JP2011237688A - Lighting control film, combined glass intermediate film and combined glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lighting control film which has quite a short time from the application of voltage to the completion of change of light transmittance.SOLUTION: In a lighting control film having an electrolyte layer and an electrochromic layer formed on at least one side of the electrolyte layer, the electrochromic layer contains an electrochromic compound and a compound for plasticizing the electrochromic layer.

Description

The present invention relates to a light control film having a very short time from application of a voltage to completion of a change in light transmittance. Moreover, it is related with the laminated glass which uses the intermediate film for laminated glasses which has this light control film, and this intermediate film for laminated glasses.

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 dimmer 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 this invention is to provide the light control film in which the time after applying a voltage until the change of the light transmittance is completed is very short. Moreover, it aims at providing the laminated glass which uses the intermediate film for laminated glasses which has this light control film, and this intermediate film for laminated glasses.

The present invention is a light control film having an electrolyte layer and an electrochromic layer formed on at least one surface of the electrolyte layer, wherein the electrochromic layer includes an electrochromic compound and a compound that plasticizes the electrochromic layer; Is a light control film containing
The present invention is described in detail below.

In the laminate of the electrochromic layer and the electrolyte layer, the present inventors have extremely high responsiveness by adding a compound that plasticizes the electrochromic layer to the electrochromic layer. The inventors have found that a light control film having a very short time until the change in transmittance can be obtained, and have completed the present invention.

The light control film of this invention has an electrochromic layer and an electrolyte layer.
The electrochromic layer contains an electrochromic compound and a compound that plasticizes the electrochromic layer.
The electrochromic compound is not particularly limited as long as it is a compound having electrochromic properties, and may be an inorganic compound or an organic compound. Note that having an electrochromic property means having a property of changing light transmittance by applying a voltage.

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 organic compound having electrochromic properties include polypyrrole, polyacetylene, polythiophene, polyparaphenylene vinylene, polyaniline, polyacene, polyethylenedioxythiophene, metal phthalocyanine, viologen, viologen salt, ferrocene, dimethyl terephthalate, diethyl terephthalate Etc. Of these, polyacetylene having an aromatic side chain is preferable.

The polyacetylene having the aromatic side chain has electrochromic properties and electrical conductivity, and is excellent in film forming properties. Therefore, if polyacetylene having an aromatic side chain is used, an electrochromic layer having excellent light control performance can be easily formed. In addition, polyacetylene having an aromatic side chain exhibits a change in absorption characteristics due to a change in structure. As a result, since the absorption spectrum extends to the near-infrared wavelength region, the dimmer has excellent dimming performance over a wide wavelength region.

The polyacetylene having the aromatic side chain is not particularly limited, but for example, polyacetylene 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), p- (diphenylmethylsilyl) Phenyl, o- (triphenylsilyl) phenyl, p- (triphenylsilyl) phenyl, o- (tolyldimethylsilyl) phenyl, p- (tolyldimethylsilyl) phenyl, o- (benzyldimethylsilyl) phenyl, p- ( Benzyldimethylsilyl) phenyl, o- (phene) Rudimethylsilyl) phenyl, p- (phenethyldimethylsilyl) phenyl and the like, biphenyl group, 1-naphthyl, 2-naphthyl, 1- (4-fluoro) naphthyl, 1- (4-chloro) naphthyl, Naphthyl groups such as 1- (4-bromo) naphthyl, 1- (4-hexyl) naphthyl, 1- (4-octyl) naphthyl, naphthalene groups, 1-anthracene, 1- (4-chloro) anthracene, 1 An anthracene group such as-(4-octyl) anthracene, a phenanthrene group such as 1-phenanthrene, a fluorene group such as 1-fluorene, a perylene group such as 1-perylene, and the like.

The compound that plasticizes the electrochromic layer preferably has a molar volume of 150 m ³ / mol or more. When the molar volume of the compound that plasticizes the electrochromic layer is less than 150 m ³ / mol, the effect of promoting the response speed may be insufficient. More preferably, the compound that plasticizes the electrochromic layer has a molar volume of 250 m ³ / mol or more.

