TWI539234B - Colored photosensitive resin composition and color filter using the same - Google Patents

Description

Colored photosensitive resin composition and color filter using the same

The present invention relates to a colored photosensitive resin composition, and more particularly, the present invention relates to a colored photosensitive resin composition for color filters used in the production of a color filter for a color liquid crystal display device or the like, and a manufactured thereon. Color filter.

Color filters are widely used in imaging elements, liquid crystal display devices, etc., and their applications are rapidly expanding. A color filter for a color liquid crystal display device or an image pickup element or the like is generally manufactured by uniformly coating a color corresponding to each color of red, green, and blue on a substrate patterned by a black matrix by spin coating. After the coloring of the photosensitive resin composition, the coating film formed by heat drying (hereinafter sometimes referred to as pre-baking) is exposed and developed, and each color is repeatedly reheated and solidified as needed (hereinafter, The operation, sometimes referred to as post-calcination, forms pixels of respective colors.

On the other hand, in the manufacturing process of the color filter, the unevenness (Mura) phenomenon of the speckle pattern occurs on the substrate, and the unevenness refers to an error or a manufacturing failure occurring in the manufacturing process of the color filter. Occurrence of uneven brightness characteristics over the entire panel or in a portion of the panel spot.

In the related art, although the conventional photosensitive resin composition is actively performing research for improving solvent resistance, heat resistance, development speed, and the like, it still has a problem of sensitivity, and the pin causes the occurrence of a color filter. Problems such as the phenomenon. For example, Korean Patent Publication No. 10-2005-0076606 discloses a photosensitive resin composition having a solvent having an average vapor pressure of less than 3.0 mmHg at 20 ° C, and Korean Patent Publication No. 10-2008-0096472, which contains a boiling point of 100 to 200. a coloring photopolymerizable composition of a solvent of °C and a solvent having a boiling point of 150 to 330 ° C, but only the combination of the boiling point of the solvent or the color filter is described, and the occurrence of unevenness caused by the pin is not proposed. s solution.

Prior art literature

Patent literature:

Patent Document 1: Korean Laid-Open Patent Publication No. 10-2005-0076606.

Patent Document 2: Korean Laid-Open Patent Publication No. 10-2008-0096472.

In view of the above, an object of the present invention is to provide a photosensitive resin composition which has high sensitivity characteristics and which does not cause unevenness due to a pin when a color filter is manufactured.

In order to achieve the above object, the present invention provides a photosensitive resin composition comprising a coloring photosensitive resin composition comprising a coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), and photopolymerization. In the initiator (D) and the solvent (E), the solvent (E) has a PMI (Pin Mura Index) value of the following Mathematical Formula 1 of 3 or less. The vapor pressure.

[Math 1] PMI = -35.6139 + 25.82603 × vapor pressure of solvent - 5.18984 × (vapor pressure of solvent) ² + 0.324966 × (vapor pressure of solvent) ³ .

In an embodiment of the present invention, the PMI may be defined by the following Math.

[Math 2] PMI=|(color of flat plate portion - (color of pin portion))|×1000, in the above formula 2, the flat plate portion refers to a substrate when vacuum drying is performed in the manufacture of the color filter. In the case where there is no pin, the pin portion refers to the portion having the pin.

In still another embodiment, when the color filter is manufactured, the coloring photosensitive resin composition described above may not cause pin unevenness.

In another embodiment, the colored photosensitive resin composition may contain 5 to 60% by weight of the coloring agent (A) and 5 to 85% by weight of the alkali-soluble resin based on the total weight of the solid content. (B), comprising 5 to 50% by weight of the photopolymerizable compound (C); and may comprise 0.1 to 40% by weight based on the total weight of the solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C) The photopolymerization initiator (D) may contain 60 to 90% by weight of the solvent (E) based on the total weight of the colored photosensitive resin composition.

In another embodiment, the colored photosensitive resin composition may further contain an additive (F).

Further, the present invention provides the above-described colored photosensitive resin composition. Color filter.

The colored photosensitive resin composition of the present invention is characterized in that surface defects such as unevenness due to the pin do not occur when the color filter is manufactured.

FIG. 1 is a graph showing the correlation between the PMI (Pin Mura Index, pin unevenness index) of the mathematical expression 1 described in the example and the vapor pressure of the solvent.

Hereinafter, the present invention will be described in detail.

The present invention provides a photosensitive resin composition comprising a coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D). And the solvent (E), the solvent (E) has a vapor pressure in which the PMI (pin unevenness index) value in the following Mathematical Formula 1 is 3 or less.

[Math 1] PMI = -35.6139 + 25.82603 × vapor pressure of solvent - 5.18984 × (vapor pressure of solvent) ² + 0.324966 × (vapor pressure of solvent) ³ .

