KR20140001522A - A colored photosensitive resin composition for color filter, color filter and liquid crystal display device having the same - Google Patents

Abstract

This invention is a coloring photosensitive resin composition containing a coloring agent (A), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), The said photopolymerizable compound (C) is a molecule | numerator A colored photosensitive resin composition comprising a photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI), glycol, and dipentaerythritol hexaacrylate (DPHA) in a solvent. It is about.

Description

Color photosensitive resin composition for color filter, color filter and liquid crystal display device having the same {A COLORED PHOTOSENSITIVE RESIN COMPOSITION FOR COLOR FILTER, COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE HAVING THE SAME}

The present invention relates to a colored photosensitive resin composition for color filters, a color filter, and a liquid crystal display device having the same.

 A color filter can be embedded in a color imaging device of an image sensor, such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD), and can be used to actually obtain a color image (PDP), a liquid crystal display (LCD), a field emission display (FEL), and a light emitting display (LED), and the application range thereof is rapidly expanding. In particular, in recent years, the use of LCD has been further expanded, and thus color filters have been recognized as one of the most important parts in reproducing the color tone of LCDs.

Such a color filter is manufactured by the method of forming a desired coloring pattern using the coloring photosensitive resin composition containing a coloring agent. Specifically, it is produced by forming a coating layer made of a colored photosensitive resin composition on a substrate, repeating a series of processes of forming a pattern on the formed coating layer, exposing and developing, heating and thermosetting.

In recent years, the pigment concentration of the colored photosensitive resin composition used in the production of a color filter has been continuously increasing to attain a high color purity. In order to improve productivity and yield in the process, a high developing speed and a low sensitivity There is a demand for a colored photosensitive resin composition having reliability.

On the other hand, it was tried to use the resin composition which further contains an adamantane derivative for the conventional coloring photosensitive resin composition. The resin compositions of Republic of Korea Patent Application Publication No. 10-2009-0085031 and Republic of Korea Patent Publication No. 10-2010-0095516 contain adamantane derivatives, which include optical properties such as transparency and light resistance, durability such as long-term heat resistance and etching resistance, In addition, although it has advantages in dielectric constant and the like, when a pigment and a dye are included together, the development speed becomes slow, problems in sensitivity and adhesion may occur, and thus peeling of the pattern may occur during the development process. There is a problem that the fairness is poor.

Republic of Korea Patent Publication No. 10-2009-0085031 Republic of Korea Patent Publication No. 10-2010-0095516

In order to solve the above problems, the present invention is a photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI, Methylene diphenyl diisocyanate), glycol and dipentaerythritol hexaacrylate (DPHA) It is an object to provide the coloring photosensitive resin composition which is excellent in a sensitivity and adhesiveness, there is no peeling of a pattern during the image development process, and is excellent in pattern straightness.

This invention is a coloring photosensitive resin composition containing a coloring agent (A), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), The said photopolymerizable compound (C) is a molecule | numerator A colored photosensitive resin composition comprising a photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI), glycol, and dipentaerythritol hexaacrylate (DPHA) in a solvent. To provide.

The colored photosensitive resin composition of this invention has the process characteristic which is excellent in a sensitivity and adhesiveness, there is no peeling of a pattern during a developing process, and an error on a pattern does not appear. Therefore, the colored photosensitive resin composition may be usefully used for the production of color filters and liquid crystal display devices of excellent quality.

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

This invention is a coloring photosensitive resin composition containing a coloring agent (A), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), The said photopolymerizable compound (C) is a molecule | numerator A colored photosensitive resin composition comprising a photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI), glycol, and dipentaerythritol hexaacrylate (DPHA) in a solvent. To provide.

More specifically, the colored photosensitive resin composition, based on the total weight of solids in the colored photosensitive resin composition, 20 to 60% by weight of the colorant (A), 10 to 30% by weight of the alkali-soluble resin (B), the photopolymerizable compound ( C) 1 to 10% by weight and 0.5 to 5% by weight of the photopolymerization initiator (D),

It is preferable to contain 30 to 60 weight% of a solvent (E) with respect to the total weight of colored photosensitive resin composition.

The components of the present invention will be described in more detail.

