JP2001083554A - Light controllable glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide light controllable glass which is less deteriorated in characteristics by long-term exposure to UV rays, is excellent in fireproof performance, wind pressure resistant strength, impact resistance and safety in the event of a failure and has a shielding function for heat rays. SOLUTION: Optical modulation materials 3 composed of at least high- polymer gel particles which are reversibly changed in volume according to external stimuli and liquid used for the volumetric change of the high-polymer gel particles are held between two sheets of parallel arranged transparent plates 2 and 2. A protective function for protecting the light controllable glass 1 from the external factors to injure the function of the light controllable glass 1 is imparted to at least one of the transparent plates 2 and 2. This light controllable glass is, for example, the light controllable glass to which the UV shielding function 5 is imparted, or the light controllable glass using at least one among tempered glass, sandwich glass, double tempered glass and wired sheet glass or the light controllable glass using a heat ray reflection layer, hot ray low radiation layer or vacuum layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light control material filled with a so-called light modulation material, which can reversibly control light transmittance, light scattering and color development in response to external stimuli such as heat, light and electricity. About glass.

[0002]

2. Description of the Related Art There have been proposed a large number of light control glasses using light control materials that reversibly control light transmittance and color development in response to external stimuli. For these, various systems such as liquid crystal, electrochromic, photochromic, and thermochromic are known.

[0003]

On the other hand, the present inventors have
Although it is unknown, a novel light modulating material containing a coloring material or a light scattering member inside the stimuli-responsive polymer gel was proposed. These include heat, light, electrical energy, etc.
In response to various external stimuli, the polymer gel swells and shrinks, and the color materials and light scattering members contained inside diffuse and agglomerate, changing the light transmittance, light scattering properties, and coloring state. It is a new material that can be.

[0004] Light-controlling glass can be easily manufactured by enclosing these materials between two parallel glass plates. Of course, when a material that responds to electric energy is used, electrodes such as ITO may be provided on opposite surfaces of the two glasses.

However, when a light control glass using these materials is actually used, a decrease in responsiveness and discoloration caused by irradiation with ultraviolet rays due to long-term outdoor exposure are prevented. It is important to improve the durability. In addition, when applied to buildings and vehicles, it is not possible to obtain by simply sandwiching and enclosing the material using ordinary glass or float glass, etc., fire protection performance, wind pressure strength, impact resistance, and safety at breakage. It is important to ensure the nature. In addition, when used for windowpanes installed in offices and other spaces where people are active, especially in the case of shading in order to reduce global warming and other environmental impacts, such as improving indoor cooling efficiency in the summer, It is important to cut off heat rays.

The object of the present invention is to achieve the above-mentioned important properties, and has been made under the intensive research of the present inventors, and to provide polymer gel particles which change in volume in response to an external stimulus. In the case of a light control glass having a light modulating material composed of a liquid used to change the volume of the polymer gel particles, the deterioration of characteristics due to long-term exposure to ultraviolet light is small, and fire resistance, wind pressure strength, and shock resistance are reduced. It is an object of the present invention to provide a light control glass which is excellent in force and safety at the time of breakage and has a function of blocking heat rays.

[0007]

The above object is achieved by the present invention described below. That is, in the present invention, at least a light modulating material composed of polymer gel particles that change in volume in response to an external stimulus and a liquid used for changing the volume of the polymer gel particles is interposed between two transparent plates. The light control glass is characterized in that at least one of the transparent plates is provided with a protection function for protecting the light control glass from an external factor that impairs the function of the light control glass. Examples of the protection function include, for example, 1) that at least one of the transparent plates is provided with an ultraviolet shielding function, and 2) at least one of the transparent plates is a netted glass plate, a lined plate glass, a tempered glass, a laminated glass. And (3) using a heat ray reflective layer, a heat ray low radiation layer, or a vacuum layer for at least one of the transparent plates. The light modulating material is preferably such that the polymer gel particles contain a light scattering member and swell and shrink reversibly by absorption and release of a liquid, and the polymer gel particles contain a coloring material, It is preferable that the polymer gel particles undergo reversible swelling / shrinking by absorption / release, and that the polymer gel particles change in volume due to a temperature change to change the light transmission amount.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As one embodiment of the light control glass 1 of the present invention, as shown in FIG. 1, two transparent plates 2 arranged in parallel, and a light enclosed and sealed therebetween. It is composed of a modulation material 3 and a sealing material 4, and at least one of the transparent plates 2 is provided with an ultraviolet shielding function. For this ultraviolet shielding function, an ultraviolet shielding layer 5 having a form such as a coating film of an ultraviolet shielding agent, an ultraviolet shielding layer containing an ultraviolet shielding agent, or an ultraviolet shielding film containing an ultraviolet shielding agent can be applied. In particular, it is preferable that the coating film of the ultraviolet shielding agent and the ultraviolet shielding film are formed on the surface facing the other transparent plate as shown in FIG. This means that when exposed to the outside,
This is because there is a concern that the desired function may not be stably maintained for a long period of time due to the fact that it is easily scratched. Therefore, when it is applied to the surface exposed to the outside, it is preferable to form the protective layer 6 thereon as shown in FIG. On the other hand, the ultraviolet cut layer in which the ultraviolet shielding agent is sealed is not particularly limited, and may be provided on the surface exposed to the outside.

As an ultraviolet absorber having an ultraviolet shielding function, an inorganic compound such as titanium oxide, zinc oxide, and cerium oxide, or an organic ultraviolet absorber is suitably used. For example, when zinc oxide is used as the inorganic fine particles, those having a particle size of 0.1 μm or less are preferably used, and they are used by being uniformly dispersed in a resin liquid for forming the ultraviolet shielding layer 5. 0.3 for resin liquid
It is preferably in the range of ５０50% by weight.

On the other hand, as the organic UV absorber,
Salicylic acids such as phenyl salicylate, p-tert-butylphenyl salicylate and p-octylphenyl salicylate, 2,4-dihydroxybenzophenone,
Benzophenones such as 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone, 2- (2'-hydroxy-5'-t-
Butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5 '
-Methylphenyl) -5-chlorobenzotriazole,
2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole,
Methyl-3- [3- (2H-benzotriazole-2-
Yl) -5-tert-butyl-4-hydroxyphenyl] propionate, 2,2′-methylenebis [4- (1,
Benzotriazoles such as 1,3,3-tetratylbutyl) -6- (2H-benzotriazole, 2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, ethyl-2-cyano-3,3 And ultraviolet absorbers such as cyanoacrylates such as diphenylacrylate, and one or more of these can be used in combination.

As a method of coating the ultraviolet absorbent on the transparent plate, a dry method such as a vacuum evaporation method, an ion plating method and a sputtering method, or a solution in which the ultraviolet absorbent is dissolved or dispersed in a solvent together with a binder can be used. A wet method in which the composition is applied to a transparent plate and the solvent is dried and cured is also applicable. As a film having an ultraviolet shielding function,
A film provided with a coating film having an ultraviolet shielding function, a film into which an ultraviolet absorbent is kneaded, and the like can be used. Further, an ultraviolet cut layer of a liquid film can also be applied, and a liquid ultraviolet absorber (for example, Tiba Geigy's T
UV absorber molecules that are liquid at room temperature, such as inuvin 109, 171, 384, 1130, etc., and UV absorbers that are solid at room temperature (for example, Tinuvin 326, 327, 328, 213, 57 manufactured by Ciba Geigy).
1, Sumitomo Chemical's Sumisorb 110, 110S, 25
0, 400, etc.) in a solvent in consideration of the solubility, a solution obtained by dissolving the solution in a high concentration to a saturation concentration (for example, a toluene solution of Sumisorb 110, a toluene solution of Sumisorb 320, etc.) is preferably used. Further, these ultraviolet absorbers may be used in combination. If necessary, light stabilizers (for example, Tinuvin 123, 2 from Ciba-Geigy)
92, 622LD etc.), antioxidants (for example, Irganox 245, 1010, 1330 of Ciba-Geigy)
Etc.) may be added. The method of manufacturing the liquid film layer may be the same as the method of laminating, sealing, and injecting the liquid crystal panel. However, the thickness of the liquid film does not need to be particularly strict, an ultra-thin layer having a thickness of 0.01 mm or less, an alignment treatment or the like is not required, and a general laminating method may be used without special measures.

