JPH0633381A - Waterproofing cloth having excellent stain-proofing property and weldability and its production - Google Patents

Abstract

PURPOSE:To obtain waterproofing cloth having excellent stain-proofing property and weldability by applying a thermoplastic resin layer, an adhesive resin layer and a metallized layer of a metal and/or a metallic compound to one or both surfaces of conventional waterproofing cloth. CONSTITUTION:The waterproofing cloth having excellent stain-proofing property is produced by applying a waterproofing resin to a surface or both surfaces of a textile substrate preferably made of polyester fiber or glass fiber and laminating the outermost layer consisting of a thermoplastic resin (e.g. acrylic resin), the 2nd layer consisting of an adhesive resin and the 3rd layer consisting of a metallized layer of a metal and/or a metallic compound to one or both surfaces of the cloth interposing the adhesive resin layer. Preferably, waterproofing cloth having excellent weather resistance and hot-air weldability can be produced by forming a metallized layer of a metal and/or a metallic compound on an easily releasable film, laminating the film on a thermoplastic resin film (e.g. polyester film), etc., interposing an adhesive resin layer and applying the obtained composite film to the waterproofing resin layer of waterproofing cloth interposing an adhesive resin layer.

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. In addition, in recent years, a large number of membrane structures have been seen at various events and the like, and the demands thereof are expanding year by year as they are used as members thereof. 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 It has a serious drawback that it cannot be removed and its aesthetic appearance is impaired, and its improvement has long been 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 penetration of auxiliary agents such as plasticizers, so that a film having a considerable thickness must be used.
Therefore, the entire waterproof cloth has a hard texture, and it 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]

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 to have excellent weather resistance and hot air adhesiveness. And a method for manufacturing the same.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a waterproof cloth having a fibrous base cloth with a waterproof resin on the front surface or the front and back surfaces thereof, and a thermoplastic resin as an outermost layer on one surface or both front and back surfaces. A layer, an adhesive resin layer as the second layer, a metal and / or metal compound vapor deposition layer as the third layer,
Further, it is achieved by a waterproof cloth excellent in antifouling property, which is formed on a waterproof cloth via an adhesive resin 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 thermoplastic resin layer as the outermost layer, an adhesive resin layer as the second layer, and a third layer on one or both front and back surfaces. As a result, a metal and / or metal compound vapor-deposited layer is provided, and the layer is formed on a waterproof cloth via an adhesive resin layer, which is achieved by a method for manufacturing a waterproof cloth having excellent antifouling property.

[0009]

The present invention will be described in detail below with reference to the drawings showing the embodiments of the present invention.

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 cotton, hemp, glass fibers, carbon fibers, mineral fibers such as asbestos, metal fibers, nylon 66, nylon 6, polyester fibers typified by polyethylene terephthalate, aromatic polyamide fibers, Acrylic fiber,
Examples thereof include polyolefin fibers, polyvinyl chloride fibers, polyvinyl alcohol fibers, acetate fibers, viscose rayon, and the like, and one or more of these fibers may be used in combination. Also, the fibers are long fiber yarns,
It may be any of short fiber spun yarn, tape yarn, slit yarn and the like, and the shape thereof is not particularly limited. Further, the shape of the fabric such as woven fabric, knitted fabric, non-woven fabric or a composite thereof is not limited. As the fibrous base cloth for 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 in the form of long fibers because of resistance to external stress. It is desirable that the cloth be plain weave.

The waterproof resin layers 2, 2'formed on the surface or both front and back surfaces of the fiber base cloth may be the same or different, and the natural resin, the synthetic resin and the natural resin are chemically treated. For example, natural rubber, chloroprene rubber, neoprene rubber, silicone rubber, rubber such as Hypalon, vinyl chloride resin, vinyl acetate resin, ethylene vinyl acetate copolymer resin, acrylic resin,
One or more of silicone resin, urethane resin, polyolefin resin, polyester resin, fluororesin, other synthetic resin, elastomer and the like can be used. Moreover, you may perform copolymerization, graft polymerization, and various modifications as needed. For such a waterproof layer, various known plasticizers, pigments, flame retardants, stabilizers, ultraviolet absorbers, antioxidants, etc. are added in order to impart functions such as flame resistance and weather resistance in addition to waterproofness. It may contain a function-imparting agent. The waterproof layer may have any thickness depending on the purpose.
2.0 mm is desirable. If the thickness is 0.05 mm or less, the essential waterproofness, flame retardancy and mechanical strength are not sufficient,
If it is 2.0 mm or more, the waterproof cloth becomes too heavy and uneconomical, but further improvement in performance cannot be expected.

