WO2012044099A2 - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
WO2012044099A2
WO2012044099A2 PCT/KR2011/007208 KR2011007208W WO2012044099A2 WO 2012044099 A2 WO2012044099 A2 WO 2012044099A2 KR 2011007208 W KR2011007208 W KR 2011007208W WO 2012044099 A2 WO2012044099 A2 WO 2012044099A2
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
monomer
binder resin
alkali
Prior art date
Application number
PCT/KR2011/007208
Other languages
French (fr)
Other versions
WO2012044099A3 (en
Inventor
Young Sung Suh
Kyung Keun Yoon
Jae Gook Han
Chung Seock Kang
Original Assignee
Kolon Industries, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kolon Industries, Inc. filed Critical Kolon Industries, Inc.
Publication of WO2012044099A2 publication Critical patent/WO2012044099A2/en
Publication of WO2012044099A3 publication Critical patent/WO2012044099A3/en

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

  • the present invention relates to a photosensitive resin composition suitable for forming a light blocking film of an image display device such as a liquid crystal display (hereinafter, referred to as "LCD”) and the like.
  • LCD liquid crystal display
  • a liquid crystal display expresses an image by using optical anisotropy and a birefringent characteristic of liquid crystals and when an electric field is applied, the alignment of the liquid crystals varies and a transmission characteristic of light also varies depending on an alignment direction of the liquid crystals which varies.
  • liquid crystal display In general, in the liquid crystal display, two substrates with field generating electrodes, respectively are placed with surfaces where the two electrodes are formed facing each other, a liquid crystal material is injected between the two substrates, and the liquid crystals are moved by an electric field generated by applying voltage to the two electrodes, and as a result, the image is displayed by changed transmittance of light.
  • the TFT-LCD includes a lower substrate where a thin film transistor and a pixel electrode are arranged, which is called an array substrate and an upper substrate a black matrix and colored layers of three colors of red, green, and blue colors are repeated on the top of a substrate made of plastic or glass, an overcoat with a thickness of 1 to 3 um, which is made of polyimide, polyacrylate, polyurethane, and the like in order to protect a color filter and maintain surface smoothness and an indium tin oxide (ITO) transparent conductive layer in which voltage for driving liquid crystals to the top of the overcoat are formed thereon, which is called a color filter substrate, and liquid crystals injected between the upper and lower substrates.
  • ITO indium tin oxide
  • the TFT-LCD has a structure in which a polarizing plate linearly polarizing visible rays (natural light) is attached to each of both surfaces of both substrates.
  • the transistor is turned on by applying voltage to a gate of the TFT forming pixels by an external peripheral circuit to input video voltage into the liquid crystals and thereafter, video information is stored by applying the image voltage and the transistor is turned off to conserve electric charges stored in a liquid crystal charger and an auxiliary charger, thereby displaying a video image for a predetermined time.
  • voltage is applied to the liquid crystals, the alignment of the liquid crystals varies.
  • light transmits the liquid crystals of this state diffraction occurs.
  • the light transmits the polarizing plate to acquire a desired video.
  • a method of manufacturing the color filter commonly uses a dyeing method, a dispersing method, an electric coating method, a printing method, a jetting method, and the like.
  • a technology of manufacturing the color filter by the jetting method using an inkjet print has merits capable of simplifying a color filter manufacturing process and reducing a manufacturing cost.
  • the color filters manufactured by the jetting method using the inkjet print have much difficulty in ensuring uniformity in a glass substrate and a display cell.
  • the cause of a uniformity defect of the color filter mainly occurs due to a difference between the ink amounts ejected by nozzles of an inkjet print head.
  • the difference between the ink amounts ejected by the nozzles of an inkjet print head is shown as a spot according to an amount of the color ink filled in each pixel area.
  • the color ink when the color ink is filed in the light blocking pattern, that is, an inner space corresponding to the pixel area defined by the black matrix, the color ink may be in a dome shape in which the surface thereof is convexly lifted due to a repulsive force between the light blocking pattern and the color ink and a surface tension of the color ink.
  • a color difference may occur due to a difference between a thickness of the color filter formed at the center of the pixel area and a thickness of the color filter formed at the edge of the pixel area by the color ink filled in the dome shape in the inner space. Accordingly, display quality is deteriorated due to the uniformity defect of the color filter due to the factors.
  • the present invention has been made in an effort to provide a photosensitive resin composition having an appropriate hydrophobic property while representing an appropriate optical density at the time of forming a cured film.
  • the present invention has been made in an effort to provide a photosensitive resin composition useful to a barrier material when a colored layer is formed by a jetting method using an inkjet printer.
  • An exemplary embodiment of the present invention provides a photosensitive resin composition including a cardo-based binder resin, in which the cardo-based binder resin contains a fluorine group.
  • the photosensitive resin composition may further include an alkali-soluble acrylic binder resin.
  • the alkali-soluble acrylic binder resin may include a monomer including an acid functional group and a monomer copolymerizable with the monomer as a base monomer.
  • the alkali-soluble acrylic binder resin may include a monomer containing an epoxy group as a base monomer.
  • the photosensitive resin composition may include: a multifunctional monomer having an ethylene unsaturated double bond; a photopolymerizable initiator; a pigment; and a solvent.
  • the content of the alkali-soluble acrylic binder resin may be 5 to 50 wt% with respect to a total solid content of the photosensitive resin composition.
  • the pigment may include carbon black having a particle size of 50 to 150 nm.
  • the fluorine content per a weight of 1g of the cured film may be 5 to 50 wt% in forming the cured film.
  • an optical density (OD) is 2.0 or more per unit thickness of 1.0 ⁇ m
  • a contact angle for water is 85° or more
  • a contact angle for 2-ethoxyethanol is 35° or more
  • Another exemplary embodiment of the present invention provides a color filter substrate including a black matrix formed by a photolithography method using the photosensitive resin composition.
  • Yet another exemplary embodiment of the present invention provides a thin film transistor substrate including a black matrix formed by a photolithography method using the photosensitive resin composition.
  • Still yet another exemplary embodiment of the present invention provides an image display device including the color filter substrate as an upper substrate.
  • Still yet another exemplary embodiment of the present invention provides an image display device including the thin film transistor substrate as a lower substrate.
  • a photosensitive resin composition having advantages of having an appropriate optical density and an appropriate hydrophobic property when a cured film is formed and prevent a color ink from being color-mixed by crossing a light blocking pattern or departed from a position when a color ink is injected by a jetting method using an inkjet print in an area defined by a light blocking pattern, in the case where a pattern having a light blocking property is formed by using the photosensitive resin composition. Therefore, a colored layer can be easily formed by the jetting method using the inkjet print and ultimately, a display defect can be reduced.
  • An exemplary embodiment of the present invention provides a photosensitive resin composition including a cardo-based resin containing a fluorine group.
  • a jetting method using an inkjet print is a method in which a light blocking pattern is formed with a photosensitive resin composition having a light blocking property by a photolithography method and then, a colored layer is formed by jetting each color ink (red, green, and blue) in an area corresponding to each pixel defined by the light blocking pattern.
  • a process can be simplified and a cost can also be reduced as compared with the method of forming the colored layer of red, green, and blue by the photolithography method.
  • a color reproduction ratio may increase according to an injecting volume such that color reproducibility is excellent and thickness and composition of a pattern may be uniformly maintained.
  • a fine circuit pattern is more easily implemented and easy to be applied for a flexible display and the like.
  • a waste of photoresist, solvent, energy, and the like is small such that the forming of the colored layer is an eco-friendly method.
  • the exemplary embodiment of the present invention relates to a photosensitive resin composition capable of forming an available light blocking pattern when the colored layer is formed by the jetting method using the inkjet print.
  • the photosensitive resin composition according to the exemplary embodiment of the present invention includes a cardo-based resin and the cardo-based resin contains a fluorine group.
  • optical density (OD) per unit thickness of 1.0 ⁇ m is 2.0 or more
  • a contact angle for water is 85° or more
  • a contact angle for 2-ethoxyethanol is 35° or more and it is preferred that the contact angle for water may be 85° to 110° and the contact angle for 2-ethoxyethanol may be 35° to 50°.
  • the optical density (OD) is less than 2.0 per unit thickness of 1.0 ⁇ m with respect to the cured film acquired from the photosensitive resin composition, even though the thickness became slightly larger, it may be difficult to achieve an appropriate light blocking effect and when the cured film serves as the light blocking film, the cured film cannot sufficiently express the light blocking property, such that light which penetrates a part other than a transparent pixel electrode not to be controlled may not be blocked.
