JP2007041579A - Light regulator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light regulator which is easy to manufacture and superior in handling and durability and quick responsiveness and whose transmissivity to light can be varied by voltage application. <P>SOLUTION: The light regulator comprises a pair of electrode substrates at least one of which is transparent and a single-layer solid-state film which is sandwiched between the electrode substrates and has conductivity and electrochromic property. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a light adjuster that is easy to manufacture, excellent in handleability and durability, excellent in responsiveness, and capable of changing light transmittance by applying a voltage.

A dimmer capable of changing the light transmittance by applying a voltage has been studied for the purpose of application to a display device such as a building, a vehicle window, or an electric light board.
The dimmers are roughly classified into those made of a liquid crystal material and those made of an electrochromic material. Among them, the dimmer made of an electrochromic material has excellent properties such as being less affected by light scattering and not affected by polarized light than those made of a liquid crystal material. Has been. As electrochromic materials, inorganic electrochromic materials and organic electrochromic materials are known.

A conventional light control body using an electrochromic material is generally composed of a structure in which a laminate composed of at least two layers of an electrochromic layer and an electrolyte layer is sandwiched between a pair of opposing electrode substrates. there were. For example, in Patent Document 1 and Patent Document 2, three layers of an electrochromic layer made of an inorganic oxide, an ion conductive layer, and an electrochromic layer made of an inorganic oxide were sequentially stacked between two conductive substrates. A light control body having a structure in which a laminate is sandwiched is disclosed. However, in order to produce such a laminated body, it is necessary to perform complicated processes such as vapor deposition and sputtering in order to form an electrochromic layer made of an inorganic oxide, and there is a problem that the production is complicated. there were. In addition, the responsiveness is inferior, and even when a voltage is applied, it takes time to complete the change in light transmittance, and color unevenness occurs.

In Patent Document 3 and Patent Document 4, a light control body having a structure in which a laminated body composed of an electrochromic layer made of an organic electrochromic material and an electrolyte layer is sandwiched between a pair of opposing electrode substrates. Is disclosed. However, a dimmer using such an organic electrochromic material is also complicated to manufacture, inferior in response, and takes time to complete the change in light transmittance even when a voltage is applied. There is a problem that color unevenness occurs.

On the other hand, Patent Document 5 encloses a mixed solution containing a low molecular weight organic electrochromic material and an electrolyte in a space in which a peripheral portion is sealed using a sealant between a pair of opposing electrode substrates. A light control body having a structure in which an electrochromic structure is sandwiched is disclosed, and high responsiveness can be obtained by using such an electrochromic structure having a single layer structure. However, the dimmer encapsulating such a liquid material has problems in terms of handleability and durability, and has a problem that high responsiveness is not actually obtained. In addition, the electrochromic property as a whole is not uniform, and color unevenness may occur.
JP 2004-062030 A JP 2005-062772 A Japanese translation of PCT publication No. 2002-526801 JP-T-2004-53770 Japanese Patent Laid-Open No. 9-120088

In light of the above-mentioned present situation, the present invention provides a dimmer that is easy to manufacture, has excellent handling and durability, has excellent responsiveness, and can change the light transmittance by applying a voltage. The purpose is to do.

The present invention is a light control device comprising a pair of electrode substrates, at least one of which is transparent, and a single-layer solid film having conductivity and electrochromic properties sandwiched between the electrode substrates. .
The present invention is described in detail below.

As a result of intensive studies, the inventors have used a single-layer solid film having conductivity and electrochromic properties, and a light control body sandwiched between a pair of electrode substrates at least one of which is transparent is relatively The present invention has been completed by finding that it can be easily produced, has excellent handleability and durability, and is extremely responsive, so that color unevenness hardly occurs.
Note that in this specification, the solid film means that the film itself is solid, for example, means that the structure is not such that a solution of a conductive substance and an electrochromic substance is sealed in a cell.

The dimmer of the present invention comprises a pair of electrode substrates and a single-layer solid film sandwiched between the electrode substrates. The single-layer solid film has conductivity and electrochromic properties.
Examples of such a single layer solid film include those containing a compound having electrochromic properties and a conductive compound. As a specific configuration, a polymer compound having an electrochromic property as a matrix resin and a conductive compound is contained, or a compound having an electrochromic property and a conductive compound, and another polymer compound as a matrix resin. The composition etc. to contain are mentioned.
Among them, those containing a conductive compound using a polymer compound having electrochromic properties as a matrix resin are suitable because they are easy to produce and have excellent responsiveness.

