KR102028483B1

KR102028483B1 - A colored photosensitive resin composition, color filter and liquid crystal display device having the same

Info

Publication number: KR102028483B1
Application number: KR1020130111790A
Authority: KR
Inventors: 김봉건; 박정효; 윤종원
Original assignee: 동우 화인켐 주식회사
Priority date: 2013-09-17
Filing date: 2013-09-17
Publication date: 2019-10-07
Also published as: KR20150032418A

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), a crosslinking agent (E), and a solvent (F), The said alkali-soluble resin The hydroxyl value of (B) is 30 to 180 mgKOH / g, the crosslinking agent (E) comprises a compound represented by the formula (1), and provides a colored photosensitive resin composition comprising an organic acid (G).

Description

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

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for color filters used when manufacturing a color filter for use in a color liquid crystal display device, a color filter manufactured using the same, and a liquid crystal having the same. It relates to a display device.

The color filter is embedded in a color photographing device of an image sensor such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD), and may be used to actually obtain a color image. In addition, it is widely used in photographing devices, plasma display panels (PDPs), liquid crystal displays (LCDs), field emission displays (FELs), and light emitting displays (LEDs), and its application range 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.

When manufacturing a color filter using the coloring photosensitive resin composition containing a dye in a coloring agent, a foreign material arises at the time of formation of a colored layer by lack of compatibility with the material used. In addition, in the case of manufacturing the color filter, the developing speed is low and the sensitivity is insufficient, so that the peeling of the pattern formed during the developing process by the alkaline developing solution occurs frequently. Accordingly, there is a need for development of a colored photosensitive resin composition suitable for a lyso process that can solve the problem of including a dye as a colorant or using a dye alone as a colorant.

In order to solve this problem, Korean Patent Laid-Open Publication No. 10-2010-0063571 discloses a colored photosensitive resin composition which improves developability, surface roughness and the like even when a pigment of high concentration is applied by applying a multifunctional macromonomer. However, there are still problems of developing speed and sensitivity, pattern peeling and reliability in developing process by alkaline developer Efforts are needed to solve such problems.

Republic of Korea Patent Publication No. 10-2010-0063571

In order to solve the above problems, it is an object of the present invention to provide a color photosensitive resin composition for a color filter which can obtain a color filter excellent in transmittance.

In addition, the present invention is to provide a coloring photosensitive resin composition having a fast development speed, excellent sensitivity and adhesion, no peeling of the pattern during the development process, excellent storage stability, no degradation of sensitivity or increase in viscosity even during long-term storage. have.

This invention is a coloring photosensitive resin composition containing a coloring agent (A), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), a crosslinking agent (E), and a solvent (F), The said alkali-soluble resin The hydroxyl value of (B) is 30-180 mgKOH / g, the crosslinking agent (E) includes a compound represented by the following formula (1), and provides a colored photosensitive resin composition comprising an organic acid (G).

[Formula 1]

In Formula 1,

R ₁ and R ₂ are independently H, C 1 -C 8 straight or branched alkyl group or cycloalkyl group,

A is a substituted or unsubstituted hydrocarbon ring having 2 to 6 carbon atoms; Or a substituted or unsubstituted hetero ring,

The substituent is an alkyl group, amino group, ether group, ketone group or ester group,

The two substituents may be linked to form a condensed ring,

The hetero atom included in the heterocycle is O, N or S.

In addition, the present invention provides a color filter comprising a color layer formed by applying the coloring photosensitive resin composition according to the present invention on a substrate and exposed and developed in a predetermined pattern.

In addition, the present invention provides a liquid crystal display device comprising the color filter.

The coloring photosensitive resin composition of this invention is excellent in developing speed and adhesiveness by including a specific crosslinking agent and organic acid together, and it is hard to generate | occur | produce the short circuit of the pattern during a developing process, and is excellent in the productivity of a color filter. In addition, the color filter manufactured using this can be excellent in reliability and can reduce the defects generated during the post-process.

The present invention also has the effect that the transmittance of the color filter is improved and the heat resistance is improved.

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), a crosslinking agent (E), and a solvent (F), The said alkali-soluble resin The hydroxyl value of (B) is 30 ~ 180mgKOH / g, the crosslinking agent (E) comprises a compound represented by the formula (1), the composition comprises a coloring photosensitive resin composition characterized in that it comprises an organic acid (G) to provide.

[Formula 1]

In Formula 1,

The two substituents may be linked to form a condensed ring,

The hetero atom included in the heterocycle is O, N or S.

