JP3337810B2 - Autonomous response laminate, manufacturing method thereof and window using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of shielding a light beam by irradiating a laminated body with sunlight rays, whereby the aqueous solution changes to cloudy turbidity due to the thermal action due to the light absorption. This enables a building, a vehicle, or the like having a window that selectively blocks light only on the surface irradiated with direct light. Also, by combining with a heat element, it can be used as a partition with an electronic curtain or an indoor window such as a door.

[0002]

2. Description of the Related Art In recent years, there has been proposed a dimming glass in which light is reversibly controlled physicochemically using a composite glass incorporating a functional material instead of a mechanical method. For example, there are liquid crystal, electromic, fine particle polarization alignment, photochromic, thermochromic, and the like. Also,
Heat ray absorbing glass, heat ray reflecting glass and the like have been used for windows in order to prevent solar energy from entering the living space.
However, heat-absorbing glass and heat-reflecting glass certainly prevent solar energy from entering the living space, but have the disadvantage that coloring and surface glare remain, reducing the original colorless and transparent nature of the glass. Even from the surface, the control of visible light, which has about half the energy of sunlight, is still insufficient. In addition, as described in detail in the New Glass Forum of the 1991 New Glass Industry Survey and Research Report (Global Warming Prevention Measures) of the New Glass Forum, the light control glass has a relationship with energy saving measures, The development of is strongly expected.

[0003] Accordingly, the present inventor has noticed that sunlight is irradiating windows. Based on the presence or absence of this energy, the window glass autonomously responded and caused a transparent-opaque reversible change to make the living space comfortable. 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, the photochromic method and the thermochromic method can be selected.However, compared to the photochromic method, which has a complicated operation mechanism and has wavelength dependence, the thermochromic method depends only on the thermal effect that can easily adjust the temperature as needed artificially. Chromic method is excellent. Note that solar energy reaching the earth is in the range of 290 nm to 2140 nm, of which about 80% is in the visible to near infrared region from 400 nm to 1100 nm, and the visible region is larger than the near infrared region. There is a need to. 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 when light is irradiated on an object, light is absorbed and converted into heat, and the heat causes the temperature of the object to rise. In addition,
The temperature may be artificially controlled by a thermal element for use.

[0004] Materials used in the thermochromic method are disclosed in the above-mentioned documents, but have insufficient properties and have not yet been put to practical use. Therefore, in order to be widely used as thermochromic 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. Achromatic or unchanged. 5. Be durable. 6. No pollution such as toxicity. As an autonomous response material that may satisfy these conditions, we focused on an aqueous solution that undergoes a phase transition from colorless and transparent to a cloudy and opaque state when the temperature of the aqueous solution rises. This is also advantageous from the viewpoint of fail-safe, since it is normally transparent and light-opaque light-shielded by the addition of energy.

Conventionally, the cloud point phenomenon of nonionic surfactants is well known as an aqueous solution which becomes cloudy and opaque due to a rise in temperature, and its application to this purpose has been studied. Phase separation easily occurred, and the above conditions 1 and 2 could not be satisfied. Also, isotropic aqueous solutions of nonionic water-soluble polymers (for example, polyvinyl alcohol partially acetalized product, hydroxypropylcellulose, N-isopropyl-acrylamide polymer, etc.) are known to show a cloudy change, Similarly, application to this purpose (Japanese Utility Model Application Publication No. 41-19256, Japanese Patent Application No. 51-04985)
6, Japanese Patent Publication No. 61-7948), however, cannot satisfy the above conditions 1 and 2, and has not been put to practical use. At room temperature, a layered product of a water-soluble polymer aqueous solution takes a colorless, transparent, and uniform aqueous solution state.However, when heated and left in a cloudy, opaque state, phase separation occurs, and unevenness in the aqueous solution occurs to maintain uniformity. Stable reversible reversible changes could not be obtained. Furthermore, when the laminate is left standing vertically, it cannot be used because of sedimentation and separation of cloudy aggregates and unevenness due to a difference in specific gravity. In particular, in order to provide practicality, it is necessary to control the white turbidity onset temperature. Therefore, when an inorganic electrolyte is added, this phenomenon has become more remarkable. This is because the destruction of the bound water is caused by the ions, and the hydrophobic bond of the water-soluble polymer is strengthened and the cohesive force is increased. Further, when the concentration of the water-soluble polymer was increased in order to sufficiently shield direct light, sedimentation and separation due to cloudiness aggregation were easily caused. If this light-shielding property is determined based on the thickness of the low-concentration aqueous solution layer, there is a problem that the low-viscosity liquid splatters at the time of breakage, causing contamination, and has not yet been put to practical use. further,
Gels obtained by mixing various compounds (international application PCT / E
P86 / 00360), but there is still a problem with stability and it has not been put to practical use.

However, the present inventor has noticed that, among water-soluble polymers, an aqueous solution of a polysaccharide derivative having a hydroxypropyl group having a good hydrophobic-hydrophilic balance can sufficiently shield the direct sunlight even in a thin film. Therefore, attention was focused on polysaccharides in the main chain and hydroxypropyl groups in the side chains. As a representative example, cellulose having structural stability was selected as the main chain, and an aqueous solution of hydroxypropyl cellulose was examined in detail.

As already known (Japanese Patent Publication No. 60-2343), an aqueous solution containing 50% by weight or more of hydroxypropylcellulose becomes a lyotropic high-molecular cholesteric liquid crystal, exhibits properties unique to cholesteric liquid crystals, and A rainbow-colored interference color that is highly chromatic with a viewing angle dependence due to selective scattering of light rays is shown. Further, the dislocation temperature shifts depending on the molecular weight, the concentration, the amount of the electrolyte added, and the like. Therefore, the present inventor further studied to satisfy Condition 4 above. The selective scattering wavelength of this liquid crystal is red-shifted due to a decrease in concentration or an increase in temperature. Therefore, the density was reduced to a density (for example, 56% by weight) at which near infrared rays were selectively scattered at around 20 ° C., so as to satisfy the achromatic condition. When the temperature was around ℃, selective scattering of red was observed, which was unsatisfactory. As described above, the change in color due to the temperature and the viewing angle hinders the degree of freedom in designing a building, a vehicle, and the like, so that it was almost impossible to use the color. Therefore, when the concentration was further reduced (for example, 52% by weight), the liquid crystal phase and the isotropic phase were changed to a two-phase state. These phenomena were slightly changed depending on the molecular weight, but were also observed. Also,
Observation from a right angle, that is, from the front, even in a colorless and transparent state that selectively scatters near infrared rays, there is still haze due to scattering and unevenness inherent to the liquid crystal composition, that is, a monodomain state cannot be obtained in a large area and it is transparent like glass Sex was not obtained. Further, once frozen, even when the temperature was returned to room temperature, unevenness of cholesteric phase linear defects occurred.

[0008] In order to be widely used in buildings, vehicles and the like with a large area like conventional glass, it is very important to ensure the original colorless transparency of glass without dependence on viewing angle. Therefore, the present inventor has focused on again an isotropic aqueous solution of a polysaccharide derivative that does not show a viewing angle dependency in both a transparent state and a cloudy opaque state, and as a result, the reversible change of the isotropic aqueous solution shows phase separation and unevenness. Thus, the present invention has been able to be repeated stably without any problem, and has solved a defect which has been a fundamental problem and has not been put to practical use.

[0009]

SUMMARY OF THE INVENTION A laminate capable of repeatedly and stably reversibly changing a transparent state and a cloudy opaque state by a temperature change without having a viewing angle dependency using an isotropic aqueous solution of a polysaccharide derivative, and a method for producing the same. And to provide windows using it.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and polysaccharide derivatives dissolved in water aggregate due to an increase in temperature to cause cloudy scattering, An isotropic aqueous solution having a low light transmittance, at least a part of which is transparent, in the autonomous response laminate sealed between two substrates capable of directly viewing the aqueous solution,
The isotropic aqueous solution has a weight average molecular weight of about 10,000 to
About 200,000 to about 25 to about 450 weight with respect to the polysaccharide derivative to 100 parts by weight of the polysaccharide derivative 100 parts by weight of
Parts of water and an amphiphile having a molecular weight of 100 to 3,000 from about 110 to about 2,000.
An autonomous response laminate that is a solution dissolved in 0 parts by weight,
The weight average molecular weight is about 10,000 to about 20
From amphiphilic Busshitsuko having a molecular weight of the amount of water and 100 to 3,000 for the polysaccharide derivative 100 parts by weight of about 25 to about 450 parts by weight based on the polysaccharide derivative 100 parts by weight of 0,000 An aqueous isotropic medium formed by dissolving in about 110 to about 2,000 parts by weight of an aqueous medium is disposed between at least a part of two substrates which are at least partially transparent and allow the aqueous solution to be directly viewed. A method for producing an autonomous response laminate including encapsulation , and an isotropic aqueous solution in which a polysaccharide derivative dissolved in water is aggregated due to an increase in temperature to cause cloudy scattering and reduce light transmittance, At least partially transparent,
In a window using an autonomous response laminate sealed between two substrates capable of directly viewing the aqueous solution, the isotropic aqueous solution has a weight average molecular weight of about 10,000 to about 200,
An aqueous medium comprising 100 parts by weight of a polysaccharide derivative of about 000 to about 25 to about 450 parts by weight of water and 100 parts by weight of the polysaccharide derivative, and an amphiphilic substance having a molecular weight of 100 to 3,000. A window is provided which is a solution dissolved in about 110 to about 2,000 parts by weight.

