KR102012954B1 - A color photosensitive resin composition, color filter and display device comprising the same - Google Patents
A color photosensitive resin composition, color filter and display device comprising the same Download PDFInfo
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- KR102012954B1 KR102012954B1 KR1020140036468A KR20140036468A KR102012954B1 KR 102012954 B1 KR102012954 B1 KR 102012954B1 KR 1020140036468 A KR1020140036468 A KR 1020140036468A KR 20140036468 A KR20140036468 A KR 20140036468A KR 102012954 B1 KR102012954 B1 KR 102012954B1
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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
- G03F7/027—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
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
- G03F7/0295—Photolytic halogen compounds
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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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Materials For Photolithography (AREA)
Abstract
The present invention relates to a colored photosensitive resin composition, a color filter and a display device including the same, and more particularly, excellent sensitivity and adhesion, so that short-circuit of the pattern is difficult to occur during the developing process, and a decrease in transmittance due to the process is minimized. The colored photosensitive resin composition, the color filter containing the same, and a display apparatus are provided.
Description
The present invention relates to a colored photosensitive resin composition, a color filter and a display device including the same, and more particularly, to a colored photosensitive resin composition which minimizes a decrease in transmittance of a color filter as the baking process proceeds, while maintaining excellent sensitivity and adhesion. The present invention relates to a color filter and a display device including the same.
Color filters are manufactured by dyeing, printing, electrodeposition, pigment dispersion, film transfer, etc., and are not only used in liquid crystal display panels (LCDs) but also charge coupled devices (CCDs). ) And liquid crystal shutters are widely used. In particular, since color filters are one of the most important parts for reproducing color tones in LCDs, research on the manufacturing method of color filters with excellent processability and product reliability has been continued in the LCD manufacturing process.
Recently, color filter materials have high sensitivity, and when forming a pattern, high reliability and high color reproducibility must be achieved, and high sensitivity and good adhesion are also required. Moreover, even when a process is repeated in order to improve process productivity and a yield, development of the coloring photosensitive resin composition which has the outstanding transmittance | permeability is calculated | required. However, as the baking process proceeds, there is a problem in that the light transmittance of the manufactured coli filter decreases.
On the other hand, Korean Patent Laid-Open Publication No. 10-2002-0006441 describes a resin composition for a color filter including a hindered phenol-based antioxidant, but the problem of decreasing transmittance as the baking process progresses is still not solved.
An object of the present invention is to provide a colored photosensitive resin composition, a color filter and a display device including the same, which have an effect of minimizing a decrease in transmittance according to a process while maintaining excellent sensitivity and adhesion.
In order to achieve the above object,
This invention is a coloring photosensitive resin composition containing a coloring agent (A), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), antioxidant (E), and a solvent (F), The said antioxidant (E) provides the coloring photosensitive resin composition characterized by including the phenolic antioxidant whose melting | fusing point is less than 200 degreeC, and the phosphorus antioxidant which has melting | fusing point less than 200 degreeC.
Moreover, this invention provides the color filter containing the said coloring photosensitive resin composition.
In addition, the present invention provides a display device including the color filter.
The colored photosensitive resin composition of the present invention is excellent in sensitivity and adhesiveness, it is difficult not only to generate a short circuit of the pattern during the developing process, but also has an effect of minimizing a decrease in transmittance due to the progress of the process.
Hereinafter, the present invention will be described in more detail.
This invention is a coloring photosensitive resin composition containing a coloring agent (A), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), antioxidant (E), and a solvent (F), The said antioxidant (E) is a coloring photosensitive resin composition characterized by including the phenolic antioxidant whose melting | fusing point is less than 200 degreeC, and the phosphorus antioxidant which has melting | fusing point less than 200 degreeC. In the present invention, using a phenolic antioxidant having a melting point of less than 200 ℃ and a phosphorus antioxidant having a melting point of less than 200 ℃ as an antioxidant (E), it was experimentally confirmed that the reduction in transmittance according to the process can be minimized.
Moreover, when using the compound which has a structure of General formula (1) of this invention as a photoinitiator (D), it showed that the effect which can maintain the outstanding sensitivity and adhesiveness was shown.
Hereinafter, the content of the present invention will be described in detail by configuration, as follows.
Colorant (A)
The coloring agent (A) contains at least one pigment (a1) and at least one dye (a2) as essential components. At least one of the pigments or dyes is preferably blue-based. In the case of dyes, one anthraquinone dye is an essential component.
Pigments a1 )
The pigment may be used an organic pigment or an inorganic pigment generally used in the art. The pigment may be used a variety of pigments used in printing inks, inkjet inks, and the like, specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin Pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinoneyl pigments, anthrapyrimidine pigments, ananthronerone pigments, indanthrone pigments, pravantron pigments, pyrantrones (pyranthrone) pigments, diketopyrrolopyrrole pigments and the like. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or a composite metal oxide. Blue, purple, magenta pigments are preferred, and the organic pigments and inorganic pigments are particularly preferred among the compounds classified as pigments in the color index (published by The society of Dyers and Colorists). Pigment Red, C.I. Pigment Violet, C.I. Pigment blue is mentioned, More specifically, Although the pigment of the following color index (C.I.) numbers is mentioned, It is not necessarily limited to these, These can be used individually or in combination of 2 or more types, respectively.
