JP2012215684A - Producing method of dimming body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a producing method of a dimming body which enables production of a laminated glass that changes in light transmittance due to the application of a voltage and has high safety.SOLUTION: A producing method of a dimming body that includes an electrochromic layer containing an organic electrochromic compound and an electrolyte layer between a pair of conductive films, includes the step for heating the electrochromic layer at a temperature equal to or higher than the glass transition temperature of the organic electrochromic compound.

Description

The present invention relates to a method for manufacturing a light adjuster that can manufacture a laminated glass having a high safety by changing the light transmittance by applying a voltage.

A dimmer 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 sheet 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.

As the light control body, a light control body is proposed in which a light control sheet composed of an electrochromic layer and an electrolyte layer is sandwiched between a pair of opposing electrode substrates. 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.

High safety is required for laminated glass regardless of whether it is used for automobiles or construction. In particular, when laminated glass is used for an automotive windshield, high penetration resistance is required. In order for the laminated glass to exhibit high penetration resistance, it is required that the glass plate and the interlayer film for laminated glass be in close contact with each other. However, when a conventional light control sheet is used as an interlayer film for laminated glass, the adhesion to the glass plate is low and not only high penetration resistance can be exhibited, but the glass plate and the interlayer film for laminated glass peel off during use. There was a risk of doing so.

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

An object of this invention is to provide the manufacturing method of the light control body which can manufacture the laminated glass which changes the transmittance | permeability of light by applying a voltage, and has high safety | security.

The present invention relates to a method for producing a light control body having an electrochromic layer containing an organic electrochromic compound and an electrolyte layer between a pair of conductive films, wherein the electrochromic layer is made of glass of the organic electrochromic compound. It is a manufacturing method of the light control body characterized by having the process heated above transition temperature.
The present invention is described in detail below.

When this inventor used the conventional light control sheet | seat as an intermediate film for laminated glasses, it examined the cause with low adhesiveness with a glass plate. As a result, it discovered that it was because the adhesiveness of the electrochromic layer which comprises a light control sheet, and the electrically conductive film of the surface of a glass plate was low. As a result of intensive studies, the present inventor prepared the light control sheet in advance, and then formed a coating film by applying an organic electrochromic compound on the conductive film, instead of forming a laminated glass. By heating the coating film at a glass transition temperature (Tg) or higher of the organic electrochromic compound, the adhesion between the electrochromic layer and the conductive film is remarkably improved, and a highly safe laminated glass can be produced. The headline and the present invention were completed.

This invention is a manufacturing method of the light control body which has an electrochromic layer and an electrolyte layer between a pair of electrically conductive films.
It is preferable that the manufacturing method of the light control body of this invention has the process of apply | coating the composition for electrochromic layers containing an organic electrochromic compound on the said electrically conductive film, and forming a coating film. The coating film has electrochromic properties and is also an electrochromic layer.

The electrochromic layer is formed using an electrochromic layer composition containing an organic electrochromic compound.
The organic electrochromic compound is an organic compound having electrochromic properties.
The electrochromic property means a property that the light transmittance is changed by applying a voltage.

Examples of the organic compounds having electrochromic properties include 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 side chain is more preferable.

The polyacetylene compound having an aromatic side chain has electrochromic properties and electrical conductivity, and can easily form an electrochromic layer. Therefore, if a polyacetylene compound having an aromatic side chain is used, an 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 electrochromic layer has excellent light control 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, a fluorene group or a perylene group, preferably an anthracene group, phenanthrene group, fluorene group or perylene group, more preferably a phenanthrene group.
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.

Moreover, you may use together an inorganic electrochromic compound as needed. The inorganic electrochromic compound is an inorganic compound having electrochromic properties, for _{example, Mo 2 O 3, Ir 2} O 3, NiO, V 2 O 5, WO 3 and the like.

