JP5564289B2 - Electrochromic composition - Google Patents

Description

  The present invention relates to an electrochromic (hereinafter referred to as “EC”) composition that decolorizes by an electrochemical reversible reaction (electrolytic oxidation-reduction reaction), and an EC device fabricated using the EC composition.

  In recent years, attempts have been made to replace a conventional paper medium display with an electronic display medium represented by electronic paper from the viewpoint of rapidly digitizing information and environmental problems. Unlike conventional electronic display media, electronic paper is a reflective display system similar to paper media. Therefore, electronic paper is a display element that consumes low power, has little discomfort in visibility, and is friendly to both the environment and people. Since the base material used for the electronic paper can be a base material that is inexpensive and excellent in flexibility, there is an advantage that mass production by a roll-to-roll method is possible and the cost can be suppressed. In addition, since a lightweight base material can be used, there is an advantage that it is lightweight and excellent in portability, so that it can be used for an inexpensive small display medium such as an electronic book represented by an electronic book or an electronic tag for information management in distribution. Expected to be used.

  These candidate technologies include a method for performing decoloration by an electrochemical redox reaction (EC method), a method for performing decoloration by moving colored particles between electrodes by electrophoresis (electrophoresis method), and two charged colors Such as a method of moving the electron powder particles in the gas phase by applying a voltage (QR-LPD method), a method of decoloring by rotating dichroic particles in an electric field (twist ball method), etc. Are known.

Among the above-described technologies, an EC element using decolorization by an electrochemical redox reaction is one of the powerful reflective display elements excellent in low power consumption and high-speed response. Such an EC element generally has a structure in which a transparent electrode is formed on an opposing substrate, at least one of which is transparent, a color developing layer is formed on the transparent electrode using an EC compound, and an electrolyte is sandwiched between the substrates. It is. Then, by applying a voltage between the base materials, an electrochemical redox reaction is generated, and the EC compound in the color forming layer is decolored to change the optical reflection characteristics.
Furthermore, as an EC element having a simple structure, an EC element in which an EC composition containing a compound that decolorizes between electrodes is sealed is known (see, for example, Patent Documents 1 to 3). These display elements have an advantage that they have a simple structure and can be manufactured at a low cost as compared with general EC elements.

Japanese Patent No. 3918961 JP-A-54-99787 JP 2005-338356 A

  An EC element having a structure in which an EC composition containing a compound exhibiting decoloration due to an electrochemical redox reaction is sandwiched between electrodes, a spacer is formed between the substrates with a photosensitive resin or the like, and a gap between the substrates is formed. There is a problem that the manufacturing process becomes complicated. In addition, when using a substrate such as a PET film having flexibility, the gap between the substrates may change due to pressing or the like, and the color density may change, or the substrates may come into contact with each other and may be damaged due to a short circuit. It was.

  The present invention has been made in view of the above-described problems, and an object of the present invention is to provide an EC composition capable of maintaining a gap between electrodes only by forming a pattern by a coating method and without separately forming a spacer. An object of the present invention is to provide an EC device using this composition.

In order to achieve the above object, according to one aspect of the present invention, a compound exhibiting a decoloration associated with an electrochemical redox reaction, a supporting electrolyte, a solvent, a thixotropic agent, and insulating particles are provided. EC compositions comprising are provided.
This makes it possible to keep the gap between the electrodes constant by simply applying the EC composition without forming a separate spacer.

Moreover, according to one form of this invention, the EC composition which further contains a high molecular compound in the said EC composition is provided. In a preferred embodiment, an EC composition comprising cellulose or a derivative thereof is provided.
Thereby, an unstable viscosity can be stabilized only by imparting a structural viscosity with the above-described thixotropic agent, and printability by various coating methods is improved.

Further, according to one aspect of the present invention, the EC composition further comprises a compound having a smaller absolute value of oxidation overvoltage and reduction overvoltage than a compound exhibiting decoloration with the electrochemical redox reaction, and / or An EC composition comprising the redox pair is provided.
Thereby, there is no fear of deterioration due to electrolysis of the compound exhibiting decoloration associated with the electrochemical redox reaction, and the compound exhibiting decolorization associated with the electrochemical redox reaction is directly oxidized / reduced. Decoloration at a lower voltage is possible.

Moreover, according to one form of this invention, EC element characterized by having the above-mentioned EC composition is provided.
As a result, as compared with an EC element using a conventional EC composition, it is possible to manufacture in a simple process, and productivity is greatly improved.

