JP2012214742A - Photochromic material, photochromic sheet, electrolyte sheet, photochromic body, intermediate film for laminated glass, and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photochromic material that can perform light control by varying light transmittance by applying voltage to one and the other surfaces and can keep transparency excellent without being colored even under repetitive light controls.SOLUTION: The photochromic material has: an electrolyte layer; and an electrochromic layer having an electrochromic compound. The electrolyte layer comprises: a vinyl acetal resin; a supporting electrolyte; a plasticizer; and at least one antioxidant selected from a group comprising a compound having a predetermined bisphenol structure in a molecule, thiobisphenol having a predetermined structure, and a styrenated phenol.

Description

The present invention can control light by changing the transmittance of light by applying a voltage to one surface and the other surface, and has excellent transparency without coloring even after repeated light control. Light control material that can be maintained, light control sheet, electrolyte sheet constituting the light control material, light control body using the light control material, interlayer film for laminated glass, and interlayer film for laminated glass It relates to laminated glass.

A dimmer whose light transmittance is changed by applying a voltage is widely used.
The dimmer is roughly classified into a dimmer using a liquid crystal material and a dimmer using an electrochromic compound. A dimmer using an electrochromic compound is characterized by less light scattering and less polarization than a dimmer using a liquid crystal material.

As a light control body using an electrochromic compound, a light control body in which a light control material having an electrochromic layer and an electrolyte layer is 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 material and an electrolyte layer are sandwiched between a pair of opposing electrode substrates.

In recent years, it has been proposed to use laminated glass using a light control body as an interlayer film for laminated glass for automobile window glass and architectural window glass. If such an interlayer film for laminated glass is used, it is considered that the light transmittance of the laminated glass can be controlled to adjust the temperature in the vehicle or the room.
However, the conventional dimming material has a problem that when it is repeatedly dimmed, it is gradually colored and its transparency is lowered.

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

The present invention can control light by changing the transmittance of light by applying a voltage to one surface and the other surface, and has excellent transparency without coloring even after repeated light control. Light control material that can be maintained, light control sheet, electrolyte sheet constituting the light control material, light control body using the light control material, interlayer film for laminated glass, and interlayer film for laminated glass An object is to provide a laminated glass.

The present invention is a light control material having an electrolyte layer and an electrochromic layer containing an electrochromic compound, wherein the electrolyte layer includes a vinyl acetal resin, a supporting electrolyte, a plasticizer, and the following general formula in the molecule: Dimming comprising at least one antioxidant selected from the group consisting of a compound having a bisphenol structure represented by (1), a thiobisphenol represented by the following general formula (2), and a styrenated phenol Material.

In formula (1), R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₃ ′, R ₄ ′, R ₅ ′, R ₆ ′, R ₇ ′ represent a hydrogen atom or a substituent. One of R ₃ , R ₅ , and R ₇ represents an OH group, and one of R ₃ ′, R ₅ ′, and R ₇ ′ represents an OH group, and the substituent adjacent to each OH group At least one of them represents a tertiary hydrocarbon group.
In the formula (2), R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₃ ′, R ₁₄ ′, R ₁₅ ′, R ₁₆ ′, R ₁₇ ′ represent a hydrogen atom or a substituent, _{One of 13} , R ₁₅ and R ₁₇ represents an OH group, and one of R ₁₃ ′, R ₁₅ ′ and R ₁₇ ′ represents an OH group, and at least one of substituents adjacent to each OH group. Represents a tertiary hydrocarbon group.

According to the observation of the present inventor, coloring when the light was repeatedly controlled was mainly generated at the interface between the electrolyte layer containing the vinyl acetal resin and the plasticizer and the electrochromic layer. This is because the concentration of the supporting electrolyte in the vicinity of the interface between the electrolyte layer and the electrochromic layer is increased by performing dimming repeatedly. As a result, the supporting electrolyte and the plasticizer react to generate radicals, and the radicals generate vinyl acetal. This may be because the resin deteriorates. As a result of intensive studies, the present inventor has found that the electrolyte layer has a bisphenol structure represented by the general formula (1) in the molecule, a thiobisphenol represented by the general formula (2), and a styrenated phenol. The present invention has found that a light-modulating material capable of maintaining excellent transparency without coloring even by repeated light control can be obtained by blending at least one antioxidant selected from the group consisting of the present invention, and the present invention. It came to complete. It is thought that this is because the antioxidant can exhibit the performance as a radical trapper and prevent the occurrence of coloring by blending the specific antioxidant.

