JPH11265005A - Laminated body and window using the body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated body produced by laminating an aq. soln. which reversibly changes with temp. changes and has a uniform white and light-scattering state when the soln. is heated between substrates. SOLUTION: This laminated body is produced by laminating an aq. soln. 2 described below between substrates 1 which are at least partly transparent and through which the aq. soln. 2 can be directly observed. Relating to the soln. 2, molecules dissolved in water aggregate to cause a white and scattering state with temp. increase, which decreases the transmittance of the soln. The aq. soln. 2 is prepared by dissolving 0.5 to 45 pts.wt. of an amphiphilic substance which causes clouding phenomenon and which is in an oily state at a room temp. and can be uniformly dissolved in water at the room temp. in 100 pts.wt. of a soln. prepared by dissolving 0.5 to 20 pts.wt. of an ionic water-soluble polymer in 100 pts.wt. of water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the fact that when a laminate is irradiated with sunlight, the aqueous solution changes to white turbidity due to the thermal action due to the absorption of light, thereby scattering and blocking light. This enables a building, a vehicle, and the like having windows that selectively block and anti-glare only the surface irradiated with direct light. Also, by combining with a heat element, it can be used as a partition with an electronic curtain, an indoor window such as a door, and the like.

[0002]

2. Description of the Related Art In recent years, under the concept of coexistence with the environment, there has been a demand for comfortable and energy-saving windows that make effective use of sunlight. Although heat ray reflective glass, heat ray absorbing glass and the like have been put into practical use for windows, they cut off natural light in winter, cloudy weather, rainy weather, etc., greatly impairing the comfort of having an open feeling, and there is a problem in daylight use. Therefore, a light control glass capable of reversibly changing and blocking light has been required.

[0003] Therefore, the present inventor has noticed that solar energy is irradiating windows. We examined whether the window glass could autonomously respond and change the transparency-light scattering reversibly depending on the presence or absence of this energy to create a comfortable living space.
We focused on this autonomous response characteristic because it is very attractive not only from the feature of shielding light only on the irradiation surface and the energy saving effect, but also from construction, maintenance and maintenance costs. From this point,
Photochromic method, thermochromic method, and thermotropic method can be selected, but thermochromic that depends only on thermal action that can easily adjust temperature as needed artificially, compared to photochromic method with complicated mechanism and wavelength dependence , Thermotropic method is excellent. The solar energy that reaches the earth is 290 nm
It should be noted that the visible to near infrared region from 400 nm to 1100 nm occupies about 80%, and the visible region is larger than the near infrared region. This indicates that controlling the visible region is important not only for the blindfold effect, but also for energy saving and anti-glare effects. The present invention utilizes the fact that the temperature of an object increases due to solar energy. Naturally, the temperature can be reversibly changed by artificially controlling the temperature by adding a heat element.

[0004] Materials used in thermochromic and thermotropic systems have insufficient properties and have not yet been put to practical use. Therefore, in order to be widely used as thermochromic glass and thermotropic glass, the following conditions must be satisfied. 1. The transparent-opaque phase change is reversible. 2. Reversible changes can be repeated without phase separation. 3. Low phase transition onset temperature. 4. Be durable. 5. No pollution such as toxicity. As an autonomous response material that may satisfy these conditions, the present inventors have paid attention to an aqueous solution that undergoes a phase transition from colorless and transparent to a cloudy light scattering state due to an increase in the temperature of the aqueous solution.

Heretofore, the cloud point phenomenon of nonionic surfactants has been well known as an aqueous solution that becomes a cloudy light scattering state due to a rise in temperature, and its application to this purpose has been studied. No phase separation was easily caused by temperature rise due to heating, and the above conditions 1 and 2 could not be satisfied. In addition, a polymer aqueous solution of a certain nonionic water-soluble polymer (for example, hydroxypropylcellulose, poly-N-isopropyl-acrylamide, polyvinyl methyl ether, etc.) is aggregated by heating, gels, and exhibits cloudy light scattering. Therefore, the application to this purpose (J.
Japanese Patent Application No. 51-049856 and Japanese Patent Publication No. 61-7948 are also being studied, but they cannot satisfy the above conditions 1 and 2 and have not been put to practical use. Further, as an application of the hydrogel, there has been an attempt to utilize the white turbidity change of a hydrogel composed of a special reaction mixture composed of at least five components as disclosed in JP-A-63-500042. It cannot be satisfied and has not been put to practical use.
Also, for example, N-isopropyl-acrylamide is
A crosslinked hydrogel such as poly-N, N'-methylenebisacrylamide gel obtained by aqueous polymerization in the presence of a water-soluble radical polymerization initiator using a small amount of N, N'-methylenebisacrylamide as a crosslinking agent has also been studied. However, the above conditions 1 and 2 cannot be satisfied, and the device has not been put to practical use. Therefore, the present inventor has studied a new method and, based on the composition described in Japanese Patent Application No. 5-62502, utilizes the principle of the sol-gel phase transition, and agglomerates and scatters white turbid light. The inventors have found that the polymer can be uniformly and reversibly changed without phase separation, and have invented a useful laminate. Therefore, the present inventor further studied the use of an oily amphiphilic substance having a cloud point phenomenon, which has been left to date, in order to easily cause a phase separation between an aqueous layer and an oil layer in a high temperature range. As a result, they have found an aqueous solution that changes reversibly with uniformity due to the sol-emulsion phase transition, and have reached the present invention.

