KR102518495B1 - A method of silicon compound, colored photosensitive resin composition, color filter and image display device comprising using the same - Google Patents

Abstract

(상기 화학식 1 내 치환기는 명세서 내 정의한 바와 같다).The present invention relates to a silicone compound, a colored photosensitive resin composition, a color filter and an image display device prepared using the same, and specifically relates to a silicone compound represented by Formula 1 below.
[Formula 1]

(Substituents in Formula 1 are as defined in the specification).

Description

Silicone compound, colored photosensitive resin composition, color filter and image display device manufactured using the same

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

Color filters are widely used in various display devices such as image pickup devices and liquid crystal displays (LCDs), and their application range is rapidly expanding. The color filter is composed of three color patterns of red, green, and blue, or three color patterns of yellow, magenta, and cyan made up of

In the color filter widely used in the display device, after uniformly applying a colored photosensitive resin composition containing a pigment dispersion composition corresponding to the color of each pattern on a substrate on which a black matrix pattern is formed, by spin or slit coating, It is manufactured by forming pixels of each color by repeating the operation of exposing and developing a coating film formed by heating and drying, and additional heat curing as necessary for each color, and also developing processes such as inkjet method and printing method other than the above coating method Even in this unnecessary step, a color filter is manufactured using a colored photosensitive resin composition using the pigment dispersion composition as a coloring material.

A color filter using the colored photosensitive resin composition as described above is required to have a high curing density without causing defects due to afterimages.

Republic of Korea Patent Publication No. 10-2016-0091233 relates to a thermosetting resin composition, a cured product thereof, and a display member using the same, (a) a curable resin, and (b) a silane-based coupling agent having a glycidyl group and a hydroxyl group and (c) at least one member selected from the group consisting of barium sulfate, silica, and talc, and (d) a colorant. It is described as having properties suitable for forming a frame portion (bezel) provided on the edge of a mold input device.

Republic of Korea Patent Publication No. 10-2016-0091233 (2016.08.02. Taiwan Taiyo Ink Company Limited)

An object of the present invention is to provide a novel silicone compound having a low polarizability.

In addition, an object of the present invention is to provide a colored photosensitive resin composition having a low dielectric constant by including a novel silicone compound, thereby preventing defects due to afterimages, and having excellent film strength and excellent adhesion.

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

The silicone compound according to the present invention for achieving the above object is characterized in that it is represented by the following formula (1).

[Formula 1]

(In Formula 1,

R ₁ is each independently hydrogen or an alkyl group having 1 to 5 carbon atoms;

R ₂ are each independently a ring-opened product of an alkylene group having 2 to 20 carbon atoms or an alkylene oxide group having 2 to 10 carbon atoms including an ester bond;

R ₃ is an alkylene group having 1 to 20 carbon atoms substituted with an epoxy group or interposed with an epoxy group, unsubstituted or substituted with a hydroxy group,

a and b are independently integers from 1 to 10,

n is an integer from 1 to 20).

In addition, the colored photosensitive resin composition according to the present invention includes at least one selected from the group consisting of the above-described silicone compound and colorant, alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, solvent, and additive, and the silicone compound includes the same. It is characterized in that it is included in 1 to 5% by weight based on the total 100% by weight of the colored photosensitive resin composition to be.

In addition, the present invention is characterized by a color filter including a cured product of the above-described colored photosensitive resin composition and an image display device including the same.

The novel silicon compound of the present invention has an effect of having a low dielectric constant due to its low polarizability.

In addition, the colored photosensitive resin composition including the novel silicone compound of the present invention has a low dielectric constant, can prevent defects due to afterimages, and has excellent effects in sensitivity, adhesion, developing stain, and solvent resistance.

In addition, a color filter made of the colored photosensitive resin composition of the present invention and an image display device including the same have an effect capable of displaying excellent images even at high resolution.

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

<Silicone compound>

One aspect of the present invention is a silicone compound represented by Formula 1 below.

[Formula 1]

(In Formula 1,

R ₁ is each independently hydrogen or an alkyl group having 1 to 5 carbon atoms;

R ₂ are each independently a ring-opened product of an alkylene group having 2 to 20 carbon atoms or an alkylene oxide group having 2 to 10 carbon atoms including an ester bond;

R ₃ is an alkylene group having 1 to 20 carbon atoms substituted with an epoxy group or interposed with an epoxy group, unsubstituted or substituted with a hydroxy group,

a and b are independently integers from 1 to 10,

n is an integer from 1 to 20).

The silicon compound is obtained by (S1) reacting a compound represented by Chemical Formula 2 with a halohydrin having 2 or 3 carbon atoms to obtain a compound represented by Chemical Formula 3; and

(S2) obtaining a compound of Formula 1 by reacting a compound represented by Formula 3 with a compound represented by Formula 4 or Formula 5;

[Formula 2]

(In Formula 2, R ₁ is each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 20).

