TWI615674B - Photosensitive resin composition, color filter with high color reproducing and liquid crystal display device using the same - Google Patents

Abstract

The present invention relates to a colored photocurable resin composition, a color filter using the same, and a liquid crystal display device including the same. The colored photocurable resin composition includes a photocurable compound (A), a binder resin (B), a photoinitiator (D), and a solvent (E), and the photocurable compound (A) includes the following The compound of the chemical formula (1), wherein the binder resin (B) contains a monomer of the following chemical formula (2) or the following chemical formula (3).

Description

Colored light-curable resin composition, color filter, and liquid crystal display device including the same

The present invention relates to a colored light-curable resin composition, a color filter, and a liquid crystal display device including the same, and more particularly, to a method for producing a color filter with high colorant content and high color reproduction. Colored photocurable resin composition.

A color filter used in a liquid crystal display device is a color filter that forms fine pixels such as red, green, and blue on a transparent substrate such as glass by a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method. Among them, recently, in order to manufacture color filters for liquid crystal display devices, a pigment dispersion method having high productivity and excellent fine processability, that is, a manufacturing method using a pigment-dispersed photocurable resin composition has been mostly used. This method is a method in which a pigment-dispersed photocurable resin composition is coated on a transparent substrate such as glass to form a coating film, and the coating film is irradiated with radiation through a mask for exposure, and then the non-exposed portion is removed by development processing. While forming a pattern. Hereinafter, the pigment-dispersed photocurable resin composition for producing a color filter is referred to as a photocurable resin composition for a color filter.

The photocurable resin composition for a color filter generally contains a pigment, a polymer resin for a binder, a photopolymerizable monomer, a photoinitiator, and a solvent, and a surfactant, an adhesion promoter, and a residue reducing compound may be added thereto as necessary. Wait. Recently, as the color filter has been gradually increased in chroma and color reproduction, the pigment concentration in the color filter composition has increased. However, when a pixel is formed using a colored light-curing resin composition having a high colorant content, there are problems in that a development residue is generated on the substrate of the unexposed portion during the developing process, or the unexposed portion is developed in a peeled form that is not completely dissolved. The developing solution blocks the color filter, and impurities that remain undissolved in the process adhere to the pixel and non-pixel substrates. Therefore, as a method of reducing the development residue of a pixel, a technique using a composition containing a polyfunctional compound imparting an acid value and improving the developability is required.

Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2010-237664.

However, at this time, the degree of curing of the pixel formed in the exposed portion is insufficient, and there is a problem that the adhesion is reduced, the pattern is peeled off, the surface of the coating film is defective, and the solvent resistance is insufficient.

On the other hand, Japanese Patent Application Laid-Open No. 2010-237664 discloses a coloring composition for a color filter. When a color filter is manufactured by an inkjet method, in order to make the pixel have sufficient flatness, it even has chemical resistance and heat resistance. Resistance and water resistance, using a polyfunctional compound with a carboxyl group and a melamine resin simultaneously. However, the aforementioned composition has the disadvantages of insufficient developability and poor solubility.

The present invention has been made in order to solve the problems in the prior art, and aims at Yu: In order to produce a color filter with high colorant content and high color reproduction, a colored light-curing resin composition is provided which not only has good curing degree and sensitivity, but also reduces development residues and increases development speed.

In order to achieve the above object, the present invention provides a colored photocurable resin composition, which is characterized by comprising a photocurable compound (A), a binder resin (B), a photoinitiator (D), and a solvent (E). The cured compound (A) contains a compound of the following chemical formula (1), and the binder resin (B) contains a monomer of the following chemical formula (2) or the following chemical formula (3).

In the aforementioned chemical formula (2), R ₁ , R ₂ , R _3, and R ₄ independently represent a hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

In the aforementioned chemical formula (3), R ₅ , R ₆ , R _7, and R ₈ independently represent a hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

The present invention also provides a color filter manufactured using the colored photocurable resin composition.

Furthermore, the present invention provides a liquid crystal display device including the color filter.

According to the colored photo-curable resin composition of the present invention, a colored photo-curable resin composition having excellent development time, development residue, sensitivity, and solvent resistance can be provided, and high color reproduction capable of including the colored photo-curable resin composition can be obtained. The advantages of color filters.

In addition, the composition in the present invention can provide a color filter having excellent developability, high curing degree, and high sensitivity and reliability.

Hereinafter, the present invention will be described in detail.

The colored photocurable resin composition in the present invention includes a photocurable compound (A), a binder resin (B), a photoinitiator (D), and a solvent (E). The photocurable compound (A) includes the following chemical formula ( The compound of 1), wherein the binder resin (B) contains a monomer of the following chemical formula (2) or the following chemical formula (3).

In the aforementioned chemical formula (2), R ₁ , R ₂ , R _3, and R ₄ independently represent a hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

In the aforementioned chemical formula (3), R ₅ , R ₆ , R _7, and R ₈ independently represent a hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

Hereinafter, each component which comprises the colored resin composition of this invention is demonstrated in detail. However, the present invention is not limited to these components.

Photocurable compound (A)

The photocurable compound (A) is characterized by including a compound of the following chemical formula (1). The compound of the chemical formula (1) is a compound having one or more carboxyl groups and five or more photocurable vinyl groups in the molecule.