The colorant (A)

The colorant (A) contained in the coloring photosensitive resin composition of this invention is not limited in color tone, It can select according to the use of the color filter manufactured using the coloring photosensitive resin composition. Specifically, any one or a mixture of two or more of pigments, dyes or natural pigments, more preferably the colorant (A) may comprise at least one pigment (a1) and may comprise at least one dye (a2). have.

Pigments a1 )

The pigment may be an organic pigment or an inorganic pigment generally used in the art. The above-mentioned pigments can be used in various kinds of pigments used in printing ink, ink jet ink and the like. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, And an anthanthrone pigment, an anthanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or composite metal oxides. In particular, the organic pigments and inorganic pigments include compounds that are specifically classified as pigments in the color index (Published by The society of Dyers and Colourists), and more specifically, the color index (CI) number of Although a pigment is mentioned, It is not necessarily limited to these.

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, 215, 216, 224, 242, 254, 255 and 264

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

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

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

C.I Pigment Brown 28

CI Pigment Black 1 and 7 etc

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

Among the CI pigment pigments exemplified above, CI Pigment Orange 38, CI Pigment Red 122, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 208, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Pigments selected from cement violet 23, CI pigment blue 15: 3, pigment blue 15: 6 can be used more preferably.

The content of the pigment (a1) is in the range of 20 to 90% by mass, preferably 30 to 70% by mass with respect to the total solid content in the pigment dispersion composition. When the content of the pigment is in the range of 20 to 90% by mass, the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, which is effective for increasing the contrast ratio.

Pigment dispersants ( a3 )

It is preferable to use the pigment dispersion liquid which the said particle size disperse | distributed uniformly. An example of a method for uniformly dispersing the particle size of the pigment is a method of containing and dispersing the pigment dispersant (a3). According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. have.

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

As the pigment dispersant (a3), other resin type pigment dispersants other than the acrylic dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine 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 ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters. DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-160, BYK (trade name) 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF brand name: 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: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical's trade names: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Trade names of Ajinomoto Co., Ltd .: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; The brand names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, etc. are mentioned. In addition to the acrylic dispersant described above, pigment dispersants of other resin types may be used alone or in combination of two or more, or may be used in combination with an acrylic dispersant.

The use amount of the pigment dispersant (a3) is in the range of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1) used. When the content of the pigment dispersant (a3) exceeds 60 parts by weight based on the above standard, the viscosity may be increased. When the amount of the pigment dispersant (a3) is less than 5 parts by weight, it may be difficult to atomize the pigment or may cause problems such as gelation after dispersion.

Dye (a2)

The dye (a2) can be used without limitation so long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility, heat resistance and solvent resistance in an alkaline developer.

The dye (a2) may be selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof, and azo and xanthene compounds. And phthalocyanine-based acid dyes and derivatives thereof can also be selected. Preferably, the dye may be a compound classified as a dye in the color index (Published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (color dyed yarn).

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

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

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

C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49 and the like;

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

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

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

C.I. C.I. excellent solubility in organic solvents in solvent dyes. Solvent red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferred, of which C.I. Solvent Red 8, 122 and 132 are more preferred.

Also, C.I. As an acid dye

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

CI 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 Yellow dyes such as, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251

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

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

Violet dyes such as C.I.acid violet 6B, 7, 9, 17, 19, 66, etc.

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

C.I. Acid Red 92 with good solubility in organic solvents in acid dyes; C. I. Acid Blue 80, 90; C.I. acid violet 66 is preferred.

Also as a C.I. direct dye,

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

CI 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 , Yellow dyes such as 136, 138, and 141;

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

CI 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, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 Blue dyes such as, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc .;

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.

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

CI Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

CI Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes;

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

Violet colored dyes such as C.I. Modanth 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, etc. are mentioned.

These dyes can be used individually or in combination of 2 or more types, respectively.

It is preferable that 0.5-80 weight% is contained with respect to the total weight of solid content in a coloring agent (A), 0.5-60 weight% is more preferable, and, as for the content of the dye in the said coloring agent (A), 1-50 weight% is especially preferable. Do. When the content of the dye in the coloring agent (A) is in the above range on the basis of the above standard, it is possible to prevent the problem of lowering the reliability that the dye is eluted by the organic solvent after the pattern formation, it is preferable because the sensitivity is excellent.

The content of the coloring agent (A) may be included in 20 to 60% by weight, preferably 25 to 55% by weight, more preferably 25 to 40% by weight based on the total weight of solids in the color photosensitive resin composition. . In the case where the coloring agent (A) is included at 20 to 60% by weight based on the above standard, even if a thin film is formed, the color density of the pixel is sufficient, and residues are unlikely to occur because the omission of the non-pixel portion during development is not reduced. desirable.

