WO2003074180A1

WO2003074180A1 - Material for film structure

Info

Publication number: WO2003074180A1
Application number: PCT/JP2002/002148
Authority: WO
Inventors: Akira Fujishima; Kazuhito Hashimoto; Kazuhiro Abe; Hiroshi Toyoda; Takayuki Nakata
Original assignee: Taiyo Kogyo Corporation
Priority date: 2002-03-07
Filing date: 2002-03-07
Publication date: 2003-09-12
Also published as: JPWO2003074180A1; JP3858176B2; AU2002236255A1

Abstract

A material for a film structure having a base fabric comprising a glass fiber as a primary material and, formed on the surface of the fabric, a fluororesin surface layer, characterized in that the fluororesin surface layer contains a colorless and transparent or a white photocatalyst powder being carried thereon in an exposed state. The photocatalyst is preferably an anatase-type titanium dioxide having a high photocatalyst activity, and the fluororesin is preferably a tetrafluoroethylene-hexafluoropropylene copolymer. The material for a film structure is capable of decomposing and removing a stain comprising an organic material sticked thereto through decomposition or hydrophilization by photooxidation and thus exhibits high antifouling property for a long period of time. Further, the material allows the suppression of static electricity generated and accumulated by the friction or abrasion due to the fluttering by wind or the like or the contact with another material, which leads to the reduction of the sticking of dust, fine sands, or the like causing a stain.

Description

Description Membrane structural materials Technical field

The present invention relates to a membrane structure material used for a roof material of a permanent membrane structure building such as a dome stadium, a gymnasium, a stadium, a multipurpose hall, etc., which has a self-cleaning function to withstand long-term use. And it has high antifouling properties. Background art

In recent years, as a roofing material for permanent membrane structures such as dome stadiums, gymnasiums, stadiums, and multipurpose halls, a woven fabric mainly composed of glass fiber has been used as a base fabric, and this surface is covered with a fluororesin layer. Is used. This membrane-structured material has a light-transmitting property, is nonflammable, has high mechanical strength, and is light and flexible. .

However, this membrane-structured material has a problem in that when used for many years, substances such as soot, dust and fine sand in the air adhere to the membrane surface and gradually become dirty, resulting in a poor appearance. This is because fluororesins have non-adhesive properties and are excellent in mold release properties, but their surface and volume resistances are extremely large and their dielectric constant is small, so static electricity is applied to the film material due to fluttering of wind and the like. accumulate. As a result, substances such as dust and fine sand are adsorbed on the film surface by static electricity, and in urban areas, organic substances such as exhaust gas (eg, oil stains) are used as a binder to attach dirt and the like. '

In factories and construction sites that manufacture membrane-structured buildings using this membrane-structured material, not only does the dust adhere to the membrane surface and become dirty before the construction is completed due to static electricity, and workers accumulate in the membrane-structured material. There is also a problem that an electric shock is caused by the generated static electricity.

According to the present invention, a film structure that exhibits high antifouling properties over a long period of time by removing organic dirt adhering to the film structure material by photooxidative decomposition and hydrophilization using a photocatalyst. The purpose is to provide building materials.

Further challenges include fluttering of the wind and the like, and friction due to contact with objects (substances). A film structure that suppresses static electricity generated and accumulated due to abrasion and reduces the adhesion of dust and fine sand that cause dirt. The purpose is to provide the material. Disclosure of the invention

In the present invention, a film structure material in which a fluororesin surface layer is provided on the surface of a base fabric mainly composed of glass fiber, and a colorless transparent or white photocatalyst powder is carried and exposed on the fluororesin surface layer It was used as a film structure material.

In this way, organic dirt adhering to the surface of the film structure material is decomposed by photo-oxidative decomposition and hydrophilization by a photocatalyst and washed away. In addition, by using a colorless, transparent or white photocatalyst, it does not affect the translucency of the film structure material even if it is carried and exposed to the film structure material family.

The photocatalyst used for the above is preferably anatase type titanium dioxide having high photocatalytic activity. '

The fluororesin used for the above is preferably a tetrafluoroethylene-hexafluoropropylene copolymer.

If a tetrafluoroethylene-hexafluoropropylene copolymer is used, bonding of the membrane structural materials becomes possible by heat welding.

Furthermore, in the present invention, a structural material comprising a fluorine resin surface layer provided on the surface of a base fabric mainly composed of glass fiber, wherein the fluororesin surface layer comprises a colorless transparent or white photocatalyst powder. The film structure material was made by carrying and exposing a colorless transparent or white conductive powder.

In this way, in addition to the photo-oxidative decomposition and hydrophilizing actions of the photocatalyst, the film structure material has a conductive action, and no static electricity is accumulated in the film structure material.

The photocatalyst used in the above invention is preferably anatase-type titanium dioxide having high photocatalytic activity. The fluororesin used in the above invention is preferably a tetrafluoroethylene-hexafluoropropylene copolymer.

If tetrafluoroethylene-hexafluoropropylene copolymer is used, bonding of the film structural materials by heat welding becomes possible.

The conductive powder can be tin dioxide. -Tin dioxide is white and stable even when heated in air, so there is no effect when the film structure material is joined by heat.

The conductive powder may be rutile titanium dioxide whose surface is coated with antimony-doped tin dioxide.

Further, the conductive powder may be an anatase-type titanium dioxide whose surface is coated with tin dioxide doped with antimony. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is based on a woven fabric whose main material is glass fiber used as a roof material of a permanent membrane structure building, and the outermost surface of the membrane structure material obtained by coating this surface with a fluororesin layer. A film structure material having a fluororesin layer, in which a photocatalyst powder is used alone or in combination with a conductor powder in the fluororesin. Hereinafter, the method for forming the fluororesin on the base fabric will be described in detail.

