WO2003072350A1 - Film material - Google Patents

Abstract

A gas barrier layer and a light resisting layer to be able to be used in an atmosphere of -80°C to 80°C are formed on a base fabric composed of a plurality of sheet-form yarn groups each having yarns arranged in one direction, respective sheet-form yarn groups being placed in layers so that the arranging direction of yarns are different from one another, and the intersections of respective yarns being integrally bonded with adhesive, thereby it is possible to provide a film material that is excellent in light resistance, light in weight, high in strength, and capable of suitably used for the ship body material of a soft air ship or the like applicable to earth observing, meteorological observing and radio repeating.

Description

 Description Membrane materials Technical field

 The present invention relates to a membrane material, and more specifically, can be suitably used as a material for a hull of a soft flying ship used for earth observation, meteorological observation, radio wave relay, and the like, which is retained in the stratosphere. It is related to membrane materials. Background art

 In recent years, the spread of personal computers and mobile phones has been rapidly progressing, and the necessity of network maintenance has increased accordingly. In addition, global environmental issues such as ozone holes, global warming and marine pollution have been highlighted, and the need to build a system to monitor them is increasing.

 Under such circumstances, research is being conducted to make airships equipped with communication devices, observation sensors, and the like in the stratosphere afloat and use them for observation of the global environment, meteorological observation, telephone relay, and the like.

As a membrane material used for the hull of an airship, for example, Japanese Patent Application Laid-Open No. 2001-239605 discloses a sheet formed by laminating a woven fabric and a film. The fineness of the yarn constituting the woven fabric is 10 to 250 dte X, the strength is 10 cN / dtex or more, the elastic modulus is 350 cN / dtex or more, and the fabric weight is 10 to 200. g / m ² , and that the finolem is a film made of an ethylene-vinylinoleanol copolymer having a thickness of 10 to 40 μm.

Also, JP-A-2001-2777391 discloses that, in a sheet formed by laminating a woven fabric and a film, the yarn constituting the woven fabric comprises a melt anisotropic aromatic polyester as a core component. And Polyphenylene Sulfur It is disclosed that it is a core-sheath type composite fiber having an iod as a sheath component. Further, Japanese Patent Application Laid-Open Publication No. 2001-3344594 discloses that in a sheet in which a woven fabric and a film are laminated, the yarn constituting the woven fabric is formed of polybenzoxazole and / or polybenzoxane. It is composed of a fiber mainly composed of thiazole, the fineness of the yarn is 10 to 300 d t'ex, and the strength is

It is disclosed that the elastic modulus is not less than 200 cNZ dtex and the elastic modulus is not less than 700 cN / dtex.

 However, the above-mentioned known membrane material was unsuitable as an airship membrane material used in the stratosphere in the following points. That is, the outermost film of the film material does not have sufficient light resistance, so that deterioration due to light occurs, and the film cannot be used for a long period of time. In addition, since the base fabric of the film material is a woven fabric, its constituent yarns are bent. However, there has been a problem that the inherent strength of the yarn cannot be fully exhibited. Disclosure of the invention

 An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a light-weight, high-strength film material having excellent light resistance.

The present inventor has conducted intensive studies to achieve the above object, and as a result, has used a laminate of a group of sheet-like yarns in which yarns are arranged in the negative direction as a base fabric of the film material. When forming a resin layer with excellent gas barrier properties and a light-resistant resin layer that can be used in an atmosphere of minus 80 ° C to 80 ° C while maximizing the strength, on the surface of the laminate It was determined that a desired film material could be obtained.

That is, according to the present invention, a base fabric, a gas barrier layer and a light-resistant resin layer are provided, and the base fabric is composed of a plurality of sheet-like yarn groups in which the yarns are arranged in the negative direction, and The film material is characterized in that the sheet-like yarn groups are laminated so that the arrangement direction of the yarns is different from each other, and the intersections of the yarns are bonded and integrated with an adhesive. Provided. ―

3 BEST MODE FOR CARRYING OUT THE INVENTION

 In the present invention, a plurality of sheet-like yarn groups in which the yarns are arranged in the minus direction are laminated as a base fabric of the membrane material so that the arrangement direction of the yarns in each sheet-like yarn group is different from each other. Use the laminated body.

