JP2003266612A - Heat barrier anti-staining film material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat barrier anti-staining film material excellent in heat barrier/anti-staining effect, withstanding long-term outdoor use and useful for an outdoor tent. <P>SOLUTION: The heat barrier anti-staining film material includes a heat controllable resin layer containing 1-30 mass % of a metal powder and/or a ceramics powder (an additive volatilization preventing layer for preventing the volatilization of additives for a resin may be formed on the surface of the heat controllable resin layer) formed on at least one of the upper and rear surfaces of a sheetlike base material through a resin foamed layer or without interposing the resin foamed layer, a photocatalytic action cutting-off protective layer formed on the heat controllable resin layer through a metal oxide transparent layer and/or a metal thin film layer or without interposing the same and a photocatalyst-containing layer formed on the protective layer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film material having a heat shield function and an antifouling function for sustaining an effect of efficiently attenuating sunlight heat in outdoor applications. More specifically, the present invention provides an awning tent that provides a comfortable space for humans and animals, a sheet house, and a truck hood and cargo bed that can prevent excessive temperature rise of goods and foods during distribution. The present invention relates to a heat-shielding antifouling film material suitably used for a cover and the like. In particular, the film material of the present invention has a function of preventing dust and dirt from adhering, which causes attenuation of the heat shield function, can efficiently maintain the heat shield function, and is therefore effective as an industrial material. .

[0002]

2. Description of the Related Art As a conventional waterproof canvas used for building structures such as sunshade tents, medium and large-sized tents, tent warehouses, and truck hoods and luggage carrier covers,
A fiber composite membrane material obtained by using a fiber woven fabric as a base fabric and coating the surface of the fabric with a soft blended polyvinyl chloride resin is mainly used. These membrane materials are flexible and tough,
Also, since it has excellent weather resistance, it can withstand long-term outdoor use. Ideally, these fiber composite membrane materials have a high degree of heat shielding property in terms of their applications.
Since the current polyvinyl chloride resin fiber composite membrane material has a low heat-shielding property, the temperature inside the tent warehouse and truck hood rises, especially in the summer, even though direct sunlight is blocked. As a result, particularly in summer, luggage and materials stored in the warehouse and luggage being transported may rise to a temperature as high as the outside temperature. This is not limited to the polyvinyl chloride resin fiber composite membrane material. For example, even if the polyvinyl chloride resin is replaced with a thermoplastic resin such as polyethylene resin, polypropylene resin, polyurethane resin, or polyester resin, the result is Is the same as above. Therefore, the conventional fiber composite membrane material for industrial materials does not have a sufficient heat shielding effect.

A material that generally forms an enclosed space,
For example, in a building or a container, in order to effectively block the transfer of heat from the inside to the outside and from the outside to the inside, an inorganic or organic heat insulating material layer is formed with a corresponding thickness. It is necessary. As the inorganic heat shield, for example, glass wool, glassy heat insulator such as foam glass, asbestos, mineral wool, perlite, mineral heat shield such as vermiculite, porous silica, porous alumina, alumina, magnesia, Ceramic-based heat shields such as zirconia and refractory bricks, carbon-based heat shields such as graphite and carbon fiber are used. Further, as the organic heat shielding material, foam trace resin such as expanded polyethylene, expanded polystyrene, expanded polyurethane, wood board, cork,
Natural material-based heat shields such as plant fibers are also used. In addition, an air cell-containing heat insulating material in which a low thermal conductivity of a gas such as air, nitrogen, or helium is used and which is enclosed in aluminum, paper, plastic, or the like is also effectively used. These heat shields are formed of a material having low heat conductivity to suppress heat transfer, or a substance having low heat conductivity such as gas is enclosed in pores or voids to prevent heat transfer. It attenuates movement. Generally, with a porous heat shield, it is possible to increase the heat shield effect by increasing the thickness of the heat shield itself, but increasing the volume for heat shield alone has a large practical disadvantage. .

On the other hand, the fiber composite membrane material used in the above-mentioned tent structure, truck hood, etc. does not incorporate a design having a heat shield layer, and therefore has a problem that its heat shield property is extremely low. ing. Therefore, in order to solve this problem 1). Membrane material in which a foam layer is inserted in the layer structure of the fiber composite membrane material, 2). A film material in which an inorganic metal compound powder is kneaded into the resin coating layer of the fiber composite film material, and 3). Membrane materials and the like that combine these have been proposed. However, in the case of a membrane material including a foam layer, it is necessary to reduce the density of the membrane material itself by increasing the number of foam cells or increasing the size of voids in order to enhance the heat shielding effect. However, in this case, not only the thickness of the foam layer increases and the handling property becomes poor, but also the mechanical strength of the film material becomes insufficient. In addition, a film material obtained by only kneading the inorganic metal compound powder could not provide a long-term heat shielding effect.

On the other hand, especially as a means for preventing a temperature rise due to direct sunlight, 4). A method of providing a light-reflecting metal foil layer on the surface of a film material, and 5). A film material in which metal powder is kneaded into the resin coating layer, 6). Further, a multi-layer structure film material by using a metal foil layer and a layer containing an inorganic metal compound powder, 7).
Also, in combination with a metal foil layer and an inorganic metal compound powder-containing layer,
Further, a multi-layered film material and the like, which is used in combination with a foam layer, has been proposed. Certainly, in the film materials of the modes of 4 to 7) and the like, direct sunlight can be efficiently reflected, and the heat storage of the film material itself and the heat conduction to the inside of the film material can be suppressed.

However, the film material using the metal foil layer is inferior in the followability of the metal foil layer to the elongation of the film material and the bending durability,
In addition, in the film material of the modes of 4 to 7), the surface of the film material is contaminated due to the adhesion of exhaust gas or soot dust floating in the air with the progress of use, thereby reducing the reflectance of direct sunlight. As a result, there is a problem that the initial heat shield effect cannot be maintained.

Further, as a heat-shielding material 8). A film material in which metal vapor deposition films are laminated, 9). A film material in which a near infrared absorbing compound is added to the resin coating layer, 10). Film materials with organic pigments, dyes, etc. added to the resin coating layer have been proposed, but these film materials also have a heat shielding effect due to the accumulation of dirt on the surface of the film material over time. Has been a problem.

Therefore, in particular, a daily tent, a medium and large tent,
A fiber composite for industrial materials that has a heat shield function and is capable of sustaining a stable heat shield effect without being affected by environmental dirt such as soot and dust in building structure applications such as tent warehouses. The development of membrane materials was sought after.

[0009]

DISCLOSURE OF THE INVENTION The present invention provides a heat-insulating antifouling film material capable of effectively preventing, for a long period of time, soot-adhering dirt (environmental dirt) that hinders the heat-shielding effect when used outdoors. In particular, the present invention intends to provide a heat-shielding antifouling film material for industrial materials suitable for use in building structures such as absolete tents, medium and large tents, and tent warehouses.

[0010]

Means for Solving the Problems The present inventor has conducted research and examination in view of the above-mentioned circumstances, and as a result, used a specific substance and a photocatalytic substance in combination, and further used a specific metal thin film layer in combination, A composite membrane material having a photocatalyst layer as an outermost layer obtained by using a specific metal oxide transparent layer in combination, and further using a specific foaming layer in combination, has an excellent heat-shielding function, which was difficult to achieve in the above-mentioned conventional techniques. The present inventors have completed the present invention by finding that the problem of stably obtaining the above can be solved.

The heat-shielding antifouling film material of the present invention is a sheet-like base material.
And at least one of the front and back surfaces of this sheet-shaped substrate
Resin component formed and consisting of at least one polymer
And at least one of metal powder and ceramic powder.
Control of containing 99: 1 to 70:30
On the heat-controllable resin layer and at least one heat-controllable resin layer
A formed photocatalyst containing a photocatalytic substance and a binder
A heat-controllable resin layer and a photocatalyst-containing layer.
Between the layered layer, the heat control resin layer, the photocatalyst containing
Contains as a main component a resin material that blocks the photocatalytic action of the layer
It is characterized in that a protective layer is formed.
In the heat-shielding antifouling film material of the present invention, the heat control resin layer
However, in addition to the resin component and the powder component, volatility and / or
Contains a migratory additive and is formed on its surface.
And the volatilization of the volatile and / or migrating additive.
With a resin material as a main component for preventing dispersion and / or migration
It is preferable to have an additional additive volatilization prevention layer
Good In the heat-shielding antifouling film material of the present invention, the additive
The resin material contained in the volatilization prevention layer is acrylic resin, energy
Lugie wire curable acrylic resin, polyurethane resin, ethyl resin
Small amount selected from ren-vinyl alcohol copolymer resin
It is preferable to include at least one kind. The heat-shielding and antifouling property of the present invention
In the film material, the metal powder contained in the heat control resin layer
But aluminum, stainless steel, nickel,
Select from at least one powder selected from copper and tin
It is preferable to be exposed. Odor of the heat-shielding antifouling film material of the present invention
Then, the ceramic powder contained in the heat controllable resin layer,
Titanium oxide, zinc oxide, aluminum oxide (aluminum
Na), magnesium oxide, zirconium oxide (zirconia
A), tin oxide, indium oxide, tin-doped oxide oxide
Indium-doped, tin oxide, antimony-doped
Tin oxide, aluminum borate, magnesium borate,
Zirconium silicate, aluminum nitride, silicon nitride,
And at least one kind of fine particles selected from boron nitride
It is preferably selected from For the heat-shielding antifouling film material of the present invention
The particles of the ceramic powder are aluminum,
Stainless steel, nickel, tin, chrome, zinc, gold, silver,
Surface coated with one or more metals selected from copper
Is preferred. Odor of the heat-shielding antifouling film material of the present invention
The sheet-like base material is a fiber cloth or a flexible resin film.
Film or sheet, and fibers coated with a flexible resin
It is preferably selected from textiles. The heat shield of the present invention
In the fouling film material, the fiber cloth for the sheet-shaped substrate is
Filament woven fabric with a void ratio of 6-40%, and empty space
It is preferable to select from short fiber spun fabrics with a porosity of 0 to 10%.
Good In the heat-shielding antifouling film material of the present invention, the sheet
Of the base material is 1 to 10% by weight based on its weight.
It is preferable that the powder contains the powdered flour. Thermal insulation of the present invention
In the antifouling film material, the ceramic contained in the sheet-shaped substrate is used.
Mix powder is titanium oxide, zinc oxide, aluminum oxide
(Alumina), magnesium oxide, zirconium oxide
(Zirconia), tin oxide, indium oxide, tin oxide
Indium oxide, indium-doped tin oxide, anti
Mon-doped tin oxide, aluminum borate, borate mug
Nesium, zirconium silicate, aluminum nitride, nitrogen
At least one selected from silicon oxide and boric acid nitride
It is preferable that the fine particles of The heat-shielding and antifouling property of the present invention
In the film material, the resin material contained in the protective layer is
Con resin, fluorine resin, melamine resin, epoxy
At least selected from resin series and phosphazene resin
It is also preferable to include one kind. Thermal barrier antifouling film material of the present invention
In the above, the protective layer is polysiloxane or colloidal.
Silica, silica containing at least one selected from silica
It is preferable to further contain an element-containing substance. Of the present invention
In the heat shield antifouling film material, the photocatalyst containing layer is 10
70% by mass of photocatalytic substance and 25 to 95% by mass of metal
At least selected from oxide gel and metal hydroxide gel
1 type and 1 to 20 mass% of silicon-containing substance
And are preferred. In the heat-shielding antifouling film material of the present invention, the
The photocatalytic substance is titanium oxide (TiO 2 ₂ ), Titanium peroxide
(Peroxotitanic acid), zinc oxide (ZnO), oxidation
Tin (SnO₂ ), Strontium titanate (SrTi
O₃ ), Tungsten oxide (WO₃ ), Bismuth oxide
(Bi₂O₃), Iron oxide (Fe₂O₃1) or more selected from
It is preferable to contain the above metal oxide. The shielding of the present invention
In the thermal antifouling film material, the photocatalytic substance is titanium oxide.
(TiO ₂ ), Titanium peroxide (peroxotitanium
Acid), zinc oxide (ZnO), tin oxide (SnO)₂ ), Chi
Strontium titanate (SrTiO₃ ), Oxidized tongue
Ten (WO₃ ), Bismuth oxide (Bi₂O₃),iron oxide
(Fe₂O₃) One or more metal oxides selected from
It is preferable to contain the inorganic porous fine particles that carry these.
Good In the heat shielding antifouling film material of the present invention, the heat control
Metal and inorganic metal between the protective resin layer and the protective layer
Metal thin film layer composed of a compound, and a metal acid containing a metal oxide
It is preferable that at least one transparent oxide layer is formed.
Good In the heat-insulating antifouling film material of the present invention, the metal thin film
When both the film layer and the metal oxide transparent layer are included, the thermal control
The metal thin film layer is formed on the control resin layer, and the metal thin film layer is formed on the metal thin film layer.
The metal oxide transparent layer is formed, and the protective layer is formed thereon.
Are preferably formed. The heat-shielding and antifouling property of the present invention
In the film material, the metal thin film layer is made of aluminum or nickel.
Kel, chrome, stainless steel, copper, tin metal, and
One or more selected from these oxides, nitrides and carbides
It is preferably a metal vapor deposition layer. The heat-shielding and antifouling property of the present invention
In the film material, the metal oxide transparent layer is zinc oxide or acid.
Tin oxide, zirconium oxide, indium oxide, tin oxide
Indium oxide, indium-doped tin oxide, and
At least one metal acid selected from antimony-doped tin oxide
It is preferable that it is a stuttering layer or a vapor deposition layer of
Good In the heat-shielding antifouling film material of the present invention, the sheet
Shaped substrate and at least one of its front and back surfaces
Between the heat control resin layer, the resin matrix and this resin
Tree consisting of many bubbles distributed in matrix
It is preferable that a fat foam layer is formed. The shielding of the present invention
In the thermal antifouling film material, the resin matrix of the resin foam layer is used.
It is preferable that the particles contain ceramic powder. Starting
In the heat-insulating antifouling film material of Ming, it is contained in the resin foam layer.
Ceramics powder is titanium oxide, zinc oxide, oxide
Aluminum (alumina), magnesium oxide, dioxide
Ruconium (zirconia), tin oxide, indium oxide
Aluminum, tin-doped indium oxide, indium-doped oxide
Tin, antimony-doped tin oxide, aluminum borate
Aluminum, magnesium borate, zirconium silicate, nitride
Selected from Luminium, Silicon Nitride, and Boron Nitride
It is preferably one or more types of fine particles.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The heat-shielding antifouling film material of the present invention is shown in FIGS.
The embodiment having the laminated structure shown in FIG. In FIG. 1, a heat-shielding antifouling film material 1 of the present invention is a sheet-shaped substrate 2
And a powder component formed on at least one of the front and back surfaces of the sheet-shaped substrate, the resin component including at least one polymer, and the powder component including at least one metal powder and ceramic powder. : 1 to 70:30 contained front and back side heat controllable resin layers 3a, 3b, and a photocatalyst containing layer 5 formed on the front side heat controllable resin layer 3a and containing a photocatalytic substance and a binder. A protective layer formed between the surface-side heat-controllable resin layer 3a and the photocatalyst-containing layer 5 and containing the heat-controllable resin layer as a main component for blocking the photocatalytic action of the photocatalyst-containing layer. And layer 4. When the surface-side heat-controllable resin layer 3a contains an additive having volatility and / or migration in addition to the resin component and the powder component, as shown in FIG. The layer 3a further has an additive volatilization prevention layer 6 formed on the surface thereof and containing a resin material as a main component for preventing volatilization and / or migration of the volatile and / or migrating additive. However, these may constitute the heat controllable resin layer 3c with the additive volatilization prevention layer.

The thermal barrier antifouling film material 1 of the present invention shown in FIG. 2 has a laminated structure similar to that shown in FIG. 1, except that the surface with the additive volatilization prevention layer 6 is provided. A metal oxide transparent layer 7 is further formed between the additive volatilization prevention layer 6 and the protective layer 4 of the side heat controllable resin layer 3c. In this case, the arrangement of the additive volatilization prevention layer 6 may be omitted. Further, the heat-shielding antifouling film material 1 of the present invention shown in FIG. 3 has the same laminated structure as that shown in FIG. 2, except that the metal oxide transparent layer in FIG. Instead of 7, a metal thin film layer 8 made of a metal and an inorganic metal compound is formed, and the protective layer 4 is formed thereon. In the heat-shielding antifouling film material 1 of the present invention shown in FIG.
3 has the same laminated structure as the above, except that the metal oxide transparent layer 7 is further formed on the metal thin film layer 8 in FIG. 3, and the protective layer 4 is formed thereon.

