JP3031616B2 - Waterproof sheet that can be heat-sealed - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof sheet which can be sewn by heat-sealing, and more particularly to a waterproof sheet which is excellent in antifouling property and weather resistance and can be sewn by high-frequency heat-sealing. About. 2. Description of the Related Art Conventionally, for example, a flexible sheet having a soft vinyl chloride (PVC) resin layer on one or both sides of a fibrous base fabric has been used for a large tent such as an air dome.
Such sheets have the inherent advantages of PVC in terms of processability, economy, flame resistance, etc., while such tents are exposed outdoors for long periods of time, Even if sufficient examination was made, etc., the resin gradually decomposed over the years, and the plasticizer migrated to the surface and gradually became sticky, and dust etc. adhered to the surface It had serious drawbacks such as contamination. As a countermeasure, an acrylic resin film layer is formed on the upper surface of the PVC layer to cover the drawbacks of the conventional laminate having only the PVC layer and to obtain a predetermined effect. However, depending on the use condition of the laminated product, cracks may occur in the acrylic resin film layer under conditions such as strong rubbing, which may result in significantly shortening the useful life of the laminated product, and this measure is sufficient. Has not been reached. [0004] Thus, the surface of such a laminated sheet is constituted by adhering a film composed of vinylidene fluoride resin / acrylic resin / PVC resin, and the vinylidene fluoride resin layer is used as the outer surface. A method for improving weather resistance and stain resistance has been found. When such a waterproof sheet is used by sewing with a sewing machine, water leaks from the stitches, and the sewing of the sewing machine is often inefficient because of the poor work efficiency. However, even if an attempt is made to join the laminated sheet having the vinylidene fluoride resin layer as an outer surface by using heat fusion sewing, the vinylidene fluoride resin layer is opposed to another resin layer,
For example, it does not adhere to the PVC layer, so this sheet is also in need of further improvement. SUMMARY OF THE INVENTION The present invention has excellent antifouling properties and weather resistance, and can perform heat fusion sewing, particularly high frequency heat fusion sewing, and has high durability. An object is to provide an extremely useful waterproof sheet having antifouling properties. SUMMARY OF THE INVENTION A heat-seamable and sewable waterproof sheet according to the present invention is formed on a fibrous base cloth and on the surface or both sides thereof, and is made of natural rubber, synthetic rubber or synthetic rubber. A waterproof sheet substrate having a waterproof layer made of resin, and formed on the outermost layer on the upper surface of the waterproof sheet substrate, and
A vinylidene fluoride resin layer having a thickness of 0.3 to 10 μm, and an acrylic resin layer formed by coating on the entire outermost layer on the lower surface of the waterproof sheet substrate, and having a thickness of 0.5 to 30 μm. It is characterized by the following. An example of the waterproof sheet of the present invention will be described with reference to FIG. In the embodiment of the waterproof sheet of the present invention shown in FIG. 1, waterproof layers 2 and 2 ′ made of natural rubber, synthetic rubber or synthetic resin are formed on the front and back surfaces of the fibrous base fabric 1, and the waterproof sheet base 1 a is thereby formed. Be composed.
On the outermost layer on the upper surface side of the waterproof layer 2, a vinylidene fluoride resin layer 3 is formed. If necessary, these waterproof layers 2
A polyurethane resin layer or a cyanoethylated ethylene-vinyl alcohol copolymer layer may be formed between and the vinylidene fluoride resin layer 3 and these layers. On the other hand, an acrylic resin layer 4 is formed on the lowermost outermost layer on the side of the waterproof layer 2 'so as to be continuous with the waterproof layer 2' and form the entire outermost layer.
Is formed by application. In another embodiment of the waterproof sheet of the present invention,
The waterproof layer 2 as described above may be formed of a polyurethane resin or a cyanoethylated ethylene-vinyl alcohol copolymer, and the waterproof layer 2 'is formed of an acrylic resin, a polyurethane resin, or a cyanoethylated ethylene-vinyl alcohol copolymer. May be. In addition, the waterproof layer 2
And a polyurethane resin layer or cyanoethylated ethylene-
Any other layer can be formed between the vinyl alcohol copolymer layer and the waterproof layer 2 ′ and the acrylic resin layer 4.
