KR20140116670A - Colored photosensitive resin composition and color filter - Google Patents
Colored photosensitive resin composition and color filter Download PDFInfo
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- KR20140116670A KR20140116670A KR1020130031536A KR20130031536A KR20140116670A KR 20140116670 A KR20140116670 A KR 20140116670A KR 1020130031536 A KR1020130031536 A KR 1020130031536A KR 20130031536 A KR20130031536 A KR 20130031536A KR 20140116670 A KR20140116670 A KR 20140116670A
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- resin composition
- photosensitive resin
- colored photosensitive
- alkali
- pigment
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
The present invention relates to a colored photosensitive resin composition and a color filter.
A color filter can be embedded in a color imaging device of an image sensor, such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD), and can be used to actually obtain a color image (PDP), a liquid crystal display (LCD), a field emission display (FEL), and a light emitting display (LED), and the application range thereof is rapidly expanding. Particularly, in recent years, the use of the liquid crystal display (LCD) has been further expanded, and accordingly, the color filter has been recognized as one of the most important components in reproducing the color tone of the LCD.
Such a color filter is produced by a method of forming a desired coloring pattern by using a colored photosensitive resin composition containing a coloring agent. Specifically, it is manufactured by forming a coating layer of a colored photosensitive resin composition on a substrate, forming a pattern on the formed coating layer, exposing and developing the coating layer, and heating and thermally curing the coating layer.
As a colorant, a pigment is used. However, in this case, there is a problem that a desired luminance can not be obtained by a user. Recently, there has been an attempt to use a dye having high brightness and excellent heat resistance. The colorant is preferably used because it can realize all the excellent characteristics of the dye in the case of using only the dye, but the compatibility of the dye with the other components of the composition is worse than that of the pigment. Therefore, although a method of using a hybrid type coloring agent using both a pigment and a dye as coloring agents has been attempted, development characteristics are deteriorated. In the case of producing a color filter, the developing speed is slow and the sensitivity is insufficient. There is a problem that peeling of the formed pattern frequently occurs. Therefore, it is required to develop a colored photosensitive resin composition suitable for a lithographic process which can simultaneously satisfy the maintenance of a high luminance and the maintenance of good developing characteristics.
As the invention using a conventional colored photosensitive resin composition, Korean Patent Laid-Open Publication No. 10-2004-0026095 discloses a dye-containing curable composition, but in the case of the above-mentioned conventional techniques, a developing speed is slowed and sensitivity and adhesion are problematic Peeling of the pattern may occur during the development process, resulting in poor processability, and low transmittance, chemical resistance and sensitivity.
Therefore, the colored photosensitive resin composition and the color filter according to the present invention provide a colored photosensitive resin composition which can obtain a color filter excellent in transmittance and excellent in reliability, has a high developing speed and is excellent in sensitivity and adhesion, It is an object of the present invention to provide a colored photosensitive resin composition and a color filter which are free from peeling, excellent in chemical resistance, and excellent in storage stability, and which do not decrease in sensitivity or increase in viscosity even when stored for a long time.
According to an aspect of the present invention for achieving the above object, the present invention provides a photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the alkali- , And the acid value of the alkali-soluble resin is 30 to 150 mgKOH / g.
(Formula 1)
In Formula 1,
R1 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 3 to 20 carbon atoms; R2 and R3 are independent of each other and are an alkyl group having 1 to 12 carbon atoms. An alkenyl group having 2 to 12 carbon atoms or an aryl group having 3 to 12 carbon atoms; A1 is a divalent connecting group, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms; And X is a carboxylate (-COO -) a, sulfonate (-SO 3 - -) or sulfate (-OSO 3).
The present invention also provides a color filter comprising the colored photosensitive resin composition.
Therefore, the colored photosensitive resin composition of the present invention according to the above-mentioned object of the present invention is intended to uniformly disperse the dyes in the photosensitive composition by introducing a binder resin into which monomers capable of salt formation in the molecule are introduced, It is possible to provide a colored photosensitive resin composition for a color filter which can obtain an excellent color filter. Accordingly, it is possible to provide a color filter excellent in contrast ratio, transmittance, chemical resistance and sensitivity by using the colored photosensitive resin composition of the present invention which is excellent in sensitivity and adhesion and can prevent occurrence of a short circuit in the development process, Can be produced.
