KR20160084894A - Photo-sensitive resin and manufacturing method of insulation layer for display - Google Patents
Photo-sensitive resin and manufacturing method of insulation layer for display Download PDFInfo
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- KR20160084894A KR20160084894A KR1020150001124A KR20150001124A KR20160084894A KR 20160084894 A KR20160084894 A KR 20160084894A KR 1020150001124 A KR1020150001124 A KR 1020150001124A KR 20150001124 A KR20150001124 A KR 20150001124A KR 20160084894 A KR20160084894 A KR 20160084894A
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- photosensitive resin
- diisocyanate
- fluorene
- monomer
- acrylate
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- 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
Abstract
Description
The present invention relates to a photosensitive resin and a method for producing an insulating layer for a display, and more particularly, to a photosensitive resin and a display insulating material which can manufacture an insulating layer for a display with reliability by using a photosensitive resin having thermal and chemical stability. Layer fabrication method.
The photosensitive resin for pattern formation includes a binder, a polyfunctional monomer, a photoinitiator and a solvent. If color is desired in the pattern to be formed, colored particles can be added to this composition. Among them, the binder greatly affects the patternability, and the pattern can be easily separated from the substrate when the molecular weight of the binder is low. On the other hand, when the molecular weight of the binder is high, formation of a fine pattern becomes difficult. If the acid value of the binder is large, the pattern is quickly erased at the time of development, and if the acid value is small, no pattern is formed at the time of development.
Acrylic binders generally used in such photosensitive resins have a problem in formation of fine patterns due to their low photosensitivity. In particular, it is difficult to form a black matrix in the formation of a black matrix containing a black pigment. In addition, the pattern formed is also low in heat resistance and chemical resistance, resulting in a problem of product reliability. Bisphenol A (BPA) -based binders or novolac-based binders are used in order to solve problems of fine pattern formation and heat resistance of such acrylic binders.
A black matrix for a color filter of a liquid crystal display, or the like is formed by using a photosensitive resin. Liquid crystal displays are fabricated through various high-temperature processes including a process of forming a black matrix using black resin and a process of over 200 ° C. Therefore, the thermal stability is important in order that the black matrix formed in the initial process is not affected by the subsequent process.
As a result, there has been a demand for developing a photosensitive resin having a high level of thermal chemical stability, although a bisphenol A-based binder or a novolak-based binder has been used to increase the heat resistance.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the above problems, and it is an object of the present invention to provide a photosensitive resin and a method for manufacturing an insulating layer for a display, which can produce a reliable electromagnetic shielding film.
According to an aspect of the present invention, there is provided a photosensitive resin comprising a monomer having a bisphenol fluorene structure, a binder, a photoinitiator, and a solvent.
Here, the monomer may be a bisphenol fluorene-based polyfunctional acrylate monomer, and the bisphenol fluorene-based polyfunctional acrylate monomer may be formed by reacting a fluorene derivative, an isocyanate derivative and a (meth) acrylate derivative.
Fluorene derivatives include 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- 4,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxyphenyl) fluorene, 3-methylphenyl) fluorene).
Examples of the isocyanate derivatives include diisocyanate compounds such as 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (TDI), 2, 6-toluene diisocyanate (TDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 1,4-cyclohexane diisocyanate (1, 4-Cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), tetramethyl-1,3-xylene diisocyanate (TMXDI), dimeryl diisocyanate DDI), hexamethylene diisocyanate (HDI), 1,1,6,6-tetrahydroperfluoro-hexamethylene diisocyanate (THFDI), and Diisocyanate trimer chain HDI-triline It may be at least any one of (HDI-trimer) and IPDI- trimer (IPDI-trimer).
The (meth) acrylate derivative is preferably selected from the group consisting of 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate acrylate, 3-hydroxypropyl methacrylate, pentaerythritol triacrylate, pentaerythrytol propoxylate triacrylate, acrylic acid (acrylic acid) ), Methacrylic acid, and 2-carboxyethyl acrylate.
The photosensitive resin according to the present invention may further comprise an aliphatic acrylate monomer.
The binder may be at least one of an acrylic resin, an epoxy resin, a polyimide resin, a novolac resin, and a cadene resin.
According to another aspect of the present invention, there is provided a method for manufacturing a light emitting device, comprising: forming a photosensitive resin layer containing a monomer having a fluorene structure, a binder, a photoinitiator, a solvent, and black particles on a substrate; Positioning and exposing the mask on the photosensitive resin layer; And a step of developing the photosensitive resin layer.
