JPS6151991B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a flexible sheet formed by combining a soft PVC layer and a metal vapor deposited layer formed on its surface with a fibrous base fabric. Prior Art Various attempts have been made to form a metal deposited layer on one or both sides of a PVC film or sheet. In this case, since the soft PVC contains a large amount of plasticizer, the plasticizer bleeds out to the surface, and the formed deposited layer is therefore likely to peel off, making it impractical. As a solution to this problem, metal vapor deposition is performed on polyester film, etc., and this is applied to soft PVC.
A method has been adopted in which the plasticizer is attached to the surface of a film or sheet to suppress bleed-out of the plasticizer. However, this method is complicated to operate;
It is also economically disadvantageous. Therefore, a PVC cross-linked layer is formed on the surface of a soft PVC film or sheet by low-temperature plasma treatment, and a metal vapor deposited layer is formed on top of that to improve the adhesion of the metal vapor deposit layer to the soft PVC layer and improve durability. Consideration was given to giving it a gender. However, the flexible sheet obtained in this way, whose basic constituent layers are a soft PVC layer, a soft PVC cross-linked layer, and a metal vapor deposited layer, effectively maintains durability for applications that are relatively less subject to stress; When used in tents, eaves tents, etc., relatively large stress is applied, which causes the film or sheet to stretch significantly.
The PVC crosslinked layer and metal vapor deposited layer cannot follow this elongation and cracks occur. Then, the plasticizer begins to bleed out from these cracks.
This impairs the adhesion of the metal vapor-deposited layer on the surface and reduces the durability of the sheet. OBJECT OF THE INVENTION An object of the present invention is to provide a flexible sheet that can maintain sufficient durability even for applications where large stress is expected. Structure of the Invention According to the present invention, a fibrous base fabric, a soft PVC intermediate layer formed on at least one surface thereof, a metal vapor deposited layer formed on the intermediate layer, and a A flexible sheet is provided that includes a flexible PVC crosslinked layer at the interface between the layer and the metallized layer. Detailed Description of the Structure of the Invention The fibrous base fabric used in the flexible sheet of the present invention includes natural fibers such as cotton and hemp, inorganic fibers such as glass fiber, and recycled fibers such as viscose rayon and kyupra. semi-synthetic fibers such as di- and triacetate fibers, and synthetic fibers such as nylon 6, nylon 66, polyester (such as polyethylene terephthalate) fibers, aromatic polyamide fibers, acrylic fibers, polyvinyl chloride fibers and polyolefin fibers. It consists of at least one type selected from the following. The fibers in the base fabric may be in any form such as short fiber spun yarn, long fiber yarn, split yarn, or tape yarn, and the base fabric may be a woven fabric, a knitted fabric, a nonwoven fabric, or a composite fabric thereof. It's okay. Generally, the fibers used in the flexible sheet of the present invention are preferably polyester fibers, and considering that they have little elongation under stress, these fibers are preferably in the form of long fibers (filaments), and they do not form a plain woven fabric. It is preferable that The fibrous base fabric is useful for maintaining the mechanical strength of the resulting flexible sheet at a high level. Furthermore, if we consider the tensile strength of the resulting flexible sheet, crack resistance in cold weather, flex crack resistance when the sheet is rubbed, and distribution of stress applied to the surface layer, special Preferably, a structured woven fabric is used as the fibrous fabric.
That is, the special structure woven base fabric is made of natural fibers, e.g.
Inorganic fibers such as cotton, linen, etc., such as glass fibers, recycled fibers, such as viscose rayon, kyupra, etc., semi-synthetic fibers, such as g- and tri-acetate fibers, and synthetic fibers, such as nylon 6, It is made of at least one type selected from nylon 66, polyester (polyethylene terephthalate, etc.) fiber, aromatic polyamide fiber, acrylic fiber, polyvinyl chloride fiber, polyolefin fiber, and the like. 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. These are arranged in parallel to each other, and the warp and weft layers thus formed are laminated so as to intersect with each other, and are loosely connected by long leno threads at the intersections of the warp and weft threads. The leno thread is made of polyester, nylon, aromatic polyamide and other known synthetic fibers, glass fiber,
It may be selected from steel fibers and other known inorganic fibers, with polyester filament yarns being particularly suitable. Now, for example, as warp and warp yarns, we are using tensile strength single yarns.
When 1.3Kg of Vinylon 10S/1 spun yarn is used, the tensile strength per unit denier is as a leno yarn.
