CN107793327A - Compounds, nucleocapsid dyestuff, Photosensitve resin composition and colored filter - Google Patents

Compounds, nucleocapsid dyestuff, Photosensitve resin composition and colored filter Download PDF

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Publication number
CN107793327A
CN107793327A CN201710739700.6A CN201710739700A CN107793327A CN 107793327 A CN107793327 A CN 107793327A CN 201710739700 A CN201710739700 A CN 201710739700A CN 107793327 A CN107793327 A CN 107793327A
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Prior art keywords
chemical formula
core
dyestuff
shell structure
compound
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CN107793327B (en
Inventor
辛明晔
徐惠瑗
朴彩媛
申先雄
郑义树
崔圭汎
韩圭奭
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/76—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and etherified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/30—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having nitrogen atoms of imino groups quaternised
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/64—Quaternary ammonium compounds having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/78—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/007—Squaraine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

The present invention discloses a kind of compound represented by chemical formula 1 and nucleocapsid dyestuff, separately disclosing a kind of Photosensitve resin composition comprising the compound represented by chemical formula 1 or the nucleocapsid dyestuff and the colored filter manufactured using the Photosensitve resin composition, the nucleocapsid dyestuff is included：Core, include the compound represented by chemical formula 1；And shell, around the core.The colored filter of compound or nucleocapsid dyestuff comprising the present invention has the brightness improved and contrast.[chemical formula 1]In chemical formula 1, each substituent with it is defined identical in the description.

Description

Compounds, core-shell structure copolymer dyestuff, Photosensitve resin composition and colored filter
Technical field
The present invention relates to a kind of compounds, core-shell structure copolymer dyestuff, include the compounds or the core-shell structure copolymer dyestuff Photosensitve resin composition and the colored filter that is manufactured using the Photosensitve resin composition.
Background technology
In the display of all multiple types, liquid crystal display device has that light, thin, cost is low, operation is low in energy consumption and to integrated Circuit it is supportive high the advantages of, and be more broadly used for laptop computer, monitor and video screen.Liquid crystal display fills Put including lower substrate and upper substrate, formed with black matrix", colored filter and tin indium oxide pixel in lower substrate Electrode, formed with the active circuitry region including liquid crystal layer, thin film transistor (TFT) and capacitor layer and oxidation in upper substrate Indium tin pixel electrode.It is (in general, (such as red by three primary colors by sequentially stacking multiple colored filters according to predesigned order Color (R), green (G) and blueness (B)) formed) colored filter is formed in pixel region to form each pixel, and with predetermined Pattern is set black-matrix layer on a transparent substrate to form the border between each pixel.As each of formation colored filter A kind of pigment dispersion method of method in kind method, it is provided through coloured film by repeating a series of following techniques：Example Exposed as the photopolymerizable composition comprising colouring agent is coated in the transparent substrates including black matrix", by the pattern formed Light, remove the part not being exposed with solvent and heat cure is carried out to it.For manufacturing colored filter according to pigment dispersion method The colored photosensitive resin composition of mating plate generally comprises alkali soluble resins, photopolymerizable monomer, Photoepolymerizationinitiater initiater, asphalt mixtures modified by epoxy resin Fat, solvent, other additives etc..Pigment dispersion method is energetically applied to manufacture such as mobile phone, laptop computer, monitor And the liquid crystal display such as TV.However, the Photosensitve resin composition for colored filter used in pigment dispersion method is recent Need to improve performance and needed that there are excellent pattern properties.Specifically, be badly in need of high color reprodubility and high brightness and High contrast features.Imaging sensor be Portable mobile phone camera or digital camera (digital still camera, DSC it is used for the part of shooting image in).Image sensor visual manufacturing process and application process and be classified as Charged Couple dress Put (charge-coupled device, CCD) imaging sensor and complementary metal oxide semiconductor (complementary Metal oxide semiconductor, CMOS) imaging sensor.For charge coupled device image sensor or complementary gold The color image forming apparatus of category oxide semiconductor image sensor includes each of colored filter, the colored filter With the filter segment for being mixed with red, green and these blue primary colors, and the color is separation.Installed in colour Recent colored filter in imaging device has 2 μm or the pattern magnitude less than 2 μm, and the pattern magnitude is liquid crystal display The 1/100 to 1/200 of the pattern magnitude of the traditional color filter pattern of device.Therefore, increase resolution ratio and reduce pattern residual Thing is to determine an important factor for device performance.The colored filter manufactured using conventional pigment type Photosensitve resin composition is due to face Expect the size of particle and there is limitation in terms of brightness and contrast.In addition, the color image forming apparatus for imaging sensor needs Less dispersion particle diameter is wanted to form fine pattern.In order to meet the requirements, attempt not forming the dyestuff of particle by introducing And non-pigment prepares the Photosensitve resin composition suitable for the dyestuff, so as to realize the coloured silk with the brightness improved and contrast Colo(u)r filter.However, dyestuff has durability (such as light resistance and heat resistance) of difference etc. relative to pigment, and therefore brightness can It is able to can deteriorate.
The content of the invention
The embodiment of the present invention provides a kind of compounds with the brightness improved and contrast.
Another embodiment provides a kind of core-shell structure copolymer dyestuff for including the compounds.
Another embodiment provides a kind of Photosensitve resin composition comprising the compounds or the core-shell structure copolymer dyestuff.
Another embodiment provides a kind of colored filter manufactured using the Photosensitve resin composition.
The embodiment of the present invention provides a kind of compound represented by chemical formula 1.
[chemical formula 1]
In chemical formula 1,
R1And R2The C1 that is substituted or is unsubstituted independently is to C20 alkyl, the C3 for being substituted or being unsubstituted to C20 Cycloalkyl or the C6 that is substituted or is unsubstituted to C20 aryl, its restrictive condition be R1And R2Independently and it must include by changing The functional group and chiral carbon that formula 1-1 is represented, and
R3And R4The C1 that is substituted or is unsubstituted independently is to C20 alkyl or the C6 for being substituted or being unsubstituted extremely C20 aryl,
[chemical formula 1-1]
*-O-R6
Wherein, in chemical formula 1-1,
R6For the C1 that is substituted or is unsubstituted to C20 alkyl.
R1And R2Independently it can be represented by chemical formula 2-1 or chemical formula 2-2.
[chemical formula 2-1]
[chemical formula 2-2]
In chemical formula 2-1 and chemical formula 2-2,
L1For singly-bound, the C1 for being substituted or being unsubstituted to C10 alkylidenes or the C3 for being substituted or being unsubstituted to C10 Cycloalkylidene,
L2For the C1 that is substituted or is unsubstituted to the C10 alkylidenes or C3 for being substituted or being unsubstituted to C10 Asias ring Alkyl, and
R5And R6The C1 that is substituted or is unsubstituted independently is to C20 alkyl.
R6Can be the C1 through ' C1 to C10 alkyl or C6 to C20 aryl ' substitution to C20 alkyl.
R6It can be represented by chemical formula 3.
[chemical formula 3]
In chemical formula 3,
R7And R8The C1 that is substituted or is unsubstituted independently is to C10 alkyl.
R3And R4It can independently be and substitute or without the alkyl-substituted C6 of C1 to C10 to C20 aryl through C1 to C10 alkyl.
The compound represented by chemical formula 1 can be one of compound represented by chemical formula 4 to chemical formula 10.
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
It is described to have maximum absorption wavelength (λ into 700nm in 600nm by the compound that chemical formula 1 representsmax)。
Another embodiment provides a kind of core-shell structure copolymer dyestuff, and the core-shell structure copolymer dyestuff includes：Core, include what is represented by chemical formula 1 Compound；And shell, around the core.
The shell can be represented by chemical formula 11 or chemical formula 12.
[chemical formula 11]
[chemical formula 12]
In chemical formula 11 and chemical formula 12,
LaTo LdIt independently is singly-bound or the C1 that is substituted or is unsubstituted is to C10 alkylidenes.
LaTo LdThe C1 that is substituted or is unsubstituted can independently be to C10 alkylidenes.
The shell can be represented by chemical formula 11-1 or chemical formula 12-1.
[chemical formula 11-1]
[chemical formula 12-1]
The cage width (cage width) of the shell can be betweenExtremelyScope.