[Formula 3]

[Formula 4]

[Formula 5]

(S1) The step of reacting the compound represented by Formula 2 with a halohydrin having 2 or 3 carbon atoms to obtain the compound represented by Formula 3 may be performed in an environment of 70 to 80° C. for a reaction time of 2 to 4 hours. there is.

At this time, a ketone system and a glycol ether system may be used as the solvent, and the ketone system may include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc., and the glycol ether system may be glycol As ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-pentyl ether, ethylene glycol mono-n-hexyl ether, ethylene ethylene glycol monoethers such as glycol mono-2-ethylbutyl ether, ethylene glycol mono-2-ethylhexyl ether, and ethylene glycol monophenyl ether; ethylene glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol dibutyl ether; propylene glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, and propylene glycol mono-t-butyl ether; propylene glycol diethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol methyl ethyl ether; 3-methoxy-1-butanol, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butanol, 3-methoxy-1-butylacetate, 3-methyl-3-methoxy-1- Butylene glycol derivatives such as butyl acetate, diethyl glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, etc. ethyl glycol monoethers; diethylene glycol diethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; dipropylene glycol monoethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether; dipropylene glycol diethers such as dipropylene glycol dimethyl ether; And it may be one selected from the group consisting of combinations thereof.

In addition, dibutyl tin laurate may be used as a catalyst.

(S2) reacting the compound represented by Formula 3 with the compound represented by Formula 4 or Formula 5 to obtain the compound of Formula 1 is reacted for a reaction time of 2 to 4 hours in an environment of 90 to 100 ° C, It may be performed by drying at a temperature of 140 to 160 ° C. for 4 to 6 hours. At this time, a ketone system and a glycol ether system may be used as the solvent, and the ketone system may include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc., and the glycol ether system may be glycol As ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-pentyl ether, ethylene glycol mono-n-hexyl ether, ethylene ethylene glycol monoethers such as glycol mono-2-ethylbutyl ether, ethylene glycol mono-2-ethylhexyl ether, and ethylene glycol monophenyl ether; ethylene glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol dibutyl ether; propylene glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, and propylene glycol mono-t-butyl ether; propylene glycol diethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol methyl ethyl ether; 3-methoxy-1-butanol, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butanol, 3-methoxy-1-butylacetate, 3-methyl-3-methoxy-1- Butylene glycol derivatives such as butyl acetate, diethyl glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, etc. ethyl glycol monoethers; diethylene glycol diethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; dipropylene glycol monoethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether; dipropylene glycol diethers such as dipropylene glycol dimethyl ether; And it may be one selected from the group consisting of combinations thereof.

In addition, dibutyl tin laurate may be used as a catalyst.

The silicone compound of the present invention includes an epoxy group and an ethylene oxide group, so it has excellent insulating properties, and depending on the composition, oxygen hindrance can be suppressed to increase surface curing. In addition, it can have a low dielectric constant due to excellent heat resistance, chemical resistance, and insulation.

<Colored photosensitive resin composition>

The colored photosensitive resin composition of the present invention is the silicone compound described above; and at least one selected from the group consisting of a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a solvent, and an additive.

silicone compound

The silicone resin contains an epoxy group and exhibits low dielectric constant characteristics due to the insulating properties of the silicone resin. The silicone resin is preferably included in an amount of 1 to 5% by weight based on 100% by weight of the entire colored photosensitive resin composition, and when the content of the silicone resin is less than the above range, it is difficult to obtain the expected low dielectric constant. It is difficult to expect improvement in sensitivity and adhesion, and there are problems in that coating properties may be deteriorated by decreasing dispersion stability and increasing the viscosity of the composition.

coloring agent

pigment

As the pigment, organic or inorganic pigments generally used in the art may be used. In addition, if necessary, the pigment is resin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment of the pigment surface using a polymer compound, etc., atomization treatment by a sulfuric acid atomization method, etc., to remove impurities A washing treatment with an organic solvent or water or a treatment for removing ionic impurities by an ion exchange method or the like may be performed.

As the organic pigment, various pigments used in printing ink, inkjet ink, etc. may be used. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, Perylene Pigment, Perinone Pigment, Dioxazine Pigment, Anthraquinone Pigment, Dianthraquinonyl Pigment, Anthrapyrimidine Pigment, Ananthrone Pigment, Indanthrone Pigment, Pravanthrone Pigment, Pyranthrone Pigment, Diketopyrororopyrrole Pigment etc. can be mentioned.

