KR20150106637A - Colored photosensitive resin composition and color filter using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for a color filter used for producing a color filter used in a color liquid crystal display device or the like, and a color filter manufactured using the same. The colored photosensitive resin composition of the present invention is excellent in development speed and adhesion, and is less likely to cause VD unevenness, and thus has excellent productivity of a color filter.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition and a color filter using the colored photosensitive resin composition.

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for a color filter used for producing a color filter used in a color liquid crystal display device or the like, and a color filter manufactured using the same.

BACKGROUND ART [0002] Color filters are widely used in imaging devices, liquid crystal display devices, and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display device, an image pickup device, or the like is a device for uniformly applying a colored photosensitive resin composition containing a coloring agent corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern- The coating film formed by heating and drying (hereinafter also referred to as preliminary firing) may be exposed and developed, and if necessary, further heat curing (hereinafter also referred to as post-firing) may be repeated for each color, Color pixels are formed.

As the coloring agent in the colored photosensitive resin composition, a pigment dispersion system is generally used. For this purpose, a pigment dispersion method is used. As the pigment dispersion method, there is a method of producing a color filter by photolithography using a coloring and radiation-sensitive composition in which pigments are dispersed in various photosensitive compositions. This method has been widely used as a preferable method for producing a color filter for a large-screen and high-resolution color display because it can secure sufficient reliability against light or heat since a pigment is used.

However, conventional photosensitive resin compositions still have problems such as development speed and sensitivity, and VD unevenness. For example, Korean Patent Laid-Open No. 10-2010-0051395 discloses a photosensitive resin composition comprising a first solvent at 110 to 145 占 폚, a second solvent of PGMEA, and a third solvent having a boiling point higher by 30 占 폚 or higher than PGMEA However, if the solvent is changed to improve the VD unevenness, a high boiling point solvent should be applied. If a high boiling point solvent is used, the flowability of the coating film is secured in the VD process, but the time required for volatilization of the solvent is increased, There is a problem that defects such as pin staining due to residual solvent of the coating film may occur.

Korean Patent Publication No. 10-2010-0051395

Accordingly, the present invention provides a colored photosensitive resin composition which is excellent in surface characteristics using a photopolymerizable compound having a specific viscosity, can shorten a tact time in an LCD process, and can improve a VD defect .

In order to achieve the above object, the present invention provides a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable material (C), a photopolymerization initiator (D), and a solvent (E) Wherein the synthetic material (C) comprises a photopolymerizable compound having a viscosity of at most 20 mPa · s at 25 ° C., and the photopolymerization initiator (D) comprises a structural unit (d1) to provide:

[Chemical Formula 1]

In Formula 1, R ₁ is represented by the following Formula 2,

R ₂ is a C1-C8 alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group,

R ₃ is substituted or unsubstituted diphenyl sulfide,

(2)

In the general formula (2), R ₄ is an alkyl group having 1 to 4 carbon atoms,

R ₅ is a C3 to C8 ring structure.

In one embodiment, the colored photosensitive resin composition contains 5 to 60% by weight of the colorant (A), 10 to 80% by weight of the alkali-soluble resin (B) based on the total weight of solids, The photopolymerization initiator (D) is contained in an amount of 0.1 to 40% by weight based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C) ) May be contained in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition.

In another embodiment, the hydroxyl value of the alkali-soluble resin (B) may be 30 to 150 mgKOH / g.

In yet another embodiment, the photopolymerizable material (C) may comprise a photopolymerizable compound having a viscosity of at most 20 mPa · s at 25 ° C and a multifunctional photopolymerizable compound.

In another embodiment, the photopolymerizable compound having a viscosity of less than or equal to 20 mPa · s at 25 ° C is selected from the group consisting of diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6- 1,9-nonanediol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate , 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and 2-methyl-1,8-octanediol diacrylate .

In another embodiment, the photopolymerizable compound having a viscosity of 20 mPa · s or less at 25 ° C may be 5 to 50% by weight based on the total weight of the photopolymerizable material.

In another embodiment, the compound of Formula 1 may be 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (o-benzoyloxime).

In another embodiment, the structural unit (d1) of the general formula (1) may be contained in an amount of 10 to 100% by weight based on the total weight of the total photopolymerization initiator.

