CN106462071A - Photosensitive resin composition for light shielding and light-shielding layer formed therefrom - Google Patents
Photosensitive resin composition for light shielding and light-shielding layer formed therefrom Download PDFInfo
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- CN106462071A CN106462071A CN201580034918.0A CN201580034918A CN106462071A CN 106462071 A CN106462071 A CN 106462071A CN 201580034918 A CN201580034918 A CN 201580034918A CN 106462071 A CN106462071 A CN 106462071A
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- resin composition
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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
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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
-
- 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
- G03F7/075—Silicon-containing compounds
Abstract
The present invention relates to a photosensitive resin composition for light shielding, and a light-shielding layer formed using the same. The photosensitive resin composition for light shielding contains (A) a siloxane resin, (B) a pigment, (C) a photopolymerization initiator, and (D) an organic solvent, and optionally may further contain (E) a multi-functional monomer having an unsaturated bond. A coating film for a light shielding layer, formed of the photosensitive resin composition for light shielding, is characterized in that the coating film has excellent electrical characteristics, excellent adhesive strength with a substrate, and no deterioration in optical density, even after a high-temperature process at 300 DEG C or higher.
Description
Technical field
The present invention relates to a kind of photosensitive resin composition for shading and a kind of light shield layer for being formed by which.More specifically
Ground, the present invention relates to a kind of photosensitive resin composition, which can be used to prepare used in various types of electronics dresses by photoetching process
Light shield layer in putting；And a kind of light shield layer of the thin film including being formed by solidifying said composition.
This application claims the korean patent application No.10-2014-0079876 for submitting in Korea on June 27th, 2014
Priority, by quoting, the disclosure of which is incorporated herein.
Background technology
With the electronic product for including panel display apparatus such as liquid crystal indicator or touch screen device for manufacture
The development of technology, the size of cutback in demand product and thickness.In order to reduce size and the thickness of the product, inevitably
Increase the inner member integrated level of the product, and correspondingly, needing badly improves the electricity of the material used in the inner member is manufactured
Performance.
Usually, black matrix" photosensitive resin composition is that one kind includes in display element such as liquid crystal for manufacture
The necessary material of the color filter in showing device, organic electroluminescent device and display floater.Black matrix" light-sensitive resin composition
Thing is used to the color mixture between the R in the color filter for prevent liquid crystal indicator (redness), G (green) and B (blueness), or
It is used for covering the frame of the X and Y metal electrode in touch control panel device.
For for display liquid crystal indicator, recently, as with exceed super definition (UD) high-resolution and
The device that high-speed driving more than 240Hz is used, is actively studying low temperature polycrystalline silicon (LTPS) and oxide thin film transistor.
Usually, because the characteristic of semiconductor of oxide thin film transistor is changed due to light, introduce light shield layer with
Minimize the problems referred to above.Metal light shield layer is mainly used as the light shield layer, this is because in high temperature after the light shield layer is formed
Under carry out including the subsequent technique of PE-CVD, however, there is following point by the light shield layer that metal is formed：Due to the metal shading
Layer has high reflectance, and therefore light is reflected back toward and enters between source electrode and drain electrode and light shield layer；And in the source electrode
Stray voltage the factor as the operation for giving resisting apparatus is produced and drain electrode between, so as to cause to increase the negative of data wire
Carry.
Additionally, in touch control panel device, in order to reduce the thickness of product, gluing from glass cover-plate is made with contact panel glass
Knot conventional art development together, is studying monolithic glass solution (OGS) technology, and which forms on glass cover-plate and touches
Control panel.In OGS contact panel, the light shield layer (frame) for being formed on glass cover-plate is initially formed, is then formed and touch
Control panel driving unit.In the technique of transparency electrode of the contact panel driver element is formed, need to carry out high temperature gas phase and sink
Product or annealing process.However, the black matrix" ultraviolet curable resin for being conventionally used to light shield layer has electricity in such high-temperature technology
The shortcoming of performance degradation.
Content of the invention
Invent problem to be solved
The present invention provides a kind of photosensitive resin composition for shading, even if needed for which still produces after high-temperature technology
Electrical property (including resistance and dielectric constant) and required optical property (including optical density and reflectance).
In order to means to solve the problem
In order to above-mentioned purpose is reached, in one embodiment of the invention, a kind of photosensitive resin composition is provided, bag
Include：(A) silicone resin, which contains the polymerized unit for being represented by following chemical formula 1 and the polymerization list for being represented by following chemical formula 2
Unit；(B) pigment；(C) Photoepolymerizationinitiater initiater；(D) organic solvent.
[chemical formula 1]
R in formula1It is the straight chain with 1 to 20 carbon atom or branched chain alkylidene, the Asia virtue with 6 to 20 carbon atoms
Base, the total alkylidene with 7 to 20 carbon atoms with aryl substituent, with alkyl substituent total have 7 to
The arlydene of 20 carbon atoms or wherein alkylidene are linked to total group with 7 to 20 carbon atoms of arlydene.
X be hydroxyl, carboxylic acid, carboxylic acid anhydrides, polycalboxylic. anhydride derivative, acid imide, imide derivative, amide, amide derivatives,
Amine or sulfydryl.
[chemical formula 2]
R2 nSiO(4-n)/2
R in formula2Be each independently hydrogen, have the straight chain of 1 to 20 carbon atom, branched chain or cyclic alkyl, have 6 to
The aryl of 10 carbon atoms, the unsaturated alkyl with 2 to 10 carbon atoms or the acyloxy with 2 to 10 carbon atoms, point
Multiple R in son2Can be identical or different.
N is 0 to 3 integer, and wherein n be 3 polymerized unit can be another polymerized unit group in addition to 3 with wherein n
Close and use.
On the basis of total 100 moles of % of the polymerized unit of the polymerized unit of chemical formula 1 and chemical formula 2, the siloxanes
Resin can be made up of the polymerized unit of the polymerized unit of the chemical formula 1 of 5-40 mole of % and the chemical formula 2 of 95-60 mole of %.
Titrated by KOH, the silicone resin has the acid number in the range of 10-200mg KOH/g resin.
Photosensitive resin composition can further include the polyfunctional monomer of (E) with unsaturated bond.
The pigment can be black pigment.
And, the pigment can be any one of group selected from following person composition：White carbon black, titanium are black, nigrosine, black,
Strontium titanates, chromium oxide and cerium oxide or its mixture.
And, on the basis of the silicone resin of 100 weight portions or when using the multifunctional list with unsaturated bond
During body on the basis of total 100 weight portions of the silicone resin and the polyfunctional monomer with unsaturated bond, the pigment is permissible
Exist with the amount of 20-130 weight portion.
And, on the basis of the silicone resin of 100 weight portions or when using the multifunctional list with unsaturated bond
During body on the basis of total 100 weight portions of the silicone resin and the polyfunctional monomer with unsaturated bond, the photopolymerization is drawn
Send out agent to exist with the amount of 1-30 weight portion.