In the present invention, the photocurable compound may additionally contain a polymerizable monomer such as an active group and an acid generated from a photoinitiator by light irradiation. Specific examples of the aforementioned monomer include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and Pentylene glycol diacrylate, pentaerythritol acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate , Trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethyl Acrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like.

The weight ratio of the photo-curable compound to the solid content in the photo-curable resin composition is preferably 5 to 45% by weight, and more preferably 10 to 35% by weight. When the content of the photocurable compound is within a range of 5 to 45% by weight on the basis of the foregoing, the strength and flatness of the pixel portion are good, which is preferable.

In the photocurable compound of the present invention, the compound of the following chemical formula (1) may be 30 to 100% by weight. When the compound of the following chemical formula (1) is within the aforementioned range, it has the effect of improving the development speed.

[Chemical formula (1)]

Adhesive resin (B)

The binder resin of the present invention may be a copolymer containing monomers of the following chemical formulas (2) (B1) or (3) (B2). Preferably, a copolymer of a carboxyl group-containing monomer and other monomers copolymerizable with the monomer may be additionally listed.

In the aforementioned chemical formula (2), R ₁ , R ₂ , R _3, and R ₄ independently represent a hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

In the aforementioned chemical formula (3), R ₅ , R ₆ , R _7, and R ₈ independently represent a hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms (the organic residue may contain an oxygen atom).

公司產品)、三乙胺(

公司產品)和2-(羥甲基)丙烯酸甲酯(

公司產品)的聚合而得到。前述聚合使用的溶劑可使用丙二醇甲醚(TCI公司產品)和2,2’-偶氮二異丁腈(Wako公司產品)。 The polymer containing the monomer of the aforementioned chemical formula (2) can be obtained by methyl 2- (bromomethyl) acrylate (

Company products), triethylamine (

Company products) and methyl 2- (hydroxymethyl) acrylate (

Company products). As the solvent used in the aforementioned polymerization, propylene glycol methyl ether (product of TCI company) and 2,2'-azobisisobutyronitrile (product of Wako company) can be used.

The copolymer containing the monomer of the aforementioned chemical formula (3) can be polymerized in the same manner as in the chemical formula (2) using a substituted or unsubstituted dihydrofuran or the like.

In the aforementioned binder resin, the monomer content ratio of the chemical formula (2) or the chemical formula (3) is 1 to 50% by weight, preferably 1 to 20% by weight, and more preferably 1 to 10% by weight relative to the total content. . If it is in the said range, since a hardening degree can be improved and a composition with a high pigment content can form a pattern correctly at the time of image development, it is preferable.

The adhesive resin of the present invention may contain a carboxyl group-containing monomer in addition to the monomers of the aforementioned chemical formula (2) or chemical formula (3). Examples of the carboxyl group-containing monomer include unsaturated polycarboxylic acids having one or more carboxyl groups in a molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid.

Examples of the unsaturated monocarboxylic acid include acrylic acid and methacrylic acid. Acids, crotonic acid, α-chloroacrylic acid and cinnamic acid.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, ningconic acid, and mesaconic acid.

The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and ningconic anhydride. In addition, the aforementioned unsaturated polycarboxylic acid may be a mono (2-methacryloxyalkyl) ester thereof, for example, succinic acid mono (2-propylenepropoxyethyl), succinic acid mono (2-methylpropene) Ethoxyethyl), phthalic acid mono (2-propenyloxyethyl) and phthalic acid mono (2-methacryloxyethyl). The aforementioned unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends thereof, for example, ω-carboxy polycaprolactone monoacrylate and ω-carboxy polycaprolactone monomethacrylate, etc. .

The aforementioned carboxyl group-containing monomers may be used alone or in combination of two or more kinds.

The binder resin of the present invention may contain other monomers copolymerizable with the aforementioned carboxyl group-containing monomer.

Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, O-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl Aromatic vinyl compounds such as benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and indene; methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid Ethyl ester, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate , Sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate , 2-hydroxypropyl methacrylate, acrylic acid-3 -Hydroxypropyl, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate , 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, methacrylic acid ring Hexyl ester, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, methacrylic acid-2 -Phenoxyethyl ester, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate , Methoxypropyl glycol acrylate, methoxypropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene acrylate, dicyclopentadiene methacrylate, acrylic acid-2 -Hydroxy-3-phenoxypropyl, 2-hydroxy-3-phenoxypropyl methacrylate, glyceryl monoacrylate, and mono Unsaturated carboxylic acid esters such as glyceryl methacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethyl methacrylate Aminoaminoethyl, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, acrylic acid-3 -Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate; acrylic acid Unsaturated carboxylic acid glycidyl esters such as glycidyl ester and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; vinyl methyl ether , Unsaturated ethyl ethers such as vinyl ethyl ether and allyl glycidyl ether; acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and vinyl cyanide compounds such as vinylidene chloride; acrylamide, methyl acrylamide, α - chloro acrylamide, N-2- hydroxyethyl acrylamide and N-2- hydroxyethyl Bing Xixi Unsaturated fluorenimides; maleimide, N-phenylmaleimide and N-cyclohexylmaleimide, etc .; unsaturated 1,3-butadiene, isoprene Aliphatic conjugated dienes such as diene and chloroprene; and in polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysilicon The macromolecular monomers of the oxane polymer molecular chain have a monoacrylfluorenyl group or a monomethacrylfluorenyloxy group at the end. These monomers can be used individually or in mixture of 2 or more types.

