KR102028579B1 - Colored photosensitive resin composition - Google Patents
Colored photosensitive resin composition Download PDFInfo
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- KR102028579B1 KR102028579B1 KR1020130103606A KR20130103606A KR102028579B1 KR 102028579 B1 KR102028579 B1 KR 102028579B1 KR 1020130103606 A KR1020130103606 A KR 1020130103606A KR 20130103606 A KR20130103606 A KR 20130103606A KR 102028579 B1 KR102028579 B1 KR 102028579B1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/001—Axicons, waxicons, reflaxicons
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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
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
- G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
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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
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Abstract
The present invention relates to a colored photosensitive resin composition, and more particularly includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the coefficient of thermal expansion with the substrate is applied when the coating film is formed on the substrate to form a coating film. By making the difference 5 * 10 -6 to 200 * 10 -6 ° C -1 , the heat resistance is remarkably excellent, and even when exposed to the high and low temperature conditions during the process conditions, the pattern is not generated and the coating film with excellent stability is produced. It is related with the coloring photosensitive resin composition which can be formed.
Description
The present invention relates to a colored photosensitive resin composition.
The viewing unit of an image display device such as a liquid crystal display, an organic field display, a plasma display, or the like is divided into a display unit and a non-display unit.
1 illustrates a mobile phone as an example of an image display apparatus. In the image display apparatus, a display unit refers to a portion where an image is displayed, and a non-display portion refers to an edge portion where an image is not displayed. The non-display portion is a top layer seen by the consumer, and the light shielding layer is formed so that the lower wiring and the like are not visible to the user.
The light blocking layer may be formed directly on the cover window glass of the display device or may be formed on a separate substrate and included in the image display device.
As a method of forming the light shielding layer, photolithography is typically used, and the light shielding layer forming process by photolithography includes a plurality of processes having different temperature conditions from room temperature to a high temperature of about 250 ° C.
Since the thermal expansion rate between a base material and a coating film differs from each other, in each of these processes, a stress may accumulate by the difference of a thermal expansion rate at the interface of a coating film and a base material, and defect may arise. This difference in thermal expansion may become more problematic as it becomes larger.
Accordingly, there is a need for a method of forming a pattern having excellent heat resistance.
Korean Patent Laid-Open No. 2012-0010622 discloses a resin black matrix material and a liquid crystal display device.
An object of this invention is to provide the coloring photosensitive resin composition which can form the coating film excellent in heat resistance.
An object of this invention is to provide the optical laminated body which was excellent in the heat resistance of a coating film.
1. A colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the difference in coefficient of thermal expansion with the substrate is 5 * 10 -6 to 200 * 10 -6 when applied to the substrate to form a coating film. Colored photosensitive resin composition which is ° C- 1 .
2. In the above 1, the substrate is glass, silicone resin, styrene-butadiene copolymer resin, butadiene-acrylonitrile copolymer resin, epoxy resin, nylon resin, phenol resin, polybutyrene terephthalate resin, polycarbonate resin , At least one selected from the group consisting of polyester resins, polyether ether ketone resins, polyethylene resins, polyethylene terephthalate resins, polymethyl methacrylate resins, polypropylene resins, polystyrene resins, polytetrafluoroethylene resins and polyvinyl chloride resins Colored photosensitive resin composition which is formed of one material.
3. In the above 1, wherein the photopolymerization initiator is at least one selected from the group consisting of triazine-based compound, acetophenone-based compound, biimidazole-based compound and oxime-based compound, colored photosensitive resin composition.
4. according to the above 1, further comprising at least one photopolymerization initiation aid of the amine compound and the carboxylic acid compound, the coloring photosensitive resin composition.
5. according to the above 1, in the total weight of the coloring photosensitive resin composition based on solids, the colorant is 10 to 70% by weight, alkali-soluble resin is 3 to 80% by weight, the photopolymerizable compound is 1 to 60% by weight and the photopolymerization initiator is 1 to 40 wt%;
A colored photosensitive resin composition, wherein the solvent is contained in 50 to 90% by weight of the total weight of the colored photosensitive resin composition.