Although it does not specifically limit as said high molecular compound which has electrochromic property, It is preferable that it is a high molecular compound which has electrochromic property and electroconductivity. The polymer compound is not particularly limited, and examples thereof include a polypyrrole compound having a substituent, a polythiophene compound having a substituent, and a polyacetylene compound having an aromatic side chain.
The polypyrrole compound having a substituent, the polythiophene compound having a substituent, and the polyacetylene compound having an aromatic side chain have not only electrochromic properties but also excellent electrical conductivity and excellent moldability. . Therefore, if these polymer compounds are used, a single-layer solid film having excellent light control performance can be formed. In addition, these polymer compounds exhibit excellent changes in absorption characteristics due to structural changes, and the change in absorption spectrum extends to the near-infrared wavelength region. It has a light effect. Among them, the polythiophene compound having a substituent and the polyacetylene compound having an aromatic side chain can easily adjust the degree of absorption in the visible region by adjusting the voltage, and color control is easy. is there.
These polymer compounds having electrochromic properties may be used alone or in combination of two or more.

Although it does not specifically limit as a polypyrrole-type compound which has the said substituent, For example, polypyrrole derivatives, such as poly (3,4-dibutyl pyrrole) and poly (3,4-ethylene dioxypyrrole), etc. are mentioned. Among these, polypyrrole having an alkyl group having 1 to 15 carbon atoms as a substituent is particularly preferable because it has high solubility and excellent moldability.

The polythiophene compound having the substituent is not particularly limited, and examples thereof include poly (3,4-ethylenedioxythiophene), poly (thieno [3,4-b]) thiophene, and poly (3,4-dibutyl). Thiophene), poly (3,4-ethylenedimethoxythiophene), poly (3,4-butylenedioxythiophene) and other polythiophene derivatives. Among these, poly (3,4-ethylenedioxythiophene) is preferable in terms of durability, film formability, and ease of color control.
Since the polythiophene-based compound having the above substituent can take a state of having a small absorption in the visible region and a large absorption in the near-infrared region by controlling the electrochromic state, the obtained dimmer is transparent. It can be used for members that require heat shielding properties.

The polyacetylene compound having an aromatic side chain is not particularly limited, but for example, polyacetylene having a mono- or di-substituted aromatic in the side chain is suitable.
The substituent constituting the aromatic side chain is not particularly limited, and examples thereof include phenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-iodophenyl, p-hexylphenyl, and p-octylphenyl. , P-cyanophenyl, p-acetoxyphenyl, p-acetophenyl, biphenyl, o- (dimethylphenylsilyl) phenyl, p- (dimethylphenylsilyl) phenyl, o- (diphenylmethylsilyl), p- (diphenylmethylsilyl) ) Phenyl, o- (triphenylsilyl) phenyl, p- (triphenylsilyl) phenyl, o- (tolyldimethylsilyl) phenyl, p- (tolyldimethylsilyl) phenyl, o- (benzyldimethylsilyl) phenyl, p- (Benzyldimethylsilyl) phenyl, o- ( Optionally substituted phenyl group such as ethenyldimethylsilyl) phenyl, p- (phenethyldimethylsilyl) phenyl; biphenyl group; 1-naphthyl, 2-naphthyl, 1- (4-fluoro) naphthyl, 1- ( An optionally substituted naphthyl group such as 4-chloro) naphthyl, 1- (4-bromo) naphthyl, 1- (4-hexyl) naphthyl, 1- (4-octyl) naphthyl; naphthalene group; 1-anthracene, Optionally substituted anthracene group such as 1- (4-chloro) anthracene, 1- (4-octyl) anthracene; phenanthrene group such as 1-phenanthrene; fluorene group such as 1-fluorene; perylene such as 1-perylene Groups and the like.

As the polyacetylene compound having an aromatic side chain, for example, those having a repeating unit represented by the following general formula (1), the following general formula (2) or the following general formula (3) are preferable. The polyacetylene compounds having these aromatic side chains are particularly excellent because the change in light transmittance due to the presence or absence of electrical stimulation exhibits a large contrast in a wide wavelength region including the near infrared region. Shows dimming effect.

