JPH0564101B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a sheet material that has excellent stain resistance, heat resistance, weather resistance, and waterproof properties. [Prior Art] Conventionally, silicone polymer sheet materials made of silicone resin or silicone rubber, and sheet materials in which a fiber base fabric is coated with a silicone polymer material such as silicone resin or silicone rubber, have good heat resistance and are used for various purposes. used in However, the surface of silicone polymer materials is extremely prone to staining during use, and since the surface of silicone polymer materials is soft and brittle, various solid dust powders may adhere to or penetrate and become buried. There are drawbacks to doing so. In order to eliminate these drawbacks of silicone polymer sheet materials, it is possible to provide an antifouling/weather resistant coating layer formed from a thermoplastic synthetic resin with excellent antifouling and weather resistance on the surface of the silicone polymer material. Proposed by the inventor of the present invention. Formation of such an antifouling and weather-resistant coating layer has certainly solved the problem of various solid dust powders adhering to, penetrating, and being buried in the silicone polymer material. However, it has been desired to further improve the adhesive strength between the surface of the silicone polymer material and the antifouling/weather-resistant coating layer, and the durability of this adhesive. [Problems to be Solved by the Invention] The present invention provides a conventional sheet material having a silicone polymer layer and an antifouling/weather resistant coating layer.
The present invention aims to solve problems regarding the adhesive strength and durability between the silicone polymer layer and the antifouling/weather-resistant coating layer. [Means and effects for solving the problems] The antifouling sheet material of the present invention comprises a silicone polymer layer formed from a silicone polymer material containing at least one selected from silicone resin and silicone rubber; an antifouling/weather resistant coating layer covering at least one surface of the silicone polymer layer, the antifouling/weather resistant coating layer comprising a fluorine-containing resin layer,
It is formed of an acrylic resin layer, a laminate of a polyvinylidene fluoride resin layer and an acrylic resin layer, or a laminate of a polyvinylidene fluoride resin layer, an acrylic resin layer, and a polyvinyl chloride resin layer, and the silicone A low-temperature plasma modified layer obtained by subjecting the surface of the silicone polymer layer to low-temperature plasma treatment is formed between the polymer layer and the antifouling/weather-resistant coating layer, The layer and the antifouling/weather resistant coating layer are bonded to each other via the low temperature plasma modified layer. Another antifouling sheet material of the present invention includes a base fabric made of organic fiber fabric, and a silicone material covering at least one surface of the base fabric and containing at least one selected from silicone resin and silicone rubber. A silicone polymer layer formed from a polymer material, and an antifouling/weather resistant coating layer covering at least one surface of the silicone polymer layer, the antifouling/weather resistant coating layer being made of a fluorine-containing resin. layer,
It is formed of an acrylic resin layer, a laminate of a polyvinylidene fluoride resin layer and an acrylic resin layer, or a laminate of a polyvinylidene fluoride resin layer, an acrylic resin layer, and a polyvinyl chloride resin layer, and the silicone A low-temperature plasma modified layer obtained by subjecting the surface of the silicone polymer layer to low-temperature plasma treatment is formed between the polymer layer and the antifouling/weather-resistant coating layer, The layer and the antifouling/weather resistant coating layer are bonded to each other via the low temperature plasma modified layer. The structure of the antifouling sheet material of the present invention will be explained with reference to the accompanying drawings. In the antifouling sheet material shown in FIG. 1, low temperature plasma modified layers 3a and 3b are formed on both sides of the silicone polymer layer 2, and antifouling and weatherproof coating layers 5a and 5b are formed on each of the layers. has been done. In addition, the antifouling sheet material shown in FIG.
Base fabric 1, silicone polymer layers 2a and 2b formed on both surfaces thereof, low temperature plasma modified layers 3a and 3b formed on each of these silicone polymer layers, and each of these low temperature plasma modified layers. It consists of adhesive layers 4a, 4b applied thereon, and antifouling/weatherproof coating layers 5a, 5b applied on each of these adhesive layers. In the antifouling sheet material shown in FIG.