The core can have 1nm to 3nm length.
The core can have maximum absorption band in 530nm to 680nm wavelength.
The core-shell structure copolymer dyestuff may be selected from the compound represented by chemical formula 13 to chemical formula 26.
[chemical formula 13]
[chemical formula 14]
[chemical formula 15]
[chemical formula 16]
[chemical formula 17]
[chemical formula 18]
[chemical formula 19]
[chemical formula 20]
[chemical formula 21]
[chemical formula 22]
[chemical formula 23]
[chemical formula 24]
[chemical formula 25]
[chemical formula 26]
The core-shell structure copolymer dyestuff can be with 1:1 mol ratio includes the core and the shell.
The core-shell structure copolymer dyestuff can be green colouring material.
The core-shell structure copolymer dyestuff can have maximum absorption wavelength (λ into 700nm in 600nmmax)。
Another embodiment provides a kind of Photosensitve resin composition comprising the compound or the core-shell structure copolymer dyestuff.
The Photosensitve resin composition can further include adhesive resin, photopolymerizable monomer, photopolymerization initiator with And solvent.
The Photosensitve resin composition can further include pigment.
In terms of the total amount of the Photosensitve resin composition, the Photosensitve resin composition can include 0.5wt% to 10wt% The compound or the core-shell structure copolymer dyestuff；0.1wt% to 30wt% described adhesive resin；0.1wt% is to 30wt%'s The photopolymerizable monomer；0.1wt% to the 5wt% Photoepolymerizationinitiater initiater；And the solvent of surplus.
The Photosensitve resin composition can further include malonic acid, 3- amido-1,2-propanediols, comprising vinyl or Silane system coupling agent, levelling agent, surfactant, radical polymerization initiator or its combination of (methyl) acryloxy.
Another embodiment provides a kind of colored filter manufactured using the Photosensitve resin composition.
The other embodiment of the present invention is included in the following detailed description.
It can be realized with the brightness improved and the colorized optical filtering of contrast according to the compound of embodiment or core-shell structure copolymer dyestuff Piece.
Brief description of the drawings
Fig. 1 is the view for showing the cage width by the chemical formula 11-1 shells represented.
Embodiment
Hereinafter, embodiments of the invention are elaborated.However, these embodiments are exemplary, the present invention not only limits Defined in this and the present invention by the scope of claim.
In this manual, when offer is not specifically defined in addition, " being substituted " refers at least one hydrogen of compound Atom is replaced by following substituent：Halogen atom (F, Cl, Br or I), hydroxyl, C1 to C20 alkoxies, nitro, cyano group, amido, Imino group, azido, amidino groups, diazanyl, hydrazono-, carbonyl, carbamyl, mercapto (thiol group), ester group, ether, carboxylic Base or its salt, sulfonic group or its salt, phosphoric acid or its salt, C1 to C20 alkyl, C2 to C20 alkenyls, C2 to C20 alkynyls, C6 to C30 Aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl groups, C3 to C20 cycloalkynyl radicals, C2 to C20 Heterocyclylalkyls, C2 to C20 heterocycle alkene Base, C2 to C20 heterocycles alkynyl or its combination.
In this manual, when offer is not specifically defined in addition, " Heterocyclylalkyl ", " heterocycloalkenyl ", " heterocycle alkynyl " And " sub- Heterocyclylalkyl " refers to comprising at least one heteroatomic cycloalkyl, cycloalkenyl group, cycloalkynyl radical and the sub- ring in N, O, S or P Each cyclic compound of alkyl.
In this manual, when not in addition provide be specifically defined when, " (methyl) acrylate " refer to " acrylate " and Both " methacrylate ".
In this manual, when not providing definition in addition, " combination " refers to mixing or combined polymerization.In addition, " combined polymerization " Refer to that block copolymerization is bonded to random copolymerization, and " copolymer " refers to block copolymer to random copolymer.
In the chemical formula of this specification, be specifically defined unless otherwise provided, otherwise when chemical bond is not plotted in should be to During source, hydrogen bond knot is in the opening position.
In addition, in this manual, when not providing definition in addition, " * " refers to chiral carbon.Chiral carbon is indicated in carbon surrounding Center carbon with four different functional groups, and the real image with chiral carbon compound is not overlapping with its mirror image.
In addition, unless providing definition in addition in this manual, otherwise chiral carbon is included selected from R configurations, S configurations, outside it One of racemic mixture and combinations thereof.
In this manual, when not providing definition in addition, " * " instruction connects identical or different atom or chemical formula Point.
Represented according to the compound of embodiment by chemical formula 1.
[chemical formula 1]
In chemical formula 1,
R1And R2The C1 that is substituted or is unsubstituted independently is to C20 alkyl, the C3 for being substituted or being unsubstituted to C20 Cycloalkyl or the C6 that is substituted or is unsubstituted to C20 aryl, its restrictive condition be R1And R2Independently and it must include by changing The functional group and chiral carbon that formula 1-1 is represented, and
R3And R4The C1 that is substituted or is unsubstituted independently is to C20 alkyl or the C6 for being substituted or being unsubstituted extremely C20 aryl,
[chemical formula 1-1]
*-O-R6
Wherein, in chemical formula 1-1,
R6For the C1 that is substituted or is unsubstituted to C20 alkyl.
The compound represented by chemical formula 1 has excellent green spectral characteristic and high molar extinction coefficient (molar Extinction coefficient) and can be used as green colouring material.However, compound durability deficiency compared with pigment, And therefore it can make deterioration in brightness during the baking process for being formed to carry out after colour resist.According to the chemical combination of embodiment Thing must be included by the chemical formula 1-1 functional groups represented and the chiral carbon as one of the substituent being connected with nitrogen-atoms, And therefore can improve durability and thus realize the colored filter with high brightness and high-contrast.
In chemical formula 1, R1And R2Independently it can be represented by chemical formula 2-1 or chemical formula 2-2.
[chemical formula 2-1]
[chemical formula 2-2]
In chemical formula 2-1 and chemical formula 2-2,
L1For singly-bound, the C1 for being substituted or being unsubstituted to C10 alkylidenes or the C3 for being substituted or being unsubstituted to C10 Cycloalkylidene,
L2For the C1 that is substituted or is unsubstituted to the C10 alkylidenes or C3 for being substituted or being unsubstituted to C10 Asias ring Alkyl, and
R5And R6The C1 that is substituted or is unsubstituted independently is to C20 alkyl.
In chemical formula 2-1 and chemical formula 2-2, R6Can be the C1 through ' C1 to C10 alkyl or C6 to C20 aryl ' substitution extremely C20 alkyl.
In chemical formula 2-1 and chemical formula 2-2, L1Can be singly-bound, the C1 that is substituted or is unsubstituted to C10 alkylidenes, And L2Can be the C3 that is unsubstituted to C10 cycloalkylidenes.
For example, R6It can be represented by chemical formula 3.
[chemical formula 3]
In chemical formula 3,
R7And R8It can independently be and substitute or without the alkyl-substituted C6 of C1 to C10 to C20 aryl through C1 to C10 alkyl.
Work as R6When being represented by chemical formula 3, had according to the compound of embodiment and include alkane branched alkyl as substituent Epoxide rather than comprising alkoxy non-branched-chain alkyl (alkyl being unsubstituted) as substituent, and therefore can further improve bright Degree and contrast.
R3And R4It can independently be and substitute or without the alkyl-substituted C6 of C1 to C10 to C20 aryl through C1 to C10 alkyl.
For example, R3And R4It can independently be represented by chemical formula A, but be not limited only to this.
[chemical formula A]
In chemical formula A,
R9It is the C1 that is substituted or is unsubstituted to C10 alkyl, and
N is the integer between 1 to 5 scope.
For example, in chemical formula A, n can be 1 or 2 integer.
For example, in chemical formula A, R9It may be present at ortho position and/or contraposition.
When using the compound represented by chemical formula 1 (such as dyestuff) in Photosensitve resin composition, later Solubility in the solvent can be more than or equal to 5, for example, between 5 to 10 scope.Solubility can be molten by being dissolved in 100g The amount (g) of dyestuff (compound) in agent obtains.When the solubility of the compound (such as dyestuff) is in the scope When, the compound can ensure that (that is, adhesive resin described below, light can with the other components in Photosensitve resin composition Polymerized monomer and photopolymerization initiator) compatibility and coloring property, and dye precipitated can be prevented.
