WO2013051805A2 - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
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- WO2013051805A2 WO2013051805A2 PCT/KR2012/007648 KR2012007648W WO2013051805A2 WO 2013051805 A2 WO2013051805 A2 WO 2013051805A2 KR 2012007648 W KR2012007648 W KR 2012007648W WO 2013051805 A2 WO2013051805 A2 WO 2013051805A2
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- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- photosensitive resin
- column spacer
- acrylic binder
- weight
- Prior art date
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Classifications
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- 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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- 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
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- 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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13396—Spacers having different sizes
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- 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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13398—Spacer materials; Spacer properties
-
- 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
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
- G02F2202/023—Materials and properties organic material polymeric curable
Definitions
- Liquid crystal display devices render images using the optical anisotropy and birefringence of liquid crystal molecules.
- the array of liquid crystals is changed, and light transparency may also vary depending on changes in the array of the liquid crystals.
- a liquid crystal display device is configured such that two substrates respectively having electrodes which produce electric power are disposed so that surfaces on which the two electrodes are formed face each other, a liquid crystal material is injected between the two substrates, and voltage is applied to the two electrodes to produce an electric field which allows the liquid crystal molecules to move, thereby displaying an image depending on changes in light transmittance.
- a further object of the present invention is to provide a photosensitive resin composition which may simultaneously form a gap column spacer pattern and a pressure column spacer pattern lower than the gap column spacer pattern on an upper substrate using masks having different transmittances.
- Another embodiment of the present invention provides a display substrate, comprising a black matrix and a column spacer formed using the above photosensitive resin composition.
- a photosensitive resin composition comprises 100 parts by weight of an acrylic binder resin, 10 ⁇ 20 parts by weight of a pigment and 10 ⁇ 15 parts by weight of a photoinitiator, and the acrylic binder resin includes a first acrylic binder resin having an acid value of 50 ⁇ 90 mg(KOH)/g and a weight average molecular weight of 8,000 ⁇ 13,000 g/mol and a second acrylic binder resin having an acid value of 100 ⁇ 150 mg(KOH)/g and a weight average molecular weight of 4,000 ⁇ 7,000 g/mol.
- the first acrylic binder resin and the second acrylic binder resin may include a polymer compound formed by binding the above copolymer with an ethylenically unsaturated compound containing an epoxy group.
- the ethylenically unsaturated bond provided in the acrylic binder resin may carry out a crosslinker function upon polymerization via photo exposure, thus enhancing adhesion to a substrate and coating properties.
- the acrylic binder resin includes two or more kinds of acrylic binders having different weight average molecular weights and acid values, thus maintaining pattern stability of a cured film for a column spacer upon developing and easily adjusting the height of a cured film for a column spacer in a developing process depending on the transmittance of a mask upon photo exposure, whereby spacers having different heights may be formed via a single process.
- the photosensitive resin composition of the invention may include a multifunctional monomer, which functions to form a photoresist phase using light and is specifically one or a mixture of two or more selected from among propyleneglycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentylglycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol acrylate tetraethyleneglcyol methacrylate, bisphenoxy ethylalcohol diacrylate, trishydroxyethylisocyanurate trimethacrylate, trimethylpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate and dipentaerythritol hexamethacrylate.
- a multifunctional monomer which functions to form a photo
- the black matrix and the column spacer may be formed at the same time to have a step corresponding to a predetermined height via patterning by means of a slit mask or a half-tone mask, and also a column spacer may be further formed at a position where a black matrix is formed, or a black matrix to be formed may be provided to function as a column spacer. Also, column spacers having different heights may be formed at the same time.
- the development initiation time was determined in such a manner that a resin black matrix was applied on a glass substrate, prebaked and then photoexposed, after which the time into the developing process at which the resin black matrix was developed and at which the pattern began to form was measured with the naked eye.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Liquid Crystal (AREA)
- Materials For Photolithography (AREA)
Abstract
This invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition wherein two or more kinds of acrylic binder resins having different weight average molecular weights and acid values are contained at a specific ratio, and a cured film is formed therefrom, whereby in a structure in which a color resist is formed on an array substrate (a lower substrate) upon fabrication of a liquid crystal display device, a black matrix and a dual type column spacer can be formed at the same time on an upper substrate.
Description
The present invention relates to a photosensitive resin composition, and, more particularly, to a photosensitive resin composition which is useful in forming a black matrix and a dual type column spacer on the upper substrate of a liquid crystal display device.
Liquid crystal display devices render images using the optical anisotropy and birefringence of liquid crystal molecules. When electric power is applied, the array of liquid crystals is changed, and light transparency may also vary depending on changes in the array of the liquid crystals.
Typically, a liquid crystal display device is configured such that two substrates respectively having electrodes which produce electric power are disposed so that surfaces on which the two electrodes are formed face each other, a liquid crystal material is injected between the two substrates, and voltage is applied to the two electrodes to produce an electric field which allows the liquid crystal molecules to move, thereby displaying an image depending on changes in light transmittance.