[0006]

An aqueous solution of an amphiphilic substance which is oily at room temperature and has a cloud point phenomenon and is uniformly dissolved in water at room temperature does not phase-separate into an aqueous layer and an oil layer due to an increase in temperature.
It is an object of the present invention to find an aqueous solution composition in which the sol-emulsion phase transition is stably and reversibly changed depending on the temperature, and to obtain a laminate having an aqueous solution in which a transparent state and a cloudy light-shielding state are reversibly changed, and a window using the same.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the molecules dissolved in water aggregate due to an increase in temperature to cause cloudy scattering,
In a laminate in which at least a part of an aqueous solution whose light transmittance is small is transparent and the aqueous solution is laminated on a substrate that can be directly viewed, the aqueous solution is 100 parts by weight of water and 0.5 part by weight of an ionic water-soluble polymer. 1 to 20 parts by weight of the solution 1
A laminate which is an aqueous solution having 0.5 to 45 parts by weight of an amphiphilic substance which is uniformly dissolved in water at room temperature, which is oily at room temperature and has a cloud point phenomenon of 00 parts by weight. Molecules dissolved in agglomeration cause cloudy scattering,
In a window using a laminate in which an aqueous solution having a low light transmittance is at least partially transparent and the aqueous solution is laminated on a substrate that can be directly viewed, the laminate has a high ionic water-soluble property in 100 parts by weight of water. 0.5 parts by weight of an amphiphilic substance having a cloud point phenomenon and being oily at room temperature and uniformly dissolved in water at room temperature having a cloud point phenomenon in 100 parts by weight of a solution in which 0.5 to 20 parts by weight of a molecule is dissolved.
An object of the present invention is to provide a window which is a laminate which is an aqueous solution obtained by dissolving 45 parts by weight.

BEST MODE FOR CARRYING OUT THE INVENTION

The basis of the present invention is to utilize a cloud point phenomenon in which an aqueous solution in which an amphipathic substance is uniformly dissolved, the amphipathic substance is aggregated by heating and becomes a cloudy light scattering state. The aqueous solution of the amphiphilic substance causing the cloud point phenomenon easily separated into an oil layer and an aqueous layer upon heating, and did not obtain a uniform reversible change. Therefore, the present inventors have intensively studied an aqueous solution capable of stably and uniformly reversibly changing a transparent state and a cloudy state by a temperature change. As a result, it was surprisingly found that, when an aqueous solution of an ionic water-soluble polymer, water and an amphiphile was used as the three components, the reversible change was performed stably with uniformity. This seems to be due to the fact that the microaggregates of the amphipathic substance that aggregated due to the heating were trapped by the chains of the ionic water-soluble polymer and were maintained in a uniformly microdispersed state. Therefore, it is considered that the fine aggregates further aggregated to grow into large aggregates, thereby preventing the water layer and the oil layer from being separated. As a result, cloudy light scattering was exhibited due to the difference in the refractive index between the microaggregate of the amphiphilic substance and the medium. This can be said as follows. In the aqueous solution of the present invention, in a low temperature range, the amphipathic substance uniformly dissolves in water to take a sol state of a transparent solution, and in a high temperature range, the amphipathic substance aggregates to form an emulsion state of a white emulsion. Was. This emulsion state was stabilized by the emulsifying action of the ionic water-soluble polymer. As a result, this reversible change, which can be called a sol-emulsion phase transition, has been made possible. in this way,
The present invention is a laminate having an aqueous solution based on a ternary composition of an ionic water-soluble polymer, an amphipathic substance causing a cloud point phenomenon, and pure water.