In addition, as the inorganic pigment, metal compounds such as metal oxides and metal complex salts may be used. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, organic oxides of metals or composite metal oxides, such as black pigments, titanium black, and pigments that produce black by mixing red, green, and blue colors; and the like.

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

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125,128, 137, 138, 139, 147 , 148, 150, 153, 154, 166, 173, 180, 185, 194 and 214;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 264 and 265;

C.I. Pigment Violet 1, 19, 23, 29, 32, 36 and 38;

C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.) and 60;

C.I. Pigment Green 7, 36, 58, 59, 62 and 63;

C.I Pigment Brown 23 and 25;

pigments such as C.I Pigment Black 1 and 7;

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

The pigment is included in an amount of 15 to 45% by weight, preferably 20 to 40% by weight, based on the total weight of the solid content in the colorant. If the content of the pigment is less than the above range, it is difficult to implement color reproducibility, and if it exceeds the above range, solubility in a developing solution is lowered and pattern formation becomes difficult.

As the pigment, it is preferable to use a pigment dispersion in which the particle size of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle size of the pigment include a method of dispersing treatment by containing a pigment dispersant, and according to the method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

The pigment dispersant is added to maintain the deagglomeration and stability of the pigment, and specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants. , These can be used individually or in combination of 2 or more types, respectively.

Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and Alkylaryl sulfonic acid salts, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines may be mentioned. there is.

In addition, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Commercial products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the acrylate-based dispersant may be used alone or in combination of two or more. can

As the pigment dispersant, other resin-type pigment dispersants may be used in addition to the acrylate-based dispersant. The other resin-type pigment dispersants include known resin-type pigment dispersants, particularly polycarboxylic acid esters represented by polyurethane and polyacrylate, 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.

Commercially available products of the other resin-type pigment 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 acrylate-based dispersants, other resin-type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylate-based dispersant.

The pigment dispersant may be included in an amount of 0 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 1 part by weight of the colorant. When the content of the pigment dispersant is included within the above range, a uniformly dispersed pigment may be obtained.

dyes

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 developing solution, heat resistance, and solvent resistance while having solubility in organic solvents.

As the dye, acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof may be used. Acid dyes of the system and their derivatives may also be selected. Preferably, the dyes include compounds classified as dyes in the color index (published by The Society of Dyers and Colourists) or known dyes described in dyeing notes (dyed yarns).

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

C.I. Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146 and 179;

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

C.I. Solvent Violet 8, 9, 13, 14, 36, 37, 47 and 49;

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

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

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

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

Also, C.I. as an acid dye

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 ; ,217,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,308,312,315,316,339,341,345,346,349 , 382, 383, 394, 401, 412, 417, 418, 422 and 426;

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 ;

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

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

C.I. Acid Violet 6B, 7, 9, 17, 19 and 66;

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

Among the C.I. acid dyes, C.I. Acid Red 92; C.I. Acid Blue 80, 90; and C.I. Acid Violet 60 are preferred because of their excellent solubility in organic solvents.

In addition, as a C.I. direct dye,

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

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138 and 141;

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

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

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

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

In addition, as a C.I. modanto dye,

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

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

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

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

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

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

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

The content of the dye in the colorant is 0.5 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 1 to 50% by weight based on the total weight of the solid content in the colorant. When the content of the dye in the colorant is within the above range, it is possible to prevent a problem of deterioration in reliability in which the dye is eluted by an organic solvent after pattern formation, and sensitivity can be increased.

The content of the colorant is 1 to 60% by weight, preferably 5 to 50% by weight, based on 100% by weight of the entire colored photosensitive resin composition. When the content of the colorant is within the above range, it is possible to form a pattern having sufficient color concentration and sufficient mechanical strength when manufacturing a color filter.

alkali soluble resin

The alkali-soluble resin usually has reactivity and alkali solubility by the action of light or heat, and acts as a colorant dispersion medium.

The alkali-soluble resin contained in the colored photosensitive resin composition of the present invention acts as a binder resin for a colorant, and is not particularly limited in kind, as long as it is a binder resin soluble in an alkaline developer used in the developing step for producing a color filter. All can be used.

The alkali-soluble resin may be, for example, a copolymer of a monomer containing a carboxyl group and another monomer copolymerizable with the monomer containing the carboxyl group.

Specific examples of the monomer containing a carboxyl group include unsaturated polycarboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids having at least one carboxyl group in a molecule. A carboxylic acid etc. are mentioned.

Specific examples of the unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.

Specific examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid.

The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride.

In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, specifically, for example, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacrylic acid) royloxyethyl), phthalic acid mono(2-acryloyloxyethyl), phthalic acid mono(2-methacryloyloxyethyl), and the like.

