KR19980086510A - Laminates and Windows Using the Same - Google Patents

Abstract

A laminate comprising an aqueous solution, wherein two molecules dissolved in water exhibit a cloud-scattering property that aggregates with increasing temperature to reduce light transmission, and at least partially transparent to allow direct visibility of the aqueous solution. A vinyl-based nonionic water soluble polymer or ionic that is sealed between the dogs and that the aqueous solution undergoes a temperature dependent reversible sol-emulsion phase transition and does not exhibit a cloud point at temperatures below about 45 ° C. with 100 parts by weight of water as solvent. A laminate comprising 0.5 to 45 parts by weight of a bipolar substance dissolved in 100 parts by weight of a 0.5 to 40 parts by weight solution of a water-soluble polymer and exhibiting a cloud point and being uniformly dissolved in water at room temperature, and a window using the same.

Description

Laminates and Windows Using the Same

The present invention relates to a laminated body consisting of an aqueous solution that is blurred to disperse and block light due to the thermal action caused by absorption of light when irradiated with direct sunlight. The present invention can be applied to buildings and vehicles with windows to selectively block light and prevent glare only at the surface to which light is directly irradiated. In addition, thermal components may also be blended for indoor windows such as partitions and doors equipped with electronic curtains.

In recent years, the goal of environmental compliance has been to achieve more comfortable and energy saving windows through the effective use of daylight. Although heat-reflective glass and heat-absorbing glass are actually applied to windows, their use for direct sun protection causes problems by blocking natural light in winter, rainy or cloudy days, while also opening and comforting. Is greatly reduced. Therefore, adjustable glasses have been desired to block light by reversible conversion.

The inventors focus on the direct sunlight energy irradiated to the window and absorb this energy as a self-response of the window glass to provide a more comfortable living space, causing a reversible conversion between light scattering and permeability. Or sustainability studies. The inventors have found that this property of self-response can be noted not only in terms of blocking light on the irradiated surface and providing an energy saving effect, but also in terms of finishing, maintenance, maintenance costs and the like. In this respect, phtochromic systems, thermochromic systems or thermotropic systems could be selected for research, but their mechanisms of operation were complex and could be easily adjusted by manually adjusting the temperature as needed. Thermochromic and pyrogenic systems, which depend only on controllable thermal action, are superior to photochromic systems, which depend on the wavelength of light. Daylight reaching the earth is in the range of 290 to 2140 nm, of which about 80% belong to visible light rather than the near infrared region of 400 to 1100 nm, and the fact that the visible light region is larger than the near infrared region should also be considered. Therefore, controlling the visible light region not only has a blocking effect, but also is important for energy saving and glare reduction effects. The present invention takes advantage of the temperature increase of the object caused by sunlight energy. Of course, heating components can also be added for artificial temperature control to create light scattering conditions that can block light.

At present, the materials used in thermochromic and pyrogenic systems have inadequate properties and are therefore impractical. Thermochromic glass and thermochromic glass, which can be widely used, must satisfy the following conditions.

1. The phase transition between permeability and opacity must be reversible.

2. The reversible transformation must be repeatable without phase separation.

3. The phase transition starting temperature should be low.

4. The glass must be durable.

5. The substances shall not be toxic or polluted with the environment.

The present inventors have focused on the aqueous solution which progresses the phase transition from the colorless and transparent state to the cloud-scattering state in the aqueous solution as a self-reactive material capable of satisfying such conditions.

Solutions that are known to change to a light-scattering state in the cloud by increasing temperature include nonionic surfactants that exhibit cloud point phenomena, although such applications have also been studied, phase separation readily occurs due to temperature increases and It will be clear that it does not satisfy 2. In addition, an aqueous solution of a nonionic non-aqueous polymer (e.g., hydroxypropyl cellulose, poly-N-isopropylacrylamide, polyvinyl methyl ether, etc.) exhibiting clouding and light scattering effects due to aggregation and colliding by increasing temperature. In addition, although it has been studied for similar applications (Japanese Utility Model Publication No. 41-19256, Japanese Patent Publication No. 51-049856, and Japanese Patent Publication No. 61-7948), these also meet the conditions 1 and 2 above. It has not been met and thus has not been put to practical use. Moreover, as disclosed in Japanese Patent Laid-Open No. 63-500042, it has been attempted to apply a hydrogel to take advantage of the change in opacity of a hydrogel consisting of specific reaction mixtures of five or more components, but here too, Conditions 1 and 2 could not be met and therefore not put to practical use. In addition, poly-N, N'-methylenebisacrylamide obtained by aqueous solution polymerization of N-isopropylacrylamide in the presence of a water-soluble radical polymerization initiator using a small amount of N, N'-methylenebisacrylamide as a crosslinking agent. Crosslinkable hydrogels, such as gels, have also been studied, but they have also failed to meet conditions 1 and 2 and have not been put to practical use. Therefore, the present inventors use the sol-gel phase transition principle based on the composition as disclosed in Japanese Patent Laid-Open No. 5-62502, so that the nonionic water-soluble polymer that proceeds to agglomerate to have a cloud-like and light scattering property without phase separation. Useful laminates have been invented based on the fact that they are reversible transformed in a single way and the study of new methods. The inventors also conducted extensive research on the use of clouded, oily bipolar materials, which have been ignored so far, due to the prepared phase separation between the water-soluble and oil layers in the high temperature range. As a result, the present invention has been completed by the discovery of an aqueous solution in which the reversible conversion proceeds uniformly by sol-emulsion phase transition.

Summary of the Invention

The inventors of the present invention have a cloud-like process in which a stable reversible change is carried out by a temperature-dependent sol-emulsion phase transition in which an oil phase at room temperature is uniformly dissolved in room temperature water and an aqueous phase composition does not proceed with an increase in temperature. A bipolar material with dots was found, thereby completing the present invention of a laminate containing an aqueous solution and a window using the same, which undergoes a reversible conversion between a transparent state and an opaque state on a cloud.