The ionic water-soluble polymer useful in the present invention is described below. The ionic water-soluble polymer can form a highly viscous aqueous solution at a low concentration depending on the molecular weight. Specifically, sodium carboxymethylcellulose (for example, CMC Daicel of Daicel Chemical Industries, Ltd.) as an example of a cellulose derivative, and sodium polyacrylate (Aqualic-I of Nippon Shokubai Co., Ltd.) as an example of a vinyl polymer.
H, Aqualic DL-522, etc.), sodium polystyrene sulfonate, etc., and examples of vinyl monomer copolymers having an anionic group and a nonionic group include A118 and A161 from Aronfloc, and a cationic group and a nonionic group are used. Examples of vinyl monomer copolymers having C-303, C-302, C-508 and C-
And Kuraray's Isovan-110 ionized copolymer of isobutylene and maleic anhydride. As a modified polyvinyl alcohol, a carboxyl group is converted to a hydroxyl group of a polyvinyl alcohol through a methylene group through a methylene group to about 12 per hydroxyl group. KE of Daiichi Kogyo Pharmaceutical Co., Ltd.
Goselan L3266, L0301, F7 of Nippon Synthetic Chemical Industry Co., Ltd. containing sulfate groups, such as C-polymer of Kuraray having a cationic quaternary ammonium salt such as PS-1224A.
8 and the like are also useful. As described above, any ionic water-soluble polymer can be used in the present invention without particular limitation. The turbidity onset temperature of the laminate of the present invention also changed depending on the structure, molecular weight, and concentration of the polymer. Naturally, the higher the molecular weight, the higher the viscosity, so even at lower concentrations,
The emulsion state could be kept uniform. Therefore, if the molecular weight is high, there is no need to particularly limit the molecular weight. However, when the molecular weight was low, the emulsifying action due to the polymer effect was weak, and when the concentration was increased, it was difficult to obtain a transparent state. Although the molecular weight depends on the structure of the polymer, the weight average molecular weight may be 20,000 or more, preferably 50,000 or more. It only has to be dissolved in water, and about several million are usually available. The concentration may be about 0.5 part to about 20 parts by weight, preferably about 1.5 parts by weight to about 15 parts by weight, more preferably about 2 parts by weight to 100 parts by weight of water.
It may be about 10 parts by weight. Also, as the concentration increased, the cloudiness onset temperature shifted to a lower direction. The higher the density of the ionic functional group in the water-soluble polymer, the more steep the change rate from the cloudiness onset temperature to the cloudiness saturation temperature, and the larger the cloudiness light-shielding property.

The present inventors have focused on sodium carboxymethylcellulose as an ionic water-soluble polymer having weather resistance and being uniformly dissolved in water. For example, CMC Daicel 1170, 1220, 1260, 1
290, 1330, 1380, 2260, etc., which can be widely used without any particular limitation on molecular weight and degree of etherification. Furthermore, the fact that the pH of these aqueous solutions is near neutrality is also important from the viewpoint of durability. If the pH deviates from the vicinity of neutrality, it promotes the depolymerization of the cellulose skeleton and the decomposition of the amphipathic substance, thereby significantly reducing the durability. As described above, an ionic water-soluble polymer that is uniformly dissolved in water and has weather resistance in an aqueous solution state is particularly useful.

Next, amphiphilic substances useful in the present invention include:
It is a compound that has a cloud point phenomenon and is oily at room temperature and is uniformly dissolved in water at room temperature. This amphiphile is widely known,
For example, a polymer of propylene oxide (for example, Newpole PP series of Sanyo Chemical Industry Co., Ltd.), a copolymer of propylene oxide and ethylene oxide of low molecular weight (for example, Epan 420, 720 of Daiichi Kogyo Seiyaku Co., Ltd.)
Etc.), poly (oxyethylene oxypropylene) glycol monoether (for example, New Paul 50HB series of Sanyo Chemical Industries, which is a butyl alcohol derivative), and derivatives containing an oxypropylene group or an oxyethylene oxypropylene group. Triols (for example, Sanyo Kasei Kogyo's Newpole / GP series, T
P-series, GL-series, GEP-series, TL-series, etc., and a compound obtained by adding polyoxyethylene to a higher alkylphenol (for example, Lion-based nonylphenol-based Liponox NC-86).
Etc.) and compounds in which polypropylene oxide and polyethylene oxide are added to a higher alkyl group (e.g., an alkyl group having 12 or 13 carbon atoms) (e.g., Lion Co., Ltd., Leocol SC-70, Leocol SC-80). Further, modified dimethylpolysiloxanes to which oxyethylene and oxypropylene are added (for example, KF6008, KF6012, and KF615A manufactured by Shin-Etsu Chemical Co., Ltd., TSF4450, TSF4452, and TSF manufactured by Toshiba Silicone Co., Ltd.)
4440, Toray Dow Corning Silicone SH
3748, SH3749, SH8700, SF8410
And the like, were also very useful in the present invention. As already known, the cloudiness onset temperature could be adjusted by the ratio of oxyethylene to oxypropylene (for example, a ratio of 1: 1).

An amphiphilic substance having a cloud point phenomenon and being oily at room temperature and homogeneously dissolved in water at room temperature can be defined as follows. Oil at room temperature refers to a temperature near room temperature, more specifically 25
Liquid at 100C. In addition, the uniform dissolution in water at room temperature means that when the required amount is added to water at a temperature lower than the temperature at which the cloud point phenomenon occurs, the amphipathic substance is uniformly dissolved in a transparent state or almost transparent state without phase separation. is there. More specifically, it is to uniformly dissolve a 2% by weight aqueous solution in a transparent state or almost transparent state without phase separation at a temperature below the cloud point phenomenon. For example, in the case of a polymer of propylene oxide (for example, Newpole PP series of Sanyo Chemical Industry Co., Ltd.), if the molecular weight is too small, self-aggregation does not occur, so that it does not show turbid light scattering. No transparent state is shown. Thus, the weight average molecular weight is preferably from about 400 to less than about 1,000. On the other hand, a low molecular weight copolymer consisting of propylene oxide and ethylene oxide alone does not dissolve even in a low temperature region when the content of ethylene oxide is as low as about 10% and does not show a transparent state. However, since self-aggregation does not occur, it does not show cloudy light scattering. Therefore, an ethylene oxide content of about 15% to 30% was preferred.