In the heat-insulating and antifouling film material of the present invention shown in FIG. 5, the laminated structure is the same as that shown in FIG. 1, except that the sheet-shaped substrate 2 and the front and back surfaces thereof. Of the heat controllable resin layer formed on at least one surface of the backside heat controllable resin layer 3b in FIG. 5, and a large number of bubbles distributed in the resin matrix. A resin foam layer 9 is formed.

The heat-shielding antifouling film material 1 of the present invention shown in FIG. 6 has a laminated structure similar to that shown in FIG. 5, except that the surface with the additive volatilization prevention layer 6 is A metal oxide transparent layer 7 is further formed between the additive volatilization prevention layer 6 and the protective layer 4 of the side heat controllable resin layer 3c. Further, in the heat-shielding antifouling film material 1 of the present invention shown in FIG. 7,
It has a laminated structure similar to that shown in FIG. 6, except that instead of the metal oxide transparent layer 7 in FIG.
A metal thin film layer 8 made of a metal and an inorganic metal compound is formed, and a protective layer 4 is formed thereon. The thermal barrier antifouling film material 1 of the present invention shown in FIG. 8 has a laminated structure similar to that of FIG. The layer 7 is formed and the protective layer 4 is formed thereon.

The sheet-shaped base material used for the heat-insulating and antifouling film material of the present invention is not particularly limited in its shape, size and material, but is preferably a flexible resin film, sheet or fiber cloth. And a fiber cloth surface-coated with a flexible resin. The fiber cloth used as the sheet-shaped substrate for the heat-insulating and antifouling film material of the present invention may be in any form such as woven cloth, knitted cloth, and non-woven cloth,
Woven or knitted fabrics are particularly preferred. Woven fabrics include plain weave (having a minimum constitutional unit of at least two warp and weft yarns), twill fabric (having a minimum constitutional unit of at least three warp yarns and weft yarns): 3 sheets, diagonal (Sheet-slanted pattern, 5-slanted pattern, etc.), satin fabric (has a minimum constitutional unit of at least 5 warp yarns and weft yarns: regular skipping such as 2 jumps, 3 jumps, 4 jumps) can be used. Especially, it is preferable to use a plain weave fabric. It is particularly preferable to use Russell knitting as the knitted fabric.

The warp of the fiber woven fabric and the yarns forming the weft or the knitted fabric include synthetic fibers, natural fibers (cotton, hemp, etc.),
Semi-synthetic fibers (rayon, acetate, etc.), inorganic fibers or mixed fibers composed of two or more of these are suitable. Particularly, the fiber fabric used in the present invention includes polypropylene fiber, polyethylene fiber, polyvinyl alcohol fiber, Vinylon fiber, polyester fiber, nylon fiber,
Synthetic fibers such as polyamide fibers, acrylic fibers, polyurethane fibers, and mixed fibers thereof are preferably used. Examples of these fiber yarns include monofilament yarns, multifilament yarns, short fiber spun yarns, split yarns, tape yarns and the like. Also,
As the inorganic fiber, multifilament yarns such as glass fiber, silica fiber, alumina fiber and carbon fiber can be preferably used.

In the present invention, among these fiber yarns, polyester fiber, nylon fiber, polyamide fiber, glass fiber, which has high versatility and excellent balance of physical properties such as tensile strength, tear strength, and heat-resistant creep characteristics, etc. It is preferable to use a multi-filament plain woven fabric or a short fiber spun (spun) plain woven fabric woven from alumina fibers, mixed fibers thereof, mixed fibers, and the like. These fiber woven fabrics can be woven using a conventionally known loom such as a shuttle loom, a shuttleless loom (a rapier system, a gripper system, a water jet system, an air jet system). Further, the above fiber woven fabric is subjected to known fiber treatment, for example, scouring treatment, bleaching treatment, dyeing treatment, softening treatment, water repellent treatment, waterproofing treatment, mildewproofing treatment, flameproofing treatment, hair-burning treatment, calendar treatment. , And those treated with a binder resin can also be used.

The fiber woven fabric used in the present invention is preferably a filament woven fabric having a mesh porosity of 6 to 40% or a short fiber spun fabric having a mesh porosity of 0 to 10%. When the fiber fabric used in the present invention is a filament fabric, the mesh void ratio is 6 to 40%, particularly 10 to 30%.
Is preferable from the viewpoint of the laminating property of the film forming the heat control resin layer described later, that is, the bridge fusion property of the front and back film layers. When the mesh porosity exceeds 40%, not only the dimensional stability of the resulting membrane material is poor, but also the strength is weakened, and it becomes difficult to use it for industrial material applications. Further, the filament woven fabric is preferably a woven fabric composed of multifilament yarns, and the multifilament yarns are obtained by heat-melting a fiber-forming thermoplastic resin spinning raw material to form a viscous liquid, or in a specific solvent. It can be obtained by dissolving it in, and passing it through a spinneret having a large number of pores of a specific diameter, extruding, spinning, cooling, or desolvation. As this multifilament yarn, 111-
A long fiber yarn having a fineness in the range of 2222 dtex, particularly 138 to 1111 dtex is preferably used. The fineness of the yarn is 11
If it is smaller than 1 dtex, the tear strength of the obtained membrane material may be insufficient, and if it is larger than 2222 dtex, the tear strength and tear strength of the obtained membrane material are excellent,
Since the unevenness of the woven intersection is increased and the dust and dirt is likely to be accumulated, the heat shield effect may be insufficient. As for the warp and weft driving densities of the woven fabric, a woven fabric in which the above-mentioned yarn is woven by driving 4 to 30 yarns per inch, particularly 8 to 20 yarns per inch as the weft yarn can be preferably used. This yarn may be untwisted or twisted. The basis weight of these woven fabrics is preferably 35 to 300 g / m ² for the present invention.

When the fiber woven fabric used in the present invention is a short fiber spun woven fabric, the mesh porosity is 0 to 10%, particularly 0 to 5%, which forms the heat controllable resin layer described later. It is preferable from the viewpoint of coatability of the resin liquid. When the mesh void ratio exceeds 10%, it becomes difficult to apply the resin liquid for forming the heat controllable resin layer. However, as an exception, in the case of laminating a film for forming a heat controllable resin layer on a short fiber spun fabric, the mesh void ratio of these may exceed 10%, and the upper limit thereof is 40%. it can. Further, the short fiber spun fabric is preferably a woven fabric composed of short fiber spun yarns, and the short fiber spun yarns are obtained by heat-melting a fiber-forming thermoplastic resin spinning raw material to form a viscous liquid, or by specifying A long fiber spinning bundle (tow) obtained by solubilizing in a solvent of (1), extruding it through a spinneret having a large number of pores of a specific diameter, spinning, cooling, or desolvating.
Open the staple obtained by cutting 2 to 6 cm in length, stretch the doubling draft and kneading sliver to make the fiber parallelism uniform and make it as roving (coarse yarn). It is preferably tow-spun with a draft and twist.

These are single-twisted yarns obtained by aligning single yarns or two or more single yarns and twisted by S (right) twist or Z (left) twist, single yarns or two or more single yarns. It is possible to use various twisted yarns in which two or more twisted yarns twisted and twisted together are subjected to upper twisting, and other strong twisted yarns. The number of short fiber spun yarns is 591 dtex (10 count), 29
5dtex (20th), 197dtex (30th), 148
Those in the range of dtex (40th), 97dtex (60th), especially 591dtex (10th), 422dtex (14th), 370dtex (16th), 295dtex (20th), 246dtex (24th), 197dtex (30th) A short fiber spun yarn in a range such as (count) can be used. (The number of these counts is not limited to a multiple of 10.)
When the short fiber spun yarn is smaller than 97 dtex (60 count), the tear strength of the obtained membrane material is poor, and when it exceeds 591 dtex (10 count), the tear strength and tear strength of the obtained membrane material are excellent. However, since the unevenness of the woven intersection is increased and the dust and dirt are likely to be accumulated, the heat shield effect may be insufficient. These short fiber spun yarns are single yarns, twin yarns, twisted yarns of three or more single yarns, or two-plied yarns thereof,
Alternatively, two yarns such as a double twisted yarn are used as warp and weft yarns.
A spun plain woven fabric obtained by driving 30 to 160 strands in a 5.4 mm (1 inch) is preferably used in the present invention. Especially preferably 295 dtex (20 count) single yarn, or 295
25.4 mm (1 inch) using dtex (20th count) twine
A spun plain woven fabric obtained by striking the yarn with a weaving density of 50 to 70 warps and 40 to 60 wefts is suitable.

In addition, it is also possible to use a spun plain woven fabric obtained from a core-spun yarn obtained by winding a multifilament yarn as a core layer and a short fiber yarn wound as a sheath layer on the core layer. The basis weight of these woven fabrics is 100 to 50.
Those of 0 g / m ² are suitable for the present invention. In addition, if necessary, a monofilament yarn, a tape yarn, a split yarn, or the like can be used in the present invention. The monofilament yarn is produced by increasing the diameter of the spinneret in the above-mentioned multifilament manufacturing machine. The tape yarn is produced by extruding a fiber-forming thermoplastic resin spinning raw material (particularly polypropylene or polyethylene) with a T-die extruder to obtain a film having a thickness of 50 to 300 μm and a width of 2 to 50 mm. Is a flat yarn having a width of 1 to 30 mm obtained by uniaxially stretching it by slitting in the flow direction, and a split yarn is a uniaxially stretched flat yarn with a needle blade roll. It is further split and mechanically made into a multifilament.

The mesh porosity of the above-mentioned fiber woven fabric is obtained by taking the area of the yarn in a unit area of the woven fabric as a percentage and
It can be obtained as a value subtracted from 0. It is easy to find the mesh porosity as a unit area of 10 cm in the warp direction and 10 cm in the weft direction. The filament woven fabric and the short fiber spun woven fabric used in the present invention are particularly preferably polyester fiber woven fabrics from the viewpoint of versatility, and specific examples of the polyester fiber include polycondensation of terephthalic acid and ethylene glycol. Examples of the obtained polyethylene terephthalate (PET), polybutylene terephthalate (PBT) obtained by polycondensation of terephthalic acid and butylene glycol, and the like. Particularly, a polyester fiber melt-spun from a polyethylene terephthalate resin has high strength and It is preferable from the viewpoint of spinnability.

From the viewpoint of heat shielding property, it is preferable that the fiber yarns constituting the fiber woven fabric used in the membrane material of the present invention contain ceramic powder, and the ceramic powder is used for the fiber-forming thermoplastic resin spinning raw material. 0.1 to 10% by mass, particularly preferably 1 to 5% by mass. When the content of the ceramic powder is less than 0.1% by mass, the heat-shielding effect of the obtained film material may be insufficient, and when the content exceeds 10% by mass, the spinnability is deteriorated and the fiber Spinning may be difficult. Multifilament yarns, short fiber spun yarns, and other fiber yarns (monofilament yarns, tape yarns, split yarns) containing ceramics powders have fiber-forming properties in the manufacturing process of the above fiber yarns. It can be obtained by adding ceramic powder in the step of heat melting the thermoplastic resin or the step of solubilizing it in a specific solvent.

Specific examples of the ceramic powder to be mixed with the fiber-forming thermoplastic resin raw material include titanium oxide, zinc oxide, aluminum oxide (alumina), magnesium oxide, zirconium oxide (zirconia), tin oxide, indium oxide, and tin-doped oxide. Indium, indium-doped tin oxide, antimony-doped tin oxide, aluminum borate, magnesium borate, zirconium silicate,
It is preferable that one or more kinds of fine particles selected from aluminum nitride, silicon nitride, and boron nitride have an average particle diameter of 1 μm or less, particularly 0.1 to 0.6 μm.
Further, those having a range of 0.05 to 0.35 μm are preferable. If the average particle size exceeds 1 μm, the fibers may be easily broken and spinning may be difficult.

The surface of these fine particles is lubricated with a fatty acid such as stearic acid, palmitic acid, oleic acid or linoleic acid for the purpose of improving the dispersibility in the fiber-forming thermoplastic resin raw material, or silane coupling. From the viewpoint of spinnability during spinning, it is preferable to use those having improved adhesion to the fiber-forming thermoplastic resin raw material by agent treatment or organic titanate coupling agent treatment.

The fiber woven fabric (woven fabric) and the fiber woven fabric (woven fabric) containing the ceramic powder are preferably surface-coated with a heat-controllable resin layer, and particularly in the membrane material of the present invention. It is preferable that both sides of the void plain woven fabric are surface-coated with the heat control resin layer from the viewpoints of the heat shielding effect and durability, and the heat fusion bonding of the film material. As the thermoplastic resin forming the heat controllable resin layer, in general,
A soft polyvinyl chloride resin is most preferable, and a fluorocopolymer resin is most preferable from the viewpoint of long-term durability. In addition, especially in consideration of environmental problems, when a membrane material with a halogen-free design that does not discharge hydrogen halide gas at the time of incineration is desired, acrylic resin, polyurethane resin, polyester resin, ethylene resin Copolymer resin: [ethylene-α-olefin copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid (ester) copolymer resin], polypropylene resin, and styrene copolymer resin Combined resin, other, ionomer resin, ethylene-vinyl alcohol copolymer resin,
A single-layer structure or a multi-layer structure of one or more selected from a thermoplastic resin such as a nylon resin or a polycarbonate resin can be preferably used.

In the present invention, the thickness of the heat controllable resin layer is not particularly limited, but the thickness is preferably 50 to 500 μm, more preferably 100 to 350 μm. The heat control resin layer is 1). Metal powder, and /
Alternatively, a method of film-forming the above-mentioned thermoplastic resin containing ceramic powder by a known molding method such as calendar molding or T-die extrusion molding 2). A method in which a resin solution obtained by solubilizing the above-mentioned thermoplastic resin containing metal powder and / or ceramic powder in an organic solvent is uniformly applied by a known coating method such as a coating method or a dipping method, and then dried 3). A method in which a water-dispersed resin solution (emulsion, dispersion) of the above-mentioned thermoplastic resin mixed with metal powder and / or ceramic powder is uniformly applied by a known coating method such as a coating method or a dipping method, and then dried. ). It can be obtained by any method such as a method of uniformly coating a paste vinyl chloride resin mixed with metal powder and / or ceramics powder by a known coating method such as a dipping method or a gelling method. .

As the metal powder used in the heat control resin layer of the film material of the present invention, it is preferable to use at least one selected from aluminum, stainless steel, nickel, copper and tin. These powders are obtained by crushing metal chips and metal foils by a wet ball mill method, a vibration ball mill method, an attritor method, have a smooth ground surface, and have a particle size of 5 to 150 μm.
It is a scale-like powder of m. For the purpose of surface protection and imparting dispersibility to the surface of these powders, those that have been lubricated with a fatty acid such as stearic acid, palmitic acid, oleic acid, and linoleic acid, or a silane coupling agent treatment,
It may be one which is provided with adhesion to a thermoplastic resin by treatment with an organic titanate coupling agent, or one whose surface is protected and coated with an acrylic resin, a melamine resin, an alkyd resin or the like. By doing so, it is preferable to improve durability. The metal powder used for the heat controllable resin layer is particularly preferably aluminum powder or stainless steel powder from the viewpoint of direct sunlight reflectivity. Particularly, aluminum powder is a paste-like form wet with mineral spirits, and a thermoplastic resin is used as a binder for aluminum. A master batch form in which powder is kneaded at a high concentration and a paint form in which aluminum powder is dispersed in a thermoplastic resin solution can also be used. The above metal powder is preferably contained in an amount of 1 to 30% by mass, particularly 5 to 20% by mass based on the thermoplastic resin, from the viewpoint of the heat shielding property of the obtained film material, and the above metal powder is used in combination with the following ceramic powder. It is more preferable that the total amount of the metal powder and the ceramic powder is 1 to 30% by mass, especially 5 to 20% by mass, relative to the thermoplastic resin, from the viewpoint of improving the heat shielding property of the obtained film material. In this case, the combined amount of the ceramic powder with respect to the total amount of the metal powder and the ceramic powder is not particularly limited. When the content of the metal powder or the content of the metal powder and the ceramic powder exceeds 30% by mass, the strength of the heat control resin layer of the obtained film material may be reduced and the fatigue durability may be deteriorated.

