CN105949821B - A kind of dye composite, ink and the electric moistening display including the ink - Google Patents
A kind of dye composite, ink and the electric moistening display including the ink Download PDFInfo
- Publication number
- CN105949821B CN105949821B CN201610424227.8A CN201610424227A CN105949821B CN 105949821 B CN105949821 B CN 105949821B CN 201610424227 A CN201610424227 A CN 201610424227A CN 105949821 B CN105949821 B CN 105949821B
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- ink
- positive
- epoxide
- dye composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0055—Mixtures of two or more disazo 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
- C09B67/0079—Azoic dyestuff preparations
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B26/00—Optical devices or arrangements for the control of light using movable or deformable optical elements
- G02B26/004—Optical devices or arrangements for the control of light using movable or deformable optical elements based on a displacement or a deformation of a fluid
- G02B26/005—Optical devices or arrangements for the control of light using movable or deformable optical elements based on a displacement or a deformation of a fluid based on electrowetting
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a kind of dye composite, ink and electric moistening display including the ink, the dyestuff with higher molar absorption coefficient, in non-polar organic solvent with high solubility, a kind of ink shown suitable for electrowetting can be obtained by being dissolved in organic solvent, visible ray effectively can equably be absorbed by the compounding of different dyes, available for the black electrowetting ink for preparing high-contrast.The present invention replaces 2 in the Dyes structural formulae being related in the A1 of patent US 20150015931 with heterocyclic diazo component, 4 dinitro phenyl ring, the color coverage of ink material can not only be improved, due to reducing the highly polar group in structural formula, its solubility in non-polar solven can also be increased substantially.
Description
Technical field
The present invention relates to electrowetting display technology field, more particularly to a kind of dye composite, ink and including the ink
Electric moistening display.
Background technology
Electrowetting Display Technique (Electrofluide display, EFD), the also referred to as display of electricity moistening, it is that Holland flies profit
The display prototype that principle is shown as with electrowetting that Pu company developed first in 2003.The displaying principle is to utilize change
Voltage changes contact angle of the ink layer on hydrophobic layer so as to control the surface property of hydrophobic layer：When being not powered on pressure, ink pair
Insulating barrier uniform wet, form a Colored pixels point；When applying voltage, the effect of electric field changes the surface property of hydrophobic layer
The interfacial tension between ink-polar liquid-hydrophobic layer three-phase is set to change, ink is compressed, and forms transparent or substrate base
The pixel of color, so as to obtain display image effect.
In order to realize that colored electroweting is shown, Dutch Liquvista companies propose two kinds of possible structural models：Individual layer
Or sandwich construction.The colored display of individual layer electrowetting realized using black ink collocation colored filter, this method as a result of
Optical filter, the utilization ratio of light is reduced, contrast declines, but device is simple, easily prepared；And multilayer electrowetting is colored aobvious
Showing can use three primary colours (green grass or young crops, product, Huang) being formed by stacking, higher to the utilization ratio of light, but due to only with green grass or young crops, product,
Superposition of yellow, the three layers of dyestuff to light is absorbed to realize black, and what is only obtained is grey, therefore, in order to realize high-contrast
Black display, be inadequate only with three layers of color addition, it is also necessary to increase by one layer have high contrast black ink.
The black ink materials requirement of high contrast is sufficiently absorbed to the light wave in visible-range, therefore, when adopting
When being prepared with multiple inks material, it is desirable to which it is more wide better to prepare absorption of each component of ink material to visible ray, from this angle
For on degree, it is not suitable for for the three primary colours blue or green (C) of electrowetting display design, product (M), Y (Huang) or red (R), green (G), blue (B)
Black ink is prepared, because their saturation degree is high, black ink blackness narrow to the absorption region of visible ray, therefore being prepared
Not enough.
It is related to the structural formula of a kind of bisazo class organic dyestuff in patent US20150015931A1In the structure shown here, in order to obtain preparing black ink materials institutes
What is needed is black-and-blue, and usual X, X ' are needed for strong electron-withdrawing group group, such as nitro.The introducing of highly polar group result in dyestuff in non-pole
Property solvent in solubility decline, the solubility of the structure type dyestuff between 15~20%, be not easy prepare to black requirement
High electrowetting ink.Need further to research and develop a kind of big dyestuff of solubility in non-polar solven, and need to be somebody's turn to do
Dyestuff can obtain saturate ink after being dissolved in non-polar solven.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of dye composite, ink and the electrowetting including the ink
Display.