The compound that plasticizes the electrochromic layer preferably has a solubility parameter difference (ΔSP value) of 2.5 or less with respect to the electrochromic compound. When the difference in solubility parameter (ΔSP value) between the compound that plasticizes the electrochromic layer and the electrochromic compound exceeds 2.5, the compatibility is low, and the transparency of the resulting light control film may be lowered. . More preferably, the compound that plasticizes the electrochromic layer has a difference in solubility parameter (ΔSP value) from the electrochromic compound of 1.0 or less.
In the present specification, the solubility parameter (SP value) means a value calculated by the Fedors method.

Examples of the compound that plasticizes an electrochromic layer having a molar volume of 150 m ³ / mol or more include dimethyl phthalate, diethyl phthalate, diisodecyl phthalate, dibutyl fumarate, dimethyl maleate, dibutyl maleate, and bis maleate. (2-ethylhexyl), dibutyl adipate, bis (2-butoxyethyl) adipate, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether and the like. When the polyacetylene having an aromatic side chain is used as the electrochromic compound, the compound that plasticizes these electrochromic layers has a difference in solubility parameter (ΔSP value) of 2.5 or less from the electrochromic compound.

The compounding amount of the compound that plasticizes the electrochromic layer in the electrochromic layer is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the electrochromic compound is 30 parts by weight, and a preferable upper limit is 200 parts by weight. Outside this range, the effect of promoting the response speed may be insufficient. The minimum with more preferable compounding quantity of the compound which plasticizes the said electrochromic layer is 60 weight part, and a more preferable upper limit is 100 weight part.

The electrochromic layer may further 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 thickness of the electrochromic layer is not particularly limited, but a preferable lower limit 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 be changed sufficiently even when a voltage is applied to the electrochromic layer. The transparency of the entire film may be impaired. 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.

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, a solvent, and a binder resin.

The binder resin is not particularly limited. For example, polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, polytrifluoride ethylene, acrylonitrile-butadiene-styrene copolymer, polyester, poly Examples include ether, polyamide, polycarbonate, polyacrylate, polymethacrylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl acetal, and ethylene-vinyl acetate copolymer. Among these, polyvinyl acetal and ethylene-vinyl acetate copolymer are preferable, and polyvinyl acetal is more preferable. Since an electrolyte layer having high transparency is obtained, polyvinyl acetal obtained by acetalization with an aldehyde having 4 or 5 carbon atoms is more preferable.

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 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 liquid plasticizer. By using a liquid plasticizer as the solvent, flexibility can be imparted to the electrolyte layer.
The liquid plasticizer is not particularly limited. For example, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH), tetraethylene glycol di-2-ethylhexa Noate (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 electrochromic layer may not change. The electrolyte layer may not maintain the membrane 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.

Although it does not specifically limit as thickness of the said electrolyte layer, A preferable minimum is 0.1 mm and a preferable upper limit is 3 mm. When the thickness of the electrolyte layer is less than 0.1 mm, it may not be possible to give the property of changing the light transmittance by applying a voltage to the electrochromic layer. May become too thick. A more preferable lower limit of the thickness of the electrolyte layer is 0.3 mm, and a more preferable upper limit is 1 mm.

The method for producing the light control film is not particularly limited. For example, the electrolyte and the binder resin are mixed to produce a mixture. The obtained mixture is formed into a film by hot pressing or the like to produce an electrolyte layer. Next, the electrochromic compound dissolved in an appropriate solvent and the compound that plasticizes the electrochromic layer are applied onto the obtained electrolyte layer and dried to obtain a light control film.

The use of the light control film of the present invention is not particularly limited, and by adjusting the absorption of light in the visible light region, optical components such as various colored filters, window materials for vehicles, window materials for buildings, and materials for spectacles Can be used as Moreover, it can be used for near infrared absorption filters and various screens of various display panels, window materials for vehicles, window materials for buildings, etc. by reducing the transmittance of near infrared rays and infrared regions. In particular, when a polyvinyl acetal resin such as polyvinyl butyral is used as the binder resin, the light control film of the present invention is suitable as an interlayer film for laminated glass having a light control function.
The interlayer film for laminated glass having the light control film of the present invention is also one aspect of the present invention.