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

The colored photosensitive resin composition of the present invention is excellent in development speed and adhesion, and is less likely to cause VD unevenness, and thus has excellent productivity of a color filter.

Hereinafter, the present invention will be described in detail.

The present invention provides a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable material (C), a photopolymerization initiator (D), and a solvent (E) A photopolymerizable compound having a viscosity of at most 20 mPa · s at 25 ° C., wherein the photopolymerization initiator (D) comprises a structural unit (d1) represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ is represented by the following Formula 2,

R ₂ is a C1-C8 alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group,

R ₃ is substituted or unsubstituted diphenyl sulfide,

(2)

In the general formula (2), R ₄ is an alkyl group having 1 to 4 carbon atoms,

R ₅ is a C3 to C8 ring structure.

In the present invention, VD unevenness refers to unevenness that occurs due to the low fluidity of the coating film in the VD process and unevenness due to fine bubbles.

Hereinafter, each configuration will be described in more detail.

The colorant (A)

The colorant (A) comprises at least one pigment (a1) or at least one dye (a2), and may preferably comprise a pigment dispersant (a3).

Pigment ( a1 )

The pigment may be an organic pigment or an inorganic pigment generally used in the art.

The organic pigments may be various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, An anthanthrone pigment, an indanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, A pyranthrone pigment, a diketopyrrolopyrrole pigment, 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.

Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number Pigments, but are not limited thereto.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185

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

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264

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

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

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

C.I Pigment Brown 28

C.I Pigment Black 1 and 7, etc.

The above-mentioned pigments may be organic pigments or inorganic pigments generally used in the art. These pigments may be used alone or in combination of two or more.

The exemplified C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. Pigment Green 58 may be preferably used.

It is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment dispersion (a3) by containing 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 cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, and polyamine surfactants. These surfactants may be used singly or in combination of two or more thereof .

Pigment dispersant ( a3 )

The pigment dispersant (a3) is added for maintenance of deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. (Hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by a living control method as disclosed in Korean Patent Laid-Open Publication No. 2004-0014311. DISCLOSURE OF INVENTION It is an object of the present invention to provide an acrylic dispersant, 2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The acrylic dispersants exemplified above may be used alone or in combination of two or more.

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) An amine salt of a polycarboxylic acid, an alkylamine salt of a polycarboxylic acid, a polysiloxane, a long chain polyaminoamide phosphate salt, an ester of a hydroxyl group-containing polycarboxylic acid and a modified product thereof, Oil 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 and DISPER BYK-160 available from BYK (Big) Chemie are commercially available as the above-mentioned resin type pigment dispersant. BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

In addition to the above acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylic dispersant.

The amount of the pigment dispersant (a3) to be used 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). If the content of the pigment dispersant (a3) exceeds 60 parts by weight, the viscosity may be increased. If the content of the pigment dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

dyes( a2 )

The dye can be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance.

Examples of the dye include acid dyes having an acidic group such as sulfonic acid and carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, Based acid dyes and derivatives thereof.

Preferably, the dye is a compound classified as a dye in a color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (coloring yarn).

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

C.I. Yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

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

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

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

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

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

C.I. Solvent dye having excellent solubility in an organic solvent. Solvent Yellow 14, 16, 21, 56, 151, 79, 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferred, and C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent orange 45, 62 is more preferable.

Also, C.I. As an acid dye

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 1,1,1,2,2,2,2,2,2,23,28, 240,242, 243,251 and the like, such as, for example, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, ;

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;

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 and the like;

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

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

As a C.I. direct dye,

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;

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;

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 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;

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

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

Also, C.I. As a modantoic dye

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. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,

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

The content of the dye in the colorant (A) is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, particularly preferably 1 to 50% by weight, based on the total weight of the solid content of the colorant (A) Do. When the content of the dye in the colorant (A) is within the above range, it is possible to prevent the problem of lowering the reliability of dye elution by the organic solvent after forming the pattern, and it is preferable since the sensitivity is excellent.

The content of the colorant (A) is 5 to 60% by weight, preferably 10 to 45% by weight, based on the total solid weight of the colored photosensitive resin composition. When the colorant (A) is contained in an amount of 5 to 60% by weight based on the above standard, the color density of the pixel is sufficient even when a thin film is formed, and the residue of the non- 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.