An adhesive may be applied between the low-temperature plasma modified layers 3a, 3b and the antifouling/weatherproof coating layers 5a, 5b. Further, in the antifouling sheet material shown in FIG. 2, the adhesive layer may not necessarily be necessary. In addition, in the stain-resistant sheet material shown in Figure 1 or Figure 2, a silicone polymer layer, a low-temperature plasma modified layer, an adhesive layer, and a stain-proof/weather-resistant coating layer are laminated on only one side of the base fabric. may have been done. In this case, only the silicone polymer layer may be formed on the other surface of the base fabric. The silicone resin and silicone rubber used in the silicone polymer layer in the present invention include, for example, organopolysiloxane, polyacryloxyalkylalkoxysilane silicone resin, polyvinylsilane silicone resin, polysilthian, polysilazane, and silicone-containing side chain. It can be selected from carbon-based polymers, polysilanes, etc. For example, flame-retardant silicone resins KR166, KR168, KR202, KR2038, and KR-101-10 manufactured by Shin-Etsu Chemical can be used in the present invention. The silicone resin may be modified into silicone rubber using a curing agent (vulcanizing agent). The organopolysiloxane resin used in the present invention includes vinyl groups, allyl groups, hydroxyl groups,
Having at least one organic substituent such as an alkoxy group, amino group, or mercapto group having 1 to 4 carbon atoms, such as polydimethylsiloxane silicone resin, polydiphenylsiloxane silicone resin, polymethylphenylsiloxane silicone resin , and resins made of copolymers thereof. The polyacryloxyalkylalkoxysilane silicone resin used in the present invention has the general formula (R is a monovalent hydrocarbon group having 1 to 10 carbon atoms,
R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R'' is a divalent hydrocarbon group having 2 to 10 carbon atoms, and n is an integer of 1 to 3.) It includes a copolymer of the represented acryloxyalkylalkoxysilane with at least one ethylenically unsaturated monomer. Furthermore, the polyvinylsilane silicone resin used in the present invention has the following general formula: [However, R' and n are the same as above, and B represents OR' or an OR''-OR' group (R' and R'' are the same as above). ] A vinyl silane compound represented by
It also includes copolymers with other ethylenically unsaturated monomers. The above-mentioned ethylene monomer may be copolymerized in the silicone resin at a content of 1 to 50% by weight. Examples of such monomers include styrene, methylstyrene, dimethylstyrene, ethylstyrene, chlorostyrene, bromostyrene, fluorostyrene, nitrostyrene, acrylic acid, methacrylic acid, methyl acrylate,
Ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate,
Butyl methacrylate, acrylamide, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinyl halogen compounds, and There are vinyl ethers, etc. The above-mentioned silicone resins may be modified with other resins, such as epoxy resins, polyester resins, alkyd resins, amino resins, etc., or may be modified with fatty acids. In the stain-resistant sheet material of the present invention, when self-extinguishing properties when heated to high temperatures are important, in the case of organopolysiloxane-based silicone resin, the polysiloxane component is preferably 70% in the silicone resin. In polyacrylooxyalkylalkoxysilane silicone resins and polyvinylsilane silicone resins, the amount of the ethylenically unsaturated monomer to be copolymerized is preferably 50% by weight or less, particularly 20% by weight or less. In addition, when flexibility of the material is important as well as self-extinguishing property, an unmodified organopolysiloxane silicone resin is preferable. These silicone resins may be solid at room temperature, flexible pastes, liquids, or dispersions such as emulsions, and are used with the addition of an appropriate solvent if necessary. In addition, silicone rubber is classified by curing mechanism into room temperature curing type, heat curing type, and ultraviolet or electron beam curing type.
