JP5181438B2 - Tin oxide porous layer forming method and electrochromic display element - Google Patents

Description

  The present invention relates to a method for forming a tin oxide porous layer and an electrochromic display element having a tin oxide porous layer formed by low-temperature heating.

  In recent years, with the increase in the operating speed of personal computers, the spread of network infrastructure, the increase in capacity and price of data storage, information such as documents and images provided on printed paper on paper has become easier to use electronic information. Opportunities to obtain and browse electronic information are increasingly increasing.

  As such electronic information browsing means, conventional liquid crystal displays and CRTs, and in recent years, light-emitting types such as organic EL displays are mainly used. Particularly, when electronic information is document information, it is relatively long time. It is necessary to pay close attention to this browsing means, and these actions are not necessarily human-friendly means. Generally, as a drawback of light-emitting displays, eyes flicker due to flickering, inconvenient to carry, reading posture is limited It is known that it is necessary to adjust the line of sight to a still screen, and that power consumption increases when read for a long time.

  As a display means to compensate for these drawbacks, a reflection type display that uses external light and does not consume power for image retention (memory type) is known, but has sufficient performance for the following reasons. It's hard to say.

  That is, the method using a polarizing plate such as a reflective liquid crystal has a low reflectance of about 40% and is difficult to display white, and many of the production methods used for producing the constituent members are not easy. In addition, the polymer dispersed liquid crystal requires a high voltage and utilizes the difference in refractive index between organic substances, so that the resulting image has insufficient contrast. In addition, the polymer network type liquid crystal has problems such as a high voltage and a complicated TFT circuit required to improve the memory performance. In addition, a display element based on electrophoresis requires a high voltage of 10 V or more, and there is a concern about durability due to electrophoretic particle aggregation.

  On the other hand, the electrochromic display element can be driven at a low voltage of 3 V or less, but the color quality of black or color (yellow, magenta, cyan, blue, green, red, etc.) is not sufficient, and the memory property is low. There is a concern that a complicated film structure such as a vapor deposition film is necessary for the display cell in order to ensure.

  As a method for improving the problems of these electrochromic display methods, for example, between two conductive substrates, at least one of which is transparent, reversibly develops or discolors by at least one of a porous layer, an oxidation reaction, and a reduction reaction. An electrochromic display device using an electrochromic element formed by interposing an electrolyte containing an electrochromic dye is disclosed, and is said to be simple in structure, bright and easy to see, and capable of reducing power consumption. Yes. (For example, refer to Patent Documents 1 and 2).

As a result of studying in more detail, the present inventor produced a full-color electrochromic display element by the method disclosed in Patent Documents 1 and 2 and evaluated display characteristics. Since baking at .about.500.degree. C. is necessary, it has been found that the characteristics of transparent electrodes such as ITO and TFTs are deteriorated and the display speed is lowered. In addition, it is effective to use a plastic resin substrate for reducing the weight and flexibility of the element. However, in the formation of the above-described tin oxide layer, firing at 400 to 500 ° C. is a bottleneck. It was.
International Publication No. 2004/068231 Pamphlet International Publication No. 2004/0667673 Pamphlet

  The present invention has been made in view of the above problems, and its object is to provide an electrochromic display element that is excellent in display speed, lightweight, and flexible, and a method for forming a tin oxide porous layer used in the electrochromic display element Is to provide.

  The above object of the present invention is achieved by the following configurations.

1. After forming a tin oxide paste layer using a tin oxide paste containing 0.1 to 5% of silver oxide in a mass ratio with respect to tin oxide, heat treatment is performed at a temperature of 100 to 250 ° C. to form a tin oxide porous layer A method for forming a tin oxide porous layer.

  2. 2. The method for forming a porous tin oxide layer according to 1 above, wherein the tin oxide paste contains a reducing agent.

  3. 3. The method for forming a tin oxide porous layer according to 2 above, wherein the reducing agent is ethylene glycol, formalin, hydrazine, ascorbic acid or an alcohol compound.

  4). The counter electrode has at least one porous layer containing titanium oxide adsorbed with an electrochromic dye, and at least one tin oxide porous layer, and the tin oxide porous layer is any one of the above 1 to 4 An electrochromic display element, which is formed by the method according to claim 1.

  5. 5. The electrochromic display element as described in 4 above, wherein the electrochromic dye is represented by the following general formula (1).

[Wherein, R ¹ is — (CH ₂ ) _m — (wherein m represents an integer of 0 or 1 to 10), each an arylene group having up to 14 carbon atoms, a heteroarylene group, or each carbon atom. A branched alkylene group, alkenylene group, or cycloalkylene group of up to several tens, and each arylene group, heteroarylene group, branched alkylene group, branched alkenylene group, or cycloalkylene group is optionally -P (O) (OH) ₂ group - (CH _{2) n} - may have through a group. Moreover, you may substitute arbitrarily. n represents 0 or an integer of 1 to 10.

R ² is a group represented by R ³ R ^4, R ³ _{is, - (CH 2) p -} (. P is an integer of 0 or 1 to 10) represent, R ⁴ is -P (O) (OH) ₂ represents an aryl group or heteroaryl group having up to 14 carbon atoms, a branched alkyl group having up to 10 carbon atoms, an alkenyl group, or a cycloalkyl group.

X ⁻ represents an ion that neutralizes charge.

However, when R ² is — (CH ₂ ) ₂ —P (O) (OH) ₂ , R ¹ is not — (CH ₂ ) _m — (where m is 2 or 3). In addition, when R ² is a phenyl group, R ¹ is not — (CH ₂ ) _m — (m is 2). ]
6). 5. The electrochromic display element as described in 4 above, wherein the electrochromic dye is represented by the following general formula (2).