The amount of the amphiphilic substance depends on the solubility in water. Generally, the smaller the amount of the amphiphilic substance, the lighter the opaque light is scattered, and the more the amount of the amphiphilic substance increases, the more the turbidity becomes cloudy. However, if the amount is too large, the transparent state cannot be obtained even in a low temperature range, and the film becomes cloudy, which is not suitable for the present invention. However, amphipathic substances that are sufficiently soluble in water at room temperature, such as the triol Newpole / GP600 from Sanyo Chemical Industries, may be added in large amounts. As described above, the addition amount of the amphiphilic substance may be 0.5 to 45 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the aqueous solution of the ionic water-soluble polymer. Good. The molecular weight of this amphiphile depends on the molecular structure, but the weight average molecular weight is about 240 to
About 20,000 is preferred. The hydrocarbon-based amphiphile may have a weight average molecular weight of about 240 to about 10,000, and preferably has a weight average molecular weight of about 240 to about 8,000.
The weight average molecular weight is more preferably about 240 to about 5,000. It can be said that a molecular weight of 10,000 or more makes synthesis, purification and the like difficult and impractical. Also,
The polysiloxane type does not necessarily have to have a molecular weight of about 20,000 or less because of the high atomic weight of silicon, but it has a molecular weight of 20,000 for the same reason because a functional group is added to a side chain.
It can be said that it is difficult to manufacture a product having a size of 00 or more, which is not practical. In order to obtain the effect of the siloxane chain, the polysiloxane has a large molecular weight and a weight average molecular weight of about 1,
2,000 to about 20,000, preferably about 2,000 to about 18,000, more preferably about 3,000 to about 15,000.
Is good.

For example, the modified dimethylpolysiloxane is
When added and dissolved in an aqueous solution of sodium carboxymethylcellulose, the solution was completely transparent in a low temperature range, and suddenly changed to cloudy and was strongly shielded from light. The temperature difference from the start of cloudiness to almost saturation cloudiness was as steep as about 5 ° C. It should be noted that the degree of light shielding of cloudy light scattering could be adjusted by the amount of the modified dimethylpolysiloxane added. Further, the white turbidity onset temperature could be adjusted by changing the concentration of sodium carboxymethylcellulose, and the higher the concentration, the lower the onset temperature. Thus, by adjusting the density, the light-shielding characteristics and the starting temperature thereof could be varied. Further, with respect to the degree of etherification of carboxymethylcellulose sodium, when it was 0.7 or less, even in a transparent state at the bottom temperature range, the film was slightly hazy and had poor transparency, but there was a sufficient change in the cloudy light-shielding. Normally,
It was observed that the degree of etherification was good in the range of 0.8 to 1.5, and as the degree of etherification became larger than 1.0 or more, the steepness of the change in cloudiness became weaker. In addition, 1.5 or more
It can be said that the synthesis becomes very difficult and impractical. The molecular weight of sodium carboxymethylcellulose is 1% aqueous solution / 25 ° C.
From C Daicel 1220/10 cps to CMC Daicel 2
A wide range up to 260/6000 cps can be used, and the molecular weight is not particularly limited.

As the water, distilled water, purified water and the like may be used. Further, water obtained by distilling ion-exchanged water is preferable. The reason is that contact with heavy metal ions tends to promote oxidative deterioration. The pH of the aqueous solution is preferably around neutral 7, preferably from 6 to 8, and more preferably from 6.5 to 7.5. In addition, an appropriate amount of an antioxidant, a coloring agent, a preservative, an ultraviolet absorber or the like may be added as an additive. Further, it is preferable that the dissolved oxygen be degassed or replaced with an inert gas because oxidation deterioration can be prevented.

As a specific example of the laminate, sodium carboxymethylcellulose (CMC Daicel 1220 manufactured by Daicel Chemical Industries, Ltd .: weight average molecular weight / about 50,000) 2
100 parts by weight of a polymer solution in which 30 parts by weight of
6 parts by weight of poly (oxyethylene / oxypropylene) methylpolysiloxane (KF6012 from Shin-Etsu Chemical Co., Ltd.)
A colorless and transparent aqueous solution was prepared at 20 ° C by adding parts by weight. Next, this aqueous solution was provided in a thickness of 0.3 mm between 10 cm square float soda glasses having a thickness of 3 mm to form a laminate. This laminate had good reversible stability at room temperature and 60 ° C. and stability for standing at 60 ° C. for 12 hours without phase separation. In addition, the laminate started scattering white turbid light from about 24 ° C., reached saturation at about 29 ° C., and was strongly shielded from light.

Next, using a U-4000 type spectrophotometer manufactured by Hitachi, Ltd., which is suitable for the measurement of a large sample that scatters light, the center of the laminate is brought close to the window of the integrating sphere (about 1 m).
m) and the laminate was placed and measured. The measurement temperature was a room temperature of about 21 ° C. in the bottom temperature range and about 42 ° C. in the high temperature range. In consideration of the fact that the temperature of the laminate changes during the measurement, only the visible wavelength of 400 nm to 800 nm was measured at about 21 ° C. (transparent state) and about 42 ° C. (white turbid light scattering state). The results are shown in FIG. In addition, 300 nm to 400 nm
And the near-infrared region from 800 nm to 2,500 nm were also confirmed, but were sufficiently shielded as in the visible region.

