JP3915339B2 - Light control glass - Google Patents

Description

【００８０】
この結果からわかるように、本発明の強化ガラスを用いた調光ガラスは、調光機能に加えて通常のフロートガラスで構成された調光ガラスに比べて約２．５倍の強度を有することがわかった。
【００８１】
（実施例３）
ポリカーボネート樹脂１００部をジクロロメタンに溶かし、赤外線吸収剤として３，６−オクタフルオロ−（４，５−オクタキスアニリノ）オキシバナジウムフタロシアニン０．１重量部を均一に分散させた。樹脂溶液を片方のガラス基板上に塗布し、溶媒が揮発するまで静置して、厚み０．１３ｍｍの熱線遮蔽層を有するガラス基板を得た。
次に、もう一方のガラス基板には、厚さ２ｍｍのフロートガラスを用い、これら２枚のガラス基板を対向させ、シール用エポキシ接着剤およびスペーサを介して、約０．５ｍｍの間隔を保持して平行に配置した。そして、２枚のガラス基板の間に形成された密閉空間に、実施例１と同様の光変調材料を用い封入することにより、熱線遮蔽機能を有する調光ガラスを作製した。
次に、この調光ガラスを１面に取り付けた箱を用意し、外部から４００Ｗの赤外線ランプにより調光ガラスに熱線を照射した。調光ガラスの熱遮断結果を図９に示した。図９には、このときの内部の時間に依存した温度変化を測定した結果を示した。また、比較のため、熱線遮蔽機能を有しないこと以外全く同様な構成の調光ガラスについて行った測定結果も併記した。
この結果から分かるように、熱線遮蔽機能を有する調光ガラスでは、内部の温度上昇が軽減されることが確認できた。したがって、本発明の調光ガラスは、温度上昇による調光機能に加えて熱線遮蔽効果をも有することが確認された。
【００８２】
【発明の効果】
本発明の調光ガラスに用いられる光変調材料は、内部に光散乱部材を含有する刺激応答性高分子ゲル粒子の体積変化を利用すると、調光状態が安定しており、コントラストが高く刺激応答が速い。そして、本発明の調光ガラスは、保護機能として紫外線遮蔽機能が付与されていると、紫外線の照射による光変調材料の刺激応答機能の低下を軽減することができ、長期間の紫外線曝露を受けるような環境での使用においても、調光機能が安定している。また、本発明の調光ガラスに、網入り板ガラス、線入り板ガラス、強化ガラス、合わせガラス、倍強度ガラスなどを用いると、普通ガラスやフロートガラスなどを用いて該材料を挟持封入しただけでは得られない、耐風圧強度、耐衝撃力、防火性能、および破損時における安全性などが得られる。また、本発明の調光ガラスに、熱線反射層、熱線低放射層、あるいは真空層を用いると、内部への熱の侵入を低減できる。その結果、オフィスなど内部で人間が活動する空間に設置される窓ガラスに使用する場合、特に夏期の室内の冷房効率向上など、地球温暖化防止をはじめとする環境負荷低減に寄与することができる。
【図面の簡単な説明】
【図１】 本発明の調光ガラスの一実施の形態を示す概略的構成図である。
【図２】 本発明の調光ガラスの他の実施の形態を示す概略的構成図である。
【図３】 本発明の調光ガラスの更に他の実施の形態を示す概略的構成図である。
【図４】 本発明の調光ガラスの更に他の実施の形態を示す概略的構成図である。
【図５】 本発明の調光ガラスの更に他の実施の形態を示す概略的構成図である。
【図６】 本発明の調光ガラスの更に他の実施の形態を示す概略的構成図である。
【図７】 本発明の調光ガラスの更に他の実施の形態を示す概略的構成図である。
【図８】 本発明の調光ガラスの耐候試験の結果を示すグラフである。
【図９】 本発明の調光ガラスの熱線遮蔽試験の結果を示すグラフである。
【符号の説明】
１．調光ガラス、２．透明板、３．光変調材料、４．封止材、５．紫外線遮蔽層、６．保護層、７．強度・安全性向上ガラス、８．熱線反射層（熱線遮蔽層）、９．調光シート、１０，１２．スペーサ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a light control glass filled with a so-called light modulation material capable of reversibly controlling light transmittance, light scattering property, color development state, and the like according to external stimuli such as heat, light, and electricity.
[0002]
[Prior art]
Many light control glasses using light control materials that reversibly control light transmittance, color development state, etc. in response to external stimuli have been proposed. For example, various systems such as liquid crystal, electrochromic, photochromic, and thermochromic are known.
[0003]
[Problems to be solved by the invention]
On the other hand, the present inventors have proposed a novel light modulation material that is unknown but contains a coloring material or a light scattering member inside the stimulus-responsive polymer gel. In response to various external stimuli such as heat, light, and electrical energy, the polymer gel swells and shrinks, and the color materials and light scattering members contained in the inside diffuse and aggregate, resulting in light transmittance. It is a novel material that can change the light scattering property and color development state.
[0004]
The light control glass can be easily produced by encapsulating these materials between two parallel glass plates. Of course, in the case of using a material that responds to electric energy, an electrode such as ITO may be provided on the opposing surfaces of the two glasses.
[0005]
However, when using dimming glass using these materials, it is possible to prevent deterioration of responsiveness and discoloration caused by exposure to ultraviolet rays due to exposure to the outdoors for a long period of time. It is important to improve performance. In addition, when applied to buildings and vehicles, fire resistance, wind pressure strength, impact strength, and safety in the event of breakage cannot be obtained simply by sandwiching and enclosing the material using ordinary glass or float glass. Ensuring sex is important. In addition, when used for window glass installed in a space where people are active inside offices, etc., in order to reduce environmental impacts such as prevention of global warming, such as improving the cooling efficiency of indoors, especially in the summer, light shielding alone It is important to cut off the heat.
[0006]
The object of the present invention was made under the earnest research of the present inventors in order to obtain the above-mentioned important characteristics, and is a polymer gel particle that changes in volume in response to an external stimulus, In the case of light control glass having a light modulation material composed of a liquid used for volume change of molecular gel particles, there is little deterioration of properties due to long-term ultraviolet exposure, fire resistance performance, wind pressure strength, impact resistance, and An object of the present invention is to provide a light control glass which is excellent in safety at the time of breakage and has a function of blocking heat rays.
[0007]
[Means for Solving the Problems]
The above object is achieved by the present invention described below. That is, the present invention includes at least a polymer gel particle that changes in volume in response to an external stimulus, and a liquid that is used to change the volume of the polymer gel particle. The polymer gel particle contains a light scattering member having a saturation scattering concentration or more in a contracted state, and reversibly swells and contracts by absorption and release of the liquid. The light modulation material is interposed between two transparent plates, and at least one of the transparent plates is provided with a protective function for protecting the light control glass from external factors that impair the function of the light control glass. It is the light control glass characterized.
Examples of protection functions include, for example, 1) that at least one of the transparent plates is provided with an ultraviolet shielding function, and 2) that at least one of the transparent plates has a mesh plate glass, a wire plate glass, a tempered glass, and a laminated glass. 3) the use of any one of double strength glass, 3) the use of a heat ray reflective layer, a heat ray low radiation layer, or a vacuum layer on at least one of the transparent plates.