INDUSTRIAL APPLICABILITY As described above, according to the embodiments of the present invention, it is possible to manufacture a black matrix, which is an insulating layer for a display, using a photosensitive resin for a fine pattern having excellent thermal and chemical stability, thereby ensuring product reliability.
Figure 1 is an image of a fine pattern produced according to an embodiment of the present invention.
Hereinafter, embodiments of the present invention will be described.
The photosensitive resin according to the present invention comprises a monomer having a bisphenol fluorene structure, a binder, a photoinitiator and a solvent.
The photosensitive resin according to the present invention comprises a monomer having a bisphenol fluorene structure as a monomer. The monomer forms a photopolymer by forming a photopolymer through a polymerization reaction initiated by radicals formed from a photoinitiator by irradiation of light in an exposure process, thereby forming a photoresist layer. Thus, the monomer may be a monomer that can be polymerized, for example, through a radical reaction by irradiation of light. Or the monomer may be a monomer of a photopolymer capable of forming a copolymer with the binder.
The content of the monomer according to the present invention is 1 to 25 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the photosensitive resin. When the content of the monomers is within the above-mentioned range, for example, crosslinking and pattern formation and binding force with colored particles can be enhanced through ultraviolet irradiation through a radical reaction by a photoinitiator described later. If the content of the monomer is less than the above-mentioned range, the phenomenon may occur excessively and the film of the cured photoresist may not be clear, and if it exceeds the above-mentioned range, it may not be developed.
The photoinitiator which can be included in the photosensitive resin according to the present invention acts as an initiator for polymerization of monomers by forming radicals by irradiation of light in an exposure process using a photomask. Therefore, the photopolymerization reaction occurs only in the photoresist in the exposure region irradiated with the light in the exposure process, and the monomer is cured, but the photopolymerization reaction does not occur in the non-exposure region, so that the monomer can not be cured and a pattern can be formed.
The photosensitive resin of the present invention may be a bisphenol fluorene-based polyfunctional acrylate monomer as a monomer, and the bisphenol fluorene-based polyfunctional acrylate monomer may be formed by reacting a fluorene derivative, an isocyanate derivative and a (meth) .
A bisphenol fluorene derivative having a bisphenol fluorene structure represented by the general formula (1) among fluorene derivatives has excellent aromatic groups and chemical resistance and heat resistance. In the case of a photosensitive resin, a pattern is formed through a photolithography process, and then a process of 200 ° C or more is required in order to secure heat resistance and chemical resistance. The use of bisphenol fluorene-based monomers is advantageous for high temperature processes because the heat resistance of the photosensitive resin can be further increased. Accordingly, it can be used as a material for fabricating a pixel define layer of an OLED display requiring high reliability, and can be applied to a metal-based touch panel, thereby reducing reflectivity and improving visibility.
[Chemical Formula 1]
The bisphenol fluorene-based polyfunctional acrylate monomer may be formed by reacting a fluorene derivative, an isocyanate derivative, and a (meth) acrylate derivative. Formula 2 is an example of a bisphenol fluorene-based polyfunctional acrylate monomer, and is a bisphenol fluorene-based urethane acrylate.
(2)
Here, R < 1 >
(3)
Examples of the fluorene derivative that can be used for the synthesis of the bisphenol fluorene-based polyfunctional acrylate monomer used in the photosensitive resin of the present invention include 9,9-bis [4- (2-hydroxyethoxy) phenyl] 9,9-Bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, and And 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.
Examples of the isocyanate derivative that can be used in the synthesis of the bisphenol fluorene-based polyfunctional acrylate monomer used in the photosensitive resin of the present invention include 4,4'-diphenylmethane diisocyanate (4,4'- Diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI), 4,4'-dicyclohexyl Diisocyanate (4,4'-Dicyclohexylmethane diisocyanate, H12MDI), 1,4-cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), tetramethyl- 1,3-xylene diisocyanate (TMXDI), dimeryl diisocyanate (DDI), hexamethylene diisocyanate (HDI), 1,1,6,6-tetrahydro-naphthalene diisocyanate purple Oro - a hexamethylene diisocyanate (1,1,6,6, -Tetrahydroperfluoro-hexamethylene diisocyanate, THFDI) and diisocyanate trimers HDI- chain trimer (HDI-trimer) and IPDI- trimer (IPDI-trimer).