In the manufacturing process of the color filter, a phenomenon of unevenness (Mura) in the speckle pattern occurs on the substrate, and the unevenness refers to the entire panel or the panel due to an error or a manufacturing failure occurring in the color filter manufacturing process. A portion of the area exhibits spots that exhibit uneven brightness characteristics. In the VCD (Vacuum Dry) device, the memory is pinned, and due to the pin, the color of the pin on the substrate and the portion where there is no pin occur. Poor, and uneven recognition due to chromatic aberration.

The present invention has completed the present invention by experimentally demonstrating that the vapor pressure of the solvent contained in the colored photosensitive resin composition has a relationship with PMI as in the above mathematical formula 1.

The PMI is a value obtained by defining the unevenness caused by the pin at the time of vacuum drying by the following Mathematical Formula 2 and data-forming.

[Math 2] PMI=|(Color of flat part - (color of pin part))|×1000

In the above formula 2, the flat plate portion refers to a portion where no pin is present in the substrate when vacuum drying is performed, and the pin portion refers to a portion having a pin.

The color can be defined in the following manner and measured and determined by a colorimeter device.

Red: R _x

Green: G _y

Blue: B _y

For example, in the case of red (Red), the color of the flat portion obtained by the colorimeter device and the color of the pin portion can be substituted into the above Equation 2 to calculate the PMI.

If the PMI value is 3 or less, unevenness does not occur. Therefore, it is possible to manufacture a photosensitive resin composition which can reduce the unevenness due to the pin by adjusting the vapor pressure of the solvent by the above-described Mathematical Formula 1 and having a low PMI value.

Hereinafter, each configuration will be described in more detail.

Colorant (A)

The coloring agent (A) may optionally contain one or more dyes (a2) as one or more pigments (a1) as essential components. Further, a pigment dispersant (a3) may preferably be contained.

Pigment (a1)

An organic pigment or an inorganic pigment which is generally used in the art can be used as the above pigment.

As the above organic pigment, various pigments for printing inks, inkjet inks and the like can be used, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinophthalone pigments, and isoindolinone pigments. , isoporphyrin pigment, anthraquinone pigment, pirinone pigment, dioxazine pigment, anthraquinone pigment, hydrazine pigment, quinone pyrimidine pigment, tribenzo [ cd, jk ] 芘-5, An anthanthrone pigment, an indanthrone pigment, a ketone pigment, a pyranthrone pigment, and a diketopyrrolopyrrole pigment.

The inorganic pigment may, for example, be a metal compound such as a metal oxide or a metal complex salt, and specific examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, cerium, and carbon black. Metal oxide or composite metal oxide, etc.

In particular, the above-mentioned organic pigments and inorganic pigments may specifically be exemplified by a compound which is classified into a pigment in a color index (published by The Society of Dyers and Colourists), and more specifically, the following are exemplified as follows Color index (CI) numbered pigments, but not limited to this.

Such as 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.

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

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

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76.

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

C.I. Pigment ash 28.

C.I. Pigment Black 1 and 7, etc.

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

Among the CI pigments exemplified above, those selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Orange 38, CI Pigment Red 122, CI Pigment Red 166, CI Pigment can be preferably used. Red 177, CI Pigment Red 208, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Violet 23, CI Pigment Blue 15:3, CI Pigment Blue 15:6, CI Pigment Green 7, CI Pigment Green 36 and pigments in CI Pigment Green 58.

As the above pigment, it is preferred to use a pigment dispersion liquid whose particle diameter is uniformly dispersed. As an example of a method for uniformly dispersing the particle diameter of the pigment, a package may be mentioned A method of performing a dispersion treatment on the basis of a pigment-containing dispersant (a3), according to which a pigment dispersion liquid in which a pigment is uniformly dispersed in a solution can be obtained.

The content of the pigment (a1) is in the range of 10 to 50% by weight, preferably 15 to 45% by weight based on the total solid content of the pigment dispersion composition. When the content of the pigment is in the range of 15 to 40% by weight based on the above criteria, the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, so that the light-dark ratio is effectively increased.

Pigment dispersant (a3)

The pigment dispersant (a3) is added for the anti-agglomeration and maintenance stability of the pigment, and a pigment dispersant which is generally used in the art can be used in an unrestricted manner. Specific examples of the above-mentioned pigment dispersing agent include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine. These may be used alone or in combination of two or more. The above pigment dispersant comprises an acrylate dispersant (hereinafter referred to as an acrylate dispersant), and the acrylate dispersant comprises BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate) ester). In this case, the acrylate dispersant is preferably produced by an activity control method as disclosed in Korean Patent Publication No. 2004-0014311, and an acrylate-based dispersant produced by the above-described activity control method is commercially available. Take DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc.

The above-exemplified acrylate dispersants may be used singly or in combination of two or more.