As shown in FIG. 4, at least one of the transparent plates 2 has (1) an improvement in wind pressure resistance, (2) an improvement in impact resistance, (3) an improvement in fire resistance, and (4). In order to improve safety and the like, any one of tempered glass, laminated glass, double-strength glass, plate glass with mesh, and plate glass with wire has been used.
At this time, although there is no particular limitation, it is preferable to use the strength / safety improving glass as the outermost layer to protect the light control layer.

In order to improve the wind pressure resistance of (1), it is preferable to use tempered glass or double-strength glass. In the case of a light control glass composed of only float glass, although the strength varies depending on the area, sealing method, etc., the strength is equal to or slightly superior to one float glass used, and the strength is improved by increasing the thickness. Can not expect. On the other hand, the use of tempered glass or double strength glass can improve the wind pressure resistance of the light control glass. This is clear from the value of the strength coefficient (α) used in calculating the wind pressure strength applied to the Notification No. 109 of the Ministry of Construction. The float glass has a strength coefficient of 0.
8 and 1.0 for those exceeding 6 mm.
On the other hand, tempered glass and double-strength glass are each 3.
0 and 2.0, and its wind pressure resistance is high. Therefore, the wind pressure resistance of the light control glass of the present invention using them is also improved. When used as a building material, the area of the opening is defined by the wind pressure resistance and the ground height of the installed portion. Usually, in order to secure the required wind pressure resistance, a thick glass must be used, and accordingly, the light control glass also becomes thick. For this reason, installation on a general-purpose sash, frame, or the like becomes difficult, and it may not be used, which is extremely inconvenient. However, it is preferable that at least one of the transparent plates is made of tempered glass or double-strength glass because a desired wind pressure resistance can be obtained without increasing the thickness of the light control glass. This increases the usable area of the light control glass for the building and reduces the restrictions when using the light control glass. In particular, it is preferable to apply the light control glass to a window glass for a building having a large cooling load, since the cooling load can be remarkably reduced by increasing the area of the light control glass, which greatly contributes to energy saving. This effect depends on the tempered glass and the double-strength glass used, and it is preferable to use these glasses for all of the transparent plates used for the light control glass, because the effect becomes more remarkable.

In order to improve the impact resistance of (2), the use of tempered glass is preferred. As with the wind pressure resistance, ordinary glass cannot be expected to improve its strength by increasing the thickness of the light control glass. For this reason, it is not preferable to use a thick glass in order to obtain a desired strength. On the other hand, tempered glass is preferable because it has 3 to 5 times the bending strength and impact strength as compared with ordinary plate glass, so that the above problems can be avoided and desired properties can be obtained without increasing the thickness of the light control glass. This depends on the tempered glass used,
If all the transparent plates to be used are made of tempered glass, the effect becomes more remarkable, which is preferable.

In order to improve the fire protection of (3), it is preferable to use a net-in sheet glass or a wire-in sheet glass. That is,
Compared to ordinary flat glass, frosted flat glass, polished flat glass, dimmable glass composed only of flat glass, mold glass, etc., cracks occur in the net and flat glass. Even if cracks occur, even if cracks occur, the fragments are supported by the net or metal wire, preventing the fragments from falling off and creating holes in the glass surface, preventing the spread of fire due to the intrusion of flames from the holes it can. Thus, the fire control performance of the light control glass is improved, and its safety is increased. The use of double-strength glass also has about twice the thermal crack strength as compared with float glass, and is preferred for the same reason. These properties depend on the screened, lined and double-strength glass used. When these glasses are used for all the transparent plates of the light control glass, the effect becomes more remarkable, which is preferable. It is unconfirmed whether the light control glass of the present invention can be applied to `` fire doors '' defined by the Building Standards Law, etc., but in parts not specified here, fire resistance is improved compared to conventional products. , Increase safety.

In order to improve the safety in (4) glass breakage, it is preferable to use tempered glass or laminated glass.
Even if the tempered glass is broken, it will be broken into fine and granular pieces, not sharp pieces, and its safety is high. Also,
Even if the laminated glass is broken, the laminated glass is unlikely to cause penetration or separation or scattering of fragments, and is excellent in safety. In addition, when all of the transparent plates to be used are made of these glasses, the effect becomes more remarkable, which is preferable. One of the two transparent plates 2 is made of any of net-in glass, wire-in glass, tempered glass, laminated glass, and double-strength glass, and the other transparent plate is ordinary glass, float glass, or the like. And organic glass such as polycarbonate. As described above, net-filled glass, wire-filled glass, tempered glass, laminated glass, and double-strength glass have excellent properties in at least one of fire resistance, wind pressure resistance, impact resistance, and safety at breakage of glass. The glass to be actually used is appropriately selected from these depending on the object to be used, the use conditions, and the like. However, the two transparent plates 2 can be made of the same type of glass selected from net-inserted glass, wire-inserted glass, tempered glass, laminated glass, and double-strength glass, or different types of glass.

Such tempered glass, laminated glass,
The double-strength glass, the net-entering glass, and the wire-entering glass are configured as follows.

The tempered glass is obtained by heat-treating a sheet glass to form a strong compressive stress layer on the glass surface, to increase the breaking strength, and to form small pieces when broken. The tempered glass is preferably a JIS R3206 standard product, but is not limited thereto. Double-strength glass is also called HS glass, and is a processed glass whose wind-resistant strength has been increased to about twice that of float glass of the same thickness by a high-precision heat treatment process. Such glass has twice or more the strength against thermal cracking.

The laminated glass is made by bonding an intermediate film to two or more sheet glass sheets and sandwiching the entire surface thereof. Even if the laminated glass is broken by the action of an external force, most of the fragments are not scattered. Depending on the type of sheet glass to be used, it is classified into float laminated glass, template laminated glass, netted type laminated glass, lined type laminated glass, netted polished glass, lined polished glass, tempered laminated glass, etc. You. The laminated glass is preferably a JIS R3205 standard product, but is not limited thereto. Generally, a laminated glass is a product obtained by pressure bonding two or more sheet glasses with a flexible and tough interlayer, mainly polyvinyl butyral. Since the fragments are hardly separated or scattered, the glass is excellent in safety, and its properties are further given by the type of glass used.

The net-filled glass and the wire-filled glass are sheet glass in which a metal net or wire is inserted into the glass when being formed by a rolling roll. The types of the glazed and lined glazings include template glass and polished glazing, and the glazed glass is further subdivided into diamond netting and square netting. As the net-filled glass and wire-filled glass, JIS
R3204 standard products are preferred, but not limited thereto. More specifically, the net-filled glass is a flat glass in which a metal net is inserted inside the glass, and the wire-filled glass is a parallel glass wire so that the direction of the metal wire is the flow direction at the time of manufacturing. It is a sheet glass inserted inside.
The mesh-filled glass is a metal mesh of a square mesh, in which the direction of the metal wire is oblique to the flow direction at the time of plate making, and the direction of two metal wires passing through the intersection is Is a plate glass enclosed in the glass so as to be symmetrical to each other with respect to the straight line in the flow direction of the glass plate. Is a plate glass inserted into the glass so as to be in a flow direction at the time of plate making and a direction perpendicular thereto. In addition, these template glass refers to those having a pattern on one side as they are formed by a rolling roll, and polished plate glass refers to those having both sides polished to be extremely smooth.

As shown in FIG. 5, there is no particular limitation on the case where a heat ray reflective layer (heat ray shielding layer) 8 is provided, but when a light modulating layer using a thermosensitive gel is used, its heat sensitive action is not hindered. Thus, it is preferable to provide it on the outermost layer on the indoor side. As the heat ray reflective layer 8, a three-layer film composed of a CrN film and a TiO film can be used. The heat ray reflective layer 8 may function as a low heat ray radiation layer instead of the heat ray reflective layer 8, and in this case, an Ag film And a five-layer film composed of a ZnO film and the like. Further, as the heat ray reflection layer 8, a method of adhering a heat ray reflection film formed by forming a metal thin film of Al, Ag, Au or the like by sputtering or vapor deposition on the surface of a transparent plate (Japanese Patent Laid-Open No. 57-59748, JP-A-57-5
9749) and a method of forming an infrared absorbing layer by coating an organic infrared absorbing agent on a glass surface (Japanese Patent Laid-Open No. 4-160037).