Examples of the (meth) acrylate derivative that can be used in the synthesis of the bisphenol fluorene-based polyfunctional acrylate monomer used in the photosensitive resin of the present invention include 2-hydroxyethyl acrylate (HEA) Hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, pentaerythritol triacrylate, Acrylate, pentaerythritol trioxylate triacrylate, acrylic acid, methacrylic acid, and 2-carboxyethyl acrylate. .
The photosensitive resin according to the present invention may contain an aliphatic acrylate monomer in addition to a bisphenol fluorene-based polyfunctional acrylate monomer. The aliphatic acrylate monomer serves to improve patternability, which can be cured after exposure with a bisphenol fluorene-based polyfunctional acrylate monomer to form a polymer. For example, the aliphatic acrylate monomer may be selected from the group consisting of dipentaerythritol penta- / hexa-acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate ( Pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, pentaerythritol triacrylate, Pentaerythritol propoxylate triacrylate, glycerol propoxylate triacrylate, di (trimethylolpropane) tetraacrylate, and the like.
The photosensitive resin according to the present invention comprises a photoinitiator capable of initiating photopolymerization. As the photoinitiator, any photoinitiator capable of forming radicals by irradiation of light in a photolithography process can be used. For example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound including monophenyl, an oxime-based compound, and the like can be used as a photoinitiator. The photoinitiator that can be used in the present invention is not particularly limited, but is preferably a triazine-based compound or a oxime-based compound having a non-phenyl structure having good developability by an aqueous alkali solution used as a developer and having excellent sensitivity even at the same exposure dose Compounds.
Acetophenone-based compounds that can be used as photoinitiators include, for example, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-phenylacetophenone, 2,2'- Benzoyloxycarbonyl), 2-benzyl-2-dimethylamino-1- (4-methoxyphenyl) Morpholinophenyl) -butan-1-one and the like.
Examples of benzophenone-based compounds that can be used as photoinitiators include benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl- Benzoyl benzoic acid, benzoyl benzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, and 4,4'- have. Examples of thioxanthone compounds that can be used as photoinitiators include thioxanthone, 2-crothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 1- [9-ethyl- ) -9H-carbazol-3-yl] -1- (O-acetyloxime), 2,4-diethylthioxanthone, 2,4- diisopropylthioxanthone, And Santon.
Examples of the benzoin compound which can be used as a photoinitiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.
Triazine-based compounds that can be used as photoinitiators include, for example, 4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s (Trichloromethyl) -s-triazine, 2- (p -tryl) -4,6-bis (trichloromethyl) -s Triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, bis ) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol- 4-trichloromethyl (piperonyl) -6-triazine, and 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine.
Oxime compounds which can be used as photoinitiators include, for example, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- And oxime A (Oxime A) or oxime E (Oxime E), which are oxime ester compounds, can be used in the present invention. .
In addition, carbazole-based compounds, diketone compounds, sulfonium borate compounds, diazo compounds, and imidazole-based compounds can also be used as photoinitiators for photosensitive resins according to the present invention.
The photoinitiator according to the present invention may be contained in an amount of 1 to 25 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin. When the content of the photoinitiator is less than the above range, the photopolymerization reaction does not sufficiently take place and it is difficult to form a stable black matrix pattern. If the content of the photoinitiator is less than this range, the solubility of the black matrix pattern may be decreased, Implementation can be difficult.
The photosensitive resin according to the present invention may comprise a binder of at least one of an acrylic resin, an epoxy resin, a polyimide resin, a novolac resin and a cardade resin. The binder serves as a support in the photosensitive resin according to the present invention and reacts with light in the exposure process to form a photoresist layer.
The acrylic binder can control the flowability of the finally prepared black matrix pattern and can form a binder suitable for the application through the introduction of various monomers. The epoxy binder has an annular structure, and the alkali resistance of the cured photoresist is improved. And the cation binder is excellent in controlling the developability of the pattern through acid value control.
As the acrylic binder, an acrylic binder soluble in alkali which is used as a developer can be used. Preferably, the acrylic binder can improve the strength of the photoresist as compared with that by homopolymerization, by using a copolymer of a monomer having an acid functional group and another monomer capable of copolymerizing with the monomer. In addition, the acrylic binder may contain a fluorine group so as to exhibit hydrophobicity when forming a cured photoresist film.
In addition to the above-described alkali-soluble acrylic binder, it is possible to use a cadmium binder which can easily control pattern development through acid value control, and can achieve affinity and high sensitivity to colored particles.
The acid value of the binder contained in the photosensitive resin of the present invention is preferably in the range of, for example, 50 to 300 KOH mg / g. When the acid value is less than 50, the solubility in the alkali developing solution is low, so that the development time is long and the residue may remain on the substrate. If the acid value exceeds 300, the pattern is desorbed and the pattern straightness can not be secured.
The weight average molecular weight of the binder is preferably in the range of 1,000 to 200,000. When the weight average molecular weight of the binder is less than 1,000, the binding function between the components is weak and the physical properties such as pattern disappearance in the developing process can not be satisfied. On the other hand, when the weight average molecular weight exceeds 200,000, the development with respect to the alkaline developer hardly occurs, the efficiency of the developing process is lowered, and the flowability is deteriorated, so that it may be difficult to secure the uniformity of the pattern thickness.
The binder that serves as a support for the photoresist obtained from the photosensitive resin of the present invention may be contained in an amount of 1 to 35 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the photosensitive resin. When the content of the binder is less than the above range, the coating property may be deteriorated. If the content of the binder exceeds this range, the cured photoresist may not have desired optical properties.
The photosensitive resin according to the present invention comprises a solvent for controlling the viscosity. Examples of the solvent that can be used in the photosensitive resin of the present invention include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Ethyl acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethyl glycol methyl acetate, dipropylene glycol methyl ether, methyl ethoxypropionate, ethyl ethoxypropionate, Compounds selected from the group consisting of butyl acetate, cyclohexanone, acetone, methyl isobutyl ketone, dimethyl formamide, N, N'-dimethylacetamide, N-methylpyrrolidone, toluene and combinations thereof may be used .
The solvent has a viscosity such that the finally obtained photosensitive resin can be suitably applied on the substrate, while the content can be controlled in consideration of the dispersibility of the colored particles, etc. The content of the solvent depends on the content of the photosensitive resin 100 May be 50 to 85 parts by weight based on parts by weight.
The photosensitive resin according to the present invention may further comprise colored particles. The photosensitive resin according to the present invention may contain colored particles such as red pigment, green pigment, blue pigment, white pigment and black pigment depending on the kind.
When the photosensitive resin is used in a black matrix, the colored particles include a black pigment such as carbon black, which is preferably used for realizing the light shielding function of the black matrix and preferably has good light shielding function. At this time, the carbon black as the black pigment may be used singly or in combination with other colored pigments. Other color pigments that can be used include, for example, carmine 6B, phthalocyanine blue, azo pigments, strontium titanate, and chromium oxide as a color correcting agent in addition to black pigments such as titanium black, acetylene black, aniline black, perylene black, But other color pigments may also be used.
According to the present invention, the colored particles contained in the photosensitive resin may be contained in an amount of 5 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the total composition. If the content of the colored particles is less than this range, it is difficult to achieve a sufficient light-shielding effect and / or a desired optical density, and if it is larger than this range, the viscosity of the composition may increase and the safety of the pattern or the adhesion to the substrate may be deteriorated. The colored particles can be used, for example, in the form of a millbase or dispersion in combination with a solvent or a dispersant. For example, the colored particles having an average particle size of 20 to 200 nm can be used so that a fine black matrix pattern can be formed, which can be appropriately dispersed as a dispersion, but the present invention is not limited thereto.
Meanwhile, in the photosensitive resin according to the present invention, nonionic, cationic and anionic dispersing agents may be used as dispersing agents for dispersing the colored particles. Specifically, dispersants such as polyalkylene glycols and esters thereof, alkylene oxide adducts of polyoxyalkylene polyhydric alcohol esters, alcohol alkylene oxide adducts, sulfonic acid esters, carboxylic acid esters, carboxylic acid salts and alkyl amines can be used. The content of the dispersing agent is less than about 1 part by weight, for example, 0.1 to 0.9 part by weight based on 100 parts by weight of the photosensitive resin according to the present invention.
In addition, various additives may be added to improve the function of the photosensitive resin according to the present invention. For example, a coupling agent (adhesion promoter) for improving the adhesion of a photosensitive resin (photoresist) coated on a substrate and a surface active agent to improve the coating stability of the photosensitive resin to the substrate; At least one additive selected from an antioxidant, a curing accelerator, an ultraviolet absorber, a thermal polymerization inhibitor and a leveling agent may be used.
Examples of the surfactant include cationic surfactants such as organosiloxane polymers, (meth) acrylic acid-based (co) polymer polyflows and polyoxyethylene alkylamine glycols; Include polyoxyethylene fatty acid ethers or polyoxyethylene fatty acid esters such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether , Nonionic surfactants such as polyhydric alcohol fatty acid esters such as polyethylene glycol dilaurate, polyethylene glycol distearate and sorbitan fatty acid ester, alkylphosphate-based anionic surfactants and fluorinated surfactants can be used.
Examples of the coupling agent include vinyltrialkoxysilane, 3-methacryloxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3- Glycidoxypropyltriethoxysilane, and the like. As the antioxidant, 2,2-thiobis (4-methyl-6-t-butylphenol) or 2,6-di-t-butylphenol and the like can be used. As the curing accelerator, 2-mercaptobenzo Imidazole, 2-mercaptobenzothiazole, or pentaerythritol-tetrakis (3-mercaptopropionate). Examples of the ultraviolet absorber include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole and alkoxybenzophenone. Examples of the heat polymerization inhibitor include hydroquinone, p -Methoxyphenol, t-butyl catechol, and benzoquinone. These additives may exhibit sufficient effects even when a trace amount is added. Usually, these additives may be contained in an amount of less than 1 part by weight, for example, 0.01 to 0.5 part by weight, based on 100 parts by weight of the photosensitive resin.
According to another aspect of the present invention, there is provided a method for manufacturing a light emitting device, comprising: forming a photosensitive resin layer containing a monomer having a fluorene structure, a binder, a photoinitiator, a solvent, and black particles on a substrate; Positioning and exposing the mask on the photosensitive resin layer; And a step of developing the photosensitive resin layer.
In the method for manufacturing an insulating layer for a display according to the present invention, a photosensitive resin composition is formed by mixing a monomer having a fluorene structure, a binder, a photoinitiator, a solvent, and black particles, and applying the composition to a substrate to form a photosensitive resin layer. As a method of applying the photosensitive resin composition on a substrate, methods such as dip coating (immersion), spin coating, roller coating, spray coating, bar coating, or slit coating can be used.
In addition to glass, the substrate may be formed of a material selected from the group consisting of polyester, aromatic polyamide, polyamideimide, polyimide, triacetyl cellulose (TCA), polycarbonate (PC), polyether sulfone (PES), polyethylene terephthalate Polyethylene terephthalate (PET), Polyethylene naphthalate (PEN), Polyvinyl alcohol (PVA), Polymethyl methacrylate (PMMA) or Cyclo-Olefin polymer Etc. may be used. At this time, the substrate may be a substrate subjected to an appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, or vacuum deposition depending on the purpose.
If necessary, the photosensitive resin applied on the substrate is pre-baked at 80 to 130 ° C, preferably 90 to 110 ° C for 80 to 300 seconds, preferably 90 to 200 seconds, before the exposure process is performed, A relatively firm photoresist film can be formed on the substrate by performing a baking (soft baking, drying, pre-curing) process. Through the pre-baking process, the solid component of the photosensitive resin according to the present invention is not pyrolyzed, but most of the solvent components are evaporated and the concentration of the solvent can be minimized.
Once the photosensitive resin layer is formed, the mask is positioned and exposed on the photosensitive resin layer. In order to perform the exposure process, an exposure mask is interposed over the substrate on which the photosensitive resin layer is formed. Accordingly, the photosensitive resin laminated on the substrate is divided into an exposure region where light is irradiated and a non-exposure region where light is not irradiated. In the photosensitive resin in the exposure area, the monomer is photopolymerized by the photoinitiator, whereas the photosensitive resin in the non-exposure area is not irradiated with light, so that no reaction takes place, so that the monomer in this area is not polymerized and remains in monomer form have. As a result, the monomer in the photosensitive resin in the exposure area is photopolymerized. The exposed photosensitive resin layer is developed to form an insulating layer pattern for display.
Hereinafter, the present invention will be described in more detail with reference to Examples.
<Examples>
[Synthesis of bisphenol fluorene-based polyfunctional acrylate monomer]
Fluorene derivative 9,9-bis (4-hydroxyphenyl) fluorene (8.0 g) and isocyanate derivative 2,4-toluene diisocyanate (7.95 g) were dissolved in methyl ethyl ketone (16 g). This solution is added with dibutyltin dilaurate (0.08 g) and stirred at 60 ° C for 3 hours. To this solution, an acrylate derivative pentaerythritol triacrylate (13.61 g) was added and the mixture was reacted at a temperature of 60 ° C for 3 hours.
[Synthesis of bisphenol A-based binder]
A mixture of bisphenol A glycerolate glycerolate (1 glycerol / phenol) diacrylate (31.61 g), triphenylphosphine (0.03 g), and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride 9.59 g) is dissolved in propylene glycol monomethyl ether acetate (63.22 g). The solution was stirred at 100 < 0 > C for 4 hours and then tetrahydrophthalic anhydride (4.96 g) was added. The solution is further stirred at 100 ° C for 3 hours and then cooled.
[Example]
(0.275 g), bisphenol A-based binder (0.55 g), photoinitiator (0.076 g), black pigment (0.55 g) and PGMEA (2.75 g) Forming black photosensitive resin.
The resin is coated on a glass substrate by a spin coating method, pre-baked at 100 ° C for 3 minutes, and exposed to UV for 3 minutes using a photomask having a 10 μm mesh pattern. The substrate was developed with a DPD-200 solution and then washed with water to obtain a 10 μm fine mesh pattern.
[Comparative Example]
The same experiment was carried out except that in Example 1, dipentaerythritol 5/6-acrylate (0.55 g) was used without using a monomeric bisphenol fluorene-based polyfunctional acrylate monomer.
Figure 1 is an image of a fine pattern produced according to an embodiment of the present invention. It was confirmed that an excellent 10 mu m fine mesh pattern was formed using the black photosensitive resin prepared according to the present example 1. [ On the other hand, in the case of the comparative example, fine patterns were not formed well. Therefore, it has been confirmed that the photosensitive resin using the bisphenol fluorene-based polyfunctional acrylate according to the present invention exhibits heat resistance and chemical resistance, but also has an excellent pattern forming function.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the invention as defined by the appended claims. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (8)
The monomer may be,
A photosensitive resin which is a bisphenol fluorene-based polyfunctional acrylate monomer formed by reacting a fluorene derivative, an isocyanate derivative and a (meth) acrylate derivative.
The fluorene derivative may be,
(9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene), 9,9-bis 4,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, fluorene). < / RTI >
The isocyanate derivative,
4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (2, 6-Toluene diisocyanate (TDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 1,4-cyclohexane diisocyanate (CHDI) But are not limited to, isophorone diisocyanate (IPDI), tetramethyl-1,3-xylene diisocyanate (TMXDI), dimeryl diisocyanate (DDI), hexamethylene diisocyanate Hexamethylene diisocyanate (HDI), 1,1,6,6-tetrahydroperfluoro-hexamethylene diisocyanate (THFDI), HDI-trimer ) And an IPDI-trimer (IPDI-trimer).
The (meth) acrylate derivative may be, for example,
2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, But are not limited to, 3-hydroxypropyl methacrylate, pentaerythritol triacrylate, pentaerythritol propoxylate triacrylate, acrylic acid, methacrylic acid ), And 2-carboxyethyl acrylate.
A photosensitive resin further comprising an aliphatic acrylate monomer.
Wherein the binder is at least one of an acrylic resin, an epoxy resin, a polyimide resin, a novolac resin, and a cadene resin.
Positioning and exposing a mask on the photosensitive resin layer; And
And developing the photosensitive resin layer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150001124A KR20160084894A (en) | 2015-01-06 | 2015-01-06 | Photo-sensitive resin and manufacturing method of insulation layer for display |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150001124A KR20160084894A (en) | 2015-01-06 | 2015-01-06 | Photo-sensitive resin and manufacturing method of insulation layer for display |
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| KR20160084894A true KR20160084894A (en) | 2016-07-15 |
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| KR1020150001124A KR20160084894A (en) | 2015-01-06 | 2015-01-06 | Photo-sensitive resin and manufacturing method of insulation layer for display |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112162463A (en) * | 2020-08-28 | 2021-01-01 | 上海玟昕科技有限公司 | Negative high-elasticity photosensitive resin composition |
| EP3418782B1 (en) * | 2016-12-26 | 2023-05-03 | LG Chem, Ltd. | Polarizer protection film, polarizing plate comprising the same, liquid crystal display comprising the polarizing plate, and coating composition for polarizer protecting film |
-
2015
- 2015-01-06 KR KR1020150001124A patent/KR20160084894A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3418782B1 (en) * | 2016-12-26 | 2023-05-03 | LG Chem, Ltd. | Polarizer protection film, polarizing plate comprising the same, liquid crystal display comprising the polarizing plate, and coating composition for polarizer protecting film |
| CN112162463A (en) * | 2020-08-28 | 2021-01-01 | 上海玟昕科技有限公司 | Negative high-elasticity photosensitive resin composition |
| CN112162463B (en) * | 2020-08-28 | 2021-09-28 | 上海玟昕科技有限公司 | Negative high-elasticity photosensitive resin composition |
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