The compound represented by chemical formula 1 can have excellent heat resistance.That is, thermogravimeter is passed through The heat decomposition temperature of (thermogravimetric analyzer, TGA) measurement can be more than or equal to 200 DEG C, heat decomposition temperature For example, 200 DEG C to 300 DEG C.
The compound represented by chemical formula 1 has three kinds of resonant structures as shown below, but in this manual, for side Just for the sake of, the compound for having a kind of resonant structure and being represented by chemical formula 1 is shown.In other words, the change represented by chemical formula 1 Compound can have any of three kinds of resonant structures structure.
[figure]
There can be maximum absorption wavelength (λ in the range of 600nm to 700nm by the compound that chemical formula 1 representsmax) (ginseng Examine cyclohexanone).
The compound represented by chemical formula 1 may be selected from the compound represented by chemical formula 4 to chemical formula 10.
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
There is the structure formed by core and around the shell of the core according to the core-shell structure copolymer dyestuff of another embodiment.Core include by The compound that chemical formula 1 represents.Specifically, shell can be huge ring-shaped compound, and girdle is around the chemical combination represented by chemical formula 1 Thing is to form coating.
In embodiment, as the compound that chemical formula 1 represents be as girdle corresponding with huge ring-shaped compound around, i.e., by The compound that chemical formula 1 represents is present in inside huge ring, and can improve the durability of core-shell structure copolymer dyestuff whereby, and can realize Colored filter with high brightness and high-contrast.
The length for being contained in core or forming the compound represented by chemical formula 1 of core can be 1nm to 3nm, be, for example, 1.5nm to 2nm.When the length of the compound represented by chemical formula 1 is in the scope, core-shell structure copolymer dyestuff can be easy to have Structure of the girdle around core.In other words, the length of the compound represented by chemical formula 1 is in the scope, and therefore described Compound can have structure of the huge ring-shaped compound (that is, shell) around the compound represented by chemical formula 1.When using at length When compound beyond the scope, structure of the girdle around nuclear compound can not be obtained, and durability can not be improved.
It is contained in core or forms being had in 530nm to 680nm wavelength by the compound that chemical formula 1 represents for core Maximum absorption band.Using with the spectral characteristic by the compound that chemical formula 1 represents as core core-shell structure copolymer dyestuff for example with Make green colouring material, and can provide for the Photosensitve resin composition with high brightness and the colored filter of high-contrast whereby.
Shell around the core comprising the compound represented by chemical formula 1 can be represented by chemical formula 11 or chemical formula 12.
[chemical formula 11]
[chemical formula 12]
In chemical formula 11 and chemical formula 12,
LaTo LdIt independently is singly-bound or the C1 that is substituted or is unsubstituted is to C10 alkylidenes.
In chemical formula 11 or chemical formula 12, LaTo LdThe C1 that is substituted or is unsubstituted can independently be to C10 alkylenes Base.In such a situation, it is easily formed with the solubility and girdle improved around the core for including the compound represented by chemical formula 1 Structure.
For example, non-covalent bond is included according to the core-shell structure copolymer dyestuff of embodiment, i.e., the compound represented by chemical formula 1 Hydrogen bond between the nitrogen-atoms of oxygen atom and the shell represented by chemical formula 11 or chemical formula 12.
Shell can be represented for example by chemical formula 11-1 or chemical formula 12-1.
[chemical formula 11-1]
[chemical formula 12-1]
The cage width of shell can be betweenExtremelyScope, and the volume of shell can be betweenExtremelyScope.This Cage width in invention refers to the inner distance of shell, such as in the shell by chemical formula 11-1 or chemical formula 12-1 expressions, refers to The distance between two different phenylenes of two methylene through connection (referring to Fig. 1).When the cage width of shell is in the model When enclosing interior, it can obtain with the core-shell structure copolymer dyestuff that circular structure is carried out to the core comprising the compound represented by chemical formula 1, and Therefore when adding core-shell structure copolymer dyestuff into Photosensitve resin composition, can be achieved with the durability improved and the colour of high brightness Optical filter.
Core-shell structure copolymer dyestuff is with 1:1 mol ratio includes core and shell comprising the compound represented by chemical formula 1.At existing When core and shell in the mol ratio, it can well be formed and the core comprising the compound represented by chemical formula 1 is surround Coating (shell).
Core-shell structure copolymer dyestuff can have maximum absorption wavelength (λ in the range of 600nm to 700nmmax) (referring to cyclohexanone).
For example, core-shell structure copolymer dyestuff can be by selected from one of the compound represented by chemical formula 13 to chemical formula 26 table Show, but be not limited only to this.
[chemical formula 13]
[chemical formula 14]
[chemical formula 15]
[chemical formula 16]
[chemical formula 17]
[chemical formula 18]
[chemical formula 19]
[chemical formula 20]
[chemical formula 21]
[chemical formula 22]
[chemical formula 23]
[chemical formula 24]
[chemical formula 25]
[chemical formula 26]
Core-shell structure copolymer dyestuff can be used alone as green colouring material and can also be mixed with auxiliary dyestuff.
It can be triarylmethane based dye, anthraquinone based dye, benzylidene based dye, cyanine based dye, phthalein to aid in dyestuff Cyanines based dye, aza porphyrin based dye, indigo based dye, xanthene based dye, azo based dye etc..
Core-shell structure copolymer dyestuff can be mixed with pigment.
Pigment can be red pigment, viridine green, blue pigment, yellow uitramarine, black pigment etc..
The example of red pigment can be color index (C.I.) red pigment 254, C.I. red pigments 255, C.I. red Pigment 264, C.I. red pigments 270, C.I. red pigments 272, C.I. red pigments 177, C.I. red pigments 89 etc..Green The example of pigment can be C.I. viridine greens 36, C.I. viridine greens 7, C.I. viridine greens 58, C.I. viridine greens 59, C.I. Viridine green 62 etc..The example of blue pigment can be copper phthalocyanine, such as C.I. blue pigments 15:6th, C.I. blue pigments 15th, C.I. blue pigments 15:1st, C.I. blue pigments 15:2nd, C.I. blue pigments 15:3rd, C.I. blue pigments 15:4th, C.I is blue Color pigment 15:5th, C.I. blue pigments 16 etc..The example of yellow uitramarine can be isoindoline series pigments, such as C.I. yellow uitramarines 139；Quinophthalone series pigments, such as C.I. yellow uitramarines 138；Nickel complex pigment, such as C.I. yellow uitramarines 150 etc..Black The example of pigment can be nigrosine, black, titanium is black, carbon black etc..The pigment can be used alone or as both or more persons' Form of mixtures uses, but is not limited only to this.
Pigment can be contained in the Photosensitve resin composition for colored filter with dispersible pigment dispersion state.Pigment disperses Liquid can be made up of pigment and solvent, dispersant, dispersion resin etc..
Solvent can be Ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, ring Hexanone, propylene glycol monomethyl ether etc., and preferably propylene glycol methyl ether acetate.
Dispersant contributes to the dispersed of pigment, and may include non-ionic dispersing agent, anionic dispersing agents or cation Dispersant.Instantiation can be PAG or its ester, polyoxyalkylene, polyol ester oxirane additive product, alcohol epoxy Alkane addition compound product, sulphonic acid ester, sulfonate, carboxylate, carboxylate, alkylamide oxirane additive product, alkylamine, and these points Powder can be used alone or be used as the form of mixtures of both or more persons.
Dispersion resin can be to wrap carboxylic acrylic resin, and improve the stability of dispersible pigment dispersion and the figure of pixel Case property.
When core-shell structure copolymer dyestuff is mixed with pigment, core-shell structure copolymer dyestuff can be with 1 with pigment:9 to 9:1 weight ratio and specific For with 3:7 to 7:3 weight ratio is mixed.When core-shell structure copolymer dyestuff is mixed with pigment in the range of the weight ratio, High brightness and contrast can be obtained while color characteristic is maintained.