Any other layer can be formed between the first and second layers. Also,
The waterproof layer 2 'may be omitted, or the waterproof layer 2' may be omitted and another arbitrary layer may be formed instead. That is, the essential requirements of the waterproof sheet of the present invention are to have a fibrous base cloth in the inner layer, to have a waterproof layer, and to form a 0.3 to 10 μm thick fluoride on the outermost layer on the upper surface. The vinylidene resin layer is formed, and the entire outermost layer on the lower surface is formed of an acrylic resin layer formed by coating and having a thickness of 0.5 to 30 μm. Hereinafter, the present invention will be described more specifically. Fibrous base fabric used for the waterproof sheet of the present invention,
Natural fibers, for example, cotton, hemp, etc., inorganic fibers, for example,
Recycled fiber, such as glass fiber, carbon fiber, metal fiber,
For example, semi-synthetic fibers such as viscose rayon and cupra, for example, di- and tri-acetate fibers, and synthetic fibers, for example, polyamide (nylon 6, nylon 66, etc.) fibers, polyester (polyethylene terephthalate, etc.) fibers, aromatic It is composed of at least one member selected from group A polyamide fibers, acrylic fibers, polyvinyl chloride fibers, polyolefin fibers and the like. The fibers in the base fabric may be in any shape such as a spun short fiber yarn, a long fiber yarn, a split yarn, a tape yarn, and the base fabric may be a woven fabric, a knitted fabric, a nonwoven fabric, or a composite thereof. Any of cloths may be used. In general, the fibers used in the waterproof sheet of the present invention are preferably polyester fibers, and the fibers are preferably in the form of long fibers (filaments), and preferably form a plain woven fabric. In addition, a woven fabric formed by overlapping warp yarns and weft yarns arranged in parallel so as to intersect with each other and pressing them with twine yarns is particularly preferable. The fibrous base fabric is useful for maintaining the mechanical strength of the obtained waterproof sheet at a high level. In the present invention, a waterproof sheet is formed by forming a waterproof layer on the surface or both sides of the fibrous base fabric. The waterproof layer may be made of natural rubber, neoprene rubber, chloroprene rubber, silicone, or the like. Rubber, Hypalon or other synthetic rubber, or PVC resin, ethylene-vinyl acetate copolymer (EVA) resin, acrylic resin (formed immediately below the vinylidene fluoride resin layer, which is the outermost layer on the top surface, and forms a waterproof layer ), Silicone resin, urethane resin, polyethylene (PE) resin, polypropylene (PP) resin, polyester resin, fluorine resin and other synthetic resins. The waterproof layer made of such a material has a thickness sufficient to give desired waterproofness and flame retardancy and mechanical strength to the obtained waterproof sheet, for example, 0.05 mm or more, preferably 0.05 to
It has a thickness of 2.0 mm. These waterproof layers are formed by using a rubber or resin film, solution, paste or straight as described above by a known method such as topping, calendering, coating and dipping.
It can be formed on a fibrous base fabric. These rubbers or resins may contain plasticizers, stabilizers, colorants, ultraviolet absorbers, and other function-imparting agents. On the upper surface of the waterproof sheet according to the present invention, a vinylidene fluoride resin layer is formed as an outermost layer. Examples of the vinylidene fluoride resin include a vinylidene fluoride homopolymer and 70 mol% or more of vinylidene fluoride, and a monomer copolymerizable therewith, for example, ethylene tetrafluoride, ethylene trifluoride, or fluorine fluoride. Copolymers obtained by copolymerizing one or more monomers selected from vinyl chloride, ethylene trifluoride chloride, fluorochlorovinylidene, hexafluorovinylidene and the like are used. In some cases, the mixture may be a mixture obtained by adding another resin having good compatibility with these homopolymers or copolymers. Examples of the resin having good compatibility with such a vinylidene fluoride resin include, for example, a polymer or a copolymer mainly composed of methyl methacrylate or methyl acrylate, a polyurethane resin or a cyanoethylated ethylene-vinyl alcohol copolymer. is there. However, the content of these other resin components is preferably within 30 PHR of the constituent resin. If necessary, the vinylidene fluoride resin layer may contain processing aids such as stabilizers and lubricants and UVA. In particular, the addition of UVA, if necessary,