Light modulation material is a polymer gel particle that contains a light scattering member and reversibly swells and contracts by absorption and release of liquid. Because Furthermore, it is preferable that the polymer gel particles change in volume due to a change in temperature to change the light transmission amount.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
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, a light modulation material 3 sandwiched and enclosed between them, and sealing The material 4 is configured, and at least one of the transparent plates 2 has an ultraviolet shielding function. For this ultraviolet shielding function, an ultraviolet shielding layer 5 having a form of a coating film of an ultraviolet shielding agent, an ultraviolet cut layer encapsulating the ultraviolet shielding agent, or an ultraviolet shielding film containing an ultraviolet shielding agent can be applied. In particular, the coating film of the ultraviolet shielding agent and the ultraviolet shielding film are preferably formed on the surface facing the other transparent plate as shown in FIG. This is because if exposed to the outside, there is a concern that scratches and the like are likely to occur and the desired function cannot be stably maintained for a long period of time. Therefore, when applying to the surface exposed outside, it is preferable to form the protective layer 6 on it as shown in FIG. On the other hand, the ultraviolet cut layer encapsulating the ultraviolet shielding agent is not particularly limited, and may be applied to the surface exposed to the outside.
[0009]
As the ultraviolet absorber having an ultraviolet shielding function, inorganic compounds such as titanium oxide, zinc oxide and cerium oxide, or organic ultraviolet absorbers are preferably used. For example, when zinc oxide is used as the inorganic fine particles, those having a particle diameter of 0.1 μm or less are preferably used, and are used by being uniformly dispersed in the resin liquid for forming the ultraviolet shielding layer 5. The content is preferably in the range of 0.3 to 50% by weight with respect to the resin liquid.
[0010]
On the other hand, examples of the organic ultraviolet absorber include salicylic acid series such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- Benzophenones such as 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-benzotriazo Ru-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate, 2,2′-methylenebis [4- (1,1,3,3-tetratylbutyl)]-6- (2H-benzo Examples include ultraviolet absorbers such as benzotriazoles such as triazole, cyanoacrylates such as 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3-diphenyl acrylate, and the like. 1 type or 2 types or more can be mixed and used.
[0011]
As a method of coating the transparent plate with the ultraviolet absorber, a dry method such as a vacuum deposition method, an ion plating method, a sputtering method, or a solution obtained by dissolving or dispersing the ultraviolet absorber in a solvent together with a binder is used. A wet method of applying to the body and drying and curing the solvent can also be applied. As the film having an ultraviolet shielding function, a film provided with a coating film having an ultraviolet shielding function, a film kneaded with an ultraviolet absorber, or the like can be used.
In addition, an ultraviolet cut layer of a liquid film can be applied, such as a liquid ultraviolet absorber (for example, Tinuvin 109, 171, 384, 1130, etc. manufactured by Ciba Geigy Co., Ltd.) in which the ultraviolet absorber molecule is liquid at room temperature. A solid ultraviolet absorber (eg, Tinuvin 326, 327, 328, 213, 571, Sumitomo Chemical's Sumsorb 110, 110S, 250, 400, etc. manufactured by Ciba Geigy Co., Ltd.) at room temperature is considered to be a saturated concentration in consideration of solubility in a solvent. A solution having a high concentration dissolved therein (for example, a toluene solution of Sumisorb 110, a toluene solution of Sumisorb 320, etc.) is preferably used. Moreover, you may use these ultraviolet absorbers in mixture. Note that a light-resistant stabilizer (for example, Tinuvin 123, 292, 622LD, etc. manufactured by Ciba Geigy), an antioxidant (for example, Irganox 245, 1010, 1330, etc., manufactured by Ciba Geigy) or the like may be added as necessary.
The manufacturing method of this liquid film layer may be the same as the method for laminating, sealing, and pouring the liquid crystal panel. However, the thickness of the liquid film does not need to be particularly strict, and it is not necessary to perform an ultrathin layer having a thickness of 0.01 mm or less, or an orientation treatment, and a general lamination method may be used without any special contrivance.
[0012]
Further, as shown in FIG. 4, at least one of the transparent plates 2 has (1) improved wind pressure strength, (2) improved impact resistance, (3) improved fire resistance, and (4) safety. In order to improve the strength and safety, any one of tempered glass, laminated glass, double-strength glass, mesh-containing plate glass, and wire-containing plate glass is used. In this case, although not particularly limited, the strength / safety-enhancing glass is preferably used as the outermost layer in order to protect the light control layer.
[0013]
In order to improve the wind pressure strength of (1), it is preferable to use tempered glass or double strength glass. In the case of light control glass composed only of float glass, the strength is equivalent to or slightly superior to that of one float glass used, although it varies depending on the area and sealing method, etc., and the strength is improved by increasing the thickness. Cannot be expected. In contrast, by using tempered glass or double-strength glass, the wind pressure strength of the light control glass can be improved. This is apparent from the value of the strength coefficient (α) when calculating the wind pressure strength applied to Notification No. 109 of the Ministry of Construction. The strength coefficient of the float glass is 0.8 when the thickness is 6 mm or less, and 1.0 when the thickness exceeds 6 mm. On the other hand, tempered glass and double-strength glass are 3.0 and 2.0, respectively, and their wind pressure strength is high. Therefore, the wind pressure strength of the light control glass of the present invention using these is also improved. When used as a building material, the area of the opening is defined by the wind pressure strength and the ground height of the installed part. Usually, in order to ensure the required wind pressure strength, a thick glass must be used, and the light control glass also becomes thick. For this reason, installation on a general-purpose sash or frame becomes difficult, and it may not be used, which is extremely inconvenient. However, it is preferable to use at least one transparent plate made of tempered glass or double-strength glass because a desired wind pressure strength can be obtained without increasing the thickness of the light control glass. This increases the usable area of the light control glass to the building and reduces the restrictions when using the light control glass. In particular, it is preferable to apply this light control glass to a building window glass or the like having a large cooling load, since the cooling load can be remarkably reduced by increasing the area of the light control glass and greatly contribute to energy saving. This effect depends on the tempered glass and double-strength glass to be used. If these glasses are used for all of the transparent plates used for the light control glass, the effect becomes more remarkable and preferable.
[0014]
In order to improve the impact resistance of (2), it is preferable to use tempered glass. Similar to the wind pressure strength, normal glass cannot be expected to improve the strength by increasing the thickness of the light control glass. For this reason, in order to obtain a desired intensity | strength, if a thick glass is used, a problem will arise and it is unpreferable. On the other hand, tempered glass is preferred because it has a bending strength and impact strength 3 to 5 times that of ordinary plate glass, so that the above-mentioned problems can be avoided and desired characteristics can be obtained without increasing the light control glass. This depends on the tempered glass to be used. If all the transparent plates to be used are made of tempered glass, the effect becomes more remarkable and preferable.
[0015]
In order to improve the fireproof property of (3), it is preferable to use a mesh-inserted plate glass or a wire-inserted plate glass. In other words, compared with light control glass composed only of plain plate glass, plain plate ground glass, float plate glass, polished plate glass, mold plate glass, etc. In addition, even if cracks occur, the fragments are supported by a net or metal wire, preventing the fragments from falling off and making holes in the glass surface, and spreading fire due to the intrusion of flame from the holes Can be prevented. Therefore, the fireproof performance of the light control glass is improved, and its safety is increased. Also, the use of double strength glass has a thermal cracking strength about twice that of float glass, which is preferable for the same reason. These properties depend on the netted glass, wire-filled glass, and double-strength glass used. If these glasses are used for all the transparent plates of the light control glass, the effect becomes more remarkable and 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 fire resistance is improved compared to conventional products in parts that are not stipulated here. , Safety increases.