C.I. Pigment Violet 1, 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
Among the CI pigment pigments exemplified above, pigments selected from pigment violet 23, CI pigment blue 15: 3 and pigment blue 15: 6 can be preferably used.
It is preferable to use the pigment dispersion liquid which the said particle size disperse | distributed uniformly. An example of a method for uniformly dispersing the particle size of the pigment is a method of containing and dispersing 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 surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and these may be used alone or in combination of two or more thereof. .
Pigment dispersants ( a3 )
The pigment dispersant (a2) is added to maintain the deagglomeration and stability of the pigment can be used without limitation to those commonly used in the art. Preferably, it contains an acrylate dispersant (hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). In this case, it is preferable to apply the acrylic dispersant prepared by the living control method as shown in Korean Patent Application Publication No. 2004-0014311, a commercially available product of the acrylate-based dispersant prepared through the living control method DISPER BYK- 2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc. are mentioned.
The illustrated acrylic dispersants may be used alone or in combination of two or more thereof.
As the dispersant (a3), a pigment dispersant of another resin type may be used in addition to the acrylic dispersant described above. The other resin type pigment dispersants include (partially) known pigment dispersants of known resin types, in particular polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids represented by polyurethanes, polyacrylates. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free ) Oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with a poly (lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, phosphate esters, and the like. As a commercial item of the said resin type dispersing agent, As a cationic resin dispersing agent, For example, brand names of BYK (Big) Chemi Corporation: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF brand name: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical's trade names: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Trade names of Ajinomoto Co., Ltd .: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; The brand names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, etc. are mentioned. In addition to the acrylic dispersant described above, pigment dispersants of other resin types may be used alone or in combination of two or more thereof, or may be used in combination with acrylic dispersion.
The usage-amount of the said dispersing agent (a3) is 5-60 mass parts with respect to 100 mass parts of solid content of the pigment (a1) used, More preferably, it is the range of 15-50 mass parts. If the content of the dispersing agent (a3) exceeds 60 parts by mass based on the above criteria, 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 may cause problems such as gelation after dispersion.
dyes( a2 )
The dye includes one anthraquinone dye as an essential component. Anthraquinone-based dyes are excellent in solubility in solvents and excellent in heat resistance compared to other dyes to prevent a decrease in luminance during hard baking. Specific examples of the anthraquinone dyes are as follows.
C.I. Solvent Blue 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139
CI Solvent Violet 11, 13, 14, 26, 31, 38, 47, 48, 51, 59, 60
The dye may be used without any further limitation as 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. Preferred colors include blue, purple and magenta dyes, which are classified as dyes in the Color Index (published by The Society of Dyers and Colourists), and red among known dyes described in dyeing notes (color dyeing yarn); There is a blue, violet dye.
These dyes can be used individually or in combination of 2 or more types, respectively.
It is preferable that 0.5-80 mass% is contained in mass fraction with respect to solid content in a coloring agent (A), content of the dye in the said coloring agent (A) is more preferable, 0.5-60 mass% is especially preferable, 1-50 mass% 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 5-50 mass%, Preferably it is 10-45 mass% in mass fraction with respect to the total mass of colored photosensitive resin composition. When the colorant (A) is included in the range of 5 to 60% by mass, 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.
Alkali-soluble resin (B)
In order to have solubility with respect to the alkaline developing solution used at the image development process at the time of forming a pattern, it manufactures by copolymerizing with ethylenically unsaturated monomer (b1) which has a carboxyl group as an essential component. In addition, in order to ensure compatibility with the dye (a2) and storage stability of the coloring photosensitive resin composition, the acid value of the alkali-soluble resin (B) is characterized in that 30 ~ 150mgKOH / g. When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH / g, it is difficult to secure a sufficient developing speed of the coloring photosensitive resin composition, and when it exceeds 150 mgKOH / g, the adhesion to the substrate is reduced, so that short circuit of the pattern is likely to occur. A problem arises in that the compatibility of the dye causes precipitation of the dye in the photosensitive resin composition, or the storage stability of the photosensitive resin composition is lowered, which tends to increase the viscosity.
Specific examples of the ethylenically unsaturated monomer (b1) having the carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and the like, and acrylic acid and methacrylic acid are preferred.
In order to give a hydroxyl group to alkali-soluble resin (B), it can be manufactured by copolymerizing the ethylenically unsaturated monomer (b1) which has a carboxyl group, and the ethylenically unsaturated monomer (b2) which has a hydroxyl group, and the ethylenically unsaturated monomer (b1) which has a carboxyl group It can be manufactured by further reacting the compound (b3) which has glycidyl group with the copolymer of. Moreover, it can manufacture by making the copolymer of the ethylenically unsaturated monomer (b1) which has a carboxyl group, and the ethylenically unsaturated monomer (b2) which has a hydroxyl group react further with the compound (b3) which has a glycidyl group.