It is preferable from the viewpoint of preventing photodeterioration of these resins in the vicinity of a bonding surface with a polyurethane resin layer or a cyanoethylated ethylene-vinyl alcohol copolymer layer formed thereunder as the case may be. However, the amount of UVA that is compatible with the vinylidene fluoride resin in the homogeneous phase is not very large, and is generally 3% or less. Further, since the vinylidene fluoride resin layer is generally extremely thin, it is hardly expected that the UVA of this layer alone protects the waterproof layer completely. The vinylidene fluoride resin layer protects only the surface layer of the sheet, has a thickness of 0.3 to 10 μm, and preferably has a thickness of 1 to 5 μm. In the present invention, it is preferable to form an acrylic resin layer, a polyurethane resin layer or a cyanoethylated ethylene-vinyl alcohol copolymer layer immediately below the uppermost outermost vinylidene fluoride resin layer, and the thickness of these layers is The thickness is preferably 0.5 to 30 μm, more preferably 2 to 20 μm, and is generally larger than the thickness of the vinylidene fluoride resin layer. The acrylic resin constituting the acrylic resin layer useful in the present invention is mainly composed of a polymer or a copolymer mainly composed of an ester of C ₁ -C ₄ alcohol of acrylic acid or methacrylic acid. Resins are preferred. The main constituent monomer of such an acrylate-based resin is, specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate and butyl methacrylate, especially methyl acrylate and methyl Methacrylate is preferred. Examples of monomers to be copolymerized with these main constituent monomers include, for example, esters of C _{1 to} C ₁₂ alcohols of acrylic acid or methacrylic acid, vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, vinyl acetate, and styrene. , Acrylonitrile, methacrylonitrile, butadiene and the like. These copolymers are not limited to random copolymers, but may be graft copolymers. For example, a polymer obtained by adding vinylidene fluoride to a methyl methacrylate polymer and then graft-polymerizing the same can be used. In addition, an acrylate containing an amino group, an imino group, an ethyleneimine residue, or an alkylenediamine residue can be used, but particularly preferable results are obtained when an acrylate containing an aziridinyl group is used. The acrylic resin layer may contain a small amount of another resin having good compatibility with the acrylic resin. In particular, PVC resin, polyurethane resin and vinylidene fluoride resin are all useful because they have good compatibility with acrylic resin. The same can be said for the cyanoethylated ethylene-vinyl alcohol copolymer. In addition, an ultraviolet absorber (UVA) may be added to these resin layers in order to provide durable weather resistance. It is preferable that the blending amount of UVA is determined so as to block incident ultraviolet rays by about 50% or more. The amount of this ultraviolet ray blocking is determined by the concentration of UVA in these resin layers containing UVA and the thickness of this layer.
If the concentration is too low, it is necessary to increase the thickness of these resin layers and thus the UVA of these resin layers
The concentration is preferably at least 0.3%, more preferably 1.0%.
Should be at least%. However, UVA in this resin layer
If the concentration is too high, bleeding occurs at the interface with the vinylidene fluoride resin layer that constitutes the outermost layer on the upper surface, which may undesirably lower the adhesive strength with this layer. Of course, U
The compatibility of these resins and vinylidene fluoride resin differs depending on the type of VA, so the upper limit of the concentration is different. However, even a benzotriazole-based UVA having a relatively high affinity for vinylidene fluoride resin is 30 PHR.
If it exceeds 300, it is easy to peel off at the interface between both layers.
