KR20200113862A - A colored photosensitive resin composition and a color filter and a display device using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition including a colorant, binder resin, photopolymerizable compound, photopolymerization initiator and a solvent, wherein 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. The colored photosensitive resin composition can inhibit generation of reverse taper upon the formation of a colored pattern, has excellent sensitivity to reduce generation of line tearing of a pattern during a development process, and shows excellent reliability, such as solvent resistance, and a property of preventing water spot generation. The present invention also relates to a color filter and display device obtained by using the colored photosensitive resin composition.

Description

A colored photosensitive resin composition, a color filter and a display device manufactured using the same TECHNICAL FIELD {A COLORED PHOTOSENSITIVE RESIN COMPOSITION AND A COLOR FILTER AND A DISPLAY DEVICE 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.

The color filter used in the display device is composed of three colored patterns of red, green, and blue, or three types of yellow, magenta, and cyan. It consists of a colored pattern of colors.

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

In recent years, the market demand for high-quality displays with high color reproducibility is increasing, and accordingly, the content of colorants contained in the colored photosensitive resin composition used to manufacture color filters is continuously increasing, and colorants having better color reproducibility and contrast ratio are increasing. Use is being considered.

However, when the content of the colorant is increased, a reverse taper phenomenon occurs when a pattern is formed with the colored photosensitive resin composition, and the sensitivity decreases, thereby causing problems such as line tearing and a decrease in reliability of the pattern.

In this regard, Korean Patent Laid-Open Publication No. 10-2009-0098689 discloses a technology related to a photosensitive resin composition including a colorant, but the disclosed patent does not provide an alternative to the above-described 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 colored 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 photoinitiator and a solvent,

The photopolymerization initiator includes a compound represented by the following Formula 1, and further comprises at least one of a compound represented by the following Formula 2 and a compound represented by the following Formula 3, providing a colored photosensitive resin composition.

[Formula 1]

[Formula 2]

[Chemical Formula 3]

In Formulas 2 and 3, R ¹ 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, C ₃ -C ₁₀ cycloalkyl 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 It is an organic residue.

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

Further, 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 pattern tearing during the development process. It is possible to provide excellent effects in terms of reliability, such as cleaning resistance, and water stain prevention properties.

Therefore, 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 a compound represented by Formula 1, a compound represented by Formula 2, and a compound represented by Formula 3. By further including at least one of the compounds to be used, 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 occurring during the development process due to excellent sensitivity characteristics, A colored photosensitive resin composition having excellent reliability such as solvent resistance and water stain prevention properties, and a color filter and a display device manufactured using the same are provided.

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) contains at least one pigment and/or at least one dye.

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, and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoin Doline Pigment, Ferriene Pigment, Perinone Pigment, Dioxazine Pigment, Anthraquinone Pigment, Dianthraquinonyl Pigment, Anthrapyrimidine Pigment, Antanthrone Pigment, Indanthrone Pigment, Fravantron Pigment, Pyran A pyranthrone pigment, a diketopyrropyrrole pigment, etc. are mentioned. Examples of the inorganic pigment include metal compounds such as metal oxides, complex metal oxides or 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 pigments and inorganic pigments specifically include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists), and more specifically, the color index (CI) number as follows. 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.

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

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. Pigments selected from Pigment Green 58 can be preferably used.

It is preferable to use a pigment dispersion in which the pigment particle diameter is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment may include a method of dispersing by containing a pigment dispersant (a2), and a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained. have.

Pigment dispersant (a2)

The pigment dispersant is added for deagglomeration and stability of the pigment, and specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine. And these may be used alone or in combination of two or more. In addition, it is preferable to include an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing 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 dispersants can be used alone or in combination of two or more. I can. As the pigment dispersant (a2), other resin type pigment dispersants may be used in addition to the acrylate-based dispersant. The other resin type pigment dispersants include known resin type pigment dispersants, especially polyurethanes, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partially) of 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 modified products thereof, or free ) An oily dispersant such as an amide formed by the reaction of a polyester having a carboxyl group with a poly (lower alkyleneimine) 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; And phosphate esters and adducts of ethylene oxide/propylene oxide.