The present invention has been completed to solve the problems described above, the present invention exhibits a cloud light scattering property in which the molecules dissolved in water agglomerates and decreases the light transmittance as the temperature increases, at least partially transparent to Provided are laminates of aqueous solutions sealed between two substrates that allow direct visibility, wherein the aqueous solution undergoes a temperature dependent reversible sol-emulsion phase transition and at about 45 ° C. or less, with 100 parts by weight of water as solvent. 0.5 to 45 weight percent of a bipolar material that exhibits a cloud point and is oil at room temperature and uniformly soluble in room temperature water, dissolved in 100 parts by weight of a vinyl-based nonionic water soluble polymer or 0.5 to 40 parts by weight of a solution having no cloud point. The aqueous solution is made by. The present invention further provides a substrate which is at least partially transparent so that molecules dissolved in water aggregate with increasing temperature to show cloud-scattering properties, thereby reducing light transmittance and allowing direct transmission of the aqueous solution. A window using a laminate of aqueous solutions sealed between the two is provided, wherein the aqueous solution undergoes a temperature dependent reversible sol-emulsion phase transition and exhibits a cloud point at about 45 ° C. or less, with 100 parts by weight of water as a solvent. It consists of 0.5 to 45 parts by weight of a bipolar material, which is a cloud point and is oil at room temperature and is uniformly dissolved in room temperature water, dissolved in 100 parts by weight of a vinyl-based nonionic water soluble polymer or 0.5 to 40 parts by weight of a solution of ionic water-soluble polymer. The laminate contains an aqueous solution.

1 is a longitudinal sectional view of a specific example of a laminate according to the present invention.

It is a longitudinal cross-sectional view of another specific example of the laminated body by this invention.

3A and 3B are longitudinal cross-sectional views of another specific example of the laminate according to the present invention.

4 is a graph showing a change in light transmittance at a wavelength of 400 to 800 nm for the laminate according to the present invention.

5 is a graph showing a change in light transmittance at a wavelength of 400 to 800 nm for another laminate according to the present invention.

The basic principle of the present invention is to take advantage of the cloud point phenomenon of a homogeneously dissolved aqueous solution of bipolar material, whereby heating causes the bipolar material to agglomerate into clouds and make it light scattering. The aqueous solution of the bipolar material exhibiting such clouding phenomenon tends to undergo phase separation between the oil layer and the aqueous solution layer as the temperature increases, making it impossible to achieve uniform reversible conversion. Here, the inventors focused their research on finding an aqueous solution capable of advancing a reversible change stably and uniformly between a transparent state and a turbid state by a temperature change. As a result, it was surprisingly found that by adding the bipolar materials to the aqueous solution of the water-soluble polymer, the reversible conversion can be achieved uniformly and stably. It is believed that this is because fine aggregates of agglomerated bipolar material are trapped in the water soluble polymer chain due to the increase in temperature, thereby maintaining a uniform fine dispersion state. Perhaps this will prevent further agglomeration from the fine agglomerates to larger agglomerates, thereby preventing layer separation of the aqueous and oil layers. Thus, the light scattering effect on the cloud is caused by the difference in refractive index between the fine aggregate of the bipolar material and the water-soluble polymer solution medium. In other words, The aqueous solution of the present invention was a bipolar material uniformly dissolved in water, which was a transparent solution in a sol state at a low temperature. However, at a high temperature, the bipolar material was agglomerated to produce a white cloudy emulsion state. This emulsion state was stabilized by the emulsifying effect of the water soluble polymer. As a result, a reversible transformation called sol-emulsion phase change could be achieved. Accordingly, the present invention is a laminate comprising three components, that is, a water-soluble polymer, a bipolar material having a cloud point phenomenon, and an aqueous solution based on pure water.

The water soluble polymers useful in the present invention are described below. The water soluble polymer used may be ionic or nonionic. Ionic water-soluble polymers can form highly viscous aqueous solutions at low temperatures depending on their molecular weight. Specific examples include cellulose derivatives such as sodium carboxymethyl cellulose (e.g., CMC Daicel of Daicel Chemical Industries, Ltd.) and vinyls such as sodium polyacrylate (Aqualic-IH of Nippon Shokubai Co., Ltd., Aqualic DL-522). Basic polymers and sodium polystyrenesulfonates, and examples of vinyl monomer copolymers having anionic and nonionic groups include A181 and A161 of Aronfloc Co., Ltd., which have cationic and nonionic groups. Examples of vinyl monomer copolymers include Isoban-110 from Kuraray Co., Ltd. and C-303, C-302, C-508 from Aronfloc Co., Ltd., which are ionized copolymers of isobutylene and maleic anhydride. C-500, and examples of the modified polyvinyl alcohol include those of Daiichi Kogyo Seiyaku Co., Ltd. having about 12% of the carboxyl group added to the hydroxyl group of the polyvinyl alcohol via the methylene group to the hydroxyl group. KEPS-1224 A, CM-318 of Kuraray Co., Ltd. having a cationic quaternary ammonium base group in the backbone chain, and F78 of Nippon Gohsei Co., Ltd. containing a sulfate group. Many such materials can be used, and the starting turbidity temperature of the laminates of the invention can also vary depending on the structure, molecular weight and concentration of the polymer. Of course, the higher the molecular weight, the higher the viscosity, thus maintaining a uniform emulsion even at low temperatures. However, when the molecular weight was small, the emulsification of the polymer was small and increasing the concentration made it difficult to achieve a clear state. Although the molecular weight will vary depending on the structure, it is generally in the unit of the average molecular weight can be more than 20,000, preferably 50,000, and evenly dissolved in water, even if the viscosity increases due to the increase in molecular weight, making it difficult to dissolve in water Is sufficient, and generally useful polymers will not exceed millions. The concentration may be about 0.5 to 20 parts by weight, preferably about 1.5 to 15 parts by weight and even more preferably about 2 to 10 parts by weight, relative to 100 parts by weight of water. In addition, the turbidity onset temperature was lowered with increasing concentration. The more dense water-soluble polymers of the ionic functional water-soluble polymers exhibited a more abrupt transition from the starting turbidity temperature to the saturated turbidity temperature, and tended to have greater cloud light blocking properties.