 Here, as the yarn, it is preferable to use a fiber yarn having a tensile strength of 14 lcN / dtex or more, which is called a so-called high-strength fiber, so that the obtained membrane material has as high a strength as possible. .

 Specific examples of the above-mentioned high-strength fiber include para-aramid fibers such as polyparaphenylene-terephthalate-noreamide fibers, copolymer fibers of para-aramid and meta-aramid, or aromatic ethers, for example, 3,4- Para-based aramide fibers copolymerized with diaminodivinyl ether, as well as polypropylene raphenylene benzobisoxazole fibers, polyimide fibers, wholly aromatic polyester fibers, polyarylate fibers, and polyetherimids. Fiber, polyetheretherketone fiber, or a mixed fiber thereof.

 Of these, polyparafene nitrene terephthalamide fibers (Dupont, Kepler, Teijin Twaron, Twaron) and para-aramid fibers copolymerized with 3,4 diamino diphenyl ether (Teijin shares) Company "Technola"), or polyparaphenylene benzobisoxazole fiber (manufactured by Toyobo Co., Ltd., "Xylon") has excellent heat resistance and is particularly preferably exemplified.

 In addition, a sheet-like yarn group in which yarns are arranged in one direction is a sheet-like material in which the fiber yarns are arranged in a minus direction and fixed with an adhesive resin sheet or a film or the like. In the present invention, the base fabric is formed by laminating a plurality of sheets so that the arrangement direction of the yarns is different from each other.

Here, the arrangement direction of the yarns in each sheet-like yarn group may be different from each other, and is not particularly limited, but when the number of laminations is two, the yarns may be arranged in any direction of the base fabric. When you express strength in a well-balanced manner From the perspective of, in _c the base fabric is preferable to the arrangement direction of the yarn 9 0 ° different, the intersection of the yarns constituting the sheet-like yarn group is bonded and integrated with an adhesive It is necessary. By adopting such a configuration, the yarns are arranged linearly without adopting a bent structure as in a woven fabric, so that the inherent strength of the yarns can be sufficiently exhibited.

 In the present invention, it is necessary to form a gas barrier layer on the base cloth. This is because when used as a membrane material for airships, it is to contain the helium gas that is injected into the interior.

 As the gas barrier layer, a film or film of polyvinylidene chloride, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyethylene naphthalate, polyketone, phenoxy resin, or the like can be used. However, it is better to use ethylene-vinyl alcohol-based copolymer (“Kebare”, “EVAL”), which has a particularly excellent gas shielding performance, in order to confine gas with small molecules such as helium. . Further, one layer of the gas barrier may be subjected to aluminum vapor deposition for the purpose of further improving gas barrier properties and weather resistance.

 As the method for forming the gas barrier layer, a conventionally known method can be arbitrarily adopted. Specifically, a method of melt-coating or wet-coating the resin, a method of laminating a film made of the resin, and the like are exemplified.

Furthermore, membrane materials used for airships and the like need to have extremely high weather resistance because they are used in the stratosphere. That is, in the stratosphere, the sun is constantly exposed to sunlight during the daytime and the outside temperature reaches nearly 80 ° C, while at night the temperature drops and drops to minus 80 ° C. Therefore, the film material of the present invention can withstand such severe conditions for a long period of time, so that the base fabric and one layer of the gas barrier can be used even in an atmosphere of minus 80 ° C to 80 ° C. It is preferably covered with a light-resistant resin layer. Examples of light-resistant resins that can be used in an atmosphere of minus 80 ° C to 80 ° C include fluorine-based resins, such as polytetrafluoroethylene, polyvinylidene fluoride, and polyvinylfluoride. , Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluorolobe pyrene copolymer, vinylidene phenolic copolymer Propylene copolymer, vinylidenefluoride dotetratetranoleole-ethylene-hexafluoropropylene copolymer, polycyclo-triphenylene-olethrene ethylene, ethylene-chloro-trifluoroethylene copolymer, etc. are preferred. Is exemplified.

