JPH0633372A - Waterproof cloth excellent in stain-proofing property and its production - Google Patents

Abstract

PURPOSE:To provide the waterproof cloth excellent in stain-proofing property and weather resistance by forming the vapor deposited layer(s) of a metal and/or a metal compound as the outermost layer or layers on one surface or both the front and back surfaces of ordinary waterproof cloth. CONSTITUTION:In waterproof cloth produced by disposing a waterproof resin on one surface or both the front and back surfaces of fiber base cloth preferably comprising polyester fibers or glass fibers, the vapor deposited layer or layers of one kind selected from metals and/or metal compounds, preferably aluminum, chromium, silicon, etc., are formed on one surface or both the front and back surfaces of the waterproof cloth as the uppermost layer(s) to provide the objective waterproof cloth excellent in the stain-proofing property. Preferably, on the formation of the waterproof cloth, the metal and/or the metal compound are deposited on a releasable synthetic resin film, etc., by a vacuum-deposition method, etc., and subsequently bonded to the surface or both the front and back surfaces of the waterproof cloth through an adhesive resin, followed by peeling the releasable film to provide the waterproof cloth excellent in the weather resistance and adhesion on by hot air. The waterproof cloth is suitable as a wide industrial material and a building material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for improving the antifouling property of a waterproof cloth used as an industrial material such as a building member or a truck hood.

[0002]

2. Description of the Related Art Conventionally, a waterproof cloth in which a thermoplastic resin layer is formed on the front surface or both front and back surfaces of a fibrous base cloth by a calendering method, a coating method or the like has a processability, an economical efficiency, and a degree of freedom in design. It has advantages such as large size, and has been used for tarpaulins, tent warehouses, oil resistant aprons, etc. Further, in recent years, a large number of membrane structures have been seen at various events and are used as members thereof, and the demand thereof is expanding year by year. However, due to long-term exposure, deterioration of the surface, and in some cases, auxiliary agents such as plasticizers contained in the thermoplastic resin layer migrate to the surface, dust easily adheres to it, and even if wiped There is a serious drawback that it cannot be removed and it impairs its aesthetic appearance, and its improvement has been earnestly desired.

Therefore, conventionally, there has been proposed a method of protecting a surface by applying a surface treatment agent in which a vinyl acetate-vinyl chloride copolymer resin, an acrylic resin or the like is dissolved in an organic solvent to a base cloth. In addition, various other methods have been proposed. For example, JP-A-59-171649 discloses PV.
One in which a fluororesin is pressure-bonded and laminated on the surface of C resin through an adhesive resin layer, one in which a polymethacrylic acid film is laminated on a PVC sheet as described in JP-A-56-167445, and one which is actually developed. Japanese Patent Application Laid-Open No. 50-101684 proposes, for example, an acrylic resin, a film, or a sheet fixedly laminated on a base cloth.

However, even if an acrylic resin film such as polymethylmethacrylate is used, it is essentially impossible to prevent the penetration of auxiliary agents such as plasticizers, so that a film having a considerable thickness must be used. The entire waterproof cloth has a hard texture, and also makes cold resistance and hot air weldability difficult.

Further, in the method of directly coating a thermoplastic resin such as an acrylic resin, since a resin dissolved in an organic solvent is used in many cases, a large amount of the plasticizer migrates to the coating resin layer during coating, Its antifouling effect is minimal or nonexistent.

[0006] Further, the one to which a metal foil such as an aluminum foil is attached has a problem that the transparency is impaired and the handling is difficult due to its large thickness.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problem that a waterproof cloth is basically liable to be soiled, and yet has excellent weather resistance and hot air adhesiveness. And a method for manufacturing the same.

[0008]

The object of the present invention is to provide a waterproof cloth in which a waterproof resin is arranged on the front surface or both front and back surfaces of a fibrous base cloth, and a metal and / or an outermost layer is formed on one surface or both front and back surfaces. This is achieved by a waterproof cloth having an excellent antifouling property, which is characterized by having a metal compound vapor deposition layer.