[0011] The aqueous solution used in the present invention is a polysaccharide derivative which becomes an isotropic aqueous solution in which the polysaccharide derivative dissolved in water is aggregated due to an increase in temperature to cause cloudy scatter and reduce light transmittance. It is an autonomous response type isotropic aqueous solution which has a basic composition of a water-soluble substance and water and satisfies the following conditions. 1. The transparent-opaque phase change is reversible. 2. Reversible changes can be repeated without phase separation. 3. Low phase transition onset temperature. 4. Achromatic or unchanged. 5. Be durable. 6. No pollution such as toxicity. That is, the purpose was satisfied for the first time by adding the amphiphilic substance to the aqueous solution of the polysaccharide derivative. As described above, the present invention has made it possible for the first time to be able to stably and reversibly change an isotropic aqueous solution composed of a polysaccharide derivative which becomes cloudy and opaque with an increase in temperature.

This polysaccharide derivative is composed of a nonionic functional group and is uniformly dissolved at room temperature even at a high concentration of about 25% to about 50% by weight to form an aqueous solution. It can be used in the present invention. The raw material polysaccharide is not particularly limited, cellulose,
There are pullulan, dextran and the like, which can be widely used, and specific examples of the derivatives include hydroxypropylcellulose, hydroxypropylpullulan, and hydroxypropyldextran obtained by adding propylene oxide at a high level. Among them, cellulose derivatives are important because they have high stability. Unless otherwise specified, the description is mainly made of a cellulose derivative, but of course, the present invention is not limited to this. If the weight average molecular weight of the polysaccharide derivative is small, aggregation is small and cloudiness is weak, and if it is large, aggregation is too large due to the polymer effect and phase separation is liable to occur, which is not suitable. Therefore, from about 10,000 to about 200,000
And preferably from about 15,000 to about 100,000. Further, two or more kinds of derivatives having a molecular weight distribution may be mixed and used.

Cellulose becomes soluble in many solvents when a functional group is added. In order for such an aqueous solution of a cellulose derivative to aggregate and become cloudy due to an increase in temperature, a hydrophobic bond (binding force due to an increase in affinity between hydrophobic groups due to destruction of bound water) must act on the functional group. There is. For this purpose, if the functional group is an ionic group, ionic repulsion acts and is unsuitable for this purpose, and a hydrophilic group such as a hydroxyl group, an ether bond, an ester bond, an amide bond, and a hydrophobic group, For example, a compound having a methyl group, an ethyl group, and the like is preferably a nonionic group. For example, when comparing a hydroxyethyl group and a hydroxypropyl group, hydroxyethyl cellulose has a hydrophilic group and is water-soluble, but does not have a hydrophobic group and thus cannot be aggregated and does not produce a cloudy state. In contrast, hydroxypropylcellulose is
It is water-soluble and can produce an agglomerated cloudy state. Thus, as represented by a hydroxypropyl group, a functional group having both a nonionic hydrophilic group and a hydrophobic group is added, and a high concentration of about 25% to about 50% by weight at room temperature is added. However, a water-soluble polysaccharide derivative that is uniformly dissolved in water is useful in the present invention. The addition of the functional group may be a single kind or a plurality of kinds, and is not particularly limited.
For example, there are a derivative in which an additional functional group is added to a hydroxyl group of an added hydroxypropyl group, a derivative in which a hydroxypropyl group is added as an additional functional group (for example, addition to hydroxyethyl cellulose), and the like, in which a single functional group is added. It is not limited to derivatives. These functional groups and their addition methods are disclosed in detail in Daikagaku Kagaku, Vol. 19, published by Asakura Shoten. By combining these methods with general addition reactions, hydroxyl groups, lower alkyl groups, halogens, By adding a group or the like, the hydrophilic-hydrophobic balance can be adjusted.

The amphiphilic substance is a compound having both a hydrophilic part and a hydrophobic part, and functions to prevent phase separation when the above-mentioned isotropic aqueous solution of the polysaccharide derivative is clouded and agglomerated. The principle of action of the amphiphile is that when a polysaccharide derivative is clouded and agglomerated, it is taken up inside the aggregate at the molecular or micellar level and also incorporates water molecules, making the water molecules bound water. It appears to be that no separation occurs. However, even when the amphiphile is added, the concentration of the polysaccharide derivative in water is about 18%.
Weight percent or less, more certainly about 25 weight percent or less,
Insufficient incorporation of water molecules can lead to increased free water, causing water separation and phase separation. In fact, in general, the addition of amphiphiles weakens aggregation and shifts the onset temperature of cloudy aggregation to a few degrees higher. However, the onset temperature of cloudy aggregation can be easily controlled by the composition of the aqueous medium (mixing ratio of water-amphiphilic molecules), the concentration of the polysaccharide derivative-aqueous medium, etc. ,
It can be further lowered to room temperature. Further, the onset temperature of cloudy aggregation can also be lowered by adding an electrolyte such as sodium chloride, and the onset temperature can be controlled by the amount of addition. This is because ions have a function of promoting the hydrophobic bonding by breaking the bound water having an ice-like structure near the hydrophobic group. Furthermore, at this time, the hydrophobic group of the amphiphile forms a hydrophobic bond with the hydrophobic group of the polysaccharide derivative, and the hydrophilic group maintains the uptake of water molecules by hydration, and It is likely that the specific action keeps the overall phase balance and thus prevents phase separation. On the other hand, when the amphiphilic substance does not exist, a hydrophobic bond is generated between the molecules of the polysaccharide derivative, and together with the macromolecular effect, aggregation becomes dense, phase separation occurs, and the system becomes irreversible. Therefore, by laminating this isotropic aqueous solution between the substrates, having an onset temperature of cloudy aggregation at or near room temperature,
An unprecedented autonomous response laminate that can stably and repeatedly change reversibly can be obtained. The hydrophilic portion of the amphiphilic substance is preferably neutral for the stability of the aqueous solution, but may be an ionic one, for example, a sodium salt of a sulfonic acid group. , For example, a hydroxyl group.

This basic principle can be widely used without particular limitation as long as it is a polysaccharide derivative having a hydrophobic group that causes cloudiness aggregation when the temperature of an aqueous solution rises due to the effect of hydrophobic bonding. On the low concentration side, the ratio of the water-polysaccharide derivative is preferably about 18% by weight or more, more preferably about 25% by weight or more, as a ratio of the water-polysaccharide derivative from the phase separation of water. On the high concentration side, it is not necessary to make it particularly high.On the contrary, the effect of the hydrophobic bond is weakened and phase separation does not occur, but the cloudy light shielding is weakened and the viscosity becomes high, and it is difficult to laminate uniformly without bubbles. Therefore, it is preferably about 50% by weight or less. Therefore, the amount is not limited to about 50% by weight or less. For example, in the case where the amount of the amphiphilic substance is small and a liquid crystal phase such as hydroxylpropylcellulose exhibits an interference color, about 50% by weight is used. %, It is difficult to obtain a colorless and transparent isotropic aqueous solution. However, for example, a composition of 75% by weight of hydroxylpropylcellulose (the remaining 25% by weight is a 5% by weight aqueous solution of sodium chloride) may have an amphipathic substance, for example, polyoxypropylene 2-ethyl-2-hydroxymethyl- having a molecular weight of 400. 1,3-propanediol and the like are added as a solvent, and the ratio of hydroxylpropylcellulose to the total amount is about 30% by weight.
, A change in cloudiness appeared at about 67 ° C. By utilizing the solvent action of the nonionic amphiphile, the concentration (the ratio of the water-polysaccharide derivative) is not limited to about 50% by weight or less. In addition, from the standpoint of practicality, the production becomes much easier when the viscosity is reduced by controlling the overall ratio of the polysaccharide derivative. For example, the concentration of the polysaccharide derivative that can be obtained by ordinary stirring and mixing is about 30% by weight.
A moderately isotropic aqueous solution can be relatively easily defoamed. For example, this isotropic aqueous solution was placed on a substrate, laminated and pressurized, washed, and sealed around the periphery to obtain a bubble-free uniform laminate. Thus, the amount of water (which may contain electrolytes) is
About 25 to about 45 per 100 parts by weight of the polysaccharide derivative
It is preferably 0 parts by weight, preferably from about 50 to about 300 parts by weight.