  According to the EC composition of the present invention, since the gap between the electrodes can be kept constant without forming a separate spacer, the EC element can be manufactured by a simple process compared to the conventional EC composition. Fabrication is possible.

It is a schematic sectional drawing which shows EC element in one form of this invention.

  In order to solve the above problems, the inventors of the present invention have studied an EC composition exhibiting decoloration by an electrochemical redox reaction. As a result, a thixotropic agent, insulating particles, and It has been found that by premixing, the effect of the thixotropic agent prevents sedimentation of the blended insulating particles and further suppresses the movement of the insulating particles in the EC element. In addition, the gap between the electrodes can be maintained by blending the insulating particles, and the gap between the electrodes can be kept constant only by applying the EC composition without forming a separate spacer. As a result, it has been found that an EC device can be produced by a simple manufacturing process as compared with a conventional EC composition, and the present invention has been completed.

  The EC composition according to the present invention comprises a compound that exhibits decoloration in association with an electrochemical redox reaction (hereinafter referred to as “decoloring agent”), a supporting electrolyte, a solvent, a thixotropic agent, an insulating material. And particles.

Further, in order to control the viscosity to a property suitable for various printing methods, it is preferable to add a polymer compound as another component. Further, in order to prevent degradation of the decoloring agent due to electrolysis, a compound having an oxidation overvoltage and reduction overvoltage smaller than the absolute values of the oxidation overvoltage and reduction overvoltage of the decolorization agent (hereinafter referred to as “compound (1)”). ), And a compound (hereinafter referred to as “compound (2)”) which is a redox pair thereof.
In addition, the oxidation overvoltage and the reduction overvoltage in this specification refer to the voltage required for the actual oxidation reaction and reduction reaction of a compound to occur.

Hereinafter, each component of the EC composition according to the present invention will be described in detail.
The decoloring agent in the present embodiment is not particularly limited as long as it is a compound that can be reversibly decolored or colored by an electrochemical redox reaction, and is an oxidation coloring type that develops color in an oxidized state, and develops color in a reduced state. Any of the reduction coloring types can be used.

  Examples of such decolorizing agents include polynuclear metal complexes such as tungsten oxide, Prussian blue, nickel hydroxide oxide, metal phthalocyanine coordination polymers, 3,3-bis (p-dimethylaminophenyl) -6-dimethyl. Triallylmethane compounds such as aminophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide Diphenylmethane compounds such as 4,4'-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenyl-leucooramine, N-2,4,5-trichlorophenylleucooramine, 7-dimethylamino-3- Chlorofluorane, 7-dimethylamino-3-chloro-2-methylfluorane, 2-phenyl Fluorane compounds such as amino-3-methyl-6- (N-ethyl-Np-tolylaminofluorane, thiazine compounds such as benzoyl leucomethylene blue and p-nitrobenzyl leucomethylene blue, 3-methyl-spiro-dinaphthopyran And spiro compounds such as 3-ethyl-spiro-dinaphthopyran, 3-propyl-spiro-dinaphthopyran, and 3-propyl-spiro-dibenzopyran.

The supporting electrolyte is not particularly limited as long as it is used for facilitating current flow in the EC composition, is soluble in a polar solvent, and exhibits conductivity in a form dissolved in the solvent.
Examples of such a supporting electrolyte include halides of alkali metals such as lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, Lithium perchlorate, sodium perchlorate, potassium perchlorate, rubidium perchlorate, alkali metal perchlorates such as cesium perchlorate, alkali metal nitrates such as lithium nitrate, alkali metal such as lithium sulfate Tetrafluoroborate of alkali metals such as sulfate and lithium borofluoride, and quaternary ammonium such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetraethylammonium borofluoride, tetrabutylammonium borofluoride, tetrabutylammonium perchlorate salt Spiro - (1,1 ') - the quaternary ammonium salts having bipyrrolidinium tetrafluoroborate spiro type like cation.

  The thixotropic agent has an effect of suppressing sedimentation of the insulating particles, and when the thixotropic agent is not added, the sedimentation of the insulating particles is likely to occur. Another effect is that structural viscosity is imparted to the EC composition, making it possible to increase the viscosity and increase the TI (thixotropic index) without degrading the decoloring performance of the EC composition. Various coating methods can be selected by increasing the viscosity of the composition. Further, since the liquid composition is increased by increasing the TI, the fluidity is lost as if it were a solid in a stationary state, so that the pattern shape formed by coating can be maintained. Furthermore, an EC element manufactured using this EC composition can prevent leakage of the EC composition for the reasons described above.