A widely useful thin film transistor-liquid crystal display (TFT-LCD) is illustratively configured to include a lower substrate on which a thin film transistor and a pixel electrode are disposed, namely, an array substrate; an upper substrate, namely, a color filter substrate, wherein a black matrix and a colored layer of three colors including red, green and blue are repeated on a substrate made of plastic or glass, and to protect the color filter and maintain the surface flatness, an overcoating layer is formed thereon to a thickness of 1 ~ 3 ㎛ using a material such as polyimide, polyacrylate, polyurethane or the like, and an indium tin oxide (ITO) transparent conductive layer to which voltage is applied to drive liquid crystals is formed on the overcoating layer; and liquid crystals loaded between the upper and lower substrates, and also configured such that polarizer plates which linearly polarize visible rays (natural light) are individually attached on both surfaces of the two substrates. When voltage is applied to the gate of TFT which forms pixels by an external peripheral circuit, the transistor is turned on to form a state in which the image voltage may be input to the liquid crystals. Then, the image voltage is applied to store image information in liquid crystals. Thereafter, when the transistor is turned off, charges stored in a liquid crystal capacitor and an assistant capacitor are retained, thus displaying an image for a predetermined period of time. When voltage is applied to liquid crystals, the array of liquid crystals is changed. The case where light is passed through such liquid crystals causes diffraction. This light is passed through the polarizer plate, thereby obtaining a desired image.
Conventionally there is disclosed a photosensitive resin composition useful in forming a cured film that is able to perform the functions of a column spacer as well as of a light shielding film on a lower substrate by applying the entire color filter on a TFT substrate (a lower plate).
In this case (upon applying the color filter to the lower plate), however, the process of manufacturing the lower substrate becomes complicated, and thus recently a structure (Color Filter on TFT Array; COT) is being designed in which only red (R), green (G) and blue (B) colors are formed on the lower substrate, and a black matrix (BM) and a column spacer (CS) are applied to the upper substrate, thus ensuring simplification of the process and manufacturing stability.
When functioning as a column spacer, a conventional gap column spacer in which the column spacer is put in contact with both the upper and lower substrates may cause stains upon driving due to high density of the spacer. To solve this problem, the height of the gap column spacer may be partially decreased to form a pressure column spacer which does not make contact with the lower substrate. Thereby, as well as solving stain problems upon driving, a dual type spacer may be formed, which performs the conventional cell gap supporting function when pressure is applied to the screen.
Accordingly, the present inventors have made an effort to develop a photosensitive resin composition, which may function as a black matrix and as a dual type spacer that is able to prevent touch defects and press defects while maintaining the cell gaps of a liquid crystal panel, and thus have ascertained that when two or more of acrylic binder resins having different weight average molecular weights and acid values are contained at a specific ratio and a patterned cured film is formed using the same, a stable development pattern may be formed for a short development time, and a dual type spacer may be formed by adjusting the transmittance of a mask upon photo exposure while retaining appropriate light shielding properties, which culminated in the present invention.
Therefore, an object of the present invention is to provide a photosensitive resin composition which is useful in forming a black matrix and a column spacer on an upper substrate in a structure in which, upon fabrication of a liquid crystal display device, a color resist is formed on an array substrate (a lower substrate).
Another object of the present invention is to provide a photosensitive resin composition which is useful in forming a pattern necessary for performing functions of both a black matrix and a column spacer on an upper substrate.
A further object of the present invention is to provide a photosensitive resin composition which may simultaneously form a gap column spacer pattern and a pressure column spacer pattern lower than the gap column spacer pattern on an upper substrate using masks having different transmittances.
Yet another object of the present invention is to provide a display substrate, a liquid crystal panel and a liquid crystal display device, including a black matrix and a column spacer formed using the photosensitive resin composition.
An embodiment of the present invention provides a photosensitive resin composition, comprising 100 parts by weight of an acrylic binder resin, 10 ~ 20 parts by weight of a pigment, and 10 ~ 15 parts by weight of a photoinitiator, wherein the acrylic binder resin comprises a first acrylic binder resin having an acid value of 50 ~ 90 mg(KOH)/g and a weight average molecular weight of 8,000 ~ 13,000 g/mol and a second acrylic binder resin having an acid value of 100 ~ 150 mg(KOH)/g and a weight average molecular weight of 4,000 ~ 7,000 g/mol.
In the embodiment of the invention, the first acrylic binder resin and the second acrylic binder resin may be included at a weight ratio of 3 ~ 7 : 7 ~ 3.
In the embodiment of the invention, the pigment may comprise one or more selected from among carbon black, titanium black, acetylene black, aniline black, perylene black, strontium titanate, chromium oxide and ceria.
In the embodiment of the invention, the pigment may comprise carbon black having a particle size of 90 ~ 110 ㎚.
In the embodiment of the invention, the photoinitiator may comprise one or more selected from among an oxime ester based compound, a ketone, a halogen compound, a peroxide, and an acyl phosphine oxide.
In the embodiment of the invention, upon forming a cured film using the photosensitive resin composition, an optical density (OD) per unit thickness of 1.0 ㎛ may be 0.5 ~ 1.0.
In the embodiment of the invention, in a column spacer formed from the photosensitive resin composition, a difference between the height of the column spacer formed using a mask having a transmittance of 100% and the height of the column spacer formed using a mask having a transmittance of 10% upon photo exposure may be 0.5 ~ 1 ㎛.
Another embodiment of the present invention provides a display substrate, comprising a black matrix and a column spacer formed using the above photosensitive resin composition.
A further embodiment of the present invention provides s liquid crystal panel comprising the above display substrate as an upper substrate.
Still a further embodiment of the present invention provides a liquid crystal display device comprising the above liquid crystal panel.
