CN103959167B - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
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- CN103959167B CN103959167B CN201280059588.7A CN201280059588A CN103959167B CN 103959167 B CN103959167 B CN 103959167B CN 201280059588 A CN201280059588 A CN 201280059588A CN 103959167 B CN103959167 B CN 103959167B
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- resin composition
- photosensitive resin
- column spacer
- liquid crystal
- weight
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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
-
- 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
-
- 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
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/20—Exposure; Apparatus therefor
-
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
- G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
- G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Optical Filters (AREA)
Abstract
The present invention relates to a kind of photosensitive resin composition, more specifically, it is related to a kind of photosensitive resin composition and the cured film formed by said composition, two or more weight average molecular weight containing special ratios acryl adhesive resin different with acid number in the photosensitive resin composition, thus, when preparing liquid crystal display device, the column spacer of black matrix" and double type can be simultaneously formed on upper substrate on array base palte (infrabasal plate) formed with the structure of colour resist.
Description
Technical field
The present invention relates to photosensitive resin composition, more specifically, is related to a kind of photosensitive resin composition, said composition can
For forming the column spacer of black matrix" and double type on the upper substrate of liquid crystal display device.
Background technology
Image is presented using the optical anisotropy and birefringence of liquid crystal molecule in liquid crystal display device.When application electric power
When, the arrangement of liquid crystal is changed, and optical transparency can also change according to the change of liquid crystal arrangement.
Typically, liquid crystal display device configuration is as follows：The substrate respectively to two with the electrode for producing electric power is carried out
Arrangement so that the surface formed with the two electrodes is relative to each other, between liquid crystal material is injected into two substrates, and to two electricity
Pole apply voltage with produce can make liquid crystal molecule move electric field, thus according to light transmittance change and display image.
Widely used TFT-LCD display device (TFT-LCD) exemplarily configure it is as follows, including：Lower base
Plate, i.e. array base palte, are disposed with thin film transistor (TFT) and pixel electrode thereon；Upper substrate, i.e. colored filter substrate, wherein,
By repeating to set black matrix" on substrate made of plastics or glass and including the dyed layer of three kinds of colors of red, green, blue, use example
Such as polyimides, polyacrylate or polyurethane material are formed on the outer coating (overcoating that thickness is 1 to 3 μm
Layer) to protect colored filter and holding surface flatness, and formed on the outer coating and apply voltage to drive liquid crystal
Tin indium oxide (ITO) transparency conducting layer；And the liquid crystal loaded between the upper substrate and infrabasal plate, also, also this two
The Polarizer that linear polarization is carried out to visible ray (natural light) is attached on two surfaces of individual substrate respectively.When passing through outer periphery
When circuit applies voltage to the TFT gate for forming pixel, transistor is connected and formation can be to the shape of liquid crystal input picture voltage
State.Then, image voltage is applied to store image information in liquid crystal.Thereafter, when the transistor turns off, retain and be stored in liquid crystal
Electric charge in capacitor and auxiliary capacitor, image is thus set to show the predetermined time.When to liquid crystal applied voltages, liquid crystal
Arrangement changes.Diffraction can be produced in the case where making light pass through this liquid crystal.Light is set to pass through Polarizer, needed for obtaining
Image.
Routinely, a kind of photosensitive resin composition is disclosed, by the way that whole colored filter is applied in into TFT substrate (bottom
Plate) on, said composition, which can be used for being formed on infrabasal plate, can play column spacer (column spacer) and light shield
The cured film of film effect.
However, in this case (when colored filter is applied into bottom plate), preparing the process of infrabasal plate becomes multiple
It is miscellaneous, therefore a kind of structure (Color Filter on TFT Array are being designed recently；COT), wherein, on infrabasal plate only
Red (R), green (G) and blue (B) color are formed, and black matrix" (BM) and column spacer (CS) are applied to upper substrate, by
This ensures the stability of simplification and the preparation of process.
When as column spacer, to the conventional gap for making column spacer all be contacted with upper substrate and infrabasal plate
When column spacer (gap column spacer) is driven, spot may be produced because the density of sept is higher.For
Solve this problem, can partly reduce the height of gap column spacer to form the pressured column not contacted with infrabasal plate
Shape sept (pressure column spacer).Thus, spot problem during driving is not only solved, and can be formed
The sept of double type (dual type), conventional cell gap supporting role is played when applying pressure to screen.
Therefore, the present inventor makes great efforts to develop a kind of photosensitive resin composition, and said composition may be used as black matrix", and
And it may be used as to prevent from touching defect and the double type of pressing defect while liquid crystal panel unit gap is kept
Sept, thus clear and definite herein below and complete the present invention：When with special ratios contain two or more have it is different heavy
The acryl adhesive resin of average molecular weight and acid number, and during the use resin formation figuratum cured film of tool, Ke Yi
Stable developing pattern is formed in shorter developing time, also, by being adjusted in the case where retaining appropriate light-shielding property
The light transmittance of mask during exposure, the sept of double type can be formed.
The content of the invention
Technical problem
Therefore,, should when preparing liquid crystal display device it is an object of the present invention to provide a kind of photosensitive resin composition
In structure of the composition formed with colour resist (color resist) on array base palte (infrabasal plate), available in upper base
Black matrix" and column spacer are formed on plate.
