JPH0428225B2 - - 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, and is highly durable. [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 the silicone polymer material is easily soiled during use, and since the surface of the silicone polymer material is soft and brittle, various solid dust particles may adhere to it, enter it, 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. The formation of such an antifouling and weatherproof 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 anti-fouling/weather-resistant coating layer that covers at least one side of the silicone polymer layer and is made of a thermoplastic material with excellent anti-fouling/weather resistance; The surface of the silicone polymer layer is modified by corona discharge treatment, and the surface of the silicone polymer layer is obtained by graft polymerizing at least one monomer selected from ethyleneimine, acrylic acid, and acrylamide onto the modified surface. It is characterized in that a graft layer is formed. Another antifouling sheet material of the present invention includes a base fabric made of fibrous fabric, and a silicone polymer material covering at least one surface of the base fabric and containing at least one selected from silicone resin and silicone rubber. and an antifouling/weather-resistant coating layer that covers at least one side of the silicone polymer layer and is made of a thermoplastic synthetic resin material with excellent antifouling and weather resistance. The surface of the silicone polymer layer facing the antifouling/weather-resistant coating layer is modified by corona discharge treatment, and at least one selected from ethyleneimine, acrylic acid, and acrylamide is coated on the modified surface. It is characterized by the formation of a graft layer obtained by graft polymerization of one type of monomer. The structure of the antifouling sheet material of the present invention will be explained with reference to the accompanying drawings. In the sheet material shown in FIG. 1, corona discharge treated modified surfaces 6a and 6b are formed on both sides of the silicone polymer layer 2, and graft layers 3a and 3b are formed on the modified surfaces, respectively. Antifouling/weather resistant coating layers 5a and 5b are formed on top. In addition, the sheet material shown in FIG.
, silicone polymer layers 2a and 2b formed on both surfaces thereof, and silicone polymer layers 2a and 2b formed on each of these silicone polymer layers. Graft layers 3a, 3b
, adhesives 4a and 4b coated on each of these graft layers, and antifouling/weatherproof coating layer 5a, coated on each of these adhesive layers.
5b. Corona discharge treated modified surfaces 6a and 6b are formed on the surface of the silicone polymer layer. In the sheet material shown in FIG.
An adhesive may be applied between b. Also,
In the sheet material shown in FIG. 2, an adhesive layer may not necessarily be necessary. Also, antifouling and
The weather-resistant coating layer and the graft layer thereunder may be formed on only one side 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,
It can be selected from polyvinylsilane silicone resins, polysilthian, polysilazane, carbon polymers having silicon-containing side chains, polysilanes, and the like. For example, flame-retardant silicone resin manufactured by Shin-Etsu Chemical
KR166, KR168, KR202, KR2038 and KR−
101-10 and the like can be used in the present invention. The silicone resin may be modified into silicone rubber using a curing agent (vulcanizing agent). The silicone resins used in the present invention include organopolysiloxane silicone resins, polyacryloxyalkylalkoxysilane silicone resins, and polyvinylsilane silicone resins.
and at least one selected from modified silicone resins. 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 hydrogen or a monovalent hydrocarbon group with 1 to 10 carbon atoms, R'' is a divalent hydrocarbon group with 2 to 10 carbon atoms, and n is an integer of 1 to 3. It includes a copolymer of oxyalkylalkoxysilane and at least one ethylenically unsaturated monomer. Furthermore, the polyvinylsilane silicone resin used in the present invention has the following general formula; [However, R' is the same as above, B is OR' or OR''-
It also includes a copolymer of a vinyl silane compound represented by OR′ (R′, R″ are the same as above) and at least one ethylenically unsaturated monomer. The above-mentioned ethylene monomer is silicone It may be copolymerized in the resin at a content of 1 to 50% by weight. Examples of such monomers include styrene, methylstyrene, dimethylstyrene, ethylstyrene, chlorostyrene, bromostyrene, fluorostyrene, and nitrostyrene. , or 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, polyester, 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. Furthermore, when looking at the silicone rubber curing mechanism, silicone rubber is classified 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 walate, 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 may be formed into a matrix of silicone polymer agent material, in which 30% of the weight of the matrix is added. -300%, preferably 100-250% of other fillers such as silica-based fillers, potassium titanate-based fillers, asbestos fibers, mica and other inorganic heat-resistant materials may be mixed. The filler serves to reinforce the resin layer formed by the silicone resin varnish, and includes various inorganic materials such as titanium oxide, mica, alumina, talc, glass fiber powder, asbestos fine fibers, silica powder, and clay. However, when it is desired that the resulting sheet has surface smoothness, it is generally preferable to use a fine powder having a particle size of 50 μm or less so as not to impair the surface smoothness of the sheet. 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 sheet material of the present invention maintains sufficient disaster prevention properties. The antifouling sheet material of the present invention may include a base fabric made of fibrous fabric as a base. Fibrous fabrics useful in the present invention include natural fibers such as cotton, linen, etc., inorganic fibers such as glass fibers, carbon fibers, asbestos fibers, metal fibers, etc.