The ceramic powder used for the heat control resin layer of the film material of the present invention includes titanium oxide, zinc oxide,
Aluminum oxide (alumina), magnesium oxide, zirconium oxide (zirconia), tin oxide, indium oxide, tin-doped indium oxide, indium-doped tin oxide, antimony-doped tin oxide, aluminum borate, magnesium borate, zirconium silicate, aluminum nitride, One or more kinds of fine particles selected from silicon nitride and boron nitride are preferable, and these have an average particle diameter of 1 μm or less, particularly 0.1 to 0.6 μm, and further 0.05 to 0.35 μm. Those are preferable.
For the purpose of imparting dispersibility, the surfaces of these fine particles are lubricated with a fatty acid such as stearic acid, palmitic acid, oleic acid, and linoleic acid, or treated with a silane coupling agent or an organic titanate coupling agent. From the viewpoint of durability, it is preferable to use a resin having improved adhesion to a plastic resin. Further, as the above-mentioned ceramic powder, a ceramic powder whose surface is coated with a metal such as aluminum, stainless steel, nickel, tin, chromium, zinc, gold, silver or copper can also be preferably used. The metal coating method of the ceramic powder can be carried out by a known vapor deposition method, sputtering method, electrolytic plating method (particularly copper-nickel-chromium plating, nickel-chromium plating) and the like. The blending amount of the ceramic powder is 1 to 30 with respect to the thermoplastic resin.
From the viewpoint of the heat shielding property of the obtained film material, it is preferably 5% by mass, particularly 5 to 20% by mass. Further, it is more preferable to use the above metal powder in combination with these ceramic powders from the viewpoint of improving the heat shielding effect, and the total amount of the ceramic powder and the metal powder is 1 to 30% by mass with respect to the thermoplastic resin.
It is particularly preferable to contain 5 to 20 mass%. In this case, the combined amount of the metal powder with respect to the total amount of the ceramic powder and the metal powder is not particularly limited. When the content of the ceramic powder or the content of the ceramic powder and the metal powder exceeds 30% by mass, the strength of the heat control resin layer of the obtained film material may be reduced and the fatigue durability may be deteriorated.

The polyvinyl chloride resin forming the heat control resin layer in the film material of the present invention includes a vinyl chloride copolymer resin, specifically, a polyvinyl chloride resin,
Vinyl chloride-ethylene copolymer resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl ether copolymer resin, vinyl chloride-vinylidene chloride copolymer resin,
Vinyl chloride-maleic acid ester copolymer resin, vinyl chloride- (meth) acrylic acid copolymer resin, vinyl chloride-
(Meth) acrylic acid ester copolymer resin, vinyl chloride-urethane copolymer resin, etc.
It is also possible to use together more than one species.

The above polyvinyl chloride resin has a number average molecular weight, P = 700 to 3800, preferably 1000 to 20.
00 straight vinyl chloride polymer, and the copolymerization component contained in the vinyl chloride copolymer resin is preferably 2 to 30 mass%.
In the present invention, when a polyvinyl chloride resin is used in the heat-controllable resin layer for coating the plain weave woven fabric, it is preferable to use a known soft blend, and particularly a phthalate ester-based plasticizer is used as the plasticizer for the soft blend. In addition to known general-purpose plasticizers typified by plasticizers, the average molecular weight is 900 to 6000, particularly 1000 to 32 from the viewpoint of the plasticizer volatilization prevention effect.
No. 00 polyester plasticizer is used, and from the viewpoint of the plasticizer volatilization prevention effect, an average molecular weight of 10,000 or more, particularly 20,000 or more ethylene-vinyl acetate-carbon monoxide terpolymer resin, ethylene- (meth) It is preferable to use a plasticizer containing a polymer plasticizer such as an acrylate-carbon monoxide terpolymer resin. As the polyester-based plasticizer, those arbitrarily synthesized from dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and phthalic acid and ethylene glycol, 1,2-butanediol, 1,6-hexanediol, etc. can be used. .

Specifically, the heat controllable resin layer comprises i). 50 to 100 parts by mass of the total amount of the plasticizer is used with respect to 100 parts by mass of the straight vinyl chloride polymer, and a polyester plasticizer is used as 30 to 100% by mass of the plasticizer.
-Mold into a film by a known molding method such as die extrusion molding. Also, ii). The total amount of the plasticizer is 60 to 14 with respect to 100 parts by mass of the straight vinyl chloride polymer.
A compound containing a polymer plasticizer in an amount of 0 part by mass and 30 to 100% by mass of the plasticizer was calendered, T
-Mold into a film by a known molding method such as die extrusion molding. In these soft polyvinyl chloride resin compositions, the stabilizer may be appropriately selected and used from known ones, and if necessary, a colorant, a lubricant, a flame retardant, a foaming agent,
Antistatic agent, surfactant, water repellent, oil repellent, cross-linking agent, curing agent, filler, ultraviolet absorber, antioxidant, HALS
Known additives such as a system weather resistance stabilizer can be used.

When the heat controllable resin layer is a polyvinyl chloride resin having a soft blending property, the heat controllable resin layer is used for the purpose of preventing environmental pollution of the film material due to volatilization and volatilization of plasticizers and additives. It is preferable to provide an additive volatilization prevention layer on the surface of the. The additive volatilization preventive layer is preferably an acrylic resin (particularly preferably an ultraviolet curable type), a polyurethane resin, an ethylene-vinyl alcohol copolymer resin, etc., which may be formed by coating or a film formed thereof. May be formed by stacking.

In the membrane material of the present invention, the fluorocopolymer resin forming the heat control resin layer is preferably a fluoroolefin copolymer resin, and the fluoroolefin unit is, for example, vinyl fluoride (VF). , Vinylidene fluoride (VdF), trifluoroethylene (T
rEE), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP) and other olefin skeletons containing one or more fluorine atoms in the constitutional unit, such as ethylene, propylene, and α-olefin. There is no particular limitation as long as it is a monomer. The fluoroolefin copolymer resin is obtained by copolymerizing two or more kinds selected from resin fluoroolefin units, and these are specifically VdF-TFE copolymer resin and VdF-CTFE copolymer resin. , VdF-
HFP copolymer resin, TFE-CTFE copolymer resin,
TFE-HFP copolymer resin, CTFE-HFP copolymer resin, VdF-TFE-CTFE copolymer resin, Vd
F-TFE-HFP copolymer resin, TFE-CTFE-
HFP copolymer resin, VdF-CTFE-HFP copolymer resin, VdF-TFE-CTFE-HFP copolymer resin and the like. Moreover, these can also use 2 or more types together.

The acrylic resin constituting the heat control resin layer in the film material of the present invention includes i). A radical polymer resin of an alkyl acrylate having an alkyl group having 1 to 18 carbon atoms, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid i
-Butyl, t-butyl acrylate, 2-ethylhexyl acrylate, and the like are the polymers obtained as monomers. ii). The acrylic resin is a radical polymer resin of an alkyl methacrylic acid ester having an alkyl group having 1 to 18 carbon atoms, and examples thereof include methyl methacrylate, ethyl methacrylate, and methacrylate n.
-Propyl, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate and the like are the polymers obtained as monomers. iii).
The acrylic resin used in the present invention may be a copolymer resin composed of two or more kinds of the above-mentioned monomers, and these acrylic resins may contain the following copolymerizable monomer having reactivity with the acrylic monomer. It may be contained by substituting with a system monomer. These copolymerized monomers may be, for example, a). Ethylenically unsaturated carboxylic acids such as maleic acid and itaconic anhydride, b). Amide compounds such as acrylamide, methacrylamide, N-methylacrylamide, c). Hydroxyl group-containing (meth) acrylic acids such as hydroxyethyl acrylate and hydroxyethyl methacrylate, d). Glycidyl acrylate,
Epoxy group-containing (meth) acrylic acids such as glycidyl methacrylate, e). Α-olefins such as ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, f). Vinyl ethers such as ethyl vinyl ether and cyclohexyl vinyl ether,
g). Alkenyls such as polyoxyethylene allyl ether and ethyl allyl ether, h). Vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, i).
It can be selected from aromatic vinyl compounds such as styrene and α-methylstyrene.

In the membrane material of the present invention, the ethylene copolymer resin forming the heat controllable resin layer is ethylene-α.
-Olefin copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid (ester)
A copolymer resin, such as a copolymer resin, i). The ethylene-α-olefin copolymer resin is, for example, in the presence of a Ziegler-Natta catalyst or a metallocene catalyst,
Examples of the α-olefin monomer include an ethylene-α-olefin copolymer resin obtained by copolymerizing ethylene and an α-olefin having 3 to 18 carbon atoms by a gas phase method, a slurry liquid phase method, or a high pressure method. Is, for example, propylene, butene-1, 4-methylpentene-1, hexene-
1, heptene-1, octene-1, nonene-1, decene-1 and the like. ii). The ethylene-vinyl acetate copolymer resin has a vinyl acetate component content of 5 to 35, which is produced by radical copolymerizing ethylene and vinyl acetate.
An ethylene copolymer resin containing mass% iii).
Further, the ethylene- (meth) acrylic acid (ester) copolymer resin is produced by radical copolymerization of ethylene and (meth) acrylic acid. Ethylene-containing 5 to 35 mass% of (meth) acrylic acid component
Acrylic acid copolymer resin and 5 to 35% by mass of (meth) acrylic acid ester component produced by radical copolymerization of ethylene and (meth) acrylic acid ester
Examples thereof include ethylene- (meth) acrylic acid ester copolymer resins. Specific examples of the (meth) acrylate ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate.
Glycidyl acrylate and the like.

The polypropylene resin constituting the heat control resin layer in the film material of the present invention includes i). A homopolymer obtained by homopolymerization of propylene, ii). And an ethylene-propylene copolymer resin obtained by copolymerizing propylene and ethylene, iii). Propylene and α
-Propylene obtained by copolymerizing with olefin-α-
Olefin copolymer resin, iv). And a propylene / ethylene-propylene copolymer elastomer obtained by multi-step polymerization of continuously copolymerizing a propylene monomer with the ethylene-propylene copolymer obtained by preliminary polymerization, and ethylene obtained by preliminary polymerization- Propylene-
Examples thereof include a propylene-ethylene / propylene / non-conjugated diene copolymer elastomer obtained by multistage polymerization in which propylene is continuously copolymerized with a non-conjugated diene copolymer. As the α-olefin used as a comonomer of the propylene-α-olefin copolymer resin,
Α-olefin monomers having 4 to 10 carbon atoms, for example, butene-1, pentene-1, hexene-1, octene-1, heptene-1,3-methyl-butene-1,4-
Methyl-pentene-1, 4-methyl-hexene-1, etc. may be mentioned, and the obtained propylene-based copolymer may be either a random copolymer or a block copolymer. Good. Of these, as the polypropylene resin, particularly, a polypropylene resin having a syndiotactic stereoregularity polymerized by a gas phase method in the presence of a metallocene catalyst, a slurry liquid phase method, or a high pressure method, or A polypropylene resin having isotactic stereoregularity is preferable from the viewpoint of flexibility of the heat controllable resin layer. Further, the propylene-ethylene / propylene-based copolymer elastomer and the propylene-ethylene / propylene / non-conjugated diene-based copolymer elastomer are specifically, as the first step, a titanium compound catalyst and an aluminum compound catalyst, or a metallocene. In the presence of a system catalyst, propylene and, if necessary, α-olefin other than propylene are polymerized to obtain a first propylene-based polyolefin. This polyolefin is propylene homopolymer, propylene-ethylene copolymer, propylene-α-
It is an olefin copolymer or the like, and is obtained as a second step by copolymerizing with the next olefin (for example, a monomer such as ethylene, propylene or a non-conjugated diene) while containing the catalyst.

For the purpose of improving flexibility and processability, the ethylene-based copolymer resin and the polypropylene-based resin include soft components such as ethylene-propylene rubber and ethylene-propylene-conjugated diene rubber, and the above polyolefin. It is also possible to use a blend of a olefin thermoplastic elastomer (TPO), which is a vulcanized alloy, crosslinked with a system resin. In particular, for the purpose of softening the tent film material, it is preferable to blend a styrene-based copolymer resin with the ethylene-based copolymer resin and the polypropylene-based resin, and the styrene-based copolymer resin may be i). ．
ABA type styrene block copolymer resin (A is a styrene polymer block, B is a butadiene copolymer block,
It is an isoprene polymer block or a vinyl isoprene polymer block. ), Ii). A-B type styrene block copolymer resin (A and B are as defined above), styrene random copolymer resin, iii). And hydrogenated resins of these styrene-based copolymer resins (having double bonds replaced with hydrogen). Specific examples of these commercially available products include shell. Styrenic block copolymer resin (trademark: Kraton G) of Chemical Co.,
Asahi Kasei Corporation's styrene block copolymer resin (trademark: Tuftec), Kuraray's styrene block copolymer resin (trademark: High Blur, trademark: Septon), Japan Synthetic Rubber Co., Ltd. styrene resin Random copolymer resin (trademark: Dynaron) and the like can be mentioned. These styrene-based copolymer resins are polyolefin-based resins 1
It can be used by blending 5 to 80 parts by mass with respect to 00 parts by mass.

The polyurethane resin forming the heat control resin layer in the film material of the present invention comprises a diisocyanate compound and at least one selected from polyol compounds having two or more hydroxyl groups in the molecular structure. A thermoplastic polyurethane resin obtained by an addition polymerization reaction with a compound having a functional group that reacts with an isocyanate group, and in some cases used in combination with an amine compound. The polyurethane-based resin can be selected from polyester-based polyurethane resin, polyether-based polyurethane resin, polycarbonate-based polyurethane resin, polycaprolactone-based polyurethane resin, etc. depending on the type of the polyol compound used. Diisocyanates include aromatic, aliphatic, and alicyclic (including hydrogenated products)
The diisocyanate compound of, for example, these include tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. In the invention,
Those polymerized with an aliphatic or alicyclic diisocyanate compound from the viewpoint of weather resistance are preferable, and as the polyol compound, for example, polytetramethylene ether glycol, dihydroxy polyethylene adipate, polyethylene glycol, polypropylene glycol is used. Polymerized ones are preferred.

The polyester resin constituting the heat control resin layer in the film material of the present invention includes polyethylene terephthalate (PET) obtained by polycondensation of terephthalic acid and ethylene glycol, polycondensation of terephthalic acid and butylene glycol. And a high melting point crystalline polyester segment (A) as an elastomer, such as polybutylene terephthalate (PBT) obtained by
A block copolymer resin composed of a low melting point polymer segment (B) composed of an aliphatic polyether unit and / or an aliphatic polyester unit may be mentioned. This (A) segment is a polyester obtained by polymerizing a dicarboxylic acid and a diol, and as the dicarboxylic acid component,
For example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and cyclopentanedicarboxylic acid; and fats such as adipic acid, sebacic acid, and azelaic acid. Group dicarboxylic acids and the like. The diol component has 2 to 12 carbon atoms.
Of the aliphatic or alicyclic diols, such as ethylene glycol, propylene glycol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol and the like. Further, as the aliphatic polyether unit constituting the (B) segment,
Polyethylene glycol, polypropylene glycol,
Examples include poly (tetramethylene oxide) glycol and glycols of their copolymers. On the other hand, (B)
As the aliphatic polyester unit constituting the segment, poly ε-caprolactone, polyenanthlactone,
Examples thereof include polycaprylolactone, polybutylene adipate, and polyethylene adipate.

The heat control resin layer described above may be colored by including a near infrared ray absorbing substance and / or an organic pigment, if necessary. As the near infrared absorbing substance, for example, a phthalocyanine compound, a naphtholquinone compound, an immonium compound, an anthraquinone compound, an aluminum compound, a nickel-thiol complex compound, and the like can be used. 51-135886, JP-A-56-143242.
JP-A-58-13676, JP-A-60-
No. 23451, JP-A-61-115958,
JP-A-63-295578 and JP-A-4-1744
No. 02, No. 5-93160, No. 5-93160.
It can be used by selecting from known dyes described in JP-A-222302 and JP-A-6-264050. The amount of the near-infrared absorbing substance added is 0.01 to 3.0% by mass, and particularly 0.1 to 3.0% by mass based on the heat control resin layer.
It is preferably 1.0% by mass. Examples of organic pigments suitable for coloring include azo pigments (insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex salt azo pigments), phthalocyanine pigments (phthalocyanine blue, phthalocyanine green), and dyeing lakes. Pigments (acid dye lake pigments, basic dye lake pigments), condensed polycyclic pigments (anthraquinone pigments, thioindigo pigments, perinone pigments, perylene pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, Quinophthalone pigments, isoindoline pigments), and other organic pigments such as nitroso pigments, alizarin lake pigments, metal complex salt azomethine pigments, and aniline pigments. There is no particular limitation on the amount of pigment added.

