KR19990063587A - Elastomer Sheet Laminate and Water-Resistant Sheet for Waterproofing by the Laminate - Google Patents

Abstract

The present invention is a water barrier sheet for waterproofing roofs, floors, walls, reservoirs or industrial waste treatment plants, etc., which has less color unevenness and delicate color tones, and does not cause warping, is excellent in weather resistance, and has no fear of discoloration even when colored. An object of the present invention is to provide a laminate in an elastomeric sheet, and a solution thereof is to integrally stack an elongated porous polytetrafluoroethylene (ePTFE) film 4 on the elastomeric sheet 2, and between them, a thermoplastic resin film. It is suitable to use the colored film laminated | stacked integrally through (3) and especially an ePTFE film and a thermoplastic resin film.

Description

Elastomer Sheet Laminate and Water Resistant Sheet for Waterproofing by the Laminate

Generally used for exterior materials that are left exposed for a long time after being exposed to the outside, for example, the sheets used for waterproofing water barrier sheets installed on roofs, floors, walls or reservoirs of industrial buildings, industrial waste treatment plants, etc. It is used to prevent the invasion of water into the ground or to prevent the water of the reservoir from seeping into the ground. Currently, it is a waterproofing method for waterproofing roofs or reservoirs of buildings. Many methods of laying an elastomeric sheet made of the like or the like have been adopted.

However, the rubber sheet of these sheets is relatively excellent in the weather resistance of the material itself, and can withstand long-term use, but other sheets such as polyvinyl chloride and polyethylene are excellent in initial properties and impact resistance, but are inadequate in weather resistance. Improvement is needed.

Therefore, it is proposed to improve the weather resistance of the sheet by laminating a fluororesin layer having excellent weather resistance on the sheet as disclosed in Japanese Patent Application Laid-open No. 3-92228.

In addition, recently, water-resistant water barrier sheets installed on roofs, floors, walls, or reservoirs of buildings require not only waterproofness and durability but also colored elastomeric sheets for appearance and aesthetics.

However, in recent years, due to appearance and aesthetic demands, the elastomeric sheet material itself is blended with a coloring elastomer sheet or a colored rubber sheet is laminated on a conventional black rubber sheet to form a vulcanized unit for use as a waterproof water barrier sheet. Doing.

Moreover, laminating | stacking the colored Tedlar (made by DuPont, polyvinyl fluoride) film integrally to a rubber sheet is also performed.

However, there is a possibility that the sheet laminated with the fluorine resin has a difference in expansion shrinkage between the fluorine resin and the sheet made of rubber, polyvinyl chloride, polyethylene, chlorosulfonated polyethylene, etc. There is.

In addition, the colored elastomer sheet has the following problems in addition to the problem of bending from the difference between the two components.

For example, a colored rubber sheet with a colorant mixed with rubber is clearly superior in appearance compared to a conventional black rubber sheet, but is inferior in weatherability to a black sheet. In addition, as the color tone, the brightness was low, and only an unsuitable color was obtained. In addition, the color unevenness between the lot is severe and also lacks in weather resistance, there is a problem of discoloration with the passage of time was not enough to satisfy the demand.

Moreover, the coloring sheet of polyvinyl chloride, the coloring sheet which consists of chlorosulfonated polyethylene, or the coloring sheet which consists of polyethylene by itself is not suitable for outdoor use for a long period of time because of poor weather resistance. And the sheet | seat which laminated | stacked the polyvinyl chloride film and the vulcanized rubber sheet | seat had the problem that a curvature generate | occur | produces from the difference of both properties.

In addition, polyvinyl fluoride (Dedra) is excellent in weather resistance, so that the water-resistant water barrier sheet laminated with this film and rubber sheet can prevent natural deterioration or discoloration. Could not be resolved.

In order to solve the problems described above, the present invention uses a particularly elongated porous polytetrafluoroethylene (hereinafter abbreviated as "ePTFE") film to reduce color unevenness, thereby producing a delicate color tone. It is also an object of the present invention to provide an elastomeric sheet including a rubber sheet that does not cause warpage and is excellent in weather resistance and does not cause discoloration even when colored.