  • the cured film formed from the photosensitive resin composition according to the exemplary embodiment may have the contact angle for water of 85° or more and the contact angle for 2-ethoxyethanol of 35°or more.
  • the light blocking pattern is generally formed on a glass surface and the color ink is injected in the light blocking pattern, in view of preventing a mixed color and position separation after injecting the color ink, surface tension of the glass surface has to be larger than or at least equal to the surface tension of the color ink and the surface tension of the light blocking pattern has to be smaller than the surface tension of the color ink.
  • the photosensitive resin composition according to an exemplary embodiment of the present invention may have the contact angle for water of 85° to 110° and the contact angle for 2-ethoxyethanol of 35° to 50° in the formation of the cured film.
  • an alkali-soluble acrylic resin binder configuring the photosensitive resin composition a monomer including an acid functional group and a copolymer formed by copolymerization of the monomer and a monomer copolymerized with the monomer may be used.
  • strength of the film may increase as compared with the resin fabricated by a single polymerization.
  • a macromolecular compound fabricated by a macromolecule reaction of the formed copolymer and an ethylene unsaturated compound containing an epoxy group may be used.
  • the alkali-soluble acrylic resin binder may use a copolymer formed by the copolymerization of a monomer including the acid functional group and a monomer copolymerized with the monomer. Further, a macromolecular compound formed by bonding the ethylene unsaturated compound containing an epoxy group in the copolymer structure may be used together with the copolymer.
  • Nonrestrictive examples of the monomer including the acid functional group are (meth)acrylate, crotonic acid, itanconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, stylene sulfonic acid, 5-norbornene-2-carboxylic acid, and the like. They may be used singly or by mixing two or more.
  • the binder resin containing an epoxy group is preferable as the monomer and as a result, it is preferred that the monomer containing the epoxy group is used together with the monomer including the acid functional group in fabricating the alkali-soluble resin.
  • Examples of the monomer containing the epoxy group may be glycidyl acrylate, glycidyl methacrylate, ⁇ -ethyl glycidyl acrylate, ⁇ -n-propyl glycidyl acrylate, ⁇ -n-butyl glycidyl acrylate, 3,4-epoxy butyl acrylate, 3,4-epoxy butyl methacrylate, 6,7-epoxy heptyl acrylate, 6,7-epoxy heptyl methacrylate, ⁇ -ethyl-6,7-epoxy heptyl acrylate, o-vinyl benzyl grycidyl ether, m-vinyl benzyl grycidyl ether, p-vinyl benzyl grycidyl ether, and the like, but they are not limited thereto.
  • the alkali-soluble acrylic binder resin may include a fluorine group.
  • the content of the monomer containing the fluorine group may be controlled according to the content of the fluorine group in the monomer and so as to satisfy the contact angles for water and 2-ethoxyethanol and not to hinder a developing property, a coating property, dispersion stability, it is preferred that the content of fluorine in the alkali-soluble acrylic binder may be controlled by 5 to 50 wt%.
  • the hydrophobic property increases but a processing property may be hindered, such that the content is preferably 5 to 50 wt% with respect to total solid weight of the photosensitive resin composition.
  • the acquired alkali-soluble acrylic binder resin may be included as the binder resin and the hydrophobic property may be implemented by adding a small amount of the resin during a fabricating process of a coloring agent to be described below.
  • the alkali-soluble acrylic binder resin containing the fluorine group is added in the coloring agent, the content thereof is preferably 1 to 30 wt% based on the solid content in view of dispersion of pigment and implementation of hydrophobic property.
  • the photosensitive resin composition according to the exemplary embodiment of the present invention includes a cardo-based binder resin as the binder resin and a compound of the cardo-based binder resin refers to an acrylic binder resin containing a fluorine group in a main chain and is not particularly structurally limited.
  • cardo-based binder resin may be a compound represented by the following chemical formula 1.
  • the X may be a compound represented by the following chemical formula 2.
  • the n is an integer of 1 to 100.
  • the Y may be a first acid anhydride residue selected from maleic anhydride, siccinic anhydride, cis-1,2,3,6-Tetrahydrophthalic anhydride, 3,4,5,6-Tetrahydrophthalic anhydride, phthalic anhydride, itaconic anhydride, 1,2,4-benzenetricarboxylic anhydride, methyl-tetrahydrophthalic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, cis-5-norbonene-endo-2,3-dicarboxylic anhydride, and 1,8-naphthalic anhydride.
  • the Z may be a second acid anhydride residue selected from 1,2,4,5-bezenetetracarboxylic dianhydride, 4,4'-biphthalic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, pyromelitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,4,5-tetracarboxylic anhydide, methylnorbonene-2,3-dicarboxylic anhydride, 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]diphthalic anhydride, 4,4 ⁇ -oxydiphthalic anhydride, ethylene glycol bis (anhydro trimelitate).
  • a functional group having the hydrophobic property may be introduced in the structure of the cardo-based binder resin and particularly, as described above, the fluorine group may be introduced.
  • a method of introducing the fluorine group in a fabricating process of the cardo-based binder resin and an example of a compound used for introduction are not limited and a particular example of the compound may be a compound acquired from the following Reaction Equation 1.
  • R is a C1-C12 alkyl group.
  • the Reaction Equation 1 is an example introducing the fluorine group to the cardo-based binder resin and the cardo-based binder resin containing a fluorine group usable in the exemplary embodiment is not limited.
  • the cardo-based binder resin is preferably 1 to 40 wt% and more preferably about 20 to 30 wt% with respect to a total solid weight of the photosensitive resin composition. If the fluorine group is contained in the cardo-based binder resin, considering the hydrophobic property implementation, the developing property, the coating property, and the dispersion stability, the cardo-based binder resin is preferably 5 to 10 wt% with respect to a total solid weight of the photosensitive resin composition.
  • the photosensitive resin composition is fabricated by using only the cardo-based binder resin, since the cured film having a thickness of 2.2 ⁇ m or more is formed by reacting with the multifunctional monomer having an ethylene unsaturated double bond due to the photo curing, only the surface curing rapidly occurs and a wrinkle due to an inner contraction may occur in the heat curing.
  • the multifunctional monomer having the ethylene unsaturated double bond is included in the photosensitive resin composition according to the exemplary embodiment of the present invention and acts to form a photoresist pattern due to the light.
  • An example of the multifunctional monomer may be a mixture of one or two or more types selected from a group consisting of propylene glycol methacrylate, dipentaerythritol hexacrylate, dipentaerythritol acrylate, neopentyl glycol diacrylate, 1,6-hexan dioldiacrylate, 1,6-hexandiol acrylate tetraethylene glycol methacrylate, bisphenoxy ethylalcohol diacrylate, trihydroxy ethylisocyanurate trimethacrylate, trimethylpropane trimethacrylate, pentaerithritol trimethacrylate, pentaerithritol tetramethacrylate, and dipentaerithritol he
  • the content thereof is preferably in the range of 0.1 to 99 parts by weight with respect to 100 parts by weight shown in Chemical Formula 1 in that the pattern is formed and the binding force with the pigment and particle components increases by crosslinkage due to radical reaction of a photoinitiator by UV to increase optical density.
  • a monomer having the hydrophobic property may be further added in the monomer and the monomer may be selected so as to implement the hydrophobic property while the monomer does not hinder the coating property, an adhesive force, and a labeling property of the photosensitive resin composition.
  • An example thereof may be a fluorine-based epoxy compound classified as CH 2 (O)CHCH 2 (CF 2 ) x CF 3 (herein, x is an integer of 1 to 12 ) and a siloxane-based compound containing a fluorine group, for example, CF 3 (CF 2 ) y Si(OMe) 3 (herein, y is an integer of 1 to 12).
  • the content thereof may vary according to the coating property, the adhesive force, the labeling property, and the hydrophobic property and preferably, may be 1 to 12 wt% based on the total solid content.
  • a photopolymerizable initiator may included in the photosensitive resin composition according to the exemplary embodiment of the present invention and an example of the photopolymerizable initiator may be selected from 1-[9-ethyl-6-(2-methybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1,2-octanedione-1[(4-phenylthio)phenyl]-2-benzoyl-oxime which are oxime ester-based compounds and thioxanetone, 2,4-diethyl thioxanetone, thioxaneton-4-sulfonic acid, benzophenone, 4,4'-bis(diethyl amino)benzophenone, acetophenone, p-dimethylaminoacetophenone, dimethoxyacethoxy benzophenone, 2,2'-dimethoxy-2-phethylacetophenone, p-methoxyacetophenone, 2-
  • the photopolymerizable initiator is preferably included by 1 to 30 wt% of the entire photosensitive resin composition.