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 to use a thermoplastic resin layer 3 as the outermost layer, an adhesive resin layer 4 as the second layer, and a metal and / or metal compound vapor deposition as the third layer. The layer 5 is characterized in that it is formed on the surface or both front and back surfaces of a waterproof cloth composed of the fibrous base cloth 1 and the waterproof resins 2, 2'through the adhesive resin layer 6. The resin used as the outermost thermoplastic resin layer 3 is not particularly limited as long as it is a thermoplastic resin. For example, natural rubber, chloroprene rubber, chlorosulfonated polyethylene, polyolefin resin, polyester resin, Natural resin such as acrylic resin, fluorine resin, vinyl acetate resin, vinyl chloride resin, urethane resin, synthetic resin,
Various elastomers can be used, and they can be used alone, or can be used as a mixture within a range where they are compatible with each other, or can be used as a composite such as a multilayer or an IPN. Among these, for example, the diol component units such as polyethylene terephthalate and polybutylene terephthalate have 2 to 8 carbon atoms and 6 dicarboxylic acid components.
Containing polyester resin in the range from 40 to 40, polytrifluorochloroethylene, polyhexafluoropropylene, polyvinyl fluoride, ethylene tetrafluoroethylene copolymer, polyvinylidene fluoride, fluororubber, and graft polymerization of these units. Fluorine-based resins such as impregnated resins, acrylic ester resins in which the alkyloxy group has 1 to 6 carbon atoms, or acrylic-based resins such as methacrylic acid resins and acrylonitrile are the weather resistance, water resistance, and thermal adhesiveness of the resin itself. Is particularly preferable and has the ability to well express the object of the present invention, and thus is particularly preferably used.

Further, if necessary, auxiliary agents such as stabilizers, lubricants and weathering agents may be used for the thermoplastic resin layer 3.
In particular, the addition of a weatherproofing agent is highly desirable from the viewpoint of preventing deterioration of the adhesive resin layers 4 and 6 thereunder and protecting the joint surface of the thermoplastic resin layer 3 or the vapor deposition layer 5. The amount thereof can be used within a range that can ensure uniform compatibility or dispersibility with the thermoplastic resin layer 3.

As the method for forming the thermoplastic resin layer 3, a known film forming method such as a method of dissolving in a solvent and coating on the adhesive resin layer 4 and drying, a casting method, a melt extrusion method, an inflation method or the like is used. There is no particular limitation as long as a flat surface can be obtained as a result of the method of forming into a film, and the difference in the method does not affect the performance.

Next, since the thickness of the thermoplastic resin layer 3 is for functionalizing the surface layer portion on the front surface and / or the back surface of the waterproof cloth, it can be arbitrarily set, but about 2 to 200 microns is preferably used. . If it is less than 2 microns, the process passability will be hindered and sufficient performance cannot be obtained. If it is more than 200 microns, further improvement in performance cannot be expected, and it is economically disadvantageous and flame retardant. The property may be impaired, and the application may be limited due to the increase in weight.

Next, the metal and / or the metal formed as the third layer
Alternatively, the material used for the metal compound vapor deposition layer 5 is not particularly limited as long as the vapor deposition method can be applied to the material. For example, aluminum, boron, silicon, tin, titanium, indium, tungsten, gold, silver, copper, platinum, chromium,
Metals such as lead, magnesium, zinc and nickel and their oxides, nitrides, compounds such as carbides can be mentioned.
Further, 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 that the vapor deposition film can be formed stably and densely, which is advantageous in achieving the purpose, and the vapor deposition rate is very fast, and is very preferably used from the economical point of view.