Next, the amphiphilic substance is a compound having both a hydrophilic group and a hydrophobic group and being dissolved or uniformly dispersed in water at room temperature. Examples of the hydrophilic group include a nonionic group such as a hydroxyl group, an ether bond, an ester bond, and an amide bond, and an ionic group such as a sodium sulfonate base. Examples of the hydrophobic group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, and alkyl groups having 6 to 22 carbon atoms, such as a linear alkyl group, a branched alkyl group, and an aromatic alkyl group. There are non-ionic groups. When it is an ionic group, the pH of the resulting solution can be adjusted with a buffer, but a neutral salt is preferred from the viewpoint of stability. If the molecular weight of the amphipathic substance is too large, it tends to show irreversible changes due to the macromolecular effect, and the viscosity of the isotropic aqueous solution is increased, especially not a large molecular weight showing a better action,
Poor workability. Those having a halogen substituent such as chlorine (simply increasing the molecular weight) are not particularly effective. Therefore, this molecular weight may be about 3000 or less in the oligomer region, and is more preferably about 1,000 or less, because it is easy to use. On the other hand, if the molecular weight is too small, such as about 100 or less, it becomes difficult to exhibit the effect as the amphiphilic substance of the present invention, and preferably about 140 or more is useful for the present invention. In addition, since the ionic group has a very high hydrophilicity, the hydrophobic group is preferably an alkyl group having 6 to 22 carbon atoms for balancing.

Thus, examples of nonionic amphiphiles include dipropylene glycol monomethyl ether,
Tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, molecular weight 200 to
1,000 polypropylene glycol, molecular weight 400
~ 1,000 polyoxypropylene glycerin, molecular weight 300 to 800 polyoxypropylene 2-ethyl-
2-hydroxymethyl-1,3-propanediol, a block co-oligomer of polyoxyethylene-polyoxypropylene having a molecular weight of 300 to 2,000 and a proportion of about 50% by weight, a molecular weight of 250 to 3,000 and a proportion of about 50% by weight. Examples include poly (oxyethylene oxypropylene) glycol monobutyl ether, polyoxypropylene sorbitol having a molecular weight of 700 to 3,000, and polyoxyethylene higher fatty acid monoethanolamide (for example, Amidget 5C and 5L manufactured by Kawaken Fine Chemical Co., Ltd.). Thus, a compound having both a nonionic hydrophilic group such as a hydroxyl group and an ether bond and a hydrophobic group of a lower alkyl group having 1 to 4 carbon atoms, a polyoxyethylene group, and a hydrophilic group such as an amide bond. A compound having a hydrophobic group of a higher fatty acid group can be widely used. The amphiphile is used in an amount of about 0.5 to about 800 parts by weight, especially about 3 to about 600 parts by weight, based on 100 parts by weight of water present in the isotropic aqueous solution. Preferably, two or more amphiphilic substances may be mixed and used. Further, as described above, the amount of water is 100 parts by weight based on 100 parts by weight of the polysaccharide derivative.
Even if the amount is less than parts by weight, a colorless and transparent isotropic aqueous solution can be obtained by increasing the amount of the nonionic amphiphilic substance added. This seems to indicate that the amphiphile acts as a solvent. Further, when the amount of water is relatively small, the cohesive force is weakened, and a higher temperature is required to strongly shield the cloudiness. Thus, based on 100 parts by weight of the polysaccharide derivative, the amount of the aqueous medium consisting of water (which may include an electrolyte) and the amphiphile is about 100 to about 2,000 parts by weight. Preferably, it is about 150 to about 1,800 parts by weight. Further, as shown in the examples, by adjusting the composition of the isotropic aqueous solution, the white turbidity change rate and the white turbidity onset temperature can be freely designed,
The cloudiness onset temperature can be easily reduced to about 5 ° C. This is useful for indoor and outdoor windows requiring a translucent state at room temperature, electronic curtains such as indoor partitions for controlling the temperature with a thermal element, and special industrial applications (for example, temperature sensors). Examples of the ionic amphiphile include sodium lauryl sulfonate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene higher fatty acid monoethanolamide sulfonate (for example, Amidget S3L of Kawaken Fine Chemical Co., Ltd.), and amphoteric higher amphiphile. Fatty acid amidopropyl betaine (for example, Softakazoline CPB-R, LPB-R of Kawaken Fine Chemical Co., Ltd.)
Etc.). Thus, compounds having both an ionic hydrophilic group which becomes dissociated and neutral and a hydrophobic group such as an alkyl group having 6 to 22 carbon atoms can be widely used. The amount of this addition
It is within the non-ionic amphiphiles described above.

In order to shift the temperature at which the phase transition to the cloudy state occurs to a lower temperature, an inorganic electrolyte may be added as a temperature shifting agent. Preferably, a neutral salt is used, and examples thereof include sodium chloride, potassium chloride, lithium chloride, sodium nitrate, and sodium sulfate. The amount of addition is 100
0.1 to 10 parts by weight with respect to parts by weight,
Usually, about 1 to 8 parts by weight is preferable for use in windows and the like. Further, the substance which is a temperature shift agent and also has a solvent action includes low molecular alcohols (eg, ethyl alcohol, sec-butyl alcohol, propylene glycol, etc.) which are usually used as solvents. Ethyl alcohol and propylene glycol contribute to a rise in temperature, and sec-butyl alcohol contributes to a fall in temperature. The addition amount may be 0.5 to 500 parts by weight with respect to 100 parts by weight of water, and usually about 3 to 300 parts by weight is preferable for use in windows and the like. Further, two or more kinds of temperature shift agents may be mixed and used. In addition, a low molecular alcohol can also be considered as a part of aqueous medium.

In addition, a coloring agent for optional coloring of the isotropic aqueous solution or an ultraviolet absorber for improving light resistance, or a near infrared absorber for absorbing heat rays may be added. Good. The coloring agent may be dissolved in water, for example,
C. I. Direct Blue 86, C.I. I. Aci
d Red8, C.I. I. Acid Yellow 11 and the like. The addition amount may be 0.01 to 2 parts by weight based on 100 parts by weight of the isotropic aqueous solution. The ultraviolet absorber must be water-soluble, and is, for example, Sumisorb 110S of Sumitomo Chemical Co., Ltd. The addition amount is from 0.01 parts by weight to 2 parts by weight based on 100 parts by weight of the isotropic aqueous solution.
It may be parts by weight. Further, if air (oxygen) dissolved in the isotropic aqueous solution is replaced with an inert gas (for example, nitrogen, helium, etc.) in order to further stabilize, an antioxidant effect can be obtained. It is particularly preferable when used for a long period of time. The water may be ordinary pure water. The aqueous medium in the present invention is a low-viscosity liquid composed of water and an amphiphilic substance, and may further contain the aforementioned low-molecular alcohol, electrolyte and other additives.

The temperature dependency of the autonomous response laminate of the present invention is as follows:
Depends on the isotropic aqueous solution used. For example, using a nonionic amphiphilic substance, hydroxylpropyl cellulose (hydroxylpropyl group: 62.4%, 2% aqueous viscosity: 8.5 cps, weight average molecular weight: about 60,0
00) 100 parts by weight of polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3- having an average molecular weight of 400
A colorless and transparent isotropic aqueous solution was prepared at 20 ° C., comprising 10 parts by weight of propanediol, 6 parts by weight of sodium chloride, and 200 parts by weight of pure water. Asahi Glass Company's 10cm square, thickness 6
This isotropic aqueous solution was provided in a thickness of 0.2 mm between float soda glasses having a thickness of 0.2 mm to form a laminate. This laminate had good reversible stability at room temperature and 60 ° C. and long-term storage stability at 60 ° C. without any phase separation. Further, the rate of change was very steep, and the cloudiness began to be observed at about 34 ° C., and at about 40 ° C., the clouded light was strongly shielded, and a state in which the image could not be seen at all was reached. Using a U-4000 type spectrophotometer manufactured by Hitachi, Ltd., which is suitable for measuring a large sample that scatters light, place the center of the laminate close to the window of the integrating sphere (approximately 1 mm).
FIG. 8 shows the results of measuring light transmission spectra in the ultraviolet, visible, and near-infrared regions from 0 nm to 1,500 nm.
It is. 1 is an initial spectrum at room temperature (about 20 ° C.), 2
Is a spectrum at about 45 ° C., and those measured while allowing to cool from this temperature are spectra of 3, 4, 5, and 6. Surprisingly, it can be seen that the light returns to the original initial spectrum while maintaining the light-shielding properties almost uniformly over the entire wavelength range. This is from 250 nm to 2,500
The same was true in a wide wavelength range of nm. This tendency was observed when a nonionic amphiphile was used. When this laminate was observed directly through the sun,
The light-shielding property in the state of spectrum 2 was only a uniform cloudy state, and even the outline of the sun could not be seen at all. In consideration of the summer season, when the solar direct light of Tokyo was selectively irradiated in February at an atmosphere of 28 ° C. at 45 ° in an atmosphere of 28 ° C., the irradiating part was strongly shielded from cloudiness and could not be seen through. The non-irradiated part was colorless and transparent without any change, and the cloudy light-shielding surface also moved with the movement of the irradiated part.