  The thixotropic agent is not particularly limited as long as it has a thixotropic property. For example, organic thixotropic agents include animal and plant thixotropic agents such as castor oil, hydrogenated castor oil, beeswax and carnauba wax, amide thixotropic agents such as stearic acid amide and hydroxystearic acid ethylenebisamide, modified urea, urea Examples include urea thixotropic agents such as modified urethane.

  Examples of the inorganic thixotropic agent include fine silica and sukumite. These thixotropic agents can be used alone or in combination of two or more. Among these, an organic thixotropic agent is preferable because it can be easily dissolved in a solvent and has transparency. Furthermore, among these, a thixotropic agent having a urea structure excellent in transparency is preferable.

  The TI value of the EC composition in which the above-mentioned thixotropic agent is dispersed is preferably 1.3 to 6.0 in consideration of handling properties during printing and coating. The TI value is a value calculated by calculation based on the cone plate viscosity described later.

  The insulating particles are not particularly limited as long as the gap between the electrodes can be maintained at a constant interval, and inorganic fillers, organic fillers, and mixtures thereof can be used. Examples of inorganic fillers include spherical silica, spherical alumina, spherical glass, glass obtained by cutting a monofilament of glass very short, and a micro rod. Examples of organic fillers include PMMA beads, PAN beads, polyurethane beads, and the like. On the other hand, when conductive particles are used as a spacer, electricity flows through the arranged particles, which is not preferable because the electrodes are short-circuited. Moreover, a transparent thing is preferable so that EC composition may not be colored.

  The average particle size of such insulating particles is preferably 5 to 100 μm. When the average particle diameter is smaller than 5 μm, the gap between the electrodes is not sufficient, and there is a possibility that the color density is lowered or the electrodes come into contact with each other at the time of pressing and short-circuit. In addition, when the size is larger than 100 μm, the distance between the electrodes is too far, and power consumption for decoloring increases, or the color where the insulating particles exist is displayed as if the color is lost. Will occur. More preferably, it is 10-100 micrometers.

  Furthermore, the ratio of such insulating particles in the composition is preferably 0.1 to 10% by mass. If it is lower than 0.1% by mass, the number of insulating particles is too small, and it becomes difficult to keep the gap between the electrodes constant. On the other hand, when the content is higher than 10% by mass, the ratio of the color erasing agent is lowered, and the color density is lowered.

A solvent will not be specifically limited if it has polarity, For example, a protic polar solvent, an aprotic polar solvent, and a mixture thereof can be used.
Examples of the protic polar solvent include alcohols and glycol ethers. Examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, t-butyl alcohol, pentyl alcohol, hexyl alcohol, cyclohexanol, and benzyl alcohol. , Ethylene glycol, propylene glycol, glycerin and the like. Among these, aliphatic alcohols having 1 to 4 carbon atoms are particularly preferable. Examples of glycol ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and the like. Among these, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and dipropylene glycol monomethyl ether are preferable.

  Examples of the aprotic polar solvent include carbonates such as propylene carbonate and dimethyl carbonate, cyclic amides such as N-methylpyrrolidone, amides such as dimethylacetamide and dimethylformamide, nitriles such as acetonitrile, butyronitrile, and glutaronitrile. , Ethers such as dimethoxyethane, lactones such as γ-butyrolactone, methyl acetate, ethyl acetate, methyl propionate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Examples include esters.

  In addition, in order to prevent degradation due to the electrochemical redox reaction of the decolorizer, the absolute value of the oxidation overvoltage and the reduction overvoltage is smaller than the absolute value of the oxidation overvoltage and reduction overvoltage of the decolorizer and the electrochemical redox reaction A compound (compound (1)) that exchanges protons can be contained.

  As a result, the redox reaction is performed at a voltage lower than the absolute value of the oxidation overvoltage and reduction overvoltage of the decolorizer, and the decoloration of the decolorizer is indirectly performed with the exchange of protons at that time. There is no risk of the electrochromic agent being electrolyzed, and decoloration can be performed at a lower voltage than when the decolorizing agent is directly oxidized and reduced.