Further, in the heat control resin layer, if necessary, a lubricant, a flame retardant, a foaming agent, an antistatic agent, a surfactant, a water repellent, an oil repellent, a cross-linking agent, a curing agent and a filler. ,
Known additives such as an ultraviolet absorber, an antioxidant and a HALS weather resistance stabilizer can be used. Particularly, the heat control resin layer contains 0.1 to 3.0% by mass of an ultraviolet absorber (benzotriazole type, benzophenone type, salicylate type, cyanoacrylate type) with respect to the thermoplastic resin.
And polymer type ultraviolet absorber (benzotriazole type,
Benzophenone-based) 1 to 5% by mass,
The heat shielding efficiency of the obtained film material may be further improved.

In the heat-shielding antifouling film material of the present invention, between the heat-controllable resin layer and the photocatalyst-containing layer on the sheet-shaped substrate,
A protective layer is formed. The protective layer contains as a main component a resin material that blocks the photocatalytic action of the photocatalyst containing layer from the heat controllable resin layer. Examples of the resin material used for this protective layer include a silicone resin, a fluorine resin, a melamine resin, an epoxy resin, and a phosphazene resin. It is preferable that these resins have a film-forming ability by heat or ultraviolet rays. Of these, the silicon-based resin includes an alkyl group, an alkenyl group,
Allyl group, chlorosilanes or alkoxysilanes having 1 to 3 hydrogens bonded singly or individually, linear silicone resins obtained by hydrolyzing and polymerizing a plurality of kinds in solvent-free or organic solvents, copolymerized silicone resins, silicone rubbers, etc. In particular, an alkyl titanate catalyst comprising a bifunctional or higher functional modified silicone having a Si—OH group or a Si—OMe group (for example, a methylmethylphenyl silicone resin having a silanol group or an alkoxy group) as a copolymerized silicone resin and an alcoholic hydroxyl group-containing resin. Modified silicones obtained by reacting in the presence of, for example, acrylic modified silicone resin, acrylic-urethane modified silicone resin, urethane modified silicone resin, urethane modified silicone-fluorine copolymer resin,
Examples thereof include epoxy modified silicone resin, polyester modified silicone resin, alkyd modified silicone resin, and phenol modified silicone resin. Further, a siloxane-crosslinkable silicon-modified copolymer, a siloxane-crosslinkable silicon-modified oligomer, an isocyanate-crosslinkable silicon-modified copolymer, an isocyanate-crosslinkable silicon-modified oligomer and the like can also be used.

Examples of the fluorine-based resin for the protective layer include vinyl ether-fluoroolefin copolymer resin, vinyl ester-fluoroolefin copolymer resin, and a combination composition of these fluorine-based resin (containing a hydroxyl group) and an isocyanate compound. Can be mentioned. In particular, as a fluoroolefin copolymer resin, vinylidene fluoride (Vd
F), a copolymer resin containing tetrafluoroethylene (TFE) and chlorotrifluoroethylene (CTFE) components are preferable, and these are VdF-TFE copolymer resin, VdF-CTFE copolymer resin, TFE-CTFE.
It is a copolymer resin, VdF-TFE-CTFE copolymer resin, or the like. These copolymer resins may contain fluoroolefin monomers such as vinyl fluoride (VF), trifluoroethylene (TrEE), and hexafluoropropylene (HFP) by further copolymerization. As the melamine resin, cyanuramide,
Cyanuric acid triamide, cyanuric acid amide, 2,4,6
An organic solvent as butylated methylolmelamine by reacting formalin with one or more melamine compounds selected from triamino-1,3,5-triazine and derivatives thereof and modifying the initial condensation product of methylolated melamine with butanol. And butyl dimethylol melamine dissolved in an organic solvent together with an alkyd resin.

Examples of the epoxy resin for the protective layer include those obtained by the ring-opening addition reaction of epichlorohydrin and polyhydric phenols, and generally, polycondensates obtained by the reaction of epichlorohydrin with bisphenol A or resole. It can be used, and a curing agent such as amines, organic acids, acid anhydrides and polyisocyanate compounds can be used in combination in an organic solvent. Further, those used in combination with alkyd resin, melamine resin, butylated melamine resin and the like can be mentioned. Examples of the phosphazene-based resin for the protective layer include phosphazene chlorides such as (PNCl ₂ ) _n (n = 1, 2, 3, 4) and linear phosphazene chloride oligomers, or (PNCl ₂ ) _n (n = 2, 3, 4), a 4-membered, 6-membered, or 8-membered cyclic chlorophosphazene chloride is used as a raw material, and an ultraviolet-cured product of a reactive phosphazene compound in which chlorine is substituted with an acrylic acid compound. Examples of the acrylate compound added and substituted to the phosphazene compound include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ( Examples thereof include diethylaminoethyl (meth) acrylate and glycidyl (meth) acrylate.

In the present invention, the protective layer is preferably a resin layer containing a silicon compound from the viewpoint of adhesion to the photocatalyst containing layer formed on the outermost surface, and the silicon compound used by being contained in the protective layer is , Polysiloxane, colloidal silica, and silica. As the polysiloxane, those obtained by hydrolyzing and polycondensing an alkoxysilane compound by a sol-gel method are preferable. For example, as an alkoxysilane, a general formula: Y _n SiX _4-n (n =
One or more hydrolyzed condensates of silicon compounds represented by 1 to 3) and co-hydrolyzed compounds are suitable. In the above general formula, Y can be, for example, an alkyl group, a fluoroalkyl group, a vinyl group, a mercapto group, an amino group or an epoxy group, and X can be, for example, a halogen, a methoxyl group, an ethoxyl group, or an acetyl group. You can The silicon compound represented by the general formula is specifically an alkyl group-substituted trichlorosilane, an alkyl group-substituted tribromosilane, an alkyl group-substituted trimethoxysilane, an alkyl group-substituted triethoxysilane, an alkyl group-substituted triisopropoxysilane, an alkyl group. Substitution Tri-t
-Butoxysilane, etc., and the alkyl group includes a methyl group, an ethyl group, an n-propyl group, and an n-group, respectively.
A hexyl group, an n-decyl group, an n-octadecyl group and a phenyl group. Further, specifically, the alkyl group of the alkyl-substituted silane compound is modified to a trifluoropropyl group, the alkyl group of the alkyl-substituted silane compound is modified to a vinyl group, the alkyl group of the alkyl-substituted silane compound is Those modified to γ-methacryloxypropyl group, those modified from the alkyl group of the above alkyl-substituted silane compound to γ-aminopropyl group, those modified from the alkyl group of the above alkyl-substituted silane compound to γ-mercaptopropyl group, etc. Is mentioned.

As the colloidal silica for the protective layer, silica sol (SiO ₂ ) which is an aqueous dispersion medium obtained by cation exchange of a sodium silicate solution can be mentioned, but as the colloidal silica used for the protective layer, an organic type is used. As a solvent, an alcohol solvent such as methanol, isopropanol or n-butanol, an aromatic hydrocarbon solvent such as toluene or xylene, an aliphatic hydrocarbon solvent such as hexane or heptane, an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane. Type solvent, ketone type solvent such as methyl ethyl ketone, cyclohexanone, N, N-
Disperse any one or more of amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone, ester solvents such as ethyl acetate and butyl acetate, and other organic solvents selected from one or more such as tetrahydrofuran. A medium having a BET average particle size of 10 to 20 nm is suitable. Examples of silica (SiO ₂ ) include synthetic amorphous silica obtained by a wet method in which sodium silicate is reacted with mineral acid (sulfuric acid) and salts in an aqueous solution.
Synthetic amorphous silica has a surface silanol group (Si-OH
It is a hydrous silica having water bound to a group) by a hydrogen bond and water present as a hydroxyl group contained in the silanol group itself as bound water. The average aggregate particle size of the amorphous hydrous silica is 1
It is preferable to use amorphous hydrous silica having a particle size of ˜20 μm, especially 2 to 10 μm, and a water content of 3 to 15% by mass.
It is particularly preferable to use hydrous silica of 5 to 10 mass%. These silicas can be used after being surface-treated with a silane coupling agent.

The added amount of the silicon compound contained in the protective layer is the polysiloxane, colloidal silica,
And at least one selected from silica are preferably 5 to 35 mass% with respect to the total solid content of the resin constituting the protective layer. When the silicon compound content of the protective layer is less than 5% by mass, the adhesion between the protective layer and the photocatalyst containing layer may be insufficient, and when it exceeds 35% by mass, the protective layer and the photocatalyst containing layer may be Although the adhesion is improved, the abrasion resistance of the protective layer may be insufficient. The method for forming the protective layer is not particularly limited, but a coating method capable of uniformly and uniformly applying a coating solution of the binder resin containing a silicon compound to the heat controllable resin layer, for example, The gravure coating method, the microgravure coating method, the comma coating method, the roll coating method, the reverse roll coating method, the bar coating method, the kiss coating method, the flow coating method and the like are preferable. The coating amount of the protective layer formed by the coating solution is not particularly limited, any of the above coating methods, or a combination,
2-20 g / m ^{2 in} terms of solid content, particularly 3-10 g / m
It is preferably formed into ² . 2g of solid content adhered /
If it is less than m ^2, the outdoor durability of the film material of the present invention may be insufficient, and if it exceeds 20 g / m ² , the flexural strength of the protective layer may be lowered. The coating amount of the protective layer, that is, the film thickness can be set by controlling the amount of the organic solvent of the coating agent. The thickness of the protective group is preferably 0.3 to 20 μm from the viewpoint of heat shield property and bending strength. Examples of the organic solvent contained in the coating agent include alcohol solvents such as isopropanol and n-butanol, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane and heptane, and cyclohexane. Alicyclic hydrocarbon solvents such as methylcyclohexane, ketone solvents such as methyl ethyl ketone and cyclohexanone, amide solvents such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone, and ethyl acetate and butyl acetate. Examples include ester solvents and tetrahydrofuran.

Further, in the heat-shielding antifouling film material of the present invention,
A metal thin film layer may be provided between the heat control resin layer and the protective layer. This metal thin film layer is made of aluminum,
Metals of nickel, chromium, stainless steel, copper, tin, and at least one metal selected from oxides, nitrides, and carbides of these metals are used as a target material and vapor-deposited on the heat control resin layer. From the viewpoint of metallic luster (reflecting direct sunlight), it is preferable that the half mirror layer has a metallic luster that reflects direct sunlight, and particularly a half mirror layer obtained by vapor deposition of aluminum. As the vapor deposition method, various known vapor deposition methods can be used, for example,
Any of a vacuum deposition method, a sputtering method, an ion plating method, a CVD (chemical vapor deposition) method and the like may be used. The thickness of the metal thin film layer (half mirror layer) is 5 to 60.
nm (50-600Å), especially 10-30 nm (100-3
It is preferable that it is 00Å) from the viewpoint of the heat shield effect. When the thickness of the metal thin film layer is less than 5 nm (50 Å), the heat shielding effect of the obtained film material is insufficient, and the thickness of 60 nm (600
Those exceeding Å) will not hinder the use in the present invention, but the heat-shielding effect often reaches the ceiling.

In the present invention, particularly when the heat controllable resin layer is a polyvinyl chloride resin having a soft blending property, the heat controllability can be prevented for the purpose of preventing vaporization inhibition due to volatilization and volatilization of plasticizers and additives during vapor deposition. An additive volatilization prevention layer is preferably provided on the surface of the resin layer. For the additive volatilization prevention layer, acrylic resin, (energy ray curable acrylic resin is preferable, and ultraviolet ray curable acrylic resin is more preferable), polyurethane resin, ethylene-vinyl alcohol copolymer resin, etc. are suitable. May be formed by coating or may be formed by laminating films.

The heat-insulating antifouling film material of the present invention containing a metal thin film layer (half mirror layer) has the following features: 1). Metal powder, and /
Alternatively, in a substrate having a heat controllable resin layer containing ceramic powder, a metal thin film layer is provided on the surface of the heat controllable resin layer (if necessary, an additive volatilization prevention layer is provided on the surface). A film material having a protective layer thereon and a photocatalyst-containing layer provided on the surface of the protective layer, 2). In the film material of 1) above, a film material in which a metal oxide transparent layer is formed between a metal thin film layer and a protective layer, 3). The film material according to 1) or 2) above, which has a resin foam layer on at least one of the heat-controllable resin layer and the fiber woven fabric constituting the substrate. Moreover, the aspect of the heat-shielding antifouling film material of this invention containing a metal oxide transparent layer is 4). In a substrate having a heat controllable resin layer containing a metal powder and / or a ceramic powder, a metal is provided on the surface of the heat controllable resin layer (an additive volatilization prevention layer is provided, if necessary, on the surface). A film material having an oxide transparent layer, a protective layer provided thereon, and a photocatalyst-containing layer provided on the surface of the protective layer, and 5). 4) above
Examples of the membrane material include a membrane material having a fat foam layer on at least one of the heat controllable resin layer constituting the base material and the fiber woven fabric.

In the film material of the present invention, a metal thin film layer or a metal oxide transparent layer is provided between the heat controllable resin layer and the protective layer, or a metal thin film layer and a metal oxide layer. When the transparent layer is provided at the same time, the heat shield effect can be further improved. The metal oxide transparent layer is formed by zinc oxide (ZnO), tin oxide (SnO ₂ ), zirconium oxide (ZrO ₂ ), indium oxide (In ₂
O ₂ , In ₂ O ₃ , tin-doped indium oxide (TI
O), indium-doped tin oxide (ITO), and antimony-doped tin oxide (ATO) as one or more kinds of metal oxides, which are used as a target material, on the thermally controllable resin layer or the metal thin film layer. It can be formed by vapor deposition. As the vapor deposition method, various known vapor deposition methods can be used, and for example, any of a vacuum vapor deposition method, a sputtering method, an ion plating method, a CVD (chemical vapor deposition) method, etc., can be used, but a sputtering method is particularly preferable. Is preferred. The thickness of the metal oxide transparent layer is 3
~ 30 nm (30-300Å), especially 5-15
nm (50 to 150Å) is preferable from the viewpoint of transparency and heat shielding effect. The thickness of the metal oxide transparent layer is 30Å
If it is less than 300, the heat shielding effect of the obtained film material may be insufficient, and if it exceeds 300 Å, the transparency of the obtained film material may be insufficient. Especially in the aspects 2) and 3) of the film material of the present invention, when the metal oxide is vapor-deposited on the metal thin film layer, the light reflection effect of the lower metal thin film layer may not be effectively obtained. . In the present invention, tin-doped indium oxide (TIO) and indium-doped tin oxide (IT) are used to form the metal oxide transparent layer.
O) and one or more kinds of metal oxides selected from antimony-doped tin oxide (ATO) are preferably used for the vapor deposition using a target material in terms of transparency and heat shielding efficiency.
Further, in the present invention, particularly when the heat controllable resin layer is a polyvinyl chloride resin with a soft blending, the plasticizer is added to the heat controllable resin layer for the purpose of preventing vaporization volatilization of the plasticizer during vapor deposition and vapor deposition inhibition by volatilization. It is preferable to provide a migration prevention layer.
The plasticizer migration prevention layer is an acrylic resin (preferably an energy ray-curable acrylic resin, more preferably an ultraviolet-curable acrylic resin), a polyurethane resin, an ethylene-vinyl alcohol copolymer resin. Etc. are suitable, and these may be formed by coating or may be formed by laminating films.

The photocatalyst-containing layer in the film material of the present invention comprises
Photocatalytic substance 10 to 70 based on the total mass of the photocatalyst-containing layer
It is preferable to contain 25% by mass of the metal oxide gel and / or 25 to 90% by mass of the metal hydroxide gel and 1 to 20% by mass of the silicon compound. The photocatalyst-containing layer is formed by applying a coating solution containing a photocatalytic substance, a metal oxide gel and / or a metal hydroxide gel, and a silicon compound onto the surface of the protective (silicon compound-containing resin) layer and drying the coating liquid. It The metal oxide gel and / or metal hydroxide gel contained in the photocatalyst containing layer fixes the photocatalytic substance and firmly adheres to the surface of the protective layer, and further these metal oxide gel and / or Alternatively, since the metal hydroxide gel is porous, it has a large surface area, and therefore, the photocatalytic activity can be effectively exhibited. The content of the metal oxide gel and / or the metal hydroxide gel contained in the photocatalyst containing layer is preferably 25 to 90 mass% with respect to the photocatalyst containing layer. If the content is less than 25% by mass, the adhesion to the protective layer may be insufficient, and if it exceeds 90% by mass, the content of the photocatalytic substance may be so small that the photocatalytic activity cannot be sufficiently exhibited. There is. Further, the specific surface area of the dried product of the metal oxide gel and / or the metal hydroxide gel is preferably 100 m ² / g or more, whereby the adhesion to the protective layer and the photocatalytic activity efficiency can be improved. it can.

