JPS6237157A - Antifouling sheet material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sheet material that has excellent stain resistance, heat resistance, weather resistance, and waterproof properties.

[Conventional technology]

Conventional 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. .

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, it is difficult for various solid dust powders to adhere to, penetrate and become buried. There are some drawbacks. 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. Such antifouling and
The formation of a weather-resistant coating certainly eliminates the problem of various solid dust powders adhering to, penetrating, and becoming embedded 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.

[Problem that the invention seeks to solve]

The present invention relates to a conventional sheet material having a silicone polymer layer and an antifouling/weather resistant coating layer, and the present invention provides adhesive strength and durability between the silicone polymer layer and the antifouling/weather resistant coating layer. This is an attempt to solve the problems related to

[Means and actions for solving the problem] 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, and this silicone polymer layer. a stain/weather resistant coating layer that covers at least one side of the combined layer and is formed from a thermoplastic synthetic resin material with excellent stain resistance and weather resistance; A corona discharge modified layer obtained by subjecting the surface of the silicone polymer layer to a corona discharge treatment is formed between the silicone polymer layer and the antifouling/weather resistant coating. The present invention is characterized in that the two layers are adhered to each other via the corona discharge modified layer.

Another antifouling sheet material of the present invention includes a base fabric made of a fibrous fabric, and at least one surface of the base fabric is coated, and
A silicone polymer layer formed from a silicone polymer material containing at least one selected from silicone resin and silicone rubber, and a heat-resistant material that coats at least one surface of this silicone polymer layer and has excellent stain resistance and weather resistance. an antifouling/weather resistant coating layer formed from a plastic synthetic resin material, and a corona discharge is applied to the surface of the silicone polymer layer between the silicone polymer layer and the antifouling/weather resistant coating layer. A corona discharge modified layer obtained by the treatment is formed, and the silicone polymer layer and the antifouling/weather resistant coating layer are bonded via the corona discharge modified layer. That is.

The structure of the antifouling sheet material of the present invention will be explained with reference to the accompanying drawings.

In the sheet material 1 shown in FIG. 1, on both sides of the silicone polymer layer 2 there is a corona discharge modified layer 3m.

3b is formed, and an antifouling/weatherproof coating layer 5m, 5b is formed on each of them.

Further, the sheet material 11 shown in FIG. 2 includes a base fabric 6,
Silicone polymer layers 2m and 2b formed on both sides thereof
and a corona discharge modified layer 3a formed on each of these silicone polymer layers.

3b, an adhesive layer 4a e 4b coated on each of these corona discharge modified layers, and an antifouling/weatherproof coating layer 5m coated on each of these adhesive layers.
, 5b.

In the sheet material 1 shown in FIG.
An adhesive may be applied between 5b.

Also, in the sheet material 11 shown in FIG. 2, an adhesive layer may not necessarily be necessary.

In addition, in the sheet material shown in @Figure 1 or Figure 2, a silicone polymer layer, a corona discharge modified layer, an adhesive layer, and an antifouling/weatherproof coating layer are laminated on only one side of the base fabric. good. In this case, only the silicone polymer layer may be formed on the other surface of the base fabric.

The silicone resin and silicone coat used in the silicone polymer layer in the present invention include, for example, organopolysiloxane, polyacryloxyalkylalkoxysilane silicone resin, polyvinylsilane silicone resin, polysilthian, polysiladene, and silicone containing side chains. You can choose from carbon polymer, polysilane, etc.

For example, Shin-Etsu Chemical's flame-retardant silicone resin KR166,
KR168, KR202, KR2038 and KR-1
01-10 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 organopolysiloxane resin used in the present invention is
It has at least one organic substituent such as vinyl group, allyl group, hydroxyl group, alkoxy group having 1 to 4 carbon atoms, amino group, mercapto group, etc. It includes all lydimethylsiloxane silicone resins, polydiphenylsiloxane silicone resins, polymethylphenylsiloxane silicone resins, 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, and R' is hydrogen 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.) and at least one ethylenically unsaturated monomer. This includes copolymers with

Further, the polyvinylsilane silicone resin used in the present invention has the following general formula: % formula % [However, R' is the same as above, and B is OR' or OR' -
It also includes a copolymer of a vinylsilane compound not represented by OR' (R/, R1 are the same as above) and at least 1 m of ethylenically unsaturated monomer.