  • a solvent may be included in the photosensitive resin composition according to the exemplary embodiment of the present invention and the solvent may be selected and used from propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, methylcellosolve acetate, ethylcellosolve acetate, diethyl glycol methyl acetate, ethylethoxy propionate, methylethoxy propionate, butyl acetate, ethyl acetate, cyclohexanone, acetone, methylisobutylketone, dimethylformamide, N,N ⁇ -dimethylacetamide, N-methylpyrolidinone, dipropylene glycol methylether, toluene, methylcellosolve, and ethylcellosolve.
  • PMEA propylene glycol methyl ether acetate
  • the content thereof may be generally about 20 to 60 wt% of the entire photosensitive resin composition.
  • the solvent may further include a general additive.
  • the photosensitive resin composition according to the exemplary embodiment of the present invention may contain at least two pigment mixing components capable of substantially expressing a black color by being mixed in the coloring agent having the light blocking property.
  • a black pigment is included in the photosensitive resin composition in order to have the light blocking property and an example thereof may use carbon black or titan black.
  • An example of the black pigment may be carbon black or titan black but is not limited thereto.
  • the pigment mixing component may include a red pigment of 10 to 50 wt%, a blue pigment of 10 to 50 wt%, a yellow pigment of 1 to 20 wt%, and a green pigment of 1 to 20 wt% on the basis of the solid content of a total weight of the coloring agent.
  • the pigment mixing component may include a violet pigment of 1 to 20 wt% on the basis of the solid content of the total weight of the coloring agent.
  • the black pigment is preferably added by 10 wt% or less on the basis of the solid content of the total weight of the coloring agent. Since the black pigment has electric conductivity in many cases, dielectric constant increases and the electric characteristic of the cured film may be hindered. Accordingly, in the case where the black pigment is included, a pigment having high resistance is preferably selected and the used amount thereof is more preferably 15 wt% or less based on the solid content of a total weight of the coloring agent.
  • the optical density and the electric resistance of the light blocking film formed from the photosensitive resin composition may vary according to a dispersion degree of the pigment and as a result, the coloring agent may include a pigment dispersing agent.
  • a pigment dispersing agent may use a polymer dispersing agent such as modified polyurethane, modified polyacrylate, modified polyester, modified polyimide, and the like, a surfactant such as phosphoric acid ester, polyester, alkyl amine, and the like.
  • the acrylic dispersing agents as a detailed example, the pigment dispersing agents such as Disperbyk-2000, Disperbyk-2001, LP-N-21116, and LP-N-21208 of BYK chemie Co., Ltd.
  • EFKA-4300, EFKA-4330, EFKA-4340, EFKA-4400, EFKA-4401, EFKA-4402, EFKA-4046 or EFKA-4060 of Ciba Co., Ltd. and the like may be more advantageous in view of stably implementing the dispersion stability, the optical density, and electric characteristic.
  • the content of the pigment dispersing agent is preferably 3 to 20 wt% based on the solid content of the total weight of the coloring agent.
  • the entire amount of the coloring agent is preferably 20 to 80 wt% and more preferably about 30 to 66 wt% with respect to the total weight of the photosensitive resin composition.
  • the content of the mixed pigment is less than 20 wt%, the optical density of the formed light blocking film is low so as not to has a sufficient light blocking property and when the content of the mixed pigment is more than 80 wt%, the amount of the photosensitive resin component decreases and a curing defect occurs such that the developing property may be deteriorated and the residue may be generated.
  • the photosensitive resin composition may be fabricated by mixing (a) a pigment mixture, (b) an alkali-soluble acrylic binder resin, (c) a cardo-based binder resin, (d) a multifunctional monomer having an ethylene unsaturated double bond, (e) a photopolymerizable initiator, if necessary, an organic additive, and (f) a solvent by a mixer and filtering them with a membrane filter of 5 ⁇ m.
  • the photosensitive resin composition is coated on a glass substrate having a clean surface or a glass substrate including a transparent electrode layer (for example, glass substrate deposed with ITO or IZO) by a contactless coating apparatus such as a spin coater (rotary coating apparatus) or a slit coater (no-rotary coating apparatus).
  • a contactless coating apparatus such as a spin coater (rotary coating apparatus) or a slit coater (no-rotary coating apparatus).
  • a silane coupling agent may be mixed and coated on the substrate.
  • the resin coating layer was dried at a temperature of 80 to 120°C, preferably 80 to 100°C for 60 to 150 seconds by using a hot plate or left at room temperature for several hours to several days, or the solvent is removed in a hot-wind heater and an infrared heater for several minutes to several hours (so-called a pre-bake) so as to control a thickness of the coating layer in the range of 1.0 to 5 ⁇ m, and thereafter, actinic energy rays such as infrared rays is exposed in the range of a radiated energy amount of 30 mJ/cm 2 through a mask.
  • the radiated energy amount may vary according to a kind of the used light blocking photosensitive composition.
  • the film acquired by exposing is developed with a developer by an immersion method, a spray method, and the like to form the cured film pattern.
  • the developer used for the development may be organics such as monoethanolamine, diethanolamine, triethanolamine, and the like, or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt, and the like.
  • the post-bake may be performed after developing and more particularly, the post-bake may be performed at 150 to 250°C for 20 to 40 minutes.
  • the light blocking film acquired from the exemplary embodiment of the present invention preferably has an appropriate light blocking property when the content of the fluorine per cured film weight of 1g is about 5 to 50 wt% and satisfies an appropriate hydrophobic property.
  • the cured film acquired as described above has the appropriate light blocking property and satisfies the appropriate hydrophobic property and particularly, when the colored layer is formed by the jetting method using the inkjet print, the cured film may be used for forming the light blocking pattern.
  • the liquid crystal display is exemplified above, but it is not limited.
  • An example of various display devices requiring the colored layer may be a plasma display device, an EL display device, a CRT display device, and the like.
  • the liquid crystal display capable of applying the present invention is not particularly limited and various modes of liquid crystal displays are applied.
  • the display device of the present invention may adopt various kinds of display modes such as ECB(Electrically Controlled Birefringence), TN(Twisted Nematic), IPS(In-PlaneSwitching), FLC(Ferroelectric Liquid Crystal), OCB(Optically Compensatory Bend), STN(Supper Twisted Nematic), VA(Vertically Aligned), HAN(Hybrid Aligned Nematic), GH(Guest Host).
  • the display device with the colored layer formed by the photosensitive resin composition of the present invention may be applied to even a display device having a large screen such as a display for a laptop computer, a television monitor, or the like.
  • 1,2,3,6-tetrahydro phthalic anhydride of 32.57 g was mixed with bisphenol fluorene type epoxy acrylate of 300 g which was acquired as above, slowly heated, and reacted at 120°C for 20 hours to acquire a cardo-based compound (Preparation Examples 1 to 5).
  • a composition component shown in Table 2 was put in a 1000 ml flask and stirred for 30 minutes while blowing nitrogen thereinto. Next, by increasing the temperature slowly, the composition component reacted at 65°C for 4 hours and thereafter, by increasing the temperature to 80°C, the composition component further reacted for 2 hours to synthesize the alkali-soluble acrylic binder resin.
  • Table 2 shown below a content unit is gram.
  • MAA methacrylic acid
  • MMA methyl methacrylate
  • Sty styrene
  • KBM503 3-(methacryl oxypropyl)trimethoxysilane, product of Shin-Etsu Chemical
  • PGMEA propylene glycol monomethyl ether acetate
  • the carbon black (KLBK-103, product of Mikuni Co., Ltd., a particle size of 80 to 120 nm) was put into the cardo-based compound acquired from Preparation Examples 1 to 5 as shown in the following Table 3 and the alkali soluble acryl-based binder resin acquired from Preparation Example6, the multi-functional monomer (dipenta erythritol hexacrylate) and the photopolymerizable initiator were put, the solvent (propylene glycol monomethyl ether acetate (PGMEA)) and other additives (fluorine surfactant and coupling agent) were put, and thereafter, stirred for 3 hours, thereby to prepare the photosensitive resin composition.