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

Alkali-soluble resin (B)

Alkali-soluble resin (B) included in the colored photosensitive resin composition of the present invention serves to remove the non-exposed areas of the colored photosensitive resin layer formed by using the colored photosensitive resin composition during the development process during the photoresist process. Any one commonly used in the art can be used.

As said alkali-soluble resin (B), the copolymer with a carboxyl group-containing monomer and the other monomer copolymerizable with this monomer, etc. are mentioned, for example.

 As said carboxyl group-containing monomer, For example, unsaturated monocarboxylic acid, unsaturated carboxylic acid, such as unsaturated polyhydric carboxylic acid which has one or more carboxyl groups in molecules, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, etc. are mentioned. Can be mentioned.

Here, as said unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxy Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have. These carboxyl group-containing monomers may be used alone or in combination of two or more.

As another monomer copolymerizable with the said carboxyl group-containing monomer, For example, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro styrene, o-methoxy styrene, m-meth Oxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Relate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol meta Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadier Nylacrylate, dicyclopentadiethyl methacrylate, 2-hydroxy Unsaturated carboxylic acid esters such as 3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylamino ethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as dimethylaminopropyl 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,? -Chloroacrylonitrile, and vinylidene cyanide;

Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide;

Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

Polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polysiloxane Macromonomers; and the like. These monomers may be used alone or in combination of two or more.

The content of the carboxyl group-containing monomer unit in the alkali-soluble resin (B) is 10 to 50% by weight, preferably 15 to 40% by weight, more preferably 25 to 40% by weight. If the content of the carboxyl group-containing monomer unit is 10 to 50% by weight, the solubility in the developer is good and the pattern during development tends to be formed accurately, which is preferable.

Examples of the alkali-soluble resin include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2- (Meth) acrylate / benzyl (meth) acrylate copolymer, a (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, Acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, Acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxy Acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer / styrene / benzyl (Meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer.

Of these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl / Methyl (meth) acrylate / styrene copolymer is preferably used.

The acid value of the alkali-soluble resin of the present invention is in the range of 20 to 200 (KOH mg / g). When the acid value is in the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion 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 titration using an aqueous potassium hydroxide solution.

The weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") in terms of polystyrene measured by gel permeation chromatography (GPC; tetrahydrofuran as an eluting solvent) is 3,000 to 200,000, preferably 5,000 to 100,000 Alkali-soluble resins are preferable. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution tends to be improved.

The alkali-soluble resin (B) of the present invention is preferably contained in 10 to 30% by weight, more preferably in 12 to 16% by weight based on the total weight of the solid content of the color photosensitive resin composition for color filters. A pattern can be formed in it being the said range, and since it is a tendency for the resolution and the residual film rate to improve, it is preferable.

Photopolymerization  The compound (C)

The photopolymerizable compound (C) included in the colored photosensitive resin composition of the present invention is a compound which can be polymerized by an active radical, an acid, etc. generated from the photopolymerization initiator (D) by irradiation with light, for example, a carbon-carbon unsaturated bond. It may be a compound having. In the present invention, in particular, the photopolymerizable compound (C) is reacted with methylene diphenyl diisocyanate (MDI, Methylene diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate), glycol and dipentaerythritol hexaacrylate (DPHA) in the molecule. It is preferable to include the photopolymerizable compound (C-1) manufactured.

The photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI, Methylene diphenyl diisocyanate), glycol and dipentaerythritol hexaacrylate (DPHA) in the molecule can be seen as an oligomer, and methylene di Molecular structures of phenyl diisocyanate (MDI, Methylene diphenyl diisocyanate), glycol and dipentaerythritol hexaacrylate (DPHA) are present in the oligomeric structure. When using a photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI, Methylene diphenyl diisocyanate), glycol and dipentaerythritol hexaacrylate (DPHA) in the molecule, the amount is lower than that of the prior art. Also, the coloring photosensitive resin composition excellent in the sensitivity and adhesiveness can be manufactured.

