JPH07171925A - Laminate and window using the same - Google Patents

Abstract

PURPOSE:To provide a sufficient light resistance against direct rays of the sun over a long period of time in a laminate formed by laminating an aq. soln. compsn. showing a cloud point phenomenon to a substrate and at least partially transparent and to provide a window using the laminate. CONSTITUTION:A laminate has substrates 2, 3, 4 having an ultraviolet rays cutting layer 1 of a liquid film in order to protect an aq. soln. compsn. 5 showing a cloud point phenomenon and the substrates of the laminate are set on a solar ray side to form a window.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having an aqueous solution composition exhibiting a cloud point phenomenon in which a transparent state and a cloudy state are reversibly changed by a heat action such as heating and light absorption, and a window using the same. Is. For example, when this laminated body is irradiated with direct sunlight, the aqueous solution changes to white turbidity due to the heat effect due to the absorption of light, thereby providing an unprecedented window that blocks direct light. This enables buildings, vehicles, etc. with windows that selectively shield only the surface exposed to direct sunlight.

[0002]

2. Description of the Related Art In recent years, a light control glass has been proposed in which a glass having a functional material is used instead of a mechanical method to control light rays reversibly physicochemically. For example, liquid crystal,
There are methods such as electromic, fine particle polarization alignment, photochromic, and thermochromic. Further, in recent years, heat ray absorbing glass, heat ray reflecting glass, and the like, which prevent sunlight energy from entering the living space, have been used for windows. However, heat-absorbing glass and heat-reflecting glass certainly prevent the penetration of solar energy into the living space, but the coloring and surface glare still remain, and in terms of energy saving, visible light that has about half the energy of sunlight is also visible. Control was still insufficient. In addition, as for dimming glass, as described in detail in 1991 New Glass Industry Countermeasures Research Report (Global Warming Prevention Measures) of New Glass Forum,
There is a strong expectation for future development due to the relationship with energy conservation measures.

Therefore, the present inventor has noticed that sunlight energy is applied to the window. We examined whether or not this energy causes the window glass to autonomously make a transparent and opaque reversible change to make it a comfortable living space. This autonomous response characteristic is not only a feature that shields only the direct light irradiation surface and energy saving effect, but also construction, maintenance,
We paid attention to the fact that it is very attractive in terms of maintenance costs. From this point, the photochromic method and the thermochromic method can be selected, but rather than the photochromic method, which has a complicated mechanism of action and wavelength dependence, a thermochromic method that can easily adjust the temperature as needed artificially is only dependent on the thermal action. The chromic method is excellent. Note that the solar energy reaching the earth is in the range of 290 nm to 2140 nm, of which approximately 80% in the visible to near infrared region of 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 range is important not only for the blindfold effect but also for energy saving and antiglare effects. The present invention is
When light is applied to an object, it absorbs light and is converted into heat, which causes the temperature of the object to rise.

Therefore, the present inventor has paid attention to an aqueous solution composition which exhibits a cloud point phenomenon in which it is clouded and scattered by heating in the thermochromic system and exhibits a cloud point phenomenon, and a comfortable living space is obtained by controlling direct response of direct sunlight. A multi-faceted study was conducted on a practical method that can achieve energy saving. As a result, the inventors have proposed a laminate having a transparent-opaque reversible change due to a change in white turbidity due to a temperature change (cloud point phenomenon) and excellent weather resistance, and a window using the same. This window has an ideal blind that selectively and automatically shades only the part exposed to direct sunlight in summer when the temperature is high. It becomes a normal window to enter. As described above, since the energy of direct sunlight is directly utilized, it is an essential condition to surely cut off ultraviolet rays as in the present invention in order to protect the water-soluble composition exhibiting the cloud point phenomenon.