The above-mentioned ethylene monomer is contained in the silicone resin in an amount of 1 to 5.
It may be copolymerized at a content of 0 polymerization. Such monomers include, for example, styrene, 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 acetate, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene /mylide, vinyl halodane compounds, vinyl ethers, etc.

The silicone resins mentioned above may be combined with other resins, such as epoxies,
It may be modified with polyester, alkyd resin, amino resin, etc., or it may be modified with fatty acid.

In the antifouling sheet material of the present invention, when self-extinguishing properties when heated to high temperatures are important, in the organopolysiloxane silicone resin, the polysiloxane component is preferably 701Ik in the silicone resin. In polyacrylooxyalkyl alkoxysilane silicone resins and polyvinylsilane silicone resins, the amount of ethylenically unsaturated monomer to be copolymerized is preferably 5ON 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 yeast, liquid, or dispersion such as emulsion, and may be used by adding an appropriate solvent if necessary. Also, when looking at silicone rubber by its curing mechanism, silicone rubber is room temperature curing type,
It is classified into heat curing type, ultraviolet ray curing type, or electron beam curing type, and curing agents and curing accelerators that are generally well known to those skilled in the art, such as metal carboxylates such as zinc, lead, cobalt, and iron, dibutyltin octoate, Organotin compounds such as dibutyltin walate, titanium chelate compounds such as tetrapropyl titanate and tetraoctyl titanate, tertiary amines such as N-N-trimethylaniline and triethanolamine,
Or peroxides such as penzoyl oxide, dicumyl peroxide, t-butyl oxide,
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 have a silicone polymer material as a matrix, and therein, 30 to 30% of the matrix weight is
300%, preferably 100-250% of other fillers,
For example, it may be a mixture of a silica filler, a titanium-based potassium 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, Merck, glass fiber powder, rock wool fine fibers, silica powder, and clay. However, if you want the resulting sheet to have surface smoothness, use a general VC50 so as not to impair the surface smoothness of the sheet.
It is preferable to use a powder in the form of a micrometer or less.

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 flame retardant properties.

100 parts by weight of silicone resin (hereinafter, parts by weight are abbreviated as parts).

), the amount of alkali titanate added is 1 to 20
0 parts, preferably 30 to 100 parts, and if a high refractive index inorganic compound and/or an endothermic inorganic compound are added to these, the amount is up to 400 parts, and 1/1 part from the same weight.
Although it can be blended in place of an alkali titanate equivalent to up to 4 parts by weight, a range of 10 to 300 parts is usually preferred.

Note that part or all of these high refractive index inorganic compounds and endothermic inorganic compounds can be replaced with commonly used inorganic pigments, inorganic extender fillers, inorganic powders that impart flame retardancy, etc. The amount used is preferably 400 parts or less, more preferably 300 parts or less, per 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 halodane compound type, and phosphazene compound type, calcined gypsum, alum, calcium carbonate, and hydroxide. There are endothermic decomposition type inorganic compounds made of inorganic compounds such as aluminum, hydrotalcite-based aluminum silicate, crystal water quantity type, carbon dioxide gas releasing type, dispersed endothermic type, and phase change type, and inorganic flame retardants such as antimony compounds. .

There are no particular limitations on the weight or thickness of the silicone polymer layer, but generally the N amount is 10-100777 m on one side, preferably 50-70097 m, and 10-500 m on one side.
Preferably, it is formed with a thickness of microns.

In the sheet material of the present invention, a corona discharge modified layer obtained by corona discharge treatment is formed on the surface of the silicone polymer layer. In this corona discharge treatment, a high voltage is applied between a roller that supports the sheet material to be treated and an electrode placed opposite it to generate a corona discharge, during which time the surface of the sheet material is sequentially treated while moving. It's something to do.

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 21 and 22 each have one metal electrode core 23.
24 and a non-electrically conductive resin layer 25 and 26 that completely covers it.
(for example, a rubber layer). The electrode core 23 of one roll-shaped discharge electrode is connected to a high-voltage power source 27, and the electrode core 24 of the other roll-shaped electrode is connected to ground 28. The sheet material 20 to be processed, fed through the guide roll 29, is moved between the electrodes at a constant speed (for example, 2 to 1 ion/min) with its back surface 30 in contact with the surface of the rolled electrode 22 connected to the ground. ) to migrate. At this time, when applying 200V to 200V, corona discharge of 10 to 60A occurs, and this corona discharge causes the sheet material to
0 surface 31 undergoes treatment.