Further, the use of various metal vapor deposition layers and certain kinds of metal compounds gives a product with very excellent aesthetics, and the use of metal compound vapor deposition layers including various oxides is generally transparent vapor deposition layers. Therefore, it is possible to enjoy a secondary gain of providing a product having excellent light-transmitting property, and the usefulness of the present invention can be inferred from that point as well. Halides can also serve the purpose of the present invention, but are not suitable for the present invention because they are economically disadvantageous and have poor water resistance.

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, sputtering, and ion plating, CV
A chemical vapor deposition method such as method D can also be used. An example is a continuous vapor deposition apparatus equipped with a differential evacuation system, using about 10 ⁻³ to 10 ⁻⁵ Torr of argon or argon −.
Target metal is vaporized by electron beam in oxygen atmosphere 70
It is possible to cite a method in which vapor deposition is carried out on an adherend that is continuously fed with the temperature controlled before and after.

In this way, the vapor deposition layer 5 is formed, and is combined with the thermoplastic resin layer 3 which is another component.
In this combination, it is necessary that the adhesive resin layer 4 is interposed. Further, the adhesive resin layer 6 is also necessary.
If these adhesive resin layers do not exist, they are easily peeled off at the interface of the vapor deposition layer when stress is applied. These can be used in multiple layers.

The adhesive resin layer 4 may be a thermoplastic resin, a thermosetting resin, or a photocurable resin, and may be in the form of a solution, a film, or the like when used in combination. Examples of such resins include acrylic resins, urethane resins, epoxy resins, phenol resins, polyester resins, chloroprene resins, nitrile rubber resins, fluorine resins, silicone resins, polyolefin resins,
Organic resin compounds such as vinyl acetate resins and inorganic compounds such as phosphazene compounds can be used. As a forming method, for example, the adhesive resin layer can be applied at the same time when the vapor deposition layer 5 and the thermoplastic resin layer 3 are combined, but either the vapor deposition layer 5 or the thermoplastic resin layer 3 or both of them can be applied. Examples include a method of forming the layer in advance and then performing an adhesion operation.

As another method, the vapor deposition layer 5 is formed on the waterproof layer 2 via the adhesive resin layer 6 and then the vapor deposition layer 5 is formed.
An example is a method in which after the adhesive resin layer 4 is applied on top of the adhesive resin layer 4, it is combined with the thermoplastic resin layer 3 to obtain a waterproof cloth.

Since the adhesive resin layer 6 is basically required to have the same properties as the adhesive resin layer 4, a thermoplastic resin, a thermosetting resin or a photocurable resin may be used. The same composition as the adhesive resin layer 4 or a different composition does not adversely affect the effects of the present invention.

As described above, the outermost layer is the thermoplastic resin layer 3, the second layer is the adhesive resin layer 4, the third layer is the metal and / or metal compound vapor deposition layer 5, and the adhesive resin layer 6 is further provided. Various methods can be adopted as a method of forming on the waterproof cloth through the above. Above all, the bonding between the thermoplastic resin layer 3 and the vapor deposition layer 5 can be made strong, surely and uniformly, and the process passability is very high. Since it is good, the thermoplastic resin layer 3 is formed beforehand into a film or sheet by a melt extrusion method or the like and wound on a roll, and on the other hand, the vapor deposition layer 5 is formed on a flat surface having easy peeling property. Is made into a composite film by using the adhesive resin layer 4 and a method such as dry lamination or wet lamination to obtain a composite film, and thereafter, a waterproof film composed of a fibrous base cloth and a waterproof resin layer is formed. It is desirable to use a method in which formed on tarpaulin via the adhesive resin layer 6 on the resin layer.

At this time, for obtaining a flat surface having easy peeling property, for example, silicone resin, polyolefin resin,
Examples thereof include those having a release agent formed on the surface of a chemical product such as polyester resin and fluororesin, and films or sheet-like materials formed of these resins themselves.

