JP2006159865A - Composite film made of cloth and clay - Google Patents
Composite film made of cloth and clay Download PDFInfo
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- JP2006159865A JP2006159865A JP2004358627A JP2004358627A JP2006159865A JP 2006159865 A JP2006159865 A JP 2006159865A JP 2004358627 A JP2004358627 A JP 2004358627A JP 2004358627 A JP2004358627 A JP 2004358627A JP 2006159865 A JP2006159865 A JP 2006159865A
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- clay
- multilayer film
- film
- film according
- resin
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- 239000004927 clay Substances 0.000 title claims abstract description 115
- 239000004744 fabric Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims description 11
- 230000004888 barrier function Effects 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000835 fiber Substances 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 35
- 239000000654 additive Substances 0.000 claims description 31
- 230000000996 additive effect Effects 0.000 claims description 28
- 239000012779 reinforcing material Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 13
- 229920000620 organic polymer Polymers 0.000 claims description 13
- 230000035699 permeability Effects 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 10
- 239000001307 helium Substances 0.000 claims description 10
- 229910052734 helium Inorganic materials 0.000 claims description 10
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011810 insulating material Substances 0.000 claims description 10
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 9
- 229910001882 dioxygen Inorganic materials 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 229920005749 polyurethane resin Polymers 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- -1 stevensite Inorganic materials 0.000 claims description 8
- 238000007740 vapor deposition Methods 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000005871 repellent Substances 0.000 claims description 6
- 239000011491 glass wool Substances 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 239000002557 mineral fiber Substances 0.000 claims description 5
- 229910052902 vermiculite Inorganic materials 0.000 claims description 5
- 239000010455 vermiculite Substances 0.000 claims description 5
- 235000019354 vermiculite Nutrition 0.000 claims description 5
- 229920001817 Agar Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 102000053602 DNA Human genes 0.000 claims description 4
- 108020004414 DNA Proteins 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 4
- 229920001353 Dextrin Polymers 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 108010068370 Glutens Proteins 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 239000008272 agar Substances 0.000 claims description 4
- 235000010419 agar Nutrition 0.000 claims description 4
- 229920000180 alkyd Polymers 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 4
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 235000019425 dextrin Nutrition 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 235000013312 flour Nutrition 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 235000021312 gluten Nutrition 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229910000271 hectorite Inorganic materials 0.000 claims description 4
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000113 methacrylic resin Substances 0.000 claims description 4
- 229910000273 nontronite Inorganic materials 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000009719 polyimide resin Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 235000018102 proteins Nutrition 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 229920002477 rna polymer Polymers 0.000 claims description 4
- 229910000275 saponite Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 230000004580 weight loss Effects 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000004455 differential thermal analysis Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000003566 sealing material Substances 0.000 claims description 3
- 230000002940 repellent Effects 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- 239000004952 Polyamide Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000615 nonconductor Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 180
- 239000010410 layer Substances 0.000 description 33
- 239000006185 dispersion Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 25
- 239000007788 liquid Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000012856 packing Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 239000002734 clay mineral Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 239000002612 dispersion medium Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001308 poly(aminoacid) Polymers 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 238000006884 silylation reaction Methods 0.000 description 1
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- 239000007784 solid electrolyte Substances 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Insulating Bodies (AREA)
- Laminated Bodies (AREA)
Abstract
【課題】自立膜として利用可能な機械的強度と靭性を有し、柔軟性が高く、耐熱性が高く、電気絶縁体であり、熱伝導率が低い、布と粘土層からなる多層膜を提供する。
【解決手段】布と粘土層から構成される多層膜であり、布及び粘土層の両者が密着して成型されており、物体表面上の支持膜として、あるいは自立膜としての形態を有する粘土膜であって、粘土層にクラックやピンホールなどが存在しない、粘土層が布の片面あるいは両面に存在するか、布が粘土層の両面に存在するか、これらの構造を含む多層膜。
【効果】耐水性、ガスバリア性、あるいは機械的強度を改善させた多層膜、及びそれらの製品を提供できる。
【選択図】図１Provided is a multilayer film composed of a cloth and a clay layer that has mechanical strength and toughness that can be used as a self-supporting film, has high flexibility, high heat resistance, is an electrical insulator, and has low thermal conductivity. To do.
A clay film comprising a cloth and a clay layer, in which both the cloth and the clay layer are in close contact with each other, and has a form as a support film on the object surface or as a self-supporting film. A multilayer film including a structure in which a clay layer is free of cracks or pinholes, a clay layer is present on one or both sides of a cloth, or a cloth is present on both sides of a clay layer.
[Effect] A multilayer film with improved water resistance, gas barrier property, or mechanical strength, and products thereof can be provided.