The composition for an electrochromic layer may contain a binder resin.
The binder resin used for the electrochromic layer is not particularly limited. For example, polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, polytrifluoride ethylene, acrylonitrile-butadiene-styrene copolymer Examples of the polymer include polyester, polyether, polyamide, polycarbonate, polyacrylate, polymethacrylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl acetal, and ethylene-vinyl acetate copolymer. Of these, polyvinyl acetal and ethylene-vinyl acetate copolymer are preferable.

The composition for an electrochromic layer may further contain a heat ray absorbent or an adhesive strength modifier.
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.

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 examples thereof include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, 2-ethylbutanoate, 2- Examples include potassium ethyl butanoate, magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate and the like. These adhesive force regulators may be used alone or in combination.

The composition for an electrochromic layer can be prepared by dissolving the above-described electrochromic compound and, if necessary, a binder resin, a heat ray absorbent, and an adhesive strength modifier in an appropriate solvent.

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 conductive film is preferably formed on a glass plate.
As said glass plate, the transparent plate glass generally used can be mentioned. 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, organic plastics boards, such as a polyethylene terephthalate, a polycarbonate, a polyacrylate, can also be used.

The method for applying the electrochromic layer composition and drying to form a coating film is not particularly limited and may be any known method, such as bar coating, spin coating, dip coating, and screen. Examples include printing, roll coating, and spray coating.
The coating amount of the electrochromic layer composition may be appropriately adjusted so that an electrochromic layer having a desired thickness can be obtained.

The manufacturing method of the light control body of this invention has further the process of heating the said coating film above the glass transition temperature (Tg) of the said organic electrochromic compound.
By heating the coating film at the above-described temperature, the adhesion between the conductive film and the electrochromic layer can be significantly improved.

When the heating temperature of the coating film is lower than the glass transition temperature (Tg) of the organic electrochromic compound, the adhesion between the conductive film and the electrochromic layer becomes insufficient.
The glass transition temperature (Tg) is a temperature obtained by measuring at a heating rate of 10 ° C./min by differential scanning calorimetry based on JIS K7121.
For example, when a polyacetylene compound having an aromatic side chain is used as the organic electrochromic compound, the heating temperature is preferably 230 ° C. or higher.

Although the upper limit of the said heating temperature is not specifically limited, It is preferable that it is less than the deterioration temperature or decomposition temperature of the said organic electrochromic compound.
For example, when a polyacetylene compound having an aromatic side chain is used as the organic electrochromic compound, the substantial upper limit of the heating temperature is 320 ° C.
The heating method is not particularly limited, and may be a known method. Examples thereof include heating with hot air, infrared irradiation, light irradiation, and microwave.

Although the thickness of the said 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 electrochromic layer is less than 0.05 μm, the light transmittance may not be changed sufficiently even when a voltage is applied to the electrochromic layer. 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.

It is preferable that the manufacturing method of the light control body of this invention further has the process of laminating | stacking an electrolyte layer and a electrically conductive film on the formed electrochromic layer.
The method for laminating the electrolyte layer and the conductive film on the electrochromic layer is not particularly limited and may be any known method. For example, the electrolyte layer is separately manufactured in advance and the electrochromic layer is formed on the electrochromic layer. There is a method of laminating the electrolyte layer, laminating a glass plate on which a conductive film is formed so that the conductive film is in contact with the electrolyte layer, and press-bonding these laminates.

The electrolyte layer is a layer having a role of changing a light transmittance of the electrochromic layer by applying a voltage to the electrochromic layer by conducting ions.
The electrolyte layer preferably contains a binder resin, a supporting electrolyte salt, and a solvent.

The binder resin for the electrolyte layer is not particularly limited, but is preferably a thermoplastic resin.
Examples of the binder resin include polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, polytrifluoride ethylene, acrylonitrile-butadiene-styrene copolymer, polyester, polyether, and polyamide. , Polycarbonate, polyacrylate, polymethacrylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl acetal resin, ethylene-vinyl acetate copolymer, and the like. Of these, polyvinyl acetal resins and ethylene-vinyl acetate copolymers are preferable, and polyvinyl acetal resins are more preferable.

