Anthraquinone dye as well as preparation method and application thereof

Abstract

The invention discloses an anthraquinone dye as well as a preparation method and application thereof. The anthraquinone dye disclosed by the invention comprises a compound with a chemical formula as shown in formula (I): # imgabs0 #, wherein W1-W8 are independently selected from H, OH, substituted or unsubstituted C1-C30 alkyl groups or groups containing adamantyl groups; and at least one of W1-W8 is a group containing adamantyl. The anthraquinone dye with high solubility and optical aging resistance is obtained by modifying an anthraquinone main body through adamantane and utilizing high chemical stability and steric hindrance effect of adamantane. The ink prepared from the anthraquinone dye has stability and excellent display effect in electrowetting display, and electrowetting with high light stability is obtained.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrowetting materials, and in particular relates to an anthraquinone dye and a preparation method and application thereof. Background Art

[0002] Electrowetting display (EFD), also known as electrowetting display technology, is a prototype display based on the electrowetting principle first developed by Philips of the Netherlands in 2003. This display principle uses voltage to control the surface properties of a hydrophobic layer, thereby changing the contact angle of the ink layer on the hydrophobic layer. When no voltage is applied, the ink uniformly wets the insulating layer, forming a colored pixel. When voltage is applied, the electric field alters the surface properties of the hydrophobic layer, causing a change in the interfacial tension between the ink, polar liquid, and hydrophobic layer. This compresses the ink, forming transparent pixels or pixels that reflect the substrate's base color, thereby displaying an image.

[0003] Electrowetting display ink materials are proprietary materials for electrowetting display colors. However, currently, the photostability of commonly used electrowetting display ink materials is poor, which to some extent affects the application of electrowetting devices. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides an anthraquinone dye with good photostability and good application prospects in electrowetting devices.

[0005] The invention also provides a preparation method of anthraquinone dyes.

[0006] The present invention also provides an ink.

[0007] The present invention also provides an electrowetting display device.

[0008] In a first aspect of the present invention, an anthraquinone dye is provided, comprising a compound represented by formula (I):

[0009]

[0010] Wherein, W1-W8 are independently selected from H, OH, substituted or unsubstituted C1-C 30 An alkyl group or an adamantyl-containing group; at least one of W1 to W8 is an adamantyl-containing group.

[0011] The anthraquinone dyes according to the embodiments of the present invention have at least the following beneficial effects:

[0012] In this invention, an anthraquinone dye with high solubility and resistance to optical aging is obtained by modifying an anthraquinone host with adamantane, leveraging its high chemical stability and steric hindrance. Inks formulated with these anthraquinone dyes exhibit good stability and excellent display effects in electrowetting displays, resulting in highly photostable electrowetting displays.

[0013] In some embodiments of the present invention, W1, W4, W5, and W8 are independently selected from H, OH, or a group containing an adamantyl group; W2, W3, W6, and W7 are independently selected from H, substituted or unsubstituted C1-C 30 An alkyl group or an adamantyl group-containing group.

[0014] In some embodiments of the present invention, at least two of W1 to W8 are adamantyl-containing groups.

[0015] In some embodiments of the present invention, the adamantyl-containing group includes the group At least one of; wherein:

[0016] R 1～2 Each occurrence is independently selected from NH, NHC n H 2n ,O,C n H 2n O, alkylenephenol; wherein n is an integer, and each occurrence of n is independently selected from 1 to 30;

[0017] R 3～6 Each occurrence is independently selected from substituted or unsubstituted C1 to C 30 Alkyl, substituted or unsubstituted C6~C 30 Alkoxyphenyl, substituted or unsubstituted C6~C 30 of alkylphenyl.

[0018] R 1～2 The group in can be connected to the anthraquinone core at either end and to the adamantyl-containing group at the other end. n H 2n When the NH in R1 is connected to the anthraquinone nucleus, the C in R1 can also be connected to the anthraquinone nucleus. n H 2n Connected to the anthraquinone nucleus.

[0019] In some embodiments of the present invention, the number of carbon atoms contained in the alkylene group of the alkylene phenol group is selected from 1 to 15.

[0020] In some embodiments of the present invention, the compound represented by formula (I) includes at least one of the compounds represented by formula (I-1), (I-2) or (I-3):

[0021]

[0022] Wherein the group W2 is selected from Substituted or unsubstituted C1~C 30 an alkyl group, a dimethyladamantyl group substituted with an amino group, or a dimethyladamantyl group substituted with an alkoxy group;

[0023] R 1～2 Each occurrence is independently selected from NH, NHC n H 2n ,O,C n H 2n O, alkylenephenol; wherein n is an integer, and each occurrence of n is independently selected from 1 to 30;

[0024] R 3～6 Each occurrence is independently selected from substituted or unsubstituted C1 to C 30 Alkyl, substituted or unsubstituted C6~C 30 Alkoxyphenyl, substituted or unsubstituted C6~C 30 of alkylphenyl.

[0025] In some embodiments of the present invention, the alkoxy group is selected from substituted or unsubstituted C1 to C 30 Alkoxy. Such as substituted or unsubstituted C1~C 10 of alkoxy.

