KR20130048072A - A colored photosensitive resin composition, color filter and liquid crystal display device having the same - Google Patents
A colored photosensitive resin composition, color filter and liquid crystal display device having the same Download PDFInfo
- Publication number
- KR20130048072A KR20130048072A KR1020110112994A KR20110112994A KR20130048072A KR 20130048072 A KR20130048072 A KR 20130048072A KR 1020110112994 A KR1020110112994 A KR 1020110112994A KR 20110112994 A KR20110112994 A KR 20110112994A KR 20130048072 A KR20130048072 A KR 20130048072A
- Authority
- KR
- South Korea
- Prior art keywords
- photosensitive resin
- resin composition
- weight
- alkali
- pigment
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
-
- 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
-
- 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
-
- 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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
The present invention relates to a colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same. More specifically, the colored photosensitive resin composition and color filter for a color filter used when producing a color filter for use in a color liquid crystal display device and the like. And it relates to a liquid crystal display device having the same.
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. In particular, in recent years, the use of LCD has been further expanded, and thus color filters have been recognized as one of the most important parts in reproducing the color tone of LCDs.
Such a color filter is manufactured by the method of forming a desired coloring pattern using the coloring photosensitive resin composition containing a coloring agent. Specifically, it is produced by forming a coating layer made of a colored photosensitive resin composition on a substrate, repeating a series of processes of forming a pattern on the formed coating layer, exposing and developing, heating and thermosetting.
Pigment was used as a colorant, but in recent years, there is an attempt to use a dye having high brightness and excellent heat resistance. When only a dye is used as the colorant, it is preferable to implement all excellent properties of the dye, but the dye has a limitation in its use because it is less compatible with other components of the composition than the pigment. Therefore, a method of using a hybrid type colorant using both a pigment and a dye as a colorant has been attempted, but until now, the problem of using a colorant including a dye has not been completely solved.
When manufacturing a color filter using the coloring photosensitive resin composition containing a dye in a coloring agent, a foreign material arises at the time of formation of a colored layer by lack of compatibility with the material used. In addition, in the case of manufacturing the color filter, the developing speed is low and the sensitivity is insufficient, so that the peeling of the pattern formed during the developing process by the alkaline developing solution occurs frequently. Accordingly, there is a need for development of a colored photosensitive resin composition suitable for a lyso process that can solve the problem of including a dye as a colorant or using a dye alone as a colorant.
On the other hand, it was tried to use the resin composition which further contains an adamantane derivative for the conventional coloring photosensitive resin composition. The resin compositions of Republic of Korea Patent Application Publication No. 10-2009-0085031 and Republic of Korea Patent Publication No. 10-2010-0095516 contain adamantane derivatives, which include optical properties such as transparency and light resistance, durability such as long-term heat resistance and etching resistance, In addition, although it has advantages in dielectric constant and the like, when a pigment and a dye are included together, the development speed becomes slow, problems in sensitivity and adhesion may occur, and thus peeling of the pattern may occur during the development process. There is a problem that the fairness is poor.
The present invention has a purpose of providing a colored photosensitive resin composition having both a pigment and a dye as a colorant but having a high development speed, excellent sensitivity and adhesion, no peeling of the pattern during the developing process, and excellent solvent resistance.
In addition, the present invention maintains high surface energy even after the development process to provide a color filter excellent in processability due to less staining.
Another object of the present invention is to provide a liquid crystal display device having the color filter.
In order to achieve the above object, the present invention, (A) colorant, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, (E) solvent, (F) additive and (G) reactivity As a coloring photosensitive resin composition containing an adamantane fluorinated derivative,
The colorant (A) includes a pigment and a dye, and the (B) alkali-soluble resin includes a structural unit represented by the following Chemical Formula 1, and the (G) reactive adamantane fluorinated derivative is represented by the following Chemical Formula 2 It provides the coloring photosensitive resin composition characterized by the above-mentioned.
[Formula 1]
(R3, R4 are each independently hydrogen or methyl)
[Formula 2]
R 1 and R 2 are each independently F, OH, or an active radical or a heat curable reactive group, and neither R 1 nor R 2 can be F or OH.
