KR102529875B1 - Colored photosensitive resin composition, color filter, and image display apparatus comprising the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, a color filter, and an image display device having the same, and more particularly, includes at least one of a green colorant and a yellow colorant, and the yellow colorant is 40% based on the total weight of the colorant. Characterized in that it comprises from 70% by weight,
The colored photosensitive resin composition has an effect of improving sensitivity and redissolvability by including a yellow colorant in a specific amount.

Description

Colored photosensitive resin composition, color filter and image display device having the same

The present invention relates to a colored photosensitive resin composition having excellent sensitivity and redissolvability, a color filter, and an image display device having the same.

Color filters are widely used in imaging devices, liquid crystal display devices, and the like, and their application range is rapidly expanding. A color filter used in a color liquid crystal display device or an imaging device is obtained by uniformly applying a photosensitive resin composition containing colorants corresponding to each color of red, green, and blue on a substrate on which a black matrix is patterned, by spin coating. , heat-drying (hereinafter sometimes referred to as pre-baking), exposure and development of the formed coating film, and, if necessary, further heating and curing (hereinafter sometimes referred to as post-baking) are repeated for each color to produce pixels of different colors. It is manufactured by forming.

More specifically, the color filter is a thin film type optical component that extracts three colors, red, green, and blue, from white light and makes it possible in fine pixel units, and the size of one pixel is about tens to hundreds of micrometers. These color filters include a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between each pixel and a plurality of colors (generally, red (R), green (G)) to form each pixel. and blue (B)) have a structure in which pixel units in which three primary colors are arranged in a predetermined order are sequentially stacked. In general, color filters can be produced by coating three or more colors on a transparent substrate by dyeing, electrodeposition, printing, pigment dispersion, etc. Recently, pigment dispersion using pigment dispersion type photosensitive resin is the mainstream. achieve

The pigment dispersion method, which is one of the methods for realizing a color filter, coats and forms a photosensitive resin composition including a colorant, an alkali-soluble resin, a photopolymerization monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives on a transparent substrate provided with a black matrix. It is a method of forming a colored thin film by repeating a series of processes of exposing a desired pattern and then removing the unexposed area with a solvent and curing it with heat. is being applied In recent years, even in the photosensitive resin composition for color filters using the pigment dispersion method, which has various advantages, not only excellent pattern characteristics but also high color reproducibility and sensitivity due to deterioration of developability during pattern formation, redissolvability and wire tearing have been further improved. Performance is required.

Korean Patent Publication No. 10-2014-0073999 discloses a photosensitive resin composition for a color filter comprising an acrylic binder resin containing a repeating unit represented by at least one specific chemical formula, a photopolymerizable monomer, a photopolymerization initiator, a colorant and a solvent, and using the same. It relates to a color filter, and has excellent developability and chemical resistance.

However, the prior art recognizes only developability and chemical resistance, and problems such as sensitivity and re-dissolution peeling occur.

Republic of Korea Patent Publication No. 10-2014-0073999 (2014.06.17. Cheil Industries Co., Ltd.)

The object of the present invention is to provide a colored photosensitive resin composition having improved sensitivity and redissolvability, a color filter, and an image display device having the same by including a yellow colorant in a specific amount to solve the above problems. there is

The colored photosensitive resin composition according to the present invention for achieving the above object includes at least one of a green colorant or a yellow colorant, and 40 to 70% by weight of a yellow colorant based on the total weight% of the colorant. .

As described above, the colored photosensitive resin composition according to the present invention includes a yellow colorant in a specific amount, thereby improving sensitivity and redissolvability.

A color filter made of the colored photosensitive resin composition and an image display device including the color filter have excellent fairness.

1 shows the sensitivity evaluation criterion of the present invention.
Figure 2 shows the re-solubility evaluation criterion of the present invention.

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

<Colored photosensitive resin composition>

The colored photosensitive resin composition according to the present invention includes at least one of a green colorant and a yellow colorant, and includes 40 to 70% by weight of a yellow colorant based on the total weight% of the colorant.

coloring agent

The colorant may have at least one pigment or at least one dye as an essential component.

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 Pigments may be mentioned, but are not necessarily limited thereto, and these may be used individually or in combination of two or more.

C.I. Pigment Yellow 13, 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, 208, 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, 58 and 59

C.I Pigment Brown 28

C.I Pigment Black 1 and 7, etc.

As the pigment, organic pigments or inorganic pigments generally used in the art may be used, and these may be used alone or in combination of two or more.

The above exemplified C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, 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 Violet 23, C.I. Pigment Blue 15:3, Pigment Blue 15:6, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. A pigment selected from Pigment Green 58 can be preferably used.