In addition to the above acrylate dispersants, other resin types can be used. A material dispersant was used as the above pigment dispersant (a3).

As the pigment dispersant of the above other resin type, a pigment dispersant of a known resin type can be used, and in particular, a polycarboxylate represented by polyurethane, polyacrylate, an unsaturated polyamine, a polycarboxylic acid, or a polycarboxylic acid can be used. (partially) an amine salt, an ammonium salt of a polycarboxylic acid, an alkylamine salt of a polycarboxylic acid, a polyoxyalkylene oxide, a long-chain polyaminoguanamine phosphate, an ester of a hydroxyl group-containing polycarboxylic acid, and a modification thereof Or a polyester having a free carboxyl group and an emulsifying dispersant such as an amine formed by a reaction with poly(lower alkyleneimine) or a salt thereof; a (meth)acrylic styrene copolymer, Water-soluble resin or water-soluble polymer such as (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; polyester; modified poly Acrylate; additional product of ethylene oxide/propylene oxide and phosphate ester.

As a commercial product of the above-mentioned resin type pigment dispersant, as a cationic resin dispersing agent, for example, BYK Chemical Company's trade name: 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 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, EFKA-4800; Lubirzol Trade name: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Chuanyan Fine Chemicals (KAWAKEN Fine Chemicals) company's trade name: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Ajinomoto company's trade name: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823 The trade name of Kyoeisha Chemical Co., Ltd.: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc.

Other resin type pigment dispersing agents other than the above acrylate dispersing agent may be used singly or in combination of two or more kinds, and may be used in combination with an acrylate dispersing agent.

The amount of the pigment dispersant (a3) used is 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, per 100 parts by weight of the solid content of the pigment (a1) to be used. When the content of the pigment dispersant (a3) exceeds 60 parts by weight, the viscosity may be increased, and if it is less than 5 parts by weight, the pigment may be difficult to be microparticulated, or the pigment may be gelated after being dispersed.

Dye (a2)

The use of the above dyes is not limited as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and which can ensure solubility in an alkali developing solution, heat resistance, solvent resistance, and the like.

The dye may be selected from an acid dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or the like, and a derivative thereof. Acid dyes of azo, xanthene, and phthalocyanine and their derivatives are selected.

Preferably, the above dyes can be exemplified in the color index (British dyeing and A compound classified as a dye in the Society of Dyers and Colourists or a well-known dye described in the dyeing manual (color dyeing company).

As a specific example of the above dye, as the C.I. solvent dye, there are mentioned:

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

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

C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 45, 56, 62 and other orange dyes.

C.I. Blue dyes such as solvent blue 5, 35, 36, 37, 44, 59, 67, 70.

C.I. Solvent violet 8, 9, 13, 14, 36, 37, 47, 49 and other purple dyes.

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

Preferably, CI Solvent Yellow 14, 16, 21, 56, 151, 79, 93 which is excellent in solubility in an organic solvent in a CI solvent dye; CI Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; CI Solvent Orange 41, 45, 62; CI Solvent Blue 35, 36, 44, 45, 70; CI Solvent Violet 13, among which CI Solvent Yellow 21, 79; CI Solvent Red 8, 122, 132; CI Solvent Orange 45, 62.

Further, as the C.I. acid dye, there are mentioned:

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

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, and 426.

C.I. Orange dyes such as acid oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173.

CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 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, 340 and other blue dyes.

C.I. Acid violet 6B, 7, 9, 17, 19, 66 and other purple dyes.

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

It is preferably C.I. Acid Yellow 42, C.I. Acid Red 92, C.I. Acid Blue 80, C.I. Acid Blue 90, C.I. Acid Violet 66, C.I. Acid Green 27 which is excellent in solubility in an organic solvent in an acid dye.

Further, as the C.I. direct dye, there are mentioned:

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, 141 and other yellow dyes.

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 Red dyes such as 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250.

C.I. Orange dyes such as direct oranges 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107.

CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 114,115,117,119,137,149,150,153,155,156,158,159,160,161,162,163,164,166,167,170,171,172,173,188,189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, Blue dyes such as 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293.

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

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

Further, as the C.I. medium dye, there are mentioned:

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

CI medium 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 Red dyes such as 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95.

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

CI Medium 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 Blue dyes such as 44, 48, 49, 53, 61, 74, 77, 83, and 84.

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

C.I. Medium Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and other green dyes.

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

The content of the dye in the coloring agent (A) is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, particularly preferably 1 to 50% by weight based on the total weight of the solid content of the coloring agent (A). . When the content of the dye in the coloring agent (A) is within the above range, the problem that the reliability of the dye elution due to the organic solvent is lowered after the pattern is formed can be prevented, and the sensitivity is excellent, which is more preferable.