It is a further object to provide a kind of photosensitive resin composition, said composition can be used for the shape on upper substrate
The pattern into necessary to playing the effect of both black matrix" and column spacer simultaneously.
A further object of the present invention is to provide a kind of photosensitive resin composition, and said composition can utilize light transmittance different
Mask, on upper substrate simultaneously form gap column spacer patterns and the pressurization less than the gap column spacer patterns
Column spacer patterns.
It is also another object of the present invention to provide a kind of display base plate, liquid crystal panel and liquid crystal display device, the display
The black matrix" and columnar interval that substrate, liquid crystal panel and liquid crystal display device are formed including the use of above-mentioned photosensitive resin composition
Thing.
Technical scheme
One embodiment of the invention provides a kind of photosensitive resin composition, comprising：The acrylic compounds of 100 parts by weight glue
The light trigger of mixture resin, the pigment of 10 to 20 parts by weight and 10 to 15 parts by weight, wherein, the acrylic adhesives tree
Fat includes the first acrylic adhesive that acid number is 50 to 90mg (KOH)/g and weight average molecular weight is 8,000 to 13,000g/mol
Agent resin, and acid number is 100 to 150mg (KOH)/g and weight average molecular weight is 4,000 to 7,000g/mol the second acrylic acid
Class adhesive resin.
In the embodiment of the present invention, first acryl adhesive resin and second acrylic acid are included
The weight ratio of class adhesive resin can be 3~7:7~3.
In the embodiment of the present invention, the pigment can be included selected from carbon black, titanium is black, acetylene black, nigrosine,
One or more in black (perylene black), strontium titanates, chromium oxide and ceria.
In the embodiment of the present invention, the pigment can include the carbon black that particle diameter is 90 to 110nm.
In the embodiment of the present invention, the light trigger can be included selected from oxime ester compound, ketone, halogenated
One or more in compound, peroxide and acylphosphine oxide.
In the embodiment of the present invention, when forming cured film using the photosensitive resin composition, every 1.0 μm of lists
The optical density (OD) of position thickness can be 0.5 to 1.0.
In the embodiment of the present invention, in the column spacer formed by the photosensitive resin composition, exposing
The height for the column spacer that the mask that light time is 100% using light transmittance is formed is formed with the mask for the use of light transmittance being 10%
Column spacer height difference can be 0.5 to 1 μm.
Another embodiment of the invention provides a kind of display base plate, and the display base plate is including the use of above-mentioned photosensitive resin
The black matrix" and column spacer that composition is formed.
Yet another embodiment of the present invention provides a kind of liquid crystal panel, and the liquid crystal panel includes above-mentioned display base plate conduct
Upper substrate.
Another embodiment of the invention provides a kind of liquid crystal display device, and the liquid crystal display device includes above-mentioned liquid crystal
Panel.
Beneficial effect
According to the present invention, photosensitive resin composition can be configured to make colour resist form the liquid on array base palte
In crystal device, the column spacer of double type is readily formed on upper substrate, and the column spacer can be with
As optical screen film, so that process simplification, and ensure that the stability of preparation.Furthermore, it is possible to significantly reduce product into
This, but also the yield of liquid crystal display device can be improved.
Embodiment
Unless otherwise defined, whole technologies and scientific and technical terminology used herein have with it is of the art general
The identical meanings that logical technical staff is generally understood that.Typically, nomenclature used herein by this area public affairs
Know, and be to use in the usual manner.
As used herein, it is unless specifically mentioned in addition, when any part "comprising" or any key element of " comprising ", be
Finger is not excluded for other key elements, but can also include these key elements.
According to embodiment of the present invention, photosensitive resin composition includes：The acrylic adhesives tree of 100 parts by weight
The light trigger of fat, the pigment of 10 to 20 parts by weight and 10 to 15 parts by weight, the acryl adhesive resin include acid number
It is 8 for 50 to 90mg (KOH)/g and weight average molecular weight, 000 to 13,000g/mol the first acryl adhesive resin, with
And the second acrylic adhesives that acid number is 100 to 150mg (KOH)/g and weight average molecular weight is 4,000 to 7,000g/mol
Resin.
It is as follows, the present invention is described in more detail.
(A) acryl adhesive resin
In the photosensitive resin composition of the present invention, it is 50 to 90mg that the acryl adhesive resin, which includes acid number,
(KOH)/g and weight average molecular weight are 8,000 to 13,000g/mol the first acryl adhesive resin, and acid number is 100
To the second acryl adhesive resin that 150mg (KOH)/g and weight average molecular weight are 4,000 to 7,000g/mol.
Post is being formed using the photosensitive resin composition comprising the first acrylic resin for meeting above-mentioned acid value
In the case of shape sept, the thickness that the cured film of column spacer can be used in developing process keeps uniform.Also,
Column is being formed using the photosensitive resin composition comprising the first acrylic resin for meeting above-mentioned weight average molecular weight range
In the case of sept, the pattern form that can be used in the cured film of column spacer is consistent.
Also, carrying out shape using the photosensitive resin composition comprising the second acrylic resin for meeting above-mentioned acid value
In the case of column spacer, it is easy to adjust the height of cured film according to the light transmittance of mask during exposure in developing process
Degree.Also, come using the photosensitive resin composition comprising the second acrylic resin for meeting above-mentioned weight average molecular weight range
In the case of forming column spacer, the pattern form of the cured film for column spacer can be easily controlled.
