WO1997010952A1

WO1997010952A1 - Elastomer sheet laminate and waterproof water-barrier sheet formed of the laminate

Info

Publication number: WO1997010952A1
Application number: PCT/JP1996/002704
Authority: WO
Inventors: Sadayoshi Sakanaka; Hikaru Kano; Koji Yano; Yoshihiro Chikamori; Norimasa Kato
Original assignee: Mitsuboshi Belting Ltd.; Japan Gore-Tex Inc.
Priority date: 1995-09-19
Filing date: 1996-09-19
Publication date: 1997-03-27
Also published as: AU7001296A; CA2232617A1; JPH09141784A; JP4100581B2; KR19990063587A

Abstract

An elastomer sheet laminate for use as a waterproof water-barrier sheet for a roof, floor or wall of a building, a reservoir or an industrial waste disposal facility. It can be colored evenly and delicately, hardly warped, and is superior in weatherability. The color does not shade. It comprises an elastomer sheet (2), a stretched porous polytetrafluoroethylene (ePTFE) film (4), and a thermoplastic resin film (3) interposed between the sheet (2) and film (4). In particular the ePTFE film and thermoplastic resin film are preferably colored.

Description

Specification

Elastomer sheet laminate and waterproof / waterproof sheet using the laminate

INDUSTRIAL APPLICABILITY The present invention is used for applications such as exterior materials that are left for a long period of time while being exposed to the outside world.Elastomer sheets and eyebrow bodies that are required to have excellent weather resistance and to be resistant to discoloration are also used. In particular, the present invention relates to a waterproof impermeable sheet laid on a building roof, floor, wall, storage pond, or industrial waste disposal site, which has excellent aesthetics and weather resistance, and has no discoloration problem. Background art

Generally used for applications such as exterior materials that are left for a long period of time while being exposed to the outside world, for example, waterproof roofing sheets laid on the roof, floor, walls or reservoirs of buildings, industrial waste disposal sites, etc. These sheets are primarily used to prevent rainwater from entering the interior of the building and to prevent the water in the reservoir from seeping into the ground. As a method of waterproofing the roof of a building or waterproofing a reservoir, there are many methods of laying an elastomer sheet made of rubber, polyvinyl chloride, polyethylene, ethylene vinyl acetate, chlorinated polyethylene, modified asphalt, etc. Has been adopted.

However, among such sheets, the rubber sheet is excellent in the weather resistance of the material itself and can withstand long-term use. However, other sheets such as polyvinyl chloride-polyethylene are not suitable for initial use. Although excellent in properties such as physical properties and impact resistance, the weather resistance was insufficient, and improvement was required.

Therefore, it has been 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 Utility Model Laid-Open No. 3-92228. In recent years, waterproof waterproofing sheets laid on the roofs, floors, walls, or reservoirs of buildings have been required not only to have waterproof and weatherproof properties but also to have colored elastomer sheets due to appearance and aesthetic issues. Has been done.

By the way, recently, due to the demand for appearance and aesthetics, a colorant has been added to the elastomer material itself. A colored elastomer sheet is compounded, or a colored rubber sheet laminated on a conventional black rubber sheet and vulcanized and integrated is used as the waterproof / waterproof sheet.

In addition, colored Tedlar (Polyvinyl Fluoride, DuPont) film is laminated and integrated on a rubber sheet.

However, the sheet on which the fluororesin is applied has a difference in the expansion and contraction properties between the fluororesin and the sheet made of rubber, polyvinyl chloride, polyethylene, chlorosulfonated polyethylene, etc. In that case, there is a problem that warping occurs due to the difference.

In addition, regarding the colored elastomer sheet, there are the following problems in addition to the problem that warpage occurs due to the difference in properties between the two.

For example, a color rubber sheet in which a colorant is mixed with rubber is certainly better in appearance than a conventional black rubber sheet, but is inferior in weather resistance to a black sheet. In addition, as for the color tone, the brightness was low and only a delicate color tone could be obtained. In addition, there was a problem that the color variation between lots was severe, and there was also a problem that the weather resistance was poor and the color changed over time, which did not satisfy the requirements.

Furthermore, a colored sheet made of polyvinyl chloride and a colored sheet made of black sulfonated polyethylene and a colored sheet made of polyethylene are in themselves poor in weather resistance and unsuitable for long-term outdoor use. there were. Then, a sheet obtained by laminating a film of bolivinyl chloride with a vulcanized rubber sheet had a problem that warpage was generated due to the difference in properties between the two.