The alkali-soluble resin (B)

Is copolymerized with an ethylenically unsaturated monomer (b1) having a carboxyl group as an essential component in order to obtain solubility in an alkali developing solution used in a development processing step for forming a pattern. The acid value of the alkali-soluble resin (B) is 30 to 150 mgKOH / g in order to ensure compatibility with the dye (a2) and storage stability of the colored photosensitive resin composition. When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH / g, it is difficult to ensure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, , The dye in the colored photosensitive resin composition is precipitated or the storage stability of the colored photosensitive resin composition is lowered, and the viscosity tends to rise.

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

In order to impart a hydroxyl group to the alkali-soluble resin (B), an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group can be copolymerized with an ethylenically unsaturated monomer having a carboxyl group (b3) having a glycidyl group may be further reacted with the copolymer of (b1). (B3) having a glycidyl group in addition to the copolymer of the ethylenically unsaturated monomer (b1) having a carboxyl group and the ethylenically unsaturated monomer (b2) having a hydroxyl group.

Specific examples of the ethylenically unsaturated monomer (b2) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxyethylacrylamide and the like, and 2-hydroxyethyl (meth) acrylate is preferable and two or more of them can be used in combination.

Specific examples of the glycidyl group-containing compound (b3) include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl But are not limited to, ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, Ether, and methacrylic acid glycidyl ester, and butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more kinds thereof can be used in combination.

The copolymerizable unsaturated monomers (b4) in the production of the alkali-soluble resin (B) are exemplified below, but are not limited thereto.

Specific examples of the copolymerizable unsaturated monomers (b4) include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Aromatic vinyl compounds such as ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; 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; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds.

The monomers exemplified in the above (b4) may be used alone or in combination of two or more.

Is in the range of 10 to 80% by weight, preferably 10 to 70% by weight based on the solid content in the photosensitive resin composition. When the content of the alkali-soluble resin (B) is 10 to 80% by weight based on the above-mentioned criteria, the solubility in a developing solution is sufficient and pattern formation is easy. In the development, film reduction of the pixel portion of the exposed portion is prevented, It is preferable that the dropout property is improved.

Photopolymerization  Substance (C)

The photopolymerizable material (C) is a compound capable of polymerizing under the action of a photopolymerization initiator described later, and contains at least one photopolymerizable compound having a viscosity at 25 ° C of 20 mPa · s or less.

The lower the viscosity of the photopolymerizable compound, the more fluidity is secured and the possibility of occurrence of VD unevenness is lowered. Therefore, when the photopolymerizable compound having a viscosity at 25 캜 of 20 mPa s or less is not included, it is difficult to expect the improvement effect of VD unevenness.

In order to ensure sufficient curing of the colored photosensitive resin composition of the present invention, the photopolymerizable material (C) is preferably a mixture of a photopolymerizable compound having a viscosity at 25 ° C of 20 mPa · s or less and a multifunctional photopolymerizable compound.

Specific examples of the photopolymerizable compound having a viscosity at 25 캜 of not more than 20 mPa 로 include diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1 Diethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,9-nonanediol dimethacrylate, triethylene glycol dimethacrylate, Hexanediol diacrylate, 1,9-nonanediol diacrylate, 2-methyl-1,8-octanediol diacrylate, and the like.

Specific examples of the polyfunctional photopolymerizable compound include pentaerythritol triacrylate and dipentaerythritol pentaacrylate, which may be used alone or in combination of two or more. Commercially available products include NK ESTER, 701A (NK ESTER), A-TMM-3L (NK ESTER) and KAYARAD DPHA.

The photopolymerizable material (C) is preferably contained in an amount of 5 to 45% by weight, more preferably 7 to 45% by weight, based on the total weight of the solid content of the colored photosensitive resin composition. When the photopolymerizable material (C) is contained in an amount of 5 to 45% by weight based on the above-mentioned criteria, the strength and smoothness of the pixel portion are preferably improved.

The content of the photopolymerizable compound having a viscosity of 20 mPa · s at 25 ° C is preferably 5 to 50 wt% of the total photopolymerizable material (C), and it is difficult to expect a VD improvement when the amount is less than 5 wt% , The curing degree of the colored photosensitive resin composition is insufficient and a reliability distribution such as solvent resistance is likely to occur.

Light curing Initiator (D)

The photopolymerization initiator (D) comprises a photopolymerization initiator (d1) having a structure represented by the following general formula (1).

