KR102497611B1 - A colored photosensitive resin composition and a color filter and a display device using the same - Google Patents

Abstract

The present invention is a colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerization initiator includes the compound represented by Formula 1, the compound represented by Formula 2 and the compound represented by Formula 3 By further including at least one of the compounds, it is possible to suppress the occurrence of reverse taper when forming a colored pattern, and to reduce the occurrence of line tearing of the pattern that occurs during the developing process due to excellent sensitivity characteristics, Provided are a colored photosensitive resin composition having excellent reliability such as solvent resistance and water stain prevention properties, a color filter and a display device manufactured using the same.

Description

Colored photosensitive resin composition, color filter and display device manufactured using the same

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

Color filters are widely used in various display devices such as image pickup devices, liquid crystal displays (LCDs) and organic light emitting diodes (OLEDs), and their application range is rapidly expanding.

Color filters used in display devices consist of three color patterns of red, green, and blue, or three colors of yellow, magenta, and cyan. It is made up of colored patterns.

Each color pattern of the color filter is generally formed using a colored photosensitive resin composition containing a colorant such as a pigment and/or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Color pattern processing using the colored photosensitive resin composition is usually performed through a lithography process.

In recent years, market demand for high-quality displays with high color reproducibility has increased, and accordingly, the content of colorants included in the colored photosensitive resin composition used in the manufacture of color filters has been continuously increased, and colorants with better coloring strength and contrast ratio have been added. Use is being reviewed.

However, when the content of the colorant is increased, a reverse taper phenomenon occurs during pattern formation with the colored photosensitive resin composition, and sensitivity is lowered, thereby causing problems such as tearing of the pattern and deterioration in reliability.

In this regard, Korean Patent Publication No. 10-2009-0098689 discloses a technology for a photosensitive resin composition including a colorant, but the published patent does not provide an alternative to the above problems.

Republic of Korea Patent Publication No. 10-2009-0098689

An object of the present invention is to provide a colored photosensitive resin composition having excellent color pattern formation characteristics, sensitivity and reliability, a color filter manufactured using the same, and a display device including the color filter.

The present invention is a colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

The photopolymerization initiator includes a compound represented by Chemical Formula 1, and further includes at least one of a compound represented by Chemical Formula 2 and a compound represented by Chemical Formula 3 to provide a colored photosensitive resin composition.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 2 and 3, R ¹ to R ¹² are each independently hydrogen, halogen, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ hydroxyalkyl group, C ₂ - A C ₂₄ hydroxyalkoxyalkyl group, a C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₀ aryl group, a C ₃ -C ₁₀ aralkyl group, an amino group, a nitro group, a cyano group, a hydroxy group, or is an organic residue.

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

In addition, the present invention provides an image display device including the color filter.

The colored photosensitive resin composition according to the present invention can suppress the occurrence of reverse taper when forming a colored pattern, and has excellent sensitivity characteristics to reduce the occurrence of line tearing in the pattern during the development process. It is possible to provide excellent effects in terms of reliability and anti-water staining properties.

Accordingly, the above-described colored photosensitive resin composition can be usefully applied to color filters and display devices requiring high color reproducibility.

The present invention is a colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerization initiator includes the compound represented by Formula 1, the compound represented by Formula 2 and the compound represented by Formula 3 By further including at least one of the compounds, it is possible to suppress the occurrence of reverse taper when forming a colored pattern, and to reduce the occurrence of line tearing of the pattern that occurs during the developing process due to excellent sensitivity characteristics, Provided are a colored photosensitive resin composition having excellent reliability such as solvent resistance and water stain prevention properties, a color filter and a display device manufactured using the same.

Hereinafter, each component constituting the colored photosensitive resin composition of the present invention will be described in detail. However, the present invention is not limited by these components.

<Colored photosensitive resin composition>

The colored photosensitive resin composition according to the present invention includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and may further include additives if necessary.

Colorant (A)

In one embodiment of the present invention, the colorant (A) comprises one or more pigments and/or one or more dyes.

pigment (a1)

As the pigment, organic or inorganic pigments generally used in the art may be used.

As the organic or inorganic pigment, various pigments used in printing ink, inkjet ink, etc. may be used. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoin Doline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyrans A pyranthrone pigment, a diketopyrroropyrrole pigment, etc. are mentioned. Examples of the inorganic pigment include metal compounds such as metal oxides, composite metal oxides, and metal complex salts; or carbon black. Specifically, examples of the metal include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. In particular, the organic and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists), more specifically, the following color index (C.I.) numbers Although a pigment can be mentioned, it is not necessarily limited to these.

For example, 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, 58, 59, 62 and 63;

C.I Pigment Brown 28;

C.I Pigment Black 1 and 7 and the like.

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

The above 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. A pigment selected from Pigment Green 58 can be preferably used.

As the pigment, it is preferable to use a pigment dispersion in which the particle size of the pigment is uniformly dispersed. As an example of a method for uniformly dispersing the particle size of the pigment, a method of dispersing treatment by containing a pigment dispersant (a2) may be mentioned. According to the above method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. there is.