Further, in a waterproof cloth in which a waterproof resin is arranged on the front surface or both front and back surfaces of a fibrous base cloth, a metal and / or a metal compound vapor-deposited layer may be formed on the waterproof cloth on one surface or both front and back surfaces. This is achieved by a method for producing a waterproof cloth having excellent antifouling properties.

[0010]

The present invention will be described in detail below with reference to the exemplary drawings.

The fibrous base fabric 1 referred to in the present invention may be natural fibers or synthetic fibers, or may be organic fibers or inorganic fibers. Examples of fibers that meet such purposes include mineral fibers such as cotton, hemp, glass fibers, carbon fibers, and asbestos, metal fibers, nylon 66, nylon 6, polyester fibers represented by polyethylene terephthalate, and aromatic polyamide fibers. , Acrylic fiber, polyolefin fiber, polyvinyl chloride fiber, polyvinyl alcohol fiber, acetate fiber, viscose rayon, etc., and one kind or several kinds of fibers may be used in combination. Further, the fiber is not limited in shape such as long fiber yarn, short fiber spun yarn, tape yarn, slit yarn and the like. Further, the shape of the fabric such as woven fabric, knitted fabric, non-woven fabric or a composite material thereof is not restricted. As the fibrous base fabric for the waterproof cloth of the present invention, polyester fibers or glass fibers are preferable as the fibers in terms of weather resistance, water resistance, mechanical properties, economical efficiency, and are long fiber shapes because of resistance to external stress. A plain weave cloth is desirable.

As the waterproof resin layers 2, 2'formed on the front surface or both front and back surfaces of the fiber base cloth, natural resin, synthetic resin, natural resin chemically treated, etc. may be used. For example, rubbers such as natural rubber, chloroprene rubber, neoprene rubber, silicone rubber, and Hypalon, vinyl chloride resin, vinyl acetate resin, ethylene vinyl acetate copolymer resin, acrylic resin, silicone resin, urethane resin, polyolefin resin One or a plurality of types such as polyester resin, fluororesin, other synthetic resin, and elastomer can be used, and 2, 2 '
May be different from each other. Moreover, you may perform copolymerization, graft polymerization, and various modifications as needed. For the waterproof layer made of such a material, in order to impart functions such as flame retardancy and weather resistance in addition to waterproofness, various known plasticizers, pigments,
A function-imparting agent such as a flame retardant, a stabilizer, an ultraviolet absorber and an antioxidant may be contained. The thickness of the waterproof layer may be any thickness depending on the purpose, but the thickness is preferably 0.05 to 2.0 mm.
If the thickness is 0.05 mm or less, the essential waterproofness, flame retardancy and mechanical strength are not sufficient, and if it is 2.0 mm or more, the waterproof cloth becomes too heavy and uneconomical, but the waterproof performance is improved. I can't hope.

Next, the structure formed on the waterproof cloth according to the present invention will be described.

The means for improving the antifouling property which is the object of the present invention is characterized by having a metal and / or metal compound vapor deposition layer 3 as the outermost layer. The material used for the metal and / or metal compound vapor deposition layer 3 is not particularly limited as long as a known vapor deposition method can be applied to the material. For example, aluminum, boron, silicon, tin, titanium, indium, tungsten, gold, silver, copper, platinum, chromium, lead, magnesium,
Examples thereof include metals such as zinc and nickel, and compounds such as oxides, carbides, and nitrides thereof, various alloys can be used, and two or more kinds of materials can be used simultaneously or separately. Among them, aluminum, silicon, chromium, and oxides thereof are advantageous in achieving the purpose because the vapor deposition film can be formed stably and densely, and the vapor deposition rate is very fast, and they are very preferably used from the economical point of view.

Further, the use of various metal vapor deposition layers and certain kinds of compounds gives a product with very excellent aesthetics, and the use of various metal compound vapor deposition layers such as oxides gives almost transparent vapor deposition layers. Since it gives, it is possible to enjoy a secondary gain of giving a product having excellent translucency, and the usefulness of the present invention can be inferred from that point as well. Halides can fulfill the purpose of the present invention for the time being, but they are economically disadvantageous and lack water resistance, so they are not suitable for the present invention.