Specific butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether of the compound (b3) having the glycidyl group, Ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butylbenzoate, glycidyl stearate, aryl glycidyl ether, Methacrylic acid glycidyl ester and the like, butyl glycidyl ether, aryl glycidyl ether and methacrylic acid glycidyl ester are preferable, and two or more kinds can be used in combination.
The unsaturated monomers (b3) copolymerizable in the preparation of the alkali-soluble resin (B) are illustrated below, but are not necessarily limited thereto.
Specific examples of the polymerization monomer (b4) having an unsaturated bond capable of copolymerization include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o Aromatic vinyls such as vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether compound;
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;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-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; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decane-8-yl (meth) acrylate, 2- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide;
Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. Unsaturated oxetane compounds and the like.
The monomers illustrated by said (b3) can be used individually or in combination of 2 types or more, respectively.
Content of the said alkali-soluble resin (B) is 10-50 mass% in mass fraction with respect to the gross mass of the photosensitive resin composition, Preferably it is the range of 10-40 mass%. When content of the said alkali-soluble resin (B) is 10-50 mass% on the said reference | standard, the solubility to a developing solution is enough and pattern formation is easy, and the film reduction of the pixel part of an exposure part is prevented at the time of image development, It is preferable because omission becomes good.
Photopolymerizable Compound (C)
The photopolymerizable compound (C) is a compound capable of polymerizing under the action of the following photopolymerization initiator (D), and may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer, and preferably a bifunctional or higher polyfunctional monomer. Can be used.
Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N-vinylpi Or the like, but 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, and triethylene glycol di (meth) acrylate. , Bis (acryloyloxyethyl) ether of bisphenol A or 3-methylpentanediol di (meth) acrylate, and the like, but is not limited thereto.
Specific examples of the polyfunctional monomer include trimethylol propane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) ) Acrylate or dipentaerythritol hexa (meth) acrylate, and the like, but is not limited thereto.
It is preferable that the said photopolymerizable compound (C) is contained 5-45 mass% in mass fraction with respect to the gross mass in a coloring photosensitive resin composition. When the said photopolymerizable compound (C) is contained 5 to 45 mass% on the said reference | standard, since the intensity | strength and smoothness of a pixel part become favorable, it is preferable.
Photopolymerization Initiator (D)
Said photoinitiator (D) has photoinitiator (d1) which is a structure of following General formula (1) as a component.
(Formula 1)
In Formula 1, R1 is represented by the following formula (2), R2 is a C1-C8 alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, R3 is a diphenyl sulfide group,
(Formula 2)
In Formula 2, R4 is C1 ~ C4 hydrocarbon, R5 is C3 ~ C8 alkyl group and may have a ring structure.
More preferably, the photopolymerization initiator (D) may include a photopolymerization initiator (d1) having a structure of Formula 1-1.
(Formula 1-1)
1- [4- （phenylthio） phenyl] -3-cyclopentyl propane-1,2-dione-2- (o-benzoyloxime)
The photopolymerization initiator (d1) having the structure of Chemical Formula 1 is an oxime ester-based photoinitiator including a diphenylsulfide structure, which prevents a decrease in sensitivity and transmittance by dyes and thus provides effective photopolymerization characteristics in a colored photosensitive resin composition including a dye as a colorant. Expression.
Moreover, the photoinitiator (d2) of that excepting the above can also be used together in the range which does not impair the effect of this invention. Typically, at least one compound selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, and thioxanthone compounds is preferably used.
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 biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4, The imidazole compound etc. which the phenyl group of a 4'5,5'- tetraphenyl- 1,2'- biimidazole or a 4,4 ', 5,5' position are substituted by the carboalkoxy group are mentioned. 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.
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.
The photopolymerization initiator (D) may further include a photopolymerization initiation aid (d3) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The coloring photosensitive resin composition which concerns on this invention contains a photoinitiation adjuvant (d3), and can raise a sensitivity further and can improve productivity.
As the above (d3), 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 can be preferably used.
It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone ), 4,4'-bis (diethylamino) benzophenone and the like can be used.
The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, 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 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) may be included in an amount of 0.1 to 40% by mass, preferably 1 to 30% by mass, based on the total mass of the colored photosensitive resin composition of the present invention. When the (D) photoinitiator is in the range of 0.1 to 40 mass% described above, the colored photosensitive resin composition is highly sensitive and exposure time is shortened, which is preferable because productivity can be improved and high resolution can be maintained. In addition, the strength of the pixel portion formed using the composition under the above-described conditions and smoothness on the surface of the pixel portion can be improved. In addition, in the case of (d1), 10 to 100% by mass of the total photopolymerization initiator, preferably 20 to 100% by mass should be included. When the ratio of (d1) in all the photoinitiators is less than 10 mass%, the fall of the sensitivity by a dye cannot be overcome and a short circuit of a pattern during a developing process will occur easily.
