JP6700522B2 - High heat shield and antifouling film material - Google Patents

Description

  The present invention relates to a film material having both high heat shielding properties and high antifouling properties. More specifically, the present invention is excellent in weather resistance, durability, in high temperature regions and in environments where dust and soot may fly. The present invention relates to a high heat-insulating and anti-fouling film material used for awnings, medium and large tents, truck hoods and the like. In particular, the film material of the present invention has a function of preventing soot and dirt that reduces the heat shield function, and has a high heat shield and antifouling film that can effectively maintain the heat shield function of infrared reflectance of 90% or more. It concerns materials.

  As a waterproofing cloth used for building structures such as awning tents, medium and large tents, and truck hoods, a textile fabric is used as a base cloth and a soft blended polyvinyl chloride resin is used on its surface. A fiber composite membrane material obtained by coating is used. In recent years, due to the influence of global warming, the demand for a film material having an excellent heat shielding property is increasing year by year. Patent Document 1 describes that it relates to a heat-shielding film material and obtains heat-shielding properties with titanium oxide, but does not describe that antifouling properties are necessary to maintain heat-shielding properties.

  Patent Document 2 describes a heat-shielding film material having an antifouling property provided by a photocatalyst layer, but with such a film material, the photocatalyst layer, which is an obstacle during sewing, has to be scraped off.

JP, 2010-030203, A JP, 2007-131004, A

  The present invention provides a film material having both a high heat shielding property and a high antifouling property, and is excellent in weather resistance and durability, and can be used for sunshades, medium and large tents, and truck hoods in high temperature areas and environments where dust and soot can fly. It is intended to provide a high heat-insulating and antifouling film material that has a function of preventing dust and dirt that deteriorates the heat-shielding function and can effectively maintain the heat-shielding function.

As a result of repeated research on the above problems, a fluororesin film is laminated on one side or more of a composite sheet composed of a base fabric layer and one or two thermal barrier coating layers of a thermoplastic resin, for a membrane structure A film material containing at least 30 g/m ^{2 of} titanium oxide in the heat-shielding coating layer of at least the surface on which the fluororesin film is laminated, and the composite sheet has an infrared reflectance (JIS R 3106) of 85% or more. And, the film material obtained by making the thickness of the fluorine film 10 μm to 100 μm, the infrared reflectance (JIS R 3106) 55% or more, and the ultraviolet transmittance (JIS R 3106) less than 5%, The present inventors have found that it has a function of preventing dust and dirt from adhering to soot that deteriorates the heat-shielding function, whereby the heat-shielding function can be efficiently maintained, and thus completed the high heat-insulating and antifouling film material of the present invention.

  In the highly heat-insulating and highly antifouling film material of the present invention, the film material for a film structure preferably has an infrared reflectance (JIS R 3106) of 90% or more.

  In the highly heat-insulating and antifouling film material of the present invention, the fluorine content of the fluororesin film is preferably 48 to 76% by mass.

  It is preferable that the fluororesin film contains 0.01 to 5.0% by mass of surface-treated titanium oxide having a primary particle diameter of 30 to 300 nm.

  According to the present invention, the film material of the present invention has a function of preventing dust and dirt from adhering to a high temperature region and an environment in which dust and soot are present, medium and large tents, truck hoods, etc. Since a film material having excellent weather resistance and durability that can effectively maintain its function can be obtained, it can be used even in a high temperature area and an area where dust and soot are scattered.

  The type of the base fabric used for the base fabric layer of the high heat insulating and antifouling film material of the present invention is a known woven fabric or knitted fabric such as a plain weave, a twill weave, a satin weave, a triaxial weave, and a tetraaxial weave. Known fibers such as polyester fibers, nylon fibers, vinylon fibers, aramid fibers, carbon fibers and glass fibers can be used as the constituent fibers. These base fabrics can be appropriately subjected to known fiber treatments such as water absorption prevention treatment, adhesion treatment, flameproof treatment, and mildewproof treatment as long as the effects of the present invention are not impaired.