[Selection] Figure 1
Description
本発明は、布と粘土からなる複合膜に関するものであり、更に詳しくは、自立膜として利用可能な機械的強度を有し、高いガスバリア性を有し、柔軟性が高く、耐熱性が高く、電気絶縁体であり、断熱性に優れる、新規複合多層膜に関するものである。本発明は、耐熱フィルムの作製技術及びその製品の技術分野において、従来法では、自立膜として利用可能な機械的強度を有し、高いガスバリア性を有し、柔軟性が高く、耐熱性が高く、電気絶縁体であり、熱伝導率が低い多層膜を製造することは困難であり、その開発が強く要請されていたことを踏まえ、本発明は、自立膜として利用可能な機械的強度を有し、しかも、優れたガスバリア性や柔軟性や熱安定性を併せ持つ多層膜、及び電気絶縁フィルム、断熱材等の新技術・新素材を提供するものとして有用である。 The present invention relates to a composite film composed of cloth and clay, more specifically, has mechanical strength that can be used as a self-supporting film, has high gas barrier properties, high flexibility, high heat resistance, The present invention relates to a novel composite multilayer film that is an electrical insulator and has excellent heat insulation properties. The present invention has a mechanical strength that can be used as a self-supporting film, a high gas barrier property, a high flexibility, and a high heat resistance in the technical field of the heat-resistant film and the product technical field. In view of the fact that it is difficult to produce a multilayer film that is an electrical insulator and has low thermal conductivity, and that its development has been strongly demanded, the present invention has mechanical strength that can be used as a self-supporting film. In addition, it is useful as a multilayer film having excellent gas barrier properties, flexibility and thermal stability, as well as new technologies and new materials such as electrical insulating films and heat insulating materials.
一般に、多くの化学産業分野において、高温条件下での種々の生産プロセスが用いられている。それらの生産ラインの配管連結部などでは、例えば、パッキンや溶接などによって、液体や気体のリークを防止する方策がとられている。これまで、例えば、フレキシビリティーに優れたパッキンは、有機高分子材料を用いて作られていた。しかしながら、その耐熱性は、液晶ポリエステルの３５０℃が最高であり、これ以上の温度では、金属製パッキンを用いなければならないが、その金属製パッキンは、有機高分子材料のものと比較して、フレキシビリティーに劣るという問題点があった。アルミあるいは銅製等の金属パッキンは、完全なガスバリア性を得るためには強く締め付けることが必要であり、そのため、フランジのような締め付け機構を必要とする。また、金属パッキンは、周辺部品に傷をつけやすいという問題点がある。そのため、螺子部に巻きつけるシール材として利用することはできない。また、金属パッキンは、導電性であるため、絶縁をとる必要がある部分には適していないという問題点がある。一方、高温条件下で用いられるグランドパッキンとしては、粘土鉱物であるマイカやバーミキュライト等を用いたシートが用いられている（特許文献１，２，３，４）。しかし、これらのシートは、クラックやピンホールを完全に排除することができないため、これらのシートにより作製されたパッキン及びガスケットは、完全なガスシール性を有していないという問題点がある。 In general, various production processes under high temperature conditions are used in many chemical industry fields. In the pipe connection parts of these production lines, measures are taken to prevent liquid and gas leaks, for example, by packing or welding. Until now, for example, packing excellent in flexibility has been made using an organic polymer material. However, the heat resistance of the liquid crystal polyester is the highest at 350 ° C., and at a temperature higher than this, a metal packing must be used, but the metal packing is compared with that of an organic polymer material, There was a problem that it was inferior in flexibility. A metal packing such as aluminum or copper needs to be tightened strongly in order to obtain a complete gas barrier property, and therefore requires a tightening mechanism such as a flange. In addition, the metal packing has a problem that peripheral parts are easily damaged. Therefore, it cannot be used as a sealing material wound around the screw portion. Further, since the metal packing is conductive, there is a problem that it is not suitable for a portion that needs to be insulated. On the other hand, as a gland packing used under high temperature conditions, sheets using clay minerals such as mica and vermiculite are used (Patent Documents 1, 2, 3, and 4). However, since these sheets cannot completely eliminate cracks and pinholes, there is a problem in that packings and gaskets made from these sheets do not have complete gas sealing properties.
粘土は、水やアルコールに分散し、その分散液をガラス板の上に広げ、静置乾燥することにより粒子の配向の揃った膜を形成することが知られており、例えば、この方法でＸ線回折用の定方位試料が調製されてきた（非特許文献１）。しかしながら、ガラス板上に膜を形成した場合、ガラス板から多層膜を剥がすことが困難であり、剥がす際に膜に亀裂が生じるなど、自立膜として得ることが難しいという問題があった。また、膜を剥がせたとしても、得られた膜が脆く、強度が不足であった。 It is known that clay is dispersed in water or alcohol, and the dispersion is spread on a glass plate and allowed to stand and dry to form a film having a uniform particle orientation. A fixed orientation sample for line diffraction has been prepared (Non-Patent Document 1). However, when a film is formed on a glass plate, it is difficult to peel off the multilayer film from the glass plate, and there is a problem that it is difficult to obtain a self-supporting film, for example, when the film is cracked. Moreover, even if the film was peeled off, the obtained film was brittle and the strength was insufficient.