The binder resin (B) may be used in a range of 1 to 60% by weight, and preferably in a range of 5 to 50% by weight based on the total weight of the solid content in the colored photocurable resin composition. When the binder resin (B) is in the range of 1 to 60% by weight as the reference, the solubility is good, and the pattern forming property is excellent.

Colorant (C)

The coloring agent of the present invention is characterized by containing one or more pigments or one or more dyes.

Pigment (c1)

As the aforementioned pigment, an organic pigment or an inorganic pigment generally used in this field can be used.

As the organic pigment or the inorganic pigment, various pigments used in printing inks, inkjet inks, and the like can be used. Specific examples include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, and isocyanate. Indolinone pigment, isoindoline pigment, osmium pigment, fluorenone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinone pigment, anthracene pigment, anthracene anthraquinone pigment, indanthrone Pigments, flavanone pigments, dermatanone pigments, and diketopyrrolopyrrole pigments.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex compounds, and specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and Oxides of metals such as carbon black or composite metal oxides.

In particular, as the aforementioned organic pigments and inorganic pigments, specifically, compounds classified as pigments under the color rendering index (published by The society of Dyers and Colourists) can be listed, and more specifically, as shown below Color index (CI) numbered pigments are not necessarily limited thereto.

CI 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; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71; CI Pigment Red 9, 97, 105, 122, 123, 144, 149 , 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, and 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, and 38; CI Pigment Blue 15 ( 15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, and 76; CI Pigment Green 7, 10, 15, 25, 36, 47, and 58; CI Pigment Brown 28; CI Pigment Black 1 And 7th.

The said pigment (c1) can be used individually or in combination of 2 or more types.

Among the CI pigments exemplified above, pigments selected from the following pigments: CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Orange 38, and CI Pigment Red 122 may also be used more appropriately. , CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 208, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Purple 23, CI Pigment Blue 15: 3, CI Pigment Blue 15: 6, CI Pigment Green 7, CI Pigment Green 36 and CI Pigment Green 58.

The pigment is preferably a pigment dispersion liquid in which the particle diameter is uniformly dispersed. As an example of a method for uniformly dispersing the particle diameter of a pigment, a method including dispersing treatment containing a pigment dispersant (c2) may be mentioned. According to this method, pigment dispersion in a state where the pigment is uniformly dispersed in a solution can be obtained liquid.

Pigment dispersant (c2)

The pigment dispersant is added for pigment deflocculation and stability maintenance. Specific examples of the pigment dispersant include cationic, Anionic, nonionic, amphoteric, polyester, and polyamine surfactants, etc. These pigment dispersants can be used alone or in combination of two or more.

Further, it is preferable to include an acrylate dispersant (hereinafter referred to as an acrylic dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate-based dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150. The acrylate-based dispersants can be used alone or in combination. Use as above.

The pigment dispersant (c2) can use other resin-based pigment dispersants in addition to the acrylic dispersant. Examples of the other resin-based pigment dispersants include well-known resin-based pigment dispersants, particularly polycarboxylic acid esters represented by polyurethanes and polyacrylates, unsaturated polyamines, polycarboxylic acids, and polycarboxylic acids. (Partial) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminophosphonium phosphates, hydroxy-polycarboxylic acid-containing acid esters, and their modifications Sexual products, or ammonium amines formed by the reaction of a polyester having a free carboxyl group with poly (lower alkyleneimine) or an oily dispersant such as these salts; (meth) acrylic acid-styrene Copolymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene-maleic acid copolymer, water-soluble resin or water-soluble polymer compound such as polyvinyl alcohol or polyvinylpyrrolidone; polyester; modified Polyacrylate; ethylene oxide / propylene oxide addition products and phosphate esters.

(HINOACT)T-6000、HINOACTT-7000和HINOACTT-8000；味之素公司的商品名：

(AJISPUR)PB-821、AJISPURPB-822和AJISPURPB-823；共榮社化學公司的商品名：

(FLORENE)DOPA-17HF、FLORENEDOPA-15BHF、FLORENEDOPA-33和FLORENEDOPA-44等。 Among the commercially available resin-based dispersants, examples of the cationic resin dispersant include: BYK Chemical Company's trade 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, and DISPER BYK-184; BASF's trade 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 and EFKA-4800; Trade names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, and NBZ-4204 / 10; trade names of Chuanyan Fine Chemicals:

(HINOACT) T-6000, HINOACTT-7000 and HINOACTT-8000; trade names of Ajinomoto:

(AJISPUR) PB-821, AJISPURPB-822 and AJISPURPB-823; trade names of Kyoeisha Chemical Co., Ltd .:

(FLORENE) DOPA-17HF, FLORENEDOPA-15BHF, FLORENEDOPA-33 and FLORENEDOPA-44, etc.

In addition to the aforementioned acrylic dispersant, other resin-based pigment dispersants can be used alone or in combination of two or more kinds, and can also be used simultaneously with the acrylic dispersant.

The content of the pigment dispersant (c2) is in a range of 5 to 60 parts by weight, and more preferably in a range of 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (c1) used. When the content of the pigment dispersant (c2) exceeds 60 parts by weight based on the aforementioned standard, the viscosity increases, and when the content is less than 5 parts by weight, This causes problems such as difficulty in micronization of the pigment or gelation after dispersion.