であるか、または酸素原子もしくは硫黄原子を表し、Ｒ_４は水素原子、または置換基を表す。〕
７．前記エレクトロクロミック色素を吸着させた酸化チタンを含む多孔質層、または、酸化スズを含む多孔質層の厚みが１〜５μｍであることを特徴とする請求項４〜６の何れか１項に記載のエレクトロクロミック表示素子。 [Wherein, R ₁ represents a substituted or unsubstituted aryl group, and R ₂ and R ₃ each represent a hydrogen atom or a substituent. X is the following general formula:

Or it is, or represents an oxygen atom or a sulfur atom, R ₄ represents a hydrogen atom or a substituent. ]
7). 7. The thickness of the porous layer containing titanium oxide to which the electrochromic dye is adsorbed or the porous layer containing tin oxide is 1 to 5 μm. 8. Electrochromic display element.

  8). The electrochromic display element according to any one of 4 to 7, wherein a plurality of the electrochromic display elements are stacked so that a plurality of colors can be displayed.

  9. Any one of the above 4 to 7, wherein a plurality of colors can be displayed by disposing a porous layer containing titanium oxide adsorbing different electrochromic dyes in a pattern between opposing electrodes. The electrochromic display element described in 1.

  10. 9. The method according to any one of 4 to 8, wherein a plurality of colors can be displayed by adsorbing a plurality of types of electrochromic dyes to a porous layer containing the same titanium oxide on the counter electrode. Electrochromic display element.

  11. 11. The electrochromic display element according to any one of 4 to 10, wherein at least one of the electrodes is formed on a plastic substrate.

  By the above means of the present invention, it is possible to provide an electrochromic display element that is excellent in display speed, lightweight and flexible, and a method for forming a tin oxide porous layer used in the electrochromic display element.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventor has at least one counter electrode, at least one porous layer containing titanium oxide adsorbed with an electrochromic dye, and at least one tin oxide porous layer. The tin oxide porous layer is formed by forming a tin oxide using a tin oxide paste containing 0.1 to 5% by weight of silver oxide and then heat-treating at a temperature of 100 to 250 ° C. The present inventors have found that an electrochromic display element that is excellent in display speed, light weight, and flexibility can be realized by the electrochromic display element characterized in that the present invention has been achieved.

(Electrochromic dye)
The electrochromic dye according to the present invention may be any compound that exhibits electrochromic properties.

  Specifically, JP-A-62-297382, JP-A-62-228689, JP-A-3-54528, JP-A-5-224242, JP-A-5-98251, JP-A-2004-01729, JP-A-2000-2000. -241835, the pigment | dye described in the international publication 2004/066773 pamphlet etc. can be mentioned.

  For example, the compound represented by the general formula (1) is mentioned.

The arylene group, heteroarylene group having up to 14 carbon atoms, branched alkylene group, branched alkenylene group, or cycloalkylene group each having up to 10 carbon atoms represented by R ¹ optionally have a substituent. These groups may be substituted by one or two or more, and when a plurality of groups are substituted, they may be different from each other or the same substituent.

  Examples of these substituents include the following groups.

  Lower alkyl group, lower alkenyl group, phenyl substituted-lower alkyl group, diphenyl substituted-lower alkyl group, phenyl group, phenoxy group, lower alkanoyloxy group, halogen atom, amino group, cyano group, nitro group, lower alkylamino group, Di (lower alkyl) amino group, phenylamino group, lower alkanoylamino group, benzoylamino group, lower alkylsulfonylamino group, phenylsulfonylamino group, lower alkanoyl group, benzoyl group, carboxyl group, lower alkoxycarbonyl group, carbamoyl group, N-lower alkylcarbamoyl group, N, N-di- (lower alkyl) carbamoyl group, ureido group, N-lower alkylureido group, lower alkylsulfonyl group, phenylsulfonyl group, hydroxyl group, lower alkoxy group, Mino group, lower alkylamino group, di (lower alkyl) amino group, lower alkoxy group substituted by halogen atom, carboxyl group or lower alkoxycarbonyl group, alkoxy group having 3 to 7 carbon atoms, and divalent methylene A dioxy group etc. are mentioned.

  Moreover, all the phenyl groups contained in the above phenyl group, benzoyl group, phenylamino group, etc. may be substituted with a lower alkyl group, a lower alkoxy group, a halogen atom, a hydroxy group, and / or a nitro group. .

Also, the aryl group, heteroaryl group, branched alkyl group, alkenyl group, cycloalkyl group, etc. represented by R ⁴ may be unsubstituted, but ^one of them is defined by the group defined as the substituent of R ^1. Or more than one may be substituted.

In the general formula (1), as a preferable compound, R ¹ is — (CH ₂ ) _m — (m represents 1, 2, 3), a phenyl group (— (CH ₂ ) _n — group). P-position is substituted with -P (O) (OH) ₂ group, n represents 1 or 2, and in R ² (represented by R ³ R ⁴ ), R ₃ is-( CH ₂ ) _p — (p represents 0, 1, 2, 3), and R ⁴ represents unsubstituted phenyl or naphthyl, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, A phenyl or naphthyl group mono-, di- or tri-substituted by a nitro group, a phenoxy group or a benzoyl group.

X ⁻ is Cl ⁻ , Br ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , C ₂ F ₆ NO ₄ S ₂ ⁻ , or CF ₃ SO ₃ ⁻ , and particularly preferably Cl ⁻ , PF ₆ ⁻ .

