CN105949821A - Dye composition, ink and electrowetting display comprising ink - Google Patents
Dye composition, ink and electrowetting display comprising ink Download PDFInfo
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- CN105949821A CN105949821A CN201610424227.8A CN201610424227A CN105949821A CN 105949821 A CN105949821 A CN 105949821A CN 201610424227 A CN201610424227 A CN 201610424227A CN 105949821 A CN105949821 A CN 105949821A
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- 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
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- 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
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- 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 dye composition, ink and an electrowetting display comprising the ink. The dye composition has the high molar light absorptivity, has the quite high solubility in a non-polar organic solvent and can obtain the ink applicable for electrowetting displaying when dissolved in the organic solvent. Visible light can be effectively and uniformly absorbed by compounding different types of dye, and the dye composition can be used for preparing the balck electrowetting ink with the high contrast. Heterocyclic diazonium components are adopted for replacing 2,4-dinitrobenzene in a dye formula involved in the patent US20150015931A1, the color coverage range of the ink material can be enlarged, and due to the fact that strong polar groups in the structural formula are reduced, the solubility of the dye composition in the non-polar solvent can be greatly improved.
Description
Technical field
The present invention relates to electrowetting Display Technique field, particularly relate to a kind of dye composite, ink and include the electricity profit of this ink
Wet display.
Background technology
The moistening display of electrowetting Display Technique (Electrofluide display, EFD), also referred to as electricity, is PHILIPS Co. of Holland
The display prototype being shown as principle with electrowetting developed first in 2003.This displaying principle be utilize change voltage thus
Control the surface property of hydrophobic layer, change ink layer contact angle on hydrophobic layer: when being not powered on pressure, ink is equal to insulating barrier
Even moistening, forms a Colored pixels point；When applying voltage, the effect of electric field change the surface property of hydrophobic layer make ink-
Interfacial tension between polar liquid-hydrophobic layer three-phase changes, and ink is compressed, and forms the transparent or pixel of substrate background color,
Thus obtain display image effect.
Showing to realize colored electroweting, Liquvista company of Holland proposes two kinds of possible structural models: single or multiple lift
Structure.Monolayer electrowetting colour display use black ink collocation colored filter realize, the method owing to have employed optical filter,
Reducing the utilization ratio of light, contrast declines, but device is simple, it is easy to preparation；And multilamellar electrowetting colour shows and can adopt
With being formed by stacking of three primary colours (green grass or young crops, product, Huang), higher to the utilization ratio of light, but due to only with green grass or young crops, product, Huang,
The superposition of light is absorbed and realizes black by three layers of dyestuff, and only obtain is Lycoperdon polymorphum Vitt, therefore, in order to realize the black of high-contrast
Color shows, is inadequate only with three layers of color addition, in addition it is also necessary to increase by one layer of black ink with high contrast.
The black ink materials of high contrast requires sufficiently to absorb the light wave in visible-range, therefore, multiple when using
Ink material preparation time, it is desirable to preparation ink material each component the widest more good to the absorption of visible ray, from this angle for,
Inapplicable for three primary colours blue or green (C), the product (M) of electrowetting display design, Y (yellow) or red (R), green (G), indigo plant (B)
In preparation black ink, because their saturation is high, narrow to the absorption region of visible ray, the black oil therefore prepared is pitch-dark
Degree is not.
The structural formula of a class bisazo class organic dyestuff is related in patent US20150015931A1In the structure shown here, in order to obtain preparing black ink materials institute
Need is black-and-blue, and usual X, X ' need for strong electron-withdrawing group group, such as nitro.The introducing of highly polar group result in dyestuff in non-pole
Property solvent in dissolubility decline, the dissolubility of this structure type dyestuff between 15～20%, be difficult to prepare high to black requirement
Electrowetting ink.Need to research and develop further a kind of dyestuff that dissolubility is big in non-polar solven, and need this dyestuff molten
Saturate ink can be obtained after non-polar solven.
Summary of the invention
The technical problem to be solved is to provide a kind of dye composite, ink and includes the electric moistening display of this ink.
