JPH0628938B2 - Transparent heat insulating material and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a transparent heat insulating material and a method for producing the same, and in particular, it has excellent durability and antifouling property, and visible light included in solar radiation. The present invention relates to a transparent heat insulating material that transmits and reflects infrared rays, and a method for manufacturing the same. More specifically, when the present invention is used in a harsh environment such as a window of a building, a window of a show, a window of a vehicle / aircraft, a shade tent, a house tent, a truck hood, etc. In particular, the present invention relates to a transparent heat insulating material having excellent durability and antifouling property, and a method for producing the same.

[Conventional technology]

Aluminum, silver, on the organic polymer film as a transparent heat insulating material for transmitting visible light and blocking infrared rays,
A laminated film is known in which a metal such as gold or copper is vacuum-deposited in a thickness that does not impair the transparency. Furthermore, as a thin film that more positively transmits visible light, a so-called selective transmission film, a three-layer structure in which a metal thin film as disclosed in JP-A-51-66841 is sandwiched by a transparent high refractive index thin film, or indium oxide So-called Drude Mi using a thin film of tin oxide
The rror type is also well known.

By the way, when these thin films are actually used, not only the performance that was originally the main purpose such as transparency to visible light and reflection to infrared rays, but also abrasion resistance, light resistance, corrosion resistance -Practical performance such as durability against stains and physical / environmental factors such as water resistance and antifouling property is also required.

However, since the above-mentioned thin film itself is insufficient in durability and antifouling property, it was necessary to provide some kind of transparent protective layer at the time of use.

Such a transparent protective layer is generally formed by coating a transparent coating agent, but when it is applied to a transparent heat insulating film, there are the following problems.

If the protective layer is made sufficiently thick, the necessary protective effect can be obtained. However, when the material forming the coating agent has absorptivity to infrared rays, heat is absorbed by the protective layer, and the absorbed thermal energy is re-radiated as heat rays, or due to conduction / convection. The protective layer prevents the heat-reflecting effect of the transparent insulating material from being transmitted to the surroundings.

Moreover, as a matter of course, this tendency becomes stronger as the thickness of the protective layer is increased.

When the protective layer is made thin to reduce the heat absorption by the protective layer as much as possible, it depends on the refractive index, but when the film thickness is around 1 μm, a rainbow-colored stripe pattern is generated due to interference, and the appearance It is not preferable. If the protective layer is made thinner to prevent this interference, the effect required as the protective layer cannot be obtained.

In order to solve the above-mentioned problems, Japanese Patent Laid-Open No. 61-167546 takes measures to improve the durability of the transparent heat insulating layer itself. That is, when using a transparent heat insulating layer having a three-layer structure in which a metal thin film is sandwiched by a thin film of a transparent high refractive index substance, a zirconium compound-silicon compound mixed thin film having good durability is used as the transparent high refractive index substance thin film. That is.

With such a transparent heat insulating material, the protection layer does not absorb heat and its durability can be improved to some extent. However, in the end, the transparent heat insulating layer is exposed to the outside, and this structure is insufficient in resistance to mechanical external force, particularly in abrasion resistance.

Further, JP-A-57-107834 discloses a method of coating a protective layer containing (meth) acrylonitrile as a main component, which has excellent abrasion resistance and weather resistance, and has a small infrared ray absorption. In order to reinforce the property, it is disclosed that a polyurethane having a three-dimensional crosslinked structure is coated in advance, whereby a protective layer having high durability and suppressing infrared absorption as much as possible can be obtained.

However, the resin containing (meth) acrylonitrile that forms the outermost layer has insufficient antifouling property. Therefore, when dirt adheres to the resin, the infrared ray reflectivity changes with time due to the diffusion of the dirt component into the resin layer. Had the drawback that

[Problems to be Solved by the Invention]

The present invention has the above-mentioned problems that the conventional transparent heat insulating material has, namely, lack of durability against physical / environmental factors such as abrasion resistance, light resistance, corrosion resistance, and water resistance.
Also, it eliminates the problems of lack of infrared reflection performance over time, and has excellent durability and antifouling properties, and flexibility even under the severe operating conditions of being directly exposed to the atmosphere or sunlight outdoors. (EN) An inexpensive transparent insulating material and a method for producing the same.