Pigment Dispersant (a2)

The pigment dispersant is added to maintain the deagglomeration and stability of the pigment, and specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants. , These can be used individually or in combination of 2 or more types, respectively. In addition, it is preferable to include an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 or DISPER BYK-2150, and the acrylate-based dispersant may be used alone or in combination of two or more. can As the pigment dispersant (a2), other resin-type pigment dispersants may be used in addition to the above acrylate-based dispersants. The other resin-type pigment dispersants include known resin-type pigment dispersants, particularly polycarboxylic acid esters represented by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, and (partial) polycarboxylic acids. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) an oily dispersant such as an amide formed by reaction of a polyester having a carboxyl group with a poly(lower alkylenimine) or a salt thereof; water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylate; adducts of ethylene oxide/propylene oxide and phosphate esters; and the like.

Examples of commercially available resin type dispersants include, for example, BYK (Big) Chemie brand names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- as cationic resin dispersants. 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF brand names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemical: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Co., Ltd.: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 and the like. In addition to the above 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 content of the pigment dispersant (a2) is 5 to 60 parts by weight, preferably 10 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 (a2) exceeds 60 parts by weight, viscosity may increase, and if it is less than 5 parts by weight, it may be difficult to atomize the pigment or may cause problems such as gelation after dispersion.

Dye (a3)

The dye may be used without limitation as long as it has solubility in organic solvents. Preferably, it is preferable to use a dye capable of securing reliability such as solubility in an alkaline developing solution, heat resistance, and solvent resistance while having solubility in organic solvents. As the dye, acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof may be used. Acid dyes of the system and their derivatives can also be selected. Preferably, the dye may be a compound classified as a dye in the color index (published by The Society of Dyers and Colourists) or a known dye described in a dyeing note (dyed yarn).

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

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

C.I. Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67 and 70;

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

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

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

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

C.I. Among solvent dyes, C.I. Solvent Yellow 14, 16, 21, 56, 79, 93, 151; 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, among which C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent Orange 45 and 62 are more preferred.

Also, C.I. As an acid dye,

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 217 ,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349 , 382, 383, 394, 401, 412, 417, 418, 422 and 426;

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 ;

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

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

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

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

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

Also as a C.I. direct dye,

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

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

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

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

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

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

Also as a C.I. modanto dye,

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

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

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

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

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

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

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

The content of the colorant (A) may be included as 10 to 70% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition of the present invention. When the colorant is included in the above range, it is possible to form a pattern having sufficient color density and sufficient mechanical strength when made into a color filter.

Binder Resin (B)

The binder resin usually makes the non-exposed portion of the colored photosensitive resin layer formed using the colored photosensitive resin composition alkali-soluble, and also acts as a binder resin and a dispersion medium for the colorant. As the binder resin, one that is soluble in an alkaline developer used in the developing step for manufacturing the color filter is used.

In an exemplary embodiment, the binder resin included in the colored photosensitive resin composition of the present invention may include a repeating unit represented by Chemical Formula 4 and a repeating unit represented by Chemical Formula 5 below.

[Formula 4]

[Formula 5]

The binder resin may be a block copolymer in which the repeating units represented by Chemical Formulas 4 and 5 are constantly repeated, or a random copolymer in which these repeat units are randomly repeated.

In the present invention, the binder resin includes a repeating unit represented by Chemical Formula 4 and a repeating unit represented by Chemical Formula 5 including an epoxy group, thereby improving low-temperature reactivity of the colored photosensitive resin composition and improving hardness through a crosslinking reaction. As a result, reliability such as solvent resistance and chemical resistance can be improved.

The binder resin may include 5 to 95 mol% of the repeating unit represented by Chemical Formula 4 and 5 to 95 mol% of the repeating unit represented by Chemical Formula 5, based on 100 mol% of the total repeating units constituting the binder resin. there is.

When the repeating units represented by Chemical Formulas 4 and 5 are included in the mol% range, respectively, a binder resin having excellent developability and high degree of curing and reliability can be obtained.

In addition to the repeating unit represented by Chemical Formula 4 and the repeating unit represented by Chemical Formula 5, the binder resin of the present invention may include various polymers commonly used in this field.

For example, the binder resin may be copolymerized by further including at least one other monomer copolymerizable with the monomers of Chemical Formulas 4 and 5.

Other monomers copolymerizable with Chemical Formulas 4 and 5 include 3,4-epoxycyclohexylmethyl (meth)acrylate (CYM-M100, Daicel Co.), (hydroxyethyl) (Hydroxyethyl)methacrylate; HEMA) and/or 4-methacryloyloxyethy trimellitate anhydride; 4-META; and the like, but are not limited thereto.

The content of the other monomers is not particularly limited, but may be included in an amount of 5 to 70 mol% based on 100 mol% of the entire repeating unit constituting the binder resin.

The weight average molecular weight of the binder resin may be 3,000 to 20,000, preferably 5,000 to 15,000. When the weight average molecular weight is within the above range, the hardness of the coating film is improved, the residual film rate is high, the solubility of non-exposed parts in the developing solution is excellent, and the resolution tends to be improved, which is preferable.