The photopolymerizable compound (C) has an acid value in the range of 10 to 80 KOHmg / g, and includes a urethane bond in the main chain, more preferably having 6 to 12 acrylic functional groups. When the acid value of the photopolymerizable compound (C) is less than 10 KOHmg / g, the developing speed of the color photosensitive resin composition for color filters drops sharply, and when the acid value exceeds 80 KOHmg / g, the sensitivity at the time of development decreases, so that at a small exposure amount, This is because a pattern cannot be formed.

In addition, the urethane bond in the compound may be included in any position in the molecule, but is preferably included in the main chain (main chain), the number of the acrylic functional group is not particularly limited, but the main chain in the number of 6 to 12 It is more preferable to be included in a part or the end of.

The photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI), glycol and dipentaerythritol hexaacrylate (DPHA) in the molecule contains a compound having a glycol and an isocyanate group having two hydroxyl groups. It can be prepared by reacting a polymolecule urethane compound and reacting the polyfunctional acrylate containing a hydroxyl group thereto.

Compounds having two hydroxyl groups include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propanediol, butanediol, hexanediol, methylpropanediol, neopentylglycol and butyl Preferably, one or two or more selected from the group consisting of ethyl propanediol, and the two hydroxyl groups are preferably located at the sock end.

In addition, the compound having an isocyanate group is preferably diisocyanate, for example, toluene diisocyanate, xylene diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, tetramethyl xylene diisocyanate, hexane diisocyanate, iso It is preferable that it is 1 type (s) or 2 or more types chosen from the group which consists of poron diisocyanate and cyclohexyl methylene diisocyanate.

In addition, the polyfunctional acrylate containing a hydroxyl group is one or a mixture of two or more selected from pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate Is preferably. As used herein, (meth) acrylate means acrylate and / or methacrylate.

The photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI, Methylene diphenyl diisocyanate), diethylene glycol and dipentaerythritol hexaacrylate (DPHA) in the molecule is diethylene glycol and MDI. It is more preferable that it is made by making it react, and synthesize | combining a medium molecular urethane compound, and making it react with dipentaerythritol hexaacrylate (DPHA).

The photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI), glycol and dipentaerythritol hexaacrylate (DPHA) in the molecule is 5 parts by weight based on 100 parts by weight of the photopolymerizable compound (C). It is preferably included in an amount of 100 to 100 parts by weight, and more preferably 20 to 80 parts by weight. 5 to 100 parts by weight of the photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI), glycol and dipentaerythritol hexaacrylate (DPHA) in the above is excellent in sensitivity and resolution. Even in a composition containing a colored body (A) at a high concentration, sufficient pattern shape can be obtained, and it is possible to manufacture a photosensitive resin composition excellent in straightness and the like without pattern tearing during development.

In addition, the photopolymerizable compound (C) of the present invention is a diphentaerythritol hexaacrylate (DPHA), dipentaerythritol polyacrylate (Dipentaerythritol polyacrylate), polyethoxylated pentaerythritol tet r aacrylate, It may further comprise one or two or more selected from the group consisting of ethoxylated pentaerythritol tetraacrylate and dipentaerythritol tetraacrylate.

The photopolymerizable compound (C) is preferably included in 1 to 10% by weight, more preferably 2 to 8% by weight based on the total weight of solids in the colored photosensitive resin composition. Within this range, a sufficient pattern shape can be obtained even in a composition containing the colorant (A) at a high concentration with excellent sensitivity and resolution, and excellent photosensitive resin composition can be prepared without tearing the pattern during the development process.

Photopolymerization Initiator (D)

As long as it can superpose | polymerize the said photopolymerizable compound (C) and the said alkali-soluble resin (B), the photoinitiator (D) contained in this invention can be used without a restriction | limiting in particular. In particular, the photopolymerization initiator (D) is acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, triazine-based, oxime-based, onium salt-based in terms of polymerization characteristics, starting efficiency, absorption wavelength, availability, price, etc. It is preferable to contain at least 1 sort (s) of compound chosen from nitrobenzyl tosylate system or benzointosylate system, and a light stabilizer can be used together.

Preferred examples of the acetophenone compound in the present invention include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- 2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl Ketone and oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan- Methylthiophenyl) propan-1-one are more preferable. It is also possible to use a combination of a plurality of acetophenone compounds and other photopolymerization initiators. Examples of the photopolymerization initiator other than the acetophenone-based compound include an active radical generator, a sensitizer, and an acid generator that generate an active radical by irradiating light.

