KR102510303B1 - A colored photo sensitive resin composition, a color filter comprising the same, and an image display devide comprising the color filter - Google Patents

Abstract

The present invention is a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photoacid generator, an epoxy compound, a scattering agent and a solvent, wherein the photoacid generator has a maximum absorbance in a wavelength range of 300 to 400nm. contains a sulfonate compound, the epoxy compound includes a compound represented by Formula 1 below, and the scattering material includes at least one selected from the group consisting of TiO ₂ , SiO ₂ , ZnO ₂ and Al ₂ O ₃ It provides a colored photosensitive resin composition, a color filter prepared using the same, and an image display device including the color filter.

Description

A colored photosensitive resin composition, a color filter prepared using the same, and an image display device including the color filter

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

As display device technology develops, development of a brighter and clearer display is required. Accordingly, a higher quality light source is required, and existing light sources are being replaced with light sources of self-luminous materials such as organic light emitting diodes (OLEDs) or quantum dots.

On the other hand, in a display device having such a self-luminous material as a light source, a retardation film and a polarizer are located inside the cover glass, and through this, reflection of light incident from the outside is suppressed and the efficiency of the light source is increased to improve the display quality. .

In this regard, Korean Patent Publication No. 10-2009-0101628 discloses an EL light emitting display device, an external light transmission plate provided on top of the EL light emitting display device, and the external light transmission plate in a region between the EL light emitting display device and the external light transmission plate. Disclosed is an organic light emitting display device comprising a polarizing film provided on a lower surface of a light transmission plate and a phase retardation layer formed of a liquid crystal polymer having birefringence between the polarizing film and the EL light emitting display device. . However, such a phase retardation layer and polarizing film not only increase the thickness of the panel, but also increase the manufacturing cost of the display device.

Therefore, the development of technology to introduce the functions of the retardation layer and the polarizing film into the color filter itself is being attempted, and in particular, due to the nature of the self-luminous material, the development of a technology that allows the color filter to have a high degree of curing even in a low-temperature process is required. .

Republic of Korea Patent Publication No. 10-2009-0101628

The present invention is to improve the above-mentioned problems of the prior art, suppresses the reflection of light incident from the outside, minimizes the decrease in transmittance to the light source, has excellent color purity, and has excellent sensitivity in low-temperature processes as well as conventional high-temperature processes. It aims at providing a colored photosensitive resin composition.

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

In order to achieve the above object, the present invention is a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photoacid generator, an epoxy compound, a scattering agent and a solvent, wherein the photoacid generator is 300 to 500 It includes a sulfonate compound having maximum absorbance in the 400 nm wavelength range, the epoxy compound includes a compound represented by Formula 1 below, and the scattering body is a group consisting of TiO ₂ , SiO ₂ , ZnO ₂ and Al ₂ O ₃ It provides a colored photosensitive resin composition comprising one or more selected from.

[Formula 1]

(In Formula 1, R is an alkyl group having 1 to 10 carbon atoms including an oxygen atom or a sulfur atom,

n is an integer from 1 to 3.)

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

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

The colored photosensitive resin composition of the present invention includes a specific photoacid generator and an epoxy compound together with a scattering body, thereby minimizing the decrease in transmittance of a coating film to a light source while improving light extraction efficiency and visibility. In particular, when preparing a color filter with the colored photosensitive resin composition of the present invention, even if a separate scattering layer is not included, reflection of light incident from the outside is suppressed and transmittance to the light source is minimized to provide an effect of excellent color purity. can

In addition, the colored photosensitive resin composition of the present invention has excellent solvent resistance and pattern straightness, and excellent sensitivity, providing an effect of obtaining a sufficient degree of curing when manufacturing a color filter through a low-temperature process.

The present invention is a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photoacid generator, an epoxy compound, a scattering agent and a solvent, wherein the photoacid generator has a maximum absorbance in a wavelength range of 300 to 400nm. contains a sulfonate compound, the epoxy compound includes a compound represented by Formula 1 below, and the scattering material includes at least one selected from the group consisting of TiO ₂ , SiO ₂ , ZnO ₂ and Al ₂ O ₃ It relates to a colored photosensitive resin composition, a color filter prepared using the same, and an image display device including the color filter, wherein the colored photosensitive resin composition according to the present invention is a specific photoacid generator and an epoxy compound together with a scattering body. By including, it is possible to improve the light extraction efficiency and visibility while minimizing the decrease in the transmittance of the coating film to the light source, and the solvent resistance and pattern straightness are excellent, and the sensitivity is excellent, so that sufficient curing degree can be obtained when manufacturing a color filter through a low-temperature process. The present invention was completed by experimentally confirming that it could be obtained. In particular, when preparing a color filter with the colored photosensitive resin composition of the present invention, even if a separate scattering layer is not included, reflection of light incident from the outside is suppressed and transmittance to the light source is minimized to provide an effect of excellent color purity. can Therefore, the colored photosensitive resin composition of the present invention is also suitable for use in a color filter that does not include a separate scattering layer, and furthermore, the color filter and image display device of the present invention do not include a separate scattering layer. can

Hereinafter, each component constituting the colored photosensitive resin composition of the present invention will be described in detail. However, the present invention is not limited by these components.

<Colored photosensitive resin composition>

coloring agent

The colorant is characterized in that it contains at least one pigment (a1).

