JPWO2011074640A1 - Light control body, light control sheet, interlayer film for laminated glass and laminated glass - Google Patents

Abstract

The present invention provides a dimmer that has a very short time from application of a voltage to completion of a change in light transmittance. Moreover, the light control sheet | seat in which the time after applying a voltage until the change of light transmittance is completed is very short is provided. It aims at providing the laminated glass provided with the intermediate film for laminated glasses using this light control sheet, and this intermediate film for laminated glasses. In the present invention, an anode electrochromic layer containing a conductive polymer, an electrolyte layer, and a cathode electrochromic layer containing a mixed valence complex are sequentially laminated between a pair of transparent plates having a conductive film. It is a dimmer.

Description

The present invention relates to a light adjuster that has a very short time from application of a voltage to completion of a change in light transmittance. The present invention also relates to a light control sheet in which the time from application of voltage to completion of change in light transmittance is extremely short. The present invention relates to an interlayer film for laminated glass using the light control sheet, and a laminated glass including the interlayer film for laminated glass.

2. Description of the Related Art A light control body including a light control film whose light transmittance is changed by applying a voltage is widely used. Studies have been repeated for the purpose of applying this light control body to a display device such as a building or a lightning board. In recent years, a laminated glass using a light control film as an interlayer film for laminated glass has been proposed in order to control the temperature inside a vehicle such as an automobile. It is considered that the light transmittance of the laminated glass can be controlled by using such an interlayer film for laminated glass.

The dimmer is roughly classified into a dimmer using a liquid crystal material and a dimmer using an electrochromic compound. Among them, a light control body using an electrochromic compound has excellent properties such as less light scattering and no influence of polarization compared to a light control body using a liquid crystal material.

As electrochromic compounds, inorganic electrochromic compounds and organic electrochromic compounds are known. Moreover, as an organic electrochromic compound, the low molecular weight organic electrochromic compound and the high molecular compound which shows electrochromic property are examined.

As a light control body using an electrochromic compound, a light control body in which an electrochromic layer and an electrolyte layer are sandwiched between a pair of opposing electrode substrates has been proposed. For example, Patent Document 1 and Patent Document 2 include two laminates in which three layers of an electrochromic layer containing an inorganic oxide, an ion conductive layer, and an electrochromic layer containing an inorganic oxide are sequentially laminated. A light control member sandwiched between conductive substrates is disclosed. Patent Document 3 and Patent Document 4 disclose a light adjuster in which an electrochromic layer containing an organic electrochromic compound and an electrolyte layer are sandwiched between a pair of opposing electrode substrates.
However, since the conventional light adjuster has poor responsiveness, there is a problem that it takes time to complete the change in light transmittance even when a voltage is applied.

JP 2004-062030 A JP 2005-062772 A Japanese translation of PCT publication No. 2002-526801 JP-T-2004-53770

An object of the present invention is to provide a light adjuster that has a very short time from application of a voltage to completion of a change in light transmittance. It is another object of the present invention to provide a light control sheet in which the time from application of voltage to completion of change in light transmittance is extremely short. It aims at providing the laminated glass provided with the intermediate film for laminated glasses using this light control sheet, and this intermediate film for laminated glasses.

In the present invention, an anode electrochromic layer containing a conductive polymer, an electrolyte layer, and a cathode electrochromic layer containing a mixed valence complex are sequentially laminated between a pair of transparent plates having a conductive film. It is a dimmer.
The present invention is described in detail below.

In the laminate of the electrochromic layer and the electrolyte layer, the inventors have remarkably responsive by laminating an anode electrochromic layer on one surface of the electrolyte layer and a cathode electrochromic layer on the other surface. The present inventors have found that a light control body having a high time and a very short time from application of voltage to completion of change in light transmittance can be obtained, and the present invention has been completed. This is because the redox reaction between the anode electrochromic layer formed on one side of the electrolyte layer and the cathode electrochromic layer formed on the other side is paired, so that the oxidation required for the change in light transmittance This is considered to be because the reduction potential can be lowered.

In the dimmer of the present invention, an anode electrochromic layer containing a conductive polymer, an electrolyte layer, and a cathode electrochromic layer containing a mixed valence complex are sequentially disposed between a pair of transparent plates having a conductive film. Are stacked.
The anode electrochromic layer is preferably laminated so as to be in contact with the conductive film, and the cathode electrochromic layer is preferably laminated so as to be in contact with the conductive film.

The electrolyte layer has a role of applying a voltage to the electrochromic layer by conducting ions to change the light transmittance of the electrochromic layer.
The electrolyte layer preferably contains a supporting electrolyte salt and a binder resin. For example, the electrolyte layer is preferably formed using a resin composition containing a binder resin and a supporting electrolyte salt.

It is preferable that the electrolyte layer further contains a compound represented by the following formula (1) or a compound represented by the following formula (2). By adding the compound having the specific structure to the electrolyte layer, a light control body is obtained that has higher responsiveness and a very short time from application of voltage to completion of light transmittance change. .

In formula (1), n represents an integer of 2 to 4, R ¹ represents a hydrogen atom, an acyl group having an organic group having 1 to 7 carbon atoms, or an organic group having 1 to 8 carbon atoms, and R ² represents ethylene. R ³ represents a hydrogen atom, an acyl group having an organic group having 1 to 7 carbon atoms or an organic group having 1 to 8 carbon atoms, and at least ^{one of} R ^{1 and} R ³ represents an acyl group. Have.

In Formula (2), R ⁴ has 2 to 8 carbon atoms and represents an organic group having an oxygen atom, R ⁵ represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 12 carbon atoms, R ⁶ has 2 to 8 carbon atoms and represents an organic group having an oxygen atom. R ⁴ and R ⁶ may be the same or different.

The compound represented by the above formula (1) or the compound represented by the above formula (2) may be used alone or in combination. Among them, the compound represented by the above formula (1) is obtained because the light-adjusting material having improved durability and shorter time from application of voltage to completion of change in light transmittance can be obtained. It is preferable to contain.

In the above formula (1), R ¹ represents a hydrogen atom, an acyl group having an organic group having 1 to 7 carbon atoms, or an organic group having 1 to 8 carbon atoms. Among them, since the compatibility with the binder resin is further improved, it is preferred that R ¹ is an organic group having 1 to 8 carbon acyl group or C having an organic group having 1 to 7 carbon atoms, 1 to 4 carbon atoms It is more preferably an acyl group having -7 organic groups, and further preferably an acyl group having an alkyl group having 1 to 7 carbon atoms.

The preferable lower limit of the carbon number of the organic group in the acyl group having an organic group of 1 to 7 carbon atoms representing R ¹ in the above formula (1) is 2, and the preferable upper limit is 6. When the number of carbon atoms is 2 or more, the durability of the electrolyte layer is improved. When the number of carbon atoms is 6 or less, a dimmer with a shorter time from application of voltage to completion of change in light transmittance is obtained. It is done. The more preferable lower limit of the carbon number is 3, a more preferable upper limit is 5, and a more preferable upper limit is 4.

The organic group having 1 to 7 carbon atoms may be an organic group having a linear structure or an organic group having a branched structure, and may be an alkyl group having a linear structure or an alkyl group having a branched structure. Preferably there is. In the organic group having a branched structure or the alkyl group having a branched structure, the organic group or the branched chain of the alkyl group preferably has 3 or less carbon atoms, more preferably 2 or less, and more preferably 1 or less. Is more preferable.