The technical solution used in the present invention is:
A kind of dye composite, including shown in the compound shown in the compound shown in formula (I), formula (II), formula (III)
At least one in compound,
In formula (I), formula (II) and formula (III),
R1For hydrogen, nitro, chlorine, bromine, C1～C12Alkyl or C1～C12Alkoxyl；N is the integer of 0～2, as n=2, point
2 R contained in minor structure1Can 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～C12Branched alkyl；
R7、R9、R14It is each independently hydrogen or-OR17The group represented, wherein, R17For C1～C12 straight chained alkyl or C1～C12
Branched alkyl；
R4、R10It is each independently hydrogen, C1～C4Alkyl or-NHCOR18The group represented, wherein, R18For hydrogen, C1～C12
Straight chained alkyl or C1～C12 branched alkyl.
In some specific embodiments, described R1For hydrogen, nitro, chlorine, bromine, methyl, methoxyl group, ethyl, n-pro-pyl,
Arbitrary in isopropyl, normal-butyl, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, octyloxy or different octyloxy
Individual.
In further preferred embodiment, described R7For hydrogen or methoxyl group.
In the most preferred embodiment, described R2、R3、R4、R5、R6Be separately methyl, ethyl, third
Base, butyl, amyl group, n-hexyl, n-heptyl, n-octyl, iso-octyl, nonyl, certain herbaceous plants with big flowers base, n-undecane base or n-dodecane
Any one in base.
In some specific embodiments, described R8For hydrogen, methyl, ethyl, n-pro-pyl, 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, described R9For hydrogen, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, just
Amoxy, positive hexyloxy, epoxide in positive heptan, n-octyloxy, different octyloxy, positive nonyl epoxide, n-decyloxy, n-undecane epoxide
Or any one in n-dodecane epoxide.
In the most preferred embodiment, described R10For hydrogen, methyl, ethyl, n-pro-pyl, normal-butyl or-NHCOR18,
Wherein, R18For hydrogen, methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl,
Any one in n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl.
In the most preferred embodiment, described R11、R12Be separately hydrogen, methyl, ethyl, n-pro-pyl,
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 positive ten
Any one in dialkyl group.
In some specific embodiments, described R13For hydrogen, methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, just
Any one in hexyl, 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, described R14For hydrogen, methoxyl group, ethyoxyl, positive propoxy, n-butoxy,
N-pentyloxy, positive hexyloxy, epoxide in positive heptan, n-octyloxy, different octyloxy, positive nonyl epoxide, n-decyloxy, n-undecane oxygen
Any one in base or n-dodecane epoxide.
In the most preferred embodiment, described R15、R16Be separately hydrogen, methyl, ethyl, n-pro-pyl,
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 positive ten
Any one in dialkyl group.
Present invention also offers a kind of ink, described ink is dissolved in 70～99 by the dye composite as above of 1～30 mass parts
The non-polar organic solvent of mass parts obtains.
Present invention also offers a kind of electric moistening display, described electric moistening display includes ink as above.
The invention has the beneficial effects as follows:
The invention provides a kind of bisazo class organic dyestuff, described organic dyestuff has higher molar absorption coefficient, in non-pole
Property organic solvent in there is high dissolubility, being dissolved in organic solvent can obtain a kind of being applicable to the ink that electrowetting shows, logical
Cross the compounding of different dyes can visible ray be absorbed the most equably, can be used for preparing the black electrowetting oil of high-contrast
Ink.The present invention replaces the 2,4-bis-in the Dyes structural formulae related in patent US 20150015931A1 with heterocyclic diazo component
Nitro phenyl ring, is possible not only to improve the color coverage of ink material, owing to reducing the highly polar group in structural formula, also
Its dissolubility in non-polar solven can be increased substantially.
Accompanying drawing explanation
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.
Detailed description of the invention
Embodiment 1:
Weigh 3.7g (110g/mol, 0.0344mol) hydroquinone to be dissolved in 30mL ethanol, addition 23.2g (192g/mol,
0.12mol) bromo-iso-octane and 4.99g (0.089mol, 56g/mol) potassium hydroxide, back flow reaction 24h, fall product
Entering in 500mL water, extract with toluene, separate oil phase, rotation is evaporated dry, column chromatography for separation, and eluant: petroleum ether obtains first
IntermediateYield 60%.Rf=0.64 (petroleum ether).
Weigh 12g (334g/mol, 0.036mol) first step intermediate to be dissolved in 50mL chloroform, be cooled with an ice bath to 0～5 DEG C,
Weigh 4.1g (70%, 0.045mol) nitric acid dropping in above-mentioned solution, sustained response 1h.Reactant liquor is used after terminating by reaction
Water washs 2-3 time, separates oil phase, and rotation is evaporated dry, obtains 11.1g the second intermediateYield 81.6%.