The technical solution used in the present invention is：
A kind of dye composite, including shown in the compound shown in formula (I), the compound shown in formula (II), formula (III)
At least one of compound,
In formula (I), formula (II) and formula (III),
R1For hydrogen, nitro, chlorine, bromine, C1~C12Alkyl or C1~C12Alkoxy；N is 0~2 integer, as n=2, point
2 R contained in minor structure1It can be the same or different；
R2、R3、R5、R6、R8、R10、R11、R12、R13、R15、R16It is each independently hydrogen, C1~C12Straight chained alkyl or C1~C12
Branched alkyl；
R7、R9、R14It is each independently hydrogen or-OR17The group of expression, wherein, R17For C1~C12 straight chained alkyls or C1~
C12 branched alkyls；
R4、R10It is each independently hydrogen, C1~C4Alkyl or-NHCOR18The group of expression, wherein, R18For hydrogen, C1~C12
Straight chained alkyl or C1~C12 branched alkyls.
In some specific embodiments, the R1For hydrogen, nitro, chlorine, bromine, methyl, methoxyl group, ethyl, n-propyl,
Any one in isopropyl, normal-butyl, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, octyloxy or different octyloxy.
In further preferred embodiment, the R7For hydrogen or methoxyl group.
In embodiment still more preferably, the R2、R3、R4、R5、R6It is separately methyl, ethyl, third
In base, butyl, amyl group, n-hexyl, n-heptyl, n-octyl, iso-octyl, nonyl, certain herbaceous plants with big flowers base, n-undecane base or dodecyl
Any one.
In some specific embodiments, the R8For hydrogen, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, just oneself
Any one in base, n-heptyl, n-octyl, iso-octyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl.
In further preferred embodiment, the R9For hydrogen, methoxyl group, ethyoxyl, positive propoxy, n-butoxy,
N-pentyloxy, positive hexyloxy, positive epoxide in heptan, n-octyloxy, different octyloxy, positive nonyl epoxide, n-decyloxy, n-undecane epoxide or
Any one in n-dodecane epoxide.
In embodiment still more preferably, the R10For hydrogen, methyl, ethyl, n-propyl, normal-butyl or-
NHCOR18, wherein, R18For hydrogen, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, different pungent
Any one in base, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl.
In embodiment still more preferably, the R11、R12Separately for hydrogen, methyl, ethyl, n-propyl,
Normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or n-dodecane
Any one in base.
In some specific embodiments, the R13For hydrogen, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, just oneself
Any one in base, n-heptyl, n-octyl, iso-octyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl.
In further preferred embodiment, the R14For hydrogen, methoxyl group, ethyoxyl, positive propoxy, n-butoxy,
N-pentyloxy, positive hexyloxy, positive epoxide in heptan, n-octyloxy, different octyloxy, positive nonyl epoxide, n-decyloxy, n-undecane epoxide or
Any one in n-dodecane epoxide.
In embodiment still more preferably, the R15、R16Separately for hydrogen, methyl, ethyl, n-propyl,
Normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or n-dodecane
Any one in base.
Present invention also offers a kind of ink, the ink is molten by the dye composite as described above of 1~30 mass parts
Obtained in the non-polar organic solvent of 70~99 mass parts.
Present invention also offers a kind of electric moistening display, the electric moistening display includes ink as described above.
The beneficial effects of the invention are as follows：
The invention provides a kind of bisazo class organic dyestuff, the organic dyestuff have higher molar absorption coefficient,
There is high solubility in non-polar organic solvent, being dissolved in organic solvent can obtain a kind of showing suitable for electrowetting
Ink, visible ray effectively can equably be absorbed by the compounding of different dyes, available for the black of preparation high-contrast
Color electrowetting ink.The present invention replaces the Dyes structural formulae being related in patent US 20150015931A1 with heterocyclic diazo component
In 2,4- dinitro phenyl ring, can not only improve the color coverage of ink material, it is strong in structural formula due to reducing
Polar group, its solubility in non-polar solven can also be increased substantially.