The metal oxide gel and / or metal hydroxide gel for the photocatalyst containing layer is one or more selected from metals of silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten and tin. It is preferably an oxide gel or hydroxide gel of two or more kinds of metals, and specific examples thereof include silica sol, alumina sol, zirconia sol, niobium oxide sol and the like. Further, as a mixed gel of these, it can be used as a complex oxide gel obtained by a coprecipitation method. The mixing of these metal oxide gels and / or metal hydroxide gels with the photocatalytic substance is carried out in the state of the sol before becoming these gels, or the stage of the raw material before adjusting the sol. It is preferable to mix with. Methods for preparing a metal oxide gel and / or a metal hydroxide gel include a method of hydrolyzing a metal salt, a method of neutralizing decomposition, and a method of ion exchange. Any method can be used as long as it can be uniformly dispersed. As the oxide sol used in the photocatalyst-containing layer of the film material of the present invention, particularly oxide sol of zirconium and aluminum can be preferably used in terms of durability.

In the film material of the present invention, for the photocatalyst containing layer
As a photocatalytic substance, ₂ , ZnO, SrT
iO, CdS, GaP, InP, GaAs, BaTiO
₃ , K₂ NbO₃ , Fe₂O₃, Ta₂O_Five, WO₃ , Sn
O₂ , Bi₂O₃, NiO, Cu₂O 2, SiC, SiO
₂ , MoS₂ , InPb, RuO₂ , CeO₂ For example
Pt,
Rh, RuO₂ , Nb, Cu, Sn, NiO, etc.
All known genus and metal oxides can be used.
Wear. Among these photocatalytic substances, especially titanium oxide
(TiO₂ ), Titanium peroxide (peroxotitanic acid),
(Zinc oxide (ZnO), tin oxide (SnO₂ ), Titanic acid
Strontium (SrTiO₃ ), Tungsten oxide
(WO₃ ), Bismuth oxide (Bi₂O₃), Iron oxide (Fe
₂O₃) And the like, and further, these photocatalytic substances
It is also possible to use inorganic porous fine particles to be supported.
It Inorganic porous fine particles carrying the above photocatalytic substance
As the inorganic porous fine particles used, silica, (synthetic)
Zeolite, titanium zeolite, zirconium phosphate,
Calcium phosphate, zinc calcium phosphate, hydrota
Lucite, hydroxyapatite, silica-alumina, ke
Calcium formate, magnesium aluminate silicate, silica
Soil soil, etc., and the average of these inorganic porous fine particles
The primary particle size is 0.01 to 10 μm, especially 0.05 to 5 μm
Those with m are preferred. Inorganic porous photocatalytic substance
To support fine particles, a metal containing a photocatalytic substance
Applied sol-gel thin film manufacturing process by alcoholate
Surface treatment is preferred.

As the photocatalytic substance contained in the photocatalyst-containing layer of the present invention, titanium oxide, which is a versatile metal oxide having a high bandgap energy and being chemically stable, can be used. preferable. In titanium oxide used as a photocatalytic substance, titanyl sulfate, titanium chloride, titanium oxide sol obtained by thermally hydrolyzing a titanium compound such as titanium alkoxide, and titanium oxide obtained as an alkali neutralized product of titanium oxide sol, and the like, Anatase-type peroxotitanic acid dispersion liquid in which ultrafine particles of titanium hydroxide and titanium oxide are peroxoed with peroxide such as hydrogen peroxide and dispersed in water is preferable. Titanium oxide may be either anatase type or rutile type, but anatase type titanium oxide is preferable from the viewpoint of magnitude of photocatalytic activity. Specifically, hydrochloric acid peptizing type anatase titania sol, nitric acid peptizing type anatase type titania sol and the like having an average crystallite diameter of 5 to 20 nm can be preferably used. Since the smaller the particle size of the photocatalytic substance is, the better the photocatalytic activity is, a photocatalytic substance having an average particle size of 50 nm or less, more preferably 20 nm or less is suitable. The titanium oxide also includes hydrous titanium oxide, hydrated titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide and the like. The content of the photocatalytic substance in the photocatalyst containing layer increases as the photocatalytic activity increases, but it is preferably 70% by weight or less, and more preferably 10 to 70% by weight from the viewpoint of adhesion to the protective layer. If the amount of the photocatalytic substance is less than 10% by mass, the photocatalytic activity may be insufficient, and if the amount of the photocatalytic substance is more than 70% by mass, the photocatalytic activity will be high but the adhesion to the protective layer will be high. The photocatalyst-containing layer may have insufficient surface abrasion resistance, and thus the outdoor durability may not be sufficiently obtained.

As the silicon compound used in the photocatalyst-containing layer, polysiloxane can be preferably used, and those obtained by hydrolyzing and polycondensing an alkoxysilane compound by a sol-gel method are particularly preferable. As these alkoxysilane compounds, those exemplified as the alkoxysilane compounds that can be used in the protective layer of the film material of the present invention can be used. These silicon compounds are 1 to the photocatalyst containing layer.
It is preferable to use 20% by mass. The method of applying the coating liquid containing the photocatalytic substance is not particularly limited, but the coating liquid containing these photocatalytic substances is uniformly and uniformly applied on the surface of the protective layer. A coating method capable of being desirable is preferable, for example, a gravure coating method, a micro gravure coating method, a comma coating method, a roll coating method, a reverse roll coating method, a bar coating method,
A kiss coat method, a flow coat method and the like are preferable. The thickness of the photocatalyst containing layer formed by the above coating agent is preferably 0.1 to 10 [mu] m formed by any of the above coating methods or a combination thereof. If the thickness of the photocatalyst-containing layer is less than 0.1 μm, the antifouling property of the obtained film material cannot be satisfactorily obtained, and if it exceeds 10 μm, the bending durability of the photocatalyst-containing layer is poor and cracks may occur. .

In the film material of the present invention, in order to obtain a more effective heat shielding effect, a resin matrix is provided between at least one of the front and back surface side heat controllable resin layers and the sheet-shaped substrate. It is preferable to provide a resin foam layer composed of cells distributed in the resin matrix, and the resin foam layer is a bubble mark-containing thermoplastic resin having a density of 0.3 to 0.9 g / cm ^3. It is preferable. As an aspect having a resin foam layer in the membrane material of the present invention, 1). A resin foam layer is provided between at least one layer of the heat controllable resin layer containing metal powder and / or ceramics powder and the sheet-shaped substrate, and a protective layer is further provided on the surface of the heat controllable resin layer. A film material having a photocatalyst-containing layer provided on the surface of the protective layer, 2).
In the film material of the above 1), an additive volatilization prevention layer is provided on the surface of the heat controllable resin layer as needed, and a metal thin film layer is provided on the surface (heat controllable resin layer or additive volatility prevention layer). A film material provided with a protective layer and a photocatalyst containing layer formed on the surface of the protective layer, 3). 2) above
In the above film material, there is an embodiment such as a film material in which a metal oxide transparent layer is further provided between the metal thin film layer and the protective layer. The method for forming the resin foam layer used in the membrane material of the present invention may be a resin foam sheet adhered and laminated, or an unfoamed resin foam layer precursor sheet (containing a chemical foaming agent) may be adhered and laminated. After that, the resin foam layer may be formed by foaming by post-treatment heating. The resin matrix of the resin foam layer preferably contains ceramic powder. The ceramic powder contained in this resin foam layer is titanium oxide,
Zinc oxide, aluminum oxide (alumina), magnesium oxide, zirconium oxide (zirconia), tin oxide,
At least one kind of fine particles selected from indium oxide, tin-doped indium oxide, indium-doped tin oxide, antimony-doped tin oxide, aluminum borate, magnesium borate, zirconium silicate, aluminum nitride, silicon nitride, and boron nitride. Is preferred.

The thermoplastic resin forming the resin foam layer is not particularly limited, but from the viewpoint of the adhesiveness with the heat controlling resin layer, it is the same as the thermoplastic resin forming the heat controlling resin layer (described above). The same quality is preferable, and it is preferable that these thermoplastic resins contain the above-mentioned ceramic powder in an amount of 1 to 30 mass% with respect to the thermoplastic resin, from the viewpoint of improving the heat shielding property of the film material. The resin foam layer precursor sheet contains a known chemical foaming agent, and a resin foaming layer can be obtained by exposing this to the thermal decomposition temperature of the chemical foaming agent for a certain period of time. It is determined by the type and the blending amount. This resin foam layer has a thickness of 0.
It is preferable to have a density of ^{3 to} 0.9 g / cm ^{3 from} the viewpoint of the heat shield effect. If the density of the resin foam layer is higher than 0.9 g / cm ^3, the heat shielding effect of the obtained film material may be insufficient, and if the density is lower than 0.3 g / cm ³ , the heat shielding effect may be insufficient. Although the heat effect is sufficient, the flexural strength of the film material may be insufficient due to the decrease in the strength of the resin foam layer. The thickness of the resin foam layer is not particularly limited, but the preferable thickness range is 1 to 5 mm. If the thickness of the resin foam layer is less than 1 mm, it may be insufficient to impart an effective heat shielding effect to the obtained film material, and if the thickness of the resin foam layer exceeds 5 mm, The film material becomes thick and handling may be difficult. Examples of the chemical foaming agent used for forming the resin foam layer include azodicarbonamide, (ADCA), dinitrosopentamethylenetetramine (DPT), and 4,4′oxybisbenzenesulfonyl. Hydrazide (O.B.S.
1) or 2 or more of H) for thermoplastic resin
It is preferably used in the range of 10 to 10% by mass.

Bonding of film materials of the present invention (overlap adhesion)
In the exposed part of the heat controllable resin layer, it is possible to easily perform joining by heat fusion using a high frequency welder machine. As the high frequency fusion method, a sheet material is placed between two electrodes (one electrode is a weld bar), and a potential difference that oscillates at a high frequency (1 to 200 MHz) is applied while applying pressure with the weld bar, and the film material is applied. The resin layer is melted by molecular frictional heat and bonded. As another joining method, ultrasonic energy (16 to 30 KH
z) The amplitude is amplified, and the ultrasonic welder fusion method is used to perform heat fusion using the frictional heat generated at the boundary surface of the film material, or stepwise setting to 20 to 700 ° C by electric control of the heater. Hot air is blown between the film materials through a nozzle to instantly heat-melt the surface of the film material, and immediately after that the film material is pressure-bonded for adhesion, or a heater above the melting temperature of the heat controllable resin layer. Bonding is also possible by a hot plate fusion method in which adherends are pressure-bonded and adhered by using a mold (trowel) that is internally heated.

[0062]

EXAMPLES The present invention will be explained more specifically by the following examples, but the present invention is not limited to the scope of these examples. In the following examples and comparative examples, the performance of the test film materials such as heat shielding property and antifouling property was measured and evaluated by the following test methods.

(I) Heat-shielding property <Test environment> A rectangular bar made of acrylic resin having a vertical and horizontal 0.5 cm square cross section is used as a beam, and the outer diameter is 5 mm.
Assemble a box-shaped frame of cm x width 10 cm x length 15 cm with an instant adhesive, and put the test film material on the four side surfaces, top surface and bottom surface of the box-shaped frame so that the surface faces outward. An airtight box was prepared by attaching and fixing with tape. In addition, the heat flow meter (Sh
othrm HFM heat flow meter: Showa Denko KK sensor was attached and fixed. Next, the box-shaped inner diameter is height 4
Incandescent lamp (100 cm)
A V and 500 W photo reflector lamp (for daylight color: Toshiba Corp.) was attached and fixed as a test environment for heat insulation evaluation. (Not used) was attached to the center of the bottom surface of the box-shaped structure, and fixed so that the center of the lamp and the center of the test box overlap in the vertical direction. The distance from the tip of the lamp inside the box-shaped structure to the ceiling of the test box was 35 cm. <Test> A). Put the test box without test film material into the box-shaped structure, place it in a sealed state, turn on the lamp, measure the internal temperature and heat flow rate (kcal / m ² h) of the test box every 1 minute, and After a minute, the temperature and the heat flow rate qn (kcal / m ² h) were measured. After returning the temperature inside the box-shaped structure to the outside temperature, put the test box with the membrane material in the box-shaped structure and place it in a sealed state. Then, turn on the lamp, and the test box internal temperature and heat flow (kcal / m ² h) was measured every 1 minute, the temperature after 30 minutes and the heat flow rate qc (kcal / m ² h) were measured, and the heat shield coefficient was determined by the following formula. The outside temperature is 2
A constant temperature environment of 0 ° C. was used. It was judged that the larger the heat shield coefficient pf, the higher the heat shield property. Heat shield pf (%) = [(qn-qc) / qn] × 100 B). In the test of A), the time T ₃₀ until the internal temperature of the test box reaches 30 ° C. was measured. T ₃₀ is, the higher the value, the greater was determined that the heat shielding properties is high.

(II) Antifouling property by outdoor spreading The test film material with a width of 20 cm and a length of 2 m was installed with the photocatalyst-containing layer forming surface on the front side. The test piece was continuously spread by 1 m in each of the vertical and vertical directions, and an outdoor stain test was conducted for 12 months. After 6 months and 12 months of spreading, small sample pieces were sampled, the color difference ΔE (JIS Z-8729) from the unstretched film material was determined, and the antifouling property was evaluated according to the following criteria. * Outdoor exhibition started in March in Soka City, Saitama Prefecture. ΔE = 0 to 1.9: ⊚ = Good with no stain. The initial state is maintained. ΔE = 2 to 3.5: ◯ = Slightly soiled, but there is no problem in practical use. ΔE = 3.6 to 5.0: Δ = Dirt and rain lines are noticeable. ΔE = 5.1 to: × = Stain and rain lines are severe, and there is a practical problem.

(III) Outdoor Heat Spreading Property of Outdoor Membrane Material (II): A 6 month and 12 month outdoor heat spread sample was taken and the same heat shield test as in (I) -A was conducted to determine the heat shield rate pf. ₆ and pf ₁₂ are obtained, and the heat shield coefficient pf ₀ of the unstretched film material
Was compared (heat shield coefficient difference). * 6 month heat shield coefficient difference = pf ₀ -pf ₆ * 12 month heat shield coefficient difference = pf ₀ -pf ₁₂ ○: The decrease in heat shield coefficient is less than 4%. (Triangle | delta): The fall of the heat shield is less than 4-8%. X: The reduction of the heat shield rate is 8% or more.

Example 1- (i) Preparation of short fiber spun yarn (containing ceramics powder) -Polyethylene terephthalate (PET) resin having an intrinsic viscosity of 0.69 and a melting point of 256 ° C was used as ceramics powder and had an average particle diameter of 0. .3 μm zirconium oxide powder (Toyo Soda Co., Ltd./Trademark: Zirconia powder 3YA)
Of 3% by mass (3 parts by mass relative to 100 parts by mass of PET) was melt-kneaded by an extruder and melt-spun at 270 ° C. by using a melt spinning machine.
It was drawn at a draw ratio of 3 times at 0 ° C. and twisted to obtain a multifilament raw yarn. Next, staples obtained by cutting the spun raw yarn into 6 cm are opened, and the sliver kneaded while stretching the doubling draft is stretched to make the fiber parallelism constant and roving (coarse yarn). 16
Twisting of 2.54 cm twist and draft, two tow-spun rovings (295 dtex) were twisted 12 times / 2.54 cm and twisted to 295 dtex / x by heat setting at 160 ° C.
No. 2 590 dtex (No. 20 twin yarn) was obtained. -(Ii) Fabrication of short fiber spun yarn woven fabric (span) -Ceramic powder-containing PET590 dtex (20
No. 5 plain weave short fiber spun yarn fabric (warp yarn density: 48 yarns / 2.54 cm × weft yarn density: 44 yarns / 2.
54 cm: Porosity: 1% or less: Fabric mass: 245 g / m
² ) was used as a fiber cloth (base cloth).