When such a waterproof cloth is processed for use, the front and back surfaces of a plurality of waterproof cloths are often joined by 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 needed for the purpose of improving the bonding strength between the respective waterproof cloths and for the purpose of functionalizing the back surface of the waterproof cloth. For example, when used for the purpose of making hot air weldability possible, it is important to use a thermoplastic resin, especially a resin that is compatible with the waterproof layer 2 ′ and the thermoplastic resin layer 3. Such resins include acrylic resins, polyester resins, polyamide resins, polyurethane resins, fluororesins, vinyl acetate resins, cyanoethylated ethylene vinyl alcohol copolymers, etc. It may be used in various forms such as a polymer, a modified product and a mixture, and may be selected and used depending on the material type of the thermoplastic resin layer 3 and the waterproof layer 2 '.

Examples of methods for applying the adhesive resin layers 4, 6, and 7 described above include gravure coating, bar coating, knife coating, and laminating, and the method is not limited. The adhesive resin layer thus formed is dried or the like if necessary, and then provided for compounding. As a method for forming a composite, a known method, for example, a method using a laminating device can be mentioned.

[0028]

The waterproof cloth having antifouling property according to the present invention comprises the thermoplastic resin layer 3 as the outermost layer, the adhesive resin layer 4 as the second layer, and the metal and / or metal compound vapor deposition layer 5 as the third layer. Is disposed on the waterproof cloth via the adhesive resin layer 6 to solve the conventional problem that the waterproof cloth is easily soiled and impairs other characteristics. Can be used without any. Therefore, it can be widely used as an industrial material and a building material, and its industrial value is extremely large.

[0029]

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.

Fabric 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-based stabilizer: 3 parts by weight Ultraviolet absorber: 0.5 parts by weight Pigment: 7 parts by weight On the other hand, a thickness of 25 μm Silicone treatment agent (Toray Dow Corning Silicone Co., Ltd.,
The product name "SD7223") was applied, dried and cured, and an aluminum vapor-deposited film was formed on the easily peelable film by a vacuum vapor deposition method for 10 seconds using a resistance heating type board of 3 kW in an argon atmosphere of 10-4 Torr. The thickness of the vapor deposition layer at that time was 250 Å (Sample 2).

Examples 1, 2, 3, 4 and Comparative Example 1 Next, another polyester film (manufactured by Toray Industries, Inc.) and an acrylic resin film film (Mitsubishi Rayon Co. Ltd.) were used as the thermoplastic resin layer 3 (thickness: 25 μm). Made by the company),
A fluorine-based thermoplastic elastomer (manufactured by Central Glass Co., Ltd.) was used to form an adhesive (SC-210, manufactured by Sony Chemical Co., Ltd., adhesive resin layer 4) thereon, and an aluminum vapor deposition film was transferred from Sample 2. This was heat-cured to obtain a composite film. Next, an adhesive (SC-21 manufactured by Sony Chemical Co., Ltd.) is attached to the aluminum deposition surface side of this composite film.
0, the adhesive resin layer 6) was applied and attached to the surface of Sample 1.

On the other hand, the sample 2 was oxidized to obtain an aluminum oxide vapor deposition film. This was similarly transferred to a polyester film by the same method as described above, and similarly adhered to the above-mentioned sample 1 using an adhesive.

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

The waterproof cloth thus obtained was contaminated by placing it outdoors on an exposure stand inclined at 45 ° to the south surface for one year, and after observing the contaminated condition, the contaminated sample was wetted on the contaminated surface. It was lightly wiped with a cloth to check whether the attached stains could be removed, and the result was evaluated in 5 grades. 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 Thermoplastic resin layer 3 Vapor-deposited layer 5 Stain adhesion and stain removal Example 1 Polyester resin Aluminum 〇 〇 〇 〇 Example 2 Acrylic resin Aluminum 〇 〇 〇 〇 _{Example 3} Fluorine-based thermoplastic _{aluminum 〇 〇 〇 ○} Elastomer Example 4 Polyester resin Aluminum oxide ○ ○ ○ ○ Comparative example 1 None None × × ○ ○ ○: Particularly effective, ○ ○: Very effective, ○: Effective, △: Slightly effective, ×: Conventional Product Level As can be seen from Table 1, the waterproof cloth of the present invention has excellent antifouling property.