Below, the preferable specific example of a compound represented by General formula (1) is given.
(1) 1-phosphonoethyl-1 ′-(3-propylphenyl) -4,4′-bipyridinium dichloride (2) 1-phosphonoethyl-1 ′-(3-propylphenyl) -4,4′- Bipyridinium bis-hexafluorophosphate (3) 1-phosphonoethyl-1 '-(2,4,6-trimethylphenyl) -4,4'-bipyridinium dichloride (4) 1-phosphonoethyl-1'-( 2,4,6-trimethylphenyl) -4,4'-bipyridinium bis-hexafluorophosphate (5) 1-phosphonoethyl-1 '-(naphthyl) -4,4'-bipyridinium dichloride (6) 1- Phosphoethyl-1 ′-(4-cyanonaphthyl) -4,4′-bipyridinium dichloride (7) 1-phosphonoe 1 '-(4-methylphenyl) -4,4'-bipyridinium dichloride (8) 1-phosphonoethyl-1'-(4-cyanophenyl) -4,4'-bipyridinium dichloride (9) 1- Phosphoethyl-1 ′-(4-fluorophenyl) -4,4′-bipyridinium dichloride (10) 1-phosphonoethyl-1 ′-(4-phenoxyphenyl) -4,4′-bipyridinium dichloride (11) 1-phosphonoethyl-1 '-(4-t-butylphenyl) -4,4'-bipyridinium dichloride (12) 1-phosphonoethyl-1'-(2,6-dimethylphenyl) -4,4 ' -Bipyridinium dichloride (13) 1-phosphonoethyl-1 '-(3,5-dimethylphenyl) -4,4'-bipyridini Dichloride (14) 1-phosphonoethyl-1 ′-(4-benzophenone) -4,4′-bipyridinium dichloride (15) 1-phosphonobenzyl-1 ′-(3-propylphenyl) -4,4 ′ -Bipyridinium dichloride (16) 1-phosphonobenzyl-1 '-(3-propylphenyl) -4,4'-bipyridinium bis-hexafluorophosphate (17) 1-phosphonobenzyl-1'-(phosphonoethyl) ) -4,4'-bipyridinium dichloride (18) 1-phosphonobenzyl-1 '-(2,4-dinitrophenyl) -4,4'-bipyridinium dichloride (19) 1-phosphonobenzyl-1'-( 2,4-dinitrophenyl) -4,4'-bipyridinium bis-hexafluoroph Sulfate (20) 1-phosphonobenzyl-1 ′-(4-phenoxyphenyl) -4,4′-bipyridinium dichloride (21) 1-phosphonobenzyl-1 ′-(4-phenoxyphenyl) -4,4 ′ -Bipyridinium bis-hexafluorophosphate (22) 1-phosphonobenzyl-1 '-(4-fluorophenyl) -4,4'-bipyridinium dichloride (23) 1-phosphonobenzyl-1'-(4-methyl Phenyl) -4,4'-bipyridinium dichloride (24) 1-phosphonobenzyl-1 '-(2,4,6-trinitrophenyl) -4,4'-bipyridinium dichloride (25) 1-phosphonobenzyl- 1 '-(benzyl) -4,4'-bipyridinium dichloride (26) 1-phos Phonobenzyl-1 '-(naphthyl) -4,4'-bipyridinium dichloride (27) 1-phosphonobenzyl-1'-(phenyl) -4,4'-bipyridinium dichloride (28) 1-phosphonobenzyl-1 '-(4-Cyanophenyl) -4,4'-bipyridinium dichloride (29) 1-phosphonobenzyl-1'-(4-benzophenone) -4,4'-bipyridinium dichloride (30) 1-phosphonobenzyl- 1 ′-(4-cyanophenyl) -4,4′-bipyridinium dichloride (31) 1-phosphonobenzyl-1 ′-(2,6-dimethylphenyl) -4,4′-bipyridinium dichloride (32) 1- Phosphonobenzyl-1 '-(3,5-dimethylphenyl) -4,4'-bipyridinium Dichloride (33) 1-phosphonobenzyl-1 ′-(2,4,6-trimethylphenyl) -4,4′-bipyridinium trifluoromethanesulphonimide A method for producing these compounds is disclosed in International Publication No. WO 2004/066773. It is described in the pamphlet.

  Moreover, as a preferable electrochromic compound in this invention, the compound represented by the said General formula (2) is mentioned.

In the general formula (2), R ₁ represents a substituted or unsubstituted aryl group, and R ₂ and R ₃ each represent a hydrogen atom or a substituent, and the substituents represented by R ₁ , R ₂ , and R ₃ Specific examples of these include, for example, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, etc.), cycloalkyl group (for example, cyclohexyl group, cyclopentyl group, etc.). ), Alkenyl group, cycloalkenyl group, alkynyl group (for example, propargyl group), glycidyl group, acrylate group, methacrylate group, aromatic group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), heterocyclic group (for example, , Pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, Ridazinyl group, selenazolyl group, sliphoranyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group) Etc.), aryloxy group (eg phenoxy group etc.), alkoxycarbonyl group (eg methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group etc.) , Sulfonamide groups (for example, methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group, hexanesulfonamide group, cyclohexanesulfonamide group, benzenesulfonamide group) Amoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, phenylaminosulfonyl group, 2-pyridylaminosulfonyl group), urethane group ( For example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, phenylureido group, 2-pyridylureido group, etc.), acyl group (for example, acetyl group, propionyl group, butanoyl group, hexanoyl group, cyclohexanoyl group) Group, benzoyl group, pyridinoyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylamino) Nocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group etc.), acylamino group (eg acetylamino group, benzoylamino group, methylureido group etc.), amide group (eg acetamido group, propion) Amide group, butanamide group, hexaneamide group, benzamide group, etc.), sulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, phenylsulfonyl group, 2-pyridylsulfonyl group, etc.), sulfonamide Group (for example, methylsulfonamide group, octylsulfonamide group, phenylsulfonamide group, naphthylsulfonamide group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butyrate) Amino group, cyclopentylamino group, anilino group, 2-pyridylamino group, etc.), halogen atom (eg, chlorine atom, bromine atom, iodine atom, etc.), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group, phosphono group (For example, phosphonoethyl group, phosphonopropyl group, phosphonooxyethyl group), oxamoyl group, and the like can be given. Further, these groups may be further substituted with these groups.

R ₁ is a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl group, more preferably a substituted or unsubstituted 2-hydroxyphenyl group or 4-hydroxyphenyl group.