Examples of the active radical generator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, triazine-based compounds, and oxime-based compounds. As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example. As said benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned. As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro, for example 4-propoxy city oxanthone etc. are mentioned. As said triazine type compound, 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- (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 Methyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino -2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3 , 5-triazine and the like. Examples of the oxime compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl-phenyl) -butane-1, 2-Butane-2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid Ethyl ester-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -ethyl acetate-O-benzoate, and the like.

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, phenylglyoxylate, titanocene compound and the like Can be mentioned.

As said acid generator, 4-hydroxyphenyl dimethyl sulfonium p-toluene sulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxy phenyl dimethyl sulfonium p-toluene, for example Sulfonate, 4-acetoxyphenylmethyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate And onium salts such as diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylates, benzointosylates and the like. Further, among these compounds, there are also compounds which simultaneously generate an active radical and an acid. For example, the triazine-based photopolymerization initiator can also be used as an acid generator. It is preferable that the photoinitiator of this invention is contained in 0.5 to 5 weight% with respect to the total weight of solid content of a coloring photosensitive resin composition, and it is more preferable to contain 0.5 to 3 weight%. When the content of the photopolymerization initiator is contained in 0.5 to 5% by weight, it is highly sensitive to shorten the exposure time, thereby improving productivity and maintaining high resolution.

The coloring photosensitive resin composition of this invention may further contain a photoinitiation adjuvant (d2). The photopolymerization start adjuvant (d2) may be used in combination with the photopolymerization initiator (d1), and is used to promote polymerization of the photopolymerizable compound in which polymerization is initiated by the photopolymerization initiator. An amine compound, an alkoxy anthracene type compound, a thioxanthone type compound etc. are mentioned as said photoinitiator starting adjuvant. Examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate and 2-dimethylamino benzoate. Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4 '-Bis (ethylmethylamino) benzophenone and the like can be given, and among these, 4,4'-bis (diethylamino) benzophenone is preferable. As an alkoxy anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene, for example. Etc. can be mentioned. As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-, for example 4-propoxy city oxanthone etc. are mentioned. Said photoinitiator can be used individually or in combination of 2 or more types. In addition, a commercially available product may be used as the photopolymerization start adjuvant, and commercially available photopolymerization start adjuvant includes, for example, EAB-F (product of Hodoga Yagaku Kogyo Co., Ltd.). As a combination of the photoinitiator and photoinitiator adjuvant which are preferable for the coloring photosensitive resin composition of this invention, diethoxy acetophenone / 4,4'-bis (diethylamino) benzophenone, 2-methyl- 2-morpholino-1 -(4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-phenylpropan-1-one / 4,4'-bis (Diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane-1-one / 4,4'-bis (diethylamino) benzo Phenone, 1-hydroxycyclohexylphenylketone / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 Oligomer / 4,4'-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'-bis Combinations of (diethylamino) benzophenone and the like, and more preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4'-ratio. There is a combination of s (diethylamino) benzophenone. When the photopolymerization initiator and the photopolymerization initiation aid are used together as described above, the photopolymerization initiation assistant is preferably used in an amount of 10 mol or less per mole of the photopolymerization initiator, and more preferably 0.01 to 5 mol. When the usage-amount of the said photoinitiator is in the said range, since the sensitivity of a coloring photosensitive resin composition becomes high and the productivity of the color filter formed using this composition improves, it is preferable.

Solvent (E)

As long as the solvent (E) is effective for dissolving other components contained in the colored photosensitive resin composition, a solvent used in a conventional colored photosensitive resin composition can be used without particular limitation, and in particular, an ether, an aromatic hydrocarbon, Alcohols, esters, amides and the like are preferable.

Specific examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Ethylene, such as diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, methyl cellosolve acetate, and ethyl cellosolve acetate Glycol alkyl ether acetates;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate;

Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

The solvent (E) is preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ in terms of applicability and dryness, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used.

The above-exemplified solvents (E) may be used alone or in combination of two or more, and may include 30 to 60% by weight, preferably 30 to 55% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. Can be. If the solvent (F) is in the range of 30 to 60% by weight as described above, the coating property becomes good when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (or die coater), inkjet, or the like. Provide effect.

Additive (F)

The coloring photosensitive resin composition of this invention may further contain an additive.

As the additive (F) can be selectively added as needed, for example, other polymer compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents and the like.