Curing agents and curing accelerators generally known to those skilled in the art, such as metal carboxylates of zinc, lead, cobalt, iron, etc., organotin compounds such as dibutyltin octoate, dibutyltin laurate, tetrapropyl titanate, tetraoctyl titanate, etc. titanium chelate compound, N-N-dimethylaniline,
Tertiary amines such as triethanolamine, or peroxides such as benzoyl peroxide, dicumyl peroxide, t-butyl peroxide,
and a platinum-based catalyst, etc., it is cured into a desired three-dimensional network structure. The silicone polymer layer may be formed only from the silicone resin and/or silicone rubber as described above, but these materials form a matrix of silicone polymer material, and the silicone polymer layer contains 30 to 30% of the weight of the matrix. 300%, preferably 100
~250% other fillers, e.g. silica-based fillers,
It may be a mixture of a potassium titanate filler, asbestos fiber, mica, and other inorganic heat-resistant materials. Fillers serve to reinforce the resin layer formed by silicone resin varnish, and include various inorganic materials such as titanium oxide, mica, alumina, talc, glass fiber powder, rock wool fine fibers, silica powder, and clay. However, when it is desired to impart surface smoothness to the resulting stain-resistant sheet material, fine powder with a particle size of 50 μm or less is generally used so as not to impair the surface smoothness of the stain-resistant sheet material. It is preferable to use Furthermore, among inorganic fillers, it is particularly effective to use alkali titanate to improve the heat resistance of the product. That is, the alkali titanate is used by being blended into the silicone resin varnish, and is used to ensure that the antifouling sheet material of the present invention maintains sufficient flame retardant properties. The amount of alkali titanate added to 100 parts by weight of the silicone resin is 1 to 200 parts by weight, preferably 30 to 100 parts by weight, and in addition, a high refractive index inorganic compound and/or an endothermic inorganic compound, etc. When blending, up to 400 parts by weight can be added in place of an alkali titanate corresponding to the same weight to 1/4 of the weight, but a range of 10 to 300 parts by weight is usually preferred. In addition, some or all of these high refractive index inorganic compounds and endothermic inorganic compounds are
Commonly used inorganic pigments, inorganic extender fillers, inorganic powders that impart flame retardancy, etc. can be substituted, but the amount used is 400 parts by weight or less per 100 parts by weight of silicone resin. The amount is preferably 300 parts by weight or less. In order to improve the effects of the present invention, a flame retardant may be added to the silicone polymer layer. The flame retardants used here are not particularly limited, but include, for example, organic flame retardants such as phosphate ester type, organic halogen compound type, and phosphazene compound type, calcined gypsum, alum, calcium carbonate,
Inorganic flame retardants such as endothermic decomposition type inorganic compounds such as crystal water releasing type, carbon dioxide gas releasing type, dispersion endothermic type and phase change type such as aluminum hydroxide and hydrotalcite aluminum silicate, and antimony compounds, etc. There is. There is no particular limitation on the weight or thickness of the silicone polymer layer, but it generally has a weight of 10 to 1000 g/m ² on one side, preferably 50 to 700 g/m ² , and a weight of 10 to 500 μm on one side.
It is preferable that it is formed with a thickness of m. In the antifouling sheet material of the present invention, a low temperature plasma modified layer obtained by low temperature plasma treatment is formed on the surface of the silicone polymer layer.