A wide range of vinyl-based nonionic water soluble polymers can also be used in the present invention. Examples thereof include polyvinyl alcohol, polyvinylpyrrolidone and polyvinyl acrylamide. As another example, the nonionic water-soluble polymer (eg, OKS-9065N of Nippon Gohsei Co., Ltd., polyvinyl alcohol containing an oxypropylene group) which has the side chain group to which the side chain of polyvinyl alcohol was added is mentioned. The molecular weight will vary depending on the type of polymer, but in units of average molecular weight it can generally be at least 10,000, preferably at least 15,000 and more preferably at least 20,000, and higher molecular weights make it more difficult to dissolve in water. The only problem is that there is no need to limit so long as it is a homogeneous dissolution in water, but usually the polymers commonly available will not exceed millions. The concentration may be about 1 to 40 parts by weight, preferably about 5 to 35 parts by weight, relative to 100 parts by weight of water. However, vinyl-based nonionic water-soluble polymers, which dissolve in water at room temperature in a transparent state, but at high temperatures, are agglomerated by gelation and precipitation and phase separated, are difficult to maintain uniformly in aqueous solution. More specifically, these are water soluble polymers (eg, poly-N-isopropylacrylamide and polyvinyl methyl ether) which aggregate at gelation and precipitation at temperatures below about 45 ° C. to cause phase separation. Accordingly, the vinyl-based nonionic water soluble polymers useful in the present invention are polymers that do not exhibit cloud point phenomena at temperatures below about 45 ° C.

We have determined sodium carboxymethyl cellulose as an ionic water soluble polymer that is resistant to weathering and is uniformly soluble in water. Examples thereof include CMC Daicel 1170, 1220, 1260, 1290, 1330, 1380, and 2260 of Daicel Chemical Industries, Ltd., and a wide range of variations may be used without particular limitation on the degree of etherification or molecular weight. In addition, the pH of this aqueous solution near neutral is important from the standpoint of durability. If the pH deviates from neutral, depolymerization of the cellulose backbone and degeneration of the bipolar material proceed, and durability will be greatly reduced. Polyvinyl alcohols are vinyl-based nonionic polymers that are resistant to diaries and are uniformly soluble in water, examples of which are Gohsenol NH-26, NL-05, GH-20, GL- from Nippon Gohsei Co., Ltd. 03, KL-11, and NH-17Q, which may be used in various ways without particular limitation on the degree of saponification and molecular weight. As mentioned above, modified polyvinyl alcohol may also be used. Thus, water-soluble polymers that are uniformly soluble in water and resistant to weathering in the aqueous state are particularly useful. However, the resistance to this weather is less important for indoor use (eg partitions) in which heating components are added together.

Bipolar materials useful by the present invention are compounds that have an oil at room temperature and have a cloud point that dissolves uniformly at room temperature. Numerous bipolar materials are known and examples are propylene oxide polymers (e.g., Newpol PP series from Sanyo Chemical Industries, Ltd.), copolymers of low molecular weight propylene oxide and ethylene oxide (e.g. Daiichi Kogyo Seiyaku Co., Ltd. Epan 420 and 720), poly (oxyethylene / oxypropylene) glycol monoether (e.g., butyl alcohol derivative of Newpol 50HB series of Sanyo Chemical Industries, Ltd.), oxypropylene group or oxyethylene group / oxypropylene group Triols (e.g., Newpol / GP series, TP series, GL series, GEP series and TL series from Sanyo Chemical Industries, Ltd.) and polyoxyethylene compounds added to larger alkyl phenols (e.g., Lion Corp. Propylene oxide and polyethylene jade added to nonyl phenol Liponox NC-86) and larger alkyls (such as alkyl groups of 12 and 13 carbon atoms) The compounds of the beads (for example, Leocol SC-70 and Leocol SC-80 of Lion Corp.) may be mentioned. In addition, silicone compounds comprising modified dimethylpolysiloxanes with added oxyethylene and oxypropylene (eg, KF6008, KF6012 and KF615A from Shin-Etsu Chemical Co., Ltd., TSF4450 from Toshiba Silicone Co., Ltd., TSF4452 and TSF4440, and SH3748, SH3749, SH8700 and SF8410 from Toray-Dow Corning Silicone Co., Ltd.) are also very useful in the present invention. As already known, the onset clouding temperature is controlled according to the ratio of oxyethylene and oxypropylene (eg, a ratio of 1: 1).

Bipolar materials that are oil at room temperature and have a cloud point that dissolve uniformly in room temperature water can be defined in the following manner. To be oil at room temperature means to be liquid at temperatures around room temperature. In addition, uniform dissolution in room temperature water means that the bipolar material is dissolved in a uniformly transparent state or near transparent state without phase separation when the required amount is added to water at room temperature below the temperature at which the clouding phenomenon occurs. More specifically, it means that the 2 wt% aqueous solution is uniformly dissolved in a transparent state or near transparent state at room temperature below the temperature at which the cloud phenomenon occurs. For example, in the case of propylene oxide polymers (such as the Newpol PP series of Sanyo Chemical Industries, Ltd.), if the molecular weight is very small, no self-agglomeration will occur, and therefore, cloud light scattering properties will not appear, and if the molecular weight is very large, It will not dissolve evenly at low temperatures and will not be transparent. Therefore, a preferable weight average molecular weight is about 400-1,000. In addition, in the case of a low molecular weight copolymer composed only of propylene oxide and ethylene oxide, if the content of ethylene oxide is low as about 10%, the copolymer will not be uniformly dissolved even at low temperatures and cannot be transparent. As high as 40%, no self-agglomeration will occur, resulting in no cloud scattering. Thus, the preferred ethylene oxide content is about 15-30%.