  • the multi-functional monomer dipenta erythritol hexacrylate
  • the photopolymerizable initiator were put
  • the solvent propylene glycol monomethyl ether acetate (PGMEA)
  • other additives fluorine surfactant and coupling agent
  • the part by weight is written as the content with respect to the solid content of 100 parts by weight of the entire binder resin (cardo-based binder resin and acrylic binder resin).
  • Carbon black particle size of 90nm to 110nm
  • GPTMS glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
  • the development start time, the pattern critical dimension (resolution), the development pattern stability, the pattern profile, the optical density, and the like were measured by methods as described below with respect to the photosensitive resin composition manufactured by Examples and the result was shown in the following Table 4.
  • the cured film pattern was formed by the following method using the photosensitive resin composition acquired as above.
  • a resin coating layer was formed by coating the cured film pattern on a glass substrate having a clean surface at 500 rpm by using a spin coater. After coating, the resin coating layer was dried at 100°C for 100 seconds by using a hot plate so as to have a thickness of 1.5 ⁇ m of the coating film. Subsequently, actinic energy rays such as infrared rays were exposed in the range of a radiated energy amount of 30 mJ/cm 2 through a mask (with a gap of 100 ⁇ m).
  • the film acquired through the exposure was developed by using a development solution (KOH aqueous solution of 0.032%, 25°C) (a development time: 60 seconds) to form the cured film pattern. After the development, the film was put in a convection oven at 230°C and thereafter, postbaking was performed for 30 minutes.
  • a development solution KOH aqueous solution of 0.032%, 25°C
  • a development time 60 seconds
  • the resin black matrix was developed in a development process, such that the time when the pattern started to be formed was verified with the naked eye.
  • the resin black matrix was coated, prebaked, exposed, developed, and postbaked on the glass substrate and thereafter, any ten places where the critical dimension of the pattern designed on a mask of the substrate was 30 ⁇ m were selected, such that the critical dimension of the pattern was measured by using an optical microscope.
  • optical density of the cured film acquired as above was measured by using a reference in which the optical density is 2.4 with a PMT apparatus of Otsuka Electronics and disclosed in Table 4.
  • the contact angle for 2-ethoxyethanol (99%, product of Aldrich) was measured by using 2-ethoxyethanol instead of water.
  • the product of Kruss CO., Ltd. (model name: E-EM03-T13-01) was used as a measuring equipment for the contact angle.
  • a taper angel was measured by using a SEM with respect to the acquired cured film pattern.
  • the coating, prebaking, and exposure processes of the resin black matrix were performed on the glass substrate and the resin black matrix was developed, such that the pattern started to be formed (the development start time). Thereafter, the development was performed for each predetermined time to verify the critical dimension of the pattern and the linearity of the pattern through an optical microscope. A section in which a decrease degree of the critical dimension was 1 ⁇ m or less with the development time of the unit of 5 s was verified.
  • the development pattern stability of Examples 4, 8, and 12 using the cardo-based binder resin of Preparation Example 5 is within 5s such that it is judged that the development pattern stability is not good as compared with other Examples. Accordingly, when the fluorine content of a predetermined level or more is added, it was judged that the pattern stability of the black matrix was disadvantageous.
  • the pattern profile increased (as compared with Comparative Examples 1,2, and 3 and Examples 1, 5, and 9), but the pattern stability was relatively disadvantageous (as compared with Examples 3, 7, and 11).
  • the most optimal Examples may be 2, 3, 6, 10, and the like in that there were no problems in that the color ink was mixed by crossing the barrier between the barriers of the cured film or the color ink strayed out of the area defined as the barrier and damage on other evaluation values was prevented or minimized.

Abstract

Disclosed is a photosensitive resin composition having advantages of having an appropriate optical density and an appropriate hydrophobic property and preventing color mixing or departure from a position when a color ink is injected by a jetting method using an inkjet print in an area defined as a barrier after forming the barrier (a light blocking film).

Description

PHOTOSENSITIVE RESIN COMPOSITION
The present invention relates to a photosensitive resin composition suitable for forming a light blocking film of an image display device such as a liquid crystal display (hereinafter, referred to as "LCD") and the like.
A liquid crystal display expresses an image by using optical anisotropy and a birefringent characteristic of liquid crystals and when an electric field is applied, the alignment of the liquid crystals varies and a transmission characteristic of light also varies depending on an alignment direction of the liquid crystals which varies.
In general, in the liquid crystal display, two substrates with field generating electrodes, respectively are placed with surfaces where the two electrodes are formed facing each other, a liquid crystal material is injected between the two substrates, and the liquid crystals are moved by an electric field generated by applying voltage to the two electrodes, and as a result, the image is displayed by changed transmittance of light.
In one example of a structure of a thin film transistor liquid crystal display (LCD) that is widely used, the TFT-LCD includes a lower substrate where a thin film transistor and a pixel electrode are arranged, which is called an array substrate and an upper substrate a black matrix and colored layers of three colors of red, green, and blue colors are repeated on the top of a substrate made of plastic or glass, an overcoat with a thickness of 1 to 3 um, which is made of polyimide, polyacrylate, polyurethane, and the like in order to protect a color filter and maintain surface smoothness and an indium tin oxide (ITO) transparent conductive layer in which voltage for driving liquid crystals to the top of the overcoat are formed thereon, which is called a color filter substrate, and liquid crystals injected between the upper and lower substrates. The TFT-LCD has a structure in which a polarizing plate linearly polarizing visible rays (natural light) is attached to each of both surfaces of both substrates. The transistor is turned on by applying voltage to a gate of the TFT forming pixels by an external peripheral circuit to input video voltage into the liquid crystals and thereafter, video information is stored by applying the image voltage and the transistor is turned off to conserve electric charges stored in a liquid crystal charger and an auxiliary charger, thereby displaying a video image for a predetermined time. When voltage is applied to the liquid crystals, the alignment of the liquid crystals varies. When light transmits the liquid crystals of this state, diffraction occurs. The light transmits the polarizing plate to acquire a desired video.
In recent years, an effort to increase the opening aperture by forming the color filter of the liquid crystal display on not the upper substrate, i.e., the color filter substrate but the lower substrate, i.e., the array substrate and reduce a manufacturing cost while decreasing a manufacturing process has been in active progress.
Although considering the structural change, a method of manufacturing the color filter commonly uses a dyeing method, a dispersing method, an electric coating method, a printing method, a jetting method, and the like. A technology of manufacturing the color filter by the jetting method using an inkjet print has merits capable of simplifying a color filter manufacturing process and reducing a manufacturing cost. However, the color filters manufactured by the jetting method using the inkjet print have much difficulty in ensuring uniformity in a glass substrate and a display cell. The cause of a uniformity defect of the color filter mainly occurs due to a difference between the ink amounts ejected by nozzles of an inkjet print head. There is a problem in that the difference between the ink amounts ejected by the nozzles of an inkjet print head is shown as a spot according to an amount of the color ink filled in each pixel area. Further, when the color ink is filed in the light blocking pattern, that is, an inner space corresponding to the pixel area defined by the black matrix, the color ink may be in a dome shape in which the surface thereof is convexly lifted due to a repulsive force between the light blocking pattern and the color ink and a surface tension of the color ink. As described above, a color difference may occur due to a difference between a thickness of the color filter formed at the center of the pixel area and a thickness of the color filter formed at the edge of the pixel area by the color ink filled in the dome shape in the inner space. Accordingly, display quality is deteriorated due to the uniformity defect of the color filter due to the factors.
The present invention has been made in an effort to provide a photosensitive resin composition having an appropriate hydrophobic property while representing an appropriate optical density at the time of forming a cured film. In particular, the present invention has been made in an effort to provide a photosensitive resin composition useful to a barrier material when a colored layer is formed by a jetting method using an inkjet printer.
An exemplary embodiment of the present invention provides a photosensitive resin composition including a cardo-based binder resin, in which the cardo-based binder resin contains a fluorine group.
The photosensitive resin composition may further include an alkali-soluble acrylic binder resin.
The alkali-soluble acrylic binder resin may include a monomer including an acid functional group and a monomer copolymerizable with the monomer as a base monomer.
The alkali-soluble acrylic binder resin may include a monomer containing an epoxy group as a base monomer.
The photosensitive resin composition may include: a multifunctional monomer having an ethylene unsaturated double bond; a photopolymerizable initiator; a pigment; and a solvent.
The content of the alkali-soluble acrylic binder resin may be 5 to 50 wt% with respect to a total solid content of the photosensitive resin composition.
The pigment may include carbon black having a particle size of 50 to 150 nm.
The fluorine content per a weight of 1g of the cured film may be 5 to 50 wt% in forming the cured film.