Commercially available products of the above resin-type dispersants include cationic resin dispersants, for example, BYK (Big) Chemie's brand names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's 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; Kawaken Fine Chemical's trade names: Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto's brand names: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; Kyoeisha Chemical Co., Ltd. brand names: FLORENE DOPA-17HF, Florene DOPA-15BHF, Floren DOPA-33, Florene DOPA-44, and the like. In addition to the above acrylic dispersants, other resin type pigment dispersants may be used alone or in combination of two or more, or 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, the viscosity may increase, and if it is less than 5 parts by weight, it may be difficult to atomize the pigment or cause problems such as gelation after dispersion.

Dye (a3)

The dye may be used without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye that has solubility in an organic solvent and can secure reliability such as solubility in an alkali developer, heat resistance, and solvent resistance. As the dye, one selected from acidic dyes having an acidic group such as sulfonic acid or carboxylic acid, salts of acidic dyes and nitrogen-containing compounds, sulfonamides of acidic dyes, and derivatives thereof. In addition, azo-based, xanthene-based, phthalocyanine Acid dyes of the system and derivatives thereof can also be selected. Preferably, the dye is a compound classified as a dye in the color index (published by The Society of Dyers and Colourists), or a known dye described in the dye note (color dyeing company).

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

C.I. Among solvent dyes, C.I. has excellent solubility in organic solvents. 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, and 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,

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 , 382, 383, 394, 401, 412, 417, 418, 422 and 426;

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243 and 251;

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;

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

C.I. acid yellow 42 having excellent solubility in organic solvents in C.I. 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.

Also as a C.I. direct dye,

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

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 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;

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;

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, are mentioned.

Also as a C.I.modernto dye,

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

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

CI Moderno 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, are mentioned.

Each of the above dyes may be used alone or in combination of two or more.

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

Binder resin (B)

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

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 Formula 4 below and a repeating unit represented by 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 regularly repeated, or a random copolymer in which they 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 the low-temperature reactivity of the colored photosensitive resin composition and improving the hardness through a crosslinking reaction. As a result, reliability such as solvent resistance and chemical resistance can be improved.

The binder resin may contain 5 to 95 mol% of the repeating unit represented by Formula 4 and 5 to 95 mol% of the repeating unit represented by Formula 5 with respect to 100 mol% of the total repeating units constituting the binder resin. have.

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 can be obtained with excellent reliability.

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

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

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

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

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

In addition, the acid value of the binder resin is 50 to 200 mgKOH/g based on solid content, and within the above range, developability against alkali development is excellent, the occurrence of residues is suppressed, and the adhesion of the pattern can be improved.

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 in the above range, the solubility in the developer is sufficient, so that the development residue is difficult to occur on the substrate in the non-pixel portion, and film reduction in the pixel portion of the exposed portion is difficult to occur during development, so that the non-pixel portion It is preferable because there is a tendency that the omission property of is 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 polyfunctional monomers. .

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethylacrylate, and N-vinylpi And rolidone. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 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, di And pentaerythritol hexa(meth)acrylate. Among these, a bifunctional or higher polyfunctional monomer can be preferably used.

The photopolymerizable compound (C) may be contained 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 in the above range, it is preferable because the strength and smoothness of the pixel portion tend to be improved.

Photopolymerization initiator (D)

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

[Formula 1]

[Formula 2]

[Chemical Formula 3]

In Formulas 2 and 3, R ¹ 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, C ₃ -C ₁₀ cycloalkyl 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 It 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 in the present specification means a straight-chain or branched hydrocarbon consisting of 1 to 12 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl , Nonyl, and the like are included, but are not limited thereto.

The C ₁ -C ₁₂ alkoxy group used in the present specification refers to a straight-chain or branched alkoxy group consisting of 1 to 12 carbon atoms, and includes, but is limited to, methoxy, ethoxy, propanoxy, butoxy, pentoxy, etc. It is not.

The aryl group used herein includes both an aromatic group and a heteroaromatic group, and partially reduced derivatives thereof. The aromatic group is a 5 to 15 membered simple or fused cyclic group, and the heteroaromatic group refers to an aromatic group containing at least one oxygen, sulfur, or nitrogen. Examples of representative aryl groups include phenyl, naphthyl, pyridinyl, furanyl, pyrrolyl, thiophenyl, benzothiophenyl, indolyl, and quinoli Neil (quinolinyl), imidazolinyl (imidazolinyl), oxazolyl (oxazolyl), thiazolyl (thiazolyl), tetrahydronaphthyl, and the like, but are not limited thereto.