  Such a compound (1) is not particularly limited as long as it has an oxidation overvoltage and a reduction overvoltage lower than the absolute values of the oxidation overvoltage and reduction overvoltage of the decolorizer as described above and can exchange protons. Not, for example, hydroquinone, chlorohydroquinone, methylhydroquinone, t-butyl-hydroquinone, 2,5-di-t-butyl-hydroquinone, 1-naphthol, 4,4′-biphenol, 4,4′-dihydroxydiphenyl ether, etc. And amine compounds such as diethylamine and t-butylamine.

  The absolute value of the oxidation overvoltage and reduction overvoltage of the compound (1) is preferably 0.1 V or more smaller than the absolute value of the oxidation overvoltage and reduction overvoltage of the decolorizer. More preferably, it is 0.3 V or more.

  Furthermore, by containing the compound (compound (2)) that acts as a redox pair for the compound (1), the oxidation-reduction reaction of the compound (1) can be promoted, and stable proton exchange can be performed. The redox pair for compound (1) is not particularly limited. For example, when compound (1) undergoes an oxidation reaction at the anode, compound (2) undergoes a reduction reaction at the cathode. It is preferable that

  Examples of such compound (2) include 1,4-benzoquinone, 1,4-naphthoquinone, p-toluquinone, methylbenzoquinone, t-butyl-1,4-benzoquinone, and 2,5-di-t-butyl. And quinone compounds such as -1,4-benzoquinone.

  In the case of forming a colored layer instead of being transparent at the time of decoloring the decoloring agent, a coloring agent can be added as necessary.

  Such a colorant is not particularly limited as long as it colors the EC composition layer, and examples thereof include organic pigments, inorganic pigments, dyes, metal powders, and colored glass. These colorants must have a smaller particle size than the insulating particles to be added. When a colorant having a particle size larger than that of the insulating particles is used, the colorant acts as a gap and the dimensional stability is impaired.

  Examples of organic pigments include azo pigments, polycondensed azo pigments, metal complex azo pigments, flavanthrone pigments, benzimidazolone pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, anthrapyridine pigments. And pyranthrone pigments, dioxazine pigments, perylene pigments, perinone pigments, isoindolinone pigments, quinophthalone pigments, thioindigo pigments, and indanthrene pigments.

  Examples of inorganic pigments include zinc white, titanium oxide, zinc oxide, zirconium oxide, antimony white, carbon black, iron black, titanium carbide, Bengala, mapico yellow, red lead, cadmium yellow, zinc sulfide, lithopone, barium sulfide, selenium. Examples thereof include cadmium fluoride, barium sulfate, lead lead chromate sulfate, barium calcium carbonate, lead white, and alumina white. Among these, from the viewpoint of visibility, black display is preferable on a white background, and titanium oxide is preferable as the white particle pigment.

Examples of the dye include nigrosine dyes, phthalocyanine dyes, azo dyes, anthraquinone dyes, quinophthalone dyes, and methine dyes.
Further, if necessary, known thickeners, antifoaming agents, leveling agents, coupling agents, flame retardant aids and the like can be used.

  Moreover, a high molecular compound can be mix | blended in order to improve the printability of a composition. The polymer compound is added to impart viscosity to the EC composition, and the unstable viscosity can be stabilized only by imparting the structural viscosity with the above-described thixotropic agent. Printability is improved.

  Such a polymer compound is not particularly limited as long as it is soluble in the above-described solvent, but if a functional group that acts as an oxidizing agent and a reducing agent is present, the decoloring agent is stationary. Since there is a possibility of color development in a state, a product having no functional group acting as an oxidizing agent and a reducing agent is preferable. In addition, in order to perform the oxidation-reduction reaction in the composition quickly, it is preferable that the ratio of the polymer compound in the composition is low, so that the viscosity of the composition can be increased with a small amount of 10,000 or more. Is preferred.

  Examples of such a high molecular compound include acrylic resin, acrylic-styrene resin, polyvinylidene fluoride resin, polyester resin, polyvinyl alcohol, polyether sulfone resin, polyurethane resin, cellulose and derivatives thereof, starch containing amylose and amylopectin. Etc. Among these, cellulose and its derivatives are preferable because of the high viscosity increase rate per blending amount.

  These polymer compounds can be used alone or in combination of two or more. In addition, as described above, in order to quickly perform the oxidation-reduction reaction in the composition, since the ratio of the polymer compound in the composition is preferably low, the weight ratio of the polymer compound in the composition is 20% or less. Is preferred. More preferably, it is 10% or less.