According to another embodiment, there is provided a kind of to include the compound represented by chemical formula 1 or the photosensitive resin of core-shell structure copolymer dyestuff Composition.
Photosensitve resin composition includes (A) colouring agent (compound or core-shell structure copolymer dyestuff that are represented by chemical formula 1), (B) is bonded Agent resin, (C) photopolymerizable monomer, (D) Photoepolymerizationinitiater initiater and (E) solvent.
Hereinafter, it is specifically described each component.
(A) colouring agent
Colouring agent can include the compound that is represented by chemical formula 1 and/or core-shell structure copolymer dyestuff, and described be represented by chemical formula 1 Compound and/or core-shell structure copolymer dyestuff are described above.
Colouring agent can further include face in addition to comprising the compound represented by chemical formula 1 and/or core-shell structure copolymer dyestuff Material, and the pigment is described above.
For the total amount meter of the Photosensitve resin composition of colored filter, can include 0.5wt% to 10wt% (such as 0.5wt% to 5wt%) amount the compound represented by chemical formula 1 and/or core-shell structure copolymer dyestuff.When being used in the scope The compound represented by chemical formula 1 and/or during core-shell structure copolymer dyestuff, high brightness and height with desired color coordinate can be achieved Contrast.
(B) adhesive resin
Adhesive resin is the first ethene system unsaturated monomer and can be with the second ethene system unsaturated monomer of its combined polymerization Copolymer, and be the resin for including at least one acrylic acid series repeat unit.
First ethene system unsaturated monomer is the ethene system unsaturated monomer comprising at least one carboxyl.The reality of the monomer Example includes (methyl) acrylic acid, maleic acid, itaconic acid, fumaric acid or its combination.
In terms of the total amount of adhesive resin, the of 5wt% to 50wt% (such as 10wt% to 40wt%) amount can be included One ethene system unsaturated monomer.
Second ethene system unsaturated monomer can be aromatic vinyl compound, such as styrene, α-methylstyrene, ethene Base toluene, vinyl benzene dimethyl cellosolve etc.；Unsaturated carboxylic ester compound, such as (methyl) methyl acrylate, (methyl) propylene Acetoacetic ester, (methyl) butyl acrylate, (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 2- hydroxy butyl esters, (methyl) propylene Sour benzene methyl, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate etc.；Unsaturated aminoalkylcarboxylate's compound, Such as (methyl) acrylic acid 2- amino ethyl esters, (methyl) acrylic acid 2- dimethylamino ethyl esters etc.；Vinyl esters of carboxylic acids compound, Such as vinyl acetate, vinyl benzoate etc.；Unsaturated glycidyl carboxylate compound, such as the contracting of (methyl) acrylic acid Water glycerine base ester etc.；Acrylonitrile compound, such as (methyl) acrylonitrile etc.；Unsaturated acyl amines, such as (methyl) propylene Acid amides etc.；Etc., and the second ethene system unsaturated monomer can be used alone or the mixture shape as both or more persons Formula uses.
The instantiation of adhesive resin can be methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/ Benzyl methacrylate/styrol copolymer, methacrylic acid/benzyl methacrylate/HEMA Copolymer, methacrylic acid/benzyl methacrylate/styrene/methacrylic acid 2- hydroxyl ethyl ester copolymers etc., but not only It is limited to this.These adhesive resins can be used alone or be used as the form of mixtures of both or more persons.
The weight average molecular weight of adhesive resin can be 3,000g/mol to 150,000g/mol (such as 5,000g/mol To 50,000g/mol and such as 20,000g/mol to 30,000g/mol).When the weight average molecular weight of adhesive resin is in When in the scope, it is improved with the close contact property and physicochemical properties of substrate, and viscosity is appropriate.
The acid number of adhesive resin can be 15mgKOH/g to 60mgKOH/g (such as 20mgKOH/g to 50mgKOH/g).When When the acid number of adhesive resin is in the scope, excellent pixel resolution can be obtained.
In terms of the total amount of Photosensitve resin composition, 0.1wt% to 30wt% (such as 5wt% to 20wt%) amount can be included Adhesive resin.When comprising adhesive resin in range above, can improve can developability, and can be filtered in colour Improve excellent surface flatness due to improved crosslinking during the manufacture of mating plate.
(C) photopolymerizable monomer
Photopolymerizable monomer can be (methyl) the acrylic acid simple function or more for including at least one ethene system unsaturated double-bond Function ester.
Photopolymerizable monomer can cause enough because of ethene system unsaturated double-bond during the exposure of patterning process Polymerization, and form the pattern with excellent heat resistance, light resistance and chemical resistance.
The instantiation of photopolymerizable monomer can be ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) propylene Acid esters, triethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, neopentyl glycol two (methyl) acrylic acid Ester, 1,4- butanediols two (methyl) acrylate, 1,6-HD two (methyl) acrylate, bisphenol-A two (methyl) acrylic acid Ester, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylic acid Ester, pentaerythrite six (methyl) acrylate, dipentaerythritol two (methyl) acrylate, dipentaerythritol three (methyl) propylene Acid esters, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, bisphenol-A epoxy base (methyl) Acrylate, glycol monoethyl ether (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three (methyl) propylene Acyloxy etherophosphoric acid, novolak epoxy (methyl) acrylate etc..
The commercial examples of photopolymerizable monomer can be as follows.Simple function (methyl) acrylate may include Aronix (Aronix)(East Asia synthesizes Chemical Co., Ltd. (Toagosei Chemistry Industry Co.,Ltd.))；Ka Yala get (KAYARAD)(Japanese chemical drug Co., Ltd (Nippon Kayaku Co.,Ltd.))；(Osaka organic chemical industry Co., Ltd (Osaka Organic Chemical Ind., Ltd.)) etc..The example of two functions (methyl) acrylate may include Aronix (Aronix)(East Asia Chemical Co., Ltd.), Ka Yala get (KAYARAD)(Japanese chemical drug Co., Ltd),V-335(Osaka organises Work Co., Ltd) etc..The example of trifunctional (methyl) acrylate may include Aronix (Aronix)(East Asia Chemical Co., Ltd.), card Ya La get (KAYARAD) (Japanese chemical drug is limited Company),(Osaka organic chemical industry Co., Ltd) etc.. These photopolymerizable monomers can be used alone or be used as the form of mixtures of both or more persons.
Photopolymerizable monomer can be handled so that improve can developability with acid anhydrides.
In terms of the total amount of Photosensitve resin composition, 0.1wt% to 30wt% (such as 5wt% to 20wt%) amount can be included Photopolymerizable monomer.When comprising photopolymerizable monomer in the scope, the manufacture in colored filter can be improved The pattern properties of period and can developability.
(D) Photoepolymerizationinitiater initiater
Photoepolymerizationinitiater initiater can be acetophenone based compound, benzophenone based compound, thioxanthones based compound, styrax Based compound, triazine based compound, oxime compound etc..
The example of acetophenone based compound can be 2,2'- diethoxy acetophenones, 2,2'- dibutoxies acetophenone, 2- hydroxyls Base -2- methyl phenyl ketones (2-hydroxy-2-methylpropinophenone), to tert-butyl group trichloroacetophenone, to the tert-butyl group The chloro- 4- metaphenoxy acetophenones of dichloroacetophenone, 4- chloro-acetophenones, 2,2'- bis-, 2- methyl isophthalic acids-(4- (methyl mercapto) phenyl) -2- Quinoline base propyl- 1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butyl- 1- ketone etc..
The example of benzophenone based compound can be benzophenone, benzoic acid benzoyl ester, phenylamino benzoic acid formoxyl first Double (dimethylamino) benzophenone of ester, 4- phenyl benzophenones, dihydroxy benaophenonel, acrylated benzophenone, 4,4'-, 4,4'- double (diethylamino) benzophenone, 4,4'- dimethylamino benzophenones, 4,4'- dichloro benzophenones, 3,3'- bis- Methyl -2- methoxy benzophenones etc..
The example of thioxanthones based compound can be thioxanthones, 2- methyl thioxanthones, isopropyl thioxanthone, 2,4- diethyl thiophenes Ton ketone, 2,4- diisopropylthioxanthones, CTX etc..