The amount of bipolar material added will depend on its solubility in water, but in general, lower amounts result in faint clouding and light scattering, while increasing amounts produce stronger clouding. However, if the amount is too high, a cloudy state appears in place of the transparent state even in the low temperature range, which makes it unsuitable for the present invention. However, in the case of a bipolar material suitably dissolved in room temperature water, such as Newpol / GP600 of Sanyo Chemical Industries, Ltd., it may be added in large amounts. Thus, the amount of the bipolar material added may be 0.5 to 45 parts by weight, preferably 1 to 40 parts by weight, relative to 100 parts by weight of the aqueous solution of the water-soluble polymer. Although the molecular weight of this bipolar material depends on the molecular structure, the weight average molecular weight is preferably about 240 to 20,000. The hydrocarbon-based bipolar material may be used with a weight average molecular weight of about 240 to 10,000, preferably a weight average molecular weight of 240 to 8,000 and more preferably a weight average molecular weight of 240 to 5,000. Molecular weights above 10,000 are not practical because they are difficult to synthesize and purify. The polysiloxane system is not necessarily limited to a molecular weight of about 20,000 or less because of the large atomic weight of silicon, but for the same reason, a molecular weight exceeding 20,000 due to the functional groups added to the side chain is not practical because it is difficult to manufacture. Polysiloxane systems must have a high molecular weight in order to obtain the siloxane chain effect, with an average molecular weight of about 1000 to 20,000, preferably an average molecular weight of about 2000 to 18,000 and more preferably an average molecular weight of about 3000 to 15,000.

For example, when modified dimethylpolysiloxanes were added and dissolved in an aqueous solution of ionic water soluble polymer carboxymethyl cellulose, they showed overall transparency in the low temperature range, which then abruptly clouded for strong light blocking properties. In particular, the temperature difference from initiation of clouding to substantial saturated clouding was very sudden, about 5 ° C. Stack C of Example 5 exhibited its onset clouding at about 30 ° C. and reached substantial saturation of light blocking properties at about 35 ° C. By varying the amount of modified addition dimethylpolysiloxane, the degree of opacity due to cloud light scattering can be controlled. The clouding onset temperature can also be controlled by adjusting the concentration of carboxymethyl cellulose, but the higher the concentration, the lower the onset temperature. Therefore, starting temperature and light blocking characteristic can also be changed by adjusting concentration. In the degree of etherification of the carboxymethyl cellulose, when it is 0.7 or less, a faint haze image appears even in a transparent state in the low temperature range, even if a sufficient change in cloud light blocking interferes with the visibility. In most cases, a degree of esterification of 0.8 to 1.5 is preferred, and a tendency toward sudden changes in clouding has been observed as the degree of esterification increases above 1.0. Above 1.5, synthesis is difficult and no longer practical. In addition, the molecular weight of the carboxymethyl cellulose may be a wide range in which viscosity is given in a range from CMC Daicel 1220/10 cps to CMC Daicel 2260/6000 cps as measured by a cyclic viscometer at 1% aqueous solution / 25 ° C. There is no particular limitation on the molecular weight.

The water can typically be distilled water, pure water and the like. In order to transfer the turbidity onset temperature to a lower temperature, neutral inorganic salts (eg, sodium chloride, potassium chloride, lithium chloride, sodium nitrate, sodium sulfate) may be added in the case of a nonionic water-soluble polymer aqueous solution. It may be added in an amount of 0.1 to 10 parts by weight relative to 100 parts by weight of the nonionic water-soluble polymer aqueous solution. However, it has been found that adding these salts to ionic water soluble polymers is undesirable because these salts affect the ionic decomposition reaction, affecting uniformity and viscosity. The pH of the aqueous solution used in the present invention may be approximately close to neutral 7, or may range from 6 to 8 or more preferably 6.5 to 7.5. In addition, appropriate amounts of antioxidants, colorants, preservatives, ultraviolet absorbers and the like can also be used as additives. By degassing the dissolved oxygen or replacing it with an inert gas, oxidative decay can be prevented and suitable for long-term applications such as windows.

When the laminate is used as a window, it may be a window having a weak light blocking property but providing visibility and preventing glare, or a window having a strong light blocking property and an appropriate energy saving effect. As an example of the former type, the inventors have found that 7 parts by weight of polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol (Newpol Tp-400 of Sanyo Chemical Industries, Ltd.) having an average molecular weight of 5 Colorless and permeable at 20 ° C. by adding 1 part by weight of a water-soluble polymer solution having an average molecular weight of 20,000 polyvinyl alcohol (Gohsenol GL-03 of Nippon Gohsei Co., Ltd.) dissolved in 2 parts by weight of an aqueous solution of wt% sodium chloride. An aqueous solution A having was prepared. As an example of the latter type, the inventors have found that carboxymethyl cellulose (CMC) dissolved in 6 parts by weight of poly (oxyethylene / oxypropylene) methylpolysiloxane (KF6012 from Shin-Etsu Chemical Co., Ltd.) in 30 parts by weight of pure water. Daicel 1220 (average molecular weight: 50,000, Daicel Chemical Industries, Ltd.) 2 parts by weight of 100 parts by weight of a polymer aqueous solution was added to prepare a colorless and transparent aqueous solution B at 20 ° C. Next, the aqueous solution A and the aqueous solution B were applied to a thickness of 0.3 mm between 10 cm-square and 3 mm-thick soda lime glass plates, respectively, to prepare laminate A and laminate B. All of the laminates had satisfactory reversible stability at room temperature and 60 ° C., and had satisfactory stability by keeping at 60 ° C. for 12 hours without phase separation. In addition, the laminate A began to exhibit cloud-shaped light dispersibility from about 26 ℃ and gradually improved cloud light blocking with temperature, while faint visibility was also verified at about 42 ℃, and the anti-glare effect was satisfactory. . Stack B exhibited cloud light scattering from about 24 ° C., reaching saturation at about 29 ° C., providing a strong light blocking effect.