In addition, since polyvinyl fluoride (Tedla-1) has excellent weather resistance, a waterproof and water-proof sheet made by integrally laminating the film and rubber sheet has been improved to prevent natural deterioration and discoloration. The problem of warpage due to the force <, which is also the difference in expansion and contraction properties, cannot be eliminated.

The present invention addresses the above-described problems, and in particular, uses a stretched porous polytetrafluoroethylene (hereinafter abbreviated as “ePTFE”) film to reduce color variation and to provide a delicate color tone. As well as no sleds, An object of the present invention is to provide an elastomer sheet including a rubber sheet having excellent weather resistance and having no problem of discoloration even when colored. Disclosure of the invention

That is, the inventors of the present invention have conducted intensive studies, and as a result, the ability to laminate and integrate an ePTFE film with or without a thermoplastic resin film in an elastomer sheet to form a composite sheet. The inventors have found that the present invention is effective in achieving the above object, and have completed the present invention.

The present invention is based on the above viewpoint, and firstly features an elastomer sheet laminate in which an ePTFE film is integrally laminated on an elastomer sheet. Further, laminating a thermoplastic resin film between the above elastomer sheet and the ePTFE film, using a colored ePTFE film as the ePTFE film, and using a rubber sheet as the elastomer sheet, It is also advantageous to use a colored film as the thermoplastic resin film, which is a feature of the present invention.

Further, the present invention adopts the above-mentioned configuration particularly in a waterproof impermeable sheet laid on a roof, a floor, a wall, a reservoir, an industrial waste disposal site, or the like of a building, and laminates the ePTFE film on an elastomer sheet. It is characterized by the following.

In addition, a thermoplastic resin film is interposed between the elastomer sheet and the ePTFE film, a colored ePTFE film is used as the ePTFE film, a rubber sheet is used as the elastomer sheet, and the thermoplastic resin is used. The present invention is also characterized by using a colored film as a fat film and combining with the above configuration, and is included in the present invention.

The elastomer sheet laminate and the waterproof / waterproof sheet according to the present invention are not deteriorated by ultraviolet rays and have an extremely excellent weather resistance e-PTFE film laminated on the surface of the elastomer sheet, so that the weather resistance can be greatly increased. This makes it possible to use elastomer materials that were previously excellent in initial physical properties but could not be used for long-term exposure due to weather resistance problems. In addition, ePTFE film is flexible and plastic, has unique properties along with those of any shape, and is soft like rubber. _C and钦elastomeric one material can follow freely the shape change of the Elastica Bok mer also »layer Thus, if e PTFE film laminated with the elastomeric sea Bok,剝scree by not follow the deformation of the elastomer Shi Bok Nor warp the elastomer sheet.

When the ePTFE sheet is laminated with a thermoplastic resin film on the surface of the elastomer sheet, when the thermoplastic resin film is heated and melted, the melted thermoplastic resin becomes the pores of the ePTFE film. PTFE, which is a fluororesin film that cannot normally be firmly bonded by heat fusion, can be fused with sufficient strength. It is possible to obtain a waterproof / waterproof sheet excellent in color tone and weather resistance and free from discoloration, separation of a laminated sheet, and warpage. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a cross-sectional view showing one embodiment of an elastomer sheet laminate according to the present invention and a waterproof / waterproof sheet using the laminate.

FIG. 2 is a cross-sectional view showing another embodiment of the waterproof sheet provided with the elastomer sheet laminate and the eyebrows according to the present invention.

FIG. 3 is an explanatory view showing a vulcanizing step and a film crimping step in a method for manufacturing a waterproof and water-impermeable sheet by using the elastomer sheet according to the present invention.

[Explanation of symbols]

1 Elastomer sheet laminate (waterproof / waterproof sheet), 2, 15 Elastomer sheet (vulcanized rubber sheet), 3, 17 Thermoplastic resin film, 4 e PTFE film, 10 unvulcanized rubber sheet Hereinafter, the above-mentioned elastomer sheet laminate according to the present invention and the waterproof / waterproof sheet made of the fertilizer will be described in more detail.

