CN106054520A - Colored photosensitive resin composition and black column spacer prepared therefrom - Google Patents
Colored photosensitive resin composition and black column spacer prepared therefrom Download PDFInfo
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- CN106054520A CN106054520A CN201610177193.7A CN201610177193A CN106054520A CN 106054520 A CN106054520 A CN 106054520A CN 201610177193 A CN201610177193 A CN 201610177193A CN 106054520 A CN106054520 A CN 106054520A
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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
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13398—Spacer materials; Spacer properties
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- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
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Abstract
The invention provides a colored photosensitive resin composition. The colored photosensitive resin composition includes a copolymer, an epoxy resin compound or a derived compound therefrom, a photopolymerisable compound, a photopolymerization initiator and a colorant. The photopolymerisable compound contains a compound of a formula 1 and a compound of a formula 3. The colored photosensitive resin composition can be used for preparing a black column spacer having a complex structure of a duotone structure and improved resolution and surface characters.
Description
Technical field
The present invention relates to a kind of photosensitive composition, it is suitable for forming liquid crystal display (LCD) or organic
Sept employed in the panel of light emitting diode (OLED) display, light-blocking member etc.；With by described compositions
The cured film formed, especially black column spacer (BCS), wherein column spacer and black matix are integrated into one
Individual module.
Background technology
Recently, use the sept formed by photosensitive polymer combination saturating to the top in the liquid crystal cells maintaining LCD
Distance between bright substrate and lower transparent substrate.LCD is a kind of by constant to be injected between two transparent substrates
Liquid crystal material in gap applies the electro-optical device that voltage drives, and the most crucially maintains between two substrates
Clearance constant.If the gap between transparent substrates is non-constant, then the voltage that applies to it and penetrate this region
Transmittance may change, and causes the defect that brightness space is uneven.According to the recent demand to large-scale LCD panel,
Maintain the constant clearance between two transparent substrates the most crucial.
By being applied on substrate by photosensitive polymer combination and coated substrate can be made above to have shade
In the case of be exposed to ultraviolet light etc., make it develop subsequently, form sept.In this, Korean Patent No. 1,373,984
Number disclose a kind of photosensitive polymer combination for transparent cylindrical sept and prepared therefrom there is large plastometric set
Column spacer, described photosensitive polymer combination uses with a certain weight range to be had the light of polycaprolactone skeleton and can gather
Polymerisable compounds.
Meanwhile, the most attempting column spacer and black matix being integrated into the black post of a module by research and development
Shape sept simplifies manufacturing process.It addition, carrying out various research to prepare the black post with duotone structure
Shape sept.But, because the commonly required high-resolution of transparent cylindrical sept is also between baroque black column
Needed for parting, so excellent surface characteristic is also that it is required.
Summary of the invention
Therefore, it is an object of the present invention to provide a kind of photosensitive composition, from described coloring phototonus tree
Oil/fat composition can be prepared to be had such as the labyrinth of duotone structure and has resolution and the surface characteristic of improvement
Black column spacer.
According to an aspect of the present invention, it is provided that a kind of photosensitive composition, it comprises (a) copolymer；(b)
Epoxy resin compound or the compound derived by it；(c) photopolymerizable compound；(d) Photoepolymerizationinitiater initiater；And
E () coloring agent, wherein said photopolymerizable compound includes the first acrylic compounds photopolymerizable unsaturated compound of formula 1
With the second acrylic compounds photopolymerizable unsaturated compound being different from the first acrylic compounds photopolymerizable unsaturated compound:
[formula 1]
In formula 1,
R1To R6It is hydrogen or the substituent group represented by formula 2, wherein R independently of one another1To R6In at least one be by
The substituent group that formula 2 represents, wherein n is 1 or 2,
[formula 2]
In formula 2,
R7It is the C that can be substituted2-20Epoxide alkylidene；
R8It is H or methyl；And
N is the integer of 0 to 2.
The photosensitive composition of the present invention represents exposure tolerance limit and the Development margin of improvement, and therefore, it can
Have such as the labyrinth of duotone structure to be used for preparing and there is the resolution of improvement and the black post of surface characteristic
Shape sept.
Accompanying drawing explanation
Fig. 1 is schematic diagram (A: the thickness of column spacer parts, the B: black of the exemplary cross-sectional of black column spacer
The thickness of color base element, the critical dimension (CD) of C: column spacer parts).
Fig. 2 is by consolidating that 100% panchromatic tune column spacer (CS) pattern and 20% halftoning black matrix patterns are constituted
Change the schematic diagram (panchromatic tune (F/T) the territory size of D: shade) of film.
Detailed description of the invention
Hereinafter, the present invention will be described in more detail.
Photosensitive composition
According to embodiments of the invention, described photosensitive composition comprises (a) copolymer；(b) asphalt mixtures modified by epoxy resin
Compound or the compound derived by it；(c) photopolymerizable compound；(d) Photoepolymerizationinitiater initiater；And (e)
Coloring agent, wherein said photopolymerizable compound includes the first acrylic compounds photopolymerizable unsaturated compound and not of formula 1
It is same as the second acrylic compounds photopolymerizable unsaturated compound of the first acrylic compounds photopolymerizable unsaturated compound:
[formula 1]
In formula 1,
R1To R6It is hydrogen or the substituent group represented by formula 2, wherein R independently of one another1To R6In at least one be by
The substituent group that formula 2 represents, wherein n is 1 or 2,
[formula 2]
In formula 2,
R7It is the C that can be substituted2-20Epoxide alkylidene；R8It is H or methyl；And n is the integer of 0 to 2.
Additionally, photosensitive composition of the present invention optionally comprise (f) solvent, (g) surfactant and/or
(h) silane coupling agent.
In the present invention, " (methyl) acryloyl group " means " acryloyl group " and/or " methylacryloyl ", and
And " (methyl) acrylate " means " acrylate " and/or " methacrylate ".
Hereinafter, will be explained in every kind of component of photosensitive composition.