In addition, the binder resin has an acid value of 50 to 200 mgKOH/g based on solid content, and within the above range, it has excellent alkali developability, suppresses residue generation, and improves pattern adhesion.

The binder resin (B) may be included in an amount of usually 5 to 75% by weight, preferably 10 to 65% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the binder resin (B) is included within the above range, the solubility in the developing solution is sufficient so that it is difficult to generate development residues on the substrate in the non-pixel portion, and it is difficult to cause film reduction in the pixel portion of the exposed portion during development. It is preferable because the omission of the tends to be good.

Photopolymerizable Compound (C)

In one embodiment of the present invention, the photopolymerizable compound (C) is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, bifunctional monomers, and other multifunctional monomers. .

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpy Rolidone etc. are mentioned. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Pentaerythritol hexa(meth)acrylate etc. are mentioned. Among these, bifunctional or more functional monomers may be preferably used.

The photopolymerizable compound (C) may be included in an amount of usually 5 to 50% by weight, preferably 7 to 45% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the photopolymerizable compound (C) is contained within the above range, it is preferable because the strength and smoothness of the pixel portion tend to be good.

Photopolymerization initiator (D)

In one embodiment of the present invention, the photopolymerization initiator (D) is a photopolymerization initiator containing an oxime-based compound, a compound represented by the following formula (1); and at least one of a compound represented by Formula 2 below and a compound represented by Formula 3 below.

[Formula 1]

[Formula 2]

[Formula 3]

In Formula 2 and Formula 3, R ¹ to R ¹² are each independently hydrogen, halogen, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ hydroxyalkyl group, C ₂ - A C ₂₄ hydroxyalkoxyalkyl group, a C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₀ aryl group, a C ₃ -C ₁₀ aralkyl group, an amino group, a nitro group, a cyano group, a hydroxy group, or is an organic residue.

The organic residue may be an organic residue having 1 to 20 carbon atoms.

In addition, the C ₁ -C ₁₂ alkyl group used herein refers to a straight-chain or branched hydrocarbon having 1 to 12 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl , nonyl, and the like, but are not limited thereto.

As used herein, the C ₁ -C ₁₂ alkoxy group refers to a straight-chain or branched alkoxy group having 1 to 12 carbon atoms, and includes methoxy, ethoxy, propanoxy, butoxy, pentoxy, etc., but is limited thereto It is not.

Aryl groups as used herein include both aromatic groups, heteroaromatic groups, and partially reduced derivatives thereof. The aromatic group is a 5- to 15-membered simple or fused ring, and the heteroaromatic group refers to an aromatic group containing at least one oxygen, sulfur, or nitrogen. Representative examples of aryl groups include phenyl, naphthyl, pyridinyl, furanyl, pyrrolyl, thiophenyl, benzothiophenyl, indolyl, quinoyl, quinolinyl, imidazolinyl, oxazolyl, thiazolyl, tetrahydronaphthyl, etc., but are not limited thereto.

As used herein, the aralkyl group refers to a complex group formed by substituting an aryl group (aromatic hydrocarbon group) on the carbon of an alkyl group, and includes, for example, benzyl, phenethyl, thiophenylpropyl, pyridinylmethyl, etc. but is not limited thereto.

As used herein, the C ₁ -C ₁₂ hydroxyalkyl group refers to a straight-chain or branched hydrocarbon having 1 to 12 carbon atoms substituted with a hydroxy group, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, etc. Including, but not limited to.

As used herein, the C ₂ -C ₂₄ hydroxyalkoxyalkyl group refers to a complex group formed by substituting a straight-chain or branched alkoxy group having 1 to 12 carbon atoms substituted with a hydroxy group on the carbon of an alkyl group having 1 to 12 carbon atoms, Examples include, but are not limited to, hydroxymethoxymethyl, hydroxyethoxymethyl, hydroxymethoxyethyl, and the like.

As used herein, the C ₃ -C ₁₀ cycloalkyl group refers to a simple or fused cyclic hydrocarbon having 3 to 10 carbon atoms, and examples thereof include, but are limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. it is not going to be

In the aryl group and aralkyl group, one or more hydrogens may be substituted with a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, or the like.

Examples of the compound represented by Formula 2 include Formulas 2-1 and 2-2 below, but are not limited thereto.

[Formula 2-1]

[Formula 2-2]

Examples of the compound represented by Formula 3 include Formulas 3-1 to 3-5 below, but are not limited thereto.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

In one embodiment of the present invention, the weight ratio of the oxime-based compound represented by Formula 1 and at least one oxime-based compound of the compound represented by Formula 2 and the compound represented by Formula 3 is 1 to 60:40 to 99, preferably 10 to 30:70 to 90.

When the weight ratio of the oxime-based compound represented by Formula 1 and at least one oxime compound of the compound represented by Formula 2 and the compound represented by Formula 3 is in the above range, there is little inverse taper occurrence and pattern tearing does not occur. It can have excellent pattern formation.