R ₂ and R ₃ are preferably an alkyl group, a cycloalkyl group, an aromatic group, or a heterocyclic group, more preferably one of R ₂ and R ₃ is a phenyl group, the other is an alkyl group, and more preferably R ₂ and R ₃ are both phenyl groups.

X is preferably> N—R ₄ . R ₄ is preferably a hydrogen atom, an alkyl group, an aromatic group, a heterocyclic group, or an acyl group, more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms, or acyl. It is a group.

  Specific examples of the electrochromic compound represented by the general formula (2) are shown below, but the present invention is not limited thereto.

(Counter electrode)
As the counter electrode according to the present invention, a metal electrode or a transparent electrode can be used. As the metal electrode, for example, known metal species such as platinum, gold, silver, copper, aluminum, zinc, nickel, titanium, bismuth, and alloys thereof can be used. As an electrode manufacturing method, an existing method such as an evaporation method, a printing method, an ink jet method, a spin coating method, or a CVD method can be used.

  The transparent electrode is not particularly limited as long as it is transparent and conducts electricity. For example, Indium Tin Oxide (ITO: Indium Tin Oxide), Indium Zinc Oxide (IZO: Indium Zinc Oxide), Fluorine Doped Tin Oxide (FTO), Indium Oxide, Zinc Oxide, Platinum, Gold, Silver, Rhodium, Copper, Examples thereof include chromium, carbon, aluminum, silicon, amorphous silicon, and BSO (Bismuth Silicon Oxide). In order to form the electrode in this manner, for example, an ITO film may be vapor-deposited on the substrate by a sputtering method or the like, or an ITO film may be formed on the entire surface and then patterned by a photolithography method. The surface resistance value is preferably 100Ω / □ or less, and more preferably 10Ω / □ or less. The thickness of the transparent electrode is not particularly limited, but is generally 0.1 to 20 μm.

  As the counter electrode of the present invention, a transparent electrode is preferably used in order to obtain a sufficiently large color gamut for full color display, and an ITO electrode is particularly preferable from the viewpoint of light transmittance and resistance.

(Porous layer)
It is preferable to use a metal oxide for the porous layer according to the present invention. Examples of the metal oxide include titanium oxide, silicon oxide, zinc oxide, tin oxide, Sn-doped indium oxide (ITO), antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), and aluminum-doped zinc oxide. Or a mixture thereof.

  In the present invention, one of the porous layers adjacent to the counter electrode includes titanium oxide, and the other includes tin oxide. By using a combination of titanium oxide and tin oxide, a highly reversible electrochromic dye can be developed and decolored at an applied voltage of about 3 V or less.

The porous layer is formed by binding or contacting a plurality of fine particles of the metal oxide. The average primary particle of the metal oxide fine particles is preferably 5 to 100 nm, more preferably 20 to 80 nm. The specific surface area of the metal oxide fine particles is preferably ^{1 × 10 -3 ~1 × 10 2} m 2 / g by a simple BET method, more preferably at 1 × 10 ^-2 ~10m ² / g . The metal oxide fine particles may have any shape such as an indefinite shape, a needle shape, or a spherical shape.

  The thickness of the porous layer according to the present invention is preferably 1 to 5 μm. If it is 1 μm or less, a sufficient amount of electrochromic dye cannot be adsorbed, resulting in a decrease in contrast. If it exceeds 5 μm, the resolution is decreased, which is disadvantageous.

  As a method for forming or binding metal oxide fine particles, a known sol-gel method or sintering method can be employed. For example, 1) Journal of the Ceramic Society of Japan, 102, 2, p200 (1994), 2 ) Ceramics Association Journal 90, 4, p157, 3) J. of Non-Cryst. Solids, 82, 400 (1986) and the like. In addition, a method of obtaining a porous electrode by dispersing titanium oxide dendrimer particles prepared by a vapor phase method on a solution and applying the particles on a substrate and drying at a temperature of about 120 to 150 ° C. to remove the solvent is used. You can also.

  In addition, a low temperature process such as a chemical solution deposition method described in “Low Resistance / Low Temperature / Large Area Film Formation Technology of Transparent Conductive Film” (July 2005, ISBN4-86104-078-7 C3058 published by the Japan Society of Technology) In particular, when the porous layer is connected to a part of the pixel circuit through the transparent electrode, the pixel pixel circuit is less damaged, and the display variation between the pixels in the display display in which the pixel circuit is integrated is small. There is an advantage that can be reduced.

  The metal oxide fine particles are preferably bound, and preferably have a resistance of 0.1 g or more, preferably 1 g or more with a continuous load type surface property measuring instrument (for example, a scratch tester).

  Porous as used in the present invention refers to a penetrating state in which a porous layer is arranged, a potential difference is applied between the counter electrodes, and a silver dissolution and precipitation reaction can be caused, and ionic species can move in the porous layer. Say.

[Method of forming tin oxide paste and tin oxide porous layer]
The solvent used in the tin oxide paste according to the present invention is selected from solvents having a boiling point exceeding 100 ° C. such as ethanol, isopropyl alcohol, butanol, terpineol, butyl carbitol, butyl carbitol acetate, xylene, toluene, acetylacetone and acetonitrile. It is preferable.

The silver oxide used in the tin oxide paste according to the present invention is preferably added in the range of 0.1 to 5% by mass ratio with respect to tin oxide in the form of Ag ₂ O.

  As the reducing agent used in the tin oxide paste according to the present invention, a general reducing agent can be used. In particular, at least one of ethylene glycol, formalin, hydrazine, ascorbic acid, and alcohol compounds is used. Is desirable.

  The tin oxide used in the tin oxide paste according to the present invention may be doped with Sb.

  The tin oxide paste according to the present invention is recommended to be stored in a cool and dark place at the time of storage, and it is desirable that the tin oxide paste is left at room temperature before use and redispersed as necessary.