Since a light control body with a shorter time from application of voltage to completion of change in light transmittance is obtained, when the organic group having 1 to 7 carbon atoms has a linear structure, the carbon The acyl group having an organic group having 1 to 7 carbon atoms has 1 to 7 carbon atoms and has an organic group having a linear structure, or 1 to 7 carbon atoms, and has a linear structure. It is preferably an acyl group having an alkyl group having

Since a dimmer with a shorter time from application of voltage to completion of the change in light transmittance is obtained, when the organic group having 1 to 7 carbon atoms has a branched structure, the carbon number The acyl group having 1 to 7 organic groups is an acyl group having 1 to 7 carbon atoms and having an organic group having a branched structure, or alkyl having 1 to 7 carbon atoms and having a branched structure. It is preferably an acyl group having a group, more preferably an acyl group having 1 to 7 carbon atoms, a branched structure, and an alkyl group having 3 or less branched carbon atoms, More preferably, it is an acyl group having an alkyl group having 1 to 7 carbon atoms, having a branched structure, and having 2 or less carbon atoms in the branched chain, having 1 to 7 carbon atoms, and having a branched structure. And having a branched chain having 1 or less carbon atoms And particularly preferably an acyl group having Le group.
The acyl group having an organic group having 1 to 7 carbon atoms means that the organic group has 1 to 7 carbon atoms, and the acyl group having an alkyl group having 1 to 7 carbon atoms. , It means that the alkyl group has 1 to 7 carbon atoms.

When R ¹ in the formula (1) is an organic group having 1 to 8 carbon atoms, the compatibility with the binder resin is further improved, so the organic group having 1 to 8 carbon atoms is 8 alkyl groups are preferred.
The preferable lower limit of the carbon number in the organic group having 1 to 8 carbon atoms representing R ¹ in the above formula (1) is 2, and the preferable upper limit is 7. When the number of carbon atoms is 2 or more, the durability of the electrolyte layer is improved. When the number of carbon atoms is 7 or less, a dimmer with a shorter time from application of voltage to completion of change in light transmittance is obtained. It is done. The more preferable lower limit of the carbon number is 3, a more preferable upper limit is 6, a further preferable lower limit is 4, and a more preferable upper limit is 5.

The organic group having 1 to 8 carbon atoms may be an organic group having a linear structure or an organic group having a branched structure, and may be an alkyl group having a linear structure or an alkyl group having a branched structure. Preferably there is. In the organic group having a branched structure or the alkyl group having a branched structure, the organic group or the branched chain of the alkyl group preferably has 3 or less carbon atoms, more preferably 2 or less, and more preferably 1 or less. Is more preferable.

Since a dimmer having a shorter time from the application of voltage to the completion of the change in light transmittance is obtained, when the organic group having 1 to 8 carbon atoms has a linear structure, the carbon The organic group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms and a linear structure.

Since a dimmer with a shorter time from application of voltage to completion of the change in light transmittance is obtained, when the organic group having 1 to 8 carbon atoms has a branched structure, the carbon number The organic group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms and having a branched structure, having 1 to 8 carbon atoms, having a branched structure, and branched carbon. More preferably, it is an alkyl group having a number of 3 or less, more preferably an alkyl group having 1 to 8 carbon atoms, having a branched structure, and having a branched chain having 2 or less carbon atoms, It is particularly preferable that the alkyl group has 1 to 8 carbon atoms, has a branched structure, and has 1 or less carbon atoms in the branched chain.

In the formula (1), R ² represents an ethylene group or a propylene group. The propylene group may be an n-propylene group or an isopropylene group. It is preferable that R ² is an ethylene group because a light adjuster with a shorter time from application of voltage to completion of change in light transmittance is obtained.

The formula (1), R ³ represents a hydrogen atom, an acyl group or an organic group having 1 to 8 carbon atoms having an organic group having 1 to 7 carbon atoms. Among them, since the compatibility with the binder resin is further improved, it is preferred that R ³ is an organic group having 1 to 8 carbon acyl group or C having an organic group having 1 to 7 carbon atoms, 1 to 4 carbon atoms It is more preferably an acyl group having -7 organic groups, and further preferably an acyl group having an alkyl group having 1 to 7 carbon atoms.

The preferable lower limit of the carbon number of the organic group in the acyl group having an organic group of 1 to 7 carbon atoms representing R ³ in the above formula (1) is 2, and the preferable upper limit is 6. When the number of carbon atoms is 2 or more, the durability of the electrolyte layer is improved. When the number of carbon atoms is 6 or less, a dimmer with a shorter time from application of voltage to completion of change in light transmittance is obtained. It is done. The more preferable lower limit of the carbon number is 3, a more preferable upper limit is 5, and a more preferable upper limit is 4.

The organic group having 1 to 7 carbon atoms may be an organic group having a linear structure or an organic group having a branched structure, and may be an alkyl group having a linear structure or an alkyl group having a branched structure. Preferably there is. In the organic group having a branched structure or the alkyl group having a branched structure, the organic group or the branched chain of the alkyl group preferably has 3 or less carbon atoms, more preferably 2 or less, and more preferably 1 or less. Is more preferable.

Since a light control body with a shorter time from application of voltage to completion of change in light transmittance is obtained, when the organic group having 1 to 7 carbon atoms has a linear structure, the carbon The acyl group having an organic group having 1 to 7 carbon atoms has 1 to 7 carbon atoms and has an organic group having a linear structure, or 1 to 7 carbon atoms, and has a linear structure. It is preferably an acyl group having an alkyl group having

Since a dimmer with a shorter time from application of voltage to completion of the change in light transmittance is obtained, when the organic group having 1 to 7 carbon atoms has a branched structure, the carbon number The acyl group having 1 to 7 organic groups is an acyl group having 1 to 7 carbon atoms and having an organic group having a branched structure, or alkyl having 1 to 7 carbon atoms and having a branched structure. It is preferably an acyl group having a group, more preferably an acyl group having 1 to 7 carbon atoms, a branched structure, and an alkyl group having 3 or less branched carbon atoms, More preferably, it is an acyl group having an alkyl group having 1 to 7 carbon atoms, having a branched structure, and having 2 or less carbon atoms in the branched chain, having 1 to 7 carbon atoms, and having a branched structure. And having a branched chain having 1 or less carbon atoms And particularly preferably an acyl group having Le group.
The acyl group having an organic group having 1 to 7 carbon atoms means that the organic group has 1 to 7 carbon atoms, and the acyl group having an alkyl group having 1 to 7 carbon atoms. , It means that the alkyl group has 1 to 7 carbon atoms.

In the above formula (1), at least ^{one of} R ^{1 and} R ³ has an acyl group. Thereby, high compatibility with the binder resin is obtained. Among them, R ¹ represents an acyl group having an alkyl group having 1 to 7 carbon atoms, R ² represents an ethylene group or a propylene group, and R ³ represents an acyl group having an alkyl group having 1 to 7 carbon atoms. Is more preferable.

Specific examples of the compound represented by the above formula (1) are shown in the following formulas (1-1) to (1-28).

In the above formula (2), ^{R 4} is a 2 to 8 carbon atoms, an organic group having an oxygen atom.
The lower limit of the number of carbon atoms of the organic group having 2 to 8 carbon atoms representing R ⁴ in the above formula (2) and having an oxygen atom is 3, and the preferable upper limit is 7. When the number of carbon atoms is 3 or more, the durability of the electrolyte layer is improved. When the number of carbon atoms is 7 or less, a dimmer with a shorter time from application of voltage to completion of change in light transmittance is obtained. It is done. The more preferable lower limit of the carbon number is 4, and the more preferable upper limit is 6.

In the above formula (2), ^{R 5} represents an alkylene group or an arylene group having 6 to 12 carbon atoms having 2 to 8 carbon atoms. Among them, since the compatibility with the binder resin is further improved, it is preferred that R ⁵ is an alkylene group having 2 to 8 carbon atoms.

The preferable lower limit of the carbon number of the alkylene group having 2 to 8 carbon atoms representing R ⁵ in the above formula (2) is 3, and the preferable upper limit is 7. When the number of carbon atoms is 3 to 7, a light adjuster with a shorter time from application of voltage to completion of change in light transmittance is obtained. The more preferable lower limit of the carbon number is 4, and the more preferable upper limit is 6.