The example of styrax based compound can be styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, peace Cease fragrant isobutyl ether, benzyl dimethyl ketal etc..
The example of triazine based compound can be 2,4,6- trichloto-s-triazines, double (the trichloromethyl)-s- three of 2- phenyl 4,6- Double (the trichloromethyl)-s- triazines of piperazine, 2- (3', 4'- dimethoxy-styryl) -4,6-, 2- (4'- methoxyl groups naphthyl) -4,6- Double (the trichloromethyl)-s- triazines of double (trichloromethyl)-s- triazines, 2- (p-methoxyphenyl) -4,6-, 2- (p-methylphenyl) -4, Double (the trichloromethyl)-s- triazines of 6-, double (the trichloromethyl)-s- triazines of 2- xenyls 4,6-, double (trichloromethyl) -6- styrene Double (the trichloromethyl)-s- triazines of base-s- triazines, 2- (naphthoyl 1- yls) -4,6-, 2- (4- methoxyl group naphthoyl 1- yls) -4,6- double (three Chloromethyl)-s- triazines, 2-4- trichloromethyls (piperonyl) -6- triazines, 2-4- trichloromethyls (4'- methoxyl-styrenes) -6- Triazine etc..
The example of oxime compound can be 2- (o-benzoyl base oxime) -1- [4- (thiophenyl) phenyl] -1,2- acetyl caproyls, 1- (adjacent acetyl group oxime) -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] ethyl ketone etc..
In addition to the compound, Photoepolymerizationinitiater initiater can further include carbazole based compound, diketone based compound, boron Sour sulfonium based compound, diazonium based compound, imidazole compound, bisglyoxaline based compound, fluorenes based compound etc..
In terms of the total amount of Photosensitve resin composition, 0.1wt% to 5wt% (such as 1wt% to 3wt%) amount can be included Photoepolymerizationinitiater initiater.When comprising Photoepolymerizationinitiater initiater in the scope, the composition is when for preparing colour Photopolymerization can be fully carried out when being exposed during the patterning process of optical filter, to realize excellent sensitiveness and improve transmission Rate.
(E) solvent
There is no particular restriction for solvent, and is, for example, specifically alcohol, such as methanol, ethanol etc.；Ether, such as dichloroether, N-butyl ether, isoamyl ether, methyl phenylate, tetrahydrofuran etc.；Glycol ethers, such as ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propane diols first Ether etc.；Cellosolve acetate, such as methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol diethyl ether acetic acid esters etc.；Card Must alcohol, such as Methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol two Methyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether etc.；Propylene glycol alkyl ether acetic acid ester, such as propylene glycol monomethyl ether second Acid esters, propylene glycol propyl ether acetic acid esters etc.；Aromatic hydrocarbon, such as toluene, dimethylbenzene etc.；Ketone, such as methyl ethyl ketone, cyclohexanone, 4- Hydroxy-4-methyl-2-pentanone, methyl-positive acetone, methyl-positive butanone, methyl-positive pentanone, 2-HEPTANONE etc.；Representative examples of saturated aliphatic list Alkyl carboxylates, such as ethyl acetate, n-butyl acetate, isobutyl acetate etc.；Lactic acid alkyl ester, such as methyl lactate, lactic acid Ethyl ester etc.；Hydroxyacetic acid Arrcostab, such as hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate etc.；Acetic acid alkoxy Arrcostab, such as methoxy methyl yl acetate, methoxyethyl acetate, methoxybutyl acetic acid esters, (ethoxymethyl) guanidine-acetic acid Ester, ethoxyethyl acetate etc.；3- hydroxyalkyl propionates, such as 3- hydroxy methyl propionates, 3- hydroxypropionates etc.；3- Alkoxypropan acid alkyl ester, such as 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxyl ethyl propionates, 3- second Epoxide methyl propionate etc.；2 hydroxy propanoic acid Arrcostab, such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid Propyl ester etc.；2- alkoxypropan acid alkyl esters, such as 2- methoxy methyl propionates, 2- methoxypropionates, 2- ethoxy-propionic acids Ethyl ester, 2- ethoxypropanoates etc.；2- hydroxy-2-methyl alkyl propionates, such as 2- hydroxy-2-methyls methyl propionate, 2- Hydroxy-2-methyl ethyl propionate etc.；2- alkoxies -2 Methylpropionic acid Arrcostab, such as 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyls -2 Methylpropionic acid ethyl ester etc.；Ester, such as propionic acid -2- hydroxy methacrylates, propionic acid -2- hydroxy-2-methyls ethyl ester, acetic acid Hydroxy methacrylate, 2- hydroxy-3-methyl methyl butyrates etc.；Or keto ester, such as ethyl pyruvate etc., and be in addition N- methyl formyls Amine, N,N-dimethylformamide, N- methyl formyl anilines, N- methylacetamides, DMAC N,N' dimethyl acetamide, N- crassitudes Ketone, dimethyl sulfoxide (DMSO), benzyl ether, hexyl ether, acetylacetone,2,4-pentanedione, isophorone, caproic acid, octanoic acid, 1- octanols, 1 nonyl alcohol, Phenmethylol, phenylmethyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, carbonic acid Asia second Ester, propylene carbonate, ethylene glycol monophenyl ether acetic acid esters etc., the solvent can be used alone or the mixture as both or more persons Form uses.
In view of compatibility and reactivity, solvent can be desired for ketone, such as cyclohexanone etc.；Glycol ethers, such as ethylene glycol list Ether etc.；Ethylene glycol alkyl ether acetic acid esters, such as ethyl cellosolve acetate etc.；Ester, such as propionic acid -2- hydroxy methacrylates etc.；Two Ethylene glycol, such as diethylene glycol monomethyl ether etc.；Propylene glycol alkyl ether acetic acid ester, such as propylene glycol methyl ether acetate, propane diols Propyl ether acetic acid esters etc..
In terms of the total amount of Photosensitve resin composition, solvent is used with surplus, and is specifically 20wt% to 90wt%. Photosensitve resin composition for colored filter has coating property, and can maintain thickness as the excellent of 3 μm or the film more than 3 μm Different flatness.
(F) other additives
Photosensitve resin composition can further include additive, such as malonic acid；3- amido-1,2-propanediols；Include second The silane system coupling agent of alkenyl or (methyl) acryloxy；Levelling agent；Fluorine system surfactant；Radical polymerization initiator Deng to prevent spot or spot during coating, levelling is adjusted or prevent from producing pattern residue due to not developing.
In addition, Photosensitve resin composition can further include the additive such as epoxide, to improve and substrate It is in close contact property.
The example of epoxide can be phenol novolac epoxy compound, tetramethyl biphenyl epoxy compound, bisphenol-A ring Oxygen compound, alicyclic ring epoxy compound or its combination.
The amount of additive can be controlled according to desired property.
Another embodiment provides a kind of colored filter manufactured using the Photosensitve resin composition.Manufacture colorized optical filtering The method of piece is as described below.
Using proper methods such as spin coating, slot coateds, there is the thickness to be in naked glass substrate or in coated thereonExtremelySiNxHave as the Photosensitve resin composition for colored filter is applied in the glass substrate of protective layer 3.1 μm to 3.4 μm of thickness.After the coating, irradiation light is to form the pattern required for colored filter.In irradiation Afterwards, coated layer is handled with alkaline-based developer, and can dissolve the non-radiative area of coated floor, so as to be formed for image The pattern of colored filter.This process is repeated depending on the required number of red, green and blueness, is schemed so as to make with desired The colored filter of case.
In addition, by heat treatment, actinic ray radiation etc. to being solidified by the acquired picture pattern that develops, as a result Improve crack resistance, solvent resistance etc..
Hereinafter, the preferred embodiment of the present invention is illustrated.However, these examples are not necessarily to be construed as limiting in any sense The scope of the present invention.
(preparation of unimolecule compound)
(synthesis example 1：Intermediate A synthesis)
Aniline (10mol), 4- toluene bromides (10mol), Pd are with the addition of into toluene2(dba)3(0.1mol) and Xphos (0.1mol), and the mixture heat and stirred 24 hours at 100 DEG C.Acetic acid is with the addition of into this solution Ethyl ester, and washed the mixture obtained twice to extract organic layer with water.The organic layer extracted is entered under reduced pressure Go and distilled and purifying has been carried out by column chromatography to obtain intermediate A.