When the polyfunctional monomer with unsaturated bond is used, on the basis of the silicone resin of 100 weight portions, this is many
Functional monomer can be present to be more than 0 weight portion and the amount less equal than 100 weight portions.
On the basis of the total amount of the 100 weight portion photosensitive resin compositions, the organic solvent can be with 20-90 weight portion
Amount exist.
According to a further aspect in the invention, a kind of light shield layer is provided, and which includes and is formed by above-mentioned photosensitive resin composition
Thin film.
The light shield layer can with per unit thickness (μm) between 1.0 and 4.0 in the range of optical density.
According to another aspect of the invention, a kind of method for preparing the thin film for light shield layer is provided, including：(S1) in base
The photosensitive resin composition for shading of the embodiment being coated with plate according to the present invention；(S2) remove from said composition
Solvent is to form coat film；(S3) the exposed and developed coat film is to form thin film；(S4) at 200 DEG C to be up to less than 300
Heat treatment thin film at a temperature of between DEG C.
And, after (S4), the method can further include：(S5) at 300 DEG C with up to less than 600 DEG C of temperature
The heat treatment thin film.
The effect of invention
According to the photosensitive resin composition for shading of an embodiment of the present invention, can pass through in alkali after exposure
Aqueous developer in property aqueous solution and form pattern, and after forming the pattern, even if the pattern for being formed is in 300 DEG C or higher of temperature
Its shape is still maintained after the technique of degree.
And, the thin film for being formed by the photosensitive resin composition for solidifying for shading has electrical insulating property, including
Surface resistivity is less than or equal to 45 more than or equal to 1.0E+10 and dielectric constant, and maintains shading performance, for example, per unit
The optical density of thickness (μm) is more than or equal to 1.0, preferably between 1.0 and 4.0, and is therefore used as hiding
Light film.
Specific embodiment
Hereinafter, the present invention is described in detail.It should be understood that the art used in description and appended claim
Language should not be construed as limited to general sense and dictionary meanings, but should be based on and allow inventor suitably to define the term
Explained with obtaining principle, the implication based on the technical elements corresponding to the present invention and the concept of best interpretations.
According to the photosensitive resin composition of one embodiment of the invention, including：(A) silicone resin, which contains
The polymerized unit for being represented by following chemical formula 1 and the polymerized unit for being represented by following chemical formula 2；(B) pigment；(C) photopolymerization is drawn
Send out agent；And (D) organic solvent, if desired, the polyfunctional monomer of (E) with unsaturated bond can be further included.
[chemical formula 1]
R in formula1It is the straight chain with 1 to 20 carbon atom or branched chain alkylidene, the Asia virtue with 6 to 20 carbon atoms
Base, the total alkylidene with 7 to 20 carbon atoms with aryl substituent, with alkyl substituent total have 7 to
The arlydene of 20 carbon atoms or wherein alkylidene are linked to total group with 7 to 20 carbon atoms of arlydene.
X be hydroxyl, carboxylic acid, carboxylic acid anhydrides, polycalboxylic. anhydride derivative, acid imide, imide derivative, amide, amide derivatives,
Amine or sulfydryl.
[chemical formula 2]
R2 nSiO(4-n)/2
R in formula2Be each independently hydrogen, have the straight chain of 1 to 20 carbon atom, branched chain or cyclic alkyl, have 6 to
The aryl of 10 carbon atoms, the unsaturated alkyl with 2 to 10 carbon atoms or the acyloxy with 2 to 10 carbon atoms, its
Multiple R in middle molecule2Can be identical or different.
N is 0 to 3 integer, and wherein n be 3 polymerized unit can be another polymerized unit group in addition to 3 with wherein n
Close and use.
R1The non-limiting examples straight-chain alkyl-sub-that may include with 1 to 20 carbon atom, which can be that alkyl is for example sub-
Methyl, ethylidene, propylidene, butylidene and pentylidene；And branched chain alkylidene, such as isopropylidene and isobutylidene.
The instantiation of the polymerized unit for being represented by following chemical formula 1 is shown, but not limited to this.
[chemical formula 1a]
[chemical formula 1b]
[chemical formula 1c]
[chemical formula 1d]
[chemical formula 1e]
[chemical formula 1f]
[chemical formula 1g]
[chemical formula 1h]
[chemical formula 1i]
[chemical formula 1j]
[chemical formula 1k]
[chemical formula 1l]
[chemical formula 1m]
[chemical formula 1n]
(in other formula, m and n each stands alone as 1 to 20 integer)
R2The instantiation aliphatic alkyl that can include with 1 to 20 carbon atom independently of one another, such as methyl, second
Base, n-pro-pyl, isopropyl, normal-butyl, isobutyl group and n-pentyl, and the instantiation of annular aliphatic alkyl may include ring penta
Base, cyclohexyl, norborny and adamantyl.The instantiation of the acyloxy with 2 to 10 carbon atoms may include acryloyl
Epoxide methyl, acryloyl-oxyethyl, acryloxypropyl, acryloxy butyl, methacryloxymethyl, methyl
Acryloyl-oxyethyl, methacryloxypropyl and methacryloxy butyl.Virtue with 6 to 10 carbon atoms
The instantiation of base may include phenyl, naphthyl, anthryl, phenanthryl and pyrenyl.
The monomer for constituting the polymerized unit for being represented by chemical formula 2 may include, but be not limited to, for example：Tetraalkoxysilane, three
Alkoxy silane, methyl trialkoxysilane, ethyltrialkoxysilanes, n-pro-pyl trialkoxy silane, three alcoxyl of isopropyl
Base silane, normal-butyl trialkoxy silane, tert-butyl group trialkoxy silane, phenyl trialkoxysilane, Petroleum tri-alkoxy
Silane, vinyl trialkyl oxysilane, methacryloxymethyl trialkoxy silane, 2- methacryloxyethyl three
Alkoxy silane, 3- methacryloxypropyl trialkoxy silane, 3- methacryloyloxypropyl methyl dialkoxy
Silane, 3- methacryloxypropyl ethyl dialkoxy silicane, acryloyloxymethyl trialkoxy silane, 2- acryloyl
Epoxide ethyltrialkoxysilanes, 3- acryloxy propyl trialkoxy silane, 3- acryloxypropyl dialkoxy
Base silane, 3- acryloxypropyl ethyl dialkoxy silicane, 3- glycidyloxypropyl silane, 2- epoxy
Butylcyclohexyl ethyltrialkoxysilanes, 3- expoxycyclohexyl propyl trialkoxy silane, dimethyl alkoxy silane, diethyl
Base dialkoxy silicane, dipropyl dialkoxy silicane, diphenyl dialkoxy silicane, diphenyl silanodiol and phenyl first
Base dialkoxy silicane.Herein, alkoxyl is straight chain with 1 to 7 carbon atom, branched chain or annular aliphatic or aromatics alkane
Epoxide, and can be hydrolyzable halogen contained compound.
