CN107428766A - Compounds, photosensitive resin composition and colored filter containing it - Google Patents
Compounds, photosensitive resin composition and colored filter containing it Download PDFInfo
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- CN107428766A CN107428766A CN201580077258.4A CN201580077258A CN107428766A CN 107428766 A CN107428766 A CN 107428766A CN 201580077258 A CN201580077258 A CN 201580077258A CN 107428766 A CN107428766 A CN 107428766A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/08—Copper compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/06—Zinc compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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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
Abstract
The present invention provides compound, the photosensitive resin composition comprising the compound and the colored filter manufactured using the photosensitive resin composition represented by specified chemical formula.
Description
Technical field
Photosensitive resin composition and colorized optical filtering the present invention relates to a kind of compounds, comprising the compound
Piece.
Background technology
The colored filter manufactured by using the photosensitive resin composition of pigment type is because of pigment particle size and in brightness
And there is limitation in terms of contrast ratio.In addition, imaging transformer device needs smaller dispersion particle diameter to form fine pattern.To meet
The demand, the dyes instead of pigments for having attempted not formed particle by introducing manufacture photosensitive resin composition realization with warp
The colored filter of the color characteristic (such as brightness, contrast ratio etc.) of improvement.
Therefore, it is necessary to study the appropriate compound for being used to manufacture photosensitive resin composition as dyestuff.
The content of the invention
[technique direction]
One embodiment provides a kind of compounds.
Another embodiment provides a kind of photosensitive resin composition for including the compound.
Another embodiment provides a kind of colored filter manufactured using the photosensitive resin composition.
[Technical Solving]
One embodiment of the present of invention provides a kind of compound represented by chemical formula 1.
[chemical formula 1]
In chemical formula 1,
M is Cu, Zn, Co or Mo,
R1To R16Independently be hydrogen atom, halogen atom, the C1 that is substituted or is unsubstituted to C20 alkyl, be substituted or
The C3 being unsubstituted to C20 alkoxies, the C6 for being substituted or being unsubstituted to C20 aryl or the C6 for being substituted or being unsubstituted extremely
C20 aryloxy group, and
R1To R16At least one of represented by chemical formula 2,
[chemical formula 2]
Wherein, in chemical formula 2,
R17And R18The 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 2 can be represented by chemical formula 3.
[chemical formula 3]
In chemical formula 3,
R17And R18The C1 that is substituted or is unsubstituted independently is to C20 alkyl or the C6 for being substituted or being unsubstituted extremely
C20 aryl.
R1To R16At least one of can be represented by chemical formula 2, and R1To R16At least one of can be by chemical formula 4 to change
One of formula 7 represents.
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
In chemical formula 6 and chemical formula 7,
L1It is the C1 that is substituted or is unsubstituted to C10 alkylidenes, and
R19For the C1 that is substituted or is unsubstituted to C10 alkyl.
R1To R4At least one of can be represented by chemical formula 2, R5To R8At least one of can be by chemical formula 4 to chemistry
The expression of one of formula 7, R9To R12At least one of can be represented by one of chemical formula 4 to chemical formula 7, and R13To R16
At least one of can be represented by one of chemical formula 4 to chemical formula 7.
R1To R4At least one of can be represented by chemical formula 2, R5To R8At least one of can be represented by chemical formula 2, R9
To R12At least one of can be represented by chemical formula 4 to chemical formula 7, and R13To R16At least one of can be by chemical formula 4 to change
One of formula 7 represents.
R1To R4At least one of can be represented by chemical formula 2, R5To R8At least one of can be by chemical formula 4 to chemistry
The expression of one of formula 7, R9To R12At least one of can be represented by chemical formula 2, and R13To R16At least one of can be by changing
Formula 4 to one of chemical formula 7 represents.
R1To R4At least one of can be represented by chemical formula 2, R5To R8At least one of can be represented by chemical formula 2, R9
To R12At least one of can be represented by chemical formula 2, and R13To R16At least one of can be by chemical formula 4 into chemical formula 7
One represents.
R1To R4At least one of can be represented by chemical formula 2, R5To R8At least one of can be represented by chemical formula 2, R9
To R12At least one of can be represented by chemical formula 2, and R13To R16At least one of can be represented by chemical formula 2.
The compound represented by chemical formula 1 can be represented by one of chemical formula 8 to chemical formula 16.
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
[chemical formula 11]
[chemical formula 12]
[chemical formula 13]
[chemical formula 14]
[chemical formula 15]
[chemical formula 16]
The compound can be green colouring material.
Green colouring material can have maximum transmission rate in 445nm to 560nm wavelength.
Another embodiment provides a kind of photosensitive resin composition for including the compound.
The photosensitive resin composition can also include alkali soluble resins, photopolymerizable compound, photopolymerization initiator and
Solvent.
The photosensitive resin composition can also include pigment.
The pigment can be yellow uitramarine.
Another embodiment provides a kind of colored filter manufactured using the photosensitive resin composition.
The other embodiment of the present invention includes in the following embodiments.
[Advantageous Effects]
Having for fabulous green spectral feature, high mole extinction coefficient and improvement is had according to the compound of one embodiment
Solvent dissolubility, and therefore can be used as dyestuff during the preparation for the photosensitive resin composition of green color filter, and
Colored filter comprising the dyestuff can have fabulous brightness and contrast ratio.
Embodiment
Embodiments of the invention are described in more detail below.However, these embodiments are exemplary, and the present invention is not
It is limited to this.
As used herein, when offer is not specifically defined in addition, term " being substituted " refers to through selected from following substituent
Substitution：Halogen (F, Br, Cl or I), hydroxyl, nitro, cyano group, amido (NH2、NH(R200) or N (R201)(R202), wherein R200、
R201And R202To be identical or different and independently be C1 to C10 alkyl), carbonamidine base, diazanyl, hydrazone group, carboxyl, be substituted or not
The alkyl that is substituted, the alkenyl for being substituted or being unsubstituted, the alkynyl that is substituted or is unsubstituted, it is substituted or is unsubstituted
The function of alicyclic ring organic group, the aryl for being substituted or being unsubstituted and the heterocyclic radical replacement present invention for being substituted or being unsubstituted
Base.
As used herein, when do not provide in addition be specifically defined when, term " alkyl " refers to C1 to C20 alkyl and in specific words
C1 to C15 alkyl, term " cycloalkyl " refer to C3 to C20 cycloalkyl and in specific words C3 to C18 cycloalkyl, term " alkoxy "
Refer to C1 to C20 alkoxies and in specific words for C1 to C18 alkoxies, term " aryl " refers to C6 to C20 aryl and in specific words
C6 is to C18 aryl, and term " alkenyl " refers to C2 to C20 alkenyls and in specific words C2 refers to C1 to C18 alkenyls, term " alkylidene "
To C20 alkylidenes and in specific words C1 is to C18 alkylidenes, and term " arlydene " refers to C6 to C20 arlydene and in specific words
C6 is to C16 arlydene.
As used herein, when offer is not specifically defined in addition, " (methyl) acrylate " refers to " acrylate " or " first
Base acrylate " and " (methyl) acrylic acid " refers to " acrylic acid " or " methacrylic acid ".
As used herein, when not providing definition in addition, term " combination " refers to mixing or combined polymerization.In addition, " copolymerization
Close " refer to block copolymerization or random copolymerization, and " copolymer " refers to block copolymer or random copolymer.
In the chemical formula of this specification, it is specifically defined unless otherwise provided, otherwise when chemical bond is not showed that should be to
During source, hydrogen bond knot is in the opening position.