[Means for Solving the Problems]

The transparent heat insulating material of the present invention is a transparent resin film layer having a total light transmittance of 80% or more for light having a wavelength of 400 to 2100 nm, and an adhesive resin layer on one side of the transparent resin film layer. An infrared-reflecting layer that is substantially transparent to visible light and is made of at least one selected from the group consisting of metals and metal oxides. A modified layer formed by low-temperature plasma treatment or corona discharge treatment is formed on the one surface of the film.

The method of the present invention for producing the transparent heat insulating material is 400 to 210.
For light having a wavelength of 0 nm, one side of the transparent resin film having a total light transmittance of 80% or more, low-temperature plasma treatment, or subjected to corona discharge treatment, a modified layer on the surface portion of the one side. And forming an adhesive resin layer on the modified layer, and on the adhesive resin layer, at least one selected from a metal and a metal oxide by a vacuum vapor deposition method or a sputtering method. It is characterized by forming a single infrared reflection layer that is substantially transparent to visible light.

Other transparent heat insulating material of the present invention, for light having a wavelength of 400 to 2100 nm, a transparent resin film layer having a total light transmittance of 80% or more, on one surface of the transparent resin film layer, adhesiveness An infrared reflection composite having at least one layer, which is bound through a resin layer and is made of at least one selected from metals and metal oxides, and an infrared reflection layer which is almost transparent to visible light. And a substrate, which is bound via an adhesive layer on the infrared reflective layer of the composite and contains a transparent polymer material, and a low temperature plasma treatment on the one surface of the transparent resin film, Alternatively, the modified layer is formed by corona discharge treatment.

The method of the present invention for producing the above transparent heat insulating material is 400 to 2
For light having a wavelength of 100 nm, one side of the transparent resin film having a total light transmittance of 80% or more, low-temperature plasma treatment, or subjected to corona discharge treatment, a modified layer on the surface portion of the one side And forming an adhesive resin layer on the modified layer, and on the adhesive resin layer, at least one selected from a metal and a metal oxide by a vacuum vapor deposition method or a sputtering method. An infrared reflective layer that is substantially transparent to visible light is formed to form an infrared reflective composite, and a transparent polymer material is provided on the infrared reflective layer of the composite via an adhesive layer. It is characterized by binding a base body containing the same.

As described above, the transparent heat insulating material of the present invention has a transparent resin film and an infrared reflective layer, and if necessary, an infrared reflective composite including the transparent resin film and the infrared reflective layer, A substrate containing a transparent resin material is laminated and united.

In the heat insulating material of the present invention having the above structure, one surface of the transparent resin film to be joined to the infrared reflection layer is
A modified layer formed by low-temperature plasma treatment or corona discharge treatment is formed, and the transparent resin film and the infrared reflective layer are firmly bonded through the modified layer and the adhesive resin layer formed thereon. Is glued to.

The transparent heat insulating material of the present invention shown in FIG. 1 includes a transparent resin film layer 1, a modified layer 2 formed on one surface thereof, and an adhesive resin layer 3 formed on the modified layer 2. The transparent resin film layer 1 through the modified layer 2 and the adhesive resin layer 3
And an infrared reflection layer 4 laminated and adhered to.

The transparent heat insulating material of the present invention shown in FIG. 2 has the same transparent resin film layer 1, modified layer 2 and adhesive resin layer 3 as in FIG.
And an infrared reflective composite 5 comprising an infrared reflective layer 4,
The composite 5 comprises a transparent substrate 7 laminated and adhered to the infrared reflection layer 4 via an adhesive layer 6. In this case, the transparent substrate 7 is composed of a single transparent polymer layer.

The transparent heat insulating material of the present invention shown in FIG. 3 has the same structure as that shown in FIG. 2, but its transparent substrate 7 has two transparent polymer material layers 7a. , And the fibrous material layer 8 sandwiched therebetween.

As the transparent resin film used in the present invention, JIS A-
Light transmittance by the 5759 method, that is, wavelength 400 to 2100n
It has a total light transmittance of 80% or more for m light. As the resin forming such a transparent resin film, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether, Fluorine-containing resin such as tetrafluoroethylene-ethylene copolymer and chlorotrifluoroethylene-ethylene copolymer, polyolefin resin such as polyethylene and polypropylene, acrylic resin such as polymethyl acrylate and polybutyl acrylate, polycarbonate-based resin There are resins and polyester resins such as polyethylene terephthalate and polybutylene terephthalate, and films made of these resins may be used alone or in a laminated form. Kill. In particular, the fluorine-containing resin film and the polyolefin-based resin film are excellent in light transmittance, and also excellent in durability against physical and environmental factors and antifouling property.