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

The C ₁ -C ₁₂ hydroxyalkyl group used in the present specification 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. Included, but not limited thereto.

The C ₂ -C ₂₄ hydroxyalkoxyalkyl group used in the present specification refers to a complex group formed by a straight-chain or branched alkoxy group having 1 to 12 carbon atoms substituted with a hydroxy group substituted with 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.

The C ₃ -C ₁₀ cycloalkyl group used herein refers to a simple or fused cyclic hydrocarbon consisting of 3 to 10 carbon atoms, and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., but is limited thereto. It does not become.

The aryl group and aralkyl group may be substituted with one or more of the hydrogen an alkyl group of C ₁ -C _12, alkoxy groups such as C ₁ -C _12.

As the compound represented by Formula 2, the following Formulas 2-1 to 2-2 may be exemplified, but the present invention is not limited thereto.

[Formula 2-1]

[Chemical Formula 2-2]

As the compound represented by Formula 3, the following Formulas 3-1 to 3-5 may be exemplified, but the present invention is not limited thereto.

[Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

[Formula 3-4]

[Formula 3-5]

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

When the weight ratio of the oxime compound represented by Formula 1, the compound represented by Formula 2, and at least one oxime compound of the compound represented by Formula 3 is within the above range, there is little reverse taper 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 in the above range, photopolymerization occurs sufficiently during exposure in the pattern formation process, and a decrease in transmittance due to an unreacted initiator remaining after photopolymerization may not occur.

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 an appropriate viscosity and can easily dissolve the remaining components, and various organic solvents used in the field of the colored photosensitive resin composition You can use

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 styrene 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 γ-butyrolactone, etc. are mentioned.

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

Each of the solvents (E) may 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 total color photosensitive resin composition. When the solvent (E) is included in the above range, the coating property becomes good 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), or inkjet. It is preferable because it tends to.

Additive (F)

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

Examples of the dispersant include polyalkylene glycol and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylate, alkyl An amide alkylene oxide adduct, an alkylamine, or 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 coating improving agent such as a silicone-based or fluorine-based coating agent, or an adhesion improving agent to improve adhesion to a substrate, if necessary to improve coating properties and defoaming properties. The coating improving agent and the adhesion improving agent may be included in an amount of 0.01 to 1% by weight based on 100% by weight of the photosensitive resin composition.

In addition, in order to prevent spots 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 agents; Fluorine-based surfactant; Other additives such as a radical polymerization initiator may be further included. The amount of these additives can be easily adjusted according to the 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. The epoxy compound may be included in an amount of 0.01 to 10% by weight based on the total 100% by weight of the colored photosensitive resin composition, and when the content of the epoxy compound is within the above range, storage properties and process margin are excellent.

Specific examples of the silane-based coupling agent are vinyl trimethoxysilane, vinyl tris (2-methoxyethoxysilane), 3-glycidoxypropyl trimethoxysilane, 2-(3,4-epoxy cyclohexyl) Ethyl trimethoxysilane, 3-chloropropyl methyldimethoxysilane, 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 the total 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 by 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 and exposing and developing it in a predetermined pattern.

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

The method for forming a pattern using the colored photosensitive resin composition of the present invention may be a method known in the art, but is usually a coating step; Exposure step; And a removing step. By coating 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 was applied on a glass substrate to which nothing was applied and a glass substrate on which SiNx (protective film) was applied to a thickness of 500 to 1,500 Å by using a suitable method such as spin coating or slit coating, from 2.0 to Apply to a thickness of 3.4 μm. After application, light is irradiated to form a pattern necessary for the color filter. After light is irradiated, the coating layer is treated with an alkali developer to dissolve the unirradiated portion of the coating layer and a pattern necessary for the color filter is formed. By repeatedly performing this process according to the number of red (R), green (G), and blue (B) colors required, a color filter having a desired pattern can be obtained. In addition, in the above process, crack resistance, solvent resistance, etc. can be further improved by heating the image pattern obtained by development again or curing it by irradiation with actinic rays.

<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 manufactured using the colored photosensitive resin composition according to the present invention, thereby providing an effect of having a wide high color area and excellent color reproducibility.