The method for forming a tin oxide paste layer using the tin oxide paste according to the present invention can be selected from conventional methods such as a blade method, an ink jet method, a screen printing method, and a gravure printing method according to the application. is there.

The heating after the tin oxide paste layer is formed is heated for 30 minutes to 2 hours in the range of 100 to 250 ° C., thereby promoting the fusion by evaporation of the solvent and the reduction of the silver oxide, and the resistance of the tin oxide porous layer The value can be lowered. When heating above 200 ° C., it is desirable to evaporate the solvent by preheating at 100 to 150 ° C. and then heat to the desired temperature.

[Electrolyte material]
In the electrochromic display element (hereinafter, also referred to as display element) of the present invention, the following compound can be contained in the electrolyte in the electrolyte solvent. KCl, KI, KBr, etc. as potassium compounds, LiBF ₄ , LiClO ₄ , LiPF ₆ , LiCF ₃ SO ₃ etc. as lithium compounds, tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetraethylammonium borofluoride as tetraalkylammonium compounds And tetrabutylammonium borofluoride and tetrabutylammonium halide. Moreover, the molten salt electrolyte composition described in JP-A-2003-187881 paragraphs [0062] to [0081] can also be preferably used. Furthermore, a compound that becomes a redox pair such as I ⁻ / I ₃ ⁻ , Br ⁻ / Br ₃ ⁻ , and quinone / hydroquinone can be used.

[Solvent for electrolyte addition]
In the display element of the present invention, a solvent can be used as long as the object effects of the present invention are not impaired. Specifically, tetramethylurea, sulfolane, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 2- (N-methyl) -2-pyrrolidinone, hexamethylphosphortriamide, N-methylpropionamide, N, N-dimethylacetamide, N-methylacetamide, N, N dimethylformamide, N-methylformamide, butyronitrile, propionitrile, acetonitrile, acetylacetone, 4-methyl-2-pentanone, 2-butanol, 1-butanol, 2 -Propanol, 1-propanol, ethanol, methanol, acetic anhydride, ethyl acetate, ethyl propionate, dimethoxyethane, diethoxyfuran, tetrahydrofuran, ethylene glycol, diethylene glycol, triethylene glycol monobuty Ether, water and the like. Among these solvents, it is preferable to include at least one solvent having a freezing point of −20 ° C. or lower and a boiling point of 120 ° C. or higher.

Furthermore, as a solvent which can be used in the present invention, J.P. A. Riddick, W.M. B. Bunger, T.A. K. Sakano, “Organic Solvents”, 4th ed. , John Wiley & Sons (1986), Y. Marcus, “Ion Solvation”, John Wiley & Sons (1985), C.I. Reichardt, “Solvents and Solvent Effects in Chemistry”, 2nd ed. VCH (1988), G .; J. et al. Janz, R.A. P. T.A. Tomkins, “Nonqueous Electronics Handbook”, Vol. 1, Academic Press (1972) can be mentioned [Thickener with electrolyte addition]
In the display element of the present invention, a thickener can be used for the electrolyte. For example, gelatin, gum arabic, poly (vinyl alcohol), hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate, cellulose acetate butyrate, poly ( Vinylpyrrolidone), poly (alkylene glycol), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly ( Styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (PVC Redene), poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, poly (amides), hydrophobic transparent binders such as polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, Examples include polycarbonate, polyacrylic acid, polyurethane and the like.

  These thickeners may be used in combination of two or more. Moreover, the compound as described in pages 71-75 of Unexamined-Japanese-Patent No. 64-13546 can be mentioned. Among these, the compounds preferably used are polyvinyl alcohols, polyvinyl pyrrolidones, hydroxypropyl celluloses, and polyalkylene glycols from the viewpoint of compatibility with various additives and improvement in dispersion stability of white particles.

[Other additives]
Examples of the constituent layers of the display element of the present invention include auxiliary layers such as a white scattering layer, a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer. Among these auxiliary layers, Various additives such as chemical sensitizers, noble metal sensitizers, photosensitive dyes, supersensitizers, couplers, high boiling point solvents, antifoggants, stabilizers, development inhibitors in the following research disclosures, Bleaching accelerator, fixing accelerator, color mixing inhibitor, formalin scavenger, toning agent, hardener, surfactant, thickener, plasticizer, slip agent, ultraviolet absorber, irradiation prevention dye, filter light absorbing dye, Additives listed as antifungal agents, polymer latex, heavy metals, antistatic agents, matting agents, and the like can be included as necessary.

  More specifically, these additives described above are described in detail in Research Disclosure (hereinafter abbreviated as RD), Volume 176 Item / 17643 (December 1978), Volume 184, Item / 18431 (August 1979), Volume 187. Item / 18716 (November 1979) and Volume 308 Item / 308119 (December 1989).

  The types of compounds and their descriptions shown in these three research disclosures are listed below.