In addition, the unsaturated polyhydric carboxylic acid may be mono(meth)acrylate of a dicarboxy polymer at both terminals, specifically, for example, ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethaacrylate. A acrylate etc. are mentioned.

The monomers containing the carboxyl group may be used alone or in combination of two or more.

As other monomers copolymerizable with the monomer containing the carboxyl group, specifically, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxy Styrene, m-methoxy styrene, p-methoxy styrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycy Aromatic vinyl compounds, such as dil ether, p-vinylbenzyl glycidyl ether, and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl meth acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Rate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl Acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- unsaturated carboxylic acid esters such as phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate and polysiloxane have a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain. and macromonomers having These monomers can be used individually or in mixture of 2 or more types, respectively.

In addition, as the alkali-soluble resin, which is a copolymer of a monomer containing a carboxyl group and another monomer copolymerizable with the monomer containing the carboxyl group, specifically, for example, (meth)acrylic acid / methyl (meth)acrylate copolymer, ( meth)acrylic acid/benzyl (meth)acrylate copolymer, (meth)acrylic acid/2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate copolymer, (meth)acrylic acid/methyl (meth)acrylate/ Polystyrene macromonomer copolymer, (meth)acrylic acid/methyl (meth)acrylate/polymethyl (meth)acrylate macromonomer copolymer, (meth)acrylic acid/benzyl (meth)acrylate/polystyrene macromonomer copolymer, (metha)acrylate macromonomer copolymer, ) Acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer , (meth)acrylic acid/2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate/polymethyl (meth)acrylate macromonomer copolymer, (meth)acrylic acid/styrene/benzyl (meth)acrylate/ N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono(2-acryloyloxy)/styrene/benzyl(meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono(2- -Acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer and (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) Acrylate copolymer etc. are mentioned.

Among them, (meth)acrylic acid/benzyl (meth)acrylate copolymer, (meth)acrylic acid/benzyl (meth)acrylate/styrene copolymer, (meth)acrylic acid/methyl (meth)acrylate copolymer and (meth)acrylic acid /methyl (meth)acrylate/styrene copolymer can be preferably used.

When the alkali-soluble resin is a copolymer of a monomer containing a carboxyl group and another monomer copolymerizable with the monomer containing a carboxyl group, the monomer containing a carboxyl group is 10 to 50 weight percent based on 100% by weight of the total alkali-soluble resin. %, preferably 15 to 40% by weight, more preferably 25 to 40% by weight. When the monomer containing the carboxyl group is included within the above range, solubility in a developing solution is excellent, and a pattern can be accurately formed during development.

In addition, the alkali-soluble resin preferably has an acid value of 20 to 200 mgKOH/g. In the above acid value range, the solubility in the developing solution is improved so that the unexposed part is easily dissolved and the sensitivity may be increased, and as a result, a pattern of the exposed part remains during development, thereby improving the film remaining ratio.

The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titrating with an aqueous potassium hydroxide solution.

In addition, the weight average molecular weight in terms of polystyrene of the alkali-soluble resin measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) (hereinafter simply referred to as 'weight average molecular weight') is 3,000 to 200,000, preferably It is preferably 5,000 to 100,000. When the weight average molecular weight of the alkali-soluble resin is within the range of 3,000 to 200,000, the hardness of the coating film is improved, the remaining film rate is high, the solubility of the non-exposed part in the developing solution is excellent, and the resolution can be improved.

In the present invention, the alkali-soluble resin may be included in 1 to 80% by weight, preferably 3 to 70% by weight, based on 100% by weight of the entire colored photosensitive resin composition, and when the content of the alkali-soluble resin is within the above range, the pattern can be formed, and the resolution and remaining film rate can be improved.

photopolymerization monomer

The photopolymerizable compound, which is one of the colored photosensitive resin compositions of the present invention, must be a compound that can be polymerized by the action of a photopolymerization initiator described later.

As the photopolymerizable compound, a monofunctional monomer, a bifunctional monomer, or a multifunctional monomer may be used, preferably a bifunctional or higher functional monomer, and more preferably a pentagonal or higher functional multifunctional monomer, but is not limited thereto.

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

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

Specific examples of the multifunctional monomer 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 or dipentaerythritol hexa (meth) acrylate, but the like, but is not limited thereto.

The photopolymerizable monomer is included in 0.1 to 50% by weight, preferably 1 to 45% by weight, based on 100% by weight of the entire colored photosensitive resin composition of the present invention. When the photopolymerizable compound is included within the above range, strength or flatness of the pixel portion may be improved.

light polymerization initiator

The photopolymerization initiator preferably includes an acetophenone-based compound.