Specifically, the display device may include other components that can be commonly included in the 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. I don't.

The display device includes, for example, not only a liquid crystal display (LCD), but also an electroluminescent display (EL), a plasma display (PDP), a field emission display (FED), an organic light-emitting device (OLED), etc. Devices may be mentioned, but the present invention is not limited thereto.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It is natural that such modifications and modifications fall within the appended claims. In the following Examples and Comparative Examples, "%" and "parts" indicating the content 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

Add 0.2 mol diphenyl sulfide, 0.22 mol AlCl3 (powder) and 150 ml dichloroethane to a 500 ml four-neck flask, stir, and inject argon gas to protect it, put it in ice water, and cool it to a temperature of 0°C. When it is lowered, 42 g of cyclohexylacetyl chloride is added, and the temperature is lowered to 10°C or less for about 1.5 hours, and then the temperature is increased to 15°C and continuously stirred for 2 hours to obtain a product.

The post-processing steps are as follows.

While stirring, the product was slowly added to dilute hydrochloric acid mixed with 400 g ice and 65 ml concentrated hydrochloric acid, and the lower layer was separated with a separating funnel, and the supernatant was extracted with 50 ml dichloroethane, and the extract and the raw material solution were combined. Washed with a NaHCO ₃ solution formulated with g NaHCO ₃ and 200 g water, and washed 3 times with 200 ml water to make the pH value neutral. Then, it was dried over 60 g of anhydrous MgSO ₄ to remove moisture and rotary evaporated to obtain dichloroethane. After evaporation, the crude product in the flask for a rotary evaporator is in the form of a solid powder, which is put in 200 ml petroleum ether evaporated at room temperature to leach, put it in 150 ml anhydrous ethyl alcohol, heated to reflux, and cooled to room temperature. Then, it was frozen again for 2 hours, and leached to obtain 1-(4-thiophenyl phenyl)-(2-cyclohexyl)-propan-1-one as a white flake-shaped solid. Thereafter, it was dried in an oven at 50° C. for 2 hours to obtain a product of 53.4 g, and the yield reached 86% and the purity was 98% or more.

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

In a 500 ml four-necked flask, 40 g of the reaction step 1 product, 400 g tetrahydrofuran, 200 g concentrated hydrochloric acid, and 24.2 g amyl nitrite were added, followed by continuous stirring at room temperature for 5 hours to obtain a product. The product is precipitated.

The post-processing steps are as follows.

Put the product in a large beaker, add 1000 ml of water, stir, spend the night in a state of standing, and partition to obtain a yellow viscous liquid, extract dichloroethane, and add 50 g anhydrous MgSO ₄ thereto. After drying and leaching, the filtrate was rotary evaporated. At this time, an oily adhesive is obtained in the flask for a rotary evaporator, which is placed in 150 ml petroleum ether, stirred to precipitate, and leached to obtain a white powdery solid, dried at 60° C. for 5 hours, and 29.4 g product (1-( 4-thiophenyl phenyl)-(2-cyclohexyl)-propane-1,2-dione-2-oxime) was obtained, and the yield reached 67.2% and the purity was over 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, put in ice water and cooled to 0°C. When the temperature was 0°C, 15.7 g benzoyl chloride and A solution composed of 15 g dichloroethane began to be dropped and all dropped in about 1.5 hr. After continuing to stir for 1 hour, drop 500 ml of cooling water, divide it with a separating funnel, wash once with 200 ml 5% NaHCO ₃ solution, wash twice with 200 ml water to make it neutral, then dilute hydrochloric acid (20 g concentrated After washing with hydrochloric acid + 400 ml water) once and again with 200 ml water three times, drying with 100 g anhydrous MgSO ₄ and rotating to evaporate the solvent, a viscous liquid was obtained. Thereafter, when an appropriate amount of methanol is added thereto, a white solid product can be precipitated, which is filtered and dried to produce 33 g of product (1-(4-thiophenyl phenyl)-(2-cyclohexyl)-propane-1, 2-dione-2-benzoic acid oxime ester) was obtained, and the yield reached 76.5% and the purity was 98% or higher.