The light control material of this invention has an electrolyte layer and an electrochromic layer.
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 includes a vinyl acetal resin, a supporting electrolyte, a plasticizer, a compound having a bisphenol structure represented by the general formula (1) in the upper molecule, a thiobisphenol represented by the general formula (2), And at least one antioxidant selected from the group consisting of styrenated phenols. When the electrolyte layer contains a specific antioxidant, the light control material of the present invention can maintain excellent transparency without being colored even if light control is repeated.

In the above formula (1), R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₃ ′, R ₄ ′, R ₅ ′, R ₆ ′, R ₇ ′ are hydrogen atoms or substituents Represents.
R ₂ represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkyl group having at least one functional group selected from the group consisting of a carboxyl group, an ester group, an ether group, an amino group, a mercapto group, and a hydroxyl group. And its derivatives are preferred, and hydrogen and alkyl groups having 1 to 6 carbon atoms are more preferred.

R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₃ ′, R ₄ ′, R ₅ ′, R ₆ ′, R ₇ ′ are alkyl groups, ether groups, hydroxyl groups, carboxyl groups, ester groups, Amino groups, mercapto groups and derivatives thereof are preferred.
Here, one of R ₃ , R ₅ , and R ₇ represents an OH group, and one of R ₃ ′, R ₅ ′, and R ₇ ′ represents an OH group. Furthermore, at least one of the substituents adjacent to each OH group represents a tertiary hydrocarbon group.
R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₃ ′, R ₄ ′, R ₅ ′, R ₆ ′ and R ₇ ′ excluding the hydroxyl group may be the same or different. It may be.

In the formula _{(2), R 13, R} 14, R 15, R 16, R 17, R 13 ', R 14', R 15 ', R 16', R 17 ' represents a hydrogen atom or a substituent.
R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₃ ′, R ₁₄ ′, R ₁₅ ′, R ₁₆ ′, R ₁₇ ′ are an alkyl group, an ether group, a hydroxyl group, a carboxyl group, an ester group, Amino groups, mercapto groups and derivatives thereof are preferred.
Here, one of R ₁₃ , R ₁₅ and R ₁₇ represents an OH group, and one of R ₁₃ ′, R ₁₅ ′ and R ₁₇ ′ represents an OH group, and a substituent adjacent to each OH group. At least one of them represents a tertiary hydrocarbon group.
R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₃ ′, R ₁₄ ′, R ₁₅ ′, R ₁₆ ′ and R ₁₇ ′ excluding the hydroxyl group may be the same or different. It may be.

Specific examples of the antioxidant that is a compound having a bisphenol structure represented by the general formula (1) in the molecule include 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) ( For example, “ANTAGE W500” manufactured by Kawaguchi Chemical Co., Ltd.), 2,2′-methylenebis (4-methyl-6-tert-butylphenol) (for example, “ANTAGE W400” manufactured by Kawaguchi Chemical Co., Ltd.), 4,4′-butylidenebis (3 -Methyl-6-tert-butylphenol) (for example, “ANTAGE W300” manufactured by Kawaguchi Chemical Co., Ltd.), bis [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid] ethylene (for example, Clariant Japan “HOSTANOX O3”) and the like.

Examples of the antioxidant which is a compound having a thiobisphenol structure represented by the general formula (2) include 4,4′-thiobis (3-methyl-6-tert-butylphenol) (for example, manufactured by Kawaguchi Chemical Co., Ltd.). "Antage Crystal").
As an antioxidant which is the styrenated phenol, mono-styrenated phenol, di-styrenated phenol, tri-styrenated phenol or a mixture thereof (for example, “ANTAGE SP” manufactured by Kawaguchi Chemical Co., Ltd.) can be used. .

The blending amount of the antioxidant in the electrolyte layer is preferably 0.05 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the vinyl acetal resin. When the blending amount of the antioxidant is less than 0.05 parts by weight, the light control material to be obtained has low repetition durability, and may be colored when repeated light control is performed and transparency may be lowered. If it exceeds 10 parts by weight, coloring by the antioxidant itself may occur. A more preferable lower limit of the blending amount of the antioxidant is 0.5 parts by weight, and a more preferable upper limit is 5 parts by weight.