Hereinafter, each structure is demonstrated in detail.

(A) colorant

The colorant (A) may include at least one pigment (a1) as an essential component and at least one dye (a2).

Pigments a1 )

The pigment may be used an organic pigment or an inorganic pigment generally used in the art. The pigment may be used a variety of pigments used in printing inks, inkjet inks, and the like, specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin Pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinoneyl pigments, anthrapyrimidine pigments, ananthronerone pigments, indanthrone pigments, pravantron pigments, pyrantrones (pyranthrone) pigments, diketopyrrolopyrrole pigments and the like.

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

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 weight, preferably 30 to 70% by weight, based on the total solids in the pigment dispersion composition. If the content of the pigment is in the range of 20 to 90% by weight based on the above standards, it is preferable because the viscosity is low, the storage stability is high, and the dispersion efficiency is high, which is effective in 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. .

The pigment dispersant (a3) may be a pigment dispersant of a resin type other than the acrylic dispersant described above. The other resin type pigment dispersants include (partially) known pigment dispersants of known resin types, in particular polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids represented by polyurethanes, polyacrylates. 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 modified products thereof, or free ) Oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with a poly (lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, phosphate esters, and the like.

As a commercial item of the said resin type dispersing agent, As a cationic resin dispersing agent, For example, brand names of BYK (Big) Chemi Corporation: 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, DISPER BYK-2001; 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 thereof, or may be used in combination with an acrylic dispersant.

The usage-amount of the said pigment dispersant (a3) is 5-60 weight part with respect to 100 weight part of solid content of the pigment (a1) used, More preferably, it is the range of 15-50 weight part. 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.

dyes( 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-based and xanthene-based 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 and the like; And

C.I. Green dyes, such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. are mentioned.

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

In addition, 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, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 Blue dyes such as, 335 and 340;

Violet dyes such as C.I. acid violet 6B, 7, 9, 17, 19, 66, and the like; And

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.

CI acid red 92 having excellent solubility in organic solvents in acid dyes; CI acid blue 80, 90; CI 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 Red dyes such as, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 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 and the like;

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. modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

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

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

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

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

Green dyes, such as CI 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.

The content of the dye in the coloring agent (A) is preferably contained 0.5 to 90% by weight, more preferably 0.5 to 60% by weight, particularly preferably 1 to 50% by weight relative to the total weight of solids in the coloring agent (A). 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 the range of 5 to 60% by weight, preferably 10 to 45% by weight based on the total weight of solids in the colored photosensitive resin composition. When the colorant (A) is included in the range of 5 to 60% by weight, the color density of the pixel is sufficient even when a thin film is formed, and the residue is unlikely to occur because the omission of the non-pixel portion during development is not reduced. Do.

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.

(B) alkali soluble resin

In order to have solubility with respect to the alkaline developing solution used at the image development process at the time of forming a pattern, it manufactures by copolymerizing with ethylenically unsaturated monomer (b1) which has a carboxyl group as an essential component.

The alkali-soluble resin (B) contains a hydroxyl group. By including a hydroxyl group, the developing speed is improved. The hydroxyl value of alkali-soluble resin (B) is limited to 30 mgKOH / g or more and 180 mgKOH / g or less. If the value of hydroxyl group is less than 30mgKOH / g, sufficient developing speed cannot be secured. If it exceeds 180mgKOH / g, the dimensional stability of the formed pattern is lowered, so the straightness of the pattern is poor and compatibility with dye is lowered. The problem of storage stability is likely to occur.

In addition, the alkali-soluble resin included in the present invention is characterized in that the reactive unsaturated group is contained in 50 mol% to 70 mol%. When a reactive unsaturated group is included in the alkali-soluble resin, a hydroxyl group is generated, and thus, the thermosetting property is represented in the present invention, and may have the hydroxyl value.

Specific examples of the ethylenically unsaturated monomer (b1) having the carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate, and the like, and acrylic acid and methacrylic acid are preferred.

Alkali-soluble resin (B) may be prepared by copolymerizing an ethylenically unsaturated monomer (b1) having an carboxyl group with an ethylenically unsaturated monomer (b2), and having a compound having a carboxyl group having an ethylenically unsaturated monomer (b1) and a glycidyl group ( b3) can be prepared by reacting. Furthermore, it can manufacture by making the copolymer of the ethylenically unsaturated monomer (b1) which has a carboxyl group, and the ethylenically unsaturated monomer (b2) which has a hydroxyl group further react with the compound (b3) which has a glycidyl group.