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 ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be mentioned.

The surfactant may be used to further improve the film formability of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF-4460 , And TSF-4452. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. The above-exemplified surfactants may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth And oxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter is preferably included in 0.01 to 10% by weight relative to the total weight in the solid content of the colored photosensitive resin composition, more preferably 0.05 to 2% by weight may be included.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

Method for producing colored photosensitive resin composition

The manufacturing method of the coloring photosensitive resin composition of this invention is demonstrated, for example as follows.

First, the pigment (a1) in the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, part or all of the pigment dispersant (a3), the alkali-soluble resin (B), or the dye (a2) can be mixed with the solvent (E) to dissolve or disperse.

In the mixed dispersion, a dye (a2), the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D) and, if necessary, the (F) additive and the (E) solvent are adjusted to a predetermined concentration. It can be further added and the coloring photosensitive resin composition which concerns on this invention can be manufactured.

The present invention also provides a color filter made of the colored photosensitive resin composition.

The color filter according to the present invention comprises a step of applying the solution of the colored photosensitive resin composition, applying the patterned exposure to a dry coating film obtained by pre-baking, and then developing the color filter, thereby obtaining a color of the coloring agent A pixel or a black matrix corresponding to the black matrix is obtained. In addition, the color filter can be obtained by repeating this process for the number of colors required for the color filter.

The construction and fabrication of color filters are well known in the art and can be used to make color filters.

The present invention relates to a liquid crystal display device including the color filter.

The liquid crystal display device includes a configuration known to those skilled in the art, except for having the color filter. That is, all of the liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is faced at predetermined intervals, and a liquid crystal material is injected into the gap to form a liquid crystal layer. Can be. There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer.

As another example, a liquid crystal display device including a TFT (Thin Film Transistor) substrate joined on a transparent electrode of a color filter, and a backlight fixed at a position where the TFT substrate overlaps the color filter. The TFT substrate includes an outer frame made of a light-proof resin surrounding the peripheral surface of the color filter, a liquid crystal layer made of a nematic liquid crystal placed in the outer frame, a plurality of pixel electrodes , A transparent glass substrate on which pixel electrodes are formed, and a polarizing plate formed on the exposed surface of the transparent glass substrate.

Hereinafter, the present invention will be described in more detail with reference to examples and test examples. Since these examples and test examples are only for illustrating the present invention, the scope of the present invention is not construed as being limited by these examples and test examples.

Synthetic example  One. Photopolymerization  Compound synthesis

64.4 parts by weight MDI (Kumho Mitsui Chemicals, Methylene diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate), 13.6 parts by weight of diethylene glycol, catalyst 0.6 parts by weight of dibutyltin laurate (Akema, FASCAT 4202) was added and reacted at 75 ° C. for 2 hours. At this time, NCO% was 8.5%. 438.5 parts by weight of dipentaerythritol / hexaacrylate (Nihon Kayaku Co., KAYARD DPHA) was added thereto and reacted at 100 ° C. for 9 hours to terminate the reaction when 2260 kaiser, a characteristic peak of isocyanate on the infrared spectroscopy spectrum, disappeared.

Example  1, 2, and Comparative Example  1, 2. Production of colored photosensitive resin composition for color filters

In Example 1 and Example 2 was mixed and dispersed in the photopolymerizable compound prepared in Synthesis Example 1 with the components and compositions as shown in Table 1 below to prepare a color photosensitive resin composition for color filters according to the present invention. . In addition, Comparative Example 1 and Comparative Example 2 to prepare a colored photosensitive resin composition according to the known technology.

(Unit: parts by weight) Example 1 Example 2 Comparative Example 1 Comparative Example 2 The colorant (A) (A-1) 3.81 3.89 3.81 3.89 Alkali-soluble resin (B) (B-1) 2.12 2.05 2.12 2.05 Photopolymerizable Compound (C) (C-1) 0.94 0.37 0 0 (C-2) 0 0.55 0.94 0.92 Photopolymerization Initiator (D) (D-1) 0.1502 0.1837 0.1502 0.1837 Solvent (E) (E-1) 7.11 7.24 7.11 7.24

(A-1) Colorant: C. I. Pigment Blue 15: 6

(B-1) methacrylic acid and benzyl methacrylate copolymer 20:80

(C-1) Synthesis Example 1

(C-2) dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D-1) Irgacure OXE01 (manufactured by BASF Corporation)

(E-1) Propylene Glycol Monomethyl Ether Acetate

Color filter manufacturers

Color filters were prepared using the colored photosensitive resin compositions for color filters prepared according to Examples 1 and 2 and Comparative Examples 1 and 2, respectively.