6. The base material and the coating film formed from the coloring photosensitive resin composition of any one of Claims 1-5 on one side of the said base material, The difference of the thermal expansion coefficient of the said base material and a coating film is 5 * 10 <-6> -200 * 10 <-6> degreeC -1 phosphorus, optical laminate.
7. In the above 6, the substrate is glass, silicone resin, styrene-butadiene copolymer resin, butadiene-acrylonitrile copolymer resin, epoxy resin, nylon resin, phenol resin, polybutyrene terephthalate resin, polycarbonate resin , At least one selected from the group consisting of polyester resins, polyether ether ketone resins, polyethylene resins, polyethylene terephthalate resins, polymethyl methacrylate resins, polypropylene resins, polystyrene resins, polytetrafluoroethylene resins and polyvinyl chloride resins It is formed of one material, optical laminate.
8. according to the above 6, the thickness of the substrate is 20 to 1,000㎛, colored photosensitive resin composition.
9. In the above 6, the thickness of the coating film is 1 to 100㎛, colored photosensitive resin composition.
10. The optical laminate according to 6 above, wherein the coating is a light shielding layer.
The coloring photosensitive resin composition of this invention can form the coating film excellent in heat resistance.
The optical laminated body of this invention is remarkably excellent in the heat resistance of a coating film. Accordingly, even when exposed to high and low temperature conditions during the process conditions, the pattern is not raised and the stability is excellent.
1 shows an example (mobile phone) of an image display apparatus.
It is a front view of the coating film of the optical laminated body of Example 1. FIG.
It is a front view of the coating film of the optical laminated body of a comparative example.
The present invention includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the difference in coefficient of thermal expansion with the substrate is 5 * 10 -6 to 200 * 10 - when applied on the substrate to form a coating film. By setting it as 6 degreeC- 1 , it is remarkably excellent in heat resistance, and it is related with the coloring photosensitive resin composition which can form the coating film which is excellent in stability, even if it is exposed to high temperature and low temperature conditions in process conditions, and a pattern does not arise.
Hereinafter, the present invention will be described in detail.
<Coloring Photosensitive Resin Composition>
The colored photosensitive resin composition is applied onto a substrate to form a coating film, and the forming process of such coating film includes a process such as drying and exposure.
These processes may be performed under different conditions from room temperature to a high temperature of about 250 ° C. Since the thermal expansion coefficients of the coating film and the substrate are different from each other, the stress due to the difference in thermal expansion coefficient at the interface between the coating film and the substrate in each of these processes is increased. Accumulation may cause defects. This difference in thermal expansion may become more problematic as it becomes larger.
However, the coloring photosensitive resin composition of this invention contains a coloring agent, alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and the difference of a thermal expansion coefficient with a base material is 5 * 10 when it is apply | coated on a base material and forms a coating film. is -6 to 200 * 10 -6 ℃ -1. When the difference in thermal expansion coefficient is in the said range, occurrence of the said problem by stress accumulation can be suppressed.
The method for adjusting the coefficient of thermal expansion is not particularly limited, and for example, it may be based on a method of controlling the degree of crosslinking by the alkali-soluble resin and the photopolymerizable compound used in the pigment and the colored photosensitive resin composition, the rigidity between the molecular chains, and the like. .
The composition of the colored photosensitive resin composition and the substrate which can be used are not particularly limited as long as they are within a range capable of satisfying the difference in thermal expansion coefficient, and will be specifically described below with reference to examples.
coloring agent
Colorants include organic pigments and inorganic pigments.
The organic pigment is not particularly limited, and may be a pigment used in a printing ink, an inkjet ink, and the like, and specifically, a water-soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a quinacridone pigment, an isoindolinone pigment, Indolin pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthhraquinoneyl pigments, anthrapyrimidine pigments, ananthronerone pigments, indanthrone pigments, pravantron pigments, Pyranthrone pigments, diketopyrrolopyrrole pigments and the like. These can be used individually or in mixture of 2 or more types.