最近、ラングミュアーブロジェット法（Ｌａｎｇｍｕｉｒ−Ｂｌｏｄｇｅｔｔ Ｍｅｔｈｏｄ）を応用した粘土薄膜の作製が行われている（非特許文献２）。しかし、この方法では、粘土薄膜は、ガラス等の材料でできた基板表面上に形成されるものであり、多孔体にはならない。更に、自立膜としての強度を有する粘土薄膜を得ることができなかった。更に、従来、例えば、機能性粘土薄膜等を調製する方法が種々報告されている。例えば、ハイドロタルサイト系層間化合物の水分散液を膜状化して乾燥することからなる粘土薄膜の製造方法（特許文献５）、層状粘土鉱物と燐酸又は燐酸基との反応を促進させる熱処理を施すことによる層状粘土鉱物が持つ結合構造を配向固定した層状粘土鉱物薄膜の製造方法（特許文献６）、スメクタイト系粘土鉱物と２価以上の金属の錯化合物を含有する皮膜処理用水性組成物（特許文献７）、等をはじめ、多数の事例が存在する。しかしながら、これまで、自立膜として利用可能な機械的強度を有し、柔軟性に優れた多層膜の開発例はなかった。 Recently, a clay thin film using a Langmuir-Blodgett method has been produced (Non-patent Document 2). However, in this method, the clay thin film is formed on the surface of the substrate made of a material such as glass, and does not become a porous body. Furthermore, a clay thin film having strength as a self-supporting film could not be obtained. Furthermore, conventionally, for example, various methods for preparing functional clay thin films have been reported. For example, a method for producing a clay thin film comprising forming an aqueous dispersion of a hydrotalcite-based intercalation compound into a film and drying (Patent Document 5), and a heat treatment for promoting the reaction between the layered clay mineral and phosphoric acid or phosphate groups A method for producing a layered clay mineral thin film in which the bonded structure of the layered clay mineral is oriented and fixed (Patent Document 6), an aqueous composition for film treatment containing a complex compound of a smectite clay mineral and a divalent or higher metal (Patent Document 6) There are many cases including literature 7). However, until now, there has been no development example of a multilayer film having mechanical strength that can be used as a free-standing film and excellent in flexibility.
種々の繊維から作製された布、例えば、平織布、不織布等が市販されており、これらの布は十分な機械的強度を有し、柔軟であり、繰り返し曲げに対しても耐久性を有するなどの特徴がある。これらの布の耐熱性や耐薬品性は、布を構成する繊維原料に依存している。布を構成する繊維としては、鉱物繊維、グラスウール、セラミックス繊維、金属繊維、セラミックス繊維、植物繊維、有機高分子繊維などがある。しかしながら、これらの布は、織目を完全にシールすることができず、ガスバリア性を有しないという問題点がある。 Fabrics made from various fibers, such as plain woven fabrics and nonwoven fabrics, are commercially available. These fabrics have sufficient mechanical strength, are flexible, and are durable against repeated bending. There are features such as. The heat resistance and chemical resistance of these cloths depend on the fiber raw material constituting the cloth. Examples of fibers constituting the cloth include mineral fibers, glass wool, ceramic fibers, metal fibers, ceramic fibers, plant fibers, and organic polymer fibers. However, these fabrics have a problem in that they cannot completely seal the texture and do not have gas barrier properties.
このような状況の中で、本発明者らは、上記従来技術に鑑みて、自立膜として利用可能な機械的強度を有し、しかも、優れたガスバリア性とフレキシビリティーを有し、高温度条件下で使用できる新しい膜を開発することを目標として鋭意研究を積み重ねる過程で、粘土に必要に応じて少量の添加物あるいは少量の補強材を含む均一な分散液を調製し、この分散液を布の表面に塗布する、あるいは布を分散液に浸した後、分散媒である液体を種々の乾燥方法、例えば、真空乾燥、凍結真空乾燥、又は加熱蒸発法で除去し、布の片面あるいは両面に粘土層を形成させることにより機械的強度が著しく高まった多層膜を得られることに注目し、更に研究を重ねて、均一な厚みで、布と粘土との密着性に優れた多層膜を得ることに成功し、本発明を完成するに至った。本発明は、自立膜として利用可能な機械的強度と靭性を有し、しかも、優れたガスバリア性、柔軟性、熱安定性、多孔性を併せ持つ多層膜、及び電気絶縁材、断熱材として使用可能な部材等の新技術・新素材を提供することを目的とするものである。 