According to the present invention, a photosensitive resin composition can easily form a dual type column spacer which can also function as a light shielding film on an upper substrate in a liquid crystal display device which is configured such that a color resist is formed on an array substrate, thus simplifying the process and ensuring manufacturing stability. Furthermore, the price of products can be remarkably decreased, and also, the yield of a liquid crystal display device can be increased.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Generally, the nomenclature used herein is well known in the art and is the one normally used.
As used herein, when any part “comprises” or “includes” any element, this indicates that other elements are not excluded but may be further included unless otherwise specifically mentioned.
According to an embodiment of the invention, a photosensitive resin composition comprises 100 parts by weight of an acrylic binder resin, 10 ~ 20 parts by weight of a pigment and 10 ~ 15 parts by weight of a photoinitiator, and the acrylic binder resin includes a first acrylic binder resin having an acid value of 50 ~ 90 mg(KOH)/g and a weight average molecular weight of 8,000 ~ 13,000 g/mol and a second acrylic binder resin having an acid value of 100 ~ 150 mg(KOH)/g and a weight average molecular weight of 4,000 ~ 7,000 g/mol.
The present invention is described in more detail as follows.
(A) Acrylic binder resin
In the photosensitive resin composition of the invention, the acrylic binder resin includes a first acrylic binder resin having an acid value of 50 ~ 90 mg(KOH)/g and a weight average molecular weight of 8,000 ~ 13,000 g/mol and a second acrylic binder resin having an acid value of 100 ~ 150 mg(KOH)/g and a weight average molecular weight of 4,000 ~ 7,000 g/mol.
In the case where a column spacer is formed using the photosensitive resin composition including the first acrylic binder resin which satisfies the above acid value range, the thickness of a cured film for a column spacer may be maintained uniform during a developing process. Furthermore in the case where a column spacer is formed using the photosensitive resin composition including the first acrylic binder resin which satisfies the above weight average molecular weight range, the pattern shape of a cured film for a column spacer may be maintained uniform.
Also in the case where a column spacer is formed using the photosensitive resin composition including the second acrylic binder resin which satisfies the above acid value range, it is easy to adjust the height of the cured film in a developing process depending on the transmittance of a mask upon photo exposure. Furthermore in the case where a column spacer is formed using the photosensitive resin composition including the second acrylic binder resin which satisfies the above weight average molecular weight range, the pattern shape of a cured film for a column spacer may be easily controlled.
The weight ratio of the first acrylic binder resin to the second acrylic binder resin is preferably set to 3 ~ 7 : 7 ~ 3. If the weight ratio of the first acrylic binder resin to the second acrylic binder resin falls in the above range, the height or pattern shape of the cured film for a column spacer may be easily adjusted in a developing process depending on the transmittance of a mask upon photo exposure. In contrast, if this ratio falls out of the above range, the combination of two kinds of acrylic binder resins may exhibit the same properties as would the acrylic binder resin used alone, making it impossible to easily adjust the height or pattern shape of the cured film.
Also, the first acrylic binder resin and the second acrylic binder resin may be a copolymer of a monomer containing an acid functional group and another monomer copolymerizable therewith, or a compound resulting from polymerizing the copolymer and an ethylenically unsaturated compound containing an epoxy group. The above copolymer may further enhance the strength of a film compared to when using a homopolymer. As such, the acid value and the weight average molecular weight of the acrylic binder resin may be easily adjusted by the amounts of the monomer containing an acid functional group, the monomer copolymerizable with the monomer containing an acid functional group, and the ethylenically unsaturated compound containing an epoxy group.
The non-limiting examples of the monomer containing an acid functional group may include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2-carboxylic acid, etc., which may be used alone or in combinations of two or more.
The non-limiting examples of the monomer copolymerizable with the monomer containing an acid functional group may include unsaturated carboxylic acid esters selected from among benzyl(meth)acrylate, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, ethylhexyl(meth)acrylate, 2-phenoxyethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxy-3-chloropropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, acyloctyloxy-2-hydroxypropyl(meth)acrylate, glycerol(meth)acrylate, 2-methoxyethyl(meth)acrylate, 3-methoxybutyl(meth)acrylate, ethoxydiehtyleneglycol(meth)acrylate, methoxytriethyleneglycol(meth)acrylate, methoxytripropyleneglycol(meth)acrylate, poly(ethyleneglycol) methylether(meth)acrylate, phenoxydiethyleneglycol(meth)acrylate, p-nonylphenoxypolyethyleneglycol(meth)acrylate, p-nonylphenoxypolypropyleneglycol(meth)acrylate, tetrafluoropropyl(meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl(meth)acrylate, octafluoropentyl(meth)acrylate, heptadecafluorodecyl(meth)acrylate, tribromophenyl(meth)acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, dicycyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl oxyethyl (meth)acrylate, and dicyclopentenyl oxyethyl (meth)acrylate; aromatic vinyls selected from among styrene, α-methylstyrene, (o,m,p)-vinyltoluene, (o,m,p)-methoxy styrene, and (o,m,p)-chlorostyrene; unsaturated ethers selected from among vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; N-vinyl tertiary amines selected from among N-vinyl pyrrolidone, N-vinyl carbazole, and N-vinyl morpholine; unsaturated imides selected from among N-phenyl maleimide, N-(4-chlorophenyl) maleimide, N-(4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide; maleic anhydrides, such as maletic anhydride and methyl maleic anhydride; unsaturated glycidyl compounds selected from among allyl glycidyl ether, glycidyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate; and mixtures thereof.