(synthesis example 2：Intermediate B-1 synthesis)
2,4- dimethyl diphenyls amine (10mol), 1,2- oxepanes are with the addition of into N,N-dimethylformamide (12mol) and sodium hydride (12mol), and the mixture heat and stirred 24 hours at 90 DEG C.It is molten to this Ethyl acetate is with the addition of in liquid, and has been washed the mixture obtained twice to extract organic layer with water.Under reduced pressure to institute The organic layer of extraction has carried out distillation and has carried out separation by column chromatography to obtain intermediate B-1.
(synthesis example 3：Intermediate B-2 synthesis)
Except be instead of using 1,2- epoxy butanes beyond 1,2- oxepanes, closed according to the identical method of synthesis example 2 Into intermediate B-2.
(synthesis example 4：Intermediate B-3 synthesis)
Except be instead of using intermediate A beyond 2,4- dimethyl diphenyl amine, closed according to the identical method of synthesis example 2 Into intermediate B-3.
(synthesis example 5：Intermediate B-4 synthesis)
Except be instead of using HEO beyond 1,2- oxepanes, according to the identical method of synthesis example 2 Intermediate B-4 is synthesized.
(synthesis example 6：Intermediate C-1 synthesis)
Intermediate B-1 (10mmol), iodomethane (15mmol) and sodium hydride are with the addition of into N,N-dimethylformamide (15mmol), and at room temperature stirred the mixture 24 hours.Ethyl acetate is with the addition of into this solution, and will with water The mixture obtained has been washed twice to extract organic layer.Under reduced pressure the organic layer extracted distill and pass through Column chromatography has carried out separation to obtain intermediate C-1.
(synthesis example 7：Intermediate C-2 synthesis)
In addition to it instead of iodomethane using 2- iodopropanes, intermediate has been synthesized according to the identical method of synthesis example 6 C-2。
(synthesis example 8：Intermediate C-3 synthesis)
In addition to it instead of intermediate B-1 using intermediate B-2, in having been synthesized with the identical method of synthesis example 6 Between thing C-3.
(synthesis example 9：Intermediate C-4 synthesis)
In addition to it instead of iodomethane using iodoethane, intermediate C- has been synthesized according to the identical method of synthesis example 8 4。
(synthesis example 10：Intermediate C-5 synthesis)
In addition to it instead of iodomethane using 2- iodopropanes, intermediate has been synthesized according to the identical method of synthesis example 8 C-5。
(synthesis example 11：Intermediate C-6 synthesis)
In addition to it instead of intermediate B-1 using intermediate B-3, in having been synthesized with the identical method of synthesis example 6 Between thing C-6.
(synthesis example 12：Intermediate C-7 synthesis)
In addition to it instead of intermediate B-1 using intermediate B-4, in having been synthesized with the identical method of synthesis example 6 Between thing C-7.
(synthesis example 13：The compound represented by chemical formula 4 synthesizes)
Intermediate C-1 (60mmol) and 3,4- dihydroxy -3- rings are with the addition of into toluene (200mL) and butanol (200mL) Butine -1,2- diketone (30mmol), and removed using Dean-Stark (Dean-stark) distiller by the mixing Thing is flowed back and caused water.After the stirring of 12 hours is carried out, distillation has been carried out to green reaction agent simultaneously under reduced pressure Purified by column chromatography, to obtain the compound represented by chemical formula 4.
(synthesis example 14：The compound represented by chemical formula 5 synthesizes)
In addition to it instead of intermediate C-1 using intermediate C-2, according to synthesized with the identical method of synthesis example 13 by The compound that chemical formula 5 represents.
(synthesis example 15：The compound represented by chemical formula 6 synthesizes)
In addition to it instead of intermediate C-1 using intermediate C-3, according to synthesized with the identical method of synthesis example 13 by The compound that chemical formula 6 represents.
(synthesis example 16：The compound represented by chemical formula 7 synthesizes)
In addition to it instead of intermediate C-1 using intermediate C-4, according to synthesized with the identical method of synthesis example 13 by The compound that chemical formula 7 represents.
(synthesis example 17：The compound represented by chemical formula 8 synthesizes)
In addition to it instead of intermediate C-1 using intermediate C-5, according to synthesized with the identical method of synthesis example 13 by The compound that chemical formula 8 represents.
(synthesis example 18：The compound represented by chemical formula 9 synthesizes)
In addition to it instead of intermediate C-1 using intermediate C-6, according to synthesized with the identical method of synthesis example 13 by The compound that chemical formula 9 represents.
(synthesis example 19：The compound represented by chemical formula 10 synthesizes)
In addition to it instead of intermediate C-1 using intermediate C-7, according to synthesized with the identical method of synthesis example 13 by The compound that chemical formula 10 represents.
(synthesis example 20：The core-shell structure copolymer dyestuff represented by chemical formula 13 synthesizes)
The compound (5mmol) represented by chemical formula 4 is dissolved in 600mL chloroform solvents, and lasts 5 hours in room temperature Under be added dropwise thereto by the way that isophthaloyl chlorine (20mmol) and paraxylene diamines (20mmol) are dissolved in 60mL chloroforms to obtain The solution obtained.After 12 hours, under reduced pressure the mixture obtained distill and carry out by column chromatography Separation, to obtain the compound represented by chemical formula 13.
MALDI _ TOFMS (Matrix-assisted laser desorption Ionization-time of flight mass spectrometry, Maldi-tof MS)：1232.64m/z
(synthesis example 21：The core-shell structure copolymer dyestuff represented by chemical formula 14 synthesizes)
The compound (5mmol) represented by chemical formula 4 is dissolved in 600mL chloroform solvents, and adds three second thereto Base amine (50mmol).It is dissolved in by 2,6- pyridine dicarbapentaborane dichloride (20mmol) and to xylylene amine (20mmol) In 60mL chloroforms, and last 5 hours and with the addition of the solution thereto at room temperature.After 12 hours, under reduced pressure to institute The mixture of acquisition is distilled and separated by column chromatography, to obtain the compound represented by chemical formula 14.
MALDI _ TOFMS：1234.63m/z
(synthesis example 22：The core-shell structure copolymer dyestuff represented by chemical formula 15 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 5, according to conjunction The compound represented by chemical formula 15 has been synthesized into the identical method of example 20.
MALDI _ TOFMS：1288.70m/z
(synthesis example 23：The core-shell structure copolymer dyestuff represented by chemical formula 16 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 5, according to conjunction The compound represented by chemical formula 16 has been synthesized into the identical method of example 21.
MALDI _ TOFMS：1290.69m/z
(synthesis example 24：The core-shell structure copolymer dyestuff represented by chemical formula 17 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 6, according to conjunction The compound represented by chemical formula 17 has been synthesized into the identical method of example 20.
MALDI _ TOFMS：1176.57m/z
(synthesis example 25：The core-shell structure copolymer dyestuff represented by chemical formula 18 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 6, according to conjunction The compound represented by chemical formula 18 has been synthesized into the identical method of example 21.
MALDI _ TOFMS：1178.56m/z
(synthesis example 26：The core-shell structure copolymer dyestuff represented by chemical formula 19 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 7, according to conjunction The compound represented by chemical formula 19 has been synthesized into the identical method of example 20.
MALDI _ TOFMS：1204.60m/z
(synthesis example 27：The core-shell structure copolymer dyestuff represented by chemical formula 20 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 7, according to conjunction The compound represented by chemical formula 20 has been synthesized into the identical method of example 21.
MALDI _ TOFMS：1206.59m/z
(synthesis example 28：The core-shell structure copolymer dyestuff represented by chemical formula 21 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 8, according to conjunction The compound represented by chemical formula 21 has been synthesized into the identical method of example 20.
MALDI _ TOFMS：1232.64m/z
(synthesis example 29：The core-shell structure copolymer dyestuff represented by chemical formula 22 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 8, according to conjunction The compound represented by chemical formula 22 has been synthesized into the identical method of example 21.
MALDI _ TOFMS：1234.63m/z
(synthesis example 30：The core-shell structure copolymer dyestuff represented by chemical formula 23 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 9, according to conjunction The compound represented by chemical formula 23 has been synthesized into the identical method of example 20.