Above all, a near-infrared absorbing film having a large visible light transmittance is preferable. Specifically, Japanese Patent Application Laid-Open No. 61-15 / 1986
4888, JP-A-61-197281, JP-A-61-2
46091, JP-A-63-37991, JP-A-63-3793
9388, JP-A-62-233288, JP-A-63-3
12889, JP-A-2-43269, JP-A-2-138
382, JP-A-2-296885, JP-A-3-4346
1, JP-A-3-77840, JP-A-3-100066,
Phthalocyanines or naphthalocyanines disclosed in JP-A-3-62878, JP-A-3-338557, JP-A-3-99730, JP-A-3-252414, etc .; Sho 61-2916
52, JP-A-62-15260, JP-A-62-1329
63, JP-A-1-129068, JP-A-1-17245
8, etc., anthraquinones. The total amount of the near infrared absorbing dye used is 1 to 10,000 mg / m with respect to the area of the near infrared absorbing film to be produced.
² is preferred.

As the heat ray shielding layer, a layer containing heat ray shielding inorganic fine particles is also preferably used. The particle diameter of the heat ray shielding inorganic fine particles is preferably 0.1 μm or less. As the heat-ray shielding inorganic fine particles used in the present invention, a conductive substance is used, and in addition to antimony-containing tin oxide (ATO), indium-containing tin oxide (ITO), copper sulfide (CuS), a conductive oxide, a conductive oxide, and the like. Sex sulfide,
Fine particles such as conductive carbide and conductive nitride can be used. Particularly preferred are ATO fine particles and ITO.
Fine particles. In the present invention, the heat ray-shielding inorganic fine particles are used by being uniformly dispersed together with a dispersant in a resin liquid for forming the heat ray-shielding layer 8. As the dispersant used here, carboxylate, sulfonate, sulfate ester salt,
Nonionic surfactants such as phosphate ester salts and phosphonate salts, and polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, polyoxyethylene alkyl esters, and sorbitan alkyl esters are used. Can be The amount of these dispersants is 1 to 1 with respect to the heat ray shielding inorganic fine particles.
Preferably, the content is about 20% by weight.

If necessary, aliphatic hydrocarbons such as hexane, heptane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, etc.
Alcohols such as propanol and butanol, acetone,
Solvents such as ketones such as methyl ethyl ketone, 2-pentanone and isophorone, and esters such as ethyl acetate and butyl acetate can also be used. Dispersion of the heat ray shielding inorganic fine particles can be performed using a dispersing machine such as a sand mill, an attritor, a colloid mill, a ball mill, a high-pressure homogenizer, and the particle size of the fine particles is 0.1 μm or less, preferably 0.05 μm or less. Disperse up to When the particle size of the heat ray-shielding inorganic fine particles is larger than 0.1 μm, the transparency of the heat ray-shielding film is deteriorated, and the visible light transmittance is deteriorated. When the heat ray shielding inorganic fine particles are contained in the heat ray shielding layer, the blending amount of the heat ray shielding inorganic fine particles is 10 to 85.
It is preferred to be in the range of weight%.

In order to provide a heat ray shielding function to at least one of the transparent plates, a vacuum layer can be provided as a heat ray shielding layer. In this case, as the vacuum layer, it is possible to use a double-layered glass formed by separating two glass plates at the peripheral portion via a spacer, sealing the peripheral portion and bleeding the air inside. . At this time, the substrate on which the vacuum layer is formed is a common glass plate such as a normal plate glass, a frosted plate glass of a normal plate glass, a float plate glass and a polished plate glass, a template glass, a special glass such as a netted glass, a tempered glass, and other acrylics. A substrate made of a resin such as polystyrene, polycarbonate, or the like can be used. The thickness is preferably about 1 mm to 20 mm, and is not particularly limited as long as a vacuum layer formed inside can be maintained. If the thickness is less than 1 mm, a sufficient heat-insulating effect cannot be obtained, so the thickness of the formed vacuum layer is preferably 1 mm or more. On the other hand, there is no particular upper limit, but it is better not to be too thick in production, and preferably 10 mm or less.

Next, the light modulation material in the present invention will be described. The light modulating material is composed of at least polymer gel particles whose volume changes in response to an external stimulus, and a liquid used for changing the volume of the polymer gel particles. That is, as the polymer gel constituting the light modulation material used in the present invention, heat, light, electricity, application of energy such as magnetism, pH change, oxidation / reduction, ion concentration change, adsorption / desorption of chemical substances,
A stimulus-responsive polymer gel that absorbs and releases a liquid by various stimuli such as a change in the solvent composition and reversibly changes in volume (swelling and shrinking) is preferable.

Specifically, as the polymer gel which responds stimulus by a pH change due to an electrode reaction or the like, an electrolyte polymer gel is preferable, and a crosslinked product of poly (meth) acrylic acid or a metal salt thereof; Crosslinked product of a copolymer of an acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, alkyl (meth) acrylate, or a metal salt thereof; maleic acid (meth) acrylamide, hydroxyethyl (meth) acrylate, ( Meta)
Cross-linked products of copolymers with acrylic acid alkyl esters and their metal salts; Cross-linked products of polyvinyl sulfonic acid and their metal salts; vinyl sulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid Cross-linked products of copolymers with alkyl esters, etc. and metal salts thereof; Cross-linked products of polyvinyl benzene sulfonic acid and metal salts thereof; vinyl benzene sulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid Crosslinked product of a copolymer with an alkyl ester or the like, or a metal salt thereof; Crosslinked product of a polyacrylamide alkylsulfonic acid or a metal salt thereof; acrylamide alkylsulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic With acid alkyl esters Cross-linked product or metal salt thereof; polydimethylaminopropyl (meth) acrylamide cross-linked product or hydrochloride thereof; polydimethylaminopropyl (meth) acrylamide and (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acryl Cross-linked products of copolymers with acid alkyl esters and the like and metal salts and 4
Grade salt; crosslinked product of a complex of polydimethylaminopropyl (meth) acrylamide and polyvinyl alcohol and a quaternary salt thereof; crosslinked product of a complex of polyvinyl alcohol and poly (meth) acrylic acid and a metal salt thereof; carboxyalkyl Crosslinked products of cellulose metal salts; partially hydrolyzed products of crosslinked products of poly (meth) acrylonitrile and metal salts thereof.

As the polymer gel which responds to stimulus by adsorption and desorption of a chemical substance such as a surfactant by an electric field, a strongly ionic polymer gel is preferable, and a crosslinked product of polyvinyl benzene sulfonic acid or vinyl benzene sulfonic acid and (meth) Crosslinked product of copolymer with acrylamide, hydroxyethyl (meth) acrylate, alkyl (meth) acrylate; crosslinked product of polyacrylamidoalkylsulfonic acid or acrylamidoalkylsulfonic acid with (meth) acrylamide, hydroxyethyl (meth) yl Crosslinked products of copolymers with acrylates, alkyl (meth) acrylates, and the like can be given. These are used in combination with a cationic surfactant such as an alkylpyridinium salt such as n-dodecylpyridinium chloride, an alkylammonium salt, a phenylammonium salt, and a phosphonium salt such as tetraphenylphosphonium chloride.

As the polymer gel which responds to stimulation by oxidation / reduction by electricity, a cationic polymer gel is preferable, and a crosslinked product of polyamino-substituted (meth) acrylamide such as polydimethylaminopropylacrylamide; polydimethylaminoethyl (meth) acrylate Polydiethylaminoethyl (meth) acrylate; poly (meth) acrylate such as polydimethylaminopropyl (meth) acrylate
Crosslinked products of amino-substituted alkyl acrylates; crosslinked products of polystyrene; crosslinked products of polyvinylpyridine; crosslinked products of polyvinylcarbazole; crosslinked products of polydimethylaminostyrene, and the like. These are used as a CT complex (charge transfer complex) in combination with an electron accepting compound. As the electron accepting compound preferably used at this time, benzoquinone; 7, 7, 8, 8-tetracyanoquinodimethane (TCNQ); tetrabutylammonium perchlorate; tetracyanoethylene; chloranil;
Trinitrobenzene; maleic anhydride; iodine and the like.