(a) copolymer
Copolymer used in the present invention can comprise (a-1) derived from alkene system unsaturated carboxylic acid, alkene system unsaturated carboxylic acid anhydrides
Or the unit of its mixture, and (a-2) is derived from the unit of the alkene system unsaturated compound containing aromatic ring.Described
Copolymer can comprise (a-3) list derived from the alkene system unsaturated compound being different from (a-1) and (a-2) further
Unit.
Described copolymer is a kind of alkali soluble resins, and it provides developing function in development step, is used simultaneously as being formed
The substrate of coating and the structure of the final pattern of formation.
(a-1) derived from alkene system unsaturated carboxylic acid, alkene system unsaturated carboxylic acid anhydrides or the unit of its mixture
In the present invention, unit (a-1) is derived from alkene system unsaturated carboxylic acid, alkene system unsaturated carboxylic acid anhydrides or its mixture.
Alkene system unsaturated carboxylic acid and alkene system unsaturated carboxylic acid anhydrides are the polymerizable unsaturations in molecule with at least one hydroxy-acid group
Monomer.The example includes unsaturated monocarboxylic, such as (methyl) acrylic acid .beta.-methylacrylic acid, α-chloroacrylic acid, cinnamic acid etc.；
Unsaturated dicarboxylic and its anhydride, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid (itaconic
Acid), itaconic anhydride, citraconic acid (citraconic acid), citraconic anhydride, mesaconic acid (mesaconic acid) etc.；
The unsaturated polyester carboxylic acid of trivalent or more high price and its anhydride；List [(methyl) acryloxy of bivalence or the more polycarboxylic acids of high price
Alkyl] ester, such as list [2-(methyl) acryloyl-oxyethyl] succinate, the adjacent benzene two of list [2-(methyl) acryloyl-oxyethyl]
Formic acid esters etc..Derived from above Exemplary compounds unit can with single compound form two or plural
Combining form is contained in copolymer.
In terms of the total mole number of the unit constituting described copolymer, the amount of unit (a-1) can be that 5 moles of % rub to 65
You are %, preferably 10 moles % to 50 mole of %.In this weight range, resin combination may easily maintain it to develop
Characteristic.
(a-2) derived from the unit of the alkene system unsaturated compound containing aromatic ring
Unit (a-2) is derived from the alkene system unsaturated compound containing aromatic ring.The example can include (methyl) propylene
Acid phenenyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid 2-phenoxy ethyl, phenoxy group diethylene glycol (methyl) propylene
Acid esters, to Nonylphenoxy Polyethylene Glycol (methyl) acrylate, to Nonylphenoxy polypropylene glycol (methyl) acrylate,
(methyl) tribromophenyl acrylate；Styrene；There is the styrene of alkyl substituent, such as methyl styrene, dimethyl benzene
Ethylene, trimethyl styrene, ethyl styrene, diethyl, triethylbenzene ethylene, propylstyrene, butyl
Styrene, hexyl benzene ethylene, heptyl benzene ethylene, octyl styrene etc.；There is the styrene of halogen, as fluorobenzene ethylene,
Chlorostyrene, bromstyrol, iodobenzene ethylene etc.；There is the styrene of alkoxy substituent, such as methoxy styrene, second
Epoxide styrene, propoxyl group styrene etc.；4-Vinyl phenol, to hydroxy-alpha-methyl styrene, acetylbenzene ethylene；
Vinyltoluene, divinylbenzene, vinylphenol, adjacent vinyl benzene methyl ether, a vinyl benzene methyl
Ether, to vinyl benzene methyl ether, adjacent vinyl benzene methyl glycidyl ether, a vinyl benzene methyl glycidyl ether,
To vinyl benzene methyl glycidyl ether etc..
Unit derived from above Exemplary compounds can be with single unit form or two or plural combination shape
Formula is contained in copolymer.
In described compound, the compound of styrene-based is preferred in view of its polymerism.
In terms of the total mole number of the unit constituting described copolymer, the amount of unit (a-2) can be that 2 moles of % rub to 70
You are %, preferably 5 moles % to 60 mole of %.In described weight range, resin combination can have favourable resistance toization
The property learned.
(a-3) derived from the unit of the alkene system unsaturated compound being different from (a-1) and (a-2)
In addition to (a-1) and (a-2), copolymer used in the present invention can comprise further derived from being different from (a-1)
(a-2) unit of alkene system unsaturated compound.
The example of the alkene system unsaturated compound being different from (a-1) and (a-2) can include esters of unsaturated carboxylic acids, such as (first
Base) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylate,
(methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid ethyl are own
Ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) 2-(Acryloyloxy)ethanol, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) propylene
Acid 2-hydroxyl-3-chlorine propyl ester, (methyl) acrylic acid 4-hydroxy butyl ester, (methyl) glycerol acrylate, Alpha-hydroxy methacrylic acid
Methyl ester, Alpha-hydroxy ethyl methacrylate, Alpha-hydroxy propyl methacrylate, Alpha-hydroxy butyl methacrylate, (methyl)
Acrylic acid 2-methoxy acrylate, (methyl) acrylic acid 3-methoxybutyl, ethoxydiglycol (methyl) acrylate,
Methoxy triethylene (methyl) acrylate, methoxyl group tripropylene glycol (methyl) acrylate, PEG methyl ether (first
Base) acrylate, (methyl) acrylic acid tetrafluoro propyl ester, (methyl) acrylic acid 1,1,1,3,3,3-hexafluoro isopropyl ester, (methyl) propylene
Acid octafluoro pentyl ester, (methyl) acrylic acid 17 fluorine ester in the last of the ten Heavenly stems, (methyl) isobornyl acrylate, (methyl) acrylic acid bicyclo-penta
Ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid two cyclopentyloxy ethyl ester, (methyl) acrylic acid cyclopentenes oxygen
Base ethyl ester etc.；There is the tertiary amine of N-vinyl, such as NVP, N-VCz, N-vinyl
Quinoline etc.；Unsaturated ethers, such as vinyl methyl ether, EVE etc.；There is the alkene system unsaturated compound of epoxy radicals,
Such as (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxy radicals butyl ester, (methyl) acrylic acid 4,5-epoxy radicals penta
Ester, (methyl) acrylic acid 5, the own ester of 6-epoxy radicals, (methyl) acrylic acid 6,7-epoxy radicals heptyl ester, (methyl) acrylic acid 2,3-ring
Epoxide ring pentyl ester, (methyl) acrylic acid 3,4-epoxycyclohexyethylSiOi ester, acrylic acid α-ethyl glycidyl ester, acrylic acid α-just
Propylglycidyl ester, acrylic acid α-n-butyl glycidyl ester, N-(4-(2,3-epoxy radicals propoxyl group)-3,5-dimethyl benzene
Methyl) acrylamide, N-(4-(2,3-epoxy radicals propoxyl group)-3,5-dimethylphenylpropyl) acrylamide, (methyl) acrylic acid
4-hydroxybutyl glycidyl ether, allyl glycidyl ether, 2-methacrylic glycidyl ether etc.；Unsaturated acyl is sub-
Amine, such as N-phenylmaleimide, N-(4-chlorphenyl) maleimide, N-(4-hydroxy phenyl) maleic
Imidodicarbonic diamide, N-cyclohexylmaleimide etc..