A water-soluble composition exhibiting a cloud point phenomenon is composed of water, a water-soluble organic compound having a hydrophobic group, an additive such as a water-soluble inorganic salt, and a lyotropic cholesteric liquid crystal,
Polymer aqueous solutions, gels, etc. have been pursued for this purpose. However, the durability against light has not been sufficiently examined. In particular, when used for a window as in the present invention, it is necessary to satisfy light resistance. The water-soluble composition used in the present invention is a colorless compound and does not absorb in the visible to near infrared region from 400 nm to 1100 nm, which accounts for about 80% of solar radiant energy. Therefore, it can be said that the water-soluble composition used in the present invention is essentially stable to sunlight having a wavelength in the visible region or higher. In addition, the soda-lime plate glass that is widely used as a window glass is usually 290n.
It absorbs light with a wavelength of m or less. However, in order to use it for windows of buildings, vehicles, etc. that are used for a long period of time, it is very important to surely cut ultraviolet rays of 290 nm to 380 nm, preferably 400 nm without changing for a long period of time. Furthermore, it is necessary to completely cut off ultraviolet rays of 350 nm or less in order to stabilize a water-soluble organic compound having a hydrophobic group which exhibits a cloud point phenomenon.

[0006]

The problem to be solved by the invention is to provide a laminate in which a water-soluble composition exhibiting a cloud point phenomenon is laminated on a substrate and at least a part of which is transparent, and the ultraviolet rays are cut so that it is exposed to direct radiation for a long period of time. It is an object of the present invention to provide a laminate having sufficient light resistance against sunlight irradiation and a window using the laminate.

[0007]

The present invention has been made to solve the above-mentioned problems, and an aqueous solution composition exhibiting a cloud point phenomenon is laminated between substrates and at least a part thereof is transparent. In a laminated body in which an aqueous solution composition exhibiting a cloud point phenomenon is laminated between substrates and at least a part of which is transparent, at least one substrate is a laminated substrate having an ultraviolet ray blocking layer of a liquid film. In a window using a laminate in which the laminate and an aqueous solution composition exhibiting a cloud point phenomenon are laminated between substrates and at least a part of which is transparent, at least one substrate of the laminate has an ultraviolet ray blocking layer of a liquid film. A window characterized in that a laminated substrate is used and the substrate is provided on the sunlight side.

The basic structure of the present invention is, as shown in FIG. 1, an aqueous solution composition 5 exhibiting a cloud point phenomenon between a glass substrate 4 and a substrate obtained by combining an ultraviolet ray blocking layer 1 of a liquid film with glass substrates 2 and 3. Are laminated. Although not shown in the drawings, the conventional method was a method of laminating the aqueous solution composition 5 between ordinary glass substrates. As the glass substrate, soda lime glass and its processed glass, which are usually used for building materials, are usually used, but the glass substrate is not limited thereto.

As a representative example of the aqueous solution composition 5 exhibiting the cloud point phenomenon, the present inventors selected cellulose having high stability among polysaccharides, and prepared hydroxypropyl cellulose obtained by reacting the cellulose with propylene oxide. It has been selected, but is not particularly limited thereto. FIG. 2 is a spectroscopic absorption spectrum of the 1% by weight aqueous solution of hydroxypropylcellulose placed in a 1 cm cell made of quartz and measured in the ultraviolet region of 190 nm to 400 nm. Thus, even with a water-soluble polymer having no aromatic ring, absorption due to tailing from the shoulder is observed at a wavelength in the ultraviolet region of 290 to 380 nm. In practice, the value of this absorption is even higher due to the high concentration used. In order to make it semi-permanently usable for buildings, vehicles, etc., in particular, it is necessary to sufficiently block ultraviolet rays having a wavelength of 350 nm or less in order to maintain the cloud point phenomenon. In order to ensure stable light-shading characteristics for a long period of time, 3
It is better to cut off ultraviolet rays up to 80 nm, and it is more preferable to cut off ultraviolet rays up to 400 nm. In fact, the laminate having no liquid crystal ultraviolet ray blocking layer 1 had a problem in the light-shielding property due to a change in the cloudiness characteristic in the light resistance test.

The spectral transmittance of commonly used soda lime glass (for example, float glass from Central Glass Co., Ltd.) at 350 nm is 3 mm thickness / 78.1%,
5mm thickness / 70.3%, 10mm thickness / 54.0%, 19
Even at a thickness of 19 mm, such as mm thickness / 33.7%, about a third of the amount of light is still transmitted. Further, the spectral transmittance at 380 nm is 3 mm thickness / 86.5%, 5 mm thickness / 83.2.
%, 10 mm thickness / 75.6%, 19 mm thickness / 63.6%
Is. Spectral transmittance at 400 nm is 3 mm thickness / 89.
8%, 5 mm thickness / 88.6%, 10 mm thickness / 85.8
%, 19 mm thickness / 80.8%.