When a cured film is formed, conditions that an optical density (OD) is 2.0 or more per unit thickness of 1.0 ㎛, a contact angle for water is 85° or more, and a contact angle for 2-ethoxyethanol is 35° or more may be satisfied.
Another exemplary embodiment of the present invention provides a color filter substrate including a black matrix formed by a photolithography method using the photosensitive resin composition.
Yet another exemplary embodiment of the present invention provides a thin film transistor substrate including a black matrix formed by a photolithography method using the photosensitive resin composition.
Still yet another exemplary embodiment of the present invention provides an image display device including the color filter substrate as an upper substrate.
Still yet another exemplary embodiment of the present invention provides an image display device including the thin film transistor substrate as a lower substrate.
According to exemplary embodiments of the present invention, it is possible to provide a photosensitive resin composition having advantages of having an appropriate optical density and an appropriate hydrophobic property when a cured film is formed and prevent a color ink from being color-mixed by crossing a light blocking pattern or departed from a position when a color ink is injected by a jetting method using an inkjet print in an area defined by a light blocking pattern, in the case where a pattern having a light blocking property is formed by using the photosensitive resin composition. Therefore, a colored layer can be easily formed by the jetting method using the inkjet print and ultimately, a display defect can be reduced.
An exemplary embodiment of the present invention provides a photosensitive resin composition including a cardo-based resin containing a fluorine group.
Hereinafter, the present invention will be described below in more detail.
In a manufacture of a color filter, a jetting method using an inkjet print is a method in which a light blocking pattern is formed with a photosensitive resin composition having a light blocking property by a photolithography method and then, a colored layer is formed by jetting each color ink (red, green, and blue) in an area corresponding to each pixel defined by the light blocking pattern.
In the forming of the colored layer by the method described above, a process can be simplified and a cost can also be reduced as compared with the method of forming the colored layer of red, green, and blue by the photolithography method. Further, a color reproduction ratio may increase according to an injecting volume such that color reproducibility is excellent and thickness and composition of a pattern may be uniformly maintained. In addition, a fine circuit pattern is more easily implemented and easy to be applied for a flexible display and the like. In addition, a waste of photoresist, solvent, energy, and the like is small such that the forming of the colored layer is an eco-friendly method.
However, in the jetting method using the inkjet print, accuracy and capacity of the inkjet printing are required and related materials for the inkjet printing are required.
The exemplary embodiment of the present invention relates to a photosensitive resin composition capable of forming an available light blocking pattern when the colored layer is formed by the jetting method using the inkjet print.
The photosensitive resin composition according to the exemplary embodiment of the present invention includes a cardo-based resin and the cardo-based resin contains a fluorine group.
When a cured film is formed with the photosensitive resin composition, it is satisfied that optical density (OD) per unit thickness of 1.0㎛ is 2.0 or more, a contact angle for water is 85° or more, and a contact angle for 2-ethoxyethanol is 35° or more and it is preferred that the contact angle for water may be 85° to 110° and the contact angle for 2-ethoxyethanol may be 35° to 50°.
If the optical density (OD) is less than 2.0 per unit thickness of 1.0 ㎛ with respect to the cured film acquired from the photosensitive resin composition, even though the thickness became slightly larger, it may be difficult to achieve an appropriate light blocking effect and when the cured film serves as the light blocking film, the cured film cannot sufficiently express the light blocking property, such that light which penetrates a part other than a transparent pixel electrode not to be controlled may not be blocked.
Further, the cured film formed from the photosensitive resin composition according to the exemplary embodiment may have the contact angle for water of 85° or more and the contact angle for 2-ethoxyethanol of 35°or more.
In the formation of cured film, when the contact angle for water is smaller than 85° there are problems in that ink in a pixel area overflows or an amount of filled color ink varies in the ink jetting.
Further, when the contact angle for 2-ethoxyethanol is smaller than 35° there are problems in that ink in a pixel area overflows or an amount of filled color ink varies in the ink jetting.
Since the light blocking pattern is generally formed on a glass surface and the color ink is injected in the light blocking pattern, in view of preventing a mixed color and position separation after injecting the color ink, surface tension of the glass surface has to be larger than or at least equal to the surface tension of the color ink and the surface tension of the light blocking pattern has to be smaller than the surface tension of the color ink.
In the viewpoint, preferably, the photosensitive resin composition according to an exemplary embodiment of the present invention may have the contact angle for water of 85° to 110° and the contact angle for 2-ethoxyethanol of 35° to 50° in the formation of the cured film.
Meanwhile, as an alkali-soluble acrylic resin binder configuring the photosensitive resin composition, a monomer including an acid functional group and a copolymer formed by copolymerization of the monomer and a monomer copolymerized with the monomer may be used. In the case of the copolymerization, strength of the film may increase as compared with the resin fabricated by a single polymerization. In addition, a macromolecular compound fabricated by a macromolecule reaction of the formed copolymer and an ethylene unsaturated compound containing an epoxy group may be used.
That is, the alkali-soluble acrylic resin binder may use a copolymer formed by the copolymerization of a monomer including the acid functional group and a monomer copolymerized with the monomer. Further, a macromolecular compound formed by bonding the ethylene unsaturated compound containing an epoxy group in the copolymer structure may be used together with the copolymer.
Nonrestrictive examples of the monomer including the acid functional group are (meth)acrylate, crotonic acid, itanconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, stylene sulfonic acid, 5-norbornene-2-carboxylic acid, and the like. They may be used singly or by mixing two or more.
In particular, considering high alkali-resistance of the cured film, the binder resin containing an epoxy group is preferable as the monomer and as a result, it is preferred that the monomer containing the epoxy group is used together with the monomer including the acid functional group in fabricating the alkali-soluble resin.
Examples of the monomer containing the epoxy group may be glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxy butyl acrylate, 3,4-epoxy butyl methacrylate, 6,7-epoxy heptyl acrylate, 6,7-epoxy heptyl methacrylate, α-ethyl-6,7-epoxy heptyl acrylate, o-vinyl benzyl grycidyl ether, m-vinyl benzyl grycidyl ether, p-vinyl benzyl grycidyl ether, and the like, but they are not limited thereto.
Further, when the cured film is formed from the photosensitive resin composition of the exemplary embodiment, in view of implement a hydrophobic property, the alkali-soluble acrylic binder resin may include a fluorine group.
In this case, the monomer containing an available fluorine group can be copolymerized with other monomers and is not particularly limited so long as it has one carbon-double bond, but as an example, the monomer may be CH2=CHC(O)OCHCH2(CF2)xCF3 (herein, x is an integer of 1 to 12).
The content of the monomer containing the fluorine group may be controlled according to the content of the fluorine group in the monomer and so as to satisfy the contact angles for water and 2-ethoxyethanol and not to hinder a developing property, a coating property, dispersion stability, it is preferred that the content of fluorine in the alkali-soluble acrylic binder may be controlled by 5 to 50 wt%.
As the content of the alkali-soluble acrylic binder resin including the fluorine group increases, the hydrophobic property increases but a processing property may be hindered, such that the content is preferably 5 to 50 wt% with respect to total solid weight of the photosensitive resin composition.
The acquired alkali-soluble acrylic binder resin may be included as the binder resin and the hydrophobic property may be implemented by adding a small amount of the resin during a fabricating process of a coloring agent to be described below.
If the alkali-soluble acrylic binder resin containing the fluorine group is added in the coloring agent, the content thereof is preferably 1 to 30 wt% based on the solid content in view of dispersion of pigment and implementation of hydrophobic property.
Meanwhile, if the photosensitive resin composition is fabricated by using only the alkali-soluble acrylic binder resin, a large quantity of a multifunctional monomer has to be used when the light blocking film having the thickness of 2.2㎛ or more is formed and as a result, surface curing due to photo curing rapidly occurs such that a crease may occur in heat curing. The photosensitive resin composition according to the exemplary embodiment of the present invention includes a cardo-based binder resin as the binder resin and a compound of the cardo-based binder resin refers to an acrylic binder resin containing a fluorine group in a main chain and is not particularly structurally limited.
An example of the cardo-based binder resin may be a compound represented by the following chemical formula 1.
[Chemical Formula 1]
Figure PCTKR2011007208-appb-I000001
Herein, the X may be a compound represented by the following chemical formula 2. In addition, the n is an integer of 1 to 100.