The photopolymerization initiator (D) may be included in an amount of 0.1 to 10% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the photopolymerization initiator (D) is included within the above range, photopolymerization may sufficiently occur during exposure in the pattern forming process, and transmittance may not decrease due to remaining unreacted initiator after photopolymerization.

Solvent (E)

In one embodiment of the present invention, the solvent (E) is not particularly limited as long as the colored photosensitive resin composition has appropriate viscosity and can easily dissolve the remaining components, and various organic solvents used in the field of colored photosensitive resin compositions. can be used.

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 ethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; 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; Cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned.

Among the solvents (E), organic solvents having a boiling point of 100° C. to 200° C. are preferably used in terms of coating properties and drying properties, and more preferably, alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy and esters such as ethyl propionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and 3-ethoxylates. Ethyl oxypropionate, methyl 3-methoxypropionate, etc. are mentioned.

These solvents (E) can be used alone or in combination of two or more.

The solvent (E) may be included in an amount of usually 50 to 90% by weight, preferably 55 to 80% by weight, based on 100% by weight of the entire colored photosensitive resin composition. When the solvent (E) is contained within the above range, coating properties are improved when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, or the like. It is desirable because it tends to

Additive (F)

The colored photosensitive resin composition may further include a nonionic, anionic or cationic dispersant as needed to improve the dispersibility of the pigment.

The dispersant includes polyalkylene glycol and its esters, polyoxyalkylenes, polyhydric alcohol esters, alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylate salts, alkyl Amidoalkylene oxide adducts, alkylamines and the like may be added alone or in combination of two or more. The dispersant may be included in an amount of 10 to 20 parts by weight based on 100 parts by weight of the pigment.

In addition, the colored photosensitive resin composition may further include a silicone-based or fluorine-based coating improver or an adhesion improver to improve adhesion with a substrate, if necessary, in order to improve coating properties and antifoaming properties. The coating improver and adhesion improver may be included in an amount of 0.01 to 1% by weight based on 100% by weight of the entire photosensitive resin composition.

In addition, in order to prevent stains or spots during application and to prevent the generation of residues due to leveling properties or undeveloped, the colored photosensitive resin composition may include an epoxy compound; malonic acid; 3-amino-1,2-propanediol; a silane-based coupling agent having a vinyl group or a (meth)acryloxy group; leveling agent; fluorine-based surfactants; Other additives such as a radical polymerization initiator may be further included. The amount of these additives used can be easily adjusted according to desired physical properties. Examples of the epoxy compound include phenol novolac epoxy resin, tetramethyl bi-phenyl epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, ortho-cresol novolac resin, and the like. The epoxy compound may be included in an amount of 0.01 to 10% by weight based on 100% by weight of the entire colored photosensitive resin composition, and when the content of the epoxy compound is within the above range, storage stability and process margin are excellent.

Specific examples of the silane-based coupling agent include vinyl trimethoxysilane, vinyl tris (2-methoxyethoxysilane), 3-glycidoxypropyl trimethoxysilane, 2- (3,4-epoxy cyclohexyl) Ethyl trimethoxysilane, 3-chloropropyl methyl dimethoxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, and the like. The silane-based coupling agent may be included in an amount of 0.01 to 2% by weight based on 100% by weight of the colored photosensitive resin composition, and when the content of the silane-based coupling agent is within the above range, adhesion, storage stability and coating properties are excellent.

<Color filter>

One embodiment of the present invention relates to a color filter formed using the colored photosensitive resin composition described above. A color filter according to an embodiment of the present invention is characterized in that it includes a colored pattern formed by applying the above-described colored photosensitive resin composition on a substrate, exposing and developing in a predetermined pattern.

Hereinafter, the pattern formation method using the colored photosensitive resin composition of the present invention will be described in detail.

A method for forming a pattern using the colored photosensitive resin composition of the present invention may use a method known in the art, but typically includes an application step; exposure step; and a removal step. By applying the colored photosensitive resin composition of the present invention on a substrate, photocuring and developing to form a pattern, it can be used as a colored pixel (colored image).

Specifically, the colored photosensitive resin composition is applied on a glass substrate to which nothing is coated and a glass substrate to which SiNx (protective film) is coated to a thickness of 500 to 1,500 Å using an appropriate method such as spin coating or slit coating, It is applied in a thickness of 3.4 μm. After application, light is irradiated to form a pattern required for the color filter. After light is irradiated, when the coating layer is treated with an alkaline developer, the unirradiated portion of the coating layer is dissolved and a pattern required for the color filter is formed. By repeating this process according to the required number of red (R), green (G), and blue (B) colors, a color filter having a desired pattern can be obtained. In addition, in the above process, crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing by irradiation with actinic rays or the like.

<Display device>

In addition, the present invention provides a display device including the color filter according to the present invention.

The display device includes a color filter prepared using the colored photosensitive resin composition according to the present invention, thereby providing a wide high color gamut and excellent color reproducibility.

Specifically, the display device may include other components that can be included in a conventional display device, such as a light emitting device such as a light source, a light guide plate, and a liquid crystal display including a color filter according to the present invention, and the present invention is limited thereto. I don't.