As used herein, when offer is not specifically defined in addition, " * " instruction connects identical or different atom or chemical formula
Point.
One embodiment provides a kind of compound represented by chemical formula 1.
[chemical formula 1]
In chemical formula 1,
M is Cu, Zn, Co or Mo,
R1To R16Independently be hydrogen atom, halogen atom, the C1 that is substituted or is unsubstituted to C20 alkyl, be substituted or
The C3 being unsubstituted to C20 alkoxies, the C6 for being substituted or being unsubstituted to C20 aryl or the C6 for being substituted or being unsubstituted extremely
C20 aryloxy group, and
R1To R16At least one of represented by chemical formula 2,
[chemical formula 2]
Wherein, in chemical formula 2,
R17And R18The C1 that is substituted or is unsubstituted independently is to C20 alkyl or the C6 for being substituted or being unsubstituted extremely
C20 aryl.
The compound represented by chemical formula 1 has fabulous green spectral feature and high mole extinction coefficient.In addition, by changing
The compound that formula 1 represents must include the substituent represented by chemical formula 2 and therefore can have what is improved in organic solvent
Solubility, and show fabulous brightness when applied to colored filter.
In one exemplary embodiment, M can be Zn.
Chemical formula 2 can be represented by chemical formula 3.
[chemical formula 3]
In chemical formula 3,
R17And R18The C1 that is substituted or is unsubstituted independently is to C20 alkyl or the C6 for being substituted or being unsubstituted extremely
C20 aryl.
The substituent represented by chemical formula 2, example must be included according to the compound represented by chemical formula 1 of one embodiment
Such as chemical formula 3 and red shift is caused, therefore compared with the constituent of the pigment comprising such as viridine green, according to one embodiment
The compound represented by chemical formula 1 shows fabulous brightness.
In addition, the substitution represented by chemical formula 2 must be included according to the compound represented by chemical formula 1 of one embodiment
Base, such as chemical formula 3, and the solubility that display improves significantly in organic solvent, and the dye of the phthalocyanine system comprising amide substituents
The solubility of material compound in organic solvent drastically deteriorates.
R1To R16It can be represented by chemical formula 2, and R1To R16At least one of can be by one in chemical formula 4 to chemical formula 7
Person represents.
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
In chemical formula 6 and chemical formula 7,
L1It is the C1 that is substituted or is unsubstituted to C10 alkylidenes, and
R19For the C1 that is substituted or is unsubstituted to C10 alkyl.
For example, L1Can be the methylene for being substituted or being unsubstituted, the ethylidene that is substituted or is unsubstituted, through taking
Generation or be unsubstituted propylidene, be substituted or be unsubstituted butylidene, be substituted or be unsubstituted pentylidene, be substituted
Or be unsubstituted hexylidene, be substituted or be unsubstituted heptamethylene, be substituted or be unsubstituted octamethylene, be substituted or
The nonylene being unsubstituted or the decylene for being substituted or being unsubstituted.
In addition to the substituent represented by chemical formula 2, also included according to the compound of one embodiment by chemical formula 4 to change
One of formula 7 represent substituent and solubility in organic solvent can be increased and improve coloring properties.
For example, in chemical formula 1, R1To R4It can be represented by chemical formula 2, R5To R8At least one of can be by chemistry
Formula 4 to one of chemical formula 7 represents, R9To R12At least one of can be represented by one of chemical formula 4 to chemical formula 7,
And R13To R16At least one of can be represented by one of chemical formula 4 to chemical formula 7.
For example, in chemical formula 1, R1To R4It can be represented by chemical formula 2, R5To R8At least one of can be by chemistry
Formula 2 represents, R9To R12At least one of can be represented by one of chemical formula 4 to chemical formula 7, and R13To R16In at least
One can be represented by one of chemical formula 4 to chemical formula 7.
For example, in chemical formula 1, R1To R4It can be represented by chemical formula 2, R5To R8At least one of can be by chemistry
Formula 4 to one of chemical formula 7 represents, R9To R12At least one of can be represented by chemical formula 2, and R13To R16In at least
One can be represented by one of chemical formula 4 to chemical formula 7.
For example, in chemical formula 1, R1To R4It can be represented by chemical formula 2, R5To R8At least one of can be by chemistry
Formula 2 represents, R9To R12At least one of can be represented by chemical formula 2, and R13To R16At least one of can by chemical formula 4 to
One of chemical formula 7 represents.
For example, in chemical formula 1, R1To R4It can be represented by chemical formula 2, R5To R8At least one of can be by chemistry
Formula 2 represents, R9To R12At least one of can be represented by chemical formula 2, and R13To R16At least one of can be by the table of chemical formula 2
Show.
For example, the compound represented by chemical formula 1 can represent by one of chemical formula 8 to chemical formula 16, but not
It is limited to this.
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
[chemical formula 11]
[chemical formula 12]
[chemical formula 13]
[chemical formula 14]
[chemical formula 15]
[chemical formula 16]
Due to the compound according to one embodiment can the substituent that represents of reason chemical formula 2, such as chemical formula 3, and be
Make to realize clearer colour with small amount, therefore fabulous colour can be had as colouring agent manufacture by using the compound
The display device of feature, such as display device with fabulous brightness, contrast ratio etc..For example, the compound can
For colouring agent, such as dyestuff, such as there can be the green colouring material of such as maximum transmission rate in 445nm to 560nm wavelength.
In general, dyestuff is for most expensive among the component of colored filter.It is thus, it may be desirable to use more
Expensive dyestuff is to realize required effect, such as high brightness, high contrast ratio etc. and therefore increases the unit cost of production.However,
When being used as the dyestuff of colored filter according to the compound of one embodiment, still realized even if the compound can use on a small quantity
Fabulous color property, the color property of high brightness, high contrast ratio etc. is such as realized, and reduce the unit cost of production.
In addition, the substituent represented by chemical formula 2 can be removed according to the compound of one embodiment, such as chemical formula 3, outside
Comprising the substituent represented by one of chemical formula 4 to chemical formula 7, and it therefore can be displayed in the dissolving improved in organic solvent
Degree and the coloring properties of improvement.
According to one embodiment, there is provided include the photosensitive resin composition of the compound according to above-described embodiment.
For example, photosensitive resin composition is included and can gathered according to the compound of above-described embodiment, alkali soluble resins, light
Polymerisable compounds, photopolymerization initiator and solvent.
Colouring agent (such as dyestuff, such as green is played in photosensitive resin composition according to the compound of one embodiment
Color dyestuff) effect and can realize fabulous color property.
In terms of the total amount of photosensitive resin composition, 1 weight % to 10 weight %, such as 3 weight % to 7 weights can be included
Measure the compound according to one embodiment of % amount.During compound in comprising the scope, color reprodubility and contrast
Rate is changed into fabulous.
Photosensitive resin composition can also include pigment, such as yellow uitramarine.
Yellow uitramarine can be C.I. pigment yellow 13s 9, C.I. pigment yellow 13s 8, C.I. in color index (Color Index)
Pigment yellow 150 etc., and these pigment can use individually or with both or more than both form of mixtures.
Pigment can be contained in photosensitive resin composition in the form of dispersible pigment dispersion.
Dispersible pigment dispersion can include solid pigment, solvent and the dispersant for being homogeneously dispersed in pigment in solvent.