[Chemical Formula 2]
Figure PCTKR2011007208-appb-I000002
Further, the Y may be a first acid anhydride residue selected from maleic anhydride, siccinic anhydride, cis-1,2,3,6-Tetrahydrophthalic anhydride, 3,4,5,6-Tetrahydrophthalic anhydride, phthalic anhydride, itaconic anhydride, 1,2,4-benzenetricarboxylic anhydride, methyl-tetrahydrophthalic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, cis-5-norbonene-endo-2,3-dicarboxylic anhydride, and 1,8-naphthalic anhydride.
Further, the Z may be a second acid anhydride residue selected from 1,2,4,5-bezenetetracarboxylic dianhydride, 4,4'-biphthalic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, pyromelitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,4,5-tetracarboxylic anhydide, methylnorbonene-2,3-dicarboxylic anhydride, 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]diphthalic anhydride, 4,4`-oxydiphthalic anhydride, ethylene glycol bis (anhydro trimelitate).
A functional group having the hydrophobic property may be introduced in the structure of the cardo-based binder resin and particularly, as described above, the fluorine group may be introduced.
A method of introducing the fluorine group in a fabricating process of the cardo-based binder resin and an example of a compound used for introduction are not limited and a particular example of the compound may be a compound acquired from the following Reaction Equation 1.
(Reaction Equation 1)
Figure PCTKR2011007208-appb-I000003
Herein, R is a C1-C12 alkyl group.
The Reaction Equation 1 is an example introducing the fluorine group to the cardo-based binder resin and the cardo-based binder resin containing a fluorine group usable in the exemplary embodiment is not limited.
The cardo-based binder resin is preferably 1 to 40 wt% and more preferably about 20 to 30 wt% with respect to a total solid weight of the photosensitive resin composition. If the fluorine group is contained in the cardo-based binder resin, considering the hydrophobic property implementation, the developing property, the coating property, and the dispersion stability, the cardo-based binder resin is preferably 5 to 10 wt% with respect to a total solid weight of the photosensitive resin composition.
However, if the photosensitive resin composition is fabricated by using only the cardo-based binder resin, since the cured film having a thickness of 2.2㎛ or more is formed by reacting with the multifunctional monomer having an ethylene unsaturated double bond due to the photo curing, only the surface curing rapidly occurs and a wrinkle due to an inner contraction may occur in the heat curing.
The multifunctional monomer having the ethylene unsaturated double bond is included in the photosensitive resin composition according to the exemplary embodiment of the present invention and acts to form a photoresist pattern due to the light. An example of the multifunctional monomer may be a mixture of one or two or more types selected from a group consisting of propylene glycol methacrylate, dipentaerythritol hexacrylate, dipentaerythritol acrylate, neopentyl glycol diacrylate, 1,6-hexan dioldiacrylate, 1,6-hexandiol acrylate tetraethylene glycol methacrylate, bisphenoxy ethylalcohol diacrylate, trihydroxy ethylisocyanurate trimethacrylate, trimethylpropane trimethacrylate, pentaerithritol trimethacrylate, pentaerithritol tetramethacrylate, and dipentaerithritol hexamethacrylate.
The content thereof is preferably in the range of 0.1 to 99 parts by weight with respect to 100 parts by weight shown in Chemical Formula 1 in that the pattern is formed and the binding force with the pigment and particle components increases by crosslinkage due to radical reaction of a photoinitiator by UV to increase optical density.
In the exemplary embodiment of the present invention, a monomer having the hydrophobic property may be further added in the monomer and the monomer may be selected so as to implement the hydrophobic property while the monomer does not hinder the coating property, an adhesive force, and a labeling property of the photosensitive resin composition.
An example thereof may be a fluorine-based epoxy compound classified as CH2(O)CHCH2(CF2)xCF3 (herein, x is an integer of 1 to 12 ) and a siloxane-based compound containing a fluorine group, for example, CF3(CF2)ySi(OMe)3 (herein, y is an integer of 1 to 12).
When the monomer is added as an additive, the content thereof may vary according to the coating property, the adhesive force, the labeling property, and the hydrophobic property and preferably, may be 1 to 12 wt% based on the total solid content.
A photopolymerizable initiator may included in the photosensitive resin composition according to the exemplary embodiment of the present invention and an example of the photopolymerizable initiator may be selected from 1-[9-ethyl-6-(2-methybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1,2-octanedione-1[(4-phenylthio)phenyl]-2-benzoyl-oxime which are oxime ester-based compounds and thioxanetone, 2,4-diethyl thioxanetone, thioxaneton-4-sulfonic acid, benzophenone, 4,4'-bis(diethyl amino)benzophenone, acetophenone, p-dimethylaminoacetophenone, dimethoxyacethoxy benzophenone, 2,2'-dimethoxy-2-phethylacetophenone, p-methoxyacetophenone, 2-methyl[4-(methylthio)phenyl]-2-morpholino-1-prophanone, 2-benzil-2-diethylamino-1-(4-morpholinophenyl)-butane-1-on, 2-hydroxy-2-methyl-1-phenylpropane-1-on, ketones such as 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, and the like, quinones such as anthraquinone, 1,4-naphthoquinone, and the like; halogen compounds such as 1,3,5-tris(trichrloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2-chlorophenyl)-s-triazine, 1,3-bis(trichlorophenyl)-s-triazine, phenacylchloride, tribromomethyl phenylsulfone, tris(trichloromethyl)-s-triazine, peroxide such as di-t-butyl peroxide, and acyl phosphine oxides such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide).
The photopolymerizable initiator is preferably included by 1 to 30 wt% of the entire photosensitive resin composition.
A solvent may be included in the photosensitive resin composition according to the exemplary embodiment of the present invention and the solvent may be selected and used from propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, methylcellosolve acetate, ethylcellosolve acetate, diethyl glycol methyl acetate, ethylethoxy propionate, methylethoxy propionate, butyl acetate, ethyl acetate, cyclohexanone, acetone, methylisobutylketone, dimethylformamide, N,N`-dimethylacetamide, N-methylpyrolidinone, dipropylene glycol methylether, toluene, methylcellosolve, and ethylcellosolve.
The content thereof may be generally about 20 to 60 wt% of the entire photosensitive resin composition.
In addition, if necessary, the solvent may further include a general additive.
The photosensitive resin composition according to the exemplary embodiment of the present invention may contain at least two pigment mixing components capable of substantially expressing a black color by being mixed in the coloring agent having the light blocking property.
A black pigment is included in the photosensitive resin composition in order to have the light blocking property and an example thereof may use carbon black or titan black. An example of the black pigment may be carbon black or titan black but is not limited thereto.
The pigment mixing component may include a red pigment of 10 to 50 wt%, a blue pigment of 10 to 50 wt%, a yellow pigment of 1 to 20 wt%, and a green pigment of 1 to 20 wt% on the basis of the solid content of a total weight of the coloring agent. In addition, the pigment mixing component may include a violet pigment of 1 to 20 wt% on the basis of the solid content of the total weight of the coloring agent. In addition, the black pigment is preferably added by 10 wt% or less on the basis of the solid content of the total weight of the coloring agent. Since the black pigment has electric conductivity in many cases, dielectric constant increases and the electric characteristic of the cured film may be hindered. Accordingly, in the case where the black pigment is included, a pigment having high resistance is preferably selected and the used amount thereof is more preferably 15 wt% or less based on the solid content of a total weight of the coloring agent.
Meanwhile, the optical density and the electric resistance of the light blocking film formed from the photosensitive resin composition may vary according to a dispersion degree of the pigment and as a result, the coloring agent may include a pigment dispersing agent. An example of the pigment dispersing agent may use a polymer dispersing agent such as modified polyurethane, modified polyacrylate, modified polyester, modified polyimide, and the like, a surfactant such as phosphoric acid ester, polyester, alkyl amine, and the like. Even among them, the acrylic dispersing agents, as a detailed example, the pigment dispersing agents such as Disperbyk-2000, Disperbyk-2001, LP-N-21116, and LP-N-21208 of BYK chemie Co., Ltd. , EFKA-4300, EFKA-4330, EFKA-4340, EFKA-4400, EFKA-4401, EFKA-4402, EFKA-4046 or EFKA-4060 of Ciba Co., Ltd. and the like may be more advantageous in view of stably implementing the dispersion stability, the optical density, and electric characteristic.
However, when the pigment dispersing agent is excessively included, the dispersion stability is deteriorated or the pattern stability is deteriorated due to the degradation of a specific functional group. Accordingly, the content of the pigment dispersing agent is preferably 3 to 20 wt% based on the solid content of the total weight of the coloring agent.