The display device includes, for example, not only a liquid crystal display (LCD) but also various image displays such as an electroluminescence display (EL), a plasma display (PDP), a field emission display (FED), and an organic light emitting diode (OLED). device, but is not limited thereto.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but the following examples are merely illustrative of the present invention, and various changes and modifications are possible within the scope and spirit of the present invention. It is obvious to those skilled in the art, It goes without saying that these variations and modifications fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "parts" representing contents are based on weight unless otherwise specified.

<Example>

Synthesis Example 1: Compound of Formula 1

Reaction Step 1: Preparation of 1-(4-thiophenyl phenyl)-(2-cyclohexyl)-propan-1-one

0.2 mol diphenylsulfide, 0.22 mol AlCl3 (powder state), and 150 ml dichloroethane were added to a 500 ml four-neck flask, stirred, and then injected with argon gas to protect, put in ice water, and cooled to bring the temperature to 0°C. When it was lowered, 42 g of cyclohexylacetyl chloride was added, and the temperature was lowered for about 1.5 hr in a state where the temperature was controlled to 10 ° C or less, and then the temperature was raised to 15 ° C and stirred continuously for 2 hr to obtain a product.

The post-processing steps are as follows.

While stirring, the above product was slowly added to dilute hydrochloric acid mixed with 400 g ice and 65 ml concentrated hydrochloric acid, the lower layer liquid was separated with a separatory funnel, the upper layer liquid was extracted with 50 ml dichloroethane, and the extract liquid and the raw material liquid were combined to obtain 10 The pH value was neutralized by washing with a NaHCO ₃ solution formulated with g NaHCO ₃ and 200 g water and then washed three times with 200 ml water. Then, it was dried with 60 g of anhydrous MgSO ₄ to remove moisture, and dichloroethane was obtained by rotary evaporation. After evaporation, the crude product in the rotary evaporator flask is in the form of a solid powder, which is put into 200 ml petroleum ether evaporated at room temperature for leaching, then put into 150 ml anhydrous ethyl alcohol, heated to reflux, and then cooled to room temperature. and then frozen for another 2 hr, followed by leaching to obtain 1-(4-thiophenylphenyl)-(2-cyclohexyl)-propan-1-one as a white flaky solid. Then, it was dried in an oven at 50 ° C. for 2 hr to obtain a product of 53.4 g, with a yield of 86% and a purity of 98% or more.

Reaction Step 2: Preparation of 1-(4-thiophenyl phenyl)-(2-cyclohexyl)-propane-1,2-dione-2-oxime

40 g of the product of reaction step 1, 400 g of tetrahydrofuran, 200 g of concentrated hydrochloric acid, and 24.2 g of amyl nitrite were added to a 500 ml four-necked flask and stirred continuously at room temperature for 5 hr to obtain a product. product is precipitated.

The post-processing steps are as follows.

After putting the product in a large beaker, adding 1000 ml of water, stirring, leaving it to stand overnight, and then dividing it to obtain a yellow viscous liquid, which was then extracted with dichloroethane, and 50 g of anhydrous MgSO ₄ was added thereto. After drying and leaching, the filtrate was rotary evaporated. At this time, an oily viscous substance is obtained in the rotary evaporator flask, which is put into 150 ml petroleum ether, stirred to precipitate and leached, and a white powdery solid is obtained and dried at 60 ° C. for 5 hr to obtain a product of 29.4 g (1-( 4-thiophenylphenyl)-(2-cyclohexyl)-propane-1,2-dione-2-oxime) was obtained with a yield of 67.2% and a purity of more than 98%.

Reaction Step 3: Preparation of 1-(4-thiophenylphenyl)-(2-cyclohexyl)-propane-1,2-dione-2-benzoic acid oxime ester

The reaction operation accordingly is as follows.

In a 1000 ml four-necked flask, 33 g of the product of the above reaction step 2, 350 ml dichloroethane, and 12.7 g triethylamine were added and stirred, and cooled in ice water. When the temperature was 0 ° C, 15.7 g of benzoyl chloride and A solution composed of 15 g of dichloroethane was started to drop and dripped completely in about 1.5 hr. Then, after continuously stirring for 1 hr, 500 ml of cooling water was dropped and the layers were separated with a separatory funnel, washed once with 200 ml 5% NaHCO ₃ solution and washed twice with 200 ml water to make it neutral, then diluted hydrochloric acid (20 g concentrated hydrochloric acid + 400 ml water) and washed again with 200 ml water three times, dried with 100 g anhydrous MgSO ₄ and rotated to evaporate the solvent to obtain a viscous liquid. Then, when an appropriate amount of methanol is added thereto, a white solid product can be precipitated, which is filtered and dried to obtain a 33 g product (1-(4-thiophenylphenyl)-(2-cyclohexyl)-propane-1, 2-dione-2-benzoic acid oxime ester) was obtained, the yield reached 76.5% and the purity was 98% or more.

Synthesis Example 2: Compound of Formula 3

Reactant 1.