MALDI _ TOFMS：1204.60m/z
(synthesis example 31：The core-shell structure copolymer dyestuff represented by chemical formula 24 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 9, according to conjunction The compound represented by chemical formula 24 has been synthesized into the identical method of example 21.
MALDI _ TOFMS：1206.59m/z
(synthesis example 32：The core-shell structure copolymer dyestuff represented by chemical formula 25 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 10, according to The identical method of synthesis example 20 has synthesized the compound represented by chemical formula 25.
MALDI _ TOFMS：1228.60m/z
(synthesis example 33：The core-shell structure copolymer dyestuff represented by chemical formula 26 synthesizes)
In addition to it instead of the compound represented by chemical formula 4 using the compound that is represented by chemical formula 10, according to The identical method of synthesis example 21 has synthesized the compound represented by chemical formula 26.
MALDI _ TOFMS：1230.59m/z
(compare synthesis example 1：By synthesizing for the chemical formula X compounds represented)
[chemical formula X]
In addition to it instead of intermediate C-1 using intermediate B-3, according to synthesized with the identical method of synthesis example 13 by The compound that chemical formula X is represented.
MALDI _ TOFMS：672.39m/z
(compare synthesis example 2：By synthesizing for the chemical formula Y compounds represented)
[chemical formula Y]
398mg side's acid and 2.23g 2- (3- (methyl (phenyl) amino) the third amino) third are put into 100mL 3 neck flasks Olefin(e) acid ethyl ester, adds 40mL n-butanols and 20mL toluene thereto, and heats and flowed back 5 by the mixture at 120 DEG C Hour.Caused water during reaction is removed using Dean-Stark separator group (Dean-Stark trap set), and is promoted Enter the reaction.After completion is reacted, the gains from it are cooled down, and is then extracted simultaneously with dichloromethane Handled by column chromatography, so as to the compound represented with the synthesis of 60% yield by chemical formula Y.
MALDI _ TOFMS：514.26m/z
(compare synthesis example 3：The synthesis of core-shell structure copolymer dyestuff)
398mg side's acid and 2.23g 2- (3- (dibutylamino) phenoxy group) acrylic acid are put into 100mL 3 neck flasks Ethyl ester, 40mL n-butanols and 20mL toluene are added thereto, and it is at 120 DEG C that the mixture obtained heating and backflow 5 is small When.Caused water during reaction is removed using Dean-Stark separator group, and promotes the reaction.When reaction completion Afterwards, the gains from it are cooled down, and is then extracted with dichloromethane and handled by column chromatography, from And the compound represented by chemical formula Z-1 is obtained with 60% yield.Then, 0.72g (1mmol) is represented by chemical formula Z-1 Compound and 2.02g (1mmol) represented by chemical formula Z-2 triacetyl beta-schardinger dextrin (chemical abstracts service number (CAS#) 23739-88-0, Ti Xiai chemical company (TCI Chemicals)) it is dissolved in 50ml dichloromethane, at room temperature By the solution stir about 12 hours, and be dried under reduced pressure to removing the residue after solvent completely, with for The about 2.7g core-shell structure copolymer dyestuffs of solid state.The core-shell structure copolymer dyestuff has the compound represented by chemical formula Z-2 around by chemistry The structure for the compound that formula Z-1 is represented.
[chemical formula Z-1]
[chemical formula Z-2]
(preparation of Photosensitve resin composition)
Photosensitve resin composition is prepared for using following components.
(A) dyestuff
(A-1) the unimolecule dyestuff (being represented by chemical formula 4) prepared in synthesis example 13
(A-2) the unimolecule dyestuff (being represented by chemical formula 5) prepared in synthesis example 14
(A-3) the unimolecule dyestuff (being represented by chemical formula 6) prepared in synthesis example 15
(A-4) the unimolecule dyestuff (being represented by chemical formula 7) prepared in synthesis example 16
(A-5) the unimolecule dyestuff (being represented by chemical formula 8) prepared in synthesis example 17
(A-6) the unimolecule dyestuff (being represented by chemical formula 9) prepared in synthesis example 18
(A-7) the unimolecule dyestuff (being represented by chemical formula 10) prepared in synthesis example 19
(A-8) the core-shell structure copolymer dyestuff (being represented by chemical formula 13) prepared in synthesis example 20
(A-9) the core-shell structure copolymer dyestuff (being represented by chemical formula 14) prepared in synthesis example 21
(A-10) the core-shell structure copolymer dyestuff (being represented by chemical formula 15) prepared in synthesis example 22
(A-11) the core-shell structure copolymer dyestuff (being represented by chemical formula 16) prepared in synthesis example 23
(A-12) the core-shell structure copolymer dyestuff (being represented by chemical formula 17) prepared in synthesis example 24
(A-13) the core-shell structure copolymer dyestuff (being represented by chemical formula 18) prepared in synthesis example 25
(A-14) the core-shell structure copolymer dyestuff (being represented by chemical formula 19) prepared in synthesis example 26
(A-15) the core-shell structure copolymer dyestuff (being represented by chemical formula 20) prepared in synthesis example 27
(A-16) the core-shell structure copolymer dyestuff (being represented by chemical formula 21) prepared in synthesis example 28
(A-17) the core-shell structure copolymer dyestuff (being represented by chemical formula 22) prepared in synthesis example 29
(A-18) the core-shell structure copolymer dyestuff (being represented by chemical formula 23) prepared in synthesis example 30
(A-19) the core-shell structure copolymer dyestuff (being represented by chemical formula 24) prepared in synthesis example 31
(A-20) the core-shell structure copolymer dyestuff (being represented by chemical formula 25) prepared in synthesis example 32
(A-21) the core-shell structure copolymer dyestuff (being represented by chemical formula 26) prepared in synthesis example 33
(A-22) the unimolecule dyestuff (being represented by chemical formula X) prepared in relatively synthesis example 1
(A-23) the unimolecule dyestuff (being represented by chemical formula Y) prepared in relatively synthesis example 2
(A-24) the core-shell structure copolymer dyestuff prepared in relatively synthesis example 3
(A') dispersible pigment dispersion
(A'-1) C.I. viridine greens 7
(A'-2) C.I. viridine greens 58
(B) adhesive resin
Methacrylic acid/benzyl methacrylate copolymer (mixing weight that weight average molecular weight is 22,000g/mol Amount ratio：15wt%/85wt%)
(C) photopolymerizable monomer
Dipentaerythritol acrylate
(D) Photoepolymerizationinitiater initiater
(D-1) 1,2- acetyl caproyls
(D-2) 2- dimethylaminos -2- (4- Metfayl-benzyls) -1- (4- morpholines -4- bases-phenyl)-butyl- 1- ketone
(E) solvent
(E-1) cyclohexanone
(E-2) propylene glycol methyl ether acetate
Example 1 is to example 21 and comparative example 1 to comparative example 5
By the way that each component in table 1 to the composition shown in table 3 is mixed to prepare Photosensitve resin composition. Specifically, by Photoepolymerizationinitiater initiater dissolving in a solvent, the solution is stirred 2 hours at room temperature, addition thereto contaminates Expect (or dispersible pigment dispersion), the mixture is stirred 30 minutes, add adhesive resin and photopolymerizable monomer thereto, and The mixture obtained is stirred 2 hours at room temperature.Solution filtering with removal of impurity and is prepared into photosensitive resin three times Composition.
[table 1]
(unit：Wt%)
[table 2]
(unit：Wt%)
[table 3]
(unit：Wt%)
(assessment)
Assess 1：Brightness and contrast
Respectively by according to example 1 to example 21 and comparative example 1 to comparative example 5 in the thick degreasing glass substrates of 1mm Photosensitve resin composition coating, to 3 μ m-thicks, and dries 2 minutes to obtain film for 1 μm in 90 DEG C of heating plate.Then, with master Wavelength is that 365nm high-pressure sodium lamp exposes the film, and has dried 5 points in the forced convertion drying oven of 200 DEG C of baking oven Clock.Using spectrophotometer (MCPD3000, great Zhong Electronics Co., Ltd. (Otsuka electronic Co., Ltd.s)) to picture The brightness of plain layer and contrast are measured, and result is shown in Table 4.