[0016]
In order to improve the safety at the time of glass breakage of (4), it is preferable to use tempered glass or laminated glass. Even if the tempered glass breaks, it becomes fine granular fragments, not sharp fragments, and its safety is high. In addition, the laminated glass is excellent in safety due to the action of the intermediate film, so that even if it is broken, penetration, separation of fragments or scattering hardly occur. In addition, it is preferable that all of the transparent plates to be used are made of these glasses because the effect becomes more remarkable.
One transparent plate of the two transparent plates 2 is composed of any one of netted plate glass, wire-filled plate glass, tempered glass, laminated glass, and double-strength glass, and the other transparent plate is ordinary glass, float glass, etc. Inorganic glass, organic glass such as polycarbonate, and the like. As described above, netted 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 when glass breaks. The glass to be actually used is appropriately selected from these according to the object to be used and the use conditions. However, the two transparent plates 2 can also be composed of the same type of glass selected from netted plate glass, wire-inserted plate glass, tempered glass, laminated glass, and double-strength glass, or different types of glass.
[0017]
Such tempered glass, laminated glass, double-strength glass, netted glass, and lined glass are configured as follows.
[0018]
The tempered glass is obtained by heat-treating a plate glass to form a strong compressive stress layer on the glass surface, increasing the breaking strength, and forming a fine piece when broken. The tempered glass is preferably a JIS R3206 standard product, but is not limited thereto. The double-strength glass is also called HS glass, and is a processed glass whose wind pressure strength is increased to about twice that of float glass of the same thickness by a heat treatment process with high accuracy. Such glass has twice or more strength against thermal cracking.
[0019]
Laminated glass is obtained by attaching an intermediate film to two or more material plate glasses and bonding them all over, so that even if broken by the action of external force, most of the fragments are not scattered. Depending on the type of sheet glass used, it is classified into float laminated glass, mold laminated glass, net-filled laminated glass, wire-filled laminated glass, mesh-filled laminated glass, line-filled laminated glass, tempered laminated glass, etc. The The laminated glass is preferably a JIS R3205 standard product, but is not limited thereto. In general, laminated glass is a product in which two or more sheet glasses are pressure-bonded with a flexible and tough intermediate film, mainly polyvinyl butyral. Since it is difficult for separation or scattering of fragments, the glass is excellent in safety, and the characteristics are further imparted depending on the glass type used.
[0020]
The net-inserted plate glass and the wire-inserted plate glass are plate glasses in which a metal net or wire is inserted into the glass when forming with a rolling roll. There are types of glass, polished glass, and the like for both glass and lined glass, and the glass is further subdivided into diamond and square mesh. As the net-inserted plate glass and the wire-inserted plate glass, JIS R3204 standard products are preferable, but are not limited thereto. More specifically, a mesh-inserted plate glass is a plate glass in which a metal mesh is inserted into the glass, and a wire-inserted glass is a glass parallel so that the direction of the metal wire is the flow direction at the time of plate-making. It is a plate glass inserted inside. The mesh netting glass is a square mesh metal mesh in which the direction of the metal wire is oblique to the flow direction during plate making, and the direction of the two metal wires passing through the intersection is Is a plate glass enclosed inside the glass so as to be symmetrical to each other with respect to a straight line in the flow direction, and the square plate glass is a direction of two metal lines passing through the intersection of the above-mentioned metal mesh of the mesh netting plate glass. Is a plate glass inserted into the glass so that it is in the direction of flow during plate making and the direction perpendicular thereto. Moreover, these type | mold plate glass points out what has a pattern on one side with shaping | molding by a rolling roll, and polished glass points out the thing which polished both surfaces and became very smooth.
[0021]
Further, as shown in FIG. 5, when the heat ray reflective layer (heat ray shielding layer) 8 is provided, there is no particular limitation. However, when a light control layer using a heat sensitive gel is used, the heat sensitive response function is not disturbed. It is preferable to provide the innermost outermost layer. As the heat ray reflective layer 8, a three-layer film made of a CrN film and a TiO film can be used, and instead of the heat ray reflective layer 8, it may function as a heat ray low radiation layer. A five-layer film composed of ZnO film and ZnO film can be used. Further, as the heat ray reflective layer 8, a method of sticking a heat ray reflective film formed by sputtering or vapor deposition of a metal thin film such as Al, Ag, Au or the like on the surface of a transparent plate (Japanese Patent Application Laid-Open No. 57-59748, JP-A-57-59749) and a method of forming an infrared absorption layer by coating an organic infrared absorber on a glass surface (JP-A-4-160037) are also known.
[0022]
Among these, a near-infrared absorbing film having a large visible light transmittance is preferable. Specifically, JP 61-154888, JP 61-197281, JP 61-246091, JP 63-37991, JP 63-39388, JP 62-233288, JP 63-312889, JP-A-2-43269, JP-A-2-138382, JP-A-2-29685, JP-A-3-43461, JP-A-3-77840, JP-A-3-100066, JP-A-3-62878, Japanese Patent Application No. 3 -338557, Japanese Patent Application No. 3-99730, Japanese Patent Application No. Hei 3-252414, etc., phthalocyanines or naphthalocyanines, JP-A-61-291651, JP-A-61-291652, JP-A-62-2 15260, Japanese Patent Application Laid-Open No. 62-132963, Japanese Patent Application Laid-Open No. 1-129068, Japanese Patent Application Laid-Open No. 1-172458, etc. Kind, and the like. 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.
[0023]
A heat ray shielding layer containing heat ray shielding inorganic fine particles is also preferably used. The particle size 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 material is used, and in addition to antimony-containing tin oxide (ATO), indium-containing tin oxide (ITO), copper sulfide (CuS), conductive oxide, conductive Fine particles such as conductive sulfide, 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 the resin liquid forming the heat ray shielding layer 8. Dispersants used here include anionic surfactants such as carboxylates, sulfonates, sulfate esters, phosphate esters, phosphonates, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers Nonionic surfactants such as polyoxyethylene alkyl esters and sorbitan alkyl esters are used. The blending amount of these dispersants is preferably about 1 to 20% by weight with respect to the heat ray shielding inorganic fine particles.
[0024]
If necessary, aliphatic hydrocarbons such as hexane, heptane, cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, butanol, etc. Solvents such as alcohol, acetone, methyl ethyl ketone, ketones such as 2-pentanone and isophorone, and esters such as ethyl acetate and butyl acetate can also be used. The heat ray shielding inorganic fine particles can be dispersed by using a dispersing machine such as a sand mill, attritor, colloid mill, ball mill, high pressure homogenizer, etc., and the particle diameter of the fine particles is 0.1 μm or less, preferably 0.05 μm or less. Disperse until. When the particle diameter 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 preferably in the range of 10 to 85% by weight.
[0025]
Moreover, 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 multilayer glass formed by separating two glass plates around the periphery via a spacer, sealing the periphery and venting the air inside. . At this time, the substrate on which the vacuum layer is formed is a common glass plate such as ordinary plate glass, ordinary plate glass ground plate glass, float plate glass, polished plate glass, and molded plate glass, special glass such as netted glass and tempered glass, and other acrylics. Alternatively, a resin substrate such as polystyrene or polycarbonate can be used. These thicknesses are preferably about 1 mm to 20 mm, and are not particularly limited as long as a vacuum layer formed inside can be maintained. Moreover, since sufficient heat insulation effect is not acquired if it is 1 mm or less, as for the thickness of the vacuum layer formed, 1 mm or more is preferable. On the other hand, there is no particular upper limit, but it is preferable that the thickness is not so large in production, and 10 mm or less is preferable.