Hereinafter, specific details of the color photosensitive resin composition and the color filter according to the present invention will be described.
(A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E) Wherein the colorant (A) comprises at least one colorant selected from the group consisting of a pigment and a dye.
(Formula 1)
In Formula 1,
R1 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 3 to 20 carbon atoms; R2 and R3 are independent of each other and are an alkyl group having 1 to 12 carbon atoms. An alkenyl group having 2 to 12 carbon atoms or an aryl group having 3 to 12 carbon atoms; A1 is a divalent connecting group, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms; And X is a carboxylate (-COO -) a, sulfonate (-SO 3 - -) or sulfate (-OSO 3).
1 to 60% by weight of the colorant, 10 to 80% by weight of an alkali-soluble resin, 1 to 45% by weight of a photopolymerizable compound based on the total solid content of the colored photosensitive resin composition based on the total solid content of the colored photosensitive resin composition, Wherein the photopolymerization initiator comprises 0.01 to 40% by weight based on the content of the alkali-soluble resin and the photopolymerizable compound, and the solvent comprises 1 to 90% by weight based on the total weight of the colored photosensitive resin composition desirable.
Hereinafter, the constituent elements constituting the present invention will be described in detail.
The colorant (A)
The colorant preferably includes at least one member selected from the group consisting of a pigment and a dye. The pigment or dye is polymerized and crosslinked together with the alkali-soluble resin containing the compound of Formula 1 to determine the solvent resistance of the colored photosensitive resin composition It plays a role of improving.
The pigment (a1)
The pigment may be an organic pigment or an inorganic pigment generally used in the art. The above-mentioned pigments can be used in various kinds of pigments used in printing ink, ink jet ink and the like. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, And an anthanthrone pigment, an anthanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or composite metal oxides. Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number Pigments, but are not limited thereto.
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 7 Light
The above-mentioned pigments (a1) may be used alone or in combination of two or more.
Of the exemplified CI pigment pigments, CI Pigment Orange 38, CI Pigment Red 122, 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 Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, Pigment Blue 23, CI Pigment Blue 15: 3, Pigment Blue 15: 6 can be preferably used.
It is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment dispersion (a3) by containing the pigment dispersant (a3). According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained have.
Specific examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, and polyamine surfactants. These surfactants may be used singly or in combination of two or more thereof .
The content of the pigment (a1) is in the range of 20 to 90% by mass, preferably 30 to 70% by mass with respect to the total solid content in the pigment dispersion composition. When the content of the pigment is in the range of 20 to 90% by mass, the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, which is effective for increasing the contrast ratio.
As the dispersant (a3), other resin type pigment dispersants other than the acrylic dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters. DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-160, BYK (trade name) 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co., In addition to the acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, or may be used in combination with acrylic dispersion.
The amount of the dispersant (a3) to be used is in the range of 5 to 60 parts by mass, more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the solid content of the pigment (a1). If the content of the dispersant (a3) exceeds 60 parts by mass, the viscosity may be increased. If the content of the dispersant (a3) is less than 5 parts by mass, it may be difficult to atomize the pigment or cause gelation after dispersion.
The dye (a2)
The dye can be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance.
Examples of the dye include acid dyes having an acidic group such as a sulfonic acid and a carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthate, phthalocyanine Based acid dyes and derivatives thereof. Preferably, the dye is a compound classified as a dye in a color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (coloring yarn).
Specific examples of the dyes include, as CI solvent dyes,
C.I. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;
C.I. Blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 59, 67 and 70;
C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49;
C.I. Yellow dyes such as Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C.I. Solvent Orange Orange dye such as 2, 7, 11, 15, 26, 56
Green dye such as CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34,
CI Solvent Red 8, 49, 89, 111, 122, 132, 146, 179 having excellent solubility in organic solvents in CI solvent dyes; CI Solvent Blue 35, 36, 44, 45, 70; CI Solvent Violet 13 is preferred, and CI Solvent Red 8, 122, 132 is more preferred.
Also, C.I. As an acid dye
CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 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 Yellow dyes such as 1,1,1,2,2,2,2,2,2,23,28, 240,242, 243,251 and the like, such as, for example, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214,
CI Acid Orange An orange dye such as 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169,
CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335, 340 and the like;
CI Acid Violet 6B, violet dyes such as 7, 9, 17, 19 and 66
Green dyes such as CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106,
CI Acid Red 92 with high solubility in organic solvents in acid dyes; CI Acid Blue 80, 90; CI Acid Violet 66 is preferred.