As the vapor deposition method, various known vapor deposition methods can be used. For example, in addition to physical processing methods such as vacuum deposition method, sputtering, and ion plating, C
A chemical vapor deposition method such as the VD method can also be used. As an example, a continuous vapor deposition apparatus equipped with a differential evacuation system is used to vaporize a target metal by an electron beam in an argon or argon-oxygen atmosphere at about 10 ⁻³ to 10 ⁻⁵ Torr.
It is possible to cite a method of vapor deposition on an adherend that is continuously fed at a temperature controlled around 0 degree.

The vapor deposition layer 3 can be formed directly or indirectly on the waterproof resin layers 2, 2 '. However, in view of the following points, it is desirable to use the method of forming indirectly.

First, when the vapor deposition layer 3 is formed directly on the waterproof resin layer, the waterproof resin layers 2 and 2'may contain an auxiliary agent as described above. However, vaporization of the auxiliary agent, bleeding, or the like may cause difficulty in vapor deposition or insufficient adhesion of the vapor deposition layer 3. In such a case, the protective resin layer 5 can be used on both the front surface and the back surface of the waterproof resin layer.

The protective resin layer 5 is not particularly limited in material and thickness as long as it has a function of suppressing volatilization or bleeding of an auxiliary agent when the vapor deposition layer 3 is formed, and examples thereof include natural rubber, chloroprene rubber and neoprene. Rubber, silicone rubber, hypalon, chlorosulfonated polyethylene,
Polyolefin resin, acrylic resin, urethane resin, fluorine resin, vinyl acetate resin, ethylene vinyl acetate copolymer resin, vinyl chloride resin, epoxy resin, phenol resin, polyester resin, chloroprene resin,
Examples thereof include organic resin compounds such as nitrile rubber resins and silicone resins, and inorganic compounds such as phosphazene compounds. You may use these 1 type or multiple types.

The protective resin layer 5 may be applied by a known film forming method such as a method of dissolving it in a solvent and coating it on the waterproof resin layers 2, 2'and drying, a casting method or a melt extrusion method. There is no particular limitation as long as the surface can be obtained as a result, such as a method in which the film is formed into a film and then attached to the waterproof resin layers 2 and 2 '.

Next, as a method of indirectly forming the vapor-deposited layer 3 on the waterproof cloth, for example, a vapor-deposited layer is previously formed on the film or sheet 8 and the film or sheet 8 is attached to the waterproof cloth. Examples thereof include a method of attaching the film, a method of transferring the vapor deposition layer from the film or sheet 8 to the waterproof cloth, and the like. A known film or sheet-like material 8 can be used, and a film is appropriately formed when a vapor deposition layer is previously formed on the film or sheet-like material 8 and the film or sheet-like material 8 is attached to a waterproof cloth. Alternatively, the adhesive resin layer 6 may be provided so that the adhesive resin layer 6 is formed between the sheet-shaped material 8 and the vapor deposition layer 3, but in particular, the metal and / or metal compound vapor deposition layer 3 and the waterproof cloth are joined together. Can be made strong, surely and uniformly, and the process passability is very good. Therefore, the vapor deposition layer 3 is previously formed on the easily peelable film or sheet-like material 8 to waterproof the vapor deposition layer 3. It is desirable to use a method of transferring and forming on a cloth.

At this time, the easily peelable film or sheet-like material 8 has a release agent formed on the surface thereof, which is a chemical product such as a silicone resin, a polyolefin resin, a polyester resin, a fluororesin, or the like. The thing formed with the resin itself can be illustrated.

When the waterproof cloth is compounded on the front surface or both the front and back surfaces of the waterproof cloth, it may be directly adhered by heat or the adhesive resin layer 4 may be used, but it is possible to firmly form the vapor deposition layer on the waterproof cloth. Since it is possible, the method using the adhesive resin layer 4 is preferable. The adhesive resin layer 4 may be a thermoplastic resin, a thermosetting resin, or a photocurable resin, and may be in a solution form, a film form, or the like when used in a composite. Examples of such resin include acrylic resin, urethane resin, epoxy resin, phenol resin, polyester resin, chloroprene resin, nitrile rubber resin, fluorine resin, silicone resin, polyolefin resin, vinyl acetate. An organic resin compound such as a resin and an inorganic compound such as a phosphazene compound can be used. Further, this adhesive resin layer can be applied at the same time when the metal and / or metal compound vapor deposition layer 3 is compounded, but either or both of the metal and / or metal compound vapor deposition layer 3 and the waterproof cloth can be provided. Examples include a method of forming the layer in advance and then performing an adhesion operation.