Brief description of the drawings
Fig. 1 is the visible absorption spectra figure of black ink 1；
Fig. 2 is the visible absorption spectra figure of black ink 2；
Fig. 3 is the visible absorption spectra figure of black ink 3；
Fig. 4 is the visible absorption spectra figure of existing black ink.
Embodiment
Embodiment 1：
Weigh 3.7g (110g/mol, 0.0344mol) hydroquinones to be dissolved in 30mL alcohol, add 23.2g (192g/
Mol, 0.12mol) bromo-iso-octane and 4.99g (0.089mol, 56g/mol) potassium hydroxide, back flow reaction 24h, by product
Pour into 500mL water, extracted with toluene, separate oil phase, rotate drying, column chromatography for separation, eluant, eluent：Petroleum ether, obtain in first
MesosomeYield 60%.Rf=0.64 (petroleum ether).
Weigh 12g (334g/mol, 0.036mol) first step intermediate to be dissolved in 50mL chloroforms, be cooled with an ice bath to 0~5
DEG C, 4.1g (70%, 0.045mol) nitric acid droppings are weighed into above-mentioned solution, sustained response 1h.React reaction solution after terminating
It is washed with water 2-3 times, separates oil phase, rotates drying, obtain the intermediates of 11.1g secondYield
81.6%.
11.1g (0.0293mol, 379g/mol) second step intermediate is weighed to be dissolved in 20mL ethanol, 20mL ethyl acetate,
8.79g (0.14mol, 60g/mol) glacial acetic acids and 9.5g (0.14mol, 65g/mol) zinc powder are added, reaction 4h is stirred at room temperature.Instead
Filtered after should terminating, collect filtrate revolving drying, column chromatography for separation, obtain the intermediates of 8.7g the 3rd
Yield 85%.
2.25g (183g/mol, 0.015mol) 2- amino-6-nitrobenzothiazoles are weighed to be dissolved in 50mL concentrated phosphoric acids, it is cold
But to -10 DEG C~-5 DEG C, 5.5g nitrosyl sulfuric acids (40wt%), diazotising 2h are added.Weigh 5.2g (379g/mol,
0.015mol) the 3rd intermediate is dissolved in 50mL ethanol, is added 30g sodium acetates and 5g sulfamic acids, is cooled with an ice bath to 0~5
℃.Above-mentioned diazol is slowly dropped in above-mentioned coupling component, reacts 3h, reaction pours into product in 300mL water after terminating
Separate out, filter, dry the 4th intermediate4.58g, yield 59.8%.
Weigh 3.16g (0.02mol, 158g/mol) m-acetamidoaniline, 8.0g (0.042mol, 192g/mol) bromo
Isooctane, 4.1g (0.03mol, 138g/mol) potassium carbonate are dissolved in 70mL dimethyl acetamide (DMAc), are passed through N2Protection,
It is warming up to 140 DEG C of insulation 10h.Then solution is poured into 100mL water and separates out oil product, product 100mL n-hexane extractions,
Separation, is washed with 10% aqueous hydrochloric acid solution and removes mono-substituted products several times, obtain the 5th intermediate, the 5th intermediate structure
Formula isHead product 1.69g, yield 22.6%.
Take the intermediates of 1.69g the 5th (374g/mol, 0.00452mol) to be dissolved in 20mL ethanol, add 10 times of moles
The concentrated hydrochloric acid of (0.0452mol, 3.8mL), back hydrolysis is warming up to, reacts 2h, TLC detection reactions terminate.Cooling, addition etc. rubs
In your amount potassium hydroxide aqueous solution and hydrochloric acid, n-hexane extraction obtain product, rotate, dry, obtain the intermediates of 1.21g the 6th, structure
Formula isYield 81.0%.
5g (0.015mol, 332g/mol) the 6th intermediates are dissolved in 30mL DMF, add 3.2g (101g/
Mol, 0.03mol) triethylamine, weigh 5.1g (162g/mol, 0.031mol) different caprylyl chloride and be added drop-wise in above-mentioned solution, room temperature is anti-
Should, reaction end is detected using Ai Lixi reagents.Rf=0.5 (toluene/petroleum ether=1/2), obtains the 7th intermediate, structure isYield 100%.