The ethylenically unsaturated monomer (b2) is a compound having a polymerizable unsaturated bond with (b1), and may be used without limitation as long as the compound has a polymerizable unsaturated double bond. Specific examples thereof include unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate. Unsubstituted or substituted alkyl ester compounds; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, pentyl (meth) acrylate, cyclophene Tenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, pentadienyl (meth) acrylate, isobornyl (meth) acrylic Unsaturated carboxylic ester compounds including alicyclic substituents such as late, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pineneyl (meth) acrylate; 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3-((meth) acryloyloxymethyl) -2-methyl Unsaturated carboxylic ester compounds containing thermosetting substituents such as oxetane and 3-((meth) acryloyloxymethyl) -2-trifluoromethyloxetane; Monosaturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate; Unsaturated carboxylic ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate and phenoxy (meth) acrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Carboxylic acid vinyl esters, such as vinyl acetate and a vinyl propionate; And vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile. Among these, an aromatic vinyl compound is preferable for sensitivity improvement and outgas reduction. These can be used individually or in combination of 2 types or more, respectively.

As the compound (b3) having the glycidyl group, butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl Glycidyl ether, glycidyl isopropyl ether, t-butylglycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butylbenzoate, glycidyl stearate, aryl glycidyl ether, meta Acrylate glycidyl ester and the like, butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more kinds can be used in combination.

The alkali-soluble resin (B) may be prepared by copolymerizing an additional copolymerizable unsaturated monomer (b4). The copolymerizable unsaturated monomer (b4) is illustrated below, but is not necessarily limited thereto.

Specific examples of the polymerizable monomer (b4) having a copolymerizable unsaturated bond include styrene, vinyltoluene, a-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, aromatics such as 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, and p-vinyl benzyl glycidyl ether Vinyl compounds;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide;

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

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide;

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

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

The monomers exemplified as the copolymerizable unsaturated monomers (b4) may be used alone or in combination of two or more thereof.

It is preferable that content of the said alkali-soluble resin (B) is contained in 10 to 80 weight% with respect to the total weight of solid content in a coloring photosensitive resin composition, More preferably, it is the range of 10 to 70 weight%. When the content of the alkali-soluble resin (B) is 10 to 80% by weight based on the above criteria, the solubility in the developing solution is sufficient, so that pattern formation is easy. It is preferable because omission becomes good.

(C) Photopolymerizable compound

The photopolymerizable compound (C) is a compound capable of polymerizing under the action of the following photopolymerization initiator (D), and may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer, and preferably a bifunctional or higher polyfunctional monomer. Can be used.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N-vinylpi Or the like, but 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-methylpentanediol di (meth) acrylate, and the like, but is not limited thereto.

Specific examples of the polyfunctional monomer include trimethylol propane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) ) Acrylate or dipentaerythritol hexa (meth) acrylate, and the like, but is not limited thereto.

The photopolymerizable compound (C) is preferably contained 5 to 45% by weight, more preferably 7 to 45% by weight based on the total weight of solids in the colored photosensitive resin composition. When the said photopolymerizable compound (C) is contained 5 to 45 weight% by said reference | standard, since the intensity | strength and smoothness of a pixel part become favorable, it is preferable.

(D) Photopolymerization Initiator

The photoinitiator (D) can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C). In particular, the photopolymerization initiator (D) is an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound and a tee from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price. It is preferable to use at least one compound selected from the group consisting of oxatone compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 -One, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4, And imidazole compounds in which a phenyl group of 4 ?? 5,5 ??-tetraphenyl-1,2 ??-biimidazole or a 4,4 ', 5,5' position is substituted by a carboalkoxy group. have. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4 ?? 5,5 ??-tetraphenyl-1,2 ??-biimidazole It is preferably used.

Specific examples of the oxime compound include o-ethoxycarbonyl-a-oxyimino-1-phenylpropan-1-one and the like, and OXE01 and OXE02 manufactured by BASF are typical examples of commercial products.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.

The photopolymerization initiator (D) may further include a photopolymerization initiation aid (d1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The coloring photosensitive resin composition which concerns on this invention contains a photoinitiation start adjuvant (d1), and can raise a sensitivity further and can improve productivity.

As the photopolymerization initiation assistant (d1), for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone ), 4,4'-bis (diethylamino) benzophenone and the like can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

Specific examples of the organic sulfur compound having the thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Late), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. are mentioned. Can be.