In addition, when using the said photoinitiator (d3) further, the said photoinitiator (d3) is based on the total mass of the coloring photosensitive resin composition of this invention, (B) alkali-soluble resin (C) of a photopolymerizable compound. The content may be included in an amount of 0.1 to 40 mass%, preferably 1 to 30 mass%. When the usage-amount of (d3) is in the range of 0.1-40 mass% mentioned above, the sensitivity of a coloring photosensitive resin composition becomes high and the productivity of the color filter formed using this composition improves.
Antioxidant (E)
Antioxidant (E) is composed of at least one phenolic antioxidant and at least one phosphorus antioxidant, and its melting point should be less than 220 ° C. In the case of the blue coloring photosensitive resin composition, most of the decrease in permeability is caused by yellowing during hard baking, and the reduction of permeability can be suppressed by using the antioxidant. Especially, since most of the hard bake proceeds at 220 ° C. or higher, the effect of antioxidant To maximize, antioxidants should be present in the liquid phase during hard baking. In the case of antioxidants with melting points above 220 ℃, the amount of antioxidant should be 2 ~ 3 times higher than the antioxidants below 220 ℃ for the yellowing suppression effect. The use of such excess antioxidants causes yellowing of the antioxidants, resulting in a decrease in permeability. It is difficult to expect a deterrent effect. In addition, the use of the antioxidant that satisfies the above conditions can be continued during the post-process to minimize the decrease in transmittance during the post-process.
Specific examples of the phenolic antioxidant having a melting point of less than 220 ℃ are as follows.
1,1,3-tris (2-methyl-4-hydroxy-5-tertiary-butylphenyl) butane (1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane Melting point 184 ° C.), octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; melting point 51 ° C.), pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) Melting point 115 ° C.), 3,9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4, 8,10-tetraoxaspiro [5.5] undecane (3,9-Bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2, 4,8,10-tetraoxaspiro [5.5] undecane: Melting point 110 ° C., Sumilizer AG 80), 3'-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N'- Hexamethylenedipropionamide (3'-Bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N'-hexamethylenedipropionamide; melting point 156 ° C.), triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate; melting point 76 ℃), etc
Specific examples of phosphorus antioxidants having a melting point of less than 220 ° C. are as follows.
Triphenyl phosphate (melting point 22 ° C.), isodecyl diphenyl phosphate ( melting point 18 ° C.), tris (2,4-di-tert-butylphenyl) phosphate (Tris (2,4-di) -tert-butylphenyl) phosphate; melting point 180 DEG C), 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (3, 9-Bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane; melting point 47 ° C.), 2,2′-methylenebis (4,6-di-tertiary-butyl -Phenyl) -2-ethylhexyl phosphate (2,2'-methylenebis (4,6-di-tert-butyl-phenyl) -2-ethylhexyl phosphate; melting point 146 DEG C), etc.
The antioxidant may be included 0.1 to 20% by mass, preferably 0.2 to 15% by mass based on the total mass of the colored photosensitive resin composition of the present invention. When the said antioxidant is in the range of 0.1-20 mass% mentioned above, since the coloring photosensitive resin composition can expect the transmittance | permeability improvement without degrading a sensitivity, it is preferable. If it is less than 0.1% by mass, it is difficult to expect improvement in transmittance. If it exceeds 20% by mass, the sensitivity decrease due to dye cannot be overcome and high sensitivity is not easily achieved, and a pattern short circuit occurs easily during the developing process.
Solvent (F)
The solvent (F) may be used without particular limitation as long as it is effective in dissolving the other components included in the colored photosensitive resin composition, especially solvents, aromatic hydrocarbons, ketones, Alcohols, esters or amides are preferable.
The said (F) solvent specifically, ethylene glycol monoalkyl ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether,
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether,
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, 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, methoxy butyl acetate, and methoxy pentyl acetate;
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene,
Ketones such as cyclohexanone such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and 4-hydroxy-4-methyl-2-pentanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin,
Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.
The solvent (F) is preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ in terms of applicability and drying properties, 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 can be used.
The above-exemplified solvents (F) may be used alone or in combination of two or more thereof, and may be included in an amount of 30 to 90% by mass, preferably 40 to 85% by mass, based on the total mass of the colored photosensitive resin composition of the present invention. have. When the said solvent (F) is the range of 40-90 mass% mentioned above, it apply | coats when it apply | coats with application 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 the effect that the sex is good.
Additive (G)
The black photosensitive resin composition of this invention uses additives (G), such as a filler, another high molecular compound, a hardening | curing agent, an adhesion promoter, a ultraviolet absorber, and an anti-agglomerate, as needed by those skilled in the art in the range which does not impair the objective of this invention other than the said component. It is also possible.
Specifically, the filler may be glass, silica, alumina, or the like, but is not limited thereto.
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. It may be, but is not limited thereto.
The curing agent is used to increase the core hardening and mechanical strength, and specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. may be used, but is not limited thereto. Specific examples of the epoxy compound include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins, other aromatic epoxy resins, cycloaliphatic epoxy resins, and glyce Aliphatic, cycloaliphatic or aromatic epoxy compounds other than cydyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene (co) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate and the like can be used, but are not limited thereto. Specifically, the oxetane compound may include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane, and the like. It is not.