The transparent resin film preferably has a thickness of 6 to 100 μm. If the thickness is less than 6 μm, it may be difficult to handle such a film during various processes, and if it exceeds 100 μm, the infrared transmittance may be significantly reduced. , Will be high price again.

In the present invention, the preferable thickness of the transparent resin film is 5
˜70 μm, more preferably 10-70 μm thickness.

In the present invention, the modified layer is formed on the adhesive surface of the transparent resin film by the low temperature plasma treatment and the corona discharge treatment.

Generally, the low temperature plasma treatment is performed at a pressure of 0.001 to 10 Torr using a low temperature plasma of a gas having no plasma polymerizability. As such gas, helium,
One or more mixed gas selected from neon, argon, nitrogen, nitrous oxide, nitrogen dioxide, oxygen, air, carbon monoxide, carbon dioxide, hydrogen, chlorine, hydrogen chloride, sulfurous acid gas, hydrogen sulfide, etc. Is used. Especially 20% by volume or more,
It is preferable to use a gas containing oxygen at a content rate of preferably 60 to 100% by volume.

Low temperature plasma can also be generated by conventional methods. Generally, in a low temperature plasma generator, the gas pressure is adjusted to 0.001-10 torr and between the electrodes, for example 13.56 MH.
z, 10 to 500 watts of power is applied. The discharge at this time may be either polar discharge or non-polar discharge, and the plasma treatment time is generally preferably several seconds to several tens of minutes depending on the applied voltage.

In addition to the above method, low-temperature plasma treatment may use low frequency as a discharge frequency band, microwave, or may use direct current, and further, as a plasma generation mode, glow discharge, corona discharge, spark discharge. , Silent discharge, etc. may be used. There is no particular limitation on the structure of the electrode.

Known methods such as a spark gap method, a vacuum tube method, and a solid state method can be used for the corona discharge treatment used in the present invention. In order to improve the surface workability of the material to be treated, for example, the adhesiveness, it is preferable that its critical surface tension is 35 to 60 dyn / cm, and for this purpose, the substrate surface is 5 to 50,000 W / m ² / Min, preferably 15
It is preferable to impart a processing energy of 0 to 40,000 W / m ² / minute. The amount of energy to be applied (voltage, amount of current, distance between electrodes, etc.) is determined in consideration of the width of the material to be processed, processing speed, and the like. For example, when a corona discharge treatment is applied to a material surface having a width of 2 m at a processing speed of 10 m / min, the output (power consumption) is preferably about 4 kw to 800 kw. However, the condition is not necessarily limited to this.

In the present invention, as the adhesive resin used for the transparent resin film, from the visible region, it is preferable to use a material having no or little absorption over the infrared region, and at the time of vacuum vapor deposition or sputtering treatment. It is preferable that the material does not deform or color due to heat. As such an adhesive resin material, an acrylic resin, a polyester resin, and a polyolefin resin are suitable, and they are used alone or in combination. Further, this adhesive resin material may contain an ultraviolet absorber or an antioxidant, if necessary.

Although the thickness of the adhesive resin layer varies depending on its refractive index, it is preferable that the thickness that causes interference, specifically, the thickness of 0.5 to 1.5 μm is avoided, and the maximum thickness thereof is Depending on the infrared absorptivity of the adhesive resin, it is preferably in the range that does not impair the heat ray reflectivity, generally 20 μm or less, and more preferably 10 μm or less. When the transparent resin film is a fluorine-containing resin film, the total thickness of this film layer and the adhesive resin layer is preferably 100 μm or less.

In order to form the adhesive resin layer, the adhesive resin coating liquid may be applied onto the modified layer of the transparent resin film by a common coating method such as doctor coating, roll-on coating, or spray coating, and then solidified.

In the present invention, at least one layer of an infrared reflective layer, which is substantially (approximately) transparent to visible light, is formed on the adhesive resin layer and is made of at least one selected from metals and metal oxides. To be done.

In the present invention, as the infrared reflection layer, a metal thin film sandwiched by a thin film of a transparent high refractive index material, or a so-called Drude Mirror formed by a metal oxide thin film is used.
It is preferable to use the type, but depending on the purpose, a single layer of a metal thin film, that is, a so-called half mirror type may be used.