The distance A between both electrode surfaces is less than 30 m, generally 5 to 20 m.
It is. The corona discharge treated sheet material 20 is passed through an idle roll 32 and wound up to form a roll 33. ``For the corona discharge treatment, a 14-square gap method, a vacuum tube method, a solid state method, etc. can be used. In order to improve the adhesion of the treated sheet material, its critical surface tension should be 35~60.

dyn/cm, and for this purpose, the surface of the sheet material is preferably 5 to 50 dyn/cm. OOOW/m/min,
Preferably, it is preferable to apply processing energy of about 150 to 40,000 base 47 minutes. The amount of energy to be applied (voltage, current amount, distance between electrodes, etc.) is determined in consideration of the width of the sheet material, the speed of the wire, etc. For example, for a sheet material surface with a width of 2 m, it is preferable that the corona radiation output at a speed of 10 m/min is approximately kW to 800 kW. However, it is not necessarily limited to this condition.

The corona discharge device used in the method of the invention may be of the usual metal electrode type.

A highly adhesive corona discharge modified layer is formed on the surface of the silicone polymer layer which has been subjected to the corona discharge treatment as described above. This corona discharge modified layer is strongly bonded to the unmodified portion of the silicone polymer layer and significantly improves its adhesion.

Next, the silicone 1 combined layer and the stain-proof/weather-resistant coating layer are
Bonded with or without adhesive via a corona discharge modified layer.

Examples of useful adhesives include melamine adhesives, phenolic 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 adhesives, vinyl acetate-ethylene adhesives, etc., and in particular epoxy adhesives, polyethyleneimine 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 resin forming the groove bottom of the fluorine-containing 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 a part thereof. There are various polyfluorochloroethylenes containing chlorine, such as polytrifluorochloroethylene, but also polyvinyl fluoride, polyvinylidene fluoride, polydichlorodifluoroethylene,
Others are also included. All of these fluorine-containing resins have high melting points, so normal calendar processing cannot be performed, 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 0.01 to 0.5 m, preferably 5 to 50 m.
The thickness is about microns, but there are no particular limitations as long as the book achieves the objectives of weather resistance, antifouling properties, and durability, and can be made thicker or thinner. Further, the fluorine-containing resin film may be mixed with other resins such as Onibutsu or the like, as long as the object of the present invention is achieved. Commercially available fluorine-containing resin films used in the present invention include Tetra Film (Dupont Trademark) and Afflex Film (Asahi Glass Trademark).

The method may be based on the die method, the inflation method, or any other method. Also, it may be stretched or unstretched, but
The elongation is preferably about 100 to 300%. Also,
As mentioned above, the thickness & main is usually about 5μ to 50μ,
It may be made somewhat thicker or thinner as long as sufficient weather resistance and antifouling properties are achieved. The film material is a polyalkyl methacrylate film, such as a film mainly made of methyl methacrylate, ethyl methacrylate, globil methacrylate, butyl methacrylate, etc., or acrylate, divinyl acetate, vinyl chloride, styrene, acrylonitrile, methacrylonitrile, etc. It is preferable to use a homopolymer or copolymer as a homomonomer or comonomer component molded 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 adhesive surface thereof is subjected to low-temperature glazma 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 corona discharge modified layer formed on the silicone polymer layer using an adhesive.

However, as another method for forming an antifouling/weather-resistant coating layer, a solution or emulsion of the above resin is applied to the surface of the corona discharge modified layer or the adhesive layer coated thereon, and then dried and solidified. There is a way to do it.

The film used for forming the antifouling/weather resistant coating layer preferably has a tensile strength of 100 kg/7 m or more. In addition, the antifouling/weatherproof coating layer is 1 to 50 g/m,
Preferably 3-30. ! NfI′ of iI/n1, or
Preferably, the thickness is 5 microns or more (usually 10 to 50 microns), more preferably 30 to 15 microns.

It may be made of a laminate of a rill resin layer and a polyvinyl chloride resin layer. In these laminates, Ron and
The thickness of the polyvinyl chloride resin layer is preferably 40 to 45 microns, but is not limited to these values.

The antifouling sheet material of the present invention may include a wire or a base fabric made of a male fabric as a base.