The content of the coloring agent (A) is 5 to 60% by weight, preferably 10 to 45% by weight based on the total weight of the solid content of the colored photosensitive resin composition. In the case where the coloring agent (A) is contained in an amount of 5 to 60% by weight based on the above criteria, even if a film is formed, the color density of the pixel is full, and the leakage of the non-pixel portion does not decrease during development, which is difficult Residue is generated, which is preferable.

In the present invention, the total solid content in the colored photosensitive resin composition means the total content of the remaining components other than the solvent in the colored photosensitive resin composition.

Alkali soluble resin (B)

In the present invention, the alkali-soluble resin is a solvent which can be dissolved in the solvent of the present invention and has a function of light or heat, has a function as a binder resin to the coloring agent, and can be dissolved in an alkaline developer. The acrylic copolymer can be used without particular limitation.

The acrylic copolymer may, for example, be a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the above monomer.

Specific examples of the carboxyl group-containing monomer include a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid. An unsaturated carboxylic acid such as an unsaturated polycarboxylic acid having a carboxyl group as described above.

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

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride.

The unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester thereof, and examples thereof include succinic acid mono(2-propenyl oxiranyl) ester and succinic acid mono (2-methyl). Propylene oxyethyl) ester, mono(2-propenyl oxiranyl) phthalate, mono(2-methylpropoxy oxy) phthalate, and the like. Further, the above unsaturated polycarboxylic acid may be a mono(meth)acrylate whose both ends are a dicarboxy polymer, and for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypoly Lactone monomethacrylate and the like.

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

Specific examples of the other monomer copolymerizable with the above carboxyl group-containing monomer may, for example, be styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene or p-chlorostyrene. , o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, o-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl An aromatic vinyl compound such as glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, hydrazine; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate Acrylic Propyl ester, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate , sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy propyl methacrylate Ester, 3-hydroxypropyl acrylate, 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 cyclohexane Ester, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate Ester, methoxy diethylene glycol acrylate, methoxy diethylene glycol Acrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, A Oxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxy acrylate Unsaturated carboxylic acid esters such as propyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerin monoacrylate, glycerol monomethacrylate; 2-aminoethyl acrylate, 2-methacrylic acid 2- Aminoethyl ester, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate Ester, methacrylic acid 2- Unsaturated carboxylic acid amino group such as dimethylaminopropyl ester, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate Alkyl esters; glycidyl acrylates such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate Non-saturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; cyanide vinyl compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and divinyl cyanoethylene ; unsaturated amides such as acrylamide, methacrylamide, α-chloropropenylamine, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide; Malay Unsaturated quinone imines such as quinone imine, N-phenyl maleimide, N-cyclohexylmaleimide, etc.; 1,3-butadiene, isoprene, chloroprene and other fats Group conjugated dienes; polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate Macromonomers having a mono Bing Xixi group or the like monomethyl Bing Xixi group at the end of the polymer chains of poly-silicon siloxane.

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

The content of the carboxyl group-containing monomer unit in the alkali-soluble resin may be 10 to 50% by weight, preferably 15 to 40% by weight, and more preferably 25 to 40% by weight based on the total monomer content. When the content of the carboxyl group-containing monomer unit is from 10 to 50% by weight, the solubility in the developer is good, and the pattern tends to be formed accurately when developing, which is preferable.

The acrylic copolymer may, for example, be a (meth)acrylic acid/(meth)acrylic acid methyl ester copolymer, a (meth)acrylic acid/(meth)acrylic acid benzyl ester copolymer, or a (meth)acrylic acid/( Methyl)acrylic acid 2- Hydroxyethyl ester/benzyl (meth)acrylate copolymer, (meth)acrylic acid/methyl (meth)acrylate/polystyrene macromonomer, (meth)acrylic acid/(meth)acrylic acid Methyl ester/poly(methyl) acrylate macromonomer copolymer, (meth)acrylic acid/benzyl methacrylate/polystyrene macromonomer, (meth)acrylic acid/(methyl) Benzyl acrylate/poly(methyl) acrylate macromonomer copolymer, (meth)acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene Macromonomer copolymer, (meth)acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / poly (meth) acrylate macromonomer copolymer, (methyl Acrylic/styrene/benzyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono(2-propenyloxy)ester/styrene/( Benzyl methacrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono(2-propenyl oxiranyl) ester/styrene/(meth)acrylic allylate Base ester / N-phenyl maleimide copolymer, (meth) acrylic acid / (methyl) Benzyl acrylate/N-phenylmaleimide/styrene/glycerin mono(meth)acrylate copolymer, and the like. Among them, (meth) acrylate means acrylate or methacrylate.

Among them, (meth)acrylic acid/benzyl (meth)acrylate copolymer, (meth)acrylic acid/benzyl (meth)acrylate/styrene copolymer, (meth)acrylic acid/(methyl) is preferably used. A methyl acrylate copolymer, a (meth)acrylic acid / methyl (meth) acrylate / styrene copolymer.