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 diameter of the pigment is a method of dispersing treatment by containing a pigment dispersant, and according to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

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. .

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. 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, other resin-type pigment dispersants may be used in addition to the above-described acrylic dispersant. 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 used is preferably 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 used. When the content of the pigment dispersant exceeds the above range, the viscosity may increase, and when it is below the above range, it may be difficult to atomize the pigment or cause problems such as gelation after dispersion.

The dye may be used without limitation as long as it has solubility in organic solvents. Preferably, it is preferable to use a dye capable of securing reliability such as solubility in an alkaline developer, solvent resistance, and stability over time 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. yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

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

C.I. orange dyes such as Solvent Orange 2, 7, 11, 15, 26, 41, 45, 56, 62;

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

C.I. Among solvent dyes, C.I. Solvent Yellow 14, 16, 21, 56, 151, 79, 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent Violet 13 is preferred and the dual C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. is more preferable.

Also, C.I. 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, 1 78, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 2 51st of yellow 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 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, 426 and the like red dyes;

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.

Among acid dyes, C.I. Acid Yellow 42 having excellent solubility in organic solvents; C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.

Also as C.I. direct dyes, 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, yellow dyes such as 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, 250;

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

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, 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 the 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.

The content of the colorant is preferably 5 to 60 parts by weight, more preferably 10 to 45 parts by weight, based on the total solids in the colored photosensitive resin composition. When the colorant is contained within the above range, the color density of the pixel is sufficient even when a thin film is formed, and the omission of non-pixel parts is not deteriorated during development, so residue is hardly generated.

In particular, the colorant includes at least one of a green colorant and a yellow colorant, and preferably contains 40 to 70% by weight of the yellow colorant, more preferably 50 to 60% by weight, based on the total weight% of the colorant. do. When the yellow colorant is less than the above range, an Adobe Green pattern cannot be provided, and when the yellow colorant exceeds the above range, color reproduction of Adobe Green may be difficult.

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

alkali soluble resin

The alkali-soluble resin may include a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R is hydrogen or an alkyl group, and R' is hydrogen, an alkyl group, a heterocyclic group, a heterocyclic aromatic group or an aromatic group.

The alkali-soluble resin has a molecular weight of 10,000 to 15,000 Mw through appropriate reaction time and acid value control, an acid value of 90 to 120 mgKOH / g, and a degree of dispersion (Mw / Mn) may have a range of 1.5 to 3.0. If the molecular weight, acid value and degree of dispersion of the alkali-soluble resin are out of the above ranges, problems may arise in process characteristics such as re-solubility and sensitivity.

More specifically, the acid value of the alkali-soluble resin is preferably 90 to 120 mgKOH/g in order to ensure compatibility with dyes and stability over time of the colored photosensitive resin composition. If the acid value of the alkali-soluble resin is less than 90mgKOH/g, it is difficult to secure a sufficient development rate for the colored photosensitive resin composition, and if it exceeds 120mgKOH/g, the adhesion with the substrate is reduced, resulting in easy pattern short circuit and compatibility with dyes This problem arises and the dye in the colored photosensitive resin composition is precipitated, or the stability over time of the colored photosensitive resin composition is lowered and the viscosity is likely to increase.

In addition, the alkali-soluble resin includes the compound of Formula 1, and copolymerizes an ethylenically unsaturated monomer having a carboxyl group as an essential component to be soluble in an alkali developing solution used in a developing process when forming a pattern. can be manufactured

A hydroxyl group may be added to secure additional developability of the alkali-soluble resin. Although there is an effect of improving the development rate of imparting a hydroxyl group, it is preferable that the sum of the hydroxyl value of the alkali-soluble resin and the polyfunctional monomer is 50 mgKOH/g to 250 mgKOH/g. If the sum of hydroxyl groups is less than 50mgKOH/g, sufficient development speed cannot be secured, and if it exceeds 250mgKOH/g, the dimensional stability of the formed pattern is lowered, and the straightness of the pattern is likely to be poor, and compatibility with dyes is lowered. It is easy to cause the problem of stability over time.

Specific examples of the ethylenically unsaturated monomer 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; Mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, are preferred, and acrylic acid and methacrylic acid are more preferred.

In order to impart a hydroxyl group to the alkali-soluble resin, it can be prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group, and a compound having a glycidyl group is added to the copolymer of the ethylenically unsaturated monomer having a carboxyl group. It can be prepared by reacting with In addition, it can be produced by reacting a compound having a glycidyl group with a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group.