(a1) pigment

As the pigment, organic or inorganic pigments generally used in the art may be used.

As the pigment, various pigments used in printing ink, inkjet ink, etc. may be used, and specifically, water-soluble azo pigment, insoluble azo pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone (pyranthrone) pigments, diketopyrroropyrrole pigments, and the like.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. Or a composite metal oxide etc. are mentioned.

In particular, the organic and inorganic pigments include compounds classified as pigments in color index (published by The Society of Dyers and Colourists), more specifically, the following color index (C.I.) numbers Although a pigment can be mentioned, it is not necessarily limited to these.

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38

C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58

C.I. Pigment Brown 28

C.I. Pigment Black 1 and 7, etc.

The above pigments (a1) may be used alone or in combination of two or more.

The above exemplified C.I. Among the pigment pigments, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Violet 23, C.I. A pigment selected from the group consisting of Pigment Blue 15:3 and Pigment Blue 15:6 may be preferably used.

The content of the pigment (a1) is in the range of 20 to 90% by weight, preferably 30 to 70% by weight, based on the total weight of the solid content of the colorant. When the content of the pigment (a1) is in the range of 20 to 90% by mass based on the above standards, it is preferable because it is effective in increasing the contrast ratio with low viscosity, excellent storage stability, and high dispersion efficiency.

As the pigment, it is preferable to use a pigment dispersion in which the particle size of the pigment is uniformly dispersed. As an example of a method for uniformly dispersing the particle size of the pigment, (a2) a method of dispersing treatment by containing a pigment dispersant, etc., and according to the above method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. there is.

(a2) pigment dispersant

The pigment dispersant is added to maintain the deagglomeration and stability of the pigment, and those generally used in the art may be used without limitation.

Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester-based, and polyamine-based surfactants, and these may be used alone or in combination of two or more. .

As the pigment dispersant, other resin-type pigment dispersants may be used in addition to those described above. 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. Pigment dispersants of other resin types may also be used. 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. The above 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 pigment dispersant may be included in an amount of 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the total solid content of the pigment. If the pigment dispersant exceeds 60 parts by weight, the viscosity may increase, and if it is included in an amount of less than 5 parts by weight, it is difficult to atomize the pigment, and problems such as gelation after dispersion may occur.

(a3) dye

In one embodiment of the present invention, the colorant (A) may further include a dye (a3) generally used in the art.

The dye (a3) may be additionally used without limitation as long as it has solubility in organic solvents or is dispersible. Preferably, it is preferable to use a dye capable of ensuring 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 (dyed yarn).

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

C.I. red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 59, 67, and 70;

C.I. violet dyes such as Solvent Violet 8, 9, 13, 14, 36, 37, 47, 49;

C.I. yellow dyes such as Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Orange dyes such as Solvent Orange 2, 7, 11, 15, 26, 56

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

The C.I. As a solvent dye, C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent Violet 13 is preferred, C.I. Solvent Red 8, 122 and 132 are more preferable.

Also, C.I. As an acid dye,

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, 88 217 ,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, 426 and the like red dyes;

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, etc.

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

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

Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66

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

C.I. Acid Red 92 having excellent solubility in organic solvents as the acid dye; C.I. Acid Blue 80, 90; C.I. Acid Violet 66 is preferred.

Also, C.I. As a direct dye,

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, 250;

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, yellow dyes such as 141;

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

C.I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, blue dyes such as 293;

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

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

Also, C.I. As a modanto dye,

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

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, red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

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

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, blue dyes such as 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

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

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

These dyes can be used individually or in combination of two or more types, respectively.

When the dye is further included in the colorant, the content of the dye is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, and 1 to 50% by weight based on the total weight of the solid content of the colorant. is particularly preferred. When the content of the dye in the colorant is within the above range, it is possible to prevent a decrease in reliability in which the dye is eluted by an organic solvent after pattern formation, and it is preferable because the sensitivity is excellent.

The content of the colorant may be included as 5 to 60% by weight, preferably 10 to 45% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the colorant is included within the above range, it is preferable because the color density of pixels is sufficient during thin film formation and the omission of non-pixel areas is not reduced during development, so that residues are difficult to generate.

In the present invention, the total solid weight of the colored photosensitive resin composition means the total weight of the remaining components except for the solvent in the colored photosensitive resin composition.

alkali soluble resin

In order to have solubility with respect to the alkali developing solution used in the development process at the time of forming a pattern, it is preferable that alkali-soluble resin is manufactured by copolymerizing the ethylenically unsaturated monomer (b1) which has a carboxyl group. In addition, in order to secure the developability of the colored photosensitive resin composition, the acid value of the alkali-soluble resin is preferably 30 to 150 mgKOH/g. If the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it is difficult to secure a sufficient development rate for the colored photosensitive resin composition, and if it exceeds 150 mgKOH / g, the adhesion to the substrate is reduced and the short circuit of the pattern is likely to occur.

Specific examples of the ethylenically unsaturated monomer (b1) having a carboxyl group 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 these dicarboxylic acids; and mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as omega-carboxypolycaprolactone mono(meth)acrylate. Among these, acrylic acid and methacrylic acid are preferable.

During preparation of the alkali-soluble resin, polymerization may be performed by adding the copolymerizable unsaturated monomer (b2) to the ethylenically unsaturated monomer (b1) having a carboxyl group. The copolymerizable unsaturated monomers (b2) are exemplified below, but are not necessarily limited thereto.