In addition, the present invention provides a color filter comprising a color layer formed by applying the coloring photosensitive resin composition according to the invention on the substrate and exposed and developed in a predetermined pattern on the substrate to achieve the above object. .
In addition, the present invention provides a liquid crystal display device comprising the color filter in order to achieve the above object.
The coloring photosensitive resin composition of the present invention contains a pigment and a dye as a colorant, but also has a fast developing speed, excellent sensitivity and adhesion, no peeling of the pattern during the developing process, excellent solvent resistance and high surface energy even after the developing process. It is possible to manufacture high quality color filter because of less processability and excellent processability.
Hereinafter, the present invention will be described in detail.
The coloring photosensitive resin composition which concerns on this invention is a (A) coloring agent, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, (E) solvent, (F) additive, and (G) reactive adamant Carbon fluorinated derivatives.
The colorant (A)
The said coloring agent (A) contains a pigment and dye.
The pigment may be used an organic pigment or an inorganic pigment generally used in the art, these may be used alone or in combination of two or more.
If necessary, the pigment may be a resin treatment, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the surface of the pigment with a high molecular compound or the like, an atomization treatment by a sulfate atomization method or the like to remove impurities. Washing treatment with an organic solvent, water, or the like, removing ionic impurities by an ion exchange method, or the like can also be performed.
As the organic pigment, various pigments used in inkjet inks and the like may be used, and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin pigments, and perylene pigments. , Perinone pigments, dioxazine pigments, anthraquinone pigments, dianthhraquinoneyl pigments, anthrapyrimidine pigments, ananthanthrone pigments, indanthrone pigments, pravantron pigments, pyranthrone pigments, And diketopyrrolopyrrole pigments.
In addition, metal compounds such as metal oxides and metal complex salts may be used as the inorganic pigment, and specific examples include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. Oxides or composite metal oxides.
In particular, the pigment may be a compound that is specifically classified as a pigment in the color index (Published by The society of Dyers and Colourists), more specifically, a pigment having the following color index (CI) number can be used It is not necessarily limited to these.
C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185
C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71
C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 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 Brown 28
C.I Pigment Black 1 and 7, etc.
Among the CI pigment pigments exemplified above, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Orange 38, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Violet 23, CI Pigment Blue 15: 6, CI Pigment Green 7, CI Pigment Green 36, or CI Pigment Green 58 The pigment selected can be preferably used.
It is preferable to use the pigment dispersion liquid which the said particle size disperse | distributed uniformly. As an example of the method for uniformly dispersing the particle size of the pigment, a method of containing and dispersing the pigment dispersant may be used. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.
As said pigment dispersant, surfactant, such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine type, etc. are mentioned, for example, These can be used individually or in combination of 2 or more types, respectively. Can be.
Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethyleneimine (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac (Manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kasei MEGAFAC (manufactured by Dainippon Ink and Chemicals, Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.
The pigment dispersant is usually used in an amount of 1 parts by weight or less, preferably 0.05 to 0.5 parts by weight, based on 1 part by weight of solids of the pigment. When the pigment dispersant is used in such a content, it is preferable because a dispersed pigment of uniform particle size can be obtained.
The dye can be used without limitation so long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility, heat resistance and solvent resistance in an alkaline developer.
The dye may be selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof, and azo, xanthene, and phthalocyanines. Acid dyes and derivatives thereof can also be selected.
Preferably, the dye may be a compound classified as a dye in the color index (Published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (color dyed yarn).
Specific examples of the dye include C.I. As solvent dyes,
C.I. Yellow dyes such as solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C.I. Red dyes such as solvent red 8, 45, 49, 122, 125 and 130;
C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 56;
C.I. Blue dyes such as solvent blue 35, 37, 59, 67 and the like;
C.I. Green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like.
C.I. As an acid dye
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, 426;
Orange dyes such as C.I. Acid Orange 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 Blue dyes such as, 335 and 340;
Violet dyes such as CI acid violet 6B, 7, 9, 17, 19 and the like;
Green dyes, such as CI acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. are mentioned.