Under such circumstances, the present inventors have a mechanical strength that can be used as a self-supporting film in view of the above-described prior art, and have an excellent gas barrier property and flexibility, and a high temperature. In the process of intensive research with the goal of developing a new membrane that can be used under conditions, a uniform dispersion containing a small amount of additives or a small amount of reinforcing material as needed is prepared for the clay. After applying to the surface of the cloth or immersing the cloth in the dispersion, the liquid as the dispersion medium is removed by various drying methods, for example, vacuum drying, freeze vacuum drying, or heat evaporation, and one or both sides of the cloth is removed. Focusing on the fact that a multilayer film with significantly increased mechanical strength can be obtained by forming a clay layer, and further research is conducted to obtain a multilayer film having a uniform thickness and excellent adhesion between the cloth and clay. Succeeded in making the present invention This has led to the formation. The present invention has mechanical strength and toughness that can be used as a self-supporting film, and can be used as a multilayer film having excellent gas barrier properties, flexibility, thermal stability, and porosity, as well as an electrical insulating material and a heat insulating material. The purpose is to provide new technologies and new materials such as new materials.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）布と粘土から構成され、柔軟性を有し、自立膜として利用可能であり、耐熱性を有し、粘土層にクラックやピンホールが存在せず、ガスバリア性を有する、粘土層及び布の複合多層構造を有することを特徴とする多層膜。
（２）粘土層が、布の片面あるいは両面に存在するか、又は布が粘土層の両面に存在するか、又はそれらの構造を含む前記（１）に記載の多層膜。
（３）粘土層が、粘土のみ、粘土と少量の添加物、粘土と少量の補強材、又は粘土と少量の添加物と少量の補強材から構成される前記（１）に記載の多層膜。
（４）粘土層の主要構成成分が、天然粘土又は合成粘土である前記（１）に記載の多層膜。
（５）前記天然粘土又は合成粘土が、雲母、バーミキュライト、モンモリロナイト、鉄モンモリロナイト、バイデライト、サポナイト、ヘクトライト、スチーブンサイト、及びノントロナイトからなる群のうちの一種以上である前記（４）に記載の多層膜。
（６）添加物が、エチレングリコール、グリセリン、イプシロンカプロラクタム、デキストリン、澱粉、セルロース系樹脂、ゼラチン、寒天、小麦粉、グルテン、アルキド樹脂、ポリウレタン樹脂、エポキシ樹脂、フッ素樹脂、アクリル樹脂、メタクリル樹脂、フェノール樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリイミド樹脂、ポリビニル樹脂、ポリエチレングリコール、ポリアクリルアマイド、ポリエチレンオキサイド、タンパク質、デオキシリボヌクレイン酸、リボヌクレイン酸及びポリアミノ酸、フェノール類、安息香酸類化合物、及びシリコン樹脂のうちから選択される一種以上である前記（１）に記載の多層膜。
（７）補強材が、鉱物繊維、グラスウール、セラミックス繊維、セラミックス繊維、植物繊維、及び有機高分子繊維からなる群のうちの一種以上である前記（１）に記載の粘土膜。
（８）布が、有機高分子繊維、シリカ繊維、アルミナ繊維、ガラス繊維、セラミックス繊維、又はそれらの中間組成物、あるいはそれら二種以上からなる複合体である前記（１）に記載の多層膜。
（９）加熱、光照射等の任意の手段により、付加反応、縮合反応、重合反応等の化学反応を行わせ、粘土、添加物、及び布の成分同士、あるいは成分間において、新たな化学結合を生じさせて、耐水性、ガスバリア性、又は機械的強度を改善させた前記（１）から（７）のいずれかに記載の多層膜。
（１０）室温における、空気、酸素ガス、窒素ガス、水素ガス、又はヘリウムガスに対する透過係数が、１×１０−１２ｃｍ２ｓ−１ｃｍＨｇ−１未満である前記（１）に記載の多層膜。
（１１）６００℃、２４時間、通常空気雰囲気下で熱処理後の、空気、酸素ガス、窒素ガス、水素ガス、又はヘリウムガスに対する透過係数が、１×１０−１２ｃｍ２ｓ−１ｃｍＨｇ−１未満である前記（１）に記載の多層膜。
（１２）通常空気雰囲気下の示差熱分析で、２００℃から６００℃までの減量が５％以下である前記（１）に記載の多層膜。
（１３）円、正方形、長方形等の任意の平面形状を有し、自立膜として用いることが可能である前記（１）に記載の多層膜。
（１４）粘土層の厚さが、１ｍｍよりも薄く、多層膜の面積が、１ｃｍ２よりも大きい前記（１）に記載の多層膜。
（１５）添加物の、全固体に対する重量割合が、３０パーセント以下である前記（１）に記載の多層膜。
（１６）補強材の、全固体に対する重量割合が、３０パーセント以下である前記（１）に記載の多層膜。
（１７）表面処理を施して、撥水、防水、補強、及び／又は表面平坦化をした前記（１）に記載の多層膜。
（１８）前記表面処理が、フッ素系膜、シリコン系膜、ポリシロキサン膜、フッ素含有オルガノポリシロキサン膜、アクリル樹脂膜、塩化ビニル樹脂膜、ポリウレタン樹脂膜、高撥水メッキ膜、金属蒸着膜、又はカーボン蒸着膜を表面に形成することである前記（１７）に記載の多層膜。
（１９）膜に対して、垂直方向の直流電気抵抗が、１メガΩ以上である前記（１）に記載の多層膜。
（２０）前記（１）から（１９）のいずれかに記載の多層膜からなることを特徴とするガスバリア性、水蒸気バリア性、及び／又は電気絶縁性を有する部材。
（２１）部材が、シール材、絶縁材、又は断熱材である前記（２０）に記載の部材。
The present invention for solving the above-described problems comprises the following technical means.
(1) It is composed of cloth and clay, has flexibility, can be used as a self-supporting film, has heat resistance, has no cracks or pinholes in the clay layer, and has a gas barrier property, A multilayer film characterized by having a composite multilayer structure of cloth.