Specific examples of the polymerizable monomer (b2) having an unsaturated bond capable of copolymerization include:

glycidyl methacrylate, which is an unsaturated monomer having a glycidyl group;

2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, N -ethylenically unsaturated monomers having a hydroxyl group such as hydroxyethyl (meth)acrylates such as hydroxyethyl acrylamide;

Styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinyl Aromatic vinyl compounds, such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;

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;

Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, Alkyl (meth)acrylates, such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-methylcyclohexyl(meth)acrylate, tricyclo[5.2.1.0 2,6]decan-8-yl(meth)acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate;

aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate;

3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds and the like.

The monomers exemplified by the above (b2) can be used individually or in combination of two or more types, respectively.

In addition to the above-mentioned monomers, an unsaturated monomer (b3) may be added and polymerized in order to provide a cured product having more improved heat resistance, hardness, colorant dispersibility, and the like. It is preferable to set it as 60 mass % or less, and, as for the content rate of the said monomer, it is more preferable to set it as 50 mass % or less in 100 mass % of the total amount of the said monomer component. In particular, when an N-substituted maleimide-based monomer is contained, the content ratio thereof is preferably 2 to 60% by mass, more preferably 2 to 60% by mass, from the viewpoint of heat resistance, hardness, colorant dispersibility, developing speed, transparency, etc. It is 50 mass %, More preferably, it is 3-40 mass %.

Examples of the N-substituted maleimide-based monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, and N-t-butylmaleimide. Mead, N-dodecyl maleimide, N-benzyl maleimide, N-naphthyl maleimide, etc. are mentioned, One type or two or more types of these can be used. Especially, from a viewpoint of transparency, N-phenyl maleimide and N-benzyl maleimide are preferable, and N-benzyl maleimide is especially preferable.

The monomer component may further contain other monomers. As the other monomer, for example, one or two or more such as (meth)acrylic acid ester type monomers and aromatic vinyl type monomers are preferably used. Examples of the (meth)acrylic acid ester monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate s-butyl, (meth)acrylate t-butyl, (meth)acrylate n-amyl, (meth)acrylate s-amyl, (meth)acrylate t-amyl, (meth)acrylate n-hexyl, (meth)acrylate ) 2-ethylhexyl acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, ( Lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, (meth)acrylate 4-hydroxybutyl, (meth)acrylate 2-methoxyethyl, (meth)acrylate 2-ethoxyethyl, (meth)acrylate phenoxyethyl, (meth)acrylate tetrahydrofurfuryl, (meth)acrylate Glycidyl acrylate, (meth)acrylate β-methylglycidyl, (meth)acrylate β-ethylglycidyl, (meth)acrylate (3,4-epoxycyclohexyl)methyl, (meth)acrylate N,N-dimethylamino Ethyl, α-hydroxymethyl methyl acrylate, α-hydroxymethyl ethyl acrylate, and the like.

The alkali-soluble resin of the present invention may have a weight average molecular weight (Mw) of 5,000 to 16,000.

The content of the alkali-soluble resin may be included as 10 to 80% by weight, preferably 10 to 70% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the alkali-soluble resin is included within the above range, the solubility in the developing solution is sufficient to facilitate pattern formation, and film reduction of the pixel portion of the exposed portion is prevented during development, so that the omission of the non-pixel portion becomes good, which is preferable. do.

photopolymerizable compound

The photopolymerizable compound is a compound that can be polymerized by the action of the following photopolymerization initiator, and includes, but is not limited to, monofunctional monomers, bifunctional monomers, and other multifunctional monomers. Preferably, bifunctional or higher functional monomers are used. can

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N-vinyl group. Rolidone and the like, but are not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanedioldi(meth)acrylate, ethylene glycoldi(meth)acrylate, neopentylglycoldi(meth)acrylate, and triethylene glycoldi(meth)acrylate. , bis(acryloyloxyethyl) ether of bisphenol A or 3-methylpentanedioldi(meth)acrylate, but is not limited thereto.

Specific examples of the multifunctional monomer include trimethylol-propane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and pentaerythritol tri (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate ) acrylate or dipenta erythritol hexa (meth) acrylate, but is not limited thereto.

The amount of the photopolymerizable compound may be included in 5 to 45% by weight, preferably 7 to 45% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the photopolymerizable compound is contained within the above range, it is preferable because the strength and smoothness of the pixel portion become good.

photopolymerization initiator

The photopolymerization initiator preferably contains an oxime ester photopolymerization initiator (d1).

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. Commercially available oxime ester photopolymerization initiators include BASF's Irgacure® OXE 01, Irgacure® OXE 02, and Irgacure® OXE 03, and Tronly's PBG-304, PBG-326, PBG-327, PBG-345, and PBG-3057. And since each absorbance and generated radical species are diverse, it is preferable to use two or more species in combination.

The amount of the photopolymerization initiator (d1) may be 10 to 100% by weight, preferably 20 to 100% by weight, based on the total weight of the photopolymerization initiator. When the photopolymerization initiator is included in an amount of less than 10% by weight, the decrease in sensitivity due to the dye cannot be overcome, and short circuiting of the pattern is likely to occur during the developing process.