Preferably, it is a feature of the present invention that at least one for the polymerized unit for being represented by above-mentioned chemical formula 2 is methyl-prop
Alkene pivaloyloxymethyl trialkoxy silane, 2- methacryloxyethyl trialkoxy silane, 3- methacryloxy third
Base trialkoxy silane, 3- methacryloyloxypropyl methyl dialkoxy silicane, 3- methacryloxypropyl ethyl
Dialkoxy silicane, acryloyloxymethyl trialkoxy silane, 2- acryloyl-oxyethyl trialkoxy silane, 3- acryloyl
Epoxide propyl trialkoxy silane, 3- acryloxypropyl dialkoxy silicane and 3- acryloxypropyl.
Titrated by KOH, (A) silicone resin can be with the acid number in the range of 10-200mg KOH/g resin.
When using silicone resin, due to the heat stability of the silicone resin, between the carbon granule as pigment
Even if distance still suitably can be maintained after the high-temperature technology greater than or equal to 300 DEG C, high electrical insulating properties are presented.
The acid number of silicone resin, by using the titration of 0.1N KOH solution, preferably per 1g resin glue 10 to
200mg[KOH].
When the acid number of silicone resin is less equal than 10mg [KOH]/g [resin], manifest heliosensitivity due to lacking
Feasibility and produce residual film, and when working as the acid number than or equal to 200mg [KOH]/g [resin], it may occur that for example pattern is damaged
The problem of mistake.
(B) pigment is the pigment with light-proofness, it is however preferred to have the black pigment of light-proofness.Non- limit as the pigment
Based on their property, property example processed, can use that white carbon black, titanium be black, nigrosine, black, strontium titanates, chromium oxide and cerium oxide, but
The pigment is not limited to this.Preferably white carbon black.
White carbon black may include Cisto series purchased from Tokai Carbon, purchased from Mitsubishi Chemical
Diagram series and MA series, purchased from DK Dong Shin PRINTEX series and purchased from Columbian Chemicals's
Raven series.
The particle size of pigment is preferably adjusted to the scope between 50 to 150nm, the model more preferably between 50 to 80nm
Enclose.When the pigment of the particle size having less than 50nm is dispersed in photosensitive resin composition, even if using identical
Pigment content, optical density can still reduce.Additionally, when the pigment of the particle size having more than 150nm is dispersed in heliosensitivity tree
When in oil/fat composition, the electrical insulating property of thin film and roughness properties are deteriorated.
On the basis of the silicone resin of 100 weight portions, or when the polyfunctional monomer with unsaturated bond is used with silicon
On the basis of total 100 weight portions of oxygen alkane resin and the polyfunctional monomer with unsaturated bond, pigment is with 20-130 weight portion
Amount is present, and the content can change in numerical range according to application target.When the pigment is present with the amount less than 20 weight portions
When, the sensitivity of photosensitive resin composition and the electrical insulating property of thin film and roughness are enhanced, it can be difficult to expected optical density
More than or equal to 1.0 per units thickness (μm).And, when the pigment content is more than 130 weight portion, satisfaction is more than or equal to
The optical density of 4.0 per units thickness (μm), but the sensitivity of electrical insulating property step-down and photosensitive resin composition reduces.
(C) Photoepolymerizationinitiater initiater is to produce free radical by light and induce the material of crosslinking, and its non-limiting examples is excellent
Elect at least one of the group selected from following person composition as：Triazine system (triazine-based) compound, 1-Phenylethanone. system
(acetophenone-based) compound, bisglyoxaline system (biimidazole-based) compound and oxime system (oxime-
Based) compound.
The non-limiting examples of triazine based compound include double (the trichloromethyl) -6- (4- methoxyphenyl) -1,3 of 2,4-,
Double (trichloromethyl) -6- (4- methoxyl group the naphthyl) -1,3,5- triazines of 5- triazine, 2,4-, double (the trichloromethyl) -6- Fructus Piperiss of 2,4-
Double (trichloromethyl) -6- [2- (5- methylfuran -2- base) the vinyl] -1,3,5- triazines and 2 of base -1,3,5- triazine, 2,4-,
Double (trichloromethyl) -6- [2- (furan -2- base) the vinyl] -1,3,5- triazines of 4-.The non-limiting reality of 1-Phenylethanone. based compound
Example include 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 1- (4- isopropyl phenyl) -2- hydroxy-2-methyl propane -1- ketone,
4- (2- hydroxyl-oxethyl)-phenyl-(2- hydroxyl -2- propyl group) ketone, 1- hydroxycyclohexylphenylketone, benzoin methyl ether, benzene idol
Relation by marriage ethylether, benzoin isobutyl ether, benzoin butyl ether, 2,2- dimethoxy -2- phenyl acetophenone, 2- methyl-(4- first sulfur
Base) phenyl -2- morpholino -1- propane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butane -1- ketone,
2- (the bromo- benzyl -2- dimethylamino -1- of 4- (4- morphlinophenyl)-butane -1- ketone and 2- methyl isophthalic acid-[4- (methyl mercapto) benzene
Base] -2- morpholino propane -1- ketone.
Additionally, the non-limiting examples of bisglyoxaline based compound include double (2- chlorphenyl) -4,4', 5,5'- tetra- benzene of 2,2-
Double (o- chlorphenyl) -4,4', 5,5'- tetraphenyl bisglyoxalines of base bisglyoxaline, 2,2'-, double (o- the chlorphenyl) -4,4' of 2,2'-, 5,
Double (2,3- the Dichlorobenzene base) -4,4' of 5'- tetra- (3,4,5- trimethoxyphenyl) -1,2'- bisglyoxaline, 2,2'-, 5,5'- tetraphenyl
Bisglyoxaline and double (o- chlorphenyl) -4,4', 5,5'- tetraphenyl -1,2'- bisglyoxalines of 2,2'-.
Additionally, the non-limiting examples of oxime compound include OXE-02 (trade mark is purchased from BASF), N1919, NCI-
831 (trade mark is purchased from Adeka), 1,2- acetyl caproyl (octadion) -1- (4- thiophenyl) phenyl -2- (o- benzoyl
Oxime) and ethyl ketone -1- (9- ethyl) -6- (2- methyl benzoyl -3- base) -1- (O- acetyl group oxime).
On the basis of the silicone resin of 100 weight portions, or when the polyfunctional monomer with unsaturated bond is used with silicon
Oxygen alkane resin and the polyfunctional monomer with unsaturated bond add up to 100 weight portions on the basis of, Photoepolymerizationinitiater initiater can with 1 to
The amount of 30 weight portions is present.