Next, the structure of the laminate according to the present invention and the window using the same will be described. 1, 2, 3 and 4 are schematic cross-sectional views of one embodiment of the laminate of the present invention, wherein 1 is a substrate, 2 is an aqueous solution, 3 is sealing, and 4 is transparent without change. The liquid 5 is a hollow rod, and 6 is a double glass.

The laminate shown in FIG. 1 has the basic form of the laminate according to the present invention, and is formed by laminating an aqueous solution 2 between a substrate 1 which is at least partially transparent and allows the aqueous solution 2 to be directly viewed.
The layer thickness of the aqueous solution 2 is not particularly limited, but is not limited to 0.1.
The thickness may be from about 01 mm to about 2 mm, and sufficient light shielding can be achieved with a thickness of about 0.2 mm. The seal 3 is provided to prevent evaporation of water, and may be disposed between the substrates at the outer peripheral portion or may be disposed outside the substrate. Examples of the sealant include an epoxy resin adhesive (for example, Flep of Toraythio Coal), an acrylic resin adhesive (for example, a photo bond of Sunrise Meisey, which is a photosensitive resin), and a multi-layer glass. Isobutylene sealant, polysulfide sealant,
Urethane sealants, silicone sealants, and the like can be used. In particular, although not shown, it is preferable to seal the isobutylene-based sealant (inside) and a sealing agent (outside) having an adhesive property to the glass substrate in at least two stages between the substrates, and it is also possible to perform multistage sealing. Of course, if the isobutylene-based sealant and the aqueous solution 2 come into direct contact with each other, which is inconvenient, a barrier layer may be provided to avoid contact.

In order to reliably control the thickness, although not particularly shown, the aqueous solution 2 is not limited to the sealing portion but may be a spacer (for example, glass beads, ceramic beads, or the like).
Resin beads, metal beads, etc.). Especially 5
When the size became 0 cm square or more, the spacer was useful for maintaining the liquid layer thickness. Further, it is preferable to use a transparent substance having a refractive index close to the refractive index of the aqueous solution 2 because it becomes difficult to recognize the transparent substance. The sealing portion can be used for spacers such as metal wires, glass fibers, and thin plates.

The substrate is only required to be partially transparent and capable of directly viewing the aqueous solution 2. Various materials, for example, glass, plastic, ceramics, and metals can be used. A material, a material whose surface is processed, or the like can be used, and a combination thereof may be used. In addition, the glass plate as a window material is a simple single-pane glass, tempered glass, netted glass, heat-absorbing glass, heat-reflecting glass, heat-absorbing and reflecting glass, laminated glass, UV cut glass, transparent conductive glass, double-glazed glass, There is a composite glass of transparent veneer glass and polycarbonate, etc., which can be used as a pair of substrates according to the purpose by appropriately combining types, thicknesses and the like. In particular, as shown in FIG.
Compounding with a multi-layer glass having a gas layer results in a glass having both light-shielding properties and heat-insulating properties, which is very useful for energy saving and comfort.

When the present invention is applied to a window, it is strongly exposed to the direct rays of the sun for a very long period of time. Therefore, it is preferable to use an ultraviolet cut glass for at least the outer substrate. For example, ultraviolet absorbing glass (for example, green glass),
There is a glass coated with an ultraviolet absorbing layer, an ultraviolet absorbing laminated glass, and the like. When the thickness of the substrate outside the window is about 5 mm or more, the transmittance of ultraviolet rays of 330 nm or less rapidly decreases, which is preferable in terms of weather resistance. In the case of a window, a horizontal state and a vertical state are used. However, in the vertical state, care must be taken because unevenness due to convection due to a temperature difference may occur if the viscosity of the aqueous solution 2 is too low.

The laminate shown in FIG. 2 is a laminate obtained by combining a reversibly changing aqueous solution 2 and a non-changing transparent liquid 4 and disposing them between the same substrates. The transparent liquid 4 that does not change reversibly is a liquid or a gel whose transmittance of light does not particularly change even when heated. For example, the aqueous solution of the present invention to which no amphiphilic substance is added. As the molecular weight increases, self-diffusion becomes negligible, and is 2,000 or more, preferably 3,000 or more, and more preferably 5,
000 or more is good. Also, a method of providing a liquid that does not mix with water (for example, liquid paraffin, silicone oil, silicone gel, or the like) can ensure transparency. Although not particularly shown, the layer thickness of the aqueous solution 2 is continuously changed, and the degree of the cloudy and opaque state is continuously changed. The unevenness is provided on the substrate to secure the transparency by changing the layer thickness of the aqueous solution 2. The laminated body and the like are also included in the present invention. These can be used for, for example, a rear window of an automobile, an advertisement device that displays image information, and the like, while ensuring partial transparency. There is also a method of providing a thermal element in order to widen the use range of the laminate of the present invention. This also serves as a partition for blocking the line of sight by artificially controlling the heat as an electronic curtain. As the thermal element, there are a transparent conductive film, a carbon paste, a metal paste, a metal wire, a barium titanate-based ceramic, and the like, and a thermoelectric element that can be heated and cooled (for example, a thermo panel of Komatsu Electronics Co., Ltd.) and the like. Can also. The setting of the heat element may be inside or outside the substrate, or may be the entire surface or part of the substrate. Further, the thermal element may be divided and arranged in a linear shape or a stripe shape. Image information can also be displayed by selectively heating the substrate surface with a matrix of thermal elements, infrared rays (eg, laser, etc.), and the like.