The inorganic pigment is not particularly limited and may be a metal compound such as a metal oxide or a metal complex salt, and specifically, a group consisting of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black. It may be an oxide of one or more metals selected from. These can be used individually or in mixture of 2 or more types.
Organic pigments and inorganic pigments may use compounds classified as pigments in the color index (published by The society of Dyers and Colourists), specifically, for example, 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; CI Pigment Brown 28; C.I. Pigment white 4, 5, 6, 6: 1, 7, 18, 18: 1, 19, 20, 22, 25, 26, 27, 28 and 32; C.I pigment blacks 1, 7, and 32, etc., Preferably, C.I. Pigment red 122 and 254; C.I. Pigment yellow 138, 139, 150 and 185; C.I. Pigment orange 38; C.I. Pigment violet 23; C.I. Pigment blue 15: 6; C.I. Pigment green 7, 36 and 58; C.I. Pigment white 6, 22, etc. are mentioned. These can be used individually or in mixture of 2 or more types.
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.
The content of the colorant is not particularly limited, and may be included in 10 to 70% by weight of the total weight of the colored photosensitive resin composition, preferably 30 to 50% by weight on a solids basis. When the content of the colorant is within the above range, the sensitivity of the pattern prepared therefrom is excellent, and development can be easily performed.
Colorants are added to the composition in the form of a dispersion for uniform mixing in the composition. The dispersion may be prepared by further comprising a solvent used in the dispersant and the composition in addition to the colorant.
Dispersants are added to maintain the stability of the pigment and deagglomeration, can be used without limitation, those commonly used in the art. An acrylate dispersant preferably comprising BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate); Polycarboxylic acid esters; Unsaturated polyamides; Polycarboxylic acid; (Partial) amine salts of polycarboxylic acids; 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; Amides or salts thereof formed by the reaction of a polyester having a free 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. These can be used individually or in mixture of 2 or more types.
Commercially available dispersants usable in the present invention include, for example, 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, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 (BYK Chemi Corporation); 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 (BASF Corporation); SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10 (Lubirzol); HINOACT T-6000, Hinoact T-7000, Hinoact T-8000 (Kawaken Fine Chemicals); AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 (Ajinomoto Co., Ltd.); FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44 (Kyoeisha Chemical Co., Ltd.), etc. are mentioned. These can be used individually or in mixture of 2 or more types.
The content of the dispersant is not particularly limited, and may be included, for example, in an amount of 5 to 60 parts by weight, and preferably 15 to 50 parts by weight, based on 100 parts by weight of the pigment on a solid basis. When the content of the dispersant is within the above range, the pigment is well atomized and the colorant may have an appropriate viscosity.
Alkali soluble resin
The alkali-soluble resin can be used without any particular limitation as long as it is a resin that can be dissolved in the solvent of the present invention and has reactivity to the action of light or heat, and functions as a binder resin for the colorant and can be dissolved in an alkaline developer. have.
Alkali-soluble resins according to the invention can be, for example, copolymers of carboxyl group-containing monomers and other monomers copolymerizable therewith.
As a carboxyl group-containing monomer, unsaturated carboxylic acid etc. which have 1 or more carboxyl groups in molecules, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid, are mentioned, for example. These can be used individually or in mixture of 2 or more types.
As unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example.
As unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example.
The unsaturated carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. The unsaturated carboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, mono succinate (2-acryloyloxyethyl), mono succinate (2-methacryloyloxyethyl ), Mono phthalate (2-acryloyloxyethyl), mono phthalate (2-methacryloyloxyethyl), etc. are mentioned. The unsaturated carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. Can be.
Specific examples of other monomers copolymerizable with the carboxyl group-containing monomers include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene and m-methoxy Styrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl Aromatic vinyl compounds such as benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol meth Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadier Nylacrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate, glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polysiloxane Macromonomers; and the like. These can be used individually or in mixture of 2 or more types.