The polystyrene-equivalent weight average molecular weight of the alkali-soluble resin may be usually from 5,000 to 50,000, preferably from 8,000 to 40,000, more preferably from 10,000 to 10,000. 35000, most preferably 10,000~30000. When the molecular weight of the alkali-soluble resin is from 5,000 to 50,000, the hardness of the coating film is increased, the residual film ratio is also high, the solubility of the unexposed portion in the developer is good, and the resolution is improved.

The acid value of the alkali-soluble resin is usually 50 to 150, preferably 60 to 140, more preferably 80 to 135, and most preferably 80 to 130. When the acid value is 50 to 150, the solubility in the developer is improved, the unexposed portion is easily dissolved, and the sensitivity is increased, so that the pattern of the exposed portion remains when the development is performed, and the residual film ratio is increased. The trend is therefore preferred. Here, the acid value is a value measured by the amount (mg) of potassium hydroxide required for neutralizing 1 g of the acrylic polymer, and is usually determined by titration with an aqueous potassium hydroxide solution.

The alkali-soluble resin may be contained in an amount of 5 to 85% by weight, preferably 10 to 70% by weight based on the total weight of the solid content of the colored photosensitive resin composition of the present invention. When the alkali-soluble resin is contained in an amount of 5 to 85% by weight based on the above-mentioned criteria, it is difficult to cause development residue on the substrate of the non-pixel portion due to sufficient solubility in the developer, and it is difficult to perform development when performing development. It is preferable that the film of the pixel portion of the exposed portion is reduced and the non-pixel portion has a good drop-off property.

Photopolymerizable compound C

In the present invention, the photopolymerizable compound is a compound which can be polymerized by an active radical, an acid or the like which is generated from a photopolymerization initiator by irradiation of light. In the present specification, the term "photopolymerizable compound" means a monomer having one or more functional groups, and is described as monofunctional depending on the number of functional groups. A polymerizable compound, a difunctional polymerizable compound, a trifunctional polymerizable compound, or the like.

Specific examples of the monofunctional polymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and acrylic acid 2- Hydroxyethyl ester or N-vinylpyrrolidone.

Specific examples of the difunctional polymerizable compound include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. , triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, butanediol di(methyl) Acrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, and the like.

Specific examples of the trifunctional polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and ethoxytrimethylolpropane tri(meth)acrylate. And propoxytrimethylolpropane tri(meth)acrylate, glyceryl propoxy triacrylate, isocyanurate triacrylate, and the like.

Specific examples of the tetrafunctional polymerizable compound include pentaerythritol tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, and the like.

Further, specific examples of the pentafunctional polymerizable compound include dipentaerythritol penta (meth) acrylate, and specific examples of the hexafunctional photopolymerizable compound may, for example, be dipentaerythritol hexa(meth)acrylate.

Among them, a difunctional or higher polyfunctional polymerizable compound can be preferably used, and a pentafunctional or higher polyfunctional polymerizable compound can be most preferably used.

The photopolymerizable compound (C) is preferably contained in an amount of 5 to 50% by weight, and more preferably 7 to 45% by weight based on the total weight of the solid content in the colored photosensitive resin composition. When the photopolymerizable compound (C) is contained in an amount of 5 to 50% by weight based on the above criteria, the strength or smoothness of the pixel portion tends to be good, which is preferable.

Photopolymerization initiator (D)

In the present invention, the type of the photopolymerization initiator can be used without limitation as long as the alkali-soluble resin and the photopolymerizable compound can be polymerized. In particular, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price, it is preferred to contain an acetophenone-based, benzoin-based compound, benzophenone-based, thioxanthone-based, or triazine-based compound. , 肟, A light stabilizer may be used in combination with one or more compounds selected from the group consisting of a salt system, a nitrobenzyl tosylate salt, and a benzoin tosylate salt. The photopolymerization initiator can be classified into an active radical generator which generates active radicals by irradiation of light, a reducing agent, an acid generator, and the like.

The living radical generating agent may, for example, be a benzoin system, an acetophenone system, a benzophenone system, a thioxanthone system, a triazine system or an anthraquinone compound.

Specific examples of the acetophenone-based compound include diethoxyacetophenone and 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, and 2 -hydroxyl -2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane Oligomers of 1-ketone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, etc. Preferred is 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one. The acetophenone-based compounds may be used singly or in combination of two or more kinds thereof, or may be used in combination with other photopolymerization initiators.

Specific examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Specific examples of the benzophenone-based compound include benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyl Phenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. , 1-chloro-4-propoxythioxanthone, and the like.

Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis ( Trichloromethyl)-6-(4-methoxynaphthyl)-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-three Pyrazine, 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, 2,4-bis(trichloromethyl)-6-[2 -(3,4-Dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.

