KR102560329B1 - 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, an alkali-soluble resin containing a compound represented by Formula 1; And a carbazole-based photopolymerization initiator comprising a compound represented by Formula 2 below;
The colored photosensitive resin composition includes an alkali-soluble resin represented by a specific chemical formula and a carbazole-based photopolymerization initiator represented by a specific chemical formula, thereby improving wire tearing, sensitivity, and redissolvability:
[Formula 1]

[Formula 2]

(The substituents in Formulas 1 and 2 are as defined in the specification).

Description

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

The present invention relates to a colored photosensitive resin composition with excellent wire tearing, 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. Color filters used in color liquid crystal display devices, imaging devices, etc. are usually manufactured by spin-coating uniformly a photosensitive resin composition containing colorants corresponding to the respective colors of red, green, and blue on a substrate on which a black matrix is patterned, then heat-drying (hereinafter sometimes referred to as pre-baking), exposing and developing a formed coating film, and, if necessary, further heat-curing (hereinafter also referred to as post-baking) repeatedly for each color to form pixels of each color.

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. Such a color filter has a structure in which a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between pixels and a pixel unit in which three primary colors of a plurality of colors (usually, red (R), green (G), and blue (B)) are arranged in a predetermined order to form each pixel are sequentially stacked. In general, a color filter can be produced by coating three or more colors on a transparent substrate by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, etc., and recently, a pigment dispersion method using a pigment dispersion type photosensitive resin is the mainstream.

The pigment dispersion method, which is one of the methods for realizing a color filter, is a method of forming a colored thin film by repeating a series of processes of coating a photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerization monomer, a photopolymerization initiator, an epoxy resin, a photopolymerization monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives on a transparent substrate provided with a black matrix, exposing a pattern in the form to be formed, and then removing the unexposed area with a solvent and thermally curing it, thereby forming a colored thin film. In recent years, even in the photosensitive resin composition for a color filter using a pigment dispersion method having various advantages, not only excellent pattern characteristics but also further improved performance such as re-solubility, sensitivity, and tearing are required.

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

However, the prior art recognizes only developability and chemical resistance, and problems such as residual film, sensitivity, and wire tearing occur at a high film thickness.

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

The present invention is to solve the above problems, by including an alkali-soluble resin represented by a specific chemical formula and a carbazole-based photopolymerization initiator represented by a specific chemical formula, thereby improving wire tearing, sensitivity, and redissolvability. An object of the present invention is to provide a colored photosensitive resin composition, a color filter, and an image display device having the same.

Colored photosensitive resin composition according to the present invention for achieving the above object is an alkali-soluble resin containing a compound represented by the following formula (1); And a carbazole-based photopolymerization initiator comprising a compound represented by Formula 2 below; characterized in that it comprises:

[Formula 1]

[Formula 2]

(The substituents in Formulas 1 and 2 are as defined in the specification).

As described above, the colored photosensitive resin composition according to the present invention includes an alkali-soluble resin represented by a specific chemical formula and a carbazole-based photopolymerization initiator represented by a specific chemical formula, thereby improving wire tearing, 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 tearing evaluation criterion of the present invention.
2 shows the sensitivity evaluation criterion of the present invention.
Figure 3 shows the re-solubility evaluation criterion of the present invention.

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

<Colored photosensitive resin composition>

Colored photosensitive resin composition according to the present invention is an alkali-soluble resin containing a compound represented by the following formula (1); And a carbazole-based photopolymerization initiator including a compound represented by Formula 2 below; and may further include one or more of a colorant, a multifunctional monomer, and a solvent.

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

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically include metal oxides or composite metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. In particular, the organic and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists), and more specifically, pigments having the following color index (C.I.) numbers, but are not necessarily limited thereto, and these may be used alone 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, and polyamine surfactants, which 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 presented in Korean Patent Publication No. 2004-0014311, commercially available products of the acrylate-based dispersant prepared through the living control method include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and the like.