Preferred upper limit of the number of carbon atoms of the arylene group having 6 to 12 carbon atoms representing the R ⁵ in the formula (2) is 10. When the number of carbon atoms is 10 or less, a light adjuster with a shorter time from application of voltage to completion of change in light transmittance can be obtained. A more preferable upper limit of the carbon number is 8.

In the above formula (2), ^{R 6} is 2 to 8 carbon atoms, an organic group having an oxygen atom.
The lower limit of the number of carbon atoms of the organic group having 2 to 8 carbon atoms representing R ⁶ in the above formula (2) and having an oxygen atom is 3, and the preferable upper limit is 7. When the number of carbon atoms is 3 or more, the durability of the electrolyte layer is improved. When the number of carbon atoms is 7 or less, a dimmer with a shorter time from application of voltage to completion of change in light transmittance is obtained. It is done. The more preferable lower limit of the carbon number is 4, and the more preferable upper limit is 6.

A specific example of the compound represented by the above formula (2) is shown in the following formula (2-1).

The compounding amount of the compound represented by the formula (1) and the compound represented by the formula (2) in the electrolyte layer is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the binder resin is 15 parts by weight, preferably. The upper limit is 200 parts by weight. When the compounding amount of the compound represented by the above formula (1) and the compound represented by the above formula (2) is 15 parts by weight or more, the time from when the voltage is applied until the change of the light transmittance is completed Becomes even shorter. The penetration resistance of a light control body becomes it high that the compounding quantity of the compound represented by the said Formula (1) and the compound represented by the said Formula (2) is 200 weight part or less. The more preferable lower limit of the compounding amount of the compound represented by the above formula (1) and the compound represented by the above formula (2) is 30 parts by weight, the still more preferable lower limit is 40 parts by weight, and the particularly preferable lower limit is 60 parts by weight. A more preferred upper limit is 150 parts by weight, a still more preferred upper limit is 120 parts by weight, and a particularly preferred upper limit is 100 parts by weight.

The supporting electrolyte salt is not particularly limited, and is preferably an alkali metal salt such as a lithium salt, a potassium salt, or a sodium salt. The alkali metal salt is preferably an inorganic acid and alkali metal salt or an organic acid and alkali metal salt. Examples of the inorganic acid and alkali metal salt include an inorganic acid anion lithium salt, an inorganic acid anion potassium salt, or an inorganic acid anion sodium salt, and the organic acid and alkali metal salt include an organic acid anion lithium. Examples thereof include a salt, an organic acid anion potassium salt, and an organic acid anion sodium salt.
Among them, the supporting electrolyte salt is preferably a lithium salt, and is an inorganic acid anion lithium salt such as lithium perchlorate, lithium borofluoride, or lithium phosphofluoride, or lithium trifluoromethanesulfonate, bistrifluoromethanesulfonate imide. An organic acid anion lithium salt such as lithium is more preferable.

The supporting electrolyte salt may be a salt of an ammonium cation and an anion.
The ammonium cation is not particularly limited, and examples thereof include alkylammonium cations such as tetraethylammonium, trimethylethylammonium, methylpropylpyrrolidinium, methylbutylpyrrolidinium, methylpropylpiperidinium, methylbutylpiperidinium, and ethylmethyl Examples include imidazolium, dimethylethylimidazolium, methylpyridinium, ethylpyridinium, propylpyridinium, and butylpyridinium.
The anion is not particularly limited, and examples thereof include perchlorate anion, borofluoride anion, phosphofluoride anion, trifluoromethanesulfonate anion, and bistrifluoromethanesulfonate imide anion.

The blending amount of the supporting electrolyte salt in the electrolyte layer is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the binder resin is 3 parts by weight, and a preferable upper limit is 60 parts by weight. When the blending amount of the supporting electrolyte salt is 3 to 60 parts by weight, the time from when the voltage is applied until the change of the light transmittance is completed is further shortened. A more preferred lower limit of the amount of the supporting electrolyte salt is 10 parts by weight, a still more preferred lower limit is 20 parts by weight, a more preferred upper limit is 50 parts by weight, and a still more preferred upper limit is 40 parts by weight.

The electrolyte layer preferably contains a solvent. The solvent is not particularly limited, for example, ester compounds such as acetonitrile, nitromethane, propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, etc. Substituted tetrahydrofuran compounds, ether compounds such as 1,3-dioxolane, 4,4-dimethyl-1,3-dioxolane, t-butyl ether, isobutyl ether, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, Organic solvents such as ethylene glycol, polyethylene glycol sulfolane, 3-methylsulfolane, methyl formate, methyl acetate, N-methylpyrrolidone, dimethylformamide It is.
Further, as the solvent, a diester compound such as triethylene glycol di-2-ethylhexanoate, triethylene glycol di-2-ethylbutyrate, tetraethylene glycol di-2-ethylhexanoate or the like may be used. .

Although the compounding quantity of the solvent in the said electrolyte layer is not specifically limited, The preferable minimum with respect to 100 weight part of said binder resins is 30 weight part, and a preferable upper limit is 150 weight part. When the blending amount of the solvent is 30 parts by weight or more, the time from the application of voltage to the completion of the change in light transmittance is further shortened. The penetration resistance of a light control body becomes it high that the compounding quantity of the said solvent is 150 weight part or less. A more preferred lower limit of the amount of the solvent is 50 parts by weight, and a more preferred upper limit is 100 parts by weight.

The binder resin is not particularly limited, but is preferably a thermoplastic resin.
The binder resin is, for example, polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, polytrifluoride ethylene, acrylonitrile-butadiene-styrene copolymer, polyester, polyether, polyamide, Examples include polycarbonate, polyacrylate, polymethacrylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl acetal resin, and ethylene-vinyl acetate copolymer. Of these, polyvinyl acetal resins and ethylene-vinyl acetate copolymers are preferable, and polyvinyl acetal resins are more preferable. Since an electrolyte layer having high transparency is obtained, a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol is more preferable. In particular, the polyvinyl acetal resin is preferably a polyvinyl butyral resin.

The polyvinyl acetal resin preferably has an acetyl group content of 15 mol% or less. When the amount of acetyl groups in the polyvinyl acetal resin exceeds 15 mol%, the electrolyte layer may be whitened.
The polyvinyl acetal resin preferably has a hydroxyl group content of 30 mol% or less. When the amount of hydroxyl groups in the polyvinyl acetal resin exceeds 30 mol%, the compatibility with the solvent may be lowered, and the transparency of the electrolyte layer may be lowered.
The acetyl group amount and the hydroxyl group amount can be determined by a titration method according to JIS K 6728.

The polyvinyl acetal resin is obtained by acetalizing polyvinyl alcohol with an aldehyde. The aldehyde is preferably an aldehyde having 4 or 5 carbon atoms. The preferable lower limit of the average degree of polymerization of the polyvinyl alcohol is 500, and the preferable upper limit is 5000. The penetration resistance of a light control body becomes it high that the average degree of polymerization of the said polyvinyl alcohol is 500 or more. When the average degree of polymerization of the polyvinyl alcohol is 5000 or less, the time from the application of voltage to the completion of the change in light transmittance is further shortened. The average degree of polymerization of the polyvinyl alcohol is determined by dividing the weight average molecular weight of the polyvinyl alcohol obtained by polystyrene conversion by GPC method (gel permeation chromatography) by the molecular weight per segment of polyvinyl alcohol. Examples of the column for measuring the weight average molecular weight in terms of polystyrene by the GPC method include Shodex LF-804 (manufactured by Showa Denko KK).

When the electrolyte layer contains the compound represented by the formula (1) or the compound represented by the formula (2), the compound represented by the formula (1) and the formula (2) In this case, the polyvinyl acetal resin has a acetyl group content of 5 mol% or more (hereinafter also referred to as “polyvinyl acetal resin A”) and acetal. Polyvinyl acetal resin having a degree of conversion of 70 to 85 mol% (hereinafter also referred to as “polyvinyl acetal resin B”), or polyvinyl obtained by acetalizing polyvinyl alcohol using an aldehyde having 6 or more carbon atoms It is preferably an acetal resin (hereinafter also referred to as “polyvinyl acetal resin C”).