The present invention is used for the use of exterior materials such as long-term exposure to the outside exposed to the outside, it is excellent in durability and hardly discolored elastomeric sheet laminates and this sheet, especially the roof, floor, wall, reservoir or industrial of buildings The present invention relates to a water-proof water barrier sheet installed in a waste treatment plant, which is excellent in aesthetics and weather resistance and has no fear of discoloration.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a sectional view showing a first embodiment of a laminate of an elastomeric sheet according to the present invention and a water-resistant water barrier sheet by the laminate.

2 is a cross-sectional view showing another embodiment of a laminate of the elastomeric sheet according to the present invention and a water-resistant water barrier sheet by the laminate.

3 is an explanatory diagram showing a vulcanization step and a film pressing step in the method for producing an elastomeric sheet laminate according to the present invention and a water-resistant water barrier sheet using the laminate.

※ Explanation of symbols about main part of drawing ※

1: Elastomer Sheet Laminate (Water Resistant Sheet)

2,15: elastomeric sheet (vulcanized rubber sheet)

3,17: thermoplastic resin film

4: ePTFE film 10: unvulcanized rubber sheet

The inventors of the present invention have completed the present invention by finding that it is effective to achieve the above object by laminating the ePTFE film integrally and constructing a composite sheet without or without interposing a thermoplastic resin film on the elastomeric sheet. did.

The present invention is characterized in that the elastomeric sheet laminate in which the ePTFE film is integrally laminated to the elastomeric sheet as described above. In addition, laminating a thermoplastic resin film between the elastomer sheet and the ePTFE film via lamination, using a colored ePTFE film as the ePTFE film, using a rubber sheet as the elastomer sheet, and using a colored film as the thermoplastic resin film An advantageous configuration is a feature of the present invention.

In another aspect, the present invention is characterized in that the ePTFE film is laminated on the elastomeric sheet using the above-described configuration in a water-proof water barrier sheet installed on a roof, floor, wall reservoir or industrial waste treatment plant of a building.

A thermoplastic resin film is interposed between the elastomeric sheet and the ePTFE film, a colored ePTFE film is used as the ePTFE film, a rubber sheet is used as the elastomeric sheet, and a colored film is used as the thermoplastic resin film. It is also included in the present invention as a feature to combine with the configuration.

The elastomeric sheet laminate and the waterproofing water barrier sheet according to the present invention can significantly increase weather resistance because the ePTFE film is laminated on the surface of the elastomeric sheet without deterioration due to ultraviolet rays and has excellent weather resistance, but excellent in conventional initial properties. Due to the problem of weather resistance, it can be used even in the elastomeric sheet material which has not been available for long-term use. In addition, the ePTFE film is flexible, plastic, has a unique property according to an arbitrary shape, and can be freely adapted to the shape change of the elastomer even when laminated with a flexible elastomeric material such as rubber. Therefore, when the ePTFE film is laminated with the elastomeric sheet, the ePTFE film does not peel off or cause warpage of the elastomer due to deformation of the elastomer.

When laminating the ePTFE film by interposing a thermoplastic resin film on the surface of the elastomeric sheet, when the thermoplastic resin film is heated and melted, the fused thermoplastic resin enters the pores of the ePTFE film. Even a film of polytetrafluoroethylene (PTFE), which is a resin film, can be fused with sufficient strength and excellent in color tone and weather resistance, and thus a water-proof water barrier sheet can be obtained without problems such as discoloration, peeling and warping of laminated sheets.

Next, the elastomeric sheet laminate according to the present invention and the water blocking sheet for waterproofing by the laminate will be described in detail.

The elastomeric sheet laminate according to the present invention shown in FIG. 1 and the water-resistant water barrier sheet 1 by the laminate include, for example, a thermoplastic resin film 3 on one side of an elastomeric sheet 2 such as vulcanized rubber. ) Is composed of a three-layer structure in which the ePTFE film 4 is integrally laminated. As another embodiment, as shown in FIG. 2, there is also a two-layer structure in which the ePTFE film 4 is directly laminated on the elastomeric sheet 2, which has a relatively lighter weight than the three-layer structure. There is an advantage.