Next, a U-4000 spectrophotometer manufactured by Hitachi, Ltd., which is suitable for the measurement of large light scattering samples, is placed on each stack so that its center plane is very close to the window of the integrating sphere (about 1 mm). ) To be used for measurement. The measured temperature was about 21 ° C. in the low temperature range and about 42 ° C. in the high temperature range. For the temperature change of the laminate during the measurement, the measurement wavelength is limited to light between 400 nm and 800 nm at about 21 ° C. (transparent state) and about 42 ° C. (cloudy light scattering state). The results are shown in FIGS. 4 and 5. 4 shows the laminate A and FIG. 5 shows the laminate B. FIG. Verification was performed with light wavelengths of 300 to 400 nm and 800 to 2500 nm. Light blocking was observed in the ultraviolet and infrared ranges close to visible light.

The laminate structure of the present invention and its use as a window will be described next. 1, 2, 3a and 3b are schematic longitudinal cross-sectional views of specific examples of laminates according to the invention, where 1 represents a substrate, 2 represents an aqueous solution, and 3 represents a waterproofing agent.

The laminate of FIG. 1 is a basic type of laminate according to the invention, wherein aqueous solution 2 is laminated between substrates 1 which have at least a part of the permeability so that aqueous solution 2 has direct visibility. The layer thickness of the aqueous solution 2 is not particularly limited, but may be about 0.1 to 2 mm, and sufficient light blocking may be achieved with a thickness of about 0.2 mm. Repellent 3 prevents the evaporation of water and may be provided around the substrate or outside of the substrate. Waterproofing agents that may be used include for sealing epoxy-based resin adhesives (e.g., Flep of Toray-Thiocoll Co.), acrylic-based resin adhesives (e.g., photosensitive resins manufactured by Sunrise Meisei Co., Photobond) and insulating glass. Silicone repellents, urethane repellents, polysulfide repellents and isobutyrene repellents used. In particular, although not shown, it has been found that it is desirable to provide a double waterproofing agent between at least the substrate as an isobutyrene waterproofing agent (internal) and an adhesive waterproofing agent (outer) to the glass substrate. Naturally, if contact between the isobutylene waterproofing agent and the aqueous solution 2 is not suitable, a barrier layer may be provided to avoid such contact.

Although not specifically shown, in order to ensure the thickness adjustment, a space filling material (glass beads, ceramic beads, resin beads or metal beads, etc.) may be used in the aqueous solution 2 instead of the waterproofing agent. Space-filled materials can be used to maintain liquid thickness, especially for sizes of 50 cm square or more. In addition, a substance whose refractive index is close to the aqueous solution 2 is preferable because it is difficult to distinguish from each other. A wide variety of space fillers may be used for the sealing portion, including steel wool, glass fibers, sheet metal and the like.

The substrates must be transparent so that at least one of the substrates is visible so that the aqueous solution 2 can be seen directly, and a number of different materials, including glass, plastics, ceramics, metals, etc., which can be simple or surface-treated complex materials if paneled, It may be preferably used in various combinations. Glass panels used as window materials include simple single panel glass, tempered glass, wire glass, heat-absorbing glass, heat-reflecting glass, heat-absorbing / reflecting glass, sandwich glass, sun protection glass, permeable conductive glass, insulating glass, Multilayer glass, transparent single panel glass, or polycarbonate composite glass, and the like, and substrate pairs of appropriate combinations of various types and thicknesses may also be used depending on the purpose. In particular, the composite of multilayer glass provides a laminate having both thermal insulation and light blocking properties, which is very useful in energy saving and comfort.

When the present invention is used for a window, since it is subjected to direct sunlight for a very long time, it is preferable to use the sunscreen glass at least on the outer surface of the substrate. Examples include green glass, coated glass coated with an ultraviolet absorbing layer and ultraviolet absorbing sandwich glass. When the thickness of the substrate on the outer surface of the window is about 5 mm or more, the ultraviolet transmittance of wavelength 330 nm or less is remarkably reduced, and thus thicker substrates are naturally advantageous for selective light blocking because ultraviolet absorption also increases with thickening. Windows are sometimes used transversely and sometimes as species, and in longitudinal situations it is necessary to pay special attention so that the viscosity of the aqueous solution 2 is not too low, as this sometimes leads to irregular convection due to temperature differences.

The laminated body of FIG. 2 is a laminated body arrange | positioned between the same base materials together using the aqueous solution 2 which advances a reversible change, and the transparent liquid 4 which does not change. Transparent liquids 4 without reversible change are liquids or gels whose light permeability is not particularly affected even at high temperatures. As an example thereof, the aqueous solution of this invention to which no bipolar substance was added is mentioned. As the molecular weight increases, self-diffusion reaches negligible levels, and therefore should be at least 2000, preferably at least 3000 and more preferably at least 5000. Visibility can also be ensured by providing a liquid that can be miscible with water (eg, liquid paraffin, silicone oils, silicone gels, etc.). Further modifications not otherwise indicated are laminates in which the layer thickness of the aqueous solution 2 is continuously changed for continuous adjustment of the degree of cloud opacity, and irregularities in the substrate to change the layer thickness of the aqueous solution 2 for guaranteed visibility. Included laminates are included. They can be used, for example, to ensure partial visibility in advertising devices that initiate car tail windows and image data. There are also methods of providing heating components, which provide a broader use of the laminates of the invention. They may also be provided as electronic curtains as partitions to block visible lines by artificial thermal control. Heating components include permeable conductive films, carbon pastes, metal pastes, metal wires, and barium titanate-based ceramics, and heating components capable of heating and cooling (eg, Thermopanel manufactured by Komatsu Electronics Co., Ltd.). You can also use The heating device may be placed only inside or outside the substrate and over or in part of the entire substrate surface. The heating components may also be divided into aligned or stripped arrangements. In addition, image data may also be disclosed by selectively heating the substrate surface with infrared light (such as from a laser) or by using a heating component formed into a matrix.