A laminated glass in which the interlayer film for laminated glass of the present invention is sandwiched between glass plates on which a pair of conductive films are formed is also one aspect of the present invention.
The said glass plate can use the transparent plate glass generally 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, organic plastics boards, such as a polyethylene terephthalate, a polycarbonate, a polyacrylate, can also be used.
Two or more types of glass plates may be used as the glass plate. 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 glass 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 so as to be in contact with the surfaces of the pair of glass plates on which the conductive film is formed.
The conductive film is preferably a transparent conductive film containing a metal oxide such as tin-doped indium oxide (ITO) or fluorine-doped tin oxide (FTO).

ADVANTAGE OF THE INVENTION According to this invention, the time from application of a voltage until the change of the light transmittance is completed can provide a light control film. Moreover, the laminated glass which uses the intermediate film for laminated glasses which has this light control film, and this intermediate film for laminated glasses 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 in which 0.3 g of lithium perchlorate was dissolved in 4 g of propylene carbonate was prepared. The total amount of the obtained electrolyte solution was added to and mixed with 10 g of polyvinyl butyral resin, and then the resulting mixture was pressed with a hot press at 120 ° C. and 100 kg / cm ² for 10 minutes to obtain a thickness of 0.8 mm. An electrolyte layer was obtained.

(2) Preparation of poly (9-ethynyl-10-n-octadecylphenanthrene) A 1.6 mol / L 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. 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. Next, 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).

(3) Production of light control film A toluene solution was prepared by dissolving poly (9-ethynyl-10-n-octadecylphenanthrene) and equimolar dimethyl phthalate in toluene. On the obtained electrolyte layer, a toluene solution was applied with a bar coater, and the toluene was volatilized to form an electrochromic layer having a thickness of 0.3 μm, thereby producing a light control film.

(Examples 2 to 11, Comparative Example 1)
In the production of the light control film, a light control film was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of dimethyl phthalate.

(Evaluation)
Using a light control film heated to 85 ° C as an interlayer film for laminated glass, sandwiching between two ITO electrodes (5cm in length × 5cm in width, 10Ω / □) to produce a light control laminated glass did.
A voltage of +2 V was applied to the obtained light control laminated glass (colored state), and a transmittance T of 640 nm in a state where the transmittance was completely changed (when completely changed) was measured. Thereafter, a voltage of −2 V was applied to the light control laminated glass to change to an initial colored state. Further, the time (seconds) from when a voltage of +2 V was applied to the light control glass until the light transmittance T1 of the light control glass reached 80% of the transmittance T at the time of complete change was measured. The transmittance was measured using a spectrophotometer “V-670” manufactured by JASCO Corporation.
The results are shown in Table 1.

ADVANTAGE OF THE INVENTION According to this invention, the time from application of a voltage until the change of the light transmittance is completed can provide a light control film. Moreover, the laminated glass which uses the intermediate film for laminated glasses which has this light control film, and this intermediate film for laminated glasses can be provided.

Claims (8)

A light control film having an electrolyte layer and an electrochromic layer formed on at least one side of the electrolyte layer, wherein the electrochromic layer contains an electrochromic compound and a compound that plasticizes the electrochromic layer A light control film characterized by The light control film according to claim 1, wherein the compound for plasticizing the electrochromic layer has a molar volume of 150 m ³ / mol or more. The light control film according to claim 1, wherein the compound that plasticizes the electrochromic layer has a difference in solubility parameter (ΔSP value) from the electrochromic compound of 2.5 or less. The compound for plasticizing the electrochromic layer has a molar volume of 150 m ³ / mol or more and a difference in solubility parameter (ΔSP value) from the electrochromic compound of 2.5 or less. Light control film. The light control film according to claim 1, wherein the electrochromic compound is polyacetylene having an aromatic side chain. The light control film according to claim 1, wherein the electrolyte layer contains a supporting electrolyte salt, a solvent, and a binder resin. An interlayer film for laminated glass, comprising the light control film according to claim 1. A laminated glass, wherein the interlayer film for laminated glass according to claim 7 is sandwiched between glass plates on which a pair of conductive films are formed.