In terms of the total amount of dispersible pigment dispersion, 1 weight % to 20 weight %, such as 8 weight % to 20 weight %, example can be included
Such as 8 weight % to 15 weight %, such as 10 weight % to 20 weight % and such as 10 weight % to 15 weight % amount solid
Pigment.
Dispersant can be non-ionic dispersing agent, anionic dispersing agent, cationic dispersing agent etc..The tool of dispersant
Body example can be poly- alkane glycol and its ester, polyoxygenated alkene, polyol ester oxirane additive product, alcohol oxirane additive product,
Sulphonic acid ester, sulfonate, carboxylate, carboxylate, alkylamide oxirane additive product, alkylamine etc., and can be individually or with two
Person uses more than both form of mixtures.
The commercial examples of dispersant can include manufactured by BYK Co., Ltds DISPERBYK-101, DISPERBYK-130,
DISPERBYK-140、DISPERBYK-160、DISPERBYK-161、DISPERBYK-162、DISPERBYK-163、
DISPERBYK-164、DISPERBYK-165、DISPERBYK-166、DISPERBYK-170、DISPERBYK-171、
DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 etc.；The EFKA-47 that is manufactured by EFKA chemical companies,
EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450 etc.；By Zenika company's manufacture
Solsperse 5000、Solsperse 12000、Solsperse 13240、Solsperse 13940、Solsperse
17000th, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 etc.；
Or PB711, PB821 manufactured by aginomoto company etc..
In terms of the total amount of dispersible pigment dispersion, 1 weight % can be included to the dispersant of 20 weight % amount.When including the model
When enclosing interior dispersant, the dispersion liquid of photosensitive resin composition can be improved because viscosity is appropriate, and therefore can maintain
The optics of product, physical chemistry quality.
Solvent for dispersible pigment dispersion can be Ethylene glycol acetate, ethylene glycol ethyl ether, methyl proxitol acetate, breast
Acetoacetic ester, polyethylene glycol, cyclohexanone, methyl proxitol etc..
In terms of the total amount of photosensitive resin composition, 10 weight % to 20 weight %, such as 12 weight % to 18 can be included
The dispersible pigment dispersion of weight % amount.During dispersible pigment dispersion in comprising the scope, processing procedure nargin and color are advantageously assured that
Color repeatability and contrast ratio are changed into fabulous.
Alkali soluble resins can be acrylic resin.
Acrylic resin is the first alkene system unsaturated monomer and can be with the diene series unsaturated monomer of its combined polymerization
Copolymer, and be the resin for including at least one acrylic acid series repeat unit.
First alkene system unsaturated monomer is the alkene system unsaturated monomer comprising at least one carboxyl.The example bag of the monomer
Containing (methyl) acrylic acid, maleic acid, itaconic acid, fumaric acid or its combination.
In terms of the total amount of acrylic resin, 5 weight % to 50 weight %, such as 10 weight % to 40 weight % can be included
Amount the first alkene system unsaturated monomer.
Diene series unsaturated monomer can be aromatic vinyl compound, such as styrene, α-methylstyrene, vinyl
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- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxybutyls, (methyl)
Benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate etc.；The esterification of unsaturated carboxylic acid aminoalkyl is closed
Thing, such as (methyl) acrylic acid 2- aminoethyls, (methyl) acrylic acid 2- dimethylamino ethyl esters etc.；Vinyl carboxylates chemical combination
Thing, such as vinyl acetate, vinyl benzoate etc.；Unsaturated carboxylic acid glycidyl ester compounds, such as (methyl) third
Olefin(e) acid glycidyl esters etc.；Vinyl cyanide compound, such as (methyl) acrylonitrile etc.；Unsaturated acyl amines, it is all
Such as (methyl) acrylamide；Etc., and can be used individually or with both or more than both form of mixtures.
The instantiation of acrylic resin can be acrylic acid/benzyl methacrylate copolymer, methacrylic acid/first
Base benzyl acrylate copolymer, methacrylic acid/benzyl methacrylate/styrol copolymer, methacrylic acid/methyl
Benzyl acrylate/2-hydroxyethyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene/first
Base acrylic acid 2- hydroxy methacrylate copolymers etc., but not limited to this.These can individually or the mixture with both or more than both
Form uses.
The weight average molecular weight of alkali soluble resins can be 3,000g/mol to 150,000g/mol, such as 5,000g/mol
To 50,000g/mol and again such as 20,000g/mol to 30,000g/mol.When the weight average molecular weight of acrylic resin
When in the scope, the photosensitive resin composition for colored filter has good physics and chemical characteristic, appropriate
Viscosity and the close contact property during colored filter manufactures with substrate.
The acid number of acrylic resin can be 15mg KOH/g to 60mg KOH/g, such as 20mg KOH/g to 50mg
KOH/g.When the acid number of acrylic resin is in the scope, pattern of pixels can have fabulous resolution.
For the total amount meter of the photosensitive resin composition of colored filter, 1 weight % can be included to 30 weight %, example
Such as 1 weight % to 20 weight % amount alkali soluble resins.During alkali soluble resins in comprising above range, development can be improved
Property and fabulous surface flatness can be improved due to the crosslinking of improvement during colored filter manufactures.
Photopolymerizable compound can be the simple function ester of (methyl) acrylic acid comprising at least one alkene system unsaturated double-bond
Or multifunctional ester.
Photopolymerizable compound has alkene system unsaturated double-bond, therefore can cause foot during the exposure of patterning process
The pattern of enough polymerizations and formation with fabulous heat resistance, light resistance and chemical resistance.
The instantiation of photopolymerizable compound can be ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) third
Olefin(e) acid ester, triethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, neopentyl glycol two (methyl) acrylic acid
Ester, BDO two (methyl) acrylate, 1,6- hexylene glycols 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, tricresyl phosphate (methyl)
Acryloyloxyethyl ester, phenolic and epoxy (methyl) acrylate etc..
The commercial examples of photopolymerizable compound are as follows.The example of (methyl) acrylic acid simple function ester can include Aronix
M-M-M-(East Asia synthesizes Chemical Co., Ltd)；KAYARAD TC-TC-(Japanese chemical drug
Co., Ltd.)；V-V-(Osaka organic chemical industry Co., Ltd.) etc..The example of (methyl) acrylic acid difunctionality ester
Aronix M- can be includedM-M-(East Asia synthesizes Chemical Co., Ltd)；KAYARADHX-R-(Nippon Kayaku K. K)；V-V-V-335(Osaka organic chemical industry Co., Ltd.) etc.
Deng.The example of (methyl) acrylic acid trifunctional ester can include Aronix M-M-M-M-M-
M-M-(East Asia synthesizes Chemical Co., Ltd)；KAYARADDPCA-DPCA-DPCA-DPCA-(Nippon Kayaku K. K)；V-V-V-V-V-V-It is (big
Slope organic chemical industry Co., Ltd.) etc..These can be used individually or with both or more than both form of mixtures.
Photopolymerizable compound can be handled with acid anhydrides to improve developability.
In terms of the total amount of photosensitive resin composition, 1 weight % to 15 weight %, such as 5 weight % to 10 weights can be included
Measure the photopolymerizable compound of % amount.During photopolymerizable compound in comprising the scope, photopolymerizable compound exists
Fully solidify during the exposure of patterning process and there is fabulous reliability, and the developability of alkaline-based developer can be improved.
Photopolymerization initiator is the initiator for being usually used in photosensitive resin composition, such as acetophenone based compound, hexichol
Ketone based compound, thioxanthones based compound, styrax based compound, oxime compound or its combination.