As shown in FIG. 1, an elastomer sheet laminate and a waterproof / waterproof sheet 1 made of an eyebrow body according to the present invention include an ePTFE sheet 4 on one side of an elastomer sheet 2 such as a vulcanized rubber via a thermoplastic resin film 3. Are integrated into a three-layer structure. As another example, as shown in FIG. 2, there is a two-layer structure in which the ePTFE film 4 is directly laminated on the elastomer sheet 2, and the weight of the entire laminate sheet 1 is smaller than that of the three-layer structure. This has the advantage of being relatively light.

In the present invention, in order to impart a color to the elastomer sheet 2 or the waterproof / waterproof sheet 1, the e PTFE film 4 may be a film 4 having a desired color, or may not be colored. The original e-PTFE white film is used.

Further, when coloring is required on both sides of the laminate sheet 1 from the viewpoint of appearance and aesthetics, a colored ePTFE film 4 may be provided on both sides of the elastomer sheet 2.

The elastomer sheet used in the present invention has the same function as a waterproof waterproof sheet made of an elastomer such as a conventional vulcanized rubber or polyvinyl chloride (required for a waterproof waterproof sheet, mechanical strength, etc.). Physical and chemical properties). Therefore, the ePTFE film 4 can be used as a supplement to an elastomer sheet that provides excellent color tone by improving the weather resistance and other functions by blocking ultraviolet rays without generating warpage on the waterproof water-blocking sheet. Functions as

Examples of the elastomer constituting the elastomer sheet 2 include natural rubber, polybutadiene rubber, polyisoprene rubber, butyl rubber, chloroprene rubber, fluorine rubber, styrene-butadiene copolymer rubber, and ethylene propylene terpolymer (as other monomers). , Ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, etc.) or ethylene-vinyl acetate copolymers, olefin elastomers such as polyethylene, polypropylene, etc., orolefin thermoplastics Elastomers, thermoplastic elastomers such as urethane-based thermoplastic elastomers, styrene-butadiene copolymer thermoplastic elastomers, and blends thereof can be used. The rubber may be vulcanized by adding a vulcanizing agent, a vulcanization accelerator or the like, or may be non-vulcanized. In addition, as for the olefin-based thermoplastic elastomer and the urethane-based thermoplastic elastomer, completely cross-linked and semi-cross-linked thermoplastic elastomers are included. The most preferred of these materials is ethylene pro Pyrene turbomer is a blend of ethylene propylene turbomer and butyl rubber. Ethylene propylene terpolymer is known to be the most weather-resistant material among the currently known rubber materials, and because it contains ethylene, it can be fused with a thermoplastic resin. In addition, the reason why butyl rubber is blended is that the workability of the material is improved and the adhesiveness is improved.

Here, the thickness of the elastomer sheet 2 is preferably from 0.3 to 3.0 mm, and more preferably from 1.0 to 2.0 mm. If the thickness is larger than 3.0 mm, the flexibility of the sheet is impaired and the sheet becomes difficult to follow along with the substrate, which is not preferable. More preferably, the force is set to 1.0 to 2.0 mm. <If the thickness is thinner than 1.0 mm, the warpage of the sheet due to the difference in the thermal expansion coefficient between the laminated ePTFE film and the elastomer sheet becomes remarkable. If it is thicker than 0 mm, the step at the joint between the sheets will increase, resulting in poor appearance and impaired walking, which is not preferable. Next, the thermoplastic resin film 3, which is one component of the present invention, is an inclusion for laminating and unifying the elastomer sheet 2 and the ePTFE film 4 by heat fusion. As the thermoplastic resin film used for the sheet having the three eyebrows structure, any material can be used as long as it can be fused to both the elastomer sheet 2 and the ePTFE film 4. Preferred are ethylene methyl methacrylate and the like. More preferably, polyethylene is most suitable in terms of processability, adhesiveness, chemical stability after processing, and the like. The thickness of the thermoplastic resin film 3 is preferably at least 10 zm, and more preferably at least 20 // m. If the thickness is less than 10 /, the workability is poor, the area for fusion is small, and poor fusion occurs.