The minimum with the preferable amount of acetyl groups of the said polyvinyl acetal resin A is 6 mol%, and a preferable upper limit is 30 mol%. It can further prevent that the compound represented by the said Formula (1) and the compound represented by the said Formula (2) precipitate from the said electrolyte layer as the said acetyl group amount is 6 mol% or more. . The manufacturing efficiency of the said polyvinyl acetal resin A can be improved as the said acetyl group amount is 30 mol% or less. The more preferred lower limit of the acetyl group amount is 8 mol%, the more preferred upper limit is 28 mol%, the still more preferred lower limit is 10 mol%, the still more preferred upper limit is 25 mol%, and the particularly preferred lower limit is 12 mol%, especially A preferable upper limit is 23 mol%.

The polyvinyl acetal resin A has a preferable lower limit of the degree of acetalization of 50 mol% and a preferable upper limit of 80 mol%. When the degree of acetalization is 50 mol% or more, the compound represented by the above formula (1) and the compound represented by the above formula (2) can be further prevented from depositing from the electrolyte layer. . When the degree of acetalization is 80 mol% or less, the production efficiency of the polyvinyl acetal resin A can be increased. The more preferable lower limit of the degree of acetalization is 55 mol%, the more preferable upper limit is 78 mol%, the still more preferable lower limit is 60 mol%, the still more preferable upper limit is 76 mol%, and the particularly preferable lower limit is 65 mol%. A preferable upper limit is 74 mol%.
The polyvinyl acetal resin A is preferably a polyvinyl butyral resin.

The minimum with a preferable acetalization degree of the said polyvinyl acetal resin B is 71 mol%, and a preferable upper limit is 84 mol%. When the degree of acetalization is 71 mol% or more, the compound represented by the above formula (1) and the compound represented by the above formula (2) can be further prevented from being precipitated from the electrolyte layer. . When the degree of acetalization is 84 mol% or less, the production efficiency of the polyvinyl acetal resin B can be increased. The more preferable lower limit of the degree of acetalization is 72 mol%, the more preferable upper limit is 83 mol%, the still more preferable lower limit is 73 mol%, the still more preferable upper limit is 82 mol%, and the particularly preferable lower limit is 74 mol%. A preferable upper limit is 81 mol%.

In the polyvinyl acetal resin B, a preferable lower limit of the amount of acetyl groups is 0.1 mol%, and a preferable upper limit is 20 mol%. When the amount of the acetyl group is 0.1 mol% or more, the compound represented by the formula (1) and the compound represented by the formula (2) are further prevented from being precipitated from the electrolyte layer. Can do. The manufacturing efficiency of the said polyvinyl acetal resin B can be improved as the said acetyl group amount is 20 mol% or less. The more preferable lower limit of the acetyl group amount is 0.5 mol%, the more preferable upper limit is 15 mol%, the more preferable lower limit is 0.8 mol%, the still more preferable upper limit is 8 mol%, and the particularly preferable lower limit is 1. The mol%, particularly preferred upper limit is 7 mol%.
The polyvinyl acetal resin B is preferably a polyvinyl butyral resin.

The polyvinyl acetal resin A and the polyvinyl acetal resin B are obtained by acetalizing polyvinyl alcohol with an aldehyde. The aldehyde is preferably an aldehyde having 1 to 10 carbon atoms, and more preferably an aldehyde having 4 or 5 carbon atoms.

The polyvinyl acetal resin C is obtained by acetalizing polyvinyl alcohol using an aldehyde having 6 or more carbon atoms. The aldehyde having 6 or more carbon atoms is not particularly limited, and examples thereof include n-hexyl aldehyde, n-octyl aldehyde, n-nonyl aldehyde, and n-decyl aldehyde.

The polyvinyl acetal resin C has a preferable lower limit of the degree of acetalization of 50 mol% and a preferable upper limit of 80 mol%. When the degree of acetalization is 50 mol% or more, the compound represented by the above formula (1) and the compound represented by the above formula (2) can be further prevented from depositing from the electrolyte layer. . When the degree of acetalization is 80 mol% or less, the production efficiency of the polyvinyl acetal resin C can be increased. The more preferable lower limit of the degree of acetalization is 55 mol%, the more preferable upper limit is 78 mol%, the still more preferable lower limit is 60 mol%, the still more preferable upper limit is 76 mol%, and the particularly preferable lower limit is 65 mol%. A preferable upper limit is 74 mol%.

The electrolyte layer may contain a heat ray absorbent.
The heat ray absorber is not particularly limited as long as it has the ability to shield infrared rays, but tin-doped indium oxide particles, antimony-doped tin oxide particles, zinc oxide particles doped with elements other than zinc, lanthanum hexaboride particles, At least one selected from the group consisting of zinc antimonate particles and an infrared absorber having a phthalocyanine structure is preferred.

The electrolyte layer may contain an adhesion adjusting agent.
Examples of the adhesion adjusting agent include alkali metal salts, alkaline earth metal salts, and magnesium salts. Of these, alkali metal salts, alkaline earth metal salts, and magnesium salts of carboxylic acids having 2 to 16 carbon atoms are preferred. Specifically, for example, bis (acetic acid) magnesium, potassium acetate, bis (propionic acid) magnesium. , Potassium propionate, magnesium bis (2-ethylbutanoate), potassium 2-ethylbutanoate, magnesium bis (2-ethylhexanoate), potassium 2-ethylhexanoate and the like. These adhesive force regulators may be used alone or in combination. In the case where the electrolyte layer contains a polyvinyl acetal resin as a binder resin, the electrolyte layer preferably contains an adhesive strength modifier.

The electrolyte layer may have a single layer structure or a multilayer structure. The electrolyte layer having a multilayer structure means a structure in which two or more electrolyte layers are laminated.
When the electrolyte layer has a multilayer structure, the electrolyte layer is composed of the supporting electrolyte salt, the compound represented by the above formula (1) or the compound represented by the above formula (2), and the binder resin. It is preferable to contain a plastic resin. Examples of the compound represented by the above formula (1) or the above formula (2) include triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH). And liquid plasticizers such as tetraethylene glycol di-2-ethylhexanoate (4GO) and dihexyl adipate (DHA).
For example, by laminating electrolyte layers having different contents of the liquid plasticizer, or by laminating electrolyte layers containing polyvinyl acetal resins having different amounts of hydroxyl groups as the binder resin, sound insulation of the laminated glass obtained, etc. Can be improved.

Although the thickness of the said electrolyte layer is not specifically limited, A preferable minimum is 0.01 mm and a preferable upper limit is 3.0 mm. When the thickness of the electrolyte layer is 0.01 to 3.0 mm, the time from the application of voltage to the completion of the change in light transmittance is further shortened. The more preferable lower limit of the thickness of the electrolyte layer is 0.1 mm, the more preferable upper limit is 2.0 mm, the still more preferable lower limit is 0.3 mm, and the still more preferable upper limit is 1.0 mm.

The method for forming the electrolyte layer is not particularly limited. For example, the supporting electrolyte salt is added to the solvent, the compound (1) represented by the formula (1) or the compound (2) represented by the formula (2). A method in which an electrolyte layer is prepared by mixing the obtained solution with the above binder resin to form an electrolyte layer, or a method in which the mixture is extruded by an extruder to form an electrolyte layer Etc.

In the light control body of the present invention, an anode electrochromic layer containing a conductive polymer, an electrolyte layer, and a cathode electrochromic layer containing a mixed valence complex are sequentially laminated.
The anode electrochromic layer contains a conductive polymer. The anode electrochromic layer has a property that visible light transmittance is increased by oxidation.
Note that having an electrochromic property means having a property of changing light transmittance by applying a voltage.