To form this low-temperature plasma modified layer, the surface of the silicone polymer layer is first subjected to low-temperature plasma treatment. This low-temperature plasma treatment can be performed by exposing the surface of the silicone polymer layer to low-temperature plasma of a gas that does not have plasma polymerizability under a pressure of 0.01 to 10 Torr. For example, the plasma generation conditions are 13.56MHz, 10
It is sufficient to apply a power of ~500 W, and sufficient results can be obtained whether the discharge is a polar discharge or a non-polar discharge. The plasma processing time varies depending on the applied voltage, but generally a few seconds to several tens of minutes is sufficient. In addition, there are various methods for plasma processing other than the above-mentioned methods. For example, low frequency, microwave, direct current, etc. can be used as the discharge frequency band,
In addition to glow discharge, the plasma generation mode can also be selected from corona discharge, spark discharge, silent discharge, etc. In addition to external electrodes, the electrodes may also be internal electrodes, coil types, etc., capacitively coupled or inductively coupled. However, no matter what method is used, care must be taken to ensure that the surface of the material is not altered by excessive discharge heat. The gas that does not have plasma polymerizability is at least one selected from helium, neon, argon, nitrogen, nitrous oxide, nitrogen dioxide, oxygen, air, carbon monoxide, carbon dioxide, and hydrogen. used. A low-temperature plasma-modified layer with high adhesiveness is formed on the surface of the silicone polymer layer subjected to the low-temperature plasma treatment as described above. This low temperature plasma modified layer is strongly bonded to the unmodified portion of the silicone polymer layer and significantly improves its adhesion. The silicone polymer layer and the antifouling/weathering coating layer are then adhered with or without an adhesive via the low temperature plasma modified layer. Examples of useful adhesives include melamine adhesives, phenol adhesives, epoxy adhesives, polyester adhesives, polyethyleneimine adhesives, polyisocyanate adhesives, polyurethane adhesives, and acrylic adhesives. Adhesives, polyamide adhesives, copolymer adhesives such as vinyl acetate-vinyl chloride copolymer adhesives, vinyl acetate-ethylene copolymer adhesives, etc., and especially epoxy adhesives, polyethylene adhesives, etc. Imine adhesives, polyisocyanate adhesives, polyurethane adhesives, acrylic adhesives, etc. are preferred, but the adhesive is not limited to these, and any known adhesive can be used. As the antifouling and weather-resistant synthetic resin used in the present invention, fluorine-containing resins and acrylic resins can be used. The resins constituting the fluorine-containing resin film include various polyfluoroethylenes synthesized from monomers in which one or more hydrogen atoms of ethylene are replaced with fluorine atoms, such as polytetrafluoroethylene,
There are also various polyfluorochloroethylenes that partially contain chlorine, such as polytrifluorochloroethylene, but also polyvinyl fluoride, polyvinylidene fluoride, polydichlorodifluoroethylene,
Others are also included. These fluorine-containing resins are
Since both have high melting points, normal calender processing cannot be performed, so it is common to melt the resin and extrude it, or process and heat the powdered resin to form it into a film. The method is not limited to this method. The thickness of the film is generally
The thickness is about 0.001 to 0.5 mm, preferably about 5 to 50 μm, but there is no particular limitation as it can be made thicker or thinner as long as it achieves the objectives of weather resistance, antifouling properties, and durability. Further, the fluorine-containing resin film may be mixed with other resins such as MMA, etc., as long as the object of the present invention is achieved. Commercially available fluorine-containing resin films used in the present invention include Tedlar film (DuPont trademark) and Afrex film (Asahi Glass trademark). The antifouling material used in the antifouling sheet material of the present invention
The weather-resistant coating layer may be formed of acrylic resin. For this reason, acrylic resin films are generally used. Such an acrylic resin film may be produced by the T-die method, the inflation method, or any other method. Also,
It can be stretched or unstretched, but the elongation is 100~
About 300% is preferable. Further, as mentioned above, the thickness is usually about 5 to 50 μm, but it may be made somewhat thicker or thinner than the above if sufficient weather resistance and antifouling properties are achieved. The film material is a polyalkyl methacrylate film, for example, one whose main material is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc., or acrylate, vinyl acetate, vinyl chloride, styrene, acrylonitrile, etc.
A homopolymer or copolymer containing methacrylonitrile or the like as a homomonomer or comonomer component is preferably formed into a film. The antifouling/weather-resistant coating layer is made of a fluorine-containing resin film or an acrylic resin film having a substantially smooth surface as described above, and the adhesion surface thereof is subjected to low-temperature plasma treatment or corona discharge treatment as necessary. It is preferable to improve the adhesion by applying the following steps, and then bonding this onto the low-temperature plasma deformable layer using an adhesive. However, as another method for forming an antifouling/weather-resistant coating layer, there is a method in which a solution or emulsion of the above-mentioned resin is applied to the surface of the low-temperature plasma modified layer or the surface of the adhesive layer applied thereon, and then dried and solidified. There is. The film used for forming the antifouling/weatherproof coating layer preferably has a tensile strength of 100 Kg/m ² or more. In addition, the antifouling/weatherproof coating layer is 1~
It is preferable to have a weight of 50 g/m ² , preferably 3 to 30 g/m ² or a thickness of 5 μm or more (usually 10 to 50 μm), more preferably 30 to 50 μm. In the present invention, in addition to the above-mentioned fluorine-containing resin and acrylic resin, the antifouling and weather-resistant coating layer is a laminate of a polyvinylidene fluoride resin layer and an acrylic resin layer, or a polyvinylidene fluoride resin layer. It may be made of a laminate of an acrylic resin layer and a polyvinyl chloride resin layer. In these laminates, the thickness of the polyvinylidene fluoride resin layer is 2 to 2.