In order to block this ultraviolet ray, an ultraviolet absorbent, an ultraviolet shielding agent or the like may be added to a transparent film or clear lacquer and adhered or coated on soda lime glass to form an ultraviolet absorbing layer. For example, a 6 mm laminated glass having an interlayer film made of polyvinyl butyral to which an ultraviolet absorber is added (for example, Saflex, manufactured by Japan Monsanto Co., Ltd.), a paint containing the ultraviolet absorber and absorbing and cutting ultraviolet rays by clear (for example, Nippon Paint Company's Super Freon R, Sect Chemical Co., Ltd.'s Sieg, etc.), ultrafine titanium oxide (Idemitsu titania from Idemitsu Kosan Co., Ltd.)
Ishihara Sangyo Co., Ltd.'s Typake TTO-55), adhesive film (Lintech's Lumicool No. 1521, etc.), and the like coated or bonded. However, as can be seen from the fact that the light absorption is proportional to the concentration and thickness, it is dissolved uniformly in the polymer matrix at high concentration and uniformly to prevent the distortion of transmitted image information. It is very difficult to apply a thick film with good flatness. Therefore, it is difficult to surely cut off the ultraviolet rays by the above-mentioned method, and the leaked ultraviolet rays in a wide wavelength range change the white turbidity characteristic of the laminate to cause a problem in the light shielding characteristic. In addition, it is usually important to more surely absorb UV rays having a wavelength of 350 nm or less in order to stabilize the organic compound. As a result, it can be used for a window exposed to direct sunlight for a long period of time.

Therefore, the present inventor shows, in FIGS. 1, 3 and 4, sectional views of an embodiment of the laminated body of the present invention. Reference numeral 1 is an ultraviolet ray blocking layer of a liquid film, 2, 3, 4, and 6 are glass substrates, 5 is an aqueous solution composition exhibiting a cloud point phenomenon, and 7 is a gas layer. FIG. 3 and FIG. 4 show a double-layered glass, and the ultraviolet ray blocking layer 1 of the liquid film may be provided in front of the aqueous solution composition 5 exhibiting the cloud point phenomenon when viewed from the sunlight side when it is applied to a window. . The UV cut layer 1 of the liquid film is not intended to protect the coexisting materials from UV rays as in the case of using a general UV absorber, but is merely for the purpose of functioning as a filter that cuts UV rays in a plane. ing. Furthermore, transparency is absolutely necessary, especially for use in windows. In order to satisfy the filter function and the transparency, the present invention uses a 100% or a high concentration liquid ultraviolet absorber at room temperature for the ultraviolet cut layer 1 of the liquid film. As a result, ultraviolet rays of 350 nm or less, which strongly influences the deterioration of the organic compound, can be completely absorbed, and the laminate of the present invention can be stably used for windows.

The UV cut layer 1 of the liquid film is a liquid UV absorber (eg, Tinuvin 17 manufactured by Ciba Geigy).
1, 1130, 384, 109, etc.), which are themselves liquid at room temperature, or solid UV absorbers (for example, Tinuvin 326 from Ciba Geigy,
327, 328, 213, 571, Sumitomo Chemical Co., Ltd. Sumisorb 110, 110S, 250, 400, etc.) are dissolved in a solvent at a saturation concentration in consideration of solubility.
Also, as a matter of course, these ultraviolet absorbers may be mixed and used. Further, a liquid ultraviolet absorber and a solid ultraviolet absorber may be combined and dissolved to be used. For example, liquid Tinuvin 109: 6 having different absorption wavelengths may be used.
There is a mixed solution of 1 part by weight of Tinuvin 328 and 1 part by weight of solid state. In order to prevent the liquid from splashing at the time of breakage, an organic polymer, an oligomer, an ultrafine inorganic substance or the like may be added to the ultraviolet cut layer 1 of the liquid film for thickening. In addition, if necessary, a light stabilizer (for example, Tinuvin 123, 292, 622LD manufactured by Ciba Geigy) is used.
Etc.), an antioxidant (eg Irga of Ciba Geigy)
(nox 245, 1010, 1330, etc.) may be added. Further, a dye may be dissolved and added for coloring. Furthermore, the present invention also includes a film-shaped coating of a liquid ultraviolet absorber formed into microcapsules and apparently solidified.