[0026]
Next, the light modulation material in the present invention will be described.
The light modulation material includes at least polymer gel particles whose volume changes in response to an external stimulus, and a liquid used for volume change of the polymer gel particles. With light scattering member Consists of
That is, the polymer gel constituting the light modulation material used in the present invention includes heat, light, electricity, magnetism, etc., pH change, oxidation / reduction, ion concentration change, adsorption / desorption of chemical substances, solvent composition A stimulus-responsive polymer gel that absorbs and releases liquid by various stimuli such as changes and reversibly changes its volume (swells and contracts) is preferable.
[0027]
Specifically, as a polymer gel that stimulates and responds 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; (meth) acrylic acid and ( Cross-linked products and metal salts of copolymers with (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid alkyl ester, etc .; maleic acid (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic Crosslinks of copolymers with acid alkyl esters and their metal salts; Crosslinks of polyvinyl sulfonic acids and their metal salts; Vinyl sulfonic acids and (meth) acrylamides, hydroxyethyl (meth) acrylates, alkyl (meth) acrylates Cross-linked products of copolymers with esters, etc. and their metal salts; Cross-linked products of acid and metal salts thereof; cross-linked products and metal salts of copolymers of vinylbenzenesulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, alkyl (meth) acrylate, etc .; polyacrylamide Cross-linked products of alkyl sulfonic acids and metal salts thereof; cross-linked products of acrylamide alkyl sulfonic acids and copolymers of (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid alkyl esters and the like; and metal salts thereof; poly Cross-linked dimethylaminopropyl (meth) acrylamide and its hydrochloride; copolymer of polydimethylaminopropyl (meth) acrylamide and (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid alkyl ester, etc. Cross-linked products and their metal salts Quaternary salt; cross-linked product of polydimethylaminopropyl (meth) acrylamide and polyvinyl alcohol and its quaternary salt; cross-linked product of poly (meth) acrylic acid and metal salt thereof; carboxy Cross-linked products of alkyl cellulose metal salts; partial hydrolysates of cross-linked products of poly (meth) acrylonitrile and metal salts thereof.
[0028]
As the polymer gel that stimulates and responds by the adsorption and desorption of a chemical substance such as a surfactant by an electric field, a strong ionic polymer gel is preferable, and a crosslinked product of polyvinylbenzenesulfonic acid, vinylbenzenesulfonic acid and (meth) acrylamide, hydroxy Cross-linked products of copolymers with ethyl (meth) acrylate, alkyl (meth) acrylate, etc .; cross-linked products of polyacrylamide alkyl sulfonic acid, acrylamide alkyl sulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, ( Examples thereof include cross-linked products of copolymers with (meth) acrylic acid alkyl esters and the like. 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.
[0029]
As the polymer gel that stimulates and responds by oxidation and reduction by electricity, a cationic polymer gel is preferable, and a crosslinked product of polyamino-substituted (meth) acrylamide such as polydimethylaminopropylacrylamide; polydimethylaminoethyl (meth) acrylate; polydiethylamino Ethyl (meth) acrylate; Cross-linked product of poly (meth) acrylic acid amino-substituted alkyl ester such as polydimethylaminopropyl (meth) acrylate; Cross-linked product of polystyrene; Cross-linked product of polyvinyl pyridine; Cross-linked product of polyvinyl carbazole; Polydimethylamino Examples include cross-linked styrene. These are used as a CT complex (charge transfer complex) in combination with an electron-accepting compound. The electron accepting compound preferably used at this time is benzoquinone; 7,7,8,8-tetracyanoquinodimethane (TCNQ); tetrabutylammonium perchlorate; tetracyanoethylene; chloranil; trinitrobenzene; maleic anhydride ; Iodine etc. are mentioned.
[0030]
Polymer gels that respond to stimuli by applying heat include crosslinked polymers with LCST (lower critical solution temperature), IPN (interpenetrating network structure) of two-component polymer gels that form hydrogen bonds with each other, etc. Is preferred. The former has a property of shrinking at high temperature, specifically, a cross-linked product of poly N-alkyl-substituted (meth) acrylamide such as poly-N-isopropylacrylamide; N-alkyl-substituted (meth) acrylamide and (meth) Cross-linked products of copolymers with acrylic acid and its metal salts, (meth) acrylamide, alkyl (meth) acrylates, etc .; cross-linked products of polyvinyl methyl ether; alkyl-substituted cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, etc. Examples include cross-linked products. On the other hand, the latter has a characteristic of swelling at high temperatures. Specifically, an IPN body composed of a crosslinked product of poly (meth) acrylamide and a crosslinked product of poly (meth) acrylic acid and a partially neutralized product (acrylic) An 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, and a partially neutralized product thereof. Can be mentioned. Of these compounds, polyN-alkyl-substituted alkylamide crosslinks, poly (meth) acrylamide crosslinks and poly (meth) acrylic acid crosslinks and partially neutralized products thereof are preferably used. It is done.
[0031]
As the polymer gel that responds to stimulation by the application of light, a cross-linked product of a hydrophilic polymer compound having a molecular structure that is ionically dissociated by light, such as a triarylmethane derivative or a spirobenzopyran derivative, is preferable. Specifically, a cross-linked product of a copolymer of a vinyl-substituted triarylmethane leuco derivative and (meth) acrylamide may be used.
[0032]
Examples of the polymer gel that responds to a stimulus by applying a magnetic field include cross-linked polyvinyl alcohol containing ferromagnetic particles and a magnetic fluid, but the polymer gel itself is not particularly limited. As long as it is included in the category.
[0033]
As the polymer gel that responds by a change in the composition of the solution or a change in ionic strength, the above-described electrolyte-based polymer gel can be preferably applied.
In the present invention, each stimulus-responsive polymer gel may be used alone, or a plurality of polymer gels may be used in combination.
The above description using parentheses indicates both the compound not including the prefix in the parentheses and the compound including the compound. For example, the description of (meth) acrylic acid means acrylic acid and methacrylic acid. Is.
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.
[0036]
The light scattering member contained in the polymer gel particles of the light modulation material used in the present invention is preferably a material having a refractive index different from the refractive index of the liquid used for volume change of the polymer gel. There is no restriction | limiting in particular except that various inorganic compounds and organic compounds are applicable.
[0037]
Specific examples of inorganic materials include zinc oxide, basic lead carbonate, basic lead sulfate, lead sulfate, lithopone, muscovite, zinc sulfide, titanium oxide, anmotimone, lead white, zirconium oxide, alumina, micanite, mica Rex, quartz, calcium carbonate, gypsum, clay, silica, silicic acid, silicon earth, talc, basic magnesium carbonate, alumina white, gloss white, satin white and other inorganic oxides, zinc, alumel, antimony, aluminum, aluminum Alloy, Iridium, Indium, Osmium, Chromium, Chromel, Cobalt, Zirconium, Stainless steel, Gold, Silver, Western silver, Copper, Bronze, Tin, Tungsten, Tungsten steel, Iron, Lead, Nickel, Nickel alloy, Nickelin, Platinum, Platinum Rhodium, tantalum, duralumin, nichrome, titanium, copper Metallurgy such as copper austenitic steel, constantan, brass, platinum iridium, palladium, palladium alloy, molybdenum, molybdenum steel, manganese, manganese alloy, rhodium, rhodium gold, inorganic conductivity such as ITO (indium tin oxide) Materials and the like.