(2) The multilayer film according to (1), wherein the clay layer is present on one side or both sides of the cloth, or the cloth is present on both sides of the clay layer, or includes a structure thereof.
(3) The multilayer film according to (1), wherein the clay layer is composed of only clay, clay and a small amount of additive, clay and a small amount of reinforcing material, or clay, a small amount of additive and a small amount of reinforcing material.
(4) The multilayer film according to (1), wherein the main component of the clay layer is natural clay or synthetic clay.
(5) The natural clay or synthetic clay is at least one of the group consisting of mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, and nontronite. Multilayer film.
(6) Additives are ethylene glycol, glycerin, epsilon caprolactam, dextrin, starch, cellulosic resin, gelatin, agar, flour, gluten, alkyd resin, polyurethane resin, epoxy resin, fluororesin, acrylic resin, methacrylic resin, phenol Resin, polyamide resin, polyester resin, polyimide resin, polyvinyl resin, polyethylene glycol, polyacrylamide, polyethylene oxide, protein, deoxyribonucleic acid, ribonucleic acid and polyamino acids, phenols, benzoic acid compounds, and silicon resins The multilayer film according to (1), which is one or more selected.
(7) The clay film according to (1), wherein the reinforcing material is one or more members selected from the group consisting of mineral fibers, glass wool, ceramic fibers, ceramic fibers, plant fibers, and organic polymer fibers.
(8) The multilayer film according to (1), wherein the cloth is an organic polymer fiber, silica fiber, alumina fiber, glass fiber, ceramic fiber, an intermediate composition thereof, or a composite composed of two or more of them. .
(9) A chemical reaction such as an addition reaction, a condensation reaction, or a polymerization reaction is performed by any means such as heating or light irradiation, and a new chemical bond is formed between the clay, additive, and cloth components or between the components. The multilayer film according to any one of (1) to (7), wherein water resistance, gas barrier properties, or mechanical strength is improved by generating
(10) The multilayer film according to (1), wherein a permeability coefficient with respect to air, oxygen gas, nitrogen gas, hydrogen gas, or helium gas at room temperature is less than 1 × 10 −12 cm 2 s −1 cmHg −1. .
(11) The permeability coefficient for air, oxygen gas, nitrogen gas, hydrogen gas, or helium gas after heat treatment in a normal air atmosphere at 600 ° C. for 24 hours is 1 × 10 −12 cm 2 s −1 cmHg −1. The multilayer film according to (1), which is less than
(12) The multilayer film according to (1), wherein the weight loss from 200 ° C. to 600 ° C. is 5% or less by differential thermal analysis under a normal air atmosphere.
(13) The multilayer film according to (1), which has an arbitrary planar shape such as a circle, a square, or a rectangle and can be used as a self-supporting film.
(14) The multilayer film according to (1), wherein the thickness of the clay layer is thinner than 1 mm, and the area of the multilayer film is larger than 1 cm 2 .
(15) The multilayer film according to (1), wherein the weight ratio of the additive to the total solid is 30% or less.
(16) The multilayer film according to (1), wherein the weight ratio of the reinforcing material to the total solid is 30% or less.
(17) The multilayer film according to (1), which has been subjected to surface treatment to be water repellent, waterproof, reinforced, and / or surface flattened.
(18) The surface treatment includes a fluorine-based film, a silicon-based film, a polysiloxane film, a fluorine-containing organopolysiloxane film, an acrylic resin film, a vinyl chloride resin film, a polyurethane resin film, a highly water-repellent plating film, a metal vapor deposition film, Or the multilayer film as described in said (17) which is forming a carbon vapor deposition film on the surface.
(19) The multilayer film according to (1), wherein the direct current electric resistance in the vertical direction is 1 megaΩ or more with respect to the film.
(20) A member having a gas barrier property, a water vapor barrier property, and / or an electrical insulating property, comprising the multilayer film according to any one of (1) to (19).
(21) The member according to (20), wherein the member is a sealing material, an insulating material, or a heat insulating material.
次に、本発明について更に詳細に説明する。
本発明は、布と粘土から構成され、柔軟性を有し、自立膜として利用可能であり、耐熱性を有し、クラックやピンホールが存在せず、ガスバリア性を有すること、室温における、空気、酸素ガス、窒素ガス、水素ガス、ヘリウムガスに対する透過係数が、１×１０−１２ｃｍ２ｓ−１ｃｍＨｇ−１未満であることを特徴とする多層膜である。また、本発明は、６００℃、２４時間、通常空気雰囲気下で熱処理後の、空気、酸素ガス、窒素ガス、水素ガス、ヘリウムガスに対する透過係数は、１×１０−１２ｃｍ２ｓ−１ｃｍＨｇ−１未満であり、また、通常空気雰囲気下の示差熱分析で、２００℃から６００℃までの減量が５％以下であることを特徴とする多層膜である。
Next, the present invention will be described in more detail.