The windows according to the present invention include windows of ordinary buildings, vehicles such as automobiles and railway vehicles, and windows of transport machines such as ships, aircrafts and elevators. This window is a broad term and includes things like arcades and atriums, doors with windows, partitions, etc., as well as all-glass doors, screens and walls. Naturally, as a widely used method, a laminate is combined with a building material sash or a vehicle frame to form a laminate having a frame for each use such as a building, a vehicle, and the like, and is simply attached at the site as in the past. Window units are also included in the present invention. This unitization can more reliably seal the laminate, and is effective in preventing evaporation of water by permeation, preventing deterioration of the sealing layer by light, and the like. In particular, it is effective for semi-permanent use or severe use such as windows of ordinary buildings and windows of vehicles.

Further, a method in which the aqueous solution is applied to a substance encapsulated in a hollow body, a sphere, a microcapsule, a resin sheet, or the like, and the resulting aqueous solution is formed into a planar shape by lamination or the like is also used. If present, it is included in the laminate of the present invention. In particular, the hollow bar 5 shown in FIG. 3 is useful. The cross section can be widely used according to the purpose, such as circular, hexagonal, square, triangular, and flat. Further, the sealing can be performed by melting the glass to complete the sealing. A function of shielding light is provided by a method of arranging many hollow rods 5 in a plane. For example, a method of using blinds, brine, and the like. Of course, there is also a method of arranging many hollow rods 5 between a pair of substrates. Thus, the hollow rod 5 in FIG. 3 also belongs to the present invention as a laminate in a broad sense. In addition, the present invention also includes a planar object in which a laminate is formed into a cup, a water tank, or the like.

[0026]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Sodium carboxymethylcellulose (CMC Daicel 1260, Daicel Chemical Industries, Ltd., degree of etherification 0.9)
0) 100 parts by weight of a polymer aqueous solution obtained by dissolving 2 parts by weight of pure water in 50 parts by weight of poly (oxyethylene oxypropylene) methylpolysiloxane, KF60 of Shin-Etsu Chemical Co., Ltd.
12, 6.5 parts by weight, 1.5 parts by weight, 16 parts by weight, 32
Aqueous aqueous solutions A, B, C, and D were prepared at 20 ° C. by adding parts by weight. In the same manner as in Example 1, a laminate A, a laminate B, a laminate C, and a laminate D were obtained. The four types of laminates had good reversible stability at room temperature and 60 ° C. and stability for 12 hours at 60 ° C. without phase separation. In addition, the A-layered product started turbid light scattering from about 30 ° C., and the turbid light-shielding was sharply caused by the temperature change, and a sufficient light-shielding and anti-glare effect was observed. The B-layered product started turbid light scattering at almost the same temperature as the A-layered product, but it confirmed a sufficient anti-glare effect while maintaining the transparency even at a high temperature. The C-layered product started turbid light scattering at substantially the same temperature as the A-layered product, and the opaque light-shielding was sharply caused by the temperature change. D laminate is A
The turbid light scattering started at about the same temperature as the laminate, but was about 40 ° C.
The light-shielding characteristics at a high temperature were almost the same as those of the C laminate.

Example 2 100 parts by weight of the aqueous polymer solution of sodium carboxymethylcellulose of Example 1 were mixed with poly (oxyethylene oxypropylene) methylpolysiloxane, KF615A of Shin-Etsu Chemical Co., Ltd., and TSF4450 of Toshiba Silicone Co., Ltd.
6.5 parts by weight of TSF4452, TSF4440, and SH8700 and SF8410 manufactured by Dow Corning Toray Silicone Co., Ltd. were respectively added to prepare aqueous solutions A, B, C, D, E, and F. In the same manner as in Example 1, each aqueous solution was used as an A laminate, a B laminate, a C laminate, a D laminate, an E laminate, and an F laminate.
These laminates have reversible stability at room temperature and 60 ° C. and 6
The storage stability at 0 ° C. for 12 hours was good without any phase separation. Further, the A laminate is from about 41 ° C., the B laminate is from about 5 ° C., the C laminate is from about 26 ° C., the D laminate is from about 65 ° C., and the E laminate is about 30 ° C. From F
In the laminate, cloudy light scattering was started from about 33 ° C., and cloudy light-shielding occurred with respect to temperature change, and sufficient light-shielding and antiglare effects were observed. As described above, it was confirmed that by changing the type of poly (oxyethylene / oxypropylene) methylpolysiloxane, reversible changes could be made in a uniform state over a wide temperature range from low to high. Further, the white turbidity change rate was also unique.