3 μm, the thickness of the acrylic resin layer is 2 to 4 μm, and
The thickness of the polyvinyl chloride resin layer is preferably 40 to 45 μm, but is not limited to these values. The antifouling sheet material of the present invention may include a base fabric made of an organic fibrous fabric. Fibrous base fabrics useful in the present invention include natural fibers such as cotton, linen, etc., recycled fibers such as viscose rayon, Kyupra, etc., semi-synthetic fibers such as g- and tri-acetate fibers, and synthetic fibers. For example, at least one selected from nylon 6, nylon 66, polyester (polyethylene terephthalate, etc.) fibers, aromatic polyamide fibers, acrylic fibers, polyvinyl chloride fibers, polyolefin fibers, and water-insoluble or poorly soluble polyvinyl alcohol fibers. It consists of seeds. A small amount of inorganic fiber may be mixed with the organic fiber. The fibers in the base fabric may be in any form such as short fiber spun yarn, long fiber yarn, split yarn, or tape yarn, and the base fabric may be a woven fabric, a knitted fabric, a nonwoven fabric, or a composite fabric thereof. Good too. Generally, the fibers used in the stain-resistant sheet material of the present invention are preferably polyester fibers, and considering that they have little elongation under stress, the fibers are preferably in the form of long fibers (filaments). In addition, it is preferable that a plain woven fabric is formed. However, the weaving structure and its form are not particularly limited. The fibrous base fabric is useful for maintaining the mechanical strength of the resulting antifouling sheet material at a high level. In order to form and fix a silicone polymer layer on the base fabric, for example, a curing accelerator and an appropriate curing accelerator are added to a mixture containing a silicone resin, an alkali titanate, and if necessary, a high refractive index inorganic compound and/or an endothermic inorganic compound. After adding the additives, if necessary, add an organic solvent such as toluene, xylene, trichlene, etc. to make a dispersion with an appropriate concentration.This dispersion can be coated by dipping, spraying, roll coating, or reverse roll coating. The silicone resin is coated on one or both sides of the base fabric by a conventionally well-known coating method such as knife coating method, and then heat-treated at room temperature or under heating, preferably within the range of 150 to 200°C for 1 to 30 minutes. is cured and integrally fixed to the aforementioned base material. The blending ratio of silicone resin and alkali titanate, high refractive index inorganic compound, and/or endothermic inorganic compound, etc. varies depending on the type and particle size of the silicone resin and inorganic compound used, but in general, if there is too little silicone resin, silicone As a result of the insufficient strength of the combined layer, when used as a fire-resistant heat insulating sheet, the silicone polymer layer may crack or the silicone polymer layer may peel off from the base fabric. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 and Comparative Example 1 A bleached cotton fabric with the following structure was used as the base fabric. Tissue 16S/1 x 16S/1/75 pieces x 60 pieces/2.54
cm Weight 200g/m ³ As a silicone processing agent, 10 parts by weight of RTV silicone rubber (manufactured by Toshiba Silicone Co., Ltd.) to 1 part by weight of crosslinking agent
A mixture of parts by weight was applied onto the surface of the base fabric using a knife coater in a coating amount of 90 g/m ³ . Next, this is heated to a heating cylinder heated to 140℃, and a linear pressure of 10Kg/cm is applied to this heating cylinder.
