KR20180081035A - Colored photosensitive resin composition and color filter using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising a coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E). The coloring agent (A) comprises a pigment (a1), a dye (a2), and a pigment dispersing agent (a3); the alkali-soluble resin (B) has an acid value of 30-150 mgKOH/g; the sum of hydroxyl group values of the alkali-soluble resin (B) and the photopolymerizable compound (C) is 30-180 mgKOH/g; and the photopolymerization initiator (D) comprises a structural unit (d1) of chemical formula 1.

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, in recent years, the size of display has been rapidly increasing, and high contrast ratio has been continuously demanded. However, in the conventional pigment dispersing system, the limit of pigment particleization has reached a limit and due to problems such as color unevenness due to coarse particles, A method of simultaneously using a pigment and a dye has been studied (Korean Patent Registration No. 10-0881860).

However, when a color filter is produced by using a colored photosensitive resin composition containing a dye as a coloring agent, the light resistance and heat resistance of the dye are poor, so that color shifts occur frequently, and the development speed is slow and sensitivity is low. There is a problem that the formed pattern is peeled off during the process.

Therefore, research has been conducted to solve this problem. For example, Korean Patent Laid-Open Publication No. 2011-0085005 discloses a ketooxime ester-based photoinitiator having excellent thermal stability and a process for producing the same, in order to solve the problem of poor OXE-1 ketooxime ester photoinitiator having poor application performance and low thermal stability. / RTI >

In addition, Taiwan National Publication No. 2010-0088529 discloses that a conventional acrylate monomer has a hydroxyl value of not less than 70 mgKOH / g and not more than 130 mgKOH / g, in order to solve the problem that the adhesion, resolution, g or less, and a photosensitive resin composition for a black matrix.

However, it is still necessary to solve the problem of the developing speed and sensitivity, and the problem of delamination of the pattern in the development process by the alkali developing solution.

KR 2011-0085005 A KR 2010-0088529 A

Accordingly, it is an object of the present invention to provide a colored photosensitive resin composition for a color filter which can obtain a color filter excellent in contrast ratio.

It is another object of the present invention to provide a colored photosensitive resin composition which has a high developing speed and is excellent in sensitivity and adhesion so that there is no peeling of the pattern during the development process and the storage stability is excellent and there is no increase in sensitivity or viscosity even when stored for a long time. .

In order to achieve the above object,

A colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) (B) having an acid value of 30 to 150 mgKOH / g, the sum of the hydroxyl groups of the alkali-soluble resin (B) and the photopolymerizable compound (C) being 30 to 180 mgKOH / g And the photopolymerization initiator (D) has a structure represented by the following general formula (1).

Wherein R ₁ is represented by the following formula (2), R ₄ is a C ₁ -C ₄ alkyl and R ₅ is a C ₃ -C ₈ ring structure, and R ₂ in the formula (1) C ₁ -C ₈ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl group, and R ₃ is a substituted or unsubstituted diphenylsulfide group.

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

The colored photosensitive resin composition of the present invention is excellent in storage stability and is excellent in sensitivity and adhesion so that a pattern is not easily short-circuited during a development process, and thus the productivity of a color filter is excellent. Also, the color filter manufactured by using the same has a high contrast ratio.

Hereinafter, the roles of the constituent elements of the present invention will be described in more detail.

The present invention provides a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) Soluble resin (B) and a hydroxyl group of the photopolymerizable compound (C) is 30 to 150 mgKOH / g, wherein the alkali-soluble resin (B) Wherein the photopolymerization initiator (D) has a structure represented by the following general formula (1).

[Chemical Formula 1]

Wherein R ₁ is represented by the following formula (2), R ₄ is a C ₁ -C ₄ alkyl and R ₅ is a C ₃ -C ₈ ring structure, and R ₂ in the formula (1) C ₁ -C ₈ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl group, and R ₃ is a substituted or unsubstituted diphenylsulfide group.

(2)

Hereinafter, each configuration will be described in more detail.

The colorant (A)

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

The 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 .

The 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 mass, more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the solid content of the pigment (a1). If the content of the pigment dispersant (a3) exceeds 60 parts by mass, the viscosity may be increased. If the content of the pigment dispersant is less than 5 parts by mass, it may be difficult to atomize the pigment or cause gelation after dispersion.

The dye (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 a sulfonic acid and a carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthate, phthalocyanine 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.

* 65C.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.

A hydroxyl group may be added to secure further developability of the alkali-soluble resin (B). (B) and the hydroxyl value of the photopolymerizable compound (C) is limited to 30 mgKOH / g or more and 180 mgKOH / g or less. If the sum of the hydroxyl groups is less than 30 mgKOH / g, a sufficient developing rate can not be secured. If the sum of the hydroxyl groups is more than 180 mgKOH / g, the dimensional stability of the formed pattern is lowered, and the linearity of the pattern becomes poor, A problem of storage stability tends to occur.

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.

The content of the alkali-soluble resin (B) should satisfy the condition that the sum of the alkali-soluble resin (B) and the hydroxyl group of the photopolymerizable compound (C) is from 30 mgKOH / g to 180 mgKOH / g, Is in the range of 10 to 80% by weight, preferably 10 to 70% by weight. 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.

The photopolymerizable compound (C)

The photopolymerizable compound (C) should be a compound capable of polymerizing under the action of a photopolymerization initiator described later and must satisfy the above-described hydroxyl value for compatibility with the dye and compatibility with the dye. Although the number of functional groups is not particularly limited, a bifunctional photopolymerizable compound is preferable, and a multifunctional photopolymerizable compound having three or more functional groups which is excellent in polymerization property and can be sufficiently cured is more preferable.

Specific examples of the bifunctional photopolymerizable compound include 2-hydroxy-1,3-dimethacryloxypropane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, and the like.

Specific examples of the polyfunctional photopolymerizable compound having three or more functionalities include pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and a combination of two or more thereof can be used. Commercial products 701 (NK ESTER), 701A (NK ESTER), A-TMM-3L (NK ESTER) and KAYARAD DPHA (Nippon Kayaku) are commercially available products.

The content of the photopolymerizable compound (C) should satisfy the condition that the sum of the alkali-soluble resin (B) and the hydroxyl group of the photopolymerizable compound (C) is 50 mgKOH / g or more and 250 mgKOH / g or less. Is preferably contained in an amount of 5 to 45% by weight, more preferably 7 to 45% by weight. When the photopolymerizable compound (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.

Photopolymerization 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 the general formula 1 R ₁ is the formula (2) is represented by the general formula (2), in R ₄ is C ₁ ~ C ₄ alkyl, R ₅ is C ₃ ~ a ring structure of a C _8, the C in the formula 1 R _{2 1} to ₈ carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, and R ₃ is a substituted or unsubstituted diphenylsulfide group.

The photopolymerization initiator (d1), which is a structure of the above-mentioned formula (1), prevents photodecomposition by the dye, thereby exhibiting effective photopolymerization properties in a colored photosensitive resin composition containing a dye as a colorant.

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 0-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 compound (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 compound (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 Tartrate, 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 additive (F) may be optionally added, for example, other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an antiflocculant.

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

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

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 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 antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

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 mixing and dispersing methods for the components are not particularly limited to those known to those skilled in the art. Specifically, the dispersing machine used for dispersing the respective components in the solvent is not particularly limited and may be a kneader, a roll mill, an attritor, a super mill, a dissolver, A known dispersing machine such as a homogenizer, a sand mill or the like can be used.

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

Method for producing colored photosensitive resin composition

The process for producing the colored photosensitive resin composition of the present invention will be described as follows.

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

The dye (a2), the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D) and, if necessary, the additive (F) and the solvent (E) The colored photosensitive resin composition according to the present invention can be prepared.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are on a mass basis unless otherwise specified.

Production Example 1: Preparation of pigment dispersion composition

<Pigment dispersion composition M1>

C.I. Pigment Blue 15: 6, 4.0 parts by mass of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by mass of propylene glycol methyl ether acetate as a solvent and 40 parts by mass of propylene glycol methyl ether by means of a bead mill for 12 hours Followed by mixing / dispersing to prepare a pigment dispersion composition M1.

Synthesis Examples 1 to 4: Synthesis of alkali-soluble resin

&Lt; Synthesis Example 1 &

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 13.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 57.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecyl mercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was elevated to 110 DEG C with stirring, and the reaction was carried out for 6 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 100.2 mgKOH / g and a weight average molecular weight Mw of about 15,110 as measured by GPC.

&Lt; Synthesis Example 2 &

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 9.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 54.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate, 7.0 parts of 2-hydroxyethyl methacrylate and 3 parts of n-dodecyl mercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was elevated to 110 DEG C with stirring, and the reaction was carried out for 6 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 69.4 mgKOH / g, a hydroxyl value of 29.8 mgKOH / g, and a weight average molecular weight Mw of about 13,180 as measured by GPC.

&Lt; Synthesis Example 3 &

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 3.5 parts of acrylic acid, 10 parts of benzyl methacrylate, 66.5 parts of 4-methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecyl mercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was elevated to 110 DEG C with stirring, and the reaction was carried out for 6 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 26.5 mgKOH / g and a weight average molecular weight Mw of about 16,070 as measured by GPC.

&Lt; Synthesis Example 4 &

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 22.5 parts of acrylic acid, 10 parts of benzyl methacrylate, 47.5 parts of 4-methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecylmercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was elevated to 110 DEG C with stirring, and the reaction was carried out for 6 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 172.3 mgKOH / g and a weight average molecular weight Mw of about 14,850 as measured by GPC.

Examples 1 to 8 and Comparative Examples 1 to 7: Preparation of colored photosensitive resin composition

&Lt; Example 1 >

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 1, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl value of 41 mgKOH / g, Irgacure 369 (Manufactured by TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Example 2 >

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 1, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl value of 80 mgKOH / g, Irgacure 369 Ltd.), 0.7 part of TR-PBG-305 (TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Example 3 >

22.5 parts of the above-mentioned pigment dispersion composition M1; , 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 1, 5.1 parts of pentaerythritol acrylate having a hydroxyl value of 104 mgKOH / g, Irgacure 369 Manufactured by Toray Industries, Inc.), 0.7 part of TR-PBG-305 (TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

<Example 4>

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 1, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl group of 162 mgKOH / g, Irgacure 369 Ltd.), 0.7 part of TR-PBG-305 (TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Example 5 >

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 2, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl value of 41 mgKOH / g, Irgacure 369 Ltd.), 0.7 part of TR-PBG-305 (TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Example 6 >

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 2, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl value of 80 mgKOH / g, Irgacure 369 Ltd.), 0.7 part of TR-PBG-305 (TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Example 7 >

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 2, 5.1 parts of acrylate of pentaerythritol having a hydroxyl value of 104 mgKOH / g, Irgacure 369 Manufactured by Toray Industries, Inc.), 0.7 part of TR-PBG-305 (TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Example 8 >

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 2, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl group of 22 mgKOH / g, Irgacure 369 Ltd.), 0.7 part of TR-PBG-305 (TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Example 9 >

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 1, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl value of 80 mgKOH / g, Irgacure 369 Ltd.), 0.7 part of the photopolymerization initiator of the following formula (4), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Comparative Example 1 &

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 1, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl group of 22 mgKOH / g, Irgacure 369 Ltd.), 0.7 part of TR-PBG-305 (TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Comparative Example 2 &

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 2, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl value of 162 mgKOH / g, Irgacure 369 Ltd.), 0.7 part of TR-PBG-305 (TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Comparative Example 3 &

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 3, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl value of 80 mgKOH / g, Irgacure 369 Ltd.), 0.7 part of TR-PBG-305 (TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Comparative Example 4 &

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 4, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl value of 80 mgKOH / g, Irgacure 369 Ltd.), 0.7 part of TR-PBG-305 (TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Comparative Example 5 &

22.5 parts of the pigment dispersion composition M1, 16.8 parts of the resin of Synthesis Example 1, 5.1 parts of dipentaerythritol acrylate having a hydroxyl value of 80 mgKOH / g, 0.3 part of Irgacure 369 (manufactured by BASF), TR-PBG-305 Ltd.), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Comparative Example 6 >

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 1, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl value of 80 mgKOH / g, Irgacure 369 Ltd.), 0.7 parts of Irgacure OXE-01 (BASF), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

&Lt; Comparative Example 7 &

22.5 parts of the above-mentioned pigment dispersion composition M1; 0.3 part of Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Chemical Industries, Ltd.), 16.8 parts of the resin of Synthesis Example 4, 5.1 parts of acrylate of dipentaerythritol having a hydroxyl value of 80 mgKOH / g, Irgacure 369 Ltd.), 0.7 part of the photopolymerization initiator of the following formula (4), 20.3 parts of propylene glycol monomethyl ether acetate and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

Example coloring agent bookbinder The monomer (hydroxyl group) Photopolymerization initiator Acid value Sum of hydroxyl groups One P + D Synthesis Example 1 41 P 100.2 41 2 P + D Synthesis Example 1 80 P 100.2 80 3 P + D Synthesis Example 1 104 P 100.2 104 4 P + D Synthesis Example 1 162 P 100.2 162 5 P + D Synthesis Example 2 41 P 68 70.8 6 P + D Synthesis Example 2 80 P 68 109.8 7 P + D Synthesis Example 2 104 P 68 133.8 8 P + D Synthesis Example 2 22 P 68 51.8 9 P + D Synthesis Example 1 80 A 100.2 80

P: C.I. Pigment Blue 15: 6D: C.I. Solvent Blue 44

Synthesis Example 1: Synthesis of Compound (1) having an acid value of 100.2, a hydroxyl group of 0

Synthesis Example 2: Acid value 69.4, hydroxyl value 29.8

P: TR-PBG-305 (manufactured by TRONLY)

A:

Comparative Example coloring agent bookbinder The monomer (hydroxyl group) Photopolymerization initiator Acid value Sum of hydroxyl groups One P + D Synthesis Example 1 22 P 100.2 22 2 P + D Synthesis Example 2 162 P 68 191.8 3 P + D Synthesis Example 3 80 P 25 80 4 P + D Synthesis Example 4 80 P 173 80 5 P Synthesis Example 1 80 P 100.2 80 6 P + D Synthesis Example 1 80 O 100.2 80 7 P + D Synthesis Example 4 80 A 172.5 80

P: C.I. Pigment Blue 15: 6D: C.I. Solvent Blue 44

Synthesis Example 1: Synthesis of Compound (1) having an acid value of 100.2, a hydroxyl group of 0

Synthesis Example 2: Acid value 69.4, hydroxyl value 29.8

Synthesis Example 3: An acid value of 26.5, a hydroxyl value of 0

Synthesis Example 4: An acid value of 172.5, a hydroxyl value of 0

P: TR-PBG-305 (manufactured by TRONLY)

O: Irgacure OXE-01 (manufactured by BASF)

A:

EXPERIMENTAL EXAMPLE 1 Development speed, adhesion and line width measurement of pattern

A color filter was prepared using the colored photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 7.

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% to a step-like pattern and a line / space pattern of 1 to 50 m was placed on the thin film and the distance between the test photomask and the test photomask was set to 100 m. 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 100 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, blown with nitrogen gas, dried, and heated in a heating oven at 200 ° C for 25 minutes to prepare a color filter.

The film thickness of the color filter prepared above was 2.3 탆.

&Lt; Development speed >

The time taken for the unexposed area to completely dissolve in the developing solution at the time of development was measured and shown in Tables 3 to 4 below.

&Lt; Adhesion >

When the generated pattern was evaluated through an optical microscope, the following pattern was evaluated as a degree of peeling, and the results are shown in Tables 3 to 4 below.

○: No pattern peeling

△: 1 to 3 pattern peeling

X: Pattern peeling 4 or more

<Pattern line width>

The line width of the generated pattern was measured using a scanning electron microscope. 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 enlarged line widths of the photomask are shown in Tables 3 to 4 below.

&Lt; Experimental Example 2 > Measurement of contrast ratio

The contrast ratio was measured using the color filter manufactured in the same manner except that the test example 1 and the test photomask were not used.

The substrate of the color filter was sandwiched between two polarizing plates and the maximum value and the minimum value of the light intensity transmitted through the front side deflector plate while rotating with the fluorescent lamp (wavelength of 380 to 780 nm) (KONICA MINOLTA), and the contrast ratio, which is a value obtained by dividing the maximum value by the minimum value, is calculated and shown in Tables 3 to 4 below.