Unit derived from above Exemplary compounds can be with single unit form or two or plural combination shape
Formula is contained in copolymer.
In view of copolymerizable property and for improve dielectric layer intensity, preferably can use derived from have epoxy radicals and
/ or the unit of unsaturated imido alkene system unsaturated compound, more preferably can use and contract derived from (methyl) acrylic acid
Water glyceride, (methyl) acrylic acid 4-hydroxy butyl ester glycidyl ether and/or the unit of the substituted maleimide of N-.
In terms of the total mole number of the unit constituting described copolymer, the amount of unit (a-3) can be that 10 moles of % rub to 80
You are %, preferably 20 moles % to 75 mole of %.In described weight range, resin combination can have long storage period
And film retention rate improves when being shaped to film.
Preferably, the copolymer with said units (a-1) to (a-3) can include that (methyl) acrylic/styrene is common
Polymers, (methyl) acrylic acid/(methyl) benzyl acrylate copolymer, (methyl) acrylic/styrene/(methyl) acrylic acid first
Ester copolymer, (methyl) acrylic/styrene/(methyl) acrylic acid methyl ester ./(methyl) glycidyl acrylate copolymer, (first
Base) acrylic/styrene/(methyl) acrylic acid methyl ester ./(methyl) glycidyl acrylate/N-phenylmaleimide
Copolymer, (methyl) acrylic/styrene/(methyl) acrylic acid methyl ester ./(methyl) glycidyl acrylate/N-cyclohexyl is along fourth
Alkene imidodicarbonic diamide copolymer, (methyl) acrylic/styrene/(methyl) n-butyl acrylate/(methyl) glycidyl acrylate
/ N-phenylmaleimide copolymer, (methyl) acrylic/styrene/(methyl) glycidyl acrylate/N-phenyl
Maleimide copolymer, (methyl) acrylic/styrene/(methyl) acrylic acid 4-hydroxy butyl ester glycidyl ether/N-phenyl
Maleimide copolymer etc..
Photosensitive composition can contain one or more copolymers.
Measured by gel permeation chromatography (eluant: oxolane etc.), making with polystyrene of described copolymer
The weight average molecular weight (Mw) of reference can be 3,000 to 50,000, preferably 5,000 to 40,000.At this model
In enclosing, resin combination can have good and substrate adhesiveness, physical/chemical properties and viscosity.
(i.e. with solid content meter) based on the total amount not wrapping solvent-laden photosensitive composition, coloring phototonus
The amount of the copolymer in resin combination can be 1 weight % to 70 weight %, preferably 5 weight % are to 50 weight %.
Within the above range, resin combination can produce good pattern form when development, and such as chemical-resistant characteristic
Improvement.
Can be by molecular weight regulator, radical polymerization initiator, solvent and unit (a-1) be put to (a-3)
Putting in the reactor, nitrogen injection and being slowly agitated is polymerized wherein, prepares the copolymer of the present invention.
Molecular weight regulator is not particularly limited and can include mercaptan, such as butyl mercaptan, spicy thioalcohol etc.；Or Alpha-Methyl benzene
Ethylene dimerization body.
Radical polymerization initiator is not particularly limited and can include azo-compound, as 2,2 '-azodiisobutyronitrile,
2,2 '-azo double (2,4-methyl pentane nitrile), 2,2 '-azo double (4-methoxyl group-2,4-methyl pentane nitrile) etc.；Benzoyl peroxide,
Lauryl peroxide, the peroxide pivalic acid tert-butyl ester, 1,1-bis(t-butylperoxy) cyclohexane etc..Radical polymerization initiator
Can be used alone or use with its two or more combining form.
Additionally, any solvent for preparing copolymer can use, it can include such as propylene glycol monomethyl ether second
Acid esters (PGMEA).
(b) epoxy resin compound or the compound derived by it
The photosensitive composition of the present invention can comprise epoxy resin compound or further by its derivative change
Compound.Preferably, photosensitive composition can include having ton backbone structure epoxy resin compound or
The compound derivative by it.
Measured by gel permeation chromatography, epoxy resin compound can have 400 to 10,000 with polystyrene make
The weight average molecular weight (Mw) of reference.
For example, epoxy resin compound can be to have ton (9H-ton) backbone structure as represented by formula 4
Compound:
[formula 4]
Wherein replaced and be contained in via the carbon atom of * labelling by each carbon atom of * labelling independentlyIn；
L1It is C independently of one another1-10Alkylidene, C3-20Cycloalkylidene or C1-10Alkylene oxide group；
R1To R7It is H, C independently of one another1-10Alkyl, C1-10Alkoxyl, C2-10Thiazolinyl or C6-14Aryl；
R8It is H, methyl, ethyl, CH3CHCl-、CH3CHOH-、CH2=CHCH2-or phenyl；And
N is the integer of 0 to 10.
C1-10The instantiation of alkylidene can include methylene, ethylidene, propylidene, isopropylidene, butylidene, Asia
Isobutyl group, sub-sec-butyl, the sub-tert-butyl group, pentylidene, isoamylidene, sub-tertiary pentyl, hexylidene, heptamethylene, Ya Xin
Base, sub-iso-octyl, sub-t-octyl, 2-ethyl hexylen, different nonyl nonamethylene, sub-, decylene, sub-isodecyl etc..
C3-20The instantiation of cycloalkylidene can include cyclopropylidene, sub-cyclobutyl, cyclopentylene, cyclohexylidene, sub-cycloheptyl
Base, sub-decahydro naphthyl, sub-adamantyl etc..C1-10The instantiation of alkylene oxide group can include methylene epoxide, sub-ethoxy
Base, sub-propoxyl group, Aden's epoxide, sub-sec-butoxy, sub-tert-butoxy, sub-amoxy, sub-hexyloxy, epoxide in sub-heptan,
Sub-octyloxy, 2-ethyl-Asia hexyloxy etc..C1-10The instantiation of alkyl can include methyl, ethyl, propyl group, isopropyl
Base, butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, isopentyl, tertiary pentyl, hexyl, heptyl, octyl group, different
Octyl group, t-octyl, 2-ethylhexyl, nonyl, different nonyl, decyl, isodecyl etc..C1-10The instantiation of alkoxyl
Can include methoxyl group, ethyoxyl, propoxyl group, butoxy, sec-butoxy, tert-butoxy, amoxy, hexyloxy,
Heptan epoxide, octyloxy, 2-ethyl-hexyloxy etc..C2-10The instantiation of thiazolinyl can include vinyl, pi-allyl, fourth
Thiazolinyl, acrylic etc..C6-14The instantiation of aryl can include phenyl, tolyl, xylyl, naphthyl etc..
Compound derived from the epoxy resin of the ton backbone structure with formula 4 can be by making the ton master with formula 4
The epoxy resin of chain structure reacts generation epoxy resin adduct with unsaturated monoacid, and makes thus obtained ring subsequently
Epoxy resins adduct and multi-anhydride react acquisition, or by making thus obtained compound and simple function or multi-functional epoxy
Compound reacts acquisition further.Any unsaturated monoacid known to can using in art, such as acrylic acid,
Methacrylic acid .beta.-methylacrylic acid, cinnamic acid, sorbic acid etc..Can use in art known any in the present invention
Multi-anhydride, such as succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic dianhydride, 1,2,4,5-hexamethylene four
Formic acid dianhydride, hexahydrophthalic anhydride etc..Can use in the present invention in art known any simple function or
Multi-functional epoxy compound, such as glycidyl methacrylate, methyl glycidyl ether, ethyl ether,
Propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, bisphenol Z contract
Water glycerin ether etc..
When using the compound derived from the epoxy resin of the ton backbone structure with formula 4, ton backbone structure is permissible
Improve curing materials and the adhesiveness of substrate, alkali resistance, machinability, intensity etc..It addition, remove not solid after development
After changing part, pattern can be formed there is high-resolution image.
(i.e. with solid content meter) in terms of the total amount not wrapping solvent-laden photosensitive composition, asphalt mixtures modified by epoxy resin is esterified
Compound or the amount by its derivative compound can be 1 weight % to 70 weight %, preferably 5 weight % are to 50 weight %.
In the range of described, resin combination can have resolution and the chemical resistance of improvement.It addition, the shape of pattern keeps
Preferably, and constant altitude can advantageously be obtained between the pattern with wanted tolerance limit width (i.e. allowing width) poor.
(c) photopolymerizable compound
Photopolymerizable compound used in the present invention can be by any compound of polymerization initiator polymerization, and
And can be commonly used for preparing the polyfunctional monomer of photosensitive composition, oligomer or polymer.
Specifically, photopolymerizable compound can include formula 1 the first acrylic compounds photopolymerizable unsaturated compound and
It is different from the second acrylic compounds photopolymerizable unsaturated compound of the first acrylic compounds photopolymerizable unsaturated compound.And
And the second acrylic compounds photopolymerizable unsaturated compound of surface characteristic improvement can be the compound represented by formula 3:
[formula 1]
In formula 1,
R1To R6It is hydrogen or the substituent group represented by formula 2, wherein R independently of one another1To R6In at least one be by
The substituent group that formula 2 represents, wherein n is 1 or 2,
[formula 2]
In formula 2,
R7It is the C that can be substituted2-20Epoxide alkylidene, preferably-C5H10O-；R8It is H or methyl；And n is
The integer of 0 to 2,
[formula 3]
In formula 3,
A is the rational number of 3 to 4；And
B is the rational number of 0 to 1.
Commercially available first acrylic compounds photopolymerizable unsaturated compound can include from Nippon Kayaku K. K (Nippon
Kayaku Co., Ltd.) DPCA-20, DPCA-30, DPCA-60, DPCA-120 etc., but be not limited to this.
And the second acrylic compounds photopolymerizable unsaturated compound can include that the card from Nippon Kayaku K. K is sub-
Rad (KAYARAD) HDDA, HX-220, R-604, DPHA-40H, TMPTA, DPHA, PET-30,
TPA-330、RP-1040、T-1420；From Osaka science Co., Ltd. (Osakauki kagakugokyo) V-295,
V-300, V-360, V-GPT, V-3PA, V-400 and V-802；From Toagosei Co., Ltd (Toagosei Co.,
Ltd.) Ah's Knicks (Aronix) M-309, Ah Knicks M-400, Ah Knicks M-403, Ah Knicks M-405,
Ah Knicks M-450, Ah Knicks M-7100, Ah Knicks M-8030, Ah Knicks M-8060, TO-1382；
From La Luomo (Laromer) BDDA, HDDA, TPGDA, DPGDA etc. of BASF (BASF), but
It is not limited to this.
Photopolymerizable unsaturated compound can be used alone or uses with its two or more combining form.
(i.e. with solid content meter) in terms of the total amount not wrapping solvent-laden photosensitive composition, the first acrylic acid
The amount of class photopolymerizable unsaturated compound can be 0.5 weight % to 15 weight %, preferably 1 weight % is to 10 weight
%.
First acrylic compounds photopolymerizable unsaturated compound and the weight of the second acrylic compounds photopolymerizable unsaturated compound
Amount ratio can be 3: 100 to 24: 100, preferably 5: 100 to 22: 100.