Examples of windows according to the present invention include general building windows, windows of vehicles such as automobiles or trains, and windows of transportation engines such as ships, airplanes and elevators. Windows are quoted in a comprehensive sense and include glass ceilings in shopping malls and atriums, door windows and partitions, and doors, columns and walls of fully permeable glass. Of course, as an example of a broader application method, the present invention includes a window unit which is used in combination with a conductive material chassis or a vehicle frame and is simply mounted on a building part in the same manner as a building, a vehicle, and the related art method, and a frame suitable for each application. Also included are laminates that form mounted laminates. The use of such unit structures is effective in making it possible to seal the laminate more reliably, to prevent evaporation of water due to penetration, and to prevent deterioration of the sealing layer by light. This is particularly effective for semi-permanent applications or under harsh conditions such as in the case of typical building windows and vehicle windows.

Furthermore, in the laminate of the present invention, this aqueous solution is contained in hollow bodies, spheres, microcapsules, or resin sheets for lamination by applying to sheets, whereby a part thereof is permeable and the aqueous solution is directly Also included is a method of use provided that it can be viewed. Particularly useful are hollow bars as shown in FIG. 3. A wide variety of longitudinal cross-sectional shapes can be employed for the purpose, including round, hexagonal, square, triangular and flat shapes. The waterproofing agent may also be fused glass for full sealing. In addition, aligning the plurality of hollow rods in a plane can be used to perform light blocking action. Examples of such applications include roller screens and blinds. Of course, this hollow rod can also be disposed between a pair of substrates. Thus, the hollow rods in FIGS. 3A and 3B are also within the scope of the present invention under the generic definition of the laminate. In addition, laminates which become sheet objects having a form of a type such as a cup or a basin are also included in the scope of the present invention.

Next, an embodiment will be described for further explanation of the present invention, which should be construed as not limiting the present invention to this embodiment.

Example 1

A colorless and permeable aqueous solution at 20 ° C., an average of about 20,000 dissolved in 3 parts by weight of triol, 35 parts by weight of polyoxypropylene glycerin (Newpol GP-600 from Sanyo Chemical Industries, Ltd.) with an average molecular weight of 600 A polyvinyl alcohol having a molecular weight (Gohsenol GL-03 of Nippon Gohsei Co., Ltd., about 87.5% of saponification) was added to 100 parts by weight of an aqueous polymer solution. A 2.4 mm diameter fibrous isobutyl repellent was applied around the 30 cm-square, 3 mm thick soda-lime glass plate, an aqueous solution was placed in the center of the plate, and the corresponding plate was placed lightly before the corresponding plate. Was pressed under a reduced pressure of about 1 Torr in vacuo to push the isobutyl waterproof agent to achieve adhesion. Thereafter, the adhesive photosensitive resin to the glass was allowed to flow into the gap surrounding the outermost periphery and irradiated with light to complete the sealing. As a result, a bubble-free laminate having a thickness of 0.3 mm was obtained. This laminate had satisfactory reversible stability at room temperature and 60 ° C. and sufficient sustained stability after 12 hours at 60 ° C. without phase separation. In addition, cloud light scattering began to be observed from about 41 ℃, the cloud light blocking was gradually increased, the effect of blocking glare was confirmed while maintaining visibility.

Example 2

15 parts by weight of a colorless and permeable aqueous solution A and aqueous solution B at 20 ° C were monoether, poly (oxyethylene / oxypropylene) glycol butyl ether (Sanyo Chemical Industries, Ltd. Newpol 50HB-55) with an average molecular weight of 240 Another monoether, 6.5 parts by weight of poly (oxyethylene / oxypropylene) glycol butyl ether (Newpol 50HB-5100 by Sanyo Chemical Industries, Ltd.) having an average molecular weight of 3750 dissolved in 2 parts by weight of a 5 wt% aqueous sodium chloride solution 1 part by weight of polyvinyl alcohol 1 was added to 100 parts by weight of an aqueous polymer solution. Using these, laminate A and laminate B were produced in the same manner as in Example 1. These two laminates had satisfactory stability at room temperature and 60 ° C. and sufficient sustained stability after 12 hours at 60 ° C. without phase separation. In addition, cloud light scattering began to be observed from 32 ° C. for Stack A and from 38 ° C. for Stack B. Cloud light was gradually increased to confirm the anti-glare effect while maintaining visibility. It was made.

Example 3

10 weight percent of a colorless and permeable aqueous solution at 20 DEG C of polyoxypropylene-2-ethyl-2-hydroxymethyl-1,3-propanediol (Newpol TP-400 by Sanyo Chemical Industries, Ltd.) having an average molecular weight of 400 Part was prepared by adding 100 parts by weight of 10 parts by weight of an aqueous solution of polyvinyl alcohol (Gohsenol NH-26 from Nippon Gohsei Co., Ltd., about 99.5% of saponification degree, average molecular weight of about 120,000) dissolved in 80 parts by weight of pure water. A laminate was prepared in the same manner as in Example 1. This laminate had satisfactory reversible stability at room temperature and 60 ° C. and sufficient sustained stability after 12 hours at 60 ° C. without phase separation. In addition, the cloud light scattering properties began to be observed from about 31 ℃, the cloud light blocking was gradually increased and the effect of blocking glare was confirmed while maintaining visibility.

Example 4

A colorless, permeable aqueous solution at 20 ° C., polyoxypropylene-2-ethyl-2-hydroxymethyl-1,3-propanediol (Newpol TP-400 from Sanyo Chemical Industries, Ltd.) 6 having an average molecular weight of 400 Parts were prepared by adding 10 parts by weight of polyvinyl alcohol (Nippon Gohsei Co., Ltd. Gohsenol NL-05, saponification degree of about 98.5%, average molecular weight of about 20,000) dissolved in 30 parts by weight of pure water to 100 parts by weight of an aqueous polymer solution. . A laminate was prepared in the same manner as in Example 1. This laminate had satisfactory reversible stability at room temperature and 60 ° C. and sufficient sustained stability after 12 hours at 60 ° C. without phase separation. In addition, cloud light scattering began to be observed from about 34 ℃, the cloud light blocking was gradually increased to block the glare was confirmed while maintaining visibility.