The entire amount of the coloring agent is preferably 20 to 80 wt% and more preferably about 30 to 66 wt% with respect to the total weight of the photosensitive resin composition. When the content of the mixed pigment is less than 20 wt%, the optical density of the formed light blocking film is low so as not to has a sufficient light blocking property and when the content of the mixed pigment is more than 80 wt%, the amount of the photosensitive resin component decreases and a curing defect occurs such that the developing property may be deteriorated and the residue may be generated.
The photosensitive resin composition may be fabricated by mixing (a) a pigment mixture, (b) an alkali-soluble acrylic binder resin, (c) a cardo-based binder resin, (d) a multifunctional monomer having an ethylene unsaturated double bond, (e) a photopolymerizable initiator, if necessary, an organic additive, and (f) a solvent by a mixer and filtering them with a membrane filter of 5㎛.
The photosensitive resin composition is coated on a glass substrate having a clean surface or a glass substrate including a transparent electrode layer (for example, glass substrate deposed with ITO or IZO) by a contactless coating apparatus such as a spin coater (rotary coating apparatus) or a slit coater (no-rotary coating apparatus).
In the fabrication and coating, in order to improve adhesivity of the substrate and the photosensitive resin composition, a silane coupling agent may be mixed and coated on the substrate.
After coating, the resin coating layer was dried at a temperature of 80 to 120℃, preferably 80 to 100℃ for 60 to 150 seconds by using a hot plate or left at room temperature for several hours to several days, or the solvent is removed in a hot-wind heater and an infrared heater for several minutes to several hours (so-called a pre-bake) so as to control a thickness of the coating layer in the range of 1.0 to 5㎛, and thereafter, actinic energy rays such as infrared rays is exposed in the range of a radiated energy amount of 30 mJ/cm2 through a mask. The radiated energy amount may vary according to a kind of the used light blocking photosensitive composition. The film acquired by exposing is developed with a developer by an immersion method, a spray method, and the like to form the cured film pattern. The developer used for the development may be organics such as monoethanolamine, diethanolamine, triethanolamine, and the like, or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt, and the like.
The post-bake may be performed after developing and more particularly, the post-bake may be performed at 150 to 250℃ for 20 to 40 minutes.
The light blocking film acquired from the exemplary embodiment of the present invention preferably has an appropriate light blocking property when the content of the fluorine per cured film weight of 1g is about 5 to 50 wt% and satisfies an appropriate hydrophobic property.
The cured film acquired as described above has the appropriate light blocking property and satisfies the appropriate hydrophobic property and particularly, when the colored layer is formed by the jetting method using the inkjet print, the cured film may be used for forming the light blocking pattern.
As the display device capable of using by forming the colored layer with the photosensitive resin composition, the liquid crystal display is exemplified above, but it is not limited. An example of various display devices requiring the colored layer may be a plasma display device, an EL display device, a CRT display device, and the like.
Further, the liquid crystal display capable of applying the present invention is not particularly limited and various modes of liquid crystal displays are applied. The display device of the present invention may adopt various kinds of display modes such as ECB(Electrically Controlled Birefringence), TN(Twisted Nematic), IPS(In-PlaneSwitching), FLC(Ferroelectric Liquid Crystal), OCB(Optically Compensatory Bend), STN(Supper Twisted Nematic), VA(Vertically Aligned), HAN(Hybrid Aligned Nematic), GH(Guest Host). As described above, the display device with the colored layer formed by the photosensitive resin composition of the present invention may be applied to even a display device having a large screen such as a display for a laptop computer, a television monitor, or the like.
Hereinafter, examples and comparative examples of the present invention will be described. However, the examples described below are only an exemplary embodiment of the present invention and the present invention is not limited to the examples described below.
<Preparation Examples 1 to 5> Synthesis example of cardo-based binder resin
In a 1L flask, bisphenol fluorene type epoxy compound, acrylate, perfluoroheptanoic acid, triethylamine, and hydroquinone were added to propylene glycol methyl ether acetate (PGMEA) as a solvent by components as disclosed in the following Table 1 and thereafter, heated and dissolved at 90 to 100℃. While the solution was cloudy, the temperature of the solution slowly increased and thereafter, the solution was completely dissolved at 100℃. When the solution was completely dissolved, the temperature of the solution was maintained to 90℃ and nitrogen was injected therein at a speed of 25 ml/min for 12 hours until an acid value reaches a target.
By measuring the acid value, until the acid value was less than 3.0 mgKOH/g, heating and stirring was continued. In addition, by cooling the solution up to room temperature, colorless and transparent bisphenol fluorene type epoxy acrylate was acquired. In Table 1 shown below, a content unit is gram.
Table 1
Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5
Bisphenol fluorene type epoxy compound 232 232 232 232 232
Acrylate 72 64.8 57.6 50.4 43.2
Perfluoroheptanoic acid - 7.2 14.4 21.6 28.8
triethylamine 4.56 4.56 4.56 4.56 4.56
Hydroquinone 0.1 0.1 0.1 0.1 0.1
PGMEA(solvent) 456 456 456 456 456
1,2,3,6-tetrahydro phthalic anhydride of 32.57 g was mixed with bisphenol fluorene type epoxy acrylate of 300 g which was acquired as above, slowly heated, and reacted at 120℃ for 20 hours to acquire a cardo-based compound (Preparation Examples 1 to 5).
<Chemical Formula 3>
Figure PCTKR2011007208-appb-I000004
<Preparation example 6> Synthesis example of alkali-soluble acrylic binder resin
A composition component shown in Table 2 was put in a 1000 ml flask and stirred for 30 minutes while blowing nitrogen thereinto. Next, by increasing the temperature slowly, the composition component reacted at 65℃ for 4 hours and thereafter, by increasing the temperature to 80℃, the composition component further reacted for 2 hours to synthesize the alkali-soluble acrylic binder resin. In Table 2 shown below, a content unit is gram.
Table 2
Preparation Example 6
MAA 38.13
MMA 108.82
Sty 32.45
KBM503 11.45
Initiator 19.09
PGMEA 490.00
(Note) MAA: methacrylic acid, MMA: methyl methacrylate, Sty: styrene
KBM503: 3-(methacryl oxypropyl)trimethoxysilane, product of Shin-Etsu Chemical
Initiator: azobisisobutyronitrile
PGMEA: propylene glycol monomethyl ether acetate
<Example>
The carbon black (KLBK-103, product of Mikuni Co., Ltd., a particle size of 80 to 120 nm) was put into the cardo-based compound acquired from Preparation Examples 1 to 5 as shown in the following Table 3 and the alkali soluble acryl-based binder resin acquired from Preparation Example6, the multi-functional monomer (dipenta erythritol hexacrylate) and the photopolymerizable initiator were put, the solvent (propylene glycol monomethyl ether acetate (PGMEA)) and other additives (fluorine surfactant and coupling agent) were put, and thereafter, stirred for 3 hours, thereby to prepare the photosensitive resin composition.
In the following Table 3, the part by weight is written as the content with respect to the solid content of 100 parts by weight of the entire binder resin (cardo-based binder resin and acrylic binder resin).
Table 3
Example and Comparative Example Cardo-based binder resin(Preparation Examples 1 to 5) Alkali-soluble acrylic binder resin(Preparation Example 6) Carbon black(KLBK-103) Photoinitiator Solvent(PGMEA) Multifunctional monomer(DPHA) Additive(GPTMS)
Preparation Example Part of weight
Comparative Example 1 Preparation Example 1 100 0 226 21 240 20 2.5
Comparative Example 2 Preparation Example 1 90 10 226 21 240 20 2.5
Comparative Example 3 Preparation Example 1 80 20 226 21 240 20 2.5
Example 1 Preparation Example 2 100 0 226 21 240 20 2.5
Example2 Preparation Example 3 100 0 226 21 240 20 2.5
Example 3 Preparation Example 4 100 0 226 21 240 20 2.5
Example 4 Preparation Example 5 100 0 226 21 240 20 2.5
Example 5 Preparation Example 2 90 10 226 21 240 20 2.5
Example 6 Preparation Example 3 90 10 226 21 240 20 2.5
Example 7 Preparation Example 4 90 10 226 21 240 20 2.5
Example 8 Preparation Example 5 90 10 226 21 240 20 2.5
Example 9 Preparation Example 2 80 20 226 21 240 20 2.5
Example 10 Preparation Example 3 80 20 226 21 240 20 2.5
Example 11 Preparation Example 4 80 20 226 21 240 20 2.5
Example 12 Preparation Example 5 80 20 226 21 240 20 2.5
(Note)Resin component: 18 wt% of the entire composition
DPHA:dipenta erythritol hexacrylate
Carbon black: particle size of 90nm to 110nm
PGMEA: propylene glycol methylether acetate
GPTMS: glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
The development start time, the pattern critical dimension (resolution), the development pattern stability, the pattern profile, the optical density, and the like were measured by methods as described below with respect to the photosensitive resin composition manufactured by Examples and the result was shown in the following Table 4.