The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. Specifically, the curing auxiliary compound may be a polyhydric carboxylic acid, a polyhydric carboxylic anhydride, an acid generator, or the like. As said carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As said commercially available 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) are mentioned, for example. (Manufactured by Nippon Ewha Co., Ltd.).
The hardening | curing agent and hardening auxiliary compound which were illustrated above can be used individually or in mixture of 2 or more types, respectively.
Specific examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto propyl tree It is possible to use alone or mixtures thereof selected from the group consisting of methoxysilane, 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.
Specifically, the ultraviolet absorber may use 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone, and the like, but is not limited thereto.
The aggregation inhibitor may specifically use sodium polyacrylate, but is not limited thereto.
The additive may be included in 0.01 to 10% by mass, preferably 0.05 to 2% by mass relative to the total mass of the composition.
In addition, the present invention provides a color filter made of a colored photosensitive resin composition and a display device having the same.
First, a coloring photosensitive resin composition is apply | coated on a board | substrate (usually glass) or the layer which consists of solid content of the coloring photosensitive resin composition formed previously, and heat-drying removes volatile components, such as a solvent, and obtains a smooth coating film.
As a coating method, it can carry out by a spin coat, cast coating method, the roll coating method, the slit and spin coat, the slit coat method, etc., for example. It heats after application | coating and heat-drying (prebaking) or drying under reduced pressure, and volatilizes volatile components, such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The coating film thickness after heat drying is about 1-8 micrometers normally. The ultraviolet-ray is irradiated through the mask for forming the target pattern on the coating film obtained in this way. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate is performed. When ultraviolet light is irradiated, the site to which ultraviolet light is irradiated is hardened.
G-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used as the ultraviolet rays. The irradiation dose of ultraviolet rays may be appropriately selected as necessary, and the present invention is not limited thereto. When the coating film after hardening is contacted with a developing solution and the non-exposed part is melted and developed, the spacer which has a target pattern shape can be obtained.
The developing method is not particularly limited to the liquid addition method, the dipping method, the spray method and the like. In addition, during development, the substrate may be tilted at any angle. The developer is usually an aqueous solution containing an alkaline compound and a surfactant.
The alkaline compound is not particularly limited to an inorganic or organic alkaline compound. Examples of the inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, Potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.
Moreover, as an organic alkaline compound, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine And monoisopropylamine, diisopropylamine and ethanolamine.
The said inorganic or organic alkaline compound can be used individually or in mixture of 2 or more types, respectively. The concentration of the alkaline compound in the developer is 0.01 to 10% by mass, preferably 0.03 to 5% by mass relative to the total mass of the developer.
The surfactant in the developer may be one or more selected from the group consisting of the aforementioned nonionic surfactants, anionic surfactants and cationic surfactants. The concentration of the surfactant in the developer is contained in an amount of 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass relative to the total mass of the developer. After image development, it washes with water and can also carry out post-baking for 10 to 60 minutes at 150-230 degreeC as needed.
Using the coloring photosensitive resin composition of this invention, a specific pattern can be formed on a board | substrate through each above process.
The manufacturing method of the coloring photosensitive resin composition of this invention is demonstrated, for example as follows.
First, the pigment (a1) in the said coloring agent (A) is mixed with a solvent (F), and it disperse | distributes using a bead mill until the average particle diameter of a pigment becomes about 0.2 micrometer or less. Under the present circumstances, a pigment dispersant (a3), a part or all of alkali-soluble resin (B), or (a2) dye can be mixed with (E) solvent, and can be melt | dissolved or disperse | distributed as needed.
In the mixed dispersion, the dye (a2), the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D) and the antioxidant (E), and (F) additives and (E) solvents as necessary. It may be further added to a predetermined concentration to prepare a colored photosensitive resin composition according to the present invention.
Hereinafter, the present invention will be described in more detail with reference to Examples, but 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 addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.
Production Example 1: Pigment Dispersion Composition
CI pigment blue 15: 6 12.0 parts by weight, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by weight of propylene glycol methyl ether acetate and 40 parts by weight of propylene glycol methyl ether by means of a bead mill Pigment dispersion M1 was prepared by mixing / dispersing for 12 hours.
Synthesis Example 1: Synthesis of Anthraquinone Dye
After adding 20 parts by mass of Acid blue 80 to the reaction vessel to form a nitrogen atmosphere, 200 parts by mass of chloroform is added and stirred for 1 hour. After stirring, add 9.7 parts by mass of N, N-dimethyl formamide and stir for 1 hour. Then 12.17 parts by mass of thionyl chloride were added and stirred for 3 hours. Thereafter, 3.77 parts by mass of Piperidine was added thereto, followed by stirring for 3 hours. Thereafter, 20 parts by mass of triethylamine and 20 parts by mass of methanol were added to terminate the reaction. The reaction was washed several times with distilled water, filtered and the obtained solid was dried under vacuum for 48 hours at room temperature to give a dye D1.
Synthesis Example 2: Synthesis of Alkali Soluble Resin
120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 13.0 parts of acrylic acid, 10 parts of benzyl methacrylate in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube 57.0 parts of 4-methylstyrene and 20 parts of methyl methacrylate and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 110 ° C. and reacted for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 100.2 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 15110.