The weight ratio preferably 3 of first acryl adhesive resin and second acryl adhesive resin
~7:7~3.If the weight of the first acryl adhesive resin and the second acryl adhesive resin ratio falls into above-mentioned model
Within enclosing, then consolidating for column spacer easily can be adjusted according to the light transmittance of mask during exposure in developing process
Change the height or pattern form of film.If on the contrary, the ratio were fallen into beyond above range, two kinds of acryl adhesive resin
Combination may show and be used alone the acryl adhesive resin identical property, it is solid so as to easily adjust
Change the height or pattern form of film.
Also, first acryl adhesive resin and second acryl adhesive resin can be containing
The monomer of acid functional group and the copolymer with another monomer of the monomers copolymerizable, or by the copolymer and contain epoxy radicals
The compound that ethylenically unsaturated compounds polymerize and generated.Compared with when using homopolymer, above-mentioned copolymer can be further
Strengthen film strength.Thus, the monomer containing acid functional group, the monomer with the monomers copolymerizable containing acid functional group are passed through
And the amount of the ethylenically unsaturated compounds containing epoxy radicals, the acryl adhesive resin can be easily adjusted
Acid number and weight average molecular weight.
The non-limiting examples of the monomer containing acid functional group can include：(methyl) acrylic acid, butenoic acid, clothing health
Acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5- ENB -2- carboxylic acids etc., this
A little monomers can use individually or with the combination of two or more.
It is described to include being selected from (methyl) with the non-limiting examples of the monomer of the monomers copolymerizable containing acid functional group
Benzyl acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid two
Methylamino ethyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl)
Isobornyl acrylate, (methyl) ethylhexyl acrylate, (methyl) acrylic acid 2- phenoxy ethyls, (methyl) acrylic acid tetrahydrochysene
Chaff ester, (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid 2- hydroxypropyl acrylates, (methyl) acrylic acid 2- hydroxyl -3- chlorine propyl ester, (first
Base) acrylic acid 4- hydroxybutyls, acyl group octyloxy -2- hydroxypropyls (methyl) acrylate, (methyl) glycerol acrylate, (first
Base) acrylic acid 2- methoxy acrylates, (methyl) acrylic acid 3- methoxybutyls, ethoxydiglycol (methyl) acrylate, first
Epoxide triethylene glycol (methyl) acrylate, methoxyl group tripropylene glycol (methyl) acrylate, methoxypolyethylene glycol (methyl) propylene
Acid esters, phenoxy group diethylene glycol (DEG) (methyl) acrylate, to Nonylphenoxy polyethylene glycol (methyl) acrylate, to nonyl benzene oxygen
Base polypropylene glycol (methyl) acrylate, (methyl) acrylic acid tetrafluoro propyl ester, (methyl) acrylic acid 1,1,1,3,3,3- hexafluoros are different
Propyl ester, (methyl) acrylic acid octafluoro pentyl ester, the fluorine last of the ten Heavenly stems ester of (methyl) acrylic acid 17, (methyl) tribromophenyl acrylate, methyl α-
Hydroxymethyl acrylate, ethyl alpha-hydroxymethyl acrylate, propyl group alpha-hydroxymethyl acrylate, butyl alpha-hydroxymethyl acrylic acid
Ester, the ring pentyl ester of (methyl) acrylic acid two, (methyl) acrylic acid dicyclopentenyl ester, bicyclopentyl epoxide ethyl (methyl) acrylate
With the unsaturated carboxylate type in dicyclopentenyl epoxide ethyl (methyl) acrylate；Selected from styrene, α-methylstyrene,
Aromatic vinyl in (o-, m-, to) vinyltoluene, (o-, m-, to) methoxy styrene and (o-, m-, to) chlorostyrene
Class；Unsaturated ether in vinyl methyl ether, EVE and allyl glycidyl ether；Selected from N- vinyl
N- vinyl tertiary amine classes in pyrrolidones, N- vinyl carbazoles and N- polyvinyl morpholinones；Selected from N-phenylmaleimide, N-
The acyl of unsaturation two in (4- chlorphenyls) maleimide, N- (4- hydroxyphenyls) maleimide and N- N-cyclohexylmaleimides
Imines；The maleic acid anhydride of such as maleic anhydride and methyl maleic anhydride；Selected from allyl glycidyl ether, (methyl) propylene
Unsaturated glycidyl compound class in acid glycidyl ester and 3,4- epoxycyclohexyl-methyls (methyl) acrylate；With
And the mixture of above-claimed cpd.
It is also, described in addition to the monomer containing acid functional group and with the copolymer of the monomer of this monomers copolymerizable
First acryl adhesive resin and the second acryl adhesive resin can be included by making above-mentioned copolymer with containing
The ethylenically unsaturated compounds of epoxy radicals with reference to and formed polymer complex (polymer compound).Particularly,
The ethylenic unsaturated bond provided in the acryl adhesive resin can play crosslinking when polymerizeing via exposure
Effect, thus strengthens the cohesive and coating performance for substrate.
The epoxide equivalent of the acryl adhesive resin, which plays, to be improved for chemicals such as anticorrosive additive stripping liquid controlling
The effect of resistance.However, because the too high situation of epoxide equivalent may adversely affect to developing performance, therefore preferably use
Epoxide equivalent is 200 to 2,000 acryl adhesive resin.