Additive RD17643 RD18716 RD308119
Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 96 III
Sensitizing dye 23 IV 648-649 996-8 IV
Desensitizing dye 23 IV 998 IV
Dye 25-26 VIII 649-650 1003 VIII
Development accelerator 29 XXI 648 Upper right Anti-fogging agent / stabilizer
24 IV 649 Upper right 1006-7 VI
Brightener 24 V 998 V
Hardener 26 X 651 Left 1004-5 X
Surfactant 26-7 XI 650 Right 1005-6 XI
Antistatic agent 27 XII 650 Right 1006-7 XIII
Plasticizer 27 XII 650 Right 1006 XII
Slipper 27 XII
Matting agent 28 XVI 650 Right 1008-9 XVI
Binder 26 XXII 1003-4 IX
Support 28 XVII 1009 XVII
〔substrate〕
Examples of the substrate that can be used in the present invention include polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene dinaphthalene dicarboxylate, polyethylene naphthalates, polyvinyl chloride, polyimide, and polyvinyl acetal. Synthetic plastic films such as polystyrene can also be preferably used. Syndiotactic polystyrenes are also preferred. These can be obtained, for example, by the methods described in JP-A Nos. 62-117708, 1-46912 and 1-178505. Further, a metal substrate such as stainless steel, a paper support such as baryta paper and resin coated paper, and a support provided with a reflective layer on the plastic film, supported by JP-A-62-253195 (pages 29 to 31) The thing described as a body is mentioned. RDNo. 17643, page 28, ibid. No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879 can also be preferably used. As these supports, those having resistance to curling due to heat treatment of Tg or less as in US Pat. No. 4,141,735 can be used. Further, the surface of these supports may be subjected to surface treatment for the purpose of improving the adhesion between the support and other constituent layers. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment. Furthermore, the support body described in pages 44 to 149 of publicly known technology No. 5 (issued by Aztec Co., Ltd. on March 22, 1991) can also be used. Furthermore, RDNo. 308119, page 1009, Product Licensing Index, Volume 92, P108, “Supports”, and the like. In addition, a glass substrate or an epoxy resin kneaded with glass can be used.

[Other components of the display element]
In the display element of the present invention, a sealant, a columnar structure, and spacer particles can be used as necessary.

  Sealing agent is for sealing so that it does not leak out. It is also called sealing agent. Epoxy resin, urethane resin, acrylic resin, vinyl acetate resin, ene-thiol resin, silicone resin, modified resin A curing type such as a polymer resin, such as a thermosetting type, a photocurable type, a moisture curable type, and an anaerobic curable type can be used.

  The columnar structure provides strong self-holding (strength) between the substrates, for example, a columnar body, a quadrangular columnar body, an elliptical columnar body, a trapezoidal array arranged in a predetermined pattern such as a lattice arrangement. A columnar structure such as a columnar body can be given. Alternatively, stripes arranged at predetermined intervals may be used. This columnar structure is not a random array, but can maintain an appropriate interval between the substrates, such as an evenly spaced array, an array in which the interval gradually changes, and an array in which a predetermined arrangement pattern is repeated at a constant period. The arrangement is preferably considered so as not to disturb the display. If the ratio of the area occupied by the columnar structure in the display area of the display element is 1 to 40%, a practically sufficient strength as a display element can be obtained.

  A spacer may be provided between the pair of substrates for uniformly maintaining a gap between the substrates. Examples of the spacer include a sphere made of resin or inorganic oxide. Further, a fixed spacer having a surface coated with a thermoplastic resin is also preferably used. In order to hold the gap between the substrates uniformly, only the columnar structure may be provided, but both the spacer and the columnar structure may be provided, or instead of the columnar structure, only the spacer is used as the space holding member. May be used. The diameter of the spacer is equal to or less than the height of the columnar structure, preferably equal to the height. When the columnar structure is not formed, the diameter of the spacer corresponds to the thickness of the cell gap.

[Screen printing]
In the present invention, a sealant, a columnar structure, an electrode pattern, and the like can be formed by a screen printing method. In the screen printing method, a screen on which a predetermined pattern is formed is placed on an electrode surface of a substrate, and a printing material (a composition for forming a columnar structure, such as a photocurable resin) is placed on the screen. Then, the squeegee is moved at a predetermined pressure, angle, and speed. Thereby, the printing material is transferred onto the substrate through the pattern of the screen. Next, the transferred material is heat-cured and dried. When the columnar structure is formed by the screen printing method, the resin material is not limited to a photocurable resin, and for example, a thermosetting resin such as an epoxy resin or an acrylic resin or a thermoplastic resin can also be used. As thermoplastic resins, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polymethacrylate resin, polyacrylate resin, polystyrene resin, polyamide resin, polyethylene resin, polypropylene resin, fluororesin, polyurethane resin , Polyacrylonitrile resin, polyvinyl ether resin, polyvinyl ketone resin, polyether resin, polyvinyl pyrrolidone resin, saturated polyester resin, polycarbonate resin, chlorinated polyether resin and the like. The resin material is preferably used in the form of a paste by dissolving the resin in an appropriate solvent.

  After the columnar structure or the like is formed on the substrate as described above, a spacer is provided on at least one of the substrates as desired, and the pair of substrates are overlapped with the electrode formation surfaces facing each other to form an empty cell. . A pair of stacked substrates is heated while being pressed from both sides, whereby the display cells are obtained. In order to obtain a display element, an electrolyte composition may be injected between substrates by a vacuum injection method or the like. Alternatively, when the substrates are bonded together, the electrolyte composition may be dropped on one substrate, and the liquid crystal composition may be sealed simultaneously with the bonding of the substrates.

[Configuration of full-color display element]
When performing full color display using the display element of the present invention,
1. A method of laminating electrochromic display elements that develop and erase colors in different colors such as yellow, magenta, cyan, red, green, blue, black,
2. A method of patterning a porous portion adsorbing an electrochromic dye that develops and decolors in different colors on a flat surface,
3. Examples include a method of adsorbing a plurality of types of electrochromic dyes that develop and decolor in different color tones to a porous layer between a pair of counter electrodes.

  In the case of 3, the electrochromic dye must have a threshold value. As a method for providing the threshold value, voltage or charge amount in the color developing or decoloring direction or voltage hysteresis in the color developing or decoloring direction is set for each dye. The method of changing to is mentioned.

[Display element driving method]
The active matrix drive according to the present invention is a method in which scanning lines, data lines, and current supply lines are formed in a grid pattern and are driven by TFT circuits provided in each grid pattern. Since switching can be performed for each pixel, there are merits such as gradation and memory function. For example, the circuit described in FIG. 5 of Japanese Patent Application Laid-Open No. 2004-29327, “Electrochromic Display” (published by 1991 Sangyo Tosho Co., Ltd.) ) 77-102.