Examples of the metal thin film layer used in the present invention include gold, silver, copper,
Aluminum, nickel, palladium, tin, chromium, titanium and alloys thereof can be used as a single layer or a laminate of a plurality of layers.

The thin film of the transparent high refractive index material has a refractive index of 1.4 or more, preferably 1.8 or more, and a visible light transmittance of 8 or more.
0% or more, preferably 90% or more is used, and examples thereof include titanium dioxide, bismuth oxide, zinc sulfide,
Examples thereof include at least one selected from tin oxide, silicon dioxide, zirconium oxide, nickel oxide, indium oxide and the like.

Indium oxide, tin oxide, and mixtures thereof are examples of the metal oxide thin film exhibiting Drude reflection.

The infrared reflective layer as described above can be formed by a conventionally selected method such as a vacuum vapor deposition method, a sputtering method, a plasma spraying method, an ion plating method, and a plating method.

There is no particular limitation on the thickness of the infrared reflecting layer used in the present invention, and it may be a single layer or a composite layer of two or more layers, but the preferable total thickness is 100 to Five
It is 000Å, and more preferably 100 to 1000Å.
In one aspect of the transparent heat insulating material of the present invention, an infrared reflection composite comprising a transparent resin film and an infrared reflection layer joined and bonded via a modified layer and an adhesive resin layer formed on one surface thereof. A substrate containing a transparent polymer may be bonded to the infrared reflection layer via an adhesive layer.

Such a substrate contains a transparent polymer material which is substantially transparent in the visible light region having a wavelength of 400 to 700 nm.

As such a transparent polymer material, transparent synthetic resin, synthetic rubber or natural rubber is used. As a preferable synthetic resin, for example, polyvinyl chloride (PVC), polyurethane, ethylene-vinyl acetate copolymer, polyacrylonitrile, polyester, polyamide, fluorine resin and silicone resin and other known materials can be used. Further, as an example of a preferable synthetic rubber, styrene-
Butadiene rubber (SBR), chlorosulfonated polyethylene rubber, polyurethane rubber, butyl rubber, isoprene rubber, silicone rubber, fluorine rubber and other known materials are available. Particularly, in consideration of flexibility, processability, versatility and cost, it is preferable to use polyvinyl chloride resin.

The polyvinyl chloride resin is a soft polyvinyl chloride resin, a hard polyvinyl chloride resin, a vinyl chloride and an olefin, for example, a copolymer resin of ethylene, propylene, or isobutylene, a copolymer resin of vinyl chloride and styrene. A copolymer resin of vinyl chloride and a diene such as butadiene or isoprene, a copolymer resin of vinyl chloride and acrylic acid, a halogenated olefin, or vinyl acetate, and the above resin, and a modified resin. Resin, for example, mixed resin with rubber such as ABS, SBR, or NBR.

Such a transparent polymer material may contain a plasticizer, a colorant, various stabilizers, a hardener, etc., as long as the object of the present invention is not impaired.

The substrate used in the present invention may contain a fibrous material as long as it does not significantly impair its transparency.

As the fibrous material, natural fiber, for example, cotton, hemp, etc., inorganic fiber, for example, glass fiber, carbon fiber, asbestos fiber, metal fiber, etc., recycled fiber, for example, viscose rayon, cupra, etc., semi-synthetic fiber, For example,
And tri-acetate fiber and the like, and synthetic fiber such as nylon 6, nylon 66, polyester (polyethylene terephthalate etc.) fiber, aromatic polyamide fiber,
It is made of at least one selected from acrylic fiber, polyvinyl chloride fiber, polyolefin fiber, and water-insolubilized or sparingly-solubilized polyvinyl alcohol fiber. The fibers in the base cloth may be of any shape such as short fiber spun yarn, long fiber yarn, split yarn, tape yarn, etc., and the base fabric is a woven fabric, a fibrous or non-woven fabric,
Alternatively, any of these composite cloths may be used.

Generally, the fibrous material contained in the substrate is preferably a polyester fiber and a glass fiber, and in consideration of the low elongation to stress, the fiber is preferably in the form of a filament (filament). It is preferable to form a plain woven fabric. However, the weaving structure of the fibrous material and its form are not particularly limited.

Fibrous materials are useful for reinforcing the mechanical strength of the substrate and maintaining high strength levels.

The substrate used in the present invention preferably has a thickness of 0.1 to 1.0 mm.