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 was maintained at 15°C. Then, 283.3 g of bromoethane was slowly added over 2 hours, and the reaction was stirred at 15° C. for 1 hour. Then, 2 L of distilled water was added to the reaction product and 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 recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed. The product obtained by distillation under reduced pressure was fractionated under reduced pressure to obtain 248.6 g of a pale yellow reactant 1 (9,9-diethyl-9H-fluorene) as a liquid with high viscosity.

Reactant 2

100.5 g of the reactant 1 was dissolved in 1 L of dichloromethane, cooled to -5°C, 72.3 g of aluminum chloride was slowly added, and propionyl chloride 50.1 diluted in 50 ml of dichloromethane, taking care not to increase the temperature of the reaction product. g was slowly added over 2 hours, and the reaction was stirred at -5°C for 1 hour. Then, the reaction product was slowly poured into 1 L of ice water and stirred for 30 minutes to separate the organic layer, washed with 500 ml of distilled water, and the product obtained by distilling the recovered organic layer under reduced pressure was subjected to silica gel column chromatography (developing solvent; ethyl acetate: n-hexane). = 1: 4) to give 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), 150 ml of 4N HCl dissolved in 1,4-dioxane and 24.7 g of isobutyl nitrous acid were sequentially added, and the reaction was stirred at 25° C. for 6 hours. Then, 500 ml of ethyl acetate was added to the reaction solution and stirred for 30 minutes to separate the organic layer, washed with 600 ml of distilled water, and then the recovered organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled under reduced pressure. Acetate: Recrystallized using 300 ml of a mixed solvent of hexane (1:6), dried, and reactant 3 (1-(9,9-diethyl-9H-fluoren-2-yl)-1, 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, and the reaction was maintained at -5°C, then 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 the reaction mixture was stirred for 30 minutes, taking care not to increase the temperature. Then, 1 L of distilled water was slowly added to the reaction product and stirred for 30 minutes to separate the 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 form a light gray solid, 1-(9,9-diethyl-9H-fluoren-2-yl)-1,2-propane. 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, a dropping funnel, and a stirrer, nitrogen was flowed at 0.02 L/min to obtain a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was added and heated to 70° C. while stirring. Subsequently, a solution is prepared by dissolving in 150 g of diethyl glycol methyl ethyl ether according to each ratio so that the total of EDCPA and AA is 1 mol. After dropping the prepared solution into a flask using a dropping funnel, 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol methylethyl ether. The solution dissolved in was added dropwise into the flask over 4 hours using a separate dropping funnel. After the dropping of the polymerization initiator solution was completed, the solution was maintained at 70° 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 lot and a nitrogen introduction tube was prepared, and as a monomer dropping lot, benzyl maleimide 74.8 g (0.20 mol), acrylic acid 43.2 g (0.30 mol), and vinyl toluene 118.0 g (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added and prepared by stirring and mixing, and as a dropping tank of a chain transfer agent, n-dodecanethiol 6g and 24g of PGMEA were put and the thing which stirred and mixed was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen from air, and the temperature of the flask was raised to 90°C while stirring. Next, dropping of the monomer and the chain transfer agent was started from the dropping lot. Dropping, while maintaining 90 ℃, proceed for 2 hours each, and after 1 hour the temperature was raised to 110 ℃ and maintained for 3 hours, and then introduced a gas introduction tube, oxygen / nitrogen = 5/95 (v / v) of the mixed gas Start bubbling. Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% based on 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 to the flask, and the reaction was continued at 110° 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.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the above resin was performed under the following conditions using the GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

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 substances for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) The ratio of the weight average molecular weight and number average molecular weight obtained above is measured in molecular weight distribution (Mw/ Mn).

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

C.I. Pigment Green G58 10.12 parts by weight, C.I. Pigment Yellow Y138 3.88 parts by weight, acrylic dispersant (DisperBYK-2000, manufactured by Vicchemy) 4.84 parts by weight, resin of Synthesis Example 4 3.88 parts by weight, propylene glycol monomethyl ether acetate 68.04 parts by weight and propylene glycol monomethyl ether 9.24 as a solvent Part by weight and 360 parts by weight of 0.2 mm diameter zirconia beads were put into a 140 ml mayonnaise bottle, and kneaded with a paint conditioner at 60° C. for 10 hours to perform dispersion treatment. Thereafter, 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

Each component was mixed in the composition of Table 1 to prepare a colored photosensitive resin composition (unit:% by weight).