-(Iii) Formation of Thermoplastic Resin Layer (Adhesion Pretreatment Layer) on Spun Fiber Cloth- Using the fiber cloth obtained in (ii) as a base material, first of all, the following paste chloride treatment was carried out as an adhesion pretreatment for the fiber cloth. Vinyl resin composition:
Dip (immerse) PVC (1) in an organosol bath diluted with a solvent, pull up the PVC (1) -impregnated fiber cloth, and at the same time nip (press) it with a mangle roller.
145 g / m ² of PVC (1) with respect to the fiber cloth
Was uniformly impregnated and adhered to both sides of the fiber cloth. next,
After semi-gelling and drying in a hot air oven at 150 ° C. for 1 minute, heat treatment is performed in a hot air oven at 175 ° C. for 1 minute to gel the resin, and immediately after that, a hot roll at 180 ° C. (press: 0. Two
Mpa), heat-press the resin-coated substrate, and
A base material having a thickness of 0.36 mm and a mass of 390 g / m ² which was surface-coated with C (1) was obtained. <Vinyl chloride resin composition for adhesion preparation: PVC (1)> Paste vinyl chloride resin (P = 1600) 100 parts by mass DINP (plasticizer) 25 parts by mass Adipic acid polyester (plasticizer) 40 parts by mass Epoxidized soybean oil (ESBO) 4 parts by mass Ba-Zn stabilizer 2 parts by mass Rutile type titanium oxide 5 parts by mass Organic antifungal agent (OBPA) 0.2 parts by mass Isocyanate trimer (curing agent) 5 parts by mass Solvent (toluene) 20 parts by mass [Note] * Vinyl chloride resin: Trademark: ZEST-P21 (Shin Daiichi PVC Co., Ltd.) * DINP: Trademark: Sanso Sizer DINP (New Japan Rika Co., Ltd.) * Adipic polyester: Trademark: Adeka Sizer PN-446 (Asahi Denka Industry Co., Ltd.) * Epoxidized soybean oil: Trademark: ADEKA CIZER O-130P (Asahi Denka Industry Co., Ltd.) * Ba-Zn system Fixed agent: Trademark: KV-400B (Kyodo Pharmaceutical Co., Ltd.) * Rutile type titanium oxide: Trademark: Titanium oxide CR: (Ishihara Sangyo Co., Ltd.) * Organic fungicides: Trademark: Vinadine BP-5-2: (10,10'-oxybisphenoxyarsine: Morton Thiocole) * Isocyanate trimer (trademark: Vulcabond VP: AKCROS CHEMICALS)

-(Iv) Formation of heat controllable resin layer on spun fiber cloth-Next, on both sides of the PVC (1) adhesive pretreatment substrate obtained in the step (iii), the heat controllable resin layer is formed. The following straight vinyl chloride resin composition compound for forming (containing 8 mass% of aluminum powder with respect to vinyl chloride resin): PVC
A film of 0.2 mm obtained by rolling the composition obtained by kneading (2) with a Banbury mixer at 140 ° C. through a calender roll at 170 ° C. was used as a heat control resin layer.
Using a laminator equipped with a heat roll set to a temperature of 60 ° C. and an infrared heater, the laminator was laminated on both sides of the base material by a thermocompression bonding method, and a heat controllable resin layer was provided on both sides of the base material. A substrate / heat controllable resin layer laminate having a weight of 0.70 mm and a mass of 880 g / m ² was obtained. <Vinyl chloride resin composition for heat control resin layer formation: PVC (2)> Straight vinyl chloride resin (P = 1050) 100 parts by mass Polymer plasticizer 55 parts by mass Adipate polyester 35 parts by mass Epoxidized soybean oil (ESBO ) 4 parts by mass Aluminum powder 8 parts by mass Ba-Zn-based composite stabilizer 2 parts by mass Rutile type titanium oxide 5 parts by mass Organic antifungal agent (TBZ) 0.2 parts by mass UV absorber 0.3 parts by mass antioxidant 0.2 parts by mass [Note] * Vinyl chloride resin: Trademark: ZEST1000S (Shin-Daiichi PVC Co., Ltd.) * Polymer plasticizer: Trademark: Elvalloy 742 (Mitsui DuPont Polychemical Co., Ltd.) * Adipic polyester: Trademark: Adeka Sizer PN-446 (Asahi Denka Kogyo Co., Ltd.) * Epoxidized soybean oil: Trademark: Adeka Sizer O-130P (Asahi Denka Co., Ltd. ) * Aluminum powder (Trademark: Alpaste Leafing Medium P0100 45μm mesh pass: Toyo Aluminum Co., Ltd.) * Ba-Zn compound stabilizer: Trademark: KV-400B (Kyodo Pharmaceutical Co., Ltd.) * Rutile type titanium oxide : Trademark: Titanium oxide CR: (Ishihara Sangyo Co., Ltd.) * Organic fungicide: Trademark: Sanaisol 100 (TBZ): Sanai Petroleum Co., Ltd. * Ultraviolet absorber: Trademark: Biosorb 510 (Kyodo Pharmaceutical Co., Ltd.) ) * Antioxidant: Trademark: Irganox E201 (Vitamin E type: Ciba Specialty Chemicals Co., Ltd.)

-(V) Formation of Additive Volatilization Prevention Layer-Next, (iv) on the surface side heat control resin layer surface of the base material, 80
12 g of the following coating liquid for forming an additive volatilization prevention layer (acrylic resin layer) is formed by using a roll coater machine having a gravure roll engraved with pyramids on mesh lines.
/ M ² (wet) is uniformly applied on the entire surface and dried in a hot air oven at 100 ° C. to form an additive volatilization prevention layer to prepare a base material / additive volatilization prevention layer-attached heat controllable resin layer laminate. . (Amount of deposited solid content: 3.6 g / m ² ) <Coating liquid for forming additive volatilization prevention layer> Trademark: Sony Bond SC-474: Sony Chemical Corp .: Acrylic copolymer resin (solid content 30% by mass) 100 parts by mass

-(Vi) Formation of protective layer (silicon compound-containing resin layer) -Next, on the surface of the substrate obtained in (ii) on which the additive volatilization prevention layer is formed,
Using a roll coater machine having a gravure roll engraved with 80 mesh lines, the following coating solution for forming a protective layer (silicon compound-containing resin layer) was used.
A protective layer was formed on the entire surface of the heat controllable resin layer by applying g / m ² (wet) and drying in a hot air oven at 100 ° C. for 1 minute.
(Amount of solid content attached 3 g / m ² ) <Silicone compound (polysiloxane) -containing resin layer coating liquid: Acrylic-silicone resin base> (1) a) Acrylic-silicone resin (silicon content 3 mol%) 100 parts by mass b) Ethanol / ethyl acetate (mass ratio 1: 1) 900 parts by mass (2) a) Ethyl silicate 40: Colcoat Co., Ltd .: 40% by mass in terms of SiO ₂ 100 parts by mass of polysiloxane with a degree of polymerization of 6 b) Hydrolysis Catalyst: 2% hydrochloric acid 3 parts by mass c) Ethanol / deionized water (mass ratio 1: 1) 400 parts by mass (3) γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd .: SH6062) 6 parts by weight [Note] * a) + b) component of (1), a) + b) + c) component of (2) (hydrolysis is performed by stirring for 2 hours), and component (3) respectively After being prepared therein, the components (1) to (3) were mixed and stirred (hydrolyzed) for 2 hours, and then used.

-(Vii) Formation of Photocatalytic Substance-Containing Layer-Next, a photocatalyst was formed on the entire surface of the protective layer formed in (vi) using a roll coater machine having gravure rolls engraved with 100 mesh lines. The following coating liquid for forming the containing layer was applied at 12 g / m ² (wet), and 10
It was dried in a hot air oven at 0 ° C. for 1 minute to obtain a film material (FIG. 1) having a mass of 888 g / m ² in which a photocatalyst-containing layer was formed on the entire outermost layer. (Amount of deposited photocatalyst-containing layer: 1 g / m ² ) <Photocatalytic substance-dispersed solution for forming photocatalyst-containing layer> a) Photocatalytic substance: Nitric acid acidic titanium oxide sol (crystal particle size 10 nm) 10 parts by mass b) Metal oxide sol: Silica sol (Trademark: Cataloid SI-30: Catalysis Co., Ltd.) 10 parts by mass c) Silane coupling agent (Trademark: SZ6300: Toray Dow Corning Silicone Co., Ltd .: vinyltrimethoxysilane) 2 parts by mass d) Diluent : Deionized water-ethanol (mass ratio 1: 1) solution 200 parts by mass [Note] * The amount of photocatalytic substance contained in the solid content of the photocatalytic substance dispersion solution is 45% by mass.

[0072]Example 2 -(I) Preparation of short fiber spun yarn- Polyethylene turf with an intrinsic viscosity of 0.69 and a melting point of 256 ° C
Talate (PET) resin is melt-kneaded with an extruder and melt-spun.
The convergent roving that was melt-spun at 270 ° C using a spinning machine
Multiply by stretching at a draw ratio of 3 times at 60 ° C and twisting it.
A filament yarn was obtained. Next, cut this spinning yarn into 6 cm
The staple obtained by cutting is opened and doubling draft
While stretching the sliver that has been formed while stretching it,
The roving (roving yarn) with a uniform degree of movement
16 times / 2.54cm twist and draft tow spinning
2 crocheted yarns (295dtex) twisted 12 times / 2.54
It is twisted in cm and heat set at 160 ℃ to 295 dtex.
A No. 20 twin yarn (590 dtex) of / * 2 was obtained. -(Ii) Fabrication of short fiber spun yarn fabric (span)- The obtained PET No. 20 double yarn is used for warp and weft, and
No. 5 plain weave short fiber woven with an air jet on a shuttleless loom
Weaving yarn fabric (warp density: 48 yarns / 2.54 cm x weft denseness
Degree: 44 / 2.54 cm: Porosity: 1% or less: Fabric quality
Amount: 245g / m ² ) As a fiber cloth (base cloth)
It was

-(Iii) Formation of thermoplastic resin layer (adhesion pretreatment layer) on spun fiber cloth-The same paste vinyl chloride resin composition as in Example 1: PV
Using C (1), the same adhesion pretreatment as in Example 1 was applied and surface-coated with PVC (1), thickness 0.36.
A base material having a mass of 390 g / m ² was obtained. -(Iv) Formation of heat controllable resin layer on spun fiber fabric-Next, for forming a heat controllable resin layer on both sides of the PVC (1) adhesive pretreatment substrate obtained in the step (iii) The following straight vinyl chloride resin composition compound (containing 5% by mass of aluminum powder and 5% by mass of zirconium oxide powder relative to vinyl chloride resin): PVC (3) was kneaded at 140 ° C. in a Banbury mixer to prepare 170 Thermocompression bonding method using a laminator equipped with a heat roll whose temperature is set at 160 ° C. and an infrared heater, using a 0.2 mm film obtained by passing through a calender roll of ℃ and rolling. It is laminated on both sides of the substrate with a heat control resin layer on both sides of the substrate, thickness 0.70 mm, mass 880 g
A base material heat controllable resin layer laminate of / m ² was obtained. <Vinyl chloride resin composition for forming heat controllable resin layer: PVC (3)> Straight vinyl chloride resin (P = 1050) 100 parts by mass Polymer plasticizer 55 parts by mass Adipic acid polyester 35 parts by mass Epoxidized soybean oil (ESBO 4 parts by mass Aluminum powder 5 parts by mass Zirconium oxide powder 5 parts by mass Ba-Zn-based composite stabilizer 2 parts by mass Rutile titanium oxide 5 parts by mass Organic antifungal agent (TBZ) 0.2 parts by mass UV absorber 0. 3 parts by mass Antioxidant 0.2 parts by mass [Note] * Aluminum powder (Trademark: Alpaste Leafing Medium P0100 45 μm mesh path: Toyo Aluminum Co., Ltd.) * Zirconium oxide powder (Trademark: Zirconia powder 3YA: Toyo Soda) Industry Co., Ltd.

-(V) Formation of additive volatilization prevention layer-The same treatment as in Example 1 (v) was performed. -(Vi) Formation of protective layer (silicon compound-containing resin layer) -The same treatment as in Example 1 (vi) was performed. -(Vii) Formation of Photocatalyst-Containing Layer-A film material (FIG. 1) having a mass of 888 g / m ² on which the photocatalyst-containing layer was formed on the entire outermost layer was subjected to the same treatment as in Example 1 (vii). Obtained.

Example 3- (i) Preparation of multifilament yarn (containing ceramics powder) -Polyethylene terephthalate (PET) resin having an intrinsic viscosity of 0.69 and a melting point of 256 ° C was used as ceramics powder and had an average particle diameter of 0. .3 μm zirconium oxide powder (Toyo Soda Co., Ltd./Trademark: Zirconia powder 3Y
A compound containing 3% by mass of A) (3 parts by mass with respect to 100 parts by mass of PET) was melt-kneaded with an extruder, and melt-spun at 270 ° C. using a melt spinning machine. The filament was drawn 3.5 times and twisted to obtain a multifilament raw yarn, which was heat set at 160 ° C. to obtain a 1111 dtex multifilament yarn. -(Ii) Preparation of Filament Plain Woven Fabric-A plain weave filament woven fabric obtained by air jet weaving the obtained ceramic powder-containing PET filament yarn for warp and weft with a shuttleless loom (warp density: 14 / 2.54 cm x Weft density: 14 threads / 2.54 cm: porosity: 13%: cloth mass: 145 g / m ² ) was used as the fiber cloth (base cloth).

-(Iii) Formation of Heat Controllable Resin Layer on Filament Plain Woven Fabric-Next, the same thermal control as in Example 2 (iv) was applied to both sides of the filament plain woven fabric obtained in the step (ii). Resin layer (containing 5% by weight of aluminum powder and 5% by weight of zirconium oxide powder with respect to vinyl chloride resin: PVC (3)) was laminated, and a heat control resin layer was provided on both surfaces of the base material. thickness:
A base material having a weight of 0.55 mm and a mass of 665 g / m ² was obtained. -(Iv) Formation of additive volatilization prevention layer-The same treatment as in Example 1 (v) was performed. -(V) Formation of protective layer (silicon compound-containing resin layer) -Next, the entire surface of the base material obtained in (iv) on which the additive volatilization prevention layer is formed has a gravure roll engraved with 80 mesh lines in a pyramid shape. Using a roll coater machine, the following coating liquid for forming a protective layer is applied at 12 g / m ² (wet)
Then, it was dried in a hot air oven at 100 ° C. for 1 minute to form a protective layer. (Amount of solid content: 6 g / m ² ) <Silicone compound (silica / polysiloxane) -containing resin layer coating liquid: Fluorine resin base> Trademark: Lumiflon LF200C: Asahi Glass Co., Ltd .: Fluoroolefin vinyl ether copolymerization (solid content 60 mass%) 167 mass parts Trademark: Takenate D-170N: Takeda Pharmaceutical Co., Ltd .: Isocyanurate body of hexamethylene diisocyanate (solid content 100 mass%) 10 mass parts Trademark: Snowtex XBA-ST: Nissan Chemical Industries ( Co., Ltd .: Colloidal silica (solid content 30% by mass) 20 parts by mass Trademark: Methyl silicate MS51: Colcoat Co., Ltd .: Polymethoxysiloxane (solid content 50% by mass) 20 parts by mass Diluent: Toluene / MEK (1: 1 mass) Ratio) 60 parts by mass- (vi) Formation of photocatalyst-containing layer-Same treatment as in Example 1 (vii) Subjected to, photocatalyst-containing layer is formed on the outermost layer over the entire surface, Mass: to give 676 g / m ² of the film material (Figure 1).

[0077]Example 4 The same substrate as in Example 1 (Examples i to v) was used, and this substrate was used.
Of volatilization of additives formed on material / heat controllable resin layer laminate
Film thickness: about 16nm (about 160Å) metallic acid on the entire surface of the stop layer
A transparent compound layer was formed. Vacuum formation of transparent metal oxide layer
Indium-doped acid is used as the metal oxide.
Target tin oxide (ITO: Sumitomo Osaka Cement Co., Ltd.)
Used for wood. Next, on the surface of the metal oxide transparent layer,
The same protective layer as in Example 1 (vi) is provided, and the surface of the protective layer is further provided.
The same photocatalyst containing layer as in Example 1 (vii) was formed on the
A medium containing layer was formed on the entire outermost layer, mass: 888 g /
m ² A film material (Fig. 2) was obtained.