Example 1: Preparation of coloring photosensitive resin composition
31.05 parts of the <pigment dispersion composition M1>, 0.41 parts of the dye D1, 16.19 parts of the resin of <Synthesis Example 1>, 5.39 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 1.29 parts of TR-PBG-305 (manufactured by TRONLY), 0.33 parts of Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (melting point 115 ℃, trade name Irganox 1010 BASF) as phenolic antioxidant, triphenyl phosphate (melting point 22 ℃, Aldrich) as phosphorus antioxidant 0.22 parts, 39.38 parts of propylene glycol monomethyl ether acetate and 5.74 parts of 4-hydroxy-4-methyl-2-pentanone were mixed to prepare a colored photosensitive resin composition.
Example 2: Preparation of coloring photosensitive resin composition
31.05 parts of the <pigment dispersion composition M1>, 0.41 parts of the dye D1, 16.19 parts of the resin of <Synthesis Example 1>, 5.39 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 1.29 parts of TR-PBG-305 (manufactured by TRONLY), As phenolic antioxidant, 3,9-Bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [ 5.5] undecane (melting point 110 ° C, trade name Sumilizer AG 80, Sumitomo Chemical Co., Ltd.), 0.33 parts, 0.22 parts of Isodecyl diphenyl phosphate (melting point 18 ° C, trade name ADK STAB 3010, Adekasa) as a phosphorus antioxidant, propylene glycol monomethyl ether acetate 39.38 To 5 parts, 4-hydroxy-4-methyl-2-pentanone was mixed to prepare a colored photosensitive resin composition.
Comparative example 1: Preparation of coloring photosensitive resin composition
31.05 parts of the <pigment dispersion composition M1>, 0.41 parts of the dye D1, 16.19 parts of the resin of <Synthesis Example 1>, 5.39 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 1.29 parts of TR-PBG-305 (manufactured by TRONLY), As a phenolic antioxidant, Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (melting point 115 ° C, trade name Irganox 1010 BASF) 0.55 parts, propylene glycol monomethyl ether acetate 39.38 parts, 4-hydroxy- 5.74 parts of 4-methyl-2-pentanone were mixed and the colored photosensitive resin composition was produced.
Comparative example 2: Preparation of coloring photosensitive resin composition
31.05 parts of the <pigment dispersion composition M1>, 0.41 parts of the dye D1, 16.19 parts of the resin of <Synthesis Example 1>, 5.39 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 1.29 parts of TR-PBG-305 (manufactured by TRONLY), A coloring photosensitive resin composition was prepared by mixing 0.55 parts of Triphenyl phosphate (melting point 22 ° C., Aldrich), 39.38 parts of propylene glycol monomethyl ether acetate, and 5.74 parts of 4-hydroxy-4-methyl-2-pentanone as a phosphorus antioxidant. .
Comparative example 3: Preparation of coloring photosensitive resin composition
31.05 parts of the above <pigment dispersion composition M1>, 0.41 parts of the dye D1, 16.19 parts of the resin of <Synthesis Example 1>, 5.39 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 1.84 parts of TR-PBG-305 (manufactured by TRONLY), 39.38 parts of propylene glycol monomethyl ether acetate and 5.74 parts of 4-hydroxy-4-methyl-2-pentanone were mixed to prepare a colored photosensitive resin composition.
Comparative example 4: Preparation of coloring photosensitive resin composition
31.05 parts of the <pigment dispersion composition M1>, 0.41 parts of the dye D1, 16.19 parts of the resin of <Synthesis Example 1>, 5.39 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 1.29 parts of Igacure 369 (manufactured by BASF), and phenolic oxidation 0.33 parts of Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) as melting inhibitor (115 ° C, trade name Irganox 1010 BASF) 0.22 parts of triphenyl phosphate (melting point 22 ° C, Aldrich) as phosphorus antioxidant 39.38 parts of propylene glycol monomethyl ether acetate and 5.74 parts of 4-hydroxy-4-methyl-2-pentanone were mixed to prepare a colored photosensitive resin composition. Igacure 369, used as photopolymerization initiator (D), is a compound having the following structural formula and a compound having a completely different structure from the general formula (1) herein:
<Igacure 369 Structural Formula>
2-Benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone
Comparative example 5: Preparation of coloring photosensitive resin composition
31.05 parts of the <pigment dispersion composition M1>, 0.41 parts of the dye D1, 16.19 parts of the resin of <Synthesis Example 1>, 5.39 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 1.29 parts of TR-PBG-305 (manufactured by TRONLY), Phenolic antioxidant, 0.33 parts of 1,3,5-Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (melting point 248 ℃, Aldrich), phosphorus antioxidant To the mixture, 0.22 parts of Triphenyl phosphate (melting point 22 DEG C, Aldrich), 39.38 parts of propylene glycol monomethyl ether acetate, and 5.74 parts of 4-hydroxy-4-methyl-2-pentanone were mixed to prepare a colored photosensitive resin composition.