Next, using an ionic amphiphile,
For example, hydroxylpropyl cellulose (hydroxylpropyl group: 62.4%, 2% aqueous solution viscosity: 8.5 c
ps, average molecular weight: about 60,000) A colorless and transparent isotropic aqueous solution at 20 ° C., comprising 100 parts by weight, 10 parts by weight of sodium lauryl sulfate, 6 parts by weight of sodium chloride and 200 parts by weight of pure water, was prepared. 0.2m in the same way as
An m-thick laminate was prepared. Room temperature and 60 ° C of this laminate
Were good without any phase separation. FIG. 9 shows the result of measuring the light transmission spectrum of the laminate by the same method as described above. 1 is an initial spectrum at room temperature (about 20 ° C.), 2
Is a spectrum at about 45 ° C., and the spectra of 3, 4, 5, and 6 were measured while cooling from this temperature. It can be seen that the laminate returns to the original initial spectrum completely while maintaining the property of selectively blocking visible and ultraviolet light. This tendency was observed when using ionic amphiphiles. Of course, ionic and nonionic amphiphilic substances may be mixed and added.

Next, the structure of the laminate according to the present invention and the window using the same will be described. 1, 2 and 3
Is a schematic cross-sectional view of one embodiment of the laminate of the present invention, 1 is a substrate, 2 is an isotropic aqueous solution, 3 is a sealant,
4 is a frame.

The laminate shown in FIG. 1 has the basic form of the laminate according to the present invention, in which an isotropic aqueous solution 2 is laminated between a substrate 1 which is at least partially transparent and allows direct observation of the isotropic aqueous solution 2. It was done. The layer thickness of the isotropic aqueous solution 2 is not particularly limited, but may be about 0.01 mm to 2 mm,
It is possible to sufficiently shield light with a thickness of about 0.2 mm. Sealant 3
Is to prevent the evaporation of water, at the outer periphery,
It may be arranged between the substrates or may be arranged outside thereof. Further, a fixing frame 4 (for example, a U-shaped member, an L-shaped member, a metal tape, or the like) may be provided via the sealant 3.
The frame 4 is particularly effective in the case of a manufacturing method in which an isotropic aqueous solution is laminated and then sealed. In addition, for stronger sealing and ease of production, for example, after temporarily sealing the outer peripheral portion with a metal tape with an adhesive, an adhesive rubber, a quick-curing resin, and the like,
The isotropic aqueous solution or the like adhering to the outer peripheral portion may be removed by washing, and then multi-stage sealing may be performed as in a method of fixing the frame via the sealant 3. Further, a corner cap may be used at the end as an auxiliary frame. In the case of a laminate provided with external terminals for energization, it is only necessary to fix the laminate while paying attention to a short circuit caused by a frame, and it is not necessary to particularly describe. Examples of the sealant 3 include an epoxy resin (for example, Flep of Toraythiol Co., Ltd.), an acrylic resin (for example, a photo bond of Sunrise Meisey Co., Ltd., a photosensitive resin), a polysulfide-based sealant, an isobutylene-based sealant, and water resistance. And an acrylic sealant (for example, Cerasolzer of Asahi Glass Co., Ltd.) that adheres to glass as needed.

In order to reliably control the thickness, a spacer (for example, a glass bead, a resin bead, etc.) is preferably used for a transparent and directly-viewable isotropic aqueous solution layer (not shown). In this case, the refractive index of the isotropic aqueous solution 2 (about 1.
It is preferable to use a substance close to 4) because it is difficult to visually recognize the substance.

The substrate only needs to be partially transparent so that the isotropic aqueous solution 2 can be directly viewed, and various materials such as glass, plastic, ceramics and metal can be used. A simple substance, a composite material, a material whose surface is processed, or the like can be used, and a combination thereof may be used. For example, a combination of glass and a blackened aluminum plate is effective for autonomous response because the aluminum plate becomes a high light absorber. In addition, glass sheets as window materials include simple single-pane glass, tempered glass, netted glass, heat absorbing glass, heat reflecting glass, heat absorbing reflecting glass, laminated glass, ultraviolet absorbing laminated glass, transparent conductive glass, and multi-layer glass. And 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. The shape of the cut surface is
A normal right angle, about 45 degrees, a partial oblique cut, and the like can be freely selected, and can be used for a sealing structure, production, and the like. Although not particularly shown, the substrate may be selected so that the sealing agent pool is provided by lamination of different size substrates, lamination of shifted substrates, or the like. In addition, it is preferable in terms of durability to protect the surface of the soda lime glass and the transparent conductive film which is in contact with the isotropic aqueous solution with silica coating.

The heat ray absorbing glass of the present invention is coated with a heat ray absorbing glass designed to absorb sunlight energy, a heat ray reflecting glass (having strong reflection and absorption), a heat ray absorbing / reflecting glass, and a near infrared ray absorbing agent. Refers to glass and the like.
Among them, for example, green heat ray absorbing glass (for example, Green Lal SP of Central Glass Co., Ltd.) designed to strongly absorb ultraviolet rays and near infrared rays due to the addition of cerium, titanium and iron, Low-E glass It is preferable to use a colorless and transparent heat ray absorbing glass, a blue-based heat ray reflecting glass, or the like. When a substrate that efficiently absorbs solar energy is used on at least one side, the thickness of both substrates may be reduced, and as a result, the heat capacity of the stacked body is reduced and the effect of returning to the transparent state quickly is obtained. . Further, for example, a composite in which Low-E glass (for example, Pilkington's K glass or the like) is multilayered by further providing a gas layer on a laminate in which an isotropic aqueous solution 2 is placed between an ultraviolet absorbing glass and a simple veneer glass. A window using a multilayer laminate can provide an unprecedented window that has a colorless and transparent, energy-saving, weather-resistant, and effectively autonomous selective light-shielding function. It is needless to say that a pair of ordinary single glazings can also be used in the present invention because they absorb solar energy and are heated. When the thickness of the substrate outside the window is about 5 mm or more, the transmission of ultraviolet light of 330 nm or less rapidly decreases, which is preferable from the viewpoint of weather resistance. is there.

Further, the laminate of FIG.
Is a layered body in which the degree of the cloudy and opaque state is continuously changed by continuously changing the layer thickness. This is effective for use in adjusting solar radiation near windows. In FIG. 3, a certain portion of the aqueous solution 2 is thinned or eliminated to ensure transparency (for example, a rear window of an automobile) or display image information such as figures, characters, and abstract patterns (for example, FIG. 3). , Advertising devices, etc.).

FIG. 4 is a schematic sectional view of another embodiment, in which isotropic aqueous solutions 2-1 and 2- having different compositions are added to the isotropic aqueous solution 2.
2 is a laminate in which image information can be displayed by a difference of the degree of white turbidity. The arrangement of the aqueous solutions 2-1 and 2-2 may be parallel or serial. Alternatively, the aqueous solution 2-2 may be formed into a normal polymer solution (for example, an aqueous solution of a polyvinyl alcohol-based polymer) which is dissolved in water having substantially the same concentration, to form a laminate capable of displaying image information based on the presence or absence of cloudiness. This image information can be used without being particularly limited to figures, characters, abstract patterns, and the like. Note that in the case of serial connection, they may be separated by thin glass, a transparent film, or the like.

FIG. 5 is a schematic sectional view of still another embodiment, in which an ultraviolet absorbing layer 5 (this substrate is set outside a window) is provided on at least one substrate. The ultraviolet absorbing layer 5 includes a substrate surface (for example, Atom Varian UV of Atom Chemical Co., Ltd.), the inside of the substrate (for example, a laminated glass having a butyral film that absorbs ultraviolet light, a laminated glass having a liquid ultraviolet absorbing agent, and the like). ) And the substrate itself (for example, Green Lal SP of Central Glass, ITY of Isuzu Seiko Glass, etc.). Normal soda lime glass absorbs ultraviolet light, but when thinner, it easily transmits ultraviolet light. Therefore, it is preferable to provide an ultraviolet absorbing layer 5 particularly when a thin plate having a thickness of about 4 mm or less is used.

FIG. 6 is a schematic cross-sectional view of still another embodiment, in which solar heat is stored in a gas layer by using the principle of a hot box, and a heat insulating effect of a conventional double glazing is provided simultaneously with a temperature increasing effect. In addition to the laminate, 6 is an additional substrate, 7 is a gas layer, and 8 is a sealing of the gas layer. This structure corresponds to a structure in which a substrate on one side of a conventional double glazing is formed into a laminate of the present invention. In addition, it is preferable to use netted glass as the additional substrate 6 with this glass surface facing the indoor side from the viewpoint of energy saving and safety such as breakage. If the temperature is too high, the glass may be broken. In particular, when combined with the ultraviolet absorbing layer of FIG. 5, it is very effective for skylights, atriums, and the like.