Specific examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy- There are 3-phenoxypropyl (meth)acrylate, N-hydroxyethyl acrylamide, etc., and 2-hydroxyethyl (meth)acrylate is preferable, and two or more types may be used in combination.

Specific butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl of the compound having a glycidyl group Dill ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl glycidyl ether, glycidyl methacrylate There are cydyl esters, and butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more may be used in combination.

In preparation of the alkali-soluble resin, copolymerizable unsaturated monomers are exemplified below, but are not necessarily limited thereto.

Specific examples of polymerizable monomers having an unsaturated bond capable of copolymerization include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, and o-vinylbenzyl. aromatic vinyl compounds such as methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl 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.

These monomers may be used alone or in combination of two or more.

The alkali-soluble resin is preferably 10 to 80% by weight, more preferably 10 to 70% by weight based on the weight% of the total solid content in the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, the developer The solubility of is sufficient to facilitate pattern formation, and film reduction in the pixel portion of the exposed portion is prevented during development, so that the omission of non-pixel portions can be improved.

polyfunctionality monomer

The multifunctional monomer is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, bifunctional monomers, and other multifunctional monomers. Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrroly. money, etc. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned. Specific examples of other multifunctional monomers include trimethylolpropane 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 dipentaeryth Ritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

Among these, bifunctional or more functional monomers may be preferably used.

The content of the multifunctional monomer is preferably 5 to 50% by weight, more preferably 7 to 50% by weight, based on the total solid weight% in the colored photosensitive resin composition. When the multifunctional monomer is included within the above range, strength and reliability of the pixel unit may be improved.

Fluorene type light polymerization initiator

The fluorene-based photopolymerization initiator may include a compound represented by Chemical Formula 2 below.

The fluorene-based photopolymerization initiator may shorten the exposure time by increasing the sensitivity of the colored photosensitive resin composition, thereby improving pattern properties and having high resolution.

[Formula 2]

In Formula 2,

R ₁ to R ₃ are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and a hydroxide having 1 to 20 carbon atoms It is selected from the group consisting of a hydroxyalkyl group, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms,

R ₄ to R ₁₀ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and a hydroxyalkyl group having 1 to 20 carbon atoms. , It is selected from the group consisting of a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an amino group, a nitro group, a cyano group and a hydroxy group,

p is 0 or 1;

The halogen is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The alkyl group refers to a straight-chain or branched-chain hydrocarbon radical composed of only carbon and hydrogen atoms, free of unsaturation, and bonded to the rest of the molecule by a single bond. The alkyl group is preferably a straight-chain or branched alkyl group having 1 to 20 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and most preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms. Examples of such unsubstituted alkyl groups include methyl group, ethyl group, n -propyl group, isopropyl group, n -butyl group, isobutyl group, sec -butyl group, t -butyl group, pentyl group, isoamyl group, and hexyl group. etc. can be mentioned. One or more hydrogen atoms included in the alkyl group may be a halogen atom, a hydroxyl group, a thiol group (-SH), a nitro group, a cyano group, an amino group, an amidino group, a hydrazine, or a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, having 1 to 1 carbon atoms. 20 alkyl group, C1-20 halogenated alkyl group, C1-20 alkenyl group, C1-20 alkynyl group, C1-20 heteroalkyl group, C6-20 aryl group, C6-20 It may be substituted with an arylalkyl group, a heteroaryl group having 6 to 20 carbon atoms, or a heteroarylalkyl group having 6 to 20 carbon atoms.

The aryl group refers to an aromatic monocyclic or multicyclic hydrocarbon ring system consisting only of hydrogen and carbon, wherein the ring system may be partially or completely saturated. At least one hydrogen atom in the aryl group may be substituted with a substituent similar to that of the alkyl group. The aryl group is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and comprises a single or fused ring system containing suitably 4 to 7, preferably 5 or 6, ring atoms in each ring, It includes even a form in which a plurality of aryls are connected by a single bond. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 18 carbon atoms.

The alkoxy group is preferably an oxygen-containing straight-chain or branched alkoxy group each having an alkyl moiety of 1 to 20 carbon atoms. An alkoxy group of 1 to 10 carbon atoms is more preferred, and an alkoxy group of 1 to 4 carbon atoms is most preferred. Examples of such an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a t -butoxy group. The alkoxy group may be further substituted with one or more halo atoms such as fluoro, chloro or bromo to provide a haloalkoxy group. Examples thereof include a fluoromethoxy group, a chloromethoxy group, a trifluoromethoxy group, a trifluoroethoxy group, a fluoroethoxy group, and a fluoropropoxy group. At least one hydrogen atom in the alkoxy group may be substituted with the same substituents as in the case of the alkyl group.

The arylalkyl group means that one or more hydrogen atoms of the alkyl group are substituted with the aryl group. The arylalkyl group preferably has 7 to 40 carbon atoms, more preferably 7 to 28 carbon atoms, and most preferably 7 to 24 carbon atoms.

The hydroxyalkyl group refers to an OH-alkyl group in which a hydroxy group is bonded to the above-defined alkyl group, and the hydroxyalkoxyalkyl group refers to a hydroxyalkyl-O-alkyl group in which the hydroxyalkyl group and the alkyl group are connected by oxygen. The hydroxyalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and most preferably 1 to 6 carbon atoms. The hydroxyalkoxyalkyl group preferably has 2 to 40 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 2 to 9 carbon atoms.

The cycloalkyl group includes not only a single ring system but also multiple ring system hydrocarbons, and at least one hydrogen atom in the cycloalkyl group may be substituted with the same substituents as in the case of the alkyl group. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms, and most preferably a cycloalkyl group having 3 to 8 carbon atoms.

The fluorene-based photopolymerization initiator represented by Chemical Formula 2 may have p of 0 or 1. When p is 0, it may be represented by Chemical Formula 3 below, and when p is 1, it may be represented by Chemical Formula 4 below.

[Formula 3]

In Formula 3,

R ₁₁ to R ₁₄ are each independently selected from hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and an aryl group having 1 to 20 carbon atoms. a hydroxyalkyl group, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms;

B is hydrogen, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, a hydroxyalkyl group of 1 to 20 carbon atoms, a hydroxyalkyl group of 2 to 40 carbon atoms A oxyalkoxyalkyl group, a cycloalkyl group having 3 to 20 carbon atoms, an amino group, a nitro group, a cyano group or a hydroxy group.

R ₁₁ to R ₁₄ are specifically hydrogen, bromine, chlorine, iodine, methyl group, ethyl group, n -propyl group, i -propyl group, n -butyl group, i -butyl group, t -butyl group, n -pentyl group, i -pentyl group, n -hexyl group, i -hexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, anthryl group, indenyl group, phenanthryl group, methoxy group, ethoxy group, n -propyloxy group, i -Propyloxy group, n -butoxy group, i -butoxy group, t -butoxy group, hydroxymethyl group, hydroxyethyl group, hydroxy n -propyl group, hydroxy n -butyl group, hydroxy i -butyl group, hydroxy hydroxy n -pentyl group, hydroxy i -pentyl group, hydroxy n -hexyl group, hydroxy i -hexyl group, hydroxymethoxymethyl group, hydroxymethoxyethyl group, hydroxymethoxypropyl group, hydroxymethoxy a butyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxypentyl group or a hydroxyethoxyhexyl group;

B is specifically hydrogen, methyl group, ethyl group, n -propyl group, i -propyl group, n -butyl group, i -butyl group, t -butyl group, phenyl group, naphthyl group, biphenyl group, terphenyl anthryl group, Nyl group, phenanthryl group, methoxy group, ethoxy group, propyloxy group, butoxy group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxymethoxymethyl group, hydroxymethoxyethyl group, hydroxy Can be a hydroxymethoxypropyl group, a hydroxymethoxybutyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, an amino group, a nitro group, a cyano group, or a hydroxy group Yes, but not limited thereto.

Preferably, R ₁₁ and R ₁₂ are each independently hydrogen or an n -butyl group; R ₁₃ is a methyl group; R ₁₄ is a methyl group, n -butyl group or a phenyl group; B may be hydrogen or a nitro group. The R ₁₁ and R ₁₂ are preferably the same.

Representative examples of the fluorene-based photopolymerization initiator of Formula 3 include the following compounds, but are not limited to the following compounds, and those that meet the above conditions and are known in the art may be used.

[Formula 4]

In Formula 4,

R ₁₅ to R ₂₅ are each independently selected from hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and an aryl group having 1 to 20 carbon atoms. A hydroxyalkyl group, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms.

R ₁₅ to R ₂₅ are specifically hydrogen, bromine, chlorine, iodine, methyl group, ethyl group, n-propyl group, i -propyl group, n -butyl group, i -butyl group, t -butyl group, n -pentyl group, i -pentyl group, n -hexyl group, i -hexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, anthryl group, indenyl group, phenanthryl group, methoxy group, ethoxy group, n -propyloxy group, i -Propyloxy group, n -butoxy group, i -butoxy group, t -butoxy group, hydroxymethyl group, hydroxyethyl group, hydroxy n -propyl group, hydroxy n -butyl group, hydroxy i -butyl group, hydroxy hydroxy n -pentyl group, hydroxy i -pentyl group, hydroxy n -hexyl group, hydroxy i -hexyl group, hydroxymethoxymethyl group, hydroxymethoxyethyl group, hydroxymethoxypropyl group, hydroxymethoxy It may be a butyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxypentyl group, or a hydroxyethoxyhexyl group.

Preferably, R ₁₅ and R ₁₆ are each independently hydrogen, methyl, ethyl, propyl, or butyl; R ₂₁ is a methyl group, an ethyl group, or a propyl group; R ₁₈ is a methyl group, an ethyl group, a propyl group, or a butyl group; R ₁₉ to R ₂₅ may be hydrogen. It is preferable that the above R ₁₅ and R ₁₆ are the same.

Representative examples of the fluorene-based photopolymerization initiator of Formula 4 include the following compounds, but are not limited to the following examples, and those known in the art that meet the above conditions may be used.

The content of the fluorene-based photopolymerization initiator is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, and 0.1 to 1% by weight based on the total weight% of the colored photosensitive resin composition. It is most preferable to be When the content of the fluorene-based photopolymerization initiator is within the above range, it is possible to prevent a phenomenon in which the pattern is dropped during the development process due to a decrease in sensitivity, and a crosslinking reaction due to an excessive reaction causes wrinkles in the coating film. The phenomenon of deterioration of physical properties can be prevented.

In addition, one or more compounds selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds and thioxanthone-based compounds may be used within a range that does not impair the effects of the present invention. can

The acetophenone-based compound is specifically, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-( 2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] propan-1-one and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one; and the like. The benzophenone-based compound is specifically, for example, benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'- tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; and the like. The triazine-based compound is specifically, for example, 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 and 2,4-bis( trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine; and the like. The biimidazole compound is specifically, for example, 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-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; can Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are preferred. used The thioxanthone-based compound is specifically, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propoxythioxanthone. Santon etc. are mentioned.

In addition, the photopolymerization initiator may further include a photopolymerization initiator to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention includes a photopolymerization initiation aid, so that sensitivity can be further improved and productivity can be increased.

As the photopolymerization initiation aid, 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.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; Methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4 and aromatic amine compounds such as '-bis(dimethylamino)benzophenone (common name: Michler's ketone) and 4,4'-bis(diethylamino)benzophenone. it is desirable

The carboxylic acid compound is, for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid , aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The organic sulfur compound having a thiol group is, for example, 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-mer captobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and tetraethylene glycol bis (3-mercaptopropionate), etc. can be heard

It is preferable to use such a photopolymerization initiation aid in an amount of usually 10 moles or less, preferably 0.01 to 5 moles, per mole of the photopolymerization initiator. When the photopolymerization initiation aid is used within the above range, an effect of improving productivity can be expected by increasing the polymerization efficiency.

solvent

As long as the solvent is effective in dissolving other components included in the colored photosensitive resin composition, solvents used in conventional colored photosensitive resin compositions may be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, and esters. or amides are preferred.

The solvent is specifically ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol 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 and mesitylene, methyl ethyl ketone , acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3- Cyclic esters, such as esters, such as methoxy methyl propionate, and (gamma)-butyrolactone, etc. are mentioned.

The solvent is preferably an organic solvent having a boiling point of 100 to 200 ° C. in terms of application and drying properties, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalactate, 3- Ethyl ethoxypropionate, 3-methoxymethylpropionate, etc. are more preferable.

Each of the solvents may be used alone or in combination of two or more, and preferably included in an amount of 60 to 90% by weight based on the total weight% of the colored photosensitive resin composition of the present invention, and more preferably included in an amount of 70 to 85% by weight. desirable. When the solvent is within the above range, coating properties may be improved when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet, etc.

In particular, the colored photosensitive resin composition according to the present invention contains 40 to 70% by weight of a yellow colorant based on the total weight% of the coloring agent, an alkali-soluble resin including the compound represented by Formula 1, and the compound represented by Formula 2 A fluorene-based photopolymerization initiator comprising a, wherein the alkali-soluble resin has an acid value of 90 to 120 mgKOH / g, and a degree of dispersion (Mw / Mn) when it has a range of 1.5 to 3.0, sensitivity and re-dissolution peeling phenomenon effect can be maximized.

<Color filter>

When the color filter of the present invention is applied to an image display device, since it emits light from a light source of the display device, superior light efficiency can be realized. In addition, color reproducibility is better because light with a color is emitted, and a viewing angle can be improved because light is emitted in all directions by photoluminescence.

The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be a substrate of the color filter itself, or may be a portion where the color filter is positioned, such as a display device, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiO _x ) or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer is a layer containing the colored photosensitive resin composition of the present invention, and may be a layer formed by applying the colored photosensitive resin composition and then exposing, developing and thermally curing the colored photosensitive resin composition in a predetermined pattern.

The pattern layer formed of the colored photosensitive resin composition may include 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. When light is irradiated, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light.

In such a case, the emission light of the light source is not particularly limited when applied to an image display device, but a light source emitting blue light may be used in terms of better color reproducibility.

According to another embodiment of the present invention, the pattern layer may include only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the pattern layer 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, when a red pattern layer and a green pattern layer are included, 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.

The color filter including the substrate and the pattern layer as described above may further include barrier ribs formed between the respective patterns, and may further include a black matrix. In addition, a protective film formed on the upper portion of the pattern layer of the color filter may be further included.

<Image display device>

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

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

The image display device of the present invention may include a color filter including 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 such a case, when applied to an image display device, the emission light of the light source is not particularly limited, but a light source emitting blue light may be preferably used in terms of better color reproducibility.

According to another embodiment of the present invention, the image display device of the present invention may 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 such a case, the color filter may further include 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, when a red pattern layer and a green pattern layer are included, 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.

The image display device of the present invention exhibits high luminance due to excellent light efficiency, excellent color reproducibility, and can have a wide viewing angle.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples may be appropriately modified or changed by those skilled in the art within the scope of the present invention. In addition, "%" and "parts" indicating content below are based on weight unless otherwise specified.

Synthesis Example 1: Synthesis of alkali-soluble resin (A-1)

400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of vinyltoluene, 58 parts of 2-phenylthioethyl acrylate, methacryl 20 parts of rate and 30 parts of methacrylic acid were added and nitrogen substitution was performed. Thereafter, while stirring, the temperature of the reaction solution was raised to 100° C., followed by reaction for 10 hours. The final solid content of the alkali-soluble resin thus synthesized was 31.0%, the solid acid value was 100 mgKOH/g, and the weight average molecular weight measured by GPC was 12,000.

Synthesis Example 2: Synthesis of alkali-soluble resin (A-2)

400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of vinyltoluene, 58 parts of 2-phenylthioethyl acrylate, methacryl 20 parts of rate and 30 parts of methacrylic acid were added and nitrogen substitution was performed. Thereafter, while stirring, the temperature of the reaction solution was raised to 100° C., followed by reaction for 7 hours. The final solid content of the alkali-soluble resin thus synthesized was 31.0%, the solid acid value was 100 mgKOH/g, and the weight average molecular weight measured by GPC was 9,000.

Synthesis Example 3: Synthesis of alkali-soluble resin (A-3)

400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of vinyltoluene, 58 parts of 2-phenylthioethyl acrylate, methacryl 20 parts of rate and 45 parts of methacrylic acid were added and nitrogen substitution was performed. Thereafter, while stirring, the temperature of the reaction solution was raised to 100° C., followed by reaction for 10 hours. The final solid content of the alkali-soluble resin thus synthesized was 31.0%, the solid acid value was 130 mgKOH/g, and the weight average molecular weight measured by GPC was 12,000.

Synthesis Example 4: Synthesis of Alkali-Soluble Resin (A-4)

400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of vinyltoluene, 58 parts of 2-phenylthioethyl acrylate, methacryl 20 parts of rate and 30 parts of methacrylic acid were added and nitrogen substitution was performed. Thereafter, while stirring, the temperature of the reaction solution was raised to 100° C., followed by reaction for 15 hours. The final solid content of the alkali-soluble resin thus synthesized was 31.0%, the solid acid value was 100 mgKOH/g, and the weight average molecular weight measured by GPC was 18,000.

Synthesis Example 5: Synthesis of Photopolymerization Initiator (C-1)

reaction 1

5.0 g of 2-nitrofluorene was dissolved in 100 ml of anhydrous nitrobenzene, 6.31 g of anhydrous aluminum chloride was added, and the reaction mixture was heated to 45 ° C. A solution of 2.79 g of acetyl chloride dissolved in 30 ml of anhydrous nitrobenzene was dissolved in 30 minutes. The mixture was added slowly over a period of time, and the reaction mixture was heated to 65° C. and stirred for 1 hour. Then, the reactant was cooled to room temperature, 70 ml of distilled water was added thereto, and the product was filtered after stirring for 30 minutes. The obtained solid product was dispersed in 50 ml of ether, stirred at room temperature for 30 minutes, filtered, and dried to obtain pale yellow reactant 1 (1-(9,9-H-7-nitrofluoren-2-yl)-ethanone) 5.08 got g.

reaction 2

1.5 g of the reactant 1 was dispersed in 30 ml of ethanol, 0.49 g of hydroxylamine hydrochloride and 0.58 g of sodium acetate were added, and then the reaction solution was gradually heated and reacted under reflux for 2 hours. The reactant was cooled to room temperature, 20 ml of distilled water was added, and the solid product obtained by stirring for about 30 minutes was filtered, washed several times with distilled water, and dried to obtain a light gray reactant 2 (1-(9, 9-H-7- Nitrofloren-2-yl)-ethanone oxime) yielded 1.38 g.

reaction 3

1.20 g of the reactant 2 was dispersed in 50 ml of ethyl acetate, 0.69 g of acetic anhydride was added, and the reaction solution was gradually heated and reacted under reflux for 3 hours. The reactant was cooled to room temperature, washed with 20 ml of saturated sodium bicarbonate aqueous solution and 20 ml of distilled water in that order, and the recovered organic layer was dried over anhydrous magnesium sulfate, and the product obtained by distillation of the solvent under reduced pressure was recrystallized with 20 ml of methanol to obtain a pale yellow photopolymerization initiator. 1.22 g of C-1(1-(9,9-H-7-nitrofloren-2-yl)-ethanone oxime-O-acetate) was obtained.

Synthesis Example 6: Synthesis of Photopolymerization Initiator (C-2)

reaction 1

200.0 g of fluorene, 268.8 g of potassium hydroxide and 19.9 g of potassium iodide were dissolved in 1 L of anhydrous dimethyl sulfoxide under a nitrogen atmosphere, and the reaction was maintained at 15 ° C. Then, 283.3 g of bromoethane was slowly added over 2 hours and the reaction was Stirred at 15° C. for 1 hour. Then, 2L of distilled water was added to the reactant, stirred for 30 minutes, the product was extracted with 2L of dichloromethane, the extracted organic layer was washed twice with 2L of distilled water, and the collected organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled under reduced pressure. The obtained product was fractionally distilled under reduced pressure to obtain 248.6 g of reactant 1 (9,9-diethyl-9H-fluorene) as a pale yellow liquid with high viscosity.

reaction 2

After dissolving 100.5g of reactant 1 in 1L of dichloromethane, cooling the reactant to -5℃, 72.3g of aluminum chloride was slowly added, and then 50.1g of propionyl chloride diluted in 50ml of dichloromethane while being careful not to raise the temperature of the reactant. was added slowly over 2 hours and the reaction mixture was stirred at -5 °C for 1 hour. Then, the reactant was slowly poured into 1 L of ice water, stirred for 30 minutes to separate the organic layer, washed with 500 ml of distilled water, and distilled the recovered organic layer under reduced pressure. The product obtained was subjected to silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1: 4) to obtain 75.8 g of reactant 2 (1-(9,9-diethyl-9H-fluoren-2-yl)-1-propanone) as a pale yellow solid.

reaction 3

44.5 g of reactant 2 was dissolved in 900 ml of tetrahydrofuran (THF), and 150 ml of 4N HCl dissolved in 1,4-dioxane and 24.7 g of isobutyl nitrous acid were sequentially added thereto, and the reaction was stirred at 25° C. for 6 hours. Then, 500 ml of ethyl acetate was added to the reaction solution, stirred for 30 minutes to separate the organic layer, washed with 600 ml of distilled water, dried the recovered organic layer with anhydrous magnesium sulfate, and distilled the solvent under reduced pressure. The obtained solid product was ethyl acetate: It was recrystallized using 300 ml of a mixed solvent of hexane (1:6) and dried to obtain a light gray solid reactant 3(1-(9,9-diethyl-9H-fluoren-2-yl)-1,2- propanedione-2-oxime) to give 27.5 g.

reaction 4

Reactant 3 was dissolved in 1L of N-methyl-2-pyrrolidinone (NMP) under a nitrogen atmosphere, the reaction was maintained at -5°C, 35.4 g of triethylamine was added, and the reaction solution was stirred for 30 minutes, followed by chlorination. A solution in which 27.5 g of acetyl was dissolved in 75 ml of N-methyl-2-pyrrolidinone was slowly added over 30 minutes, and stirred for 30 minutes while being careful not to raise the temperature of the reactant. Then, 1 L of distilled water was slowly added to the reactant, stirred for 30 minutes to separate an organic layer, and then the recovered organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled under reduced pressure. The obtained solid product was recrystallized using 1 L of ethanol and then dried to obtain light gray solid photopolymerization initiator C-2(1-(9,9-diethyl-9H-fluoren-2-yl)-1,2-propane dione-2-oxime-O-acetate) to obtain 93.7 g.