The photopolymerization initiator (D) is 0.1 to 40% by weight, preferably 1 to 1, based on the total content of the (B) alkali-soluble resin and (C) the photopolymerizable compound based on the total solids weight of the colored photosensitive resin composition of the present invention. 30 wt% may be included. When the (D) photoinitiator is in the range of 0.1 to 40% by weight as described above, the colored photosensitive resin composition is highly sensitive and exposure time is shortened, which is preferable because productivity can be improved and high resolution can be maintained. In addition, the strength of the pixel portion formed using the composition under the above-described conditions and smoothness on the surface of the pixel portion can be improved.

In addition, when using the said photoinitiator (d1) further, the said photoinitiator (d1) is based on the total weight of solid content of the coloring photosensitive resin composition of this invention, (B) alkali-soluble resin and (C) photopolymerizable property 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total content of the compound. When the amount of the photopolymerization initiation assistant (d1) used is within the range of 0.1 to 40% by weight, the sensitivity of the colored photosensitive resin composition is higher, and the productivity of the color filter formed using the composition is improved.

(E) Crosslinking agent

The crosslinking agent (E) is preferably represented by the following formula (1).

[Formula 1]

In Formula 1,

The two substituents may be linked to form a condensed ring,

The hetero atom included in the heterocycle is O, N or S.

The crosslinking agent (E) is more preferably a compound represented by the following formula (2), (3), (4) or (5).

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are independently H, C 1 -C 8 straight or branched alkyl group or cycloalkyl .

The crosslinking agent is 1,3,4,6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1h, 3h) -dione (1,3,4,6 -tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1h, 3h) -dione), 1,3-bis (methoxymethyl) -2-imidazolidone (1,3-Bis (methoxymethyl) -2-imidazolidone), bis (methoxymethyl) (oxydimethylene) urea (Bis (methoxymethyl) (oxydimethylene) urea), 3,5-bis (butoxymethyl) tetrahydro-4H-1,3 , 5-oxadiazin-4-one (3,5-Bis (butoxymethyl) tetrahydro-4H-1,3,5-oxadiazin-4-one), 3,4,6-tetrakis (butoxymethyl) tetra Hydroimidazo (4,5-d) imidazole-2,5 (1H, 3H) dione (3,4,6-Tetrakis (butoxymethyl) tetrahydroimidazo (4,5-d) imidazole-2,5 (1H, 3H ) -dione), 1,3-bis (methoxymethyl) benzimidazol-2-one (1,3-bis (methoxymethyl) benzimidazol-2-one), 1,3-bis (methoxymethyl) -1 , 3-diazin-2-one (1,3-bis (methoxymethyl) -1,3-diazinan-2-one), 1,3-bis (ethoxymethyl) imidazolidin-2-one (1 , 3-bis (ethoxymethyl) imidazolidin-2-one), 1,3 -Bis (2-methylpropoxymethyl) imidazolidin-2-one (1,3-bis (2-methylpropoxymethyl) imidazolidin-2-one) and 1,3,4,6 tetrakis (2-methylprop Foxymethyl) -3a, 6a-dihydroimidazo [4,5-d] imidazole-2,5-dione (1,3,4,6-tetrakis (2-methylpropoxymethyl) -3a, 6a-dihydroimidazo [4 , 5-d] imidazole-2,5-dione) is more preferably one or two or more selected from the group consisting of.

The crosslinking agent may be included in an amount of 0.1 to 15% by weight, and more preferably 0.5 to 10% by weight, based on the total weight of solids of the colored photosensitive resin composition. When the crosslinking agent is included in an amount of 0.1 to 15% by weight based on the total weight of solid content of the colored photosensitive resin composition, it is effective in producing a color filter having excellent development speed and adhesion and excellent reliability.

(F) solvent

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

Specific examples of the solvent 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 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, butalac Tate, 3-ethoxy propionate, methyl 3-methoxypropionate, etc. can be used.

The solvents exemplified above may be used alone or in combination of two or more thereof, and may be included in an amount of 60 to 90 wt%, preferably 70 to 85 wt%, based on the total weight of the colored photosensitive resin composition of the present invention. If the solvent is in the range of 60 to 90% by weight as described above, the coating property is good when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet Provide the effect of termination.

(G) organic acid

The present invention has found that the crosslinking reaction is accelerated when the organic acid (G) is used together with the crosslinking agent (E) and completed the present invention. The organic acid may be a compound capable of promoting a crosslinking reaction, and a monofunctional organic acid, a bifunctional organic acid or a polyfunctional organic acid may be used, and preferably an organic acid having a bifunctional or higher functionality may be used.