Further, it is preferable to use a colored thermoplastic resin film 3 for the following reasons. In the present invention, when a sheet having excellent appearance and aesthetic appearance is formed by using a colored ePTFE film, there is a particular problem.However, depending on the thickness of the ePTFE film 4, the color of the laminated elastomer sheet 2 is changed to the surface. It is powerful that it can be seen through. By coloring the thermoplastic resin film 3, it is possible to prevent the color of the elastomer 2 from appearing on the surface, and it is possible to present a clearer color. The color of the thermoplastic resin film 3 may be the same as the color of 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 laminating and integrating the elastomer sheet 2 and the e-PTFE film 4, and by using the thermoplastic resin film 3, the lamination process by fusion bonding is performed. Becomes possible. PTFE is generally known as a material that is extremely difficult to be fused or bonded.However, in the present invention, by using the ePTFE film 4 as described above, heating and melting can be performed using the pores of the stretched porous film. The elastomer sheet 2 and the ePTFE film 4 can be firmly laminated and integrated by the anchor effect of causing the thermoplastic resin in the state to bite into the inside of the hole.

On the other hand, as described above, the ePTFE film 4, which is an important component for forming the features of the present invention, does not generate warpage on the waterproof water-blocking sheet, but blocks the ultraviolet rays without causing warpage. It functions as a filler for elastomer sheets that enhances the function of the rubber and imparts excellent color tones.

The ePTFE film 4 is manufactured by a manufacturing method described in JP-B-53-39719, 51-89991, etc., and its fine structure is also known together with the manufacturing method. Specifically, the e-PTFE film is obtained by extruding a paste molded body consisting essentially of a mixture of PTFE fine powder and a lubricating aid such as petroleum naphtha through a die, and then extruding the obtained tape-shaped extrudate. It is manufactured by evaporating and removing the lubricating aid by heating, and then stretching it in one or more axial directions at a high temperature below the melting point of PTFE. In addition, a baking process is performed in which the microstructure generated by stretching is fixed, and after stretching, it is heated to a temperature equal to or higher than the melting point of PTFE and then cooled, while the state after stretching is fixed, to ensure dimensional stability. However, in the ePTFE film of the present invention, the final baking treatment is not an essential treatment.

The ePTFE film produced in this way is a soft film having a pure white and marshmallow-like feel. In addition, it can be seen that this film has air permeability, and pores called “holes” are continuous from the front surface to the back surface of the film. When observed with an electron microscope, the microstructure of the film is a unique fibrous porous material consisting of fibrils (fibrils) and nodes (nodules) passing through them both on the surface and inside. Has a body structure. The fibril node structure changes its appearance depending on the stretching direction and the stretching ratio. For example, when stretched in the uniaxial direction, the fibrils are oriented in one direction of the stretching direction and become interdigital, and the nodes passing through the fibrils are observed as elongated islands perpendicular to the stretching direction. On the other hand, when biaxially stretched, fibrils spread radially in the stretching direction, and the nodes passing through them are observed as fine particles rather than islands. Also, as the stretching ratio is increased, the fibrils generally become longer and the node shapes become relatively smaller, regardless of the stretching direction, and ultimately become a so-called nodeless structure consisting of only fibrils. e The specific gravity of the PTF E film is lower than the specific gravity of pure PTFE solids and depends on the porosity, but is often lower than the specific gravity of water.

e PTFE consists of pure PTFE, and the fibrils and nodes that characterize its structure are both PTFE. By the way, PTFE is an extremely chemically stable material, and it is unlikely to deteriorate or corrode even if it is used for drainage on roofs or water reservoirs that are exposed to sunlight or outside air for a long period of time. Therefore, e-PTFE inherently has the excellent chemical stability of PTFE, is durable to ultraviolet light, and is not oxidized by air. In addition, PTFE has excellent weather resistance, such as being not synthesized in nature and thus not being attacked by bacteria.

However, ePTFE has different mechanical and physical properties than PTFE solids.

The film made of solid PTFE has a milky white color like transparent ground glass, while the ePTFE film has a distinctly pure white color. This is thought to be due to the total reflection phenomenon caused by the microporous structure of ePTFE. In addition, PTFE solid body is generally considered to be a rigid material, but e-PTFE film has a marshmallow-like feel as described above, and can conform to the shape of other objects in any way. Strong plasticity L, material. This is also thought to be due to its unique fiber structure. In addition, it has a gentle elastic recovery force due to its network structure. Therefore, even if the elastomer-sheet laminate of the present invention is laminated, it can easily follow the expansion and contraction of the elastomer. In addition, PTF E has no affinity for other substances and is considered to be a material that is difficult to adhere to, especially as a material.However, since PTFE has a porous structure, it cannot be adhered by the so-called anchor effect. It is easy. In particular, it easily penetrates organic media with low surface tension, and is used for such processes as adhesion, impregnation, and coating.