Example 5

Colorless and permeable aqueous solution A, aqueous solution B, aqueous solution C and aqueous solution D at 20 ° C. were each weighed 6.5 parts by weight and 1.5 parts by weight of poly (oxyethylene / oxypropylene) methyl polysiloxane (KF6012 manufactured by Shin-Etsu Chemical Industries, Ltd.). Part, 16 parts by weight and 32 parts by weight of sodium carboxymethyl cellulose (CMC Daicel 1260 of Daicel Chemical Industries, Ltd., etherification degree 0.90) dissolved in 50 parts by weight of pure water was added to 100 parts by weight of an aqueous polymer solution. It was. Using these, laminate A, laminate B, laminate C and laminate D were produced in the same manner as in Example 1. These four laminates had satisfactory stability at room temperature and 60 ° C. and sufficient sustained stability after 12 hours at 60 ° C. without phase separation. In addition, the cloud light scattering property was observed in the laminate A from 30 ℃, cloud light blocking is suddenly generated by the temperature change, and sufficient light blocking is provided to confirm the anti-glare effect. Stack B began to show light scattering at nearly the same temperature as Stack A, but sufficient visibility was observed while maintaining visibility even at high temperatures. Laminate C began to exhibit light-scattering light scattering at about the same temperature as that of the laminate A, and light blocking occurred suddenly with temperature change, and thus had a stronger light blocking effect than the laminate A. Stack D began to show cloud-scattering light at nearly the same temperature as Stack A, but at a high temperature of about 40 ° C., light blocking properties were almost the same as Stack C.

Example 6

Aqueous solution A, aqueous solution B, aqueous solution C, aqueous solution D, aqueous solution E, and aqueous solution F were prepared by poly (oxyethylene / oxypropylene) methyl polysiloxane (KF615A of Shin-Etsu Chemical Industries, Ltd., TSF4450 of Toshiba Silicone Co., respectively. 6.5 parts by weight of TSF4452 and TSF4440, and SH8700 and SF8410) of Toray-Dow Corning Silicone Co., Ltd. were added to 100 parts by weight of the aqueous solution of carboxymethyl cellulose polymer of Example 5. Using these, the laminate A, the laminate B, the laminate C, the laminate D, the laminate E and the laminate F were produced in the same manner as in Example 1 above. All of these laminates had satisfactory stability at room temperature and 60 ° C. and sufficient sustained stability after 12 hours at 60 ° C., without phase separation. In addition, the cloud light scattering properties are 41 ° C. for the laminate A, 5 ° C. for the laminate B, 25 ° C. for the laminate C, 65 ° C. for the laminate D, and 30 for the laminate E. In the case of ℃ and laminate F, it was observed from 33 ℃, cloud light blocking was suddenly generated by the temperature change to ensure sufficient anti-glare effect. Thus, it has been found that by changing the type of poly (oxyethylene / oxypropylene) methyl polysiloxane used, reversible changes can be achieved in a uniform state over a wide temperature range from low to high temperatures. Changes in turbidity at various ratios also resulted in specific aspects.

Example 7

To the aqueous solution A and the aqueous solution B, 6.5 parts by weight of propylene glycol (Newpol PP-400 and PP950 of Sanyo Chemical Industries, Ltd., respectively) having an average molecular weight of 400 and 950 were added to 100 parts by weight of the aqueous solution of carboxymethyl cellulose polymer of Example 5. Prepared by addition. Using these, laminate A and laminate B were produced in the same manner as in Example 1. These laminates had satisfactory stability at room temperature and 60 ° C. and sufficient sustained stability after 12 hours at 60 ° C. without phase separation. In addition, cloud light scattering properties began to be observed with sufficient light blocking as the temperature was changed from about 60 ° C. for the laminate A and from about 18 ° C. for the laminate B, so that the anti-glare effect was confirmed. .

Example 8

An aqueous solution was prepared by adding 20 parts by weight of TP-400 of Example 4 to 100 parts by weight of the aqueous polymer solution of Example 5 containing 5 parts by weight of sodium carboxymethyl cellulose dissolved in 100 parts by weight of pure water. Using this solution, a laminate was prepared in the same manner as in Example 1. These laminates had satisfactory stability at room temperature and 60 ° C. and sufficient sustained stability after 12 hours at 60 ° C. without phase separation. In addition, cloud light scattering began to be observed from about 60 ° C. in this laminate, and cloud light blocking appeared suddenly by changing the temperature.

Example 9

KEPS-1224A, an ionic water-soluble polymer of Daiichi Kogyo Seiyaku Co., Ltd., prepared by adding a carboxyl group to a hydroxy group of polyvinyl alcohol having an average molecular weight of 100,000 to about 12% relative to this hydroxy group Purification by removing salts. A colorless and transparent aqueous solution A was prepared at 20 ° C. by adding 10 parts by weight of KF6012 of Example 5 to 100 parts by weight of purified KEPS-1224A dissolved in 100 parts by weight of pure water and 100 parts by weight of aqueous polymer solution, and was also colorless at 20 ° C. And a transparent aqueous solution B was prepared by adding 10 parts by weight of TP-400 of Example 4 to 100 parts by weight of 20 parts by weight of a polymer solution of purified KEPS-1224A dissolved in 100 parts by weight of pure water. Using these, laminate A and laminate B were produced in the same manner as in Example 1. Both of these laminates had satisfactory stability at room temperature and 60 ° C. and sufficient sustained stability after 12 hours at 60 ° C. without phase separation. In addition, cloud light scattering began to be observed at about 26 ° C. for laminate A and at about 27 ° C. for laminate B, and cloud light blocking appeared suddenly by changing the temperature to prevent sufficient light blocking and glare. The effect was observed.