20g of aromatic polyamide filament yarn is used, and if yarns of the same material are used in consideration of ease of sheet processing, for example, polyester filament yarn with a tensile strength of 8g per unit denier is used as the warp and warp yarns. Also, 10g of polyester filament yarn is used as the leno thread. A particularly preferable structure of the special structure fabric for use in the present invention is disclosed in Japanese Patent Publication No. 57-1979 filed by the present applicant.
30381, a warp layer consisting of a large number of warps arranged in parallel to each other, a weft layer consisting of a large number of wefts arranged in parallel to each other so as to be perpendicular to the warps, and the warp and weft. and a tangle thread that entangles and connects them at their intersections. The leno yarn is longer than the warp and weft, and therefore loosely connects the warp and weft, and has at least one of its tensile strength, tensile elongation, and breaking work as compared to the warp and weft. The adhesion force to the resin material is preferably greater than that of the warp and weft and/or smaller than that of the warp and weft. As the leno yarn, yarns having the characteristics shown below are particularly preferred. That is, (i) a leno yarn whose strength per unit denier is 10% or more greater than that of the warp and weft yarns constituting the base fabric. (ii) Leno yarn whose breaking work is 10% or more greater than the warp and weft yarns that make up the base fabric. (iii) Leno yarn whose elongation at break is 5% or more greater than the warp and weft yarns that make up the base fabric. (iv) Leno yarn that has a lower adhesion force to the resin coating than the warp and weft yarns that make up the base fabric. Among these, leno yarns whose tenacity per unit denier is 10% or more greater than the warp and weft are preferably used by 20 to 30% or more to substantially prevent the progress of tearing that occurs in the warp and weft. It is intended to be stopped by a large leno thread that is 10% stronger or more, and since the leno thread is longer than the warp and warp threads, and therefore has a greater degree of freedom in change and deformation than the warp threads, it is possible to continuously It can flexibly deal with and absorb tearing forces acting on the sheet. In other words, even if a tearing force acts on the sheet, causing the warp and warp threads to displace and eventually break, the leno threads follow the tearing force, displace and deform without being cut, and eventually absorb the tearing energy and stop tearing. can be done. Next, as a leno yarn, the breaking work is preferably 10% or more, more preferably 20 to 30%, than the warp and warp yarns.
% yarn can be used. The breaking work here is a value approximately expressed by the product of the strength at the time of cutting the yarn and the elongation at the time of cutting. Work at break = Tensile strength at break x Tensile elongation at break For example, polyester filament yarn with a tensile strength at break of 8.0 g per unit denier and a tensile elongation at break of 13% per unit denier is used as the warp and warp threads, and as a leno yarn, the unit 7.0g per denier, tensile elongation at break
18% polyamide fiber yarn is used. At this time, the breaking work of the leno yarn is approximately 21% greater than that of the warp and warp yarns. Furthermore, in consideration of ease of processing, it is desirable to use threads made of the same material. Furthermore, a leno yarn having a breaking elongation that is preferably 5% or more higher than that of the warp and warp yarns can also be used for the braided connection. When polyester filament yarn is used, the breaking elongation of the warp and warp yarns is preferably 15% or less, especially 8 to 12%, while the breaking elongation of the leno yarn is 15% or more, especially 20% or more, and there is no difference between the two. A difference of at least 5% or more gives good results. When the leno yarn is a synthetic fiber, the degree of polymerization of the polymer material is adjusted at the time of manufacture to maintain a predetermined strength and a desired high elongation at break; A filament with a lower drawing ratio, for example, an undrawn yarn, or a leno yarn having a desired elongation at break can be obtained by crimping during secondary processing. Furthermore, it is also possible to use leno threads that have a smaller adhesion force to the coating resin material than warp and warp threads. In this case, the leno thread may have its surface subjected to silicon processing or the like. In this case, the warp and warp threads are bonded to the coating resin material,