In addition, in the present invention, in order to give a color to the elastomeric sheet 2 or the water-blocking sheet 1 for waterproofing, the ePTFE film 4 is used with a film 4 colored in a desired color or not colored. The white film of the original ePTFE is used.

In addition, when coloring is required on both surfaces of the appearance and aesthetic appearance laminated sheet 1, you may provide the colored ePTFE film 4 on both surfaces of the elastomeric sheet 2. As shown in FIG.

The elastomer sheet used in the present invention has the same function as a water-resistant water barrier sheet made of an elastomer such as conventional vulcanized rubber and polyvinyl chloride (waterproof barrier property, mechanical strength, and other physical and chemical properties required for water-resistant water barrier sheets. Characteristics) are used. Accordingly, the ePTFE film 4 serves as a supplement to an elastomeric sheet that provides a uniform color tone by improving weather resistance and other functions by blocking ultraviolet rays without causing warpage as a waterproof barrier sheet.

Examples of the elastomer constituting the elastomer sheet 2 include natural rubber, polybutadiene rubber, polyisoprene rubber, butyl rubber, chloroprene rubber, fluorine rubber, styrenebutadiene copolymer rubber, and ethylene propylene tarpaulin (other ethyl as monoma). Rubbers such as tennobolnen, indicator cropentadiene, 1,4 hekisadiene, and the like, olefin-based elastomers such as ethylene-vinyl acetate copolymer, polyethylene, and polypropylene, olefin-based thermoplastic elastomers, and urethane-based thermoplastics. Elastomers, styrene-butadiene copolymers Thermoplastic elastomers such as thermoplastic elastomers, or blends thereof can be used. The rubber may be vulcanized by adding a vulcanizing agent, a vulcanization accelerator, or the like, or may be a non-vulcanizing one. In addition, the olefinic thermoplastic elastomer and the urethane thermoplastic elastomer include those that are fully crosslinked or semicrosslinked. Most preferred among these materials is ethylene propylene elastomer, a blend of ethylene propylene tarpaulin and butyl rubber. Ethylene propylene tarpaulin is the most weather-resistant material among the known rubber materials, and it is easy to be fused with a thermoplastic resin from the one containing ethylene. Moreover, about what mix | blended butyl rubber, the workability of a raw material becomes good and adhesiveness is mentioned as a reason.

The thickness of the elastomeric sheet 2 is preferably 0.3 to 3.0 mm, more preferably 1.0 to 2.0 mm. If the thickness is larger than 3.0 mm, it is not preferable because the flexibility of the sheet is impaired and it becomes difficult to come into close contact with the substrate. As a more preferable range, it is 1.0-2.0mm, but when it is thinner than 1.0mm, the sheet warpage becomes severe by the difference of the thermal expansion coefficient of the laminated ePTFE film and an elastomeric sheet, and when it is thicker than 2.0mm, the difference of the joint part of sheets is It becomes unfavorable because it becomes large and becomes bad in appearance, or impairs walkability. In addition, the thermoplastic resin film 3 is an inclusion for integrally laminating the elastomeric sheet 2 and the ePTFE film 4 by heat fusion. As the thermoplastic resin film used for the three-layered sheet, any material that can be fused with both the elastomeric sheet 2 and the ePTFE film 4 can be used, but polyethylene, ethylene, vinyl acetate copolymer, ethylene methyl methacrylate, and the like can be used. This is preferred. More preferably, polyethylene is most suitable in terms of processability, adhesion, chemical stability after processing, and the like. Preferably the thickness of the thermoplastic resin film 3 is 10 micrometers or more, More preferably, it is 20 micrometers or more. If the thickness is less than 10 µm, it is not preferable because of poor workability, less fusion area, and poor fusion.

Moreover, it turns out that it is preferable to use the colored thermoplastic resin film 3 for the following reasons. In the present invention, the colored ePTFE film is used to make the sheet excellent in appearance and aesthetic appearance. However, the thickness of the ePTFE film 4 makes the laminated elastomer 2 visible on the surface. do. Therefore, by coloring the thermoplastic resin film 3, the color of the elastomer 2 can be prevented from appearing on the surface, and a clearer color can be produced.

In addition, the color of the thermoplastic resin film 3 may be the same color as the ePTFE film 4 on the surface, or may be a different color.