Weigh 11.1g (0.0293mol, 379g/mol) second step intermediate to be dissolved in 20mL ethanol, 20mL ethyl acetate,
Add 8.79g (0.14mol, 60g/mol) glacial acetic acid and 9.5g (0.14mol, 65g/mol) zinc powder, reaction 4h is stirred at room temperature.
Reaction is filtered after terminating, and collects filtrate rotation and is evaporated dry, and column chromatography for separation obtains 8.7g the 3rd intermediate
Yield 85%.
Weigh 2.25g (183g/mol, 0.015mol) 2-amino-6-nitrobenzothiazole to be dissolved in 50mL strong phosphoric acid, be cooled to
-10 DEG C～-5 DEG C, add 5.5g nitrosyl sulfuric acid (40wt%), diazotising 2h.Weigh 5.2g (379g/mol, 0.015mol)
3rd intermediate is dissolved in 50mL ethanol, adds 30g sodium acetate and 5g sulfamic acid, is cooled with an ice bath to 0～5 DEG C.By upper
Stating diazol to be slowly dropped in above-mentioned coupling component, react 3h, reaction pours product in 300mL water precipitation after terminating, and takes out
Filter, is dried to obtain the 4th intermediate4.58g, yield 59.8%.
Weighing 3.16g (0.02mol, 158g/mol) m-acetamidoaniline, 8.0g (0.042mol, 192g/mol) bromo is different
Octane, 4.1g (0.03mol, 138g/mol) potassium carbonate is dissolved in the dimethyl acetylamide (DMAc) of 70mL, is passed through N2
Protection, is warming up to 140 DEG C of insulation 10h.Then solution poured into precipitation oil product in 100mL water, and product is with 100mL just
Hexane extracts, and separates, and washs with 10% aqueous hydrochloric acid solution and removes mono-substituted products several times, obtains the 5th intermediate, and the described 5th
Intermediate structure formula isHead product 1.69g, yield 22.6%.
Take 1.69g the 5th intermediate (374g/mol, 0.00452mol) to be dissolved in 20mL ethanol, add 10 times of moles
The concentrated hydrochloric acid of (0.0452mol, 3.8mL), is warming up to back hydrolysis, and reaction 2h, TLC detection reaction terminates.Cooling, adds
Entering in equimolar amounts potassium hydroxide aqueous solution and hydrochloric acid, n-hexane extraction obtains product, and rotation is steamed, and is dried, and obtains in the middle of 1.21g the 6th
Body, structural formula isYield 81.0%.
Described for 5g (0.015mol, 332g/mol) the 6th intermediate is dissolved in 30mL DMF, addition 3.2g (101g/mol,
0.03mol) triethylamine, weighs 5.1g (162g/mol, 0.031mol) different caprylyl chloride and is added drop-wise in above-mentioned solution, room temperature reaction,
Use Ai Lixi reagent detection reaction end.Rf=0.5 (toluene/petroleum ether=1/2), obtains the 7th intermediate, and structure isYield 100%.
Weigh 5.1g (510g/mol, 0.01mol) the 4th intermediate to be dissolved in 100mL NMP, be cooled to 0～5 DEG C, add
3.5g (40%, 0.011mol) nitrosyl sulfuric acid, diazotising 30min.Weigh in the middle of 3.74g (374g/mol, 0.01mol)
Body seven is dissolved in 50mL acetone, adds appropriate ice cube, and ice bath cools down.Above-mentioned diazol is slowly dropped in said components,
Reaction 3h, pours in 300mL water and separates out, and petroleum ether extraction is dried, obtains 8.2g dyestuff 1, and its structural formula isYield 84%.Its nucleus magnetic hydrogen spectrum data are: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:
Weighing 1.0g (5mmol, 201g/mol) 1-acetylaminohydroxyphenylarsonic acid 7-naphthols, 1.92g (10mmol, 192g/mol) bromo is different
Octane, 1.38g (10mmol, 138g/mol) K2CO3It is dissolved in 50mL acetonitrile, back flow reaction 9h.Developing solvent: acetone/
Petroleum ether=1/2 (volume ratio), Rf raw material=0.13, Rf product=0.55.React to be poured into by product in 100mL water after terminating and analyse
Going out oil product, use ethyl acetate extraction product, 90 DEG C of rotations are evaporated off solvent and bromo-iso-octane, obtain the 8th intermediate,Yield 88%.