Example 3 A weight-average molecular weight of 400 and 95 was added to 100 parts by weight of the aqueous solution of sodium carboxymethylcellulose in Example 1
A and B aqueous solutions were prepared by adding 6.5 parts by weight of Newpol PP-400 and PP950 from Sanyo Kasei Kogyo Co., Ltd., which are 0 propylene glycol. In the same manner as in Example 1, a laminate A and a laminate B were obtained. The laminate has a reversible stability at room temperature and 60 ° C. and 12 ° C. at 60 ° C.
The storage stability over time was good without phase separation. Further, the A-layered body is about 60 ° C., and the B-layered body is about 18 ° C.
From ℃, cloudy light scattering was started, and a sufficient light-shielding and anti-glare effect against a temperature change was observed.

Example 4 A polymer aqueous solution 100 obtained by dissolving 5 parts by weight of sodium carboxymethylcellulose of Example 1 in 100 parts by weight of pure water.
An aqueous solution A to which 20 parts by weight of the TP-400 of Example 4 was added and an aqueous solution B to which 40 parts by weight of GP-600 were added were added. Each was a colorless and transparent aqueous solution at 20 ° C. A laminated body and B laminated in the same manner as in Example 1.
A laminate was obtained. Both of these laminates were excellent in reversible stability at room temperature and 60 ° C. and stability for standing at 60 ° C. for 12 hours without phase separation. In addition, the A laminate is about 2
From 5 ° C., the B-layered product started turbid light scattering from about 45 ° C. and showed turbid light-shielding sharply against a temperature change.

Example 5 KEPS-, an ionic water-soluble polymer obtained by adding a carboxyl group to polyvinyl alcohol having a weight average molecular weight of about 100,000 by about 12% per hydroxyl group,
1224A was purified by removing organic salts with methanol. 10 parts by weight of this purified KEPS-1224A was added to pure water 1
10 parts by weight of KF6012 of Example 5 was added to 100 parts by weight of the aqueous polymer solution dissolved in 00 parts by weight, and a colorless and transparent aqueous solution of A at 20 ° C. and this purified KEPS-1224 were added.
A: 10 parts by weight of the TP-400 of Example 4 was added to 100 parts by weight of a polymer aqueous solution obtained by dissolving 20 parts by weight in 100 parts by weight of pure water to prepare a colorless and transparent B aqueous solution at 20 ° C. In the same manner as in Example 1, an A-layer and a B-layer were obtained.
The two types of laminates were good in reversible stability at room temperature and 60 ° C. and stability for standing at 60 ° C. for 12 hours without phase separation. Further, the A-layered product started to scatter turbid light from about 26 ° C. and the B-layered product from about 27 ° C., and the opaque light-shielding was sharply caused by a change in temperature.

Example 6 A polymer aqueous solution obtained by dissolving 0.5 part by weight of sodium polyacrylate having a weight average molecular weight of about 5,000,000 (Aqualic IH manufactured by Nippon Shokubai Co., Ltd.) in 100 parts by weight of pure water
A colorless and transparent aqueous solution was prepared at 20 ° C. by adding 10 parts by weight of KF6012 of Example 5 to parts by weight. Example 1
A laminate was obtained in the same manner as described above. This laminate is at room temperature and 60
Both the reversible stability at 60 ° C. and the stability for standing at 60 ° C. for 12 hours were good without phase separation. About 32 ° C
, Cloudy light scattering was started, and the cloudy light-shielding occurred sharply with respect to the temperature change, and a sufficient light-shielding and antiglare effect was observed.

Example 7 5 parts by weight of the sodium polyacrylate of Example 6 was added to pure water 1
100 parts by weight of a polymer aqueous solution dissolved in 00 parts by weight was added to Lion Co., Ltd., Leocoll SC-70 and Leocoll SC-8.
0 and 10 parts by weight of Liponox NC-86 were added, and colorless and transparent aqueous solutions A, B and C were prepared at 20 ° C., respectively. A laminate, a B laminate, and a C laminate were obtained in the same manner as in Example 1. Both of these laminates have reversible stability at room temperature and 60 ° C. and 1
The two-hour storage stability was good without any phase separation. The temperature of the A-layered product is about 32 ° C.
From ℃, the C laminate started turbid light scattering from about 32 ° C and showed sufficient opaque light shielding.

[0034]

The effect of the present invention is that an aqueous solution of an amphiphilic substance which is oily at room temperature and has a cloud point phenomenon and is uniformly dissolved in water at room temperature does not phase-separate into an aqueous layer and an oil layer due to a rise in temperature.
The inventor has found an aqueous solution composition capable of stably and reversibly changing the sol-emulsion phase transition depending on temperature, and has obtained a laminate having an aqueous solution in which a transparent state and a cloudy light-shielded state are reversibly changed, and a window using the same. The present inventors have found that when this amphiphile is added to an aqueous solution of an ionic water-soluble polymer, it is surprisingly brilliantly and stably reversibly changed.
It has been discovered that the solution becomes an aqueous solution that undergoes an emulsion phase transition. This is presumably because microaggregates of the amphiphilic substance generated by heating were trapped by the water-soluble polymer chains and maintained in a uniform emulsion state. As a result, cloudiness was blocked by light scattering due to the difference in refractive index between the microaggregate and the medium. When this laminate is applied to a window, when the window is heated by the direct rays of the sun, the irradiated portion selectively changes from a transparent state to a cloudy state, and the direct rays are shielded and glare-proof. This automatically changed from transparent to translucent to opaque according to the balance with the current environmental temperature such as season, weather, and the like. Therefore, it was possible to provide an autonomous response type energy-saving window having comfort in which the direct rays of light were blocked by the direct sunlight energy of the sun.