The non-limiting examples of the ethylenically unsaturated compounds containing epoxy radicals include：Allyl glycidol
Ether, (methyl) glycidyl acrylate, 3,4- epoxycyclohexyl-methyls (methyl) acrylate, glycidyl 5- norborneols
Alkene -2- methyl -2- carboxylates (mixture of inner mold and external form), 1,2- epoxy radicals -5- hexenes, 1,2- epoxy radicals -9- decene or
Its mixture.
Particularly, in view of the high alkali resistance of cured film, preferably uses the adhesive resin containing epoxy radicals.Therefore, making
During standby alkali soluble resins, preferably the monomer containing acid functional group is used together with the monomer containing epoxy radicals.
The example of the monomer containing epoxy radicals includes but is not limited to：Glycidyl acrylate, methacrylic acid contracting
Water glyceride, glycidyl α-ethylacrylate ester, glycidyl α-n-propyl acrylate, glycidyl α-positive fourth
Base acrylate, acrylic acid 3,4- epoxies butyl ester, methacrylic acid 3,4- epoxies butyl ester, acrylic acid 6,7- epoxies heptyl ester, methyl
Acrylic acid 6,7- epoxies heptyl ester, 6,7- epoxy heptyl α-ethylacrylates ester, adjacent vinylbenzyl glycidyl ether, a vinyl
Benzyl glycidyl ether, to vinylbenzyl glycidyl ether etc..
The acryl adhesive resin, which includes two or more, has the propylene of different weight average molecular weight and acid number
Acrylic binder, therefore the pattern stability of cured film for column spacer is maintained in development, and developing
It is easy to adjust the height of the cured film for column spacer according to the light transmittance of mask during exposure in journey, thus, it is possible to logical
Cross single process and form the sept of different height.
(B) pigment
In the photosensitive resin composition of the present invention, due to light-shielding property, the pigment can be included selected from carbon black, titanium
One or more in black, acetylene black, nigrosine, black, strontium titanates, chromium oxide and ceria, preferably include particle diameter for 90 to
110nm carbon black.In the case of including the carbon black with above-mentioned particle size range, rotary-type coating and the painting of non-rotating type are being carried out
Assign mobility during cloth, and surface residue and protrusion are formed after prebake is prevented, and enhancing optical density and to base
It is more effective in terms of the cohesive of plate.
Also, the acryl adhesive resin (the first acryl adhesive resin and based on 100 parts by weight
Diacrylate class adhesive resin), the dosage of the pigment is preferably 10 to 20 parts by weight.If the dosage of pigment is based on 100
The first acryl adhesive resin and the second acryl adhesive resin of parts by weight are less than 10 parts by weight, then optical density can
It can decline.On the contrary, if the dosage of pigment is more than 20 parts by weight, pattern stability may decline.
(C) light trigger
In the photosensitive resin composition of the present invention, the acryl adhesive resin (first based on 100 parts by weight
Acryl adhesive resin and the second acryl adhesive resin), the dosage of the light trigger is preferably 10 to 15 weights
Measure part.If first acryl adhesive resin and second acrylic compounds of the dosage of light trigger based on 100 parts by weight glue
Mixture resin is less than 10 parts by weight, then when forming black matrix pattern, in the pattern that the linearity of pattern and formation are stable
Problem on profile be present.On the contrary, if the dosage of light trigger is more than 15 parts by weight, the line width of pattern may excessively increase.
The light trigger can include being selected from：Oxime ester compound, such as 1- [9- ethyls -6- (2- methyl benzoyls) -
9H- carbazole -3- bases] -1- (adjacent acetyl group oxime) and 1,2- octadione- 1 [(4- phenyls) phenyl] -2- benzoyls-oxime；Ketone
Class, such as thioxanthones (thioxantone), 2,4- diethyl thioxanthones, thioxanthones -4- sulfonic acid, benzophenone, 4,4'- double (two
Ethylamino) benzophenone, acetophenone, to dimethylamino acetophenone, dimethoxy acetoxyl group benzophenone, 2,2'- dimethoxies
Base -2- phenyl acetophenones, acetanisole, 2- methyl [4- (methyl mercapto) phenyl] -2- morpholino -1- acetone, 2- benzyls -
2- lignocaines -1- (4- morphlinophenyls)-butyl- 1- ketone, 2- hydroxy-2-methyl -1- phenyl propyl- 1- ketone, 4- (2- hydroxyl ethoxies
Base) phenyl-(2- hydroxyl -2- propyl group) ketone, 1- hydroxycyclohexylphenylketones etc.；Quinones, such as anthraquinone, 1,4-naphthoquinone etc.；Halogen
Compound, such as 1,3,5- tri- (trichloromethyl)-s- triazines, 1,3- double (trichloromethyl) -5- (2- chlorphenyls)-s- triazines, 1,
Double (the trichlorophenyl)-s- triazines of 3-, phenacyl chloride, trisbromomethyl benzene sulfone, three (trichloromethyl)-s- triazines etc.；Peroxidating
Thing, such as di-tert-butyl peroxide etc.；Acylphosphine oxide class, such as TMDPO
Deng, and the one or more in 2,2'- azodiisobutyronitrile.