The example of acetophenone based compound can be 2,2 '-diethoxy acetophenone, 2,2 '-dibutoxy acetophenone, 2- hydroxyls
Base -2- methyl phenyl ketones, to tributyl trichloroacetophenone, to tributyl dichloroacetophenone, 4- chloro-acetophenones, 2,2 '-two
Chloro- 4- metaphenoxy acetophenones, 2- methyl isophthalic acids-(4- (methyl mercapto) phenyl) -2- morpholinyl propyl- 1- ketone, 2- benzyl -2- dimethyl
Amido -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
Ester, 4- phenyl benzophenones, dihydroxy benaophenonel, acrylated benzophenone, 4,4 '-bis- (dimethyl amido) benzophenone,
4,4 '-bis- (diethyl amido) benzophenone, 4,4 '-dimethyl amido benzophenone, 4,4 '-dichloro benzophenone, 3,3 '-two
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 group 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-, 2- biphenyl 4, double (the trichloromethyl)-s- triazines of 6-, double (trichloromethyl) -6- styryls -
Double (the trichloromethyl)-s- triazines of s- triazines, 2- (naphthols 1- yls) -4,6-, the double (trichlorines of 2- (4- methoxynaphthol 1- yls) -4,6-
Methyl)-s- triazines, double (the trichloromethyl) -6- piperonyl-s- triazines of 2-4-, double (trichloromethyl) -6- (the 4- methoxybenzenes of 2-4-
Vinyl)-s- triazines etc..
The example of oxime compound can be O- acyl groups oxime compound, 2- (o- benzoyl oximes) -1- [4- (thiophenyl) benzene
Base] -1,2- acetyl caproyls, 1- (o- acetyl group oxime) -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] ethyl ketone,
O- ethoxy carbonyls-α-epoxide amido -1- phenyl propyl- 1- ketone etc..The instantiation of O- acyl group oxime compounds can be 1,2-
Acetyl caproyl, 2- dimethyl amidos -2- (4- methylbenzyls) -1- (4- morpholines -4- bases-phenyl)-butyl- 1- ketone, 1- (4- thiophenyls
Phenyl)-butane -1,2- diketone 2- oxime-O- benzoic ethers, 1- (4- Phenylsulfanylphenyls)-octane -1,2- diketone 2- oxime-O- benzene first
Acid esters, 1- (4- Phenylsulfanylphenyls)-octyl- 1- ketoxime-O- acetic acid esters and 1- (4- Phenylsulfanylphenyls)-butyl- 1- ketoxime-O- acetic acid esters
Etc..
Photopolymerization initiator can also include carbazole based compound, diketone based compound, boric acid sulfonium in addition to the compound
Based compound, diazonium based compound, imidazole compound, bisglyoxaline based compound etc..
Photopolymerization initiator can be with that can cause chemical reaction by absorbing light and become to excite and then transmit its energy
Emulsion be used together.
The example of emulsion can be tetraethylene glycol pair -3-thiopropionate, four -3-thiopropionate of pentaerythrite, two seasons
Penta four -3-thiopropionate of tetrol etc..
In terms of the total amount of photosensitive resin composition, 0.01 weight % to 10 weight %, such as 0.1 weight % can be included extremely
The photopolymerization initiator of 5 weight % amount., can be due to being formed in pattern during photopolymerization initiator in comprising the scope
Fully solidify during the exposure of journey and ensure fabulous reliability, pattern can have fabulous resolution and close contact property with
And fabulous heat resistance, light resistance and chemical resistance, and can prevent light transmittance from deteriorating due to non-reaction initiator.
Solvent is with compatible with the compound, alkali soluble resins, photopolymerizable compound and photopolymerization initiator
Property but the material not reacted.
The example of solvent can include alcohol, such as methanol, ethanol etc.；Ether, such as dichloroether, n-butyl ether, isoamyl ether,
Methyl phenyl ether, tetrahydrofuran etc.；Glycol ethers, such as glycol monoethyl ether, ethylene glycol monoethyl ether etc.；Ethylene glycol acetic acid second
Ether, such as Propylene Glycol acetic acid ether, ethohexadiol acetic acid ether, diethyl ethylene glycol ethyl ethers acid ether etc.；Carbitol,
Such as Methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether,
Diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether etc.；Propylene glycol alkyl ether acetic acid ester, such as propylene glycol methyl ether acetate,
Propylene glycol propyl ether acetic acid esters etc.；Aromatic hydrocarbon, such as toluene, dimethylbenzene etc.；Ketone, such as MEK, cyclohexanone, 4- hydroxyls
Base -4-methyl-2 pentanone, methyl n-propyl ketone, methyl n-butyl ketone, methyl-n-amyl ketone, 2-HEPTANONE etc.；Radical of saturated aliphatic list
Alkyl carboxylates, such as ethyl acetate, n-butyl acetate, isobutyl acetate etc.；Lactate, such as methyl lactate, lactic acid second
Ester etc.；Ethoxyacetic acid Arrcostab, such as ethoxyacetic acid methyl esters, ethoxyacetic acid ethyl ester, ethoxyacetic acid butyl ester etc.；Alkoxy second
Acid alkyl ester, such as methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy
Ethyl etc.；3- epoxide alkyl propionates, such as 3- epoxides methyl propionate, 3- epoxide ethyl propionates etc.；3- alcoxyls
Base alkyl propionates, such as 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxyl ethyl propionates, 3- ethyoxyls
Methyl propionate etc.；2- epoxide alkyl propionates, such as 2- epoxides methyl propionate, 2- epoxides ethyl propionate, 2- epoxides propionic acid third
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- epoxides -2 Methylpropionic acid ester, such as 2- epoxides -2 Methylpropionic acid methyl esters, 2- oxygen
Base -2 Methylpropionic acid ethyl ester etc.；2- alkoxies -2 Methylpropionic acid Arrcostab of single epoxide monocarboxylic acid Arrcostab, such as 2- first
Epoxide -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-methyl ethyl ester, acetic acid hydroxy methacrylate, butyric acid 2- hydroxy-3-methyl methyl esters etc.；Keto ester, such as ethyl pyruvate
Etc..In addition, it is possible to use high boiling solvent, such as N-METHYLFORMAMIDE, DMF, N- methyl formyl benzene
Amine, N- methylacetamides, DMA, N- methylpyrrole pyridines ketone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl
Ether, acetylacetone,2,4-pentanedione, isophorone, caproic acid, octanoic acid, 1- octanols, 1 nonyl alcohol, phenmethylol, phenylmethyl acetate, ethyl benzoate, second
Diethyl adipate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol phenyl ether acetic acid
Ester etc..
In view of miscibility and reactivity, glycol ethers, such as ethylene glycol monoethyl ether etc. can be preferably used；Ethylene glycol alkyl
Ether acetic acid ester, such as ethohexadiol acetic acid ether etc.；Ester, such as propionic acid 2- hydroxy methacrylates etc.；Carbitol, such as diethyl
Glycol monomethyl ether etc.；And propylene glycol alkyl ether acetic acid ester, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetic acid esters
Etc..
In terms of the total amount of photosensitive resin composition, solvent is used with surplus, such as 30 weight % to 80 weight %.Work as bag
During containing solvent in the scope, photosensitive resin composition can have proper viscosity, so as to cause the coating of colored filter
The improvement of feature.
Can be tight with substrate to improve also comprising epoxide according to the photosensitive resin composition of another embodiment
Close contact performance.