(d) Photoepolymerizationinitiater initiater
Any of polymerization initiator can be used as the Photoepolymerizationinitiater initiater in the present invention.
Photoepolymerizationinitiater initiater can be selected from the group that consists of: 1-Phenylethanone., non-imidazole, triazine, salt, Benzoinum,
Benzophenone, diketone, α-diketone, multinuclear quinone, thiaxanthone, diazonium compound, acid imide sulphonic acid ester, oxime, carbazole,
Boric acid sulfonium and its mixture.
In above-claimed cpd, it is preferable that for high sensitivity, it is possible to use Korea S's Laid-Open Patent publication
No. 2004-7700, No. 2005-84149, No. 2008-83650, No. 2008-80208,2007-44062
Number, No. 2007-91110, No. 2007-44753, No. 2009-9991, No. 2009-93933,2010-97658
Number, No. 2011-59525, No. 2011-91742, No. 2011-26467 and No. 2011-15683 and international
One or more oximes disclosed in publication WO No. 2010/102502 and WO 2010/133077.It addition,
For high sensitivity and resolution, its commercially available material is preferred, such as OXE-01 (BASF), OXE-02 (Bath
Husband), N-1919 (Ai Dike (ADEKA)), NCI-930 (Ai Dike), NCI-831 (Ai Dike) etc..
(i.e. with solid content meter) in terms of the total amount not wrapping solvent-laden photosensitive composition, polymerization initiator
Amount can be 0.01 weight % to 10 weight %, preferably 0.2 weight % is to 5 weight %.In the range of described, tree
Oil/fat composition fully can solidify when being exposed in light, thus easily forms pattern.The pattern being consequently formed can be aobvious
During shadow, substrate is kept enough adhesivenesses, and the sept with splendid elastic return can be obtained.
(e) coloring agent
The photosensitive composition of the present invention gives shading characteristic containing coloring agent.
Coloring agent used in the present invention can be that two or more is inorganic or toner (preferably has high Chromaticity
Characteristic and the coloring agent of thermostability) mixture.Specifically, the mixing of two or more toner is used
Thing is advantageously possible for preventing by black matix light leak and guaranteeing transmittance so that shade is directed at.
It addition, coloring agent can comprise black colorant and blue colorant.Black colorant can be black inorganic coloring
Agent and/or black toner.
According to an embodiment, photosensitive composition can comprise black toner as coloring agent；And
And optionally, comprise black inorganic coloring agent and blue colorant further.
Known any black inorganic coloring agent, any black toner and any blue colorant in art
Can use, such as at " color index (Color Index) " (by dyestuff and division color association (Society of Dyers
And Colourists) printing) in classify as known any dyestuff in the compound of pigment and art.
The instantiation of black inorganic coloring agent can include that carbon black, titanium be black, metal-oxide is (as based on Cu-Fe-Mn
Oxide) and synthesis iron black etc..Wherein for institute's desirable pattern characteristic and chemical resistance, preferably carbon black.
It addition, the instantiation of black toner can include that nigrosine, lactams are black, black etc..Wherein for
Wanted optical density, dielectric constant, transmittance etc., preferably lactams black (black the 582 of such as BASF).
The instantiation of blue colorant can include C.I. pigment blue 15: 6, C.I. pigment blue 15: 4, C.I. pigment blue 60,
C.I. pigment blue 16 etc..Wherein for preventing light leak, preferably C.I. pigment blue 15: 6.
(i.e. with solid content meter) in terms of the total amount not wrapping solvent-laden photosensitive composition, black inorganic
The amount of toner, black toner and blue colorant can be that 0 to 20 weight %, 10 weight % are to 40 weights respectively
Amount % and 0 to 15 weight %；Preferably, 0 to 20 weight % it are greater than respectively or less than 20 weight %, more than 10
Weight % is to 40 weight % or less than 40 weight % with more than 0 to 15 weight % or less than 15 weight %；It is highly preferred that
It is greater than 0 to 10 weight % respectively or less than 10 weight %, more than 10 weight % to 40 weight % or less than 40 weight
% and 1 weight % are to 15 weight %.In the range of described, resin combination can have high light intensity to prevent light leak
Transmittance necessary with shade alignment.
Meanwhile, dispersant can be used to be scattered here and there toner when preparing the photosensitive composition of the present invention.Point
The example of powder can include any known dispersant for coloring agent.Instantiation can include cation surface activating
Agent, anion surfactant, nonionic surfactant, zwitterionic surfactant, surface activity based on silicon
Agent, surfactant based on fluorine etc..Commercial dispersants can include the Di Sibi from Bi Ke company (BYK Co.)
Gram (Disperbyk)-182, Di Sibike-183, Di Sibike-184, Di Sibike-185, Di Sibike-2000,
Di Sibike-2150, Di Sibike-2155, Di Sibike-2163 or Di Sibike-2164.These compounds can be single
Solely use or use with its two or more combining form.Dispersant can be by carrying out coloring agent with dispersant
Surface process and add in advance in coloring agent, or during the preparation of photosensitive composition with coloring agent one
Rise and add.
Or, coloring agent can mix with binding agent and be used for preparing photosensitive composition.In this case,
Binding agent can be heretofore described copolymer (a), known copolymer or its mixture.
Therefore, coloring agent used in the present invention can add color sensation to according to color dispersion liquid (i.e. colouring mill base) form
In photosensitive resin composition, described color dispersion liquid is obtained with dispersant, binding agent, solvent etc. by mixed colorant.
(f) solvent
The photosensitive composition of the present invention preferably can be prepared as liquid by mixing said ingredients and solvent
Compositions.In art, known any solvent may serve to prepare photosensitive composition, described solvent
Compatible with the component in photosensitive composition but do not react.