It is preferable to keep it at about 0 PHR or less. As UVA, not only benzotriazole-based UVA, but also benzophenone-based, salicylic-ester-based UVA, or those obtained by copolymerizing these with other resins can be used, and there is no particular limitation. . In producing the waterproof sheet of the present invention, for example, a sheet having a waterproof layer formed on the surface or both sides of a fibrous base fabric is first produced, and then a polyurethane resin or a cyanoethylated ethylene-vinyl alcohol copolymer is produced. May be applied or not, and a vinylidene fluoride resin may be applied and formed. Alternatively, a vinylidene fluoride resin / polyurethane resin or a cyanoethylated ethylene-vinyl alcohol copolymer separately produced on the surface thereof may be used. A laminated film may be attached. When the thickness of the laminated film of vinylidene fluoride resin / polyurethane resin is small and a problem occurs in workability, a water-resistant substrate such as a PVC film having a thickness of 30 to 50 μm is preferably used as a support. It is also possible to prepare a laminated film composed of vinylidene fluoride resin / polyurethane resin or cyanoethylated ethylene-vinyl alcohol copolymer / PVC resin and adhere this to the sheet. Although the production of such a laminated film is not particularly limited, the resin of each layer is subjected to composite flow from a composite T die or a composite cylindrical die, and a flat sheet or a cylinder is co-extruded and drawn by an ordinary method. It is preferable that the heat treatment be carried out by a heat treatment if necessary, from the viewpoint of the interlayer adhesion and productivity. In the waterproof sheet of the present invention, the acrylic resin layer constituting the lowermost outermost layer has a thickness of 0.5 to 30 μm, preferably 2 to 20 μm, as described above. The selection can be made in the same manner as described above. In this case, the lower surface is less likely to be exposed to direct sunlight, so there is no need to mix the UVA so much and the mixing can be omitted. This layer is formed by coating. Further, other copolymers and other processing agents can be added to this layer as long as the adhesion is not impaired. For the purpose of promoting adhesion to the waterproof layer, for example, when a PVC waterproof layer is formed, measures such as mixing PVC into this layer can be taken. 0.5 ~
The acrylic resin layer having a thickness of 30 μm is formed by coating as described in Examples below. The polyurethane resin used in the present invention can be freely selected with respect to its use form, and includes a plasticizer, a stabilizer,
A coloring agent, a lubricant and other various additives can be freely added within a known range. Hereinafter, an example of a polyurethane resin, particularly a thermoplastic polyurethane elastomer resin, useful in the present invention will be described. As the polyurethane elastomer, those obtained by reacting an organic polyisocyanate with a polymer polyol and, if necessary, a chain extender are used. As organic polyisocyanates, aliphatic, alicyclic or aromatic polyisocyanates, for example, hexamethylene diisocyanate, lysine diisocyanate, cyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenyl methane Diisocyanate (MDI), biphenylene diisocyanate,
And naphthylene diisocyanate. Among them, MDI or an organic diisocyanate mainly containing MDI is preferable. Examples of the high molecular polyol include polyether polyol, polyester polyol, polyether ester polyol, polymer polyol,
Mixtures of more than one species can be mentioned. Examples of polyether polyols include alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.),
Those obtained by polymerizing or copolymerizing (block or random) a heterocyclic ether (such as tetrahydrofuran), for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene (block or random) glycol, polytetramethylene ether glycol, polyhexa Examples include methylene ether glycol, polyoctamethylene ether glycol and mixtures of two or more thereof. As polyester polyols, dicarboxylic acids (adipic acid, succinic acid,
Sebacic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, etc.) and glycols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octamethylenediol, neopentyl glycol) , Bishydroxymethylcyclohexane, bishydroxyethylbenzene, alkyl dialkanolamine, etc.), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate: polylactone diol such as poly Caprolactone diol: and mixtures of two or more thereof. Examples of the polyetherester polyol include ether group-containing diols (the above-mentioned polyether diols, diethylene glycol, triethylene glycol, dipropylene glycol and the like) or a mixture thereof with the above-mentioned dicarboxylic acid or dicarboxylic anhydride (phthalic anhydride). Acid, maleic anhydride, etc.)
And those obtained by reacting with an alkylene oxide, for example, poly (polytetramethylene ether) adipate. As the polymer polyol, an ethylenically unsaturated monomer (such as the above-mentioned polyether polyol, polyester polyol and / or polyether ester polyol) or a mixture thereof with a medium to low molecular weight diol may be used. Acrylonitrile, styrene, etc.).