Weigh the 8th intermediate 0.88g to be dissolved in 50mL isopropanol, add 20 times amount KOH back flow reaction 5h.Developing solvent:
Acetone/petroleum ether=1/2 (volume ratio), Rf raw material=0.55, Rf product=0.63.Reaction mixture is poured into water, ethyl acetate
Extraction, rotation is evaporated dry, obtains the 9th intermediateYield 88.0%.
Weigh 2.05g (0.01mol, 205g/mol) n-octyl aniline, 4.2mL (12mol/L, 0.05mol) concentrated hydrochloric acid is dissolved in
In 20mL industrial alcohol, it is cooled to 0～5 DEG C.Weigh 0.8g (0.011mol, 69g/mol) sodium nitrite to be dissolved in 5mL water,
Disposably join in above-mentioned solution.After diazo-reaction 1h, add appropriate sulfamic acid and remove unnecessary nitrous acid.Weigh
Described second intermediate of 2.71g (0.01mol, 271g/mol) is dissolved in 50mL ethanol, is cooled to 0～5 DEG C, by above-mentioned diazonium
Salt is slowly added dropwise into.Reaction 4h, using saturated aqueous sodium carbonate regulation pH value of solution after terminating is 7, filters, is dried,
Obtain the tenth intermediateYield 67%.
Weigh 3g the tenth intermediate (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 adding, diazotising 1h.Weigh centre
Body 2.3g the 5th intermediate (374g/mol, 0.0062mol) is dissolved in 30mL ethanol, is slowly dropped in above-mentioned diazol even
Close.Being poured in 300mL water precipitation oil product after reaction 3h, collect, be 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:
Weigh 1.49g (0.01mol, 149g/mol) n-butyl aniline, 4.2mL (12mol/L, 0.05mol) concentrated hydrochloric acid is dissolved in
In 20mL water, it is cooled to 0～5 DEG C.Weigh 0.8g (0.011mol, 69g/mol) sodium nitrite to be dissolved in 5mL water, once
Property joins 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, is delayed by above-mentioned diazol
Slow dropping is come in.Reaction 4h, using saturated aqueous sodium carbonate regulation pH value of solution after terminating is 7, filters, is dried, obtains
11st intermediateYield 80%.
Weigh 6.6g (132g/mol, 0.05mol) tertbutyloxycarbonyl hydrazine and be dissolved in 50mL normal hexane, weigh 6.7g (114g/mol,
During 0.058mol) different octanal is slowly dropped to above-mentioned solution, it is warming up to back flow reaction 2h.Reaction is evaporated removing solvent after terminating,
ObtainYield 100%.WillIt is cooled to 0～5 DEG C, weighs 1mol/L boron
Alkane tetrahydrofuran solution 100mL is slowly dropped in above-mentioned reaction unit, and developing solvent is dichloromethane/petroleum ether=1:1, reaction
2h, obtainsMeasure 15mL concentrated hydrochloric acid, be slowly dropped in above-mentioned solution, treat without obvious bubble
Produce post-heating extremely backflow, react 0.5h.Cooling down after completion of the reaction, sucking filtration removes the boric acid separated out, and is evaporated dry by solution rotation.
ObtainYield 78%.Weigh 0.56gHydrochlorate (180g/mol,
0.0031mol) be dissolved in 20mL ethanol, add 1.68g Feldalat NM (54g/mol, 0.031mol), weigh 0.41g (130g/mol,
During 0.0031mol) ethyl acetoacetate is added drop-wise to above-mentioned solution, N2Protection, is warming up to 50 DEG C of reaction 3h under room temperature after reacting 3h,
Reaction uses 10% aqueous hydrochloric acid solution regulation pH value of solution to be neutrality, n-hexane extraction, Rotary drying after terminating, obtain the 12nd
Intermediate 0.51gYield 76.8%.