(Fluorine resin)

Examples of the fluororesin used in the present invention include polymers of fluororesin monomers, for example, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polytetrafluoroethylene (PTFE), and tetrafluoroethylene. Polyethylene-fluoroalkyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene-fluoroalkyl alkyl ether copolymer (EPE), 'tetrafluoroethylene Monoethylene copolymer (ETF E), polycloth trifluorethylene (PCTFE), polycloth trifluoroethylene monoethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride Ride (PVF) and the like.

When joining membrane structural materials to each other, it is preferable to use a joining method in which heat is applied to the membrane structural material to dissolve the fluororesin and to join, in order to maintain waterproofness of a joint portion. It is preferable to select tetrafluoroethylene ethylene-hexafluoropropylene copolymer (FEP), which melts easily when a temperature higher than the melting point is applied.

(photocatalyst)

Photocatalyst used (optical semiconductor), it is preferred to use a colorless transparent or white powder, anatase titanium dioxide (Ti0 _2, the band gap 3. 2 eV, wavelength 38 8 nm), zinc oxide (ZnO, the bandgap 3 . 2 eV, wavelength 388 nm), titanate strike strontium (SrTi0 _3, bandgap 3. 2 eV, wavelength 388 nm), trioxide tungsten emissions (W0 _3, bandgap 3. 2 eV, wavelength 388 nm), rutile titanium dioxide (Τί0 ₂ , the band gap 3. 0 eV, wavelength 414 nm), tin (Sn0 ₂ dioxide, the band gap 3. 8 eV, wavelength 326Nra), and the like. These are substances that exhibit a photocatalytic function by irradiating light with a wavelength having energy equal to or greater than the band gap of the photocatalyst. However, tin dioxide has a band gap of 3.8 eV (wavelength: 326 nm), and light having a wavelength at which diacid tin exhibits a photocatalytic function hardly reaches the surface of the ground, and thus does not exhibit a photocatalytic function.

These photocatalysts may exert a further effect when used alone or in combination depending on the performance and application.

(Particle diameter of photocatalyst)

In order to increase the performance efficiency of the photocatalyst, it is desirable to use one having a small particle diameter. This is because the surface area of the photocatalyst exposed on the surface can be increased by reducing the particle diameter. The particle diameter for sufficiently exhibiting the photocatalytic function is preferably in the range of 5 to 50 nm.

(Form of photocatalyst)

For the photocatalyst used in the present invention, use the photocatalyst powder as it is ) Or as a coating agent for solutions and dispersions (dispersions). -Dispersion (organosol) in which the photocatalyst is suspended or dissolved in an inorganic or organic solvent Φ such as water or alcohol, or a resin in an inorganic or organic solvent such as water or alcohol. Use at least one dispersion containing inorganic substances such as suspended dispersion, water glass, colloidal silica, polyorganosiloxane, and ammonium phosphate as a binder, taking into account the adhesion to the base fabric, as appropriate. Good to choose.

A synthetic resin such as an acrylic resin, a urethane resin, an epoxy resin, or a vinyl resin may be used between the base fabric and the fluororesin binder having a small surface energy.

In this invention, an aqueous dispersion of a fluororesin and an aqueous dispersion of a photocatalyst are used in consideration of the adhesion to the base cloth.

(Adjustment of coating agent)-The amount of photocatalyst contained in the coating agent is optional, but it is better to adjust the concentration and viscosity of the solution appropriately according to the application, performance and coating method. When thermal bonding performance is required as a product, the photocatalyst function is fully exhibited, and the amount of the photocatalyst to obtain sufficient thermal bonding performance is based on the solid content concentration in the coating agent. Therefore, the content is preferably 30 to 50% by weight.

In the manufacturing process, Cu, Sn, Al, Sb and Ag, Cu, Zn, Fe, N Zn, Au, A and Pt, Pd, Rh are added to the coating agent and powder to enhance conductivity and photocatalytic function. In some cases, a conductive function auxiliary substance such as Ru, Os, and Ir, or a photocatalytic function auxiliary substance is added or doped.

(Application)

Bar coating, air spraying, electrostatic spraying, dip coating, printing, spin coating, etc. There are a coating method, a roll coating method, a flow coating method, an impregnation method, a brush coating method, a sponge coating method, and the like, and it is preferable to appropriately select an application method suitable for a base fabric to be used and a coating material.

In addition, as a method of supporting the photocatalyst on the surface of the fluororesin layer, a chemical vapor deposition (CVD) method, a sputtering coating method, a vacuum evaporation method, an ion plating method, a thermal spraying method, etc. can be used. It is. -(Dry)

After applying the coating agent, it is preferable to dry at a temperature sufficiently lower than the firing temperature in order to maintain uniformity and finish of the coating film. Depending on the curing mechanism of the coating agent and the material of the binder used in the coating agent, there are methods of drying naturally (leaving at room temperature, air drying) or forced drying with equipment and heat source. Efficient drying can be achieved by using a heating furnace, air drying, infrared heating, infrared heating, hot air heating, etc. as the equipment and heat source used for forced drying.

In order to obtain a film with a beautiful finish and a uniform thickness, a method of finishing over a long period of time with natural drying, and using a heat source device at a high temperature (drying temperature is 100 ° C or less) and in a short time For finishing, there is a method of dividing the heating process into several stages.

(Fired)

After the drying step, the material is fired at a temperature equal to or higher than the melting point of the fluororesin in order to improve the adhesion to the base fabric. Here, if the firing temperature is higher than the melting point of the fluororesin, the coating film is fired through the process of melting the fluororesin, and each powder (particle) of the fluororesin powder and the photocatalyst fine particles Since the gaps between them are sufficiently filled, the resulting fluororesin layer has almost no pores, and is integrated with the base fabric to have excellent adhesion. '

In the present invention, a temperature about 50 ° C. higher than the melting point of the fluororesin (220 to 380 t; 320 ° C. when using tetrafluoroethylene-hexafluoropropylene copolymer (FEP)) It is good to bake with. If the temperature is higher than this, the melting point of the fluororesin will be far exceeded and the decomposition temperature of the fluororesin will be reached. Therefore, it is necessary to pay close attention to the firing temperature, as this may cause damage to the base fabric.

(Cooling)

After the above-mentioned calcination process, it is better to cool rapidly (cool) at a room temperature level lower than that of the calcination process. If possible, cool air may be blown using an air compressor or the like. By doing so, the crystallization of the fluororesin proceeds rapidly, the ratio of the amorphous portion (amorphous portion) in the crystalline polymer increases, the haze of the coating film decreases, and the transparent, dense and tough film is formed. A coating can be formed.

1. Relationship between antifouling property and thermal bonding property by mixing ratio of photocatalyst in membrane structural material

In the following, samples with different photocatalyst compounding ratios were prepared, and the relationship between the antifouling property and the thermal bonding property according to the photocatalyst compounding ratio in the film structure material was confirmed.

(Sample a)

50 g of aqueous dispurgeon (28 wt% solid content) of titanium dioxide powder (ST01 manufactured by Ishihara Sangyo Co., Ltd.), 100 g of purified water, and aqueous dispurgeon composed of tetrafluoroethylene-hexafluoropropylene copolymer (FEP) (Solid content 58 wt%), 96.6 g of silicon-based surfactant and 2.5 g (total lwt%) of silicon-based surfactant, mix and stir, and add solution A (FEP / anatase type titanium dioxide (hereinafter A - the ratio of Ti0 ₂₎ was adjusted to 8 0/2 0) '.

Wipe the fluororesin on the surface of the membrane structure material coated with fluororesin on both sides of a base fabric made of glass fiber with a Kimtowel (paper wiper made by Crescia Co., Ltd., trade name) impregnated with an appropriate amount of ethyl alcohol. After drying at room temperature, the solution A was applied to only one surface by a bar coating method. After drying the solution A coating film at room temperature, heat-dry at 60 ° C for 5 minutes, allow it to cool naturally, then heat and bake it at 380 ° C for 10 minutes, cool it naturally, and cool the sample a of the present invention. Produced.

(Sample b)

Titanium dioxide powder (ST01 manufactured by Ishihara Sangyo Co., Ltd.) (28 wt%), 50 g of purified water, 100 g of purified water, 56.3 g of an aqueous dispersion (solid content: 58 wt%) consisting of tetrafluoroethylene-hexafluoropropylene copolymer (FEP), silicon-based surfactant 2. put lg (LWT% of the total), mixed and stirred, dissolved liquid B (the ratio of FEP / A- Ti0 ₂ 70/30) was adjusted.

After wiping the fluororesin on the surface of the membrane material coated with fluororesin on both sides of the base fabric made of glass fiber with a Kimtowel (manufactured by Crecia Corporation) impregnated with an appropriate amount of ethyl alcohol and drying at room temperature, the solution B was applied to only one side by a bar coating method. After drying the coating film of the solution B at room temperature, it is dried by heating at 60 ° C for 5 minutes, naturally cooled, and then calcined by heating at 380 ° C for 10 minutes, and naturally cooled to obtain the sample b of the present invention. Produced.

(Sample c)

50 g of an aqueous dispurgeon (solid content 28 wt%) of titanium dioxide powder (ST01 manufactured by Ishihara Sangyo Co., Ltd.), 100 g of purified water, and an aqueous dispersion composed of a tetrafluoroethylene-hexafluoropropylene copolymer (FEP) John (solid content 58 wt%) to 36.2 g, (LWT% of total) a silicone surfactant 1.7g placed, mixed, stirred, dissolved solution C (F EP / A- Ti0 ₂ is the ratio of 60/40) Was adjusted.

Wipe the surface of the fluororesin structural material with Kimtowel (made by Crecia Co., Ltd.) on the surface of the film structural material in which both surfaces of the glass fabric are coated with fluororesin, and soaked with an appropriate amount of ethyl alcohol in the fluororesin. After drying at room temperature, the solution C was applied on only one side by a bar coating method. The coating film was dried at room temperature, heated and dried at 60 ° C. for 5 minutes, allowed to cool naturally, then heated and baked at 380 ° C. for 10 minutes, and cooled naturally to prepare Sample c of the present invention.

(Sample d)

50 g of an aqueous dispersion (solid content 28 wt%) of titanium dioxide powder (ST01 manufactured by Ishihara Sangyo Co., Ltd.), 100 g of purified water, and an aqueous dispersion made of tetrafluoroethylene-hexafluoropropylene copolymer (FEP) (Solid content 58wt%) 24.lg and silicon surfactant 1.8g (total lwt%), mix, stir and dissolve Liquid D (FEP ZA- Ti0 ₂ ratios 5 0/5 0) was adjusted.

Wipe the surface of the fluororesin structural material with Kimtowel (made by Crecia Co., Ltd.) on the surface of the film structural material in which both surfaces of the glass fabric are coated with fluororesin, and soaked with an appropriate amount of ethyl alcohol in the fluororesin. After drying at room temperature, the solution D was applied on only one side by a bar coating method. The coating film was dried at room temperature, heated and dried at 60 ° C. for 5 minutes, allowed to cool naturally, further heated and dried at 380 ° C. for 10 minutes, and cooled naturally to prepare Sample d of the present invention.

(Sample e)

50 g of an aqueous dispersion (solid content 28 wt%) of titanium dioxide powder (ST01, manufactured by Ishihara Sangyo Co., Ltd.), 100 g of purified water, and an aqueous dispersion of tetrafluoroethylene-hexafluoropropylene copolymer (FEP) one John (solid content 58wt%) 15. 6 g, silicon-based surfactant 1. 7 g (total l wt%) were placed, mixed and stirred, dissolved solution E (FEP ZA- Τί0 ₂ ratio 4 0/60) was adjusted.

Wipe the surface of the fluororesin structural material with Kimtowel (made by Crecia Co., Ltd.) on the surface of the film structural material in which both surfaces of the glass fabric are coated with fluororesin, and soaked with an appropriate amount of ethyl alcohol in the fluororesin. After drying at room temperature, the solution was applied on only one side by a bar coating method. The coating film was dried at room temperature, heated and dried at 60 C for 5 minutes, allowed to cool naturally, baked at 380 ° C for 10 minutes, and allowed to cool naturally to produce Sample e of the present invention.

(Comparative sample ②)

The film structure material coated with the fluororesin used when preparing samples a to e was used as comparative sample ①.

The samples a to e produced in the examples and the comparative sample ① were evaluated for dirt after the outdoor exposure test and for thermal bonding. Table 1 shows the results of the evaluation.

The outdoor exposure test was carried out by installing an outdoor exposure stand on the roof of the first factory building in the Hirakata Plant of the Taiyo Kogyo (Hirakata, Osaka Prefecture), fixing the sample on a 45 ° slope, and exposing it for 3 months. did.

• Evaluation method of dirt after outdoor exposure test

After exposing Samples a to e and Comparative Sample で for 3 months outdoors, the stain condition of the sample surface was confirmed. A sample to which almost no dirt was attached was evaluated as good (〇), a sample with a low degree of dirt or a tendency to chalk the coating film (△), and a sample with much dirt was evaluated as poor (X).

-Thermal bonding evaluation method

The evaluation of the thermal bondability of Samples a to e and Comparative sample ① was confirmed. The apparatus used for the thermal bonding was a hot plate, and the welding conditions were the same as those for the comparative sample で, which is the base material of the samples a to e, and the welding conditions were constant. The evaluation was performed using the peel strength of the comparative sample (2) as the reference strength. (〇) for those holding 80% or more of the reference strength, (（) for those holding 50 to 80% of the reference strength, Those with 50% or less were designated as (X).

【table 1 】

Samples a to e, which are examples of the present invention, were found to be more resistant to contamination by the photocatalyst than Comparative Sample I.

Sample a, in which the amount of the photocatalyst was small, had a very small degree of contamination, but slightly changed to a solid color. Sample e, which contains a large amount of photocatalyst, has a slight chokin Samples b, c, and d had good antifouling properties.

In the thermal bonding evaluation, the thermal bonding was reduced in sample d and sample e in which the proportion of the photocatalyst was 50 wt% or more, and in sample e, almost no thermal bonding was achieved. There were no particular problems with samples a, b, and c other than these.

From the above, in order to enhance antifouling properties, it is possible to increase the performance by adding a large amount of photocatalyst. However, with this, the adhesion between the fluororesin of the base fabric and the coating material containing the photocatalyst, and the thermal bonding between the fluororesin film structural materials coated with the coating material containing the photocatalyst come to be hindered. This is because the melting point of the photocatalyst is as high as 500 ° C or higher, whereas the melting point of the fluororesin is 220 to 380 ° C. Should thermal bonding be performed at a temperature of 500 ° C or more, the melting point of the fluororesin will be far exceeded, and not only will the base fabric be damaged, but also a large amount of harmful gases will be generated due to thermal decomposition. There is a concern that it will have an adverse effect on the environment and the human body. Therefore, this is not the case when the film structure materials are not thermally bonded, but when considering the antifouling property of the photocatalyst and the thermal bonding, the mixing ratio of fluororesin / photocatalyst is from 70 to 500. Consider 0 as the optimal condition.

From the above results, it is preferable that the mixing ratio of fluororesin / photocatalyst (metal oxide) be 60/40 in consideration of the antifouling property and thermal bonding property. In the following example, the fluorine resin / photocatalyst is used. Was 60/40.

2. Conductivity by applying a fluororesin coating agent using a photocatalyst alone or in combination with a conductor

Next, the conductivity by applying a photocatalyst alone or a fluororesin coating agent using a conductor together was verified.

The conductor used must be a colorless, transparent or white conductive powder (including semiconductors) so as not to affect the color and translucency of the film itself. in the example, antimony-doped tin dioxide (Sb de one flop Sn0 ₂₎ rutile type titanium dioxide coated on the surface, was used as an example tin dioxide sol, these It is not limited to. For example, electrical conductors are indium oxide (In ₂ 0 _3), oxidizing power Doniumu (CdO), it can also be selected from zinc oxide (ZnO) and the like.

(Sample f, Sample g, Sample h)

50 g of an aqueous dispersion (solid content 28 wt%) of titanium dioxide powder (ST01 manufactured by Ishihara Sangyo Co., Ltd.) and rutile titanium dioxide powder (hereinafter referred to as Sn0 powder) coated on the surface with tin dioxide doped with antimony. ₂ (Sb) -R-T1O2) (Ishihara Sangyo Co., Ltd. FT1000) 0.36g, purified water 100g, water-based dispurgeon (F EP) min 54 wt%) to 39 .9g., a silicon-based surfactant 1.9 g (1 wt% of the total) mixture, stirred, solution F (F EP / a-Ti0 2 / Sn0 2 (Sb) -R-Ti0 The ratio of ₂ was adjusted to 60/39/1).

Changing the amount in the same procedure, a solution _{G (FEP / A-Ti0 2} / Sn0 2 (Sb) -RT i0 2 ratios 6 0/3 7/3). The solution H (F EP / A- _{_{Ti0 2 / Sn0 2 (Sb)}} -R-Ti0 2 ratio was adjusted to 6 0/3 4/6).

After wiping the surface of the fluororesin film structure material with a Kim towel (manufactured by Crecia Co., Ltd.) impregnated with an appropriate amount of ethyl alcohol, the film structure material having both surfaces of the glass fiber covered with a fluororesin, and drying at room temperature, then the solution F , G and H were applied only on one side by the bulk coat method. The coating film is dried at room temperature, dried by heating at 60 ° C for 5 minutes, naturally cooled, then baked by heating at 380 ° C for 10 minutes, and naturally cooled to obtain the samples f, g, and g of the present invention. Sample h was prepared.

(Sample i, Sample j, Sample k)

Refining 50g of aqueous dispurgeon (solid content 28wt%) of titanium dioxide powder (ST01 manufactured by Ishihara Sangyo Co., Ltd.) and 5.lg of tin dioxide sol (solid content 7wt%, water-based dispersion manufactured by Nippon Chemical Industry Co., Ltd.) 100 g of water, 39.9 g of an aqueous dispersion (54 wt% solid content) composed of tetrafluoroethylene-hexafluoropropylene copolymer (F EP), 2.0 g of a silicon-based surfactant (total 1 wt%) mixture, stirred, solution I (FEPZA- Ti0 _₂ ZSn0 ₂ ratio was adjusted to 6 0/3 9/1).

Changing the amount in the same procedure solution _{J (FEP / A- Ti0 2 /} Sn0 2 ratios 6 0 / 3 7/3), the solution _{(FEP / A- Ti0 2 / Sn0} 2 ratio was adjusted to 6 0/3 4/6). After wiping the surface of the fluororesin film structure material with a Kimtowel (manufactured by Crecia Co., Ltd.) impregnated with an appropriate amount of ethyl alcohol into a film structure material whose both surfaces are coated with a fluororesin, and drying at room temperature, the solution I , J and K were applied only on one side by a vacuum coating method. The coating film is dried at room temperature, dried by heating at 60 ° C for 5 minutes, naturally cooled, and then baked by heating at 380 ° C for 10 minutes. k was prepared.

(Comparative sample ②)

Sample c (the ratio of FEP / ATi02: 60/40) prepared for examining the antifouling property and thermal bonding property was used as Comparative Sample No. _II .

(Comparative sample ③) '

A film structure material in which both surfaces of the glass fiber used as the base fabric of the samples f to k were covered with a fluororesin was used as a comparative sample ③. (Only FEP)

The half life of the electrification of the samples f to k produced in the examples and the comparative samples 1 and 3 was measured. Table 2 shows the half-life evaluation results.

• Half-life measurement

Samples used for the half-life measurement were samples f to k and comparative samples (1) and (2), and xenon (1) Xameter (WEL-75X-LHP-B · manufactured by Suga Test Instruments Co., Ltd.) Ec, irradiance 180W / m ² , wavelength 300-400nm) for 24 hours _c- measurement was performed using a honest meter (S-4104) manufactured by Nippon Statech, applying an applied voltage of 10 KV and 20 ° C-20 The test was performed under the humidity control condition of% volumes. What decision, the comparison sample ② (FEP Bruno A- Ti0 6 0/4 0 compounding ratio of ₂₎ and comparative sample ③ of (FEP Za - Ti0 ₂ mixing ratio rate 1 0 0/0) are better than (X) and those inferior to both comparative samples (2) and (3) were designated (X).

[Table 2] Sample solution FEP / A-TiO2 / Sn02 (Sb) -R-Ti02 Initial half-life After 120 seconds Evaluation

Or (Sn02 sol) 带 Seedling (V) (sec). Decay rate (? Ί)

Example f Ρ 60/39/1 (SnOZ (Sb) -R-Ti02) 760 2.7 100 ο

g G 60/37/3 (Sn02 (Sb) -R-Ti02) 740 2.7 100 ο h H 60/34/6 (Sn02 (Sb) -R-Ti02) 690 2.2 100 ο

1 I 60/39/1 (Sn02 sol) 800 4.5 100 ο j J 60 / 37Z3 (Sn02 sol) 780 3.0 100 Q k K 60Z34Z6 (Sn02 sol) 720 2.0 100 Ο Comparative example ② 60/40/0 950 7.5 74.0

③ 100/0/0 950> 120 11.0

Samples f to k, which are examples of the present invention, were compared to the ruthenium-type titanium dioxide (SnO ₂₎ coated on the surface with antimony-doped tin dioxide, as compared with the analog sample-type titanium dioxide photocatalyst alone. _{(Sb) -R-Ti0 2)} , a decrease in half-life by a combination of tin dioxide was observed. The half-life of FEP / A-Ti0 ₂ mixing ratio is 1 0 0/0 of the comparative sample ③ is at least 120 seconds, the attenuation of the voltage for conductivity there is little not very little observed. By comparison contrast sample ② blending ratio of FEP / A-Ti0 ₂ is 6 as 0/4 0/0 and anatase type titanium dioxide (A- Ti0 ₂₎ is blended with a half-life completion. 5 seconds After 120 seconds, the decay rate is 74%, and the conductive effect appears. The entire mixing ratio of the photocatalyst and conductor is constant In addition, anatase type titanium dioxide - replacing a portion of (A Τί0 ₂₎ to _{Sn0 2 (Sb) -R-Ti0} 2 or Sn0 _2, anatase diacid (spoon Chita emissions (a - by combination with Ti0 _2), the initial charging, the half-life is reduced, since the attenuation rate after 120 seconds increases, conductive performance is revealed that increased 3. Relationship between conductivity and antifouling properties

Next, we examined the relationship between conductivity and antifouling properties when using a photocatalyst and a conductor together. '

(Sample I)

Titanium dioxide powder (ST01 manufactured by Ishihara Sangyo Co., Ltd.) 28wt%), 50g of purified water, 36.2g of aqueous dispersion (solid content 58wt%) consisting of tetrafluoroethylene-hexafluoropropyl α-pyrene copolymer (F EP), silicon-based surfactant agent 2 g mixture was stirred, the solution was (FEP / A- Τί0 ₂ ratios 6 0/4 0) was adjusted.

After wiping the surface of the fluororesin film structure material with a Kimtowel (manufactured by Crecia Co., Ltd.) impregnated with an appropriate amount of ethyl alcohol on the film structure material coated on both sides of the glass fiber with a fluororesin, and drying at room temperature, the solution L Was applied on only one side by a bar coating method. The coating film was dried at room temperature, dried by heating at 60 ° C. for 5 minutes, cooled naturally, baked at 380 ° C. for 10 minutes, and cooled naturally to prepare Sample 1 of the present invention. (Sample m)

Antimony de one ping the tin dioxide was coated on the surface rutile dioxide Ji Yun _{(Sn0 2 (Sb) -R-} Ti0 2) powder (manufactured by Ishihara Sangyo Kaisha, Ltd. FT1000) 19.3g, purified water 7 5 g 50 g of an aqueous dispersion (58 wt% solid content) of tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and 2 g of a silicon surfactant were mixed and stirred, and the solution M ( _{F EP / Sn0 2 (Sb)} - R- Ti0 2) mixing ratio of adjusted their 6 0/4 0).

After wiping the surface of the fluororesin film structure material with a Kimtowel (manufactured by Crecia Co., Ltd.) impregnated with an appropriate amount of ethyl alcohol, coat the film structure material with both surfaces of the glass fiber covered with a fluororesin, and dry at room temperature. Was applied on one side only by the bulk coat method. The coating film was dried at room temperature, heated and dried at 60 ° C. for 5 minutes, cooled naturally, baked at 380 ° C. for 10 minutes, and cooled naturally to prepare Sample m of the present invention. (Sample n)

Sample 1 Preparation Sn0 the solution prepared similarly to the solution A used in ₂ (Sb) - R- Ti0 further 4.3 g mixture of _two powders (manufactured by Ishihara Sangyo Kaisha, Ltd. FT1000), stirred, solution N (F EP / A _{_{-Ti0 2 / Sn0 2 (Sb)}} - R- Ti0 2 mixing ratio) of 5 3/3 6/1 1) was adjusted. Use a Kimtowel (made by Crecia Co., Ltd.) in which a suitable amount of ethyl alcohol is impregnated with a film structure material in which both surfaces of glass fiber are coated with fluororesin. After wiping the surface and drying at room temperature, the solution N was applied only on one side by a powder coating method. The coating film was dried at room temperature, dried by heating at 60 for 5 minutes, allowed to cool naturally, and then further dried for 380. The sample was heated and baked at C for 10 minutes and cooled naturally to prepare a sample n of the present invention. (Comparative sample ④)

A suitable amount of ethyl alcohol is impregnated with a film structure material coated on both sides of a glass fiber with a fluororesin, and the surface of the fluororesin film structure material is wiped off with a Kim towel (manufactured by Crecia Co., Ltd.) and dried at room temperature. Kisafuruoropuro pyrene copolymer to ethylene one aqueous Disconnect purge Yon (solid content 58 wt%) consisting of (FEP) by (FEP ZA-TiC R- Ti0 ₂ ratios 1 0 0/0/0) a bar one coating only one surface Applied. The coating film was dried at room temperature, heated and dried at 60 ^eC for 5 minutes, allowed to cool naturally, then further heated and dried at 380 ° C for 10 minutes, and allowed to cool naturally to produce Comparative Sample II of the present invention. .

Sample 1 ~! ! The antifouling property of Comparative Sample 1 was evaluated by measuring the color difference after the outdoor exposure test. The results are shown in Table 3.

• Evaluation method of dirt after outdoor exposure test

After exposing Samples 1 to n and Comparative Sample 屋外 outdoors for 3 months, the color difference was measured. A sample having a smaller color difference than the comparative sample が has an antifouling effect (〇).

もの Those with a larger color difference had no antifouling effect and were rated (X). The outdoor exposure test was carried out by installing an outdoor exposure stand on the roof of the first factory building of the Taiyo Kogyo Hirakata Plant (Hirakata I, Osaka Prefecture) and fixing the sample on a 45 ° inclined surface.

[Table 3] Sample solution FEP / A-TiO2 / Sn02 (Sb) -R-T i 02 Color difference Evaluation Example 1 L 60/40/0 1.54 〇

m M 60/0/40 4.22 〇 n N 53/36/1 1 1.09 比較 Comparative example ④ 1 OO / O / O 6.65 All of the samples 1 to m showed a small color difference and an antifouling effect as compared with the conventional fluororesin film structure material of the comparative sample I.

There an active f raw small rutile titanium dioxide as a photocatalyst F EP disperser Ji in any sample m formulated, covered with tin dioxide doped with antimony surface _{(Sn0 2 (Sb) -R-} T1O2) The antifouling effect was recognized. This is thought to be due to the effect of suppressing contamination due to the improvement in conductivity. Photocatalytic color difference samples 1 imparted with antifouling effect by (A- Ti0 ₂₎ is a very good result and 1.54, sample n a further Sn0 ₂ (Sb) -R-T1O2 this dissolved solution was added in a small amount Has a color difference of 1.09, indicating a remarkable improvement in antifouling properties due to the photocatalyst + conductive effect.

4. ANATA one peptidase type titanium dioxide (A- Ti0 ₂₎ and the conductive effect and stain resistance when the photocatalytic function in combination with tin dioxide that does not express (SNQ ₂₎

Next, you one peptidase type titanium dioxide (A- Ti0 _2), in combination with diacid tin photocatalytic function is not expressed (Sn0 _2), it was confirmed for the conductive effect and antifouling properties.

(Sample o)

Aqueous dispurgeon consisting of 100 g of titanium dioxide powder (ST01 manufactured by Ishihara Sangyo Co., Ltd.) (solid content: 28 wt%), 150 g of purified water, and tetrafluoroethylene-hexafluoropropylene copolymer (FEP) (solid content 58 wt%) to 72.4 g, 3.2 g mixture of a silicone surfactant, was stirred, a solution 0 (F EP / a-Ti 0 2 mixing ratio is 6 0/4 0) was adjusted.

Wipe the surface of the fluororesin film structure material with Kimtowel (manufactured by Crecia Co., Ltd.) impregnated with an appropriate amount of ethyl alcohol on the film structure material coated on both sides of the glass fiber with a fluororesin. After drying at room temperature, the solution 0 was applied only on one side by the bar coating method. The coating film was dried at room temperature, heated and dried at 60 ° C. for 5 minutes, allowed to cool naturally, baked at 380 ° C. for 10 minutes, and cooled naturally to prepare Sample 0 of the present invention. (Sample P)

20 g of tin dioxide sol (solid content 7 wt%, water-based dispurgeon manufactured by Nippon Chemical Industry Co., Ltd.), 7.5 g of purified water, tetrafluoroethylene monohexafluoropropylene 3.6 g of an aqueous dispurgeon (58 wt% solids) composed of a copolymer (F EP) and 0.31 g of a silicon surfactant were mixed and stirred, and the mixing ratio of the solution P (F EP / SnO _z (sol)) was 60/40) was adjusted.

After wiping the surface of the fluororesin film structure material with a Kim towel (manufactured by Crecia Co., Ltd.) impregnated with an appropriate amount of ethyl alcohol, the film structure material coated on both sides of the glass fiber with a fluororesin, dried at room temperature, and dried at room temperature. Was applied on one side only by the bulk coat method. The coating film was dried at room temperature, heated and dried at 60 ° C. for 5 minutes, allowed to cool naturally, baked at 380 ° C. for 10 minutes, and cooled naturally to prepare a sample p of the present invention. (Sample Q)

20 g of tin dioxide sol (solid content: 7 wt%, water-based dispersion manufactured by Nippon Kagaku Sangyo Co., Ltd.) was further added to 16.5 g of the solution prepared in the same manner as solution 0 used for preparation of sample 0, and mixed and stirred. (F EP / a-Ti0 blending ratio of ₂ / SnO ₂ (sol) 4 2/2 9/2 9) was adjusted.

After wiping the surface of the fluororesin film structure material with Kimtowel (manufactured by Crecia Co., Ltd.) impregnated with an appropriate amount of ethyl alcohol on the film structure material coated on both sides of the glass fiber with fluororesin, and drying at room temperature, the solution Q Was applied on only one side by a bar coating method. The coating film was dried at room temperature, dried by heating at 60 ° C. for 5 minutes, cooled naturally, baked by heating at 380 for 10 minutes, and cooled naturally to prepare Sample q of the present invention. (Comparative sample ②)

72.4 g of an aqueous dispersion (58 wt% solid content) of tetrafluoroethylene-hexafluoropropylene copolymer (FEP), 150 g of purified water, and 2.2 g of a silicon-based surfactant were mixed and stirred. and the solution R (blending ratio of _{F EP / a-Ti0 2 /} Sn0 2 ( sol) is 1 0 0 / O.ZO) was adjusted.

After wiping the surface of the fluororesin film structure material with a Kimtowel (manufactured by Crecia Co., Ltd.) impregnated with an appropriate amount of ethyl alcohol, the film structure material coated on both surfaces of the glass fiber with a fluororesin, dried at room temperature, and dried. Only one side was applied by a bar coating method. After drying the coating at room temperature, heat and dry at 60 ° C for 5 minutes Further, the sample was heated and fired at 380 ° C for 10 minutes, and was naturally cooled to produce Comparative Sample No. 2 of the present invention.

For the antifouling property evaluation of the prepared samples 1 to n and the comparative sample 1, the color difference after the outdoor exposure test and the color difference after the indoor exposure test were measured. The results are shown in Table 4. ,

For the outdoor exposure test, an outdoor exposure stand was installed on the rooftop of the first factory building of the Taiyo Kogyo Hirakata Plant (Hirakata I, Osaka Prefecture), the sample was fixed on a 45 ° slope, and exposed outdoors for 4 months. Carried out.

The indoor exposure test was performed by installing an indoor exposure platform at the third warehouse in the Hirakata Plant of Taiyo Kogyo (Hirakata, Osaka Prefecture), fixing the sample on a 45 ° slope, and exposing it indoors for 4 months. • Dirt evaluation after outdoor exposure test

After the outdoor exposure test of Samples 0 to q and Comparative sample ⑤, the color difference was measured. A sample with a smaller color difference than the comparative sample was regarded as having an antifouling effect (〇), and a sample with a larger color difference than Comparative Sample⑤ was judged as having no antifouling effect (X).

-Dirt evaluation after indoor exposure test

After the indoor exposure test of Samples o to q and Comparative sample ⑤, the color difference was measured. A sample with a smaller color difference than the comparative sample was judged to have an antifouling effect (〇), and a sample with a larger color difference than Comparative Sample 比較 was judged to have no antifouling effect (X).