The degree of freedom for displacement and deformation decreases, but the degree of freedom for the leno thread is greater than that for the warp and warp threads, and when tearing force acts on the base fabric, the leno thread slips and is displaced and deformed. Therefore, tearing of the base fabric can be prevented. In order to reduce the adhesive force, the surface of the leno yarn should be subjected to non-adhesive treatment such as silicone treatment or oil treatment, or it should be treated with yarns that are inherently small in adhesive properties, such as polyethylene yarns and polypropylene yarns. You can use As described above, in the base fabric according to the present invention, it is preferable that the leno yarns for connecting the warp and warp yarns arranged in parallel in the warp and warp directions are substantially longer than the warp and warp yarns, and that the leno yarns are substantially longer than the warp and warp yarns. Even if the yarn is cut or displaced, at least part of it is long enough to not break, or the yarn is strong, has a large amount of work at break, and/or has a large elongation at break, or has poor adhesive strength. It is constructed with physical properties such as small size, and its tensile strength is maintained at high tension by warp and warp threads, and has leno threads to resist the impact force at the time of tearing or absorb tearing energy. Furthermore, by leaving the leno threads uncut, delamination between the resin coating and the sheet due to tearing can be prevented. Regarding the patented structure fabric according to the present invention, furthermore,
Patent Publication No. 52-50234 (Japanese Patent Publication No. 50-1668), Japanese Patent Publication No. 30381 (Sho 57-67446), Japanese Patent Publication No. 24415 (Sho 55-24415) related to the applicant's earlier application. Fabrics described in JP-A-54-139688), JP-A-55-134242, JP-A-56-159165, JP-A-57-14031, JP-A-57-14032, etc. can be suitably used. These textiles typically have a structure as shown in FIG. In the figure, 1 is a warp, 2 is a weft, and 3 is a leno thread. That is, the base fabric used in the present invention is useful for maintaining the mechanical strength of the resulting flexible sheet at a high level. In the flexible sheet of the present invention, one or both sides of a fibrous base fabric is coated with an intermediate layer made of soft PVC (polyvinyl chloride resin). This intermediate layer has a thickness sufficient to give the flexible sheet the desired flame retardancy, waterproofness, and mechanical strength, for example, 0.05 mm or more, preferably 0.05 to 1.0 mm.
It has a thickness of . The middle layer is a soft polyvinyl chloride resin film,
Alternatively, it can be formed on a fibrous base fabric using a paste, a straight material, etc., by a conventionally known method such as topping, calendering, coating, dipping, etc. The soft polyvinyl chloride resin may contain plasticizers, stabilizers, colorants, ultraviolet absorbers, and other functional agents. The surface of such a soft PVC interlayer is then crosslinked and subjected to metal vapor deposition. Surface crosslinking can be carried out by a method using a conventional crosslinking agent or by a physical method, and a metal vapor deposition layer may be formed on this crosslinked layer by a conventional method. However, it is preferable and more effective that the crosslinking of the surface of the soft PVC intermediate layer and the formation of the metal vapor deposited layer are carried out simultaneously by the treatment described in detail below. That is, the soft PVC crosslinked layer and the metal vapor deposited layer constituting the surface portion of the flexible sheet of the present invention are bonded to the resin crosslinks on the surface of the soft PVC intermediate layer and the metal vapor deposited layer in a low-temperature plasma atmosphere of inorganic gas and/or under vacuum ultraviolet light irradiation. It is preferable to form the film by simultaneously performing vapor deposition. Inorganic gases include CO, CO ₂ , O ₂ , N ₂ , H ₂ and
An inert gas such as Ar or He can be used.
Particularly effective are CO and mixtures of CO and Ar. It is optimal to introduce gas at an internal pressure of 10 ^-4 to 10 Torr; if the pressure is higher than this, the deposition rate of the evaporated metal will be extremely reduced, making it difficult to obtain the desired thickness of metal deposit. This requires a long time and is inefficient. Moreover, if the pressure is lower than this, the spatter cleaning effect due to the excited gas atoms will be poor, and the crosslinking efficiency on the surface of the molded article will also be reduced, making it difficult to obtain a metal coating with good adhesion. Vapor deposition can be performed using metals such as Al and Ti, metal oxides such as ZnO and MgO, and metal sulfides such as MoS, and other metals can be selected depending on the purpose and use. There are no particular restrictions. The low-temperature plasma treatment may be performed using any method such as high frequency discharge, microwave discharge, or corona discharge, but an internal electrode method is particularly preferable. Next, the apparatus and conditions that can be used for vapor deposition will be explained in detail with reference to FIGS. 2 and 3. For example, as shown in Fig. 2, a high-frequency ion plating device or a normal vacuum evaporation device is equipped with a high-frequency discharge electrode, a direct current applying electrode, and a gas introduction tube, and a high-frequency ion plating device as shown in Fig. Instead of electrodes, a mercury lamp can be used.