Specific examples of the monofunctional organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid and octadecanoic acid. Iksan and the like, but is not limited thereto.

Specific examples of the bifunctional organic acid include, but are not limited to, malonic acid, succinic acid, fumaric acid, adipic acid, tartaric acid, glutaric acid, maleic acid, or oxalic acid.

Specific examples of the polyfunctional organic acid include 2-hydroxypropane-1,2,3-tricarboxylic acid, 2-methylpropane-1,2,3-tricarboxylic acid, propane-1,2,3-tricarboxylic acid, and the like. It is not limited thereto.

The organic acid is preferably contained in an amount of 0.1 to 10% by weight, and more preferably in an amount of 1 to 5% by weight, based on the total weight of solids in the colored photosensitive resin composition. When the organic acid is contained in an amount of 0.1 to 10% by weight, the heat resistance and luminance of the pixel portion may be improved when the colored layer is formed.

(H) additive

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

The additives can be selectively added as needed, for example, other polymer compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation 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.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Dow Corning Toray Silicone Co., Ltd., and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, manufactured by GE Toshiba And TSF-4452. Examples of the fluorine-based surfactant include Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink & Chemicals Co., Ltd. as commercially available products. Surfactant illustrated above can be used individually or in combination of 2 types or more, respectively.

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 promoter exemplified above can be used individually or in combination of 2 or more types, respectively. 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 aggregation inhibitor include sodium polyacrylate and the like.

Preparation of colored photosensitive resin composition

As a method for preparing the colored photosensitive resin composition of the present invention, for example, a pigment and a dispersant are added and dispersed in a solvent to prepare a pigment dispersion having a uniform particle diameter, and then an alkali-soluble resin, a photopolymerizable compound, dissolved in a solvent, The photopolymerization initiator, the crosslinking agent, the organic acid, and other additives, if necessary, may be dissolved and mixed with the pigment dispersion, and may be prepared by adding a solvent as necessary.

Of color filter Produce

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

The color filter which concerns on this invention apply | coats the said colored photosensitive resin composition solution, performs the patterning exposure to the dry coating film obtained by prebaking, and develops, and then develops the color of the coloring agent which is a component of a coloring photosensitive resin composition. A pixel or black matrix corresponding to is obtained. In addition, a color filter can be obtained by repeating this process by the number of colors required for the color filter.

Since the configuration and manufacturing method of the color filter are well known in the art, it is possible to manufacture a color filter using the same.

Manufacture of LCD

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

The liquid crystal display includes a configuration known to those skilled in the art, except that the liquid crystal display includes 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 light-proof resin surrounding a peripheral surface of a color filter, a liquid crystal layer made of nematic liquid crystals imposed in the outer frame, and a plurality of pixel electrodes provided for each region of the liquid crystal layer. , A transparent glass substrate on which the pixel electrode is 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, but embodiments of the present invention disclosed below are exemplified to the last, and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and moreover contains all modifications within the meaning and range equivalent to the claims. In addition, "%" and "part" which show content in a following example and a comparative example are a basis of weight unless there is particular notice.

Preparation Example 1 Alkali-Soluble Resin

Methacrylic acid / styrene / benzylmethacrylate / N-benzylmaleimide was polymerized at a weight ratio of 25/15/40/20 to prepare an alkali-soluble resin. Solid content acid value of the manufactured alkali-soluble resin is 85 mgKOH / g, the weight average molecular weight of polystyrene conversion measured by GPC is 20,000, and molecular weight distribution (Mw / Mn) is 2.1.

Preparation Example 2 Preparation of Pigment Dispersion Composition

Pigment Dispersion Composition M1

CI pigment Bule 15: 6 12.5 parts by weight as a pigment, 4.6 parts by weight of DISPER BYK-2001 (manufactured by BYK) as a pigment dispersant, 62.9 parts by weight of propylene glycol monomethyl ether acetate and 20 parts by weight of propylene glycol monomethyl ether as a solvent Pigment dispersion composition M1 was prepared by mixing / dispersing for 12 hours with a mill.

Example And Comparative example

Comparative Example 1

30 parts by weight of the pigment dispersion composition of Preparation Example 2, 9.4 parts by weight of the alkali-soluble resin prepared in Preparation Example 1, 4.48 parts by weight of KAYARAD DPHA (Dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku), OXE-01 (BASF Corporation) Preparation) 0.90 weight part and 55.22 weight part of propylene glycol monomethyl ether acetates were mixed, and the coloring photosensitive resin composition was produced.