The conductive polymer is not particularly limited as long as it is a polymer having electrochromic properties and conductivity. For example, polypyrrole compound, polyacetylene compound, polythiophene compound, polyparaphenylene vinylene compound, polyaniline compound, polyethylenedioxythiophene Compounds and the like. Among these, a polyacetylene compound is preferable, and a polyacetylene compound having an aromatic side chain is more preferable.

The polyacetylene compound having an aromatic side chain has electrochromic properties and electrical conductivity, and can easily form an anode electrochromic layer. Therefore, if a polyacetylene compound having an aromatic side chain is used, an anode electrochromic layer having excellent light control performance can be easily formed. Moreover, the polyacetylene compound which has an aromatic side chain shows the change of an absorption characteristic, when a structure changes. As a result, since the absorption spectrum extends to the near-infrared wavelength region, the anode electrochromic layer has excellent dimming performance over a wide wavelength region.

The polyacetylene compound having an aromatic side chain is not particularly limited, and for example, a polyacetylene compound having a mono- or di-substituted aromatic in the side chain is suitable.

Although the substituent which comprises the said aromatic side chain is not specifically limited, For example, phenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-iodophenyl, p-hexylphenyl, p-octylphenyl, p -Cyanophenyl, p-acetoxyphenyl, p-acetophenyl, biphenyl, o- (dimethylphenylsilyl) phenyl, p- (dimethylphenylsilyl) phenyl, o- (diphenylmethylsilyl) phenyl, p- (diphenylmethylsilyl) Phenyl, o- (triphenylsilyl) phenyl, p- (triphenylsilyl) phenyl, o- (tolyldimethylsilyl) phenyl, p- (tolyldimethylsilyl) phenyl, o- (benzyldimethylsilyl) phenyl, p- ( Benzyldimethylsilyl) phenyl, o- ( Phenyl group such as ethenyldimethylsilyl) phenyl, p- (phenethyldimethylsilyl) phenyl, biphenyl group, 1-naphthyl, 2-naphthyl, 1- (4-fluoro) naphthyl, 1- (4-chloro) Naphtyl groups such as naphthyl, 1- (4-bromo) naphthyl, 1- (4-hexyl) naphthyl, 1- (4-octyl) naphthyl, naphthalene groups, 1-anthracene, 1- (4-chloro) anthracene And anthracene groups such as 1- (4-octyl) anthracene, phenanthrene groups such as 1-phenanthrene, fluorene groups such as 1-fluorene, and perylene groups such as 1-perylene.

The substituent constituting the aromatic side chain has at least one substituent selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a naphthalene group, an anthracene group, a phenanthrene group, a fluorene group, and a perylene group. It is preferable. Among them, since the time from application of voltage to completion of the change in light transmittance is further shortened, the substituents constituting the aromatic side chain are naphthyl group, naphthalene group, anthracene group, phenanthrene. Group, fluorene group or perylene group is more preferable, anthracene group, phenanthrene group, fluorene group or perylene group is further preferable, and phenanthrene group is particularly preferable.
In addition, some hydrogen atoms of the substituents constituting the aromatic side chain may be substituted with atoms or atomic groups other than hydrogen atoms.

The anode electrochromic layer may contain a heat ray absorbent or an adhesive strength modifier. The said heat ray absorber can use the heat ray absorber similar to the heat ray absorber contained in the said electrolyte layer. As the adhesive force adjusting agent, the same adhesive force adjusting agent as the adhesive force adjusting agent contained in the electrolyte layer can be used.

Although the thickness of the said anode electrochromic layer is not specifically limited, A preferable minimum is 0.05 micrometer and a preferable upper limit is 5 micrometers. When the thickness of the anode electrochromic layer is 0.05 to 5 μm, the time from when a voltage is applied until the change of the light transmittance is completed is further shortened. The more preferable lower limit of the thickness of the anode electrochromic layer is 0.1 μm, the more preferable upper limit is 2 μm, the still more preferable lower limit is 0.2 μm, and the still more preferable upper limit is 1 μm.

The anode electrochromic layer may contain the binder resin. As the binder resin, the same binder resin as the binder resin contained in the electrolyte layer can be used.

As a method for forming the anode electrochromic layer, a method is prepared in which a solution in which the conductive polymer is dissolved in an organic solvent is prepared, and the obtained solution is applied to one surface of the electrolyte layer to volatilize the organic solvent. Etc.

The cathode electrochromic layer contains a mixed valence complex. The cathode electrochromic layer has a property of increasing visible light transmittance upon reduction.

The mixed valence complex is not particularly limited as long as it has electrochromic properties, but is preferably a compound having a metal element and a cyano group, and preferably a compound having a metal element such as iron and a cyano group. More preferred.
Examples of the mixed valence complex include Prussian blue type complex (KFe [Fe (CN) ₆ ]). By including the mixed valence complex in the cathode electrochromic layer, a light control body in which the time from application of voltage to completion of the change in light transmittance can be obtained can be obtained.
In addition, when the said mixed valence complex is a Prussian blue type complex (KFe [Fe (CN) ₆ ]), some iron atoms may be substituted by atoms other than an iron atom.

The cathode electrochromic layer may contain a heat ray absorbent or an adhesive strength modifier. The said heat ray absorber can use the heat ray absorber similar to the heat ray absorber contained in the said electrolyte layer. As the adhesive force adjusting agent, the same adhesive force adjusting agent as the adhesive force adjusting agent contained in the electrolyte layer can be used.

Although the thickness of the said cathode electrochromic layer is not specifically limited, A preferable minimum is 0.05 micrometer and a preferable upper limit is 2 micrometers. When the thickness of the cathode electrochromic layer is 0.05 μm or more, the time from the application of voltage to the completion of the change in light transmittance is further shortened, and when the thickness is 2 μm or less, Increases transparency. A more preferable lower limit of the thickness of the cathode electrochromic layer is 0.1 μm, and a more preferable upper limit is 1 μm.

The cathode electrochromic layer may contain the binder resin. As the binder resin, the same binder resin as the binder resin contained in the electrolyte layer can be used.

As a method of forming the cathode electrochromic layer, a method of preparing a dispersion in which the mixed valence complex is dispersed in water or an organic solvent and applying the obtained solution to the electrolyte layer, or a conductive film of a transparent plate Examples thereof include a method of depositing the mixed valence complex by an electrodeposition method. For example, a step of applying a solution obtained by dissolving the conductive polymer in an organic solvent to one surface of the electrolyte layer, volatilizing the organic solvent, and forming an anode electrochromic layer; and the other side of the electrolyte layer It is preferable to perform a step of coating a surface with a solution in which the mixed valence complex is dispersed in an organic solvent, volatilizing the organic solvent, and forming a cathode electrochromic layer.
The method for dispersing the mixed valence complex in water or an organic solvent is not particularly limited. For example, the mixed valence complex is made into particles by a known method such as a sand mill, a bead mill, a mixer, or ultrasonic dispersion. The method of preparation etc. are mentioned.
Moreover, you may manufacture the light control sheet | seat by which the said anode electrochromic layer, the said electrolyte layer, and the said cathode electrochromic layer were laminated | stacked by the coextrusion method.
In addition, the laminate in which the anode electrochromic layer and the electrolyte layer are laminated and the cathode electrochromic layer formed on the conductive film of the transparent plate are laminated so that the electrolyte layer and the cathode electrochromic layer are in contact with each other. May be.

In addition to the electrolyte layer, the anode electrochromic layer, and the cathode electrochromic layer, the light control body of the present invention includes an ultraviolet absorbing layer containing an ultraviolet absorber, an infrared absorbing layer containing a heat ray absorber, and the like as necessary. You may have.

The transparent plate should just have the electrically conductive film formed in at least one surface. For example, a glass plate can be used as the transparent plate. Examples thereof include inorganic glass such as float plate glass, polished plate glass, template glass, netted glass, wire-containing plate glass, colored plate glass, heat ray absorbing glass, heat ray reflecting glass, and green glass. In addition, organic plastics plates such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polyacrylate can also be used. Two or more types of glass plates may be used as the transparent plate.