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 polyurethane, polycarboxylic acid esters represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, hydroxyl group-containing esters of polycarboxylic acids and their modified products, or free carboxyl oily dispersants such as amides formed by reaction of group-containing polyester with poly(lower alkyleneimine) or salts 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) Chemistry trade 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-1 84; 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. In addition, azo-, xanthene-, and phthalocyanine-based acid dyes and derivatives thereof may 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. as an acid dye

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 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, 19 yellow dyes such as 7, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

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, 25 7, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, red dyes such as 412, 417, 418, 422, 426;

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, blue dyes such as 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335, 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, 108, 109, 129, 13 yellow dyes such as 6, 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, 21 red dyes such as 3, 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, 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, 190, 19 2,193,194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250, blue dyes such as 251, 252, 256, 257, 259, 260, 268, 274, 275, and 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, 41, 43, 45, 46, 48, 53, 56, red dyes such as 63, 71, 74, 85, 86, 88, 90, 94, and 95;

C.I. orange dyes 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;

C.I. Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, blue dyes such as 77, 83 and 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 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 wire breakage, sensitivity and re-solubility.

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. When the acid value of the alkali-soluble resin is less than 90 mgKOH / g, it is difficult to secure a sufficient development rate for the colored photosensitive resin composition, and when it exceeds 120 mgKOH / g, the adhesion to the substrate is reduced, and short circuits of the pattern are likely to occur.

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. It can be prepared.

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 50 mgKOH / g, sufficient development rate cannot be secured, and if it exceeds 250 mgKOH / g, the dimensional stability of the pattern formed is deteriorated, and the straightness of the pattern is likely to be poor, and the compatibility with the dye is deteriorated.

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 may be prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with an ethylenically unsaturated monomer having a hydroxyl group, and a compound having a glycidyl group may be further reacted with a copolymer of an ethylenically unsaturated monomer having a carboxyl group. 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-3-phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide, etc., and 2-hydroxyethyl (meth) acrylate is preferable, and two or more may be used in combination.

Specific examples of the compound having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl There are glycidyl ether, methacrylic acid glycidyl ester, etc., and butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more types 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, o-vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p-vinylbenzylglycidyl Aromatic vinyl compounds, such as ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-substituted maleimide compounds such as N-p-methoxyphenylmaleimide; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate; alicyclic (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decan-8-yl (meth)acrylate, 2-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 and unsaturated oxetane compounds such as tan.

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 total solid weight% in the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, the solubility in the developing solution is sufficient to facilitate pattern formation, and during development, the film reduction of the pixel portion of the exposed portion can be prevented and the omission of the non-pixel portion 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-vinylpyrrolidone. 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 (acryloyl oxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other multifunctional monomers include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa( meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

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.

carbazole type light polymerization initiator

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

[Formula 2]

In Formula 2,

R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, , COR ₁₆ or NO ₂ ,

At least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ ego,

R ₉ to R ₁₂ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenyl group;

R ₁₃ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, or a naphthyl group;

R ₁₄ is hydrogen, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a phenyl group or a naphthyl group;

R ₁₅ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms;

R ₁₆ is an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms;

wherein X is CO or a direct link.

At this time, the R₁₅is preferably a phenyl group, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, CN, NO₂, OR₁₇, SR₁₈, N R₁₉R₂₀, PO(OC₂H₅)₂, an alkyl group having 1 to 10 carbon atoms including SO, or SO₂O, S or NR containing at least one member selected from the group consisting of an alkyl group having 1 to 10 carbon atoms including₂₁An alkyl group having 2 to 20 carbon atoms, or a halogen atom, COOR₁₇, CONR₁₉R₂₀, Phenyl group, cycloalkyl group having 3 to 8 carbon atoms, heteroaryl group having 3 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms, heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OR₁₇, SR₁₈, or NR₁₉R₂₀An alkyl group having 1 to 20 carbon atoms containing at least one selected from the group consisting of

R ₁₇ is a haloalkyl group having 1 to 4 carbon atoms;

R ₁₈ is a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with phenyl, or hydrogen;

R ₁₉ and R ₂₀ are each independently a substituted or unsubstituted phenyl group, a naphthyl group, or a heteroaryl group having 3 to 20 carbon atoms, and R ₂₁ is hydrogen, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 2 to 20 carbon atoms including one or more O or CO, or an alkyl group having 1 to 4 carbon atoms substituted with phenyl.