The present invention is composed of cloth and clay, has flexibility, can be used as a self-supporting film, has heat resistance, has no cracks or pinholes, has gas barrier properties, air at room temperature, , Oxygen gas, nitrogen gas, hydrogen gas, helium gas has a permeability coefficient of less than 1 × 10 −12 cm 2 s −1 cmHg −1 . In the present invention, the permeability coefficient for air, oxygen gas, nitrogen gas, hydrogen gas, and helium gas after heat treatment in a normal air atmosphere at 600 ° C. for 24 hours is 1 × 10 −12 cm 2 s −1 cmHg. The multilayer film is characterized in that the weight loss from 200 ° C. to 600 ° C. is 5% or less by differential thermal analysis under a normal air atmosphere.
本発明の多層膜は、粘土層が布の片面あるいは両面に存在するか、又は布が粘土層の両面に存在するか、又はこれらの構造を含む。本発明の多層膜は、粘土のみ、あるいは粘土と少量の添加物、あるいは粘土と少量の添加物、あるいは粘土と少量の添加物と少量の補強材から構成される。粘土層の主要構成成分は、天然粘土あるいは合成粘土である。前記多層膜の主要構成成分としては、例えば、雲母、バーミキュライト、モンモリロナイト、鉄モンモリロナイト、バイデライト、サポナイト、ヘクトライト、スチーブンサイト及びノントロナイトが例示される。 The multilayer film of the present invention includes a clay layer on one side or both sides of the cloth, or a cloth on both sides of the clay layer, or includes these structures. The multilayer film of the present invention is composed of clay alone, clay and a small amount of additive, clay and a small amount of additive, or clay, a small amount of additive and a small amount of reinforcing material. The main component of the clay layer is natural clay or synthetic clay. Examples of the main components of the multilayer film include mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, and nontronite.
前記添加物としては、例えば、エチレングリコール、グリセリン、イプシロンカプロラクタム、デキストリン、澱粉、セルロース系樹脂、ゼラチン、寒天、小麦粉、グルテン、アルキド樹脂、ポリウレタン樹脂、エポキシ樹脂、フッ素樹脂、アクリル樹脂、メタクリル樹脂、フェノール樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリイミド樹脂、ポリビニル樹脂、ポリエチレングリコール、ポリアクリルアマイド、ポリエチレンオキサイド、タンパク質、デオキシリボヌクレイン酸、リボヌクレイン酸及びポリアミノ酸、フェノール類、安息香酸類化合物、シリコン樹脂が例示される。 Examples of the additive include ethylene glycol, glycerin, epsilon caprolactam, dextrin, starch, cellulosic resin, gelatin, agar, flour, gluten, alkyd resin, polyurethane resin, epoxy resin, fluororesin, acrylic resin, methacrylic resin, Examples include phenol resin, polyamide resin, polyester resin, polyimide resin, polyvinyl resin, polyethylene glycol, polyacrylamide, polyethylene oxide, protein, deoxyribonucleic acid, ribonucleic acid and polyamino acids, phenols, benzoic acid compounds, and silicon resin. The
前記補強材としては、鉱物繊維、グラスウール、セラミックス繊維、セラミックス繊維、植物繊維、有機高分子繊維、のうちの１種以上が例示される。前記布としては、有機高分子繊維、シリカ繊維、アルミナ繊維、ガラス繊維、セラミックス繊維又はそれらの中間組成物、あるいはこれら二種以上からなる複合体が例示される。 Examples of the reinforcing material include one or more of mineral fibers, glass wool, ceramic fibers, ceramic fibers, plant fibers, and organic polymer fibers. Examples of the cloth include organic polymer fibers, silica fibers, alumina fibers, glass fibers, ceramic fibers, intermediate compositions thereof, or composites composed of two or more of these.
本発明では、例えば、加熱、光照射等の任意の方法及び手段により、付加反応、縮合反応、重合反応等の化学反応を行わせ、粘土、添加物、及び補強材の成分同士、あるいは成分間において、新たな化学結合を生じさせて、耐水性、ガスバリア性、あるいは機械的強度を改善させた多層膜も対象とされる。 In the present invention, a chemical reaction such as an addition reaction, a condensation reaction, or a polymerization reaction is performed by any method and means such as heating and light irradiation, and the components of clay, additive, and reinforcing material, or between components. In addition, a multilayer film in which a new chemical bond is generated to improve water resistance, gas barrier property, or mechanical strength is also targeted.
本発明では、例えば、室温における、空気、酸素ガス、窒素ガス、水素ガス、又はヘリウムガスに対する透過係数が、１×１０−１２ｃｍ２ｓ−１ｃｍＨｇ−１未満である多層膜を提供できる。本発明では、例えば、円、正方形、長方形等に代表される任意の二次元平面形状、あるいは平板、管、円柱、コーン、球又はその組み合わせである任意の三次元平面形状を有し、自立膜として用いることが可能であり、厚さは１ｍｍよりも薄く、面積は１ｃｍ２よりも大きい多層膜を提供できる。 In the present invention, for example, a multilayer film having a permeability coefficient of less than 1 × 10 −12 cm 2 s −1 cmHg −1 for air, oxygen gas, nitrogen gas, hydrogen gas, or helium gas at room temperature can be provided. In the present invention, for example, an arbitrary two-dimensional planar shape represented by a circle, a square, a rectangle, or the like, or an arbitrary three-dimensional planar shape that is a flat plate, a tube, a cylinder, a cone, a sphere, or a combination thereof, And a multilayer film having a thickness smaller than 1 mm and an area larger than 1 cm 2 can be provided.