The polyvinyl acetal resin is preferably a polyvinyl acetal resin obtained by acetalizing a polyvinyl 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 polyvinyl alcohol resin is 500, and the preferable upper limit is 5000. When the average degree of polymerization of the polyvinyl alcohol resin is less than 500, the shape of the electrolyte layer may not be maintained. When the average degree of polymerization exceeds 5000, the ionic conductivity becomes low, and even when a voltage is applied, the electrochromic layer The light transmittance may not change.
The average degree of polymerization of the polyvinyl alcohol resin is obtained by dividing the weight average molecular weight of the polyvinyl alcohol resin determined by polystyrene conversion using a gel permeation chromatography method (GPC method) by the molecular weight per segment of the polyvinyl alcohol resin. Can be sought.

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 hydrophobicity becomes too low, which may cause whitening of the electrolyte layer.
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 electrochromic 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 supporting electrolyte salt is not particularly limited, and is an inorganic acid anion lithium salt such as lithium perchlorate, lithium borofluoride, or lithium phosphofluoride, or an organic acid anion lithium such as lithium trifluoromethanesulfonate or lithium bistrifluoromethanesulfonate imide. Salt.

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 amount of the supporting electrolyte salt is less than 3 parts by weight, the ionic conductivity becomes low, and the light transmittance of the electrochromic layer may not change even when a voltage is applied, and exceeds 60 parts by weight. As a result, the responsiveness of the electrochromic layer may be lowered. A more preferable lower limit of the amount of the supporting electrolyte salt is 10 parts by weight, and a more preferable upper limit is 50 parts by weight.

The solvent is not particularly limited, and examples thereof include esters such as acetonitrile, nitromethane, propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, and γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, and the like. Substituted tetrahydrofurans, ethers such as 1,3-dioxolane, 4,4-dimethyl-1,3-dioxolane, t-butyl ether, isobutyl ether, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, Examples thereof include organic solvents such as ethylene glycol, polyethylene glycol sulfolane, 3-methylsulfolane, methyl formate, methyl acetate, N-methylpyrrolidone, dimethylformamide and the like.

The solvent may be a plasticizer. By using a plasticizer as the solvent, flexibility can be imparted to the electrolyte layer.
The plasticizer is not particularly limited. For example, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH), tetraethylene glycol di-2-ethylhexanoate Ate (4GO), dihexyl adipate (DHA) and the like.

Although the compounding quantity of the said 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 less than 30 parts by weight, the ionic conductivity becomes low, and even when a voltage is applied, the light transmittance of the dimmer may not change. The electrolyte layer may not maintain its shape. 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 electrolyte layer may contain a heat ray absorbent and an adhesive strength modifier.
The heat ray absorbent and the adhesive strength adjusting agent are not particularly limited, and the same additive as the additive used for the electrochromic layer can be used.

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, for example, an electrolyte layer having a different plasticizer content as the solvent is laminated, or an electrolyte layer containing a polyvinyl acetal resin having a different hydroxyl amount as the binder resin is laminated. Thus, it is possible to improve the sound insulation of the obtained light control body.

Although the thickness of the said electrolyte layer is not specifically limited, A preferable minimum is 0.1 mm and a preferable upper limit is 3.0 mm. If 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 dimmer. If 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.

The method for forming the electrolyte layer is not particularly limited. For example, a solution in which the supporting electrolyte salt is dissolved in the solvent is prepared, and a mixture obtained by mixing the obtained solution and the binder resin is used, for example, hot pressing. And a method of forming an electrolyte layer by extruding the mixture with an extruder.

When laminating the electrolyte layer on the electrochromic layer, the electrolyte layer preferably has an electrochromic layer on the surface in contact with the electrochromic layer. By having an electrochromic layer, the responsiveness of a light control body can be made more favorable. In order to distinguish from the above-described electrochromic layer, the electrochromic layer formed on the electrolyte layer is hereinafter referred to as a “second electrochromic layer”.

The second electrochromic layer preferably contains the same components as the above-described electrochromic layer.
The formation of the second electrochromic layer is not particularly limited. For example, the second electrochromic layer may be formed by applying the composition for electrochromic layer on the electrolyte layer and drying it, or for the electrochromic layer described above. The composition may be mixed by a kneader and then formed by extrusion to form a film.

When forming the second electrochromic layer, the total thickness of the above-described electrochromic layer and the second electrochromic layer is appropriately within the range of the thickness of the above-described electrochromic layer. It is preferable to adjust the coating amount.

Moreover, the manufacturing method of the light control body of this invention has further the process of laminating | stacking the ultraviolet absorption layer containing a ultraviolet absorber, the infrared rays absorption layer containing a heat ray absorber, etc. as needed. Also good. The above lamination is preferably performed by a known method.

With such a method for producing a light control body of the present invention, a light control body having an electrochromic layer and an electrolyte layer between a pair of conductive films can be obtained. The dimmer obtained by the production method of the present invention has excellent adhesion between the conductive film and the electrochromic layer.

The light control body obtained by the manufacturing method of the present invention can be applied as a laminated glass.
That is, the laminated glass has an electrochromic layer and an electrolyte layer between a pair of glass plates on which a conductive film is formed.

When the light control body obtained by the production method of the present invention is applied to laminated glass, an appropriate glass plate may be appropriately selected as the laminated glass.
Two or more types of glass plates may be used as the glass plate. For example, a transparent float plate glass may be used on one side, and a colored glass plate such as green glass may be used on the other side. Moreover, you may use the glass plate from which 2 or more types of thickness differs as said glass plate.

Although the surface density of the light control body or laminated glass obtained by the manufacturing method of this invention is not specifically limited, It is preferable that it is 12 kg / m < ² > or less.
The laminated glass obtained by the production method of the present invention can be used as a side glass, a rear glass, or a roof glass when used as an automotive glass.

ADVANTAGE OF THE INVENTION According to this invention, the transmittance | permeability of light changes by applying a voltage, and the manufacturing method of the light control body which can manufacture the laminated glass which has high safety | security 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 electrochromic (EC) layer Preparation of poly (9-ethynyl-10-n-octadecylphenanthrene) In a nitrogen atmosphere at −50 ° C., 3 g of 9-ethynylphenanthrene was dissolved in 30 mL of a tetrahydrofuran solution of normal butyllithium. A 1.6 mol / L hexane solution was added. 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., 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).
0.35 g of the obtained 9-ethynyl-10-n-octadecylphenanthrene was polymerized using a WCl ₆ catalyst to obtain 0.27 g of poly (9-ethynyl-10-n-octadecylphenanthrene).
The obtained poly (9-ethynyl-10-n-octadecylphenanthrene) had a glass transition temperature (Tg) of 230 ° C.

A solution was prepared by dissolving 3 parts by weight of the obtained poly (9-ethynyl-10-n-octadecylphenanthrene) in 10 parts by weight of toluene. This solution is applied onto a transparent conductive film of ITO glass using a bar coater so that the thickness after evaporation of toluene is 0.3 μm, and dried to form a coating film. An electrochromic layer was formed by heating at 240 ° C. for 30 minutes.

(2) Preparation of electrolyte layer Dissolve 0.67 parts by weight of bis (trifluoromethanesulfonyl) imidolithium (LiTFSI) as a supporting electrolyte salt in 2.38 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) Thus, an electrolyte solution was prepared. The total amount of the obtained electrolyte solution was mixed with 5.0 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 100 kg / cm ² for 5 minutes, and having a thickness of 400 μm. An electrolyte layer was obtained.

(3) Production of light control body An electrolyte layer is placed on the electrochromic sheet formed on the ITO glass transparent conductive film obtained above, and the ITO glass is placed on the electrochromic sheet. The film was laminated so that the electrolyte layer was in contact with the electrolyte layer. The obtained laminated body was pressure-bonded with a 90 ° C. vacuum laminator, and after pressure bonding, pressure-bonded for 20 minutes using an autoclave under conditions of 140 ° C. and 14 MPa to obtain a light control body.

(Comparative Example 1)
Instead of heating the coating film at 240 ° C., an electrochromic layer was formed in the same manner as in Example 1 except that the coating film was heated at 180 ° C., and a dimmer was prepared.
(Evaluation)
About the light control body obtained by the Example and the comparative example, it evaluated by the following method.
The results are shown in Table 1.

(1) Evaluation of adhesion to a transparent conductive film ITO glass and polyethylene terephthalate (PET) so that the electrolyte layer is in contact with the electrochromic layer formed on the transparent conductive film of ITO glass (length 25 mm x width 150 mm) A laminate was obtained by sandwiching an electrolyte layer between the film A (length 25 mm × width 150 mm × thickness 0.1 mm). When producing a laminated body, between the electrochromic layer and the electrolyte layer, one end in the lateral direction of the laminated body and one end in the lateral direction of the PET film B (length 25 mm × width 20 mm) are The PET film B was sandwiched so as to match. That is, in a region A 20 mm from one lateral end of the laminate, the glass on which the ITO transparent conductive film is formed, the electrochromic layer, the PET film B, the electrolyte layer, and the PET film A They were laminated in this order. In the other region B of the laminate, the glass on which the ITO transparent conductive film was formed, the electrochromic layer, the electrolyte layer, and the PET film A were laminated in this order.
The laminate was pressure-bonded with a 90 ° C. vacuum laminator, and pressure-bonded for 20 minutes using an autoclave under the conditions of 140 ° C. and 14 MPa to obtain a sample for peel test (length 25 mm × width 150 mm). After removing the PET film B in the region A, a peel test was conducted with a testing machine to peel off the electrolyte layer. In Example 1, when the electrolyte layer was peeled in the peel test, the electrolyte layer was peeled from the electrochromic layer, but the electrochromic layer was not peeled from the transparent conductive film. In Comparative Example 1, when the electrolyte layer was peeled in the peel test, the electrolyte layer was not peeled from the electrochromic layer, but the electrochromic layer was peeled from the transparent conductive film. The test conditions were a peeling angle of 180 °, a temperature of 25 ° C., and a peeling speed of 200 mm / min.

(2) Evaluation of electrochromic properties The electrolyte layer cut into a size of 45 mm in length and 45 mm in width is in contact with the electrochromic layer formed on the transparent conductive film of ITO glass A (length 50 mm x width 50 mm), The transparent conductive film of ITO glass B (length 50 mm × width 50 mm) was adjusted so as to be in contact with the electrolyte layer. That is, the ITO glass A, the electrochromic layer, the electrolyte layer, and the ITO glass B were laminated in this order.
The laminate was pressure bonded with a 90 ° C. vacuum laminator, and pressure bonded for 20 minutes using an autoclave under conditions of 140 ° C. and 14 MPa to obtain a light control body.
The transmittance at 640 nm of the light-modulating body in a completely colored state is TC, and the transmittance of the light-controlling body 640 nm in a completely decolored state is TB. After applying a voltage of +2 V to the fully dimmed dimmer and applying a voltage of +2 V to the dimmer, the transmittance of the dimmer from TC to T1 = TC + (TB−TC) × The time to change to 0.8 (hereinafter also referred to as the decoloring time) was confirmed. In addition, the spectrophotometer "V-670" by JASCO Corporation was used for the measurement of the transmittance | permeability.

ADVANTAGE OF THE INVENTION According to this invention, the transmittance | permeability of light changes by applying a voltage, and the manufacturing method of the light control body which can manufacture the laminated glass which has high safety | security can be provided.

Claims (2)

A method of manufacturing a light control body having an electrochromic layer containing an organic electrochromic compound and an electrolyte layer between a pair of conductive films,
A method for producing a light control body comprising a step of heating the electrochromic layer at a temperature equal to or higher than a glass transition temperature of the organic electrochromic compound. The method for producing a light control member according to claim 1, wherein the organic electrochromic compound is a polyacetylene compound having an aromatic side chain.