Comparative example 6: Preparation of coloring photosensitive resin composition
31.05 parts of the <pigment dispersion composition M1>, 0.41 parts of the dye D1, 16.19 parts of the resin of <Synthesis Example 1>, 5.39 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 1.29 parts of TR-PBG-305 (manufactured by TRONLY), 0.33 parts of Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (melting point 115 ℃, trade name Irganox 1010 BASF) as a phenolic antioxidant, Bis (2,6-di-ter- as a phosphorus antioxidant butyl-4-methylphenyl) pentaerythritol-diphosphite (melting point 234 ° C, trade name ADK STAB PEP-36 adeca) 0.22 parts, propylene glycol monomethyl ether acetate 39.38 parts, 4-hydroxy-4-methyl-2-pentanone 5.74 parts By mixing, a colored photosensitive resin composition was prepared.
Comparative example 7: Preparation of coloring photosensitive resin composition
31.05 parts of the above <pigment dispersion composition M1>, 16.19 parts of the resin of <Synthesis Example 1>, 5.39 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 1.29 parts of TR-PBG-305 (manufactured by TRONLY), Pentaerythritol as a phenolic antioxidant 0.33 parts of tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (melting point 115 ° C, trade name Irganox 1010 BASF) 0.22 parts of triphenyl phosphate (melting point 22 ° C, Aldrich) as a phosphorus antioxidant, propylene glycol mono A colored photosensitive resin composition was prepared by mixing 39.38 parts of methyl ether acetate and 5.74 parts of 4-hydroxy-4-methyl-2-pentanone.
Comparative example 8: Preparation of coloring photosensitive resin composition
31.05 parts of the <pigment dispersion composition M1>, 0.41 parts of the dye D1, 16.19 parts of the resin of <Synthesis Example 1>, 5.39 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 1.29 parts of TR-PBG-305 (manufactured by TRONLY), Phenolic antioxidant, 0.33 parts of 1,3,5-Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (melting point 248 ℃, Aldrich), phosphorus antioxidant 0.22 parts of Bis (2,6-di-ter-butyl-4-methylphenyl) pentaerythritol-diphosphite (melting point 234 ° C, trade name ADK STAB PEP-36 adexa), 39.38 parts of propylene glycol monomethyl ether acetate, 4-hydroxy 5.74 parts of 4-methyl-2-pentanone were mixed and the colored photosensitive resin composition was produced.
Experimental Example 1. Adhesiveness, pattern Line width And transmittance measurement
Color filters were prepared using the colored photosensitive resin compositions prepared in Examples 1 to 2 and Comparative Examples 1 to 8.
Specifically, each of the colored photosensitive resin composition was coated on a 2-inch angle glass substrate ("EAGLE XG" manufactured by Corning Co., Ltd.) by spin coating, then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film. I was. Subsequently, a test photomask having a pattern in which the transmittance is changed stepwise in the range of 1 to 100% and a line / space pattern of 1 µm to 100 µm is placed on the thin film, and the distance from the test photomask is 300 µm. Was investigated. At this time, the ultraviolet light source was irradiated with luminous intensity of 100 mJ / cm 2 using a 1KW high-pressure mercury lamp containing all g, h, and i rays, and no special optical filter was used. The UV-irradiated thin film was developed by soaking in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes. The thin plate coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C. for 25 minutes to prepare a color filter.
The film thickness of the color filter prepared above was 2.0 μm.
<Adhesiveness>
When the generated pattern was evaluated through an optical microscope, the degree of tearing on the following pattern was evaluated and shown in Table 1 below.
○: no tearing on the pattern
△: 1 to 3 tears on the pattern
×: 4 or more tearing pattern
<Pattern line width>
The line width of the resulting pattern was measured using a scanning electron microscope. When the line width of a pattern is measured more than the line width of a photomask, it can be said that the sensitivity of a coloring photosensitive resin composition is sufficient and the line width expanded. The enlarged line width compared to the photomask is shown in Table 1 below.
Transmittance Measurement
After measuring the transmittance of the 100 μm pattern of the substrate prepared in <Experimental Example 1> using a colorimeter (Olympus, OSP-200), after further hard bake at 230 ° C for 25 minutes and six times, the transmittance was measured again. The rate of change is shown in Table 1.
The results of Experimental Examples 1 and 2 are shown in Table 1 below.
As shown in the above experimental results, the compositions of Examples 1 and 2, which are the coloring photosensitive resin compositions of the present invention, are excellent in sensitivity and adhesion, so that short circuit of the pattern is hard to occur during the developing process, and additional baking is performed 6 times compared to the initial transmittance. After the baking, the transmittance was very high, 95% and 94%, respectively, indicating that the decrease in transmittance during the process was minimized.
In contrast, the compositions of Comparative Examples 1 to 3, which do not include phenolic antioxidants and / or phosphorus antioxidants, showed a significantly lower transmittance of less than 90% after 6 additional bakes compared to the initial transmittance, and photopolymerization. The composition of the comparative example 4 containing the compound of the structure different from General formula (1) of this invention as an initiator was inferior to adhesiveness.