[0026] In some embodiments of the present invention, the group W2 is selected from Substituted or unsubstituted C1~C 15 An alkyl group or a dimethyladamantyl group substituted with an amino group or an alkoxy group.

[0027] In some embodiments of the present invention, R 1～2 When the alkylene group is present, the alkylene group is independently selected from methylene, ethylene, propylene, butylene, pentylene, hexylene, 2-ethylhexylene, 2-nonyldecylene, 2-pentylhexylene, 2-heptyloctylene, and 2-octyldodecylene. The anthraquinone dye obtained has good solubility in non-polar solvents, which is more conducive to its use in electrowetting display inks.

[0028] In some embodiments of the present invention, R 3～6 Each occurrence is independently selected from substituted or unsubstituted C1 to C 20 Alkyl, substituted or unsubstituted C6~C 20 Alkoxyphenyl, substituted or unsubstituted C6~C 20 of alkylphenyl.

[0029] In some embodiments of the present invention, R 3～6 Each occurrence is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-nonyldecyl, 2-pentylhexyl, 2-heptyloctyl, 2-octyldodecyl, 4-butylphenyl, 4-hexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 3-octyltridecyl, 2-hexyldodecyl, 2-octyldodecyl, and 4-tert-octylphenyl.

[0030] In some embodiments of the present invention, R 3～6 Each occurrence is independently selected from n-octyl, 2-ethylhexyl, 3-octyltridecyl, 2-hexyldodecyl, 2-octyldodecyl, 4-tert-octylphenyl, 4-(2-ethylhexyl)phenyl.

[0031] Through the above implementation, the obtained anthraquinone dye has better color and better solubility in non-polar solvents, which is more conducive to its use in electrowetting display ink.

[0032] In some embodiments of the present invention, the compound represented by formula (I-2) includes at least one of the compounds represented by formula (I-2-1) or formula (I-2-2):

[0033]

[0034] Wherein, R7 is selected from substituted or unsubstituted C1~C 15 of alkyl.

[0035] In some embodiments of the present invention, R7 is selected from substituted or unsubstituted C5 to C 12 of alkyl.

[0036] In some embodiments of the present invention, R7 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, 2-nonyldecyl, 2-pentylhexyl, 2-heptyloctyl, 2-octyldodecyl, 3-octyltridecyl, 2-hexyldodecyl, and 2-octyldodecyl.

[0037] In a second aspect of the present invention, a method for preparing anthraquinone dyes is provided, comprising the steps of: reacting a dihydroxyanthraquinone substance with an adamantane amine to obtain the anthraquinone dye. The adamantane amine refers to an amine substance containing an adamantane group.

[0038] In some embodiments of the present invention, the anthraquinone dye includes at least one of the compounds represented by formula (I-1), (I-2) or (I-3).

[0039] In some embodiments of the present invention, the dihydroxyanthraquinone substance is selected from at least one of dihydroxyanthraquinone or dihydroxyanthraquinone leuco form.

[0040] In some embodiments of the present invention, the dihydroxyanthraquinone substance includes at least one of 1,4-dihydroxyanthraquinone leuco form or 1,8-dihydroxyanthraquinone leuco form.

[0041] In some embodiments of the present invention, the adamantanes include at least one of primary adamantanes or secondary adamantanes.

[0042] In some embodiments of the present invention, the adamantanes include at least one of dimethylamantadine, dimethylamantadine, or dimethylamantadine. Dimethylamantadine is also known as dimethylamantadine.

[0043] In some embodiments of the present invention, the molar ratio of the dihydroxyanthraquinones to the adamantanes is 1:(0.5-20), such as 1:(1-10).

[0044] In some embodiments of the present invention, the preparation method comprises the following steps: mixing a dihydroxyanthraquinone with a solvent I, adding an adamantane amine, and reacting the mixture at 90-140°C for 2-25 hours in a protective gas atmosphere to obtain the anthraquinone dye. Optionally, the solvent I comprises ethylene glycol monomethyl ether or N,N-dimethylformamide (DMF).

[0045] In some embodiments of the present invention, the preparation method includes the following steps: mixing a dihydroxyanthraquinone substance with solvent I, adding adamantane amine, reacting in a protective gas atmosphere, cooling, stirring, mixing the resulting reaction liquid with water, and extracting to obtain the anthraquinone dye.

[0046] The third aspect of the present invention provides a method for preparing anthraquinone dyes, comprising the following steps:

[0047] S1, taking 1,4-dihydroxyanthraquinone or leuco form of 1,4-dihydroxyanthraquinone, mixing it with a surfactant, an alkaline substance, and Na2S2O4, and reacting them to obtain compound A;

[0048] S2, reacting compound A with aldehydes and piperidinium acetate to obtain compound B;

[0049] S3, reacting compound B with adamantane amine to obtain an anthraquinone dye;

[0050] Wherein, the anthraquinone dye is a compound represented by formula (I-2-2); compounds A and B are represented by the following formula:

[0051]

[0052] In the present invention, the use of Na2S2O4 can increase the mutual solubility of reactants and improve the reaction efficiency.