Regenerated fibers, e.g. viscose rayon, cupra, etc., semi-synthetic fibers, e.g.
Acetate fibers, etc., and synthetic fibers, such as 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 at least one type selected from the following. 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 glass fibers, and considering that they have little elongation under stress, the fibers are in the form of long fibers (filaments). A plain woven fabric is preferred. 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. To form and fix a silicone polymer layer on a base fabric, a curing accelerator and additives are added to a mixture containing, for example, a silicone resin, an alkali titanate, and if necessary, a high refractive index inorganic compound and/or an endothermic inorganic compound. After adding, if necessary, add an organic solvent such as toluene, xylene, trichlene, etc. to make a dispersion of an appropriate concentration, and apply this dispersion by dipping, spraying, roll coating, reverse roll coating, knife The silicone resin is cured by applying it to one or both sides of the base fabric using a conventionally well-known coating method such as a coating method, and heat-treating it at room temperature or under heat, preferably within the range of 150 to 200°C, for 1 to 30 minutes. and is 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. Therefore, in the present invention, the amount of alkali titanate to be blended with 100 parts by weight of silicone resin (hereinafter referred to as "parts by weight") is 1 to 200 parts, preferably 30 parts by weight.
~100 parts, and if high refractive index inorganic compounds and/or endothermic inorganic compounds are added to these, up to 400 parts, and an alkali titanate equivalent to 1/4 of the same weight. Although they can be added in place, the preferred range is usually 10 to 300 parts. still,
It is possible to replace a part or all of these high refractive index inorganic compounds and endothermic inorganic compounds with commonly used inorganic pigments, inorganic bulking fillers, inorganic powders that impart flame retardancy, etc. The amount is preferably 400 parts or less, more preferably 300 parts or less based on 100 parts of silicone resin. 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,
Endothermically decomposed inorganic compounds such as crystal water releasing type, carbon dioxide releasing type, dispersion endothermic type and phase change type such as aluminum hydroxide and hydrotalcite aluminum silicate, and inorganic flame retardants such as antimony compounds are used. be. There are no particular limitations on the weight or thickness of the silicone polymer layer, but it is generally formed with a weight of 10 to 1000 g/m ² on one side, preferably 50 to 700 g/m ² , and a thickness of 10 to 500 microns on one side. It is preferable that In the sheet material of the present invention, a graft layer is formed on top of the silicone polymer layer. In order to form a graft layer, it is preferable to first subject the surface of the silicone polymer layer to a corona discharge treatment. This corona discharge treatment involves applying a high voltage between a roller that supports the sheet material to be treated and an electrode placed opposite it.
A corona discharge is generated while the sheet material is moved and its surface is sequentially treated. In the method of the present invention, the corona discharge treatment can be carried out continuously while the sheet material to be treated is moved at a predetermined speed between a pair of rolled discharge electrodes as shown in FIG. 3, for example. In FIG. 3, a pair of rolled discharge electrodes 11 and 1
2 each has one metal electrode core 13, 14 and a non-electrically conductive resin layer 15, 16 (for example, a rubber layer) covering it. The electrode core 13 of one roll-shaped discharge electrode is connected to the high-voltage power supply 17, and the electrode core 14 of the other roll-shaped electrode is connected to the ground 1.