Weigh the intermediates of 5.1g (510g/mol, 0.01mol) the 4th to be dissolved in 100mL NMP, be cooled to 0~5 DEG C, add
3.5g (40%, 0.011mol) nitrosyl sulfuric acid, diazotising 30min.It is molten to weigh 3.74g (374g/mol, 0.01mol) intermediate seven
In 50mL acetone, appropriate ice cube, ice bath cooling are added.Above-mentioned diazol is slowly dropped in said components, 3h is reacted, pours into
Separated out in 300mL water, petroleum ether extraction, dry, obtain 8.2g dyestuffs 1, its structural formula is
Yield 84%.Its nucleus magnetic hydrogen spectrum data is：1H NMR(CDCl3)：0.939(30H,m),1.337(40H,m),1.911(4H,m),
2.343(1H,m),3.433(4H,m),4.140(2H,d),4.086(2H,d),6.568(1H,s),7.400(1H,s),7.458
(1H,s),7.847(1H,d),7.921(1H,d),8.282(2H,s),8.479(1H,d).
Embodiment 2：
Weigh 1.0g (5mmol, 201g/mol) 1- acetylaminohydroxyphenylarsonic acid 7- naphthols, 1.92g (10mmol, 192g/mol) bromo
Isooctane, 1.38g (10mmol, 138g/mol) K2CO3It is dissolved in 50mL acetonitriles, back flow reaction 9h.Solvent：Acetone/petroleum ether
=1/2 (volume ratio), Rf raw materials=0.13, Rf product=0.55.Product is poured into 100mL water and separates out oily by reaction after terminating
Product, to adopt and product is extracted with ethyl acetate, 90 DEG C of revolvings remove solvent and bromo-iso-octane, obtain the 8th intermediate,Yield 88%.
Weigh the 8th intermediate 0.88g to be dissolved in 50mL isopropanols, add 20 times of amount KOH back flow reactions 5h.Solvent：Third
Ketone/petroleum ether=1/2 (volume ratio), Rf raw materials=0.55, Rf product=0.63.Reaction mixture is poured into water, ethyl acetate
Extraction, drying is rotated, obtains the 9th intermediateYield 88.0%.
It is molten to weigh 2.05g (0.01mol, 205g/mol) n-octyls aniline, 4.2mL (12mol/L, 0.05mol) concentrated hydrochloric acid
In 20mL industrial alcohol, 0~5 DEG C is cooled to.0.8g (0.011mol, 69g/mol) natrium nitrosum is weighed to be dissolved in 5mL water,
Disposably it is added in above-mentioned solution.After diazo-reaction 1h, add appropriate sulfamic acid and remove unnecessary nitrous acid.Weigh
2.71g (0.01mol, 271g/mol) second intermediates are dissolved in 50mL ethanol, are cooled to 0~5 DEG C, by above-mentioned diazol
It is slowly added dropwise into.4h is reacted, use saturated aqueous sodium carbonate to adjust pH value of solution as 7 after terminating, filtering, drying, obtains the
Ten intermediatesYield 67%.
Weigh the intermediates of 3g the tenth (487g/mol, 0.0062mol) to be dissolved in 100mL NMP+100mL acetic acid, be cooled to 0
~5 DEG C, weigh 0.64g (0.009mol, 69g/mol) and be dissolved in 2mL water and disposably add, diazotising 1h.Weigh intermediate
The intermediates of 2.3g the 5th (374g/mol, 0.0062mol) are dissolved in 30mL ethanol, are slowly dropped in above-mentioned diazol and are coupled.
It is poured into after reaction 3h in 300mL water and separates out oil product, collected, is dried, obtain dyestuff 2, its structural formula isHead product yield 80.5%.The nucleus magnetic hydrogen spectrum data of dyestuff 2 are as follows：1H NMR
(CDCl3)：0.810(16H,m),1.209(46H,m),2.242(3H,s),2.637(2H,t),3.340(4H,t),4.016
(1H,m),6.719(1H,d),6.903(1H,d),7.297(3H,m),7.690(2H,m),7.898(3H,m),8.064(1H,
m),8.850(1H,d)。
Embodiment 3：
It is molten to weigh 1.49g (0.01mol, 149g/mol) n-butyl aniline, 4.2mL (12mol/L, 0.05mol) concentrated hydrochloric acid
In 20mL water, 0~5 DEG C is cooled to.Weigh 0.8g (0.011mol, 69g/mol) natrium nitrosum to be dissolved in 5mL water, disposably
It is added in above-mentioned solution.After diazo-reaction 1h, add appropriate sulfamic acid and remove unnecessary nitrous acid.Weigh 2.71g
(0.01mol, 271g/mol) described 9th intermediate is dissolved in 50mL ethanol, is cooled to 0~5 DEG C, and above-mentioned diazol is slow
Dropwise addition is come in.4h is reacted, uses saturated aqueous sodium carbonate to adjust pH value of solution as 7 after terminating, filters, dry, obtain the 11st
IntermediateYield 80%.