In the photosensitive resin composition of the present invention, (D) organic solvent unrestrictedly includes any solvent, as long as its energy
The composition comprising silicone resin being dissolved enough and does not suppress the dispersion of pigment.The instantiation of the organic solvent includes, but not
It is limited to, ketone series solvent such as methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl Ketone, methyl n-butyl ketone, methyl tert-butyl
Base ketone, methyl-n-amyl ketone, metacetone, dipropyl ketone, diisobutyl ketone, Ketohexamethylene, Ketocyclopentane, methyl cyclohexanone, 2,4-
Pentanedione, acetonyl acetone, gamma-butyrolacton and gamma-valerolactone；Ether series solvent such as methyl ethyl ether, two-n-propyl of methyl
Ether, Di Iso Propyl Ether, tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, glycol ether, ethylene glycol bisthioglycolate butyl ether, two
Glycol methyl ethyl ether, triglyme, three glycol ether, Methylene glycol methyl ethylether, propylene glycol dimethyl ether, Propylene Glycol
Ether, Propylene Glycol-n-propyl ether, Propylene Glycol dibutyl ethers, Ethylene glycol methyl ether, glycol ethyl ether, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, propylene glycol monomethyl ether；Ether acetic acid ester series solvent such as Ethylene glycol methyl ether propionic ester, glycol ethyl ether
Propionic ester, Ethylene glycol methyl ether acetass, ethylene glycol monoethyl ether acetate, methyl proxitol acetate, propylene glycol ethyl ether
Acetass and propylene glycol propyl ether acetass；Acetonitrile, N-Methyl pyrrolidone, N- ethyl pyrrolidone, N- propyl pyrrole alkane
Ketone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, N- dimethyl sulfoxide, toluene and dimethylbenzene；And alcohol series solvent
Such as methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, Hexalin, methyl cyclohexanol, benzylalcohol, ethylene glycol, 1,2-
Propylene Glycol and diethylene glycol, which can use singularly or in combination.
The content of organic solvent can be based on silicone resin, pigment, Photoepolymerizationinitiater initiater and many officials with unsaturated bond
The content of energy monomer is suitably adjusted, and can be according to coating photosensitive resin composition in the method for formation light shield layer on substrate
And change.For example, on the basis of the total amount of the photosensitive resin composition of 100 weight portions, the scope of the content of organic solvent can
Think 20 to 90 weight portions, but not limited to this.
(E) polyfunctional monomer with unsaturated bond is a kind of reactivity unsaturated compound, and which has extremely in the molecule
An addition polymerization unsaturated group, and the compound less is selectively used singly or in combination.
The non-limiting examples of the polyfunctional monomer with unsaturated bond may include glycol diacrylate, diethylene glycol two
Acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6 hexanediol diacrylate, tetramethylolmethane
Triacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, bisphenol A epoxy acrylate, ethylene glycol
Monomethyl ether acrylate, ethylene glycol dimethacrylate or 1,6-HD dimethylacrylate.
On the basis of the silicone resin of 100 weight portions, the content of the polyfunctional monomer with unsaturated bond is 0 to 200
Weight portion.When the content is more than 200 weight portion, the compatibility of silicone resin and carbon granule can be reduced, this can make it difficult to
Control pattern form.
Polyfunctional monomer with unsaturated bond (wherein the unsaturated bond is included in resin glue) may not include
In photosensitive resin composition, but can be used for pattern form control and sensitivity.
In addition, if desired, for shading photosensitive resin composition can further include usually used in this field
Additive, such as curing accelerator, thermal polymerization inhibitor, plasticizer, filler, solvent, levelling agent and defoamer.Thermal polymerization presses down
Preparation can be hydroquinone, Hydroquinone monomethylether, pyrogaelol, tert-butyl catechol or phenothiazine.Plasticizer can be O-phthalic
Dibutyl phthalate, dioctyl phthalate or trimethylphenyl.Filler can be glass filler, silicon dioxide, Muscovitum or oxidation
Aluminum.And, defoamer or levelling agent can be such as silicon-type compound, fluorine system compound or acrylic compounds.
An embodiment for light shield layer (black matrix") being formed using photosensitive resin composition may include (S1) in base
Be coated with plate according to the present invention for shading photosensitive resin composition the step of；(S2) solvent in said composition is removed
The step of to form coat film；(S3) the step of exposed and developed coat film is to form thin film；(S4) at 200 DEG C with up to
At a temperature of between less than 300 DEG C the step of the heat treatment thin film.Additionally, after (S4), the method can further include
(S5) from 300 DEG C with up to less than 600 DEG C of temperature under the heat treatment thin film the step of.
In one embodiment of the technique for being coated with the photosensitive resin composition for shading at (S1) on substrate, the painting
Cloth can be using contact transfevent coating machine on the glass substrate on the pure surface of the clean surface with 0.5～1.1mm thickness
Such as roll coater (roll coater), reverse roll coater (reverse coater) and rod coater (bar
Coater), or contact-free applicator machine such as spinner (rotary coating machine) and showering curtain type flowing coating machine (curtain
Flow coater) carrying out.
In preparation and coating, in order to improve the cohesive of the glass substrate and the photosensitive resin composition, can add
Silane coupler or can apply on the substrate.
Subsequently, (S2) removes solvent to form coat film from said composition.
In order to carry out this step, held at a temperature of 80 DEG C～120 DEG C, preferably 90 DEG C～100 DEG C by using hot plate
Lasting a few houres～several days are kept at room temperature drying said composition, or by making said composition within continuous 60 seconds～120 seconds, or logical
Cross after said composition is placed on hot air heater or infrared heater lasting a few minutes～a few houres to remove solvent,
Can be by the scope of coat film thickness adjusted to 0.5～5 μm.
Subsequently, (S3) exposed and developed coat film is to form thin film.
Its non-limiting embodiments is may include by minus mask exposure in active energy beam, such as in emittance
Quantity of X-rays X is between 30～2000mJ/cm2Between ultraviolet and excimer laser.The emittance quantity of X-rays X can be according to
Type for the photo-sensitive composition of shading used and change.Using developing solution by infusion process or nebulization come to logical
The thin film that overexposure is obtained is developed to black matrix pattern.The developing solution of development may include monoethanolamine, diethanol
Amine and the organic solution of triethanolamine, or sodium hydroxide, potassium hydroxide, sodium carbonate, the aqueous solution of ammonia and quaternary ammonium salt.
In addition, in an embodiment of the preparation method of the present invention, the method can further include (S4) at 200 DEG C
With heat treatment thin film at a temperature of between being up to less than 300 DEG C, and (S5) after (S4), is can further include at 300 DEG C
With heat treatment thin film at up to less than 600 DEG C of temperature.
Heat treatment in (S4) can be at 200 DEG C with up to less than carrying out 5-60 minute at a temperature of between 300 DEG C, and institute
State heat treatment method and general baking oven can be used, but be not limited to this.
In addition, the heat treatment in (S5) can be carried out 5-60 minute at a temperature of between 300 DEG C to 600 DEG C, and described
Heat treatment method can use the conventional method in this area, such as baking oven, but be not specially limited.