As described above, the thermoplastic resin film 3 functions as an adhesive for integrally laminating the elastomeric sheet 2 and the ePTFE film 4, and thus the thermoplastic resin film 3 can be used for laminating by fusion processing. Become. PTFE is generally known as a material that is difficult to be fusion or adhesive processing, but in the present invention, the ePTFE film 4 is used as described above. The anchor is used to infiltrate the thermoplastic resin in the molten state into the hole using the elongated porous film. By the effect, the elastomer 2 and the ePTFE film 4 can be laminated firmly and integrally.

On the other hand, the ePTFE film 4, which is an important component for forming the features of the present invention, as described above, is a water-blocking sheet for waterproofing to block ultraviolet rays without causing warpage to improve weather resistance or other functions and impart a uniform color tone. It serves as a replenishment of the elastomeric sheet.

The ePTFE film 4 is produced by the production methods described in Japanese Patent Application Laid-Open No. 53-39719, 51-18991 and the like, and its microstructure is also known with this production method. Specifically, the ePTFE film is extruded through a die of a paste molded body consisting of a mixture of PTFE fine powder and a lubrication aid such as petroleum nough. It is manufactured by extending | stretching in the direction more than axial direction at high temperature below melting | fusing point. In addition, in the ePTFE film of the present invention, in the ePTFE film of the present invention, in the ePTFE film of the present invention, a firing treatment may be performed after heating to a temperature above the melting point of PTFE while fixing the microstructure generated by elongation and improving the dimensional stability. The process is not a necessary process.

The ePTFE film thus produced is a pure white, flexible film with a marshmallow-like texture. In addition, the film has air permeability, and it can be seen that the hollow hole called "hole" is continuous from the surface of the film to the inner surface. Observed by electron microscopy, the microstructure of the film has a unique fibrous porous structure consisting of fibrils (small fibers) and nodes connecting them (nodules) both on the surface and inside. This fibril / node structure changes shape by the stretching direction and the stretching ratio. For example, when stretched in one axial direction, fibrils are oriented along the stretch direction to form a reed screen, and the nodes connecting the fibrils are observed to have a long and thin island shape at right angles to the stretch direction. On the other hand, when biaxially elongated, fibrils spread in a radial direction in the elongated direction, and the nodes connecting them are observed to be thin particles rather than islands. In addition, when the expansion ratio is increased, the fibril generally becomes longer in spite of the extension direction, so that the node shape becomes smaller and ultimately becomes a so-called nodeless structure composed of only fibrils. The specific gravity of the ePTFE film is smaller than that of pure PTFE filler and the opening ratio, but most of them are smaller than that of water.

ePTFE is made of pure PTFE and the fibrils and nodes that characterize the structure are both PTFE. However, PTFE is a chemically stable material, and it does not deteriorate or corrode well even when used for water proofing of roof waterproofing or reservoirs that are faded by sunlight or outside air for a long time. Thus, ePTFE is inherently chemically stable with PTFE, making it resistant to UV radiation and not oxidized by air. Since PTFE is not synthesized in nature, it has excellent weather resistance such as not being eroded by bacteria.

However, ePTFE has different mechanical and physical properties than PTFE fibres. Films made of PTFE solids exhibit a milky white like transparent frosted glass, but ePTFE films are pure white. This is considered to be due to the total reflection phenomenon derived from the microporous structure of ePTFE. In addition, PTFE filler is generally considered to be a rigid material, but ePTFE film has a marshmallow-like texture, as described above, and is a plastic material that can be in close contact with an object of any shape to form another object. to be. This is also considered to be due to a unique fibrous structure. It also has a soft elastic recovery because of its mesh structure. Therefore, even when laminated as the elastomeric sheet laminate of the present invention, it is possible to easily follow the stretching of the elastomer. In addition, PTFE is considered to be a material that is difficult to bond due to its incompatibility with other materials. However, ePTFE has a porous structure, so that it is easily bonded by the anchor effect. In particular, since the organic medium having a small surface tension easily penetrates, the adhesion, impregnation, coating and the like are performed using the organic medium.