Example 5 The following straight vinyl chloride resin composition compound (for forming a heat controllable resin layer) was formed on both surfaces of a PVC (1) adhesive pretreatment substrate obtained in the same step as in Example 2 (iii). Containing 5% by mass of stainless powder and 5% by mass of zirconium oxide powder based on vinyl chloride resin): PVC (4) 140
The composition obtained by kneading the Banbury mixer at
A 0.2 mm film obtained by rolling by passing through a 0 ° C. calender roll was used as a heat control resin layer,
Using a laminator equipped with a heat roll whose temperature is set to ℃ and an infrared heater, the sheet-like base material is laminated on both sides by a thermocompression bonding method, and the sheet-like base material has a thickness of 0.70 mm and a mass of 880 g / m. ^{2 A} heat controllable resin layer was formed. <Vinyl chloride resin composition for forming heat controllable resin layer: PVC (4)> Straight vinyl chloride resin (P = 1050) 100 parts by mass Polymer plasticizer 55 parts by mass Adipate polyester 35 parts by mass Epoxidized soybean oil (ESBO ) 4 parts by mass Stainless powder 5 parts by mass Zirconium oxide powder 5 parts by mass Ba-Zn composite stabilizer 2 parts by mass Rutile titanium oxide 5 parts by mass Organic antifungal agent (TBZ) 0.2 parts by mass UV absorber 0. 3 parts by mass Antioxidant 0.2 parts by mass [Note] * Stainless powder (Trademark: NOVAMET Stainless Flake Powder Standard: Nikko Fine Products Co., Ltd.) * Zirconium oxide powder (Trademark: Zirconia Powder 3YA: Toyo Soda Industry Co., Ltd.) ) Among the obtained heat controllable resin layers, the same additive volatilization prevention layer as in Example 1 (v) was formed on the surface side heat controllable resin layer, Forming a metal oxide transparent layer having a thickness of about 16 nm (about 160 Å) on the entire surface. The metal oxide transparent layer was formed by vacuum deposition, and indium-doped tin oxide (ITO: Sumitomo Osaka Cement Co., Ltd.) was used as the target material for the metal oxide. Next, the same protective layer as in Example 1 (vi) was provided on the surface of the metal oxide transparent layer, and the same photocatalyst-containing layer as in Example 1 (vii) was further formed on the surface of the protective layer to contain a photocatalyst. Layer is formed on the entire outermost layer, mass 888 g / m
² of membrane material (Fig. 2) was obtained.

Example 6 The same adhesive pretreated filament fabric as in Example 2 (ii, iii) was used, and the same heat control resin layer as in Example 5 was laminated on both surfaces thereof. Example 1 was formed on the heat control resin layer on the front surface side.
The same additive volatilization prevention layer as in (v) was formed. Next, a film thickness of about 16 nm (about 160 nm) is formed on the entire surface of this additive volatilization prevention layer.
A transparent metal oxide layer of Å) was formed. The metal oxide transparent layer was formed by vacuum deposition, and indium-doped tin oxide (ITO: Sumitomo Osaka Cement Co., Ltd.) was used as the target material for the metal oxide. Next, the following coating for forming a protective layer (silicon compound-containing resin layer) on the entire surface of the metal oxide transparent layer using a roll coater machine having a gravure roll engraved with 80 mesh lines. Apply 12g / m ^{2 of} solution and wet to 10
The protective layer was formed by drying in a hot air oven at 0 ° C for 1 minute.
(Solid content deposition amount 5 g / m ² ) Next, the same photocatalyst containing layer as in Example 1 (vii) was formed on the surface of the protective layer, and the photocatalyst containing layer was formed on the entire outermost layer, mass 676 g / m 2. ² of membrane material (Fig. 2) was obtained. <Silicon compound (silica / polysiloxane) -containing resin layer: Epoxy-silicon resin base> Trademark: Celltop # 056: Daicel Chemical Industries, Ltd .: Epoxy-silicon copolymer (solid content 50 mass%) 200 mass Part Trademark: Takenate D-170N: Takeda Yakuhin Kogyo Co., Ltd .: Isocyanurate body of hexamethylene diisocyanate (solid content 100 mass%) 10 parts by mass Trademark: SZ6079: Toray Dow Corning Silicone Co., Ltd .: Hexamethyldisilazane 10 Parts by mass Trademark: Snowtex XBA-ST: Nissan Chemical Industries, Ltd .: Colloidal silica (solid content 30% by mass) 20 parts by mass Trademark: Methylsilicate MS51: Colcoat Co., Ltd .: Polymethoxysiloxane (solid content 50% by mass) 20 parts by mass Diluent: Toluene / MEK (1: 1 parts by mass ) 100 parts by weight

[0080]Example 7 The same substrate / heat controllable resin laminate as in Example 1 (Example i
~ V) is used to prevent the volatilization of the additive formed on this laminate.
Metal thin film with a thickness of about 16 nm (about 160Å) on the entire surface of the stop layer
Layers were formed. The metal thin film layer is formed by vacuum evaporation.
Aluminium was used as the target metal. next,
On the surface of the metal thin film layer, the same protective layer as in Example 1 (vi) is provided.
The same light as in Example 1 (vii) was provided on the surface of the protective layer.
The catalyst-containing layer is formed, and the photocatalyst-containing layer is formed on the entire outermost layer.
The mass is: 888g / m ² Obtained the membrane material (Fig. 3)
It was

Example 8 Using the same laminate as in Example 2 (Examples i to v), a film having a film thickness of about 16 nm (about 160 Å) was formed on the entire surface of the additive volatilization prevention layer formed on this laminate. A metal thin film layer was formed. The metal thin film layer was formed by vacuum vapor deposition, and aluminum was used as the target metal. Next, the same protective layer as in Example 1 (vi) was provided on the surface of the metal thin film layer, and the same photocatalyst-containing layer as in Example 1 (vii) was further formed on the surface of the protective layer. A film material (FIG. 3) having a mass of 888 g / m ² formed on the entire outermost layer was obtained.

Example 9 A film having a thickness of about 16 nm (about 160 nm) was formed on the entire surface of the additive volatilization prevention layer formed on the same laminate (Examples i to iv) as in Example 3.
The metal thin film layer of Å) was formed. The metal thin film layer was formed by vacuum vapor deposition, and aluminum was used as the target metal. Next, the following coating liquid for forming a protective layer (silicon compound-containing resin layer) was formed on the entire surface of the metal thin film layer using a roll coater having a gravure roll engraved with 80 mesh lines. 12 g / m ^{2 was} applied, and dried for 1 minute in a hot air oven at 100 ° C. to form a protective layer. (Amount of solid matter attached: 5 g / m ² ) Next,
The same photocatalyst containing layer as in Example 1 (vii) is formed on the surface of the protective layer, and the photocatalyst containing layer is formed on the entire outermost layer.
A membrane material (FIG. 3) having a mass of 676 g / m ² was obtained. <Silicon compound (silica / polysiloxane) -containing resin layer: Acrylic-silicone resin base> Trademark: Neosilica # 4000 Clear: Isam Paint Co., Ltd .: Acrylic-silicone copolymerization (solid content 50 mass%) 200 parts by mass Trademark: SZ6079: Toray Dow Corning Silicone Co., Ltd .: Hexamethyldisilazane 10 parts by mass Trademark: Methyl silicate MS51: Colcoat Co., Ltd .: Polymethoxysiloxane (solid content 50% by mass) 40 parts by mass Diluent: Toluene / MEK (1 : 1 mass ratio) 100 parts by mass

[0083]Example 10 Formed on the same laminate as in Example 1 (Examples i-v)
A film thickness of about 16 nm (about 160Å) is formed on the entire surface of the additive volatilization prevention layer.
A metal thin film layer was formed. Vacuum evaporation for the formation of thin metal layers
Therefore, using aluminum as the target metal
It was Next, a film thickness of about 12 nm (about
120 Å) a metal oxide transparent layer was formed. Metal oxide
The transparent layer is formed by vacuum evaporation, and metal oxide is
Antimony-doped tin oxide (ATO: Sumitomo Osaka Cement)
Co., Ltd.) was used as the target material. Next, the metal oxide transparent
On the surface of the light layer, the same protective layer as in Example 1 (vi) was thermally controlled.
Provided on the entire surface of the flexible resin layer, and further on the entire surface of the protective layer.
The same photocatalyst containing layer as 1 (vii) is formed, and the photocatalyst containing layer is formed.
Is formed on the entire outermost layer, mass: 888 g / m ² 
A film material (FIG. 4) was obtained.

[0084]Example 11 Formed on the same laminate as in Example 2 (Examples i-v)
A film thickness of about 16 nm (about 160 nm) is formed on the entire surface of the additive volatilization prevention layer.
The metal thin film layer of Å) was formed. Vacuum formation of metal thin film layer
The target metal is aluminum
Using. Next, a film thickness of about 12 nm (about
120 Å) a metal oxide transparent layer was formed. Metal oxide
The transparent layer is formed by vacuum evaporation, and metal oxide is
Antimony-doped tin oxide (ATO: Sumitomo Osaka Cement)
Co., Ltd.) was used as the target material. Next, the metal oxide transparent
On the surface of the light layer, the same protective layer as in Example 1 (vi) was thermally controlled.
Provided on the entire surface of the functional resin layer and further on the entire surface of the protective layer of Example 1.
The same photocatalyst containing layer as (vii) is formed, and the photocatalyst containing layer is
Formed on the entire outermost layer, mass: 888 g / m ² of
A film material (Fig. 4) was obtained.

Example 12 The same heat control resin layer as in Example 6 was laminated, and
A laminate having an additive volatilization prevention layer formed on the surface side thereof was used to form a metal thin film layer having a film thickness of about 16 nm (about 160Å) on the entire surface of the additive volatilization prevention layer. The metal thin film layer was formed by vacuum vapor deposition, and aluminum was used as the target metal. Next, a film thickness of about 12 is formed on the entire surface of the metal thin film layer.
A metal oxide transparent layer of nm (about 120Å) was formed. The metal oxide transparent layer was formed by vacuum deposition, and antimony-doped tin oxide (ATO: Sumitomo Osaka Cement Co., Ltd.) was used as the target material for the metal oxide. Next, the following coating liquid for forming a protective layer (silicon compound-containing resin layer) on the entire surface of this metal oxide transparent layer using a roll coater having a gravure roll engraved with 120 mesh lines Of 8 g / m ² (wet), and the amount of UV light is 500-1000 mj /
Irradiation was carried out at cm ² for 3 seconds, and the phosphazene resin was photocured to form a protective layer. (Solid amount attached 6 g / m ² )
Next, the same photocatalyst-containing layer as in Example 1 (vii) was further formed on the surface of this protective layer, and the photocatalyst-containing layer was formed on the entire outermost layer. The mass was 676 g / m ² (see FIG. 4)
Got <Silicon compound (silica / polysiloxane) -containing resin layer: Phosphazene resin base> Trademark: ACE-40: Idemitsu Petrochemical Co., Ltd .: 2-hydroxyethyl methacrylate substituted P-N 6-membered ring Phosphazene ( 3PC-6HEMA) 100 parts by mass Trademark: Snowtex XBA-ST: Nissan Chemical Industries, Ltd .: Colloidal silica (solid content 30% by mass) 30 parts by mass Trademark: Methyl silicate MS51: Colcoat Co., Ltd .: Polymethoxysiloxane (solid) Min 50% by mass) 20 parts by mass

Example 13- (i) Formation of resin foam layer-Using the same laminate with an adhesive pretreatment layer as in Example 2 (iii),
The following chemical foaming agent-containing paste vinyl chloride resin composition (PVC (5) sol) for forming a resin foam layer was formed on this one side by a clearance coating method to a thickness of 0.35 mm (160 g /
m ² adhered mass), evenly applied to the entire surface of the adhesive pretreatment laminate, semi-gelled and dried in a hot air oven at 150 ° C. for 1 minute, and then heated at 160 ° C. (press 0.2 Mpa) And a PVC (5) -coated substrate was hot pressed to prepare a laminate with a resin foam layer having a thickness of 0.71 mm and a mass of 550 g / m ² . <Vinyl chloride resin composition for forming resin foam layer: PVC (5)> Paste vinyl chloride resin (P = 800) 100 parts by mass DINP (plasticizer) 25 parts by mass Adipic acid polyester (plasticizer) 40 parts by mass Epoxidation large Soybean oil (ESBO) 4 parts by mass Zirconium oxide powder 5 parts by mass Chemical foaming agent (ADCA) 3 parts by mass Ba-Zn stabilizer 2 parts by mass Rutile titanium oxide 5 parts by mass Organic antifungal agent (OBPA) 0.2 parts by mass Parts Isocyanate trimer (curing agent) 5 parts by mass Solvent (toluene) 20 parts by mass [Note] * Vinyl chloride resin: Trademark: ZEST-P66 (Shin-Daiichi PVC Co., Ltd.) * DINP: Trademark: Sanso Sizer DINP ( Shin Nippon Rika Co., Ltd. * Adipic polyester: Trademark: ADEKA CIZER PN-446 (Asahi Denka Co., Ltd.) * Epoxidized soybean oil: Trademark: Decasizer O-130P (Asahi Denka Kogyo Co., Ltd.) * Zirconium oxide powder (Trademark: Zirconia Powder 3YA: Toyo Soda Co., Ltd.) * Chemical foaming agent ADCA (Trademark: Uniform AZ L-10: Azodicarbonamide: Otsuka Chemical) * Ba-Zn stabilizer: Trademark: KV-400B (Kyodo Pharmaceutical Co., Ltd.) * Rutile type titanium oxide: Trademark: Titanium oxide CR: (Ishihara Sangyo Co., Ltd.) * Organic fungicide: Trademark: Vinadine BP-5-2: (10,10'-oxybisphenoxyarsine: Morton Thiokol) * Isocyanate trimer (Trademark: Vulcabond VP: AKCROS CHEMICALS) Resin foam layer containing this chemical foaming agent The same heat control resin layer as in Example 2 (iv) was laminated on both sides of the laminate having (unfoamed), and then this laminate was placed in a hot air drying oven at 220 ° C. for 3 minutes. Through, resin foam layer (unfoamed) Density 0.7 g /
It was foamed to cm ³ . The same additive volatilization prevention layer as in Example 1 (v) was formed on the entire surface of the heat control resin layer located on the side opposite to the resin foam layer forming surface, and Example 1 (vi) was formed on the entire surface of this additive volatilization prevention layer. Same protective layer (silicon compound-containing resin layer)
And the same photocatalyst containing layer as in Example 1 (vii) is formed on the entire surface of this protective layer, and the thickness: 1.06 mm, mass:
A film material of 1078 g / m ² (FIG. 5) was obtained.

Example 14 The same film material as in Example 5 was used, except that it was placed between the short fiber spun yarn woven fabric and the heat controllable resin layer on the side opposite to the photocatalyst containing layer forming surface. By providing the same resin foam layer in the same process, thickness: 1.06 mm, mass: 1078 g /
A film material of m ² (FIG. 6) was obtained.

Example 15 A film material similar to that of Example 8 was placed between the short fiber spun yarn woven fabric and the heat control resin layer, which was located on the side opposite to the photocatalyst-containing layer forming surface, and Example 13 was used. By providing the same resin foam layer with the same process, thickness: 1.06 mm, mass: 1078 g
A film material (FIG. 7) having a thickness of / m ² was obtained.

Example 16 A film material similar to that of Example 11 was placed between the short fiber spun yarn woven fabric and the heat controllable resin layer on the side opposite to the photocatalyst-containing layer forming surface, and Example 13 was used. By providing the same resin foam layer as in the same step, thickness: 1.06 mm, mass: 1078
A film material (FIG. 8) having g / m ² was obtained.