200.0 g of fluorene, 268.8 g of potassium hydroxide and 19.9 g of potassium iodide were dissolved in 1 L of anhydrous dimethyl sulfoxide under a nitrogen atmosphere, and the reaction mixture was maintained at 15°C. Then, 283.3 g of bromoethane was added slowly over 2 hours and the reaction mixture was stirred at 15° C. for 1 hour. Then, 2 L of distilled water was added to the reactant, stirred for 30 minutes, the product was extracted with 2 L of dichloromethane, the extracted organic layer was washed twice with 2 L of distilled water, and the collected organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. The product obtained by distillation under reduced pressure was subjected to fractional distillation under reduced pressure to obtain 248.6 g of reactant 1 (9,9-diethyl-9H-fluorene) as a pale yellow liquid having high viscosity.

reactant 2

After dissolving 100.5 g of the reactant 1 in 1 L of dichloromethane, cooling to -5 ° C, 72.3 g of aluminum chloride was slowly added, and propionyl chloride 50.1 diluted in 50 ml of dichloromethane while being careful not to raise the temperature of the reactant. g was added slowly over 2 hours and the reaction was stirred at -5 °C for 1 hour. Then, the reactant was slowly poured into 1 L of ice water, stirred for 30 minutes to separate the organic layer, washed with 500 ml of distilled water, and distilled the recovered organic layer under reduced pressure. The product obtained was subjected to silica gel column chromatography (eluent solvent; ethyl acetate: n-hexane). = 1: 4) to obtain 75.8 g of reactant 2 (1-(9,9-diethyl-9H-fluoren-2-yl)-1-propanone) as a pale yellow solid.

reactant 3

44.5 g of reactant 2 was dissolved in 900 ml of tetrahydrofuran (THF), and 150 ml of 4N HCl dissolved in 1,4-dioxane and 24.7 g of isobutyl nitrous acid were sequentially added thereto, and the reaction was stirred at 25° C. for 6 hours. Then, 500 ml of ethyl acetate was added to the reaction solution, stirred for 30 minutes to separate the organic layer, washed with 600 ml of distilled water, dried the recovered organic layer with anhydrous magnesium sulfate, and distilled the solvent under reduced pressure to obtain a solid product obtained by ethyl Acetate: Recrystallized using 300 ml of a mixed solvent of hexane (1:6) and dried to obtain reaction product 3 (1-(9,9-diethyl-9H-fluoren-2-yl)-1 as a light gray solid, 2-propanedione-2-oxime) 27.5 g was obtained.

reactant 4

Reactant 3 was dissolved in 1 L of N-methyl-2-pyrrolidinone (NMP) under a nitrogen atmosphere, the reaction was maintained at -5°C, 35.4 g of triethylamine was added, and the reaction solution was stirred for 30 minutes. A solution in which 27.5 g of acetyl chloride was dissolved in 75 ml of N-methyl-2-pyrrolidinone was slowly added over 30 minutes, and stirred for 30 minutes while being careful not to raise the temperature of the reactant. Then, 1 L of distilled water was slowly added to the reactant, stirred for 30 minutes to separate an organic layer, and the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained solid product was recrystallized using 1 L of ethanol and then dried to obtain 1-(9,9-diethyl-9H-fluoren-2-yl)-1,2-propane as a light gray solid compound of Formula 4. 93.7 g of dione-2-oxime-O-acetate was obtained.

Synthesis Example 3: Binder Resin (B-1)

In a 1 L flask equipped with a reflux condenser, dropping funnel and stirrer, nitrogen was flowed at 0.02 L/min to create a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was added and heated to 70°C while stirring. Subsequently, a solution was prepared by dissolving in 150 g of diethyl glycol methyl ethyl ether according to each ratio so that the total amount of EDCPA and AA was 1 mol. After dropping the prepared solution into the flask using a dropping funnel, 27.9 g (0.11 mol) of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol methyl ethyl ether. The solution dissolved in was added dropwise into the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70 DEG C for 4 hours and then cooled to room temperature to obtain a binder resin having a solid acid value of 75 mgKOH/g. The weight average molecular weight measured by GPC was 13,000, and the molecular weight distribution (Mw/Mn) was 2.1.

Synthesis Example 4: Binder Resin (B-2)

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet pipe was prepared, and as a monomer dropping funnel, 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, and 118.0 vinyltoluene were used. g (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred and mixed to prepare, and as a chain transfer agent dropping tank, n-dodecanethiol 6 g and 24 g of PGMEA were added and stirred and mixed. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Subsequently, dropping of the monomer and chain transfer agent was started from the loading lot. Dropping proceeded for 2 hours while maintaining 90 ° C. After 1 hour, the temperature was raised to 110 ° C. and maintained for 3 hours. started bubbling. Then, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% relative to the carboxy group of acrylic acid used in this reaction)], 2,2'-methylenebis(4-methyl-6-t-butylphenol ) 0.4 g and 0.8 g of triethylamine were added into the flask, and the reaction was continued at 110 DEG C for 8 hours to obtain a binder resin having a solid acid value of 70 mgKOH/g. The weight average molecular weight measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of said resin, it was performed under the following conditions using the GPC method.