When laminating a film that lacks flexibility due to its rigidity such as PTFE-filled film, fluorine resin film other than PTFE, polyester film, and polyvinyl chloride film, and an elastomeric sheet, the laminated body may be changed due to the difference in expansion shrinkage of the constituent material. Deformation may occur or peeling may occur due to repeated bending. For example, when the fluororesin film or polyester is laminated on the elastomer, the stiffness of the fluororesin film or the polyester film is too high to conform to the deformation of the elastomer sheet, and thus the sheet is warped or peeled off. However, in the case of the ePTFE film 4, the tensile modulus of elasticity is small from the above-described configuration, and excellent in flexibility, the laminated sheet can be prevented from bending even when integrally laminated with the elastomeric sheet 2.

Table 1 shows the tensile modulus of elastic fluororesin film, polyethylene fluoride film (PFE) and ePTFE film. It can be seen from Table 1 that the tensile modulus of ePTFE film has a relatively low value and excellent flexibility compared to general fluororesin film (polyvinyl diproide) (PVDF) or polyvinyl prolide film (PVF).

Table 1

ASTM Test Method ePTFE PTFE PFE PVDF PVF Tensile Modulus (Kg / ㎠) D638 360 4100-5600 3500 10200-30000 19000

Preferred thickness of the ePTFE film 4 is an average thickness measured with a dial gauge (1/1 000 mm dial scenic gauge manufactured by Techlock Co., Ltd., measured without load other than the body spring load). It is the range of micrometers, More preferably, it is 20-100 micrometers. If the thickness is less than 3 µm, sufficient mechanical durability cannot be obtained and lamination processing becomes difficult. On the contrary, when the thickness exceeds 300㎛, the production is bad and the material cost is high.

When the ePTFE film 4 is specified by its pore size, the maximum pore size measured by the bubble point method (ASTM F-316) is preferably 0.01 to 10 m, more preferably 0.05 to 5 m. If the maximum hole diameter is less than 0.01 μm, fusion using the anchor effect becomes difficult. If the maximum hole diameter exceeds 10 μm, sufficient mechanical strength cannot be obtained.

In addition, the ePTFE film 4 may be subjected to n-force processing and to which unevenness is applied. When the color of the elastomeric sheet 2 is visible on the surface due to the thickness of the ePTFE film 4, the color seen through enbossing of the ePTFE film 4 becomes a uniform pattern, which improves the appearance. The n-force processing of the ePTFE film 4 may be processed before lamination with the elastomer sheet 2 or the thermoplastic resin film 3, or may be processed when laminating.

As a method of coloring an ePTFE film, a method of embedding a pigment in a hollow hole of a film by mixing it with a pigment during film production, and embedding a pigment in a hollow hole of a film by applying a solvent-based paint after forming a film The method and the method of dripping the film in a coating bath after forming a film and embedding a pigment in the empty hole of a film are mentioned.

The following describes a method of incorporating pigment into an ePTFE film and coloring it.

0.5-30 wt% of inorganic pigments, for example, carbon black, are mixed with PTFE resin. Although the blending amount is adjusted by the color tone or the type of pigment, pinholes or strength decrease in the film extension at 30 wt% or more. The mixing method is 1) adding a fully dried pigment to a granular PTFE resin and mixing it with a mixer. 2) mixing by adding a pigment to a liquid obtained by dispersing PTFE primary particles called dispersions in water. There is a method to make it, and any method can be used, but the latter method 2 is more suitable because more uniform pigment dispersion is possible and the color of the finally obtained colored ePTFE film is better. 17-22 wt% of hydrocarbon solvents are added to the granular PTFE as a lubricant for extrusion, and preformed by extruding. After drying and removing the lubricant from the film rolled extrudates to a predetermined thickness, 50 to 1500% preferably 500 to 1000% in the width direction at a high temperature below the melting point of the PTFE (327 ° C.) and, if necessary, the melting point of the PTFE. It heats and heat-processes to the above temperature. The film width at this time is preferably 500 mm or more, more preferably 1200 mm or more. If the film width is less than 500 m, the width of the water-repellent sheet for waterproofing finally obtained is limited to 500 mm or less, which is undesirable because of poor workability in the field.