Specific examples of the lanthanoid compound include 2-(O-benzhydrazin)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(4- Methylthio-phenyl)-butane-1,2-butane-2-indole-O-acetate, 1-(4-methylsulfanyl-phenyl)-butan-1-one oxime- O-acetate, hydroxyimino-(4-methylthio-phenyl)-acetic acid-O-acetate, hydroxyimino-(4-methylthio-phenyl)-acetic acid Ester-O-benzoate and the like.

Specific examples of the increase and decrease agent include 2,4,6-trimethylbenzimidium diphenylphosphine oxide, 2,2-bis(o-chlorophenyl)-4,4',5,5'. -tetraphenyl-1,2'-diimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzoin, 9,10-phenanthrenequinone, camphorquinone, acetophenone Methyl ester, titanocene compound, and the like.

Specific examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethyloxyphenylene. Methyl hydrazine p-toluene sulfonate, 4-ethyl methoxy phenyl methyl benzyl hexafluoroantimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyl Base iodine P-toluenesulfonate Hexafluoroantimonate Salt or nitrobenzyl tosylate, benzoin tosylate, and the like. Among the above compounds, there are also compounds which simultaneously produce active radicals and acids, such as triazine-based compounds.

The photopolymerization initiator may be contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total weight of the solid content of the alkali-soluble resin and the photopolymerizable compound of the present invention. When the photopolymerization initiator is contained in the above-described manner, the coloring photosensitive resin composition is highly sensitive, and the exposure time is shortened. Therefore, productivity can be improved and high resolution can be maintained, which is preferable.

In the present invention, a photopolymerization initiation aid may also be included together with the photopolymerization initiator. The photopolymerization initiation aid is used in combination with a photopolymerization initiator, and is used to promote polymerization of a photopolymerizable compound which initiates polymerization by means of a photopolymerization initiator. Examples of the photopolymerization initiation aid include an amine compound, an alkoxy fluorene compound, and a thioxanthone compound.

Specific examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamino group. Isoamyl benzoate, dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethyl Amino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc., preferably 4,4'-double (Diethylamino)benzophenone.

Specific examples of the alkoxy ruthenium compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2 -ethyl-9,10-diethoxyanthracene, and the like.

Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxene. Ketone, 1-chloro-4-propoxythioxanthone, and the like.

The photopolymerization initiation aid may be used alone or in combination of two or more. EAB-F (manufactured by HODOGAYA CHEMICAL CO., LTD.) or the like which is a commercially available product may be used.

Specific examples of a combination of a preferred photopolymerization initiator and a photopolymerization initiation aid include diethoxyacetophenone and 4,4'-bis(diethylamino)benzophenone; 2-methyl-2 -morpholino-1-(4-methylthiophenyl)propan-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-phenylpropan-1-one and 4,4'-bis(diethylamino)benzophenone; -hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone and 4,4'-bis(diethylamino)benzophenone; 1-hydroxycyclohexyl Phenyl ketone and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1- Oligomeric ketone and 4,4'-bis(diethylamino)benzophenone; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1- A combination of a ketone and 4,4'-bis(diethylamino)benzophenone, etc., more preferably 2-methyl-2-morpholino-1-(4-methylthiophenyl) A combination of propan-1-one and 4,4'-bis(diethylamino)benzophenone.

In the case where the photopolymerization initiator and the photopolymerization initiation aid are used together, the content of the photopolymerization initiator is preferably 10 mol or less, more preferably 0.01 to 5 m, per 1 mol of the photopolymerization initiator. . In the case of containing a photopolymerization initiator of 10 mol or less with respect to 1 mol of the photopolymerization initiator, the sensitivity of the colored photosensitive resin composition becomes higher, and the color filter formed using the composition is used. The trend of productivity improvement of the device is therefore preferred.

Solvent (E)

In the present invention, the type of the solvent is not particularly limited as long as it can effectively disperse or dissolve other components contained in the colored photosensitive resin composition, and is particularly preferably an ether, an aromatic hydrocarbon, a ketone, an alcohol or an ester. Class or guanamines, etc.

Specific examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether. Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol II Propyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether glycol, ethylene glycol methyl ether acetate, ethylene Alcohol ether acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, 3-methoxybutyl acetate, methoxy methoxy acetate, Anisole, phenethyl ether or methyl anisole.

Specific examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Specific examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone or cyclohexanone. .

Specific examples of the ethanol include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Specific examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, propyl isobutyrate, and butyl. Ethyl acetate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxy Ethyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate , propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-B Methyl oxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropionate, 2-methoxy Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl acetate Ester, methyl 2-oxobutanoate, ethyl 2-oxobutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate or γ-butyrolactone Wait.

Specific examples of the guanamines include N,N-dimethylformamide or N,N-dimethylacetamide.