The sample was passed between a pressure roller and a pressure roller that was in contact with the sample, and was then brought into contact with the surface of a heating cylinder for 45 seconds. The surface-hardened silicone polymer base coat layer is then peeled off from the heating cylinder, and the same processing agent as the silicone processing agent is applied thereon for approximately 10 minutes.
A top coat was applied at a coating amount of g/m ³ to adjust the surface condition, and finally heat treatment was performed at 180°C to obtain an intermediate sheet (Sample 1). This intermediate sheet was further subjected to the following treatments. The test piece taken from the intermediate sheet (sample 1) was placed in a low-temperature plasma processing device, the pressure inside the device was evacuated to 10 ^-5 Torr, and then argon gas was introduced into the device to reduce the pressure inside the device. was adjusted to 0.2Torr. Next, in this atmosphere, the frequency is 13.56MHz.
Using a high-frequency power source (manufactured by Nippon Koshuha Co., Ltd.), low-temperature plasma treatment with a power consumption of 100 watts was applied to the surface of the silicone polymer layer for 30 minutes to form an intermediate sheet (sample 2).
I got it. In Example 1, a polyacrylic resin adhesive (manufactured by Sony Chemical Co., Ltd., SC-462) was applied to the surface of the low-temperature plasma modified layer of Sample 2 in an amount of 20 g/m ² using a 100-mesh gravure roll, and the adhesive was heated at room temperature. It was dried. Next, a vinylidene fluoride resin film (thickness: 3 μm) was heat-pressed onto the surface of the adhesive layer. In Comparative Example 1, the surface of the silicone polymer of Sample 1 was subjected to the same antifouling/weather-resistant coating layer forming operation as in Example 1, without performing low-temperature plasma treatment. Table 1 shows the peel strength between the silicone polymer layer and the antifouling/weather-resistant coating layer of each sheet-like product obtained. Example 2 and Comparative Example 2 In Example 2, the same operations as in Example 1 were performed, and in Comparative Example 2, the same operations as in Comparative Example 1 were performed. However, an acrylic resin film with a thickness of 30 μm is used to form an antifouling and weather-resistant coating layer.
Attached using epoxy adhesive. The results are shown in Table 1. Example 3 and Comparative Example 3 In Example 3, the same operations as in Example 1 were carried out.
In Comparative Example 3, the same operations as in Comparative Example 1 were performed. However, in order to form an antifouling and weather-resistant coating layer, KFC film (manufactured by Kureha Chemical Co., Ltd.) consists of a vinylidene fluoride resin layer (2 μm thick), an acrylic resin layer (2 to 4 μm), and a polyvinyl chloride resin layer (45 μm thick). )
A three-layer structure in which the two layers were laminated was used. The results are shown in Table 1.

[Table]
Example 4 and Comparative Example 4 The same silicone polymer as described in Example 1 was casted on release paper to a thickness of 0.5 μm, and after solidification, the release paper was peeled off to form a film-like silicone polymer. Created sheet material. The obtained silicone polymer sheet material was used as sample 3.
It is written as One side of this sample 3 was subjected to low temperature plasma treatment in the same manner as described in Example 1. However, hydrogen gas was used instead of argon gas, the pressure inside the apparatus was 0.01 Torr, the power consumption was 500 W, and the processing time was 30 seconds. The obtained low-temperature plasma treated sample is referred to as sample 4. In Example 4, a polyurethane adhesive having the following composition was applied to the treated surface of this low-temperature plasma-treated silicone polymer sheet (Sample 4): Nituporan 3022 (manufactured by Nippon Urethane Co., Ltd., solid content 35%)
100 parts by weight Coronate-1-L (manufactured by Nippon Urethane Co., Ltd.)
15 parts by weight was coated with 60 mesh gravure to give 25g/
It was applied in an amount of m ² and dried. The same KFC film as described in Example 3 was heat-pressed onto the surface of this adhesive layer. In Comparative Example 4, a KFC film was attached to the surface of the sheet material of Sample 3 in the same manner as in Example 4. The peel strength and durability (change over time) of each sheet-like product obtained were measured. The results are shown in Table 2.