Examples of the polymer gel that responds to stimulation by application of heat include a crosslinked polymer having an LCST (lower critical solution temperature) and a two-component polymer gel which forms a hydrogen bond with each other (IPN (interpenetrating network structure)). Is preferred. The former has a property of shrinking at a high temperature, and specifically, poly-N such as poly-N-isopropylacrylamide.
A crosslinked product of an alkyl-substituted (meth) acrylamide; N-
Alkyl-substituted (meth) acrylamide and (meth) acrylic acid and its metal salts, (meth) acrylamide, (meth)
A cross-linked product of a copolymer with an alkyl acrylate; a cross-linked product of polyvinyl methyl ether; a cross-linked product of an alkyl-substituted cellulose derivative such as methyl cellulose, ethyl cellulose, or hydroxypropyl cellulose. On the other hand, the latter has the property of swelling at a high temperature, and specifically, is composed of a crosslinked product of poly (meth) acrylamide and a crosslinked product of poly (meth) acrylic acid.
It is composed of a PN body and its partially neutralized product (acrylic acid unit partially metallized), a crosslinked product of a copolymer mainly composed of poly (meth) acrylamide and a crosslinked product of poly (meth) acrylic acid Examples thereof include IPN bodies and partially neutralized products thereof. Among these compounds, a crosslinked product of a poly-N-alkyl-substituted alkylamide, an IPN product composed of a crosslinked product of a poly (meth) acrylamide and a crosslinked product of poly (meth) acrylic acid and a partially neutralized product thereof are preferably used. Can be

As the polymer gel which responds to stimulus by application of light, a crosslinked product of a hydrophilic polymer compound having a molecular structure which is ion dissociated by light, such as a triarylmethane derivative or a spirobenzopyran derivative, is preferable. Specific examples include a crosslinked product of a copolymer of a vinyl-substituted triarylmethane leuco derivative and (meth) acrylamide.

Examples of the polymer gel that responds to the stimulus by applying a magnetic field include ferromagnetic particles and a crosslinked product of polyvinyl alcohol containing a magnetic fluid, but the polymer gel itself is not particularly limited. What is necessary is just to be contained in the category of a polymer gel.

As the polymer gel which responds according to the change in the composition of the solution or the change in the ionic strength, the above-mentioned electrolyte polymer gel can be preferably applied. In the present invention, each stimuli-responsive polymer gel may be used alone, or a plurality of polymer gels may be used in combination. Note that the description using parentheses above indicates both a compound that does not include the prefix in the parenthesis and a compound that does not include the prefix. For example, the description of (meth) acrylic acid means acrylic acid and methacrylic acid. Things. The volume change of the polymer gel used in the present invention is desirably at least a volume ratio of 5 or more, preferably 10 or more. If the volume ratio is less than 5, sufficient light control contrast may not be obtained.

The coloring material contained in the polymer gel particles of the light modulating material used in the present invention is preferably an inorganic pigment or an organic pigment. Specifically, various pigments such as metal oxides such as titanium oxide, bronze powder, carbon black, anthraquinone-based, azo-based, phthalocyanine-based, quinacridone-based, perylene-based, and indigo-based pigments, and particularly having a high light absorption coefficient Are preferred.

When a coloring material such as a pigment is contained in the polymer gel particles, the coloring material is uniformly dispersed when the polymer gel is swollen, so that the coloring material efficiently absorbs light. ,
Light absorption efficiency is increased. On the other hand, when the polymer gel shrinks, the light absorbing area becomes smaller, and the light absorption amount decreases. Further, the coloring material has an increased density of the coloring material due to the volume shrinkage of the polymer gel, and causes aggregation of the coloring material. As a result, the color material density becomes equal to or higher than the saturation absorption density, and the amount of light absorbed per unit amount of the color material is reduced. As a result, the light absorption efficiency of the light modulation material is reduced. Due to these effects and the like, a large difference in light absorption occurs between the time of swelling and the time of contraction of the polymer gel. Therefore, when a pigment is used as a coloring material contained in the polymer gel particles, it is desirable that the pigment has a concentration equal to or higher than the saturation absorption concentration in the polymer gel particles. Here, the term “above the saturated absorption concentration” means that the polymer gel shrinks when a general pigment having a high absorption coefficient is used, that is, the polymer gel that hardly absorbs liquid due to external stimulus (or the dried state). Polymer gel)
Inside, as an index, when the average distance between the color materials is sufficiently short, the function of light absorption of the color materials changes from a primary particle-like function to a collective one, and the efficiency of light absorption increases. Is the concentration that decreases. If the definition of the saturation absorption density or more is expressed as another characteristic, the color material density is such that the relationship between the color material density and the light absorption amount under a specific optical path length deviates greatly from the linear relationship. When the color material concentration is equal to or higher than the saturation absorption concentration, the light absorption efficiency per particle of the color material is reduced, so that the light absorption amount is not proportional to the color material concentration.
It becomes lower than the light absorption expected from the following straight line. On the other hand, below the saturation absorption concentration, the amount of light absorption is proportional to the colorant concentration, and the light absorption efficiency per colorant particle is almost constant.

As the light scattering member contained in the polymer gel particles of the light modulating material used in the present invention, a material having a refractive index different from the refractive index of the liquid used for changing the volume of the polymer gel is preferable. However, other than that, there is no particular limitation, and various inorganic compounds and organic compounds can be applied.

Specific examples of the inorganic material include zinc oxide, basic lead carbonate, basic lead sulfate, lead sulfate, lithopone, muscovite, zinc sulfide, titanium oxide, ammonium oxide, lead white,
Inorganic oxides such as zirconium oxide, alumina, mycanite, mykalex, quartz, calcium carbonate, gypsum, clay, silica, silicic acid, silicon earth, talc, basic magnesium carbonate, alumina white, gloss white, satin white, Zinc, alumel, antimony, aluminum, aluminum alloy, iridium, indium, osmium, chromium, chromel, cobalt, zirconium, stainless steel, gold, silver, nickel silver, copper, bronze, tin, tungsten, tungsten steel, iron, lead, nickel , Nickel alloy, nickeline, platinum, platinum rhodium, tantalum, duralumin, nichrome, titanium, Krupp austenitic steel, constantan, brass, platinum iridium, palladium, palladium alloy, molybdenum, molybdenum steel, manganese, manganese Gold, rhodium, a metal material such as rhodium metal, ITO (indium tin oxide)
And other inorganic conductive materials.

Further, specific examples of the organic material include:
Specific examples of suitable organic materials include phenol resin, furan resin, xylene / formaldehyde resin, urea resin, melamine resin, aniline resin, alkyd resin, unsaturated polyester, epoxy resin, polyethylene, polypropylene, polystyrene, and poly-p-xylylene. , Polyvinyl acetate, acrylic resin, methacrylic resin, polyvinyl chloride, polyvinylidene chloride, fluoroplastic,
Polyacrylonitrile, polyvinyl ether, polyvinyl ketone, polyether, polycarbonate, thermoplastic polyester, polyamide, diene plastic, polyurethane plastic, polyphenylene, polyphenylene oxide, polysulfone, aromatic heterocyclic polymer, silicone, natural rubber plastic, cellulose Polymer materials such as plastics and a mixed material (polymer blend) of two or more of these polymer materials are exemplified.

Further, a polymer material containing the light scattering materials listed above can be used as the light scattering member. The polymer material is not particularly limited, and various polymer resins can be used. Specific examples of preferred polymer resins include the specific examples listed when the light-scattering material is an organic material.

When the polymer gel particles contain a light scattering member, when the polymer gel swells, the light scattering member is uniformly diffused and dispersed in the polymer gel, and the light scattering area increases. Further, in the light scattering member, the density of the light scattering member is increased due to the volume shrinkage of the polymer gel, and the light scattering member is aggregated. At this time, the light scattering member concentration reaches the saturated scattering concentration or more, and the light scattering members overlap each other. As a result, light cannot be efficiently scattered and reflected or refracted, and the light scattering ability per particle of the light scattering member is reduced to lower the light scattering efficiency. It is considered that the light modulating material causes a large difference in the amount of light scattering between the polymer gel when it swells and when it contracts due to such effects. Here, the term “saturated scattering concentration or more” means that, as one index, the average interval between the light scattering members is sufficiently short, so that the light scattering function of the light scattering members is not a primary particle but a collective one. Changes to
This is the concentration at which the efficiency of light scattering changes. In addition, if the definition of the saturation scattering concentration or more is expressed by another characteristic, the saturation scattering concentration at which the relationship between the light scattering member and the amount of light scattering under a specific optical path length deviates greatly from the relationship of the linear line. is there.