[0053] In some embodiments of the present invention, the surfactant includes but is not limited to sodium lauryl sulfate.

[0054] In some embodiments of the present invention, the alkaline substance includes but is not limited to alkaline substances such as Na2CO3, K2CO3, etc. Optionally, the alkaline substance includes at least one of Na2CO3 or K2CO3.

[0055] In some embodiments of the present invention, the aldehydes include but are not limited to 2-ethylhexanal, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, heptanal, octanal, nonanal, decanal, and the like.

[0056] In some embodiments of the present invention, in step S1, the reaction temperature is 60-100° C., and the reaction time is 0.1-2 h.

[0057] In some embodiments of the present invention, in step S1, the mass ratio of 1,4-dihydroxyanthraquinone, surfactant, alkaline substance and Na2S2O4 is (0.5~10):(0.01~1):(0.5~10):(0.5~10), or the mass ratio of 1,4-dihydroxyanthraquinone leuco body, surfactant, alkaline substance and Na2S2O4 is (0.5~10):(0.01~1):(0.5~10):(0.5~10).

[0058] In some embodiments of the present invention, in step S2, the reaction temperature is 60-100° C., and the reaction time is 15-30 h.

[0059] In some embodiments of the present invention, in step S2, the mass ratio of compound A to aldehydes and piperidinium acetate is (0.5-10):(0.5-10):(0.01-1).

[0060] In some embodiments of the present invention, in step S2, compound A is reacted with aldehydes and piperidinium acetate. After the reaction is completed, the temperature is lowered to (-25)°C to (-15)°C, ethanol is added, stirred, and filtered to obtain the compound B.

[0061] In some embodiments of the present invention, in step S3, the mass ratio of compound B to amantadine is (0.5-10):(0.01-1).

[0062] In some embodiments of the present invention, the amantadine comprises at least one of dimethylamantadine, dimethylrimantadine, or dimethylamantadine.

[0063] In some embodiments of the present invention, in step S3, compound B is mixed with solvent II, and then mixed with an adamantane amine to react to obtain an anthraquinone dye. Optionally, the reaction temperature is 100-130° C., and the reaction time is 15-35 hours.

[0064] In some embodiments of the present invention, the solvent II comprises DMF.

[0065] In some embodiments of the present invention, in step S3, compound B is mixed with solvent II, and then mixed with adamantane amine, reacted, cooled to below 10° C., water is added, and filtered to obtain an anthraquinone dye.

[0066] In a fourth aspect, the present invention provides an ink comprising the above-mentioned anthraquinone dye.

[0067] In some embodiments of the present invention, the ink is an electrowetting display ink.

[0068] In some embodiments of the present invention, the ink further comprises an organic solvent. Optionally, the organic solvent comprises a non-polar organic solvent.

[0069] In some embodiments of the present invention, the ink includes 0.5 to 100 parts by mass of anthraquinone dye and 5 to 500 parts by mass of an organic solvent.

[0070] Through the above-mentioned embodiment, anthraquinone dyes have high solubility and high optical stability in non-polar organic solvents. When dissolved in organic solvents, an ink suitable for electrowetting display can be obtained, which can be used to prepare electrowetting display devices. The obtained electrowetting display devices have high optical stability.

[0071] In some embodiments of the present invention, the ink includes 1 to 30 parts by mass of anthraquinone dye and 5 to 100 parts by mass of an organic solvent.

[0072] In some embodiments of the present invention, the ink includes 1 to 30 parts by mass of anthraquinone dye and 70 to 99 parts by mass of an organic solvent.

[0073] In some embodiments of the present invention, the organic solvent is a non-polar solvent.

[0074] In some embodiments of the present invention, the organic solvent includes at least one of n-decane (n-decane), n-dodecane, n-tetradecane, n-hexadecane, a fluorinated alkane, a silane, isomeric dodecane, isomeric hexadecane, cyclohexane, epoxy silane, a fluorinated epoxy silane, or dimethyladamantane. Here, isomeric dodecane refers to dodecane other than n-dodecane. Isomeric hexadecane refers to hexadecane other than n-hexadecane.

[0075] In a fifth aspect of the present invention, a method for preparing ink is provided, comprising the following steps: mixing an anthraquinone dye and an organic solvent to obtain the ink.

[0076] According to a sixth aspect of the present invention, an electrowetting display device is provided, comprising the above-mentioned ink.

[0077] Description and Definition

[0078] In the present invention, unless otherwise specified, scientific and technical terms used herein have the meanings commonly understood by those skilled in the art. However, for a better understanding of the present invention, definitions of some terms are provided below. When the definitions of terms provided herein are inconsistent with the meanings commonly understood by those skilled in the art, the definitions and interpretations of the terms provided herein shall prevail.

[0079] The protective gas in the "protective atmosphere" herein includes at least one of an inert gas or nitrogen.

[0080] As used herein, "substituted or unsubstituted" means that a group may or may not be further substituted by one or more groups selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, aryloxy, benzyloxy, haloalkoxy, haloalkenyloxy, haloaryloxy, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, amino, alkylamino, dialkylamino, alkenylamino, alkynylamino, arylamino, diarylamino, phenylamino, diphenylamino, benzylamino, dibenzylamino, hydrazino, acyl, acylamino, diacylamino, acyloxy, heterocyclyl, heterocyclyloxy, heterocyclylamino, haloheterocyclyl, carboxyl ester, carboxyl, carboxylamide, thiol, alkylthio, benzylthio, acylthio, and phosphorus-containing groups.