Usually, the ePTFE film is white and can be used as a water-proof water barrier sheet of white when laminated on the elastomeric sheet in such a state, and such a case is also included in the present application. As a result, when the colored material is used, an elastomer sheet colored in any color can be obtained as a result, and excellent color tone can be imparted to the appearance of the water barrier sheet for waterproofing.

In addition, when the pigment is embedded in the empty hole of the ePTFE film, a film colored in any color can be obtained. In addition, a white film can be obtained as it is by using an ePTFE film to which no pigment is added.

The following describes a method for producing the elastomeric sheet laminate of the present invention and the water-blocking sheet for coloring waterproofing.

As the elastomer sheet, for example, the vulcanized rubber sheet 2 is used and the ePTFE film 4 is integrally laminated by thermal fusion through a thermoplastic resin, and the thermoplastic resin film and the ePTFE film 4 are preheated. After laminating integrally by a method such as fusion by a roll, the vulcanized rubber sheet 2 is superposed on the thermoplastic resin film 3 side of the film in which the thermoplastic resin film 3 and the ePTFE film 4 are integrated, and then, by heat transfer or the like. Method of laminating integrally by heating and pressing, laminating the thermoplastic resin film 3 and the vulcanized rubber sheet 2 by heating and pressurizing by heating or the like, and integrally laminating the thermoplastic resin film 3 and the vulcanized rubber sheet. (2) integrally stacking the sheet and the ePTFE film (4) by a method such as fusion by heat-roll, and overlapping the ePTFE film (4) and the thermoplastic resin film (3) vulcanized rubber sheet (2) By heatrol A heating and a method of laminating integrally between the pressure to the thermoplastic resin film and between the ePTFE film and a thermoplastic resin film 3 and the vulcanized rubber sheet (2) which at the same time is also possible, such as by any way.

In another embodiment of the present invention, the above-described vulcanized rubber sheet 2 and the ePTFE film 4 are integrally laminated without the thermoplastic resin film 3, but in the case of the laminate having the two-layer structure, It can be laminated in the same manner.

When the unvulcanized rubber sheet and the ePTFE film 4 are overlapped with each other, the rubber is heated and pressurized with a vulcanization can or the like to laminate both of them.

In this case, since it has fluidity in the unvulcanized state of rubber, it can be put into the empty hole of the ePTFE film 4, so that the anchoring effect can be obtained without the thermoplastic resin film 3 interposed, and thus it can be laminated integrally.

Of course, you may laminate | stack the sheet | seat of the three-layered structure which is the above-mentioned Example via the thermoplastic resin film 3 by the method of using the same unvulcanized rubber sheet. In addition, even when the elastomer is a polymer other than rubber, it can be integrated by bonding using a chloroprene rubber, butyl rubber, epoxy resin, urethane or cyanoacrylate adhesive.

In addition, it is possible to increase the productivity of the sheet of the present invention and to produce efficiently by manufacturing in the following manner.

That is, the rubber sheet 2 immediately vulcanized is a method of laminating with the thermoplastic resin film 3 laminated integrally with the thermoplastic resin film 3 or the ePTFE film 4 using the heat while still being heated. Specifically, as shown in FIG. 3, the unvulcanized rubber sheet 10 extruded from an extruder (not shown) using the apparatus as shown in FIG. 3 is positioned on the endless belt 11, It is sent into the vulcanization can 13 set at a predetermined temperature (150-180 ° C.) and vulcanized, and is discharged out of the vulcanization can 13 from the derivation roll 14 to the pressure contact roll 16 via a plurality of guide rolls. 17) or the thermoplastic resin film 17 integrally laminated with the ePTFE film is pressed and wound on a roll 19 wound through the tension roll 18. In this case, the vulcanized rubber sheet 15 which has just been sent from the vulcanization can 13 has a surface temperature in the range of 130 to 159 ° C., so that the thermoplastic resin film 17 can be easily fused. According to this method, the press contact roll 16 does not need to be heated in advance, which can contribute to improvement of productivity and reduction of manufacturing cost.