  As the thermoplastic resin forming the heat-shielding coating layer, known thermoplastic resins such as soft vinyl chloride resin, urethane resin, olefin resin, and fluororesin elastomer can be used.

  In particular, when the thermoplastic resin constituting the heat-shielding coating layer is a soft vinyl chloride resin, its basic composition contains at least a vinyl chloride resin, a plasticizer, and titanium oxide, and the titanium oxide is 25 to 100 parts by mass of vinyl chloride. 60 parts by mass is preferable, and 30 to 40 parts by mass is particularly preferable. If the amount is less than 25 parts by mass, sufficient heat shield cannot be obtained, and if the amount is more than 60 parts by mass, the flexibility and abrasion resistance of the vinyl chloride resin may be impaired.

  The soft vinyl chloride resin may contain an antifungal agent, an ultraviolet absorber, a processing stabilizer, a filler, a flame retardant, a plasticizer, and other additives as long as they do not impair the effects of the present invention.

  The soft vinyl chloride resin preferably contains a filler such as calcium carbonate and barium sulfate, and a flameproofing agent such as aluminum hydroxide and antimony trioxide. These are 70 parts by mass with respect to 100 parts by mass of polyvinyl chloride. The following contents are desirable. If it exceeds 70 parts by mass, flexibility and wear resistance may be impaired. The plasticizer is preferably 40 to 80 parts by mass with respect to 100 parts by mass of polyvinyl chloride.

  It is preferable that the infrared reflectance of the composite sheet composed of the base cloth layer and one or two heat-shielding coating layers of a thermoplastic resin is at least 85% or more. In order to make the infrared reflectance of the composite sheet having an infrared reflectance of less than 85% 90% or more, it is necessary to use a fluororesin film containing titanium oxide in an amount of 10% by mass or more. In this case, the durability of the fluororesin film May decrease.

  The thickness of the heat-shielding coating layer is preferably 0.15 mm to 0.40 mm, particularly 0.20 mm to 0.35 mm. Further, it is necessary to have smoothness in order to evenly adhere the fluororesin film to the composite sheet base material. If the smoothness is impaired, the adhesive force of the fluororesin film becomes non-uniform, and when used as a film material, there is a concern that the fluororesin film may peel off from the portion with weak adhesive force.

  When laminating a fluororesin film on a composite sheet substrate, a transparent fluororesin film with an ultraviolet transmittance (JIS R 3106) of 5% or more transmits infrared rays and ultraviolet rays, so the soft vinyl chloride resin layer is exposed to ultraviolet rays. Then, the vinyl chloride resin is decomposed to generate chlorine gas. Fluororesin does not easily permeate hydrochloric acid gas, and if the hydrochloric acid gas remains in the membrane material, it is easy to deteriorate the composite sheet base material.

  It is preferable that the fluororesin film has an infrared reflectance of 55% or more and an ultraviolet transmittance of less than 5% (both JIS R 3106). If the infrared reflectance is less than 55%, the infrared reflectance of the high thermal barrier film material may not reach 90% or more, and if the ultraviolet transmittance is 5% or more (UV shielding rate is less than 95%), the ultraviolet rays are soft. Upon reaching the vinyl chloride resin layer, the vinyl chloride resin is decomposed and generates hydrochloric acid gas. Since fluororesin does not easily pass through hydrochloric acid gas, the composite sheet base material may be easily deteriorated by the remaining hydrochloric acid gas. Examples of products include Toyoflon (trademark) EU series manufactured by Toray Film Processing Co., Ltd.