[0081] "Alkyl" refers to a group derived from a branched or straight chain saturated aliphatic alkane with a specified number of carbon atoms by removing one hydrogen. 30 "Alkyl" means an alkyl group with a total carbon number of 1 to 30, including C1 to C 30 Straight chain alkyl, C1~C 30 Branched alkyl and C2~C 30 Cycloalkyl; for "C1~C20 The explanation of "substituted C1~C 30 "Alkyl" means C1~C 30 At least one H in the optional alkyl group is substituted by a group defined herein, and for "substituted C1-C 20 The explanation of "alkyl" is similar to this, except that the number of carbon atoms is different.

[0082] "Alkoxy" refers to an alkyl group as defined herein connected to another group through an oxygen atom, i.e. "alkyl-O-". 30 "Alkoxy" means an alkoxy group having a total carbon number of 1 to 30, including C1 to C 30 Straight chain alkoxy, C1~C 30 Branched alkoxy and C2~C 30 The cycloalkoxy group of C1-C 10 The explanation of "substituted C1~C 30 "Alkoxy" means C1~C 30 At least one H in the optional alkoxy group is substituted by a group defined herein, and for "substituted C1-C 10 The explanation is similar to this, except that the number of carbon atoms is different.

[0083] "Alkoxyphenyl" refers to a phenyl group substituted with an alkoxy group, such as "C6-C 30 "Alkoxyphenyl" refers to a phenyl group with 6 to 30 carbon atoms substituted with an alkoxy group. "Substituted C6~C 30 "Alkoxyphenyl" means C6~C 30 The alkoxyphenyl group optionally has at least one H on a carbon atom substituted by a corresponding group as defined herein.

[0084] "Alkylphenyl" refers to a phenyl group substituted with an alkyl group, such as "C6-C 30 "Alkylphenyl" refers to a phenyl group with 6 to 30 carbon atoms substituted with an alkyl group. "Substituted C6~C 30 "Alkylphenyl" means C6~C 30 The alkylphenyl group optionally has at least one H carbon atom substituted by a corresponding group as defined herein.

[0085] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0086] The present invention will be further described below with reference to the accompanying drawings and embodiments, in which:

[0087] Figure 1 This is a schematic structural diagram of an electrowetting display device according to embodiment 1 of the present invention;

[0088] Figure 2 This is the ultraviolet absorption spectrum of the n-decane solution of the blue dye in Example 1 of the present invention;

[0089] Figure 3 Calculation results of the molar absorption coefficient of the n-decane solution of the blue dye in Example 1 of the present invention are shown in FIG.

[0090] Figure 4 This is the ultraviolet absorption spectrum of the n-decane solution of the fuchsin dye according to Example 2 of the present invention;

[0091] Figure 5 Calculation results of the molar absorption coefficient of the n-decane solution of the fuchsin dye in Example 2 of the present invention are shown in FIG.

[0092] Figure 6 This is the ultraviolet absorption spectrum of the n-decane solution of the purple dye in Example 3 of the present invention;

[0093] Figure 7 Calculation results of the molar absorptivity of a n-decane solution of a purple dye in Example 3 of the present invention are shown in FIG.

[0094] Figure 8 This is a graph showing the light stability test results of the blue ink of Example 1 of the present invention;

[0095] Figure 9 This is a graph showing the light stability test results of magenta ink according to Example 2 of the present invention;

[0096] Figure 10 This is a graph showing the light stability test results of the purple ink of Example 3 of the present invention;

[0097] Figure 11 This is a microscope picture of an electrowetting device made using the ink of Example 1 of the present invention;

[0098] Figure 12 This is a response time curve diagram of the electrowetting device of Example 1 of the present invention when driven by a voltage of 30V;

[0099] Figure 13 This is a picture of the electrowetting display device according to Example 2 of the present invention;

[0100] Figure 14 This is a pixel grid switching image of the electrowetting display device according to Example 2 of the present invention;

[0101] Figure 15This is a response time curve diagram of the electrowetting display device according to Example 2 of the present invention when driven at a voltage of 30V;

[0102] Figure 16 This is a picture of the electrowetting display device according to Example 3 of the present invention;

[0103] Figure 17 This is a picture of the pixel grid switching of the electrowetting display device according to Example 3 of the present invention.

[0104] Description of reference numerals:

[0105] 1. Upper substrate; 2. Encapsulation frame; 3. Conductive lower substrate; 4. Lower substrate; 5. Hydrophobic insulating layer; 6. Pixel wall structure layer; 7. Ink; 8. Electrolyte solution. DETAILED DESCRIPTION

[0106] The following will clearly and completely describe the concept and technical effects of the present invention in conjunction with the embodiments to fully understand the purpose, features and effects of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0107] Unless otherwise specified, the temperature in the specific implementation manner is room temperature, that is, in the range of 20 to 30° C., and will not have a significant impact on the test results.