Generally speaking, it is known that thin film can be reduced and comprising the thin film at 200 DEG C or higher than the additional heat treatment at 200 DEG C
The electrical insulating property of light shield layer, and reduce its electrical insulating property further at 300 DEG C or higher than the additional heat treatment at 300 DEG C.This is
Because the conductive features of pigment such as white carbon black.That is, if heat treatment temperature is raised in the technique for prepare thin film, surround
The resin of pigment can be deteriorated and reduce the distance between pigment, cause to increase electric conductivity.As a result, become the electrical insulating property of thin film
Difference.
However, by the thin film for being manufactured according to the photosensitive resin composition of one embodiment of the invention, thin film
Can at 200 DEG C or higher than heat treatment at 200 DEG C after (even at 300 DEG C or higher than 300 DEG C after heat treatment) with good
Good electrical insulating property, and also improve the electrical insulating property of the light shield layer comprising the thin film.
The light shield layer (black matrix") for being obtained by above-mentioned preparation method can be used for multiple display devices such as liquid crystal panel
And plasma display.
Hereafter, will be described in detail by embodiment to help understand the present invention.However, embodiment of the present invention can be taken
Many other forms, and the scope of the present invention should not be construed as limited to the following example.There is provided embodiment of the present invention with
The present invention is more fully explained to tool usually intellectual in field according to the present invention.
<The synthesis of silicone resin>
Synthesis example 1
In the flask equipped with cooling tube and agitator, the 3- (triethoxysilyl) of the 250g that weighs (1.0mol)
Methyl propionate (hereinafter also referred to as ' propanoic acid '), the phenyltrimethoxysila,e (hereinafter also referred to as ' benzene of 198g (1.0mol)
Base '), the MTMS (hereinafter also referred to as ' methyl ') of 136g (1.0mol), the methyl-prop of 497g (2.0mol)
Alkene acryloxypropylethoxysilane trimethoxy silane (hereinafter also referred to as ' methylacryloyl ') and the propylene glycol monomethyl ether of 2000g
Acetass.While the solution is stirred, 35% aqueous hydrochloric acid solution of 13.0g (0.125mol) and the water of 270g is added dropwise over
Mixed solution.After being added dropwise to complete, make reaction temperature that 85 DEG C are increased to, and reaction is carried out at a temperature of the increase, and to continue 6 little
When.After completion of the reaction, implement extraction by adding ether and water, reclaim organic faciess, and by evaporation remove remnants alcohol and
Solvent, produces the silicone resin of 657g.The silicone resin of acquisition is dissolved in the propylene glycol monomethyl ether of 657g
In.The weight average molecular weight of the silicone resin is 4,800.
Synthesis example 2
In the flask equipped with cooling tube and agitator, the 3- (triethoxysilyl) of the 250g that weighs (1.0mol)
Methyl propionate, the phenyltrimethoxysila,e of 297g (1.5mol), the MTMS of 204g (1.5mol), 248g
(1.0mol) methacryloxypropyl trimethoxy silane and the propylene glycol monomethyl ether of 2000g.In stirring
While the solution, the mixed solution of 35% aqueous hydrochloric acid solution of 13.0g (0.125mol) and the water of 270g is added dropwise over.In drop
Plus after the completion of, make reaction temperature increase to 85 DEG C, and carry out reaction at a temperature of the increase to continue 6 hours.Complete in reaction
Afterwards, implement extraction by adding ether and water, organic faciess are reclaimed, and remaining alcohol and solvent is removed by evaporation, produce 608g
Silicone resin.The silicone resin of acquisition is dissolved in the propylene glycol monomethyl ether of 608g.The silicone resin
Weight average molecular weight be 4,200.
Synthesis example 3
In the flask equipped with cooling tube and agitator, the 3- (triethoxysilyl) of the 264g that weighs (1.0mol)
Methyl propionate, the phenyltrimethoxysila,e of 396g (2.0mol), the MTMS of 272g (2.0mol) and
The propylene glycol monomethyl ether of 2000g.While the solution is stirred, the 35% of 13.0g (0.125mol) is added dropwise over
The mixed solution of the water of aqueous hydrochloric acid solution and 270g.After being added dropwise to complete, reaction temperature is made to increase to 85 DEG C, and in the increase
At a temperature of carry out reaction and continue 6 hours.After completion of the reaction, implement extraction by adding ether and water, organic faciess are reclaimed, and logical
Pervaporation removes the alcohol and solvent of remnants, produces the silicone resin of 560g.The silicone resin of acquisition is dissolved in 560g's
Propylene glycol monomethyl ether.The weight average molecular weight of the silicone resin is 3,800.
<Preparation for the ultraviolet curable resin of black matrix">
Embodiment 1
On the basis of the total resin composition of 100 weight portions, mix the alkali solubility silicone resin (synthesis example of 12 weight portions
The silicone resin for synthesizing in 1, phenyl/methyl/methylacryloyl/propanoic acid=20/20/40/20, Mw 4800, acid number 36mg
[KOH]/g [resin]), the white carbon black (100nm particle size) of 3.6 weight portions (comes in the form of the dispersion liquid containing 20% white carbon black
Use.Be scaled white carbon black dispersion liquid when for 18 weight portions), the ethyl ketone -1- [9- ethyl -6- (2- methyl -4- tetrahydrochysene of 1 weight portion
Pyrans epoxide benzoyl) -9H- carbazole -3- base] -1- (o- acetyl group oxime) (OXE-02, BASF) and 69 weight portions conduct
The propylene glycol monomethyl ether of organic solvent is to prepare photosensitive resin composition.
Embodiment 2
On the basis of the total resin composition of 100 weight portions, the alkali solubility silicon of 10 weight portions used in mix embodiment 1
Oxygen alkane resin (silicone resin for synthesizing in synthesis example 1, phenyl/methyl/methylacryloyl/propanoic acid=20/20/40/20,
Mw 4800, acid number 36mg [KOH]/g [resin]), the white carbon black (100nm particle size) of 6 weight portions is (with containing 20% white carbon black
The form of dispersion liquid is using.Be scaled white carbon black dispersion liquid when for 30 weight portions), the ethyl ketone -1- [9- ethyl -6- of 1 weight portion
(2- methyl -4- tetrahydro-pyran oxy benzoyl) -9H- carbazole -3- base] -1- (o- acetyl group oxime) (OXE-02, BASF) and
The propylene glycol monomethyl ether as organic solvent of 59 weight portions is to prepare photosensitive resin composition.
Embodiment 3
On the basis of the total resin composition of 100 weight portions, the alkali solubility silicon of 9 weight portions used in mix embodiment 1
Oxygen alkane resin (silicone resin for synthesizing in synthesis example 1, phenyl/methyl/methylacryloyl/propanoic acid=20/20/40/20,
Mw 4800, acid number 36mg [KOH]/g [resin]), the white carbon black (100nm particle size) of 8 weight portions is (with containing 20% white carbon black
The form of dispersion liquid is using.Be scaled white carbon black dispersion liquid when for 40 weight portions), the ethyl ketone -1- [9- ethyl -6- of 1 weight portion
(2- methyl -4- tetrahydro-pyran oxy benzoyl) -9H- carbazole -3- base] -1- (o- acetyl group oxime) (OXE-02, BASF) and
The propylene glycol monomethyl ether as organic solvent of 50 weight portions is to prepare photosensitive resin composition.