  When the fluororesin film is laminated only on one surface of the composite sheet substrate, the thickness of the fluororesin film is preferably 10 μm to 100 μm, and particularly preferably 20 μm to 50 μm. If it is less than 10 μm, the durability and antifouling property of the film material may be deteriorated, and if it is 100 μm or more, the film material becomes hard due to strong curling (curving) on the fluororesin film laminate surface side during lamination. Since infrared rays do not pass through and are absorbed into the soft vinyl chloride resin layer, there is a concern that high heat shielding properties may not be obtained. When the highly heat-insulating and highly antifouling film material of the present invention in which the fluororesin film is laminated on only one surface is used, the fluororesin film laminated surface side needs to be the surface exposed to sunlight. The high heat-insulating and antifouling film material can be used in an arbitrary sewing form according to the shape of a sunshade, a medium- or large-sized tent, a truck hood, or the like.

  When laminating the fluororesin film on both sides of the composite sheet base material, it is desirable to use the same kind of fluororesin film with the same thickness, as much as possible, because curling is easily eliminated.

  On the surface where the fluororesin film is laminated, a fluorocarbon film is prepared by coating an adhesive acrylic resin (containing aminoethyl group), an adhesive urethane resin (containing polyisocyanate group), etc. on the composite substrate (soft vinyl chloride resin layer). And the soft vinyl chloride resin layer need to be adhered. The adhesive acrylic resin or adhesive urethane resin may be coated on the fluororesin film side (corona treated surface), or may be coated on both the soft vinyl chloride resin layer and the fluororesin film (corona treated surface). ..

  Fluororesin film is polytetrafluoroethylene (PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluorethylene-ethylene copolymer (ECTFE), etc. can be used, and the surface exposed to sunlight will always be a fluororesin film. Since such use delays the deterioration of the film material, it is possible to use high heat insulation and high stain resistance for a longer time.

  In the fluororesin film, it is preferable to add 0.01 to 5,0% by mass, preferably 0.1 to 3.0% by mass of surface-treated titanium oxide having a primary particle diameter of 30 to 300 nm. If the titanium oxide in the fluororesin film is less than 0.01% by mass, the ultraviolet transmittance of the fluororesin film may exceed 5%, and if it is 5.0% by mass or more, the durability strength of the fluororesin film may decrease. The surface treatment can be exemplified by a combination of at least one selected from silicone-based, silicon dioxide-based, hydrous silicic acid-based, aluminum oxide-based, and aluminum hydroxide-based.

Hereinafter, the present invention will be described in more detail with reference to Examples. The physical properties in the examples were evaluated by the following methods.
(1) Infrared reflectivity, ultraviolet transmissivity This was based on the test method (JIS R 3106-2) for the transmittance, reflectance, emissivity, and solar heat gain of plate glass.
(2) Outdoor extension exposure test A 10 cm wide x 2 m long sample was installed in a sunny, south-facing direction. The exposure table was tilted at 30° and vertically in the Soka city, Saitama prefecture. It was
*The survey was conducted in Soka City, Saitama Prefecture for 3 years.

In each of Example 1 and Comparative Examples 1, 2, 3, and 4, a plain weave (weight: 315 g/m) using a polyester filament yarn of 1,670 dtex with a woven density of 23 yarns/inch (vertical) and 24 yarns/inch (horizontal) is used. ² ) was used as the base fabric.

Example 1 is a film material in which a fluororesin film (PVDF) having a thickness of 25 μm is laminated on one surface of a composite sheet base material in which a soft vinyl chloride resin layer contains titanium oxide at 40.8 g/m ² .

  The fluororesin film (PVDF) contains 30% by mass of surface-treated titanium oxide having a primary particle diameter of 10×100 nm and having a silicone type/hydrous silicic acid type/aluminum hydroxide type, a fluorine content rate of 59.3%, An infrared reflectance of 61.6% and an ultraviolet transmittance of 0.01% were used.

Comparative Example 1 is a film material obtained by laminating a fluorine film (PVDF) on one surface of a composite sheet base material with titanium oxide of the soft vinyl chloride resin layer of Example 1 being 10 g/m ² . The compositions of Example 1 and Comparative Example 1 were the same except for the addition amount of titanium oxide as a heat shield.