Next, FIGS. 5 and 6 show typical examples of the transmission spectrum of the ultraviolet ray blocking layer 1 of the liquid film. Figure 3
Tinuvin 17 on mm soda lime glass substrate
2 is a transmission spectrum of a laminated substrate having an ultraviolet ray blocking layer 1 of a liquid film in which 1 is laminated in a thickness of 0.1 mm. 6 is shown in FIG.
It is the transmission spectrum which measured Tinuvin109 on the same conditions as. Needless to say, both are 380
It can be seen that ultraviolet rays of nm or less are surely cut. As for the thickness of the ultraviolet ray blocking layer 1 of the liquid film, for example, when the thickness of the liquid film of FIG. 6 was measured at 0.025 mm, the rising wavelength shifted from 412 nm to 406 nm, but 38
There was no change in the ultraviolet transmittance of 0 nm or less. As described above, the thickness of the liquid film is not particularly limited, but it is not necessary to specifically set it to 0.01 mm or less because the ultraviolet ray is more surely absorbed and cut in proportion to the thickness. Further, even if it is not particularly thick, the liquid film sufficiently absorbs ultraviolet rays in a bulk state, so that it may be about 1 mm or less that is easy to use in actual use. The absorption by the bulk can surely cut ultraviolet rays over almost the entire ultraviolet region, and in particular, it can surely cut ultraviolet rays of 350 nm or less, which strongly affects the deterioration of organic compounds, and is similar to conventional colorless and transparent general glass. It can be used with a sense. In addition, flatness and water resistance could be satisfied by the laminated structure. If necessary, the thickness of the liquid film layer may be controlled via a spacer.

Further, since a laminated body using a substrate on which a heat-generating element such as a transparent conductive film and heat-generating paint is attached can electrically control heat generation from transparent to opaque, if this is used for a window, it can be used in the presence or absence of direct sunlight. It becomes a more functional window that can be used as a window with an electronic curtain without depending on it. Further, the borosilicate glass plate is resistant to heat and is suitable for combination with a heating element.

The shape of the laminated body can be freely selected such as a flat plate and a curved surface, and the size thereof is not particularly limited as long as it has a transparent portion which can directly see the inside. The glass substrate is mainly used for inorganic glass (for example, soda lime glass, borosilicate glass, etc.) and organic glass (for example, polycarbonate plate, acrylic plate, etc.), but a counter substrate uses metal, ceramics, etc. on one side. May be. Further, commonly used processed glass (for example, tempered glass, meshed plate glass, heat ray absorbing glass, heat ray reflecting glass, heat ray absorbing and reflecting glass, etc.) can also be used. In addition, the glass substrate 3 on one side which is not exposed to direct sunlight among the laminated substrates having the ultraviolet ray blocking layer 1 of the liquid film is a transparent film (for example, polyester, triacetylcellulose, methylpentene copolymer, etc.), an ultrathin inorganic glass (for example, , 0.1 mm thick soda lime glass, etc.) can be used to achieve the advantage of weight reduction. This is very effective as it simplifies the frame strength when considering windows. The structure is not particularly limited to a thin substrate, but as a structure, the glass substrate 3 is formed by placing an internal spacer on the ultraviolet ray blocking layer 1 of the liquid film, the aqueous solution composition 5 exhibiting the cloud point phenomenon, and the gas layer 7. May be regarded as a diaphragm and may not be adhered to the encapsulant for sealing. Although not specifically described here, the sealing may be performed by band-sealing the ultraviolet ray blocking layer 1 of the liquid film and the aqueous solution composition 5 exhibiting the cloud point phenomenon, or may be sequentially performed.