The type of the substituent of the functional group (R), for which the type of the substituent is not mentioned, is not particularly limited. Reliability of the colored photosensitive resin composition may be improved by including the compound of Formula 1 as a carbazole-based photopolymerization initiator.

In addition, within a range not impairing the effects of the present invention, one or more compounds selected from the group consisting of an oxime ester-based compound, an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, and a thioxanthone-based compound may be used in addition to the carbazole-based compound.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and OXE01 and OXE02 commercially available from BASF are representative. 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-morpholinopropan-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one. Specific examples of the benzophenone-based compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone. 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. 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 preferably used. Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

The additional photopolymerization initiator may be used alone or in combination of two or more.

In the present invention, the photopolymerization initiator is preferably 0.1 to 15% by weight, more preferably 0.3 to 8% by weight, based on the total weight% of the red photosensitive resin composition. When the photopolymerization initiator is contained within the above range, it may be difficult to form a pattern and cause a decrease in sensitivity and adhesion, and when the photopolymerization initiator exceeds the above range, unnecessary fumes may be generated during a baking process.

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, esters or amides are preferred.

The solvent is specifically ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate ethylene glycol alkyl ether acetates, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc., aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone, methyl amyl ketone, ketones such as methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

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, butal lactate, 3-Ethoxypropionate, 3-methoxymethyl propionate and the like are more preferable.

The solvents may be used alone or in combination of two or more, and are preferably included in an amount of 60 to 90% by weight, and more preferably 70 to 85% by weight based on the total weight% of the colored photosensitive resin composition of the present invention. When the solvent is within the above range, coating properties can 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), or inkjet.

<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, 20 parts of methacrylate, and 30 parts of methacrylic acid were added to a 1000ml flask equipped with a stirrer, thermometer reflux condenser, dropping funnel and nitrogen inlet pipe, 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 synthesized alkali-soluble resin was 31.0%, the solid acid value was 100mgKOH/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, 20 parts of methacrylate, and 30 parts of methacrylic acid were added to a 1000ml flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet pipe, and substituted with nitrogen. 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 synthesized alkali-soluble resin 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, 20 parts of methacrylate, and 45 parts of methacrylic acid were added to a 1000ml flask equipped with a stirrer, thermometer reflux condenser, dropping funnel and nitrogen inlet pipe, and substituted with nitrogen. 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 synthesized alkali-soluble resin was 31.0%, the solid acid value was 130mgKOH/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, 20 parts of methacrylate, and 30 parts of methacrylic acid were added to a 1000ml flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet pipe, and substituted with nitrogen. 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 synthesized alkali-soluble resin was 31.0%, the solid acid value was 100mgKOH/g, and the weight average molecular weight measured by GPC was 18,000.

synthesis example 5: Synthesis of alkali-soluble resin (A-5)

400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of vinyltoluene, 58 parts of 2-phenylthioethyl acrylate, 20 parts of methacrylate, and 35 parts of methacrylic acid were added to a 1000 ml flask equipped with a stirrer, thermometer reflux condenser, dropping funnel and nitrogen inlet pipe, 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 synthesized alkali-soluble resin was 31.0%, the solid acid value was 110 mgKOH / g, and the weight average molecular weight measured by GPC was 12,000.

synthesis example 6: synthesis of alkali-soluble resin (A-6)

400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of vinyltoluene, 58 parts of 2-phenylthioethyl acrylate, 20 parts of methacrylate, and 35 parts of methacrylic acid were added to a 1000 ml flask equipped with a stirrer, thermometer reflux condenser, dropping funnel and nitrogen inlet pipe, and nitrogen substitution was performed. Thereafter, while stirring, the temperature of the reaction solution was raised to 100° C. and reacted for 12 hours after the increase. The final solid content of the synthesized alkali-soluble resin was 31.0%, the solid acid value was 110 mgKOH / g, and the weight average molecular weight measured by GPC was 14,000.