Comparative Example 2

30 parts by weight of the pigment dispersion composition of Preparation Example 2, 9.4 parts by weight of the alkali-soluble resin prepared in Preparation Example 1, 4.48 parts by weight of KAYARAD DPHA (dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku), 0.30 parts by weight of malonic acid, 0.90 parts by weight of OXE-01 (manufactured by BASF Corporation) and 54.92 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Comparative Example 3

30 parts by weight of the pigment dispersion composition of Preparation Example 2, 9.4 parts by weight of the alkali-soluble resin prepared in Preparation Example 1, 4.48 parts by weight of KAYARAD DPHA (Dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku), 0.30 parts by weight of succinic acid, OXE -01 (manufactured by BASF Corporation) 0.90 parts by weight and 54.92 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

30 parts by weight of the pigment dispersion composition of Preparation Example 2, 9.4 parts by weight of the alkali-soluble resin prepared in Preparation Example 1, 4.48 parts by weight of KAYARAD DPHA (Dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku), crosslinking agents 1,3,4 , 6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1h, 3h) -dione (Powderlink 1174, Cytec) 1.8 parts by weight, OXE-01 (BASF Ltd.) 0.90 parts by weight and 53.42 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

30 parts by weight of the pigment dispersion composition of Preparation Example 2, 9.4 parts by weight of the alkali-soluble resin prepared in Preparation Example 1, 4.48 parts by weight of the photopolymerizable compound KAYARAD DPHA (manufactured by Nippon Kayaku), 0.30 malonic acid Parts by weight, crosslinking agent 1,3,4,6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1h, 3h) -dione (Powderlink 1174, CYTEC) 1.8 weight part, 0.90 weight part of photoinitiators OXE-01 (made by BASF Corporation), and 53.12 weight part of solvent propylene glycol monomethyl ether acetate were mixed, and the coloring photosensitive resin composition was produced.

30 parts by weight of the pigment dispersion composition of Preparation Example 2, 9.4 parts by weight of the alkali-soluble resin prepared in Preparation Example 1, 4.48 parts by weight of the photopolymerizable compound KAYARAD DPHA (manufactured by Nippon Kayaku), and 0.30% of maleic acid Part 1,3,4,6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1h, 3h) -dione (Powderlink 1174, Cytec Co.) 1.8 A weight part, 0.90 weight part of photoinitiators OXE-01 (made by BASF Corporation), and 53.12 weight part of solvent propylene glycol monomethyl ether acetates were mixed, and the coloring photosensitive resin composition was produced.

30 parts by weight of the pigment dispersion composition of Preparation Example 2, 9.4 parts by weight of the alkali-soluble resin prepared in Preparation Example 1, 4.48 parts by weight of the photopolymerizable compound KAYARAD DPHA (manufactured by Nippon Kayaku), 0.30% by weight of succinic acid Part 1,3,4,6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1h, 3h) -dione (Powderlink 1174, Cytec Co.) 1.8 A weight part, 0.90 weight part of photoinitiators OXE-01 (made by BASF Corporation), and 53.12 weight part of propylene glycol monomethyl ether acetates were mixed, and the coloring photosensitive resin composition was produced.

30 parts by weight of the pigment dispersion composition of Preparation Example 2, 9.4 parts by weight of the alkali-soluble resin prepared in Preparation Example 1, 4.48 parts by weight of the photopolymerizable compound KAYARAD DPHA (Dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku), glutaric acid 0.30 part by weight, crosslinking agent 1,3,4,6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1h, 3h) -dione (Powderlink 1174, CYTEC) ) 1.8 parts by weight, 0.90 part by weight of the photopolymerization initiator OXE-01 (manufactured by BASF), and 53.12 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Example 5

30 parts by weight of the pigment dispersion composition of Preparation Example 2, 9.4 parts by weight of the alkali-soluble resin prepared in Preparation Example 1, 4.48 parts by weight of the photopolymerizable compound KAYARAD DPHA (manufactured by Nippon Kayaku), 0.30% by weight of oxalic acid Part 1,3,4,6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1h, 3h) -dione (Powderlink 1174, Cytec Co.) 1.8 A weight part, 0.90 weight part of photoinitiators OXE-01 (made by BASF Corporation), and 53.12 weight part of propylene glycol monomethyl ether acetates were mixed, and the coloring photosensitive resin composition was produced.