式（１）中、Ｒ^１、Ｒ^２、Ｒ^３は水素、炭素数１０以下のアルキル基、又は、炭素数１０以下のアルコキシ基を表し、Ｒ^１、Ｒ^２、Ｒ^３のうち少なくとも１つはアルコキシ基を表す。

In Formula (1), R ¹ , R ² , and R ³ represent hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms, and at least one of R ¹ , R ² , and R ³ Represents an alkoxy group.

式（２）中、Ｒ^４、Ｒ^５、Ｒ^６はそれぞれ水素、炭素数１０以下のアルキル基、トリフルオロメチル基、トリアルキルシリル基（ただしアルキル基は炭素数６以下）、アミノ基、アルキルアミノ基を表し、少なくとも一つは水素ではなく、それ以外の基は同一であってもよいし異なっていてもよい。

In formula (2), R ⁴ , R ⁵ , and R ⁶ are each hydrogen, an alkyl group having 10 or less carbon atoms, a trifluoromethyl group, a trialkylsilyl group (wherein the alkyl group has 6 or less carbon atoms), an amino group, and an alkyl group Represents an amino group, at least one of which is not hydrogen, and other groups may be the same or different.

式（３）中、Ｒ^７は炭素数１〜１０の分岐していてもよいアルキル基、アルキル基の炭素数が１〜１０であるアルコキシ基、アルキル基の炭素数が１〜１０であるトリアルキルシリル基を表す。

In the formula (3), R ⁷ is an alkyl group having 1 to 10 carbon atoms which may be branched, an alkoxy group having 1 to 10 carbon atoms in the alkyl group, or a tri group having 1 to 10 carbon atoms in the alkyl group. Represents an alkylsilyl group.

The polyacetylene-based compound having an aromatic side chain can take a state having a small absorption in the visible region and a large absorption in the near infrared region by controlling the electrochromic state. It can be used for members that require heat resistance and heat shielding properties.

The weight average molecular weight of the polypyrrole compound having a substituent, the polythiophene compound having a substituent, and the polyacetylene compound having an aromatic side chain is not particularly limited, but a preferable lower limit is 3000 and a preferable upper limit is 10 million. If it is less than 3000, a single-layer solid film may not be formed. If it exceeds 10 million, moldability may be inferior. A more preferred lower limit is 10,000, and a more preferred upper limit is 5 million.

The single-layer solid film contains a conductive compound.
The conductive compound has a role of transferring electrons to the compound having electrochromic properties.

The conductive compound is not particularly limited, and examples thereof include an ion conductive material and an electron conductive material. Especially, when using at least one selected from the group consisting of a polypyrrole compound having the substituent, a polythiophene compound having a substituent, and a polyacetylene compound having an aromatic side chain as the electrochromic compound For this, an ion conductive material is preferably used.

The ion conductive substance is not particularly limited as long as it is a substance exhibiting ion conductivity. For example, salts, acids, alkalis and ionic liquids which are supporting electrolytes can be used.
The salts are not particularly limited, and examples thereof include inorganic ion salts such as alkali metal salts and alkaline earth metal salts; quaternary ammonium salts and cyclic quaternary ammonium salts.
The acids are not particularly limited, and for example, inorganic acids, organic acids, and the like can be used. Specific examples include sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, and carboxylic acids.
The alkalis are not particularly limited and include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like.

The ionic liquid is not particularly limited as long as it is a substance that is liquid at room temperature and exhibits ionic conductivity, and examples thereof include quaternary ammonium salts and cyclic quaternary ammonium salts. Are N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium and the anion is tetrafluoroborate ion or (CF ₃ SO ₂ ) ₂ N ^— .
These ion conductive materials may be used alone or in combination of two or more.

The ion conductive material may be used in a solution state dispersed in an organic polar solvent.
The organic polar solvent is not particularly limited, and examples thereof include dimethyl sulfoxide, dimethoxyethane, acetonitrile, dioxolane, dimethylformamide, tetrahydrofuran, dimethylacetamide, dimethyl sulfoxide, trimethyl phosphate, polyethylene glycol, ethylene carbonate, and propylene carbonate. .

The ion conductive substance may be used in a state where it is dispersed in a polymer compound having a polar group in a repeating unit (hereinafter also referred to as a polar group-containing polymer compound).
The polar group-containing polymer compound is not particularly limited, and examples thereof include polyethers such as polyethylene oxide and polypropylene oxide, polycarbonate, and fluorine-based polymers.