Weigh 6.6g (132g/mol, 0.05mol) tertbutyloxycarbonyl hydrazine and be dissolved in 50mL n-hexanes, weigh 6.7g (114g/
Mol, 0.058mol) different octanal is slowly dropped in above-mentioned solution, it is warming up to back flow reaction 2h.Reaction is evaporated removing after terminating molten
Agent, obtainYield 100%.Will0~5 DEG C is cooled to, weighs 1mol/L
Borine tetrahydrofuran solution 100mL is slowly dropped in above-mentioned reaction unit, and solvent is dichloromethane/petroleum ether=1：1, instead
2h is answered, is obtained15mL concentrated hydrochloric acids are measured, are slowly dropped in above-mentioned solution, are treated without obvious bubble
It is heated to flowing back after generation, reacts 0.5h.Cool down after completion of the reaction, filter the boric acid for removing and separating out, solution is rotated into drying.
ArriveYield 78%.Weigh 0.56gHydrochloride (180g/mol,
0.0031mol) it is dissolved in 20mL ethanol, adds 1.68g sodium methoxides (54g/mol, 0.031mol), weigh 0.41g (130g/
Mol, 0.0031mol) ethyl acetoacetate is added drop-wise in above-mentioned solution, N2Protection, 50 DEG C are warming up to instead after reacting 3h at room temperature
Answer 3h, reaction use 10% aqueous hydrochloric acid solution regulation pH value of solution to be neutral after terminating, n-hexane extraction, Rotary drying, obtains the
12 intermediate 0.51gYield 76.8%.
Weigh the intermediates of 4.31g the 11st (431g/mol, 0.01mol) to be dissolved in 100mL NMP+100mL acetic acid, cool down
To 0~5 DEG C, weigh 0.76g (0.011mol, 69g/mol) and be dissolved in 5mL water and disposably add, diazotising 1h.Weigh 2.1g
12 intermediates(210g/mol, 0.01mol) is dissolved in 50mL ethanol, is cooled to 0-5 DEG C, by above-mentioned diazonium
Salt, which is slowly added dropwise into, to be coupled, and is used sodium hydroxide solution to adjust pH as 8-9, coupling reaction 3h, is filtered, obtain head product dyestuff 3,
Its structural formula is5.0g.Yield 77.0%.The nucleus magnetic hydrogen spectrum data of dyestuff 3 are as follows：
0.983(15H,m),1.361(20H,m),1.920(2H,m),2.726(2H,d),3.693(2H,t),2.313(3H,s),
4.120(2H,s),7.275(1H,d),7.348(3H,m),7.800(1H,d),7.839(1H,d),7.946(2H,d),8.911
(1H,d),14.44(1H,s).
Embodiment 4：
1.06g (0.01mol, 106g/mol) m-toluidine is weighed, 6.19g (0.03mol, 192g/mol) bromo is different pungent
Alkane, 2.2g (0.016mol, 138g/mol) potassium carbonate are dissolved in 50mL dimethyl acetamide (DMAc), are passed through N2Protection, rise
Warm to 140 DEG C insulation 24h.Then solution is poured into 100mL water and separates out oil product, product 100mL n-hexane extractions, point
From obtaining the 13rd intermediateColumn chromatography chromatogram separates, yield 21.4%.Among 13rd
The nucleus magnetic hydrogen spectrum data of body are as follows：1.048(12H,m),1.441(16H,m),2.354(3H,s),3.354(4H,m),1.964
(2H,t),6.678(3H,m),7.245(1H,m).Weigh the intermediates of 5.1g (510g/mol, 0.01mol) the 4thIt is dissolved in 100mL NMP, is cooled to 0~5 DEG C, adds 3.5g (40%, 0.011mol)
Nitrosyl sulfuric acid, diazotising 30min.Weigh the intermediates of 3.31g (331g/mol, 0.01mol) the 13rd
It is dissolved in 50mL acetone, adds appropriate ice cube, ice bath cooling.Above-mentioned diazol is slowly dropped in above-mentioned coupling component, instead
3h is answered, pours into 300mL water and separates out, petroleum ether extraction, dries, obtains 6.2g dyestuffs 4, its structural formula isYield 69%.