In addition, photopolymerization initiators (d2) other than the oxime ester-based photopolymerization initiator (d1) may be further used in combination. Typically, it is preferable to use at least one compound selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, thioxanthone-based compounds, and carbazole-based 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-[0107] phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4' -Tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

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.

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 is preferred. used

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

As said carbazole type compound, 3-(2-methyl-2-dimethylamino propionyl) carbazole, 3-(2-methyl-2-morpholino propionyl)-9-methylcarbazole, 3-, for example (2-methyl-hydroxypropionyl)-9-methylcarbazole, 3-(1-hydroxycyclohexanoyl)-9-butylcarbazole, and the like.

In addition, the photopolymerization initiator may further include a photopolymerization initiation auxiliary agent (d3) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains the photopolymerization initiation auxiliary agent (d3), so that the sensitivity is further increased and the productivity can be improved.

As the photopolymerization initiation aid (d3), for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds 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.

Examples of the multifunctional thiol compound include Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate.

When the (d3) photopolymerization initiation auxiliary is further included, the content of the photopolymerization initiation auxiliary is 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total solid weight of the alkali-soluble resin and the photopolymerizable compound. can When the photopolymerization initiation aid is included within the above range, the sensitivity of the colored photosensitive resin composition may be further increased, and the productivity of a color filter formed using the colored photosensitive resin composition may be improved.

The amount of the photopolymerization initiator may be included in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total solid weight of the alkali-soluble resin and the photopolymerizable compound. When the photopolymerization initiator is included within the above range, the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, which is preferable because productivity is improved and high resolution can be maintained. In addition, strength of the pixel portion formed using the colored photosensitive resin composition and smoothness on the surface of the pixel portion may be improved.

mine generator

The use of the photoacid generator is not particularly limited, but it is preferable to include a sulfonate compound having a maximum absorbance in a wavelength range of 300 to 400 nm and having good solubility in a general-purpose organic solvent due to the nature of the colored photosensitive resin composition. In particular, i It may be characterized by including a sulfonate compound having high photoactivity at a wavelength of 365 nm.

Specific examples of the sulfonate compound include sulfonic acid esters of quinonediazide derivatives such as 1,2-benzoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-4-sulfonic acid ester. ; 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-diazide-5- Sulfonic acid chlorides of quinonediazide derivatives such as sulfonic acid chloride, 1,2-naphthoquinone-1-diazide-6-sulfonic acid chloride, and 1,2-benzoquinone-1-diazide-5-sulfonic acid chloride Ryu; oxime sulfonates such as IRGACURE® PAG 103 (trade name, BASF, Germany), IRGACURE® PAG 121, IRGACURE® PAG 203, IRGACURE® CGI1380, IRGACURE® CGI 1907, and IRGACURE® CGI 725; and the like.

The content of the photoacid generator may be included in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total solid weight of the alkali-soluble resin and the photopolymerizable compound. When the photoacid generator is included within the above range, the colored photosensitive resin composition may be highly sensitive and thus reliability may be improved, and pattern straightness may be improved even at a low light exposure amount, which is preferable.

epoxy compound

The colored photosensitive resin composition of the present invention is characterized by comprising an epoxy compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R may be an alkyl group having 1 to 10 carbon atoms including an oxygen atom or a sulfur atom, preferably an alkyl group having 1 to 5 carbon atoms including an oxygen atom or a sulfur atom.

In addition, in Formula 1, n is an integer from 1 to 3.

The epoxy compound represented by Formula 1 is characterized in that it consists of an alicyclic cyclic compound. Thus, the sensitivity of the colored photosensitive resin composition can be improved by using the epoxy compound of an alicyclic structure.

Specific examples of the epoxy compound include commercially available Daicel's EHPE-3150.

The content of the epoxy compound may be included in 2 to 10% by weight, preferably 3 to 7% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the epoxy compound is included within the above range, the sensitivity of the colored photosensitive resin composition can be sufficiently improved, and the generation of residues can be prevented by having a good developing rate, which is preferable.

Scatterer

The colored photosensitive resin composition of the present invention is characterized in that it contains a scattering body.

Any kind of nanoparticles that can be dispersed in an organic solvent may be used as the scattering body. However, since high heat resistance and light resistance are required due to the characteristics of the color panel, it is preferable to use inorganic nanoparticles. In particular, it is suitable to use a metal oxide having a refractive index of 1.5 or more to improve the scattering effect, and among these metal oxides, titanium oxide (TiO ₂ ), silica (SiO ₂ ), zinc oxide (ZnO ₂ ) and aluminum oxide are selected in consideration of versatility. It is more preferable to include at least one selected from the group consisting of (Al ₂ O ₃ ).

The diameter of the metal oxide particles is preferably 200 nm to 800 nm, more preferably 200 to 500 nm. This is because if the diameter of the metal oxide particle is adjusted to be similar to the wavelength of light incident from the outside, forward scattering of light can be induced in the direction of the backlight after light is incident on the color resist coating film in which the scattering body is dispersed. Light incident from the outside is re-reflected by the metal wiring of the light emitting layer and finally incident on the external polarizer, so that visibility may be improved.