The example of epoxide can be phenol novolac epoxy compound, tetramethyl biphenyl epoxide, bisphenol-A epoxy
Compound, alicyclic ring epoxy compound or its combination.
In terms of the photosensitive resin composition of 100 parts by weight, 0.01 parts by weight to 20 parts by weight, such as 0.1 weight can be included
Part is measured to the epoxide of the amount of 10 parts by weight.During epoxide in comprising the scope, close contact can be improved
Characteristic, storage capacity etc..
Photosensitive resin composition can also include have such as carboxyl, methylacryloyl, NCO, epoxy radicals and
It is similar to the silane coupling agent of the reactive substituents of group to improve the adherence with substrate.
The example of silane coupling agent includes trimethoxy silane yl benzoic acid, γ-methylpropenyl epoxide propyl group trimethoxy
Base silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanates propyl-triethoxysilicane,
γ-glycidoxypropyltrimewasxysilane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane etc..These can
Individually or with both or more than both form of mixtures use.
In terms of the photosensitive resin composition of 100 parts by weight, 0.01 parts by weight can be included to the silane of the amount of 10 parts by weight
Coupling agent.During silane coupling agent in comprising above range, close contact property, storage characteristic etc. can be improved.
Photosensitive resin composition can be produced also comprising interfacial agent with improveing coating characteristics and suppressing spot.
The example of interfacial agent can include Fluorene systems interfacial agent, such as BM-And BM-(BM chemistry is public
Department)；MEGAFACE FFFAnd F(big Japanese ink Chemical Co., Ltd)；FULORAD FC-FULORAD FC-FULORAD FC-And FULORAD FC-(Sumitomo 3M Co., Ltd.)；
SURFLON S-SURFLON S-SURFLON S-SURFLON S-And SURFLON S-
(Asahi Glass glass Co., Ltd.)；And SH-SH-SH-SZ-And SF-Its analog (east
Beautiful silicone Co., Ltd.).
In terms of the photosensitive resin composition of 100 parts by weight, 0.001 parts by weight can be included to the interface of the amount of 5 parts by weight
Activating agent.During interfacial agent in comprising the scope, it can be ensured that coating homogeneity, do not produce spot and improvement glass lined
Moistening (wetting) characteristic at bottom.
Photosensitive resin composition can also be included in other additives of scheduled volume when it reduces characteristic, such as anti-oxidant
Agent, stabilizer etc..
According to another embodiment of the invention, there is provided a kind of colored filter manufactured using the photosensitive resin composition
Mating plate.
The patterning process of colored filter is as follows.
The process is included positive-type photosensitive resin composition in the method for spin coating, slot coated, ink jet printing etc.
It is coated on supporting substrate；Coated positive-type photosensitive resin composition is dried to form photosensitive resin composition film；Make
Positive-type photosensitive resin composition film exposes；The positive-type photosensitive resin composition film for developing in alkaline aqueous solution exposed with
Obtain photosensitive resin film；And the heat treatment photosensitive resin film.Condition for patterning process is institute in correlation technique
It is well known and will not be described in detail in this manual.
[embodiment of invention]
Hereinafter, the present invention is described in more detail with reference to example and comparative example.But, there is provided following instance and comparative example
For descriptive purposes and the invention is not restricted to this.
(compound synthesis)
Synthesize example 1：Synthesize 4- (biphenyl -2- bases epoxide) -3,5,6- tri- chloro- phthalonitriles
By 3,4,5,6- tetrachloro phthalonitriles (3,4,5,6-tetrachlorophthalonitrile) (5g), 2- benzene
Base phenol (3.201g), K2CO3(3.898g) and acetonitrile (50ml) are placed in 100ml flasks and are subsequently heated and flow back.Work as reaction
During completion, filter gains and washed with tetrahydrofuran, and then concentrate, obtain solid.Herein, the solid obtained is used
Hexane washs several times, filtering and vacuum drying, obtains 4- (biphenyl -2- bases epoxide) -3,5,6- tri- chloro- phthalonitriles.
Synthesize example 2：Synthesize 3,4,6- tri- chloro- 5- (2,6- Dimethoxv-phenoxy)-phthalonitrile
By 3,4,5,6- tetrachloro phthalonitriles (5g), 2,6- syringol (7.21g), K2CO3(3.898g) and N,
Dinethylformamide (50ml) is placed in 100ml flasks and is subsequently heated and is stirred at 70 DEG C.When the reactions are completed, gained
Thing is extracted with ethyl acetate (ethyl acetate, EA).After the extraction, gains are concentrated and are purified via col-umn chromatography, then
Concentrate and be dried in vacuo, obtain 3,4,6- tri- chloro- 5- (2,6- Dimethoxv-phenoxy)-phthalonitrile.
Synthesize example 3：Synthesize 4- (2- the tributyls-phenoxy group) -3,5,6- tri- chloro- phthalonitrile
By 3,4,5,6- tetrachloro phthalonitriles (5g), 2- tributyl phenols (6.64g), K2CO3(3.898g) and acetonitrile
(50ml) is placed in 100ml flasks and is subsequently heated and flows back.When the reactions are completed, gains are extracted with EA (ethyl acetate).
After the extraction, gains are concentrated and are purified via col-umn chromatography, then concentrates and is dried in vacuo, obtain 4- (2- the tributyls-benzene
Epoxide) -3,5,6- tri- chloro- phthalonitriles.
Synthesize example 4：Synthesize 4- (4- the tributyls-phenoxy group) -3,5,6- tri- chloro- phthalonitrile
By 3,4,5,6- tetrachloro phthalonitriles (5g), 4- tributyl phenols (6.64g), K2CO3(3.898g) and acetonitrile
(50ml) is placed in 100ml flasks and is subsequently heated and flows back.When the reactions are completed, gains are extracted with EA (ethyl acetate).
After the extraction, gains are concentrated, are purified via col-umn chromatography, and then concentrates and is dried in vacuo, acquisition 4- (4- tributyls-
Phenoxy group) -3,5,6- tri- chloro- phthalonitriles.
Synthesize example 5：Synthesize 3,4,6- tri- chloro- 5- (3- methyl-butoxies)-phthalonitrile
By 3,4,5,6- tetrachloro phthalonitriles (5g), isoamyl alcohol (5.9g), -7- alkene of 1,8- diazabicylos 11
(3.898g) and acetonitrile (50ml) are placed in 100ml flasks and are subsequently heated and flow back.When the reactions are completed, gains EA
(ethyl acetate) extracts.After the extraction, the gains of acquisition are concentrated and are purified via col-umn chromatography, then simultaneously vacuum is done for concentration
It is dry, obtain 3,4,6- tri- chloro- 5- (3- methyl-butoxies)-phthalonitrile.
Synthesize example 6：Synthesize 3,4,6- tri- chloro- 5- (4- Difluoro-phenoxies)-phthalonitrile
By 3,4,5,6- tetrachloro phthalonitriles (5g), 4- metoxyphenols (3.201g), K2CO3(6.64g) and acetonitrile
(50ml) is placed in 100ml flasks and is subsequently heated and flows back.When the reactions are completed, gains are extracted with EA (ethyl acetate).
After the extraction, the gains of acquisition are concentrated and are purified via col-umn chromatography, then concentrates and is dried in vacuo, obtain 3,4,6- tri-
Chloro- 5- (4- Difluoro-phenoxies)-phthalonitrile.