[0108] The experimental methods in the following examples, for which specific conditions are not specified, are generally performed in accordance with conventional conditions in the art or conditions recommended by the manufacturers; the raw materials and reagents used, unless otherwise specified, are all commercially available from conventional markets.

[0109] 1,4-Dihydroxyanthraquinone leuco: MacLean, CAS: 476-60-8;

[0110] 1,8-Dihydroxyanthraquinone leuco: MacLean, CAS: 117-10-2.

[0111] Example 1

[0112] This embodiment discloses an anthraquinone dye, the chemical formula of which is:

[0113]

[0114] The preparation process specifically includes: weighing 24.2 mg (0.1 mmol, 242.23 g / mol) of leuco form of 1,4-dihydroxyanthraquinone in a 50 mL double-necked reaction flask, adding 5 mL of ethylene glycol methyl ether and stirring to dissolve, weighing 1,3-dimethyladamantane methylamine (also known as 1,3-dimethyladamantane methylamine, 193.3 mg, 1 mmol, 0.2 mL) and adding it to the above solution, excluding air, introducing argon, heating to 120° C. under argon protection to react for 8 hours, introducing air and stirring and cooling to room temperature after the reaction is completed, continuing stirring for 4 hours, pouring the reaction solution into 200 mL of water, extracting with dichloromethane, and purifying by chromatography column to obtain 35 mg of blue dye (yield 60%).

[0115] The analytical data of the dye are as follows:

[0116] UV–Vis (n-decane): λmax(ε) = 648 nm.

[0117] Infrared: 2905, 2848cm -1 (C–H)adamantane, 1706 cm -1 (C=O),1598cm -1 (C=O)anthraquinone, 1516 cm -1 (N–H), 1452cm -1 (C–H), 1306 cm -1 (C–H), 810 cm -1 (C–H) aromatic out-of-plane deformation vibration, 721 cm -1 (C–H) aromatic out-of-plane deformation vibration.

[0118] 1H NMR (CDCl3) 600 Hz, 20°C: δ (ppm) = 8.39 (m, 2H), 7.67 (m, 2H), 7.29 (m, 2H), 1.70-2.04 (m, 13H, adamantane), 3.12 (d, 1H), 0.89 (m, 6H).

[0119] 13C NMR (400MHz, CDCl3): 185.2, 138.5, 133.4, 133.2, 127.0, 118.1, 110.7, 60.5, 51, 45.6, 43.8, 31.6, 30.5, 28.9, 20.4.

[0120] This embodiment discloses an ink, the preparation process of which includes: dissolving the dye prepared in this embodiment (35 mg) in 1 mL of n-decane to obtain a blue ink.

[0121] This embodiment discloses an electrowetting display device, including the ink of this embodiment. The structure and preparation method of the electrowetting display device refer to the electrowetting display structure and preparation method in the specific embodiment of CN104932097A, wherein the ink is the ink prepared in this embodiment. Specifically, Figure 1 As shown, the electrowetting display device in this embodiment includes an upper substrate 1, an encapsulating frame 2, and a lower substrate 4. The lower substrate 4 is composed of a conductive lower substrate 3, a hydrophobic insulating layer 5, and a pixel wall structure layer 6. The hydrophobic insulating layer 5 corresponds to the shape and position of the pixel grid 9 one-to-one and is arranged in a discrete lattice. Each hydrophobic insulating layer 5 is square, and the side length of the square is the same as the side length of the pixel grid 9, which is 200 μm. The spacing between two adjacent hydrophobic insulating layers 5 is slightly smaller than the width of the pixel wall 6, which is 15 μm. The spacing between two adjacent hydrophobic insulating layers is 10 μm, and the thickness of the hydrophobic insulating layer is 1 μm. The pixel wall structure layer 6 is precisely aligned with the hydrophobic insulating layer 5 and is located in the gaps of the hydrophobic insulating layer 5 lattice, completely covering the conductive lower substrate 3 in the gaps of the hydrophobic insulating layer 5. The hydrophobic insulating layer 5 and the pixel wall structure layer 6 form a continuous membrane structure, which provides insulation and protection for the conductive lower substrate 3.

[0122] Example 2

[0123] This embodiment discloses an anthraquinone dye, the chemical formula of which is:

[0124]

[0125] The preparation process specifically includes: weighing 24.2 mg (0.1 mmol, 242.23 g / mol) of leuco form of 1,8-dihydroxyanthraquinone in a 50 mL double-necked reaction flask, adding 5 mL of ethylene glycol methyl ether and stirring to dissolve, weighing 1,3-dimethyladamantamine (193.3 mg, 1 mmol, 0.2 mL) and adding it to the above solution, excluding air, passing argon, heating to 120° C. under argon protection to react for 8 hours, passing air, stirring and cooling to room temperature after the reaction is completed, continuing stirring for 4 hours, pouring the reaction solution into 200 mL of water, extracting with dichloromethane, and purifying by chromatography column to obtain 40 mg of magenta dye (yield 67%).

[0126] The analytical data of the dye are as follows:

[0127] UV–Vis (n-decane): λmax(ε)=520nm.