Dye (c3)

The dye can be used without limitation as long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and capable of ensuring reliability in solubility, heat resistance, solvent resistance, and the like to an alkaline developer is preferably used.

As the dye, a dye selected from an acidic dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide of an acidic dye, or the like, and a derivative thereof can be used. It is also possible to select azo-based, xanthene-based, phthalocyanine-based acid dyes and their derivatives. Preferably, the aforementioned dye may be a compound classified as a dye in a color rendering index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (Dyeing and Weaving Company).

In the specific examples of the aforementioned dyes, as CI solvent dyes, there are CI solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, and 179; CI solvent blue 5, 35, 36, 37, 44, 59, 67, and 70; CI Solvent Violet 8, 9, 13, 14, 36, 37, 47, and 49; CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162; CI Solvent Orange 2, 7, 11, 15, 26, and 56; CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.

Among C.I. solvent dyes, C.I. Solvent Yellow 14, 16, 21, 56, 79, 93, and 151; CI Solvent Red 8, 49, 89, 111, 122, 132, 146, and 179; CI Solvent Orange 41, 45, and 62; CI Solvent Blue 35, 36 , 44, 45, and 70; CI solvent violet 13, of which CI solvent yellow 21 and 79 are more preferred; CI solvent red 8, 122 and 132; CI solvent orange 45 and 62.

Examples of CI acid dyes include 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; CI 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; CI Acid Violet 6B, 7, 9, 17, 19, and 66; CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109 dyes.

Among the acid dyes, C.I. Acid Yellow 42; C.I. Acid Red 92; C.I. Acid Blue 80 and 90; C.I. Acid Violet 66; and C.I. Acid Green 27 are preferred.

Examples of CI direct dyes include 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; CI 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; CI Direct Purple 47, 52, 54, 59, 60 , 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, and 104; CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82 dyes.

In addition, examples of CI mordant fuel include: CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65; CI mordant yellow Agent 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; CI mordant 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 mordant 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; CI mordant Agent Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58; CI Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, Dyes such as 34, 35, 41, 43 and 53.

These dyes can be used individually or in combination of 2 or more types.

The content of the colorant (C) is preferably 5 to 80% by weight, and more preferably 10 to 45% by weight based on the total weight of the solid content of the photocurable resin composition. When the colorant (C) is contained in an amount of 5 to 80% by weight based on the above-mentioned basis, even if a thin film is formed, the color density of the pixels is sufficient, and the defectivity of the non-pixel portion is not reduced during development, so the generation of residue can be suppressed. , So it is preferred.

In the present invention, the total solid content in the photocurable resin composition refers to the total content of the residual components after the solvent is removed from the photocurable resin composition.

(D) Photoinitiator

The photoinitiator (D) is not particularly limited as long as it can polymerize the photocurable compound (A).

In particular, the photoinitiator is preferably selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, and biimidazole-based compounds from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price. One or more compounds in the group consisting of a compound, an oxime compound, and a thioxanthone-based compound.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and benzophenone dimethyl ketal. , 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4 -Methylthiophenyl) -2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Butane-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, and 2- (4-methylbenzyl) -2 -(Dimethylamino) -1- (4-morpholinophenyl) butane-1-one and the like.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, and 4-benzophenyl-4'-methyldiphenylsulfide. Ether, 3,3 ', 4,4'-tetrakis (t-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone, etc.

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

As specific examples of the aforementioned biimidazole-based compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5 ' -Tetrakis (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, and 2, 2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or the phenyl group at the 4,4', 5,5 'position is An imidazole compound or the like substituted with an alkoxycarbonyl group. Among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorobenzene) are preferably used. ) -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1 , 2'-biimidazole.

Specific examples of the oxime compound include o-ethoxycarbonyl - α - oxyimino-1-phenyl-1-one, commercially available products, typically BASF OXE01 and OXE02.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxy Thioxanthone and so on.

In addition, a photoinitiator other than the above may be used in combination to the extent that the effect of the present invention is not hindered. Examples of other photoinitiators include benzoin-based compounds and anthracene-based compounds, and these materials may be used alone or in combination of two or more.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

Examples of the anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10 -Diethoxyanthracene and the like.

As a photoinitiator, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, and biphenyl can be used together. Samarium, 9,10-phenanthrenequinone, camphorquinone, methyl phenylacetate or titanocene compound, etc.

In addition, in order to increase the sensitivity of the photocurable resin composition of the present invention, the photoinitiator may further include a photopolymerization initiation aid (d-1). The photocurable resin composition in the present invention is initiated by containing photopolymerization. The adjuvant (d-1) can further improve sensitivity and productivity.

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

As the amine compound, an aromatic amine compound is preferably used. Specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, and 4-diamine can be used. Ethyl methylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N- Dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as: mignonone) or 4,4'-bis (diethylamino) benzophenone, etc.

The carboxylic acid compound is preferably an aromatic heterocyclic acetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, Dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio Acetic acid, N-naphthyl glycine, and naphthyloxyacetic acid.

Specific examples of the aforementioned organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris ( 3-mercaptobutoxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol tetra (3-mercaptobutyrate), pentaerythritol tetra (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like.