Examples of the other solvent include N-methylpyrrolidone or dimethylammonium.

Preferably, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate or propylene glycol methyl ether is used alone or in combination of two or more.

The solvent may be contained in an amount of 60 to 90% by weight, and preferably 70 to 85% by weight based on the total weight of the colored photosensitive resin composition. When the solvent is contained in the above content, it has a roll coater, a spin coater, a slit and a spin coater, a slit coater (or "die coater"), an ink jet printer, etc. The coating property tends to be good when the coating device is applied, which is preferable.

Additive (F)

The additive (F) may be optionally added as needed, and examples thereof include other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-agglomerating agents.

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

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

Among the above curing agents, specific examples of the epoxy compound include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, and hydrogenated bisphenol F type epoxy resin. , novolac type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidylamine resin or brominated derivatives of these epoxy resins, epoxy resin and An aliphatic, alicyclic or aromatic epoxy compound other than a brominated derivative of an epoxy resin, an epoxide of a butadiene (co)polymer, or an epoxide of an isoprene (co)polymer , glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, and the like.

Among the above curing agents, specific examples of the oxetane compound include carbonate dioxetane, xylene dioxetane, adipate dioxetane, and Phthalate dioxetane, cyclohexanedicarboxylic acid dioxetane, and the like.

The curing agent may be used together with a curing agent to form a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound. Specific examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, acid generators, and the like. As the above polyvalent carboxylic acid anhydride, an epoxy resin curing agent which is commercially available can be used. Specific examples of the epoxy resin curing agent include ADEKA HARDENER EH-700 (product Name: manufactured by Adek Industries Co., Ltd., RIKACID HH (trade name) (manufactured by Shin-Nippon Chemical Co., Ltd.), MH-700 (trade name) (manufactured by Shin-Nippon Chemical Co., Ltd.), and the like. The above-exemplified curing agents may be used singly or in combination of two or more.

The surfactant may be used to further improve the film formability of the photosensitive resin composition, and a fluorine-based surfactant or a ruthenium-based surfactant may be preferably used.

The above-mentioned lanthanoid surfactants are, for example, DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Dow Corning Toray Silicone Co., Ltd., which are commercially available products, and TSF-4440, TSF-4300, TSF-4445, TSF of GE Toshiba Silicon Co., Ltd. -4446, TSF-4460, TSF-4452, etc. The fluorine-based surfactants include Megapax (registered trademark) F-470, F-471, F-475, F-482, F-489, F-554, and the like, which are commercially available from Japan Ink Chemical Co., Ltd. The surfactants exemplified above may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)decane, and N-(2-aminoethyl). -3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxy Propyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyl Dimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltrimethoxysulfonium An alkane, 3-isocyanate propyl triethoxy decane, methacryloxypropyl trimethoxy decane, and the like. The adhesion promoters exemplified above may be used singly or in combination of two or more. The adhesion promoter may be contained in an amount of 0.01 to 10% by weight, and preferably 0.05 to 2% by weight, based on the solid amount of the colored photosensitive resin composition.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

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

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

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

First, the coloring agent and the solvent are mixed and dispersed by a bead mill or the like until the average particle diameter of the coloring agent is 0.2 μm or less. At this time, if necessary, it may be dissolved or dispersed by mixing with a part or all of the pigment dispersant or the alkali-soluble resin.

To the above-mentioned mixed dispersion (hereinafter sometimes referred to as "abrasive"), the remaining portion of the remaining alkali-soluble resin, the photopolymerizable compound, and the photopolymerization initiator are added, and if necessary, an additional solvent is added to The target coloring photosensitive resin composition can be produced by reaching a predetermined concentration.

Hereinafter, the present invention will be described in more detail by way of examples, comparative examples, and experimental examples. The following examples, comparative examples and experimental examples are intended to illustrate the invention, and the scope of the invention is not limited by the following examples, comparative examples and experimental examples, and various modifications and changes can be made. and In the following examples and comparative examples, "%" and "parts" of the content are based on weight unless otherwise specified.

Examples 1 to 4 and Comparative Examples 1 to 9

The colored photosensitive resin composition was produced as shown in the following Table 1 in such a manner that the vapor pressure can be adjusted.

In the above Table 1, each component is as follows.

(A-1) Colorant: C.I. Pigment Red 254

(B-1) alkali-soluble resin: as an alkali-soluble resin, a copolymer of methacrylic acid and benzyl methyl acrylate (the molar ratio of the methacrylic acid unit and the benzyl methacrylate unit is 27:73, The acid value is 83 and the weight average molecular weight is 18,000)

(C-1) Photopolymerizable compound: dipentaerythritol hexaacrylate

(D-1) Photopolymerization initiator: 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one

(D-2) Photopolymerization initiation aid: 4,4'-bis(diethylamino)benzophenone

(D-3) Photopolymerization initiator: 2-(O-benzhydryl-1-[4-(phenylthio)phenyl]-1,2-octanedione

(F-1) Additive: Megapax (registered trademark) F554 (manufactured by Dainippon Ink and Chemicals Co., Ltd.)