Embodiment 4
On the basis of the total resin composition of 100 weight portions, the alkali solubility silicon of 8 weight portions used in mix embodiment 1
Oxygen alkane resin (silicone resin for synthesizing in synthesis example 1, phenyl/methyl/methylacryloyl/propanoic acid=20/20/40/20,
Mw 4800, acid number 36mg [KOH]/g [resin]), the white carbon black (100nm particle size) of 9.4 weight portions is (to contain 20% white carbon black
Dispersion liquid form using.Be scaled white carbon black dispersion liquid when for 47 weight portions), the ethyl ketone -1- of 1 weight portion [9- ethyl -
6- (2- methyl -4- tetrahydro-pyran oxy benzoyl) -9H- carbazole -3- base] -1- (o- acetyl group oxime) (OXE-02, BASF),
The propylene glycol monomethyl ether as organic solvent of 44 weight portions is to prepare photosensitive resin composition.
Embodiment 5
On the basis of the total resin composition of 100 weight portions, mix the alkali solubility silicone resin (synthesis example of 10 weight portions
The silicone resin for synthesizing in 2, phenyl/methyl/methylacryloyl/propanoic acid=30/30/20/20, Mw 3600, acid number 42mg
[KOH]/g [resin]), the dipentaerythritol acrylate as the polyfunctional monomer with unsaturated bond of 2 weight portions,
The white carbon black (100nm particle size) of 3.6 weight portions (is used in the form of the dispersion liquid containing 20% white carbon black.It is scaled white carbon black
Dispersion liquid when be 18 weight portions), ethyl ketone -1- [9- ethyl -6- (the 2- methyl-tetrahydro pyrans epoxide benzoyl of 1 weight portion
Base) -9H- carbazole -3- base] -1- (o- acetyl group oxime) (OXE-02, BASF), the Propylene Glycol as organic solvent of 69 weight portions
Monomethyl ether acetate is to prepare photosensitive resin composition.
Embodiment 6
On the basis of the total resin composition of 100 weight portions, the alkali solubility silicon of 8 weight portions used in mix embodiment 5
Oxygen alkane resin (silicone resin for synthesizing in synthesis example 2, phenyl/methyl/methylacryloyl/propanoic acid=30/30/20/20,
Mw 3600, acid number 42mg [KOH]/g [resin]), two seasons penta as the polyfunctional monomer with unsaturated bond of 4 weight portions
Six acrylate of tetrol, the white carbon black (100nm particle size) of 3.6 weight portions (are come in the form of the dispersion liquid containing 20% white carbon black
Use.Be scaled white carbon black dispersion liquid when for 18 weight portions), the ethyl ketone -1- [9- ethyl -6- (2- methyl -4- tetrahydrochysene of 1 weight portion
Pyrans epoxide benzoyl) -9H- carbazole -3- base] -1- (o- acetyl group oxime) (OXE-02, BASF) and 69 weight portions conduct
The propylene glycol monomethyl ether of organic solvent is to prepare photosensitive resin composition.
Embodiment 7
On the basis of the total resin composition of 100 weight portions, the alkali solubility silicon of 6 weight portions used in mix embodiment 5
Oxygen alkane resin (silicone resin for synthesizing in synthesis example 2, phenyl/methyl/methylacryloyl/propanoic acid=30/30/20/20,
Mw 3600, acid number 42mg [KOH]/g [resin]), two seasons penta as the polyfunctional monomer with unsaturated bond of 6 weight portions
Six acrylate of tetrol, the white carbon black (100nm particle size) of 3.6 weight portions (are come in the form of the dispersion liquid containing 20% white carbon black
Use.Be scaled white carbon black dispersion liquid when for 18 weight portions), the ethyl ketone -1- [9- ethyl -6- (2- methyl -4- tetrahydrochysene of 1 weight portion
Pyrans epoxide benzoyl) -9H- carbazole -3- base] -1- (o- acetyl group oxime) (OXE-02, BASF) and 69 weight portions conduct
The propylene glycol monomethyl ether of organic solvent is to prepare photosensitive resin composition.
Embodiment 8
On the basis of the total resin composition of 100 weight portions, the alkali solubility silicon of 4 weight portions used in mix embodiment 5
Oxygen alkane resin (silicone resin for synthesizing in synthesis example 2, phenyl/methyl/methylacryloyl/propanoic acid=30/30/20/20,
Mw 3600, acid number 42mg [KOH]/g [resin]), two seasons penta as the polyfunctional monomer with unsaturated bond of 4 weight portions
Six acrylate of tetrol, the white carbon black (100nm particle size) of 9.4 weight portions (are come in the form of the dispersion liquid containing 20% white carbon black
Use.Be scaled white carbon black dispersion liquid when for 47 weight portions), the ethyl ketone -1- [9- ethyl -6- (2- methyl -4- tetrahydrochysene of 1 weight portion
Pyrans epoxide benzoyl) -9H- carbazole -3- base] -1- (o- acetyl group oxime) (OXE-02, BASF), the conduct of 44 weight portions have
The propylene glycol monomethyl ether of machine solvent is to prepare photosensitive resin composition.
Comparative example 1
On the basis of the total resin composition of 100 weight portions, mix the alkali solubility card polyphyly (cardo- of 4 weight portions
Based) resin (Mw 5000, acid number 80mg [KOH]/g [resin], Adeka), 4 weight portions as having many of unsaturated bond
The dipentaerythritol acrylate of functional monomer, the white carbon black (100nm particle size) of 9.4 weight portions are (to contain 20% white carbon black
Dispersion liquid form using.Be scaled white carbon black dispersion liquid when for 47 weight portions), the ethyl ketone -1- of 1 weight portion [9- ethyl -
6- (2- methyl -4- tetrahydro-pyran oxy benzoyl) -9H- carbazole -3- base] -1- (o- acetyl group oxime) (OXE-02, BASF),
And 44 weight portion the propylene glycol monomethyl ether as organic solvent to prepare photosensitive resin composition.
Comparative example 2
On the basis of the total resin composition of 100 weight portions, mix the alkali solubility silane oxygen tree fat (synthesis example 3 of 4 weight portions
The silicone resin of middle synthesis, phenyl/methyl/propanoic acid=40/40/20, Mw 3800, acid number 40mg [KOH]/g [resin]), 4
The dipentaerythritol acrylate as the polyfunctional monomer with unsaturated bond of weight portion, the white carbon black of 9.4 weight portions
(100nm particle size) (is used in the form of the dispersion liquid containing 20% white carbon black.It is 47 weight during the dispersion liquid for being scaled white carbon black
Part), the ethyl ketone -1- [9- ethyl -6- (2- methyl -4- tetrahydro-pyran oxy benzoyl) -9H- carbazole -3- base] of 1 weight portion -
The propylene glycol monomethyl ether as organic solvent of 1- (o- acetyl group oxime) (OXE-02, BASF) and 44 weight portions with
Prepare photosensitive resin composition.