The content of the scattering body is not particularly limited, but may preferably be included in 1 to 5% by weight, more preferably 1 to 3% by weight, based on the total solid content of the colorant of the present invention. When the scattering material is included within the above range, it is more preferable because it is possible to reduce the reflectance while preventing the decrease in luminance by minimizing the decrease in transmittance.

solvent

The solvent contained in the colored photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of colored photosensitive resin compositions 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 dialkyl ethers such as diethylene glycol dimethyl ether, 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, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate alkylene glycol alkyl ether acetates such as; 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; Cyclic esters, such as esters, such as 3-ethoxy ethyl propionate and 3-methoxy methyl propionate, and (gamma)-butyrolactone, etc. are mentioned.

Among the above solvents, it is preferable to use an organic solvent having a boiling point of 100 ° C to 200 ° C in terms of coating and drying properties, more preferably alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate or 3 -Esters such as methyl methoxypropionate can be used, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxyethylpropionate, 3-methoxymethylpropionate, etc. can be used. These solvents can be used individually or in mixture of two or more types, respectively.

The solvent may be included in 55 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the colored photosensitive resin composition. When the solvent is included within the above content range, the effect of improving the coating property when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, or the like It is desirable because it provides

additive

In the colored photosensitive resin composition of the present invention, in addition to the above components, additives such as dispersants, fillers, other high molecular compounds, curing agents, adhesion promoters, ultraviolet absorbers, and aggregation inhibitors may be used in combination according to the needs of those skilled in the art within the range not impairing the object of the present invention. possible.

Commercially available surfactants may be used as the dispersant, and examples of the surfactant include silicone-based surfactants, fluorine-based surfactants, and mixtures thereof. Examples of the silicone-based surfactant include a surfactant having a siloxane bond. Commercially available products include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone 29SHPA, Toray Silicone SH30PA, polyether-modified silicone oil SH8400 (manufactured by Toray Silicone Co., Ltd.), KP321, KP322 . there is.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Prolinate (trade name) FC430, Prolinate FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Pack (trade name) F142D, Mega Pack F171, Mega Pack F172, Mega Pack F173, Mega Pack F177, Mega Pack Megapack F183, Megapack F251, Megapack F410, Megapack F430, Megapack F444, Megapack F477, Megapack F551, Megapack F553, Megapack F554, Megapack F556, Megapack F557, Megapack F558, Megapack F559 , Mega Pack F562, Mega Pack F563, Mega Pack F565, Mega Pack F570, Mega Pack R30, Mega Pack R40, Mega Pack R41, Mega Pack R43, Mega Pack R94 (manufactured by DIC, Japan), Ftop (trade name) EF301, Ftop EF303, Ftop EF351, Ftop EF352 (manufactured by Shin-Akitakasei Co., Ltd.), Suffron (trade name) S381, Suffron S382, Suffron SC101, Suffron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Genkyusho Co., Ltd.), BM-1000, BM-1100 (trade name: manufactured by BMChemie) and the like are exemplified.

When the dispersant is further included, the dispersant may be included in an amount of 0.1 to 2% by weight, preferably 0.5 to 1% by weight based on the total solid weight of the colored photosensitive resin composition.

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 or an oxetane skeleton of an oxetane compound. 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.

When the adhesion promoter is further included, the adhesion promoter may be included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total solid weight of the colored photosensitive resin 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 or the like, but is not limited thereto.

The colored photosensitive resin composition according to an embodiment of the present invention can be prepared, for example, by the following method.

First, the pigment (a1) of the colorant is mixed with a solvent and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, if necessary, the pigment dispersant (a2), part or all of the alkali-soluble resin, or dye (a3) may be mixed with a solvent to be dissolved or dispersed. The colored photosensitive resin according to the present invention is further added to the mixed dispersion with the remainder of the alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photoacid generator, an epoxy compound, a scattering agent, an additive, and, if necessary, a solvent to a predetermined concentration. composition can be prepared.

<Color filter>

One embodiment of the present invention relates to a color filter formed using the colored photosensitive resin composition described above.

As described above, when the color filter is manufactured with the colored photosensitive resin composition of the present invention, even if a separate scattering layer is not included, reflection of light incident from the outside is suppressed and the decrease in transmittance to the light source is minimized, resulting in excellent color purity. can provide. Accordingly, the color filter of the present invention may not include a separate scattering layer.

A color filter according to an embodiment of the present invention is characterized in that it includes a colored pattern formed by applying the above-described colored photosensitive resin composition on a substrate, exposing and developing in a predetermined pattern.

Hereinafter, the pattern formation method using the colored photosensitive resin composition of the present invention will be described in detail.

A method for forming a pattern using the colored photosensitive resin composition of the present invention may use a method known in the art, but typically includes an application step; exposure step; and a removal step. By applying the colored photosensitive resin composition of the present invention on a substrate, photocuring and developing to form a pattern, it can be used as a colored pixel (colored image).

Specifically, the colored photosensitive resin composition is applied on a glass substrate to which nothing is coated and a glass substrate to which SiNx (protective film) is coated to a thickness of 500 to 1,500 Å using an appropriate method such as spin coating or slit coating, It is applied in a thickness of 3.4 μm. After application, light is irradiated to form a pattern required for the color filter. After light is irradiated, when the coating layer is treated with an alkaline developer, the unirradiated portion of the coating layer is dissolved and a pattern required for the color filter is formed. By repeating this process according to the required number of R, G, and B colors, a color filter having a desired pattern can be obtained. In addition, in the above process, crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing by irradiation with actinic rays or the like.

<Image display device>

One embodiment of the present invention relates to an image display device including the color filter described above.