Also in addition to the copolymer of the monomer containing an acid functional group and the monomer copolymerizable with this monomer, the first acrylic binder resin and the second acrylic binder resin may include a polymer compound formed by binding the above copolymer with an ethylenically unsaturated compound containing an epoxy group. In particular, the ethylenically unsaturated bond provided in the acrylic binder resin may carry out a crosslinker function upon polymerization via photo exposure, thus enhancing adhesion to a substrate and coating properties.
The epoxy equivalent of the acrylic binder resin plays a role in enhancing resistance to chemicals such as a resist stripping solution. However, because the case where the epoxy equivalent is excessively high may negatively affect developability, the use of an acrylic binder resin having an epoxy equivalent of 200 ~ 2,000 is preferable.
The non-limiting examples of the ethylenically unsaturated compound containing an epoxy group include allyl glycidyl ether, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl 5-norbornene-2-methyl-2-carboxylate (endo and exo mixtures), 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene or mixtures thereof.
Particularly in consideration of high alkali resistance of the cured film, the use of a binder resin containing an epoxy group is preferable. Hence, upon preparation of an alkali soluble resin, it is preferred that a monomer having an acid functional group and a monomer having an epoxy group be used together.
Examples of the monomer having an epoxy group include but are not limited to glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethylacrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.
The acrylic binder resin includes two or more kinds of acrylic binders having different weight average molecular weights and acid values, thus maintaining pattern stability of a cured film for a column spacer upon developing and easily adjusting the height of a cured film for a column spacer in a developing process depending on the transmittance of a mask upon photo exposure, whereby spacers having different heights may be formed via a single process.
(B) Pigment
In the photosensitive resin composition of the invention, because of light shielding properties, the pigment may include one or more selected from the group consisting of carbon black, titanium black, acetylene black, aniline black, perylene black, strontium titanate, chromium oxide and ceria, and preferably comprises carbon black having a particle size of 90 ~ 110 nm. The case where carbon black having the above particle size range is included imparts flowability upon spin type coating and spinless type coating, and is effective at preventing the formation of surface residue and protrusions after prebaking and at enhancing optical density and adhesion to a substrate.
Also, the pigment is preferably used in an amount of 10 ~ 20 parts by weight based on 100 parts by weight of the acrylic binder resin (the first acrylic binder resin and the second acrylic binder resin). If the amount of the pigment is less than 10 parts by weight based on 100 parts by weight of the first acrylic binder resin and the second acrylic binder resin, optical density may decrease. In contrast if the amount thereof is greater than 20 parts by weight, pattern stability may decrease.
(C) Photoinitiator
In the photosensitive resin composition of the invention, the photoinitiator is preferably used in an amount of 10 ~ 15 parts by weight based on 100 parts by weight of the acrylic binder resin (the first acrylic binder resin and the second acrylic binder resin). If the amount of the photoinitiator is less than 10 parts by weight based on 100 parts by weight of the first acrylic binder resin and the second acrylic binder resin, pattern linearity and the formation of a stable pattern profile are problematic upon forming a black matrix pattern. In contrast, if the amount thereof is greater than 15 parts by weight, the line width of a pattern may increase excessively.
The photoinitiator may include one or more selected from among oxime ester compounds, such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and 1,2-octanedione-1[(4-phenylthio)phenyl]-2-benzoyl-oxime, and ketones such as thioxantone, 2,4-diethyl thioxantone, thioxantone-4-sulfonic acid, benzophenone, 4,4’-bis(diethylamino)benzophenone, acetophenone, p-dimethylaminoacetophenone, dimethoxyacetoxybenzophenone, 2,2’-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, etc.; quinones such as anthraquinone, 1,4-naphthoquinone, etc.; halogen compounds such as 1,3,5-tris(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2-chlorophenyl)-s-triazine, 1,3-bis(trichlorophenyl)-s-triazine, phenacyl chloride, tribromomethyl phenylsulfone, tris(trichloromethyl)-s-triazine, etc.; peroxides such as di-t-butyl peroxide, etc.; acylphosphine oxides such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, etc., and 2,2’-azobisisobutyronitrile.
(D) Multifunctional monomer
The photosensitive resin composition of the invention may include a multifunctional monomer, which functions to form a photoresist phase using light and is specifically one or a mixture of two or more selected from among propyleneglycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentylglycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol acrylate tetraethyleneglcyol methacrylate, bisphenoxy ethylalcohol diacrylate, trishydroxyethylisocyanurate trimethacrylate, trimethylpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate and dipentaerythritol hexamethacrylate.
The multifunctional monomer is preferably used in an amount of 0.1 ~ 99 parts by weight based on 100 parts by weight of the first acrylic binder resin and the second acrylic binder resin because the pattern formability and the bondability between the pigment and the particles may be increased due to crosslinking via a radical reaction of the photoinitiator by UV light to ultimately increase optical density.