[Brief description of the drawings]

FIG. 1 is a sectional view of an embodiment of the present invention.

FIG. 2 is a sectional view of an embodiment of the present invention.

FIG. 3 is a sectional view of an embodiment of the present invention.

FIG. 4 is a sectional view of an embodiment of the present invention.

FIG. 5 is a graph showing a change in transmittance of a laminate of the present invention in a range from 400 nm to 800 nm.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Aqueous solution 3 Sealing 4 Unchangeable transparent liquid 5 Hollow rod 6 Double glass with gas layer

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[Procedure amendment]

[Submission date] February 10, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0027

[Correction method] Change

[Correction contents]

Example 1 Sodium carboxymethylcellulose (CMC Daicel 1260, Daicel Chemical Industries, Ltd., degree of etherification 0.9)
0) 100 parts by weight of a polymer aqueous solution obtained by dissolving 2 parts by weight of pure water in 50 parts by weight of poly (oxyethylene oxypropylene) methylpolysiloxane, KF60 of Shin-Etsu Chemical Co., Ltd.
12, 6.5 parts by weight, 1.5 parts by weight, 16 parts by weight, 32
Aqueous aqueous solutions A, B, C, and D were prepared at 20 ° C. by adding parts by weight. Next, 30c
m square, 3mm thick float soda glass
Place a 2.4 mm diameter linear isobutyl sealant and
Place the aqueous solution in the center of the plate and lighten the counter substrate on it.
And put it inside the vacuum equipment and reduce the pressure by about 1 Torr.
Press the opposing substrate under pressure to crush the isobutyl sealant
We took close contact. Then, insert the glass into the gap left at the outermost
Pour in a photosensitive resin with adhesive properties and seal by irradiating light.
Was. As a result, 0.3 mm thick, bubble-free A stack, B volume
A laminate, a C laminate, and a D laminate were obtained. The four types of laminates had good reversible stability at room temperature and 60 ° C. and stability for 12 hours at 60 ° C. without phase separation.
In addition, the A-layered product started turbid light scattering from about 30 ° C., and the turbid light-shielding was sharply caused by the temperature change, and a sufficient light-shielding and anti-glare effect was observed. The B-layered product started turbid light scattering at almost the same temperature as the A-layered product, but it confirmed a sufficient anti-glare effect while maintaining the transparency even at a high temperature. C laminate is A
At the same temperature as that of the laminate, cloudy light scattering was started, and cloudy light-shielding occurred sharply against a change in temperature, confirming a stronger light-shielding property than the laminate A. The D laminate started scattering white turbid light at approximately the same temperature as the A laminate, but the light-shielding characteristics at a high temperature of about 40 ° C. were approximately the same as those of the C laminate.

Claims (9)

[Claims] 1. An aqueous solution in which molecules dissolved in water are aggregated due to an increase in temperature to cause cloudy scattering and light transmittance is reduced, using a substrate at least partially transparent and capable of directly viewing the aqueous solution. In the laminated body, the aqueous solution is a solution of 0.5 to 20 parts by weight of an ionic water-soluble polymer dissolved in 100 parts by weight of water. A laminate which is an aqueous solution obtained by dissolving 0.5 to 45 parts by weight of an amphipathic substance which is uniformly dissolved in water. 2. The laminate according to claim 1, comprising a combination of multiple aqueous solutions or a combination of an aqueous solution and a transparent liquid. 3. The laminate according to claim 1, further comprising a heat element capable of heating at least. 4. An aqueous solution whose light transmittance is reduced due to aggregation of molecules dissolved in water due to an increase in temperature to cause cloudiness and scattering, and a substrate which is at least partially transparent and can directly view the aqueous solution. In a window using a laminated body,
The above-mentioned laminate has a cloud point phenomenon in 100 parts by weight of a solution in which 0.5 to 20 parts by weight of an ionic water-soluble polymer is dissolved in 100 parts by weight of water. A window which is a laminate which is an aqueous solution obtained by dissolving 0.5 to 45 parts by weight of a medium substance. 5. The window according to claim 4, comprising a combination of multiple aqueous solutions or a combination of an aqueous solution and a transparent liquid. 6. The window according to claim 4, wherein at least one of the substrates is made of an ultraviolet absorbing glass, and the ultraviolet absorbing glass is directed to the outdoor side. 7. The window according to claim 4, wherein at least one of the substrates is made of a double glass. 8. The window according to claim 4, wherein a heat element capable of heating at least is provided. 9. The window according to claim 4, wherein the laminated body is combined with a building material sash or a vehicle frame to form a unit.