As a C.I. direct dye,
CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 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 , Yellow dyes such as 136, 138, and 141;
Orange dyes such as CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;
Violet dyes such as CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
Green dyes such as CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77,
Yellow dyes such as C.I. Modatto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
CI Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
CI Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes;
CI Modanito Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84;
Violet dyes such as CI Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Green dyes such as CI Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,
These dyes may be used alone or in combination of two or more.
The content of the dye in the colorant (A) is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, and particularly preferably 1 to 50% by weight, based on the solid content in the colorant (A) Do. When the content of the dye in the colorant (A) is in the above range, it is possible to prevent the problem of lowering the reliability of elution of the dye by the organic solvent after formation of the pattern.
The content of the colorant (A) is preferably 1 to 60% by weight, and more preferably 10 to 45% by weight based on the solid content in the colored photosensitive resin composition. When the colorant (A) is contained in an amount of 1 to 60% by weight based on the above standard, the color density of the pixel is sufficient even when a thin film is formed, and the residue of the non-cured portion during development is not lowered, Do.
In the present invention, the total solid content in the colored photosensitive resin composition means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition.
The alkali-soluble resin (B)
The alkali-soluble resin preferably contains a compound represented by the following formula (1) as an essential component.
(Formula 1)
In Formula 1,
R1 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 3 to 20 carbon atoms; R2 and R3 are independent of each other and are an alkyl group having 1 to 12 carbon atoms. An alkenyl group having 2 to 12 carbon atoms or an aryl group having 3 to 12 carbon atoms; A1 is a divalent connecting group, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms; And X is a carboxylate (-COO -) a, sulfonate (-SO 3 - -) or sulfate (-OSO 3).
In order to ensure compatibility and storage stability of the colored photosensitive resin composition, the acid value of the alkali-soluble resin is preferably 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it is difficult to secure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, There is a problem of stability and the viscosity tends to rise. Particularly, the present inventors have found that when a photosensitive composition using an alkali-soluble resin in the range of 30 to 150 mgKOH / g is used as the alkali-soluble resin containing the compound of Chemical Formula 1, developability (residue), residual film ratio, heat resistance, Characteristics and the like of the present invention are experimentally confirmed to complete the present invention.
The alkali-soluble resin (B) may be a copolymer of the structural unit represented by the formula (1) and one or more other monomers. The other monomer is not particularly limited.
Preferably, the alkali-soluble resin has a form of a copolymer of the structural unit of the formula (1) and at least one compound having an unsaturated bond.
The unsaturated bond-containing compound is not limited as long as it is a compound having an unsaturated double bond capable of polymerization, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) Substituted alkyl ester compounds of unsaturated carboxylic acids such as (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, pentadienyl Acrylate, norbornyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, Unsaturated carboxylic acid ester compounds containing alicyclic substituents such as 3,4-epoxycyclohexylmethyl (meth) acrylate and methyl glycidyl (meth) acrylate; Mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate; Unsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate and phenoxy (meth) acrylate; Aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene; Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; (Meth) acrylonitrile, and? -Chloroacrylonitrile; And maleimide compounds such as N-cyclohexylmaleimide and N-phenylmaleimide.
The content of the alkali-soluble resin is in the range of 10 to 80% by weight, preferably 10 to 70% by weight based on the solid content in the photosensitive resin composition. When the content of the alkali-soluble resin (B) is 10 to 80% by weight based on the above-mentioned criteria, the solubility in a developing solution is sufficient and pattern formation is easy. In the development, film reduction of the pixel portion of the exposed portion is prevented, It is preferable that the dropout property is improved.
Photopolymerization
The compound (C)
The photopolymerizable compound is a compound capable of polymerizing under the action of the photopolymerization initiator described below, and may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer, and preferably a bifunctional or multifunctional monomer may be used.
Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N- But are not limited thereto.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) , Bis (acryloyloxyethyl) ether of bisphenol A or 3-methylpentanediol di (meth) acrylate, but are not limited thereto.
Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa ) Acrylate or dipentaerythritol hexa (meth) acrylate, but are not limited thereto.