[table 4]
Brightness Contrast
Example 1 65.5 14500
Example 2 65.7 14800
Example 3 65.5 14600
Example 4 65.3 14400
Example 5 65.8 14900
Example 6 65.3 14300
Example 7 65.5 14500
Example 8 67.5 14700
Example 9 67.6 14600
Example 10 67.9 15100
Example 11 67.8 15000
Example 12 67.3 14600
Example 13 67.2 14700
Example 14 67.5 14400
Example 15 67.4 14800
Example 16 67.8 15200
Example 17 67.9 15100
Example 18 67.6 14500
Example 19 67.5 14600
Example 20 67.4 14400
Example 21 67.3 14700
Comparative example 1 64.3 13200
Comparative example 2 64.5 13400
Comparative example 3 64.2 13100
Comparative example 4 62.1 12200
Comparative example 5 63.5 12500
Reference table 4, compared with both not including unimolecule dyestuff or not including comparative example 1 to the comparative example 5 of core-shell structure copolymer dyestuff, Example 1 to example 21 comprising unimolecule dyestuff or core-shell structure copolymer dyestuff according to embodiments of the present invention shows high brightness and height Contrast.In addition, according to the compound of embodiment comprising through the alkoxy that branched alkyl substitutes as functional group's when ratio not Much excellent brightness and contrast are shown during comprising the alkoxy.
Assess 2：Durability
Respectively by according to example 8 to example 21 and comparative example 1 to comparative example 5 in the thick degreasing glass substrates of 1mm Photosensitve resin composition coating, to 3 μ m-thicks, and dries 2 minutes to obtain film for 1 μm in 90 DEG C of heating plate.It is with dominant wavelength The film is exposed and dried 20 minutes in 200 DEG C of baking oven by 365nm high-pressure sodium lamp, and uses spectrophotometer (MCPD3000, great Zhong Electronics Co., Ltd.) is measured to color coordinate change and therefore assesses durability, and result is shown in In table 5.
The assessment benchmark of durability
Well：Color coordinate change is less than or equal to 0.005
Difference：Color coordinate change is more than 0.005
[table 5]
Durability
Example 8 Well
Example 9 Well
Example 10 Well
Example 11 Well
Example 12 Well
Example 13 Well
Example 14 Well
Example 15 Well
Example 16 Well
Example 17 Well
Example 18 Well
Example 19 Well
Example 20 Well
Example 21 Well
Comparative example 1 Difference
Comparative example 2 Difference
Comparative example 3 Difference
Comparative example 4 Well
Comparative example 5 Well
Reference table 5, the composition (comparative example from including the unimolecule dyestuff different with the unimolecule dyestuff according to embodiment 1 and comparative example 2) and composition (comparative example 3) comprising the core-shell structure copolymer dyestuff different with the core-shell structure copolymer dyestuff according to embodiment compare, Example 8 comprising the core-shell structure copolymer dyestuff according to embodiment shows excellent durability to example 21.
Although combine the exemplary embodiment for being presently believed to be practical to be set forth the present invention, it should be appreciated that The present invention is not limited only to the disclosed embodiments, but on the contrary, it is contemplated that covers included in following claims Spirit and scope in various modifications and equivalent.Therefore, above-described embodiment is interpreted as exemplary, rather than with Any mode limits the present invention.

Claims (22)

1. a kind of compound, it is characterised in that represented by chemical formula 1：
[chemical formula 1]
Wherein, in chemical formula 1,
R1And R2The C1 that is substituted or is unsubstituted independently is to C20 alkyl, the C3 for being substituted or being unsubstituted to C20 cycloalkanes Base or the C6 that is substituted or is unsubstituted to C20 aryl, its restrictive condition be R1And R2Independently and it must include by chemical formula The functional group and chiral carbon that 1-1 is represented, and
R3And R4It is fragrant to C20 alkyl or the C6 for being substituted or being unsubstituted to C20 independently to be the C1 for being substituted or being unsubstituted Base,
[chemical formula 1-1]
*-O-R6
Wherein, in chemical formula 1-1,
R6For the C1 that is substituted or is unsubstituted to C20 alkyl.
2. compound according to claim 1, it is characterised in that R1And R2Represented by chemical formula 2-1 or chemical formula 2-2：
[chemical formula 2-1]
[chemical formula 2-2]
*-L2-O-R6
Wherein, in chemical formula 2-1 and chemical formula 2-2,
L1For singly-bound, the C1 for being substituted or being unsubstituted to C10 alkylidenes or the C3 for being substituted or being unsubstituted to C10 Asias ring Alkyl,
L2For the C1 that is substituted or is unsubstituted to the C10 alkylidenes or C3 for being substituted or being unsubstituted to C10 cycloalkylidenes, And
R5And R6The C1 that is substituted or is unsubstituted independently is to C20 alkyl.
3. compound according to claim 2, it is characterised in that R6To substitute through C1 to C10 alkyl or C6 to C20 aryl C1 to C20 alkyl.
4. compound according to claim 3, it is characterised in that R6Represented by chemical formula 3：
[chemical formula 3]
Wherein, in chemical formula 3,
R7And R8The C1 that is substituted or is unsubstituted independently is to C10 alkyl.
5. compound according to claim 1, it is characterised in that R3And R4Independently be through C1 to C10 alkyl substitute or not Through the alkyl-substituted C6 of C1 to C10 to C20 aryl.
6. compound according to claim 1, it is characterised in that the compound represented by chemical formula 1 is by chemistry One of compound that formula 4 represents to chemical formula 10：
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
7. compound according to claim 1, it is characterised in that the compound has maximum into 700nm in 600nm Absorbing wavelength.
A kind of 8. core-shell structure copolymer dyestuff, it is characterised in that including：
Core, include compound according to claim 1；And
Shell, around the core.
9. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the shell is represented by chemical formula 11 or chemical formula 12：
[chemical formula 11]
[chemical formula 12]
Wherein, in chemical formula 11 and chemical formula 12,
LaTo LdIt independently is singly-bound or the C1 that is substituted or is unsubstituted is to C10 alkylidenes.
10. core-shell structure copolymer dyestuff according to claim 9, it is characterised in that LaTo LdIt independently is and is substituted or is unsubstituted C1 to C10 alkylidenes.
11. core-shell structure copolymer dyestuff according to claim 9, it is characterised in that the shell is by chemical formula 11-1 or chemical formula 12-1 Represent：
[chemical formula 11-1]
[chemical formula 12-1]
12. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the shell hasExtremelyCage width.
13. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core has 1nm to 3nm length.
14. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core has in 530nm to 680nm wavelength There is maximum absorption band.
15. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core-shell structure copolymer dyestuff be selected from by chemical formula 13 to The compound that chemical formula 26 represents：
[chemical formula 13]
[chemical formula 14]
[chemical formula 15]
[chemical formula 16]
[chemical formula 17]
[chemical formula 18]
[chemical formula 19]
[chemical formula 20]
[chemical formula 21]
[chemical formula 22]
[chemical formula 23]
[chemical formula 24]
[chemical formula 25]
[chemical formula 26]
16. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core-shell structure copolymer dyestuff is with 1:1 mol ratio includes The core and the shell.
17. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core-shell structure copolymer dyestuff is green colouring material.
18. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core-shell structure copolymer dyestuff is in 600nm into 700nm With maximum absorption wavelength.
19. a kind of Photosensitve resin composition, it is characterised in that include
Compound according to claim 1 or core-shell structure copolymer dyestuff according to claim 8.
20. Photosensitve resin composition according to claim 19, it is characterised in that the Photosensitve resin composition is further Include adhesive resin, photopolymerizable monomer, Photoepolymerizationinitiater initiater and solvent.
21. Photosensitve resin composition according to claim 19, it is characterised in that the Photosensitve resin composition is further Include malonic acid, 3- amido-1,2-propanediols, silane system coupling agent, the levelling for including vinyl or (methyl) acryloxy Agent, surfactant, radical polymerization initiator or its combination.
22. a kind of colored filter, it is characterised in that made using Photosensitve resin composition according to claim 19 Make.
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CN107793327B (en) 2020-06-16

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