The rigidity of the material itself is high, such as PTFE solid film, fluororesin film other than PTF E, polyester film, polyvinyl chloride film, etc. Warpage occurs in the laminate due to differences in shrinkage, and peeling occurs due to repeated bending. For example, when a fluororesin film or polyester is laminated on an elastomer sheet, the rigidity of the fluororesin film / polyester film is too high to follow the deformation of the elastomer sheet, so that the sheet is warped. However, in the case of ePTFE film 4, the tensile elastic modulus has a small value from the above-mentioned configuration, and since it is excellent in flexibility, warpage of the laminated sheet is prevented even when laminated with the elastomer sheet 2. Is done.

Table 1 shows the tensile modulus of typical fluororesin film, polyethylene monofluoride film (PF E) and e-PTFE film. Table 1 shows that the ePTFE film has an extremely low tensile modulus compared to general fluororesin film (polyvinyl difluoride) (PVDF) or polyvinyl fluoride film (PVF), and is flexible. It turns out that it is excellent.

table 1

e The preferable thickness of the PTFE film 4 is an average thickness measured with a dial gauge (measured with a 1Z100 mm dial thickness gauge manufactured by Teklock Co., with no load other than the body panel load applied) and preferably 3 to 300 m. More preferably, it is 20-100 m. If the thickness is less than 3, sufficient mechanical durability cannot be obtained, and lamination processing becomes difficult. Conversely, if the thickness exceeds 300 // m, the productivity is poor and the material cost increases, which is not appropriate in terms of cost. The e-PTFE film 4 can be identified by the bubble point method ( The maximum pore size measured by ASTM F-3 16) is preferably from 0.01 to 10 m, more preferably from 0.05 to 5 im. If the maximum pore size is less than 0.01 m, fusion using the anchor effect becomes difficult, and if the maximum pore size exceeds 10 m, sufficient mechanical strength cannot be obtained.

Also, the ePTFE film 4 may be embossed to have irregularities. e If the color of the elastomer sheet 2 is transparent on the surface due to the thickness of the PTFE film 4, the color that can be seen through the embossing of the ePTFE film 4 becomes a uniform pattern, Appearance can be improved. e The embossing of the PTFE film 4 may be performed prior to lamination with the elastomer sheet 2 or the thermoplastic resin film 3, or may be performed when laminating.

e The method of coloring the PTFE film is to mix the pigment during film production and bury the pigment in the pores of the film, or to form a film and then apply a solvent-based paint to the film to form a film. A method of embedding a pigment in a hole, a method of forming a film and then dipping the film in a paint bath to embed the pigment in a hole of the film can be used.

Hereinafter, a method of coloring by mixing a pigment into the ePTFE film will be described.

An inorganic pigment corresponding to a color tone, for example, carbon black, is mixed with PTFE resin in an amount of 0.5 to 30%. The blending amount is adjusted depending on the color and the kind of the pigment. However, if the content is 3 Owt% or more, pinholes are generated or the strength is reduced in stretching the film. The mixing method is 1) a method in which a sufficiently dried pigment is added to the PTFE resin to be granulated and mixed by a mixer. 2) A pigment called dispurgeon, which is a dispersion of secondary PTFE particles dispersed in water. There is a method of adding and mixing, and granulation is possible.Either method is possible, but the latter method 2) has more uniform pigment dispersion, and the color e PT FE film finally obtained has uneven color. Because it is difficult, it is more suitable. Add 17 to 22% by weight of a hydrocarbon solvent as an extrusion lubricant to the granulated PTFE, mix, preform and perform base extrusion. After the lubricant is dried and removed from the film obtained by rolling the extruded product to a predetermined thickness, 50 to 500% in the width direction at a high temperature not higher than the melting point of PTFE (327 ° C), preferably 500% Stretch 100 to 100%, and if necessary, Heat and heat treat at a temperature above the melting point of PTFE. The film width at this time is preferably at least 500 mm, more preferably at least 1,200 mm. If the film width is less than 500 mm, the width of the finally obtained waterproof and impermeable sheet is limited to 500 mm or less, which is unfavorable because the workability at the site is reduced.