The laminated body has a window, an outdoor table,
Widely used outdoors such as advertising lights and tiles. In particular, an excellent window can be obtained by using this laminate for a window. Examples of the windows include windows of ordinary buildings, vehicles such as automobiles and railway cars, and windows of transport planes such as aircraft and elevators. Of course, this window is in a broad sense, and includes such things as an atrium, a skylight, a door with a window, a partition, etc., as well as transparent glass doors, partitions, and walls.

Aqueous solution compositions exhibiting the cloud point phenomenon include polyvinyl alcohol partial acetic acid, polyvinyl methyl ether,
Methyl cellulose, polyethylene oxide, polypropylene oxide, hydroxypropyl cellulose, polyvinyl methyl oxazolidinone, poly N-substituted acrylamide derivative (for example, poly N-isopropyl acrylamide, poly N-ethoxyethyl acrylamide, etc.),
Poly N-substituted methacrylamide derivative (for example, poly N
An aqueous solution of a water-soluble polymer such as isopropyl methacrylamide, poly N-3-ethoxypropyl methacrylamide, etc.), poly N, N-disubstituted acrylamide derivative (eg, poly N-methyl N-ethyl acrylamide, etc.), and water. A gel (for example, cloud gel manufactured by Suntex Co., Ltd.) as a medium is known. These aqueous solution compositions do not absorb light in the visible range of at least 400 to 800 nm, and this wavelength range does not contribute to light resistance. Next, it is necessary to fully take measures in the ultraviolet region of 290 to 400 nm, particularly 350 nm or less. In addition, 800-2140
The near-infrared region of nm is low energy light, and there is no problem in light resistance even if it absorbs light. The same applies to an aqueous solution composition in which a temperature adjusting agent (eg, sodium chloride etc.), a phase separation inhibitor (eg, polypropylene glycol oligomer etc.) and the like are added in addition to the above water-soluble polymer.

Next, the present inventor prepared a laminate of the aqueous solution composition 5 exhibiting the cloud point phenomenon and tested it for light resistance. Hydroxypropyl cellulose is used as a representative example of an aqueous solution polymer exhibiting a cloud point phenomenon, but is not limited thereto.

[0020]

【Example】

Example 1 Tinuvin 171 was laminated on a pair of soda-lime glass substrates (thickness of 3 cm and 10 cm square) having a thickness of 0.1 mm and temporarily sealed with an aluminum tape having an adhesive to obtain a laminated substrate. This substrate and soda lime glass substrate (3 mm thick 1
Hydroxypropyl cellulose (average degree of polymerization: 175, viscosity of 2% aqueous solution at 20 ° C .: 8.5 cps, hydroxypropyl group: 62.4%) during 0 cm square:
Polypropylene oligomer with 5 parts by weight and a molecular weight of 400:
1 part by weight and 3% by weight of sodium chloride water: 8 parts by weight of an evenly dissolved aqueous solution composition was laminated on the entire surface through 0.2 mm beads, and then the outer periphery was temporarily sealed with an adhesive-attached aluminum tape. After cleaning the substrate surface, a U-shaped aluminum frame was sealed with a room temperature curable epoxy resin to form a sealed laminate. Next, the laminated substrate of the laminate is placed on the light source side, and the sunshine weather meter (WEL-S manufactured by Suga Test Instruments Co., Ltd.
UN-HC type) and JIS K5400 condition 1
After irradiation for 000 hours, no particular change was observed in the light-shielding property due to white turbidity, which is a function of the laminate.

[0021]

【Example】

Example 2 The laminated body obtained in the same manner as in Example 1 had a UV light intensity of about 10 times or more the level of the weather meter and a SU of Iwasaki Electric Co., Ltd.
Using V-F2 type, UV intensity 100mw, black panel temperature 63 ° C, irradiation distance 235mm 30
After irradiation for 0 hours, no particular change was observed in the light-shielding property due to cloudiness.