The composition of the Examples and Comparative Examples are summarized in Table 1 below. In the following table, the content of components except for the solvent is expressed on a solids basis.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 Example 3 Example 4 (A) Coloring material 3.75 3.75 3.75 3.75 3.75 3.75 3.75 3.75 (B) binder resin 3.67 3.67 3.67 3.67 3.67 3.67 3.67 3.67 (C) photopolymerizable compound 3.67 3.67 3.67 3.67 3.67 3.67 3.67 3.67 (D) Photopolymerization Initiator 0.73 0.73 0.73 0.73 0.73 0.73 0.73 0.73 (E) Cross-linking system 1.48 1.48 1.48 1.48 1.48 (G-1) organic acid 0.3 0.3 (G-2) organic acid 0.3 (G-3) organic acid 0.3 0.3 (G-4) organic acid 0.3 (G-5) organic acid (F) Solvent 86.78 86.48 86.48 85.3 85 85 85 85 (H) additive 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4

(A) Coloring material: blue pigment dispersion (C.I. Pigment Blue 15: 6)

(B) Binder Resin: Alkali-soluble resin of Preparation Example 1

(C) photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(D) Photoinitiator: ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; manufactured by Ciba Specialty Chemical)

(E) Thermal crosslinking agent: 1,3,4,6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1h, 3h) -dione (Powderlink 1174, CYTEC four)

(G) Organic acid: Malonic acid, succinic acid, maleic acid, glutaric acid, oxalic acid

(F) Solvent: Propylene Glycol Monomethyl Ether Acetate

(H) additive: pigment dispersant (acrylic)

Experimental Example

A 2 square inch glass substrate (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The coated photosensitive resin composition (Table 1) was exposed on the glass substrate at an exposure amount (365 nm) of 100 mJ / cm 2, and spin-coated so that the film thickness after post-firing when the developing step was omitted was 2.2 μm, and then Preliminary drying (preliminary baking) was performed at 100 degreeC for 3 minutes in the clean oven. After cooling, the gap between the substrate coated with the colored photosensitive resin composition and a quartz glass 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) It was made into 100 micrometers, and it irradiated at 100 mJ / cm <2> exposure amount (365 nm) in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed in a water-based developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, and then dried five times at 230 ° C. for 20 minutes after washing with water (post-calcination). The brightness of each drying process was measured in Table 2 below.

(1) transmittance measurement

The transmittance in the visible region was measured with a colorimeter (Olympus, OSP-200) in the same color coordinate (color filter Bx = 0.1360, By = 0.1100). The results are shown in Table 2 below.

Transmittance Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 Example 3 Example 4 Example 5 PoB 1 time 13.53 13.57 13.56 13.57 13.64 13.62 13.62 13.65 13.62 PoB 2 times 13.41 13.42 13.43 13.46 13.56 13.55 13.54 13.57 13.54 3 PoB 13.37 13.38 13.38 13.42 13.56 13.53 13.51 13.56 13.52 4 PoB 13.32 13.35 13.34 13.35 13.49 13.47 13.44 13.48 13.46 5 PoB 13.19 13.32 13.28 13.31 13.45 13.43 13.42 13.45 13.42

Bx = 0.1360 By = 0.1100

(2) heat resistance evaluation

The manufactured color filter was baked 5 times for 20 minutes in a heating oven at 230 ° C., and color change before and after heating was measured to evaluate heat resistance according to the following criteria. A color change is shown according to Equation 1 below, and L *, a *, and b * in Equation 1 indicate color changes in a three-dimensional colorimeter.

[Equation 1]

ΔEab * = (ΔL *) 2+ (Δa *) 2+ (Δb *) 2] (1/2)

○: ΔEab is 1 to 3.

Δ: ΔEab is greater than 3 to 4 or less.

X: ΔEab is greater than 4.

The evaluation results are shown in Table 3 below.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 Example 3 Example 4 Example 5 △ Eab * 5.51 3.44 3.56 4.67 2.74 2.74 2.78 2.79 2.87 evaluation x Δ Δ x O O O O O

As shown in Table 2, the color filters using the colored photosensitive resin composition of Examples 1 to 5 according to the present invention are all higher than the transmittance of Comparative Examples 1 to 4 without organic acid and crosslinking agent and only with or without crosslinking agent. appear. That is, when the organic acid and the thermal crosslinking agent were added together in the colored photosensitive resin composition, it was confirmed that the transmittance was more excellent. As shown in Table 3, the heat resistance also showed excellent results.

Therefore, it was confirmed that the colored photosensitive resin composition of this invention can manufacture the high quality cured filter excellent in the transmittance | permeability and heat resistance by including a specific crosslinking agent and an organic acid.