Fibrous base fabrics useful in the present invention include natural fibers such as cotton, linen, inorganic fibers such as glass fiber, carbon fiber,
asbestos fibers, metal fibers, recycled fibers such as viscose rayon, cupro, etc., semi-synthetic fibers such as g- and tri-acetate fibers, and synthetic fibers such as nylon 6, nylon 66, polyester (
It consists of at least L types selected from polyethylene terephthalate, etc.) fibers, aromatic polyamide fibers, acrylic m fibers, polyvinyl chloride fibers, polyolefin fibers, and 4-lipinyl alcohol fibers made insoluble or hardly soluble in water. . 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. Generally, the fibers used in the antifouling sheet material of the present invention are preferably polyester fibers and glass fibers.
In consideration of low elongation against stress, the fibers are preferably in the form of long fibers (filaments) and preferably form a plain woven fabric. 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 additives and mourning, add organic solvents such as toluene, xylene, trichlene, etc. as needed to make a dispersion with an appropriate concentration. By applying it to one or both sides of the base fabric by a conventionally well-known coating method such as a coating method or a knife coating method, and heat-treating it at room temperature or under heating, preferably within the range of 150 to 200°C for 1 to 30 minutes. The silicone resin is cured and integrally adhered to the aforementioned base material. Silicone resin and titanate Al-b II to I-fx comparison This canned candle is made from silicone resin and alkaline titanate. It depends on the particle size, but in general, if there is too little silicone resin,
As a result of the insufficient strength of the silicone polymer layer, when used as a fireproof heat insulating sheet, there are drawbacks such as cracking in the silicone polymer layer or peeling of the silicone polymer layer from the base fabric.

〔Example〕

The present invention will be described in more detail in Example V below.

Example 1 and Comparative Example 1 A bleached cotton fabric with the following structure was used as the base fabric.

ft 200/l/m2 As a silicone finishing agent, a mixture of 10 parts by weight of RTV silicone rubber (manufactured by Toshiba Silicone Corporation) and 1 part by weight of a crosslinking agent was coated on the surface of the base fabric using a knife coater. , j77 m2. 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 pacecoat layer is then peeled off from the heating cylinder, and then a top coat of the same silicone finishing agent is applied at a coating amount of about 1097 m2 to condition the surface, and finally, Heat treated at 180°C to form an intermediate sheet (
Sample 1)' was obtained.

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 m7 such that the surface of the base fabric of the intermediate sheet was in contact with the circumferential surface of the rolled electrode connected to ground. The distance A between both electrodes is 1 on the silicone polymer layer surface of this intermediate sheet.
0m, voltage 160♂lt, current 18 ampere maximum output 8
Corona discharge treatment was performed continuously at kW (power consumption cuff, 9 kW/hr).

At this time, the diameter of the metal electrode cores of both electrodes was 20 m.

The thickness of the resin layer is 2 wm (roll diameter 20.4 am)
, the roll length was 2 m, and the length during discharge was 1.92 m. At this time, the nuclear energy radiated to the sample surface is approximately 440W/m
It was 7 minutes.

A corona discharge treated sheet (sample 2) was obtained.

In Example 1, a polyacrylic resin adhesive (manufactured by Sony Chemical Co., Ltd., 5C-4) was applied to the surface of the corona discharge modified layer of Sample 2.
62) 20 using iloo mesh gravure roll
It was coated in an amount of 9/rn and dried at room temperature. next,
7. on the surface of the adhesive layer. A vinylidene chloride resin film (thickness: 3 μff1) was heat-pressed.

In Comparative Example 1, the same antifouling and weather-resistant coating layer formation operation as in Example 1 was directly performed on the surface of the silicone polymer of Sample 1 without corona discharge 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. Similar operation is performed in Comparative Example 2
In this case, the same operation as in Comparative Example 1 is performed. however,
An acrylic resin film with a thickness of 30 μm was adhered using a polyurethane adhesive to form an antifouling and weather-resistant 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, and in Comparative Example 3, the same operations as in Comparative Example 1 were carried out. However, in order to form an antifouling and weather-resistant coating layer, KFC film (manufactured by Gugen Kagaku Co., Ltd.), a vinylidene resin layer (2 μm thick), an acrylic resin layer (2 to 4 μm), and a polyvinyl chloride J resin layer are used. (45 μm) was used).

The results are shown in Table 1.

All white below *: The adhesive film was broken without peeling.

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 layered paper was peeled off to form a film of silicone polymer. A combined sheet material was created.

The obtained silicone polymer sheet material y#+ is designated as Sample 3. One side of this sample 30 was subjected to corona discharge treatment in the same manner as described in Example 1.