Specifically as the acetophenone-based compound, 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 and 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan- 1-one oligomers and the like, preferably 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and the like.

In addition, the photopolymerization initiator may be used by mixing an acetophenone-based compound and other types of photopolymerization initiators.

Other types of photopolymerization initiators include active radical generators, sensitizers and acid generators that generate active radicals by irradiation with light.

Specific examples of the active radical generating agent include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds.

Specific examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoisobutyl ether.

Specific examples of the benzophenone-based compound include benzophenone, o-benzoylmethylbenzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'- tetra(t-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; and the like.

Specifically as the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1- Chloro-4-propoxythioxanthone etc. are mentioned.

Specifically as the triazine-based compound, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloro Methyl)-6-(4-methoxynaphthyl)-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 (trichloro) Romethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethyl amino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4dimethoxyphenyl)ethenyl]-1, 3,5-triazine etc. are mentioned.

Specifically as the sensitizer, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl -1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate and titanocene compounds etc. can be used.

The acid generator specifically includes, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p- Toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfo nate, onium salts such as diphenyliodonium and hexafluoroantimonate, nitrobenzyl tosylate, and benzoin tosylate; and the like.

In addition, as the active radical generator, some of the compounds generate an acid simultaneously with active radicals. For example, a triazine-based photopolymerization initiator may also be used as an acid generator.

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

In the present invention, the photopolymerization initiator may be included in 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on 100% by weight of the entire colored photosensitive resin composition, and when included within the above range, the colored photosensitive resin composition is highly sensitive The exposure time is shortened, and thus productivity can be improved and high resolution can be expected.

Further, in the present invention, a photopolymerization initiator may be used in addition to the photopolymerization initiator.

The photopolymerization initiation adjuvant is a compound used to promote polymerization of a photopolymerizable compound whose polymerization is initiated by a photopolymerization initiator, and examples of the photopolymerization initiation adjuvant include amine compounds and alkoxyanthracene-based compounds.

Specifically as the amine compound, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-benzoic acid Dimethylaminoethyl, 4-dimethylaminobenzoic acid, 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis( Diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable.

Specifically as the alkoxy anthracene-based compound, for example, 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene and 2-ethyl-9,10-die Toxianthracene etc. are mentioned.

In addition, commercially available photopolymerization initiation adjuvants can be used, and commercially available photopolymerization initiation adjuvants include "EAB-F" (manufacturer: Hodogaya Chemical Industry Co., Ltd.) and the like.

When the photopolymerization initiator and the photopolymerization initiation aid are mixed and used, preferred combinations specifically include, for example, diethoxy acetophenone and 4,4'-bis(diethylamino)benzophenone; 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and 4,4′-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-phenylpropan-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one and 4,4'-bis(diethylamino)benzophenone; 1-hydroxycyclohexylphenylketone and 4,4'-bis(diethylamino)benzophenone; oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one and 4,4'-bis(diethylamino)benzophenone; combinations of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 4,4'-bis(diethylamino)benzophenone; It is a combination of 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and 4,4′-bis(diethylamino)benzophenone.

In the case of using the photopolymerization initiation auxiliary agent, it is generally preferable to use it in an amount of 0.01 to 5 moles based on 1 mole of the photopolymerization initiator, and when included within the above range, the sensitivity of the colored photosensitive resin composition is higher, and the colored photosensitive resin composition Productivity of a color filter formed using the color filter may be improved.

solvent

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

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, etc. are mentioned.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 -Methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate; and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene and mesitylene.

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

Examples of the amides include dimethylformamide (DMF) and N-methyl-2-pyrilidone (NMP).

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

As the solvent, it is preferable to use an organic solvent having a boiling point of 100 to 200° C. in terms of coating and drying properties, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and 3-ethene. Ethyl oxypropionate, methyl 3-methoxypropionate, etc. are mentioned.

The solvent is included in 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition, and when included within the above range, a roll coater, spin coater, slit and spin coater, slit coater (die coater) Sometimes referred to as) and when applied with an inkjet or other coating device, coating properties can be improved.

additive

The additives may be selectively added as needed, and may include, for example, at least one selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents. there is.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane, and the like. can be heard

The curing agent is used for deep curing and increasing mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, noblock type epoxy resins, other aromatic epoxy resins, and alicyclic epoxy resins. , glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of the above epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxides, isoprene ( co)polymer epoxides, glycidyl (meth)acrylate (co)polymers, and triglycidyl isocyanurate; and the like.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with the curing agent.

Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. The polyhydric carboxylic acid anhydrides may be commercially available as epoxy resin curing agents. Examples of commercially available products include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Ricasiddo HH (manufactured by Nippon Ewha Co., Ltd.), and MH-700 (manufactured by Shinnippon Ewha Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film formation of the colored photosensitive resin composition, and silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactants, and the like may be preferably used.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Dow Corning Toray Silicon as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, and TSF of GE Toshiba Silicone. -4460 and TSF-4452.

Examples of the fluorine-based surfactant include Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink & Chemicals Kogyo Co., Ltd. as commercial products.

In addition, commercial products that can be used are KP (Shin-Etsu Chemical High School Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products), Megafac (MEGAFAC) (Dinippon Ink Kagaku High School Co., Ltd.), Flourad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) , EFKA (EFKA Chemicals), PB 821 (Ajinomoto Co., Ltd.) and Disperbyk-series (BYK-chemi).

The surfactants exemplified above may be used alone or in combination of two or more, respectively.

The type of adhesion promoter is not particularly limited, and specific examples of usable adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl) )-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. are mentioned.

The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on 100% by weight of the total solid content in the red photosensitive resin composition.

The type of the antioxidant is not particularly limited, but examples thereof include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol. .

The type of the ultraviolet absorber is not particularly limited, but specific examples that can be used include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyriazole, alkoxybenzophenone, and the like. .

The type of the aggregation inhibitor is not particularly limited, but specific examples that can be used include sodium polyacrylate and the like.

In addition to this, the colored photosensitive resin composition according to the present invention may further contain additives such as other polymer compounds, curing agents, surfactants, adhesion accelerators, antioxidants, ultraviolet absorbers, and anti-aggregation agents, and the additives achieve the effects of the present invention. A person skilled in the art can appropriately add and use it within a range that does not interfere.

<Color filter>

The present invention relates to a color filter manufactured using a colored photosensitive resin composition.

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 a color filter is positioned, such as a display device, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), 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 may be formed by performing a method commonly known in the art.

The color filter including the substrate and the pattern layer as described above may further include barrier ribs formed between each pattern, and may further include a black matrix, but is not limited thereto.

In addition, a protective film formed on an upper portion of the pattern layer of the color filter may be further included.

<Image display device>

In addition, another aspect of the present invention relates to an image display device including the color filter described above.

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 can exhibit high luminance due to excellent light efficiency, excellent color reproducibility, and high contrast.

Hereinafter, examples will be described in detail in order to specifically describe the present specification. However, the embodiments according to the present specification may be modified in many different forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present specification to those skilled in the art. In addition, "%" and "parts" indicating content below are based on weight unless otherwise specified.

Example 1: silicone compound 1

322 g of TEGOMER 2315 (hydroxidized polydimethylsiloxane), 167 g of chloroethanol, and 0.2 g of butyl tin laurate were added to a mechanical stirrer, a temperature sensor, and a heating device connected to the temperature sensor in a three-necked reactor and stirred at room temperature. At this time, 8 g of Rad2500, an antifoaming agent, was added dropwise to suppress foam generation, and the reaction temperature was maintained at 75° C. and reacted for 3 hours. After the reaction was completed, the reaction temperature was cooled to room temperature, 150 g of NaOH and 290 g of epichlorohydrin were mixed, 8 g of Rad2500 was added dropwise, reacted at a reaction temperature of 95 ° C for 3 hours, and then dried in a drying oven at 150 ° C for 5 hours. To prepare an epoxy resin from which moisture was removed. After the reaction was completed, the reaction temperature was cooled to room temperature, and the reaction was confirmed. The IR epoxy peak (910 cm ^{-1 )} increased and the -OH peak of the diol decreased. The reaction was terminated by measuring the acid value until it was 2 mgKOH/g resin or less. The reaction formula is described below.

Example 2: silicone compound 2

304 g of TEGOMER 2315 (hydroxidized polydimethylsiloxane), 185 g of chloropropanol, and 0.2 g of dibutyltin laurate were added to a mechanical stirrer, a temperature sensor, and a heating device connected to the temperature sensor in a three-necked reactor, followed by stirring at room temperature. At this time, 8 g of Rad2500, an antifoaming agent, was added dropwise to suppress foam generation, and the reaction temperature was maintained at 75° C. and reacted for 3 hours. After the reaction was completed, the reaction temperature was cooled to room temperature, 150 g of NaOH and 290 g of epichlorohydrin were mixed, 8 g of Rad2500 was added dropwise, reacted at a reaction temperature of 95 ° C for 3 hours, and then dried in a drying oven at 150 ° C for 5 hours. To prepare an epoxy resin from which moisture was removed. After the reaction was completed, the reaction temperature was cooled to room temperature, and the reaction was confirmed. The IR epoxy peak (910 cm ^{-1 )} increased and the -OH peak of the diol decreased. The reaction was terminated by measuring the acid value until it was 2 mgKOH/g resin or less. The reaction scheme is described below.