synthesis example 7: light polymerization Synthesis of Initiator (C-1)

Step 1. 13-(2- ethylhexyl )-13H- Dibenzo[a,i]carbazole manufacturing

After mixing 13H-dibenzo[a,i]carbazole (0.70g, 3.22mol) in 3mL of DMF, sodium hydride (0.19g, 4.67mmol) was added at 0°C. After stirring at 0 °C for 1 hour, 1-naphthylhydrazine hydrochloride (1.24 g, 6.44 mmol) was added at 0 °C and the mixture was stirred at room temperature overnight.

Ice water was added to the reaction mixture, and the resulting product was extracted twice with acetic acid ethyl ester. The organic layer was washed with water and brine, dried over magnesium sulfate, concentrated and dried again under vacuum to give 13-(2-ethylhexyl)-13H-dibenzo[a,i]carbazole (1.08 g) as product as a yellow liquid. The product was used in the next reaction without further purification.

Step 2. (13-(2- ethylhexyl )-5-(2,4,6- trimethylbenzoyl )-13H- Dibenzo[a,i]carbazole Preparation of -8-yl]-[4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methanone

After mixing 13- (2-ethylhexyl) -13H-dibenzo [A, I] Carbasol (47.16 g, 143.0 mmol), the product of the STEP 1 is mixed with 40 mL of chloride chloride chloride, after mixing 2,4,6-trimethyl benzoyl chloride (27.45g, 150.0 mol) and aluminum chloride (20. 00 g, 150.0mol).

After stirring at room temperature for 2 hours, aluminum chloride (22.93 g, 172.0 mol) was added at 0° C., 2,4,6-trimethylbenzoyl chloride (23.78 g, 150.0 mol) was added dropwise and the mixture was stirred at room temperature for 3 hours. Ice water was added to the reaction mixture, and the resulting product was extracted twice with methylene chloride. The organic layer was washed with water and brine and dried over magnesium sulfate.

Then, after adding 230 mL of n-hexane, methylene chloride was removed by concentration to give a beige solid. The solid was collected by filtration, washed with n-hexane and dried to give (13-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-13H-dibenzo[a,i]carbazol-8-yl]-[4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methanone (81.81 g, 95.7%) as a beige solid.

Step 3: (13-(2- ethylhexyl )-5-(2,4,6- trimethylbenzoyl )-13H- Dibenzo[a,i]carbazole -8-yl]-[4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methanone oxime manufacturing

After mixing (13-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-13H-dibenzo[a,i]carbazol-8-yl]-[4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methanone (5.98 g, 10.0 mol) prepared in step 2 with 10 mL of pyridine, 2-methoxyethanol (2. 28 g, 30.00 mol) and potassium tert-butoxide (1.68 g, 15.00 mol) were added.

After heating the mixture to 80 °C, it was stirred for 3.5 hours. Hydroxylammonium chloride (2.08 g, 30.00 mol) was then added to the reaction mixture and then the mixture was stirred at 100° C. overnight. After cooling it to room temperature, 200 mL of water was added to the reaction mixture to precipitate a solid. After filtering the precipitated solid, it was washed with methanol. A white solid (13-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-13H-dibenzo[a,i]carbazol-8-yl]-[4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methanone oxime (4.73 g, 71%) was obtained.

Step 4: (13-(2- ethylhexyl )-5-(2,4,6- trimethylbenzoyl )-13H- Dibenzo[a,i]carbazole -8-yl]-[4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methanone oxime O-acetate preparation

After mixing (13-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-13H-dibenzo[a,i]carbazol-8-yl]-[4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methanone (2.59; 3.87 mol) prepared in step 3 above with 20 mL acetone, triethylamine (0.78 g, 7.74 mol) and acetyl chloride (0.61 g, 7.74 mol) were added.