Average molecular weight of polymer polyol (by hydroxyl value titration)
Is usually 500 to 5000, preferably 700 to 400
0, particularly preferably 2000-3500. As the chain extender, a low molecular polyol having a molecular weight of less than 500, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-
Hexanediol, diethylene glycol, triethylene glycol, thiodiglycol (such as thiodiethanol); polyamines, for example, aliphatic diamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, piperazine, 1,4-diaminopiperazine, 1, Alicyclic polyamines such as 3-cyclohexylenediamine and dicyclohexylmethanediamine; aromatic polyamines such as diphenylmethanediamine, tolylenediamine and phenylenediamine; aromatic-aliphatic polyamines such as xylylenediamine; hydrazine and monoalkylhydrazine; For example, ethanolamine, propanolamine; and a mixture of two or more thereof. Of these, low molecular diols (especially ethylene glycol) are preferred. However, the present invention is not limited to the above examples, and any other thermoplastic polyurethane resin can be used. Further, the thermoplastic polyurethane resin is not limited to an ester type, an ether type or the like and is melted by heat, Any material that can be contacted (welded) can be used. The waterproof sheet thus obtained has excellent antifouling properties and weather resistance, and can be subjected to heat fusion sewing. That is, the two waterproof sheets are overlapped, and the outermost layers of the specified combination of the uppermost outermost vinylidene fluoride resin layer and the lowermost outermost acrylic resin layer are brought into contact with each other, and subjected to ultrasonic heating and high frequency heating. Alternatively, fusion bonding can be performed by hot air. If a fluororesin is used for the front surface and a resin other than the fluororesin is used for the back surface as in a conventional waterproof sheet, these are hardly fused and bonded, and a vinylidene fluoride resin layer is used for the upper surface. However, when the acrylic resin layer was not formed on the lower surface, no fusion bonding was performed, and even if the overheating and high-pressure bonding was forcibly attempted, the adhesive force was extremely small, at most 0 to 3 kg / 3 cm. However, in the case of the present invention, by specifying the combination of the uppermost outermost layer vinylidene fluoride resin and the lowermost outermost layer acrylic resin, the adhesive strength is 6 to 10 kg / 3 cm, which is about 5 kg which is required for practical use. / 3 cm. Further, by specifying this combination, high-frequency heat fusion sewing can be performed. In such a heat-sealing sewing, it is conceivable to sandwich a film made of a resin which gives a preferable adhesive force between two sheets and to perform a fusion-bonding according to a specific combination of the present invention. Has poor adhesion to the waterproof sheet, so that the adhesive strength is about 3 to 4 kg / 3 cm, and there is a difficulty in positioning necessary parts in the fusion work, which is not preferable in work. It is also conceivable to partially form these resin layers on the lower surface in place of the continuous layer as the outermost layer on the lower surface. In this case, however, work such as applying these resin layers during sewing is troublesome, and workability is reduced. Lower
Harm the working environment. Therefore, if the specific resin layer of the present invention is formed as a continuous layer from the beginning as a continuous layer on the entire lowermost outermost layer as in the waterproof sheet of the present invention, the manufacture of the waterproof sheet itself can be performed at low cost and easily. This has the advantage that it can be performed at any part that requires heat fusion sewing. The present invention will be further described with reference to the following examples. Example 1 A vinylon fiber canvas having the following structure, density (20/3 × 20/4) / (45 × 38) basis weight 360 g / m ² was used as a base cloth, which was blanched and dried. Next, a waterproofing layer of Hypalon resin, a waterproofing layer of silicone resin, a waterproofing layer of EVA resin, or a waterproofing layer of acrylic resin is formed on the base cloth to prepare a waterproofing sheet substrate. Vinylidene fluoride resin (4 μm) using acrylic resin adhesive SC462
/ A film comprising a cyanoethylated ethylene-vinyl alcohol copolymer (10 μm) was stuck so that the cyanoethylated ethylene-vinyl alcohol copolymer faced the waterproof layer (I). Similarly, a film made of vinylidene fluoride resin (4 μm) / polyurethane resin (10 μm) was stuck on the upper surface of the waterproof sheet substrate such that the polyurethane resin surface faces the waterproof layer (II). Also, an acrylic resin adhesive SC4 is attached to the lower surface of the waterproof sheet base.