&Lt; Experimental Example 3 > Measurement of viscosity change and evaluation of aged foreign matters

&Lt; Measurement of viscosity change &

The initial viscosity of the pigment dispersion composition prepared in the above Examples and Comparative Examples was measured and stored for 1 month at 5 ° C, and then the viscosity was measured to observe the viscosity change. The viscosity was measured with a Brookfield viscometer (Brookfield Viscometer DVI +, manufactured by BROOKFIELD) at 25 ° C. The measured results are shown in the following Tables 3 to 4 as storage stability.

○: Change in viscosity ± 5% or less

Δ: Change in viscosity ± 5% or more ± 10% or less

×: Change in viscosity ± 10% or more

<Evaluation of foreign objects>

The pigment dispersion compositions prepared in the above Examples and Comparative Examples were each stored at 5 占 폚 for 1 month and then observed with a reflection type optical microscope (observation magnification: 2,500 times) as in the above initial foreign matter evaluation, Are shown in Tables 3 to 4 below.

◎: Two or less foreign objects

○: 3 to 5 foreign objects

?: 6 to 10 foreign objects

X: 11 or more foreign objects

Example Development speed (s) Contrast ratio Line width expansion (㎛) Adhesiveness Storage stability Neglect One 25 5693 2.90 ○ ○ △ 2 23 5871 2.72 ○ ○ ○ 3 19 5865 2.20 ○ ○ ○ 4 16 5826 1.38 △ ○ △ 5 34 5790 3.32 ○ ○ ○ 6 32 5580 3.20 ○ ○ ○ 7 32 5567 2.28 △ △ ○ 8 35 5961 3.49 ○ ○ ○ 9 22 5808 2.65 ○ ○ ○

Comparative Example Development speed (s) Contrast ratio Line width expansion (㎛) Adhesiveness Storage stability Neglect One 40 5825 3.00 ○ ○ × 2 31 5732 2.11 × × △ 3 70 5811 4.20 ○ ○ ○ 4 14 5755 -1.20 × △ △ 5 23 3509 3.70 ○ ○ ○ 6 22 5540 -2.60 ○ ○ ○ 7 13 5771 -1.40 × △ △

As shown in Table 3, the colored photosensitive resin compositions of Examples 1 to 9 according to the present invention exhibited excellent results in terms of developing speed, contrast ratio, line width expansion, adhesion, storage stability and aged deteriorated characteristics. On the other hand, as shown in Table 4, in Comparative Examples 1 and 2 in which the sum of the hydroxyl groups was outside the range of 30 to 180 mgKOH / g, adhesion, storage stability and deteriorated foreign matter properties were poor. In the case of Comparative Example 4 in which the acid value was greatly out of the range of 30 to 150 mgKOH / g, line width expansion characteristics and adhesion were particularly poor. Also, in Comparative Example 5 not containing a dye, the contrast ratio characteristics were poor. In the case of Comparative Examples 6 and 7 in which the photopolymerization initiator was different, line width expansion characteristics and adhesion were particularly poor.

Accordingly, it can be confirmed that the colored photosensitive resin composition of the present invention can improve the process reliability, productivity and yield, and can produce a high-quality color filter with high developing speed and high sensitivity.

Claims (1)

1. A colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E)
Wherein the colorant (A) comprises at least one pigment (a1), at least one dye (a2) and at least one pigment dispersant (a3), wherein the alkali-soluble resin (B) has an acid value of 30 to 150 mgKOH / g, Wherein the sum of the hydroxyl group of the soluble resin (B) and the hydroxyl group of the photopolymerizable compound (C) is 30 to 180 mgKOH / g and the photopolymerization initiator (D) comprises the structural unit (d1) Composition.
[Chemical Formula 1]

Wherein R ₁ is represented by the following formula (2), R ₄ is a C ₁ -C ₄ alkyl and R ₅ is a C ₃ -C ₈ ring structure, and R ₂ in the formula (1) C ₁ -C ₈ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl group, and R ₃ is a substituted or unsubstituted diphenylsulfide group.
(2)