[0022]

【Example】

Example 3 Tinuvin 384 having a thickness of 0.1 mm was laminated with a soda lime glass substrate (3 mm thick, 10 cm square) to obtain a laminated substrate. This substrate and soda lime glass substrate (3 mm
Hydroxypropyl cellulose (average degree of polymerization: 175, viscosity of 2% aqueous solution at 20 ° C .: 8.5 cps, hydroxypropyl group: 62.4) during 10 cm square of thickness.
%): 5 parts by weight and 1% by weight aqueous sodium chloride: 3 parts by weight, to obtain a highly viscous aqueous solution composition in the same manner as in Example 1 to obtain a laminate. Next, the laminated substrate of the laminated body is placed on the light source side, and a sunshine weather meter (WEL-SUN-HC type manufactured by Suga Test Instruments Co., Ltd.) is used to measure JIS K5400.
Irradiation was performed for 1000 hours under the conditions described above, but there was no particular change in the light-shielding property due to white turbidity, which is a function of the laminate.

[0023]

【Example】

Example 4 The laminated body obtained in the same manner as in Example 3 has a UV light intensity of about 10 times or more that of a weather meter and is SU of Iwasaki Electric Co., Ltd.
Using V-F2 type, UV intensity 100mw, black panel temperature 63 ° C, irradiation distance 235mm 30
After irradiation for 0 hours, no particular change was observed in the light-shielding property due to cloudiness.

[0024]

【Example】

Example 5 As a comparative example, the laminated body obtained by removing the ultraviolet absorber from the laminated bodies of Examples 1 and 3 was used as the SUV-F2 type manufactured by Iwasaki Electric Co., Ltd., which has an ultraviolet light amount of about 10 times the level of a weather meter or more. As a result of irradiation for 300 hours under the conditions of an ultraviolet intensity of 100 mw, a black panel temperature of 63 ° C., and an irradiation distance of 235 mm, the light-shielding characteristics due to white turbidity were greatly deteriorated due to the occurrence of bubbles in both laminates.

[0025]

As described above, according to the present invention, it is possible to reliably and stably cut ultraviolet rays for a long term by the laminated substrate having the liquid crystal ultraviolet ray cutting layer 1 to protect the laminate. The laminate of the water-soluble composition 5 exhibiting the cloud point phenomenon, which is formed by using the ultraviolet ray blocking layer 1 of the liquid film, has sufficient light resistance against irradiation with sunlight for a long period of time. As a result, it is possible to achieve a comfortable living space in an energy-saving manner by autonomously controlling direct sunlight and controlling the direct sunlight with durability, even in windows of buildings, vehicles, and the like, which are used under extremely severe conditions.

[Brief description of drawings]

FIG. 1 is an example of a laminate having a laminated substrate having an ultraviolet ray blocking layer 1 of a liquid film according to the present invention.

FIG. 2 is a spectral absorption spectrum from 190 nm to 400 nm of a 1% by weight aqueous solution of hydroxypropyl cellulose.

FIG. 3 is an example of a multi-layer laminate having a laminated substrate having an ultraviolet ray blocking layer 1 of a liquid film according to the present invention.

FIG. 4 is an example of a multi-layer laminate having a laminated substrate having a liquid film ultraviolet blocking layer 1 according to the present invention.

FIG. 5 is an example of a transmission spectrum of a laminated substrate having a liquid film ultraviolet blocking layer 1.

FIG. 6 is an example of a transmission spectrum of a laminated substrate having a liquid film ultraviolet blocking layer 1.

[Explanation of symbols]

 1 Liquid UV Cut Layer 2 Glass Substrate 3 Glass Substrate 4 Glass Substrate 5 Water-Soluble Composition Showing Cloud Point Phenomenon 6 Glass Substrate 7 Gas Layer

Claims (4)

[Claims] 1. A laminate in which an aqueous solution composition exhibiting a cloud point phenomenon is laminated between substrates and at least a part of which is transparent,
A laminated body, wherein at least one of the substrates is a laminated substrate having a liquid film ultraviolet blocking layer. 2. The laminate according to claim 1, which blocks ultraviolet rays having a wavelength of at least 350 nm or less. 3. The laminated body according to claim 1, wherein the ultraviolet ray blocking layer of the liquid film is an ultraviolet ray absorbent which is liquid at room temperature. 4. In a window using a laminate in which an aqueous solution composition exhibiting a cloud point phenomenon is laminated between substrates and at least a part of which is transparent, at least one substrate of the laminate has an ultraviolet ray blocking layer of a liquid film. A window characterized in that a laminated substrate is used and the substrate is provided on the sunlight side.