The example of solvent can include glycol ethers, such as ethylene glycol monoethyl ether etc.；Ethylene glycol alkyl ether acetas, as ethyl is molten
Fine agent acetas etc.；Ester, such as 2 hydroxy propanoic acid ethyl ester etc.；Diethylene glycol, such as diethylene glycol monomethyl ether etc.；And third
Glycol alkyl ether acetas, such as propylene glycol monomethyl ether, propylene glycol propyl ether acetas etc.；Acetic acid alkoxyl alkane
Base ester, such as acetic acid 3-methoxybutyl etc..Solvent can be used alone or makes with its two or more combining form
With.
The amount of solvent is not particularly limited, but for the coatability of the final photosensitive composition obtained and steady
Qualitative, it may be determined that described amount is so that the total concentration (i.e. with solid content meter) of each component in addition to the solvents in compositions
Can be generally 5 weight % to 70 weight %, preferably 10 weight % are to 55 weight %.
(g) surfactant
The photosensitive composition of the present invention can comprise further surfactant to improve coatability and
Prevent defect.
Although the kind of surfactant is not particularly limited, but it is such as based on silicon surfactant or table based on fluorine
Face activating agent.
Commercially available surfactant based on silicon can include the DC3PA from the eastern beautiful silicon of DOW CORNING (Dowcorning),
DC7PA、SH11PA、SH21PA、SH8400；From general Toshiba (GE toshiba) silicone TSF-4440,
TSF-4300、TSF-4445、TSF-4446、TSF-4460、TSF-4452；From the BYK 333 of Bi Ke, BYK 307,
BYK3560, BYK UV 3535, BYK 361N, BYK 354, BYK 399 etc..
Commercially available surfactant based on fluorine can include from Dainippon Ink. & Chemicals Inc (Dainippon
Ink Kagaku Kogyo Co.；DIC) wheat lattice Fes (Megaface) F-470, F-471, F-475, F-482,
F-489、F-563、RS-55.Surfactant can be used alone or uses with its two or more combining form.
Wherein, for for coatability, it may be preferred to ground use from the BYK 333 of Bi Ke, BYK 307, from
The F-563 of DIC and from the wheat lattice Fes RS-55 of DIC as surfactant.
In terms of the gross weight of photosensitive composition, the amount of surfactant can be that 0.0001 weight % is to 10
Weight %, preferably 0.005 weight % is to 5 weight %.In this case, the weight of photosensitive composition is
The weight reference of the amount of surfactant, can be the gross weight of the compositions including solvent.In this range, color sensation
Photosensitive resin composition can represent suitable coatability.
(h) silane coupling agent
If desired, the photosensitive composition of the present invention can comprise the group having selected from consisting of further
The silane coupling agent of reactive substituents of group improves the adhesiveness with substrate: carboxyl, (methyl) acryloyl group, isocyanide
Perester radical, amino, sulfydryl, vinyl, epoxy radicals with and combinations thereof.
The kind of silane coupling agent is not particularly limited, but preferably can be selected from the group consisted of: trimethoxy
Silylation benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyl
Trimethoxy silane, γ-NCO propyl-triethoxysilicane, γ-glycidoxypropyltrimewasxysilane,
γ-glycidoxypropyl triethoxysilane, β-(3,4-expoxycyclohexyl) ethyl trimethoxy silane, phenyl amino
Trimethoxy silane and its mixture.Wherein it is preferred that γ-NCO propyl group three ethoxy with NCO
Base silane (such as from the KBE-9007 of Co., Ltd. of SHIN-ETSU HANTOTAI (Shin-Etsu Co.)) or phenyl amino trimethoxy silicon
Alkane, it has good chemical resistance and the good adhesiveness with substrate.
(i.e. with solid content meter) in terms of the total amount not wrapping solvent-laden photosensitive composition, silane coupling agent
Amount can be 0.01 weight % to 10 weight %, preferably 0.05 weight % is to 5 weight %.In the range of described,
Color sensation photosensitive resin composition can have the adhesiveness of improvement.
It addition, only just can include when the physical characteristic of photosensitive composition can not adversely be affected as anti-
Other additive such as oxidant, stabilizer.
The photosensitive composition of the present invention can provide the black post of resolution and the surface characteristic with improvement
Shape sept.
For the method preparing photosensitive composition
The photosensitive composition of the present invention comprising said components can be prepared by a conventional method, described method
During one embodiment is described below.
First, coloring agent is mixed with solvent and subsequently in middle dispersions such as ball mills, until coloring agent has and wanted average
Diameter.In this stage, it may be necessary to be added to surfactant, and can be by a part of or whole copolymer
Mixed.Add in gained dispersion liquid the copolymer of remainder and surfactant, epoxy resin compound or by
Each in its derivative compound, photopolymerizable compound and Photoepolymerizationinitiater initiater.Can be in gained mixture
Add if the additive of silane coupling agent or additional solvent is to be adjusted to desired level by its concentration.Subsequently, it is sufficiently stirred for mixing
Compound is to obtain wanted photosensitive composition.
Black column spacer (shading sept)
The present invention provides a kind of black column spacer (shading sept) formed by photosensitive composition.
Specifically, the present invention provides a kind of integration formed by photosensitive composition to have column spacer and black
The integrated black column spacer (BCS) of color base matter.Fig. 1 illustrates the exemplary pattern of BCS.
Column spacer, black matix or BCS can be formed by following steps: layer is coated, be exposed to light,
Development and heat treatment.
In layer application step, by spin-coating method or slot coated method, roll coating process, silk screen print method, medicine applying apparatus method etc.
The photosensitive composition of the present invention is applied to pretreated substrate with the wanted thickness of such as 2 to 25 μm
On, described substrate subsequently at 70 DEG C to 100 DEG C precuring 1 to 10 minutes to remove solvent and to form coating.
In order to form pattern in the coating therefore obtained, radiate after the shade well with given shape placed over
The actinic ray of 200 to 500nm.In this stage, in order to obtain integrated BCS, it is possible to use different saturating containing having
Penetrate than the shade of pattern to concurrently form column spacer and black matix.About the light source for exposure, it is possible to use
Low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, argon laser etc.；And can also make when needing
With X-ray, electron ray etc..Dosage can depend on the kind of the component of compositions and composition ratio and drying layer
Thickness and change.When using high voltage mercury lamp, dosage can be 500mJ/cm2Or less than 500mJ/cm2(at 365nm
Wavelength under).