[Product application]
The display element of the present invention can be used in an electronic book field, an ID card field, a public field, a traffic field, a broadcast field, a payment field, a distribution logistics field, and the like. Specifically, keys for doors, student ID cards, employee ID cards, various membership cards, convenience store cards, department store cards, vending machine cards, gas station cards, subway and railway cards, bus cards, Cash cards, credit cards, highway cards, driver's licenses, hospital examination cards, electronic medical records, health insurance cards, Basic Resident Registers, passports, electronic books, etc.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

<< Production of display element >>
The electrochromic dye used in the examples is shown below.

(Preparation of display element 1)
An ITO electrode is formed on a glass substrate, a dispersion of titanium oxide (average primary particle size 30 nm) dispersed in terpineol is applied on the ITO electrode, and baked at 400 ° C. for 1 hour to form a porous titanium oxide layer (dry film) 10 μm thick) was formed. This was immersed in a 10 mmol / L ethanol solution of electrochromic dye Ex1 for 4 hours to adsorb Ex1 on the titanium oxide porous layer, and the ethanol was evaporated to obtain member 1. Next, a tin oxide doped with antimony dispersed in terpineol (average primary particle size: 30 nm) is applied onto another ITO electrode and baked at 400 ° C. for 1 hour to form a porous tin oxide layer (dry film thickness) 10 μm) and a white scattering layer (dry film) by a blade coating method using a mixture of titanium oxide (average primary particle size 300 nm) coated with SiO ₂ on a tin oxide porous layer, polyvinyl alcohol, water and ethanol. A member 2 was obtained by forming a thickness of 10 μm. The members 1 and 2 are sandwiched through a 100 μm spacer, the periphery is sealed with an epoxy UV curable resin, and a γ-butyrolactone solution containing 1 mmol / L lithium perchlorate is injected between the members 1 and 2. A display element 1 was obtained.

(Preparation of display element 2)
Display element 2 was obtained in the same manner as display element 1 except that the heating temperature was changed from 400 ° C to 250 ° C.

(Preparation of tin oxide paste 1)
5 g of tin oxide doped with antimony (average primary particle size: 30 nm) was added to 10 g of terpineol, 0.003 g of silver oxide Ag ₂ O was further added, and the resulting solution was sufficiently stirred and dispersed in a bead mill. A tin oxide paste 1 was obtained.

(Preparation of tin oxide paste 2)
5 g of tin oxide doped with antimony (average primary particle size: 30 nm) was added to 10 g of terpineol, and 0.3 g of silver oxide Ag ₂ O was further added. After sufficiently stirring, the mixture was dispersed in a bead mill. A tin oxide paste 2 was obtained.

(Preparation of display element 3)
After tin oxide paste 1 is formed on the ITO electrode by screen printing, it is heated at 150 ° C. for 10 minutes, and further heated at 250 ° C. for 1 hour to form a tin oxide porous layer (dry film thickness 10 μm). A white scattering layer (dry film thickness 10 μm) is formed by a blade coating method using a mixed solution of titanium oxide (average primary particle size 300 nm), polyvinyl alcohol, water, and ethanol coated with SiO ₂ on a tin oxide porous layer. Member 3 was obtained.

  The member 1 and the member 3 obtained by the display element 1 are sandwiched through a 100 μm spacer, and the periphery is sealed with an epoxy-based UV curable resin, and a γ-butyrolactone solution containing 1 mmol / L lithium perchlorate is used as the member 1 The display element 3 was obtained by injecting between the members 2.

(Preparation of display element 4)
A display element 4 was obtained in the same manner as the display element 1 except that the tin oxide paste 2 was used.

(Preparation of tin oxide paste 3)
5 g of tin oxide doped with antimony (average primary particle size: 30 nm) was added to 10 g of terpineol, 0.005 g of silver oxide Ag ₂ O was further added, and the resulting solution was sufficiently stirred and dispersed in a bead mill. A tin oxide paste 3 was obtained.

(Preparation of tin oxide paste 4)
5 g of tin oxide doped with antimony (average primary particle size: 30 nm) was added to 10 g of terpineol, and 0.15 g of silver oxide Ag ₂ O was further added. After sufficiently stirring, the mixture was dispersed in a bead mill. A tin oxide paste 4 was obtained.

(Preparation of tin oxide paste 5)
A solution obtained by adding 5 g of tin oxide doped with antimony (average primary particle size: 30 nm) to 10 g of terpineol, adding 0.15 g of silver oxide Ag ₂ O, and further adding 0.15 g of ethylene glycol. Was sufficiently stirred and dispersed with a bead mill to obtain a tin oxide paste 5.

(Preparation of tin oxide paste 6)
A solution obtained by adding 5 g of tin oxide (average primary particle size: 30 nm) doped with antimony to 10 g of terpineol, adding 0.15 g of silver oxide Ag ₂ O, and further adding 0.15 g of formalin is obtained. After sufficiently stirring, it was dispersed with a bead mill to obtain a tin oxide paste 6.

(Preparation of tin oxide paste 7)
A liquid obtained by adding 5 g of tin oxide doped with antimony (average primary particle size: 30 nm) to 10 g of terpineol, adding 0.15 g of silver oxide Ag ₂ O, and further adding 0.15 g of hydrazine. After sufficiently stirring, it was dispersed with a bead mill to obtain a tin oxide paste 7.

(Preparation of tin oxide paste 8)
A liquid obtained by adding 5 g of tin oxide doped with antimony (average primary particle size: 30 nm) to 10 g of terpineol, adding 0.15 g of silver oxide Ag ₂ O, and further adding 0.15 g of ascorbic acid. Was sufficiently stirred and dispersed with a bead mill to obtain a tin oxide paste 8.

(Preparation of display element 5)
A display element 5 was obtained in the same manner as the display element 1 except that the tin oxide paste 3 was used.

(Preparation of display element 6)
A display element 6 was obtained in the same manner as the display element 1 except that the tin oxide paste 4 was used.