[0038]
As specific examples of organic materials, and as specific examples of suitable organic materials, phenol resin, furan resin, xylene / formaldehyde resin, urea resin, melamine resin, aniline resin, alkyd resin, unsaturated polyester, epoxy resin , Polyethylene, polypropylene, polystyrene, poly-p-xylylene, polyvinyl acetate, acrylic resin, methacrylic resin, polyvinyl chloride, polyvinylidene chloride, fluoroplastic, polyacrylonitrile, polyvinyl ether, polyvinyl ketone, polyether, polycarbonate, heat Plastic polyester, polyamide, diene plastic, polyurethane plastic, polyphenylene, polyphenylene oxide, polysulfone, aromatic heterocyclic polymer, silicone, natural rubber plastic Chick, and polymer materials such as composite material of cellulose plastic, or the like, or two or more types of polymeric material (polymer blend) is.
[0039]
Furthermore, a polymer material containing the light scattering material listed above can be applied as a light scattering member. This polymer material is not particularly limited, and various polymer resins can be used. Specific examples of preferable polymer resins include specific examples listed when the light scattering material is an organic material.
[0040]
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, the density of the light scattering member is increased by the volume contraction of the polymer gel, and the light scattering member is aggregated. At this time, the light scattering member concentration reaches or exceeds the saturation scattering concentration, and the light scattering members overlap each other. As a result, light cannot be efficiently scattered, reflected, and refracted, and the light scattering ability per particle of the light scattering member is lowered, so that the light scattering efficiency is lowered. It is considered that the light modulation material causes a large difference in light scattering amount between the swelling and the shrinkage of the polymer gel due to such an action.
Here, the saturation scattering density or more means that the average distance between the light scattering members is sufficiently shortened as one index, so that the light scattering function of the light scattering member is from a primary particle to a collective one. The concentration at which the light scattering efficiency changes.
If the definition of saturated scattering concentration or higher is expressed by another characteristic, the saturation scattering concentration is such that the relationship between the light scattering member and the amount of light scattering under a specific optical path length deviates significantly from the linear relationship. is there.
[0041]
Then above Light of There is no restriction | limiting in particular in the shape of a scattering member, Various things, such as a particulate form, a block form, a film form, an indeterminate shape, a fiber form, can be used. Among these, the particulate form is particularly preferable because of its high light scattering property and wide application range. There are no particular restrictions on the form of particles, but spheres, cubes, ellipsoids, polyhedra, porous bodies, stars, needles, hollows, flakes, and the like can be applied. Moreover, the preferable size in the case of particle | grains is the range of 0.01 micrometer-500 micrometers in an average particle diameter, More preferably, it is the range of 0.05 micrometer-100 micrometers. This is an average particle size of 0.01 μm or less or 500 μm or more. And light Required for scattering members Light This is because the scattering effect is lowered. Furthermore, when the average particle size is 0.01 μm or less, the polymer gel tends to flow out from the inside to the outside. These particles can be produced by a general physical pulverization method or chemical pulverization method.
[0042]
Also these Light of The scattering member has an acid group such as a carboxyl group or a sulfonic acid group, a hydroxyl group, an amino group, a thiol group, a halogen group, a nitro group, a carbonyl group in the molecule, and the concentration of the light scattering member in the polymer gel. Those having a characteristic of easily forming an aggregate when the A is high are also preferably used.
[0043]
light The scattering member is contained in the polymer gel and preferably does not flow out from the inside of the polymer gel. . light In order to prevent the scattering member from flowing out, the particle size is larger than the network of the polymer gel used. Light of Use of scattering material or high electrical, ionic and other physical interaction with polymer gel Light Using scattering members, chemically modifying the surface Light Examples include scattering members. Chemical modification of the surface Light Examples of the scattering member include those having a group chemically bonded to a polymer gel on the surface, or grafted with a polymer material. Light Examples include scattering members.
[0044]
Included in polymer gel Light The concentration of the scattering member is generally preferably in the range of 2% to 95% by weight, more preferably in the range of 5% to 95% by weight. . light If the concentration of the scattering member is 2% by weight or less, the volume of the polymer gel of the light modulation material may change. Ru In order to stop the change in the amount of disturbance and to obtain a sufficient light control contrast, problems such as an increase in the thickness of many light control layers occur. on the other hand ,light When the concentration of the scattering member is 95% by weight or more, the swelling / shrinking of the polymer gel does not proceed with good response, and the stimulus response characteristics and volume change amount of the present light modulation material are reduced.
[0045]
Polymer gel Light The method of incorporating the scattering member is a polymer before crosslinking. Light A method in which the scattering member is uniformly dispersed and mixed and then crosslinked, a method in which a coloring material and a light scattering member are added to the polymer precursor composition during polymerization, and the like can be applied. Oy during polymerization Light When adding a scattering member, as described above, a polymerizable group and an unpaired electron (radical) are also present. Light It is also preferable to use a scattering member and chemically bond. Also ,light The scattering member is desirably dispersed as uniformly as possible in the polymer gel. In particular, it is desirable to uniformly disperse the polymer using a mechanical kneading method, a stirring method, or a dispersing agent.
[0046]
There is no restriction | limiting in particular in the shape of the polymer gel which comprises the light modulation material used for this invention, Various things, such as a particulate form, a block form, a film form, an indeterminate form, and a fiber form, can be used. Among these, the particulate form is particularly preferable because of its features such as a high volume change speed (responsiveness) to various external stimuli and a wide application range. There are no particular restrictions on the form of particles, but spheres, ellipsoids, cubes, polyhedra, porous bodies, stars, needles, hollows, and the like can be applied. Moreover, the preferable size in the case of particle | grains is the range of 0.1 micrometer-5 mm in an average particle diameter at the time of a shrinkage | contraction state, More preferably, it is the range of 1 micrometer-1 mm. When the particle diameter is 0.1 μm or less, problems such as difficulty in handling the particles and inability to obtain excellent optical properties occur. On the other hand, when the particle diameter is larger than 5 mm, there arises a problem that the response time required for volume change is significantly delayed.
[0047]
In addition, these particles are obtained by a method of pulverizing a polymer gel by a physical pulverization method, a method of pulverizing a polymer gel before crosslinking into particles by a chemical pulverization method, and then crosslinking to form a polymer gel, or an emulsion weight. It can be produced by a general method of particle polymerization such as a combination method, a suspension polymerization method and a dispersion polymerization method.
[0048]
Further, in order to increase the volume change rate due to various stimulus responses of the polymer gel, it is also preferable to make the material porous so as to improve the ease of entering and exiting the liquid as in the known method of the polymer gel. In general, the swollen polymer gel can be made porous by freeze-drying or the like.
[0049]
The volume of the light modulation material used in the present invention can be changed variously by applying the stimulation as described above in the presence of a liquid that can be absorbed by the polymer gel constituting the light modulation material. For example, in the case of a thermoresponsive polymer gel, photoresponse is caused by application of radiant heat such as light or heat, and in the case of an electroresponsive polymer gel, pH change due to an electrode reaction, ion adsorption by an electric field, or electrostatic action. In the case of a conductive polymer gel, the volume can be greatly changed by absorbing and releasing the liquid by changing the internal structure due to the application of light.