Example 10

A colorless and transparent aqueous solution at 20 ° C., 0.5 parts by weight of polymer of average molecular weight 5,000,000 sodium polyacrylate (Aqualic IH of Nippon Shokubai Co., Ltd.) dissolved in 10 parts by weight of KF6012 of Example 5 in 100 parts by weight of pure water Prepared by adding to 100 parts by weight of an aqueous solution. A laminate was prepared in the same manner as in Example 1. This laminate had satisfactory stability at room temperature and 60 ° C. and sufficient sustained stability after 12 hours at 60 ° C. without phase separation. In addition, cloud light scattering began to be observed at about 32 ° C., and cloud light blocking suddenly occurred by changing temperature, so that sufficient light blocking and anti-glare effects were observed.

Example 11

The sodium of Example 10 wherein colorless and clear aqueous solution A, aqueous solution B and aqueous solution C were dissolved at 20 ° C., respectively, in 100 parts by weight of pure water of Leocol SC-70, Leocol SC-80 and Liponox NC-86 from Lion Corp. It was prepared by adding 5 parts by weight of polyacrylate to 100 parts by weight of an aqueous polymer solution. Stack A, Stack B and Stack C were prepared in the same manner as in Example 1. All of these laminates had satisfactory stability at room temperature and 60 ° C. and sufficient sustained stability after 12 hours at 60 ° C., without phase separation. In addition, cloud light scattering properties began to be observed at about 32 ° C. for laminate A, about 38 ° C. for laminate B, and about 32 ° C. for laminate C, and satisfactory cloud light blocking was observed. .

The effectiveness of the present invention is based on the discovery of an aqueous solution composition consisting of an aqueous solution of a bipolar material having a cloud point, which allows for a reversible change between a transparent state and a cloud-like light-blocking state, which is oily at room temperature and uniform in room temperature water. And a laminate containing an aqueous solution which proceeds stably and reversibly by temperature-dependent sol-emulsion phase transition without phase separation between the aqueous solution layer and the oil layer as the temperature increases. To provide. The addition of the bipolar material to aqueous solutions of water soluble polymers has surprisingly found that the resulting aqueous solutions lead to excellent sol-emulsion phase transitions that can be stably and reversibly modified. It is believed that this can be explained by the fine agglomerates of the bipolar material generated by heating being trapped in the water soluble polymer chain and placed in a uniform emulsion state. As a result, cloud light blocking was caused by light scattering due to the difference in refractive index between this fine aggregate and the medium. This laminate is used as a window, which window is heated by direct contact with direct sunlight, and the irradiation site is deformed into a cloud state in a transparent state to block direct sunlight and prevent glare. This change from transparent to translucent to opaque occurred spontaneously due to the balance at that time, caused by the season or by the weather. Thus, it is possible to provide a self-reactive energy saving window that conveniently blocks direct sunlight by the direct energy of the light beam.

Claims (18)

A laminate comprising an aqueous solution, wherein two molecules dissolved in water exhibit a cloud-scattering property that aggregates with increasing temperature to reduce light transmission, and at least partially transparent to allow direct visibility of the aqueous solution. A vinyl-based nonionic water soluble polymer or ionic that is sealed between the dogs and that the aqueous solution undergoes a temperature dependent reversible sol-emulsion phase transition and exhibits no cloud point at temperatures below about 45 ° C., with 100 parts by weight of water as solvent. A laminate comprising an aqueous solution, wherein the aqueous solution is composed of 0.5 to 45 parts by weight of a bipolar substance dissolved in 100 parts by weight of a 0.5 to 40 parts by weight solution of a water-soluble polymer and exhibits a cloud point and is uniformly dissolved in water at room temperature. The laminate according to claim 1, wherein said ionic water soluble polymer is sodium carboxymethyl cellulose. The laminate according to claim 1, wherein said vinyl-based nonionic water soluble polymer is polyvinyl alcohol. The laminated body of Claim 3 which adds 0.1-10 weight part of neutral inorganic salts to 100 weight part of said water. The laminate according to claim 1, wherein the bipolar material contains at least an oxypropylene group. The laminate according to claim 5, wherein the bipolar material is dimethylpolysiloxane modified by the addition reaction of hydroxyethylene and hydroxypropylene. The laminated body of any one of Claims 1-6 which consists of a compound of various aqueous solution, or the compound of aqueous solution and a transparent liquid. The laminate according to any one of claims 1 to 7, wherein at least a heating component that can be heated is provided. A window using a laminate composed of an aqueous solution, wherein the molecules dissolved in water exhibit a cloud-scattering property that aggregates with increasing temperature to reduce light transmittance, and is at least partially transparent to allow direct visibility of the aqueous solution. A vinyl-based nonionic water soluble polymer which is sealed between two substrates in which the aqueous solution undergoes a temperature dependent reversible sol-emulsion phase transition and exhibits no cloud point at temperatures below about 45 ° C., with 100 parts by weight of water as solvent. Or 0.5 to 45 parts by weight of a bipolar substance dissolved in 100 parts by weight of a solution of 0.5 to 40 parts by weight of an ionic water-soluble polymer, which is an oil phase at room temperature and uniformly dissolved in water at room temperature. Windows using laminates. 10. The window of claim 9, wherein the ionic water soluble polymer is sodium carboxymethyl cellulose. 10. The window of claim 9, wherein the vinyl-based nonionic water soluble polymer is polyvinyl alcohol. The window according to claim 11, wherein 0.1 to 10 parts by weight of a neutral inorganic salt is added to 100 parts by weight of water. 10. The window of claim 9, wherein the bipolar material contains at least an oxypropylene group. The window according to any one of claims 9 to 13, which is composed of a combination of various aqueous solutions or a combination of an aqueous solution and a transparent liquid. The window according to any one of claims 9 to 14, wherein at least one of the substrates is an ultraviolet absorbing glass, and the ultraviolet absorbing glass faces outward. The window according to any one of claims 9 to 15, wherein at least one of the substrates is a multilayer glass. The window according to claim 9, wherein at least a heating component capable of heating is provided. The window according to any one of claims 9 to 17, wherein the unit consists of a combination of the laminate and the structure chassis or the vehicle frame.