The obtained corona discharge 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 corona discharge-treated silicone polymer sheet (Sample 4): Niboran 3022 (manufactured by Nippon Urethane Co., Ltd., solid content 35%)
100 parts by weight of Coronate-1-L (manufactured by Nippon Urethane Co., Ltd., 915 parts by weight, 259 hours with a 60-mesh gravure plate)
It was applied with a base and dried.

A portion of the same KF'C 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.

*: The adhesive film was broken without being peeled off.

Example 5 An intermediate sheet material having the same corona discharge modified layer as Sample 2 was prepared by performing the same operation as in Example 1, and a polyvinylidene fluoride resin film was applied to each of both surfaces of this intermediate sheet material. (thickness = 1.5 μm) was brought into contact with one surface treated with corona discharge, and this contact surface was heated to 1180° C. to melt and adhere the polyvinylidene fluoride resin film to the corona discharge modified layer.

In the obtained antifouling sheet material, the polyvinylidene fluoride resin layer was firmly adhered to the silicone polymer layer and could not be peeled off in a peel test, and also exhibited excellent antifouling and weather resistance.

〔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 for building materials and interior materials of gymnasiums, warehouses, markets, playgrounds, factories, parking lots, various accommodation facilities, etc. where fire is expected, traps, tents, awnings, blinds, or repeated washing. It is useful as a material for sheet materials that require high-quality materials, such as hospital sheets, bed sheets, and room partitions.

[Brief explanation of drawings]

@ Figures 1 and 2 are cross-sectional explanatory views showing the structure of one embodiment of the antifouling sheet material of the present invention, and Figure 3 is a cross-sectional view showing the structure of an embodiment of the antifouling sheet material of the present invention. FIG. 2 is an explanatory diagram of an example of a corona discharge treatment apparatus used for this purpose. l, 11...Sheet material, 2m, 2b...Silicone polymer layer, 3m, 3b...Corona discharge modified layer, 4&
#4b...adhesive layer, 5m, 5b...antifouling/weatherproof coating layer, 6...base fabric, 20...sheet material to be treated,
21.22... Emission electrode, 23.24-11 pole core, 2
5.26... Resin layer, 29, 32... Guide roll, 31... Treated surface of sheet material.

Claims (1)

[Claims] 1. 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 formed from a thermoplastic synthetic resin material with excellent stain/weather resistance; A corona discharge modified layer obtained by subjecting the layer to corona discharge treatment is formed on the surface of the layer, and the silicone polymer layer and the antifouling/weather resistant coating layer are adhered via the corona discharge modified layer. A stain-resistant sheet material characterized by: 2. The corona discharge modified layer and the antifouling/weather-resistant coating layer are bonded together with an adhesive. Claim 1
Sheet materials listed in section. 3. The adhesive is selected from acrylic adhesives, epoxy adhesives, polyethyleneimine adhesives, polyisocyanate adhesives, and polyurethane adhesives,
A sheet material according to claim 2. 4. The sheet material according to claim 1, wherein the antifouling/weather-resistant synthetic resin material is made of at least one selected from fluorine-containing resins and acrylic resins. 5. The sheet material according to claim 1, wherein the antifouling/weather-resistant coating layer is formed of a laminate consisting of a polyvinylidene fluoride resin layer and a polyacrylic resin layer. 6. Claim 1, wherein the stain-proof and 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.
Sheet materials listed in section. 7. A base fabric made of fibrous 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 and weather resistance, the silicone polymer layer; A corona discharge modified layer obtained by subjecting the surface of the silicone polymer layer to corona discharge treatment is formed between the antifouling/weather resistant coating layer, and the silicone polymer layer and the anti-fouling layer A stain-resistant sheet material characterized in that a stain- and weather-resistant coating layer is bonded to the stain-resistant and weather-resistant coating layer via the corona discharge modified layer. 8. Claim 7, wherein the corona discharge modified layer and the antifouling/weather-resistant coating layer are bonded together with an adhesive.
Sheet materials listed in section. 9. The adhesive is selected from acrylic adhesives, epoxy adhesives, polyethyleneimine adhesives, polyisocyanate adhesives, and polyurethane adhesives,
A sheet material according to claim 8. 10. 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. 11. The sheet material according to claim 7, wherein the antifouling/weather-resistant synthetic resin material is made of at least one selected from fluorine-containing 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 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, according to claim 7. sheet material.