Next, the shapes of the coloring material and the light scattering member are not particularly limited, and may be in the form of particles, blocks, films, or the like.
Various shapes such as irregular shapes and fibrous shapes can be used.
Among them, the particulate form is particularly preferable because of its features such as high coloring property and light scattering property and wide application range. There is no particular limitation on the form in the form of particles, but a sphere, a cube,
An ellipsoid, a polyhedron, a porous body, a star, a needle, a hollow, a scale and the like can be applied. The preferred size of the particles is 0.01 μm to 500 μm in average particle diameter.
, More preferably in the range of 0.05 μm to 100 μm. This is because when the average particle diameter is 0.01 μm or less or 500 μm or more, the coloring effect and light scattering effect required for the coloring material and the light scattering member are reduced. Furthermore, when the average particle diameter is 0.01 μm or less, outflow from the inside of the polymer gel to the outside tends to occur. Further, these particles can be produced by a general physical pulverization method or a chemical pulverization method.

Further, these coloring materials and light scattering members have polar groups such as an acid group such as a carboxyl group and a sulfonic acid group, a hydroxyl group, an amino group, a thiol group, a halogen group, a nitro group and a carbonyl group in the molecule. Also, those having a property of easily forming an aggregate when the concentration of the light scattering member is high in the polymer gel are preferably used.

It is preferable that the coloring material and the light scattering member are contained in the polymer gel and do not flow out of the polymer gel. In order to prevent the outflow of the coloring material and the light scattering member, use a coloring material and a light scattering member having a particle diameter larger than the mesh of the polymer gel to be used, or use an electric, ionic, Other examples include using a coloring material and a light scattering member having high physical interaction, and a coloring material and a light scattering member whose surfaces are chemically modified. Examples of the coloring material and light-scattering member having a chemically modified surface include those having a surface into which a group chemically bonded to a polymer gel has been introduced, and coloring materials and light-scattering members having a polymer material grafted thereon.

The concentration of the coloring material and the light scattering member contained in the polymer gel is generally preferably in the range of 2% by weight to 95% by weight, more preferably in the range of 5% by weight to 95% by weight. When the concentration of the coloring material and the light scattering member is 2% by weight or less, the change in the amount of coloring and the amount of scattering due to the change in the volume of the polymer gel of the light modulating material does not appear. Problems such as an increase in the thickness of many light control layers occur. On the other hand, when the concentration of the coloring material and the light scattering member is 95% by weight or more, the swelling / shrinking of the polymer gel becomes difficult to progress with good response, and the stimulus response characteristics and the volume change of the light modulation material are reduced. .

The method of incorporating the coloring material and the light scattering member into the polymer gel includes a method of uniformly dispersing and mixing the coloring material and the light scattering member in the polymer before crosslinking, and a method of crosslinking after polymerization, and a method of polymer precursor composition during polymerization. For example, a method of adding a coloring material and a light scattering member to a product and polymerizing the same can be applied. When a colorant and a light-scattering member are added during polymerization, it is also preferable to use a colorant and a light-scattering member having a polymerizable group or an unpaired electron (radical) as described above and to chemically bond them. Further, it is desirable that the coloring material and the light scattering member are dispersed as uniformly as possible in the polymer gel. In particular, when dispersing in a polymer, it is desirable to uniformly disperse using a mechanical kneading method, a stirring method, or a dispersant.

The shape of the polymer gel constituting the light modulating material used in the present invention is not particularly limited, and various shapes such as a particle shape, a block shape, a film shape, an irregular shape, and a fiber shape can be used. Among them, the particulate form is particularly preferable because of its characteristics such as high speed of volume change (responsiveness) to the above-mentioned various external stimuli and wide application range. There is no particular limitation on the form in the form of particles, but a sphere,
An ellipsoid, a cube, a polyhedron, a porous body, a star, a needle, a hollow, and the like can be applied. In the case of particles, the preferred size is 0.1 μm in average particle diameter in the contracted state.
The range is from m to 5 mm, more preferably from 1 μm to 1 mm. When the particle diameter is 0.1 μm or less, problems such as difficulty in handling the particles and failure to obtain excellent optical characteristics occur. On the other hand, if the particle diameter is larger than 5 mm, there arises a problem that the response time required for the volume change is significantly delayed.

These particles can be obtained by pulverizing a polymer gel by a physical pulverization method, by forming a polymer gel before crosslinking into particles by a chemical pulverization method, and then crosslinking the polymer gel to form a polymer gel. Alternatively, it can be produced by a general method of particle polymerization such as emulsion polymerization, suspension polymerization, and dispersion polymerization.

In order to further increase the volume change rate of the polymer gel due to various stimulus responses, it is also possible to make the material porous so as to improve the accessibility of the liquid as in the known method of the polymer gel. preferable. Generally, the swollen polymer gel can be made porous by freeze-drying or the like.

The volume of the light modulating material used in the present invention can be variously changed by applying the above-described stimulus in the presence of a liquid that can be absorbed by the polymer gel constituting the material. For example, in the case of a thermoresponsive polymer gel,
By applying radiant heat such as light or heat, in the case of an electrically responsive polymer gel, the pH changes due to an electrode reaction or by ion adsorption or electrostatic action by an electric field; The volume can be largely changed by absorbing and releasing the liquid by the structural change.

The liquid usable at this time is not particularly limited, but is preferably water, an aqueous electrolyte solution, alcohols, ketones, esters, ethers, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, or the like. Propylene carbonate and the like, aromatic solvents such as xylene and toluene, and mixtures thereof can be used. In addition, the liquid contains a surfactant that absorbs and desorbs into the polymer gel, a redox agent such as a viologen derivative for promoting a change in pH of the liquid, an acid, an alkali,
Salts, dispersion stabilizers such as surfactants, and stabilizers such as antioxidants and ultraviolet absorbers may be added.

From the above characteristics, the polymer gel used in the present invention is used as a composition with a liquid. At this time, the liquid that can be used is preferably a liquid that can be absorbed by the polymer gel. When the polymer constituting the polymer gel is not cross-linked, a liquid in which the polymer can be dissolved can also be preferably used. A preferable mixing ratio of the polymer gel and the liquid as the composition is 1: 2000 to 1: 1.
(Polymer gel: liquid).

The structure of the light control layer is different from that shown in FIGS. 1 to 5 in that a light modulating material is interposed between two transparent plates as shown in FIGS. 1 to 5 or a transparent plate having an ultraviolet / heat ray shielding layer. 6 may be used. In this case, the light modulating material is polyethylene, polypropylene, polyester,
The light control layer is itself sandwiched and enclosed in a transparent film such as nylon, and the light control layer itself forms the light control sheet 9. In this case, the outer peripheral portion can be sealed by heating and fusing the transparent film in addition to using a sealing adhesive. When such a light control sheet 9 is used for the light control layer, a sealing material is not necessary,
It is preferable to use a spacer 12 around the light control layer to maintain the gap. When the light modulating material is sandwiched between a transparent plate as shown in FIGS. 1 to 5 or a transparent plate having an ultraviolet ray / heat ray shielding layer, as shown in FIG. Spacers 12 can also be used. In these cases, the shape of the spacer 12 is not particularly limited as long as it can stably maintain the gap, but is preferably a sphere, a cube, a column, or the like.

In order to maintain the dispersed state of the polymer gel contained in the light modulating material inside the light modulating layer, the inside of the light modulating layer may be segmented by using a mesh-like continuous spacer. In this case, the mesh shape of the spacer is not particularly limited as long as it can stably maintain the gap, but a polygonal shape such as a lattice shape or a honeycomb shape is mainly used. These spacers are not particularly limited as long as they are materials that are stable to the liquid constituting the light modulation material. For example, resins, metals, metal oxides,
Glass or the like can be applied. As another method for maintaining the dispersed state of the polymer gel contained in the light modulating material inside the light modulating layer, the polymer gel may be fixed. The object to be immobilized may be a transparent plate holding a polymer gel or the above-mentioned transparent film. After the polymer gel is immobilized on the support, it may be sandwiched between transparent plates.

The method of immobilizing the polymer gel contained in the light modulating material used in the present invention on a transparent plate and a support includes:
Mechanical immobilization, physical immobilization such as adhesion, and chemical immobilization such as chemical bonding can be applied. The chemical bond is
Various types such as an ionic bond, a hydrogen bond, and a covalent bond are conceivable. Among them, a covalent bond is most preferable in terms of stability.