The photopolymerizable compound is preferably contained in an amount of 1 to 45% by weight, more preferably 7 to 45% by weight based on the solid content in the photosensitive resin composition. When the photopolymerizable compound is contained in an amount of 1 to 45% by weight based on the above-mentioned criteria, the strength and smoothness of the pixel portion are preferably improved.
Light curing
Initiator
(D)
The photopolymerization initiator can be used without particular limitation as long as it can polymerize the photopolymerizable compound. Particularly, in particular, the photopolymerization initiator (D) is preferably selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a nonimidazole-based compound, an oxime compound At least one compound selected from the group consisting of a thioxanthone compound and a thioxantone compound is preferably used.
Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.
Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.
Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.
Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) Imidazole compounds in which 4'5,5'-tetraphenyl-1,2'-biimidazole or phenyl groups at 4,4 ', 5,5' positions are substituted by carboalkoxy groups. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.
Specific examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and commercially available products such as OXE01 and OXE02 from BASF.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .
The photopolymerization initiator (D) may further comprise a photopolymerization initiator (d2) to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation auxiliary (d2), whereby the sensitivity can be further increased and the productivity can be improved.
(D2) may be preferably at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.
As the amine compound, an aromatic amine compound is preferably used. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone ), 4,4'-bis (diethylamino) benzophenone, and the like.
The carboxylic acid compound is preferably an aromatic heteroacetic acid, and more specifically, it is preferably an aromatic heteroaromatic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) .
The photopolymerization initiator (D) is used in an amount of 0.01 to 40% by weight, preferably 1 to 30% by weight based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C), based on the total solid weight of the colored photosensitive resin composition of the present invention. % By weight. When the photopolymerization initiator (D) is in the range of 0.01 to 40% by weight, the color photosensitive resin composition is highly sensitized and the exposure time is shortened, which is preferable because productivity can be improved and high resolution can be maintained. Further, the strength of the pixel portion formed using the composition of the above-described conditions and the smoothness of the surface of the pixel portion can be improved.
When the photopolymerization initiator (d2) is further used, the photopolymerization initiator (d1) in the total photopolymerization initiator (D) should contain 10 to 100 wt%, preferably 20 to 100 wt% of the total photopolymerization initiator . When the proportion of (d1) in the total photopolymerization initiator is less than 10% by weight, the sensitivity deterioration due to the dye can not be overcome and the pattern is likely to be short-circuited during the development process. The photopolymerization initiator (d2) is added in an amount of 0.01 to 40% by weight, preferably 1 to 20% by weight, based on the total solid weight of the colored photosensitive resin composition of the present invention, based on the content of the alkali-soluble resin (B) 30% by weight. When the amount of the component (d2) is in the range of 0.01 to 40% by weight, the sensitivity of the colored photosensitive resin composition becomes higher and the productivity of the color filter formed using the composition is improved.
Solvent (E)
The solvent used in the conventional colored photosensitive resin composition is not particularly limited so long as it is effective in dissolving the other components contained in the colored photosensitive resin composition. The solvent may be selected from ethers, aromatic hydrocarbons, ketones, alcohols, esters And at least one selected from the group consisting of amines.
Examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether,
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether,
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate,
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate,
Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene,
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone,
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin,
Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone.
The solvent (E) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C on the application and drying surface, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.
The above-exemplified solvents (E) may be used alone or in admixture of two or more, and may be contained in an amount of 1 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention have. When the above-mentioned solvent (F) is in the range of 1 to 90% by weight, when it is coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater Thereby providing an effect of improving the property.
Additive (F)
The additive may be optionally added, for example, other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti-aggregation agent.
Specific examples of the other polymer compound include a curable resin such as epoxy resin and maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like .
The curing agent is used for deep curing and for increasing mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.
Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.
Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.
The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.
The surfactant may be used to further improve film-forming properties of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.
Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF-4460 , And TSF-4452. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. The above-exemplified surfactants may be used alone or in combination of two or more.
Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the solid content of the colored photosensitive resin composition.
Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.
Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.
On the other hand, the present invention provides a color filter comprising the colored photosensitive resin composition.
The color filter according to the present invention comprises a step of applying the solution of the colored photosensitive resin composition, applying the patterned exposure to a dry coating film obtained by pre-baking, and then developing the color filter, thereby obtaining a color of the coloring agent A pixel or a black matrix corresponding to the black matrix is obtained. In addition, the color filter can be obtained by repeating this process for the number of colors required for the color filter.