Weigh 4.31g the 11st intermediate (431g/mol, 0.01mol) to be dissolved in 100mL NMP+100mL acetic acid, cooling
To 0～5 DEG C, weigh 0.76g (0.011mol, 69g/mol) and be dissolved in 5mL water and disposably adding, diazotising 1h.Weigh 2.1g
12nd intermediate(210g/mol, 0.01mol) is dissolved in 50mL ethanol, is cooled to 0-5 DEG C, by above-mentioned
Diazol is slowly added dropwise into coupling, and using sodium hydroxide solution regulation pH is 8-9, coupling reaction 3h, and sucking filtration obtains head product
Dyestuff 3, its structural formula is5.0g.Yield 77.0%.The nucleus magnetic hydrogen spectrum data of dyestuff 3 are such as
Under: 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:
Weigh 1.06g (0.01mol, 106g/mol) m-toluidine, 6.19g (0.03mol, 192g/mol) bromo-iso-octane,
2.2g (0.016mol, 138g/mol) potassium carbonate is dissolved in the dimethyl acetylamide (DMAc) of 50mL, is passed through N2Protection,
It is warming up to 140 DEG C of insulation 24h.Then solution poured into precipitation oil product in 100mL water, and product 100mL normal hexane extracts
Take, separate, obtain the 13rd intermediateColumn chromatography chromatogram separates, yield 21.4%.Tenth
The nucleus magnetic hydrogen spectrum data of three intermediate 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 5.1g (510g/mol, 0.01mol) the 4th intermediateIt is dissolved in 100mL NMP, is cooled to 0～5 DEG C, add 3.5g (40%, 0.011mol)
Nitrosyl sulfuric acid, diazotising 30min.Weigh 3.31g (331g/mol, 0.01mol) the 13rd intermediate
Being dissolved in 50mL acetone, add appropriate ice cube, ice bath cools down.Above-mentioned diazol is slowly dropped in above-mentioned coupling component,
Reaction 3h, pours in 300mL water and separates out, and petroleum ether extraction is dried, obtains 6.2g dyestuff 4, and its structural formula isYield 69%.
Embodiment 5:
Weigh 4.31g the 11st intermediate(431g/mol, 0.01mol) is dissolved in 100mL
In NMP+100mL acetic acid, it is cooled to 0～5 DEG C, weighs 0.76g (0.011mol, 69g/mol) and be dissolved in 5mL water disposably
Add, diazotising 1h.Weigh 2.1g the 13rd intermediate(331g/mol, 0.01mol) is dissolved in 50mL
In ethanol, it is cooled to 0-5 DEG C, above-mentioned diazol is slowly added dropwise into coupling, coupling reaction 3h, sucking filtration, obtain 5.4g dye
Material 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:
Dyestuff 1-5 embodiment 1-5 prepared carries out performance evaluation respectively, obtains experimental result such as table 1.
Table 1 embodiment 1-5 prepare dyestuff performance table
From table 1 it follows that synthesized electrowetting organic dyestuff is respectively provided with the most excellent dissolubility in non-polar solven
And molar absorption coefficient, meanwhile, it is relatively big that dyestuff absorbs half-peak breadth, is suitable for preparation dark color, dark ink material.According to table
Dyestuff proportioning described in 2, mixes with darkcyan dyestuff 1, dark blue dye 4 and kermesinus dyestuff 5 respectively by dark orange 3
Preparation black ink materials, respectively obtains black ink 1, black ink 2, black ink 3, the visible absorbance light of three kinds of ink
Spectrogram is distinguished the most 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 | Black |
Use green grass or young crops, magenta and the yellow three primary colours dyestuff disclosed in patent US20110226998 A1 and patent US8143382 B2
The black ink of preparation, analyzes and obtains its visible absorption spectra figure such as Fig. 4.
It can be seen that use the bisazo class organic dyestuff of the present invention, even if also may be used only with two kinds of organic dyestuff from Fig. 1-3
Make visible absorbance scope and cover the black ink materials wide, uniform absorption, color saturation are high.By contrast, use now
The black that some green grass or young crops, product, yellow three primary colours ink material compound, it is seen that the absworption peak in abosrption spectrogram is sharp keen, the uniformity is poor,
The shortcoming covering incomplete (at especially higher than 650nm, almost without covering).And black ink of the present invention has full
, photoelectric response speed high with degree (is opened: 8ms soon；Close: advantage 10ms), and no reflow phenomenon under constant voltage, be suitable for
In electric moistening display, namely in electric wet-type display.
Claims (10)
1. a dye composite, it is characterised in that include the compound shown in the compound shown in formula (I), formula (II), formula
(III) at least one in the compound shown in,
In formula (I), formula (II) and formula (III),
R1For hydrogen, nitro, chlorine, bromine, C1～C12Alkyl or C1～C12Alkoxyl；N is the integer of 0～2, as n=2, point
2 R contained in minor structure1Can 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～C12Branched alkyl；
R7、R9、R14It is each independently hydrogen or-OR17The group represented, wherein, R17For C1～C12 straight chained alkyl or C1～C12
Branched alkyl；
R4、R10It is each independently hydrogen, C1～C4Alkyl or-NHCOR18The group represented, wherein, R18For hydrogen, C1～C12
Straight chained alkyl or C1～C12 branched alkyl.