A light control sheet in which an anode electrochromic layer containing a conductive polymer, an electrolyte layer, and a cathode electrochromic layer containing a mixed valence complex are sequentially laminated is also one aspect of the present invention. . In particular, an anode electrochromic layer containing a conductive polymer is directly laminated on one side of the electrolyte layer, and a mixed valence complex is contained on the other side opposite to the one side of the electrolyte layer. It is preferable that the cathode electrochromic layer is directly laminated.

The light control sheet of the present invention preferably has an embossed surface.
The roughness of the emboss is not particularly limited, but the preferable lower limit of the ten-point average roughness defined by JIS B 0601 is 20 μm, and the preferable upper limit is 50 μm.

The light control sheet of the present invention can be used as an interlayer film for laminated glass. The interlayer film for laminated glass is also one aspect of the present invention.

The light control sheet and the interlayer film for laminated glass according to the present invention include an adhesive layer containing a thermoplastic resin partially formed on the anode electrochromic layer or the cathode electrochromic layer in order to increase the adhesive force with the conductive film. It is preferable to have.
The shape of the partially formed adhesive layer is not particularly limited, and examples thereof include a mesh shape, a linear shape, and a spot shape.

The preferable lower limit of the area of the adhesive layer relative to the area of the anode electrochromic layer or the cathode electrochromic layer is 10%, and the preferable upper limit is 90%. When the area of the adhesive layer is 10 to 90%, the time from when the voltage is applied until the change of the light transmittance is completed becomes shorter. The more preferable lower limit of the area of the adhesive layer is 20%, the more preferable upper limit is 80%, the still more preferable lower limit is 30%, and the still more preferable upper limit is 70%.
The area X (%) of the adhesive layer with respect to the area of the anode electrochromic layer or the cathode electrochromic layer is expressed by the following formula.
X (%) = (Amm ² ) / (10 mm ² ) × 100
The total area of the anode electrochromic layer or cathode electrochromic layer after forming the adhesive layer was observed by an optical microscope, in the places any 10 adhesive layer was formed (1 mm ^2/1 point), to the presence of the adhesive layer A (mm ² ) is measured, and the area X (%) of the adhesive layer is calculated.

The upper limit of the maximum thickness of the adhesive layer is preferably 50 μm. When the maximum thickness of the adhesive layer is 50 μm or less, the time from when a voltage is applied until the change of the light transmittance is completed becomes shorter. A more preferable upper limit of the maximum thickness of the adhesive layer is 20 μm.
The maximum thickness of the adhesive layer means the maximum value of the thickness of the adhesive layer when the adhesive layer is measured with a 3D measurement laser microscope (“LEXT OLS4000” manufactured by OLYMPAS) after the adhesive layer is formed.

The method for forming the adhesive layer is not particularly limited, for example, a method in which the thermoplastic resin dissolved in an appropriate organic solvent is applied on the anode electrochromic layer or the cathode electrochromic layer by screen printing and then dried, Examples include a method of applying the thermoplastic resin dissolved in an appropriate organic solvent on the anode electrochromic layer or the cathode electrochromic layer with a spray irradiator and then drying.

A laminated glass in which the interlayer film for laminated glass of the present invention is sandwiched between a pair of glass plates on which a conductive film is formed so as to be in contact with each conductive film is also one aspect of the present invention. For example, the laminated glass which pinched | interposed the intermediate film for laminated glasses of this invention with the transparent float plate glass and the colored glass plate like green glass is mentioned. Moreover, you may use the glass plate from which 2 or more types of thickness differs as said transparent plate.

The glass plate has a conductive film formed on at least one surface. In the laminated glass of the present invention, the interlayer film for laminated glass of the present invention is sandwiched between two glass plates so as to be in contact with the surface of the glass plate on which the conductive film is formed.
The conductive film is preferably a transparent conductive film containing tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), gallium-doped zinc oxide (GZO), or the like.

The surface density of the laminated glass of the present invention is not particularly limited, but is preferably 12 kg / m ² or less.
The laminated glass of the present invention can be used as a side glass, a rear glass, or a roof glass when used as an automotive glass.

According to the present invention, it is possible to provide a dimmer that has a very short time from application of a voltage to completion of a change in light transmittance. In addition, it is possible to provide a light control sheet in which the time from application of voltage to completion of the change in light transmittance is extremely short. An interlayer film for laminated glass using the light control sheet and a laminated glass provided with the interlayer film for laminated glass can be provided.

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
(1) Preparation of electrolyte layer An electrolyte solution was prepared by dissolving 0.67 g of bis (trifluoromethanesulfonyl) imide lithium (LiTFSI) as a supporting electrolyte salt in 2.38 g of triethylene glycol di-2-ethylhexanoate as a solvent. Prepared. Polyvinyl butyral resin (acetyl group content 13 mol%, hydroxyl group content 22 mol%) 5 obtained by acetalizing polyvinyl alcohol having an average polymerization degree of 2300 as a binder resin with n-butyraldehyde as a binder resin 5 0.000 g was mixed to obtain a resin composition. The obtained resin composition was sandwiched between polytetrafluoroethylene (PTFE) sheets, pressed through a spacer having a thickness of 400 μm with a hot press at 150 ° C. and 100 kg / cm ² for 5 minutes, and having a thickness of 400 μm. An electrolyte layer was obtained.

(2) Formation of anode electrochromic layer 13.4 g of a 30 wt% hexane solution of normal butyl lithium was added to 30 mL of tetrahydrofuran solution in which 3 g of 9-ethynylphenanthrene was dissolved at −50 ° C. in a nitrogen atmosphere. Next, after cooling to −90 ° C., 15 mL of a tetrahydrofuran solution in which 1.8 g of potassium tertiary butoxide was dissolved was added, stirred at −80 ° C. for 1 hour, and heated to 5 ° C. Subsequently, 5.6 g of 1-iodooctadecane was added dropwise at −70 ° C., and the mixture was stirred at −30 ° C. for 12 hours. 100 mL of water was added dropwise at 0 ° C., 300 mL of hexane was added, and the resulting compound was extracted. This hexane layer was washed with 300 mL of distilled water three times, dried over anhydrous magnesium sulfate for 1 hour, filtered, and then the solvent was distilled off. After column purification, the solvent was distilled off, and 3.5 g of 9-ethynyl-10-n-octadecylphenanthrene was obtained by column purification using hexane as a developing solvent.
The obtained 9-ethynyl-10-n-octadecylphenanthrene was analyzed by ¹ H-NMR (270 MHz, CDCl ₃ ). As a result, δ8.7 (2H), 8.5 (1H), 8.1 (1H ), 7.7 (4H), 3.7 (1H), 3.5 (2H), 1.7 (2H), 1.6 (30H), and 1.0 (3H).

1. Poly (9-ethynyl-10-n-octadecylphenanthrene) is polymerized using 3.5 g of 9-ethynyl-10-n-octadecylphenanthrene obtained in 10.5 g of toluene using 0.2 g of WCl ₆ catalyst. 7 g was obtained.
The molecular weight of the obtained poly (9-ethynyl-10-n-octadecylphenanthrene) was measured by gel permeation chromatography (GPC method). A liquid chromatograph manufactured by Waters (Waters 2695, RI Waters 2410, UV Waters 2996) was used, and Shodex LF-804 was used as the column. 100 μL of poly (9-ethynyl-10-n-octadecylphenanthrene) dissolved in chloroform so as to be 0.2% by weight was injected, and the measurement was performed at a column temperature of 40 ° C. with the mobile phase being chloroform. The molecular weight in terms of polystyrene was a number average molecular weight of 147,000 and a weight average molecular weight of 315,000.