Example 3: silicone compound 3

322 g of TEGOMER 2315 (hydroxidized polydimethylsiloxane), 167 g of chloroethanol, and 0.2 g of dibutyl tin laurate were added to a mechanical stirrer, a temperature sensor, and a heating device connected to the temperature sensor in a three-necked reactor, followed by stirring at room temperature. At this time, 8 g of Rad2500, an antifoaming agent, was added dropwise to suppress foam generation, and the reaction temperature was maintained at 75° C. and reacted for 3 hours. After the reaction was completed, the reaction temperature was cooled to room temperature, 150 g of NaOH and 650 g of 2,3:5,6-dianhydro-1-bromo-1-deoxy-D-glucitol were mixed, and 8 g of Rad2500 was added dropwise to the reaction temperature. After reacting at 95 ℃ for 3 hours, dried in a 150 ℃ drying oven for 5 hours to prepare an epoxy resin from which moisture was removed. After the reaction was completed, the reaction temperature was cooled to room temperature, and the reaction was confirmed. The IR epoxy peak (910 cm ^-1 ) increased and the -OH peak of the diol decreased ^. The reaction was terminated by measuring the acid value until it was less than 2mg KOH/g resin. The reaction scheme is described below.

Preparation of colored photosensitive resin composition

Colored photosensitive resin compositions according to Examples 4 to 9 and Comparative Examples 1 to 7 were prepared according to the compositions shown in Table 1 below.

division Example comparative example 4 5 6 7 8 9 One 2 3 4 5 6 7 coloring agent A-1 3.23 A-2 0.78 alkali soluble resin B 4.05 4.29 4.05 4.29 4.05 4.29 4.05 4.29 4.05 4.29 4.05 4.29 4.29 silicone compound C-1 1.69 4.49 - - - - 0.67 5.03 - - - - - C-2 - - 1.69 4.49 - - - - 0.67 5.03 - - - C-3
- - - - 1.69 4.49 - - - - 0.67 5.03 - photopolymerizable monomer D 4.88 1.69 4.88 1.69 4.88 1.69 5.90 1.15 5.90 1.15 5.90 1.15 6.18 photopolymerization initiator E 0.88 solvent F 84.09 84.24 84.09 84.24 84.09 84.24 84.09 84.24 84.09 84.24 84.09 84.24 84.24 additive G-1 0.1 G-2 0.1 G-3 0.2 A-1: CI Pigment Green 7
A-2: CI Pigment Yellow 138
B: Copolymer of methacrylic acid and benzyl methacrylate (molar ratio of methacrylic acid unit to benzyl methacrylate unit is 31:69, acid value is 100 mgKOH/g, weight average molecular weight in terms of polystyrene is 20,000)
C-1: Silicone compound 1 of Example 1
C-2: Silicone compound 2 of Example 2
C-3: Silicone compound 3 of Example 3
D: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
E: 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical)
F: propylene glycol monomethyl ether acetate
G-1: Surfactant (SH-8400 manufactured by Toray Silicone)
G-2: Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Kagaku Kogyo Co., Ltd.)
G-3: Adhesion enhancer (3-methacryloxypropyltrimethoxysilane)

color filter ( Glass substrate ) manufacturing example

Color filters were prepared using the colored photosensitive resin compositions prepared in Examples 4 to 9 and Comparative Examples 1 to 7. That is, each of the colored photosensitive resin compositions was applied on a glass substrate (#1737, manufactured by Corning Co.) by spin coating, and then placed on a heating plate and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a pattern that varies stepwise in a transmittance range of 1 to 100% is placed on the thin film, the distance between the test photomask and the test photomask is set to 1000 μm, and an ultra-high pressure mercury lamp (USH-250D, Ushio Denki ( Note) was irradiated with light at an exposure amount (365 nm) of 40 mJ/cm 2 in an air atmosphere using (manufactured by). The thin film irradiated with ultraviolet rays was developed for 80 seconds using a spray developer in a developing solution of KOH aqueous solution having a pH of 12.5. The glass substrate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220° C. for 20 minutes to prepare a color filter. The pattern shape (thin film) thickness of the manufactured color filter was 1.9 to 2.1 μm.

Sensitivity evaluation

During the manufacturing process of the color filter, sensitivity, which is the minimum exposure amount (mJ/cm 2 ) required to form a thin film without tearing of the pattern after development, was measured. The evaluation criteria are as follows, and the results are shown in Table 2 below.