(D) Solvent
The photosensitive resin composition of the invention may include a solvent, which is the same as that used in typical photosensitive resin compositions. This solvent may be selected from among propyleneglycol methylether acetate (PGMEA), propyleneglycol ethylether acetate, propyleneglycol methylether, propyleneglycol propylether, methylcellosolve acetate, ethylcellosolve acetate, diethylglycol methylacetate, ethylethoxy propionate, methylethoxy propionate, butylacetate, ethylacetate, cyclohexanone, acetone, methylisobutylketone, dimethylformamide, N,N’-dimethylacetamide, N-methylpyrrolidinone, dipropyleneglycol methylether, toluene, methylcellosolve and ethylcellosolve. The solvent may be used in an amount of 20 ~ 90 wt%, preferably 60 ~ 80 wt% based on the amount of the photosensitive resin composition.
Meanwhile, the photosensitive resin composition of the invention may further include an additive, as necessary. Examples of the additive may include, in order to enhance the force of adhesion between the black matrix and the coating substrate, a silane-based coupling agent such as glycidoxy propyltrimethoxysilane, 3-(methacryloxypropyl) trimethoxysilane, etc., an amine-based coupling agent such as phenylaminopropyl trimethoxysilane, aminoethylaminopropyl trimethoxysilane and so on, a surfactant for improving the contact angle of a coated surface and preventing residue formation, etc.
The case where a cured film is formed from the photosensitive resin composition as above may exhibit an optical density (OD) of 0.5 ~ 1.0 per unit thickness of 1.0 ㎛.
Concretely, to increase an aperture ratio or the like of a liquid crystal display device, a color filter layer is formed on a lower substrate, that is, an array substrate, and the color filter layer is configured such that a black matrix is formed between red (R), green (G) and blue (B) pixels. This case may minimize the margin of the black matrix, thus increasing an aperture ratio to thereby enhance luminance. However, because the process of manufacturing the lower substrate becomes complicated, only red (R), green (G) and blue (B) colors are formed on the lower substrate, and the black matrix and the column spacer are applied to an upper substrate, thus simplifying the process and ensuring the manufacturing stability.
In particular, the formation of the black matrix and the column spacer on the upper substrate is implemented with an additional patterning process, and these may be separately formed. Typically a photosensitive resin composition for forming a light shielding film known as a black matrix and a photosensitive resin composition for forming a column spacer are different and the properties required thereof are also different.
However, taking into consideration the advancement of liquid crystal display device techniques which form the black matrix and the column spacer on the upper substrate, the use of a photosensitive resin composition that is able to form a black matrix and a column spacer at the same time enables a black matrix and a column spacer to be formed to be stepped using single photolithography, or a column spacer to be formed on a black matrix, or a single pattern responsible for the functions of a black matrix and a column spacer to be formed.
Also when performing a function as a column spacer, a conventional gap column spacer which is in contact with both the upper and lower substrates may cause stains upon driving because of high density of the spacer. To solve this problem, the design is such that the height of the spacer is partially decreased so as not to be put in contact with the lower substrate (a pressure column spacer), whereby stains may not be generated upon driving and also a conventional cell gap supporting function may be carried out when pressure is applied to a screen.
Hence, the photosensitive resin composition of the invention may exhibit an optical density (OD) of 0.5 ~ 1.0 per unit thickness of 1 ㎛ so as to satisfy minimum light shielding properties in order to function as a light shielding film. Upon photo exposure to form a cured film for a column spacer using such a photosensitive resin composition, a half-tone mask is applied, and thus a difference in height of the resulting cured film between the case where a mask transmittance is 100% and the case where a mask transmittance is 10% may be ensured to the extent of 0.5 ~ 1.0 ㎛.
In addition, the present invention pertains to a display substrate including one selected from the group consisting of a black matrix, a column spacer, and a black matrix-integrated column spacer, which are formed using the above photosensitive resin composition.
More specifically, the display substrate of the invention may include a black matrix, a column spacer, or a black matrix-integrated column spacer, which are formed via photolithography using the above photosensitive resin composition. As such, the column spacer may be of a dual type.
Below is a description of the display substrate including a black matrix and a column spacer formed using the above photosensitive resin composition according to the present invention.
A resin coating layer is formed via spin coating at 500 rpm on a glass substrate having a clear surface, and then dried on a hot plate at 100℃ for 100 sec to form a coating thickness of 3.0 ~ 3.5 ㎛. Subsequently, photo exposure is performed via a mask (gap 250 ㎛) with active energy rays such as UV light in the energy dose of 60 mJ/㎠. The resulting film is developed using a developing solution (0.04% KOH aqueous solution, 25℃) for 60 sec, thus forming a cured film pattern, after which the substrate is placed in a convection oven at 220℃ and then postbaked for 30 min.
If the optical density (OD) of the cured film is less than 0.5 per unit thickness of 1 ㎛, it is difficult to manifest appropriate light shielding effects despite the cured film being slightly thick. In the case where the cured film functions as a light shielding film, it cannot sufficiently exhibit light shielding properties, and thus cannot block non-controlled light by passing through portions other than the transparent pixel electrode. In contrast, if the optical density (OD) of the cured film is greater than 1.0, the amount of the pigment is excessively increased in the resin composition, and thus liquid crystals may be contaminated upon driving of the liquid crystal display device.
When using the above photosensitive resin composition satisfying the above properties, the black matrix and the column spacer may be formed at the same time to have a step corresponding to a predetermined height via patterning by means of a slit mask or a half-tone mask, and also a column spacer may be further formed at a position where a black matrix is formed, or a black matrix to be formed may be provided to function as a column spacer. Also, column spacers having different heights may be formed at the same time.