Synthesize example 7：Synthesize the compound represented by chemical formula 8
- 3,5,6- tri- chloro- phthalonitriles (1.0g) of 4- (biphenyl -2- bases epoxide), the synthesis example 2 of example 1 will be synthesized
3,4,6- tri- chloro- 5- (2,6- Dimethoxv-phenoxy)-phthalonitriles (0.32g), -7- of 1,8- diazabicylos 11
Alkene (0.38g), 1- pentenols (7g) and zinc acetate (0.15g) are placed in 100mL flasks and heat and stirred at 140 DEG C.When
When reaction is completed, concentrate gains and purified via col-umn chromatography.Then, the liquid from purifying is concentrated, obtains solid.Vacuum
Drying crystalline solid, obtain the compound represented by chemical formula 8.
[chemical formula 8]
Maldi-tof MS：1647.95m/z
Synthesize example 8：Synthesize the compound represented by chemical formula 9
- 3,5,6- tri- chloro- phthalonitriles (1.0g) of 4- (biphenyl -2- bases epoxide), the synthesis example 2 of example 1 will be synthesized
3,4,6- tri- chloro- 5- (2,6- Dimethoxv-phenoxy)-phthalonitriles (0.96g), -7- of 1,8- diazabicylos 11
Alkene (0.58g), 1- pentenols (14g) and zinc acetate (0.23g) are placed in 100mL flasks and are subsequently heated and are stirred at 140 DEG C
Mix.When the reactions are completed, gains are concentrated and are purified via col-umn chromatography.Then, the liquid that concentration wherein obtains certainly, consolidate
Body.Crystalline solid is dried in vacuo, obtains the compound represented by chemical formula 9.
[chemical formula 9]
Maldi-tof MS：1631.91m/z
Synthesize example 9：Synthesize the compound represented by chemical formula 10
- 3,5,6- tri- chloro- phthalonitriles (0.5g) of 4- (biphenyl -2- bases epoxide), the synthesis example 2 of example 1 will be synthesized
3,4,6- tri- chloro- 5- (2,6- Dimethoxv-phenoxy)-phthalonitriles (1.44g), -7- of 1,8- diazabicylos 11
Alkene (0.58g), 1- pentenols (14g) and zinc acetate (0.23g) are placed in 100mL flasks and are subsequently heated and are stirred at 140 DEG C
Mix.When the reactions are completed, gains are concentrated and are purified via col-umn chromatography.Then, the liquid that concentration wherein obtains certainly, consolidate
Body.Crystalline solid is dried in vacuo, obtains the compound represented by chemical formula 10.
[chemical formula 10]
Maldi-tof MS：1615.86m/z
Synthesize example 10：Synthesize the compound represented by chemical formula 11
The 4- (4- the tributyls-phenoxy group) -3 of example 4,5,6- tri- chloro- phthalonitriles (1g), synthesis example will be synthesized
The 3 of 2,4,6- tri- chloro- 5- (2,6- Dimethoxv-phenoxy)-phthalonitriles (0.33g), -7- of 1,8- diazabicylos 11
Alkene (0.41g), 1- pentenols (14g) and zinc acetate (0.16g) are placed in 100mL flasks and are subsequently heated and are stirred at 140 DEG C
Mix.When the reactions are completed, gains are concentrated and are purified via col-umn chromatography.Then, the liquid that concentration wherein obtains certainly, consolidate
Body.Crystalline solid is dried in vacuo, obtains the compound represented by chemical formula 11.
[chemical formula 11]
Maldi-tof MS：1587.98m/z
Synthesize example 11：Synthesize the compound represented by chemical formula 12
By 3,4,6- tri- chloro- 5- (3- the methyl-butoxies)-phthalonitriles (1g) for synthesizing example 5, synthesize example 2
3,4,6- tri- chloro- 5- (2,6- Dimethoxv-phenoxy)-phthalonitriles (0.40g), -7- alkene of 1,8- diazabicylos 11
(0.48g), 1- pentenols (14g) and zinc acetate (0.19g) are placed in 100mL flasks and are subsequently heated and are stirred at 140 DEG C.
When the reactions are completed, gains are concentrated and are purified via col-umn chromatography.Then, concentration obtains solid from the liquid wherein obtained.
Crystalline solid is dried in vacuo, obtains the compound represented by chemical formula 12.
[chemical formula 12]
Maldi-tof MS：1401.77m/z
Synthesize example 12：Synthesize the compound represented by chemical formula 13
By -3,5, the 6- tri- chloro- phthalonitriles (1g) of 4- (biphenyl -2- bases epoxide) for synthesizing example 1, synthesize example 5
3,4,6- tri- chloro- 5- (3- methyl-butoxies)-phthalonitriles (0.4g), 3,4, the 6- tri- chloro- 5- (2,6- bis- for synthesizing example 2
Difluoro-phenoxy)-phthalonitrile (0.48g), -7- alkene (0.58g) of 1,8- diazabicylos 11,1- pentenols (14g)
And zinc acetate (0.22g) is placed in 100mL flasks and is subsequently heated and is stirred at 140 DEG C.When the reactions are completed, concentration gained
Thing and purified via col-umn chromatography.Then, concentration obtains solid from the liquid wherein obtained.Crystalline solid is dried in vacuo, is obtained
The compound represented by chemical formula 13.
[chemical formula 13]
Maldi-tof MS：1565.89m/z
Synthesize example 13：Synthesize the compound represented by chemical formula 14
3,4,6- tri- chloro- 5- (2,6- Dimethoxv-phenoxy)-phthalonitriles (1g), 1, the 8- bis- of example 2 will be synthesized
- 7- the alkene (0.30g) of azabicyclic 11,1- pentenols (7g) and zinc acetate (0.12g) are placed in 100mL flasks and are subsequently heated
And stirred at 140 DEG C.When the reactions are completed, gains are concentrated and are purified via col-umn chromatography.Then, concentration wherein obtains certainly
Liquid, obtain solid.Crystalline solid is dried in vacuo, obtains the compound represented by chemical formula 14.
[chemical formula 14]
Maldi-tof MS：1599.82m/z
Synthesize example 14：Synthesize the compound represented by chemical formula 15
3,4,6- tri- chloro- 5- (4- Difluoro-phenoxies)-phthalonitriles (1g), the synthesis example 2 of example 6 will be synthesized
3,4,6- tri- chloro- 5- (2,6- Dimethoxv-phenoxy)-phthalonitriles (0.50g), -7- of 1,8- diazabicylos 11
Alkene (0.65g), 1- pentenols (14g) and zinc acetate (0.26g) are placed in 100mL flasks and are subsequently heated and are stirred at 140 DEG C
Mix.When the reactions are completed, gains are concentrated and are purified via col-umn chromatography.Then, the liquid that concentration wherein obtains certainly, consolidate
Body.Crystalline solid is dried in vacuo, obtains the compound represented by chemical formula 15.
[chemical formula 15]
Maldi-tof MS：1509.74m/z
Synthesize example 15：Synthesize the compound represented by chemical formula 16
The 4- (2- the tributyls-phenoxy group) -3 of example 3,5,6- tri- chloro- phthalonitriles (1g), synthesis example will be synthesized
The 3 of 2,4,6- tri- chloro- 5- (2,6- Dimethoxv-phenoxy)-phthalonitriles (0.33g), -7- of 1,8- diazabicylos 11
Alkene (0.41g), 1- pentenols (14g) and zinc acetate (0.16g) are placed in 100mL flasks and are subsequently heated and are stirred at 140 DEG C
Mix.When the reactions are completed, gains are concentrated and are purified via col-umn chromatography.Then, the liquid that concentration wherein obtains certainly, consolidate
Body.Crystalline solid is dried in vacuo, obtains the compound represented by chemical formula 16.