When the alkali-soluble resin is a copolymer of a carboxyl group-containing monomer and another copolymerizable monomer, the content of the carboxyl group-containing monomer is not particularly limited, for example, 10 to 50% by weight of the total weight of the monomer, preferably 15 to 40 Wt%, more preferably 25 to 40% by weight. When the content of the carboxyl group-containing monomer is within the above range, the solubility in the developer is good, it is possible to form an accurate pattern during development.
Alkali-soluble resin is a (meth) acrylic acid / methyl (meth) acrylate copolymer, the (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylic acid, for example. Rate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) acrylate macromonomer Copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / pol Methyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / mono (2-acryloyloxy) / styrene / Benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer, (Meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer, etc. are mentioned. Here (meth) acrylate means acrylate or methacrylate.
Among these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / Methyl (meth) acrylate / styrene copolymer is preferable.
The molecular weight of the alkali-soluble resin is not particularly limited. For example, the weight average molecular weight (hereinafter, referred to as weight average molecular weight) in terms of polystyrene may be 3,000 to 100,000, preferably 3,000 to 50,000, and more preferably 5,000 to 50,000. . When the molecular weight of alkali-soluble resin is in the said range, dispersion of a coloring agent is easy, a viscosity is low, and storage stability can be improved.
The content of the alkali-soluble resin is not particularly limited, and for example, may be included in 3 to 80% by weight of the total weight of the colored photosensitive resin composition, and may be included in 5 to 70% by weight. When the content of the alkali-soluble resin is within the above range, the colorant may be easily dispersed, the viscosity may be low, and the storage stability may be improved.
Photopolymerizable compound
The photopolymerizable compound may be a monofunctional, bifunctional or polyfunctional multimer as a component for enhancing the strength of the pattern, and preferably a bifunctional or higher monomer. Monofunctional such as nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N-vinylpyrrolidone Acid monomers; 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyl of bisphenol A) Difunctional monomers such as oxyethyl) ether or 3-methylpentanedioldi (meth) acrylate; Trimethylol propane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa ( And polyfunctional monomers such as meth) acrylate. These can be used individually or in mixture of 2 or more types.
The content of the photopolymerizable compound is not particularly limited. For example, the photopolymerizable compound may be included in an amount of 1 to 60% by weight, and preferably 5 to 50% by weight, based on the total weight of the colored photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, the intensity or smoothness of the pixel portion may be good.
Photopolymerization Initiator
The type of photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the photopolymerizable compound, and may be a photopolymerization initiator commonly used in the art, and examples thereof include triazine compounds, acetophenone compounds, and biimidazole compounds. A compound, an oxime type compound, etc. are mentioned. These can be used individually or in mixture of 2 or more types.
The triazine-based compound is not particularly limited, and for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloro Methyl) -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-methyl Furan-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.
The acetophenone compound is not particularly limited, and for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] Propan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, etc. are mentioned.
The biimidazole compound is not particularly limited, and for example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2 , 3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl ) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl ), 4,4'5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ', 5,5' position is substituted with a carboalkoxy group; , Preferably 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, etc. Can be mentioned.
The oxime-based compound is not particularly limited, and may be, for example, o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one. Examples of commercially available products include OXE01 and OXE02 manufactured by BASF Corporation. Can be.
The content of the photopolymerization initiator is not particularly limited. For example, the photopolymerization initiator may be included in an amount of 1 to 40% by weight of the total weight of the colored photosensitive resin composition, and preferably 3 to 20% by weight. When the content of the photopolymerization initiator is within the above range, the colored photosensitive resin composition may be highly sensitive to shorten the exposure time, thereby improving productivity and maintaining high resolution.
Photopolymerization Initiation aids
The colored photosensitive resin composition of the present invention may further include a photopolymerization initiation aid to improve the sensitivity.
The photopolymerization start adjuvant is not specifically limited, For example, an amine compound, a carboxylic acid compound, etc. are mentioned. These can be used individually or in mixture of 2 or more types.
An amine compound is not specifically limited, For example, Aliphatic amine compounds, such as a triethanolamine, methyl diethanolamine, and a triisopropanolamine; 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4, Aromatic amine compounds, such as 4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone, etc. are mentioned.