Usually, the ePTFE film has a white color, and can be used as a white waterproof / waterproof sheet if it is laminated on an elastomer sheet as it is, and such a case is also included in the present application. . In addition, the use of a colored material results in an elastomer sheet colored in any color, and it is possible to impart an excellent color tone to the appearance of the waterproof and impermeable sheet.

When a pigment is embedded in the pores of the ePTFE film, a film colored in any color can be obtained. Also, a pure white film can be obtained by using e-PTFE film without any pigment.

Next, a method for producing the elastomer laminate of the present invention and the colored waterproof impermeable sheet will be described.

As the elastomer sheet, for example, the above-mentioned vulcanized rubber sheet 2 is used, and the e-PTFE film 4 is laminated and integrated by thermal fusion via a thermoplastic resin. After laminating and unifying the thermoplastic resin film 3 and the e-PTFE film 4 in advance by laminating and integrating them by a method such as fusion with a heat roller, the vulcanized rubber sheet is attached to the thermoplastic resin film 3 side of the integrated film of the thermoplastic resin film 3 and the ePTFE film 4. Heating with a heat roll, etc., and laminating by pressing, laminating thermoplastic resin film 3 and vulcanized rubber sheet 2, and applying heat and pressure with a heater, etc. After lamination and integration, the sheet in which the thermoplastic resin film 3 and the vulcanized rubber sheet 2 have been integrated and the e-PTFE film 4 are attached together by a method such as adhesion using a roller. The e-PTFE film 4 and the thermoplastic resin film 3 and the vulcanized rubber sheet 2 are superimposed on each other, and heated and pressed by a heat roll, etc., so that the thermoplastic resin and the e-PTFE film A shift method such as a method of simultaneously laminating and integrating the film 3 and the vulcanized rubber sheet 2 is also possible.

Further, as another embodiment of the present invention, the above-described vulcanized rubber sheet 2 and ePTFE Some films 4 are laminated and integrated without the thermoplastic resin film 3 interposed therebetween. In the case of a double-layered eyebrow, the film 4 can be laminated by the following method. The unvulcanized rubber sheet and the ePTFE film 4 are superimposed, and the rubber is heated and pressurized in a vulcanizer or the like, and the vulcanization is performed when vulcanization is performed.

In this case, since the rubber has fluidity in an unvulcanized state, it can enter the pores of the ePTFE film 4, so that the anchor effect can be obtained without the intervention of the thermoplastic resin film 3. It can be laminated and integrated.

Of course, it is possible to laminate the three-layered sheet of the above-described embodiment in which the thermoplastic resin film 3 is interposed by a method using the same unvulcanized rubber sheet. Further, even when the elastomer is a polymer other than rubber, it can be bonded and integrated using a chloroprene rubber-based, butyl rubber-based, epoxy resin-based, urethane-based, or cyanoacrylate-based adhesive.

Further, by producing the sheet of the present invention by the following method, the productivity of the sheet of the present invention can be increased and the sheet can be produced efficiently.

That is, the rubber sheet 2 which has just been vulcanized is still in a heated state, and utilizing the heat, the thermoplastic resin film 3 or e-PTFE film 4 and the thermoplastic resin film 3 integrated with the eyebrows are used. This is a method of laminating. Specifically, as shown in Fig. 3, an unvulcanized rubber sheet 10 extruded from an extruder (not shown) using an apparatus as shown in the same figure is put on an endless belt 11 and introduced. It is fed into the vulcanizer 13 set at a predetermined temperature (150 to 180) from the roll 12 to be vulcanized, and is discharged from the roll 14 to the outside of the vulcanizer 13 to be vulcanized. After passing through the guide rolls, the press roll 16 presses the thermoplastic resin film 17 or the thermoplastic resin film 17 laminated and integrated with the e-PTFE film 17 and the tension roll 18 through the tension roll 18 to take up the roll 19 It is wound up. In this case, the surface temperature of the vulcanized rubber sheet 15 just sent from the vulcanizing can 13 is in the range of 130 to 150 ° C, and the thermoplastic resin film 17 is easily fused. can do. According to this method, it is not necessary to pre-heat the pressing roll 16, and it is possible to contribute to a reduction in manufacturing cost together with an improvement in productivity.