As described above, when the color filter is manufactured with the colored photosensitive resin composition of the present invention, even if a separate scattering layer is not included, reflection of light incident from the outside is suppressed and the decrease in transmittance to the light source is minimized, resulting in excellent color purity. can provide. Therefore, the image display device of the present invention may not include a separate scattering material layer.

The color filter of the present invention is used for various image displays such as not only a conventional liquid crystal display (LCD) but also an electroluminescence display (EL), a plasma display (PDP), a field emission display (FED), and an organic light emitting diode (OLED). applicable to the device.

The image display device of the present invention includes a configuration known in the art, except for having the color filter described above.

An image display device according to an embodiment of the present invention includes a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles in addition to the above-described color filter. A color filter may be additionally provided. In such a case, the emission light of the light source applied to the image display device is not particularly limited, but a light source emitting blue light may be preferably used in terms of better color reproducibility.

An image display device according to an embodiment of the present invention may further include a color filter including only pattern layers of two colors among a red pattern layer, a green pattern layer, and a blue pattern layer, in addition to the color filters described above. In such a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles. In the case of having only two color pattern layers, a light source emitting light of a wavelength representing the colors other than those not included may be used. For example, in the case of including only a red pattern layer and a green pattern layer, a light source emitting blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is, showing a blue color.

Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are only examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention has been indicated in the claims, and furthermore contains all changes within the meaning and range equivalent to the written claims. Incidentally, in the following examples and comparative examples, "%" and "parts" indicating content are based on mass unless otherwise specified.

<Example>

Synthesis Example: Synthesis of Alkali-Soluble Resin

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 13.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 57.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate, and 3 parts of n-dodecylmercapto were added and nitrogen substitution was performed. 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 15,110.

Production Example: Pigment Dispersion and Scattering Body Dispersion are prepared

Preparation Example 1: Pigment Dispersion M1

As a colorant, C.I. 12.0 parts by weight of Pigment Red 254, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersant, and 82.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion M1.

Preparation Example 2: Pigment Dispersion M2

As a colorant, C.I. 12.0 parts by weight of Pigment Red 177, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersant, and 82.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed using a bead mill for 12 hours to prepare a pigment dispersion M2.

Preparation Example 3: Pigment Dispersion M3

As a colorant, C.I. 12.0 parts by weight of Pigment Green 7, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersant, and 82.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion M3.

Preparation Example 4: Pigment Dispersion M4

As a colorant, C.I. 12.0 parts by weight of Pigment Yellow 138, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersant, and 82.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion M4.

Preparation Example 5: Pigment Dispersion M5

As a colorant, C.I. 12.0 parts by weight of Pigment Blue 15:6, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersant, and 82.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion M5 did

Preparation Example 6: Pigment Dispersion M6

As a colorant, C.I. 12.0 parts by weight of Pigment Violet 23, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersant, and 82.0 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion M6.

Preparation Example 7: Scattering body dispersion S1

50 parts by weight of silica (SiO ₂ ) having a diameter of 200 nm as a scattering agent, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersant, 44.0 parts by weight of propylene glycol methyl ether acetate as a solvent, mixed for 12 hours by a bead mill and It was dispersed to prepare a scattering body dispersion S1.

Preparation Example 8: Scattering body dispersion S2

50 parts by weight of zinc oxide (ZnO ₂ ) having a diameter of 200 nm as a scattering agent, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersing agent, and 44.0 parts by weight of propylene glycol methyl ether acetate as a solvent mixed for 12 hours by a bead mill and dispersed to prepare a scattering body dispersion S2.

Preparation Example 9: Scattering body dispersion S3

50 parts by weight of titanium oxide (TiO ₂ ) having a diameter of 200 nm as a scattering agent, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersing agent, and 44.0 parts by weight of propylene glycol methyl ether acetate as a solvent mixed for 12 hours by a bead mill and dispersed to prepare a scattering body dispersion S3.

Preparation Example 10: Scattering body dispersion S4

50 parts by weight of aluminum oxide (Al ₂ O ₃ ) having a diameter of 200 nm as a scattering agent, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersant, and 44.0 parts by weight of propylene glycol methyl ether acetate as a solvent for 12 hours by a bead mill While mixing and dispersing, a scattering body dispersion S4 was prepared.

Preparation Example 11: Scattering body dispersion S5

50 parts by weight of magnesium fluoride (MgF ₂ ) having a diameter of 200 nm as a scattering agent, 6.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersant, and 44.0 parts by weight of propylene glycol methyl ether acetate as a solvent mixed for 12 hours by a bead mill and dispersed to prepare a scattering body dispersion S5.

Examples 1 to 18 and Comparative Examples 1 to 6: Preparation of colored photosensitive resin composition

According to the compositions of Tables 1 and 2 below, the red, green and blue photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 6 were prepared, respectively.