[0128] Infrared: 2905, 2 848cm -1 (C–H)adamantane, 1706 cm -1 (C=O),1598cm -1(C=O)anthraquinone, 1516 cm -1 (N–H), 1452cm -1 (C–H), 1306 cm -1 (C–H), 810 cm -1 (C–H),721cm -1 (C–H).

[0129] 1H NMR (CDCl3) 600 Hz, 20°C: δ (ppm) = 9.739 (s, 2H), 7.44-7.52 (m, 6H), 7.02 (d, 2H), 1.70-2.04 (m, 13H, adamantane), 3.21 (d, 2H), 0.89 (m, 6H).

[0130] 13CNMR(400MHz, CDCl3):185.1,149.7,137.2,134.5,133.2,117.1,115.8,109.7,60.6,51,50.6,44.3,41.5,45.4,31.6,30.4,28.7,20.6.

[0131] This embodiment discloses an ink, the preparation process of which includes: dissolving the dye prepared in this embodiment (40 mg) in 1 mL of n-decane to obtain a magenta ink.

[0132] This embodiment discloses an electrowetting display device, which differs from the electrowetting display device of embodiment 1 in that the ink of embodiment 1 is replaced by the ink of this embodiment.

[0133] Example 3

[0134] This embodiment discloses an anthraquinone dye, the chemical formula of which is:

[0135]

[0136] The preparation reaction process includes:

[0137]

[0138] The preparation process specifically includes:

[0139] (I) Weigh 5 g of 1,4-dihydroxyanthraquinone, 0.1 g of sodium dodecyl sulfate, and 100 mL of water into a 200 mL reaction flask, add 5 g of Na2CO3 and 5 g of Na2S2O4, heat to 80°C, and react for 0.5 h. When the reaction liquid turns completely yellow, if the reaction is not complete, continue to add alkali (Na2CO3) and hydrosulfite (Na2S2O4). After the reaction is completed, filter and dry in a vacuum at 60°C to obtain compound 1 (yield 95%).

[0140] (II) In a three-necked flask with mechanical stirring, 50 mL of isopropanol, 2.42 g (242 g / mol, 0.01 mol) of compound 1, 3.2 g (128 g / mol, 0.025 mol) of 2-ethylhexanal, and 0.44 g (145 g / mol, 3 mmol) of piperidinium acetate were added. Nitrogen was introduced, the temperature was raised to 80°C, and the reaction was continued for 20 h. After the reaction, the reaction solution was cooled to -20°C, 200 mL of industrial ethanol (95% purity) was added, and the mixture was stirred. The mixture was further cooled for 3 h and filtered to obtain compound 3 (yield 88.6%).

[0141] (III) 0.352 g of compound 3 (352 g / mol, 1 mmol) was dissolved in 15 mL of DMF. A nitrogen atmosphere was introduced. 1,3-Dimethyladamantamine (193.3 mg, 1 mmol, 0.2 mL) was added all at once. The mixture was heated to 120°C and refluxed for 24 h. The mixture was cooled to room temperature and then cooled to below 10°C. The reaction mixture was poured into 100 mL of water and filtered to obtain a purple dye (compound 4, 30% yield).

[0142] The analytical data of the dye are as follows:

[0143] UV–Vis (n-decane): λmax(ε)=599nm.

[0144] Infrared: 2905, 2848cm -1 (C–H)adamantane, 1706 cm -1 (C=O),1598cm -1 (C=O)anthraquinone, 1516 cm -1 (N–H), 1452cm -1 (C–H), 1306 cm -1 (C–H), 810 cm -1 (C–H),721cm -1 (C–H), 1350 cm -1 (O–H).

[0145] 1H NMR (CDCl3) 600 Hz, 20°C: δ (ppm) = 14.35 (s, 1H), 10.478 (s, 1H), 8.31 (d, 2H), 7.73 (d, 2H), 7.00 (s, 1H), 1.70-2.04 (m, 13H, adamantane), 3.30 (d, 2H), 0.89 (m, 24H).

[0146] 13CNMR (400MHz, CDCl3): 185.8, 182.0, 141.7, 121.7, 108.0, 133.2, 132.5, 132.2, 118.6, 126.8 ,132.2,109.7,60.8,51,50.4,47.3,41.5,41.8,44.5,45.5,40.6,31.5,30.3,21.4,20.6,28.9.

[0147] This embodiment discloses an ink, the preparation process of which includes: dissolving the dye prepared in this embodiment (50 mg) in 1 mL of n-decane to obtain a purple ink.

[0148] This embodiment discloses an electrowetting display device, which differs from the electrowetting display device of embodiment 1 in that the ink of embodiment 1 is replaced by the ink of this embodiment.