As a C.I. direct dye
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;
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 and 250;
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 Blue dyes such as, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc .;
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 and the like;
Green dye, such as CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. are mentioned.
Also, C.I. As a modantoic dye
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 colored dyes such as C.I. 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,
It is preferable that 0.5-80 weight% of content of the dye in the said coloring agent (A) is contained by weight fraction with respect to solid content in a coloring agent (A), 0.5-60 weight% is more preferable, 1-50 weight% is especially preferable. Do. When the content of the dye in the coloring agent (A) is in the above range on the basis of the above standard, it is possible to prevent the problem of lowering the reliability that the dye is eluted by the organic solvent after the pattern formation, it is preferable because the sensitivity is excellent.
Content of the said coloring agent (A) is 5 to 70 weight% with respect to solid content in colored photosensitive resin composition, It is good to contain 10 to 50 weight% preferably. When the colorant (A) is included in the range of 5 to 70% by weight, the color density of the pixel is sufficient even when a thin film is formed, and the residue is unlikely to occur because the omission of the non-pixel portion during development is not reduced. 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.
Alkali-soluble resin (B)
The alkali-soluble resin (B) comprises a structural unit represented by the following formula (1).
[Formula 1]
(R3, R4 are each independently hydrogen or methyl)
In the alkali-soluble resin, the structural unit represented by the formula (1) is preferably contained in a mole fraction of 3 to 80 mol% with respect to the total number of moles of the alkali-soluble resin (B), more preferably 5 to 70 mol% It is preferred to be included. When the structural unit is included in the above range, the colored photosensitive resin composition is excellent in sensitivity and adhesiveness, there is no peeling of the pattern during the developing process, and exhibits excellent solvent resistance.
Alkali-soluble resin (B) having the structural unit of Formula 1 may be prepared by polymerization of various polymerizable compounds. The alkali-soluble resin (B) is preferably a polymer obtained by further reacting a monomer compound (b1) having a carboxyl group and an unsaturated bond with a copolymer (B1) of a monomer compound (b2) having an unsaturated bond and a glycidyl group. Or a polymer obtained by further reacting a monomer compound (b2) having an unsaturated bond and a glycidyl group with a copolymer (B2) of the monomer compound (b1) having a carboxyl group and an unsaturated bond. Specific examples of the monomer compound (b2) having the above unsaturated bond and glycidyl group include glycidyl methacrylate. Specific examples of the monomer compound (b1) having an unsaturated bond with the carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, and maleic acid alkyl esters. Representative maleic acid alkyl esters include monomethyl maleate, ethyl maleate, n-propyl maleate, isopropyl maleate, n-butyl maleate, n-hexyl maleate, n-octyl maleate, 2-ethyl hexyl maleate, Maleic acid, and the like. The monomers exemplified as the compound (b1) and the compound (b2) may be used alone or in combination of two or more kinds.
Specific examples of the compound (b3) other than (b1) and (b2) among the compounds used to prepare the copolymers of (B1) to (B2) are as follows, but are not necessarily limited thereto.
The compound (b3) may have an unsaturated bond copolymerizable with the compound (b1) and the compound (b2), and specific examples thereof include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether aromatic vinyl compounds such as p-vinylbenzyl glycidyl ether;
Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate;
(Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;
Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide;
3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds, and the like.
The compound (b3) illustrated above can be used individually or in combination of 2 types or more, respectively.
Alkali-soluble resin (B) according to the present invention can be used by mixing without limitation a variety of other known alkali-soluble resins generally used in the art as needed.
According to the present invention, the alkali-soluble resin (B) preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of the said alkali-soluble resin (B) exists in the range of 3,000-100,000, since film reduction is prevented at the time of image development, the omission property of a pattern part becomes favorable, and it is preferable.
The acid value of the said alkali-soluble resin (B) is 50-200 (KOHmg / g), Preferably it is 60-180 (KOHmg / g), More preferably, it is 80-160 (KOHmg / g), Most preferably 80 to 130 (KOH mg / g). When the acid value of the said alkali-soluble resin (B) is 50-200 (KOHmg / g), since the solubility to a developing solution improves and a residual film rate improves, it is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.