62 to a thickness of 5 μm to form a lowermost outermost layer,
A waterproof sheet (Group A) according to the present invention was prepared. For comparison, a sheet was prepared in which the acrylic resin adhesive was not applied to the lower surface of the waterproof sheet base, and the sheet was used as a comparative sheet (Group B). For each of these sample sheets,
As described in the above text, the ends 3 cm were overlapped, and high-frequency treatment was performed on the overlapped portions by a high-frequency oscillator having an output of 2 kW and a frequency of 40.68 MHz for 3 seconds. As a result, the peel strength (kg / 3 cm) was as follows. Surface Configuration on Waterproof Layer A Group B Group Hypalon Resin I 8.0 0.3 II 8.4 0.3 Silicone Resin I 6.50 II 6.8 0.1 EVA Resin I 8.1 9 II 8.2 0.8 Acrylic resin I 9.0 8.9 II 9.0 9.2 Among the sheets of the group B, the sheet whose waterproof layer is made of an acrylic resin is an example of the present invention. As can be seen from the above, since the upper surface of the waterproof sheet according to the present invention has the outermost layer of the upper surface of vinylidene fluoride resin, it has excellent antifouling property, weather resistance and durability. On the other hand, since the lowermost outermost layer has an acrylic resin layer on the entire surface, the combination of the uppermost outermost layer vinylidene fluoride resin layer and the lowermost outermost layer acrylic resin layer makes simple and inexpensive heat fusion sewing, particularly As a sheet that can be sewn by high-frequency heat fusion, its industrial value is extremely large.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing one example of a waterproof sheet of the present invention. DESCRIPTION OF SYMBOLS 1: Fibrous base cloth 1a: Waterproof sheet substrate 2, 2 ': Waterproof layer 3: Vinylidene fluoride resin layer 4: Acrylic resin layer

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (1)

(57) [Claims] 1. Fibrous base fabric, formed on its surface or both front and back,
And a waterproof layer made of natural rubber, synthetic rubber or synthetic resin
And a waterproof sheet base having
Formed on the outermost layer on the upper surface of the body, and 0.3 to 10 μm
Vinylidene fluoride resin layer having a thickness of, and the waterproof
Formed by coating on the entire outermost layer on the lower surface of the sheet substrate
And an acrylic tree having a thickness of 0.5 to 30 μm
A heat-seamable sewable waterproof fabric characterized by having a fat layer
To 2. On the upper surface, a waterproof layer and vinylidene fluoride resin
A polyurethane resin layer or cyanoethylated ethyl
A ren-vinyl alcohol copolymer layer is formed,
The waterproof sheet according to claim 1. 3. On the lower surface, between the waterproof layer and the acrylic resin layer
An acrylic resin layer, a polyurethane resin layer or cyano
A chilled ethylene-vinyl alcohol copolymer layer was formed.
The waterproof sheet according to claim 1, wherein the waterproof sheet is provided. 4. The acrylic resin layer forms the waterproof layer,
The waterproof sheet according to claim 1. 5. The waterproof layer has a thickness of 0.05 to 2.0 mm,
The waterproof sheet according to claim 1. 6. The acrylic resin layer is made of acrylic acid or methacrylic acid.
Luic acid C ₁ ~ C_Four Alcohol esters mainly composed of monomers
Polymer or copolymer-based resin
The waterproof sheet according to any one of claims 1 to 5, wherein the waterproof sheet comprises: 7. The acrylic resin is acrylic acid or methacrylic
Acid C₁~ C_Four If esters of alcohol and acrylic acid
Or C of methacrylic acid₁ ~ C₁₂Esters of alcohol,
Vinyl fluoride, vinylidene fluoride, vinyl chloride, vinyl chloride
Nilidene, vinyl acetate, styrene, acrylonitrile,
Copolymer with methacrylonitrile or butadiene
The waterproof sheet according to claim 6, wherein 8. The acrylic resin layer is made of PVC resin, polyurethane resin
7. The composition according to claim 6, which contains a fat or a vinylidene fluoride resin.
Or the waterproof sheet according to 7. 9. The polyurethane resin layer or cyanoethylated ethylene
-Vinyl alcohol copolymer layer of 0.5 to 30 μm
9. The waterproof case according to claim 1, which has a thickness.
To 10. The thickness of the acrylic resin layer is 2 to 20 μm
The waterproof sheet according to claim 1, wherein 11. The vinylidene fluoride resin is vinylidene fluoride alone;
Contains 70 mol% or more of polymer or vinylidene fluoride
The protection according to any one of claims 1 to 10, which is a copolymer.
Water sheet. 12. The vinylidene fluoride resin layer is vinylidene fluoride;
Good compatibility between the resin and this vinylidene fluoride resin
2. The waterproofing system according to claim 1, wherein the waterproofing system is made of a resin mixed with a resin.
To 13. Good compatibility with the vinylidene fluoride resin
Resin is methyl methacrylate or methyl acrylate
Polymer or copolymer mainly composed of
Resin or cyanoethylated ethylene-vinyl alcohol
The waterproof sheet according to claim 12, which is a polymer. 14． The vinylidene fluoride resin layer has a thickness of 1 to 5 μm.
The waterproof sheet according to any one of claims 1 to 13,
G. 15. The polyurethane resin layer, or cyanoethylated
The thickness of the styrene-vinyl alcohol copolymer layer is 2 to 20;
The waterproof sheet according to claim 9, which has a size of μm.