The method for dispersing the ion conductive substance in the polar group-containing polymer compound is not particularly limited. For example, a method in which the polar group-containing polymer compound and the supporting electrolyte are dissolved and mixed in the organic solvent, And a method of solidifying after dissolving and mixing.

Although it does not specifically limit as said electron conductive substance, For example, conventionally well-known various conjugated polymers, such as polyaniline, polypyrrole, polythiophene, etc. can be used.

The single-layer solid film may contain components other than the above components as long as the object of the present invention is not impaired. For example, for the purpose of improving moldability, a resin component having excellent moldability may be contained. The resin component having excellent moldability is not particularly limited, and examples thereof include thermoplastic resins such as polyvinyl acetal resin.

The method for producing the single-layer solid film is not particularly limited. For example, the conductive compound (the conductive organic polar solvent and / or the above-described polymer compound having the electroclock property is dissolved in a suitable solvent). Alternatively, it may be in a solution state dispersed in a polar group-containing polymer compound), and after dispersing other compounding components, a method of coating and drying may be mentioned.
The coating method is not particularly limited, and conventionally known methods such as a spin coating method and a casting method can be used.

The solvent is not particularly limited as long as it can dissolve the polymer compound and has excellent electrochromic compound and conductive compound dispersibility. For example, when the electrochromic compound is a polyacetylene compound having the aromatic side chain, a halogenated hydrocarbon such as chloroform, methylene chloride, or carbon tetrachloride; an aromatic hydrocarbon such as benzene or toluene; And ethers such as diethyl ether and tetrahydrofuran.

The dimmer of the present invention has a pair of electrode substrates, at least one of which is transparent.
The electrode substrate is not particularly limited, and materials, thicknesses, dimensions, shapes, and the like can be appropriately selected according to the purpose. For example, it may have a thickness like a window glass or may have a flexibility like a flexible substrate.

The transparent electrode substrate (hereinafter also referred to as a transparent electrode substrate) is not particularly limited, and a conventionally known transparent substrate having a transparent electrode film formed thereon can be used.
In the present specification, transparent means that the total light transmittance in a wavelength region of 400 to 800 nm is 60% or more.

The transparent substrate is not particularly limited, and for example, glass or resin can be used.
The glass is not particularly limited, and examples include soda glass, low alkali glass, non-alkali glass, and silica glass. The glass may be colorless or colored.
The resin is not particularly limited. For example, polyester such as polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene, cellulose triacetate, poly Examples thereof include methylpentene and polyarylate.

It does not specifically limit as said transparent electrode film, What consists of a conventionally well-known transparent conductive film etc. are mentioned. The transparent conductive film is not particularly limited. For example, a metal thin film such as gold, silver, chromium, copper, or tungsten; a metal oxide such as indium-doped tin oxide (ITO), tin oxide, or zinc oxide; polypyrrole , Polyacetylene, polythiophene, polyparaphenylene vinylene, polyaniline, polyacene, and those composed of conductive polymer compounds such as polyethylenedioxythiophene.
The transparent electrode film has a preferable lower limit of surface resistance of 0.5Ω / sq and a preferable upper limit of 500Ω / sq. If it is less than 0.5 Ω / sq, the dimmer may be deteriorated, and if it is 500 Ω / sq, uniform color change may not be obtained, such as color unevenness.

The method for producing the light control body of the present invention is not particularly limited, and the separately prepared single-layer solid film may be sandwiched between a pair of electrode substrates, at least one of which is transparent, On the electrode substrate, for example, a dispersion obtained by dispersing the conductive compound in a solution obtained by dissolving the electrochromic polymer compound in an appropriate solvent is applied and dried to form the single-layer solid film. Then, the other electrode substrate may be stacked.

The light control body of the present invention can be manufactured very easily by being configured as described above. In addition, since the responsiveness is high, the time from the application of voltage to the completion of the change in light transmittance is short, and the occurrence of color unevenness can be suppressed. Moreover, it is excellent in handleability and durability as compared with a liquid-sealed one.
The light control body of the present invention can be suitably used for various screens such as window glass, sunglasses, and partitions, heat shielding light control bodies for vehicles such as windshields and roofs, and various display panels.