After step of exposure, use alkaline aqueous solution (such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylphosphonihydroxide hydroxide
Base ammonium etc.) carry out development step, remove it by dissolving unnecessary portion, thus make residue exposed portion formation figure
Case.The picture pattern obtained by development is made to be cooled to room temperature and be dried in boiler hot-air circular type, at 180 DEG C
Baking 10 to 60 minutes after at 250 DEG C, thus obtain final pattern.
Consequent black column spacer, owing to its good physical characteristic, may be used for manufacturing such as LCD, OLED
The electronic units such as display.Therefore, the present invention provides a kind of electronic unit comprising black column spacer.
LCD, OLED display etc. can include digging up the roots according to those skilled in the art outside the sept of the present invention
The element known.It is to say, can include in the present invention using the LCD of the black column spacer of the present invention,
OLED display etc..
Hereinafter, it is discussed in greater detail the present invention by following instance, but these examples provide exclusively for the purposes of illustration, and
And the invention is not restricted to this.
Prepare example 1: prepare copolymer
Using the 100g monomer mixture as pointed by table 1 below, 300g as the propylene glycol monomethyl ether of solvent
(PGMEA) and 2g is as the 2 of radical polymerization initiator, 2 '-azo double (2,4-methyl pentane nitrile) is placed on 500mL
In round-bottomed flask equipped with reflux condenser and agitator.Heat the mixture to 70 DEG C and stir 5 hours and gather
Close, produce the copolymer that solids content is 31 weight %.The acid number of consequent copolymer is 100mg KOH/g,
And being measured by gel permeation chromatography, the weight average molecular weight (Mw) making reference with polystyrene is 20,000.
[table 1]
Prepare example 2: prepare the compound derived from the epoxy resin with ton backbone structure
160g is placed on equipped with agitator, thermometer, nitrogen replaceable equipment and backflow as the PGMEA of solvent
In the flask of condenser.Subsequently, in flask, add 100g 3,3 '-(spiral shell [fluorenes-9,9 '-ton]-3 ', 6 '-diyl is double (epoxide))
Double (2-hydroxyl acrylate-3,1-diyl) diacrylates and 0.1g chlordene hydrogen platinum, and heat the mixture to 80 DEG C subsequently.Single
Solely by 47.6g 1,2,4,5-cyclohexanetetracarboxylic acid dianhydrides are dissolved in 80g PGMEA, it are the most dropwise added subsequently
It is added in said mixture.Heat the mixture to 100 DEG C subsequently and keep 2 hours.Mixture is cooled to room temperature
(25 DEG C) and add 0.3g p-methyl benzenesulfonic acid pyridine.Therefore, it is thus achieved that solids content is 50 weight %, acid number is
107mg KOH/g and Mw is the copolymer compound of 6,000.
Prepare example 3: prepare color dispersion liquid
By above-mentioned for 8g prepare in example 1 obtain copolymer, 8g polymeric dispersant (Di Sibike-2000, Bi Ke),
12g carbon black, 53g are as the lactams of Organic Black black (black 582, BASF), 16g C.I. pigment blue 15: 6 and 384
G is placed on pendant because of in characteristic vibration device (painter shaker) as the PGMEA of solvent, and at 25 DEG C to 60 DEG C
Dispersed mixture 6 hours.This dispersion steps 0.3mm zirconium oxide beadlet is carried out.When dispersion steps completes, separate
Beadlet and dispersion liquid, thus produce color dispersion liquid.
Example 1 to 8 and comparative example 1 to 4: prepare photosensitive composition
By prepare in example 1 obtain copolymer, prepare in example 2 obtain derived from the ring with ton backbone structure
The compound of epoxy resins, as what the DPCA-20 (Japan's chemical medicine) of the first photopolymerizable compound, table 2 below were listed
In second photopolymerizable compound C-1 to C-8 any one, Photoepolymerizationinitiater initiater D-1 (oxime light trigger, NC1831,
Ai Dike) and D-2 (triazine light trigger, T-Y, medicine synthesis (PHARMASYNTHESE)), as surface
Wheat lattice Fes RS-55 (DIC) of activating agent and prepare the color dispersion liquid obtained in example 3 by based on such as table 3 below
Described in the amount of weight ratio of solids content be blended in solvent PGMEA by conventional method.The amount of solvent for use makes
The solids content obtaining mixture is 19 weight %.It is subsequently agitated for mixture and within 5 hours, prepares each coloring phototonus resin combination
Thing.
[table 2]
| Trade (brand) name | Manufacturer | |
| C-1 | PET-30 | Nippon Kayaku K. K |
| C-2 | DPHA | Nippon Kayaku K. K |
| C-3 | BDDA | BASF |
| C-4 | TMPTA | Nippon Kayaku K. K |
| C-5 | TPA-330 | Nippon Kayaku K. K |
| C-6 | RP-1040 | Nippon Kayaku K. K |
| C-7 | T-1420 | Nippon Kayaku K. K |
| C-8 | M-403 | Toagosei Co., Ltd |
[table 3]
Experiment embodiment 1: assessment coatability
Come by each sample being carried out spin coating while being applied to by 3g sample in glass substrate (10cm × 10cm)
The coatability of the photosensitive composition obtained in evaluation contents and comparative example.
Coating without such as Benard cell (Benard cell) and the defect of interference fringe and even spread it is to be considered
Satisfied.
Experiment embodiment 2: measure the thickness of black column spacer
By using spinner that each photosensitive composition of preparation in example and comparative example is applied to glass
Precuring forms coating in 150 seconds on substrate and at 80 DEG C.To have 100% panchromatic tune column spacer (CS) figure
The pattern shade of case and 20% halftoning black matrix patterns is placed in thus obtained coating, now film and shade location
Becoming to have 150 μm gaps between the two, making it be exposed to wavelength subsequently is 365nm and intensity is 45mJ/cm2Light
In.
Subsequently, by using for 1 weight % potassium hydroxide aqueous solution inspection breakpoint (BP) time at 23 DEG C, and hereafter
Coating is made to develop 15 seconds.After with pure water 1 minute, the pattern being consequently formed after bake at 230 DEG C in an oven
Roasting 30 minutes, it is thus achieved that cured film.