(F-2) Additive: methacryloxypropyltrimethoxydecane as adhesion promoter

(E-1) Solvent: 3-ethoxypropionic acid ethyl ester

(E-2) Solvent: 1-methoxy-2-propanol

(E-3) Solvent: propylene glycol diacetate

(E-4) Solvent: propylene glycol monomethyl ether acetate

Experimental example 1. Measuring the unevenness caused by the pin

The colored photosensitive resin compositions of the above Examples 1 to 4 and Comparative Examples 1 to 9 were applied to a 2 inch square glass substrate ("EAGLE XG" manufactured by Corning Co., Ltd.) on the upper portion of the glass substrate by a spin coating method. Thereafter, vacuum drying was carried out, followed by placing on a hot plate, and maintaining at a temperature of 100 ° C for 3 minutes to form a color layer film. Next, an experimental photomask having a pattern which changes stepwise in a range of transmittance of 1% to 100% and a line/space pattern of 1 μm to 50 μm is placed on the upper portion of the color layer film, and the experimental photomask is placed thereon. The interval was set to 100 μm to illuminate the ultraviolet rays. At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ/cm ² using a 1 kW high-pressure mercury lamp containing g, h, and i lines, and no special optical screening program was used. The color layer film irradiated with ultraviolet rays was immersed in a developing solution of KOH aqueous solution having a pH of 10.5 for 2 minutes to develop. After the glass substrate on which the developed color layer film was formed was washed with distilled water, it was dried under a nitrogen atmosphere, and heated in a heating oven at 200 ° C for 1 hour to effect heat curing, thereby producing a color filter. The color layer of the manufactured color filter had a thickness of 1.8 μm.

The PMI (pin unevenness index) defined by the following Mathematical Formula 2 and the unevenness caused by the pin were measured for the color filter obtained above, and the results are shown in Table 2 below.

Further, the relationship between the PMI and the vapor pressure of the solvent (Fig. 1) was analyzed, and the following mathematical expression 1 was derived by the relationship between the PMI and the vapor pressure of the solvent.

[Math 1] PMI = -35.6139 + 25.82603 × vapor pressure of solvent - 5.18984 × (vapor pressure of solvent) 2+0.324966 × (vapor pressure of solvent) ³

[PMI (Pan Uneven Index)]

When vacuum drying is performed, the unevenness caused by the pin is defined by the following Mathematical Formula 2 and data is made.

[Math 2] PMI=|(Color of flat part - (color of pin part))|×1000

In the above formula 2, the flat plate portion refers to a portion where the pin is not present in the substrate when vacuum drying is performed, and the pin portion refers to a portion having a pin.

The color is defined as follows, and is measured and determined by a colorimeter device.

Red: R _x

Green: G _y

Blue: B _y

○: Uneven phenomenon caused by the occurrence of sales

×: Uneven phenomenon caused by pinning

As shown in the above Table 2, when the PMI calculated by the above mathematical formula 1 is 3 or less, it is confirmed that the unevenness caused by the pin does not occur.

Claims (6)

A colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), The solvent (E) has a vapor pressure in which the PMI value in the following Mathematical Formula 1 is 3 or less, and the PMI value is a pin unevenness index, and the mathematical formula 1 PMI = -35.6139 + 25.82603 × the vapor pressure of the solvent - 5.18984 × ( The vapor pressure of the solvent is ² + 0.324966 × (vapor pressure of the solvent) ³ . The colored photosensitive resin composition of claim 1, wherein the PMI value is defined by the following mathematical formula 2, and the mathematical formula 2 PMI=| (the color of the flat portion - the color of the pin portion) | × 1000 in the mathematics In the formula 2, the flat portion refers to a portion where no pin is present in the substrate when vacuum drying is performed, and the pin portion refers to a portion having a pin. The colored photosensitive resin composition of claim 1, wherein when the color filter is manufactured, the colored photosensitive resin composition does not cause pin unevenness. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition contains 5 to 60% by weight of the coloring agent (A) based on the total weight of the solid content; and 5 to 85 parts by weight % of the alkali-soluble resin (B); comprising 5 to 50% by weight of the photopolymerizable compound (C); and 0.1 based on the total weight of the solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C) 40% by weight of the photopolymerization initiator (D); and 60 to 90% by weight of the solvent (E) based on the total weight of the colored photosensitive resin composition. The colored photosensitive resin composition of claim 1, wherein the colored photosensitive resin composition further contains an additive (F). A color filter made of the colored photosensitive resin composition according to any one of claims 1 to 5.