  The infrared reflectances of the composite sheet base materials of Example 1 and Comparative Example 1 (before laminating the fluororesin film (PVDF)) are 90.5% and 75.8%, respectively.

The infrared reflectances of the film materials of Example 1 and Comparative Example 1 (after laminating the fluororesin film (PVDF)) are 90.7% and 84.3%, respectively. The above results are shown in Table 1.

  The membrane material of Comparative Example 2 did not use a fluororesin film (PVDF), but the surface of the heat-shielding coating layer (soft vinyl chloride resin) of the composite sheet was subjected to coating treatment with a PVDF solution. Is a heat-insulating coating layer (soft vinyl chloride resin) of the composite sheet, the surface of which is coated with an acrylic resin solution. The membrane material of Comparative Example 4 is a fluororesin film (PVDF) having a primary particle diameter of 10×100 nm and containing no surface-treated titanium oxide of silicone type/hydrous silicic acid type/aluminum hydroxide type, and a fluorine content of 59. 3%, infrared reflectance 61.6%, and ultraviolet transmittance 20.6% were used. The formulations of Comparative Examples 2, 3 and 4 were the same as those of Example 1 except that the fluororesin film (PVDF) was laminated, the UV transmittance of the fluororesin film (PVDF) was different, and the formulation was not applied. Is the same as.

Table 2 shows the results of exposing the film materials of Example 1 and Comparative Examples 2, 3, and 4 to outdoor expansion for 3 years. The film material of Example 1 was free from stains and maintained in the initial state as compared with the initial state even after being exposed to the outdoor expansion for 3 years. The film material of Comparative Example 2 is inferior in antifouling property to the film material of Example 1, and the infrared reflectance is reduced by 10% after being exposed to the outdoor spread for 3 years, and the heat shielding property is maintained as compared with the film material of Example 1. Hard to do. The film material of Comparative Example 3 is further inferior in antifouling property to the film material of Comparative Example 2, and the infrared reflectance is reduced by 20% after 3 years of outdoor expansion exposure, and the heat resistance is higher than that of the film material of Comparative Example 1. Further difficult to maintain. The film material of Comparative Example 4 was more likely to cause deterioration of the base material (retention of hydrogen chloride gas in the film material) than the film material of Example 1.

[Example 1]
(1) A polyester filament plain woven fabric having the following structure was used as the base fabric and the water absorption preventing base fabric.

Vertical thread 1670dtex/1 thread × Horizontal thread 1670dtex/1 thread
23 vertical threads/inch x 24 horizontal threads/inch Weight 315g/m ²