The infrared reflective composite of the present invention and the transparent substrate are laminated and adhered via an adhesive layer. Examples of the adhesive useful in the present invention include melamine-based adhesives, phenol-based adhesives, epoxy-based adhesives, polyester-based adhesives, polyethyleneimine-based adhesives, polyisocyanate-based adhesives,
Polyurethane adhesives, acrylic adhesives, polyamide adhesives, vinyl acetate-vinyl chloride adhesives, vinyl acetate-copolymer adhesives such as ethylene adhesives, and the like,
Without being limited to these, a known adhesive can be arbitrarily selected and used.

Generally, the adhesive layer preferably has a thickness of 1 to 30 μm. Further, the method for forming the adhesive layer is not particularly limited, and a conventional adhesive applying method can be used.

〔Example〕

 Hereinafter, the present invention will be described with reference to examples.

In addition, in the examples, the heat insulation rate means that the heat flow meter (Shothe
rm HFM: Showa Denko), the heat absorption is assumed to be 100 when nothing is placed between the calorimeter sensor and the heat source, and the test sample is placed between the two to absorb heat after the heat flow is stabilized. When the amount is a, it is represented by (100−a / 100) × 100 (%). A tungsten lamp was used as the heat source. Unless otherwise specified, this measurement was performed by directly exposing the surface of the transparent resin film layer of the transparent heat insulating material to a heat source, assuming actual use conditions.

In addition, the light transmittance in the examples means the transmittance with respect to a light ray having a wavelength of 550 nm.

Example 1 NEOFLON films ETFE, CTFE and FE with a thickness of 50 μm
P (trademark of film fluorine-containing resin, manufactured by Idemomo Daikin Industries, Ltd.) KF film PVdF (Kureha Chemical Industry Co., Ltd.)
Manufactured by Toray Flon Film PFA (trademark of fluorine-containing resin manufactured by Toray Industries, Inc.),
Polyethylene film (manufactured by Toyo Soda Co., Ltd., trademark: Nipolon-L), Lumirror PET (manufactured by Toray Co., Ltd., trademark of polyester film), polycarbonate film (manufactured by Mitsubishi Gas Chemical Co., Inc., trademark: Apilon), polyacrylonitrile film ( Mitsui Toatsu Chemical Co., Ltd., trademark: Zekron), or polyurethane film (GOODRICH, trademark: Estane) on one side of each film, the amount of energy 50
Corona discharge treatment was applied under the condition of 0 W / m ² / min. afterwards,
An acrylic adhesive (trademark: SC-462, manufactured by Sony Chemical Co., Ltd.) was applied to the treated (modified layer) surface by a bar coat method to give a thickness of 5 μm.
It was applied to a thickness of m. Then, an infrared reflection layer made of a semitransparent copper layer having a film thickness of 200 Å was formed on the adhesive resin layer by a sputtering method. Each of the transparent heat insulating materials obtained as described above was measured for light transmittance with respect to light having a wavelength of 550 nm, heat insulation rate using a tungsten lamp as a heat source, and heat insulation retention, and the results are shown in Table 1.

In Table 1, the heat insulation retention is the ratio of the heat insulation coefficient measured from the transparent resin film layer side to the heat insulation coefficient value measured from the infrared reflective layer side of the transparent heat insulating material. It is a value indicating to what extent the resin film layer has been reduced by infrared absorption. That is, the larger this value, the less the infrared absorption of the transparent resin film, and the more suitable it is for the purpose of the present invention.

The results shown in Table 1 indicate that various fluorine-containing resin films and polyethylene films are more effective than other resin films in increasing the heat retention of the transparent heat insulating material of the present invention. Is shown. But first
Any of the resins shown in the table can be practically used as the transparent resin film of the transparent heat insulating material of the present invention.

Examples 2 to 5 and Comparative Examples 1 and 2 In Example 2, a pressure of 0.
Plasma treatment is performed for 30 seconds at a power density of 5 W / cm ² in an oxygen gas atmosphere of 55 torr, and then the treated surface is coated with an acrylic adhesive (Sony Chemical: SC-462) to a thickness of 6 μm by a gravure method. Then, a ZnS layer with a thickness of 300 Å, an Ag layer with a thickness of 180 Å and a thickness of 290 Å by vacuum evaporation
Then, the ZnS layer was sequentially laminated to form an infrared reflective layer, and a film having a transparent heat insulating property was manufactured.

In Example 3, the same operation as in Example 2 was performed. However, instead of plasma treatment, corona discharge treatment (energy amount 500 W / m ² / min) was performed.