The content of the alkali-soluble resin (B) is in the range of 10 to 80% by weight, preferably 10 to 70% by weight with respect to 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 criteria, the solubility in the developing solution is sufficient, so that pattern formation is easy. It is preferable because omission becomes good.
Photopolymerization The compound (C)
The above-mentioned photopolymerizable compound (C) is not particularly limited as long as it is a compound capable of polymerizing under the action of a photopolymerization initiator described later, but is preferably a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound or a trifunctional or higher- Compounds and the like.
Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. And commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nipbon Kayaku), and Biscotti 158 (Osaka Yuki Kagaku High School).
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) (Acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Commercially available products include Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600 and UA-306H (Kyoeisha Chemical Co., Ltd.).
Specific examples of the polyfunctional photopolymerizable compound having three or more functional groups include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylates such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPHA-40H (Nippon Kayaku).
Of the photopolymerizable compounds (C) exemplified above, trifunctional or higher (meth) acrylate esters and urethane (meth) acrylates are particularly preferred because they have excellent polymerizability and can improve the strength.
The photopolymerizable compounds (C) exemplified above may be used alone or in combination of two or more.
It is preferable to contain content of the said photopolymerizable compound (C) 5 to 45 weight% with respect to solid content in colored photosensitive resin composition, and it is especially preferable to contain 7 to 45 weight%. When the said photopolymerizable compound (C) is contained 5 to 45 weight% by said reference | standard, since the intensity | strength and smoothness of a pixel part become favorable, it is preferable.
Photopolymerization Initiator (D)
The photoinitiator (D) can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C). In particular, the photopolymerization initiator (D) is an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound and a tee from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price. It is preferable to use at least one compound selected from the group consisting of oxatone compounds.
Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 -One, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 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-piperonyl-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) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.
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-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferably used do.
Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and BAOX's OXE01 and OXE02 are typical examples of commercially available products.
As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.
Further, as long as the effect of the present invention is not impaired, other photopolymerization initiators and the like may be further used in combination. Examples of other photopolymerization initiators include benzoin compounds and anthracene compounds. These may be used alone or in combination of two or more.
As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.
Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. have.
Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds and the like can be mentioned as other photopolymerization initiators.
You may use combining the photoinitiator (D-1) with the said photoinitiator (D). When using a photoinitiator adjuvant (D-1) together with a photoinitiator (D), since the photosensitive resin composition containing these becomes more sensitive and improves productivity, it is preferable.
As the photopolymerization start adjuvant (D-1), for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used.
Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, N, N-dimethyl para-toluidine, 4,4'-bis (dimethylamino) benzophenone Amino) benzophenone, and the like. As the amine compound, an aromatic amine compound is preferably used.
Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid and dichloro And aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.
Specific examples of the organic sulfur compound having the 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) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Late), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. are mentioned. Can be.
The photopolymerization initiator (D) is based on the total weight of solids of the colored photosensitive resin composition of the present invention, based on the content of the alkali-soluble resin (B) and the photopolymerizable compound (C), 0.1 to 40% by weight, preferably 1 to 30 wt% may be included. When the photoinitiator (D) is within the range of 0.1 to 40% by weight, the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, so productivity is improved and high resolution can be maintained. The intensity of the pixel portion and the smoothness on the surface of the pixel portion are good, and thus are preferable.
In the case of using the photopolymerization initiation aid (D-1), the amount of the photopolymerization initiation aid (D-1) is used in terms of weight fraction based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). 0.1 to 50% by weight, preferably 1 to 40% by weight. When the usage-amount of the said photoinitiator (D-1) exists in the range of 0.1-50 weight% mentioned above, since the sensitivity of a coloring photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition improves, it is preferable. .
Solvent (E)
The solvent (E) may be used without particular limitation as long as it is effective in dispersing or dissolving the other components included in the colored photosensitive resin composition, and especially ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides. Etc. are preferable.