(D) polyfunctional monomer
The photosensitive resin composition of the present invention can include polyfunctional monomer, and the polyfunctional monomer plays shape using light
Into photoresistance phase (photoresist phase) effect, and it is specially selected from propylene glycol methyl acrylate, dipentaerythritol
Six acrylate, dipentaerythritol acrylate, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, 1,6- oneself
Butanediol acrylate, tetraethyleneglycol methacrylate, two phenoxetol diacrylates, tris(2-hydroxy ethyl)isocyanurate front three
Base acrylate, trimethyl propane trimethyl acrylic ester, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl propylene
The mixture of one or both of acid esters and dipentaerythritol hexamethacrylate or more kind.
First acryl adhesive resin and the second acryl adhesive resin based on 100 parts by weight, institute
The dosage for stating polyfunctional monomer is preferably 0.1 to 99 parts by weight because light trigger by ultraviolet light through radical reaction
And crosslink, therefore the forming property of pattern and pigment can be made to be improved with interparticle binding ability, so as to finally increase
Big optical density.
(D) solvent
The photosensitive resin composition of the present invention can include solvent, and the solvent in conventional photosensitive resin composition with using
Solvent it is identical.The solvent can be selected from propylene glycol methyl ether acetate (PGMEA), propylene-glycol ethyl ether acetic acid esters, propylene glycol monomethyl ether,
Propylene glycol propyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethyl ethylene glycol methyl acetate, ethyl ethyoxyl
Propionic ester, methyl ethoxypropionate, butyl acetate, ethyl acetate, cyclohexanone, acetone, methyl iso-butyl ketone (MIBK), dimethyl formyl
Amine, N, N'- dimethyl acetamides, 1-METHYLPYRROLIDONE, dipropylene glycol methyl ether, toluene, methyl cellosolve and ethyl cellosolve
In.Based on the amount of the photosensitive resin composition, the dosage of the solvent can be 20 to 90wt%, preferably 60 to
80wt%.
Meanwhile photosensitive resin composition of the invention can also include additive when necessary.In order to strengthen black matrix"
Bonding force between coating base plate, the example of the additive can include：Silane coupling agent, such as glycidoxy third
Base trimethoxy silane, 3- (methacryloxypropyl) trimethoxy silane etc.；Amine coupling agent, such as phenyl amino third
Base trimethoxy silane, aminoethylaminopropyl trimethoxy silane etc.；And for improving contact angle on surface of coating and preventing residual
Stay surfactant of thing formation etc..
In the case where forming cured film by photosensitive resin composition as described above, every 1.0 μm of units can be shown
The optical density (OD) of thickness 0.5 to 1.0.
Specifically, it is that colour is formed on array base palte in infrabasal plate in order to increase aperture ratio of liquid crystal display device etc.
Filter layer, and the color filter layers are configured to form black matrix" between red (R), green (G) and blue (B) pixel.This
Kind of situation can be reduced the edge of black matrix" to bottom line, thus hole diameter enlargement ratio, so as to improve brightness.However, by
Become complicated in the above-mentioned process for preparing infrabasal plate, therefore red (R), green (G) and blue (B) color only formed on infrabasal plate,
And black matrix" and column spacer are applied to upper substrate so that process simplification and ensure prepare stability.
Particularly, the above-mentioned black matrix" and column spacer of being formed on upper substrate is by other patterning process
Come what is implemented, and these black matrix"s and column spacer can be formed respectively.It is commonly used for being formed and is referred to as black matrix"
Optical screen film photosensitive resin composition from being different for forming the photosensitive resin composition of column spacer, and they
Required property also differs.
However, in view of the technology in terms of liquid crystal display device forms black matrix" and column spacer on upper substrate is entered
Step, using the photosensitive resin composition that can form black matrix" and column spacer simultaneously, can by single photoetching process and
Make black matrix" and column spacer in a manner of with jump (step) to be formed, or column spacer is formed in black
On matrix, or form the single pattern for playing black matrix" and column spacer effect.
Also, when being played a role as column spacer, the conventional gap post all contacted with upper substrate and infrabasal plate
Shape sept may produce spot in driving because sept density is higher.In order to solve this problem, such as divided into
Meter：Part reduces the height of sept, so that it does not contact (pressurization column spacer) with infrabasal plate, thus, in driving
Spot will not be produced, and conventional cell gap supporting role can also be played when applying pressure to screen.
Therefore, photosensitive resin composition of the invention can show the optical density of every 1 μm of monomer thickness 0.5 to 1.0
(OD), so as to meeting the light-shielding property as bottom line needed for optical screen film.Exposed using this photosensitive resin composition
Light and when forming the cured film for column spacer, using halftoning (half-tone) mask, it is possible thereby to will made from
Between the situation that it is 10% in the situation and mask light transmittance for being 100% between mask light transmittance that the difference in height of cured film, which ensures,
In 0.5 to 1.0 μm of degree.
Moreover, it relates to a kind of display base plate, the display base plate, which includes being selected from, uses above-mentioned photosensitive resin composition
One kind in the column spacer of the black matrix" of formation, column spacer and black matrix" integration.
More specifically, display base plate of the invention can including the use of above-mentioned photosensitive resin composition by photoetching process and
Black matrix", column spacer or the column spacer of black matrix" integration of formation.Thus, the column spacer
It can be double type.
Hereinafter, to the black matrix" and columnar interval that are formed including the use of above-mentioned photosensitive resin composition according to the present invention
The display base plate of thing is described.