That is, the colored photosensitive resin compositions for color filters of Examples 1 and 2 and Comparative Examples 1 and 2 were coated on a glass substrate 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 for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 μm to 50 μm was placed on the thin film and the distance from the test photo mask was 300 μm. Was irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with an illuminance of 60mJ / cm 2 using a 1kw high pressure mercury lamp containing all g, h, and i rays, and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed in a KOH aqueous solution developing solution of pH 10.5 by spray nozzle spraying method for 1 minute. The thin plate coated with the thin glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C. for 25 minutes to prepare a color filter. The pattern shape (film) thickness of the color filter obtained through this was 2.95 μm.

Experimental Example  1. developing speed, sensitivity, Development residue  And pattern straightness experiment

Sensitivity and pattern linearity were evaluated for the color filters made of the colored photosensitive resin compositions for color filters of Examples 1 to 2 and Comparative Examples 1 to 2, respectively, and the results are shown in Table 2 below.

Experimental Example 1 Experimental Example 2 Comparative Experimental Example 1 Comparative Experiment 2 Colored photosensitive resin composition Example 1 Example 2 Comparative Example 1 Comparative Example 2 Sensitivity (mJ / cm2) * 15 18 30 30 Pattern Straightness ** ○ ○ X X

 *: Minimum exposure required to form a flawless thin film after development

**: The degree of unevenness and curvature on the pattern when the generated pattern is evaluated through an optical microscope

○: No error on pattern

×: pattern error 4 or more

As shown in Table 2, Examples 1 and 2 including a photopolymerizable compound (C-1) prepared by reacting intramolecular MDI, glycol and DPHA according to the present invention have a sensitivity and It was found that the pattern straightness was excellent.

Claims (8)

As a coloring photosensitive resin composition containing a coloring agent (A), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E),
The photopolymerizable compound (C) comprises a photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI, Methylene diphenyl diisocyanate), glycol, and dipentaerythritol hexaacrylate (DPHA) in a molecule thereof. The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 1, wherein the photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI, Methylene diphenyl diisocyanate), glycol and dipentaerythritol hexaacrylate (DPHA) in the molecule is 10 to 80 It has an acid value of KOHmg / g, The coloring photosensitive resin composition characterized by the above-mentioned. The photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI, Methylene diphenyl diisocyanate), diethylene glycol and dipentaerythritol hexaacrylate (DPHA) in the molecule is A colored photosensitive resin composition prepared by reacting ethylene glycol and MDI to synthesize a medium molecular urethane compound, and reacting it with dipentaerythritol hexaacrylate (DPHA). The photopolymerizable compound (C-1) prepared by reacting methylene diphenyl diisocyanate (MDI), glycol and dipentaerythritol hexaacrylate (DPHA) in the molecule is a photopolymerizable compound. (C) It is contained in 5-100 weight part with respect to 100 weight part, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 1, wherein the photopolymerizable compound (C) is Dipoentaerythritol hexaacrylate (DPHA), Dipentaerythritol polyacrylate (Dipentaerythritol polyacrylate), Polyethoxylated pentaerythritol tet r aacrylate (Polyethoxylated pentaerythritol tet r aacrylate) Coloring characterized in that it further comprises one or two or more selected from the group consisting of ethoxylated pentaerythritol tetraacrylate and dipentaerythritol tetraacrylate (Pentaerythritol tetraacrylate) Photosensitive resin composition. The method of claim 1, wherein the coloring photosensitive resin composition
Regarding the total weight of solids in the colored photosensitive resin composition,
20 to 60% by weight of the coloring agent (A),
10 to 30% by weight of the alkali-soluble resin (B),
1 to 10% by weight of the photopolymerizable compound (C) and
It is contained in 0.5 to 5% by weight of the photopolymerization initiator (D),
Colored photosensitive resin composition containing 30 to 60 weight% of solvent (E) with respect to the total weight of colored photosensitive resin composition. The color filter manufactured from the coloring photosensitive resin composition of any one of Claims 1-6. A liquid crystal display device comprising the color filter of claim 7.