The construction and fabrication of color filters are well known in the art and can be used to make color filters.
Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.
< Manufacturing example >
The process for producing the colored photosensitive resin composition of the present invention will be described as follows.
First, the pigment (a1) in the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, the pigment dispersant (a3), a part or all of the alkali-soluble resin (B), or the dye (a2) may be mixed and dissolved or dispersed together with the solvent (E).
The dye (a2), the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D) and, if necessary, the additive (F) and the solvent (E) The colored photosensitive resin composition according to the present invention can be prepared.
Example 1. Preparation of colored photosensitive resin composition
(1) Production of pigment dispersion composition
4.0 parts by mass of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by mass of propylene glycol methyl ether acetate as a solvent and 40 parts by mass of propylene glycol methyl ether as a pigment were mixed with 12.0 parts by mass of CI Pigment Blue 15: 6 Followed by mixing / dispersing for 12 hours to prepare a pigment dispersion M.
(2) Synthesis of alkali-soluble resin
1) Compound (1) ( M1 And M2 ) Synthesis of
≪ Synthesis of Compound (1)
32.83 parts of endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride and 500 parts of toluene were placed in a four-necked round flask equipped with a stirrer, a condenser and a stirrer, and N, N-dimethylethylenediamine 17.63 . The reflux reaction was continued for 12 hours, and the reaction was terminated by confirming TLC. After the reactor temperature was cooled to room temperature, the organic layer was washed three times with water and ethyl acetate, and the organic layer was separated and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to obtain 38.4 parts (yield: 82%) of compound 1 as a white solid.
1H-NMR (300MHz, CDCl3) : 6.12 (s, 2H), 3.42-3.40 (m, 4H), 2.22 (6H, 2CH 3 N), 3.28 (s, 2H), 2.76-2.74 (m, 2H), 1.75 (d, 1H, J = 9.0 Hz), 1.54 (d, 1H, J = 9.0 Hz)
<Synthesis of M1>
50.7 parts of Compound 1 and 500 parts of tetrahydrofuran were placed in a four-necked round flask equipped with a stirrer, a condenser, and a stirrer, and 18.6 parts of β-propiolactone was added thereto while stirring. The reaction was continued at room temperature for 24 hours. A white precipitate was formed and separated by filtration under reduced pressure. After vacuum drying at room temperature, 61.99 g (yield 90%) of white product M1 was obtained.
1H-NMR (300MHz, CDCl3) : 6.12 (s, 2H), 3.42-3.40 (m, 4H), 3.30 (6H, 2CH 3 N), 3.28 (s, 2H), 3.24 (2H, CH 2), 2.76 -2.74 (m, 2H), 2.40 (2H, CH 2), 2.04 (2H, CH 2), 1.75 (d, 1H, J = 9.0 Hz), 1.54 (d, 1H, J = 9.0 Hz).
<Synthesis of M2>
50.7 parts of Compound 1 and 500 parts of tetrahydrofuran were placed in a four-necked round flask equipped with a thermometer, a condenser, and a stirrer, and 31.6 parts of 1,3-propanesultone was added thereto while stirring. The internal temperature of the reactor was raised to 50 DEG C and the reaction was continued for 48 hours. A white precipitate was formed and separated by filtration under reduced pressure. After vacuum drying at room temperature, 66.21 parts (yield: 86%) of white product M2 was obtained.
1H-NMR (300MHz, CDCl3) : 6.12 (s, 2H), 3.42-3.40 (m, 4H), 3.41 (2H, CH 2), 3.30 (6H, 2CH 3 N), 3.28 (s, 2H), 3.24 (2H, CH2), 2.76-2.74 ( m, 2H), 2.29 (2H, CH 2), 1.75 (d, 1H, J = 9.0 Hz), 1.54 (d, 1H, J = 9.0 Hz).
2) Synthesis of alkali-soluble resin
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of AIBN, 20 g of the above M1, 15 g of methyl methacrylate, , 25 g of benzylmethacrylate, 10 g of methacrylic acid and 3 g of n-dodecylmercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature. The alkali-soluble resin thus synthesized had a solid dispersion value of 64.2 mgKOH / g and a weight average molecular weight Mw of about 13560 as measured by GPC.