By 500rpm rotary coating, resinous coat is formed on the glass substrate of clean surface, then in electric hot plate
On dried 100 seconds at 100 DEG C, form 3.0 to 3.5 μm of coating layer thickness.It is next, (such as ultraviolet with active energy beam
Light) with 60mJ/cm2Energy dose be exposed through mask (250 μm of gap).Using developer solution (the 0.04%KOH aqueous solution,
25 DEG C) to the film development 60 seconds of gained, solidification film figure is consequently formed, thereafter, the substrate is put into 220 DEG C of convection oven
In, bakeed 30 minutes after then carrying out.
If the optical density (OD) of the every 1 μm of unit thickness of cured film is less than 0.5, even if making cured film somewhat thickening also difficult
To show suitable light shielding effect.In the case where the cured film is used as into optical screen film, the cured film can not abundant table
Reveal light-shielding property, therefore the uncontrolled light that the part beyond transparent pixel electrode passes through can not be stopped.If on the contrary,
The optical density (OD) of cured film is more than 1.0, then the pigment content in resin combination is excessive, therefore in driving liquid crystal display device
Shi Keneng pollutes to liquid crystal.
When meeting the photosensitive resin composition of above-mentioned property more than use, slit mask (slit mask) can be utilized
Or half-tone mask, it is patterned and make black matrix" and column spacer while formed and there is the rank corresponding to predetermined altitude
Difference, also, can also further form column spacer in the opening position for forming black matrix", or will can be formed
Black matrix" is used as column spacer.Furthermore, it is possible to the column spacer with different height is formed simultaneously.
In the column spacer formed using above-mentioned photosensitive resin composition, it is 100% that light transmittance is used in exposure
Mask and the difference in height of column spacer using the mask that light transmittance is 10% be preferably 0.5 to 1 μm.
Specifically, when the column spacer as holding unit gap, to routine column spacer with it is upper
When the structure (gap column spacer) that substrate and infrabasal plate all contact is driven, may because the density of sept is higher and
Produce spot.In the case where the difference in height falls into above range, form and do not contacted with infrabasal plate with holding unit gap
Column spacer (pressurization column spacer), thus solve the problems, such as on LCD Panel formed spot, meanwhile,
When applying pressure to screen, the effect in holding unit gap is shown by making the sept with screen contact.
Moreover, it relates to a kind of liquid crystal panel including the display base plate as upper substrate, and including described
The liquid crystal display device of liquid crystal panel.
The liquid crystal display device of the present invention is included on upper substrate the columnar interval formed with black matrix" and double type
The liquid crystal panel of thing, so that process simplification and ensure that preparation stability, and manufacturing cost is considerably reduced, so that
Yield is improved.
By the following examples and comparative example, it can obtain and be better understood from for the present invention.However, propose these realities
Apply example and comparative example is only used for for example, and being not construed as the limitation for the present invention.
<Preparation example 1 to 4>：The preparation of acryl adhesive resin
In the reactor equipped with cooling tube and agitator, by the light trigger 2 of 10 parts by weight, the isobutyl of 2'- azos two
Nitrile is dissolved in the propylene glycol methyl ether acetate solvent of 200 parts by weight.Next, add styrene, 15 weights of 65 parts by weight
The KBM503 of the methacrylic acid of part, the GMA of 20 parts by weight and 20 parts by weight is measured as polymerizable list
Body, the reactant mixture is purged with nitrogen, then carry out temperature and close stirring.The temperature of the reactant mixture is increased to 70 DEG C and protected
Hold the temperature 4 hours, the polymer solution containing copolymer is thus made.The solid content of the polymer solution is 35wt%.This
Process is referred to as acryl adhesive resin preparation example 1.
To carry out other preparation examples with the same way described in preparation example 1, difference is, the dosage of each component
(represented as shown in Table 1 below with parts by weight).
In addition, the acid number and weight average molecular weight of the acryl adhesive resin of preparation example 1 to 4 are shown in table 2 below.
[table 1]
(note) MAA：Methacrylic acid
GMA：GMA
Sty：Styrene
KBM503：3- (methacryloxypropyl) trimethoxy silane (Shin-Etsu Chemical)
Initiator：2,2'- azodiisobutyronitriles
PGMEA：Propylene glycol methyl ether acetate
[table 2]
Acid number and weight average molecular weight are according to following measurement.
(1) acid number：Acid number refers to the mg numbers for neutralizing KOH (potassium hydroxide) needed for 1g acid.1g samples are dissolved in 10g acetone
In, and 2 to 3 drop phenolphthalein indicators are added into the sample solution, then titrated with the 0.1N KOH aqueous solution, measure is saturating when this
Bright solution is changed into KOH mg numbers during pink.Acid number is calculated as follows.
Acid number (KOH mg/g)=(0.1 × 122.13 × KOH titers) ÷ (sample size (g) × 1000)
(2) weight average molecular weight：Measured using gel permeation chromatography (GPC) system purchased from Varian.
<Embodiment 1 to 3 and comparative example 1>：The preparation of photosensitive resin composition
Carbon black (KLBK-9232, purchased from Tokushiki, grain is added into the acryl adhesive resin of preparation example 1 to 4
Footpath 90nm), polyfunctional monomer (dipentaerythritol acrylate), light trigger (I-242, purchased from Irgacure), solvent (third
Glycol monomethylether acetate (PGMEA)) and additive, and the reactant mixture is stirred 3 hours, photosensitive resin group is thus made
Compound.