〔Effect of the invention〕

In the antifouling sheet material of the present invention, the silicone polymer layer and the antifouling/weather-resistant coating layer are firmly bonded to each other, and the durability thereof is also excellent. Furthermore, the stain-resistant sheet material of the present invention has good durability and waterproof properties, is less stained, and has excellent weather resistance. Furthermore, the antifouling sheet material of the present invention is particularly unlikely to emit smoke or generate heat even at high temperatures. Therefore, the antifouling sheet material of the present invention has a wide range of uses, especially in gymnasiums, warehouses, and other areas where flames are expected.
For building materials and interior materials for markets, playgrounds, factories, parking lots, various accommodation facilities, etc., as well as tents, awnings, blinds, and sheet materials that require repeated washing, such as hospital bed sheets and room partitions. It is useful as a material for etc.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are explanatory cross-sectional views showing the structure of one embodiment of the stain-resistant sheet material of the present invention, respectively. 1... Base fabric, 2, 2a, 2b... Silicone polymer layer, 3a, 3b... Low temperature plasma modified layer, 4
a, 4b...Adhesive layer, 5a, 5b...Antifouling/weather resistant coating layer.

Claims (1)

[Scope of Claims] 1. A silicone polymer layer formed from a silicone polymer material containing at least one selected from silicone resin and silicone rubber, and an antifouling layer covering at least one surface of this silicone polymer layer. - a weather-resistant coating layer, wherein the antifouling/weather-resistant coating layer is a fluorine-containing resin layer, an acrylic resin layer, a laminate of a polyvinylidene fluoride resin layer and an acrylic resin layer, or a polyvinylidene fluoride resin layer is formed of a laminate of an acrylic resin layer and a polyvinyl chloride resin layer, and between the silicone polymer layer and the antifouling/weather-resistant coating layer, a low temperature A low temperature plasma modified layer obtained by plasma treatment is formed, and the silicone polymer layer and the antifouling/weather resistant coating layer are bonded via the low temperature plasma modified layer. Features a stain-resistant sheet material. 2. The stain-resistant sheet material according to claim 1, wherein the low-temperature plasma modified layer and the stain-proof/weather-resistant coating layer are bonded together with an adhesive. 3. The antifouling sheet material according to claim 2, wherein the adhesive is selected from acrylic adhesives, epoxy adhesives, polyethyleneimine adhesives, polyisocyanate adhesives, and polyurethane adhesives. . 4. A base fabric made of organic fibrous fabric, and a silicone polymer layer covering at least one surface of this base fabric and made of a silicone polymer material containing at least one selected from silicone resin and silicone rubber. and an antifouling/weather resistant coating layer covering at least one surface of the silicone polymer layer, the antifouling/weather resistant coating layer comprising a fluorine-containing resin layer, an acrylic resin layer, a polyvinylidene fluoride resin layer. and an acrylic resin layer, or a laminate of a polyvinylidene fluoride resin layer, an acrylic resin layer, and a polyvinyl chloride resin layer, and the silicone polymer layer and the stain-resistant and weather-resistant A low-temperature plasma modified layer obtained by subjecting the surface of the silicone polymer layer to low-temperature plasma treatment is formed between the silicone polymer layer and the antifouling/weather-resistant coating layer. and are adhered to each other via the low-temperature plasma modified layer. 5. The stain-resistant sheet material according to claim 4, wherein the low-temperature plasma modified layer and the stain-proof/weather-resistant coating layer are bonded together with an adhesive. 6. The antifouling sheet material according to claim 5, wherein the adhesive is selected from acrylic adhesives, epoxy adhesives, polyethyleneimine adhesives, polyisocyanate adhesives, and polyurethane adhesives. . 7. The organic fibrous fabric is a natural fiber, a recycled fiber,
The antifouling sheet material according to claim 4, comprising at least one kind selected from semi-synthetic fibers and synthetic fibers.