Tables 1, 2, and 3 show the laminated structure of the heat-insulating antifouling film materials of Examples 1 to 6, 7 to 12, and 13 to 16, the heat insulating coefficient, the effect persistence, and the antifouling property, respectively. Shown in

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

Performances of Heat Shielding Antifouling Membrane Materials of Examples 1 to 16 Examples 1 to 3 (FIG. 1) are film materials containing metal powder and / or ceramic powder in the thermoplastic resin layer, Examples 4 to 6 (Fig. 2) are film materials in which a metal oxide transparent layer is provided between the heat controllable resin layer and the protective layer of Examples 1 to 3, respectively, and Examples 7 to 9 (Fig. 3) are examples 1 to 3, respectively.
3 is a film material in which a metal thin film layer is provided between the heat controllable resin layer and the protective layer, and Examples 10 to 12 (FIG. 4) are the heat controllable resin layer and the protection of Examples 1 to 3, respectively. A film material in which a metal thin film layer and a metal oxide transparent layer provided on the surface thereof are provided between the layers, and Examples 13 to 16 (FIGS. 5 to 8) are
A resin foam layer is provided between the short fiber spun yarn woven fabric and the heat controllable resin layer, which are located on the opposite sides to the photocatalyst containing layer forming surfaces of the film materials of Examples 2, 5, 8 and 11, respectively. It is a film material. In addition, Examples 1, 3, 4, 6, 6, 7, 9, 10,
In the film material of No. 12, as the fiber yarns constituting the fiber woven fabric (fiber cloth), the fiber yarns containing the ceramic powder were used in particular and combined with the heat controllable resin layer. In addition, Example 1
For the resin foaming of 3 to 16, a resin foaming layer containing ceramic powder was used and combined with the heat controllable resin layer. Each of these film materials has a high heat-shielding property (test I), and has one or more of a metal thin film layer, a metal oxide transparent layer, and a resin foam layer in the layer structure of the film material. The thing was especially excellent in the heat-shielding effect. Further, in order to further improve the heat-shielding property, it was effective to use a ceramic powder-containing fiber yarn as the fiber yarn constituting the fiber cloth. Since all of the film materials of these examples are film materials having a photocatalyst-containing layer on the outermost surface, there is very little soot dust (environmental dirt) that naturally adheres to the surface of the film material during outdoor spreading (Test II), The appearance of the material was able to maintain a beauty close to the initial state. According to the detailed observation of these film materials every month, the dust dirt adhering to the surface of the film material is effectively washed away by the rainfall, and in these film materials, the dust dirt accumulated on the surface is It was revealed that they were sequentially decomposed by the photocatalytic substance, and were always placed in a state of being easily detached from the surface of the film body. With the conventional heat-shielding film material, even if an effective heat-shielding effect is initially obtained,
Due to the adhesion of such dust and dirt, for example, the light reflection effect in the metal powder-containing layer and the light invasion into the ceramic powder-containing layer are impeded. The fact that the functional heat-shielding effect expires was unavoidable. However, according to the film material of the present invention, it is clear from Test III that the surface of the film material has a function of always maintaining a state close to the initial state, so that a stable heat shield effect can be continuously exhibited.

Comparative Example 1 A film material similar to that of Example 1 was prepared. However, the photocatalyst containing layer and the protective layer were not formed. The obtained membrane material had a sufficient heat-shielding effect at the beginning, but during the 12 months of outdoor spreading, dust and dirt gradually accumulated and adhered to the surface of the membrane material, It was revealed that the original heat-shielding effect was lost as the dust and dirt progressed. Therefore,
This film material was unsuitable for long-term use with the expectation of a heat shield effect outdoors.

Comparative Example 2 A film material similar to that of Example 5 was prepared. However, an acrylic resin (trademark: Sony Bond SC-474: Sony Chemical Co., Ltd.) used for forming the additive volatilization prevention layer of Example 5 without forming the photocatalyst containing layer and forming the protective layer ). The obtained film material had a sufficient heat-shielding effect at the beginning, but during the 12 months of outdoor spreading, dust and dirt gradually accumulated and adhered to the surface of the film material, It was revealed that the original heat-shielding effect was lost as the dust and dirt progressed. Therefore, this film material was unsuitable for long-term use in anticipation of the heat shielding effect outdoors.

Comparative Example 3 A film material similar to that of Example 9 was prepared. However, the photocatalyst-containing layer was not formed, and the protective layer was formed of the acrylic resin (trademark: Sony Bond SC-474: Sony Chemical Co., Ltd.) used for forming the additive volatilization prevention layer of Example 9. . The obtained film material had a sufficient heat-shielding effect at the beginning, but during the 12 months of outdoor spreading, dust and dirt gradually accumulated and adhered to the surface of the film material, It was revealed that the original heat-shielding effect was lost as the dust and dirt progressed. Therefore, this film material was unsuitable for long-term use in anticipation of the heat shielding effect outdoors.

Comparative Example 4 A film material similar to that in Example 12 was prepared. However, the photocatalyst-containing layer was not formed, and the protective layer was formed of the acrylic resin (trademark: Sony Bond SC-474: Sony Chemical Co., Ltd.) used for forming the additive volatilization prevention layer of Example 12. did. The obtained film material had a sufficient heat-shielding effect at the beginning, but during the 12 months of outdoor spreading, dust and dirt gradually accumulated and adhered to the surface of the film material, It was revealed that the original heat-shielding effect was lost as the dust and dirt progressed. Therefore, this film material was unsuitable for long-term use in anticipation of the heat shielding effect outdoors.

Comparative Example 5 A film material similar to that in Example 2 was prepared. However, from the soft vinyl chloride resin composition for forming the thermoplastic resin layer, 5 parts by mass of aluminum powder (trademark: Alpaste P0100: Toyo Aluminum Co., Ltd.) and zirconium oxide powder (trademark: Zirconia powder 3YA: Toyo Soda Kogyo ( 3 parts by mass of carbon black pigment (trademark: HSM5078K standard color: carbon black content 35% by mass: Hihiro Vix Co., Ltd.) instead of 5 parts by mass). The obtained black film material had no noticeable adhesion of dust and dirt for 12 months of outdoor deployment, but it had a poor heat shield effect from the initial stage and was unsuitable for applications that expect a heat shield effect. Met.

Comparative Example 6 A film material was prepared in the same manner as in Example 3. However, from the soft vinyl chloride resin composition for forming the thermoplastic resin layer, 5 parts by mass of aluminum powder (trademark: Alpaste P0100: Toyo Aluminum Co., Ltd.) and zirconium oxide powder (trademark:
Zirconia powder 3YA: Toyo Soda Kogyo Co., Ltd. (5 parts by mass) was excluded, and calcium carbonate powder (trademark: Ryton BS (Bihoku Chemical Industry Co., Ltd.) (2.0 parts by mass) was mixed instead. Although the film material had no noticeable adhesion of dust and dirt for 12 months in the outdoor deployment, it had a poor heat shielding effect from the initial stage and was unsuitable for applications that expect a heat shielding effect.

Table 4 shows the laminated structures and the test results of the film materials of Comparative Examples 1 to 6.

[0102]

[Table 4]

[0103]

As is apparent from the above-mentioned Examples and Comparative Examples, the heat-shielding antifouling film material of the present invention is provided with the photocatalyst-containing layer on the outermost surface of the film material, thereby reducing the heat-shielding function. It is possible to effectively prevent the attachment of dust and dirt (environmental dirt), which causes the heat generation, and at the same time, to maintain a stable heat shield effect for a long period of time. Therefore, the heat-shielding antifouling film material of the present invention is suitable for the purpose of preventing an excessive temperature rise of storage materials by utilizing it in awning tents, sheet houses, etc., and similarly, for products in distribution, foods, etc. A fiber composite membrane material that can be suitably used for a truck hood, a luggage carrier cover and the like for the purpose of preventing an excessive temperature rise.

[Brief description of drawings]

FIG. 1 is a cross-sectional explanatory view showing a laminated structure of one embodiment of a heat-shielding antifouling film material of the present invention.

FIG. 2 is an explanatory sectional view showing a laminated structure of another embodiment of the heat-shielding antifouling film material of the present invention.

FIG. 3 is an explanatory sectional view showing a laminated structure of still another embodiment of the heat-shielding antifouling film material of the present invention.

FIG. 4 is a cross-sectional explanatory view showing a laminated structure of still another embodiment of the heat-shielding antifouling film material of the present invention.

FIG. 5 is an explanatory sectional view showing a laminated structure of still another embodiment of the heat-shielding antifouling film material of the present invention.

FIG. 6 is an explanatory sectional view showing a laminated structure of still another embodiment of the heat-shielding antifouling film material of the present invention.

FIG. 7 is an explanatory cross-sectional view showing a laminated structure of still another embodiment of the heat-shielding antifouling film material of the present invention.

FIG. 8 is an explanatory sectional view showing a laminated structure of still another embodiment of the heat-shielding antifouling film material of the present invention.

[Explanation of symbols]

1 ... Light-blocking antifouling film material 2 ... Sheet-shaped substrate 3a, 3b ... Thermal control resin layer 3c ... Thermal control resin layer with attachment volatilization prevention layer 4 ... Protective layer 5 ... Photocatalyst containing layer 6 ... Additive volatilization prevention layer 7 ... Metal oxide transparent layer 8 ... Metal thin film layer 9 ... Resin foam layer

Continued front page    F-term (reference) 2E141 AA02 AA09 EE02 EE03 EE04                       EE05                 4F100 AA00C AA02B AA02E AA03B                       AA12B AA12E AA13B AA13E                       AA14B AA15E AA17A AA17B                       AA17C AA17E AA18A AA18B                       AA19A AA19B AA19E AA20D                       AA21A AA21B AA21C AA22E                       AA23C AA23E AA24E AA25A                       AA25B AA25C AA25E AA27A                       AA27B AA27E AA28A AA28B                       AA28C AA28E AA29A AA29B                       AA33A AA33B AA33E AB01B                       AB01E AB04B AB04E AB10B                       AB10E AB13B AB13E AB16B                       AB16E AB17B AB17E AB18B                       AB21B AB21E AB24B AB25B                       AD00A AD00B AD00E AK01A                       AK01B AK01C AK01D AK17D                       AK25B AK36D AK51B AK52D                       AK53D AK69B AS00C AT00A                       BA04 BA05 BA07 BA10A                       BA10C CA25B CA30B DE01A                       DE01B DE01C DE01E DG01A                       DG04A DG11A DG12A DJ01E                       EH66E GB90 JA13A JB14B                       JJ03 JJ10 JJ10B JK17A                       JL06 JL08C JM02E JM10C                       JN01E YY00A YY00B YY00C

Claims (22)

[Claims] 1. A sheet-like base material, a resin component formed on at least one of the front and back surfaces of the sheet-like base material, the resin component comprising at least one kind of polymer, and at least one kind of metal powder and ceramics powder. Powder component consisting of
A heat controllable resin layer containing 70:30, and a photocatalytic substance formed on the at least one heat controllable resin layer,
A photocatalyst containing layer containing a binder, between the heat controllable resin layer and the photocatalyst containing layer, the heat controllable resin layer, a resin material for blocking the photocatalytic action of the photocatalyst containing layer. A heat-shielding antifouling film material having a protective layer formed as a main component. 2. The heat controllable resin layer contains, in addition to the resin component and the powder component, an additive having volatility and / or migration property, and is formed on the surface thereof, and the volatilization is performed. The heat-insulating antifouling film material according to claim 1, further comprising an additive volatilization preventive layer containing a resin material as a main component for preventing volatilization and / or migration of the organic and / or migration additive. . 3. The resin material contained in the additive volatilization prevention layer contains at least one selected from acrylic resins, energy ray curable acrylic resins, polyurethane resins and ethylene-vinyl alcohol copolymer resins. Item 2. A heat-shielding antifouling film material according to Item 2. 4. The metal powder contained in the heat control resin layer is aluminum, stainless steel, nickel,
The heat-shielding antifouling film material according to any one of claims 1 to 3, which is selected from at least one powder selected from copper and tin. 5. The ceramic powder contained in the heat controllable resin layer is titanium oxide, zinc oxide, aluminum oxide (alumina), magnesium oxide, zirconium oxide (zirconia), tin oxide, indium oxide, tin-doped indium oxide, indium. Any one of claims 1 to 4, which is selected from at least one kind of fine particles selected from doped tin oxide, antimony-doped tin oxide, aluminum borate, magnesium borate, zirconium silicate, aluminum nitride, silicon nitride, and boron nitride. The heat-shielding antifouling film material as described in 1 above. 6. The particles of the ceramic powder are aluminum, stainless steel, nickel, tin, chromium, zinc,
The heat-shielding antifouling film material according to claim 5, which is surface-coated with at least one metal selected from gold, silver, and copper. 7. The sheet material according to claim 1, wherein the sheet-shaped base material is selected from a fiber cloth, a flexible resin film or sheet, and a fiber cloth surface-coated with a flexible resin. The heat-shielding antifouling film material described. 8. The fiber fabric for a sheet-shaped substrate is selected from a filament woven fabric having a mesh porosity of 6 to 40% and a short fiber spun fabric having a mesh porosity of 0 to 10%.
The heat-shielding antifouling film material described in. 9. The sheet-shaped base material contains 1 to 10 mass% of ceramic powder with respect to the mass thereof.
The heat-shielding antifouling film material according to any one of items 1 to 8. 10. The ceramic powder contained in the sheet-shaped substrate is titanium oxide, zinc oxide, aluminum oxide (alumina), magnesium oxide, zirconium oxide (zirconia), tin oxide, indium oxide, tin-doped indium oxide, indium. The shield according to claim 9, comprising at least one kind of fine particles selected from doped tin oxide, antimony-doped tin oxide, aluminum borate, magnesium borate, zirconium silicate, aluminum nitride, silicon nitride, and boric acid nitride. Thermal antifouling film material. 11. The resin material contained in the protective layer contains at least one selected from silicon-based resins, fluorine-based resins, melamine-based resins, epoxy-based resins, and phosphazene-based resins. Item 10. The heat-shielding antifouling film material according to any one of items 10. 12. The thermal barrier according to claim 1, wherein the protective layer further contains a silicon-containing substance containing at least one selected from polysiloxane, colloidal silica and silica. Membrane material. 13. The photocatalyst-containing layer comprises 10 to 70% by mass of a photocatalytic substance, and 25 to 95% by mass of at least one selected from a metal oxide gel and a metal hydroxide gel.
A silicon-containing substance is contained in an amount of 1 to 20% by mass.
The heat-shielding antifouling film material according to any one of 1 to 12. 14. The photocatalytic substance is titanium oxide (T
iO ₂ ), titanium peroxide (peroxotitanic acid), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO
₃ ), bismuth oxide (Bi ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ).
The heat-shielding antifouling film material according to any one of claims 1 to 13, which contains one or more metal oxides selected from the following. 15. The photocatalytic substance is titanium oxide (T
iO ₂ ), titanium peroxide (peroxotitanic acid), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO
₃ ), bismuth oxide (Bi ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ).
The heat-shielding antifouling film material according to any one of claims 1 to 14, which contains one or more metal oxides selected from the group consisting of and inorganic fine particles supporting the metal oxides. 16. A metal thin film layer made of a metal and an inorganic metal compound between the heat controllable resin layer and the protective layer,
And at least one transparent metal oxide layer containing a metal oxide
The heat shielding antifouling film material according to any one of claims 1 to 15, wherein a layer is formed. 17. When including both the metal thin film layer and the metal oxide transparent layer, the metal thin film layer is formed on the heat control resin layer, and the metal oxide transparent layer is formed on the metal thin film layer. The thermal barrier antifouling film material according to claim 16, wherein the protective layer is formed thereon. 18. The metal thin film layer comprises a metal of aluminum, nickel, chromium, stainless steel, copper or tin, and
The heat-shielding antifouling film material according to claim 16 or 17, which is one or more metal vapor deposition layers selected from these oxides, nitrides, and carbides. 19. The transparent layer of metal oxide is zinc oxide,
The stappering layer or the vapor deposition layer made of one or more metal oxides selected from tin oxide, zirconium oxide, indium oxide, tin-doped indium oxide, indium-doped tin oxide, and antimony-doped tin oxide. The heat-shielding antifouling film material described. 20. Between the sheet-shaped substrate and the heat control resin layer formed on at least one of the front and back surfaces thereof,
The heat shielding antifouling film material according to any one of claims 1 to 19, wherein a resin foam layer composed of a resin matrix and a large number of cells distributed in the resin matrix is formed. 21. The heat-shielding antifouling film material according to claim 20, wherein the resin matrix of the resin foam layer contains a ceramic powder. 22. The ceramic powder contained in the resin foam layer is titanium oxide, zinc oxide, aluminum oxide (alumina), magnesium oxide, zirconium oxide (zirconia), tin oxide, indium oxide, tin-doped indium oxide, indium-doped. The heat shield according to claim 20, which is one or more kinds of fine particles selected from tin oxide, antimony-doped tin oxide, aluminum borate, magnesium borate, zirconium silicate, aluminum nitride, silicon nitride, and boron nitride. Membrane material.