Thus, by using the manufacturing method of the present invention as described above by laminating the ePTFE film (4) on the surface of the vulcanized rubber sheet (2) through the thermoplastic resin film (3) and heat to the thermoplastic resin film (3) When melted by adding the molten thermoplastic resin into the porous film hole, PTFE resin film, which is a fluororesin film that cannot be firmly bonded by thermal fusion, can be fused with sufficient strength and is excellent in color and weather resistance. The colored rubber sheet laminated body and the water-resistant water barrier sheet 1 for coloring waterproofing which have no problems, such as peeling of a sheet | seat and curvature, can be obtained.

The sheet laminated body of the structure similar to FIG. 1 which laminated | stacked the ePTFE film 4 which consists of PTFE on the vulcanized rubber sheet 2 via the polyethylene resin film was produced as follows.

As the vulcanized rubber sheet (2), a compound sheet such as Table 2 containing ethylene propylene tarpaulin (EPT) as a main component was used.

As a polyethylene resin film, the polyethylene film (30 micrometers in thickness) by the Kasei Co., Ltd. was used.

TABLE 2

Compounding Compounding amount (part by weight) EPT Steering Acid Zincation Process Oil Carbon Black Calcium Carbonate Promoting TT Promoting DM Sulfur 100135050601.01.01.5

Example 2

The sheet laminated body of the structure similar to FIG. 1 which laminated | stacked the ePTFE film on the polyethylene sheet (high density) through the polyethylene resin film was constructed. As a polyethylene sheet, the sheet | seat of the combination of Table 3 which used the high density polyethylene (HDPE) as a main component was used. Polyethylene resin film is the same as in Example 1.

TABLE 3

Compounding agent Compounding amount (part by weight) HDPE carbon black 1001

In addition, the ePTFE film 4 was colored in gray and started by the following manufacturing method.

PTFE used Disperse Teflon manufactured by Sanyi Dupont Floro Chemical Co., Ltd.

The pigment added for coloring is made of Mitsubishi Chemical's Ketjen Black, 3 wt% of the dispersion Teflon is mixed, and PTFE is granulated to make such a PTFE extrusion lubricant, Demitsu Petrochemical Co., Ltd. 18.5 wt% was added, 700% elongation was performed in the width direction after mixing, and the resultant was heat-treated at 360 ° C. to obtain a light gray PTFE film (4). The thickness of the obtained ePTFE film 4 was 43 micrometers (measured in the state which did not apply the load other than a main body spring load with the 1/1000 mm dial slick gauge by Techlock Co., Ltd.), and the maximum hole diameter was 0.5 micrometer. (ASTM F-316)

The color tone of the obtained ePTFE film was changed from 1,3,7,10,25wt% to 1,3,7,10,25wt%, and the color of the ePTFE film obtained was changed from light gray to black as the amount of the ketchen black was increased. However, the 3 wt% of the blended ePTFE film was excellent in the color tone as gray.

Next, each of the above was laminated as follows to obtain a waterproof water barrier sheet.

First, the light gray colored ePTFE film and polyethylene film were fused by heat nip. At this time, in order to prevent a polyethylene film from melting and adhering to a heat trol, an ePTFE film was made into the heat trolley and the polyethylene film was made into the nip roll side. The temperature of the heat trol was processed at 170 degreeC, the nip pressure of 7 Kg / cm <2>, and the processing speed of 5 m / min.

The two-layer laminated product of the ePTFE film and the polyethylene film thus obtained was subjected to fusion processing using a vulcanized rubber sheet and a device as shown in FIG. The processing conditions were a temperature of 153 ° C. on the surface of the vulcanized rubber sheet, a nip pressure of 5 Kg / cm 2, and a processing speed of 5 m / min. In addition, a three-layer laminate of ePTFE film, polyethylene film and vulcanized rubber sheet was obtained.

Comparative Example 1

The color rubber sheet (0.3 mm thick) of the formulation shown in Table 4, mainly composed of ethylene propylene tarpaulin and butyl rubber (IIR), and the black rubber sheet, shown in Table 2, mainly composed of ethylene propylene styrene tarpaulin (1.2). Curly sheet which laminated | stacked mm) was made into the comparative example 1.