(1) Cured film forming method
The cured film pattern was formed by the following method using the photosensitive resin composition acquired as above. A resin coating layer was formed by coating the cured film pattern on a glass substrate having a clean surface at 500 rpm by using a spin coater. After coating, the resin coating layer was dried at 100℃ for 100 seconds by using a hot plate so as to have a thickness of 1.5㎛ of the coating film. Subsequently, actinic energy rays such as infrared rays were exposed in the range of a radiated energy amount of 30 mJ/cm2 through a mask (with a gap of 100 ㎛). The film acquired through the exposure was developed by using a development solution (KOH aqueous solution of 0.032%, 25℃) (a development time: 60 seconds) to form the cured film pattern. After the development, the film was put in a convection oven at 230℃ and thereafter, postbaking was performed for 30 minutes.
(2) Development start time
At the development start time, coating, prebaking, and exposure processes of the resin black matrix were performed on the glass substrate and thereafter, the resin black matrix was developed in a development process, such that the time when the pattern started to be formed was verified with the naked eye.
(3) Pattern critical dimension (resolution)
In a pattern critical dimension, the resin black matrix was coated, prebaked, exposed, developed, and postbaked on the glass substrate and thereafter, any ten places where the critical dimension of the pattern designed on a mask of the substrate was 30㎛ were selected, such that the critical dimension of the pattern was measured by using an optical microscope.
(4) Optical density
The optical density of the cured film acquired as above was measured by using a reference in which the optical density is 2.4 with a PMT apparatus of Otsuka Electronics and disclosed in Table 4.
(5) Method of measuring contact angle of cured film
Water (deionic water) of 5㎕ was dropped on the cured film acquired as above by using a syringe such that the contact angle for water (deionic water) was measured.
Further, the contact angle for 2-ethoxyethanol (99%, product of Aldrich) was measured by using 2-ethoxyethanol instead of water. The product of Kruss CO., Ltd. (model name: E-EM03-T13-01) was used as a measuring equipment for the contact angle.
(6) Measurement of pattern profile
A taper angel was measured by using a SEM with respect to the acquired cured film pattern.
(7) Residue
Whether the residue was present after development was verified by using an SEM.
(8) Development pattern stability
In the case of the development pattern stability, the coating, prebaking, and exposure processes of the resin black matrix were performed on the glass substrate and the resin black matrix was developed, such that the pattern started to be formed (the development start time). Thereafter, the development was performed for each predetermined time to verify the critical dimension of the pattern and the linearity of the pattern through an optical microscope. A section in which a decrease degree of the critical dimension was 1 ㎛ or less with the development time of the unit of 5 s was verified.
Table 4
Example and Comparative example Contact angle (°) Taper Angle (°) Residue generation Development start time Development start time Development pattern stability Optical density( /㎛)
DIW (water) 2-ethoxyethanol
Comparative Example 1 72 21 38 None 35 40 15s 4.0
Comparative Example 2 73 20 45 None 40 36 15s 4.0
Comparative Example 3 71 23 50 None 45 34 15s 4.0
Example 1 79 34 37 None 35 40 15s 4.0
Example2 92 44 38 None 35 40 15s 4.0
Example 3 100 48 38 None 35 40 15s 4.0
Example 4 118 59 38 Generation 35 40 5s 4.0
Example 5 76 31 45 None 40 36 15s 4.0
Example 6 89 42 45 None 40 36 15s 4.0
Example 7 95 46 45 None 40 36 10s 4.0
Example 8 114 56 45 Generation 40 36 5s 4.0
Example 9 74 30 50 None 45 35 15s 4.0
Example 10 85 40 50 None 45 35 15s 4.0
Example 11 88 43 50 None 45 35 5s 4.0
Example 12 111 53 50 Generation 45 35 5s 4.0
From the result of Table 4, when the contact angles for water and 2-ethoxyethanol of the cured film acquired from Examples 1, 5, and 9 were measured, as the fluorine content in the cardo-based binder increased, the contact angles increased.
Judging from the above result, when the color ink was injected by the jetting method using the inkjet print after forming the light blocking film, in the cured films of Examples 2,3,4,6,7,8,10,11, and 12, it may be judged that there are no problems in that the color ink is mixed by crossing the barrier or the color ink strays out of the area defined as the barrier.
Further, the development pattern stability of Examples 4, 8, and 12 using the cardo-based binder resin of Preparation Example 5 is within 5s such that it is judged that the development pattern stability is not good as compared with other Examples. Accordingly, when the fluorine content of a predetermined level or more is added, it was judged that the pattern stability of the black matrix was disadvantageous.
Further, as the content of the alkali-soluble acrylic binder resin increased in the black matrix composition, the pattern profile increased (as compared with Comparative Examples 1,2, and 3 and Examples 1, 5, and 9), but the pattern stability was relatively disadvantageous (as compared with Examples 3, 7, and 11).
From the above result, when the contact angle for water was 85° or more and the contact angle for 2-ethoxyethanol was 40° or more, the most optimal Examples may be 2, 3, 6, 10, and the like in that there were no problems in that the color ink was mixed by crossing the barrier between the barriers of the cured film or the color ink strayed out of the area defined as the barrier and damage on other evaluation values was prevented or minimized.
Simple modifications and changes and modifications of the present invention can be easily made by those skilled in the art and it can be understood that these modifications and changes are included in the scope of the present invention.

Claims (13)

  1. A photosensitive resin composition, comprising: a cardo-based binder resin, wherein the cardo-based binder resin contains a fluorine group.
  2. The photosensitive resin composition of claim 1, further comprising an alkali-soluble acrylic binder resin.
  3. The photosensitive resin composition of claim 2, wherein the alkali-soluble acrylic binder resin includes a monomer including an acid functional group and a monomer copolymerizable with the monomer as a base monomer.
  4. The photosensitive resin composition of claim 2, wherein the alkali-soluble acrylic binder resin includes a monomer containing an epoxy group as a base monomer.
  5. The photosensitive resin composition of claim 1, wherein the photosensitive resin composition includes: a multifunctional monomer having an ethylene unsaturated double bond; a photopolymerizable initiator; a pigment; and a solvent.
  6. The photosensitive resin composition of claim 2, wherein the content of the alkali-soluble acrylic binder resin is 5 to 50 wt% with respect to a total solid content of the photosensitive resin composition.
  7. The photosensitive resin composition of claim 5, wherein the pigment includes carbon black having a particle size of 50 to 150 nm.
  8. The photosensitive resin composition of claim 1, wherein the fluorine content per a weight of 1g of the cured film is 5 to 50 wt% in forming the cured film.
  9. The photosensitive resin composition of claim 1, wherein in forming the cured film, conditions that an optical density (OD) is 2.0 or more per unit thickness of 1.0 ㎛, a contact angle for water is 85° or more, and a contact angle for 2-ethoxyethanol is 35° or more are satisfied.
  10. A color filter substrate including a black matrix formed by a photolithography method using the photosensitive resin composition of claim 1.
  11. A thin film transistor substrate including a black matrix formed by a photolithography method using the photosensitive resin composition of claim 1.
  12. An image display device including the color filter substrate of claim 10 as an upper substrate.
  13. An image display device including the thin film transistor substrate of claim 11 as a lower substrate.
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KR100838452B1 (en) * 2007-03-22 2008-06-16 제일모직주식회사 Cardo-based resin having amide bond and photosensitive resin composition comprising the same and black matrix prepared therefrom
KR20100065615A (en) * 2008-12-08 2010-06-17 삼성전자주식회사 Liquid crystal display, panel therefor, and manufacturing method thereof

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KR100725023B1 (en) * 2006-10-16 2007-06-07 제일모직주식회사 Cardo type resin-containing resist composition and method for preparing a pattern by the same and a color filter using the same
KR100838452B1 (en) * 2007-03-22 2008-06-16 제일모직주식회사 Cardo-based resin having amide bond and photosensitive resin composition comprising the same and black matrix prepared therefrom
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