When the waterproof cloth is processed during use,
The front surface and the back surface of each of the plurality of waterproof cloths are often joined using a welding joining method such as hot air welding or high frequency welding.
In the present invention, the adhesive resin layer 7 can be provided as necessary and for the purpose of functionalizing the back surface of the waterproof cloth for the purpose of improving the bonding strength between the respective waterproof cloths. For example, when used for the purpose of making hot air weldability possible, a thermoplastic resin is suitable, and it is important to use a resin that is compatible with the waterproof layer 2 ′ and the metal and / or metal compound vapor deposition layer 3. Is. Such resins include acrylic resins, polyester resins, polyamide resins, polyurethane resins, fluorine resins,
Examples thereof include vinyl acetate resins, cyanoethylated ethylene vinyl alcohol copolymers, etc., which are appropriately used in various forms such as copolymers, modified products, and mixtures, and metal and / or metal compound vapor deposition layer 3, Waterproof resin layer 2,
It is selected and used according to the material type of 2 '.

For the application of the adhesive resin layers 4, 6 and 7 described above, known methods such as gravure coating, bar coating, knife coating and laminating can be exemplified. The adhesive resin layer thus formed is subjected to drying or the like, if necessary, and then provided for compounding. A known method such as a method using a laminating device can be used for the method of forming the composite.

[0026]

The waterproof cloth having antifouling property according to the present invention has the metal and / or metal compound vapor deposition layer 3 as the outermost layer.
Has a structure formed on a waterproof cloth, which solves the problem that the waterproof cloth is easily soiled, which has been a conventional problem, and can be used without impairing other characteristics. Therefore, it can be widely used as an industrial material and a building material, and its industrial value is extremely large.

[0027]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples.

A polyethylene terephthalate cloth having the following structure was used as a fibrous base cloth, washed with water and dried.

Unit weight: 350 g / m ² woven structure: plain weave Then, a processing agent having the following composition was processed on the fibrous base cloth by calendering to prepare a waterproof cloth (Sample 1).

Vinyl chloride resin: 80 parts by weight Dioctyl phthalate: 75 parts by weight Titanium oxide: 10 parts by weight Cadmium barium stabilizer: 3 parts by weight Ultraviolet absorber: 0.5 parts by weight Pigment: 7 parts by weight Examples 1, 2 3, Comparative Example 1 On the other hand, a silicone-based treatment agent (manufactured by Toray Dow Corning Silicone Co., Ltd., on a 25-micron-thick polyester film (manufactured by Toray Co., Ltd., trade name “Lumirror”)
A product name "SD7223") was applied and dried and cured to form an aluminum vapor-deposited film by a vacuum vapor deposition method for 10 seconds using a resistance heating type board of 3 kW under an argon atmosphere of 10 ^-4 Torr in an easily peelable film. . The thickness of the vapor deposition layer at that time was 250 Å (Sample 2).

Oxidation was performed in the same process as in sample 2 to obtain an aluminum oxide vapor deposition film (sample 3).

Further, a thermoplastic acrylic resin (manufactured by Toagosei Co., Ltd.) dissolved in a solvent is applied onto a polyester film (manufactured by Toray Industries, Inc.), dried, and then vapor-deposited on the surface in the same process as in Sample 2. The layers were formed and the composite film was heat treated (Sample 4).

Subsequently, in Samples 2 to 4, Sample 2 and Sample 3 were transferred onto the sample 1 by using an adhesive (manufactured by Sony Chemical Co., Ltd.) so that the deposited layer became the outermost layer. In No. 4, a composite film was attached such that the vapor deposition layer was the outermost layer.

On the other hand, Sample 1 itself was used as a comparative example.