In the following table, parts by weight refer to the parts by weight relative to 100 parts by weight of binder resin solid contents.
[table 3]
(note) resin：10 to 20wt% based on total composition
DPHA：Dipentaerythritol acrylate
PGMEA：Propylene glycol methyl ether acetate
GPTMS：Glycidoxypropyltrime,hoxysilane (silicon class compound)
BK-9232：Purchased from TOKUSHIKI charcoal blacks dispersion
The development initial time of comparative example 1 and the photosensitive resin composition of embodiment 1 to 3 is measured as follows, is shown
Column spacer height and residue generation under shadow pattern stability, optical density, different mask light transmittances etc..As a result under
Provided in table 4.
(1) formation of cured film
Adopt in the following method, solidification film figure is formed by each photosensitive resin composition of comparative example 1 and embodiment 1 to 3.
Specifically, on the glass substrate of clean surface, resinous coat is formed with 300rpm using spin coater, then in electric heating
Dried 100 seconds at 100 DEG C on plate, so as to which the thickness of the film of coating is adjusted to 3.5 μm.Next, use mask (gap
250 μm) with 60mJ/cm2Active energy beam (such as ultraviolet light) be exposed.Using developer solution, (0.04%KOH is water-soluble
Liquid, 25 DEG C) will as obtained by exposure film development 60 seconds, be consequently formed solidification film figure.Thereafter, in 230 DEG C of convection oven
Bakeed 30 minutes after progress.
(2) development initial time
Development initial time determines as follows：Resin black matrix is applied on the glass substrate, carries out prebake
Post-exposure, thereafter, with the naked eye measure the time that the time of resin black matrix development and pattern initially form in developing process.
(3) developing pattern stability
Developing pattern stability determines as follows：Resin black matrix is applied on the glass substrate, carries out preliminary drying
Post-exposure is roasted, thereafter, the time that the time and pattern that resin black matrix develops in developing process initially form (develops
Begin the time) after, the developing process of the scheduled time is carried out, and use the line width and linearity of optical microscope measuring pattern.It is right
Region of the reduction degree of per unit developing time (5 seconds) inner pattern line-width below 1 μm measures.
(4) optical density
It is right using the object of reference (reference) that optical density is 2.4 by the PMT purchased from Otsuka Electronics
The optical density of the cured film formed as described above measures.As a result it is shown in table 4 below.
(5) residue
Check that the residue after developing process has situation using SEM.
(6) the column spacer height (μm) under different mask light transmittances
When exposure forms column spacer, mask that the mask and light transmittance that the use of light transmittance are 100% are 10%
Carry out two kinds of processes.Using developer solution (the 0.04%KOH aqueous solution, 25 DEG C) will as obtained by exposure film development 60 seconds, thus shape
Into solidification film figure, thereafter, substrate is bakeed 30 minutes afterwards in 230 DEG C of convection oven.Utilize 3-D analysis tools (3-D
Profiler thus obtained cured film) is observed, the height of column spacer is compared.
[table 4]
By table 4 it is clear that in the comparative example 1 using only a kind of acrylic adhesives, when being using light transmittance
During 10% mask, the height of sept declines very slight.Light is improved compared with preparation example 1, in preparation example 2 and 3 to draw
The dosage of agent is sent out to reduce the molecular weight of resin, and in Examples 1 and 2, by two kinds of preparation example 1 and preparation example 2 or 3
When adhesive resin is mixed, the decline degree of sept height is improved.Compared with preparation example 2, carried in preparation example 3
The dosage of high methacrylic acid is to strengthen developing performance, therefore in the embodiment 3 using the preparation example, with the phase of embodiment 2
Than the height that reduce further sept.
Therefore, the composition of embodiment 1 to 3 is considered as the most suitable, because they can retain appropriate light
In the case of shielding properties, the column spacer of double type is formed by adjusting the light transmittance of mask in exposure.
Although disclosing the preferred embodiments of the invention for exemplary purposes, the technology of this area
Personnel will be understood that, disclosed in without departing substantially from such as appended claims in the case of scope and spirit of the present invention, can carry out
Various modifications, addition and replacement.
Claims (10)
1. a kind of photosensitive resin composition, comprising：
The acryl adhesive resin of 100 parts by weight；
The pigment of 10 to 20 parts by weight；With
The light trigger of 10 to 15 parts by weight,
Wherein, the acryl adhesive resin comprising acid number be 50 to 90mg KOH/g and weight average molecular weight be 8,000 to
13,000g/mol the first acryl adhesive resin, and acid number are 100 to be to 150mg KOH/g and weight average molecular weight
4,000 to 7,000g/mol the second acryl adhesive resin,
In the column spacer formed by the photosensitive resin composition, the mask shape that light transmittance is 100% is used in exposure
Into column spacer height and the use of light transmittance is 10% the difference of the height of column spacer that is formed of mask be 0.5 to
1μm。
2. photosensitive resin composition according to claim 1 comprising first acryl adhesive resin with
The weight ratio of second acryl adhesive resin is 3~7:7~3.
3. photosensitive resin composition according to claim 1, wherein, the pigment is included selected from carbon black, titanium is black, acetylene
One or more in black, nigrosine, black, strontium titanates, chromium oxide and ceria.