The aforementioned photoinitiator is compared with the solid state of the photocurable resin composition of the present invention. The total body weight is 0.1 to 10% by weight, and preferably 0.5 to 5% by weight. In the case where the photoinitiator is within the aforementioned range, the photocurable resin composition is made highly sensitive and the exposure time is shortened, so that productivity is improved, and high resolution can be maintained. Furthermore, the strength of the pixel portion formed using the composition and the smoothness of the surface of the pixel portion are improved.

In the case where the photopolymerization initiation aid is further used, it is preferable to use the same content range as the photoinitiator. When used in the range, the sensitivity of the photocurable resin composition can be further improved. The effect of increasing the productivity of color filters.

Solvent (E)

As long as the solvent can effectively dissolve other components contained in the photocurable resin composition, a solvent used in a general photocurable resin composition can be used without particular limitation, and ethers, aromatic hydrocarbons, ketones, alcohols are particularly preferably used. Class, esters or amidines.

As the aforementioned ethers, if specifically exemplified, there are ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethyl ether; Diethylene glycol dialkyl ethers such as glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; methyl cellosolve acetate and ethyl Cellulose acetate and other glycol alkyl ether acetates; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, butyl methoxy acetate, and methoxy Alkylene glycol alkyl ether acetates such as amyl acetate.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and xylene.

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, and methyl ethyl ketone. Isobutyl ketone and cyclohexanone.

The aforementioned alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerol.

Examples of the esters include esters such as ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

Among the solvents mentioned above, organic solvents having a boiling point of 100 ° C. to 200 ° C. are more preferably used in terms of coating properties and drying properties. Examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and cyclohexyl Ketones, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The aforementioned solvents can be used individually or in combination of two or more, and the solvent is 60 to 95% by weight, and preferably 70 to 85% by weight based on the total weight of the photocurable resin composition of the present invention. As long as the solvent is within the aforementioned range of 60 to 95% by weight, a roll coater, a spin coater, a slit spin coater, a slit coater (also sometimes referred to as a slot film coater), and inkjet are used. When applied by a coating device such as a formula, the effect of improving the coatability is provided.

Surfactant (F)

The aforementioned surfactant can be optionally added according to need, and can be used to further improve the film-forming property of the photocurable resin composition. Silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfaces can be preferably used. Specific examples of the active agent include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary Amine-modified polyurethanes and polyethyleneimines Class, etc.

The aforementioned silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Toray Dow Corning Silicone Co., Ltd. as commercial products, and TSF-4440, TSF-4300, TSF-4445 of GE Toshiba Silicone Co., Ltd. , TSF-4446, TSF-4460 and TSF-4452.

F-470、F-471、F-475、F-482、F-489等。此外，其他可使用的市售品可列舉出KP(信越化學工業公司製造)、POLYFLOW(共榮社化學公司製造)、EFTOP(Tochem Products公司製造)、MEGAFAC(大日本油墨化學工業公司製造)、Flourad(住友3M公司製造)、Asahi guard、Surflon(以上，旭硝子公司製造)、SOLSPERSE(捷利康公司製造)、EFKA(EFKA化學公司製造)、PB821(味之素公司製造)、Disperbyk-series(BYK-chemi)等 The fluorine-based surfactant is, for example, a commercially available product of Dainippon Ink Chemical Industry Co., Ltd.

F-470, F-471, F-475, F-482, F-489, etc. In addition, other commercially available products include KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Flourad (manufactured by Sumitomo 3M), Asahi guard, Surflon (above, manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Jelikon), EFKA (manufactured by EFKA Chemical Company), PB821 (manufactured by Ajinomoto), Disperbyk-series (BYK -chemi) etc.

Specific examples of the cationic surfactant include amine salts such as octadecylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts.

Specific examples of the aforementioned anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleate sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and twelve Alkyl aryl sulfonates such as sodium alkylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.

Specific examples of the non-ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, and oxyethylene / oxypropylene intercalation. Block copolymer, sorbitol Anhydride fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

The aforementioned surfactants can be used individually or in combination of two or more kinds.

The manufacturing method of the colored photocurable resin composition of this invention, and the manufacturing method of the color filter manufactured from it are demonstrated as follows, as follows.

First, the pigment (c1) in the colorant (C) is mixed with a solvent (E), and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant (c2), the binder resin (B), or the dye (c3) may be mixed, dissolved or dispersed together with the solvent (E).

To the mixed dispersion liquid, a dye (c3), a binder resin (B), a photocurable compound (A), a photopolymerization initiator (D), and a surfactant (F) and a solvent (E) as necessary are further added. ) The colored photocurable resin composition of the present invention can be produced at a predetermined concentration.

In addition, the present invention provides a color filter manufactured from the aforementioned colored photocurable resin composition and a display device including the aforementioned color filter. The display device can be manufactured by applying the colored photocurable resin composition to a substrate, photocuring and developing the substrate to form a pattern, as described below. First, a colored photocurable resin composition is coated on a substrate (usually glass) or a layer formed of a solid component of a colored photocurable resin composition formed in advance, and then volatile components such as solvents are removed by heating and drying to obtain smooth Coating. The coating method may be, for example, a spin coating method, a flow coating method, a roll coating method, A slit spin coating method, a slit coating method, or the like is performed. Heat drying (pre-baking) after coating, or heating under reduced pressure is performed to volatilize volatile components such as solvents. Here, the heating temperature is usually 70 to 200 ° C, and preferably 80 to 130 ° C. The thickness of the coating film after heating and drying is usually about 1 to 8 μm.