Device: HLC-8120GPC (manufactured by Toso Co., Ltd.)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40 °C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 μl

Detector: RI

Measurement sample concentration: 0.6% by mass (solvent = tetrahydrofuran)

Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Co., Ltd.) Mn).

Preparation Example 1: Preparation of colorant dispersion (A-1)

C.I. Pigment Green G58 10.12 parts by weight, C.I. 3.88 parts by weight of Pigment Yellow Y138, 4.84 parts by weight of an acrylic dispersant (DisperBYK-2000, manufactured by Big Chemie), 3.88 parts by weight of the resin of Synthesis Example 4, 68.04 parts by weight of propylene glycol monomethyl ether acetate as a solvent and 9.24 parts by weight of propylene glycol monomethyl ether Part by weight, 360 parts by weight of 0.2 mm diameter zirconia beads were put into a mayonnaise bottle having a capacity of 140 ml, and kneaded with a paint conditioner at 60 ° C. for 10 hours to perform dispersion treatment. After that, the zirconia beads were removed to obtain a dispersion. The dispersion was filtered through a membrane filter having a pore size of 1.0 μm to obtain a colorant dispersion.

Examples and Comparative Examples: Preparation of colored photosensitive resin composition

A colored photosensitive resin composition was prepared by mixing each component according to the composition shown in Table 1 below (unit: wt%).

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 colorant dispersion (A-1) 40 40 40 40 40 40 40 40 40 40 40 40 binder resin (B-1) 2.5 2.5 2.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 (B-2) 2.5 3.5 photopolymerizable compound (C-1) 3.5 3.5 3.5 2.5 2.5 2.5 3.5 2.5 2.5 2.5 2.5 2.5 photopolymerization initiator (D-1) 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 (D-2) 0.8 0.4 0.8 0.4 0.8 0.8 0.8 0.4 (D-3) 0.8 0.4 0.8 0.4 0.4 (D-4) 0.6 0.6 0.6 (D-5) 0.8 0.8 solvent (E-1) 52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5 additive (F-1) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (A-1): colored dispersion of Preparation Example 1
(B-1): Binder Resin of Synthesis Example 3
(B-2): Binder Resin of Synthesis Example 4
(C-1): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
(D-1): Compound of Formula 1 in Synthesis Example 1
(D-2): OXE-02 (BASF)
(D-3): Compound of Formula 3 in Synthesis Example 2
(D-4): OXE-01 (BASF)
(D-5): OXE-03 (BASF)
(E-1): Propylene glycol monomethyl ether acetate (PGMEA)
(F-1): SH-8400 (Dow Corning)

Experimental example

Experimental Example 1. Evaluation of double taper formation mitigation after PoB

Each of the colored photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 4 was coated on a 50 mm × 50 mm glass substrate using a spin coater, and the number of rotations was adjusted so that the film thickness after drying was 2.5 μm. After coating, it was dried in an oven at 100°C for 3 minutes. The dried substrate was exposed with a photomask at an interval of 300 μm so that the accumulated light amount of 313 nm wavelength of the fusion lamp was 40 mJ to prepare a color filter. Thereafter, using a spray developing apparatus, it was developed for 1 minute with a KOH aqueous solution of pH 10.5, washed with water, and air dried. After that, the level of reverse taper was measured by measuring the end of the fabricated pattern through a scanning electron microscope (HITACHI S4300). The measurement was compared by measuring the length of the part dug into the pattern from the end of the pattern.

< Evaluation Criteria for Mitigation of Double Taper Formation >

◎: When the double taper length difference is less than 1 μm in SEM observation (very good)

○: When the double taper length difference is greater than or equal to 1um and less than 2um in SEM observation (excellent),

△: When the double taper length difference is 2um or more and less than 4um when observed by SEM (insufficient),

X: When the double taper length difference is more than 4um in SEM observation (defective)

Experimental Example 2. Evaluation of exposure sensitivity

In the same manner as in Experimental Example 1, each of the colored photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4 were coated to form a color film, and then cured in an oven at 230 ° C. for 20 minutes to prepare a color filter. At this time, the pattern line width and the degree of peeling of the pattern formed were measured.

The degree of sensitivity was measured by checking the difference between the line width (X1) of the pattern and the line width (X2) of the photomask.

<Line width evaluation criteria>

+5 or higher: good

-5 or more to less than +5: good

Less than -5: unsuitable

<Pattern Peeling Evaluation Criteria>

○: no pattern peeling

△: 1 to 3 pattern exfoliation

X: 4 or more pattern peels

Experimental example 3. water stain measurement

After preparing a substrate for each of the colored photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 4 in the same manner as in Experimental Example 1, the color filter was left in distilled water for 10 minutes, and then dried by blowing nitrogen gas. After that, stains were observed between the part immersed in distilled water and the part that was not, with a surface inspection lamp (FY-100R). The results according to the following evaluation criteria are shown in Table 2 below.