This base cloth is dipped in an aqueous solution of a resin composition of the following formulation 1 containing a fluororesin-containing aqueous solution, the base cloth is impregnated with the aqueous solution, squeezed and dried at 150° C. for 1 minute to prevent water absorption. did.
<Formulation 1> Water-absorption prevention treatment liquid composition Water 95 parts by mass Fluorine-based resin-containing aqueous solution 5 parts by mass (2) Formation of adhesive treatment layer The base fabric treated as described above is pasted with a paste vinyl chloride resin and a heat-crosslinkable adhesive. Immersing the resin composition in Formulation 2 in a solvent diluent, impregnating the base cloth with the resin solution, squeezing and heat-treating at 185° C. for 1 minute to adhere the resin to the base cloth at 145 g/m ² and adhere. A resin layer was formed.
<Compound 2> Composition of treatment liquid for adhesive resin layer Paste Vinyl chloride resin 100 parts by mass Di-2-ethylhexyl phthalate (plasticizer) 70 parts by mass Antimony trioxide (flame retardant) 23 parts by mass Heat-crosslinkable adhesive 10 parts by mass Epoxidation Soybean oil (stabilizer) 4 parts by mass Ba-St stabilizer 0.5 parts by mass Antifungal agent 0.07 parts by mass Coal tar naphtha (solvent) 20 parts by mass (3) Formation of soft vinyl chloride resin film layer The vinyl chloride resin composition shown in the following composition 3 was calendered into a base cloth subjected to the adhesion treatment, and a film having a thickness of 0.25 mm and a film having a thickness of 0.15 mm were formed into films having the following compositions, respectively, and laminated on the front surface and the back surface. .. Titanium oxide is used only on one side and contains 40.8 g/m ² .
<Formulation 3> Soft vinyl chloride resin layer composition (surface)
Straight vinyl chloride resin 100 parts by mass Di-2-ethylhexyl phthalate (plasticizer) 50 parts by mass Titanium oxide (heat shield) 30 parts by mass Aluminum hydroxide (flame retardant) 30 parts by mass Antimony trioxide (flame retardant) 3 parts by mass Epoxidized soybean oil (stabilizer) 3 parts by mass Ba-Zn stabilizer (stabilizer) 2.4 parts by mass Tin stabilizer (stabilizer) 1.5 parts by mass Antifungal agent 0.35 parts by mass UV absorber 0.62 parts by mass (4) Adhesion treatment of fluororesin film A gravure adhesion treatment (20 g/m ² ) for adhering the fluororesin film to the composite sheet was performed.
<Formulation 4> Surface acrylic coat formulation (adhesive layer with fluororesin film)
Methyl ethyl ketone (solvent) 55 parts by mass Aminoethylated acrylic polymer 42.5 parts by mass Epoxy resin curing agent 2.5 parts by mass (5) Formation of acrylic layer In order to sew the film material of the present invention on the film material by high frequency welding, An acrylic layer capable of being melt-bonded to the fluororesin film surface of the film material was gravure coated (20 g/m ² ) on the film material surface opposite to the fluororesin film. This makes it possible to perform high-frequency welding at the overlapping portions of the film materials.
<Formulation 5> Acrylic coat formulation Acrylic copolymer resin 60 parts by mass Toluene 40 parts by mass (6) Formation of fluororesin film layer On the surface on which the adhesion treatment is performed in (4) above, a thickness of 25 μm fluororesin film (PVDF: fluorine content rate) 59.3% by mass and a titanium oxide content of 3.0% by mass) were thermally laminated to form a fluororesin film layer.

  The film material of the present invention has a function of preventing dust and dirt from adhering to a high temperature region and an environment in which dust and soot are present, medium and large-sized tents, truck hoods, etc., which reduces the heat shield function. Since a film material having excellent weather resistance and durability capable of effectively sustaining the above can be obtained, it can be used even in a high temperature area and an area where dust and soot are scattered.

Claims (4)

A membrane material for a membrane structure, in which a fluororesin film is laminated on one or more surfaces of a composite sheet composed of a base cloth layer and one or two heat-shielding coating layers made of a thermoplastic resin. Titanium oxide is contained in the thermal barrier coating layer on the surface on which the resin film is laminated at 30 g/m ² or more, the infrared reflectance (JIS R 3106) of the composite sheet is 85% or more, and the thickness of the fluorine film is 10 μm. Infrared reflectance (JIS R 3106) of 55% or more, and ultraviolet transmittance (JIS R 3106) of less than 5% at -100 μm, a high heat shield and antifouling film material.   The high heat-insulating and antifouling film material according to claim 1, wherein the film material for a film structure has an infrared reflectance (JIS R 3106) of 90% or more.   The high antifouling and high thermal barrier film material according to claim 1 or 2, wherein the fluorine content of the fluororesin film is 48 to 76% by mass.   The highly antifouling and highly heat-insulating film material according to any one of claims 1 to 3, wherein the fluororesin film contains 0.01 to 5,0% by mass of surface-treated titanium oxide having a primary particle diameter of 30 to 300 nm. ..