  In addition, the cone plate viscosity of the EC composition in which the polymer compound is dissolved is preferably 50 to 1000 dPa · Sec at 5 rpm in consideration of decoloring performance and handling / productivity during printing / coating. More preferably, it is 30-500 dPa * Sec. When the viscosity is 50 dPa · Sec or less, there are problems such as poor handling and a coating method limited to a dispenser or the like. On the other hand, when the viscosity is 1000 dPa · Sec or more, coating becomes difficult. The cone plate viscosity in the present invention is a viscosity obtained from a stress generated by rotating a cone with a sample sandwiched between a conical cone and a lithographic plate with a heater.

The basic configuration of one embodiment of the EC element according to the present invention will be specifically described with reference to FIG.
As shown in FIG. 1, an EC element 10 according to this embodiment includes an EC composition 5 according to the present invention between two substrates 7 and 8 each having electrodes 2 and 3 on electrode bases 1 and 4, respectively. It is obtained by arranging and bonding and sealing two substrates through the sealant 6. Here, any one of the electrode base materials 1 and 4 needs to be transparent, and the electrode corresponding to the electrode base material which is transparent also needs to be transparent. For example, when the electrode substrate 1 is transparent, a transparent electrode is used for the electrode 2. Further, all of the electrode base materials 1 and 4 and the electrodes 2 and 3 may be transparent. In this case, a transmissive display element is obtained.

  In addition, if necessary, the color erasing agent can be applied to the colorant color background by providing a means for color display on the lower part of the electrode or between the electrodes in order to display the display device in a colorless and transparent manner. Thus, a reflective display element capable of color display is provided. For example, when a white colorant is used, an EC element containing a black color-decoloring agent is a display element capable of displaying black on a white background.

  The electrode base materials 1 and 4 are not particularly limited as long as the electrodes 2 and 3 can be installed. Generally, it is a glass or a polymer film, and any of them can be used, but a polymer film is more desirable in consideration of the ability to impart softness to the display element.

Since the electrodes 2 and 3 need only be observable from one side in normal display recording applications as described above, one of the electrodes 2 and 3 may be transparent. For example, the electrode 2 may be transparent. For example, the electrode 3 may be opaque.
As a transparent electrode, well-known transparent electrodes, such as indium dope tin oxide (ITO), antimony dope tin oxide (ATO), fluorine dope tin oxide (FTO), aluminum dope zinc oxide (AZO), can be used, for example.

  The transparency of the transparent electrode is preferably higher because the dispersion system is seen through the transparent electrode when the display is observed, and the transmittance is preferably 75% or more. More preferably, it is 80% or more. The resistance value of the electrode is preferably smaller and is preferably 100Ω / □ or less. More preferably, it is 50 Ω / □ or less.

  As an electrode when the electrode facing the transparent electrode does not need to be transparent, electrochemically stable metals such as gold, silver, platinum, cobalt, palladium, and the like can be used.

  Further, one or both of the electrodes 2 and 3 may be divided and etched in a matrix shape such as a band shape or a dot shape, or a segment shape. These strips or dots are combined to form a predetermined shape such as letters, numbers, images, etc., and a voltage is applied to these electrodes simultaneously, or a voltage is applied by dividing by scanning, so that a still image or a moving image Can be displayed.

  Since the sealing agent 6 is disposed between the electrodes, it is not particularly limited as long as it is an insulating substance. Moreover, since the thickness gives the thickness which arrange | positions EC composition, it is determined by the white hiding property at the time of color display. However, since the power consumption increases when the thickness of the sealant 6 is thick, it is desired that the sealant 6 be thinner, for example, 500 μm or less. More preferably, it is 100 μm or less. Furthermore, it is preferable that the thickness of the sealing agent 6 is about the same as the maximum particle size of the insulating particles blended in the composition of the EC composition of the present embodiment. The display element according to the present invention can be obtained by bonding the sealant 6 to the electrode with an adhesive or the like. Furthermore, it is more preferable that the sealing agent 6 itself has a function as an adhesive that bonds electrodes together, because the manufacturing process can be shortened.

[Preparation of EC composition]
<Composition Example 1>
S-205 (Yamada Chemical Industries leuco dye: 2'-anilino-6 '-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] 5 1 part of tetrabutylammonium bromide, 1 part of hydroquinone, 1 part of 1,4-benzoquinone, 1 part of KS-66 (defoaming and leveling agent manufactured by Shin-Etsu Silicone), 11 parts of cellulose acetate propionate The mixture was thoroughly stirred and dissolved in 89 parts of rumonomethyl ether, and further 10 parts of BYK-410 (a thixotropic agent manufactured by BYK Japan), dimic beads UCN-5150D (urethane beads manufactured by Dainichi Seika Kogyo Co., Ltd .: average particle size 14 EC composition 1 was obtained by adding 3 parts with stirring and then allowing to stand for 24 hours.