[0050]
The liquid that can be used at this time is not particularly limited, but preferably water, aqueous electrolyte solution, alcohols, ketones, esters, ethers, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, propylene carbonate, and the like. Alternatively, aromatic solvents such as xylene and toluene and mixtures thereof can be used. In addition, liquids include surfactants that absorb and desorb into polymer gels, redox agents such as viologen derivatives to promote pH changes in liquids, dispersion stabilizers such as acids, alkalis, salts, and surfactants, oxidation You may add stabilizers, such as an inhibitor and a ultraviolet absorber.
[0051]
From the above characteristics, the polymer gel used in the present invention is used as a composition with a liquid. At this time, the usable liquid is preferably a liquid that can be absorbed by the polymer gel. Further, when the polymer constituting the polymer gel is not cross-linked, a liquid in which the polymer can be dissolved is also preferably applicable. In addition, it is 1: 2000 to 1: 1 (polymer gel: liquid) by the preferable mixing ratio of the polymer gel as a composition, and a liquid.
[0052]
In addition, the structure of the light control layer is shown in FIG. 6 except that the light modulation material is interposed between the two transparent plates using a transparent plate as shown in FIGS. 1 to 5 or a transparent plate having an ultraviolet ray / heat ray shielding layer. Such a configuration may be used. In this case, the light modulation material is sandwiched and enclosed in a transparent film such as polyethylene, polypropylene, polyester, and nylon, and the light control layer itself forms the light control sheet 9. In this case, the outer peripheral portion can be sealed by heat-sealing a 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, but it is preferable to use a spacer 12 around the light control layer in order to maintain the gap of the light control layer. In addition, when the light modulation 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. A spacer 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 a sphere, a cube, a columnar shape or the like is mainly preferable.
[0053]
Further, in order to maintain the dispersion state of the polymer gel contained in the light modulation material inside the light control layer, the inside of the light control layer may be segmented using a mesh-like 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 polygon such as a lattice shape or a honeycomb shape is mainly used.
These spacers are not particularly limited as long as they are stable to the liquid constituting the light modulation material, and for example, resin, metal, metal oxide, glass and the like can be applied.
Moreover, you may fix a polymer gel as another method for maintaining the dispersion state of the polymer gel contained in the light modulation material inside a light control layer. As an object to be fixed, a transparent plate that sandwiches the polymer gel, the above-described transparent film, or the like may be used. Further, after the polymer gel is fixed to the support, it may be sandwiched between transparent plates.
[0054]
Examples of the method for immobilizing the polymer gel contained in the light modulation material used in the present invention on the transparent plate and the support include mechanical immobilization, physical immobilization such as adhesion, and chemical immobilization such as chemical bonding. Applicable. Various chemical bonds such as an ionic bond, a hydrogen bond, and a covalent bond are conceivable. Among these, a covalent bond is most preferable from the viewpoint of stability.
[0055]
The mechanical immobilization is mainly due to holding in a space such as a mesh when a fibrous support is used. In this case, it is preferable that the fibrous support is not a simple fiber assembly but a structure such as a woven fabric, a nonwoven fabric, a web, or a sheet. In this case, in order to enhance the retention effect of the polymer gel, the structure in this case is formed of relatively thin fibers of about 1 to 50 μm with a basis weight of 10 g / m. ² It is better to configure with the above relatively high density.
[0056]
Next, adhesives used for physical immobilization include organic solvent volatilization type adhesives (chloroprene rubber type, urethane type, etc.), thermosetting reaction type adhesives (epoxy type, resole type, etc.), moisture curing reaction type. Adhesives (2-cyanoacrylates, silicones, etc.), UV curing reaction adhesives (acrylic oligomers, etc.), condensation reaction adhesives (urea resin), addition reaction adhesives (epoxy, isocyanate) And the like, and hot melt adhesives.
[0057]
In the present invention, a hot-melt adhesive is particularly preferable among these, for example, 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 copolymer And its maleates), polyester resins, polyamide resins, polycaprolactone resins, polystyrene resins, and derivatives thereof (polystyrene, sulfonated polystyrene, styrene-maleic anhydride copolymers, etc.), thermoplastic Urethane resins, high molecular weight polyethylene glycols, vinyl acetate resin, waxes (paraffin wax, beeswax, beef tallow, etc.), and the like long-chain fatty acid ester resin and mixtures of two or more of these.
[0058]
In the present invention, the amount 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. If the amount of the adhesive resin exceeds 50 parts by weight, the adhesion to the transparent plate or the support will be improved, but the contact ratio of the polymer gel with the adhesive resin will increase, and the swelling / contraction behavior may be hindered. Becomes higher. On the other hand, if it is less than 0.1 part by weight, the fixing to the transparent plate or the support is insufficient.
[0059]
For immobilization of the polymer gel using the adhesive resin, for example, a method of applying a heat treatment and adhering a mixture of the polymer gel and the particulate adhesive resin to the adherend surface can be applied. 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 nauter mixer, a V-type blender, a turbulizer, and a screw type line blender.
[0060]
In addition, after preparing the adhesive solution which melt | dissolved adhesive resin in the solvent and apply | coating this adhesive solution to a to-be-adhered surface, you may spray a polymer gel and may heat-process. 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 should be relatively low, and is suitably 150 ° C. or less, preferably 100 ° C. or less. , Ketones such as acetone, alcohols such as ethanol and methanol, carboxylic acid esters such as ethyl acetate, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride, ethers such as diethyl ether , Hydrocarbons such as hexane and cyclohexane, and mixtures thereof. Examples of the method for applying the adhesive solution to the adherend surface include application, spraying, and immersion.
In addition, the heat treatment for bonding is not particularly limited, but a contact air heater such as a hot air heater, an infrared heater, a high-frequency heater and a heat roller can be applied, and the heating temperature follows the melting temperature of the adhesive. It is appropriately set between about 50 ° C and 200 ° C.
[0061]
In addition, various chemical bonds in the chemical immobilization of the polymer gel contained in the light modulation material in the present invention can be considered, such as an ionic bond, a hydrogen bond, and a covalent bond. Among them, the covalent bond is most preferable from the viewpoint of stability. The reaction is carried out using various fixing agents. Application of the polymer gel and the fixing agent to the adherend surface can be performed by a method such as coating, spraying or impregnation. In the case of coating and impregnation, a solution in which a polymer gel and a fixing agent are dispersed and mixed in various solvents compatible with the fixing agent or a mixture thereof is used. The solvent is selected according to the fixing agent, ketones such as acetone, alcohols such as ethanol and methanol, carboxylic acid 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 applied. After the polymer gel and the immobilizing agent are applied to the surface to be adhered, a method such as heating to the reaction temperature inherent to the immobilizing agent to form a chemical bond and immobilizing the polymer gel on the backing surface Is applicable. In addition, a stepwise reaction in which the surface to be bonded is treated with a fixing agent and then the polymer gel is immobilized on the formed reactive group can be applied.
[0062]
Examples of the fixing agent in the polymer gel used in the present invention include compounds 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, Di (meth) acrylic acid carbamic acid esters obtained by reacting polyisocyanates such as diisocyanate and hexamethylene diisocyanate with hydroxyethyl (meth) acrylate, allylated starch, allylated cellulose, diallyl Examples thereof include polyvalent allylic compounds such as tarate, other tetraallyloxyethanes, pentane erythritol 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. Etc. are preferably used.