Embodiment 5：
Weigh the intermediates of 4.31g the 11st(431g/mol, 0.01mol) is dissolved in
In 100mLNMP+100mL acetic acid, 0~5 DEG C is cooled to, 0.76g (0.011mol, 69g/mol) is weighed and is dissolved in 5mL water once
Property add, diazotising 1h.Weigh the intermediates of 2.1g the 13rd(331g/mol, 0.01mol) is dissolved in 50mL
In ethanol, 0-5 DEG C is cooled to, above-mentioned diazol is slowly added dropwise into and is coupled, coupling reaction 3h, filters, obtains 5.4g dyestuffs
5, its structural formula isYield 69.8%.The nucleus magnetic hydrogen spectrum data of dyestuff 5 are as follows：
0.850 (21H, m), 1.237 (28H, m), 1.808 (3H, m), 2.350 (3H, s), 2.638 (2H, t), 3.305 (4H, m),
4.053(2H,m),6.584(1H,s),6.688(1H,s),6.940(1H,s),7.294(3H,m),7.692(1H,d),7.898
(3H,m),8.306(1H,d).8.839(1H,d).
Embodiment 6：
The dyestuff 1-5 that embodiment 1-5 is prepared carries out performance evaluation respectively, obtains experimental result such as table 1.
Dyestuff performance table made from the embodiment 1-5 of table 1
From table 1 it follows that synthesized electrowetting organic dyestuff be respectively provided with non-polar solven it is very excellent
Solubility and molar absorption coefficient, meanwhile, dyestuff absorption half-peak breadth is larger, is suitable for preparing dark, dark ink material.Press
Matched according to the dyestuff described in table 2, dark orange 3 is mixed with darkcyan dyestuff 1, dark blue dye 4 and kermesinus dyestuff 5 respectively
Close and prepare black ink materials, respectively obtain black ink 1, black ink 2, black ink 3, the visible absorbance light of three kinds of ink
Spectrogram is respectively as shown in Figure 1, Figure 2 and Fig. 3.
The black ink materials that table 2 is prepared
| Ink name | Dyestuff 1 | Dyestuff 3 | Dyestuff 4 | Dyestuff 5 | N-dodecane | Color |
| Black ink 1 | 0 | 0.36g | 0.17g | 0 | 5mL | Blue light is black |
| Black ink 2 | 0.18g | 0.36g | 0 | 0 | 5mL | Green glow is black |
| Black ink 3 | 0.15g | 0.30g | 0 | 0.20g | 5mL | It is black |
Using green grass or young crops, magenta and the yellow three primary colours disclosed in patent US20110226998 A1 and patent US8143382 B2
The black ink that dyestuff is prepared, analysis obtain its visible absorption spectra figure such as Fig. 4.
From Fig. 1-3 as can be seen that using bisazo class organic dyestuff of the invention, even if only with two kinds of organic dyestuff
Also visible absorbance scope can be made and cover the high black ink materials of wide, uniform absorption, color saturation.By contrast, adopt
The black compounded with existing green grass or young crops, product, yellow three primary colours ink material, it is seen that absworption peak in abosrption spectrogram is sharp keen, the uniformity
The shortcomings that difference, covering incomplete (especially higher than at 650nm, almost without covering).And black ink of the present invention has
Saturation degree is high, photoelectric response speed (is opened soon：8ms；Close：10ms) the advantages of, and no reflow phenomenon under constant voltage, it is suitable for
In electric moistening display, namely in electric wet-type display.