<Composition Example 2>
S-205 (Yamada Chemical Industries leuco dye: 2'-anilino-6 '-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] 5 1 part of tetrabutylammonium bromide, 1 part of hydroquinone, 1 part of 1,4-benzoquinone, 1 part of KS-66 (defoaming and leveling agent manufactured by Shin-Etsu Silicone), 11 parts of cellulose acetate propionate The mixture was thoroughly stirred and dissolved in 89 parts of rumonomethyl ether, and further 10 parts of BYK-410 (a thixotropic agent manufactured by BYK Japan), dimic beads UCN-5250D (urethane beads manufactured by Dainichi Seika Kogyo Co., Ltd .: average particle size 27 .3 μm) 3 parts was added with stirring, and then allowed to stand for 24 hours to obtain EC composition 2.

<Composition Example 3>
S-205 (Yamada Chemical Industries leuco dye: 2'-anilino-6 '-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] 5 1 part of tetrabutylammonium bromide, 1 part of hydroquinone, 1 part of 1,4-benzoquinone, 1 part of KS-66 (defoaming and leveling agent manufactured by Shin-Etsu Silicone), 11 parts of cellulose acetate propionate The mixture was thoroughly stirred and dissolved in 89 parts of rumonomethyl ether, and further 10 parts of BYK-410 (a thixotropic agent manufactured by BYK Japan), dimic beads UCN-5350D (urethane beads manufactured by Dainichi Seika Kogyo Co., Ltd .: average particle size 33) EC composition 3 was obtained by adding 3 parts with stirring and then allowing to stand for 24 hours.

<Composition Example 4>
S-205 (Yamada Chemical Industries leuco dye: 2'-anilino-6 '-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] 5 1 part of tetrabutylammonium bromide, 1 part of hydroquinone, 1 part of 1,4-benzoquinone, 1 part of KS-66 (defoaming and leveling agent manufactured by Shin-Etsu Silicone), 11 parts of cellulose acetate propionate The mixture was thoroughly stirred and dissolved in 89 parts of rumonomethyl ether, and further 10 parts of BYK-410 (Bix Chemie Japan thixotropic agent) and 3 parts of GS / 50 (Nippon Electric Glass Co., Ltd. glass beads: average particle size 50 μm) were added. EC composition 4 was obtained by adding with stirring and then allowing to stand for 24 hours.

<Composition Example 5>
S-205 (Yamada Chemical Industries leuco dye: 2'-anilino-6 '-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] 5 1 part of tetrabutylammonium bromide, 1 part of hydroquinone, 1 part of 1,4-benzoquinone, 1 part of KS-66 (defoaming and leveling agent manufactured by Shin-Etsu Silicone), 11 parts of cellulose acetate propionate The mixture was thoroughly stirred and dissolved in 89 parts of rumonomethyl ether, and further 10 parts of BYK-410 (Bix Chemie Japan thixotropic agent) and 3 parts of GS / 100 (Nippon Electric Glass Co., Ltd. glass beads: average particle size 100 μm). It added, stirring, and EC composition 5 was obtained by leaving still for 24 hours after that.

<Composition Example 6>
S-205 (Yamada Chemical Industries leuco dye: 2'-anilino-6 '-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] 5 1 part of tetrabutylammonium bromide, 1 part of hydroquinone, 1 part of 1,4-benzoquinone, 1 part of KS-66 (defoaming and leveling agent manufactured by Shin-Etsu Silicone), 11 parts of cellulose acetate propionate The mixture was thoroughly stirred and dissolved in 89 parts of rumonomethyl ether, and further 10 parts of BYK-410 (Bix Chemie Japan thixotropic agent) and 3 parts of tuftic (spherical cross-linked acrylic: average particle size 15 μm, manufactured by Toyobo Co., Ltd.) were stirred. After that, EC composition 6 was obtained by leaving still for 24 hours.