[0149] Example 4

[0150] This embodiment discloses an anthraquinone dye, the chemical formula of which is:

[0151]

[0152] The preparation process specifically includes: weighing 24.2 mg (0.1 mmol, 242.23 g / mol) of leuco form of 1,4-dihydroxyanthraquinone in a 50 mL double-necked reaction flask, adding 5 mL of ethylene glycol methyl ether and stirring to dissolve, weighing 1,3-dimethylamantadine (207.4 mg, 1 mmol) and adding it to the above solution, excluding air, passing argon, heating to 120° C. under argon protection to react for 8 hours, passing air and stirring and cooling to room temperature after the reaction is completed, continuing stirring for 4 hours, pouring the reaction solution into 200 mL of water, extracting with dichloromethane, and purifying by chromatography to obtain 50 mg of blue dye (yield 85%).

[0153] The analytical data of the dye are as follows:

[0154] UV–Vis (n-decane): λmax(ε) = 649 nm.

[0155] Infrared: 2905, 2 848cm -1 (C–H)adamantane, 1706 cm -1 (C=O),1598cm -1 (C=O)anthraquinone, 1516 cm -1 (N–H), 1452cm -1 (C–H), 1306 cm -1 (C–H), 810 cm -1 (C–H),721cm -1(C–H).

[0156] 1H NMR (CDCl3) 600 Hz, 20°C: δ (ppm) = 8.30 (m, 2H), 7.76 (m, 2H), 7.30 (m, 2H), 1.70-2.04 (m, 13H, adamantane), 3.32 (m, 4H), 1.38 (m, 4H), 0.89 (m, 6H).

[0157] 13CNMR(400MHz, CDCl3):185.4,138.1,133.3,131.9,117.6,126.5,110.5,46.9,50.3,49.7,44.2,44.1,40.2,38.1,31.3,30.2,28.6,16.5.

[0158] This embodiment discloses an ink, the preparation process of which includes: dissolving the dye prepared in this embodiment (50 mg) in 1 mL of n-decane to obtain a royal blue ink.

[0159] This embodiment discloses an electrowetting display device, which differs from the electrowetting display device of embodiment 1 in that the ink of embodiment 1 is replaced by the ink of this embodiment.

[0160] Test example

[0161] This test example tests the performance of the ink and electrowetting display device obtained in the example, specifically including:

[0162] 1) Calculation of ultraviolet absorption spectra and molar absorption coefficients of anthraquinone dyes:

[0163] The blue dye prepared in Example 1 was mixed with n-decane in different amounts to prepare blue dye n-decane solutions with different dye concentrations (0.358 mol / L, 1.016 mol / L, 2.291 mol / L). Figure 2-3 The following are the UV absorption spectrum and molar absorptivity calculation results of blue dye n-decane solution. The test results show that the blue dye n-decane solution has maximum absorption peaks at 600nm and 648nm, and the corresponding maximum molar absorptivity is 16971cm -1 .(mol / L) -1 .

[0164] The magenta dye prepared in Example 2 was mixed with n-decane to prepare magenta dye n-decane solutions with different dye concentrations. Figure 4-5 They are the ultraviolet absorption spectrum of magenta dye n-decane solution and the calculation results of molar absorption coefficient ( Figure 4The concentration of the dye in the n-decane solution is 0.62 mol / L). The test results show that the magenta dye n-decane solution has a maximum absorption peak at 520 nm, and the corresponding maximum molar absorption coefficient is: 11567 cm -1 .(mol / L) -1 .

[0165] The purple dye prepared in Example 3 was mixed with n-decane in different amounts to prepare purple dye n-decane solutions with different dye concentrations (0.179 mol / L, 0.451 mol / L, 1.165 mol / L). Figure 6-7 The following are the UV absorption spectrum and molar absorptivity calculation results of purple dye n-decane solution. The test results show that the purple dye n-decane solution has a maximum absorption peak at 599nm, and the corresponding maximum molar absorptivity is 7811cm -1 .(mol / L) -1 .

[0166] 2) Light stability test: The test method includes: after the electrowetting display devices of each embodiment are subjected to accelerated aging in a xenon lamp weatherproof chamber (50°C, 364nm, 0.55W / h) to simulate sunlight for 100 hours, the change in the ink absorption spectrum in each device is tested before and after to obtain the light stability of the ink material.

[0167] Figure 8 The blue ink light stability test result of Example 1 is shown in FIG. It can be seen that after 100 hours of testing, the change in ink absorbance is ΔA (λ＝648nm) =0.4% (dye degradation rate), the test results show that the light stability of the ink material is very excellent.

[0168] Figure 9 This is a graph showing the light stability test results of the magenta ink of Example 2. It can be seen that after 100 hours of light aging, the dye degradation rate is 2%.

[0169] Figure 10 This is a graph showing the light stability test results of the purple ink of Example 3. It can be seen that after 100 hours of light aging, the degradation rate of the dye is 1%.

[0170] 3) For the blue electrowetting display device in Example 1, the device performance test results are as follows:

[0171] Figure 11 These are microscope pictures of an electrowetting display device made using the ink of Example 1, where (a) shows the pixel grid in the closed state, and (b) shows the pixel grid in the open state. At a voltage of 30V, the aperture ratio is 65%.

[0172] Figure 12This is a response time curve of the electrowetting device made with the ink of Example 1 under a driving voltage of 30V. It can be seen that the response speed is: 22ms.