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 of 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 relaxation of double taper formation after PoB

Using a spin coater for each of the colored photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 4, on a glass substrate of 50 mm × 50 mm, the number of rotations was adjusted so that the film thickness after drying became 2.5 um And then applied, and dried in an oven at 100° C. for 3 minutes. The dried substrate was exposed to a photo mask with a distance of 300 μm and the accumulated light amount of 313 nm wavelength of 40 mJ of a fusion lamp to prepare a color filter. Then, using a spray developing apparatus, after developing with a KOH aqueous solution of pH 10.5 for 1 minute, it washed with water, and air-dried. Then, the reverse taper level was measured by measuring the end of the pattern produced 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.

<Double taper formation mitigation evaluation criteria>

◎: When the difference in length of double taper is less than 1 um when observed with SEM (very good)

○: When the difference in the length of the double taper is 1um or more and less than 2um during SEM observation (excellent),

△: When the difference in the length of the double taper is 2 um or more to less than 4 um during SEM observation (not enough),

X: When the difference in length of double taper is more than 4um when observed with SEM (defective)

Experimental Example 2. Exposure sensitivity evaluation

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 was applied 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 formed pattern line width and the degree of pattern peeling were measured.

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

<Line width evaluation criteria>

+5 or higher: suitable

-5 or more to less than +5: good

Less than -5: unsuitable

<Pattern peeling evaluation criteria>

○: No pattern peeling

△: 1 to 3 pattern peeling

X: pattern peeling 4 or more

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 allowed to stand in distilled water for 10 minutes and then dried by blowing nitrogen gas. After that, stains were observed with a surface inspection lamp (FY-100R) between the part contained in the distilled water and the part that did not. The results according to the following evaluation criteria are shown in Table 2 below.

<Evaluation criteria>

X: spotting was observed (strong level of water spotting)

△: Spots were observed (weak level of water spots)

○: No stain was observed (no water stain occurred)

Experimental Example 4. Solvent resistance evaluation

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

[Equation 1]

△Eab ^* =[(△L ^* ) ² + (△a ^* ) ² +(△b ^* ) ² ] ^{^0.5}

<Based on evaluation of solvent resistance>

△Eab ^* 3 or less: ○

△Eab ^* 3 or more: 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 was confirmed that the reverse taper level, sensitivity, water stain suppression, and solvent resistance all exhibited a good level or higher effect. I can. In particular, it was confirmed that when a copolymer containing a photopolymerization initiator of the present invention and a specific repeating unit was used as the binder resin, the reverse taper level and sensitivity characteristics were further improved. On the other hand, the compound represented by Formula 1 was included. In the case of Comparative Examples 1 and 2 in which the photopolymerization initiator was not used, it was confirmed that the reverse taper level, sensitivity, water stain suppression, and solvent resistance effect were all significantly lowered. In addition, even if the compound represented by Chemical Formula 1 of the present invention is included, Comparative Example 3, which does not contain at least one compound of Chemical Formulas 2 and 3, does not have excellent reverse taper level and sensitivity, and has an effect of suppressing water stain and solvent resistance It was confirmed that the remarkably decreased. Further, in the case of Comparative Example 4, which did not contain all of the compounds represented by Chemical Formulas 1 to 3, the effects 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 pattern tearing during the development process. In addition, it can be seen that reliability such as solvent resistance and water stain prevention properties can provide excellent effects.

Claims (7)

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

[Formula 2]

[Chemical Formula 3]

In Formulas 2 and 3, R ¹ 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, C ₃ -C ₁₀ cycloalkyl 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 It is an organic residue. The colored photosensitive resin composition 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:
[Formula 4]

[Formula 5]

The method according to claim 1,
Based on the total weight of the solid content in the colored photosensitive resin composition,
10 to 70% by weight of colorant;
5 to 75% by weight of the binder resin;
5 to 50% by weight of a photopolymerizable compound
1 to 10% by weight of a photopolymerization initiator; And
Based on 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 comprises at least one of the compound represented by Formula 1, the compound represented by Formula 2, and the compound represented by Formula 3 in a weight ratio of 1 to 60: 40 to 99. 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 comprising the color filter of claim 6.