In addition, the compositions of Comparative Examples 5 and 6 using a phenolic antioxidant or phosphorus antioxidant having a melting point exceeding 200 ° C. had a very low transmittance of 90% or less after 6 additional bakes compared to the initial transmittance, and The composition of Comparative Example 7, which did not contain, showed both low initial transmittance and transmittance after 6 additional bakes. In addition, the composition of Comparative Example 8 using a phenolic antioxidant and a phosphorus calculation agent having a melting point exceeding 200 ° C. had a very low transmittance of less than 90% after six additional bakes compared to the initial transmittance.
Claims (11)
The photopolymerization initiator (D) includes a photopolymerization initiator (d1) having a structure of Formula 1 below,
The antioxidant (E) is a colored photosensitive resin composition, characterized in that it comprises a phenolic antioxidant having a melting point of less than 200 ℃ and a phosphorus antioxidant having a melting point of less than 200 ℃.
(Formula 1)
In Formula 1, R1 is represented by the following formula (2), R2 is a C1-C8 alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, R3 is a diphenyl sulfide group,
(Formula 2)
In Formula 2, R4 is C1 ~ C4 hydrocarbon, R5 is C3 ~ C8 alkyl group and may have a ring structure.
The phenolic antioxidant having a melting point of less than 200 ° C is 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane (1,1,3-Tris (2-methyl- 4-hydroxy-5-tert-butylphenyl) butane; melting point 184 ° C.), octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Octadecyl 3- (3,5) -di-tert-butyl-4-hydroxyphenyl) propionate; melting point 51 ° C., pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (Pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate); melting point 115 ° C.), 3,9-bis [1,1-dimethyl-2-[(3-tertary-butyl-4-hydroxy-5-methylphenyl) Propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (3,9-Bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy- 5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane; melting point 110 ° C.), 3′-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N'-hexamethylenedipropionamide (3'-Bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N '-hexamethylenedipropionamide; melting point 156 DEG C) and triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) Coloring photosensitive resin composition, characterized in that at least one selected from the group consisting of (propionate) melting point 76 ℃).
Phosphorus-based antioxidants having a melting point below 200 ° C. are triphenyl phosphate (melting point 22 ° C.), isodecyl diphenyl phosphate (melting point 18 ° C.), tris (2,4-di-tertiary-butylphenyl ) Phosphate (Tris (2,4-di-tert-butylphenyl) phosphate; melting point 180 ° C.), 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-depot Sparspiro [5.5] undecane (3,9-Bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane; melting point 47 ° C.) and 2,2′-methylenebis ( 4,6-di-tert-butyl-phenyl) -2-ethylhexyl phosphate (2,2'-methylenebis (4,6-di-tert-butyl-phenyl) -2-ethylhexyl phosphate; melting point 146 DEG C) It is 1 or more types chosen from the group which consists of, The coloring photosensitive resin composition.
The coloring agent (A) comprises at least one pigment (a1) and at least one dye (a2), wherein at least one of the pigment or dye is a blue-based coloring photosensitive resin composition.
The coloring agent (A), the dye (a2) is an anthraquinone dye, coloring photosensitive resin composition, characterized in that.
5-50 mass% of colorants (A);
10-50 mass% of alkali-soluble resin (B);
5-45 mass% of photopolymerizable compounds (C);
0.1-40 mass% of photoinitiators (D);
Antioxidant (E) 0.1-20 mass%; And
Colored photosensitive resin composition containing 30-70 mass% of solvents (F).
The coloring photosensitive resin composition characterized by further including 1 or more types of additives (G) chosen from the group which consists of a high molecular compound, a hardening | curing agent, an adhesion promoter, a ultraviolet absorber, and an aggregation inhibitor.
5-50 mass% of colorants (A);
10-50 mass% of alkali-soluble resin (B);
5-45 mass% of photopolymerizable compounds (C);
0.1-40 mass% of photoinitiators (D);
Antioxidant (E) 0.1-20 mass%;
Solvent (F) 30 to 70 mass%; And
Colored photosensitive resin composition containing 0.01-10 mass% of additives (G).
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| JP2005290141A (en) | 2004-03-31 | 2005-10-20 | Nippon Steel Chem Co Ltd | Oxetane resin composition |
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| JP5589270B2 (en) * | 2007-10-23 | 2014-09-17 | Ｊｓｒ株式会社 | Radiation-sensitive composition for blue color filter, color filter and liquid crystal display element |
| KR101877992B1 (en) * | 2012-07-30 | 2018-07-13 | 동우 화인켐 주식회사 | Colored photosensitive resin composition |
| KR101932770B1 (en) * | 2012-11-08 | 2018-12-26 | 동우 화인켐 주식회사 | Color filter structure comprising a coated layer for control luminance |
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| JP2005290141A (en) | 2004-03-31 | 2005-10-20 | Nippon Steel Chem Co Ltd | Oxetane resin composition |
| JP2010134278A (en) * | 2008-12-05 | 2010-06-17 | Dainippon Printing Co Ltd | Inkjet ink for color filter, color filter using the inkjet ink, and liquid crystal display device using the color filter |
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