A solution was prepared by dissolving 0.04 g of the obtained poly (9-ethynyl-10-n-octadecylphenanthrene) in 1.3 g of toluene. This solution was applied to one surface of the obtained electrolyte layer using a bar coater so that the thickness after evaporation of toluene was 0.3 μm, dried, and the anode electrochromic layer / electrolyte layer A laminate was obtained.

(3) Formation of cathode electrochromic layer Using a glass plate (surface resistance 10Ω / □) on which an ITO electrode is formed, with the ITO electrode as the working electrode, the Pt line as the counter electrode, and Ag / AgCl as the reference electrode, potassium ferricyanide, chloride A Prussian blue-type complex (KFe [Fe (CN) ₆ ]) as a mixed valence complex is formed on the surface of the ITO electrode by energizing for 120 seconds at a current density of 40 μA / cm ² in an aqueous solution in which 10 mmol / L of ferrous iron is dissolved. And ITO glass having a Prussian blue complex layer on the surface of the ITO electrode.

(4) Manufacture of light control body A laminate of anode electrochromic layer / electrolyte layer heated to 85 ° C. (5 × 5 cm in width) is a glass plate (5 × 5 cm in length, 5 cm in width, A dimmer was prepared by sandwiching the electrolyte layer and the Prussian blue complex layer in contact with each other between the surface resistance of 10Ω / □) and the ITO glass having the Prussian blue complex layer on the surface of the ITO electrode.
The obtained dimmer has a structure in which a glass plate / ITO electrode / anode electrochromic layer / electrolyte layer / cathode electrochromic layer (Prussian blue complex layer) / ITO electrode / glass plate are laminated.

(Example 2)
Prussian blue (manufactured by ACROS ORGANICS) 0.2 g in ethanol 19.8 g was added to 80 g of stainless steel balls 3 mm in diameter and shaken for 1 hour with a paint shaker (Seiwa Giken Co., Ltd.). A dispersion in which the particles were dispersed in ethanol was obtained. It was 132 nm (CV value 33.8%) when the volume average particle diameter of Prussian blue particles was measured by a particle size distribution meter (manufactured by Nicomp, “380ZLS-S”).
0.5 mL of the Prussian blue dispersion obtained is dropped on a glass plate (5 cm long × 5 cm wide, surface resistance 10 Ω / □) on which an ITO electrode is formed, and the condition is 1000 rpm with a spin coater (manufactured by Active). It was applied by rotating for 10 seconds to produce ITO glass having a Prussian blue layer on the surface of the ITO electrode.
A dimmer was produced in the same manner as in Example 1 except that ITO glass having a Prussian blue layer on the ITO electrode surface was used instead of ITO glass having a Prussian blue type complex layer on the ITO electrode surface. .

(Example 3)
A dispersion liquid in which Prussian blue particles were dispersed in ethanol was obtained in the same manner as in Example 2 except that a stainless steel sphere having a diameter of 3 mm was replaced with a zirconium sphere having a diameter of 1 mm. When the volume average particle diameter of Prussian blue particles was measured in the same manner as in Example 2, it was 125 nm (CV value 38.9%).
Thereafter, an ITO glass having a Prussian blue layer on the surface of the ITO electrode was produced in the same manner as in Example 2.
A dimmer was produced in the same manner as in Example 1 except that ITO glass having a Prussian blue layer on the surface of the obtained ITO electrode was used.

Example 4
In the same manner as in Example 1, an electrolyte layer, an anode electrochromic layer / electrolyte layer laminate was obtained.
0.5 mL of the Prussian blue dispersion obtained in the same manner as in Example 2 was dropped on the surface of the obtained anode electrochromic layer / electrolyte layer laminate opposite to the anode electrochromic layer, and spin coater ( (Manufactured by Active Corporation) and rotated for 10 seconds under the condition of 1000 rpm to obtain a light control sheet in which an anode electrochromic layer / electrolyte layer / Prussian blue layer were laminated in this order.

A light control sheet is obtained by sandwiching a light control sheet (5 cm long × 5 cm wide) heated to 85 ° C. between glass plates (5 cm long × 5 cm wide, surface resistance 10 Ω / □) on which two ITO electrodes are formed. Manufactured. In addition, the light control body was manufactured so that the light control sheet and the ITO electrode might contact.

(Example 5)
A dimmer was produced in the same manner as in Example 2 except that an electrolyte layer was prepared using triethylene glycol diacetate instead of triethylene glycol di-2-ethylhexanoate as a solvent.

(Example 6)
A dimmer was produced in the same manner as in Example 2 except that the electrolyte layer was prepared using triethylene glycol di-n-butyrate instead of triethylene glycol di-2-ethylhexanoate as a solvent.

(Example 7)
A dimmer was produced in the same manner as in Example 2 except that an electrolyte layer was prepared using triethylene glycol di-2-ethylbutyrate instead of triethylene glycol di-2-ethylhexanoate as a solvent.

(Example 8)
A dimmer was produced in the same manner as in Example 2 except that an electrolyte layer was prepared using triethylene glycol di-1-propylbutyrate instead of triethylene glycol di-2-ethylhexanoate as a solvent.

Example 9
A dimmer was produced in the same manner as in Example 2 except that an electrolyte layer was prepared using dipropoxyethyl adipate instead of triethylene glycol di-2-ethylhexanoate as a solvent.

(Example 10)
Instead of polyvinyl butyral resin (acetyl group content 13 mol%, hydroxyl group content 22 mol%) obtained by acetalizing polyvinyl alcohol having an average polymerization degree of 2300 with n-butyraldehyde as the binder resin, the average polymerization degree is 2300. A dimmer as in Example 6 except that an electrolyte layer was prepared using a polyvinyl butyral resin (acetyl group content 18 mol%, hydroxyl group content 15 mol%) obtained by acetalizing a certain polyvinyl alcohol with n-butyraldehyde. Manufactured.

(Example 11)
Instead of polyvinyl butyral resin (acetyl group content 13 mol%, hydroxyl group content 22 mol%) obtained by acetalizing polyvinyl alcohol having an average polymerization degree of 2300 with n-butyraldehyde as the binder resin, the average polymerization degree is 2300. A dimmer as in Example 6 except that an electrolyte layer was prepared using a polyvinyl butyral resin (acetyl group content 6 mol%, hydroxyl group content 11 mol%) obtained by acetalizing a certain polyvinyl alcohol with n-butyraldehyde. Manufactured.

(Example 12)
Instead of polyvinyl butyral resin (acetyl group content 13 mol%, hydroxyl group content 22 mol%) obtained by acetalizing polyvinyl alcohol having an average polymerization degree of 2300 with n-butyraldehyde as the binder resin, the average polymerization degree is 2300. A dimmer as in Example 6 except that an electrolyte layer was prepared using a polyvinyl butyral resin (acetyl group content 22 mol%, hydroxyl group content 22 mol%) obtained by acetalizing a certain polyvinyl alcohol with n-butyraldehyde. Manufactured.

(Example 13)
A dimmer was produced in the same manner as in Example 6 except that in the adjustment of the electrolyte layer, 2.38 g of triethylene glycol dibutyrate was changed to 2.5 g of triethylene glycol dibutyrate.

(Example 14)
A dimmer was produced in the same manner as in Example 6 except that in the adjustment of the electrolyte layer, 2.38 g of triethylene glycol dibutyrate was changed to 5.0 g of triethylene glycol dibutyrate.

(Example 15)
7.87 g of polyvinyl butyral resin (acetyl group content 13 mol%, hydroxyl group content 22 mol%) obtained by acetalizing polyvinyl alcohol having an average polymerization degree of 1700 with n-butyraldehyde, triethylene glycol di-2-ethylhexanoate An adhesive composition was obtained by dissolving 5.1 g and 1.56 g of bis (trifluoromethanesulfonyl) imidolithium (LiTFSI) in 45 g of ethanol.