Specifically, the solvent (E) is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol di Ethers such as propyl ether and dipropylene glycol dibutyl ether; 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; Methylcellosolve acetate, ethylcellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxypropionate, methyl 3-methoxypropionate, Methoxybutyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, Lactone, etc. And the like.
Among the above solvents, organic solvents having a boiling point of 100 ° C. to 200 ° C. are preferably used in the solvent in view of coatability and dryness, and more preferably alkylene glycol alkyl ether acetates, ketones, and 3-e. Ester, such as ethyl oxypropionate and methyl 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3- Ethyl ethoxypropionate, methyl 3-methoxypropionate, and the like.
These solvents (E) can be used individually or in mixture of 2 or more types, respectively.
The solvent (E) in the colored photosensitive resin composition of the present invention may be included in an amount of 60 to 90 mass%, preferably 70 to 85 mass%, based on the total weight of the colored photosensitive resin composition of the present invention. When content of the said (E) solvent is the range of 60-90 mass% mentioned above, when apply | coated with coating apparatuses, such as a roll coater, a spin coater, a slit and spin coater, a slit coater (it may also be called a die coater), and inkjet It provides an effect of improving applicability.
Additive (F)
As the additive (F) can be selectively added as needed, for example, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents and the like.
Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be mentioned.
The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like.
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, noblock type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene ( Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.
Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane 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. Examples of the curing aid compound include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. As a specific example of the said epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) (New Nippon Ewha Co., Ltd.) etc. are mentioned. The hardeners illustrated above can be used individually or in mixture of 2 or more types.
The surfactant may be used to further improve the film formability 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, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth And oxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be included in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the weight of solids of the colored photosensitive resin composition.
Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol and the like.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.
Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.
Reactivity Adamantan Fluorinated Derivatives (G)
The reactive adamantane fluorinated derivative (G) included in the colored photosensitive resin composition of the present invention is a compound which can be polymerized by active radicals or heat generated from the photopolymerization initiator (D), and is characterized by the structure of the following formula (2).
[Formula 2]
R 1 and R 2 are each independently a polymerizable reactor that can be cured by F, OH, or an active radical or heat, and at least one of R 1 and R 2 is a polymerizable reactive group that can be cured by an active radical or heat.
Preferred examples of the polymerizable reactor which can be cured by the active radical or heat include the following Chemical Formulas 3 to 6, which may be prepared by conventional methods.
(3)
[Formula 4]
[Chemical Formula 5]
[Formula 6]
(In Formulas 3, 5, and 6, R 5 is each hydrogen or methyl.)
It is preferable that 1-30 weight% of said reactive adamantane fluorinated derivatives (G) are contained in weight fraction with respect to solid content in the photosensitive resin composition of this invention, More preferably, it is contained in 2-20 weight%. When the reactive adamantane fluorinated derivative (G) is included in the range of 1 to 30% by weight, the occurrence of stain after development is small and the solvent resistance is good, which is preferable.
Mixing and dispersing the above components is not particularly limited to those known to those skilled in the art. Specifically, the dispersing machine used for dispersing the respective components in the solvent is not particularly limited and may be a kneader, a roll mill, an attritor, a super mill, a dissolver, A known dispersing machine such as a mixer (homogenizer) or a sand mill may be used.
The color filter which concerns on this invention apply | coats the said colored photosensitive resin composition solution, performs the patterning exposure to the dry coating film obtained by prebaking, and develops, and then develops the color of the coloring agent which is a component of a coloring photosensitive resin composition. A pixel or black matrix corresponding to is obtained. In addition, a color filter can be obtained by repeating this process by the number of colors required for the color filter.
Since the configuration and manufacturing method of the color filter are well known in the art, it is possible to manufacture a color filter using the same.
The present invention relates to a liquid crystal display device including the color filter.
The liquid crystal display includes a configuration known to those skilled in the art, except that the liquid crystal display includes the color filter. That is, all liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate having a thin film transistor (TFT element), a pixel electrode, and an alignment layer are faced at predetermined intervals and a liquid crystal material is injected into the gap portion to form a liquid crystal layer . There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer.