FIG. 7 is a schematic sectional view of still another embodiment. In this embodiment, a thermal element is provided in order to further expand the range of use of the laminate of the present invention, and artificially heat-controlled as an electronic curtain. This is for blocking the line of sight, and the thermal element layer 9 is provided on the laminate. The heat element layer 9 may be provided outside the substrate, or may be provided in a state sandwiched in the laminate. 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 thermal element can be performed on the entire surface of the substrate or a part thereof. Further, the substrate may be divided into stripes so that the substrate can be heated uniformly, and the image information can be obtained by selectively irradiating the substrate surface with an imaged thermal element or by infrared rays (for example, a laser or the like). It may be displayed. Although not particularly shown, it is preferable that the sealing portion does not have a thermoelectric element so as not to be heated, or the resistance is reduced by a metal conductor. In addition, it is preferable to mask the inner peripheral portion of the sealing layer, since it is difficult to heat the transparent inner portion, which can easily shield a transparent portion which is likely to be generated on the outer peripheral portion of the laminate. Naturally, automatic control can be performed by combining with a sensor and a control circuit. Further, a cooling medium (for example, dry air,
The temperature of the laminate may be controlled by circulating antifreeze water or the like. In particular, if the light is shielded by using the waste heat of an automobile, it is effective not only in terms of comfort but also in terms of energy saving in cooling in summer. In winter, if it is made into an air layer, it becomes a multi-layer glass and can prevent cooling from the window. In addition, by using the laminate of the present invention as a window glass for the entire ceiling, it is possible to realize a new concept automobile that simultaneously satisfies a sense of openness and comfort.

The windows according to the present invention include windows of ordinary buildings, vehicles such as automobiles and railway cars, and windows of transport machines such as ships, aircraft, and elevators. The windows are broad in scope and include things like arcade and atrium glass ceilings, doors with windows, partitions, etc., as well as all-glass doors, screens, and walls. Naturally, as a widely used method, the autonomous response laminate is combined with a building material sash or a vehicle frame to form an autonomous response laminate having a frame for each application such as a building, a vehicle, etc. A window unit that is simply attached is also included in the present invention. This unitization makes it possible to seal the autonomous response laminate more securely, and is effective in preventing evaporation of water due to transmission and preventing deterioration of the sealing due to light, particularly for windows of ordinary buildings and windows of vehicles. It is effective for semi-permanent use or severe use like this.

Further, a method in which the isotropic aqueous solution is used in the form of a plate by coating and laminating a material enclosed in a hollow body, a sphere, a microcapsule, a resin sheet, or the like is also available. If it can be seen directly, it shall be included in the laminate of the present invention.

The laminate according to the present invention can be prepared by a solution method in which an isotropic aqueous solution having the above-mentioned composition is laminated between substrates, a solid coating film of a polysaccharide derivative on a substrate, a single film, a thin rod,
It can be produced by a solid method in which small balls or the like are provided and then dissolved by contact between an aqueous medium and a substrate to obtain an isotropic aqueous solution having the above-described composition. At that time, even if flow unevenness occurs during pressure lamination, if left for several days, it will be uniform by self-diffusion,
There is no particular problem.

In the solution method, since the isotropic aqueous solution has a relatively high viscosity, it is preferable to take measures against air bubbles. Bubbles mixed by ordinary stirring and dissolving may be removed by flowing a slope under reduced pressure. A more effective method is to quickly coagulate and sediment a low-concentration aqueous solution of a water-soluble polymer by heating, and remove high-concentration aggregates that have settled at the bottom of the container with a snake pump or the like to eliminate bubbles. There is a method of continuously obtaining a highly concentrated aqueous solution of the above quantitatively. In order to obtain such an aqueous solution more quickly and reliably, an aqueous solution of the polysaccharide derivative uniformly dissolved using water containing 0.1% to 5% by weight of an electrolyte (eg, sodium chloride) instead of pure water is heated. It is preferable to deaerate or defoam by stirring and reducing the pressure at the time when the viscosity suddenly lowers, and then to allow the mixture to stand and coagulate and settle. This high-concentration aqueous solution of a polysaccharide derivative and a low-viscosity medium such as an aqueous medium containing an amphipathic substance, an electrolyte, etc., are uniformly mixed with a static mixer so as to have a desired composition, thereby obtaining a bubble-free isotropic aqueous solution. Is obtained. According to this method, isotropic aqueous solutions of various polysaccharide derivatives can be easily obtained by changing the composition of the low-viscosity medium, which is very convenient.
This isotropic aqueous solution may be placed between the substrates, and after press lamination, the outer periphery may be sealed. This solution method is suitable not only for the production of the laminate of FIG. 1, but also for the production of the laminates of FIGS. 2 and 3 and laminates such as curved glass. Alternatively, an isotropic aqueous solution of a target composition may be thinly applied to the entire surface of the substrate with a coater such as an applicator, and left to remove bubbles before laminating the counter substrate.
The removal by leaving can be performed in a short time because of the thin film state. Moreover, it is good also to leave under saturated steam as needed. In the lamination, the surfaces may be brought into contact with each other from the center portion using the side portion or the bend while paying attention to the inclusion of air bubbles, and high pressure is not particularly required. Further, the layers may be stacked under reduced pressure in order to prevent air bubbles from being mixed.

The solid method is a method in which an aqueous medium is diffused in a polysaccharide derivative between substrates to obtain an isotropic aqueous solution having a uniform target composition. As described above, solids of various forms can be used. Although not required, a simple coating method is very effective. This coating film method is a method in which a polysaccharide derivative is applied to a substrate by an ordinary method, dried, and then a counter substrate is laminated at a predetermined interval. In this case, a simultaneous lamination method in which the opposing substrate is laminated via an aqueous medium and then sealing, and an injection lamination method in which an aqueous medium is injected from an injection hole into a gap after sealing the outer periphery of the substrate and then sealed, are used. is there. The latter method is
Since the temperature for forming the seal can be 100 ° C. or higher, a wide range of sealants can be selected, and good sealing can be easily obtained. In particular, it is suitable for use with solder that adheres to glass (for example, Cerasolzer of Asahi Glass Co., Ltd.). It is important to note that, when the degassed aqueous medium is not used, an infinite number of microbubbles are generated over the entire surface together with the diffusion and dissolution of water. As a result of investigating the cause of this problem, it was found that air dissolved in the aqueous medium was released by dissolution of the polysaccharide derivative. However, it has been found that this problem can be solved by using an aqueous medium from which dissolved air has been removed by heating to 60 ° C. or higher, preferably 70 ° C. or higher, or an aqueous medium degassed under reduced pressure. When the amphiphilic substance in the aqueous medium is separated by heating and degassing, the amphiphilic substance may be put into a coating film, a film, or the like of an individual. This method may be applied to other additives, and thus, it is preferable to diffuse only water or water containing an electrolyte in order to homogenize the additives. Further, according to this solid method, a coating film of a polysaccharide derivative film is periodically applied or removed in the form of a stripe or the like, and a degassed aqueous medium (for example, pure water at 80 ° C.) is provided in the recess. By filling and laminating, an excess aqueous medium is discharged from the stripe grooves and then diffused and dissolved, whereby the aqueous solution of the target composition can be laminated without a spacer. Similarly, the film may be used after processing such as stripe grooves, waving, and punching. The heated aqueous medium not only has the advantage of being degassed, but also has the advantage of being difficult to diffuse and dissolve at high temperatures and of being able to reliably discharge excess aqueous medium during lamination. Useful for preparing isotropic aqueous solutions.

[0037]

[Function] An amphiphilic substance is a compound having both a hydrophilic part and a hydrophobic part. When the temperature rises, the polysaccharide derivative dissolved in water aggregates, causing cloudy scattering and decreasing the light transmittance. The aqueous solution serves to prevent phase separation when cloudy aggregation occurs. The principle of action of amphiphiles is
When the polysaccharide derivative is clouded and agglomerated by the hydrophobic bond, the polysaccharide derivative is taken into the interior of the polysaccharide derivative at the molecular or micellar level and also takes in water. It seems that this phase transition can be repeated in a stable manner. as a result,
When this laminate with the isotropic aqueous solution is applied to a window,
The window is heated by the direct light energy of the sun, and the irradiated part selectively changes from a transparent state to a cloudy state,
Direct rays are blocked. Depending on the presence or absence of the direct rays, it is possible to provide a window in which the window is autonomously reversible between transparent and opaque.

[0038]

The present invention will be further described with reference to the following examples. Although these examples use hydroxypropylcellulose which seems to be the most suitable as a polysaccharide derivative, the present invention is not limited to these examples.