<Composition Example 7>
S-205 (Yamada Chemical Industries leuco dye: 2'-anilino-6 '-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] 5 1 part of tetrabutylammonium bromide, 1 part of hydroquinone, 1 part of 1,4-benzoquinone, 1 part of KS-66 (defoaming and leveling agent manufactured by Shin-Etsu Silicone), 11 parts of cellulose acetate propionate The mixture was thoroughly stirred and dissolved in 89 parts of rumonomethyl ether, and 10 parts of BYK-410 (Bix Chemie Japan thixotropic agent) and 3 parts of High Presilica (Ube Nitto Kasei silica beads: average particle size 12 μm) were stirred. The EC composition 7 was obtained by allowing the mixture to stand for 24 hours.

<Composition Example 8>
S-205 (Yamada Chemical Industries leuco dye: 2'-anilino-6 '-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] 5 1 part of tetrabutylammonium bromide, 1 part of hydroquinone, 1 part of 1,4-benzoquinone, 1 part of KS-66 (defoaming and leveling agent manufactured by Shin-Etsu Silicone), 11 parts of cellulose acetate propionate The mixture was thoroughly stirred and dissolved in 89 parts of rumonomethyl ether, and 10 parts of BYK-410 (a thixotropic agent manufactured by Big Chemie Japan Co., Ltd.) was added with stirring, and the mixture was allowed to stand for 24 hours. Obtained.

[Production of EC element]
The EC compositions 1 to 7 obtained by the above preparations are Examples 1 to 7 and the EC composition 8 is Comparative Example 1, respectively, using an applicator on the ITO electrode of the soda lime glass substrate with an ITO electrode, and a wet film thickness of 100 μm. It applied so that it might become. Separately, a cylindrical electrode was placed upright and placed on top so that the ITO electrode substrate faced, and an EC composition was sandwiched between the electrodes to obtain an EC element.
The obtained EC composition and EC element were evaluated as follows. The evaluation results are shown in Table 1.

Evaluation method <Printability>
The EC compositions of Examples 1 to 7 and Comparative Example 1 were subjected to pattern coating on a soda lime glass substrate by a screen printing method, and the pattern shape of the coating film was evaluated.
○: Good pattern reproducibility.
Δ: Some rubbing, chipping, etc.
×: Pattern cannot be reproduced.

<Sagging>
The EC compositions of Examples 1 to 7 and Comparative Example 1 were subjected to pattern coating on a soda lime glass substrate by screen printing, and the coated substrate was stood vertically against the rack and allowed to stand for 5 minutes. The state of sagging was evaluated.
○… No sagging.
Δ: Slightly sag.
×… It ’s dripping and blurring.

<Sedimentation>
After 20 ml of the EC compositions of Examples 1 to 7 and Comparative Example 1 were collected in a glass sample bottle and allowed to stand in a thermostatic bath at 25 ° C. for one month, sedimentation occurred in the composition visually. I evaluated it.
○: No sedimentation.
Δ: Layer separation has begun.
X: There is a layer that settles and separates at the bottom of the bottle.

<Lightness evaluation (coloring performance)>
Evaluation before voltage application:
The state of the color tone of the EC composition in a state where a load of 3.0 kg was applied on the glass substrate with an ITO electrode of the EC element produced using the EC compositions of Examples 1 to 7 and Comparative Example 1 described above. Evaluate the color tone of the EC composition as an 18-level lightness scale (unit N, 1.0 is the blackest and 9.5 is the whitest) by visual confirmation and comparison with the JIS Z8721 color chart based on the Munsell color system did.
Evaluation after voltage application:
A color tone immediately after applying a DC current of 2.5 V on a glass substrate with an ITO electrode of an EC element manufactured in the same manner as described above while applying a voltage of 2.5 V and continuing to apply a voltage for 30 seconds. Was visually confirmed, and the color tone developed was evaluated in comparison with the brightness scale.