8 is connected. The sheet material 20 fed through the guide roll 19 has its back side 21
The discharge electrodes are moved at a constant speed (for example, 2
~10m/min). At this time, when a predetermined voltage (100 to 200 V) is applied between both the rolled electrodes 11 and 12, a corona discharge of 10 to 60 A is generated, and this corona discharge causes the surface 20 of the sheet material 20 to
is processed. The distance A between the circumferential surfaces of both electrodes is 30 mm or less, generally 5 ~
It is 20mm. The corona discharge treated sheet material 20 is passed through a guide roll 23 and wound up to form a roll 24 . For corona discharge treatment, spark gap method,
Vacuum tube method, solid state method, etc. can be used. In order to improve the adhesion of the base fabric, it is preferable to have a critical surface tension of 35 to 60 dyn/cm.
50000W/ ^m2 /min, preferably 150-40000W/
It is preferable to apply processing energy of about m ² /min. The amount of energy to be applied (voltage, current amount, distance between electrodes, etc.) is determined in consideration of the width of the base fabric, processing speed, etc. For example, when performing corona discharge treatment on the surface of a sheet material with a width of 2 m at a processing speed of 10 m/min, the output (power consumption) is
It is preferably about 4kW to 800kW. but,
The conditions are not necessarily limited to these. The corona discharge device used in the method of the invention may be of the usual metal electrode type. The surface of the silicone polymer layer that has been subjected to the corona discharge treatment as described above is brought into contact with vapor of at least one polymer selected from ethyleneimine, acrylic acid, and acrylamide at 20 to 100°C, or a solution is applied. Graft polymerization is carried out using this method to form a highly adhesive graft layer. This graft layer is firmly bonded to the surface of the silicone polymer layer and significantly improves its adhesion. Generally, there are no particular limitations on the thickness of the graft layer.
Preferably, it has a thickness of 0.05 to 5 μm. Next, an antifouling and rainproof coating layer is bonded onto the graft layer with or without adhesive. 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, and vinyl acetate - PVC adhesives, vinyl acetate
Examples include copolymer adhesives such as ethylene adhesives, but the adhesive is not limited thereto, and any known adhesive can be used. As the antifouling/weather-resistant synthetic resin used in the present invention, fluorine-containing resins and polyacrylic resins can be used. That is, the antifouling/weatherproof coating layer is generally prepared by applying a corona discharge-grafting treatment to the desired silicone polymer layer, followed by a fluorine-containing polymer resin,
Alternatively, it can be formed by pasting a film made of polyacrylic resin. The resin constituting the fluorine-containing polymer resin film may be various polyfluoroethylenes synthesized from monomers in which one or more hydrogen atoms of ethylene are replaced with fluorine atoms, such as polytetrafluoroethylene, or There are various types of polyfluorochloroethylene containing partial chlorine, such as polytrifluorochloroethylene, but there are also polyvinyl fluoride,
Also included are polyvinylidene fluoride, polydichlorodifluoroethylene, and others. Since these fluorine-containing resins all have high melting points, they cannot be subjected to normal calender processing, so they must be melted and then extruded, or powdered resins must be heated under pressure and molded into a film. is common, but is not particularly limited to this method. The thickness of the film is generally 0.001 mm to 0.5 mm, preferably about 5 to 50 microns, but it can be made thicker or thinner if it achieves the objectives of weather resistance, stain resistance, and durability. There are no particular limitations. In addition, other resins such as MMA may be used for the fluorine-containing resin film.
There is no problem even if they are used in a mixed manner, such as by mixing or adhering them together, as long as the object of the present invention is achieved. Commercially available fluorine-containing polymer resin films used in the present invention include Tedlar film (DuPont trademark) and Afrex film (Asahi Glass trademark).
There is. The antifouling/weatherproof coating layer used in the sheet material of the present invention may be formed of polyacrylic resin. For this reason, polyacrylic resin films are generally used. Such a polyacrylic resin film may be produced by the T-die method, the inflation method, or any other method. Further, it may be stretched or unstretched, but the elongation is preferably about 100 to 300%. Further, as mentioned above, the thickness is usually about 5 μm to 50 μm, but it may be made somewhat thicker or thinner if sufficient weather resistance and antifouling properties are achieved.