The coating film thus obtained was irradiated with ultraviolet rays through a mask for forming a bullseye pattern. At this time, the entire exposed portion is irradiated with parallel light uniformly, and it is preferable to use a device such as a mask aligner or a stepper to align the mask and the substrate to the correct position. When the ultraviolet rays are irradiated, the portions irradiated with the ultraviolet rays are cured. The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The irradiation amount of ultraviolet rays can be appropriately selected according to needs, and the present invention is not limited thereto.

When the cured coating film is brought into contact with a developing solution, the non-exposed portion is dissolved and developed, a bullseye pattern can be formed.

The development method may be any of a liquid addition method, a dipping method, and spray coating. In addition, the substrate can be tilted at any angle during development. The developing solution is usually an aqueous solution containing a basic compound and a surfactant. The basic compound may be any of inorganic and organic basic compounds. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonium borate. Specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and trimethylamine. Ethylamine, monoisopropylamine, diisopropylamine and ethanolamine.

These inorganic and organic basic compounds can be used individually or in combination of 2 or more types. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by weight, and more preferably 0.03 to 5% by weight.

The surfactant in the alkaline developer can be used by selecting at least one kind from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the non-ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, and oxyethylene / oxypropylene. Block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid esters, and polyoxylates Vinyl alkylamines and the like.

Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleate sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and Alkyl aryl sulfonates such as sodium dialkylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as octadecylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts. These surfactants can be used alone or in combination of two or more.

The concentration of the surfactant in the developing solution is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and still more preferably 0.1 to 5% by weight. After development, it is washed with water. If necessary, it can be post-baked at 150 ~ 230 ° C for 10 ~ 60 minutes.

The colored photo-curable resin composition of the present invention is used through the above processes. Sequence, a specific pattern can be formed on the substrate.

In the following, in order to explain the present invention in detail, examples will be described in detail. However, the embodiments related to the present invention can be changed in various forms, and the scope of the present invention should not be construed as being limited to the following embodiments. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

<Manufacturing Example 1> Production of pigment dispersion composition (M1)

13.5 parts by weight of pigment CI Pigment Red 177, 5.0 parts by weight of pigment dispersant DISPERBYK-2001 (manufactured by BYK), 61.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 4-hydroxy-4-methyl- 20 parts by weight of 2-pentanone was mixed in a bead mill for 12 hours, and dispersed to produce a pigment dispersion composition M1.

<Manufacturing Example 2> Synthesis of a binder resin (B1) containing a monomer represented by the chemical formula (2)

公司產品)、15.8g的三乙胺(

公司產品)和115.0g的丙二醇甲醚(TCI公司產品)加入到裝配有滴液漏斗、溫度計、冷卻管和攪拌器的四口燒瓶中，並將四口燒瓶的內部置換為氮氣。接著，將燒瓶加熱至90℃後，以1小時滴加15.1g的2-(羥甲基)丙烯酸甲酯(

公司產品)、3.2g的2,2’-偶氮二異丁腈(Wako公司產品)和110.0g的丙二醇甲醚(TCI公司產品)的混合溶液，進行0.5小時的聚合反應以生成含吡喃的聚合物。接著，以1小時緩慢滴加37.5g的甲基丙烯酸、19.0g的甲基丙烯酸 甲酯、225.0g的丙二醇甲醚和3.2g的2,2’-偶氮二異丁腈(Wako公司產品)的混合溶液並進行8小時的聚合後，冷卻至室溫。將四口燒瓶的內部置換為氮氣後，向燒瓶內加入61.5g的甲基丙烯酸縮水甘油酯(三菱

公司產品)、3.6g的四丁基氫氧化銨(TCI公司產品)和0.15g的氫醌單甲醚(純正公司產品)，並在80℃下反應12小時，對共聚物的羧基附加GMA而得到黏合劑樹脂B1。以GPC測定的黏合劑樹脂B1的重均分子量為23000。 23.3 g of methyl 2- (bromomethyl) acrylate (

Company product), 15.8g of triethylamine (

Company product) and 115.0 g of propylene glycol methyl ether (product of TCI company) were added to a four-necked flask equipped with a dropping funnel, a thermometer, a cooling tube and a stirrer, and the inside of the four-necked flask was replaced with nitrogen. Next, after heating the flask to 90 ° C, 15.1 g of methyl 2- (hydroxymethyl) acrylate (

Company product), 3.2 g of 2,2'-azobisisobutyronitrile (a product of Wako) and 110.0 g of propylene glycol methyl ether (a product of TCI) were polymerized for 0.5 hours to produce pyran-containing Polymer. Next, 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 225.0 g of propylene glycol methyl ether, and 3.2 g of 2,2'-azobisisobutyronitrile (products of Wako) were slowly added dropwise over 1 hour. After the mixed solution was polymerized for 8 hours, it was cooled to room temperature. After replacing the inside of the four-necked flask with nitrogen, 61.5 g of glycidyl methacrylate (Mitsubishi

Company product), 3.6 g of tetrabutylammonium hydroxide (product of TCI company) and 0.15 g of hydroquinone monomethyl ether (pure product of company), and reacted at 80 ° C for 12 hours, adding GMA to the carboxyl group of the copolymer and An adhesive resin B1 was obtained. The weight average molecular weight of the binder resin B1 measured by GPC was 23,000.