The obtained adhesive composition was printed on the anode electrochromic layer of the anode electrochromic layer / electrolyte layer laminate produced by the same method as in Example 1 using a screen printing method. At this time, printing was performed in a mesh pattern so that the maximum thickness obtained from observation with a 3D measurement laser microscope (“LEXT OLS4000” manufactured by OLYMPAS) was 10 μm, and the area of the adhesive layer relative to the area of the anode electrochromic layer was 50%. After printing, the adhesive composition was dried to obtain a laminate of adhesive layer / anode electrochromic layer / electrolyte layer.
The area X (%) of the adhesive layer with respect to the area of the anode electrochromic layer was determined by observing the anode electrochromic layer after the adhesive layer was formed with an optical microscope, and at any 10 locations (1 mm ²⁾ where the adhesive layer was formed. / 1 place), the total area A (mm ² ) where the adhesive layer is present was measured and calculated by the following formula.
X (%) = A (mm ² ) / 10 (mm ² ) × 100

A laminate of an adhesive layer / anode electrochromic layer / electrolyte layer heated to 85 ° C. (5 × 5 cm in width) is a glass plate (5 × 5 cm in width, 10 Ω / □ surface resistance) on which one ITO electrode is formed. ) And an ITO glass having a Prussian blue type complex layer on the surface of the ITO electrode produced by the same method as in Example 1, so that the electrolyte layer and the Prussian blue type complex layer are in contact with each other, thereby dimming The body was made.
The obtained dimmer has a structure in which a glass plate / ITO electrode / adhesive layer / anode electrochromic layer / electrolyte layer / cathode electrochromic layer (Prussian blue type complex layer) / ITO electrode / glass plate are laminated.

(Comparative Example 1)
In the same manner as in Example 1, an anode electrochromic layer / electrolyte layer laminate was produced.
An anode electrochromic layer / electrolyte layer laminate (5 cm long × 5 cm wide) heated to 85 ° C. between a glass plate (5 cm long × 5 cm wide, surface resistance 10 Ω / □) on which two ITO electrodes are formed The light control body was produced by sandwiching between.
The obtained dimmer has a structure in which a glass plate / ITO electrode / anode electrochromic layer / electrolyte layer / ITO electrode / glass plate are laminated.

(Evaluation)
About the light control body obtained by the Example and the comparative example, the decoloring time and coloring time were measured with the following method. The results are shown in Table 1.
The transmittance of light having a wavelength of 640 nm of a light-modulating body in a completely colored state is denoted by TC, and the transmittance of light having a wavelength of 640 nm of a light-dimming body in a completely decolored state is denoted by TB.
A voltage of +2 V is applied to the fully colored dimmer, and after the voltage is applied, the transmittance of the light with a wavelength of 640 nm is changed from TC to T1 = TC + (TB−TC) × 0.8. The time required to change to was measured, and this was taken as the decoloring time.
A voltage of −2 V is applied to the dimming member in a completely decolored state, and after the voltage is applied, the transmittance of light having a wavelength of 640 nm is changed from TB to T2 = TB− (TB−TC) × The time for changing to 0.8 was measured and this was used as the coloring time.
In addition, the spectrophotometer "V-670" by JASCO Corporation was used for the measurement of the transmittance | permeability.
Moreover, the thickness of the glass plate in which the ITO electrode used in the Example and the comparative example was formed was 1 mm.

According to the present invention, it is possible to provide a dimmer that has a very short time from application of a voltage to completion of a change in light transmittance. In addition, it is possible to provide a light control sheet in which the time from application of voltage to completion of the change in light transmittance is extremely short. An interlayer film for laminated glass using the light control sheet and a laminated glass provided with the interlayer film for laminated glass can be provided.

Claims (20)

An anode electrochromic layer containing a conductive polymer, an electrolyte layer, and a cathode electrochromic layer containing a mixed valence complex are sequentially laminated between a pair of transparent plates having a conductive film. Dimmer to do. The light control body according to claim 1, wherein the conductive polymer is a polyacetylene compound having an aromatic group in a side chain. The dimmer according to claim 1 or 2, wherein the mixed-valence complex is a Prussian blue type complex. The electrolyte layer contains a supporting electrolyte salt, a binder resin, and a compound represented by the following formula (1) or a compound represented by the following formula (2). Light body.

In formula (1), n represents an integer of 2 to 4, R ¹ represents a hydrogen atom, an acyl group having an organic group having 1 to 7 carbon atoms, or an organic group having 1 to 8 carbon atoms, and R ² represents ethylene. R ³ represents a hydrogen atom, an acyl group having an organic group having 1 to 7 carbon atoms or an organic group having 1 to 8 carbon atoms, and at least ^{one of} R ^{1 and} R ³ represents an acyl group. Have.

In Formula (2), R ⁴ has 2 to 8 carbon atoms and represents an organic group having an oxygen atom, R ⁵ represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 12 carbon atoms, R ⁶ has 2 to 8 carbon atoms and represents an organic group having an oxygen atom. R ⁴ and R ⁶ may be the same or different. In formula (1), R ¹ represents an acyl group having an alkyl group having 1 to 6 carbon atoms, R ² represents an ethylene group or a propylene group, and R ³ represents an acyl group having an alkyl group having 1 to 6 carbon atoms. The light control member according to claim 4, wherein: The light control body according to claim 4 or 5, wherein the binder resin is a polyvinyl acetal resin. The light control body according to claim 6, wherein the polyvinyl acetal resin has an acetyl group content of 15 mol% or less and a hydroxyl group content of 30 mol% or less. The light control body according to claim 6, wherein the polyvinyl acetal resin has an acetyl group amount of 5 mol% or more. The light control body according to claim 6, wherein the polyvinyl acetal resin has an acetalization degree of 70 to 85 mol%. A light control sheet comprising an anode electrochromic layer containing a conductive polymer, an electrolyte layer, and a cathode electrochromic layer containing a mixed valence complex. The light control sheet according to claim 10, wherein the conductive polymer is a polyacetylene compound having an aromatic side chain. The light control sheet according to claim 10 or 11, wherein the mixed valence complex is a Prussian blue type complex. The electrolyte layer comprises a supporting electrolyte salt, a binder resin, and a compound represented by the following formula (1) or a compound represented by the following formula (2). Light sheet.

In formula (1), n represents an integer of 2 to 4, R ¹ represents a hydrogen atom, an acyl group having an organic group having 1 to 7 carbon atoms, or an organic group having 1 to 8 carbon atoms, and R ² represents ethylene. R ³ represents a hydrogen atom, an acyl group having an organic group having 1 to 7 carbon atoms or an organic group having 1 to 8 carbon atoms, and at least ^{one of} R ^{1 and} R ³ represents an acyl group. Have.

In Formula (2), R ⁴ has 2 to 8 carbon atoms and represents an organic group having an oxygen atom, R ⁵ represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 12 carbon atoms, R ⁶ has 2 to 8 carbon atoms and represents an organic group having an oxygen atom. R ⁴ and R ⁶ may be the same or different. In formula (1), R ¹ represents an acyl group having an alkyl group having 1 to 6 carbon atoms, R ² represents an ethylene group or a propylene group, and R ³ represents an acyl group having an alkyl group having 1 to 6 carbon atoms. The light control sheet according to claim 13, wherein The light control sheet according to claim 13 or 14, wherein the binder resin is a polyvinyl acetal resin. The light control sheet according to claim 15, wherein the polyvinyl acetal resin has an acetyl group amount of 15 mol% or less and a hydroxyl group amount of 30 mol% or less. The light control sheet according to claim 15, wherein the polyvinyl acetal resin has an acetyl group amount of 5 mol% or more. The light control sheet according to claim 15, wherein the polyvinyl acetal resin has an acetalization degree of 70 to 85 mol%. An interlayer film for laminated glass, wherein the light control sheet according to claim 10 or 11 is used. A laminated glass, wherein the interlayer film for laminated glass according to claim 19 is sandwiched between a pair of glass plates on which a conductive film is formed.