<Test case>
The photosensitive resin composition for shading (for black matrix") for preparing in embodiment and comparative example is led to
Cross rotary coating to be coated on the glass substrate of LCD- panel with 1.2 microns of thickness, and at 100 DEG C soft baking to remove
Solvent, forms coat film.The coat film for being formed is exposed and thin film is developed in aqueous alkali.In 230 DEG C of baking ovens
The middle glass substrate heat treatment thereon with thin film continues 30 minutes to obtain after final thin film, measurement surface resistivity, Jie
Electric constant, optical density, pin hole (pinholes) and cohesive.Afterwards, implement further heat treatment in 380 DEG C of baking ovens to hold
Continue 30 minutes and measure above-mentioned assessment in the same manner.Result according to evaluation criteria shows in Tables 1 and 2.
Surface resistivity is determined
In order to measure the surface resistivity of formed thin film, using the meter (high from Keithley
Resistance meter) carry out measurement surface resistivity.
Dielectric Coefficient
In order to measure the dielectric constant of formed thin film, shape on the glass substrate of the lower electrode for coating with ITO
Become thin film, and upper electrode is formed by al deposition.The measure of dielectric constant is carried out using Agilent 4284LCR meter.
Spectrodensitometry
In order to the optical density of formed thin film is measured, optical density O.D is measured using X-rite 361T.
Pin hole is determined
The pin hole of the thin film for being formed is determined to be included using optical microscope measuring in 10cm X 10cm glass substrate
Pinhole number.0～10 pin hole is represented with O, and 10～30 pin holes are represented with △, and 30 or more pin holes with × represent.
Adhesion test
In order to measure cohesive, after forming film on the glass substrate, using cross-cut machine (crosshatch cutter)
The sample of the final solidification of scraping is so that the substrate exposes, and peels off after 3M adhesive tape is applied.In this case, stripping area
The area in domain is exceeded the 65% of total Test surface and is represented with 0B, 35-65% is represented with 1B, and 15-35% is represented with 2B, 5-15%
Represented with 3B, represented with 4B less than 5%, and represented with 5B without stripping area.
[table 1]
[table 2]
Referring to embodiment 1 to embodiment 4, it can be seen that as the content of the silane oxygen tree fat in resin combination increases,
The dielectric constant of the thin film for being manufactured by the resin combination reduces, that is, improve electrical insulating property.
Additionally, embodiment 5 is to embodiment 8 with regard to including dipentaerythritol acrylate as with many of unsaturated key
The resin combination of functional monomer, and can see for the thin film for preparing in embodiment 5 to embodiment 8, with siloxanes tree
The content of fat increases, and they show relatively low dielectric constant and have preferably electrical insulating property.
Additionally, when respectively embodiment 5 and embodiment 8 being compared with embodiment 1 and embodiment 4, embodiment 5 and real
A part for the silicone resin content that example 8 is wherein in the resin combination of embodiment 1 and embodiment 4 is applied by with insatiable hunger
With the polyfunctional monomer alternative embodiment of key, and the thin film for being formed by embodiment 5 and embodiment 8 (as above-mentioned replacer) is relative
There is the effect of poor electrical insulating property in the thin film for being formed by embodiment 1 and embodiment 4.
Meanwhile, compared to the thin film of the resin combination manufacture by embodiment 1 to embodiment 8, by using card polyphyly resin
Comparative example 1 resin combination manufacture thin film show significantly high dielectric constant and with excessively poor electrical insulating property.
As Table 1 and Table 2 below, compared to comparative example, even after 380 DEG C of high-temperature technology, being prepared by the present invention
Thin film there is much better electrical insulating property, optical property, cohesive, pattern resolution and sensitivity, it is adaptable to need high temperature
The preparation technology of process.And, the light shield layer comprising the thin film can also present good electrical insulating property, optical property, pattern
Resolution and sensitivity.
Claims (17)
1. a kind of photosensitive resin composition for shading, comprising：Silicone resin, which contains and is represented by following chemical formula 1
Polymerized unit and the polymerized unit for being represented by following chemical formula 2；Pigment；Photoepolymerizationinitiater initiater；And organic solvent：
[chemical formula 1]
In the chemical formula 1,
R1It is straight chain with 1 to 20 carbon atom or branched chain alkylidene, there is the arlydene of 6 to 20 carbon atoms, there is virtue
The alkylidene for adding up to 7 to 20 carbon atoms of base substituent group, the Asia virtue for adding up to 7 to 20 carbon atoms with alkyl substituent
Base or wherein alkylidene are connected to the group for adding up to 7 to 20 carbon atoms of arlydene；
X be hydroxyl, carboxylic acid, carboxylic acid anhydrides, polycalboxylic. anhydride derivative, acid imide, imide derivative, amide, amide derivatives, amine or
Sulfydryl；
[chemical formula 2]
R2 nSiO(4-n)/2
In the chemical formula 2,
R2Each stand alone as hydrogen, the straight chain with 1 to 20 carbon atom, branched chain or cyclic alkyl, there are 6 to 10 carbon atoms
Aryl, there is the unsaturated alkyl of 2 to 10 carbon atoms or the acyloxy with 2 to 10 carbon atoms, in the molecule many
Individual R2May be the same or different；And
N is 0 to 3 integer, and wherein n be 3 polymerized unit can be that another polymerized unit in addition to 3 is combined and made with wherein n
With.
2. the photosensitive resin composition for shading according to claim 1, the polymerization list for wherein being represented by chemical formula 1
The group that unit constitutes selected from following chemical formula 1a to chemical formula 1n：
[chemical formula 1a]
[chemical formula 1b]
[chemical formula 1c]
[chemical formula 1d]
[chemical formula 1e]
[chemical formula 1f]
[chemical formula 1g]
[chemical formula 1h]
[chemical formula 1i]
[chemical formula 1j]
[chemical formula 1k]
[chemical formula 1l]
[chemical formula 1m]
[chemical formula 1n]
In each chemical formula, m and n is each independently 1 to 20 integer.
3. the photosensitive resin composition for shading according to claim 1, the polymerization list for wherein being represented by chemical formula 2
Unit is formed by any one of group for constituting selected from following person：Tetraalkoxysilane, trialkoxy silane, methyl tri-alkoxy
Silane, ethyltrialkoxysilanes, n-pro-pyl trialkoxy silane, isopropyl trialkoxy silane, normal-butyl tri-alkoxy silicon
Alkane, tert-butyl group trialkoxy silane, amyl group trialkoxy silane, Petroleum trialkoxy silane, vinyl trialkyl oxysilane,
Methacryloxymethyl trialkoxy silane, 2- methacryloxyethyl trialkoxy silane, 3- methacryl
Epoxide propyl trialkoxy silane, 3- methacryloyloxypropyl methyl dialkoxy silicane, 3- methacryloxy third
Base ethyl dialkoxy silicane, acryloyloxymethyl trialkoxy silane, 2- acryloyl-oxyethyl trialkoxy silane, 3-
Acryloxy propyl trialkoxy silane, 3- acryloxypropyl dialkoxy silicane, 3- acryloxypropyl
Ethyl dialkoxy silicane, 3- glycidyloxypropyl silane, 2- epoxycyclohexylethyl trialkoxy silane,
3- epoxycyclohexyl propyl trialkoxy silane, dimethyl alkoxy silane, diethyl dialkoxy silicane, dipropyl dialkoxy
Base silane, diphenyl dialkoxy silicane, diphenyl silanodiol and phenyl methyl dialkoxy silicane or its mixture.
4. the photosensitive resin composition for shading according to claim 3, the polymerization list for wherein being represented by chemical formula 2
Unit is formed by any one of group for constituting selected from following person：Methacryloxymethyl trialkoxy silane, 2- methyl
Acryloyl-oxyethyl trialkoxy silane, 3- methacryloxypropyl trialkoxy silane, 3- methacryloxy
Hydroxypropyl methyl dialkoxy silicane, 3- methacryloxypropyl ethyl dialkoxy silicane, three alkane of acryloyloxymethyl
TMOS, 2- acryloyl-oxyethyl trialkoxy silane, 3- acryloxy propyl trialkoxy silane, 3- acryloyl-oxy
Base hydroxypropyl methyl dialkoxy silicane and 3- acryloxypropyl ethyl dialkoxy silicane or its mixture.
5. the photosensitive resin composition for shading according to claim 1, wherein with the polymerized unit of chemical formula 1 and
On the basis of the polymerized unit of chemical formula 2 adds up to 100 moles of %, the silicone resin by 5-40 mole of % chemical formula 1 poly-
The polymerized unit for closing the chemical formula 2 of unit and 95-60 mole of % is constituted.
6. the photosensitive resin composition for shading according to claim 1, is wherein titrated by KOH, the silica
Alkane resin has the acid number in the range of 10-200mg KOH/g resin.
7. the photosensitive resin composition for shading according to claim 1, which includes further：With unsaturated bond
Polyfunctional monomer.
8. the photosensitive resin composition for shading according to claim 1, the wherein pigment are black pigment.
9. the photosensitive resin composition for shading according to claim 1, the wherein pigment be selected from following
Any one of group of person's composition：White carbon black, titanium are black, nigrosine, black, strontium titanates, chromium oxide and cerium oxide or its mixture.
10. the photosensitive resin composition for shading according to claim 1 or 7, wherein with described in 100 weight portions
On the basis of silicone resin, or with the silicone resin and described when using the polyfunctional monomer with unsaturated bond
On the basis of total 100 weight portions of the polyfunctional monomer with unsaturated bond, the pigment is present with the amount of 20-130 weight portion.
11. photosensitive resin compositions for shading according to claim 1 or 7, wherein with described in 100 weight portions
On the basis of silicone resin, or with the silicone resin and described when using the polyfunctional monomer with unsaturated bond
On the basis of total 100 weight portions of the polyfunctional monomer with unsaturated bond, the Photoepolymerizationinitiater initiater is with 1-30 weight portion
Amount is present.
12. photosensitive resin compositions for shading according to claim 7, wherein with the silicon of 100 weight portions
On the basis of oxygen alkane resin, the polyfunctional monomer with unsaturated bond is with more than 0 weight portion and less equal than 100 weight portions
Amount exist.
13. photosensitive resin compositions for shading according to claim 1, wherein with the use of 100 weight portions
On the basis of the total amount of the photosensitive resin composition of shading, the organic solvent is present with the amount of 20-90 weight portion.
A kind of 14. light shield layers, comprising by the ultraviolet curable resin group for shading according to any one of claim 1 to 13
The thin film that compound is formed.
15. light shield layers according to claim 14, the wherein light shield layer have per unit thickness (μm) between 1.0-4.0
Between optical density.
A kind of 16. methods for preparing the thin film for light shield layer, including：
(S1) photosensitive resin composition for shading being coated with substrate according to claim 1 or 7；
(S2) solvent is removed to form coat film from the compositionss；
(S3) the exposed and developed coat film is to form thin film；With
(S4) at 200 DEG C to carry out heat treatment to the thin film at a temperature of between being up to less than 300 DEG C.
17. methods for preparing the thin film for light shield layer according to claim 16, which includes after (S4) further：
(S5) 300 DEG C with up to less than 600 DEG C of temperature under heat treatment is carried out to the thin film.
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| KR10-2014-0079876 | 2014-06-27 | ||
| KR1020140079876A KR101537771B1 (en) | 2014-06-27 | 2014-06-27 | Photoresist composition for light shielding and Light shielding layer obtained therefrom |
| PCT/KR2015/006454 WO2015199449A1 (en) | 2014-06-27 | 2015-06-24 | Photosensitive resin composition for light shielding and light-shielding layer formed therefrom |
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| US10095102B2 (en) * | 2016-04-12 | 2018-10-09 | Taiwan Semiconductor Manufacturing Co., Ltd. | Photomask having a plurality of shielding layers |
| JP6853057B2 (en) * | 2017-01-31 | 2021-03-31 | 東京応化工業株式会社 | Polymerizable composition, method for producing cured film, and cured film |
| KR102032022B1 (en) * | 2017-05-10 | 2019-10-15 | 정의산업(주) | Ink composition for light shielding, and method for producing light shielding film using said ink composition |
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| JP4638380B2 (en) * | 2006-01-27 | 2011-02-23 | 信越化学工業株式会社 | Antireflection film material, substrate having antireflection film, and pattern forming method |
| TW201415169A (en) * | 2012-10-08 | 2014-04-16 | Everlight Chem Ind Corp | Black photosensitive resin composition and light-blocking layer using the same |
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| CN106981478A (en) * | 2017-04-07 | 2017-07-25 | 京东方科技集团股份有限公司 | Top gate type thin film transistor and preparation method thereof, array base palte, display panel |
| US10868190B2 (en) | 2017-04-07 | 2020-12-15 | Boe Technology Group Co., Ltd. | Top-gate thin film transistor, manufacturing method thereof, array substrate and display panel comprising top-gate thin film transistor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106462071B (en) | 2019-12-27 |
| TW201610587A (en) | 2016-03-16 |
| WO2015199449A1 (en) | 2015-12-30 |
| KR101537771B1 (en) | 2015-07-17 |
| TWI554834B (en) | 2016-10-21 |
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