In the column spacer formed using the above photosensitive resin composition, a difference in a height of the column spacer when using a mask having a transmittance of 100% and when using a mask having a transmittance of 10% upon photo exposure is preferably 0.5 ~ 1 ㎛.
Specifically, when functioning as a column spacer for maintaining cell gaps, a conventional structure (a gap column spacer) in which the spacer is in contact with both the upper and lower substrates may create stains upon driving because of high density of the spacer. In the case where the height difference falls in the above range, a column spacer (a pressure column spacer) which does not make contact with the lower substrate to maintain cell gaps is formed, thus solving the problem of stains forming on the screen of the liquid crystal display, and simultaneously exhibiting the function of maintaining cell gaps by putting the spacer in contact with the screen when pressure is applied to the screen.
In addition, the present invention is directed to a liquid crystal panel including the display substrate as an upper substrate, and to a liquid crystal display device including the liquid crystal panel.
The liquid crystal display device of the invention includes the liquid crystal panel having the black matrix and a dual type column spacer formed on the upper substrate, thus simplifying the process and ensuring manufacturing stability, and drastically reducing the manufacturing cost, resulting in increased yield.
A better understanding of the present invention may be obtained from the following examples and comparative example. However, such examples and comparative examples are set forth to illustrate, but are not to be construed as limiting the present invention.
<Preparation Examples 1 to 4>: Preparation of acrylic binder resin
In a reactor equipped with a cooling tube and a stirrer, 10 parts by weight of a photoinitiator 2,2’-azobis isobutyronitrile was dissolved in 200 parts by weight of a propyleneglycol monomethylether acetate solvent. Subsequently, as polymerizable monomers, 65 parts by weight of styrene, 15 parts by weight of methacrylic acid, 20 parts by weight of glycidyl methacrylate and 20 parts by weight of KBM503 were added, and the reaction mixture was purged with nitrogen and then subjected to mild stirring. The temperature of the reaction mixture was increased to 70℃, and this temperature was maintained for 4 hr thus obtaining a polymer solution containing a copolymer. The solid content of the polymer solution was 35 wt%. This is referred to as acrylic binder resin preparation example 1.
The other preparation examples were performed in the same manner as in Preparation Example 1, except for that the components were used in amounts represented by the parts by weight that are shown in Table 1 below.
Also the acid value and the weight average molecule weight of acrylic binder resins of Preparation Examples 1 to 4 are shown in Table 2 below.
| Prep.Ex.1 (parts by weight) |
Prep.Ex.2 (parts by weight) |
Prep.Ex.3 (parts by weight) |
Prep.Ex.4 (parts by weight) |
|
| MAA | 15 | 18 | 20 | 23 |
| GMA | 20 | 20 | 20 | 20 |
| Sty | 65 | 65 | 65 | 65 |
| KBM503 | 20 | 20 | 20 | 20 |
| Initiator | 10 | 12 | 14 | 14 |
| PGMEA | 200 | 200 | 200 | 200 |
Note) MAA: methacrylic acid
GMA: glycidyl methacrylate,
Sty: styrene
KBM503: 3-(methacryloxypropyl)trimethoxysilane (Shin-Etsu Chemical)
Initiator: 2,2’-azobisisobutyronitrile
PGMEA: propyleneglcyol monomethyl ether acetate
| Prep.Ex.1 | Prep.Ex.2 | Prep.Ex.3 | Prep.Ex.4 | |
| Acid Value | 85 mg(KOH)/g | 105 mg(KOH)/g | 117 mg(KOH)/g | 123 mg(KOH)/g |
| Weight Average Molecular Weight | 8500 g/mol | 6200 g/mol | 5500 g/mol | 5300 g/mol |
The acid value and the weight average molecular weight were measured as follows.
1) Acid value: the acid value indicates mg of KOH (potassium hydroxide) required to neutralize 1 g of an acid. 1 g of a sample was dissolved in 10 g of acetone, and 2 ~ 3 drops of a phenolphthalein indicator was added to the sample solution, which was then titrated with 0.1 N KOH aqueous solution to determine the mg of KOH when the transparent solution turned a pink color. The acid value is calculated as below.
Acid value (KOH mg/g) = (0.1 × 122.13 × amount of titrated KOH) ÷ (amount of sample (g) × 1000)
2) Weight average molecular weight: this was measured using a gel permeation chromatography (GPC) system available from Varian.
<Examples 1 to 3 and Comparative Example 1>: Preparation of photosensitive resin composition
To the acrylic binder resins of Preparation Examples 1 to 4, carbon black (KLBK-9232, available from Tokushiki, particle size 90 ㎚), a multifunctional monomer (dipentaerythritol hexaacrylate), a photoinitiator (I-242, available from Irgacure), a solvent (propyleneglycol methylether acetate (PGMEA)) and an additive were added, and the reaction mixture was stirred for 3 hr, thus obtaining photosensitive resin compositions.