本発明では、例えば、撥水、防水、補強、表面平坦化を目的として表面処理が行われることがあり、表面処理がフッ素系膜、シリコン系膜、ポリシロキサン膜、フッ素含有オルガノポリシロキサン膜、アクリル樹脂膜、塩化ビニル樹脂膜、ポリウレタン樹脂膜、高撥水メッキ膜、金属蒸着膜、カーボン蒸着膜を表面に形成することが可能である。前記添加物の、全固体に対する重量割合は、好適には、３０パーセント以下である。前記補強材の、全固体に対する重量割合は、好適には、３０パーセント以下である。本発明の多層膜は、容器あるいは物体表面から剥離した自立膜として、又は容器あるいは物体表面に支持されて使用される。 In the present invention, for example, surface treatment may be performed for the purpose of water repellency, waterproofing, reinforcement, and surface flattening. The surface treatment may be a fluorine-based film, a silicon-based film, a polysiloxane film, a fluorine-containing organopolysiloxane film, An acrylic resin film, a vinyl chloride resin film, a polyurethane resin film, a highly water-repellent plating film, a metal vapor deposition film, and a carbon vapor deposition film can be formed on the surface. The weight ratio of the additive to the total solid is preferably 30 percent or less. The weight ratio of the reinforcing material to the total solid is preferably 30% or less. The multilayer film of the present invention is used as a self-supporting film peeled off from the container or the object surface or supported on the container or the object surface.
本多層膜は、自立膜、柔軟、加工容易、機能化容易、厚さは、例えば、３〜１００μｍ、配向性はマイクロメートル、ナノオーダーで高配向、であるという特徴を有する。本多層膜はＪＩＳ Ｋ７１２７による引っ張り強度は１０ＭＰａ以上という特徴を有する。本多層膜の基本性能については、ガスバリア性は、ヘリウムで測定限界値未満（アルミホイル相当）、耐熱性は６００℃、２４時間処理後ガスバリア性の低減なし、引っ張り強さは１０ＭＰａ以上である。本多層膜では、特に、主要成分の粘土の割合を高めることで高い耐熱性が得られる。 This multilayer film has the characteristics that it is a free-standing film, flexible, easy to process, easy to function, has a thickness of, for example, 3 to 100 μm, has an orientation of micrometer, and is highly oriented in the nano order. This multilayer film is characterized by a tensile strength according to JIS K7127 of 10 MPa or more. Regarding the basic performance of this multilayer film, the gas barrier property is less than the measurement limit value with helium (corresponding to aluminum foil), the heat resistance is 600 ° C., the gas barrier property is not reduced after treatment for 24 hours, and the tensile strength is 10 MPa or more. In this multilayer film, high heat resistance can be obtained particularly by increasing the proportion of clay as a main component.
本発明の多層膜自体は、粘土を主原料（９０重量％以上）として用い、基本構成として、好適には、例えば，層厚約１ｎｍ、粒子径約１μｍ、アスペクト比約３００程度の天然又は合成の膨潤性粘土が９０重量％以上と、分子の大きさ数ｎｍ以下の天然又は合成の低分子・高分子の添加物が１０重量％以下の構成、が例示される。この多層膜は、例えば、厚さ約１ｎｍの層状結晶を同じ向きに配向させて重ねて緻密に積層することで作製される。得られた多層膜は、膜厚が３〜１００μｍであり、ガスバリア性能は、厚さ３０μｍで酸素透過度０．００００１ｃｃ／ｍ２／２４ｈｒ／ａｔｍ未満、水素透過度０．００２ｃｃ／ｍ２／２４ｈｒ／ａｔｍ未満であり、面積は１００×４０ｃｍ以上に大面積化することが可能であり、高耐熱性を有し、６００℃で２４時間加熱処理後もガスバリア性の低下はみられない。 The multilayer film of the present invention itself uses clay as a main raw material (90% by weight or more), and as a basic structure, for example, natural or synthetic having a layer thickness of about 1 nm, a particle diameter of about 1 μm, and an aspect ratio of about 300 The swellable clay is composed of 90% by weight or more, and a natural or synthetic low-molecular / high-molecular additive having a molecular size of several nm or less is composed of 10% by weight or less. This multilayer film is produced by, for example, densely laminating layered crystals having a thickness of about 1 nm, oriented in the same direction. The resulting multilayer film had a thickness of 3 to 100 m, the gas barrier performance, oxygen permeability 0.00001cc / m 2 / 24hr / atm less than a thickness of 30 [mu] m, hydrogen permeability 0.002cc / m 2 / 24hr / Atm, the area can be increased to 100 × 40 cm or more, has high heat resistance, and no deterioration in gas barrier properties is observed even after heat treatment at 600 ° C. for 24 hours.