According to the present invention, it is possible to provide a dimmer that is easy to manufacture, excellent in handling and durability, excellent in responsiveness, and capable of changing light transmittance by applying a voltage. it can.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
An electrolyte solution was prepared by dissolving 2.14 g of lithium perchlorate in 100 mL of propylene carbonate. To this electrolyte solution, 5 g of polyethylene glycol (molecular weight 300,000, manufactured by Wako Pure Chemical Industries, Ltd.) was added to obtain a gel electrolyte. To 10 mL of the obtained electrolyte, 5 mL of a propylene carbonate solution (manufactured by Aldrich) of poly (3,4-ethylenedioxythiophene) was added and stirred to obtain a suspension. The obtained suspension was spin-coated on an ITO layer of a transparent electrode made of a glass plate on which ITO was deposited, and dried to form a single-layer solid film.

(Example 2)
(1) Dichlorobis (triphenylphosphine) palladium (II) (manufactured by Kanto Chemical Co., Inc., 300 mg), which is a monomer synthesis catalyst, and triethylamine (manufactured by Kanto Chemical Co., 150 mL), 2-methyl-3-butyne-2- All (Kanto Chemical Co., Ltd. 10.4 mL) was added and stirred for 1 hour. Thereafter, 100 mL of triethylamine was added, and 2-iodoanisole (manufactured by Kanto Chemical Co., Inc., 25.0 g) was slowly added. The mixture was stirred for about 3 hours until the exotherm subsided, and the solvent was removed with a rotary evaporator. After extraction with ether, the solvent was removed again with a rotary evaporator, and then a finely pulverized potassium hydroxide (manufactured by Kanto Chemical Co., Ltd., 10.0 g) added with a small amount of toluene was added. Acetone was desorbed and removed by heating to 60 to 80 ° C. with a hot water bath while performing nitrogen bubbling. After stirring for about 2 hours until no acetone was produced, excess potassium hydroxide was removed by filtration and washed with hexane. The filtrate was neutralized with 5% aqueous hydrochloric acid with hexane and washed with water. After removing the solvent with a rotary evaporator, 5.5 g of o-methoxyphenylacetylene monomer was obtained by distillation under reduced pressure at 1 mmHg and 60.5 ° C.

(2) Synthesis of polymer Under nitrogen, 1.46 mg of the above monomer and 0.14 mL of chlorobenzene (manufactured by Kanto Chemical Co., Ltd.) and 1.00 mL of distilled toluene were used as a monomer solution, and tungsten chloride (VI) (manufactured by Kanto Chemical Co., Ltd.) 20 mg) and tetraphenyltin (manufactured by Kanto Chemical Co., 22 mg) plus 3.00 mL of distilled toluene was used as the catalyst batch. When 2 mL was extracted from the monomer solution and poured into the catalyst batch, the polymerization reaction proceeded. After standing for a whole day and night, the reaction was stopped by adding 0.5 mL of a toluene / methanol (4: 1) solution. The reaction product was dissolved by adding 5 mL of toluene, and poured into 1 L of methanol for reprecipitation. 21 mg of poly (o-methoxyphenylacetylene) was obtained by drying with a vacuum dryer after filtration. The obtained poly (o-methoxyphenylacetylene) had a weight average molecular weight of 10,000.

(3) Preparation of single-layer solid film and light control body To a solution of 1 g of the obtained poly (o-methoxyphenylacetylene) dissolved in 20 mL of toluene, an ionic liquid N, N-diethyl-N-methyl-N- ( 2-Methoxyethyl) ammonium tetrafluoroborate (Nisshinbo Co., Ltd.) (0.01 g) and acetonitrile (5 mL) were added and stirred using a magnetic stirrer to obtain a suspension.
The obtained suspension was spin-coated on an ITO layer of a transparent electrode made of a glass plate on which ITO was deposited, and dried to form a single-layer solid film.
As a counter electrode, a polyethylene terephthalate film on which ITO was deposited was superposed to obtain a light control member.