[chemical formula 16]
Maldi-tof MS：1587.98m/z
Compare synthesis example 1：Synthesize the compound represented by chemical formula 17
By -3,5,6- tri- chloro- phthalonitriles (1g) of 4- (butyl-phenoxies of 2- second), -7- of 1,8- diaza-bicyclos 11
Alkene (0.30g), 1- pentenols (7g) and zinc acetate (0.12g) are placed in 100mL flasks and are subsequently heated and are stirred at 140 DEG C
Mix.When the reactions are completed, gains are concentrated and are then purified via col-umn chromatography.Then, concentration obtains from the liquid wherein obtained
Obtain solid.Crystalline solid is dried in vacuo, obtains the compound represented by chemical formula 17.
[chemical formula 17]
Maldi-tof MS：1584.04m/z
(synthesis photosensitive resin composition)
Example 1
It is prepared by the component of the constituent provided according to the photosensitive resin composition of example 1 by mixing in table 1 below.
In specific words, photopolymerization initiator is dissolved in solvent, is stirred at room temperature 2 hours, adds alkali soluble thereto
Property resin and photopolymerizable compound, and mixture is stirred at room temperature 2 hours.Then, by the compound according to synthesis example 7
(being represented by chemical formula 8) and pigment (dispersible pigment dispersion form) are added in reactant as colouring agent, and are stirred at room temperature
Mixture one hour.Then, product therein is filtered three times with removal of impurity, prepares photosensitive resin composition.
[table 1]
(unit：Weight %)
Example 2
Except the compound for replacing synthesizing example 7 using the compound (being represented by chemical formula 9) for synthesizing example 8 is (by chemical formula 8
Represent) beyond, prepare photosensitive resin composition according to the identical method of example 1.
Example 3
Except the compound for replacing synthesizing example 7 using the compound (being represented by chemical formula 10) for synthesizing example 9 is (by chemical formula
8 represent) beyond, prepare photosensitive resin composition according to the identical method of example 1.
Example 4
Except the compound for replacing synthesizing example 7 using the compound (being represented by chemical formula 11) for synthesizing example 10 is (by chemistry
Formula 8 represents) beyond, prepare photosensitive resin composition according to the identical method of example 1.
Example 5
Except the compound for replacing synthesizing example 7 using the compound (being represented by chemical formula 12) for synthesizing example 11 is (by chemistry
Formula 8 represents) beyond, prepare photosensitive resin composition according to the identical method of example 1.
Example 6
Except the compound for replacing synthesizing example 7 using the compound (being represented by chemical formula 13) for synthesizing example 12 is (by chemistry
Formula 8 represents) beyond, prepare photosensitive resin composition according to the identical method of example 1.
Example 7
Except the compound for replacing synthesizing example 7 using the compound (being represented by chemical formula 14) for synthesizing example 13 is (by chemistry
Formula 8 represents) beyond, prepare photosensitive resin composition according to the identical method of example 1.
Example 8
Except the compound for replacing synthesizing example 7 using the compound (being represented by chemical formula 15) for synthesizing example 14 is (by chemistry
Formula 8 represents) beyond, prepare photosensitive resin composition according to the identical method of example 1.
Example 9
Except the compound for replacing synthesizing example 7 using the compound (being represented by chemical formula 16) for synthesizing example 15 is (by chemistry
Formula 8 represents) beyond, prepare photosensitive resin composition according to the identical method of example 1.
Comparative example 1
Except the compound for replacing synthesizing example 7 using the compound (being represented by chemical formula 17) for comparing synthesis example 1 is (by changing
Formula 8 represents) beyond, prepare photosensitive resin composition according to the identical method of example 1.
Comparative example 2
Except the constituent provided in mixture table 2 component replace table 1 in constituent in addition to, according to the identical of example 1
Method prepares photosensitive resin composition.
[table 2]
(unit：Weight %)
Comparative example 3
Except using pigment G36 dispersible pigment dispersions replace pigment G58 dispersible pigment dispersions in addition to, according to the identical of comparative example 2
Method prepares photosensitive resin composition.
Assess：Color coordinate, brightness and contrast ratio
1mm thickness will be coated on according to each cured constituent of photonasty tree of example 1 to example 9 and comparative example 1 to comparative example 3
Degreasing glass substrate on reach 1 μm to 3 μ m-thicks and dried 2 minutes in 90 DEG C of heating plates, obtain film.Then, by using
The a length of 365nm of primary waves high-pressure sodium lamp exposes film.Then, film is made to be dried 5 minutes in 200 DEG C of forced convertion drying ovens,
Obtain sample.By using spectrophotometer (MCPD3000, great Zhong Electronics Co., Ltd) with regard to color coordinate (x, y), brightness Y and
Contrast ratio measures pixel layer, and result is provided in table 3.
[table 3]
| Color coordinate (x, y) | Brightness (Y) | Contrast ratio | |
| Example 1 | (0.284,0.576) | 63.0 | 15,700 |
| Example 2 | (0.279,0.576) | 62.3 | 15,300 |
| Example 3 | (0.281,0.576) | 62.9 | 15,100 |
| Example 4 | (0.278,0.576) | 62.7 | 15,800 |
| Example 5 | (0.280,0.576) | 63.3 | 15,600 |
| Example 6 | (0.278,0.576) | 63.1 | 15,500 |
| Example 7 | (0.277,0.576) | 62.1 | 15,900 |
| Example 8 | (0.279,0.576) | 62.2 | 15,700 |
| Example 9 | (0.282,0.576) | 62.8 | 15,800 |
| Comparative example 1 | (0.275,0.575) | 60.7 | 14,800 |
| Comparative example 2 | (0.275,0.577) | 61.4 | 14,400 |
| Comparative example 3 | (0.276,0.577) | 59.7 | 14,100 |
With reference to table 3, compared with the photosensitive resin composition according to comparative example 1 to comparative example 3, comprising according to an implementation
The compound of example shows fabulous color property as the photosensitive resin composition of example 1 to the example 9 of dyestuff.
Although the exemplary embodiment that present invention combination is presently considered as practicality is described, it is to be understood that the present invention is not
It is limited to disclosed embodiment, but be intended to cover on the contrary in the spirit and scope of appended claims various repaiies
Change and equivalent.
Claims (16)
1. a kind of compound, it is characterised in that represented by chemical formula 1：
[chemical formula 1]
Wherein in chemical formula 1,
M is Cu, Zn, Co or Mo,
R1To R16Independently be hydrogen atom, halogen atom, the C1 that is substituted or is unsubstituted to C20 alkyl, be substituted or without
Substituted C3 is to C20 alkoxies, the C6 for being substituted or being unsubstituted to C20 aryl or the C6 for being substituted or being unsubstituted to C20
Aryloxy group, and
R1To R16At least one of represented by chemical formula 2,
[chemical formula 2]
Wherein in chemical formula 2,
R17And R18It 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.
2. compound according to claim 1, wherein chemical formula 2 are represented by chemical formula 3：
[chemical formula 3]
Wherein in chemical formula 3,
R17And R18It 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.
3. compound according to claim 1, wherein,
R1To R16Represented by chemical formula 2, and
R1To R16At least one of by one of chemical formula 4 to chemical formula 7 represent：
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
Wherein in chemical formula 6 and chemical formula 7,
L1It is the C1 that is substituted or is unsubstituted to C10 alkylidenes, and
R19For the C1 that is substituted or is unsubstituted to C10 alkyl.