Example 1 100 parts by weight of hydroxypropylcellulose (hydroxylpropyl group: 62.4%, 2% aqueous viscosity: 8.5 cps, weight average molecular weight: about 60,000), polyoxypropylene 2-ethyl-2- Hydroxymethyl-1,
A colorless and transparent isotropic aqueous solution was prepared at 20 ° C., comprising 20 parts by weight of 3-propanediol (average molecular weight: 400), 6 parts by weight of sodium chloride, and 200 parts by weight of pure water.
This isotropic aqueous solution was provided in a thickness of 0.2 mm between soda lime glasses each having a size of 6 cm square and a thickness of 3 mm, and sealed to form a laminate. The laminate was good without any phase separation in both the reversible repetition test at room temperature and 60 ° C. and the standing stability test at 60 ° C. for 48 hours.
Further, the laminate was placed 15 mm apart from a black-and-white striped plate having a pitch of 2 mm in a constant temperature bath, and light was illuminated from above and visually observed.
Then, cloudiness was started at 40 ° C., and the light was strongly shielded from clouding at 40 ° C., and the state was not completely visible. When left at -20 ° C, it was frozen, and the unevenness of the boundary formed at that time disappeared with the thaw and did not remain. Further, assuming the use of an automobile, the sample was left standing at 100 ° C. for 6 hours, and observed, but there was no occurrence of phase separation, and the initial state was completely and easily recovered when left at room temperature.

Example 2 Polypropylene glycol (average molecular weight: 400) was used in place of the polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol of Example 1.
A colorless and transparent isotropic aqueous solution was prepared at 20 ° C. Example 1
A laminate was prepared in the same manner as described above, and its stability and change in white turbidity were evaluated.
, Cloudy light was strongly started at 43 ° C., and it was recognized that it became impossible to see through at all.

Example 3 In place of polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol of Example 1, dipropylene glycol monomethyl ether (molecular weight: 14
As 8), a colorless and transparent isotropic aqueous solution was prepared at 20 ° C. A laminate was prepared in the same manner as in Example 1, and its stability and change in white turbidity were evaluated. As a result, no phase separation was found to be favorable. Also, white turbidity started at 36 ° C. It was recognized that it would not be possible.

Example 4 Instead of the polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol of Example 1, diethylene glycol monobutyl ether (molecular weight 16
As 2), a colorless and transparent isotropic aqueous solution was prepared at 20 ° C. A laminate was prepared in the same manner as in Example 1, and its stability and change in white turbidity were evaluated. The result was good without phase separation. Also, white turbidity was started at 34 ° C. It was recognized that it would not be possible.

Example 5 Polyoxypropylene glycerin (average molecular weight: 600) was used in place of the polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol of Example 1 and was colorless and transparent at 20 ° C. The aqueous solution was prepared. A laminate was prepared in the same manner as in Example 1, and its stability and change in white turbidity were evaluated.
It was observed that the cloudiness started at 7 ° C, and the cloudiness was strongly shielded at 44 ° C, making it impossible to see through at all. Created.

Example 6 A colorless and transparent isotropic aqueous solution was prepared at 20 ° C. as sodium lauryl sulfate instead of the polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol of Example 1. A laminate was prepared in the same manner as in Example 1,
When its stability and change in cloudiness were evaluated, it was good without phase separation, and cloudiness started at 32 ° C. and changed to 41 ° C.
, It was recognized that it was not possible to see through at all.

Example 7 100 parts by weight of the hydroxypropylcellulose of Example 1, 20 parts by weight of poly (oxyethylene / oxypropylene) glycol / monobutyl ether polyoxypropylene glycerin (average molecular weight 2,300) at a ratio of 50% by weight and pure A colorless and transparent isotropic aqueous solution comprising 20 parts by weight of water at 20 ° C. was prepared. A laminate was prepared in the same manner as in Example 1, and its stability and change in cloudiness were evaluated.
It was good without phase separation, and began to become turbid at 47 ° C. At 57 ° C, it became strongly opaque and could not be seen at all.

Example 8 In order to examine the change with the amount of the amphiphilic substance added, 100 parts by weight of the hydroxypropylcellulose of Example 1 was added to polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propane. Aqueous medium (A) consisting of diol / pure water (0.2 parts by weight / 200 parts by weight), polyoxypropylene 2-ethyl-2-hydroxymethyl-1,
Aqueous medium (B) composed of 3-propanediol / pure water (3 parts by weight / 200 parts by weight), polyoxypropylene 2
Aqueous medium (C) composed of -ethyl-2-hydroxymethyl-1,3-propanediol / pure water (200 parts by weight / 200 parts by weight), polyoxypropylene 2-ethyl-2
Four kinds of colorless and transparent isotropic aqueous solutions were prepared at 20 ° C. in an aqueous medium (D) consisting of -hydroxymethyl-1,3-propanediol / pure water (2 parts by weight / 200 parts by weight). Next, a laminate was prepared using these aqueous solutions in the same manner as in Example 1, and the stability and the change in white turbidity were evaluated. As a result, phase separation was observed in (A). In (B), there was no phase separation and the condition was good.
At 53 ° C., it becomes strongly clouded and cannot be seen at all,
Even in (C), no phase separation was observed. The cloudiness started at 43 ° C., and the cloudiness was strongly blocked at 48 ° C., making it impossible to see through at all. In (D), no phase separation was observed.
It began to be clouded at 55 ° C., and it was recognized that the cloudiness was completely blocked at 55 ° C.

Example 9 An isotropic aqueous solution was prepared in the same manner as in Example 1 except that the amounts of sodium chloride added were 0 parts by weight, 2 parts by weight and 10 parts by weight, respectively. When a laminate was prepared in the same manner as in Example 1, and the stability and the change in white turbidity were evaluated. When the added amount was 10 parts by weight, the solution was strongly aggregated and showed phase separation. In other cases, there was no phase separation and the condition was good. In the case of 0 parts by weight, cloudiness started at 49 ° C.
It began to be cloudy at 50 ° C., and at 50 ° C., it was recognized that the cloudiness was strongly shielded from light and it was impossible to see through at all. From this result, it can be seen that when the amount of sodium chloride added increases, the onset of cloudiness shifts to a lower temperature side.

Example 10 Polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol / sodium chloride / pure water (20 parts by weight) was added to 100 parts by weight of the same hydroxypropylcellulose as used in Example 1. Parts by weight / 3 parts by weight / 10
Aqueous medium (A) comprising polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol / sodium chloride / pure water (50 parts by weight / 3 parts by weight).
Parts by weight / 100 parts by weight), an aqueous medium (B) comprising polyoxypropylene 2-ethyl-2-hydroxymethyl-
1,3-propanediol / sodium chloride / pure water (2
Aqueous medium (C) consisting of 00 parts by weight / 2.4 parts by weight / 80 parts by weight), polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol / sodium chloride / pure water: 200 parts by weight /1.5 parts by weight / 50 parts by weight (D) to prepare an isotropic aqueous solution. Next, a laminate was prepared in the same manner as in Example 1, and the stability and change in white turbidity were evaluated. As a result, (A) had no phase separation and was colorless. Opaquely shielded light. (B) is colorless and good without phase separation, or starts turbidity at 32 ° C. and becomes strongly opaque at 38 ° C. and cannot be seen through at all. In (C), it is colorless and has no phase separation.
Good, the cloudiness started at 23 ° C, the cloudiness was strongly blocked at 36 ° C, and no transparency was possible. In (D), the colorlessness was good without phase separation, and the cloudiness started at 31 ° C. , And it was recognized that the opaque light was strongly blocked at 73 ° C., making it impossible to see through at all. Thus, a colorless and transparent isotropic aqueous solution is obtained when the amount of the amphiphilic substance is increased, which indicates that the amphiphilic substance has a solvent effect. In addition, when the amount of water is relatively small, the cohesive force is weakened, and it is necessary to add a temperature higher than the opacity start temperature in order to strongly opacify opacity. : 6 ° C).