M1: Pigment dispersion M1 of Preparation Example 1

M2: pigment dispersion M2 of Preparation Example 2

M3: pigment dispersion M3 of Preparation Example 3

M4: pigment dispersion M4 of Preparation Example 4

M5: pigment dispersion M5 of Preparation Example 5

M6: pigment dispersion M6 of Preparation Example 6

S1: scattering body dispersion S1 of Preparation Example 7

S2: scattering body dispersion S2 of Preparation Example 8

S3: scattering body dispersion S3 of Preparation Example 9

S4: scattering body dispersion S4 of Preparation Example 10

S5: scattering body dispersion S5 of Preparation Example 11

Alkali-soluble resin: Alkali-soluble resin of Synthesis Example 1

Photopolymerizable compound: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerization initiator: PBG-327 (manufactured by Tronley)

E1: PAG 103 (manufactured by BASF), λmax: 390 nm

E2: WPAG-336 (manufactured by Wako), λmax: 237 nm

F1: EHPE-3150 (manufactured by Daicel)

F2: PB-3600 (manufactured by Daicel)

Additive: F554 (manufactured by DIC, Japan)

Solvent: Propylene glycol monomethyl ether acetate

Manufacturing Example: Manufacturing of color filters

Color filters were prepared using the red, green and blue photosensitive resin compositions prepared in Examples 1 to 18 and Comparative Examples 1 to 6.

Specifically, each of the red, green, and blue photosensitive resin compositions were applied on a glass substrate of 1100 mmX960 mm in size using a slit coater so that the film thickness after drying was 2.5 μm, and the coating speed at this time was 200 mm / sec. After coating, the substrate on which the coating film was formed was moved to a vacuum drying chamber (VCD), and vacuum drying was performed so that the time required for the pressure to reach 65 Pa was 20 sec. After drying under reduced pressure, the substrate was moved to a heating oven and prebaked at 100° C. for 3 minutes. Subsequently, a test photomask having a pattern for changing the transmittance in a stepwise manner in the range of 1 to 100% and a line/space pattern of 1 μm to 100 μm was placed on the thin film, and an interval between the test photomask and the test photomask was set to 200 μm, and ultraviolet rays was investigated. At this time, the ultraviolet light source was irradiated with an illuminance of 50 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. In addition, the front substrate was fabricated by full exposure without using a photomask. 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 230 ° C. for 25 minutes to prepare a color resist coating film having a pattern and an overall shape.

<Experimental example>

Experimental Example 1: Permeability evaluation

The transmittance of the color resist coating film prepared in the above Examples and Comparative Examples was measured using a spectrophotometric device (OSP-SP200, OLYMPUS). The transmittance at 630 nm for the red coating film, 525 nm for the green coating film, and 445 nm for the blue coating film were respectively measured, and the transmittance (T) of each color resist coating film was calculated based on the transmittance of the color resist coating film without a scattering body. evaluated. At this time, the transmittance was evaluated according to the following criteria, and the results are shown in Tables 3 and 4 below.

<Permeability Evaluation Criteria - Red Coating>

◎: Compared to the color resist coating film that does not contain a scattering body, 80% < T,

Δ: Compared to the color resist coating film without a scattering body, 70% < T ≤ 80%,

X: Compared to the color resist coating film containing no scattering material, T ≤ 70%

<Permeability Evaluation Criteria - Green Coating>

◎: Compared to the color resist coating film that does not contain a scattering body, 75% < T,

Δ: Compared to the color resist coating film without a scattering body, 65% < T ≤ 75%,

X: Compared to the color resist coating film containing no scattering material, T ≤ 65%

<Permeability Evaluation Criteria - Blue Coating>

◎: Compared to the color resist coating film that does not contain a scattering body, 70% < T,

Δ: Compared to the color resist coating film without a scattering body, 60% < T ≤ 70%,

X: Compared to the color resist coating film without a scattering body, T ≤ 60%

Experimental Example 2: Evaluation of reflectance

The reflectance of the color resist coating film prepared in the above Examples and Comparative Examples was measured using a spectrophotometer (CM-3700d, KONICA MINOLTA). In the light source wavelength range of 360 ~ 740nm, the integrated reflectance (R) was measured in a mode including specular reflection light at a reflection angle of 8 °, and evaluated according to the following criteria. The results are shown in Tables 3 and 4 below.

<Reflectivity Evaluation Criteria - Red Coating>

◎: Compared to the color resist coating film that does not contain a scattering body, 2% < R,

Δ: Compared to the color resist coating film without a scattering body, 1% < R ≤ 2%,

X: 0.5% < R ≤ 1% compared to the color resist coating film that does not contain a scattering body

<Reflectivity Evaluation Criteria - Green Coating>

◎: Compared to the color resist coating film that does not contain a scattering body, 8% < R,

Δ: Compared to the color resist coating film without a scattering body, 4% < R ≤ 8%,

X: 1% < R ≤ 4% compared to the color resist coating film without a scattering body

<Reflectivity Evaluation Criteria - Blue Coating>

◎: Compared to the color resist coating film that does not contain a scattering body, 4% < R,

Δ: Compared to the color resist coating film without a scattering body, 2% < R ≤ 4%,

X: 1% < R ≤ 2%, compared to the color resist coating film without a scattering body

Experimental Example 3: Evaluation of solvent resistance

Solvent resistance of the color resist coating films prepared in the above Examples and Comparative Examples was evaluated. The coating film was cut into a size of 3X3cm and immersed in a vial containing N-methylpyrrolidone heated to 80 ° C, and the solvent eluted after 3 minutes was UV-Vis. The concentration was measured using a spectrophotometer (UV-2550, Shimadzu). The maximum absorbance value (A) for each coating film was measured and compared with the absorbance value (B) of a coating film not containing a scattering material, and evaluated according to the following criteria. The results are shown in Tables 3 and 4 below.