<Sensitivity Evaluation Criteria>

○ (Excellent): 30 mJ/cm ² below

Δ (good): 30 to 40 mJ/cm ²

× (poor): greater than 40 mJ/cm ²

Adhesion evaluation

Adhesion evaluation was performed by incising the fabricated substrate into 100 matrix structures within an area of 10 × 10 mm, then attaching a tape thereon and measuring the number of matrices separated while strongly releasing vertically. The evaluation criteria are as follows, and the results are shown in Table 2 below.

<Adhesion Evaluation Criteria>

○ (excellent): less than 5

△ (good): 5 to 15

× (bad): more than 15

development stain evaluation

To evaluate development stains, the colored photosensitive resin composition prepared according to Examples and Comparative Examples was applied on a glass substrate (#1737, manufactured by Corning Co.) by spin coating, then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. has formed Subsequently, light was irradiated with an exposure amount (365 nm) of 40 mJ/cm ² in an air atmosphere using an ultra-high pressure mercury lamp (USH-250D, manufactured by Ushio Denki Co., Ltd.). The thin film irradiated with ultraviolet rays was developed for 80 seconds using a spray developer in a developing solution of KOH aqueous solution having a pH of 12.5. The glass substrate coated with the thin film was washed with distilled water, then a small amount of distilled water was dropped on the thin film dried by blowing nitrogen gas to maintain its original shape, left at room temperature for 2 minutes, and then dried by blowing nitrogen gas. Subsequently, the substrate was irradiated with a Na lamp and the surface state of the coating film was observed to visually determine whether or not circular stains were generated, and evaluated according to the following criteria, and the results are shown in Table 2 below.

<Development stain evaluation criteria>

○ (Excellent): Circular water stains are not recognized on the surface of the coating film

△ (Good): Fine circular water stains were recognized on the surface of the coating film

× (defect): Circular water stains are clearly recognized on the surface of the coating film

solvent resistance evaluation

For evaluation of solvent resistance, the prepared substrate was cut into 3 × 3 cm, and then immersed in 14.6 mL of NMP solution at a temperature of 80 ° C. for 40 minutes. After that, the solution was evaluated for absorbance with a UV-Vis spectrometer, and the results are shown in Table 2 below.

○ (Excellent): Absorbance 0.5 or less

△ (good): absorbance 0.5 to 1.0

× (poor): absorbance greater than 1.0

Permittivity evaluation

For dielectric constant evaluation, dielectric constant was measured using a Precision Impedance Analyzer (LCMS-200) after forming an Al electrode on the specimen using a thermal evaporator.

The results are shown in Table 2 below.

○ (excellent): 3.5 or less

Δ (good): 3.5 to 4.0

× (poor): more than 4.0

Sensitivity adhesion developing stain solvent resistance permittivity Example 4 ○ ○ △ △ 3.7 Example 5 ○ ○ ○ ○ 3.3 Example 6 △ △ △ △ 3.7 Example 7 ○ ○ ○ ○ 3.4 Example 8 ○ ○ △ △ 3.6 Example 9 ○ ○ ○ ○ 3.2 Comparative Example 1 × × △ × 4.0 Comparative Example 2 × ○ ○ ○ 3.2 Comparative Example 3 × × △ × 4.1 Comparative Example 4 × ○ ○ △ 3.2 Comparative Example 5 × × △ × 4.0 Comparative Example 6 × △ ○ ○ 3.1 Comparative Example 7 × × × × 4.4

Referring to Table 2, the colored photosensitive resin compositions of Examples 4 to 9 containing the silicone compound according to the present invention showed excellent sensitivity compared to the colored photosensitive resin composition of Comparative Example 7 without the silicone compound, while exhibiting excellent adhesion and development. It can be confirmed that stain and solvent resistance are good, and have a low permittivity, and a color filter of excellent quality can be manufactured.

Claims (4)

A silicone compound represented by Formula 1 below:
[Formula 1]

(In Formula 1,
R ₁ is each independently hydrogen or an alkyl group having 1 to 5 carbon atoms;
R ₂ are each independently a ring-opened product of an alkylene group having 2 to 20 carbon atoms or an alkylene oxide group having 2 to 10 carbon atoms including an ester bond;
R ₃ is an alkylene group having 1 to 20 carbon atoms substituted with an epoxy group or interposed with an epoxy group, unsubstituted or substituted with a hydroxy group,
a and b are independently integers from 1 to 10,
n is an integer from 1 to 20). The silicone compound of claim 1; and
It includes at least one selected from the group consisting of a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a solvent, and an additive, and the silicone compound is present in an amount of 1 to 5% by weight based on 100% by weight of the entire colored photosensitive resin composition including the same. Colored photosensitive resin composition, characterized in that contained in %. A color filter comprising a cured product of the colored photosensitive resin composition of claim 2. An image display device comprising the color filter of claim 3.