The vinyl acetal resin is preferably a vinyl acetal resin obtained by acetalizing a vinyl alcohol resin with an aldehyde having 4 or 5 carbon atoms because an electrolyte layer having high transparency can be obtained.
The preferable lower limit of the average degree of polymerization of the vinyl alcohol resin is 500, and the preferable upper limit is 5000. If the degree of polymerization of the vinyl alcohol resin is less than 500, the shape of the electrolyte layer may not be maintained. If the degree of polymerization exceeds 5000, the ionic conductivity becomes low, and even if a voltage is applied, the light of the electrochromic layer The transmittance may not change.

The vinyl acetal resin preferably has an acetyl group content of 15 mol% or less. When the amount of acetyl groups in the vinyl acetal resin exceeds 15 mol%, the hydrophobicity becomes too low, which may cause whitening of the electrolyte layer.
The vinyl acetal resin preferably has a hydroxyl group content of 30 mol% or less. When the amount of hydroxyl groups in the vinyl acetal resin exceeds 30 mol%, the compatibility with the plasticizer 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.

Examples of the supporting electrolyte include inorganic acid anion lithium salts such as lithium perchlorate, lithium borofluoride and lithium phosphofluoride, and organic acid anion lithium salts such as lithium trifluoromethanesulfonate and lithium bistrifluoromethanesulfonate imide. .

The supporting electrolyte may be a salt of an ammonium cation and an anion.
Examples of the ammonium cation include alkylammonium cations such as tetraethylammonium, trimethylethylammonium, methylpropylpyrrolidinium, methylbutylpyrrolidinium, methylpropylpiperidinium, methylbutylpiperidinium, ethylmethylimidazolium, Examples include dimethylethylimidazolium, methylpyridinium, ethylpyridinium, propylpyridinium, butylpyridinium and the like.
Examples of the anion include perchlorate anion, borofluoride anion, phosphofluoride anion, trifluoromethanesulfonic acid anion, bistrifluoromethanesulfonic acid imide anion, and the like.

The blending amount of the supporting electrolyte in the electrolyte layer is preferably 3 parts by weight with respect to 100 parts by weight of the vinyl acetal resin, and 60 parts by weight with respect to the preferred upper limit. When the blending amount of the supporting electrolyte is less than 3 parts by weight, the ionic conductivity is lowered, and the light transmittance of the electrochromic layer may not change even when a voltage is applied. The responsiveness of the electrochromic layer may be lowered. A more preferable lower limit of the amount of the supporting electrolyte is 10 parts by weight, and a more preferable upper limit is 50 parts by weight.

The plasticizer has a role of imparting flexibility to the electrolyte layer.
Examples of the plasticizer include triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH), tetraethylene glycol di-2-ethylhexanoate (4GO). ), Dihexyl adipate (DHA) and the like.

As for the compounding quantity of the said plasticizer in the said electrolyte layer, the preferable minimum with respect to 100 weight part of said vinyl acetal resins is 30 weight part, and a preferable upper limit is 150 weight part. When the blending amount of the plasticizer is less than 30 parts by weight, the ionic conductivity becomes low, and even when a voltage is applied, the light transmittance of the electrochromic layer may not change. The electrolyte layer may not maintain its shape. The more preferable lower limit of the blending amount of the plasticizer is 50 parts by weight, and the more preferable upper limit is 100 parts by weight.

The electrolyte layer may contain a solvent.
Examples of the solvent include esters such as acetonitrile, nitromethane, propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, and γ-butyrolactone, and substituted tetrahydrofurans such as tetrahydrofuran and 2-methyltetrahydrofuran. Or ethers such as 1,3-dioxolane, 4,4-dimethyl-1,3-dioxolane, t-butyl ether, isobutyl ether, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, ethylene glycol, Examples thereof include organic solvents such as polyethylene glycol sulfolane, 3-methylsulfolane, methyl formate, methyl acetate, N-methylpyrrolidone, and dimethylformamide.

The electrolyte layer may contain a heat ray absorbent.
Examples of the heat ray absorber include tin-doped indium oxide particles, antimony-doped tin oxide particles, zinc oxide particles doped with elements other than zinc, lanthanum hexaboride particles, zinc antimonate particles, and infrared absorption having a phthalocyanine structure At least one selected from the group consisting of agents is preferred.

The electrolyte layer may contain an adhesion adjusting agent.
Examples of the adhesive strength adjusting agent include alkali metal salts and alkaline earth metal salts. Of these, alkali metal salts and alkaline earth metal salts of carboxylic acids having 2 to 16 carbon atoms are preferred, and specific examples include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, and 2-ethylbutanoic acid. Examples include magnesium, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate, and potassium 2-ethylhexanoate. These adhesive force regulators may be used alone or in combination.

The electrolyte layer may have a single layer structure or a multilayer structure. When the electrolyte layer has a multilayer structure, for example, it is possible to obtain an adjustment by stacking electrolyte layers having different plasticizer contents or stacking electrolyte layers containing vinyl acetal resins having different hydroxyl amounts. The sound insulation and the like of the light body and the laminated glass can be improved.

A preferable lower limit of the thickness of the electrolyte layer is 0.1 mm, and a preferable upper limit is 3.0 mm. When the thickness of the electrolyte layer is less than 0.1 mm, the light transmittance may not change even when a voltage is applied to the electrochromic layer. When the thickness exceeds 3.0 mm, the voltage is applied to the electrochromic layer. When is applied, the rate of change of light transmittance may decrease. A more preferable lower limit of the thickness of the electrolyte layer is 0.3 mm, and a more preferable upper limit is 1.0 mm.

As a method of forming the electrolyte layer, for example, a solution in which the supporting electrolyte is dissolved in the plasticizer is prepared, and the obtained solution is mixed with the vinyl acetal resin, and then the mixture is heated by a method such as hot pressing. Examples thereof include a method for forming a sheet, and a method for forming the mixture by extrusion using an extruder.
The electrolyte sheet comprising the above electrolyte layer is also one aspect of the present invention.

The electrochromic compound contained in the electrochromic layer may be an inorganic compound, an organic compound, or a mixed valence complex as long as it is a compound having electrochromic properties.

As the inorganic compound having the electrochromic properties, for _{example, Mo 2 O 3, Ir 2} O 3, NiO, V 2 O 5, WO 3 and the like.
Examples of the electrochromic organic compound include, for example, polypyrrole compounds, polythiophene compounds, polyparaphenylene vinylene compounds, polyaniline compounds, polyacetylene compounds, polyethylene dioxythiophene compounds, metal phthalocyanine compounds, viologen compounds, viologen salt compounds, ferrocene compounds. Dimethyl terephthalate, diethyl terephthalate and the like. Among these, a polyacetylene compound is preferable, and a polyacetylene compound having an aromatic ring in the side chain is more preferable.
Examples of the mixed valence complex having electrochromic properties include Prussian blue type complexes (such as KFe [Fe (CN) 6]).

The polyacetylene compound having an aromatic ring in the side chain has electrochromic properties and electrical conductivity, and can easily form an electrochromic layer. Therefore, if a polyacetylene compound having an aromatic ring in the side chain is used, an electrochromic layer having excellent light control performance can be easily formed. Moreover, the polyacetylene compound which has an aromatic ring in a 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 electrochromic layer has excellent light control performance over a wide wavelength region.

As the polyacetylene compound having an aromatic ring in the side chain, for example, a polyacetylene compound having a mono- or disubstituted aromatic ring in the side chain is suitable.
Examples of the substituent having an aromatic ring constituting the side chain include 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), p- (diphenylmethylsilyl) phenyl, o- (triphenylsilyl) phenyl, p- (triphenylsilyl) phenyl, o- (tolyldimethylsilyl) phenyl, p- (tolyldimethylsilyl) phenyl, o- (benzyldimethylsilyl) phenyl, p- (benzyldimethyl) Silyl) phenyl, o- (phenethyldi) Phenyl group such as (tilylsilyl) phenyl, p- (phenethyldimethylsilyl) phenyl, biphenyl group, 1-naphthyl, 2-naphthyl, 1- (4-fluoro) naphthyl, 1- (4-chloro) naphthyl, 1- A naphthyl group such as (4-bromo) naphthyl, 1- (4-hexyl) naphthyl, 1- (4-octyl) naphthyl, naphthalene group, 1-anthracene, 1- (4-chloro) anthracene, 1- ( And anthracene groups such as 4-octyl) anthracene, phenanthrene groups such as 1-phenanthrene, fluorene groups such as 1-fluorene, and perylene groups such as 1-perylene.

The 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.

A preferable lower limit of the thickness of the electrochromic layer is 0.05 μm, and a preferable upper limit is 2 μm. If the thickness of the electrochromic layer is less than 0.05 μm, the light transmittance may not change sufficiently even when a voltage is applied to the electrochromic layer. If the thickness exceeds 2 μm, the light-modulating material is transparent. May decrease. A more preferable lower limit of the thickness of the electrochromic layer is 0.1 μm, and a more preferable upper limit is 1 μm.

As a method for producing the light modulating material of the present invention, for example, a solution in which the electrochromic compound is dissolved in an organic solvent is prepared, and the obtained solution is applied to at least one surface of the electrolyte layer. The method of volatilizing is mentioned. By such a method, it is possible to obtain a light control sheet in which an electrochromic layer containing an electrochromic compound is formed on at least one surface of the electrolyte layer.
A light control sheet in which an electrochromic layer containing an electrochromic compound is formed on at least one surface of the electrolyte layer is also one aspect of the present invention.

In the case of manufacturing a light control body by sandwiching the light control material of the present invention between a pair of transparent electrode substrates facing each other, a solution in which the electrochromic compound is dissolved in an organic solvent is prepared and obtained. After apply | coating the obtained solution on the electrode surface of one transparent electrode board | substrate and volatilizing an organic solvent, you may laminate | stack the said electrolyte layer on the obtained electrochromic layer. According to such a manufacturing method, a more uniform electrochromic layer can be formed.

In the light modulating material of the present invention, an adhesive layer partially containing a thermoplastic resin may be formed on the surface of the electrochromic layer on the side in contact with the transparent electrode substrate. By partially forming the adhesive layer, adhesion to the conductive film can be improved without impairing electrochromic properties.
Examples of the shape of the partially formed adhesive layer include a mesh shape, a linear shape, and a spot shape.

Examples of the thermoplastic resin contained in the adhesive layer include polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, polytrifluoride ethylene, acrylonitrile-butadiene-styrene copolymer. , Polyester, polyether, polyamide, polycarbonate, polyacrylate, polymethacrylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, vinyl acetal resin, ethylene-vinyl acetate copolymer, and the like. Of these, vinyl acetal resins and ethylene-vinyl acetate copolymers are preferable, and vinyl acetal resins are more preferable.

The adhesive layer preferably further contains a plasticizer. By containing a plasticizer, the said adhesive layer becomes flexible and the adhesiveness with respect to the electrically conductive film of the said electrochromic layer can be improved more.
The adhesive layer preferably further contains a supporting electrolyte. By containing the supporting electrolyte, ion conductivity is imparted to the adhesive layer, and the adhesive layer can prevent the electrochromic property of the laminated glass from being lowered.
As the plasticizer and the supporting electrolyte, the same plasticizer and supporting electrolyte as those used for the electrolyte layer can be used.

The upper limit of the area of the adhesive layer relative to the area of the electrochromic layer is 90%. When the area of the adhesive layer exceeds 90%, the electrochromic property is lowered, and the light transmittance may hardly change even when a voltage is applied. A preferable upper limit of the area of the adhesive layer is 80%, and a more preferable upper limit is 70%.
The area X (%) of the adhesive layer, when observed the electrochromic layer after the adhesive layer is formed by an optical microscope, the existing area of the adhesive layer per 1mm ² A (mm ^2), the presence of the adhesive layer When the area not to be used is B (mm ² ), X = A / (A + B).

The upper limit of the maximum thickness of the adhesive layer is 50 μm. When the maximum thickness of the adhesive layer exceeds 50 μm, the electrochromic property is lowered, and there may be a portion where the light transmittance hardly changes even when a voltage is applied. A preferable upper limit of the maximum thickness of the adhesive layer is 20 μm.
The maximum thickness of the adhesive layer refers to the maximum value of the adhesive layer thickness when the adhesive layer is measured with a 3D measuring laser microscope (LEXT OLS4000 manufactured by OLYMPAS) after the adhesive layer is formed.

As the method for forming the adhesive layer, for example, the thermoplastic resin dissolved in an appropriate organic solvent is applied on the electrochromic layer by screen printing and then dried, or the heat dissolved in an appropriate organic solvent is used. A method of drying after applying a plastic resin on an electrochromic layer by spraying is mentioned.

The light control body in which the light control material or the light control sheet of the present invention is sandwiched between a pair of transparent electrode substrates facing each electrode surface is also one aspect of the present invention.

The transparent electrode substrate is obtained by forming a transparent electrode on a glass substrate.
As the glass substrate, a commonly used transparent plate glass can be used. 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. Moreover, the organic glass board which consists of organic plastics, such as a polyethylene terephthalate, a polycarbonate, a polyacrylate, can also be used.
As the glass substrate, two or more kinds of glass substrates may be used in combination. For example, a transparent float plate glass and a colored glass plate such as green glass may be combined, or an inorganic glass and an organic glass may be combined. Moreover, you may combine the glass substrate from which 2 or more types of thickness differs.
As said transparent electrode, the transparent conductive film containing tin dope indium oxide (ITO), fluorine dope tin oxide (FTO), etc. is mentioned.

The light control material or light control sheet of the present invention can be used as an interlayer film for laminated glass. An interlayer film for laminated glass using the light control material or light control sheet of the present invention is also one aspect of the present invention. A laminated glass having the interlayer film for laminated glass of the present invention as a constituent element is also one aspect of the present invention.
The interlayer film for laminated glass of the present invention has an ultraviolet absorbing layer containing an ultraviolet absorber or an infrared absorbing layer containing a heat ray absorbent, if necessary, in addition to the configuration of the light modulating material or light modulating sheet of the present invention. Etc. may be included.

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 control light by changing the light transmittance by applying a voltage to one surface and the other surface, and excellent transparency without coloring even if light control is repeated. Light control material, light control sheet, electrolyte sheet constituting the light control material, light control body using the light control material, interlayer film for laminated glass, and interlayer film for laminated glass 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 47.6 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO), 13.4 parts by weight of lithium bis (trifluoromethanesulfonyl) imidoate (LiTFSI) as a supporting electrolyte, oxidation As an inhibitor, 0.5 part by weight of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage W500) was dissolved to prepare an electrolyte solution. The total amount of the obtained electrolyte solution was mixed with 100 parts by weight of a polyvinyl butyral resin having an acetyl group amount of 13 mol%, a hydroxyl group amount of 22 mol%, and an average polymerization degree of 2300 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 9.8 MPa for 5 minutes, and an electrolyte having a thickness of 400 μm. A layer was obtained.

(2) Preparation of electrochromic layer A solution was prepared by dissolving 2.9 parts by weight of poly (9-ethynyl-10-n-octadecylphenanthrene) in 100 parts by weight of toluene. This solution is applied on the obtained electrolyte layer using a bar coater so that the thickness after evaporation of toluene is 0.3 μm, and dried to form an electrochromic layer. A membrane was prepared.

(3) Production of laminated glass The obtained interlayer film for laminated glass was cut into a size of 5 cm long by 5 cm wide. Laminated glass interlayer film cut in 5cm x 5cm width is sandwiched between a pair of 5cm x 5cm ITO glass (surface resistance 120Ω) so that the laminated glass film is in contact with each conductive film. did. The obtained laminate was pressure-bonded with a vacuum laminator at 90 ° C., and after pressure bonding, pressure-bonded for 20 minutes using an autoclave under conditions of 140 ° C. and 14 MPa to obtain a laminated glass.

(Example 2)
The electrolyte layer and the electrochromic layer were the same as in Example 1 except that the content of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) as an antioxidant was changed to 0.1 parts by weight. Preparation was performed to obtain an interlayer film for laminated glass and laminated glass.

(Example 3)
The electrolyte layer and the electrochromic layer were prepared in the same manner as in Example 1, except that the content of the antioxidant 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) was changed to 2 parts by weight. The intermediate film for laminated glass and the laminated glass were obtained.

Example 4
The electrolyte layer and the electrochromic layer were prepared in the same manner as in Example 1 except that the content of the antioxidant 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) was changed to 5 parts by weight. The intermediate film for laminated glass and the laminated glass were obtained.

(Example 5)
Except for changing the content of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) as an antioxidant to 0.05 parts by weight, the electrolyte layer and electrochromic layer were the same as in Example 1. Preparation was performed to obtain an interlayer film for laminated glass and laminated glass.

(Example 6)
The electrolyte layer and the electrochromic layer were prepared in the same manner as in Example 1 except that the content of the antioxidant 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) was changed to 10 parts by weight. The intermediate film for laminated glass and the laminated glass were obtained.

(Example 7)
As in Example 1, except that styrenated phenol (manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage SP) was used as an antioxidant instead of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol). An electrolyte layer and an electrochromic layer were prepared to obtain an interlayer film for laminated glass and a laminated glass.

(Example 8)
Instead of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage Crystal) Except that it was used as an antioxidant, an electrolyte layer and an electrochromic layer were prepared in the same manner as in Example 1 to obtain an interlayer film for laminated glass and laminated glass.

Example 9
Instead of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (4-methyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage W300) was oxidized. Except that it was used as an inhibitor, an electrolyte layer and an electrochromic layer were prepared in the same manner as in Example 1 to obtain an interlayer film for laminated glass and laminated glass.

(Example 10)
Instead of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylene-bis (4-methyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage W400) Except that was used as an antioxidant, an electrolyte layer and an electrochromic layer were prepared in the same manner as in Example 1 to obtain an interlayer film for laminated glass and a laminated glass.

(Example 11)
Instead of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid] ethylene (manufactured by Clariant Japan, HOSTANOX Except that O3) was used as an antioxidant, an electrolyte layer and an electrochromic layer were prepared in the same manner as in Example 1 to obtain an interlayer film for laminated glass and laminated glass.

(Example 12)
An electrolyte layer and an electrochromic layer were prepared in the same manner as in Example 1 except that the supporting electrolyte contained in the electrolyte membrane was potassium bis (trifluoromethanesulfonyl) imidate (KTFSI), and an interlayer film for laminated glass and laminated glass were prepared. Got.

(Comparative Example 1)
An electrolyte layer and an electrochromic layer were prepared in the same manner as in Example 1 except that 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) was not used, and an interlayer film for laminated glass and laminated glass were prepared. Got.

(Comparative Example 2)
In place of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), dibutylhydroxytoluene (BHT manufactured by Honshu Chemical Industry Co., Ltd.) not corresponding to the antioxidant of the present invention was used as an antioxidant. Prepared the electrolyte layer and the electrochromic layer in the same manner as in Example 1 to obtain an interlayer film for laminated glass and laminated glass.

(Comparative Example 3)
Instead of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxy) which does not fall under the antioxidant of the present invention. Phenyl) propionate] (IRGANOX 1010, manufactured by BASF) was used as an antioxidant, and an electrolyte layer and an electrochromic layer were prepared in the same manner as in Example 1 to obtain an interlayer film for laminated glass and laminated glass. It was.

(Comparative Example 4)
Instead of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid which does not fall under the antioxidant of the present invention An electrolyte layer and an electrochromic layer were prepared in the same manner as in Example 1 except that stearyl (manufactured by BASF, IRGANOX 1076) was used as an antioxidant to obtain an interlayer film for laminated glass and laminated glass.

(Comparative Example 5)
Instead of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,5-di-tert-amylhydroquinone not applicable to the antioxidant of the present invention (manufactured by Kawaguchi Chemical Industry Co., Ltd., ANTAGE DAH) Except that was used as an antioxidant, an electrolyte layer and an electrochromic layer were prepared in the same manner as in Example 1 to obtain an interlayer film for laminated glass and a laminated glass.

(Comparative Example 6)
In place of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 1,1′-dithiobisoctadecane (made by Clariant Japan, HOSTANOX SE-10), which is a sulfur antioxidant, is antioxidant Except that it was used as an agent, an electrolyte layer and an electrochromic layer were prepared in the same manner as in Example 1 to obtain an interlayer film for laminated glass and laminated glass.

(Comparative Example 7)
Instead of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4 ′, 4 ″, 4 ′ ″-[[(1,1′- Biphenyl-4,4′-diyl) bis (phosphinetriyl)] tetrakisoxy] tetrakis (1,3-di-tert-butylbenzene) (Clariant Japan, Sandstub P-EPQ) is used as an antioxidant Except for the above, an electrolyte layer and an electrochromic layer were prepared in the same manner as in Example 1 to obtain an interlayer film for laminated glass and a laminated glass.

(Evaluation)
About the laminated glass obtained by the Example and the comparative example, it evaluated by the following method.
The results are shown in Tables 1-3.

(1) Evaluation of electrochromic property After applying a + 2V DC voltage so that the electrochromic layer side electrode is at a high potential between the electrodes of the obtained laminated glass, a -2V DC voltage is applied, and the transmittance The change was observed visually. The case where a change in transmittance was observed was evaluated as “◯”, and the case where no change was observed was evaluated as “x”.

(2) Repetitive cycle evaluation A repetitive cycle test of 30,000 cycles was performed using a signal generation circuit by a method according to ASTM E2241-06.
The color difference of the laminated glass is measured by a method according to JIS K 7105 using a color difference meter (TC-1800MK-II, manufactured by Tokyo Denshoku Co., Ltd.), and the change amount (ΔE) of the color difference before and after the repeated cycle test is calculated by the following formula. did.
ΔE = (color difference after repeated cycle) − (color difference before repeated cycle)

According to the present invention, it is possible to control light by changing the light transmittance by applying a voltage to one surface and the other surface, and excellent transparency without coloring even if light control is repeated. Light control material, light control sheet, electrolyte sheet constituting the light control material, light control body using the light control material, interlayer film for laminated glass, and interlayer film for laminated glass Laminated glass can be provided.

Claims (10)

A dimming material having an electrolyte layer and an electrochromic layer containing an electrochromic compound,
The electrolyte layer includes a vinyl acetal resin, a supporting electrolyte, a plasticizer, a compound having a bisphenol structure represented by the following general formula (1) in the molecule, a thiobisphenol represented by the following general formula (2), and A light control material comprising at least one antioxidant selected from the group consisting of styrenated phenols.

In formula (1), R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₃ ′, R ₄ ′, R ₅ ′, R ₆ ′, R ₇ ′ represent a hydrogen atom or a substituent. One of R ₃ , R ₅ , and R ₇ represents an OH group, and one of R ₃ ′, R ₅ ′, and R ₇ ′ represents an OH group, and the substituent adjacent to each OH group At least one of them represents a tertiary hydrocarbon group.
In the formula (2), R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₃ ′, R ₁₄ ′, R ₁₅ ′, R ₁₆ ′, R ₁₇ ′ represent a hydrogen atom or a substituent, _{One of 13} , R ₁₅ and R ₁₇ represents an OH group, and one of R ₁₃ ′, R ₁₅ ′ and R ₁₇ ′ represents an OH group, and at least one of substituents adjacent to each OH group. Represents a tertiary hydrocarbon group. The light control material according to claim 1, wherein the content of the antioxidant is 0.05 to 10 parts by weight with respect to 100 parts by weight of the vinyl acetal resin. The light control material according to claim 1, wherein the electrolyte layer contains 3 to 60 parts by weight of a supporting electrolyte and 30 to 150 parts by weight of a plasticizer with respect to 100 parts by weight of the vinyl acetal resin. The vinyl acetal resin is obtained by acetalizing a vinyl alcohol resin with an aldehyde having 4 or 5 carbon atoms, and has an acetyl group content of 15 mol% or less and a hydroxyl group content of 30 mol% or less. The light control material according to claim 1. 5. The light control material according to claim 1, wherein the electrochromic compound is a polyacetylene compound or Prussian blue type complex having an aromatic ring in a side chain. An electrolyte sheet comprising the electrolyte layer according to claim 1. An electrochromic layer containing an electrochromic compound is formed on at least one surface of the electrolyte layer according to claim 1. The light control material according to claim 1, 2, 3, 4 or 5, or the light control sheet according to claim 7, is sandwiched between a pair of transparent electrode substrates facing each electrode surface. Dimmer. An interlayer film for laminated glass using the light control material according to claim 1, 2, 3, 4 or 5, or the light control sheet according to claim 7. A laminated glass comprising the interlayer film for laminated glass according to claim 9 as a constituent element.