(3) Preparation of colored photosensitive resin composition
20 g of the pigment dispersion composition (M) of the above (1), 0.6 g of CI Solvent Blue 44 (trade name: VALIFAST BLUE 2620, manufactured by Orient Kagaku Kogyo K.K.), 15.5 g of the resin of the above (2), KAYARAD DPHA (Manufactured by BASF), 48.9 g of propylene glycol monomethyl ether acetate, and 10 g of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.
Example 2: Preparation of colored photosensitive resin composition 2
A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the following steps were performed in place of 2) of Example 1 (2).
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 1.8 g of AIBN, 30 g of M1, 15 g of methyl methacrylate, 25 g of styrene, 15 g of benzyl methacrylate, 15 g of methacrylic acid and 3 g of n-dodecylmercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature. The alkali-soluble resin thus synthesized had a solid dispersion value of 99.5 mgKOH / g and a weight average molecular weight Mw of about 14150 as measured by GPC.
Example 3: Preparation of colored photosensitive resin composition 3
A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the following steps were performed in place of 2) of Example 1 (2).
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of AIBN, 17 g of M2, 15 g of methyl methacrylate, 30 g of benzylmethacrylate, 13 g of methacrylic acid and 3 g of n-dodecylmercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature. The alkali-soluble resin thus synthesized had a solid dispersion value of 86.9 mgKOH / g and a weight average molecular weight Mw of about 13680 as measured by GPC.
Example 4: Preparation of colored photosensitive resin composition 4
A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the following steps were performed in place of 2) of Example 1 (2).
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of AIBN, 28 g of M2, 15 g of methyl methacrylate, , 15 g of benzyl methacrylate, 12 g of methacrylic acid and 3 g of n-dodecylmercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature. The alkali-soluble resin thus synthesized had a solid dispersion value of 80.5 mgKOH / g and a weight-average molecular weight Mw of about 13350 as measured by GPC.
Comparative Example 1. Preparation of comparative colored photosensitive resin composition 1
(M1 and M2 which are the compounds of the formula (1) of the present invention are not included in the synthesis of the alkali-soluble resin.)
A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the following steps were performed in place of 2) of Example 1 (2).
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of AIBN, 13.0 g of the methacrylic acid, 67.0 g of 4- 10 g of methacrylate, 10 g of methyl methacrylate and 3 g of n-dodecyl mercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 81.6 mgKOH / g and a weight average molecular weight Mw of about 16110 as measured by GPC.
Comparative Example 2. Preparation of comparative colored photosensitive resin composition 2
(The compound of the formula (1) of the present invention is included in the synthesis of the alkali-soluble resin, but the acid value of the alkali-soluble resin is low.)
A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the following steps were performed in place of 2) of Example 1 (2).
In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, 120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of AIBN, 5.0 g of the above M1, 55.0 g of 4-methylstyrene, 20 g of acrylate, 20 g of methyl methacrylate and 3 g of n-dodecylmercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 17.4 mgKOH / g and a weight average molecular weight Mw of about 17370 as measured by GPC.
Comparative Example 3. Preparation of comparative colored photosensitive resin composition 3
(The compound of the formula (1) of the present invention is included in the synthesis of the alkali-soluble resin, but the acid value of the alkali-soluble resin is high.)
A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the following steps were performed in place of 2) of Example 1 (2).
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 g of propylene glycol monomethyl ether acetate, 80 g of propylene glycol monomethyl ether, 2 g of AIBN, 60.0 g of M1, 10.0 g of 4-methylstyrene, 10 g of acrylate, 10 g of methyl methacrylate and 3 g of n-dodecylmercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 172.3 mgKOH / g and a weight average molecular weight Mw of about 11874 as measured by GPC.
Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)
Column temperature: 40 DEG C
Mobile phase solvent: tetrahydrofuran
Flow rate: 1.0 ml / min
Injection amount: 50 μl
Detector: RI
Measurement sample concentration: 0.6 wt% (solvent = tetrahydrofuran)
Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)
The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).
Experimental Example
: Evaluation of physical properties of the photosensitive composition according to the present invention
The properties of the photosensitive compositions prepared in the above Examples and Comparative Examples were measured by the following methods.