The film material may be a polyalkyl methacrylate film, such as one whose main material is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, or acrylate, vinyl acetate, vinyl chloride, styrene,
A film formed from a homopolymer or copolymer containing acrylonitrile, methacrylonitrile, etc. as a homomonomer or comonomer component is preferable. The antifouling/weather-resistant coating layer is made of a fluorine-containing polymer resin film or a polyacrylic resin film having a substantially smooth surface as described above, and if necessary, the adhesive surface thereof is subjected to corona discharge treatment or low temperature treatment. It is preferable to improve the adhesion by performing plasma treatment or the like and then bonding this onto the graft 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 graft layer or the surface of the adhesive layer applied thereon and dried and solidified. 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~
Preferably, it has a weight of 50 g/m ² , preferably 3 to 30 g/m ² , or a thickness of 5 microns or more (usually 10 to 50 microns), more preferably 30 to 15 microns. In the present invention, the antifouling/weather-resistant coating layer is a laminate of a polyvinylidene fluoride resin layer and a polyacrylic resin layer, or a polyvinylidene fluoride resin layer, in addition to the fluorine-containing polymer resin and polyacrylic resin described above. It may be made of a laminate of a vinylidene resin layer, a polyacrylic resin layer, and a polyvinyl chloride resin layer. In these laminates, the thickness of the polyvinylidene fluoride resin layer is 2 to 3 microns, the thickness of the polyacrylic resin layer is 2 to 4 microns, and the thickness of polyvinyl chloride resin is 40 to 45 microns. are preferred, but are not limited to these values. [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. Structure 16S/1 x 16S/1/75 pieces x 60 pieces/2.54cm Weight 200g/m ³ As a silicone processing agent, 1 part by weight of RTV silicone rubber (manufactured by Toshiba Silicone Corporation) to 1 part by weight of crosslinking agent.
A mixture of parts by weight was applied onto one side of the base fabric using a knife coater in a coating amount of 90 g/m ² . Next, this was passed between a heating cylinder heated to 140° C. and a pressure roll that was pressed against the heating cylinder at a linear pressure of 10 kg/cm, and was then brought into contact with the surface of the heating cylinder for 45 seconds. The surface-hardened silicone polymer base coat layer is then peeled off from the heating cylinder, and then approximately 10 g/approx of the same processing agent as the silicone processing agent is applied thereon.
Apply a top coat with a coating amount of m ² to adjust the surface condition, and finally heat treat at 180℃ to create an intermediate sheet (sample 1).
I got it. This intermediate sheet was further subjected to the following treatments. One side of the intermediate sheet (sample 1) was subjected to corona discharge treatment using the apparatus shown in FIG. The intermediate sheet was fed between a pair of discharge electrodes at a speed of 10 m/min such that one side of the intermediate sheet was in contact with the circumferential surface of a rolled electrode connected to ground. On the back side of this intermediate sheet, the distance between both electrodes A
was 10 mm, voltage 160 volts, current 18 amperes, maximum output 8 kW (power consumption 7.9 kW/hr), and corona discharge treatment was performed continuously. At this time, the diameter of the metal electrode core of both electrodes was 20 cm, the thickness of the resin layer was 2 mm (roll diameter 20.4 cm), the roll length was 2 m, and the discharge width was 1.92 m. At this time, the energy radiated to the sample surface was approximately 440 W/m ² /min. Acrylic acid vapor generated at room temperature is introduced into the apparatus to the obtained corona discharge treated intermediate sheet,
Acrylic acid vapor was brought into contact with the surface of the intermediate sheet at a temperature of 60° C. for 5 minutes to form a polyacrylic acid graft layer (thickness 1.5 μm) that was graft-polymerized.
The resulting graft intermediate sheet-like material (Sample 2) was obtained. In Example 1, a polyacrylic resin adhesive (manufactured by Sony Chemical Co., Ltd.,
SC-462) was applied in an amount of 20 g/m ² using a 100 mesh gravure roll and dried at room temperature.
Next, a vinylidene fluoride resin film (thickness: 3 μm) was heat-pressed onto the surface of the adhesive layer. In Comparative Example 1, the same antifouling and weather-resistant coating layer forming operation as in Example 1 was performed on the surface of the silicone polymer of Sample 1 without subjecting it to corona discharge treatment or graft polymerization 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 operation as in Example 1 was performed, and in Comparative Example 2, the same operation as in Comparative Example 1 was performed. However, a 30 μm thick polyacrylic resin film was used to form an antifouling and weatherproof coating layer. 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.