Preparation of colored photosensitive resin composition

Example 1

As a colorant, C.I. Pigment Green 58 (pigment) 12 parts, C.I. 18 parts of Pigment Yellow 150 (pigment), 4.0 parts of BYK-2001 (from BYK) as a pigment dispersant, and 66 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill.

Thereafter, 30 parts of alkali-soluble resin A-1 of Synthesis Example 1, 6.6 parts of photopolymerizable compound A9550 (Shin Nakamura Co.), 1.3 parts of photopolymerization initiator C-1 of Synthesis Example 5, and 52.7 parts of solvent propylene glycol monomethyl ether acetate were mixed. A colored curable resin composition was obtained.

Example 2

The same composition was applied except that the photopolymerization initiator of Example 1 was replaced with Synthesis Example 6.

Comparative Example 1

The same composition was applied except that the alkali-soluble resin of Example 1 was replaced with Synthesis Example 2.

Comparative Example 2

The same composition was applied except that the alkali-soluble resin of Example 1 was replaced with Synthesis Example 3.

Comparative Example 3

The same composition was applied except that the alkali-soluble resin of Example 1 was replaced with Synthesis Example 4.

Comparative Example 4

The same composition was applied except that the photopolymerization initiator of Example 1 was replaced with PBG-305 (Tronly Co.).

Experimental example

Color filters were prepared using the photosensitive resin compositions prepared in Examples 1 to 2 and Comparative Examples 1 to 4. That is, each of the photosensitive resin compositions was coated on a bare glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100° C. for 2 minutes to form a thin film. Subsequently, a test photomask having a pattern for changing the transmittance stepwise 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. The thin film irradiated with ultraviolet rays was developed by immersing it in a KOH aqueous solution of pH 10.5 for 2 minutes. The post-process bake was carried out at 230° C. for 30 minutes. The film thickness of the color filter prepared above was 2.5 μm.

1. Sensitivity

As shown in FIG. 1, the fabricated color filter was measured for sensitivity by checking the number of remaining patterns for each transmittance. The results are shown in Table 1.

2. Redissolvability

The thin film substrate produced in the experimental example was immersed in PGMEA, waited for 2 minutes, and then the redissolving property was judged by photographing the melting state when redissolving. As shown in FIG. 3, the peeling was judged as NG and the dissolution was OK, and the results are shown in Table 1.

division Sensitivity redissolvability Example 1 8 Dissolution Example 2 8 Dissolution Comparative Example 1 8 exfoliation Comparative Example 2 8 exfoliation Comparative Example 3 8 exfoliation Comparative Example 4 3 Dissolution

As shown in Table 1, it can be confirmed that the colored photosensitive resin compositions of Examples 1 and 2, in which the composition is mixed according to the present invention, have excellent sensitivity and redissolvability.

Claims (6)

A colorant, an alkali-soluble resin and a fluorene-based photopolymerization initiator,
The colorant comprises 40 to 70% by weight of a yellow colorant based on the total weight% of the colorant,
The alkali-soluble resin includes a repeating unit derived from a compound represented by Formula 1 below,
The colored photosensitive resin composition, characterized in that the fluorene-based photopolymerization initiator comprises a compound represented by the following formula (2):
[Formula 1]

(In Formula 1,
R is hydrogen or an alkyl group, and R' is hydrogen, an alkyl group, a heterocyclic group, a heterocyclic aromatic group, or an aromatic group.)
[Formula 2]

(In Formula 2,
R ₁ to R ₃ are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and a hydroxide having 1 to 20 carbon atoms It is selected from the group consisting of a hydroxyalkyl group, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms,
R ₄ to R ₁₀ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and a hydroxyalkyl group having 1 to 20 carbon atoms. , It is selected from the group consisting of a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an amino group, a nitro group, a cyano group and a hydroxy group,
p is 0 or 1;
The halogen is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).) According to claim 1,
A colored photosensitive resin composition comprising 50 to 60% by weight of a yellow colorant based on the total weight% of the colorant. delete According to claim 1,
The alkali-soluble resin,
An acid value of 90 to 120 KOHmg/g, and a degree of dispersion (Mw/Mn) of 1.5 to 3.0, characterized in that the colored photosensitive resin composition. A color filter made of the colored photosensitive resin composition according to any one of claims 1, 2 and 4. An image display device comprising the color filter of claim 5.

Images