[0063]
Examples of the compound having two or more reactive functional groups include diglycidyl ether compounds, haloepoxy compounds, 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. . Other specific examples of the haloepoxy compound include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Specific examples of the diisocyanate compound include 2,4-tolylene diisocyanate and hexamethylene diisocyanate. Among these, ethylene glycol diglycidyl ether, hexamethylene diisocyanate and the like are particularly preferably used in the present invention.
[0064]
The amount of the polymer gel as described above is usually 0.001 to 10% by weight, preferably 0.001 to 5% by weight, based on the dry weight of the polymer gel. This is because when the amount of the immobilizing agent used is 0.001% by weight or less, the polymer gel cannot be sufficiently immobilized. On the other hand, when the amount is 10% by weight or more, the immobilization of the polymer gel is too strong and the volume change occurs. It is for inhibiting.
[0065]
In addition, as a support body used for this invention, a fibrous thing is mainly preferable, for example, as a synthetic fiber, a nylon fiber, an acrylic fiber, a polyester fiber, a polypropylene fiber, a polyvinyl chloride fiber, a polyamide fiber Natural fibers such as wood pulp, cotton, and wool, semi-synthetic fibers such as viscose rayon, acetate, and cupra, and inorganic fibers such as carbon fibers and titanium fibers can be applied. Examples of the form of the fibrous support include simple fiber aggregates and structures 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 about 10 μm to 0.5 mm, 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 2 mm. 200 g / m 2, preferably about 2 to 100 g / m 2 is appropriate.
[0066]
The sealing material 4 has an ability to suppress evaporation or volatilization of the solvent from the light modulation material 3, has adhesiveness to the transparent plate 2, does not adversely affect the characteristics of the light modulation material 3, and is actually used. Any material may be used as long as these conditions are satisfied for a long time. It is also possible to combine a plurality of sealing materials.
The sealing material 4 and the sealing method are preferably single-layer sealing in view of securing the opening area of the light control glass 1 and processing costs due to process simplification. Examples of the sealing material 4 when sealing with one layer include use of a thermosetting elastic sealing material mainly composed of an isobutylene oligomer having a reactive group at the terminal. When sealing with two layers, polyisobutylene-based sealant or the like can be exemplified as the primary sealing that contacts the light modulation material 3, and acrylic resin or the like can be exemplified as the secondary sealing. The sealing material 4 and the sealing method of this invention are not limited to the said illustration, A wide variety can be selected and you may use combining them.
[0067]
In the present invention, heat generating means and electrical means are preferably used as the stimulus applying means. In addition, when making it function as a light control glass of an autonomous response type, it is set as the structure which does not comprise especially a heat-emitting means, receives the heat from the sun, and responds. As other artificial heat generating 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 heat generating resistor such as carbon is preferably used. In the case of electrical means, electrodes made of metal films typified by copper, aluminum, silver, platinum, etc., metal oxides typified by tin oxide-indium oxide (ITO), polypyrroles, polythiophenes, polyaniline In particular, an electrode made of a conductive polymer such as polyphenylene vinylenes, polyacenes and polyacetylenes, and an electrode made of a composite material of the polymer and the aforementioned metal or metal oxide particles 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 unit.
[0068]
When an autonomous response type using heat energy from the sun or a heat generating means is provided, the above-mentioned thermoresponsive polymer gel is preferably used. In addition, when an electrical means is provided, there are a polymer gel that responds by the pH change, a polymer gel that responds by adsorption / desorption of a chemical substance such as a surfactant, and a polymer gel that responds by oxidation / reduction. It is preferably used as a constituent material of a light dimming material. Furthermore, in the case of a configuration in which light is irradiated from the outside, the above-mentioned photoresponsive polymer gel is preferably used.
[0069]
In addition, in this invention, the preferable thickness of each member which comprises the light control glass 1 is as follows. First, the transparent plate 2 is preferably at least 3 mm or more in the case of a glass having improved fracture strength, and is preferably 6 mm or more in the case of a tempered glass. In this case, the upper limit of the thickness is not particularly set, but if it is too thick, it is uneconomical, and about 50 mm may be used as a guide. Further, even in the case of a substrate whose break strength is not improved on both sides, at least 1 mm is necessary considering that it is mainly used for various windows.
[0070]
Next, the thickness of the ultraviolet ray shielding layer 5 and the heat ray shielding layer 8 depends on the type of the layer formed, but it is necessary to be 0.1 μm or more in order to obtain a sufficient shielding effect even in the thinnest case such as vacuum deposition. It is. On the other hand, there is no particular upper limit, but even when forming a liquid ultraviolet cut layer or a heat ray shielding vacuum layer, 50 mm is sufficient.
The thickness of the light control layer is required 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 it is too thick, a problem arises that the time required to exhibit the dimming function becomes too long.
[0071]
【Example】
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 having a dimming function with a 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 stirred to prepare an aqueous solution.
The above aqueous solution was put into a flask and oxygen was removed by nitrogen substitution. Then, 1.0 g of ammonium persulfate as a polymerization initiator was added, followed by heating to 60 ° C. and polymerization for 10 hours.
After completion of the polymerization, the sample was coarsely pulverized and purified by washing with a large amount of distilled water, and further dried to obtain an acrylamide gel containing a light scattering member.
[0072]
Next, 20 g of coarse particles of this acrylamide gel are put in a flask, 10 g of acrylic acid, 0.26 g of N, N′-methylenebisacrylamide and 50 g of distilled water as a cross-linking agent, and water to partially neutralize acrylic acid. Sodium oxide 0.03g (5 mol% of acrylic acid) was added. After nitrogen substitution, 0.04 g of ammonium persulfate was added thereto. This state was left for 1 hour, and the acrylamide gel was sufficiently impregnated and swollen with an acrylic acid aqueous solution, followed by heating to 60 ° C. and polymerization for 10 hours to prepare an IPN polymer gel.
After the polymerization, the produced IPN polymer gel mass was pulverized with a homogenizer, poured into a large amount of distilled water, and purified by repeating the operation of filtering it. Thereafter, it was dehydrated using a large amount of methanol and dried. The particle diameter of the obtained particles when dried was about 70 μm. The polymer gel used for the light control material of this invention which has a light control function by a temperature change was manufactured by the above preparation operation.
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, it was found that when this was heated to 30 ° C., it further swelled and exhibited a water absorption of about 160 g / g. Moreover, 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 low temperature. This change was reversible, and the particle size was about 3.4 times that of swelling / shrinkage, that is, a change of about 40 times in volume was obtained.
[0073]
The light control function of this polymer gel was evaluated as follows. An aqueous dispersion containing these particles at a constant concentration (0.20 g / l) was prepared, and this was placed in a spectrophotometer cell having an optical path length of 1 cm, and transmitted at 10 ° C. (when contracted) and 50 ° C. (when swollen). As a result of measuring the transmittance, it was found that the transmittance was 90% and the transmittance was 5%, respectively, and the transmittance changed greatly. Since both concentrations of the light scattering member are constant, it is considered that the light scattering member diffuses and aggregates due to the volume change of the polymer gel, and the light scattering efficiency changes to change the transmittance. Moreover, the transmittance change due to temperature change was reversible, and it did not deteriorate even after repeated 100 times. It was also confirmed that the transmittance change can be performed in stages.