[0173] 4) For the electrowetting display device in Example 2 (magenta electrowetting electronic paper display device), the device picture is as follows Figure 13 As shown, the test device performance results are as follows:

[0174] Figure 14 This is a picture of the pixel grid switching of an electrowetting display device.

[0175] Figure 15 This is the response time curve of the electrowetting display device when driven by a voltage of 30V. It can be seen that the response speed is: 23ms.

[0176] 5) For the electrowetting display device (purple electrowetting electronic paper display device) in Example 3, the device picture is as follows Figure 16 As shown, the test device performance results are as follows:

[0177] Figure 17 This is a picture of the pixel grid opening of an electrowetting display device, with a driving voltage of 30V and an aperture ratio of 67%.

[0178] Unless otherwise specified, the term "about" herein means that the error is within a range of ±2%. For example, "about 100" is actually 100 ± 2% × 100. "Normal temperature" or "room temperature" herein, unless otherwise specified, means approximately 20-30°C. "Between" herein includes the number itself; for example, "between 2 and 3" includes both the endpoints 2 and 3.

[0179] While the embodiments of the present invention have been described in detail above with reference to the accompanying drawings, the present invention is not limited to the embodiments described above. Various modifications may be made within the scope of knowledge possessed by a person skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof may be combined with one another unless there is a conflict.

Claims

1. An anthraquinone dye, characterized in that: Including compounds represented by formula (I): Wherein, W1-W8 are independently selected from H, OH, substituted or unsubstituted C1-C 30 An alkyl group or an adamantyl-containing group; at least one of W1 to W8 is an adamantyl-containing group.

2. The anthraquinone dye according to claim 1, characterized in that W1, W4, W5, and W8 are independently selected from H, OH, or a group containing an adamantyl group; W2, W3, W6, and W7 are independently selected from H, substituted or unsubstituted C1-C 30 An alkyl group or an adamantyl group-containing group.

3. The anthraquinone dye according to claim 1, characterized in that The adamantyl-containing groups include the group At least one of; in: R 1～2 Each occurrence is independently selected from NH, NHC n H 2n ,O,C n H 2n O, alkylenephenol; wherein n is an integer, and each occurrence of n is independently selected from 1 to 30; R 3～6 Each occurrence is independently selected from substituted or unsubstituted C1 to C 30 Alkyl, substituted or unsubstituted C1~C 30 Alkoxyphenyl, substituted or unsubstituted C6~C 30 of alkylphenyl.

4. The anthraquinone dye according to claim 1, characterized in that The compound represented by formula (I) includes at least one of the compounds represented by formula (I-1), (I-2) or (I-3): Wherein the group W2 is selected from Substituted or unsubstituted C1~C 30 an alkyl group, a dimethyladamantyl group substituted with an amino group, or a dimethyladamantyl group substituted with an alkoxy group; R 1～2 Each occurrence is independently selected from NH, NHC n H 2n ,O,C n H 2n O, alkylenephenol; wherein n is an integer, and each occurrence of n is independently selected from 1 to 30; R 3～6 Each occurrence is independently selected from substituted or unsubstituted C1 to C 30 Alkyl, substituted or unsubstituted C6~C 30 Alkoxyphenyl, substituted or unsubstituted C6~C 30 of alkylphenyl.

5. The anthraquinone dye according to claim 4, characterized in that The compound represented by formula (I-2) includes at least one of the compounds represented by formula (I-2-1) or formula (I-2-2): Wherein, R7 is selected from substituted or unsubstituted C1~C 15 of alkyl.

6. A method for preparing anthraquinone dyes according to claim 1, characterized in that: The method comprises the following steps: reacting dihydroxyanthraquinone substances with adamantane amines to obtain the anthraquinone dye.

7. The method for preparing anthraquinone dyes according to claim 6, characterized in that: The anthraquinone dye includes at least one of the compounds represented by formula (I-1), (I-2) or (I-3); And / or, the dihydroxyanthraquinone substance includes at least one of 1,4-dihydroxyanthraquinone, 1,4-dihydroxyanthraquinone leuco form, 1,8-dihydroxyanthraquinone or 1,8-dihydroxyanthraquinone leuco form; and / or, the adamantanes include at least one of dimethylamantadine, dimethylrimantadine or dimethylamantadine; And / or, the molar ratio of the dihydroxyanthraquinone substance to the adamantane amine is 1:(0.5-20).

8. A method for preparing anthraquinone dyes according to claim 1, characterized in that: The steps include: S1, taking 1,4-dihydroxyanthraquinone or leuco form of 1,4-dihydroxyanthraquinone, mixing it with a surfactant, an alkaline substance, and Na2S2O4, and reacting them to obtain compound A; S2, reacting compound A with aldehydes and piperidinium acetate to obtain compound B; S3, reacting compound B with adamantane amine to obtain an anthraquinone dye; Wherein, the anthraquinone dye is a compound represented by formula (I-2-2); compounds A and B are represented by the following formula:

9. An ink, characterized in that: The anthraquinone dye comprises the anthraquinone dye according to any one of claims 1 to 5 or the anthraquinone dye prepared by the preparation method according to any one of claims 6 to 8.

10. An electrowetting display device, characterized in that: The invention comprises the ink according to claim 9.

Images