<Manufacturing Example 3> Synthesis of a binder resin (B2) containing a monomer represented by the chemical formula (3)

公司產品)、3.6g的四丁基氫氧化銨(TCI公司產品)和0.15g的氫醌單甲醚(純正公司產品)，並在80℃下反應12小時，對共聚物的羧基附加GMA而得到黏合劑樹脂B2。以GPC測定的 黏合劑樹脂B2的重均分子量為17000。 37.5 g of methacrylic acid (product of Kyoei Corporation), 19.0 g of methyl methacrylate (product of Kyoei Corporation), 9.1 g of 2,5-dihydrofuran (product of TCI Corporation), and 225.0 g of propylene glycol methyl ester Ether (product of TCI) was added to a four-necked flask equipped with a dropping funnel, a thermometer, a cooling tube, and a stirrer, and the inside of the four-necked flask was replaced with nitrogen. Next, after heating the flask to 70 ° C, 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 9.1 g of 2,5-dihydrofuran, and 225.0 g of propylene glycol methyl ether ( TCI's product) and 3.2 g of 2,2'-azobisisobutyronitrile (Wako's product). After 8 hours of polymerization, the resultant was cooled to room temperature, and after replacing the inside of the four-necked flask with nitrogen, 61.5 g of glycidyl methacrylate (Mitsubishi

Company product), 3.6 g of tetrabutylammonium hydroxide (product of TCI company) and 0.15 g of hydroquinone monomethyl ether (pure product of company), and reacted at 80 ° C for 12 hours, adding GMA to the carboxyl group of the copolymer and An adhesive resin B2 was obtained. The weight average molecular weight of the binder resin B2 measured by GPC was 17,000.

<Manufacture of colored photocurable resin composition>

Example 1

55.45 parts by weight of 2.16 parts by weight of the pigment dispersion composition (M1) produced in the aforementioned Production Example 1 and 2.16 parts by weight of the binder resin (B1) produced in Production Example 2 and 4.25 parts by weight of CBZ-SA (Shinakamura Chemical) as a photocurable compound 0.71 part by weight of Irgacure OXE02 (manufactured by BASF) and 37.26 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to produce a colored photocurable resin composition of Example 1.

Example 2

55.45 parts by weight of the pigment dispersion composition (M1) produced in the aforementioned Production Example 1 and 2.87 parts by weight of the binder resin (B1) produced in Production Example 2; 3.54 parts by weight of CBZ-SA (Shinakamura Chemical) as a photocurable compound 0.71 part by weight of Irgacure OXE02 (manufactured by BASF) and 37.26 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to produce a colored photocurable resin composition of Example 2.

Example 3

55.45 parts by weight of 3.58 parts by weight of the pigment dispersion composition (M1) produced in the aforementioned Production Example 1 and the binder resin (B1) produced in Production Example 2 and 2.84 parts by weight of CBZ-SA (Shinakamura Chemical) as a photocurable compound 0.71 part by weight of Irgacure OXE02 (manufactured by BASF) and 37.26 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to produce a colored photocurable resin composition of Example 3.

Example 4

55.45 parts by weight of the pigment dispersion composition (M1) produced in the aforementioned Production Example 1, 2.87 parts by weight of the binder resin (B2) produced in Production Example 3, and 3.54 parts by weight of CBZ-SA (Shinakamura Chemical) as a photocurable compound. 0.71 part by weight of Irgacure OXE02 (manufactured by BASF) and 37.26 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to produce a colored photocurable resin composition of Example 4.

Example 5

55.45 parts by weight of 3.58 parts by weight of the pigment dispersion composition (M1) produced in the aforementioned Production Example 1 and the binder resin (B2) produced in Production Example 3, and 2.84 parts by weight of CBZ-SA (Shin Nakamura Chemical) as a photocurable compound. 0.71 part by weight of Irgacure OXE02 (manufactured by BASF) and 37.26 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to produce a colored photocurable resin composition of Example 5.

Comparative Example 1

55.45 parts by weight of the pigment dispersion composition (M1) produced in the aforementioned Production Example 1 and 2.87 parts by weight of the binder resin (B1) produced in Production Example 2; 3.54 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photocurable compound; 0.71 part by weight of Irgacure OXE02 (manufactured by BASF) and 37.26 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to produce a colored photocurable resin composition of Comparative Example 1.

Comparative Example 2

55.45 parts by weight of the pigment dispersion composition (M1) produced in the above Production Example 1 and 2.87 parts by weight of the binder resin (B1) produced in Production Example 3, and 3.54 parts by weight of KAYARAD DPHA (Nippon Kayaku), which is a photocurable compound. A part by weight, 0.71 part by weight of Irgacure OXE02 (manufactured by BASF), and 37.26 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to produce a colored photocurable resin composition of Comparative Example 2.

Comparative Example 3

55.45 parts by weight of the pigment dispersion composition (M1) and the binder resin (B3) produced in the aforementioned Production Example 1 (copolymer of methacrylic acid and benzyl methacrylate (polystyrene-equivalent weight average molecular weight is 26,000) ) 2.87 parts by weight, 2.84 parts by weight of CBZ-SA (Shin Nakamura Chemical) as a photo-curable compound, 0.71 parts by weight of Irgacure OXE02 (manufactured by BASF), and 37.26 parts by weight of propylene glycol monomethyl ether acetate as a solvent are mixed to produce The colored photocurable resin composition of Comparative Example 3.