Examples 5, 6 and Comparative Examples 2 and 3 An acrylic resin adhesive (manufactured by Toagosei Co., Ltd.) on the back surface of the waterproof cloth of Examples 1, 4 and Comparative Example 1 described above.
Was coated to form an adhesive resin layer 7. Subsequently, the front surface and the back surface of the waterproof cloth (that is, between the thermoplastic resin layer 3 or the coating resin layer 2 and the adhesive resin layer 7) were bonded to each of the sheets by a hot air welding method with a width of 40 mm ( Sample 3, sample 4, sample 5), respectively.

Also, using the above-mentioned sample 2 as it is, the adhesive used in the previous example was applied to the aluminum vapor-deposited surface to obtain sample 1
The surface of was laminated to obtain a waterproof cloth. Then, also for this waterproof cloth, the adhesive resin layer 7 is formed on the back surface in the same manner,
Similarly, hot air welding was performed so that the back surface and the front surface of the waterproof cloth overlapped (Sample 6).

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 Sample Peel strength (kg / cm) Example 5 Sample 3> 2.0 ^* Example 6 Sample 4> 2.0 ^* Comparative Example 2 Sample 5> 2.0 ^* Comparative Example 3 Sample 6 0. 4 ^* ) Peel strength cannot be measured due to the destruction of the waterproof material.

From the above, by disposing the adhesive resin layers 4 and 6 between the vapor deposition layer 5 and the thermoplastic resin layer 3, it is possible to obtain a strong peeling strength which is the same as the conventional one.
It is clear that 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 cross-sectional view showing an example of joining between waterproof cloths according to the present invention.

[Explanation of symbols]

 1: fibrous base cloth layer, 2, 2 ': waterproof resin layer, 3: thermoplastic resin layer, 4: adhesive resin layer, 5: vapor deposition layer, 6: adhesive resin layer, 7: adhesive resin layer

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location B32B 31/00 7141-4F C23C 14/20 9271-4K D06M 11/83 15/507 E04H 15/54 8404-2E

Claims (5)

[Claims] 1. A waterproof cloth comprising a fibrous base cloth and a waterproof resin on the front and back surfaces thereof, wherein a thermoplastic resin layer as the outermost layer, an adhesive resin layer as the second layer, and a third layer on one or both of the front and back surfaces. A waterproof cloth excellent in antifouling property, comprising a metal and / or metal compound vapor-deposited layer as a layer, and further being formed on a waterproof cloth via an adhesive resin layer. 2. The antifouling agent according to claim 1, wherein the metal and / or metal compound vapor-deposited layer of the third layer contains at least one element selected from the group consisting of aluminum, chromium and silicon. A waterproof cloth with excellent properties. 3. The waterproof cloth having excellent antifouling property according to claim 1, wherein the outermost thermoplastic resin layer is made of an acrylic resin compound, a fluororesin compound or a polyester resin compound. 4. When manufacturing 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 thermoplastic resin layer as an outermost layer and an adhesive resin layer as a second layer on one surface or both front and back surfaces. A method for producing a waterproof cloth having excellent antifouling property, which comprises disposing a metal and / or metal compound vapor-deposited layer as a third layer and further forming the layer on the waterproof cloth via an adhesive resin layer. 5. A thermoplastic resin layer as the outermost layer, an adhesive resin layer as the second layer, a metal and / or metal compound vapor deposition layer as the third layer, and further on a waterproof cloth via the adhesive resin layer. In forming, a metal and / or metal compound layer is vapor-deposited on a plane having easy peeling property, and then the vapor-deposited layer is transferred to a film or sheet made of a thermoplastic resin by using an adhesive resin, and thus obtained. 5. A waterproof cloth having excellent antifouling property according to claim 4, wherein the composite film is formed on one or both sides of a waterproof cloth composed of a fibrous base cloth and a waterproof layer via an adhesive resin layer. Method.