Example 11 Further, hydroxypropyl cellulose (hydroxylpropyl group: 62.6%, 2% aqueous solution viscosity: 5.4 cp)
s, weight average molecular weight: about 40,000) and 100 parts by weight of polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol / sodium chloride / pure water (200 parts by weight / 1.5 parts by weight). Parts / 30 parts by weight), polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol / sodium chloride / pure water (1200 parts / 12 parts by weight / 400 parts by weight) Aqueous medium (B) comprising polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3
Aqueous medium (C) consisting of propanediol / sodium chloride / pure water (800 parts by weight / 5 parts by weight / 100 parts by weight), polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol / chloride Sodium / pure water (1500 parts by weight / 9 parts by weight / 300 parts by weight)
Aqueous medium (D) comprising: polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol / sodium chloride / pure water (800 parts by weight / 6 parts by weight /
Aqueous medium (E) comprising polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-
Aqueous medium part (F) consisting of propanediol / sodium chloride / pure water (800 parts by weight / 9 parts by weight / 300 parts by weight), polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol / Aqueous medium (G) composed of sodium chloride / pure water (200 parts by weight / 2.25 parts by weight / 75 parts by weight), polyoxypropylene 2
Aqueous medium (H) composed of -ethyl-2-hydroxymethyl-1,3-propanediol / sodium chloride / pure water (200 parts by weight / 2 parts by weight / 100 parts by weight); polyoxypropylene 2-ethyl-2- Hydroxymethyl-1,
3-propanediol / sodium chloride / pure water (300
Aqueous medium (I) consisting of (weight parts / 2 weight parts / 100 weight parts), polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol / sodium chloride / pure water (300 weight parts / 2 weight) Parts / 100 parts by weight) as an aqueous medium (J).
Next, a laminate was prepared in the same manner as in Example 1, and the stability and the change in white turbidity were evaluated. In (A), the laminate was colorless and transparent at room temperature, the white turbidity changed from a high temperature of 65 ° C., and the temperature was further reduced. Even when the temperature was raised to 80 ° C., the increase in light-shielding properties was small, and strong cloudy light-shielding did not occur. In (B), the turbidity was changed from 7 ° C., and the opaque light was strongly shielded at 27 ° C., making it impossible to see through at all. In (C), the opacity was changed from 41 ° C., and the light-shielding property was increased when the temperature was further increased. However, even at 80 ° C., strong opaque light-shielding did not occur. In (D), the cloudiness changed from 16 ° C, and the cloudiness was strongly shielded at 53 ° C, making it impossible to see through at all. In (E), the opacity changed from 20 ° C., the opacity was strongly shielded at 36 ° C., and the opacity could not be seen at all. In (F), the cloudiness changed from 5 ° C., and the cloudiness was strongly shielded at 29 ° C., making it impossible to see through at all. (G) is 2
The cloudiness changed from 4 ° C, and the cloudiness was strongly shielded at 47 ° C, making it impossible to see through at all. In (H), cloudiness was changed from 31 ° C., and cloudiness was strongly blocked at 48 ° C., making it impossible to see through at all. In (I), the cloudiness was changed from 29 ° C, and the cloudiness was strongly shielded at 60 ° C, making it impossible to see through at all. (J)
A cloudiness change occurs from 25 ° C, and at 40 ° C, the cloudiness is strongly shielded,
I can no longer see through. As described above, it can be seen that the cloudiness temperature range can be freely set by changing the composition of the aqueous medium and the concentration of the polysaccharide derivative. In addition, it can be seen from the comparison with Example 1 that, when the proportion of the amphiphilic substance is relatively large, the white turbidity change rate with respect to the temperature change is small.
Further, in all the laminates, the isotropic aqueous solution was colorless and good without phase separation, and did not freeze even at -20 ° C.

Example 12 Polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol / sec-butyl alcohol / pure water was added to 100 parts by weight of the same hydroxypropylcellulose as used in Example 11. (10 parts by weight / 5
Aqueous medium (A) consisting of 0 parts by weight / 200 parts by weight), polyoxypropylene 2-ethyl-2-hydroxymethyl-
Aqueous medium (B) composed of 1,3-propanediol / sec-butyl alcohol / pure water (20 parts by weight / 100 parts by weight / 100 parts by weight), polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3 -Propanediol /
sec-butyl alcohol / sodium chloride / pure water (2
Aqueous medium (C) consisting of 0 parts by weight / 4 parts by weight / 4.8 parts by weight / 160 parts by weight), polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol /
sec-butyl alcohol / sodium chloride / pure water (2
0 parts by weight / 150 parts by weight / 1.5 parts by weight / 50 parts by weight)
(D) was prepared. Next, a laminate was prepared in the same manner as in Example 1, and the stability and the change in white turbidity were evaluated. In (A), the white turbidity was changed from 31 ° C. lost. In (B), white turbidity changes from 37 ° C.
, And the cloudiness was strongly blocked, making it impossible to see through at all. In (C), the cloudiness changed from 31 ° C., and the cloudy light was strongly shielded at 36 ° C., making it impossible to see through at all. In (D), the turbidity changed from 6 ° C., and the opaque light was strongly shielded at 56 ° C., making it impossible to see through at all. All were colorless and good without phase separation, and did not freeze even at -20 ° C.

Example 13 An aqueous medium (A) comprising 100 parts by weight of the same hydroxypropylcellulose used in Example 11 and Amidget 5C manufactured by Kawaken Fine Chemicals / pure water (20 parts by weight / 200 parts by weight) Amidget S3L / Sodium chloride / Pure water (20 parts by weight / 4.8, manufactured by Kawaken Fine Chemicals Co., Ltd.)
Aqueous medium (B) consisting of 20 parts by weight / 160 parts by weight of sodium hydroxide / pure water (20 parts by weight / 4.8 parts by weight / 160 parts by weight) of Kawaken Fine Chemical Co., Ltd. C) was adjusted. Next, Example 1
A laminate was prepared in the same manner as described above, and the stability and the change in white turbidity were evaluated. In (A), the white turbidity was changed from 37 ° C., and the opaque light was strongly shielded at 48 ° C., making it impossible to see through at all. In (B), white turbidity changes from 31 ° C. to 38 ° C.
, And the cloudiness was strongly blocked, making it impossible to see through at all. In (C), the cloudiness changed from 35 ° C., and the cloudiness was strongly shielded at 43 ° C., making it impossible to see through at all. All were colorless and good without phase separation.

Example 14 100 parts by weight of the same hydroxypropylcellulose as used in Example 1, polyoxypropylene 2-ethyl-2
An isotropic aqueous solution comprising 20 parts by weight of -hydroxymethyl-1,3-propanediol, 50 parts by weight of propylene glycol, 10 parts by weight of sodium chloride, and 200 parts by weight of pure water was prepared. Next, a laminate was prepared in the same manner as in Example 1,
When the stability and opacity change were evaluated, there was no phase separation,
It was good, and cloudiness started at 33 ° C., and it became strongly clouded at 38 ° C., making it impossible to see through at all. The laminate does not freeze even at −20 ° C. and is suitable for vehicles.

Example 15 Hydroxypropylcellulose (hydroxylpropyl group: 61.6%, 2% aqueous solution viscosity: 2.5) was used in place of the same hydroxypropylcellulose used in Example 1.
cps, average molecular weight: about 20,000) (A), hydroxypropylcellulose (hydroxylpropyl group: 6)
2.6%, 2% aqueous solution viscosity: 5.4 cps, average molecular weight: about 40,000) (B), and two kinds of colorless and transparent isotropic aqueous solutions at 20 ° C. were prepared in the same manner as in Example 1 using (B). . Next, a laminate was prepared in the same manner as in Example 1, and the stability and the change in white turbidity were evaluated. As a result, (A) was good without phase separation and started turbid at 40 ° C. and became strongly opaque at 46 ° C. (B) is good with no phase separation, starts turbidity from 38 ° C., and is 44 ° C.
It was recognized that the film became strongly clouded, and could not be seen through at all. Further, it was found that when the molecular weight was too small, the light-shielding property was weak, and when the molecular weight was too large, phase separation of water occurred.

Example 16 As a comparative example, an isotropic aqueous solution containing no polyoxypropylene 2-ethyl-2-hydroxymethyl-1,3-propanediol as an amphipathic substance in Example 1, and sodium chloride Two kinds of isotropic aqueous solutions not containing any were prepared. Further, a laminate was prepared in the same manner as in Example 1, and the stability and the change in white turbidity were evaluated. In each case, water was phase-separated and the reversible change was not obtained, and sedimentation occurred when standing upright. Thus, it can be seen that the presence of the amphiphile is very important for reversible stability.

Example 17 The aqueous solution of Example 1 having no air bubbles was 30 cm square and 3 cm thick.
1m with applicator on soda lime glass substrate
m thickness. The substrate was cooled to 0 ° C. (water vapor pressure was about 4.6 mmHg), and the pressure was reduced to 8 mmHg. A substrate of the same size having fine water droplets uniformly attached by dew condensation was placed on the substrate. More contact, gradually make surface contact, make full contact, then return to normal pressure,
The outer periphery was washed. Next, a 25 mm-wide aluminum tape coated with a sealing agent (main agent: 100 parts by weight of FLEP 60 manufactured by Toray Thiokol Co., Ltd., curing agent: 28 parts by weight of Daitokural X-2392 manufactured by Daito Sangyo Co., Ltd.) was applied to the outer periphery of the laminate. After winding around the part, it was cured at room temperature and sealed. In addition, by devising the reduced pressure and the minute water droplets, it was possible to more reliably laminate in a bubble-free state as compared with the case where the substrates were simply laminated.