The mechanical fixation is mainly when a fibrous support is used and is held in a space such as a mesh. In this case, the fibrous support is not a mere aggregate of fibers, but a woven fabric, a nonwoven fabric, a web,
It is preferable that the structure be a sheet or the like. In this case, in order to enhance the holding effect of the polymer gel, the structure in this case is preferably composed of relatively thin fibers of about 1 to 50 μm at a relatively high density with a basis weight of 10 g / m ² or more.

Next, as an adhesive used for physical fixation, an organic solvent volatile type adhesive (chloroprene rubber type, urethane type, etc.), a thermosetting reaction type adhesive (epoxy type, resol type, etc.), moisture Curable adhesive (2-cyanoacrylate, silicone, etc.), UV curable adhesive (acrylic oligomer, etc.), condensation adhesive (urea resin), addition reactive adhesive (epoxy System, isocyanate system, etc.), and a hot-melt adhesive.

In the present invention, among these, hot-melt adhesives are particularly preferable, and examples thereof include polyolefin resins (polyethylene, polypropylene, etc.), polyolefin derivatives (maleic acid-modified polyethylene, chlorinated polyethylene, maleic acid-modified polypropylene, ethylene -Acrylic acid copolymer, ethylene-maleic anhydride copolymer, propylene-acrylic acid copolymer, propylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, maleated polybutadiene, ethylene-vinyl acetate (Copolymers and maleated products thereof), polyester resins, polyamide resins, polycaprolactone resins, polystyrene resins, and derivatives thereof (polystyrene, sulfonated polystyrene, styrene-maleic anhydride copolymer, etc.) Thermoplastic polyurethane resin, high molecular weight polyethylene glycols, vinyl acetate resin, waxes (paraffin wax, beeswax, beef tallow, etc.),
Long-chain fatty acid ester resins and mixtures of two or more thereof are exemplified.

In the present invention, the ratio of the adhesive resin used is usually 0.1 to 50 parts by weight, preferably about 1 to 30 parts by weight, based on 100 parts by weight of the polymer gel. is there. If the amount of the adhesive resin exceeds 50 parts by weight, the adhesion to the transparent plate or the support is improved, but the contact ratio of the polymer gel with the adhesive resin is increased, and the swelling / shrinking behavior may be inhibited. Will be higher. On the other hand, if it is less than 0.1 part by weight, the adhesion to the transparent plate or the support becomes insufficient.

For fixing the polymer gel using the adhesive resin, for example, a method in which a mixture of the polymer gel and the particulate adhesive resin is sprayed on the surface to be bonded and then subjected to a heat treatment to bond the mixture. it can. At this time, the apparatus used for mixing is not particularly limited, and may be an ordinary powder mixing apparatus, and examples thereof include a conical blender, a Nauta mixer, a V-type blender, a turbulizer, and a screw-type line blender.

In addition, an adhesive solution in which an adhesive resin is dissolved in a solvent may be prepared, and the adhesive solution may be applied to the surface to be adhered, and then a polymer gel may be sprinkled and heat-treated. The solvent used at this time is not particularly limited as long as the adhesive resin is soluble, but the boiling point of the solvent is preferably relatively low, and 150 ° C. or less, preferably 100 ° C. or less is appropriate. Ketones such as acetone, alcohols such as ethanol and methanol, carboxylic esters such as ethyl acetate, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride, and ethers such as diethyl ether , Hydrocarbons such as hexane and cyclohexane, and mixtures thereof. The method of applying the adhesive solution to the surface to be bonded includes application, spraying, dipping, and the like. Also,
The heat treatment for bonding is not particularly limited, but a hot-air heater, an infrared heater, a high-frequency heater, a contact heater such as a heat roller, etc. can be applied, and the heating temperature is approximately 50% according to the melting temperature of the adhesive. The temperature is appropriately set between 0 ° C and 200 ° C.

Various chemical bonds such as an ionic bond, a hydrogen bond and a covalent bond can be considered in the chemical immobilization of the polymer gel contained in the light modulating material according to the present invention. Is most preferable, and the reaction is carried out using various fixing agents. The application of the polymer gel and the fixing agent to the surface to be adhered can be performed by a method such as coating, spraying, and impregnation. For application and impregnation,
A solution in which the polymer gel and the fixing agent are dispersed and mixed in various solvents compatible with the fixing agent or a mixture thereof is used. Solvents are selected according to the fixing agent, ketones such as acetone, alcohols such as ethanol and methanol, carboxylic esters such as ethyl acetate, aromatic hydrocarbons such as toluene and xylene, and halogens such as methylene chloride. Hydrocarbons, ethers such as diethyl ether, hydrocarbons such as hexane and cyclohexane, and mixtures thereof can be used. After the polymer gel and the immobilizing agent are applied to the surface to be adhered, a method such as heating to a reaction temperature specific to the immobilizing agent to form a chemical bond, and immobilizing the polymer gel on the backing surface, etc. Can be applied. In addition, a step-wise reaction of fixing the polymer gel to the formed reactive group after treating the surface to be bonded with the fixing agent can be applied.

The immobilizing agent in the polymer gel used in the present invention may be a compound having two or more polymerizable unsaturated groups and reactive functional groups. Examples of the compound having two or more polymerizable unsaturated groups include di- or tri (meth) acrylic polyols such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin. Acid esters, unsaturated polyesters obtained by reacting the polyols with unsaturated acids such as maleic acid and fumaric acid, bis (meth) acrylamides such as N, N'-methylenebis (meth) acrylamide, tris Di (meth) acrylate carbamates obtained by reacting polyisocyanate such as diisocyanate and hexamethylene diisocyanate with hydroxyethyl (meth) acrylate, allylated starch, allylated cellulose,
Examples include diallyl phthalate, other polyallyl-based compounds such as tetraallyloxyethane, pentaneerythritol triallyl ether, trimethylolpropane triallyl ether, diethylene glycol diallyl ether, and triallyl trimethyl ether. Among these, the present invention includes ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, N, N'-methylenebis (meth) acrylamide And the like are preferably used.

Examples of the compound having two or more reactive functional groups include a diglycidyl ether compound, a haloepoxy compound, and di- and triisocyanate compounds. Specific examples of the diglycidyl ether compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, and polyglycerin diglycidyl ether. . In addition, specific examples of the haloepoxy compound include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Further, specific examples of the diisocyanate compound include 2,4-tolylene diisocyanate, hexamethylene diisocyanate, and the like. Among these, ethylene glycol diglycidyl ether, hexamethylene diisocyanate and the like are particularly preferably used in the present invention.

The amount of the polymer gel used as described above is usually
It is 0.001 to 10% by weight, preferably 0.001 to 5% by weight, based on the dry weight of the polymer gel. this is,
If the amount of the immobilizing agent is 0.001% by weight or less, the polymer gel cannot be sufficiently immobilized. On the other hand, if the amount is 10% by weight or more, the immobilization of the polymer gel is too strong to inhibit a change in volume. It is.

The support used in the present invention is preferably mainly fibrous. For example, synthetic fibers such as nylon fibers, acrylic fibers, polyester fibers,
Natural fiber such as polypropylene fiber, polyvinyl chloride fiber, polyamide fiber and polyurethane fiber, wood pulp, cotton, wool, etc., semi-synthetic fiber such as viscose rayon, acetate, cupra, etc., inorganic fiber such as carbon fiber and titanium Fibers and the like can be applied. Examples of the form of the fibrous support include not only a mere aggregate of fibers but also a structure such as a woven fabric, a nonwoven fabric, a web, and a sheet. The fiber diameter of the fibrous support is 1 μm to 1 mm, preferably 10 μm to 0.5 mm.
Degree, the thickness of the substrate is about 0.1 to 10 mm, preferably about 0.1 to 5 mm, and the basis weight is about 2 to 200 g / m
2, preferably about 2 to 100 g / m2.