Thus, by using the manufacturing method of the present invention as described above, the present invention An e-PTFE film 4 is laminated on the surface of the vulcanized rubber sheet 2 via a thermoplastic resin film 3. When the thermoplastic resin film 3 is melted by applying heat, the molten thermoplastic resin becomes porous. The PTFE resin film, which is a fluororesin film that cannot be firmly bonded by heat fusion, can be fused with sufficient strength because it can penetrate into the holes of the film, and has excellent color tone and weather resistance. It is possible to obtain a colored rubber sheet laminate and a colored waterproof waterproofing sheet 1 having no problems such as discoloration, separation of the laminated sheet, and warping. BEST MODE FOR CARRYING OUT THE INVENTION

Example 1

A sheet laminate having the structure shown in FIG. 1 in which a PTFE film 4 made of PTFE was laminated on a vulcanized rubber sheet 2 with a polyethylene resin film interposed therebetween was produced as follows.

As the vulcanized rubber sheet 2, a sheet mainly composed of ethylene propylene turbomer (EPT) and having the composition shown in Table 2 was used.

As the polyethylene resin film, a polyethylene film (thickness: 30 urn) manufactured by Sanwa Kasei Co., Ltd. was used.

Table 2

Example 2

A sheet laminate having the configuration shown in Fig. 1 was prepared by laminating an ePTFE film on a polyethylene sheet (high density) with a polyethylene resin film interposed. Polyethylene Sheets containing high-density polyethylene (HDPE) as a main component and having the composition shown in Table 3 were used. The polyethylene resin film is the same as in Example 1.

Table 3

The ePTFE film 4 was colored gray and was produced by the following method.

For PTF II, use Mitsui's DuPont Fluorochemicals Co., Ltd. dispersion technician.

The pigment added for coloring is Ketjen Black manufactured by Mitsubishi Chemical, mixed with the above-mentioned Dispurge Yeon Teflon at 3 wt%, granulated PTFE, and extruded lubricant into the granulated PTFE, Idemitsu After adding 18.5 wt% of Petrochemical Co., Ltd. and mixing, it was stretched 700% in the width direction and heat-treated at 360 ° C. to obtain a light gray ePTFE film 4. The thickness of the obtained ePTFE film 4 was 43 am (measured with a 11,000 mm dial thickness gauge manufactured by Teklock Co., with no load other than the body spring load applied), and the maximum pore diameter was 0.5 m. . (A STM F-3 16)

An e-PTFE film was trial-produced by the above-mentioned processing method while changing the amount of the Ketjen black to 1, 3, 7, 10, and 25 wt%, and the color tone of the obtained e-PTFE film was as follows. The color changed from light gray to black with an increase in the blending amount of, but an ePTFE film with the most excellent gray color tone was obtained with a blending ratio of 3 wt%.

Next, in order to obtain a waterproof and impermeable sheet, each of the above was laminated as follows. First, the light gray colored e PTF E film and the polyethylene film were fused together by nip with a heat roll. At this time, in order to prevent the polyethylene film from melting and adhering to the heat roll, place the e PTF E film in the heat opening. And the polyethylene film side as the nip roll side. The processing was performed at a temperature of 170 ° C, a nip pressure of 7 Kg / cm ² , and a sprinkler of 5 mZmin.

The two-layer laminated product of ePTFE film and polyethylene film obtained in this way was pressed with a vulcanized rubber sheet and the rubber sheet was sent out of the vulcanizer using a device as shown in Fig. Was used for fusion bonding. The processing conditions were as follows: vulcanized rubber sheet surface temperature: 135 ° C, nip pressure: 5 Kg / cm ² , vulcanized speed: 5 m / min. Then, a three-layer laminate of an ePTFE film, a polyethylene film, and a vulcanized rubber sheet was obtained.

Comparative Example 1

A color rubber sheet (0.3 mm thick) containing ethylene propylene terpolymer and butyl rubber (IIR) as the main components and a black rubber sheet (0.3 mm thickness) containing ethylene propylene turbomer as the main component in Table 2 2 mm) was used as Comparative Example 1.

Table 4

Comparative Example 2

Example 1 was repeated in the same manner as in Example 1 except that an e PTF E film was replaced with a 30 fim thick paddle (DuPont polyvinyl fluoride) film colored green. A sheet laminate was prepared, and this was referred to as Comparative Example 2. Was.