[0075]
<Weather resistance test>
Using a sunshine weather meter (WEL-SUN-HC type) manufactured by Suga Test Instruments Co., Ltd. for 100 hours under the condition of a black panel temperature of 63 ° C, and comparing deterioration of dimming characteristics due to change in transmittance depending on time did.
<Measurement of fracture strength>
The fracture strength was compared by measuring the average breaking load. The average breaking load was calculated by the product of breaking wind pressure and glass area.
[0076]
Example 1
An ultraviolet shielding film was produced as follows. First, 100 parts by weight of commercially available cerium acetylacetonate (III), 19.5 parts by weight of pentaethoxyniobium, 89.5 parts by weight of diethanolamine, and 890.0 parts by weight of n-butyl alcohol are mixed, and then pentaethoxy is mixed therewith. 23.3 parts by weight of niobium were added.
This mixed solution was put into 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. Thereafter, it was dried at 120 ° C. for 10 minutes with a dryer, and further baked in air at 500 ° C. for 20 minutes to obtain an ultraviolet shielding film 5. In addition, when the film thickness obtained by one film formation was thin, film formation was repeated several times to set the film thickness to about 100 nm.
[0077]
Next, as shown in FIG. 1, another glass substrate having a thickness of 2 mm is opposed to a glass substrate having a thickness of 2 mm having the ultraviolet shielding film 5 so that the ultraviolet shielding film 5 is located on the inside. It was arranged in parallel with an interval of about 0.5 mm through the epoxy adhesive for use and a spacer. And in the sealed space formed between the two glass substrates ,in front A light modulation material comprising a 1.13 g / l concentration aqueous solution of a heat-sensitive polymer gel containing the light scattering member described above Charge By sealing, it has an ultraviolet shielding film 5 Key Optical glass was produced. In addition, soda-lime glass (Float plate glass by Central Glass Co., Ltd.) was used for the glass substrate. This Key Light glass Is high The visible light transmittance in the swollen state of the molecular gel was approximately 40%, and the visible light transmittance in the contracted state of the polymer gel was approximately 90%.
Has this ultraviolet shielding film 5 Key As a result of conducting the above-mentioned weather resistance test for optical glass, this Temporal change in transmittance of light control glass Result of The results are shown in FIG. In FIG. 8, for the purpose of comparison, the test results of the same light control glass except that there is no ultraviolet shielding film are also shown. As can be seen from the test results, it was found that the light control glass of the present invention provided with the ultraviolet light shielding film can obtain a light control function much more stably than when the ultraviolet light shielding film is not provided.
[0078]
(Example 2)
In order to improve the wind pressure strength, 6 mm thick tempered glass was used on one of the two glass substrates, and 3 mm thick float glass was used on the other. These two glass substrates were made to face each other and arranged in parallel with a gap of about 0.5 mm through an epoxy adhesive for sealing and a spacer. In the sealed space formed between the two glass substrates, the same as in Example 1. Light of The light control glass which has tempered glass was produced by enclosing using a modulation material.
With this tempered glass Key The result of the fracture strength measurement test described above was performed on optical glass. Table Shown in 1. For comparison, the test results of the light control glass having exactly the same configuration except that float glass having the same thickness was used instead of tempered glass are also shown.
[0079]
[Table 1]

[0080]
As can be seen from this result, the light control glass using the tempered glass of the present invention has about 2.5 times the strength of the light control glass composed of ordinary float glass in addition to the light control function. I understood.
[0081]
(Example 3)
100 parts of a polycarbonate resin was dissolved in dichloromethane, and 0.1 part by weight of 3,6-octafluoro- (4,5-octakisanilino) oxyvanadium phthalocyanine was uniformly dispersed as an infrared absorber. The resin solution was applied on one glass substrate and allowed to stand until the solvent was volatilized to obtain a glass substrate having a heat ray shielding layer having a thickness of 0.13 mm.
Next, float glass with a thickness of 2 mm is used for the other glass substrate, these two glass substrates are opposed to each other, and a distance of about 0.5 mm is maintained through an epoxy adhesive for sealing and a spacer. Arranged in parallel. In the sealed space formed between the two glass substrates, the same as in Example 1. Light of The light control glass which has a heat ray shielding function was produced by enclosing using a modulation material.
Next, this Key Box with light glass attached to one side For The light control glass was irradiated with heat rays from an external 400 W infrared lamp. Key The result of heat shielding of light glass In FIG. Indicated. FIG. 9 shows the result of measuring the temperature change depending on the internal time at this time. For comparison, the measurement results of the light control glass having the same configuration except that it does not have a heat ray shielding function are also shown.
As can be seen from this result, it was confirmed that the temperature rise inside the dimmable glass having a heat ray shielding function was reduced. Therefore, it was confirmed that the light control glass of this invention also has a heat ray shielding effect in addition to the light control function by a temperature rise.
[0082]
【The invention's effect】
The light modulation material used in the light control glass of the present invention is Light Using volume change of stimuli-responsive polymer gel particles containing scattering members, Light The state is stable, the contrast is high, and the stimulus response is fast. And if the light control glass of this invention is provided with the ultraviolet-ray shielding function as a protective function, the fall of the stimulus response function of the light modulation material by ultraviolet irradiation can be reduced, and it will receive long-term ultraviolet exposure The dimming function is stable even when used in such an environment. In addition, when a glass plate glass, a wire glass plate, a tempered glass, a laminated glass, a double-strength glass, etc. are used for the light control glass of the present invention, it can be obtained simply by sandwiching and enclosing the material using ordinary glass or float glass. Wind pressure strength, impact resistance, fireproof performance, safety at breakage, and the like. Moreover, when a heat ray reflective layer, a heat ray low radiation layer, or a vacuum layer is used for the light control glass of this invention, the penetration | invasion of the heat to an inside can be reduced. As a result, when it is used for window glass installed in a space where people are active inside offices and the like, it can contribute to the reduction of environmental burdens such as prevention of global warming, such as the improvement of indoor air conditioning efficiency, especially in summer. .
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram showing an embodiment of a 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. Light control glass, 2. 2. Transparent plate, 3. light modulation material; 4. sealing material; 5. UV shielding layer, 6. protective layer; Strength and safety improvement glass, 8. 8. heat ray reflective layer (heat ray shielding layer), Light control sheet 10,12. Spacer

Claims (5)

At least a polymer gel particle whose volume changes in response to an external stimulus and a liquid used for volume change of the polymer gel particle, and the polymer gel particle is a light scattering member having a saturation scattering concentration or more in a contracted state A light-modulating material that reversibly swells and shrinks due to absorption and release of the liquid , and is interposed between two transparent plates, and an external factor that impairs the function of the light control glass on at least one of the transparent plates A light control glass having a protective function for protecting the light control glass from the above.   The light control glass according to claim 1, wherein an ultraviolet shielding function is imparted to at least one of the transparent plates.   2. The light control glass according to claim 1, wherein at least one of the transparent plates is a plate glass with a mesh, a plate glass with a wire, a tempered glass, a laminated glass, or a double strength glass.   2. The light control glass according to claim 1, wherein any one of a heat ray reflective layer, a heat ray low radiation layer, and a vacuum layer is used for at least one of the transparent plates. The light control glass according to any one of claims 1 to 4 , wherein the polymer gel particles change in volume due to a temperature change to change a light transmission amount.

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