(1) Developability (Residual property)
After development, the presence or absence and remaining amount of remnants remained without being washed away were observed. It was evaluated as good when there was no residue and when it was remained, it was evaluated as defective.
(2)
The thickness was measured before and after the post-heat treatment to evaluate the difference in thickness by the following equation (2). The formula to be used at this time is calculated according to the above equation (1) representing the color change in the three-dimensional colorimeter defined by L *, a *, b *, and as the color change value is smaller, a reliable color filter can be manufactured .
Equation 1
Residual film ratio = (film thickness after post-heat treatment) / (film thickness before post-heat treatment) x 100 (%)
The larger the residual film ratio, the better.
(3) Thermal tolerance
After the pattern was finally formed, the color change at 230 deg. C / 2 hr was compared and evaluated. The formula to be used at this time is calculated by the above-described equation (2) representing the color change in the three-dimensional colorimeter defined by L *, a *, b * .
Equation 2
? Eab * = (? L *) 2+ (? A *) 2+ (? B *) 2] 1/2
(4) Solvent resistance
The prepared color filter was immersed in an N-methylpyrrolidone solvent for 30 minutes to compare and evaluate the color change before and after the evaluation. The formula to be used at this time is calculated by the above-described equation (2) representing the color change in the three-dimensional colorimeter defined by L *, a *, b * .
(5) Mechanical properties
When the pattern is deformed by 10% (or depending on conditions) of the thickness, the degree of return is referred to as the elastic restoration ratio, which varies greatly depending on the condition of the pattern. The results of Examples and Comparative Examples in which the pattern was formed under the same conditions were compared with each other, and the lowest and the highest were shown as poor and good, respectively.
The results are shown in Table 1.
: Great
: Great
: Great
: Great
: Great
: Great
: Great
: Great
: Great
: Great
: Great
: Great
: Good
: Good
: Good
: Good
: Good
: Great
: Bad
: Bad
: Bad
As shown in Table 1, Examples 1 to 4, which are photosensitive compositions comprising an alkali-soluble resin containing the compound of Chemical Formula 1 according to the present invention, are characterized in that an alkali-soluble resin containing no compound of Chemical Formula 1 according to the present invention Compared with Comparative Example 1 used, it has excellent heat resistance and excellent residue characteristics, residual film ratio, solvent resistance and mechanical properties.
The photosensitive compositions of Examples 1 to 4, in which the acid value of the alkali-soluble resin according to the present invention is 30 to 150 mgKOH / g, were prepared in the same manner as in Comparative Example 2, which is a composition using an alkali-soluble resin having an acid value outside the range of 30 to 150 mgKOH / g, 3 < tb >< TABLE >
Claims (5)
Wherein the alkali-soluble resin comprises a compound represented by the following formula (1), and the acid value of the alkali-soluble resin is 30 to 150 mgKOH / g.
(Formula 1)
In Formula 1,
R1 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 3 to 20 carbon atoms; R2 and R3 are independent of each other and are an alkyl group having 1 to 12 carbon atoms. An alkenyl group having 2 to 12 carbon atoms or an aryl group having 3 to 12 carbon atoms; A1 is a divalent connecting group, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms; And X is a carboxylate (-COO -) a, sulfonate (-SO 3 - -) or sulfate (-OSO 3).
Wherein the coloring agent comprises 1 to 60% by weight, the alkali-soluble resin is 10 to 80% by weight, and the photopolymerizable compound is 1 to 45% by weight based on the total weight of the total solid content of the colored photosensitive resin composition, And 0.01 to 40% by weight based on the total amount of the photopolymerizable compound, and the solvent comprises 1 to 90% by weight based on the total weight of the colored photosensitive resin composition.
Wherein the colored photosensitive resin composition further comprises an additive.
Wherein the coloring agent comprises at least one selected from the group consisting of a pigment and a dye.
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| CN106278998A (en) * | 2016-07-21 | 2017-01-04 | 中国科学院新疆理化技术研究所 | The synthetic method of the tripod-type function monomer molecule of norbornene imide class formation |
-
2013
- 2013-03-25 KR KR1020130031536A patent/KR20140116670A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278998A (en) * | 2016-07-21 | 2017-01-04 | 中国科学院新疆理化技术研究所 | The synthetic method of the tripod-type function monomer molecule of norbornene imide class formation |
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