm to 530 nm is 30% or more and less than 75%, and the transmittance at a spectral wavelength of 580 nm to 620 nm is 20% or more and 75% or more. %, and transmittance at a spectral wavelength of 690 nm to 780 nm is 20% or more, characterized in that the gray photosensitive resin composition. delete The method of claim 1,
The gray photosensitive resin composition, characterized in that the weight ratio of at least one selected from the group consisting of red pigment, green pigment, blue pigment, yellow pigment and purple pigment to black pigment is 99.5 ~ 90: 10 ~ 0.5. The method of claim 1,
Based on the total solid weight of the gray photosensitive resin composition,
1 to 70% by weight of the pigment dispersion composition (A);
Alkali-soluble resin (B) 5 to 80% by weight,
5 to 50% by weight of a photopolymerizable compound (C);
0.1 to 40% by weight based on the total solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C), and
A gray photosensitive resin composition comprising 25 to 80% by weight of a solvent based on the gray photosensitive resin composition. The method of claim 1,
The red pigment is characterized in that it comprises at least one selected from the group consisting of CI Pigment Red 179, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 242 and CI Pigment Red 254, A gray photosensitive resin composition. The method of claim 1,
The green pigment is characterized in that it comprises at least one selected from the group consisting of CI Pigment Green 36, CI Pigment Green 58 and CI Pigment Green 59, gray photosensitive resin composition. The method of claim 1,
The blue pigment is CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 21, CI Pigment Blue 28, CI Pigment Blue 60, CI Pigment Blue A gray photosensitive resin composition comprising at least one selected from the group consisting of 64 and CI Pigment Blue 76. The method of claim 1,
The yellow pigment comprises at least one selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 150 and CI Pigment Yellow 185, a gray photosensitive resin composition. The method of claim 1,
The purple pigments are CI Pigment Violet 14, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 33, CI Pigment Violet 36, CI Pigment Violet A gray photosensitive resin composition comprising at least one member selected from the group consisting of 37 and CI pigment violet 38. The method of claim 1,
The black pigment comprises at least one selected from the group consisting of red, blue and green pigments, CI Pigment Black 1, CI Pigment Black 7, carbon black, organic black and titanium black. , gray photosensitive resin composition. A color filter prepared using the gray photosensitive resin composition according to any one of claims 1 and 3 to 10. A display device comprising the color filter of claim 11. The method of claim 12,
Characterized in that the display element is a flexible display element, the display element. The method of claim 12,
The display device is characterized in that the organic light emitting device, the display device.