Claims (9)
- A kind of 1. dye composite, it is characterised in that including the compound shown in formula (I) and the compound shown in formula (II),In formula (I) and formula (II),R1For hydrogen, nitro, chlorine, bromine, C1~C12Alkyl or C1~C12Alkoxy；N is 0~2 integer, as n=2, molecular structure In 2 R containing1It can be the same or different；R2、R3、R5、R6It is each independently hydrogen, C1~C12Straight chained alkyl or C1~C12Branched alkyl；R4For hydrogen, C1~C4Alkyl or-NHCOR18The group of expression, wherein, R18For hydrogen, C1~C12 straight chained alkyls or C1~C12 Branched alkyl；R7For hydrogen or-OR17The group of expression, wherein, R17For C1~C12 straight chained alkyls or C1~C12 branched alkyls；R8、R11、R12It is each independently hydrogen, C1~C12Straight chained alkyl or C1~C12Branched alkyl；R9For hydrogen or-OR17The group of expression, wherein, R17For C1~C12 straight chained alkyls or C1~C12 branched alkyls；R10For hydrogen, C1~C4 alkyl or-NHCOR18The group of expression, wherein, R18For hydrogen, C1~C12 straight chained alkyls or C1~ C12 branched alkyls.
- 2. dye composite according to claim 1, it is characterised in that the dye composite also includes formula (III) institute The compound shown,In formula (III),R13、R15、R16It is each independently hydrogen, C1~C12Straight chained alkyl or C1~C12Branched alkyl；R14For hydrogen or-OR17The group of expression, wherein, R17For C1~C12 straight chained alkyls or C1~C12 branched alkyls.
- 3. dye composite according to claim 1, it is characterised in that the R8For hydrogen, methyl, ethyl, n-propyl, just Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl In any one.
- 4. dye composite according to claim 3, it is characterised in that the R9For hydrogen, methoxyl group, ethyoxyl, positive third oxygen Base, n-butoxy, n-pentyloxy, positive hexyloxy, positive epoxide in heptan, n-octyloxy, different octyloxy, positive nonyl epoxide, n-decyloxy, just Any one in hendecane epoxide or n-dodecane epoxide.
- 5. dye composite according to claim 4, it is characterised in that the R10For hydrogen, methyl, ethyl, n-propyl, just Butyl or-NHCOR18, wherein, R18For hydrogen, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, just pungent Any one in base, iso-octyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl.
- 6. dye composite according to claim 2, it is characterised in that the R13For hydrogen, methyl, ethyl, n-propyl, just Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl In any one.
- 7. dye composite according to claim 6, it is characterised in that the R14For hydrogen, methoxyl group, ethyoxyl, positive third Epoxide, n-butoxy, n-pentyloxy, positive hexyloxy, positive epoxide in heptan, n-octyloxy, different octyloxy, positive nonyl epoxide, n-decyloxy, Any one in n-undecane epoxide or n-dodecane epoxide.
- 8. a kind of ink, it is characterised in that the ink is as the dyestuff described in the claim any one of 1-7 of 1~30 mass parts Composition, which is dissolved in the non-polar organic solvent of 70~99 mass parts, to be obtained.
- 9. a kind of electric moistening display, it is characterised in that the electric moistening display includes the ink described in claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610424227.8A CN105949821B (en) | 2016-06-15 | 2016-06-15 | A kind of dye composite, ink and the electric moistening display including the ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610424227.8A CN105949821B (en) | 2016-06-15 | 2016-06-15 | A kind of dye composite, ink and the electric moistening display including the ink |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105949821A CN105949821A (en) | 2016-09-21 |
| CN105949821B true CN105949821B (en) | 2017-12-22 |
Family
ID=56906456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610424227.8A Active CN105949821B (en) | 2016-06-15 | 2016-06-15 | A kind of dye composite, ink and the electric moistening display including the ink |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105949821B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117580842A (en) * | 2021-10-11 | 2024-02-20 | 三菱化学株式会社 | Compound, composition for anisotropic dye film comprising same, anisotropic dye film, and optical element |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2853479A1 (en) * | 1978-12-11 | 1980-06-19 | Bayer Ag | DISAZO DYES |
| JPS5821451A (en) * | 1981-07-31 | 1983-02-08 | Casio Comput Co Ltd | Dichroic dye for liquid crystal |