In Examples 4 and 5, 200 μm thick soft PVC
A film prepared by coating a polyester adhesive (trade name: Elitel 3201 manufactured by Unitika Ltd.) to a thickness of 10 μm is prepared as a substrate, and the infrared reflecting composite of Example 2 is placed on the adhesive layer of the substrate. And the infrared reflection layer surface (Example 5) of Example 3 and the infrared reflection layer surface (Example 5) of the infrared reflection composite body of Example 3 are bonded by pressure bonding (120 ° C. heat roll) while heating. The adhesive strength between the substrate and the substrate was measured.

The adhesive strength was measured using Instron Strograph T (manufactured by Toyo Seiki Co., Ltd.) with a slit width of 3 cm. In Comparative Example 1, the same operation as in Example 3 was performed. However, the adhesive was not coated after the plasma treatment. The same operation as in Example 4 was performed in Comparative Example 2. However, the adhesive resin layer was formed without performing corona discharge treatment or the like.

The measurement results are shown in Table 2.

As clearly shown in Table 2, by performing low-temperature plasma treatment or corona discharge treatment on the bonding surface of the transparent resin film layer, the adhesive strength at the transparent resin film-adhesive resin interface is significantly improved, The durability of the transparent heat insulating material against physical and environmental factors is improved.

Examples 6 to 9 and Comparative Examples 3 to 5 In Example 6, the same method as in Example 2 was performed on one surface of a transparent resin film made of a FEP film having a thickness of 25 μm (trade name: NEOFLON manufactured by Daikin Industries, Ltd.). A low temperature plasma treatment was applied. However, the processing time was 2 minutes.

An acrylic adhesive (trademark: TEDLAR ADHESIVE 68080, manufactured by DUPONT, Inc.) was coated on the low-temperature plasma-treated surface of this film to a thickness of 5 μm by using a bar coder, and further, a thickness thereof was formed by a sputtering method. 250 Å TiO ₂
Layer, 180 Å Ag layer, and 250 Å TiO ₂ layer having a thickness of 250 Å are sequentially formed and laminated, and a transparent PVC sheet is used in the same manner as in Example 2 (as a reinforcing material, yarn density vertical 0.5 / cm × width 0.5). (Including books / cm plain weave) to produce a transparent insulation material.

In Examples 7 to 9, the same operation as in Example 6 was performed.
However, instead of the FET film, in Example 7,
In Example 8, a PET film having a thickness of 25 μm (trade name: Lumirror, manufactured by Toray Industries, Inc.) was used. In Example 8, a polyacrylonitrile film having a thickness of 25 μm (trade name: Zekron, manufactured by Mitsui Toatsu Chemicals, Inc.) was used. Is a 25 μm thick polyurethane film (trade name: Esmer US, manufactured by Nippon Matai Co., Ltd.)
R) was used.

Table 3 shows the performance of the above four kinds of transparent heat insulating materials. Moreover, when these were exposed outdoors for 1 year, the material of Example 6 was
Although some adhesion of stains was observed, the stains could be almost completely removed by wiping, and there was no change in appearance such as discoloration.

On the other hand, the sample of Example 7 loses gloss in about 4 months, cracks are generated at the time of bending, and at the end of 1 year, the film has been completely lost due to the wind. It was The materials of Examples 8 and 9 had a lot of stains attached, and the stains could not be completely removed by wiping. In addition, the sample of Example 9
The hue had changed to yellow.

Table 3 shows the results of evaluating the heat insulation rates of these samples before and after exposure.

In addition, the measurement of the heat insulation rate after the exposure was performed after wiping off the stains attached to the surface with a soft cloth (cotton) wet with water.

From these results, it can be seen that when the FEP film made of a fluorine-containing resin is used, a laminate having excellent antifouling property / weathering resistance and little change in heat resistance over time can be obtained.

Examples 10 and 11 In Examples 10 and 11, a PVdF film having a thickness of 25 μm was used as a transparent resin film, and a transparent heat insulating film was produced in the same manner as in Example 2.

This film was laminated and adhered to a substrate made of a PVC sheet containing a fibrous material in the same manner as in Example 2. This fibrous material was a reinforcing cloth having the following structure: vertical length 0.5 cm / cm × horizontal width 0.5 mm / cm (Example 10) vertical length 1.8 mm / 2.54 cm × horizontal width 1.8 mm / 2.54 cm (Example 11).