The carboxylic acid compound is not particularly limited, and for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chloro And aromatic heteroacetic acids such as phenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.
The content of the photopolymerization initiation assistant is not particularly limited, and may be included, for example, in an amount of 0.01 to 10% by weight, and preferably 0.01 to 5% by weight, based on the solid content of the total weight of the colored photosensitive resin composition. When the content of the photopolymerization initiation aid is within the above range, the sensitivity of the colored photosensitive resin composition may be further improved, and the productivity formed therefrom may be improved.
solvent
The solvent is not particularly limited as long as it can dissolve the above components, and examples thereof include ethers, aromatic hydrocarbons, ketones, alcohols, and esters. These can be used individually or in mixture of 2 or more types.
For example, ethylene glycol monoalkyl ethers such as 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, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether Ethers such as 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 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; Ester, such as 3-ethoxy ethyl propionate, methyl 3-methoxy propionate, (gamma) -butyrolactone, etc. are mentioned, Preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, Ethyl lactate, butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.
The content of the solvent is not particularly limited, and includes, for example, a solvent contained in the colorant dispersion, and the total content thereof may be included in 50 to 90% by weight of the total weight of the colored photosensitive resin composition, preferably 60 to 85% by weight. May be included as a%. When the content of the solvent is within the above range, the applicability may be good.
additive
The coloring photosensitive resin composition of this invention may further contain the at least 1 sort (s) of additive chosen from the group which consists of a filler, another high molecular compound, a hardening | curing agent, surfactant, an adhesion promoter, antioxidant, an ultraviolet absorber, and an aggregation inhibitor as needed.
The filler is not particularly limited, and examples thereof include glass, silica, alumina and the like.
The other high molecular compound is not particularly limited, and examples thereof include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Thermoplastic resins; and the like.
The hardening | curing agent is a component for improving core hardening and mechanical strength, The kind is not specifically limited, For example, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. are mentioned.
The epoxy compound is not particularly limited, and for example, 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 system, etc. Epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins; Aliphatic, cycloaliphatic or aromatic epoxy compounds other than the epoxy resin and its brominated derivatives; Butadiene (co) polymer epoxides; Isoprene (co) polymer epoxides; Glycidyl (meth) acrylate (co) polymers; Triglycidyl isocyanurate etc. are mentioned.
The oxetane compound is not particularly limited, and examples thereof include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, and cyclohexane dicarboxylic acid bis oxetane. .
A 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.
The curing aid compound is not particularly limited, and examples thereof include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, and acid generators. As the polycarboxylic acid anhydride, a commercially available one can be used as the epoxy resin curing agent.
It is not specifically limited as a commercial epoxy resin hardener which can be used by this invention, For example, a brand name (Adekahadona EH-700) (made by Adeka Kogyo Co., Ltd.), a brand name (Rikasitdo HH) (New Japan Ewha Co., Ltd.) The brand name (MH-700) (made by Nippon Ewha Co., Ltd.), etc. are mentioned.
Surfactant is a component which improves the film formability of the photosensitive resin composition, The kind is not specifically limited, For example, a fluorochemical surfactant, silicone type surfactant, or a mixture thereof is mentioned.
Silicone type surfactant is not specifically limited, For example, Dow Corning Toray Silicone Co., Ltd. DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc .; TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, etc. of GE Toshiba Silicone Co., Ltd. are mentioned.
A fluorine-type surfactant is not specifically limited, For example, Megapieces F-470, F-471, F-475, F-482, F-489, etc. of Dainippon Ink & Chemical Co., Ltd. are mentioned as a commercial item.
The kind of adhesion promoter is not specifically limited, For example, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl Methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned. These can be used individually or in mixture of 2 or more types.
The content of the adhesion promoter is not particularly limited. For example, the adhesion promoter may be included in an amount of 0.01 to 10% by weight of the total weight of the colored photosensitive resin composition, and may be included in an amount of 0.05 to 2% by weight.
The kind of antioxidant is not specifically limited, For example, 2,2'- thiobis (4-methyl-6-t-butylphenol), 2,6-di-t- butyl- 4-methylphenol, etc. are mentioned. Can be.
The kind of ultraviolet absorber is not specifically limited, For example, 2- (3-tert- butyl- 2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, an alkoxy benzophenone, etc. are mentioned.
The aggregation inhibitor is not particularly limited and may be, for example, sodium polyacrylate.
materials
The substrate according to the present invention is not particularly limited as long as it can satisfy the difference in coefficient of thermal expansion with the formed coating film. Examples thereof include glass, silicone resin, styrene-butadiene copolymer resin, butadiene-acrylonitrile copolymer resin, Epoxy resin, nylon resin, phenol resin, polybutyrene terephthalate resin, polycarbonate resin, polyester resin, polyether ether ketone resin, polyethylene resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, polystyrene It may be formed of a material such as resin, polytetrafluoroethylene resin, polyvinyl chloride resin. These can be used individually or in mixture of 2 or more types.
The thickness of the substrate is not particularly limited, and may be, for example, 20 to 1,000 µm, preferably 50 to 1,000 µm, and more preferably 100 to 1,000 µm. If the thickness of the substrate is less than 20㎛ may cause problems such as bending the substrate during the process, if the thickness is more than 1,000㎛ may increase the weight of the optical laminate, the handling may not be easy in the process.
<Optical Laminate >
The optical laminated body of this invention contains a base material and the coating film formed with the said coloring photosensitive resin composition on one surface of the said base material, and the difference of the thermal expansion coefficient of the said base material and a coating film is 5 * 10 <-6> -200 * 10 <-6> degreeC -1 to be.
The thickness of the substrate is not particularly limited, and may be, for example, 20 to 1,000 µm, preferably 50 to 1000 µm, and more preferably 100 to 1000 µm. If the thickness of the substrate is less than 20㎛ may cause problems such as bending the substrate during the process, if the thickness is more than 1,000㎛ may increase the weight of the optical laminate, the handling may not be easy in the process.
The thickness of the coating film is not particularly limited, and may be, for example, 1 to 100 μm. When the thickness of the coating film exceeds the above range, an excessive amount of developer may be required in a developing step to be described later, thereby reducing process efficiency. In such aspect, it may be preferably 1 to 80㎛.
The coating film may be formed by applying and curing a colored photosensitive resin composition.
The coating method of a coloring photosensitive resin composition is not specifically limited, It can be based on a well-known method, For example, a bar coater, an air knife, gravure, a reverse roll, a kiss roll, a spray, a blade, a die coater, casting, spin coating, etc. Can be used.
After application, the drying process may be further roughened as necessary.
The drying temperature and time are not particularly limited, and may be, for example, 10 seconds to 10 minutes at 50 to 150 ° C.
The curing may be performed by irradiating ultraviolet light, the illuminance and the light irradiation time is not particularly limited and may be appropriately selected from a known range.
After that, it may be manufactured through a development process as needed.
The coating film formed of the colored photosensitive resin composition can be used as the light shielding layer. For example, it may be used as a light blocking layer formed on a non-display portion of an image display device, a black matrix used for a color filter, a color filter pattern, and the like.
The optical laminate of the present invention is 5 × 10 -6 to 200 · 10 -6 ℃ difference in thermal expansion coefficient of the coating film formed of the substrate and the colored photosensitive resin composition as a 1 or less, is excellent in heat resistance less difference in thermal expansion coefficient between each other Do.
Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
Production Example
(1) Preparation of Colorant Dispersion
CI pigment blue 15: 6 35.0 g as a coloring agent, binder resin (copolymer of methacrylic acid and benzyl methacrylate, the molar ratio of methacrylic acid and benzyl methacrylate is 31 mol%: 69 mol%, polystyrene equivalent weight average molecular weight Silver 20,000g / mol) 7.0g, BYK-180 (BYK Co., Ltd.) 3.0g as a dispersant and 55.0g propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 2 hours by a bead mill to prepare a colorant dispersion.
(2) Preparation of Colorant Dispersion
A colorant dispersion was prepared in the same manner as in Production Example (1), except that 35.0 g of CI Pigment White 6 was included as the colorant.
(3) Preparation of Colorant Dispersion
A colorant dispersion was prepared in the same manner as in Production Example (1), except that 40.0 g of CI Pigment Black 7 was included as the colorant.
(4) Preparation of colored photosensitive resin composition
50.0 g of the colorant dispersion of Preparation Example 1, a copolymer of methacrylic acid and benzyl methacrylate (the molar ratio of methacrylic acid and benzyl methacrylate is 31 mol%: 69 mol%, and the polystyrene equivalent weight average molecular weight is 20,000 g / mol) 8.0 g, dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku) 17.0 g, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one 2.0 g , 0.3 g of 2,4-diethyl thioxanthone, 0.2 g of 3-methacryloxypropyltrimethoxysilane, and 150.0 g of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.
(5) Preparation of colored photosensitive resin composition
50.0 g of the colorant dispersion of Preparation Example (2), a copolymer of methacrylic acid and benzyl methacrylate (the molar ratio of methacrylic acid and benzyl methacrylate is 31 mol%: 69 mol%, and the polystyrene equivalent weight average molecular weight is 20,000 g / mol) 10.0 g, dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku) 15.0 g, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one 2.0 g , 0.3 g of 2,4-diethyl thioxanthone, 0.2 g of 3-methacryloxypropyltrimethoxysilane, and 150.0 g of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.
(6) Preparation of colored photosensitive resin composition
50.0 g of the colorant dispersion of Preparation Example 3, a copolymer of methacrylic acid and benzyl methacrylate (the molar ratio of methacrylic acid and benzyl methacrylate is 31 mol%: 69 mol%, and the polystyrene equivalent weight average molecular weight is 20,000 g / mol) 12.0 g, dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku) 13.0 g, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one 2.0 g , 0.3 g of 2,4-diethyl thioxanthone, 0.2 g of 3-methacryloxypropyltrimethoxysilane, and 150.0 g of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.
Example One
After applying the coloring photosensitive resin composition of the manufacture example (4) so that it might become 20 micrometers in thickness on the 200 micrometers-thick base material (LUPOY (PC), LG Chemical) by spin coating, it puts on a heating plate, and it is 3 minutes at the temperature of 100 degreeC To form a thin film. Subsequently, a photomask having a pattern of 50 μm was placed thereon and irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with an illuminance of 40mJ / cm 2 using a 1KW high-pressure mercury lamp containing all g, h, and i lines.
The ultraviolet-ray-coated thin film was developed by immersing in a KOH aqueous solution developing solution of pH 10.5 for 40 seconds, placed on a heating plate, and maintained at a temperature of 180 ° C. for 30 minutes to prepare an optical laminate.
Example 2
An optical laminate was prepared in the same manner as in Example 1, except that the colored photosensitive resin composition of Preparation Example (5) was applied onto a substrate (Capton, Dopont) having a thickness of 125 μm by spin coating.
Example 3
An optical laminate was prepared in the same manner as in Example 1, except that the colored photosensitive resin composition of Preparation Example 6 was coated on a substrate (Cellulose acetate, Grafix Plastics) having a thickness of 150 μm by spin coating.
Example 4
An optical laminate was prepared in the same manner as in Example 1, except that the colored photosensitive resin composition of Preparation Example (5) was subjected to spin coating on a substrate having a thickness of 150 μm (Cellulose acetate, Grafix Plastics).
Comparative example
An optical laminate was prepared in the same manner as in Example 1 except that the colored photosensitive resin composition of Preparation Example 6 was applied onto a substrate (Capton, Dopont) having a thickness of 125 μm by spin coating.
Experimental Example
(1) Measurement of coefficient of thermal expansion of coating film formed from photosensitive resin composition
The colored photosensitive resin compositions of Preparation Examples 4 to 6 were applied on a copper thin film by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, a photomask having a pattern of 1 cm * 4 cm was placed and irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with luminous intensity of 100mJ / cm 2 using a 1KW high-pressure mercury lamp containing all g, h and i lines. The thin film irradiated with ultraviolet rays was developed by immersing in a KOH aqueous solution developing solution of pH 10.5 for 40 seconds. Thereafter, the copper thin film was removed with an etchant to prepare a 1 cm * 4 cm pattern. The pattern of the prepared colored coating film was placed on a heating plate, and maintained at a temperature of 180 ° C. for 30 minutes to prepare a colored coating pattern. The thickness of the manufactured colored coating film was 4.0 micrometers.
The coefficient of thermal expansion of each coating film was measured in the range of 30 ° C. to 180 ° C. by Thermomechanical Analysis (TA instr μment).
(2) evaluation of stability of pattern
The optical laminates of Examples 1 to 4 and Comparative Examples were each placed in an oven at 180 ° C., left for 30 minutes, and then taken out and placed in a constant temperature oven at 5 ° C. for 10 minutes. This was repeated three times.
Thereafter, the pattern was lifted and visually observed to evaluate the stability of the pattern by quantifying step by step at 0 points when the pattern was confirmed to be zero, and when the pattern remained smooth and stable.
2, the coating film of the optical laminated body of Example 1 and the coating film of the optical laminated body of a comparative example were image | photographed in FIG.
Referring to Table 1, it can be seen that the thermal expansion coefficient of the coating film is different according to the composition of the colored photosensitive resin composition, and the thermal expansion coefficient is different for each substrate.
In the optical laminates of Examples 1 to 4, the difference in the coefficient of thermal expansion between the substrate and the coating film is only 57 * 10 -6 ° C -1 to 162 * 10 -6 ° C -1 , and the high-temperature and low-temperature treatment was repeatedly performed. The Edo pattern was not lifted and was smooth, and the pattern was excellent in stability.
Thus, the composition of a coloring photosensitive resin composition is selected suitably, and the base material which has a thermal expansion coefficient suitable for it is selected and used, and the difference of the thermal expansion coefficient of a base material and a coating film is 5 * 10 <-6> -200 * 10 <-6> degreeC -1 By adjusting, the stability of the pattern can be improved.
Fig. 2 shows a front view of the coating film of the optical laminated body of Example 1, but it can be confirmed that it is in a smooth state without lifting of the pattern.
However, in the optical laminate of the comparative example, the difference in thermal expansion coefficient between the substrate and the coating film was 252 * 10 -6 ° C -1, and the thermal expansion degree was greatly different from each other. .
3, the front view of the coating film of the optical laminated body of the comparative example is shown, but it can confirm that a pattern falls and stability falls.
Claims (10)
The adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane At least one selected from the group consisting of 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane,
The base material is glass, silicone resin, styrene-butadiene copolymer resin, butadiene-acrylonitrile copolymer resin, epoxy resin, nylon resin, phenol resin, polybutylene terephthalate resin, polycarbonate resin, polyester resin, polyether It is formed of at least one material selected from the group consisting of ether ketone resin, polyethylene resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, polystyrene resin, polytetrafluoroethylene resin and polyvinyl chloride resin , Colored photosensitive resin composition.
A colored photosensitive resin composition, wherein the solvent is contained in 50 to 90% by weight of the total weight of the colored photosensitive resin composition.
The optical laminated body whose difference of the thermal expansion coefficient of the said base material and a coating film is 5 * 10 <-6> -200 * 10 <-6> degreeC -1 .
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| JP2012136693A (en) * | 2010-12-08 | 2012-07-19 | Ajinomoto Co Inc | Resin composition |
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| KR20120019039A (en) * | 2010-08-24 | 2012-03-06 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter and liquid crystal display device having the same |
| KR20120067038A (en) * | 2010-12-15 | 2012-06-25 | 동우 화인켐 주식회사 | Reflector for liquid crystal display device, manufacturing method of the reflector and display device including the same |
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