As another example, a TFT (Thin Film Transistor) substrate integrated on a transparent electrode of a color filter and a liquid crystal display device including a backlight fixed at a position where the TFT substrate overlaps with a color filter can be given. The TFT substrate includes an outer frame made of light-proof resin surrounding a peripheral surface of a color filter, a liquid crystal layer made of nematic liquid crystals imposed in the outer frame, and a plurality of pixel electrodes provided for each region of the liquid crystal layer. , A transparent glass substrate on which the pixel electrode is formed, and a polarizing plate formed on the exposed surface of the transparent glass substrate.
As follows, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are exemplified to the last, and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and moreover, contains all modifications within the meaning and range equivalent to the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are on a mass basis unless otherwise specified.
Pigment dispersion M1 Manufacturing
CI pigment red 254 14.0 parts by mass, 6 parts by mass of azipa PB821 (manufactured by Ajino Moto Fine Techno Co., Ltd.) as a dispersant, 60 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and 20 parts by mass of cyclohexanone in the bead mill Pigment dispersion M1 was prepared by mixing / dispersing for 12 hours.
Synthesis of Alkali Soluble Resin
≪ Synthesis Example 1 &
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 19.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 51.0 parts of styrene, and 3 parts of n-dodecylmercapto were charged and replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 110 ° C. and reacted for 6 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, and the atmosphere of the flask was replaced with air in nitrogen. Then, 0.3 part of triethylamine and 20 parts of glycidyl methacrylate were charged and reacted at 110 DEG C for 5 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 80 mgKOH / g and a weight average molecular weight Mw of about 22,000 as measured by GPC.
Synthesis Example 2
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 108 parts of propylene glycol monomethyl ether acetate, 72 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 18 parts of acrylic acid, 22 parts of benzyl methacrylate, 40 parts, methyl methacrylate 10 parts, and n-dodecyl mercapto 3 parts were charged and replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 110 ° C. and reacted for 3 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 147 mgKOH / g and a weight average molecular weight Mw of about 21200 as measured by GPC.
Preparation of coloring photosensitive resin composition
≪ Example 1 >
29.3 parts of the <pigment dispersion liquid M1>, 15.2 parts of solvent red 8, 7.1 parts of the resin of <Synthesis example 1>, 2.4 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 0.5 parts of Irgacure OXE01 (manufactured by BASF), ADAMATATE X-F102 (Made by Idemitsu) The coloring photosensitive resin composition was manufactured by mixing 0.5 part, propylene glycol monomethyl ether acetate, and 27.5 parts of propylene glycol monomethyl ether.
<Example 2>
29.3 parts of the <pigment dispersion liquid M1>, 15.2 parts of Solvent Red 8, 7.1 parts of the resin of <Synthesis Example 1>, 2.4 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 0.5 part of Irgacure OXE01 (manufactured by BASF), ADAMATATE X-F203 (Made by Idemitsu) The coloring photosensitive resin composition was manufactured by mixing 0.5 part, propylene glycol monomethyl ether acetate, and 27.5 parts of propylene glycol monomethyl ether.
≪ Comparative Example 1 &
29.3 parts of the <pigment dispersion liquid M1>, 15.2 parts of Solvent Red 8, 7.1 parts of the resin of <Synthesis Example 2>, 2.4 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 0.5 parts of Irgacure OXE01 (manufactured by BASF), ADAMATATE X-F102 (Made by Idemitsu) The coloring photosensitive resin composition was manufactured by mixing 0.5 part, propylene glycol monomethyl ether acetate, and 27.5 parts of propylene glycol monomethyl ether.
Comparative Example 2
29.3 parts of the <pigment dispersion liquid M1>, 15.2 parts of solvent red 8, 7.1 parts of the resin of <Synthesis example 1>, 2.4 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 0.5 part of Irgacure OXE01 (manufactured by BASF), propylene glycol monomethyl 27.5 parts of ether acetate and 17.6 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.