 Examples of other light-resistant resins that can be used in an atmosphere of minus 80 to 80 ° C. include polyethylene polymerized using a meta-mouth catalyst.

 These resins may be used alone or in combination of two or more, and may be used as a multilayer. The light-resistant resin layer may cover either one side or both sides of the film material, but the surface exposed to sunlight and in contact with outside air must be coated.

 As a method for forming the light-resistant resin layer, a conventionally known method can be arbitrarily adopted. Specific examples include a method of performing wet coating using an emulsion solution of the above resin, and a method of laminating a film made of the above resin. Example

 Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited thereto.

 Examples 1-2

A yarn composed of the fibers shown in Table 1 and having a fineness of 450 dtex is wound around a yarn support member through a rotating arm, and the yarn is arranged with a density of 20 yarns Z 2.54 cm. In the group, the fibers also shown in Table 1 A yarn with a fineness of 44 dtex, consisting of fibers, is pulled out from the creel stand, and 20 yarns are arranged from the top and bottom with an arrangement density of 2.54 cm so that the arrangement directions of the yarns are 90 ° different from each other. After stacking them together, they were led to the holding jaws.

 Then, while keeping the three-layered yarn group in contact with the presser roll, the yarn group was immersed in a tank containing an acrylic ester resin emulsion adhesive to impregnate and adhere the adhesive. It was dried by bringing it into contact with a cylinder heated to C and wound up on a winding roll to obtain a base fabric on which a group of sheet-like yarns was laminated. Table 1 shows the strength utilization rate of the obtained base cloth.

 An ethylene-vinyl alcohol copolymer film (12 μm thick, made by Kuraray: “Eval”) is adhered to the above base cloth, and a 30-mm-thick tetrafluoroethylene copolymer film is attached on both sides. An ethylene copolymer film (manufactured by Asahi Glass: "Aflex") was bonded to obtain a film material.

 Table 1 also shows the performance of the obtained film material.

 In Table 1, the strength utilization rate is defined as the theoretical strength, where the tensile strength of the base fabric assuming that the tensile strength of the yarn constituting the obtained base fabric has developed 100% is defined as the theoretical strength. It was expressed as the ratio (%) of the measured tensile strength. If this value is 95% or more, it can be said that it is lightweight and has high strength.

 In addition, the light resistance was measured in accordance with JIS 1415, by measuring the tensile strength after the film material was exposed for 2000 hours, and expressed as a ratio (%) of the tensile strength to the tensile strength before the exposure. If this value is 90% or more, it can be said that the film has good light fastness.

Furthermore, whether or not the light-resistant resin can be used in an atmosphere of minus 80 ° C to 80 ° C depends on whether the resin is used in a minus 80 ° C atmosphere and in a 80 ° C atmosphere, respectively. After exposure for 24 hours, the strength was measured immediately after being taken out of the atmosphere and evaluated by the retention from the original strength. If the retention rate is 80% or more, it can be determined that it can be used. Example 3

 In Example 1, in place of the tetrafluoroethylene-ethylene copolymer film, a polyethylene film having a thickness of 60 μπι, which was polymerized using a metallocene catalyst (“Umerit” manufactured by Ube Industries, Ltd.) ) Was performed in the same manner as in Example 1 except that) was used.

 Table 1 also shows the performance of the obtained film material.

 Example 4

 In Example 2, in place of the tetrafluoroethylene-ethylene copolymer film, a polyethylene film having a thickness of 60 μιτα and polymerized using a metallocene catalyst (“Umerit J” manufactured by Ube Industries) The procedure was performed in the same manner as in Example 2 except for using.