The waterproof cloth thus obtained is contaminated by placing it on an exposure rack tilted to the south by 45 degrees outdoors for one year, and after observing the contaminated condition, the contaminated sample is wetted on the contaminated surface. It was lightly wiped with a dry cloth to examine whether the attached stains could be removed, and the evaluation was made in five levels. The results are shown in Table 1. Here, the dirt adherence indicates the difficulty of adhesion of dirt due to pollution due to one year of outdoor exposure, and the dirt removability means the resistance of dirt remaining after wiping off the dirt. Indicates.

Table 1 Vapor-deposited layer Stain adhesion Stain removal Example 1 Aluminum has effect, especially effect Example 2 Aluminum oxide has effect, especially effect _{Example 3} Aluminum / polyether effect, especially effect Film Comparative Example 1 None Conventional product Level Conventional product level As described above, it is understood that the waterproof cloth according to the present invention has excellent antifouling property.

Examples 4, 5 and 6 Comparative Example 2 Adhesive resin layer obtained by coating the back surface of the waterproof cloth of Examples 1 to 3 and Comparative Example 1 with a polyester resin adhesive (manufactured by Toagosei Kagaku Co., Ltd.). Formed 7. Subsequently, with respect to each of these sheets, the front and back surfaces of the waterproof cloth (that is, between the metal and / or metal compound vapor deposition layer 3 or the waterproof resin layer 2 and the adhesive resin layer 7) having a width of 40 mm are hot welded. ) Bonded (Sample 5, Sample 6,
Sample 7, sample 8).

The average peel strength of the joint portion of the heat-sealing waterproof cloth thus obtained was measured, and the results are shown in Table 2.

Table 2 Substrate Peel strength (kg / cm) Example 4 Sample 5> 2.0 * Example 5 Sample 6> 2.0 * Example 6 Sample 7> 2.0 * Comparative Example 2 Sample 8> 2.0 * *) Peel strength cannot be measured due to material destruction of the waterproof cloth.

From the above, the waterproof cloth according to the present invention having excellent antifouling property can obtain a strong peeling strength which is the same as the conventional one, and the antifouling property can be obtained without impairing the hot-air weldability.

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing an example of a waterproof cloth according to the present invention.

FIG. 2 is a cross-sectional view schematically showing another example of the waterproof cloth according to the present invention.

FIG. 3 is a schematic model diagram showing an example of a method of manufacturing a waterproof cloth according to the present invention.

FIG. 4 is a cross-sectional view showing an example of joining between waterproof cloths according to the present invention.

[Explanation of symbols]

 1: Fiber base fabric layer, 2, 2 ': waterproof resin layer, 3: metal and / or metal compound vapor deposition layer, 4: adhesive resin layer, 5: protective resin layer, 6: adhesive resin layer, 7 : Adhesive resin layer, 8: Film or sheet-like material

Claims (5)

[Claims] 1. A waterproof cloth comprising a fibrous base cloth and a waterproof resin disposed on the front surface or the back surface of the fibrous base cloth. The waterproof cloth has a metal and / or metal compound vapor deposition layer as an outermost layer on one surface or both surfaces. A waterproof cloth with excellent stain resistance. 2. The antifouling property according to claim 1, wherein the outermost metal and / or metal compound vapor-deposited layer contains at least one element selected from the group consisting of aluminum, chromium and silicon. Excellent waterproof cloth. 3. The waterproof cloth excellent in antifouling property according to claim 1, which has an adhesive resin layer as a second layer inside the outermost layer. 4. When forming a metal and / or metal compound vapor-deposited layer as an outermost layer on a waterproof cloth, first, the metal and / or metal compound layer is vapor-deposited on a plane having easy peeling property, and then an adhesive resin. The method for producing a waterproof cloth excellent in antifouling property according to claim 4, wherein the vapor-deposited layer is adhered to one side or both front and back sides of the waterproof cloth to peel off the easily peelable flat surface. 5. The excellent antifouling property according to claim 4, wherein the outermost metal and / or metal compound vapor deposition layer contains at least one member selected from the group consisting of aluminum, chromium and silicon. Method of manufacturing waterproof cloth.