Dye composite the most according to claim 1, it is characterised in that described R1For hydrogen, nitro, chlorine, bromine, methyl,
Methoxyl group, ethyl, n-pro-pyl, isopropyl, normal-butyl, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy,
Any one in octyloxy or different octyloxy.
Dye composite the most according to claim 2, it is characterised in that described R7For hydrogen or methoxyl group.
Dye composite the most according to claim 1, it is characterised in that described R8For hydrogen, methyl, ethyl, n-pro-pyl,
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
Any one in dodecyl.
Dye composite the most according to claim 4, it is characterised in that described R9For hydrogen, methoxyl group, ethyoxyl, positive third
Epoxide, n-butoxy, n-pentyloxy, positive hexyloxy, epoxide in positive heptan, n-octyloxy, different octyloxy, positive nonyl epoxide,
Any one in n-decyloxy, n-undecane epoxide or n-dodecane epoxide.
Dye composite the most according to claim 5, it is characterised in that described R10For hydrogen, methyl, ethyl, n-pro-pyl,
Normal-butyl or-NHCOR18, wherein, R18For hydrogen, methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl,
Any one in n-heptyl, n-octyl, iso-octyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl.
Dye composite the most according to claim 1, it is characterised in that described R13For hydrogen, methyl, ethyl, n-pro-pyl,
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
Any one in dodecyl.
Dye composite the most according to claim 7, it is characterised in that described R14For hydrogen, methoxyl group, ethyoxyl, positive third
Epoxide, n-butoxy, n-pentyloxy, positive hexyloxy, epoxide in positive heptan, n-octyloxy, different octyloxy, positive nonyl epoxide,
Any one in n-decyloxy, n-undecane epoxide or n-dodecane epoxide.
9. an ink, it is characterised in that described ink is by the dye combinations described in any one of claim 1-8 of 1～30 mass parts
Thing is dissolved in the non-polar organic solvent of 70～99 mass parts and obtaining.
10. an electric moistening display, it is characterised in that described electric moistening display includes the ink described in claim 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023063249A1 (en) * | 2021-10-11 | 2023-04-20 | 三菱ケミカル株式会社 | Compound, composition for anisotropic dye film comprising said compound, anisotropic dye film, and optical element |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0012354A1 (en) * | 1978-12-11 | 1980-06-25 | Bayer Ag | Disazo dyes, process for the preparation of binary or ternary mixtures of disazo dyes and process for the dyeing and/or the marking of organic materials |
| JPS5821451A (en) * | 1981-07-31 | 1983-02-08 | Casio Comput Co Ltd | Dichroic dye for liquid crystal |
| US5766508A (en) * | 1995-01-31 | 1998-06-16 | Kabushiki Kaisha Toyota Chuo Kenkyusho | 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 |
| 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 |
| US20150015931A1 (en) * | 2012-03-02 | 2015-01-15 | Merck Patent Gmbh | Electrowetting fluids |
| CN104703971A (en) * | 2012-08-02 | 2015-06-10 | 株式会社百奥尼 | Novel azo compound, use thereof and method for preparing same |
-
2016
- 2016-06-15 CN CN201610424227.8A patent/CN105949821B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0012354A1 (en) * | 1978-12-11 | 1980-06-25 | Bayer Ag | Disazo dyes, process for the preparation of binary or ternary mixtures of disazo dyes and process for the dyeing and/or the marking of organic materials |
| JPS5821451A (en) * | 1981-07-31 | 1983-02-08 | Casio Comput Co Ltd | Dichroic dye for liquid crystal |
| US5766508A (en) * | 1995-01-31 | 1998-06-16 | Kabushiki Kaisha Toyota Chuo Kenkyusho | 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 |
| CN104703971A (en) * | 2012-08-02 | 2015-06-10 | 株式会社百奥尼 | Novel azo compound, use thereof and method for preparing same |
Non-Patent Citations (1)
| Title |
|---|
| A. T. PETERS: ""Disazo Disperse Dyes Derived from 5,6(6,7)-Diehloro-2-Aminobenzothiazole"", 《DYES AND PIGMENTS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023063249A1 (en) * | 2021-10-11 | 2023-04-20 | 三菱ケミカル株式会社 | Compound, composition for anisotropic dye film comprising said compound, anisotropic dye film, and optical element |
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