(Example 3)
(1) Synthesis of monomer Under nitrogen, 500 mL of triethylamine was added to 496 mg of dichlorobis (triphenylphosphine) palladium (II), 19.4 mL of phenylacetylene was added with a syringe, and the mixture was stirred for about 4 to 5 minutes until the solution turned black. When a solution obtained by dissolving 50.0 g of p-bromoiodobenzene in 200 mL of triethylamine was added while cooling in a water bath, the reaction proceeded and suspended in yellow. After removing triethylamine with a rotary evaporator, extraction was performed with 750 mL of ethyl ether. The solvent was removed again with a rotary evaporator to obtain bromo-substituted diphenylacetylene. After replacing another reactor with nitrogen, 114 mL of 1.6 M n-butyllithium hexane solution (manufactured by Kanto Chemical Co., Inc.) was added with a syringe, and about 75 mL of hexane was distilled while heating with a dryer under reduced pressure of an aspirator. Left. After purging with nitrogen, the mixture was cooled to −30 ° C., and 75 mL of ethyl ether was slowly added. When the bromo-substituted diphenylacetylene previously obtained dissolved in 150 mL of ethyl ether was added dropwise thereto, the reaction proceeded, and the solution turned black. Immediately thereafter, chlorotrimethylsilane (Kanto Chemical Co., Ltd., 17.1 mL) diluted with 150 mL of ethyl ether was added dropwise, and the suspension began to suspend in yellowish white color. Water was added while cooling with ice to stop the reaction, followed by extraction with 500 mL of ethyl ether. After removing the solvent with a rotary evaporator, the residue was purified by column chromatography to obtain 0.61 mL of a trimethylsilane-substituted diphenylacetylene monomer. The monomer was oil bathed at 40-50 ° C. so as not to solidify.

(2) Polymer synthesis Under nitrogen, 180 mL of n-docosan (manufactured by Kanto Chemical Co., Inc.) and 0.61 mL of the above monomer and 1.59 mL of distilled toluene were used as a monomer solution and aged at 80 ° C. for about 15 minutes. Similarly, tantalum chloride (V) (manufactured by Kanto Chemical Co., Ltd., 36 mg) and tetrabutyltin (manufactured by Kanto Chemical Co., Inc.) toluene solution (0.2 M) added to 1.00 mL of distilled toluene under a nitrogen catalyst batch And aged at 80 ° C. for about 15 minutes. When 2 mL was extracted from the monomer solution and poured into the catalyst batch, the polymerization reaction proceeded. After standing for 2 hours, 0.5 mL of a toluene / methanol (4: 1) solution was added to stop the reaction. The reaction product was dissolved by adding 50 mL of toluene, and poured into 4 L of methanol for reprecipitation. After filtration, it was dried with a vacuum dryer to obtain 320 mg of poly [1-phenyl-2- (m-trimethylsilylphenyl) acetylene]. The obtained poly [1-phenyl-2- (m-trimethylsilylphenyl) acetylene] had a weight average molecular weight of 1,000,000.

(3) Production of single-layer solid film and light control body In a solution of 0.2 g of poly [1-phenyl-2- (m-trimethylsilylphenyl) acetylene] obtained in 40 mL of toluene, an ionic liquid N, N -Diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate (Nisshinbo Co., Ltd.) (0.005 g) and acetonitrile (10 mL) were added and stirred using a magnetic stirrer to obtain a suspension. .
The obtained suspension was spin-coated on an ITO layer of a transparent electrode made of a glass plate on which ITO was deposited, and dried to form a single-layer solid film.
As a counter electrode, a polyethylene terephthalate film on which ITO was deposited was superposed to obtain a light control member.

Example 4
(1) Synthesis of monomer 27.5 mL of a 1.6 mol / L hexane solution of normal butyllithium was added to 25 mL of a tetrahydrofuran solution of 3.05 g of ethynylnaphthalene in a nitrogen atmosphere at -50 ° C. After cooling to −80 ° C., 15 mL of a tetrahydrofuran solution containing 2.25 g of potassium tertiary butoxide was added, and the mixture was stirred at −80 ° C. for 1 hour and then heated to 5 ° C. After cooling to -70 ° C, 4.42 g of bromodecane was added dropwise, the temperature was raised to 20 ° C, and the mixture was stirred for 2 hours. After further cooling to 0 ° C., 150 mL of diethyl ether was added and 50 mL of water was added dropwise to extract the produced compound. This diethyl ether layer was washed with 50 mL of distilled water three times, dried over anhydrous magnesium sulfate for 1 hour, filtered, and the solvent was distilled off. 2.1 g of 1-ethynyl-2-n-decylnaphthalene was obtained by column formation using hexane as a developing solvent.
¹ H NMR (270 mHz, CDCl ₃ ) δ 8.3 (1H), 7.8 (2H), 7.5 (3H), 3.6 (1H), 3.0 (2H), 1.7 (2H) 1.3 (16H), 0.9 (3H)

(2) Polymer synthesis 1.0 g of 1-ethynyl-2-n-hexylnaphthalene obtained was polymerized with a WCl ₆ catalyst to obtain 0.6 g of poly (1-ethynyl-2-n-decylnaphthalene).