 Table 1 also shows the performance of the obtained film material. '' Comparative Examples 1-2

 Example 1 was carried out in the same manner as in Example 1 except that a tetrachloroethylene-ethylene copolymer film was replaced by a 30 µm-thick polychlorinated vinyl film or a polyurethane film. Table 1 also shows the performance of the obtained film material.

 Comparative Examples 4 to 5

 Example 2 was carried out in the same manner as in Example 2 except that a polychlorinated vinyl film or a polyurethane film having a thickness of 30 μm was used instead of the tetrafluoroethylene-ethylene copolymer film.

 Table 1 shows the performance of the obtained film material.

 Comparative Example 3, Comparative Example 6

 A yarn having a fineness of 450 dteX composed of the fibers shown in Table 1 was arranged in the course, and a base fabric made of a plain weave having a weave density of 20 yarns / 2.54 cm was obtained. Table 1 shows the strength utilization rate of the obtained base cloth.

An ethylene-vinyl alcohol copolymer finolem (12 μm thick, made by Kuraray Co., Ltd .: Jeval) is attached to the above base cloth, and a 30-m-thick tetrafluoroethylene Ethylene A polymer film (manufactured by Asahi Glass: “Aflex”) was attached to obtain a film material.

Table 1 also shows the performance of the obtained film material.

Base cloth strong utilization rate Weather resistance Strength retention rate (%) Knowledge IW like 1 玍 tree Us layer

(%)-80 ° C 80 ° C Comparative Example 1 Technora 9 9 Polychlorinated Bulb 8 5 6 0 8 0 Comparative Example 2 Technora 9 9 Polyurethane 8 0 5 0 7 0 Example 1 Technora 9 9 Fluorine 9 5 8 5 9 5 Comparative Example 3 Technora 8 0 Table 9 Fluorine 9 6 9 0 9 0 Comparative Example 4 Zain 98 8 Polychlorinated Bulk 8 0 6 5 8 0 Comparative Example 5 Zain 9 8 Polyurethane 7 8 4 5 6 5 Example 2 Zine 9 8 Fluorine 9 5 9 0 9 0 Comparative Example 6 Zine 7 5 Fluorine 9 5 9 0 9 5 Example 3 Technora 9 9 Polyethylene 9 Example 9 4 9 9 Polyethylene 9 0 9 0 9 0

Industrial applicability

 The film material of the present invention has excellent light resistance, is lightweight and has high strength, and is therefore suitable as a material for the hull of a soft airship used for earth observation, weather observation, radio wave relay, and the like. Can be used.

Claims

The scope of the claims 1. A base fabric, a gas barrier layer and a light-resistant resin layer, wherein the base fabric is composed of a plurality of sheet-like yarn groups in which yarns are arranged in a negative direction, and each sheet-like yarn group is A film material which is laminated so that the arrangement directions of the yarns are different from each other, and wherein intersections of the yarns are bonded and integrated with an adhesive.  2. The membrane material according to claim 1, wherein the yarn is a high-strength fiber yarn having a tensile strength of 14.1 cN / dtex or more.  3. The light-resistant resin is polytetrafluoroethylene, polyvinylidene fluoride, polyvinylfluoride, tetrafluoroethylene-perfluoroalkylbutyl ether copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene. Trifluoroethylene-hexafluorophenol-pyrene copolymer, vinylidenefluoride-dohexafluoro-propylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polycarbonate 3. The film material according to claim 1, comprising at least one fluorine-based resin selected from the group consisting of phenolic ethylene, and ethylene-trichloroethylene copolymer. 4. The film material according to claim 1, wherein the light-resistant resin includes a polyethylene resin polymerized using a meta-mouth catalyst.  5. The film material according to claim 1, 2 or 3, wherein the gas barrier layer is a film made of an ethylene-vinylinole-co-nore copolymer.