Example 18 To 100 parts by weight of the same hydroxypropylcellulose as used in Example 1, 500 parts by weight of 1% by weight sodium chloride solution was added, and the mixture was sufficiently stirred and mixed to obtain a uniform aqueous solution. Two liters of this aqueous solution was placed in a container having an inner diameter of 10 cm, the liquid temperature was set to 70 ° C., and hydroxypropyl cellulose was sufficiently stirred in a state of being settled by about 3 mm from the liquid surface to form a low-viscosity aqueous solution uniformly dispersed in cloudiness. And degassed. Thereafter, the mixture was allowed to settle in an atmosphere of 70 ° C. for 12 hours to be separated into a cloudy agglomerated layer and an upper aqueous layer. The water was removed and the temperature was returned to room temperature to obtain a high-concentration aqueous solution without bubbles. This high-concentration aqueous solution and a 50% by weight aqueous solution of polypropylene glycol (average molecular weight: 400) were uniformly mixed at a weight ratio of 1: 1 using a static mixer having 24 stages of elements to obtain an isotropic aqueous solution without bubbles. Then, Example 1
The same treatment as in Example 6 was carried out to obtain a good laminate.

Example 19 The same aqueous solution as obtained in Example 1 was further added to pure water 200
By weight, a low viscosity aqueous solution was obtained. This aqueous solution
The surface is coated with silica to suppress the dissolution of sodium, applied to a 30 cm square, 6 mm thick soda lime glass substrate with an applicator, then sprayed with 0.3 mm diameter resin beads, dried, and dried to 0.1 mm thickness Was coated as a solid film. The coated substrate was immersed in pure water at 80 ° C., which was purged with nitrogen, and the same glass substrate as the opposite substrate was laminated and pressed. The outer periphery of the laminate was temporarily sealed with a copper tape with an adhesive, and the outer periphery was sufficiently washed. afterwards,
A U-shaped aluminum frame provided with the same sealant as that used in Example 17 was fixed to the outer periphery and sealed. Thereafter, the mixture was allowed to stand to obtain a colorless and transparent bubble-free laminate having no haze.

Example 20 A 30 cm square, 6 mm thick soda lime glass substrate provided with a 0.1 mm thick solid film of the same hydroxypropylcellulose used in Example 1 cut at a 10 mm outer circumference was used. A soda lime glass substrate of the same size as a counter substrate was opened at 0.3 mm thick and 10 mm wide strip-shaped thin glass as a spacer through the sealant of Example 17 at two diagonal ends as injection holes. The layers were laminated in a state. Thereafter, the sealant was cured by heating at 120 ° C. Next, the end was immersed in the aqueous medium of Example 1 which had been degassed under reduced pressure, and was sucked up from the other end to fill the laminate. And it closed at room temperature using the corner cap via the sealant of Example 17. Thereafter, the mixture was allowed to stand to obtain a colorless and transparent bubble-free laminate having no haze.

Example 21 An aqueous solution consisting of 100 parts by weight of the same hydroxypropylcellulose used in Example 1, 10 parts by weight of dipropylene glycol monomethyl ether (molecular weight 148) and 500 parts by weight of pure water was cast to form a 0.1 mm solution. A thick film was made. Dipropylene glycol monomethyl ether was applied to a 30 cm square, 3 mm thick soda lime glass substrate, and a film of the same size as the substrate was brought into close contact with the roller via this liquid. Next, the substrate provided with the film is immersed in a 70 ° C. aqueous solution comprising 3 parts by weight of sodium chloride and 100 parts by weight of pure water, and a counter substrate of the same size is laminated in the aqueous solution via a 0.2 mm diameter spacer. After pulling out and sealing, it was left at room temperature. As a result, a good laminate without bubbles was obtained.

[0060]

The effect of the present invention is that, by adding an amphiphilic substance, a polysaccharide derivative dissolved in water is aggregated due to an increase in temperature to cause an isotropic aqueous solution which causes cloudy scattering even in a cloudy state. It is possible to stably maintain the film uniformly and to reversibly change between a cloudy state and a transparent state. As a result, when the isotropic aqueous solution used in the present invention is laminated, an autonomous response laminate that responds to environmental changes is obtained. When this autonomous response laminate is applied to a window, when the window is heated by the direct rays of the sun, the irradiated portion is selectively changed from a transparent state to a cloudy state, and the direct rays are blocked. Depending on the presence or absence of this direct ray, the intensity, and the balance with the environmental temperature at that time in summer, winter, etc., the transparency, semi-transparency and opacity are automatically changed continuously and selectively. This can provide a new autonomous response type light-shielding glass window that shields the direct light beam by the energy of the direct light of the sun itself with an energy saving effect. As described above, a building, a vehicle, or the like incorporating the window unit including the autonomous response laminate and the frame such as the sash and the frame provides a more comfortable living space with an energy saving effect. It should be noted that the temperature of the laminate can be controlled by an artificial thermal element, so that more advanced utilization is possible.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of an embodiment of an autonomous response laminate according to the present invention.

FIG. 2 is a schematic cross-sectional view of an embodiment of an autonomous response laminate in which the layer thickness of an isotropic aqueous solution is continuously changed.

FIG. 3 is a schematic sectional view of an embodiment of an autonomous response laminate in which an isotropic aqueous solution is thinned or eliminated.

FIG. 4 is a schematic cross-sectional view of an example of an autonomous response laminate in which isotropic aqueous solutions having different compositions are simultaneously placed.

FIG. 5 is a schematic sectional view of an embodiment of an autonomous response laminate having an ultraviolet absorbing layer.

FIG. 6 is a schematic sectional view of an embodiment of an autonomous response laminate having a composite multilayer structure having a gas layer.

FIG. 7 is a schematic sectional view of an embodiment of an autonomous response laminate having a thermal element layer.

FIG. 8: 350 nm to 1,500 n of the autonomous response laminate
Temperature-spectrum change in m region.

[FIG. 9] 350 nm to 1,500 n of an autonomous response laminate
Temperature-spectrum change in m region.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Isotropic aqueous solution 3 Sealant 4 Frame 5 Ultraviolet absorption layer 6 Additional substrate 7 Gas layer 8 Gas layer sealant 9 Thermal element layer

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) B32B 7/02 103 B32B 17/00 E06B 9/24 C03C 27/06 101

Claims (11)

(57) [Claims] 1. An isotropic aqueous solution in which a polysaccharide derivative dissolved in water is aggregated due to an increase in temperature to cause cloudy scattering and reduce light transmittance, at least a part of which is transparent,
An encapsulating <br/> the autonomous response laminate between the two substrates that can direct the aqueous solution, the isotropic aqueous solution, the weight average molecular weight of about 10,000 to about 200,000 multi of about 25 to about 450 parts by weight of saccharide derivative 100 parts by weight based on the polysaccharide derivative 100 parts by volume of water and 100
An autonomous responsive laminate which is a solution dissolved in about 110 to about 2,000 parts by weight of an aqueous medium comprising an amphipathic substance having a molecular weight of ~ 3,000. 2. The laminate according to claim 1 , wherein the isotropic aqueous solution further contains at least one selected from the group consisting of an electrolyte and a low molecular alcohol. 3. A laminate according to claim 1 or 2 thermal element capable of at least partially heat the laminated body is provided. 4. A weight average molecular weight of about 10,000 to about 20.
Consisting of amphiphiles with a molecular weight of the amount of water and 100 to 3,000 for the polysaccharide derivative 100 parts by weight of about 25 to about 450 parts by weight based on the polysaccharide derivative 100 parts by weight of 0,000 An isotropic aqueous solution dissolved in about 110 to about 2,000 parts by weight of an aqueous medium is placed between two substrates at least partially transparent and capable of directly viewing the aqueous solution. A method for producing an autonomous response laminate including encapsulation . 5. An isotropic aqueous solution in which the polysaccharide derivative dissolved in water is aggregated due to an increase in temperature to cause cloudy scattering and reduce light transmittance, at least a part of which is transparent,
A window using encapsulated <br/> the autonomous response laminate between the two substrates that can direct the aqueous solution, the isotropic aqueous solution, weight average molecular weight of about 10,000 to about 200 ,
Aqueous medium comprising 100 parts by weight of a polysaccharide derivative of 000 with respect to 100 parts by weight of the polysaccharide derivative in an amount of about 25 to about 450 parts by weight of water and an amphiphilic substance having a molecular weight of 100 to 3,000. A window which is a solution dissolved in about 110 to about 2,000 parts by weight. 6. The window according to claim 5 , wherein the isotropic aqueous solution further contains at least one selected from the group consisting of an electrolyte and a low molecular alcohol. 7. A window according to claim 5 or 6 thermal elements are provided which can at least partially heat the laminated body. 8. The window according to claim 5 , 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. 9. The window according to claim 5 , wherein a gas layer is provided on the autonomous response laminate. 10. The window according to claim 9, wherein a cooling medium or a heat medium is circulated through the gas layer to control the temperature of the autonomous response laminate. 11. The window according to claim 5 , wherein the autonomous response laminate and the window frame are combined to form a unit.