4. compound according to claim 1, wherein,
R1To R4At least one of represented by chemical formula 2,
R5To R8At least one of by one of chemical formula 4 to chemical formula 7 represent,
R9To R12At least one of by one of chemical formula 4 to chemical formula 7 represent, and
R13To R16At least one of by one of chemical formula 4 to chemical formula 7 represent：
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
Wherein in chemical formula 6 and chemical formula 7,
L1It is the C1 that is substituted or is unsubstituted to C10 alkylidenes, and
R19For the C1 that is substituted or is unsubstituted to C10 alkyl.
5. compound according to claim 1, wherein,
R1To R4At least one of represented by chemical formula 2,
R5To R8At least one of represented by chemical formula 2,
R9To R12At least one of by one of chemical formula 4 to chemical formula 7 represent, and
R13To R16At least one of by one of chemical formula 4 to chemical formula 7 represent：
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
Wherein in chemical formula 6 and chemical formula 7,
L1It is the C1 that is substituted or is unsubstituted to C10 alkylidenes, and
R19For the C1 that is substituted or is unsubstituted to C10 alkyl.
6. compound according to claim 1, wherein,
R1To R4At least one of represented by chemical formula 2,
R5To R8At least one of by one of chemical formula 4 to chemical formula 7 represent,
R9To R12At least one of represented by chemical formula 2, and
R13To R16At least one of by one of chemical formula 4 to chemical formula 7 represent：
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
Wherein in chemical formula 6 and chemical formula 7,
L1It is the C1 that is substituted or is unsubstituted to C10 alkylidenes, and
R19For the C1 that is substituted or is unsubstituted to C10 alkyl.
7. compound according to claim 1, wherein,
R1To R4At least one of represented by chemical formula 2,
R5To R8At least one of represented by chemical formula 2,
R9To R12At least one of represented by chemical formula 2, and
R13To R16At least one of by one of chemical formula 4 to chemical formula 7 represent：
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
Wherein in chemical formula 6 and chemical formula 7,
L1It is the C1 that is substituted or is unsubstituted to C10 alkylidenes, and
R19For the C1 that is substituted or is unsubstituted to C10 alkyl.
8. compound according to claim 1, wherein,
R1To R4At least one of represented by chemical formula 2,
R5To R8At least one of represented by chemical formula 2,
R9To R12At least one of represented by chemical formula 2, and
R13To R16At least one of represented by chemical formula 2.
9. compound according to claim 1, wherein the compound is by chemical formula 8 to one of chemical formula 16 table
Show：
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
[chemical formula 11]
[chemical formula 12]
[chemical formula 13]
[chemical formula 14]
[chemical formula 15]
[chemical formula 16]
10. compound according to claim 1, wherein the compound is green colouring material.
11. compound according to claim 10, wherein the green colouring material has in 445nm to 560nm wavelength
Maximum transmission rate.
12. a kind of photosensitive resin composition, it is characterised in that including the chemical combination as any one of claim 1 to 11
Thing.
13. photosensitive resin composition according to claim 12, wherein the photosensitive resin composition also includes alkali
Soluble resin, photopolymerizable compound, photopolymerization initiator and solvent.
14. photosensitive resin composition according to claim 13, wherein the photosensitive resin composition also includes face
Material.
15. photosensitive resin composition according to claim 14, wherein the pigment is yellow uitramarine.
16. a kind of colored filter, it is characterised in that manufactured using photosensitive resin composition as claimed in claim 12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2015-0062056 | 2015-04-30 | ||
| KR1020150062056A KR101881942B1 (en) | 2015-04-30 | 2015-04-30 | Novel compound, photosensitive resin composition comprising the same and color filter |
| PCT/KR2015/008106 WO2016175390A1 (en) | 2015-04-30 | 2015-08-03 | Novel compound, photosensitive resin composition containing same and color filter |
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| Publication Number | Publication Date |
|---|---|
| CN107428766A true CN107428766A (en) | 2017-12-01 |
| CN107428766B CN107428766B (en) | 2020-07-07 |
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|---|---|---|---|
| CN201580077258.4A Active CN107428766B (en) | 2015-04-30 | 2015-08-03 | Compound, photosensitive resin composition containing same and color filter |
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| Country | Link |
|---|---|
| KR (1) | KR101881942B1 (en) |
| CN (1) | CN107428766B (en) |
| TW (1) | TWI576348B (en) |
| WO (1) | WO2016175390A1 (en) |
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| KR102067083B1 (en) * | 2016-11-25 | 2020-01-16 | 삼성에스디아이 주식회사 | Photosensitive resin composition and photosensitive resin layer using the same and color filter |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060051685A1 (en) * | 2004-09-03 | 2006-03-09 | Fuji Photo Film Co., Ltd. | Negative dye-containing curable composition, color filter and method of producing the same |
| JP2013182214A (en) * | 2012-03-02 | 2013-09-12 | Fujifilm Corp | Colored curable composition and color filter |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001100040A (en) * | 1999-09-30 | 2001-04-13 | Fuji Photo Film Co Ltd | Polarizing sheet consisting of discotic liquid crystal film including disk-shaped coloring matter |
| WO2012108435A1 (en) * | 2011-02-10 | 2012-08-16 | 富士フイルム株式会社 | Colored curable composition, and color filter |
| JP5914379B2 (en) * | 2012-03-02 | 2016-05-11 | 富士フイルム株式会社 | Colored curable composition and color filter |
| KR101988047B1 (en) * | 2012-09-17 | 2019-06-11 | 엘지디스플레이 주식회사 | High transmissional green dye for lcd and synthetic method thereof |
| JP2014132296A (en) * | 2013-01-07 | 2014-07-17 | Toyo Ink Sc Holdings Co Ltd | Coloring composition for color filter, and color filter |
-
2015
- 2015-04-30 KR KR1020150062056A patent/KR101881942B1/en not_active Application Discontinuation
- 2015-08-03 CN CN201580077258.4A patent/CN107428766B/en active Active
- 2015-08-03 WO PCT/KR2015/008106 patent/WO2016175390A1/en active Application Filing
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2016
- 2016-02-02 TW TW105103203A patent/TWI576348B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060051685A1 (en) * | 2004-09-03 | 2006-03-09 | Fuji Photo Film Co., Ltd. | Negative dye-containing curable composition, color filter and method of producing the same |
| JP2013182214A (en) * | 2012-03-02 | 2013-09-12 | Fujifilm Corp | Colored curable composition and color filter |
Non-Patent Citations (3)
| Title |
|---|
| DEBASIS SWAIN，等: "Sterically demanding zinc(II) phthalocyanines: synthesis, optical, electrochemical, nonlinear optical, excited state dynamics studies", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
| LINGAMALLU GIRIBABU，等: "Sterically demanded unsymmetrical zinc phthalocyanines for dye-sensitized solar cells", 《DYES AND PIGMENTS》 * |
| TAKURO IKEUCHI，等: "Molecular engineering of zinc phthalocyanine sensitizers for efficient dye-sensitized solar cells", 《CHEM. COMMUN.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107428766B (en) | 2020-07-07 |
| KR101881942B1 (en) | 2018-07-26 |
| WO2016175390A1 (en) | 2016-11-03 |
| TWI576348B (en) | 2017-04-01 |
| TW201638095A (en) | 2016-11-01 |
| KR20160129619A (en) | 2016-11-09 |
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