<Experimental Example 1> Development time and development residue evaluation of the photocurable resin composition

Each of the photocurable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was coated on a glass substrate of 50 mm × 50 mm by a spin coating method so that the film thickness after drying was 2.5 μm. After that, it was dried in an oven at 100 ° C for 3 minutes. After that, it was developed with a KOH aqueous solution of pH 10.5 using a jet developing device for one minute, and then washed with water and dried with air. At this time, the time at which the red coating film was washed away by the developing solution was measured as the development time (seconds), and is shown in Table 1. In addition, the developed substrate was wiped with a cotton swab moistened with ethanol, and the degree of reddening was confirmed. The results are shown in Table 1.

Development residue

○: No reddish matter was seen on the cotton swab

△: Reddish substance is slightly seen on cotton swabs

×: Reddish substance was seen on cotton swabs

<Experimental Example 2> Sensitivity Evaluation of Photocurable Resin Composition

Each of the photocurable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was coated on a glass substrate of 50 mm × 50 mm by a spin coating method so that the film thickness after drying was 2.5 μm. After that, it was dried in an oven at 100 ° C for 3 minutes. The interval between the dried substrate and the photomask was set to 300 μm, and exposure was performed so that the cumulative light amount of the 313 nm wavelength of the electrodeless lamp was 40 mJ to produce a color filter. After that, it was developed with a KOH aqueous solution of pH 10.5 using a jet developing device for one minute, and then washed with water and dried with air. After that, it was dried in an oven at 230 ° C. for 20 minutes for curing, and the pattern line width and pattern peeling degree of the color filter were measured.

The difference between the pattern line width (X1) and the photomask line width (X2) is shown, and the degree of sensitivity is measured.

○: No pattern peeling; △: 1 to 3 pattern peels; ×: 4 or more pattern peels

<Experimental Example 3> Evaluation of Solvent Resistance of Photocurable Resin Composition

Each of the photocurable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was coated on a glass substrate of 50 mm × 50 mm by a spin coating method so that the film thickness after drying was 2.5 μm. After that, it was dried in an oven at 100 ° C for 3 minutes. The interval between the dried substrate and the photomask was set to 300 μm, and exposure was performed so that the cumulative light amount of the 313 nm wavelength of the electrodeless lamp was 40 mJ to produce a color filter. After that, it was developed with a KOH aqueous solution of pH 10.5 using a jet developing device for one minute, and then washed with water and dried with air. After that, it was dried in an oven at 230 ° C for 20 minutes for curing. After the color filter was immersed in a normal temperature NMP solution for 30 minutes, 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 formula used at this time is calculated by the following mathematical formula 1 that expresses the color change under the three-dimensional colorimeter defined by L *, a *, b *. The smaller the color change value, the more reliable the filter can be manufactured. Color device, but if the value obtained by the following formula is less than 3, it is a level suitable for mass production.

[Mathematical formula 1] △ Eab ^* = [(△ L ^* ) 2+ (△ a ^* ) 2+ (△ b ^* ) 2] ˆ0.5

From the foregoing results, it was confirmed that Examples 1 to 5 of the photocurable resin composition of the present invention as the binder resin containing the compound of the aforementioned chemical formula (1) and the chemical formula (2) or the chemical formula (3) had development time, development residue, Features excellent sensitivity and solvent resistance. In contrast, it was confirmed that the photocurable resin composition of Comparative Example 3 had excellent developability, but the sensitivity and solvent resistance were poor, and the photocurable resin composition of Comparative Examples 1 and 2 had excellent sensitivity and solvent resistance, but developability Worse.

Therefore, it can be said that the colored photo-curable resin composition of the present invention has excellent developing ability capable of solving the problems of development time and sensitivity generated when producing a color filter with high color reproduction.

Claims (5)

A colored photocurable resin composition comprising a photocurable compound (A), a binder resin (B), a photoinitiator (D), and a solvent (E). The photocurable compound (A) includes the following chemical formula (1) Compound, the binder resin (B) contains a monomer of the following chemical formula (3), and the colored photocurable resin composition includes 5 to 45% by weight of the photocurable compound based on the total weight of the solid content 1 to 60% by weight of the binder resin (B), based on the total weight of the colored photocurable resin composition, containing: 0.1 to 10% by weight of the photoinitiator (D); 60 to 95% by weight % Of the solvent (E),

The compound of the chemical formula (1) is a compound containing one or more carboxyl groups and five or more photocurable vinyl groups. In the chemical formula (3), R ₅ , R ₆ , R ₇ and R ₈ are each independently represented. A hydrogen atom, a halogen atom, or an organic residue having 1 to 20 carbon atoms, and the organic residue may contain an oxygen atom. The colored light-curable resin composition according to claim 1, wherein the binder resin (B) contains 1 to 50% by weight of the monomer of the chemical formula (3) with respect to the total content. The colored photocurable resin composition according to claim 1, wherein the colored photocurable resin composition further comprises a colorant and a surfactant, and the colorant contains one or more pigments or one or more dyes. A color filter manufactured using the colored photocurable resin composition according to any one of claims 1 to 3. A liquid crystal display device includes a color filter as claimed in claim 4.