Comparative Example 3

A sheet laminate was prepared in the same manner as in Example 2 except that the ePTFE film was not used in Example 2, and this was used as Comparative Example 3.

Table 5 shows comparison data between the above example and each comparative example.

In the table, the perimeter and the outdoor exposure test were based on the following conditions, respectively.

Weather meter; 100 hours after exposure based on JISA 14 15 Outdoor exposure test; 6 months later

Table 5 Example 1 Example 1 Example 2 Comparative example 1 Example 2 Comparative example 3 Color tone Good Good Good Good Good Good Color tone variation None None Lot-to-lot difference None None Fading None None Fading None Fading

The separation Film rupture Film rupture Empty rubber rupture Film rupture None

Me

1 Sorry Almost none None None On film side None Even + 15mm sled

1

Surface crack None None None None Cracking Fading None None Slight fading None Fading Outside 外 Release Film rupture Film rupture Color rubber rupture Film rupture None

Interface

π

No warpage None None None On film side Test + 12 mm warp crack Surface crack None None None None

According to the above table, the color rubber sheet of Comparative Example 1 had good color tone of the sheet, but there was color variation between lots, and remarkable fading occurred after the exposure test with a ditherometer and outdoor. In addition, the polyvinyl fluoride laminate sheet of Comparative Example 2 had a good color tone and no color variation, and did not show any discoloration after an outdoor exposure test with a diagonal meter. Warpage occurred due to the difference in the coefficient of thermal expansion between the two, and in the separation test, it was found that a portion where the film was partially broken and a portion where the interface was separated appeared. In Comparative Example 3, the color tone was good, but fading was observed. In contrast, all of the examples according to the present invention had good color tone, and did not cause discoloration, separation of the e-PTFE film, or warping even after various light fastness exposure tests. Comparative Example 1, Comparative Example 2, Comparative Example Very good results were obtained compared to 3. Industrial applicability

As described above, the present invention uses an ePTFE film and laminates it with an elastomer sheet, and as a sheet having waterproofness and water-blocking properties, conventionally, there are advantages and disadvantages in various sheets, and it is not essential. It was possible to improve the point which was not enough, to have a small color variation, and to show a delicate color tone, and it was not possible to use because of no warping and because of poor weather resistance in the past. It has a remarkable effect that sufficient weather resistance can be imparted to the elastomer material, and a waterproof water-shielding sheet having no problem of discoloration and separation can be obtained.

Claims

The scope of the claims

1. An eyebrow body with an elastomer sheet, characterized in that a stretched porous polytetrafluoroethylene (ePTFE) film is laminated on an elastomer sheet.

2. The elastomer sheet laminate according to claim 1, wherein a thermoplastic resin film is interposed between the elastomer sheet and the ePTFE film.

3. The elastomer sheet laminate according to claim 1, wherein a colored film is used as the ePTFE film.

4. The elastomer sheet laminate according to claim 2, wherein a colored film is used as the thermoplastic resin film.

5. The elastomer sheet laminate according to claim 1, 2, 3, or 4, wherein a rubber sheet is used as the elastomer sheet.

6. Waterproof impermeable sheets laid on roofs, floors, walls, storage ponds or industrial waste disposal sites of buildings, etc., characterized by laminating an ePTFE film on an elastomeric sheet. .

7. A thermoplastic resin film was interposed between the elastomer sheet and the e-PTFE film on the waterproof, water-impervious sheet laid on the building roof, floor, wall, reservoir, or industrial waste disposal site. 7. The waterproof and impermeable sheet according to claim 6.

8. Claims 6 or 7 in which e-PTFE colored e-PTFE film is used in a waterproof impermeable sheet laid on a building roof, floor, wall, reservoir, industrial waste disposal site, etc. Waterproof and impermeable sheet according to the item.

9. Claims 7 or 8 in which a waterproof resin sheet laid on the roof, floor, wall, reservoir, or industrial waste disposal site of a building, etc. uses a colored film of thermoplastic resin film. The waterproof and impermeable sheet according to 1.

10. Claims 6, 7, and 8 using rubber sheets as elastomer sheets for waterproofing and waterproofing sheets laid on roofs, floors, walls, storage ponds or industrial waste disposal sites of buildings, etc. 10. The waterproof impermeable sheet according to item 8 or 9.