The water resistance, heat resistance and strength of these sheets were evaluated. The results are shown in Table 4.

As shown in Table 4, the transparent heat insulating material of the present invention having a substrate containing a fibrous material is excellent in dimensional stability and strength, and is particularly used for tents such as sunshades requiring strength. Suitable for applications such as truck hoods.

〔The invention's effect〕

The transparent heat insulating material of the present invention has the following properties.

1. Outermost layer, that is, the protective layer is a transparent resin film, for example, a fluorine-containing resin film, or good mechanical strength by forming a polyolefin resin film,
In particular, even under severe usage conditions such as direct exposure to the outdoors, the excellent weather resistance and antifouling property are exhibited, and the initial performance and appearance can be maintained for a long period of time.

2. Low temperature plasma treatment on the bonding surface of the transparent resin film,
By performing the corona discharge treatment, the adhesive strength between the transparent resin film layer and the adhesive resin layer is improved, and a transparent heat insulating material having excellent durability can be obtained.

3. By forming the transparent substrate from, for example, a polyvinyl chloride resin, it is possible to obtain an inexpensive and flexible sheet material having transparency and heat insulation properties that cannot be obtained by conventional polyvinyl chloride resin molded products.

As described above, the transparent heat insulating material obtained by the present invention is excellent in weather resistance and antifouling property, has little deterioration in infrared reflection performance over time, and can be compounded with various materials.

In particular, by using, for example, a polyvinyl chloride resin molded product containing a fibrous material as a substrate, a transparent heat insulating material having excellent product strength can be obtained. It is useful for applications such as partition sheets and truck hoods.

[Brief description of drawings]

1 to 3 are cross-sectional explanatory views showing the constitution of one embodiment of the transparent heat insulating material of the present invention. 1 ... Transparent resin film layer, 2 ... Modified layer, 3 ... Adhesive resin layer, 4 ... Infrared reflecting layer, 5 ... Infrared reflecting complex, 6 ... Adhesive layer, 7 ... Transparent substrate , 7a: transparent polymer material layer, 8: fibrous material layer.

Claims (4)

[Claims] 1. For light having a wavelength of 400 to 2100 nm, 8
A transparent resin film layer having a total light transmittance of 0% or more, and at least one selected from a metal and a metal oxide, which is bound to one surface of the transparent resin film layer via an adhesive resin layer. At least one layer of an infrared-reflecting layer substantially transparent to visible light, and a modified layer formed by low-temperature plasma treatment or corona discharge treatment on the one surface of the transparent resin film. It is a transparent heat insulating material. 2. For light having a wavelength of 400 to 2100 nm, 8
On one surface of the transparent resin film having a total light transmittance of 0% or more, low-temperature plasma treatment, or subjected to corona discharge treatment, to form a modified layer on the surface portion of the one surface, on the modified layer An adhesive resin layer is formed, and at least one layer made of at least one selected from a metal and a metal oxide is exposed to visible light on the adhesive resin layer by a vacuum deposition method or a sputtering method. A method for producing a transparent heat insulating material, comprising forming a transparent infrared reflective layer. 3. For light having a wavelength of 400 to 2100 nm, 8
A transparent resin film layer having a total light transmittance of 0% or more, and at least one selected from a metal and a metal oxide, which is bound to one surface of the transparent resin film layer via an adhesive resin layer. An infrared-reflecting composite comprising at least one layer of a seed and an infrared-reflecting layer that is substantially transparent to visible light; and an infrared-reflecting layer of the composite, which is bound via an adhesive layer, And a substrate containing a transparent polymer material, and a modified layer formed by low temperature plasma treatment or corona discharge treatment is formed on the one surface of the transparent resin film. material. 4. For light having a wavelength of 400 to 2100 nm, 8
On one surface of the transparent resin film having a total light transmittance of 0% or more, low-temperature plasma treatment, or subjected to corona discharge treatment, to form a modified layer on the surface portion of the one surface, on the modified layer An adhesive resin layer is formed, and at least one layer made of at least one selected from a metal and a metal oxide is exposed to visible light on the adhesive resin layer by a vacuum deposition method or a sputtering method. A transparent infrared reflective layer is formed to form an infrared reflective composite, and a base material containing a transparent polymer material is laminated and bound on the infrared reflective layer of the composite via an adhesive layer. A method for producing a transparent heat insulating material, comprising: