JPH10237769A - Tent canvas supporting photocatalyst and structure using tent canvas supporting photocatalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tent canvas supporting a photocatalyst, rich in durability and having effect such as antifouling, antimicrobial or fungi-proof effect by forming a photocatalyst layer through an adhesive onto tent canvas. SOLUTION: An adhesive layer having 0.5-5mm thickness and comprising a resin containing a silicone-modified resin such as an acryl-silicone resin having 2-60wt.% silicone content, a resin containing 3-60wt.% polysiloxane such as hydrolyzate of silicone alkoxide having a 1-5C alkoxy group or a resin containing 5-40wt.% colloidal silica having >=10nm particle diameter is formed on the surface of of class C or B tent canvas. Then, a photocatalyst layer having 0.1-5μm thickness and comprising a photocatalyst particle complex containing 25-95wt.% (hydr)oxide gel of one or two or more kinds of a metals selected from silicon, aluminum, titanium, zirconium, magnesium, etc., and having >=100m<2> /g specific surface area is formed on the adhesive layer to provide the objective tent canvas supporting the photocatalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tent canvas having a photocatalyst and a structure using the tent canvas having a photocatalyst, which has effects such as antifouling, antibacterial and antifungal.

[0002]

2. Description of the Related Art Titanium oxide as an n-type semiconductor has been known as a photocatalyst for promoting various chemical reactions such as sterilization and decomposition of organic substances by the energy of ultraviolet rays. Various methods for supporting a photocatalyst on glass, metal, plastic, tile, and the like have been proposed (JP-A-62-68661, JP-A-5-309267, EP633064, US488).
8101, WO 96/14938). However, the photocatalyst is supported on a tent canvas, especially widely used type B tent fabric or class C tent canvas without deteriorating the catalytic activity, and the photocatalytic action is effectively utilized to prevent the photocatalyst. There is no report on how to maintain soil, antibacterial and antifungal properties over time.

[0003]

The problems that must be solved in order to support a photocatalyst on a tent canvas are as follows. 1. good adhesion between the photocatalyst and the tent canvas. 2. The photocatalytic activity is not reduced by being carried on the tent canvas. The tent ground canvas and the adhesive layer are not deteriorated by the supported photocatalyst, and the strength of the tent and the adhesion of the photocatalyst are maintained for a long period of time to maintain durability. Conventionally,
Tent ground installed outdoors, especially B impregnated with vinyl chloride
The seed or class C tent canvas has a serious drawback that it tends to adhere to dust and soot in the outside air, usually turns black in a few months, and the pollution progresses, thereby impairing the aesthetic appearance.
In addition, mold is easily generated due to a plasticizer component contained in a large amount in a vinyl chloride resin, and as a countermeasure, a method of coating the surface with a fluororesin has been adopted. However, the fluororesin coat has a drawback that oil stains such as soot and the like easily adhere to the surface because the water repellency of the surface is increased and the lipophilicity is increased as conventionally known. Further, in a usual tent impregnated with vinyl chloride, a large amount of a plasticizer component diffuses into the photocatalyst layer, so that there is a problem that the photocatalytic activity is reduced. The plasticizer component that has diffused into the photocatalyst layer is
There is a problem in that the photocatalytic activity is degraded earlier than the intended decomposition target due to the photocatalytic action, so that the apparent photocatalytic activity is significantly reduced.

[0004]

The tent fabric canvas supporting the photocatalyst according to the present invention has a structure in which an adhesive layer is provided between the photocatalyst layer and the tent fabric canvas, and the adhesive layer has a silicon content of 2%. A silicon-modified resin, a resin containing 3 to 60% by weight of polysiloxane or a resin containing 5 to 40% by weight of colloidal silica, wherein the photocatalytic layer is a metal oxide gel or a metal hydroxide. It is a photocatalyst particle composite containing 25 to 95% by weight of a gel. The organic dirt adhering to the surface of the photocatalytic layer is quickly decomposed by the photocatalytic action, and the remaining inorganic dirt is quickly washed away during rainfall because there is no organic dirt serving as an adhesive. And can maintain antifouling properties for a long period of time. Further, the antibacterial property and the antifungal property can be further improved by the components of silver and copper added in a small amount in the photocatalyst layer.

[0005] The adhesive layer provided between the photocatalyst layer and the tent ground canvas functions to firmly adhere the photocatalyst layer to the tent ground canvas, and to prevent a decrease in photocatalytic activity due to a plasticizer component diffused from the tent ground canvas. It has the function of preventing the tent ground canvas from deteriorating due to the photocatalytic action, and has the characteristic that the adhesive itself is not easily degraded by the photocatalytic action.

As the resin used as the adhesive layer, acrylic resin, acryl-silicone resin, epoxy-silicone resin, silicon-modified resin, urethane resin, epoxy resin in which silicon, polysiloxane or colloidal silica is introduced by a usual method. Resin, polyester resin,
An alkyd resin or the like can be used, but a silicon-modified resin containing an acryl-silicon resin or an epoxy-silicon resin is most excellent in terms of durability.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As the material of the adhesive in the present invention, a silicon-modified resin such as an acryl-silicon resin or an epoxy-silicon resin having a silicon content of 2 to 60% by weight and a polysiloxane containing 3 to 60% by weight are contained. Resin or a resin containing 5 to 40% by weight of colloidal silica strongly adheres the photocatalyst, prevents a decrease in photocatalytic activity due to a plasticizer component diffused from the tent ground canvas, and reduces the tent ground canvas from oxidative decomposition by the photocatalyst. Appropriate to protect. Silicon-modified resin such as acryl-silicon resin or epoxy-silicon resin having a silicon content of less than 2% by weight, resin having a polysiloxane content of less than 3% by weight, or colloidal silica content of 5% by weight
With less than the resin, the adhesion to the photocatalyst layer is poor,
The adhesive layer is deteriorated by the photocatalyst, and the photocatalyst layer is easily peeled. Acrylic containing more than 60% by weight of silicon
Silicon-modified resins such as silicone resin and epoxy-silicone resin have poor adhesion between the adhesive layer and the carrier, and have low abrasion resistance due to low hardness of the adhesive layer. In the case of a resin having a polysiloxane content of more than 60% by weight or a resin having a colloidal silica content of more than 40% by weight, the adhesive layer becomes porous or the adhesiveness between the carrier and the adhesive layer becomes poor, and the photocatalyst becomes poor. Is easier to peel off than tent canvas.

When the adhesive layer resin is a silicon-modified resin such as acryl-silicon resin or epoxy-silicon resin,
There are various methods for introducing silicon into a resin, such as transesterification, grafting using silicon macromers or reactive silicon monomers, hydrosilylation, and block copolymerization, but any method can be used. it can. Acrylic resin or epoxy resin is the best resin to introduce silicon in terms of film formability, toughness, and adhesion to carrier, but any resin such as alkyd resin, urethane resin, and polyester resin can be used. it can. These resins can be used either in a type dissolved in a solvent or in an emulsion type. There is no problem even if additives such as a crosslinking agent are included.

When the adhesive layer resin contains a polysiloxane, when the polysiloxane is a hydrolyzate of a silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or a product formed from the hydrolyzate, the adhesiveness of the polysiloxane is reduced. In addition, a photocatalyst-loaded tent ground canvas having improved durability can be obtained. When the unit number of the alkoxy group of the silicon alkoxide exceeds 6, the compound is expensive and has a very low hydrolysis rate, so that it is difficult to cure the resin in a resin, and the adhesiveness and durability deteriorate. Polysiloxane obtained by hydrolyzing silicon alkoxide partially containing chlorine can be used.However, if polysiloxane containing a large amount of chlorine is used, the carrier may be corroded by chlorine ions as an impurity, or the adhesiveness may be deteriorated. Make it worse. As a method for introducing polysiloxane into a resin, a method in which a silicone alkoxide monomer is mixed with a resin solution and then hydrolyzed with moisture in the air at the time of forming an adhesive layer, a product obtained by partially hydrolyzing a silicon alkoxide in advance with a resin. There are various methods such as mixing and further hydrolyzing with moisture in the air when forming the adhesive layer,
Any method may be used as long as it can be uniformly mixed with the resin. In order to change the hydrolysis rate of silicon alkoxide, a small amount of an acid or base catalyst may be added. As the resin for introducing the polysiloxane, any resin such as acrylic resin, acrylic-silicone resin, epoxy-silicone resin, silicon-modified resin, urethane resin, epoxy resin, polyester resin, and alkyd resin can be used. Silicon-modified resins including resins and epoxy-silicon resins are excellent in durability.

When the adhesive layer is a resin containing colloidal silica, the particle size of the colloidal silica is 10 nm.
The following is preferred. When the thickness is 10 nm or more, not only the resin in the adhesive layer is easily deteriorated by the photocatalyst, but also the adhesion between the photocatalyst layer and the adhesive layer is deteriorated. The simplest method of introducing the colloidal silica into the resin is to mix the resin solution and the colloidal silica solution and then apply and dry to form a protective film, but the resin is dispersed in the colloidal silica state. Polymerized and synthesized products may be used. In order to improve the adhesiveness and dispersibility between the colloidal silica and the resin, the colloidal silica may be treated with a silane coupling agent before use. As the resin for introducing colloidal silica, any resin such as acrylic resin, acrylic-silicone resin, epoxy-silicone resin, silicon-modified resin, urethane resin, epoxy resin, polyester resin, and alkyd resin can be used. A resin or a silicon-modified resin including an epoxy-silicon resin is most excellent in durability. As the colloidal silica, any of silica sol produced by cation exchange of a sodium silicate solution and silica sol produced by hydrolyzing silicon alkoxide can be used.

The durability can be improved by mixing a light stabilizer and / or an ultraviolet absorber for the purpose of suppressing the deterioration of the adhesive layer resin due to the photocatalytic action. As a light stabilizer that can be used, a hindered amine type is preferable, but other substances can also be used. As the ultraviolet absorber, a triazole type or the like can be used. The amount of addition is 0.005 to 10% by weight, preferably 0.01 to 5% by weight, based on the resin. Further, when the adhesive layer is treated with a silane-based or titanium-based coupling agent, the adhesiveness to the photocatalyst layer may be improved. The surfactant is contained in the solution of the adhesive layer in an amount of 0.00001% by weight to 0.1% by weight.
A good photocatalyst carrier can be obtained by adding 1% by weight.

As a method of applying the adhesive layer to the tent fabric canvas, a method of coating and drying a resin solution by a printing method, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, or the like can be used. The drying temperature varies depending on the application method, the solvent and the type of the resin of the tent ground canvas, but is generally preferably 150 ° C. or less. The thickness of the adhesive layer is preferably 0.5 μm or more.

The metal oxide gel or metal hydroxide gel in the photocatalyst layer not only fixes the photocatalyst powder and firmly adheres to the adhesive layer, but also has an adsorptive property because the gel is porous. It also has the effect of increasing photocatalytic activity. The content of the metal oxide gel or metal hydroxide gel in the photocatalyst layer is preferably 25 to 95% by weight. When the content is 25% by weight or less, the adhesion to the adhesive layer becomes insufficient. When the content is 95% by weight or more, the photocatalytic activity becomes insufficient. The specific surface area of the metal oxide gel or metal hydroxide gel is 100 m ^2.
/ G or more, the adhesiveness becomes stronger and the catalytic activity also improves. As the material, an oxide gel or a hydroxide gel of a metal of silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, or tungsten is preferable. Also, even with a gel that mixes these,
A composite oxide gel made by a method such as a coprecipitation method may be used. In order to mix with the photocatalyst, it is desirable to mix in a sol state before forming a gel or in a raw material stage before preparing a sol. Methods for preparing the gel include a method of hydrolyzing a metal salt, a method of neutralizing and decomposing, a method of performing ion exchange, a method of hydrolyzing a metal alkoxide, and the like.The photocatalyst powder is uniformly dispersed in the gel. Any method can be used as long as it can be obtained in a state where it is placed. However, if a large amount of impurities are present in the gel, the adhesion and catalytic activity of the photocatalyst will be adversely affected.
Gels with less impurities are preferred. In particular, when an organic substance is present in the gel in an amount of 5% or more, the photocatalytic activity decreases.
When a photocatalyst layer containing zirconium or aluminum oxide sol was used, it passed the tape peeling test after a 15-minute boiling water test in tap water and a 24-hour immersion test in a 5% sodium carbonate aqueous solution Since it is possible to obtain a material that passes the subsequent tape peeling test, it can be particularly preferably used.

As the photocatalyst in the photocatalyst layer, TiO ₂ ,
ZnO, SrTiO ₃ , CdS, GaP, InP, Ga
As, BaTiO ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta
₂ O ₅ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , NiO, Cu
₂ O, SiC, SiO ₂ , MoS ₂ , InPb, RuO
_2, CeO _2, etc. and, Pt these photocatalysts, R
Any known metal to which metals such as h, RuO ₂ , Nb, Cu, Sn, Ni, and Fe and oxides of these metals are added can be used. The larger the content of the photocatalyst in the photocatalyst layer, the higher the catalytic activity. However, from the viewpoint of adhesiveness, the content is preferably 75% by weight or less. In order to further improve the antibacterial and antifungal properties, the titanium oxide photocatalyst in the photocatalyst layer is 0.05 to
It is also preferable to add 5% by weight of silver or copper metal or metal oxide. When the addition amount is less than 0.05% by weight, the effect of improving the antifungal property is poor, and when the addition amount is more than 5% by weight, a phenomenon that the photocatalyst layer is discolored or the like occurs. In some cases.

To form the photocatalyst layer on the adhesive layer, a suspension in which the photocatalyst is dispersed in a metal oxide gel or a metal hydroxide gel solution is coated by the same coating method as that for forming the adhesive layer. be able to. Disperse the photocatalyst in the state of the precursor solution of the metal oxide gel or metal hydroxide gel,
During coating, it may be hydrolyzed or neutralized and decomposed to form a sol or a gel. When using a sol, an acid or alkali peptizer may be added for stabilization. Also, a surfactant or a silane coupling agent of 5% by weight or less is added to the photocatalyst in the sol suspension,
Adhesion and operability can be improved. The drying temperature at the time of forming the photocatalytic layer varies depending on the coating method, the material of the tent canvas, and the resin material in the adhesive layer, but is generally preferably 150 ° C. or lower.

As for the thickness of the photocatalyst layer, the larger the thickness, the higher the activity. 5μ
When the molecular weight is less than m, the catalyst exhibits high catalytic activity and translucency, so that the catalyst layer is not conspicuous, which is preferable. However, when the thickness is 0.1 μm or less, although the translucency is improved, a high activity cannot be expected because ultraviolet light used by the photocatalyst is transmitted. The thickness of the photocatalyst layer is set to 0.1 μm or more and 5 μm or less, and the photocatalyst particles having a crystal particle diameter of 40 nm or less and a specific surface area of 100 m ² /
When a metal oxide gel or a metal hydroxide gel of g or more is used, it has high photocatalytic activity and does not impair the texture of the underlying tent canvas, so that it is useful from the aesthetic standpoint.

The photocatalyst-loaded tent fabric canvas of the present invention has a high photocatalytic activity and therefore has a photocatalytic activity higher than that of decomposing the plasticizer component diffused into the photocatalyst layer. Even when compared to the tent ground canvas to which the agent was applied, as shown in Examples and Comparative Examples, the antifouling property was excellent. In addition, the photocatalyst supporting tent ground canvas of the present invention has an ultraviolet intensity of 3 m.
Even after irradiation with black light of W / cm ^{2 at} a temperature of 40 ° C. and a relative humidity of 90% for 500 hours, JIS K
A material having high durability such that the adhesion by a crosscut tape method of 5400 maintains an evaluation score of 6 or more can also be obtained.

The tent canvas having the adhesive layer and the photocatalyst layer of the present invention can be obtained with respect to any existing tent canvas. Base fabric woven from fibers such as polyester resin, PVC-impregnated base fabric processed by coating and impregnating the base fabric with vinyl chloride resin, Surface treatment by coating the surface of the PVC-impregnated base fabric with acrylic, fluororesin, etc. The present invention can be applied to everything called a tent canvas, such as a PVC-impregnated base fabric, but can be particularly preferably used for a widely used tent canvas of a class B or a tent of class C. Further, the photocatalyst-supporting tent ground canvas of the present invention is widely used as a general building material, for example, roofs of tent warehouses, hoods for transport equipment such as truck sheets, open stacking sheets, decorative tents for stores, eaves shades for shops, etc. , Various arcade roofs, roofs and side covers of exhibition pavilions, etc., gas station roofs and side covers, waterproof protection sheets, snow protection sheets, air domes, pool covers, etc. It can be particularly preferably used for maintaining the beautiful state of the surface for a long period of time by utilizing its excellent antifouling property, antibacterial property and antifungal property in many necessary situations.

[0019]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Photocatalyst-supporting Class C Tent Canvas Falcon KN-C2000 (103 cm wide × 50 m 207) which is a Class C tent canvas manufactured by Kuraray Co., Ltd.
White) was cut into A4 size, and xylene-isopropanol (50/50) solution containing 10% by weight of an acryl-silicone resin having a silicon content of 3% by weight was mixed with polysiloxane (methyl silicate 5 manufactured by Colcoat Co., Ltd.).
1) 30% by weight based on the acrylic-silicone resin;
The solution added and mixed with the surfactant was designated as No. 7
And coated at 60 ° C. for 30 minutes to form an adhesive layer. After cooling at room temperature, a nitric acid-titania sol having a titanium oxide content of 5% by weight was used as a photocatalyst layer.
It was dispersed in a weight% nitric acid acidic silica sol in the presence of a surfactant to obtain a coating solution for the photocatalytic layer. Using this solution, no. 7 was applied to the surface of the adhesive layer with a bar coater and dried at 60 ° C. for 30 minutes to obtain a photocatalyst-supporting C-type tent ground canvas. (Sample.1)

Example 2 Photocatalyst-Supported Class B Tent Canvas A class B tent canvas manufactured by Kanebo Co., Ltd., was cut out into a sheet of A4 size, and a solution of the adhesive layer prepared in the same manner as in Example 1 was prepared. , No. 7, and dried at 60 ° C. for 30 minutes to form an adhesive layer. After cooling at room temperature, the coating solution for the photocatalyst layer prepared in the same manner as in Example 1 7 was applied to the surface of the adhesive layer with a bar coater, and dried at 60 ° C. for 30 minutes to obtain a photocatalyst-supporting Class B tent canvas. (Sample.2)

Example 3 Photocatalyst-supporting tent canvas A tent canvas manufactured by Kuraray Co., Ltd., which is an E5 flameproof turret set (102 cm wide x 50 m ivory) was used.
The polysiloxane (methyl silicate 51 manufactured by Colcoat Co., Ltd.) was acryl-cut into a xylene-isopropanol (50/50) solution containing 10% by weight of an acrylic-silicon resin having a silicon content of 3% by weight.
A solution prepared by adding and mixing 20% by weight with respect to the silicone resin together with a surfactant was formed by the same bar coater method as in Example 2, and dried at 60 ° C. for 20 minutes. After cooling at room temperature, a nitric acid-titania sol having a titanium oxide content of 5% by weight was dispersed in a nitric acid-acidic silica sol having a silicon oxide content of 5% by weight in the presence of a surfactant to form a photocatalytic layer coating solution. Using this solution, apply it to the surface of the above adhesive layer by the same dipping method.
For 20 minutes to obtain a photocatalyst supporting tent canvas. (Sample.3)

Example 4 Tent Canvas Supporting Copper Additive Photocatalyst E5 flameproof turret set (102 cm wide × 50 m ivory), which is a tent canvas manufactured by Kuraray Co., Ltd.
The polysiloxane (methyl silicate 51 manufactured by Colcoat Co., Ltd.) was acryl-cut into a xylene-isopropanol (50/50) solution containing 10% by weight of an acrylic-silicon resin having a silicon content of 3% by weight.
Using a solution prepared by adding and mixing 20% by weight with respect to the silicone resin together with a surfactant, an adhesive layer was formed in the same manner as in Example 1, and dried at 60 ° C. for 20 minutes. After cooling at room temperature, a nitric acid-titania sol having a titanium oxide content of 5% by weight was used as a photocatalyst layer.
Copper nitrate was added in an amount of 0.5% by weight to titanium oxide in a weight-% nitric acid-acidified silica sol, and dispersed in the presence of a surfactant to obtain a coating solution for the photocatalyst layer. Using this solution, apply to the surface of the adhesive layer in the same manner as in Example 1, and apply
It dried at 20 degreeC for 20 minutes, and made the photocatalyst carrying tent ground canvas. (Sample.4)

Example 5 Coating by gravure printing machine A lead film was attached before and after an E5 flameproof turret set (102 cm wide x 50 m ivory), which was a tent canvas made by Kuraray Co., Ltd., and was set on a gravure printing machine. Isopropanol-ethyl acetate (5%) containing 10% by weight of an acrylic-silicone resin having a content of 3% by weight.
0/50) solution with polysiloxane (Colcoat Co., Ltd.)
Using a solution prepared by adding and mixing 20% by weight of methyl silicate 51) with an acryl-silicone resin together with a surfactant, a film was formed at a film forming speed of 10 m / min and a drying temperature of 90 ° C. After winding, a coating solution for the photocatalyst layer in which a nitric acid-titania sol having a titanium oxide content of 5% by weight was dispersed in a nitrate-acidic silica sol having a silicon oxide content of 5% by weight in the presence of a surfactant was used as a photocatalyst layer. Then, the film was set in a gravure printing machine, and a film was formed at a film forming speed of 20 m / min and a drying temperature of 90 ° C., thereby forming a photocatalyst-supporting tent ground canvas of 50 m. (Sample.5)

Comparative Example 1 Falcon KN-C2000 (103 cm wide × 50 m 207), which is a class C tent canvas manufactured by Kuraray Co., Ltd.
White) was cut out in A4 size, and the characteristics shown in Table 1 were evaluated.

COMPARATIVE EXAMPLE 2 The same tent canvas and the adhesive layer solution as those used in Example 5 were coated at a film forming speed of 10 m using a gravure printing machine.
/ Min at a drying temperature of 90 ° C. After winding, a photocatalytic coating agent ST-Ishihara Sangyo Co., Ltd.
Using K03, set it on the gravure printing machine,
A film was formed at a film forming speed of 20 m / min and a drying temperature of 90 ° C., thereby forming a photocatalyst-supporting tent canvas on a 50 m length.

<Evaluation of Photocatalytic Activity> Stain resistance, antibacterial property, antifungal property, adhesion and durability as photocatalytic activity were examined by the methods described below. The results are shown in Table 1.

1) Stain resistance (stain resistance) A sample cut to a size of 20 cm × 15 cm is of the same size and the same size without carrying a photocatalyst on a fence facing a general road (traffic volume of trucks: about 500 to 1000 vehicles / day). After 3 months, the degree of contamination of the tent ground surface was evaluated by a spectrocolorimeter based on a comparative sample stored in a cool dark place. Degree of discoloration after three months ΔE Change rate Evaluation 10% or less A 30 to 10% B 50 to 30% C 80 to 50% D 80% or more E

2) Evaluation of antibacterial activity A sample cut into a square of 5 cm is disinfected with 80% ethanol, dried at 150 ° C., sterilized, and pre-cultured and diluted to adjust the bacterial concentration to 10 ⁵ cells / ml. The prepared E. coli bacterial solution is dropped on a 0.2 ml sample surface and set in an incubator. Four samples are set under each of two types of light irradiation conditions, that is, a light irradiated with a white fluorescent lamp (15 W × 2, a distance of 10 cm from the light source) and a light not irradiated at all. After a predetermined time (1, 2, 3, 4 hours), the sample is taken out, and the bacterial solution on the sample is wiped off with sterile gauze immersed in sterile physiological saline. Put the wiped sterile gauze in 10 ml of sterile physiological saline and mix well. The supernatant is inoculated on an autoclave-sterilized 95 mmφ petri dish agar medium, and cultured at 36 ° C. for 24 hours, and the number of E. coli colonies is counted. A sample for measuring the standard number of bacteria was prepared in the same manner as described above except that the procedure of dropping the bacterial solution of Escherichia coli into the incubator was performed in exactly the same manner. After culturing, the number of E. coli colonies is counted. The survival rate of E. coli after a predetermined time of each sample is calculated based on the numerical value. After 4 hours, the residual ratio of Escherichia coli is evaluated according to the following evaluation criteria. Escherichia coli residual rate after 4 hours Evaluation 20% or less A 20-40% B 40-60% C 60-80% D 80% or more E

3) Mold resistance test The degree of the occurrence of green mold on the surface of the sample used for the evaluation of the stain resistance was evaluated by comparing and contrasting a sample stored in a cool and dark place with the following criteria. Evaluation of the degree of generation of mold on the sample surface Almost no occurrence A Partially slight occurrence B evident occurrence C

4) Evaluation of Adhesion Adhesion was evaluated by a cross-cut tape test specified in JIS K5400. The interval between cuts was 2 mm, and the number of squares was 25. Evaluation score is JIS
The measurement was performed according to the standards described in K5400.

5) Evaluation of durability The carried sample was irradiated with black light at an ultraviolet intensity of 3 mW / c.
After irradiating with a light of m2 in a thermo-hygrostat at a temperature of 40 DEG C. and a relative humidity of 90% for 500 hours, the adhesion was measured by a grid tape method specified in JIS K5400, and the durability was evaluated. The evaluation score is the same as the evaluation of adhesion.

[0033]

[Table 1]

[0034]

According to the present invention, a tent canvas having a high photocatalytic activity and carrying a photocatalyst having excellent durability can be used for antifouling, antibacterial,
It can be applied to a wide range of applications such as tent warehouses, truck seats, building materials, etc. for the purpose of preventing mold and the like.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a cross section of a photocatalyst-supporting tent ground canvas of the present invention.

[Explanation of symbols]

 1: Photocatalytic layer 2: Adhesive layer 3: Tent canvas

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI E04H 15/54 D06M 11/12

Claims (23)

[Claims] An adhesive layer is provided between a photocatalyst layer and a tent ground canvas, wherein the adhesive layer has a silicon content of 2%.
60% by weight of silicone-modified resin and polysiloxane
A resin containing 5 to 40% by weight of colloidal silica; and a photocatalyst layer composite containing 25 to 95% by weight of a metal oxide gel or a metal hydroxide gel. A tent canvas carrying a photocatalyst, characterized in that: 2. The tent canvas carrying a photocatalyst according to claim 1, wherein the adhesive layer is a silicon-modified resin, and the silicon-modified resin is an acryl-silicon resin. 3. The adhesive layer is a resin containing a polysiloxane, wherein the polysiloxane is a hydrolyzate of a silicon alkoxide having a C ₁ -C ₅ alkoxy group or a product formed from the hydrolyzate. A tent ground canvas carrying the photocatalyst according to claim 1. 4. The tent ground canvas supporting a photocatalyst according to claim 1, wherein the adhesive layer is a resin containing colloidal silica, and the particle diameter of the colloidal silica is 10 nm or less. 5. A tent canvas carrying a photocatalyst according to claim 1, wherein the adhesive layer is a silicon-modified resin containing polysiloxane. 6. The tent canvas carrying a photocatalyst according to claim 1, wherein the adhesive layer is a silicon-modified resin containing colloidal silica. 7. The metal oxide gel or metal hydroxide gel in the photocatalyst layer is a porous metal oxide gel or metal hydroxide gel having a specific surface area of 100 m ² / g or more, wherein silicon, aluminum, Titanium, zirconium,
The photocatalyst according to claim 1, comprising an oxide gel or a hydroxide gel of one or more metals selected from magnesium, niobium, tantalum, and tungsten. Tent canvas. 8. The tent fabric canvas carrying a photocatalyst according to claim 1, wherein the adhesive layer has a thickness of 0.5 to 5 μm. 9. The tent ground canvas carrying a photocatalyst according to claim 1, wherein the photocatalyst layer has a thickness of 0.1 to 5 μm. 10. Irradiation with black light having an ultraviolet intensity of 3 mW / cm ² for 500 hours at a temperature of 40 ° C. and a relative humidity of 90% for 500 hours. The tent ground canvas supporting the photocatalyst according to any one of claims 1 to 9, wherein: 11. A class B tent or a class C tent canvas carrying the adhesive layer and the photocatalyst layer according to claim 1. 12. A tent using the tent ground canvas carrying the photocatalyst according to claim 1. 13. An air dome using a tent ground canvas carrying the photocatalyst according to claim 1. 14. A tent sheet warehouse using the tent ground canvas carrying the photocatalyst according to claim 1. 15. A track sheet using a tent ground canvas carrying the photocatalyst according to claim 1. Description: 16. An oil fence using a tent canvas carrying the photocatalyst according to claim 1. Description: 17. A roof-shaped tent using the tent canvas carrying the photocatalyst according to claim 1. 18. A flexible container using the tent canvas carrying the photocatalyst according to claim 1. Description: 19. An arcade using a tent canvas carrying the photocatalyst according to claim 1. Description: 20. A seat shutter using a tent canvas carrying the photocatalyst according to claim 1. 21. An architectural curing sheet using the tent canvas carrying the photocatalyst according to claim 1. 22. An eaves shade that uses the tent canvas carrying the photocatalyst according to any one of claims 1 to 11. 23. A radar dome using the tent ground canvas carrying the photocatalyst according to claim 1.