In the following table, wt part means parts by weight relative to 100 parts by weight of solid content of binder resin.
|
|
1st Acrylic Binder Resin | 2nd Acrylic Binder Resin | Black Pigment (BK-9232) Wt part |
Photo-Initiator (I-242) |
Solvent (PGMEA) |
Multi-functional Monomer (DPHA) Wt Part |
Additive (GPTMS) Wt part |
||
| Kind | Wt Part | Kind | Wt Part | ||||||
| Comp.Ex. 1 | Prep.Ex.1 | 100 | - | - | 15 | 12 | 150 | 40 | 2.5 |
| Ex.1 | Prep.Ex.1 | 50 | Prep.Ex.2 | 50 | 15 | 12 | 150 | 40 | 2.5 |
| Ex.2 | Prep.Ex.1 | 50 | Prep.Ex.3 | 50 | 15 | 12 | 150 | 40 | 2.5 |
| Ex.3 | Prep.Ex.1 | 50 | Prep.Ex. 4 | 50 | 15 | 12 | 150 | 40 | 2.5 |
Note) Resin: 10 ~ 20 wt% based on the total amount of the composition
DPHA: dipentaerythritol hexaacrylate
PGMEA: propyleneglycol methylether acetate
GPTMS: glycidoxy propyltrimethoxysilane (silicon based compound)
BK-9232: carbon black pigment dispersion available from TOKUSHIKI
The development initiation time, development pattern stability, optical density, height of the column spacer at different mask transmittances, residue generation and so on of the photosensitive resin compositions of Comparative Example 1 and Examples 1 to 3 were measured as follows. The results are given in Table 4 below.
(1) Formation of cured film
A cured film pattern was formed from the photosensitive resin composition of each of Comparative Example 1 and Examples 1 to 3 using the following method. Specifically, a resin coating layer was formed at 300 rpm on a glass substrate having a clear surface using a spin coater, and then dried on a hot plate at 100℃ for 100 sec so that the thickness of the applied film was adjusted to 3.5 ㎛. Subsequently, photo exposure was performed using a mask (gap 250 ㎛) with active energy rays such as UV light at 60 mJ/㎠. The film resulting from photo exposure was developed using a developing solution (0.04% KOH aqueous solution, 25℃) for 60 sec, thus forming a cured film pattern. Thereafter, postbaking was carried out in a convection oven at 230℃ for 30 min.
(2) Development initiation time
The development initiation time was determined in such a manner that a resin black matrix was applied on a glass substrate, prebaked and then photoexposed, after which the time into the developing process at which the resin black matrix was developed and at which the pattern began to form was measured with the naked eye.
(3) Development pattern stability
The development pattern stability was determined in such a manner that a resin black matrix was applied on a glass substrate, prebaked and photoexposed, after which a developing process was carried out for predetermined time after the time into the developing process at which the resin black matrix was developed and at which the pattern began to form (that is, the development initiation time), and the line width and linearity of the pattern were measured using an optical microscope. The zones where the extent to which the line width of the pattern was decreased was 1 ㎛ or less per unit of development time (5 sec) were measured.
(4) Optical density
The optical density of the cured film formed as above was measured using a reference having an optical density of 2.4 by means of PMT available from Otsuka Electronics. The results are shown in Table 4 below.
(5) Residue
The presence of a residue after the developing process was checked using SEM.
(6) Height (㎛) of column spacer at different mask transmittances
Upon photo exposure to form a column spacer, two kinds of processes were conducted using a mask having a transmittance of 100% and a mask having a transmittance of 10%. The film resulting from photo exposure was developed using a developing solution (0.04% KOH aqueous solution, 25℃) for 60 sec, thus forming a cured film pattern, after which the substrate was postbaked in a convection oven at 230℃ for 30 min. The cured films thus obtained were observed using a 3-D profiler to compare the column spacer heights.
|
|
Develop. Initiation Time (s) |
Develop. pattern stability (s) |
Optical Density ( /1㎛) | Column Spacer Height | Residue | ||
| Mask Transmit. 100% |
Mask Transmit. 10% |
Height Difference | |||||
| Comp.Ex.1 | 45s | 15s(good) | 0.6 | 3.06 | 2.94 | 0.2 | No |
| Ex.1 | 43s | 15s(good) | 0.6 | 3.07 | 2.49 | 0.5 | No |
| Ex.2 | 41s | 15s(good) | 0.6 | 3.03 | 2.42 | 0.6(good) | No |
| Ex.3 | 40s | 15s(good) | 0.6 | 3.04 | 2.31 | 0.8(good) | No |
As is apparent from Table 4, in Comparative Example 1 using only one kind of acrylic binder, the height of the spacer was very slightly decreased when using a mask having a transmittance of 10%. In Preparation Examples 2 and 3, the amount of the photoinitiator was increased to reduce the molecular weight of the resin compared to Preparation Example 1, and in Examples 1 and 2, a reduction in height of the spacer was increased when mixing two kinds of binder resins of Preparation Example 1 and Preparation Example 2 or 3. In Preparation Example 3, the amount of methacrylic acid was increased to enhance developability compared to Preparation Example 2, and thus in Example 3 using this preparation example, the height of the spacer was further decreased, compared to Example 2.
Hence, the compositions of Examples 1 to 3 are regarded as the most appropriate because a dual type column spacer can be formed by adjusting the transmittance of the mask upon photo exposure while retaining proper light shielding properties.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (12)
- A photosensitive resin composition, comprising:
100 parts by weight of an acrylic binder resin;
10 ~ 20 parts by weight of a pigment; and
10 ~ 15 parts by weight of a photoinitiator,
wherein the acrylic binder resin comprises a first acrylic binder resin having an acid value of 50 ~ 90 mg(KOH)/g and a weight average molecular weight of 8,000 ~ 13,000 g/mol and a second acrylic binder resin having an acid value of 100 ~ 150 mg(KOH)/g and a weight average molecular weight of 4,000 ~ 7,000 g/mol.