11 is a substrate (cathode), 12 is a vapor deposition tank (anode), and the heating temperature thereof is determined depending on the evaporation source used and the heat resistance temperature of the molded product. The evaporation tank may be a crucible type or an electron beam type, and is not limited to the device shown in the figure. The optimum processing power of the high frequency discharge coil 15 is 50 to 500W, especially 50 to 500W.
Preferably it is 300W. 15' is a mercury lamp, the optimum processing power is 100-500W, the ultraviolet range is 100-250nm, particularly preferably the processing power
200~350W, UV range 100~200nm. 1
Reference numeral 6 designates a shielding plate, and although the material is not particularly selected, it is preferable that the substrate side surface be coated with a metal having ultraviolet reflecting ability such as AlMgF ₂ in order to improve efficiency. Reference numeral 19 denotes a DC power supply, and the applied voltage thereof is generally 0.05 to 5 KV, but the optimum value is determined depending on the metal to be deposited.
In addition, in FIG. 2 and FIG. 3, 13 is a heating beater, 14 is a gas introduction tube, 17 is a sample for vapor deposition, and 20
21 is a gas cylinder, 21 is a high frequency power source, 21' is an optical oscillation circuit, 22 is a vacuum pump, and 23 is a thermocouple. When performing deposition in a low temperature plasma atmosphere, 20
It is optimal to carry out the treatment for ~80 minutes; if the treatment is shorter than this, the crosslinked layer on the surface of the molded product will become thinner, making it impossible to obtain a product with satisfactory adhesion and durability. Furthermore, if the length is longer than this, the etching of the metal surface by the excited gas molecules will proceed, making it impossible to obtain a smooth surface. Further, when vapor deposition is performed under vacuum ultraviolet light irradiation, a treatment time of 10 to 60 minutes is optimal. If it is shorter than this, a vapor deposited metal layer with a sufficient thickness cannot be obtained, while if it is longer than this, the resin of the molded product itself will deteriorate. The shape of the final product obtained in this way is as follows: viewed from the metal surface side, the vapor-deposited metal layer 24, the soft PVC
It has a structure of at least four layers (Fig. 4) consisting of a crosslinked layer 25, a soft PVC layer 26, and a fibrous base layer 27, and the soft PVC crosslinked layer acts as a layer to prevent leaching of plasticizers and other adhesion inhibiting substances. do. Also, depending on the application, metal vapor deposited layers may be provided on both sides, or one side may have a metal vapor deposited layer and the other side may have a crosslinked layer formed only by low temperature plasma treatment and/or vacuum ultraviolet light irradiation. good. A transparent film layer may be separately formed as a protective layer on the surface of the metal vapor deposited layer thus formed. Further, such a flexible sheet according to the present invention may be formed by first forming an integral body of a fibrous base fabric and a soft PVC layer, and then performing resin crosslinking and metal vapor deposition, or by first forming a soft PVC layer. It may be formed by preparing a metallized film and then integrating this with a fibrous base fabric. The flexible sheet of the present invention having the above configuration has a wide range of applications and uses, for example,
Products with aluminum vapor-deposited on the surface can not only be used in fields that were considered impossible with conventional flexible PVC films, such as heat-insulating wall materials, thermal/cold bags, and packaging films, but also in other fields. It can also be applied to large tents such as air domes, tents with eaves, packaging materials for heavy objects (heavy bags), and other heavy uses. Examples Next, examples of the present invention will be shown. Example 1 PVC (Denka SS-103) 100 parts by weight, DOP (dioctyl phthalate) 60
parts by weight, 3 parts by weight of EPS (epoxidized soybean oil),
The mixture was adjusted using 2 parts of Ba--Zn stabilizer and made into a 0.1 mm film using a heated roll.
This film is woven into a specially structured fabric as shown in Figure 1 using 11 polyester multifilament 1000 denier yarns as the warp and weft, and nylon 6 multifilament 75 denier yarn as the leno yarn. Attach it to a base fabric and use it as a sample. Place the sample in the specified position in the device shown in Figure 2, and then open the container.
After exhausting to 10 ^-5 Torr, through the gas introduction pipe
CO/Ar gas (mixing ratio 7/3) was introduced. Power consumption is 200W while maintaining the pressure inside the chamber at 0.05Torr.