4. photosensitive resin composition according to claim 1, wherein, the pigment includes the charcoal that particle diameter is 90 to 110nm
It is black.
5. photosensitive resin composition according to claim 1, wherein, the light trigger includes being selected from oxime esters chemical combination
One or more in thing, ketone, halogen compounds, peroxide and acylphosphine oxide.
6. photosensitive resin composition according to claim 1, wherein, forming cured film using the photosensitive resin composition
When, the optical density (OD) of every 1.0 μm of unit thickness is 0.5 to 1.0.
7. a kind of display base plate, the column that the display base plate is formed including the use of the photosensitive resin composition described in claim 1
Sept.
8. a kind of display base plate, the black that the display base plate is formed including the use of the photosensitive resin composition described in claim 1
The column spacer of matrix integration.
9. a kind of liquid crystal panel, the liquid crystal panel is including the display base plate described in claim 7 or 8 as upper substrate.
10. a kind of liquid crystal display device, the liquid crystal display device includes the liquid crystal panel described in claim 9.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 | ||
| PCT/KR2012/007648 WO2013051805A2 (en) | 2011-10-02 | 2012-09-24 | Photosensitive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103959167A CN103959167A (en) | 2014-07-30 |
| CN103959167B true CN103959167B (en) | 2017-11-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280059588.7A Expired - Fee Related CN103959167B (en) | 2011-10-02 | 2012-09-24 | Photosensitive resin composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5901778B2 (en) |
| KR (1) | KR101688464B1 (en) |
| CN (1) | CN103959167B (en) |
| TW (1) | TWI477905B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6048670B2 (en) * | 2013-03-27 | 2016-12-21 | Jsr株式会社 | Radiation sensitive resin composition |
| KR102112320B1 (en) * | 2014-03-17 | 2020-05-18 | 동우 화인켐 주식회사 | Black photo sensitive resin composition with stair difference and color filter manufacturing method using the same |
| KR101474803B1 (en) | 2014-03-27 | 2014-12-19 | 제일모직주식회사 | Method of manufacturing black column spacer, black column spacer, and color filter |
| KR102361595B1 (en) * | 2015-03-11 | 2022-02-11 | 동우 화인켐 주식회사 | Black photosensitive resin composition, and black matrix and column spacer for liquid crystal display manufactured thereby |
| KR101897858B1 (en) * | 2015-03-26 | 2018-09-12 | 동우 화인켐 주식회사 | Black photo sensitive resin composition, a color filter comprising a black metrics and/or a column spacer prepared by using the composition, and a liquid crystal display comprising the color filter |
| KR102438341B1 (en) * | 2015-06-03 | 2022-08-31 | 주식회사 동진쎄미켐 | Negative photosensitive resin composition |
| TWI614575B (en) * | 2017-01-12 | 2018-02-11 | 住華科技股份有限公司 | Photosensitive resin composition |
| TWI690751B (en) | 2017-07-27 | 2020-04-11 | 南韓商Ｌｇ化學股份有限公司 | Substrate, method of producing the same and optical device |
| KR102307921B1 (en) * | 2017-12-22 | 2021-10-01 | 쇼와 덴코 가부시키가이샤 | Polymer composition, photosensitive resin composition and color filter |
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| JP3720478B2 (en) * | 1996-07-23 | 2005-11-30 | 富士写真フイルム株式会社 | Photosensitive resin composition |
| JP2002031713A (en) * | 2000-02-01 | 2002-01-31 | Mitsubishi Chemicals Corp | Composition for color filter, and color filter |
| 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 |
| JP4954194B2 (en) * | 2006-03-14 | 2012-06-13 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin laminate |
| JP5523655B2 (en) * | 2007-02-23 | 2014-06-18 | 富士フイルム株式会社 | Pigment dispersion composition, curable composition, color filter and method for producing the same |
| KR20090071032A (en) * | 2007-12-27 | 2009-07-01 | 주식회사 코오롱 | Photoresist composition, black matrix and color filter substrate |
| JP5073556B2 (en) * | 2008-03-31 | 2012-11-14 | 富士フイルム株式会社 | Photosensitive resin composition, light-shielding color filter, method for producing the same, and solid-state imaging device |
| JP2010039345A (en) * | 2008-08-07 | 2010-02-18 | Toray Ind Inc | Resin composition for liquid crystal display and method for producing substrate for liquid crystal display |
| CN101738857A (en) * | 2008-11-07 | 2010-06-16 | 京东方科技集团股份有限公司 | Black photo resist and preparation method and picture composition method thereof |
| 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 | The high lightshielding blackmatrix composition having improved adhesion properties |
| JP5505066B2 (en) * | 2010-04-28 | 2014-05-28 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, interlayer insulating film of display element, protective film and spacer, and method for forming them |
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- 2012-08-20 KR KR1020120090624A patent/KR101688464B1/en active IP Right Grant
- 2012-09-24 CN CN201280059588.7A patent/CN103959167B/en not_active Expired - Fee Related
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| TWI477905B (en) | 2015-03-21 |
| TW201316124A (en) | 2013-04-16 |
| KR101688464B1 (en) | 2016-12-22 |
| CN103959167A (en) | 2014-07-30 |
| KR20130036142A (en) | 2013-04-11 |
| JP5901778B2 (en) | 2016-04-13 |
| JP2014534460A (en) | 2014-12-18 |
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