| JP3453956B2 (en) * | 1995-01-31 | 2003-10-06 | 株式会社豊田中央研究所 | Liquid crystal composition |
| JPH10183122A (en) * | 1996-10-24 | 1998-07-14 | Sharp Corp | Guest-host type liquid crystal composition |
| JP2004001375A (en) * | 2002-03-25 | 2004-01-08 | Ricoh Co Ltd | Write once photorecording medium and recording agent for the medium |
| JP2010230924A (en) * | 2009-03-26 | 2010-10-14 | Fujifilm Corp | Method for manufacturing light absorption anisotropic film and light absorption anisotropic film |
| JP2012057046A (en) * | 2010-09-08 | 2012-03-22 | Fujifilm Corp | Liquid crystal composition, liquid crystal element and liquid crystal display |
| US20150015931A1 (en) * | 2012-03-02 | 2015-01-15 | Merck Patent Gmbh | Electrowetting fluids |
| WO2013175687A1 (en) * | 2012-05-25 | 2013-11-28 | 保土谷化学工業株式会社 | Bis azo pigment for electronic device and electronic device using bis azo pigment |
| CN104703971B (en) * | 2012-08-02 | 2018-08-21 | 株式会社百奥尼 | Novel azo compound and its utilization and its manufacturing method |
-
2016
- 2016-06-15 CN CN201610424227.8A patent/CN105949821B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105949821A (en) | 2016-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104498025B (en) | Many phenyl benzene constructs cyano-containing light emitting molecule and its production and use | |
| CN105949821B (en) | A kind of dye composite, ink and the electric moistening display including the ink | |
| CN106905169B (en) | A kind of vinyl conjugation tri-arylamine group charge transport materials and preparation method thereof | |
| CN108912012A (en) | A kind of power causes ratio off-color material and preparation method thereof | |
| CN103396366A (en) | Production method of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole | |
| CN105348848B (en) | A kind of bisazo cudbear and its application | |
| CN105670332B (en) | Green colouring material and preparation method thereof, ink and electric moistening display | |
| Kim et al. | Synthesis and characterization of novel perylene dyes with new substituents at terminal-position as colorants for LCD color filter | |
| CN105837630B (en) | A kind of decyl imidazoles blue emission luminous organic material and preparation method thereof | |
| CN103145696B (en) | Organic ligand and metal organic frame based on Cu(II) ion, as well as synthesis method and application thereof | |
| CN100569782C (en) | Zinc complex luminescent material | |
| CN111574578B (en) | Circular polarization luminescent material with intelligent response multicolor conversion and preparation method and application thereof | |
| CN102942920A (en) | Iridium complex phosphorescence material with trifluoroacetyl phenyl substituent quinolone as ligand and preparation method thereof | |
| CN102660254B (en) | Iridium complex-containing phosphorescent material, preparation method and application in mercury ion detection | |
| Sun et al. | A novel squaraine dye with squaramide as a scaffold and the colorimetric detection of amine | |
| CN103613948B (en) | Flexible thioether chain-containing near infrared squaric acid dye, and preparation method and application thereof | |
| CN107383928B (en) | A kind of di-azo dyes, ink and electric moistening display | |
| CN103012245B (en) | Chemical synthesis method of phthalimide structure containing coupling components and disperse dyes | |
| CN112341391B (en) | Naphthalimide organic dye, electrowetting display ink and electrowetting display | |
| Choi et al. | Synthesis, spectral property and dyeing assessment of azo disperse dyes containing carbonyl and dicyanovinyl groups | |
| CN113651817B (en) | Organic dye and preparation method and application thereof | |
| CN105694521B (en) | A kind of azo dyes and preparation method thereof, ink and electric moistening display | |
| CN107353669B (en) | A kind of weld, ink and electric moistening display | |
| KR101845190B1 (en) | Novel compound and colorfilter for liquid crystal display comprising the compound | |
| CN108884390A (en) | For synthesizing the intermediate and process of functional material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20160921 Assignee: Guangxian Technology (Guangdong) Co.,Ltd. Assignor: SHENZHEN GUOHUA OPTOELECTRONICS Co.,Ltd.|ACADEMY OF SHENZHEN GUOHUA OPTOELECTRONICS Contract record no.: X2023980038754 Denomination of invention: A dye composition, ink, and an electrowetting display including the ink Granted publication date: 20171222 License type: Exclusive License Record date: 20230728 |