[Table 4]

For samples o to q, the color difference after the outdoor exposure test and indoor exposure test was It was smaller than the conventional fluororesin film structural material of Example 1 and its antifouling effect was also recognized. Outdoor violence in exposure studies anatase type titanium dioxide (A- Ti0 ₂₎ alone is sufficient antifouling effect even when a photocatalyst is observed by further combination with tin (Sn0 ₂₎ dioxide, further antifouling It was recognized that the effect was improved. This is because the band gap of tin dioxide (SnO ₂ ) is 3.8 eV (wavelength 326 nm), and the light at the wavelength for activating this photocatalyst has hardly reached the ground. It is thought that this is not due to the improvement in conductivity due to the addition of tin dioxide (SnO ₂ ). This means that, as a result of the indoor exposure test (the photooxidative decomposition action of the photocatalyst does not work because the amount of ultraviolet light is 0), the antifouling property of the samples o to q to which the photocatalyst was added was improved compared to the comparative sample ⑤ It is clear from that.

[Summary of the relationship between conductivity and antifouling properties when using conductors together]

As described above, it was confirmed that when tin dioxide (SnO ₂ ), which is a conductor, was used in combination with the photocatalyst, the antifouling effect due to the improvement in conductivity was increased as compared with when the photocatalyst was used alone.

Further, the conductive metal small rutile titanium dioxide down the doping photocatalytic activity _{(Sn0 2 (Sb) -R-} Ti0 2) and a large Ana evening one peptidase type titanium dioxide of the photocatalytic activity (A- Ti0 ₂₎ a combination of In this case, it was confirmed that the antifouling property was increased by improving the conductivity as compared with the case of using tin dioxide (SnO ₂ ).

Large anatase titanium dioxide of a photocatalytic activity (A- Ti0 ₂₎ and a photocatalytic function is solely tin dioxide that does not express (Sn0 _2), the antifouling property when used in combination outdoor, carried out violent exposure test indoors evaluated. Indoor exposure test (ANATA one peptidase type titanium dioxide for UV is zero (A-Ti0 ₂₎ also photocatalytic function is not expressed), it was confirmed that the antifouling property is improved by improving the conductivity. In outdoor exposure tests, improvement in antifouling properties due to the photocatalytic function and the conductive effect was remarkably observed.

Note that this conductivity can be greatly changed by the paint and the thickness of the coating film. To emphasize conductivity, these effects can be amplified by increasing the coating thickness and increasing the proportion of photocatalysts and other conductors in the paint. Oh _O

As described above, the photocatalytic fluororesin film structural material having a layer in which the photocatalyst is used alone or in combination with other conductors in the fluororesin on the outermost layer surface has a significantly improved conductivity, so that the surface of the film structural material is improved. It is difficult for dirt to adhere. The dirt composed of organic substances such as oily dirt attached to the surface of the film structure material is exposed to sunlight when the surface of the film structure material is exposed to sunlight. The lost inorganic dirt is easily washed away, so that the appearance can be maintained semi-permanently. Moreover, for expressing antibacterial, even deodorizing function by the photocatalyst, N0 is malodorous substances and air pollutants present in the vicinity of the photocatalyst _X, SO, by oxidation decomposition substances like, it can be removed.

As described above, in the film structure material of the present invention, the photocatalyst is supported and exposed on the surface, and the organic matter attached to the surface of the film structure material is decomposed by photooxidative decomposition and hydrophilization by the photocatalyst and washed away. However, it can exhibit high antifouling properties over a long period of time.

Furthermore, by using a powder having a conductive action together with a photocatalyst, the material of the membrane structure has a conductive action, and static electricity is not accumulated in the material of the membrane structure. Static electricity generated due to friction and abrasion caused by contact with water is suppressed, and the adhesion of dust, fine sand, etc., which cause soiling, is reduced, so that higher antifouling properties can be exhibited.

Furthermore, by using a powder having a conductive action together with a photocatalyst, the conductivity of the film forming material is improved, so that it is difficult to accumulate static electricity, and there is an effect that an electric shock accident of a worker is eliminated.

Claims

The scope of the claims

1. A film structure material in which a fluororesin surface layer is provided on the surface of a base fabric mainly composed of glass fiber. A colorless, transparent or white photocatalyst powder is carried on the fluororesin surface layer.

-Exposed film structure material.

2. The film structure material according to claim 1, wherein the photocatalyst is anatase type titanium dioxide.

3. The film structure material according to claim 1, wherein the fluororesin on the surface is a tetrafluoroethylene-hexafluoropropylene copolymer.

4. A film structure material in which a fluororesin surface layer is provided on the surface of a base fabric mainly composed of glass fiber, and a colorless transparent or white photocatalyst powder and a colorless transparent or white A film structure material characterized by carrying and exposing a powder having a conductive action as described above.

5. The film structure material according to claim 4, wherein the photocatalyst is anatase type titanium dioxide.

6. The film structure material according to claim 4, wherein the fluororesin on the surface is a tetrafluoroethylene-hexafluoropropylene copolymer.

7. The film structure material according to claim 4, wherein the powder having a conductive action is tin dioxide. .

8. The film structure material according to claim 6, wherein the conductive powder is tin dioxide.

9. The film structure material according to claim 4, wherein the conductive powder is a rutile-type titanium dioxide whose surface is coated with tin dioxide doped with antimony.

10. The film structure material according to claim 6, wherein the conductive powder is rutile-type tidan dioxide whose surface is coated with tin dioxide doped with antimony.

11. The film structure material according to claim 4, wherein the conductive powder is an anatase-type titanium dioxide whose surface is coated with tin dioxide doped with antimony.

12. The film structure material according to claim 6, wherein the conductive powder is an anatase-type titanium dioxide whose surface is coated with tin dioxide doped with antimony.