The sealing material 4 has the ability to suppress evaporation or volatilization of the solvent from the light modulating material 3, has an adhesive property to the transparent plate 2, and does not adversely affect the characteristics of the light modulating material 3. Any material may be used as long as it satisfies these conditions for a long time under actual use conditions. It is also possible to combine a plurality of sealing materials.
When the sealing material 4 and the sealing method are taken into consideration, such as securing the opening area of the light control glass 1 and processing costs due to simplification of the process,
One layer sealing is preferred. The use of a thermosetting elastic sealing material mainly composed of an isobutylene oligomer having a reactive group at the terminal as the sealing material 4 when performing sealing with one layer can be exemplified. When sealing with two layers, the light modulating material 3
For example, a polyisobutylene-based sealant can be used for the primary sealing in contact with the resin, and an acrylic resin or the like can be used for the secondary sealing. The sealing material 4 and the sealing method of the present invention are not limited to the above examples, and various types can be selected, and they may be used in combination.

In the present invention, heat generating means and electric means are preferably used as the stimulus applying means. When functioning as an autonomous response type dimming glass, a configuration is provided in which no heat-generating means is provided and a response is received by receiving heat from the sun. As other artificial heating means, a combination of the electrode and a metal typified by a Ni—Cr compound, a metal oxide such as tantalum oxide or ITO, or a heating resistor such as carbon is preferably used. Also,
In the case of electrical means, an electrode composed of a metal film represented by copper, aluminum, silver, platinum, etc., a metal oxide represented by tin oxide-indium oxide (ITO), polypyrroles, polythiophenes, polyanilines, An electrode made of a conductive polymer typified by polyphenylenevinylenes, polyacenes, polyacetylenes, and the like, and an electrode made of a composite material of a polymer and particles of the above-described metal or metal oxide are preferably used. In addition to the above, a layer for applying light, a magnetic field, an electromagnetic field, or the like can be provided as a stimulus applying means.

In the case of an autonomous response type using heat energy from the sun or when a heating means is provided, the above-mentioned thermoresponsive polymer gel is preferably used. When an electric means is provided, a polymer gel which responds by the above-mentioned pH change, a polymer gel which responds by adsorption and desorption of a chemical substance such as a surfactant, and a polymer gel which responds by oxidation and reduction are included. It is preferably used as a constituent material of a light control material. Further, in the case of a configuration in which light is irradiated from the outside, the above-described photoresponsive polymer gel is preferably used.

In the present invention, the preferred thickness of each member constituting the light control glass 1 is as follows. First, when the transparent plate 2 is made of glass with improved breaking strength, it is preferably at least 3 mm or more, and in the case of tempered glass, it is preferably 6 mm or more. In this case, the upper limit of the thickness is not particularly set. However, if the thickness is too large, it is uneconomical, and the thickness may be set to about 50 mm. Also, even in the case of a substrate that does not improve the breaking strength on both sides, considering that it is mainly used for various windows,
At least 1 mm is required.

Next, the ultraviolet ray shielding layer 5 and the heat ray shielding layer 8
Although it depends on the type of the formed layer, the thickness is required to be 0.1 μm or more in order to obtain a sufficient shielding effect even in the thinnest case by vacuum evaporation or the like. On the other hand, there is no particular upper limit, but even when a liquid ultraviolet cut layer or a vacuum layer for shielding heat rays is formed, a thickness of 50 mm is sufficient. Further, the thickness of the light control layer needs to be at least 0.1 μm or more, and is preferably 1 μm or more in order to obtain a sufficient light control function. On the other hand, the upper limit is about 5 mm. This is because if the thickness is too large, there is a problem that the time required for exerting the dimming function becomes too long.

[0071]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. <Preparation of Thermosensitive Polymer Gel Containing Light Scattering Member> A polymer gel used in the present invention, which has a dimming function by temperature change, was produced by the following method. 10 g of acrylamide, 0.27 g of N, N'-methylenebisacrylamide as a crosslinking agent, 50 g of distilled water, and 10 g of titanium oxide (refractive index: 2.7) having an average primary particle diameter of about 0.2 μm as a light scattering member. The solution was added and mixed with stirring to prepare an aqueous solution. After placing the above aqueous solution in a flask and removing oxygen by replacing with nitrogen, adding 1.0 g of ammonium persulfate which is a polymerization initiator, heating to 60 ° C. for 10 hours,
Polymerization was performed. After completion of the polymerization, the sample was coarsely pulverized, purified by washing with a large amount of distilled water, and further dried to obtain an acrylamide gel containing a light scattering member.

Next, the coarse particles 2 of this acrylamide gel
0 g was placed in a flask, 10 g of acrylic acid was added thereto, and N, N′-methylenebisacrylamide 0.2 was used as a crosslinking agent.
6 g and 50 g of distilled water and 0.03 g of sodium hydroxide (5 mol% of acrylic acid) were added to partially neutralize the acrylic acid. After purging with nitrogen, 0.04 g of ammonium persulfate was added. After standing for 1 hour in this state, the acrylamide gel was sufficiently impregnated with and swelled with an acrylic acid-based aqueous solution, and then heated to 60 ° C. and polymerized for 10 hours to prepare an IPN polymer gel. After completion of the polymerization, the generated IPN polymer gel mass was pulverized with a homogenizer, poured into a large amount of distilled water, and the operation of filtering the same was repeated for purification. Then, it was dehydrated using a large amount of methanol and dried. The dried particles had a particle size of about 70 μm. By the above-described preparation operation, a polymer gel used for the light control material of the present invention having a light control function by temperature change was prepared. This particulate polymer gel was added to a large amount of distilled water to swell. The water absorption during equilibrium swelling at a temperature of 10 ° C. was about 4 g / g. However, when this was heated to 30 ° C., it swelled further, and about 160
It was found to show a water absorption of g / g. Further, the phase transition point was in a temperature range of 15 to 20 ° C. That is, it swells at a temperature higher than the phase transition point and contracts at a lower temperature. This change was reversible, and the size of the particles was changed about 3.4 times, that is, about 40 times in volume by swelling / shrinking.

The light control function of this polymer gel was evaluated as follows. An aqueous dispersion containing the particles at a constant concentration (0.20 g / l) was prepared, placed in a spectrophotometer cell having an optical path length of 1 cm, and transmitted at 10 ° C. (when shrunk) and 50 ° C. (when swelled). As a result of measuring the transmittance, the transmittance was 90
%, And the transmittance was 5%, indicating that the transmittance greatly changed. Since both concentrations of the light scattering member are constant, it is considered that the light scattering member diffuses and agglomerates due to a change in the volume of the polymer gel, and the transmittance changes due to a change in the light scattering efficiency. Further, the transmittance change due to the temperature change was reversible, and there was no deterioration even after repeating 100 times. It was also confirmed that the transmittance change could be performed stepwise.

<Preparation of Thermosensitive Polymer Gel Containing Coloring Material> Instead of a light scattering member, a primary material having a primary particle diameter of about 0.1 was used as a coloring material.
1 μm carbon black pigment (Showa Cabot Co., Ltd.
Except that 10 g of Show Black N762) was used,
A thermosensitive polymer gel containing a coloring material was produced in exactly the same manner as the method for preparing the thermosensitive polymer gel containing the light scattering member. This particulate polymer gel was added to a large amount of distilled water to swell. The water absorption during equilibrium swelling at a temperature of 10 ° C. was about 4 g / g. However, this is 30
It was found that when heated to ° C, it swelled further and exhibited a water absorption of about 160 g / g. The phase transition point is 15-20 ° C.
Temperature range. That is, it swells at a temperature higher than the phase transition point and contracts at a lower temperature. This change is reversible,
Due to swelling / shrinking, the size of the particles was changed about 3.4 times, that is, about 40 times in volume. The dimming function of this polymer gel was evaluated as follows. An aqueous dispersion containing the particles at a constant concentration (0.20 g / l) was prepared, placed in a spectrophotometer cell having an optical path length of 1 cm, and transmitted at 10 ° C. (when contracted) and 50 ° C. (when swelled). As a result of measuring the transmittance, it was found that the transmittance was 90% and the transmittance was 5%, respectively, indicating that the transmittance greatly changed. Since the concentration of the coloring material is constant, it is considered that the coloring material diffuses and agglomerates due to the volume change of the polymer gel, and the transmittance changes due to the change in the light absorption efficiency. Further, the transmittance change due to the temperature change was reversible, and there was no deterioration even after repeating 100 times. It was also confirmed that the transmittance change could be performed stepwise.

<Weather resistance test> Using a sunshine weather meter (WEL-SUN-HC type) manufactured by Suga Test Instruments, the test was performed for 100 hours under the condition of a black panel temperature of 63 ° C. The deterioration of the dimming characteristics was compared. <Measurement of breaking strength> The breaking strength was compared by measuring the average breaking load. The average breaking load was calculated from the product of the breaking wind pressure and the glass area.