Table 4

Compounding Compounding amount (part by weight) EPTIIR zinc steering wheel tar SW SW heavy calcium carbonate Silica paraffin type oil carbon black vulcanizer TMTDMBT sulfur 70305140302030110.51

Comparative Example 2

In Example 1, a sheet laminate was prepared in the same manner as in Example 1, except that a 30 µm thick Tedra (Polyvinyl Prolide) product instead of ePTFE film was colored green. did.

Comparative Example 3

Except not using an ePTFE film in Example 2, the sheet laminated body was created like Example 2, and it was set as the comparative example 3.

Table 5 shows the comparative data of the said Example and each comparative example.

Weatherometer and outdoor exposure test in the table were carried out under the following conditions, respectively.

Weathermeter; After 1000 hours according to JIS A 1415

Outdoor exposure test: 6 months later

Table 5

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 hue Good Good Good Good Good Unevenness of hue none none Each lot has a car none none Weatherometer Fading none none Fading none Fading Peeling Film breaking Film breaking Color rubber breaking Film wave step peeling none warp Almost none none none + 15mm bends on the film side none Surface crack none none none none Crack Outdoor exposure test Fading none none Slightly faded none Fading Peeling Film breaking Film breaking Color rubber breaking Film Breaking Interfacial Peeling none warp Almost none none none + 12mm bends on the film side none Surface crack none none none none Crack

In the table, the color rubber sheet of Comparative Example 1 had a good color tone, but there was a color unevenness between the lots, so that the color rubber sheet remarkably faded after the weatherometer and outdoor exposure test. In addition, the polyvinyl prolide laminated sheet of Comparative Example 2 had good color tone, no color unevenness, and no fading after weatherometer and outdoor exposure test, but warpage was caused by the difference in thermal expansion coefficient between rubber and polyvinyl prolide. In addition, the peel test showed that the film was partially broken and the interface peeled. In Comparative Example 3, the color tone was good but the color faded.

On the other hand, all of the examples according to the present invention had good color tones and did not cause discoloration or peeling or warping even after various light exposure tests, and compared with Comparative Example 1, Comparative Example 2, and Comparative Example 3, extremely good results were obtained. there was.

The present invention is laminated with an elastomeric sheet using an ePTFE film as described above as a sheet having water resistance and water barrier properties, and various sheets have a single piece, which is not enough to improve the point of insufficient color unevenness and delicate color tone. At the same time, it is possible to impart sufficient weather resistance to the elastomeric material, which is not warped and can not be used in the past due to weather resistance, and has the effect of obtaining a water-resistant water barrier sheet without fear of discoloration or peeling.

Claims (10)

An elastomeric sheet laminate comprising an elongated porous polytetrafluoroethylene (ePTFE) film laminated on an elastomeric sheet. The method of claim 1, An elastomeric sheet laminate comprising a thermoplastic resin film interposed between an elastomeric sheet and an ePTFE film. The method according to claim 1 or 2, An elastomeric sheet laminate characterized by using a colored film as an ePTFE film. The method of claim 2 or 3, An elastomeric sheet laminate comprising a colored film as a thermoplastic resin film. The method according to claim 1, 2, 3 or 4, An elastomeric sheet laminate comprising a rubber sheet as an elastomeric sheet. A water resistant sheet for waterproofing, which is laminated to an elastomeric sheet in a water resistant sheet for laying on a roof, a floor, a wall, a reservoir or an industrial waste treatment plant of a building. The method of claim 6, A water-proof water barrier sheet installed on a roof, a floor, a wall, a reservoir, or an industrial waste treatment plant of a building, wherein the water-resistant water barrier sheet is interposed between an elastomeric sheet and the ePTFE film. The method according to claim 6 or 7, A water barrier sheet for waterproofing water, comprising: ePTFE colored on an ePTFE film in a water barrier sheet for installation on a roof, floor, wall, reservoir, or industrial waste treatment plant. The method according to claim 7 or 8, A water-proof water barrier sheet using a colored film of thermoplastic resin in a water-resistant water barrier sheet installed on a roof, a floor, a wall, a reservoir, or an industrial waste treatment plant of a building. The method according to claim 6, 7, 8, or 9, A water-resistant water barrier sheet using an rubber sheet as an elastomeric sheet in a water-resistant water barrier sheet installed on a roof, a floor, a wall, a reservoir, or an industrial waste treatment plant.