The mixture was stirred for 2 hours, and after the reaction was completed, water was added to the reaction mixture, and then the product was extracted with tert-butylmethylether. The organic layer was washed with water and brine, dried over magnesium sulfate and concentrated to give a residue. The residue was recrystallized from tert-butylmethylether to give (13-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-13H-dibenzo[a,i]carbazol-8-yl]-[4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methanone oxime O-acetate (2.00 g, 73%) as a white solid. It is composed of a mixture of substances.

Preparation of colored photosensitive resin composition

Example One

As a colorant, C.I. Pigment Green 58 (pigment) 25 parts, C.I. 5 parts of Pigment Yellow 150 (pigment), 4.0 parts of BYK-2001 (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 to obtain a colored curable resin composition.

Example 2

The same composition was applied except that the alkali-soluble resin of Example 1 was replaced with Synthesis Example 5.

Example 3

The same composition was applied except that the alkali-soluble resin of Example 1 was replaced with Synthesis Example 6.

comparative example One

The same composition was applied except that the photopolymerization initiator of Example 1 was replaced with I-369 (BASF).

comparative example 2

The same composition was applied except that the photopolymerization initiator of Example 1 was replaced with OXE-01 (BASF).

comparative example 3

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

comparative example 4

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

comparative example 5

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

comparative example 6

The same composition was applied except that the alkali-soluble resin of Example 1 was replaced with SPCY-1L (Showa Polymer).

Experimental example

Color filters were prepared using the photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 6. 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 ultraviolet rays were irradiated at an interval of 200 μm from the test photomask. At this time, the ultraviolet light source was irradiated with an illuminance of 50 mJ/cm 2 using a 1 kW high-pressure mercury lamp containing all of 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 for 30 minutes. The film thickness of the color filter prepared above was 2.5 μm.

1. Wire tear evaluation

The prepared color filter was confirmed for straightness in reflection mode using an ECLIPSE LV100POL Model (manufactured by Nikon) optical microscope. The wire tearing criterion was judged as O, X based on the same level as in FIG. 1, and the results are shown in Table 1.

2. Sensitivity

As shown in FIG. 2, 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.

3. 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 tearing Sensitivity redissolvability Example 1 O 9 Dissolution Example 2 O 8 Dissolution Example 3 O 8 Dissolution Comparative Example 1 X 3 Dissolution Comparative Example 2 X 2 Dissolution Comparative Example 3 O 8 exfoliation Comparative Example 4 O 9 exfoliation Comparative Example 5 O 8 exfoliation Comparative Example 6 O 8 exfoliation

As shown in Table 1, it can be confirmed that the colored photosensitive resin compositions of Examples 1 to 3 in which the composition was mixed according to the present invention were excellent in tear resistance, sensitivity, and redissolution.

Claims (6)

An alkali-soluble resin including a copolymer obtained by copolymerizing a compound represented by Formula 1 below; and
A carbazole-based photopolymerization initiator comprising a compound represented by Formula 2 below;
The alkali-soluble resin has an acid value of 90 mgKOH / g to 120 mgKOH / g, and a molecular weight of Mw 10,000 to 15,000 Colored photosensitive resin composition, characterized in that:
[Formula 1]

(In Formula 1 above,
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 above,
R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, , COR ₁₆ or NO ₂ , and at least one of R ₁ to R ₈ is,

At least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ ego,
R ₉ to R ₁₂ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenyl group;
R ₁₃ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, or a naphthyl group;
R ₁₄ is hydrogen, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a phenyl group or a naphthyl group;
R ₁₅ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms;
R ₁₆ is an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms;
wherein X is CO or a direct link). delete According to claim 1,
The alkali soluble resin is
The colored photosensitive resin composition, characterized in that the degree of dispersion (Mw / Mn) is 1.5 to 3.0. According to claim 1,
The colored photosensitive resin composition further comprises at least one of a colorant, a polyfunctional monomer and a solvent. A color filter made of the colored photosensitive resin composition according to any one of claims 1, 3 and 4. An image display device comprising the color filter of claim 5.