Further, in Comparative Example 3, the same operation as in Comparative Example 1 was 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]
Examples 4 and 5 and Comparative Example 4 In 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. A film-like silicone polymer sheet material was prepared. The obtained silicone polymer sheet material was used as sample 3.
shall be. One side of this sample 3 was subjected to corona discharge treatment in the same manner as described in Example 1. The modified surface of this corona discharge-treated silicone polymer sheet was subjected to the same graft polymerization treatment as described in Example 1. However, acrylamide vapor was used instead of acrylic acid vapor, and the contact time was 3 minutes. The thickness of the formed graft layer is 1.8μm
It was hot. The obtained intermediate sheet material is designated as Sample 4. In Example 4, a polyurethane adhesive having the following composition was applied to the surface of the graft layer of Sample 4: Nitsuporan 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 Example 5, the same operations as in Example 4 were performed. However, in the graft polymerization process, ethyleneimide was used instead of acrylamide. The thickness of the obtained graft layer was 2 μm. In Comparative Example 4, a KFC film was directly 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 fire is 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 drawings]

FIG. 1 and FIG. 2 are cross-sectional explanatory views showing the structure of one embodiment of the stain-resistant sheet material of the present invention, and FIG. FIG. 2 is an explanatory diagram of an example of a corona discharge treatment device used for. 1... Base fabric, 2, 2a, 2b... Silicone polymer layer, 3a, 3b... Graft layer, 4a, 4b
...Adhesive layer, 5a, 5b...Antifouling/weatherproof coating layer. 6a, 6b...corona discharge modified surface, 11,
12...discharge electrode, 13,14...electrode core, 1
5, 16... Resin layer, 19, 23... Guide roll, 20... Sheet material to be treated, 22... Surface to be treated of sheet material.

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;・Includes an antifouling/weather resistant coating layer formed from a thermoplastic material with excellent weather resistance, and the surface of the silicone polymer layer facing the antifouling/weather resistant coating layer is modified by corona discharge treatment. and ethyleimine on this modified surface,
An antifouling sheet material comprising a graft layer obtained by graft polymerization of at least one monomer selected from acrylic acid and acrylamide. 2. The sheet material according to claim 1, wherein the graft layer and the antifouling/weather-resistant coating layer are bonded together with an adhesive. 3. The sheet material according to claim 1, wherein the graft layer has a thickness of 0.05 to 5 μm. 4. The sheet material according to claim 1, wherein the antifouling/weather-resistant synthetic resin is made of at least one selected from fluorine-containing polymer resins and polyacrylic resins. 5. Claim 1, wherein the antifouling and weather-resistant coating layer is formed of a laminate consisting of a polyvinylidene fluoride resin layer and a polyacrylic resin layer.
Sheet materials listed in section. 6. The antifouling/weather-resistant coating layer is formed of a laminate of a polyvinylidene fluoride resin layer, a polyacrylic resin layer, and a polyvinyl chloride resin layer.
A sheet material according to claim 1. 7. A base fabric made of fibrous non-woven fabric; and a silicone polymer layer covering at least one surface of the base fabric and formed from a silicone polymer material containing at least one selected from silicone resin and silicone rubber. , an antifouling/weather resistant coating layer that covers at least one side of the silicone polymer layer and is formed from a thermoplastic synthetic resin material with excellent antifouling/weather resistance, the antifouling/weather resistant coating. The surface of the silicone polymer layer facing the layer is modified by corona discharge treatment, and at least one monomer selected from ethyleneimine, acrylic acid, and acrylamide is graft-polymerized on the modified surface. An antifouling sheet material characterized by forming the obtained graft layer. 8. The sheet material according to claim 7, wherein the graft layer and the antifouling/weather-resistant coating layer are bonded together with an adhesive. 9. The sheet material according to claim 7, wherein the fibrous fabric is made of at least one selected from natural fibers, inorganic fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers. 10. The sheet material of claim 7, wherein the graft layer has a thickness of 0.05 to 5 μm. 11. The sheet material according to claim 7, wherein the antifouling/weather-resistant synthetic resin is made of at least one selected from fluorine-containing polymer resins and polyacrylic resins. 12. The sheet material according to claim 7, wherein the antifouling/weather-resistant coating layer is formed of a laminate consisting of a polyvinylidene fluoride resin layer and a polyacrylic resin layer. 13. The sheet according to claim 7, wherein the antifouling/weather-resistant coating layer is formed of a laminate of a polyvinylidene fluoride resin layer, a polyacrylic resin layer, and a polyvinyl chloride resin layer. material.