(Preparation of display element 7)
A display element 7 was obtained in the same manner as the display element 1 except that the tin oxide paste 5 was used.

(Preparation of display element 8)
A display element 8 was obtained in the same manner as the display element 1 except that the tin oxide paste 6 was used.

(Preparation of display element 9)
A display element 9 was obtained in the same manner as the display element 1 except that the tin oxide paste 7 was used.

(Preparation of display element 10)
A display element 10 was obtained in the same manner as the display element 1 except that the tin oxide paste 8 was used.

(Preparation of display elements 11-15)
Display elements 11 to 15 were fabricated in the same manner as display element 7 except that Ex1 of display element 7 was changed to electrochromic dye Ex2, (3), (15), 107, and 109.

<< Evaluation of display element >>
(Measurement of display speed)
A voltage of 1.5 V was applied to each of the display devices prepared above for 0.5 seconds, and the reflectance in the colored state was measured with a spectrocolorimeter CM-3700d manufactured by Konica Minolta Sensing. The minimum value of the measured reflectance was R _min, and R _min was used as an indicator of display speed. Here, the lower the R _min , the higher the display speed.

  The evaluation results are shown in Table 1.

  As is clear from the results shown in Table 1, the display element 1 formed by firing at 400 ° C. to form the tin oxide porous layer has a lower display speed due to an increase in the ITO resistance value. It can be seen that the display element 2 in which the tin oxide porous layer is formed by heating at 250 ° C. in order to avoid the increase is greatly reduced in display speed because the resistance value of the tin oxide layer does not sufficiently decrease.

  Moreover, the display elements 3-15 which formed the tin oxide porous layer using the tin oxide paste containing silver oxide suppressed the raise of the resistance value of ITO by heating at 250 degreeC, and the resistance value of a tin oxide layer was It can be seen that the display speed is improved.

  However, it is understood that the display elements 3 and 4 in which the addition amount of silver oxide is not within the range of 0.1 to 5% of the present invention are insufficient in the improvement of the display speed, and are slower than the display element 1. .

  In particular, the elements 7 to 15 in which the tin oxide porous layer is formed using the tin oxide paste containing the reducing agent and the addition amount of the silver oxide in the range of 0.1 to 5% of the present invention are displayed speeds. It can be seen that is significantly improved.

  It was confirmed that the above effects were sufficiently effective even when an electrode of a plastic substrate was used.

Claims (11)

After forming a tin oxide paste layer using a tin oxide paste containing 0.1 to 5% of silver oxide in a mass ratio with respect to tin oxide, heat treatment is performed at a temperature of 100 to 250 ° C. to form a tin oxide porous layer A method for forming a tin oxide porous layer.   The method for forming a tin oxide porous layer according to claim 1, wherein the tin oxide paste contains a reducing agent.   3. The method for forming a tin oxide porous layer according to claim 2, wherein the reducing agent is ethylene glycol, formalin, hydrazine, ascorbic acid, or an alcohol compound. Counter electrode, at least one porous layer containing titanium oxide was adsorbed electrochromic dye, and a tin oxide porous layer having at least one layer, and oxide-tin porous layer according to claim 1 to 3 It is formed by the method of any one of Claims 1, The electrochromic display element characterized by the above-mentioned. The electrochromic display element according to claim 4, wherein the electrochromic dye is represented by the following general formula (1).

[Wherein, R ¹ represents — (CH ₂ ) _m — (wherein m represents 0 or an integer of 1 to 10), each an arylene group having up to 14 carbon atoms, a heteroarylene group, or each carbon atom. A branched alkylene group, alkenylene group, or cycloalkylene group of up to several tens, and each arylene group, heteroarylene group, branched alkylene group, branched alkenylene group, or cycloalkylene group is optionally -P (O) (OH) ₂ group - _{(CH 2) n} - may have through a group. Moreover, you may substitute arbitrarily. n represents 0 or an integer of 1 to 10.
R ^{2 is} a group represented by ^{R 3} R ^4, R 3 _{is, - (CH 2) p -} (. P is an integer of 0 or 1 to 10) represent, ^{R 4} is -P (O) (OH) ₂ groups or aryl groups and heteroaryl groups having up to 14 carbon atoms, branched alkyl groups, alkenyl groups, or cycloalkyl groups each having up to 10 carbon atoms.
X ⁻ represents an ion that neutralizes charge.
However, when R ² is — (CH ₂ ) ₂ —P (O) (OH) ₂ , R ¹ is not — (CH ₂ ) _m — (m is 2 or 3). In addition, when R ² is a phenyl group, R ¹ is not — (CH ₂ ) _m — (m is 2). ] The electrochromic display element according to claim 4, wherein the electrochromic dye is represented by the following general formula (2).

[Wherein, R ₁ represents a substituted or unsubstituted aryl group, and R ₂ and R ₃ each represent a hydrogen atom or a substituent. X is the following general formula:

Or it is, or represents an oxygen atom or a sulfur atom, R ₄ represents a hydrogen atom or a substituent. ]   7. The thickness of the porous layer containing titanium oxide to which the electrochromic dye is adsorbed or the porous layer containing tin oxide is 1 to 5 μm. 8. Electrochromic display element.   The electrochromic display element according to claim 4, wherein a plurality of the electrochromic display elements are stacked so that a plurality of colors can be displayed.   8. A plurality of colors can be displayed by arranging a porous layer containing titanium oxide on which different electrochromic dyes are adsorbed in a pattern between opposing electrodes. The electrochromic display element according to item.   9. The display device according to claim 4, wherein a plurality of colors can be displayed by adsorbing a plurality of types of electrochromic dyes to a porous layer containing the same titanium oxide on the counter electrode. 10. Electrochromic display element.   The electrochromic display element according to any one of claims 4 to 10, wherein at least one of the electrodes is formed on a plastic substrate.