(3) Production of single-layer solid film and light control body A light control body was obtained in the same manner as in Example 2 except that 0.2 g of the obtained poly (1-ethynyl-2-n-decylnaphthalene) was used. It was.

(Comparative Example 1)
A solution obtained by dissolving 1 g of poly (o-methoxyphenylacetylene) obtained in Example 2 in 20 mL of toluene was spin-coated on an ITO layer of a transparent electrode substrate made of a glass plate on which ITO was deposited, and dried to a thickness. An electrochromic layer containing 2500 liters of polyacetylene compound was formed.
Next, 2.14 g of lithium perchlorate was dissolved in 100 mL of propylene carbonate to prepare an electrolyte solution. To this electrolyte solution, 5 g of polyethylene glycol (molecular weight 300,000, manufactured by Wako Pure Chemical Industries, Ltd.) was added to form a gel, which was applied to the polyacetylene compound-containing layer to form a solid electrolyte layer. Further, a counter electrode substrate was laminated thereon to obtain a light control body composed of an electrochromic layer and an electrolyte layer.

(Evaluation)
About the light control body manufactured in Examples 1-4 and the comparative example 1, it evaluated by the following method.
The results are shown in Table 1.

(1) Observation of color change When a voltage of 3 V was applied between the electrodes using the transparent electrode as the anode and the counter electrode as the cathode, the monolayer solid film was changed from blue to light gray. When a voltage of −3 V was applied, the color changed from light gray to reddish purple. In the changed color, no color unevenness was observed. Further, when the potential was repeatedly changed between 3V and -3V, a color change from blue to light gray occurred reversibly.
When the voltage of 3 V was applied between the two electrodes using the transparent electrode as the anode and the counter electrode as the cathode, the single-layer solid film changed from red purple to light gray. When a voltage of −3 V was applied, the color changed from light gray to reddish purple. In the changed color, no color unevenness was observed. Further, when the potential was repeatedly changed between 3V and -3V, a color change from red purple to light gray occurred reversibly.
When the voltage of 3V was applied between the two electrodes using the transparent electrode as the anode and the counter electrode as the cathode, the single-layer solid film changed from blue-violet to light gray, and the light control body produced in Example 4 was -3V. When the voltage was applied, the color changed from light gray to blue-violet. In the changed color, no color unevenness was observed. Further, when the potential was repeatedly changed between 3V and -3V, a color change from blue purple to light gray occurred reversibly.
When a voltage of 3 V was applied between the two electrodes using the transparent electrode as the anode and the counter electrode as the cathode, the single-layer solid film changed from reddish purple to light gray, and −3 V When the voltage was applied, the color changed from light gray to reddish purple. In the changed color, no color unevenness was observed. Further, when the potential was repeatedly changed between 3V and -3V, a color change from red purple to light gray occurred reversibly.

(2) Responsiveness of color change when applied by changing the voltage between both electrodes using the transparent electrode as the anode and the counter electrode as the cathode was evaluated according to the following criteria.
○: Good responsiveness and quick color change.
Δ: Slightly poor responsiveness, and it takes time for the color change to appear.
X: Responsiveness is poor and it takes a long time for the color change to appear.

(3) Repeated durability The durability when applying and not applying a voltage was repeatedly evaluated according to the following criteria.
A: Dimming performance is not inferior even when it is repeated 10,000 times or more.
O: Remarkable deterioration of the light control performance is observed by repeating about 5000 times.
Δ: Remarkable deterioration in light control performance is observed by repeating about 1000 times.
X: Remarkable deterioration of the light control performance is observed by repeating about 500 times.

According to the present invention, it is possible to provide a dimmer that is easy to manufacture, excellent in handling and durability, excellent in responsiveness, and capable of changing light transmittance by applying a voltage. it can.

Claims (4)

A dimmer comprising a pair of electrode substrates, at least one of which is transparent, and a single-layer solid film having conductivity and electrochromic properties sandwiched between the electrode substrates. The light control body according to claim 1, wherein the single-layer solid film contains a compound having electrochromic properties and a conductive compound. The dimmer according to claim 2, wherein the compound having electrochromic properties is a polymer compound having electrochromic properties. The light control body according to claim 3, wherein the polymer compound having electrochromic properties has electrocomic properties and electrical conductivity.