≪ Comparative Example 3 &
29.3 parts of the <pigment dispersion liquid M1>, 15.2 parts of solvent red 8, 7.1 parts of the resin of <Synthesis Example 2>, 2.4 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 0.5 part of Irgacure OXE01 (manufactured by BASF), ADAMATATE X-F203 (Made by Idemitsu) The coloring photosensitive resin composition was manufactured by mixing 0.5 part, propylene glycol monomethyl ether acetate, and 27.5 parts of propylene glycol monomethyl ether.
Manufacture of color filters
After applying the colored photosensitive resin composition prepared in Examples 1 to 2 and Comparative Examples 1 to 3 by the spin coating method on the glass substrate, it is placed on a heating plate and maintained for 3 minutes at a temperature of 100 ℃ to form a colored layer thin film I was. Subsequently, a test photomask having a pattern changing stepwise in a range of transmittance of 1 to 100% and a line / space pattern of 1 to 50 μm was placed on the color layer thin film and the distance from the test photomask was set to 100 μm. Was irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated at a light intensity of 100 mJ / cm 2 using a 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The ultraviolet-ray colored layer thin film was developed by immersing in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes. The glass substrate on which the developed color layer thin film was formed was washed with distilled water, dried under a nitrogen gas atmosphere, and heated in a 200 ° C. heating oven for 30 minutes to thermoset. The thickness of the color layer of the produced color filter was 2.0 μm.
< Experimental Example 1> Measurement of color filter characteristics
The color filter manufactured as described above was evaluated to show whether it is stable to heat and solvents used in manufacturing color filters or in manufacturing liquid crystal display devices through experiments for measuring development stains, adhesion and solvent resistance.
The occurrence and development of the development unevenness of the manufactured color filters was measured and evaluated in the following manner, and the results are shown in Table 1 below.
<Development stain>
* Evaluation standard
- No stains on the substrate: ○
- On the substrate, development stain is weak: △
-Severe stain on the substrate occurs: X
≪ Adhesion >
When the generated patterns of the manufactured color filters were evaluated through an optical microscope, the degree of tearing was evaluated on the following patterns.
* Evaluation standard
○: No pattern peeling
△: 1 to 3 pattern peeling
X: Pattern peeling 4 or more
< Solvent resistance >
The produced color filter was immersed in N-methylpyrrolidone solvent for 30 minutes, and the color change before and after evaluation was evaluated. At this time, the equation to be used is calculated by the following Equation (1) representing the color change in the three-dimensional colorimeter defined by L *, a *, b *, the smaller the color change value, it is possible to manufacture a highly reliable color filter .
[Mathematical expression (1)]
ΔEab * = [(ΔL *) 2+ (Δa *) 2+ (Δb *) 2] (1/2)
As shown in Table 1 above,
In the goodness of the development stain, the development stains of Examples 1 to 2 and Comparative Examples 1 and 3 using the reactive adamantane fluorinated derivative are better than Comparative Example 2, which is not particularly reactive to ADAMATATE X-F102. For Example 1 and Comparative Example 1 used as the carbon fluorinated derivative, it was confirmed that the development stains of Example 2 and Comparative Example 3 using ADAMATATE X-F203 as the reactive adamantane fluorinated derivative were better.
In addition, in the adhesiveness and the solvent resistance, Examples 1 and 2 and Comparative Example 2 using a reactive alkali-soluble resin is superior to Comparative Examples 1 and 3 that are not, in particular, Examples 1 to 2 are more excellent. Could.
Therefore, it can be seen that the colored photosensitive resin composition of the present invention can improve the process productivity and yield and produce a high quality color filter having excellent adhesion.
Claims (6)
The colorant (A) includes a pigment and a dye, and the (B) alkali-soluble resin includes a structural unit represented by the following Chemical Formula 1, and the (G) reactive adamantane fluorinated derivative is represented by the following Chemical Formula 2 The coloring photosensitive resin composition characterized by the above-mentioned.
[Formula 1]
(R3, R4 are each independently hydrogen or methyl)
(2)
(R 1 and R 2 are each independently a polymerizable reactor that can be cured by F, OH, or an active radical or heat, and at least one of R 1 and R 2 is a polymerizable reactor that can be cured by an active radical or heat.)