- The photosensitive resin composition of claim 1, wherein the first acrylic binder resin and the second acrylic binder resin are included at a weight ratio of 3 ~ 7 : 7 ~ 3.
- The photosensitive resin composition of claim 1, wherein the pigment comprises one or more selected from among carbon black, titanium black, acetylene black, aniline black, perylene black, strontium titanate, chromium oxide and ceria.
- The photosensitive resin composition of claim 1, wherein the pigment comprises carbon black having a particle size of 90 ~ 110 ㎚.
- The photosensitive resin composition of claim 1, wherein the photoinitiator comprises one or more selected from among an oxime ester based compound, a ketone, a halogen compound, a peroxide, and an acyl phosphine oxide.
- The photosensitive resin composition of claim 1, wherein upon forming a cured film using the photosensitive resin composition, an optical density (OD) per unit thickness of 1.0 ㎛ is 0.5 ~ 1.0.
- The photosensitive resin composition of claim 1, wherein in a column spacer formed from the photosensitive resin composition, a difference between a height of the column spacer formed using a mask having a transmittance of 100% and a height of the column spacer formed using a mask having a transmittance of 10% upon photo exposure is 0.5 ~ 1 ㎛.
- A display substrate, comprising a black matrix formed using the photosensitive resin composition of claim 1.
- A display substrate, comprising a column spacer formed using the photosensitive resin composition of claim 1.
- A display substrate, comprising a black matrix-integrated column spacer formed using the photosensitive resin composition of claim 1.
- A liquid crystal panel comprising the display substrate of any one of claims 8 to 10 as an upper substrate.
- A liquid crystal display device comprising the liquid crystal panel of claim 11.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201280059588.7A CN103959167B (en) | 2011-10-02 | 2012-09-24 | Photosensitive resin composition |
| JP2014534464A JP5901778B2 (en) | 2011-10-02 | 2012-09-24 | Photosensitive resin composition |
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| KR10-2011-0100402 | 2011-10-02 | ||
| KR20110100402 | 2011-10-02 | ||
| KR1020120090624A KR101688464B1 (en) | 2011-10-02 | 2012-08-20 | Photopolymerizable Resin Composition |
| KR10-2012-0090624 | 2012-08-20 |
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| WO2013051805A2 true WO2013051805A2 (en) | 2013-04-11 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015099263A (en) * | 2013-11-19 | 2015-05-28 | 東京応化工業株式会社 | Method for forming line pattern |
| JP2015518978A (en) * | 2012-05-25 | 2015-07-06 | エルジー・ケム・リミテッド | Photosensitive resin composition, pattern formed using the same, method for producing pattern, and display panel including the same |
| JP2015194583A (en) * | 2014-03-31 | 2015-11-05 | Jsr株式会社 | Resin composition for forming cured film, cured film and method for forming the same, and display element |
| TWI705303B (en) * | 2015-06-03 | 2020-09-21 | 南韓商東進世美肯股份有限公司 | Negative photosensitive resin composition, manufactory method of organic insulating film and display element |
| TWI832940B (en) * | 2018-12-21 | 2024-02-21 | 南韓商羅門哈斯電子材料韓國公司 | Colored photosensitive resin composition and black matrix prepared therefrom |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4012193B2 (en) * | 2004-11-08 | 2007-11-21 | 富士フイルム株式会社 | Method for producing light-shielding multicolor image sheet |
| KR20090071032A (en) * | 2007-12-27 | 2009-07-01 | 주식회사 코오롱 | Photosensitive Resin Compositions, Black Matrix and Color Filter Substrates |
| JP5021046B2 (en) * | 2009-02-26 | 2012-09-05 | エルジー ケム． エルティーディ． | Photosensitive resin composition |
| KR101068622B1 (en) * | 2009-12-22 | 2011-09-28 | 주식회사 엘지화학 | High light-shielding black matrix composition with improved substrate adhesion |
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2012
- 2012-09-24 WO PCT/KR2012/007648 patent/WO2013051805A2/en not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015518978A (en) * | 2012-05-25 | 2015-07-06 | エルジー・ケム・リミテッド | Photosensitive resin composition, pattern formed using the same, method for producing pattern, and display panel including the same |
| US9341946B2 (en) | 2012-05-25 | 2016-05-17 | Lg Chem, Ltd. | Photosensitive resin composition, pattern formed using same and display panel comprising same |
| JP2015099263A (en) * | 2013-11-19 | 2015-05-28 | 東京応化工業株式会社 | Method for forming line pattern |
| JP2015194583A (en) * | 2014-03-31 | 2015-11-05 | Jsr株式会社 | Resin composition for forming cured film, cured film and method for forming the same, and display element |
| TWI705303B (en) * | 2015-06-03 | 2020-09-21 | 南韓商東進世美肯股份有限公司 | Negative photosensitive resin composition, manufactory method of organic insulating film and display element |
| TWI832940B (en) * | 2018-12-21 | 2024-02-21 | 南韓商羅門哈斯電子材料韓國公司 | Colored photosensitive resin composition and black matrix prepared therefrom |
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| WO2013051805A3 (en) | 2013-06-13 |
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