Glow discharge was performed at Al as vapor deposited metal
Vapor deposition was performed using a DC applied voltage of 200 V, a substrate temperature of 80°C, and a crucible temperature of 900°C. The adhesive strength between the metal and the film of the obtained sheet was measured by the following grid method. The results are shown in Table 1. Checkerboard method: Cut a film whose surface is coated with resin or metal into 1cm squares, and cut 1mm squares in both the vertical and horizontal directions.
Make cuts at intervals to make a total of 100 squares.
Attach commercially available cellophane tape to the film,
Rub the surface strongly 10 times with a metal rod weighing 1 kg. After that, remove the sellotape and check the degree of peeling of the coating. The peeling state is expressed by the number of squares (retention rate; %) of the remaining coating material.

[Table] Example 2 The same sample used in Example 1 was set at a predetermined position in the apparatus shown in FIG. After evacuating the chamber, set CO/Ar gas (7/3) to the chamber pressure.
The sample was introduced at a pressure of 0.05 Torr, and then treated with ultraviolet light at a wavelength of 185 nm or 254 nm using a 300 W mercury lamp. Al was used as the deposition metal, and the deposition was performed under the conditions of an applied voltage of 200 V, a substrate temperature of 80°C, and a crucible temperature of 900°C. Adhesion was evaluated using the aforementioned grid method.
Furthermore, in order to examine the effect of exudation of adhesion inhibitors,
For comparison, measurements were also performed on samples subjected to the bleed acceleration test. The results are shown in Table 2. Bleed acceleration test Leave in a gear oven at 70℃ for one week.

[Table] In addition, when samples obtained in the same manner as these samples were subjected to a load of 20 kg/3 cm five times and then subjected to the same test as above, there was almost no difference in the results. However, when a similar test was conducted on a sample obtained in exactly the same manner as above except that the fibrous base fabric was not used,
The retention rate was extremely low at 0-4%. Furthermore, polyester multifilament 500 denier yarn was used as the warp and weft, each having a diameter of 22
A flexible sheet (hereinafter referred to as the former) was produced in the same manner as in Example 2 using a plain woven cloth woven at a density of 1/4 inch, and was evaluated in the same manner as in Example 2. The results of the 20Kg/3cm repeated load test were almost the same as the flexible sheet obtained in Example 2 (hereinafter referred to as the latter) and were good. In addition, when we tested these by gently rubbing them 10 times, the retention rate of the latter was 80 to 100.
%, while the former's was 60-80%, which is good for both, but the latter was slightly better. In addition, the results of cold weather crack resistance tests conducted on the former and the latter showed that the latter could withstand temperatures of about -20 to -25°C, while the former could withstand temperatures of about 5 to -5°C.
The latter gave more favorable results.

[Brief explanation of the drawing]

Fig. 1 is a schematic diagram showing an example of a specially structured woven fabric base fabric useful in the present invention, Fig. 2 is a schematic diagram of a glow discharge plasma treatment apparatus useful in manufacturing the flexible sheet of the present invention, and Fig. 3 is a schematic diagram showing an example of a special structure fabric base fabric useful in the present invention. FIG. 4 is a schematic cross-sectional view of an example of the flexible sheet of the present invention. 1... warp, 2... weft, 3... leno thread, 11... substrate (cathode), 12... crucible (anode), 13... heater, 14... gas introduction tube, 15... high frequency coil,
15'...Mercury lamp, 18...Metal for vapor deposition, 19...
DC power supply, 24... Vapor deposited metal layer, 25... Crosslinked resin layer, 26... Resin layer, 27... Fibrous base fabric layer.

Claims (1)

[Scope of Claims] 1. A fibrous base fabric, a soft PVC intermediate layer formed on at least one surface thereof, a metal vapor deposition layer formed on the intermediate layer, and the intermediate layer and the metal vapor deposition layer. A flexible sheet containing a soft PVC crosslinked layer existing at the interface with. 2. The fibrous base fabric has a warp layer consisting of a large number of warps arranged in parallel to each other, a weft layer consisting of a large number of wefts arranged in parallel to each other so as to be perpendicular to the warps, and the warp and weft. 2. The flexible sheet according to claim 1, which is a specially structured woven fabric base fabric consisting of leno threads entangled and bonded at their intersections. 3. The soft PVC cross-linked layer and the metal vapor deposited layer on the soft PVC intermediate layer are exposed to the soft
The flexible sheet according to claim 1, which is formed by simultaneously performing resin crosslinking and metal vapor deposition on the surface of the PVC intermediate layer.