The polymerizable reactor which can be cured by the active radical or heat The polymerizable reactor is any one of the following Chemical Formulas 3 to 6, characterized in that the coloring photosensitive resin composition.
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
(In Formulas 3, 5, and 6, R 5 is each hydrogen or methyl.)
The colored photosensitive resin composition contains, based on the total solid weight,
Colorant (A) comprises 5 to 70% by weight, alkali-soluble resin (B) comprises 10 to 80% by weight, photopolymerizable compound (C) comprises 5 to 45% by weight, and additive (F) Comprises 0.01 to 10% by weight, reactive adamantane fluorinated derivative (G) comprises 1 to 30% by weight,
The photoinitiator (D) comprises 0.1 to 40% by weight relative to the content of the alkali-soluble resin (B) and the photopolymerizable compound (C),
The solvent (E) is 60-90 weight% based on the total weight of the said coloring photosensitive resin composition, The coloring photosensitive resin composition characterized by the above-mentioned.
The structural unit represented by Formula (2) contained in the (B) alkali-soluble resin is contained in the molar fraction of 3 to 80 mol% based on the total number of moles of the (B) alkali-soluble resin, the coloring photosensitive resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110112994A KR20130048072A (en) | 2011-11-01 | 2011-11-01 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110112994A KR20130048072A (en) | 2011-11-01 | 2011-11-01 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20130048072A true KR20130048072A (en) | 2013-05-09 |
Family
ID=48659297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020110112994A KR20130048072A (en) | 2011-11-01 | 2011-11-01 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20130048072A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170064793A (en) * | 2015-12-02 | 2017-06-12 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter and image display device produced using the same |
| KR20170111912A (en) * | 2016-03-30 | 2017-10-12 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter and image display device using the same |
-
2011
- 2011-11-01 KR KR1020110112994A patent/KR20130048072A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170064793A (en) * | 2015-12-02 | 2017-06-12 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter and image display device produced using the same |
| KR20170111912A (en) * | 2016-03-30 | 2017-10-12 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter and image display device using the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4998906B2 (en) | Colored photosensitive resin composition, color filter produced using the same, and liquid crystal display device | |
| KR20120021752A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR20120035995A (en) | Colored photosensitive resin composition, color filter and liquid crystal display using same | |
| JP2014005466A (en) | Alkali-soluble resin, photosensitive resin composition containing the same, and color filter using the same | |
| KR20120036117A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR20120046462A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR20140100261A (en) | Colored photosensitive resin composition | |
| KR20150011496A (en) | A colored photosensitive resin composition, color filter and display device comprising the same | |
| KR20140008033A (en) | Colored photosensitive resin composition and color filter using the same | |
| KR20120044603A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR20140020495A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR20130051320A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR20130015631A (en) | A colored photosensitive resin composition, colored pattern, color filter and liquid crystal display device having the same | |
| KR102012523B1 (en) | Colored photosensitive resin composition, color filter and liquid crystal display having the same | |
| KR102012520B1 (en) | A colored photosensitive resin composition, colored pattern,color filter and liquid crystal display device having the same | |
| KR20130060826A (en) | A colored photosensitive resin composition | |
| KR101932770B1 (en) | Color filter structure comprising a coated layer for control luminance | |
| JP2019079047A (en) | Coloring photosensitive resin composition, pattern layer produced using the same, color filter containing the pattern layer, and display device including the color filter | |
| KR102078594B1 (en) | A colored photosensitive resin composition for color filter, color filter and liquid crystal display device having the same | |
| KR20130048072A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same | |
| KR20130048642A (en) | A colored photosensitive resin composition, colored pattern, color filter and liquid crystal display device having the same | |
| KR20140014622A (en) | A colored photosensitive resin composition | |
| KR20140000774A (en) | Colored photosensitive resin composition and color filter | |
| KR20130060772A (en) | Colored photoresist composition, color filter fabricated by the same and screen display device comprising the color filter | |
| KR20140020502A (en) | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WITN | Withdrawal due to no request for examination |