＊１ ：S-205（山田化学工業社製：ロイコ染料）
＊２ ：テトラブチルアンモニウムブロマイド
＊３ ：ハイドロキノン（化合物（１））
＊４ ：1,4-ベンゾキノン（レドックスペア；化合物（２））
＊５ ：ジプロピレングリコールモノメチルエーテル
＊６ ：CAP482-20（イーストマンケミカル社製：セルロースアセテートプロピオネート）
＊７ ：KS-66（信越シリコーン社製）
＊８ ：BYK（登録商標）-410（ビックケミージャパン社製）
＊９ ：ダイミックビーズUCN-5150D（大日精化社製：ポリウレタンビーズ 平均粒径 14.4μｍ）
＊１０：ダイミックビーズUCN-5250D（大日精化社製：ポリウレタンビーズ 平均粒径 27.4μｍ）
＊１１：ダイミックビーズUCN-5350D（大日精化社製：ポリウレタンビーズ 平均粒径 33.4μｍ）
＊１２：GS/50（日本電気硝子社製：ガラスビーズ 平均粒径 50μｍ）
＊１３：GS/100（日本電気硝子社製：ガラスビーズ 平均粒径 100μｍ）
＊１４：タフチック（東洋紡社製：球状架橋アクリル 平均粒径 15μｍ）
＊１５：ハイプレシリカ（宇部日東化成社製：球状シリカ 平均粒径 12μｍ）

* 1: S-205 (Yamada Chemical Industries, Ltd .: leuco dye)
* 2: Tetrabutylammonium bromide * 3: Hydroquinone (compound (1))
* 4: 1,4-benzoquinone (redox pair; compound (2))
* 5: Dipropylene glycol monomethyl ether * 6: CAP482-20 (Eastman Chemical Co., Ltd .: cellulose acetate propionate)
* 7: KS-66 (Shin-Etsu Silicone)
* 8: BYK (registered trademark) -410 (by Big Chemie Japan)
* 9: Dymic beads UCN-5150D (manufactured by Dainichi Seika Co., Ltd .: polyurethane beads average particle size 14.4 μm)
* 10: Dymic beads UCN-5250D (manufactured by Dainichi Seika Co., Ltd .: polyurethane beads average particle size 27.4μm)
* 11: Dymic beads UCN-5350D (manufactured by Dainichi Seika Co., Ltd .: polyurethane beads average particle size 33.4μm)
* 12: GS / 50 (Nippon Electric Glass Co., Ltd .: Glass beads average particle size 50μm)
* 13: GS / 100 (Nippon Electric Glass Co., Ltd .: Glass beads average particle size 100μm)
* 14: Tough tic (Toyobo Co., Ltd .: spherical cross-linked acrylic average particle size 15 μm)
* 15: High pre-silica (manufactured by Ube Nitto Kasei Co., Ltd .: spherical silica average particle size 12 μm)

  In Examples 1 to 7 and Comparative Example 1, it was possible to obtain good printability in screen printing. Also, the obtained pattern was good without changing its shape in terms of sagging properties. Furthermore, in terms of sedimentation, sedimentation of insulating particles was not confirmed in the sample after 1 month at 25 ° C., which was good.

  Examples 1 to 7 are cases in which the EC composition according to the present invention was used, and by adding insulating particles to the composition, a color of lightness N6.0 to 1.0 was shown by voltage application. In other words, the electrodes are not in contact with each other, and it is considered that a current flows through the EC composition. Therefore, it can be seen that the EC element manufactured using this composition maintains the gap between the electrodes.

On the other hand, in Comparative Example 1, when the insulating particles are not blended in the EC composition, the lightness remains N9.5 even after voltage application, the color development is not confirmed, and the electrodes are in contact with each other. Thus, it is considered that no current flows through the EC composition. Therefore, it can be seen that in Comparative Example 1, the gap between the electrodes is not maintained.
In this way, by blending the insulating particles in the EC composition, the gap between the electrodes is maintained without forming a separate spacer, the color development performance is good, and the short circuit due to the contact between the electrodes is prevented. EC element can be obtained.

DESCRIPTION OF SYMBOLS 1, 4 ... Electrode base material 2, 3 ... Electrode 5 ... EC composition 6 ... Insulating substance (sealing agent)
7, 8 ... Board

Claims (6)

An electrochromic composition comprising a compound that decolorizes in association with an electrochemical redox reaction, a supporting electrolyte, an organic thixotropic agent, a solvent, and insulating particles.   The electrochromic composition according to claim 1, comprising a polymer compound.   The electrochromic composition according to claim 2, wherein the polymer compound includes cellulose or a derivative thereof.   4. The compound according to claim 1, comprising a compound having a smaller absolute value of an oxidation overvoltage and a reduction overvoltage and / or a redox pair thereof than a compound that decolorizes along with the electrochemical oxidation-reduction reaction. The electrochromic composition according to one item.   The electrochromic composition according to any one of claims 1 to 4, wherein the compound that decolorizes with the electrochemical redox reaction is a leuco dye.   An electrochromic device comprising the electrochromic composition according to any one of claims 1 to 5.

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