<Solvent Resistance Evaluation Criteria>

◎: Compared to the color resist coating film that does not contain a scattering body, 1 < A / B ≤ 2,

Δ: Compared to the color resist coating film without a scattering body, 2 < A / B ≤ 3,

X: Contrast of color resist coating film without scattering material, 3 < A/B

Experimental Example 4: Evaluation of pattern straightness

The color resist pattern coating film was prepared in the same manner except that the illuminance of the ultraviolet light source was changed to 50 mJ/cm 2 in the production conditions of the color resist coating film. Thereafter, a line pattern having a line width of 100 μm was observed using an optical microscope (LV100POL, NIKON). Among the total 10 line patterns, the number (N) of patterns having partial loss or poor straightness was counted and evaluated based on the following criteria. The results are shown in Tables 3 and 4 below.

<Pattern Straightness Evaluation Criteria>

◎: N ≤ 1;

Δ: 1 < N ≤ 3;

X: 3 ≤ N

Example One 2 3 4 5 6 7 8 9 10 11 12 permeability ◎ ◎ ◎ ◎ ◎ Δ ◎ ◎ ◎ ◎ ◎ Δ reflectivity ◎ ◎ ◎ ◎ Δ ◎ ◎ ◎ ◎ ◎ Δ ◎ solvent resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ pattern straightness ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

Example comparative example 13 14 15 16 17 18 One 2 3 4 5 6 permeability ◎ ◎ ◎ ◎ ◎ Δ ◎ ◎ ◎ ◎ ◎ Δ reflectivity ◎ ◎ ◎ ◎ Δ ◎ X X X ◎ ◎ x solvent resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X X ◎ pattern straightness ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ Δ ◎

Referring to the results of Tables 3 and 4, in the case of Examples 1 to 18 including a specific photoacid generator and an epoxy compound together with a scattering body, excellent effects were exhibited in terms of transmittance, reflectance, solvent resistance and pattern straightness. can confirm that

On the other hand, in the case of Comparative Examples 1 to 3 not including a scattering body, it can be seen that the reflectance characteristics are significantly lowered, and in the case of Comparative Examples 4 and 5 which do not use the photoacid generator or the epoxy compound according to the present invention, the solvent resistance is excellent. Significantly deteriorated, it can be seen that the pattern straightness is also not excellent.

In addition, in the case of Comparative Example 6 using magnesium fluoride (MgF ₂ ), which is not a scattering material according to the present invention, it can be seen that the reflectance characteristic is significantly lowered, and the transmittance is also not excellent.

From the above results, the colored photosensitive resin composition of the present invention can improve the light extraction efficiency and visibility while minimizing the decrease in the transmittance of the coating film to the light source, has excellent solvent resistance and pattern straightness, and has excellent sensitivity through a low temperature process. It can be seen that the effect of obtaining a sufficient degree of curing can be provided during the manufacture of the color filter.

Claims (10)

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photoacid generator, an epoxy compound, a scattering agent and a solvent,
The alkali-soluble resin does not include a cardo-based resin,
The photoacid generator includes a sulfonate compound having maximum absorbance in a wavelength range of 300 to 400 nm,
The epoxy compound includes a compound represented by Formula 1 below,
The scattering body is a colored photosensitive resin composition comprising at least one selected from the group consisting of TiO ₂ , SiO ₂ , ZnO ₂ and Al ₂ O ₃ .
[Formula 1]

(In Formula 1, R is an alkyl group having 1 to 10 carbon atoms including an oxygen atom or a sulfur atom,
n is an integer from 1 to 3.) The method of claim 1,
The photopolymerizable compound is nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, 1 6-hexanedioldi(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxy of bisphenol A) Ethyl) ether, 3-methylpentanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate ) Acrylates, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, A colored photosensitive resin composition, characterized in that at least one selected from the group consisting of propoxylated dipentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. The method of claim 1,
The photopolymerization initiator is a colored photosensitive resin composition comprising an oxime ester-based compound. The method of claim 1,
The colored photosensitive resin composition further comprises at least one additive selected from the group consisting of a dispersing agent, a filler, another polymer compound, a curing agent, an adhesion accelerator, an ultraviolet absorber, and an aggregation inhibitor. The method of claim 1,
Based on the total solid weight of the colored photosensitive resin composition, 5 to 60% by weight of a colorant, 10 to 80% by weight of an alkali-soluble resin, 5 to 45% by weight of a photopolymerizable compound and 2 to 10% by weight of an epoxy compound,
Based on the total weight of the solid content of the alkali-soluble resin and the photopolymerizable compound, 0.1 to 40% by weight of a photopolymerization initiator and 0.1 to 40% by weight of a photoacid generator,
Based on the total weight of the solid content of the colorant, including 1 to 5% by weight of the scattering body,
The colored photosensitive resin composition, characterized in that it comprises 55 to 90% by weight of the solvent based on the total weight of the colored photosensitive resin composition. The method of claim 1,
A colored photosensitive resin composition for use in a color filter that does not include a separate scattering layer. A color filter comprising a colored pattern made of the colored photosensitive resin composition of any one of claims 1 to 6. The method of claim 7,
A color filter that does not contain a separate scatterer layer. An image display device comprising the color filter of claim 7. The method of claim 9,
An image display device that does not include a separate scatterer layer.