[Chemical Formula 1]

(2)

In Formula 1, R ₁ is represented by Formula 2, R ₄ is C1-C4 alkyl, and R ₅ is a C3-C8 ring structure. In Formula 1, R ₂ is C1-C8 alkyl , Substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, and R ₃ is substituted or unsubstituted diphenylsulfide.

In addition, the photopolymerization initiator (d2) other than those described above may be further used in combination within the range not impairing the effect of the present invention. Typically, it is preferable to use at least one compound selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a nonimidazole-based compound, and a thioxanthone-based compound.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Examples of the benzophenone compound include benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) Imidazole compounds in which 4'5,5'-tetraphenyl-1,2'-biimidazole or phenyl groups at 4,4 ', 5,5' positions are substituted by carboalkoxy groups. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

The photopolymerization initiator (D) may further comprise a photopolymerization initiator (d3) to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation auxiliary (d3), whereby the sensitivity is further increased and the productivity can be improved.

As the photopolymerization initiation aid (d3), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound and an organic sulfur compound having a thiol group can be preferably used.

As the amine compound, an aromatic amine compound is preferably used. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone ), 4,4'-bis (diethylamino) benzophenone, and the like.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and more specifically, it is preferably an aromatic heteroaromatic acid such as 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 a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) Triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate). .

The photopolymerization initiator (D) is used in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight based on the total amount of the alkali-soluble resin (B) and the photopolymerizable material (C) based on the total solid weight of the colored photosensitive resin composition of the present invention. % By weight. When the photopolymerization initiator (D) is contained in the range of 0.1 to 40% by weight, the color photosensitive resin composition is highly sensitized and the exposure time is shortened, which is preferable because productivity can be improved and high resolution can be maintained. Further, the strength of the pixel portion formed using the composition of the above-described conditions and the smoothness of the surface of the pixel portion can be improved. In case of (d1), 10 to 100% by weight, preferably 20 to 100% by weight, based on the total weight of the total photopolymerization initiator, should be included. If the ratio of (d1) based on the total weight of the total photopolymerization initiator is less than 10% by weight, the sensitivity deterioration due to the dye can not be overcome and the pattern is likely to be short-circuited during the development process.

When the photopolymerization initiator (d3) is further used, the photopolymerization initiator (d3) is added to the alkali-soluble resin (B) and the photopolymerizable material (C) based on the total solid weight of the colored photosensitive resin composition of the present invention. By weight, preferably 1 to 30% by weight, based on the total weight of the composition. When the amount of (d3) is within the above range of 0.1 to 40% by weight, the sensitivity of the colored photosensitive resin composition becomes higher and the productivity of the color filter formed using the composition is improved.

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; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 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? -Butyrolactone.

The solvent (E) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in terms of coatability and dryness, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl Lactate, butylacetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

Each of the above-mentioned solvents (E) may be used alone or in combination of two or more. The solvent (E) may include 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention have. When the content of the solvent (E) is within the range of 60 to 90% by weight, it is coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater Thereby providing an effect of improving the applicability.

Additive (F)

The above-mentioned additive (F) may be optionally added, for example, other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an ultraviolet absorber and an antiflocculating agent.

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

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

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

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

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used for further improving the film-forming property of the photosensitive resin composition, and a silicone, fluorine, ester, cationic, anionic, nonionic or amphoteric surfactant may be used. For example, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines and the like can be used have.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the solid content of the colored photosensitive resin composition.

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

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

The thus-prepared colored photosensitive resin composition is advantageous for achieving a high concentration and a high transmittance, and is excellent as a dispersion stability and excellent in characteristics along with time. Therefore, it is useful as a raw material for forming a coloring pattern constituting a color filter.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples and experimental examples, and can be variously modified and changed.

Manufacturing example  1. Preparation of pigment dispersion composition

12 parts by weight of CI Pigment Red 254 as a pigment, 6 parts by weight of DISPERBYK-2001 (BYK) as a pigment dispersant, 61.5 parts by weight of propylene glycol methyl ether acetate as a solvent and 61.5 parts by weight of 4-hydroxy-4-methyl- Were mixed and dispersed for 12 hours using a bead mill to prepare a pigment dispersion composition M1.

Synthetic example  1. Alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 13 parts by weight of acrylic acid, 10 parts by weight of 4-methylstyrene, 20 parts by weight of methylmethacrylate and 3 parts by weight of n-dodecylmercapto were charged and replaced with nitrogen. The solid content of the synthesized alkali-soluble resin was 100.2 mgKOH / g, and the weight average molecular weight (Mw) measured by GPC was 100.2 mgKOH / g. The alkali- Was about 15,110.

Example  1 to 3 and Comparative Examples 1 to 4: Preparation of colored photosensitive resin composition

≪ Example 1 >

47.50 parts by weight of the pigment-dispersed composition M1 of Production Example 1, 8.64 parts by weight of the alkali-soluble resin of Synthesis Example 1, 0.58 parts by weight of 1,6-hexane diol diacrylate as a photopolymerizable compound (viscosity at 25 占 폚, 2.30 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a multifunctional photopolymerizable compound, 0.57 parts by weight of TR-PBG-305 (Tronisia) represented by the following formula 3 as an initiator, 4-hydroxy- 8.50 parts by weight of methyl-2-pentanone, 31.79 parts by weight of propylene glycol monomethyl ether acetate, 0.1 part by weight of 33-methacryloxypropyltrimethoxysilane (Shinetsu) as an adhesion promoter, and SH-8400 Dow Corning Corp.) were mixed to prepare a colored photosensitive resin composition.

(3)

≪ Example 2 >

47.50 parts by weight of the pigment-dispersed composition M1 of Production Example 1, 8.64 parts by weight of the alkali-soluble resin of Synthesis Example 1, 0.58 parts by weight of 1,4-butanediol dimethacrylate as a photopolymerizable compound (viscosity at 25 ° C 2.30 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a polyfunctional photopolymerizable compound, 0.57 parts by weight of TR-PBG-305 (Tronysa) containing the structural unit of the formula (I) as an initiator, -4-methyl-2-pentanone, 31.79 parts by weight of propylene glycol monomethyl ether acetate, 0.1 part by weight of 3-methacryloxypropyltrimethoxysilane (Shinetsu) as an adhesion promoter, and SH -8400 (Dow Corning Toray Co., Ltd.) were mixed to prepare a colored photosensitive resin composition.

≪ Example 3 >

47.50 parts by weight of the pigment-dispersed composition M1 of Production Example 1, 8.64 parts by weight of the alkali-soluble resin of Synthesis Example 1, 2.30 parts by weight of 1,6-hexane diol diacrylate as a photopolymerizable compound (viscosity at 25 占 폚, 0.58 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a polyfunctional photopolymerizable compound, 0.57 parts by weight of TR-PBG-305 (Tronisia) containing a structural unit of the formula (I) as an initiator, 8.50 parts by weight of 4-methyl-2-pentanone, 31.79 parts by weight of propylene glycol monomethyl ether acetate, 0.1 part by weight of 33-methacryloxypropyltrimethoxysilane (Shinetsu) as an adhesion promoter, 8400 (Dow Corning Toray Co., Ltd.) were mixed to prepare a colored photosensitive resin composition.

≪ Comparative Example 1 &

47.50 parts by weight of the pigment-dispersed composition M1 of Production Example 1, 8.64 parts by weight of the alkali-soluble resin of Synthesis Example 1, 0.58 parts by weight of 2-hydroxy-3-acryloyloxypropylmethacrylate as a photopolymerizable compound 0.57 parts by weight of TR-PBG-305 (TRONISA) containing structural units represented by the formula (I) as an initiator, KAYARAD DPHA (Nippon Kayaku Co., Ltd.) as a polyfunctional photopolymerizable compound at a viscosity of 71.8 mPa · s at 25 ° C, 8.50 parts by weight of 4-hydroxy-4-methyl-2-pentanone, 31.79 parts by weight of propylene glycol monomethyl ether acetate, 0.1 part by weight of 3-methacryloxypropyltrimethoxysilane (Shinetsu) as an adhesion promoter, 0.02 part by weight of an active agent SH-8400 (Dow Corning) was mixed to prepare a colored photosensitive resin composition.

≪ Comparative Example 2 &

47.50 parts by weight of the pigment-dispersed composition M1 of Production Example 1, 8.64 parts by weight of the alkali-soluble resin of Synthesis Example 1, 0.58 parts by weight of dimethiol tricyclodecane diacrylate as a photopolymerizable compound (having a viscosity of 160 mPa 2.30 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a polyfunctional photopolymerizable compound, 0.57 parts by weight of TR-PBG-305 (Tronisia) containing a structural unit of the formula (1) as an initiator, -Methyl-2-pentanone, 31.79 parts by weight of propylene glycol monomethyl ether acetate, 0.1 part by weight of 3-methacryloxypropyltrimethoxysilane (Shinetsu) as an adhesion promoter, and SH-8400 (Dow Corning Toray Co., Ltd.) were mixed to prepare a colored photosensitive resin composition.

≪ Comparative Example 3 &

47.50 parts by weight of the pigment-dispersed composition M1 of Production Example 1, 8.64 parts by weight of the alkali-soluble resin of Synthesis Example 1, 2.88 parts by weight of KAYARAD DPHA (Nippon Kayaku, viscosity of 7000 mPa s or more at 25 캜) as a photopolymerizable compound, 0.57 parts by weight of TR-PBG-305 (Tronison) containing the structural unit represented by the formula (1), 8.50 parts by weight of 4-hydroxy-4-methyl-2-pentanone, 31.79 parts by weight of propylene glycol monomethyl ether acetate, , 0.1 part by weight of 3-methacryloxypropyltrimethoxysilane (Shinetsu) and 0.02 part by weight of a surfactant, SH-8400 (Dow Corning) were mixed to prepare a colored photosensitive resin composition.

≪ Comparative Example 4 &

47.50 parts by weight of the pigment-dispersed composition M1 of Production Example 1, 8.64 parts by weight of the alkali-soluble resin of Synthesis Example 1, 0.58 parts by weight of 1,6-hexane diol diacrylate as a photopolymerizable compound (viscosity at 25 占 폚, 2.30 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a polyfunctional photopolymerizable compound, 0.57 parts by weight of Irgacure 369 (BASF) as a initiator, 8.50 parts by weight of 4-hydroxy-4-methyl- , 31.79 parts by weight of propylene glycol monomethyl ether acetate, 0.1 part by weight of 33-methacryloxypropyltrimethoxysilane (Shinetsu) as an adhesion promoter, and 0.02 part by weight of a surfactant, SH-8400 (Dow Corning) To prepare a photosensitive resin composition.

Experimental Example  1. Development speed, adhesion and pattern Line width  Measure

A color filter was prepared using the colored photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4.

Specifically, each of the above colored photosensitive resin compositions was applied on a 2-inch-square glass substrate ("EAGLE XG", manufactured by Corning Inc.) by spin coating, then placed on a heating plate and held 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 in the range of 1 to 100% in a stepwise manner and a line / space pattern of 1 to 50 m was placed on the thin film, and the interval between the test photomask and the test photomask was set to 300 [ Respectively. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 60 mJ / cm 2, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 25 minutes to prepare a color filter. The film thickness of the color filter was 2.3 μm.

≪ Development speed >

The faster the developing speed, the lower the defect rate due to the residue and the unexplored phenomenon, the higher the yield of the product, and the higher the product production speed. In order to confirm the developing speed, the time taken for completely dissolving the unexposed portion in the developer during development was measured, and the results are shown in Table 1 below.

As shown in Table 1, Examples 1 to 3 exhibited a short time or similar time until the non-visible portion was completely dissolved in the developer as compared with Comparative Examples 1 to 4.

≪ Adhesion >

The better the adhesion, the less the defect rate due to the peeling of the pattern, and the higher the yield of the product. When the pattern was evaluated through an optical microscope, the degree of peeling phenomenon was evaluated on the pattern to evaluate the adhesiveness. The results are shown in Table 1 below.

In Table 1, 'o' means no pattern peeling, '△' means 1 to 3 pattern peeling, and 'x' means pattern peeling 4 or more.

As shown in Table 1, Examples 1 to 3 exhibited generally excellent adhesion or similar adhesion as compared with Comparative Examples 1 to 4.

<Pattern line width>

When the line width of the pattern is measured to be not less than the line width of the photomask, the sensitivity of the colored photosensitive resin composition is sufficient and the line width is enlarged. The line width of the generated pattern was measured using a scanning electron microscope, and the enlarged line width of the resulting photomask was shown in Table 1 below.

division Dissolution time
(Developing speed) Adhesiveness Pattern line width △ E * ab
(Solvent resistance) VD stain Example 1 19 ○ +8 3.2 ○ Example 2 21 ○ +9 3.0 ○ Example 3 10 △ +0 3.6 ○ Comparative Example 1 25 ○ +11 3.1 △ Comparative Example 2 30 ○ +11 3.5 × Comparative Example 3 22 ○ +13 2.8 × Comparative Example 4 20 × -4 7.4 ○

Experimental Example  2. Solvent resistance  Measure

Test A color filter was prepared in the same manner as in Experimental Example 1 except that the photomask was not used.

<Solvent resistance>

The lower the value of DELTA E * ab is, the more excellent the color filter with excellent solvent resistance can be produced.

In order to evaluate the solvent resistance, the fabricated color filter was immersed in a solvent of N-methylpyrrolidone for 30 minutes, and ΔE * ab was determined from the chromaticity of the color pattern before and after immersion. The results are shown in Table 1. The higher the value of? E * ab is, the poorer the solvent resistance is, so the various solvent resistance which can be used for the panel treatment in the production of the liquid crystal display device becomes insufficient, causing practical problems. The lower the value of? E * ab is, It is possible to manufacture a color filter with high reliability.

Experimental Example  3. VD  Stain measurement

The lower the incidence of VD unevenness, the lower the defect due to VD unevenness, and the yield of the product can be improved. The colored photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were each coated on a 2-inch glass substrate ("EAGLE XG", manufactured by Corning Inc.) by spin coating, And the results are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

"○" in Table 1 means no more than 5 VD streaks, "Δ" means more than 5 VD streaks and 10 or less, and "×" means more than 10 VD streaks respectively.

As shown in Table 1, Comparative Examples 1 and 4 had VD spots of more than 5 and less than 10, and Comparative Examples 2 and 3 had more than 10 VD spots. On the other hand, in Examples 1 to 3, the incidence of VD unevenness was low because the VD unevenness was 5 or less.

Claims (9)

1. A colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable material (C), a photopolymerization initiator (D), and a solvent (E)
Wherein the photopolymerizable material (C) comprises a photopolymerizable compound having a viscosity of 20 mPa s or less at 25 캜,
Wherein the photopolymerization initiator (D) comprises a structural unit (d1) represented by the following formula (1):
[Chemical Formula 1]

In Formula 1, R ₁ is represented by the following Formula 2,
R ₂ is a C1-C8 alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group,
R ₃ is substituted or unsubstituted diphenyl sulfide,
(2)

In the general formula (2), R ₄ is an alkyl group having 1 to 4 carbon atoms,
R ₅ is a C3 to C8 ring structure. The method according to claim 1,
The colored photosensitive resin composition contains, based on the total solid weight,
The colorant (A) is contained in an amount of 5 to 60% by weight,
The alkali-soluble resin (B) contains 10 to 80% by weight,
The photopolymerizable material (C) is contained in an amount of 5 to 45% by weight,
The photopolymerization initiator (D) is contained in an amount of 0.1 to 40% by weight based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C)
Wherein the solvent (E) is contained in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition. The method according to claim 1,
Wherein the photopolymerizable material (C) comprises a photopolymerizable compound having a viscosity of 20 mPa 占 퐏 or less at 25 占 폚 and a multifunctional photopolymerizable compound. The method of claim 3,
The photopolymerizable compound having a viscosity of 20 mPa 占 퐏 or less at 25 占 폚 is selected from the group consisting of diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9- Hexanediol diacrylate, nonanediol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexane 1,9-nonanediol diacrylate, and 2-methyl-1,8-octanediol diacrylate. 2. The colored photosensitive resin composition according to claim 1, The method according to claim 1,
Wherein the photopolymerizable compound having a viscosity of 20 mPa 占 퐏 or less at 25 占 폚 is 5 to 50% by weight based on the total weight of the photopolymerizable material. The method according to claim 1,
Wherein the compound represented by Formula 1 is 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (o-benzoyloxime). The method according to claim 1,
Wherein the structural unit (d1) of the formula (1) is contained in an amount of 10 to 100% by weight based on the total weight of the total photopolymerization initiator. The method according to claim 1,
The hydroxyl value of the alkali-soluble resin (B) is 30 to 150 mgKOH / g. A color filter made of the colored photosensitive resin composition according to any one of claims 1 to 8.