Therefore, prepare black matix and column spacer be integrated into a module black column spacer patterns (referring to
Fig. 1).By using height measuring equipment (SIS-2000, SNU are accurate (SNU precision)) to measure between column
The thickness of spacer member (A) and the thickness of black matix parts (B).When the thickness of black matix parts (B) is 2.0 ± 0.2
Time in μ m, it would be desirable to shading characteristic.
Experiment embodiment 3: measure the CD size of black column spacer
Program according to experiment embodiment 2 is prepared by 100% panchromatic tune column spacer (CS) pattern (after rear baking
Thickness: 3.0 (± 0.2) μm) and the 20% halftoning black matrix patterns (thickness after rear baking: 2.0 (± 0.2)
μm) cured film that constitutes.
Panchromatic tune (F/T) territory size (D) for the shade of preparation 100% panchromatic tune column spacer (CS) pattern
(referring to Fig. 2) is 10 μm.
By using 3-dimensional surface measurement equipment (SIS-2000, SNU are accurate) to measure the critical chi of black column spacer
Very little (CD) size.
Consequently found that, 100% panchromatic tune column spacer (CS) pattern obtained from the resin combination of example 1 to 8
CD size (C) (referring to Fig. 1) be 35 μm or less than 35 μm after rear baking, preferably 30 μm or little
In 30 μm.
Experiment embodiment 4: the surface characteristic of assessment black matix
The amount of photosensitive composition is improper causes resin combination excessively to develop during developing programs.Therefore,
The roughness on black matix surface dramatically increases, and this causes occurring surface peeling phenomenon after rear baking.
If not observing surface peeling phenomenon under an optical microscope, then the surface characteristic of black matix is considered as well.
The result of above-mentioned experiment embodiment is shown in table 4 below.
[table 4]
As shown in table 4, the photosensitive composition of example 1 to 8 and cured film prepared therefrom (such as post
Shape sept and black matix) in terms of coatability, thickness, CD size and surface characteristic, show improved characteristics.
Therefore, may be used for manufacturing the such as electricity such as OLED display, LCD according to the photosensitive composition of the present invention
Subassembly.
By contrast, photosensitive composition and the cured film prepared therefrom of comparative example 1 to 4 shows above-mentioned
At least one characteristic in characteristic is undesirable.Especially, from the resin combination of comparative example 1 to 4 obtain black
The CD size of color column spacer is more than 35 μm or less than the reference value of 35 μm.
Claims (6)
1. a photosensitive composition, it comprises:
(a) copolymer；(b) epoxy resin compound or the compound derived by it；(c) photopolymerizable compound；
(d) Photoepolymerizationinitiater initiater；And (e) coloring agent, wherein said photopolymerizable compound includes the one the third of formula 1
Olefin(e) acid class photopolymerizable unsaturated compound and be different from described first acrylic compounds photopolymerizable unsaturated compound
Second acrylic compounds photopolymerizable unsaturated compound:
[formula 1]
In formula 1,
R1To R6It is hydrogen or the substituent group represented by formula 2, wherein R independently of one another1To R6In at least one be
The substituent group represented by formula 2, wherein n is 1 or 2,
[formula 2]
In formula 2,
R7It is the C that can be substituted2-20Epoxide alkylidene；R8It is H or methyl；And n is the integer of 0 to 2.
Photosensitive composition the most according to claim 1, wherein said second acrylic compounds photopolymerizable
Unsaturated compound is represented by formula 3:
[formula 3]
In formula 3,
A is the rational number of 3 to 4；And
B is the rational number of 0 to 1.
Photosensitive composition the most according to claim 1, wherein said first acrylic compounds photopolymerizable
The amount of unsaturated compound is that 0.5 weight % is to 15 weight with the solid content meter of described photosensitive composition
%, and described first acrylic compounds photopolymerizable unsaturated compound is unsaturated with described second acrylic compounds photopolymerizable
The weight ratio of compound is 3: 100 to 24: 100.
Photosensitive composition the most according to claim 3, wherein said first acrylic compounds photopolymerizable
Unsaturated compound is 5: 100 to 22 with the weight ratio of described second acrylic compounds photopolymerizable unsaturated compound: 100.
Photosensitive composition the most according to claim 1, wherein said epoxy resin compound has
Ton backbone structure.
Photosensitive composition the most according to claim 1, comprises with described coloring phototonus resin combination
The solid content meter of thing more than 0 to 20 weight % or less than 20 weight % amount black inorganic coloring agent, more than 10 weights
Amount % to 40 weight % or less than 40 weight % amount black toner and more than 0 to 15 weight % or be less than
The blue colorant of the amount of 15 weight % is as described coloring agent.
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| TWI788421B (en) * | 2017-09-26 | 2023-01-01 | 日商富士軟片股份有限公司 | Curable composition, cured film, solid-state imaging device, and method for producing cured film |
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| KR101832097B1 (en) | 2016-10-31 | 2018-02-23 | 롬엔드하스전자재료코리아유한회사 | Colored photosensitive resin composition and light shielding spacer prepared therefrom |
| KR102529781B1 (en) * | 2016-11-25 | 2023-05-08 | 동우 화인켐 주식회사 | Black photosensitive resin composition, black matrix, column sapcer and column spacer combined with black matrix for image display device produced using the same |
| KR102105048B1 (en) * | 2017-06-28 | 2020-04-27 | 삼성에스디아이 주식회사 | Photosensitive resin composition, black photosensitive resin layer using the same and color filter |
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| KR102066281B1 (en) * | 2013-02-15 | 2020-01-15 | 롬엔드하스전자재료코리아유한회사 | Colored photosensitive resin composition and light shielding spacer prepared therefrom |
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2015
- 2015-04-02 KR KR1020150047092A patent/KR102437844B1/en active IP Right Grant
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| TW201636389A (en) | 2016-10-16 |
| KR20160118666A (en) | 2016-10-12 |
| KR102437844B1 (en) | 2022-08-31 |
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Application publication date: 20161026 |