<Evaluation Criteria>

X: Staining observed (water staining intensity level)

△: stain observed (weak level of occurrence of water stain)

○: No stain observed (no water stain)

Experimental Example 4. Evaluation of solvent resistance

In the same manner as in Experimental Example 2, each colored photosensitive resin composition prepared in Examples 1 to 8 and Comparative Examples 1 to 4 was coated to prepare a color filter, and then the substrate was placed in an NMP solution at room temperature for 30 minutes. After being immersed, washed with ultrapure water and dried for 2 minutes on a hot plate heated to 120° C., the chromaticity before and after immersion was measured. The equation used at this time is calculated by Equation 1 below, which represents the color change in the three-dimensional colorimetric system defined by L ^* , a ^* , and b ^* , and the smaller the color change value, the more reliable the color filter can be manufactured.

[Equation 1]

ΔEab ^* =[(ΔL ^* ) ² + (Δa ^* ) ² +(Δb ^* ) ² ] ^{^0.5}

<Solvent Resistance Evaluation Criteria>

△Eab ^* 3 or less: ○

△Eab ^* greater than 3: X

Reverse Taper Level (um) Sensitivity water stain solvent resistance line width pattern peeling Example 1 ○ fitness ○ ○ ○ Example 2 ○ fitness ○ ○ ○ Example 3 ○ fitness ○ ○ ○ Example 4 ◎ fitness ○ ○ ○ Example 5 ○ fitness ○ ○ ○ Example 6 ◎ fitness ○ ○ ○ Example 7 △ Good ○ △ ○ Example 8 △ Good ○ △ ○ Comparative Example 1 X incongruity X X X Comparative Example 2 X incongruity X X X Comparative Example 3 △ Good △ X X Comparative Example 4 X incongruity X X X

Referring to the results of Table 2, in the case of Examples 1 to 8 containing the photopolymerization initiator according to the present invention, it can be confirmed that all of them exhibit good or better effects in terms of reverse taper level, sensitivity, water staining inhibition, and solvent resistance. can In particular, when a copolymer including the photopolymerization initiator of the present invention and a specific repeating unit as a binder resin was used, it was confirmed that the reverse taper level and sensitivity characteristics were further improved. On the other hand, including the compound represented by Formula 1 In the case of Comparative Examples 1 and 2 using an untreated photopolymerization initiator, it was confirmed that the reverse taper level, sensitivity, inhibition of water stain generation, and solvent resistance were all remarkably reduced. In addition, Comparative Example 3, which does not include at least one compound of Formulas 2 and 3, even though it includes the compound represented by Formula 1 of the present invention, is not excellent in reverse taper level and sensitivity, and has water stain suppression and solvent resistance effects. A significant decrease was observed. Furthermore, in the case of Comparative Example 4, which did not include all of the compounds represented by Formulas 1 to 3, the effect of reverse taper level, sensitivity, water staining inhibition, and solvent resistance were all significantly reduced.

From the above results, the colored photosensitive resin composition of the present invention can suppress the occurrence of reverse taper when forming a colored pattern, and has excellent sensitivity characteristics to reduce the occurrence of tearing of the pattern during the developing process. In addition, it can be seen that reliability such as solvent resistance and water stain prevention properties can provide excellent effects.

Claims (7)

A colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,
The photopolymerization initiator includes a compound represented by Formula 1 below, and further comprises at least one of a compound represented by Formula 2 and a compound represented by Formula 3 below, a colored photosensitive resin composition:
[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 2 and 3, R ¹ , R ² and R ⁴ to R ¹² are each independently hydrogen, halogen, C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ hydroxyalkyl group, C ₂ -C ₂₄ hydroxyalkoxyalkyl group , a C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₁₀ aryl group, a C ₃ -C ₁₀ aralkyl group, an amino group, a nitro group, a cyano group, a hydroxyl group or an organic residue,
R ³ is hydrogen, halogen, C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ hydroxyalkyl group, C ₂ -C ₂₄ hydroxyalkoxyalkyl group, substituted or unsubstituted C ₃ -C ₁₀ aryl group, C ₃ -C ₁₀ aralkyl group, amino group, nitro group, cyano group, hydroxy group or organic residue. The method according to claim 1, wherein the binder resin is a copolymer comprising a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula (5), the colored photosensitive resin composition:
[Formula 4]

[Formula 5]

The method of claim 1,
With respect to the total weight of solids in the colored photosensitive resin composition,
10 to 70% by weight of a colorant;
5 to 75% by weight binder resin;
5 to 50% by weight of photopolymerizable compound
1 to 10% by weight of a photopolymerization initiator; and
With respect to the total weight of the colored photosensitive resin composition,
A colored photosensitive resin composition containing 50 to 90% by weight of a solvent. The method according to claim 1, wherein the photopolymerization initiator is at least one of the compound represented by the formula (1), the compound represented by the formula (2) and the compound represented by the formula (3) in a weight ratio of 1 to 60:40 to 99. That is, the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, further comprising an additive. A color filter comprising a colored pattern made of the colored photosensitive resin composition of any one of claims 1 to 5 A display device including the color filter of claim 6.