(Example 1) An ultraviolet shielding film was produced as follows. First, 100 parts by weight of commercially available cerium acetylacetonate (III) and pentaethoxyniobium
5 parts by weight, 89.5 parts by weight of diethanolamine and 890.0 parts by weight of n-butyl alcohol were mixed, and 23.3 parts by weight of pentaethoxyniobium was added thereto. This mixture was placed in a flask and refluxed at 130 to 140 ° C. for 2 hours to obtain a brown solution. This solution was coated on one surface of the first glass substrate by spin coating. Then, it is dried at 120 ° C. for 10 minutes in a dryer, and further dried at 500 ° C.
For 20 minutes in the air to obtain an ultraviolet shielding film 5. When the film thickness obtained by one film formation was small, the film formation was repeated a plurality of times to make the film thickness about 100 nm.

Next, as shown in FIG.
The ultraviolet shielding film 5 on a 2 mm thick glass substrate having
The other glass substrate having a thickness of 2 mm was opposed to the glass substrate so that the inside of the glass substrate was located inside, and was placed in parallel with an interval of about 0.5 mm via an epoxy adhesive for sealing and a spacer. Then, in a closed space formed between the two glass substrates, a light modulating material composed of an aqueous solution having a concentration of 1.13 g / l of the heat-sensitive polymer gel containing the light-scattering member was used. The other was to encapsulate two types of light modulating glass having an ultraviolet shielding film 5 by enclosing a light modulating material comprising a 1.13 g / l aqueous solution of a thermosensitive polymer gel containing a coloring material. . In addition, soda lime glass (float plate glass manufactured by Central Glass) is used for the glass substrate.
Was used. Each of the two types of light control glass had a visible light transmittance of about 40% when the polymer gel was swollen, and a visible light transmittance of about 90% when the polymer gel was contracted. As a result of performing the above-mentioned weather resistance test on the two types of light control glass having the ultraviolet shielding film 5,
Each of the two types of light control glass shows the same value with respect to the change over time in the transmittance, and the results are shown in FIG. FIG.
For comparison, the same test results of a light control glass except that there was no ultraviolet shielding film are also shown for comparison. As can be seen from the test results, the dimming glass of the present invention provided with the ultraviolet shielding film can obtain a much more stable dimming function than the case where the ultraviolet shielding film is not provided.

Example 2 In order to improve the wind resistance, one of the two glass substrates was made of tempered glass having a thickness of 6 mm, and the other was made of float glass having a thickness of 3 mm. These two glass substrates are opposed to each other, and are placed in a range of about 0.1 through an epoxy adhesive for sealing and a spacer.
They were arranged in parallel with an interval of 5 mm. Then, a light modulating glass having a tempered glass was produced by enclosing the same two light modulating materials as in Example 1 in a closed space formed between the two glass substrates. As a result of performing the above-described fracture strength measurement test on two types of light control glass having the tempered glass, the two types of light control glass exhibited the same average breaking strength, and this value is shown in Table 1. Also, for comparison, the test results of a light control glass having exactly the same configuration except that a float glass having the same thickness was used instead of the tempered glass are also shown.

[0079]

[Table 1]

As can be seen from the results, the light control glass using the tempered glass of the present invention has about 2.
It was found to have five times the strength.

(Example 3) Polycarbonate resin 100
Was dissolved in dichloromethane, and as an infrared absorber,
6-octafluoro- (4,5-octakisanilino)
0.1 parts by weight of oxyvanadium phthalocyanine was uniformly dispersed. Apply the resin solution on one glass substrate,
The glass substrate having a heat ray shielding layer having a thickness of 0.13 mm was obtained by allowing the solvent to evaporate to stand. Next, a float glass having a thickness of 2 mm is used for the other glass substrate, these two glass substrates are opposed to each other, and a gap of about 0.5 mm is maintained via an epoxy adhesive for sealing and a spacer. Arranged in parallel. Then, a light modulating glass having a heat ray shielding function was produced by enclosing the same two light modulating materials as in Example 1 in a closed space formed between two glass substrates. Next, a box in which the two types of light control glass were attached to one surface was prepared for each of the two types of light control glass, and heat rays were applied to the light control glass from outside using a 400 W infrared lamp. As a result, the two types of light control glass exhibited the same thermal heat shutoff results. FIG. 9 shows the result of measuring the internal time-dependent temperature change at this time. Also, for comparison, the results of measurements performed on a light control glass having exactly the same configuration except that it has no heat ray shielding function are also shown. As can be seen from the results, it was confirmed that the temperature control inside the light control glass having the heat ray shielding function was reduced. Therefore, it was confirmed that the light control glass of the present invention also has a heat ray shielding effect in addition to a light control function due to a temperature rise.

[0082]

According to the light modulating material used in the light control glass of the present invention, if the volume change of the stimuli-responsive polymer gel particles containing a colorant or a light scattering member is used, the light control / coloring state is improved. Stable, high contrast, fast stimulus response. When the light control glass of the present invention is provided with an ultraviolet ray shielding function as a protective function, it is possible to reduce a decrease in the stimulus response function of the light modulation material due to the irradiation of ultraviolet rays, and to receive long-term exposure to ultraviolet rays. Even in use in such an environment, the dimming function is stable. Further, when the light control glass of the present invention uses a sheet glass with a net, a sheet glass with a line, a tempered glass, a laminated glass, a double-strength glass, or the like, it can be obtained only by sandwiching and enclosing the material using ordinary glass or float glass. Unobstructed, wind pressure resistance, impact resistance, fire protection performance, safety at breakage, etc. are obtained.
Further, when a heat ray reflective layer, a heat ray low radiation layer, or a vacuum layer is used for the light control glass of the present invention, the penetration of heat into the inside can be reduced. As a result, when used for windowpanes installed in spaces where people are active inside offices and the like, it can contribute to reduction of environmental load such as prevention of global warming, especially improvement of indoor cooling efficiency in summer. .

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing one embodiment of the light control glass of the present invention.

FIG. 2 is a schematic configuration diagram showing another embodiment of the light control glass of the present invention.

FIG. 3 is a schematic configuration diagram showing still another embodiment of the light control glass of the present invention.

FIG. 4 is a schematic configuration diagram showing still another embodiment of the light control glass of the present invention.

FIG. 5 is a schematic configuration diagram showing still another embodiment of the light control glass of the present invention.

FIG. 6 is a schematic configuration diagram showing still another embodiment of the light control glass of the present invention.

FIG. 7 is a schematic configuration diagram showing still another embodiment of the light control glass of the present invention.

FIG. 8 is a graph showing the results of a weather resistance test of the light control glass of the present invention.

FIG. 9 is a graph showing the results of a heat ray shielding test of the light control glass of the present invention.

[Explanation of symbols]

1. 1. light control glass; 2. transparent plate; Light modulation material; 4. 4. sealing material; 5. UV shielding layer, 6. protective layer; 7. Glass with improved strength and safety; 8. heat ray reflection layer (heat ray shielding layer); Light control sheet, 10,12. Spacer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference)

Claims (7)

[Claims] 1. A light modulating material comprising at least polymer gel particles whose volume changes in response to an external stimulus and a liquid used to change the volume of the polymer gel particles is interposed between two transparent plates. A light control glass, wherein at least one of the transparent plates is provided with a protection function for protecting the light control glass from an external factor that impairs the function of the light control glass. 2. The light control glass according to claim 1, wherein at least one of the transparent plates has an ultraviolet shielding function. 3. The glass sheet according to claim 1, wherein at least one of the transparent plates is made of one of a netted glass, a lined glass, a tempered glass, a laminated glass, and a double-strength glass. Dimming glass. 4. The light control glass according to claim 1, wherein at least one of the transparent plates uses one of a heat ray reflection layer, a heat ray low emission layer, and a vacuum layer. 5. The polymer gel particle according to claim 1, wherein the polymer gel particle contains a light scattering member, and swells and contracts reversibly by absorption and emission of the liquid. Dimming glass. 6. The polymer gel particle contains a coloring material,
The light control glass according to any one of claims 1 to 4, wherein the liquid crystal swells and contracts reversibly by absorption and release of the liquid. 7. The light control glass according to claim 1, wherein the volume of the polymer gel particles changes due to a change in temperature to change the amount of transmitted light.