Claims

The coloring photosensitive resin composition containing a coloring agent (A), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), a crosslinking agent (E), a solvent (F), and an organic acid (G), The said alkali The hydroxyl value of the soluble resin (B) is 30 ~ 180mgKOH / g, the crosslinking agent (E) comprises a compound represented by the following formula (1),
The organic acid may be acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, octadecanoic acid, malonic acid, Succinic acid, fumaric acid, adipic acid, tartaric acid, glutaric acid, maleic acid, 2-hydroxypropane-1,2,3-tricarboxylic acid, 2-methylpropane-1,2,3-tricarboxylic acid and propane-1,2 It is 1 type (s) or 2 or more types selected from the group which consists of a 3-tricarboxylic acid, The coloring photosensitive resin composition.
[Formula 1]

In Formula 1,
R ₁ and R ₂ are independently H, C 1 -C 8 straight or branched alkyl group or cycloalkyl group,
A is a substituted or unsubstituted hydrocarbon ring having 2 to 6 carbon atoms; Or a substituted or unsubstituted hetero ring,
The substituent is an alkyl group, amino group, ether group, ketone group or ester group,
The two substituents may be linked to form a condensed ring,
The hetero atom included in the heterocycle is O, N or S.

The method according to claim 1,
The colored photosensitive resin composition is based on the total weight of solids,
The colorant (A) is 5 to 60% by weight;
The alkali-soluble resin (B) is 10 to 80% by weight;
The photopolymerizable compound (C) is 5 to 45% by weight;
The crosslinking agent (E) is 0.1 to 15% by weight; And
The organic acid (G) is included in 0.1 to 10% by weight,
The photopolymerization initiator (D) is contained in an amount of 0.1 to 40% by weight based on the total content of the alkali-soluble resin (B) and the photopolymerizable compound (C),
The solvent (F) is a coloring photosensitive resin composition, characterized in that contained in 60 to 90% by weight based on the total weight of the coloring photosensitive resin composition.

The colored photosensitive resin composition according to claim 1, wherein the crosslinking agent (E) is a compound represented by the following Formula (2), (3), (4) or (5).
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ are independently H, C1-C8 straight or branched alkyl group or cycloalkyl .

The method of claim 1, wherein the crosslinking agent is 1,3,4,6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1h, 3h) -dione (1, 3,4,6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1h, 3h) -dione), 1,3-bis (methoxymethyl) -2-imidazolidone ( 1,3-Bis (methoxymethyl) -2-imidazolidone), bis (methoxymethyl) (oxydimethylene) urea (Bis (methoxymethyl) (oxydimethylene) urea), 3,5-bis (butoxymethyl) tetrahydro- 4H-1,3,5-oxadiazine-4-one (3,5-Bis (butoxymethyl) tetrahydro-4H-1,3,5-oxadiazin-4-one), 3,4,6-tetrakis ( Butoxymethyl) tetrahydroimidazo (4,5-d) imidazole-2,5 (1H, 3H) dione (3,4,6-Tetrakis (butoxymethyl) tetrahydroimidazo (4,5-d) imidazole-2, 5 (1H, 3H) -dione), 1,3-bis (methoxymethyl) benzimidazol-2-one (1,3-bis (methoxymethyl) benzimidazol-2-one), 1,3-bis (meth) Methoxymethyl) -1,3-diazin-2-one (1,3-bis (methoxymethyl) -1,3-diazinan-2-one), 1,3-bis (ethoxymethyl) imidazolidine- 2-one (1,3-bis (ethoxymet) hyl) imidazolidin-2-one), 1,3-bis (2-methylpropoxymethyl) imidazolidin-2-one (1,3-bis (2-methylpropoxymethyl) imidazolidin-2-one) and 1, 3,4,6 trakis (2-methylpropoxymethyl) -3a, 6a-dihydroimidazo [4,5-d] imidazole-2,5-dione (1,3,4,6-tetrakis ( 2-methylpropoxymethyl) -3a, 6a-dihydroimidazo [4,5-d] imidazole-2,5-dione). The coloring photosensitive resin composition characterized by the above-mentioned.

delete

The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition further comprises an additive.

The colored photosensitive resin composition according to claim 6, wherein the additive is one kind or two or more kinds selected from the group consisting of a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomerating agent.

The color filter manufactured from the coloring photosensitive resin composition in any one of Claims 1-4 and 6-7.

A liquid crystal display device comprising the color filter of claim 8.