本発明は、多層膜であって、布と粘土から構成され、柔軟性を有し、自立膜として利用可能であり、耐熱性を有し、クラックやピンホールが存在せず、ガスバリア性を有するものであって、粘土層が布の片面あるいは両面に存在するか、布が粘土層の両面に存在するか、あるいはこれらの構造を含み、自立膜あるいは支持膜の形態をとることを特徴とするものである。 The present invention is a multilayer film composed of cloth and clay, has flexibility, can be used as a self-supporting film, has heat resistance, has no cracks or pinholes, and has gas barrier properties. The clay layer is present on one or both sides of the cloth, or the cloth is present on both sides of the clay layer, or includes these structures and is in the form of a self-supporting film or a support film Is.
次に、本発明の多層膜の作製方法について説明すると、本発明では、粘土として、天然あるいは合成物、好ましくは、天然スメクタイト及び合成スメクタイトの何れか、あるいはそれらの混合物を用い、これを、水あるいは水を主成分とする液体に加え、希薄で均一な分散液を調製する。粘土として、雲母、バーミキュライト、モンモリロナイト、鉄モンモリロナイト、バイデライト、サポナイト、ヘクトライト、スチーブンサイト及びノントロナイトからなる群のうちの一種以上を用いることができる。粘土分散液の濃度は、好適には０．５から１５重量パーセント、より好ましくは、１から１０重量パーセントである。このとき、粘土分散液の濃度が薄すぎる場合、乾燥に時間がかかりすぎるという問題がある。また、粘土分散液の濃度が濃すぎる場合、よく粘土が分散しないため、粘土粒子の配向が悪く、均一な膜ができ難いという問題がある。 Next, the production method of the multilayer film of the present invention will be described. In the present invention, natural or synthetic products, preferably natural smectites and synthetic smectites, or a mixture thereof are used as clay. Alternatively, a dilute and uniform dispersion is prepared in addition to a liquid mainly composed of water. As the clay, one or more members selected from the group consisting of mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, and nontronite can be used. The concentration of the clay dispersion is suitably from 0.5 to 15 weight percent, more preferably from 1 to 10 weight percent. At this time, if the concentration of the clay dispersion is too thin, there is a problem that it takes too long to dry. Further, when the concentration of the clay dispersion is too high, clay does not disperse well, so that there is a problem that the orientation of clay particles is poor and it is difficult to form a uniform film.
次に、必要に応じて、秤量した固体状あるいは液体状の添加物を、粘土分散液に加え、均一な分散液を調製する。添加物としては、多層膜のフレキシビリティーあるいは機械的強度を向上させる、粘土と均一に混合するものであれば、特に限定されないが、例えば、エチレングリコール、グリセリン、イプシロンカプロラクタム、デキストリン、澱粉、セルロース系樹脂、ゼラチン、寒天、小麦粉、グルテン、アルキド樹脂、ポリウレタン樹脂、エポキシ樹脂、フッ素樹脂、アクリル樹脂、メタクリル樹脂、フェノール樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリイミド樹脂、ポリビニル樹脂、ポリエチレングリコール、ポリアクリルアマイド、ポリエチレンオキサイド、タンパク質、デオキシリボヌクレイン酸、リボヌクレイン酸及びポリアミノ酸、フェノール類、安息香酸類化合物、シリコン樹脂のうちの１種以上を用いることができる。添加物の全固体に対する重量割合は、３０パーセント以下であり、好ましくは１パーセントから１０パーセントである。このとき、添加物の割合が低過ぎる場合、添加の効果が現れず、添加物の割合が高すぎる場合、調製した膜中で添加物と粘土の分布が不均一になり、結果として得られる多層膜の均一性が低下し、やはり添加効果が薄れる。また、添加物の割合が高すぎる場合、多層膜の耐熱性が低下する。 Next, if necessary, a weighed solid or liquid additive is added to the clay dispersion to prepare a uniform dispersion. The additive is not particularly limited as long as it is homogeneously mixed with clay, which improves the flexibility or mechanical strength of the multilayer film. For example, ethylene glycol, glycerin, epsilon caprolactam, dextrin, starch, cellulose Resin, gelatin, agar, flour, gluten, alkyd resin, polyurethane resin, epoxy resin, fluororesin, acrylic resin, methacrylic resin, phenol resin, polyamide resin, polyester resin, polyimide resin, polyvinyl resin, polyethylene glycol, polyacrylamide One or more of polyethylene oxide, protein, deoxyribonucleic acid, ribonucleic acid and polyamino acids, phenols, benzoic acid compounds, and silicon resins can be used. The weight ratio of the additive to the total solids is 30 percent or less, preferably 1 to 10 percent. At this time, if the ratio of the additive is too low, the effect of the addition does not appear, and if the ratio of the additive is too high, the distribution of the additive and clay in the prepared film becomes non-uniform, resulting in the resulting multilayer The uniformity of the film is lowered and the effect of addition is also diminished. Moreover, when the ratio of an additive is too high, the heat resistance of a multilayer film will fall.
次に、秤量した補強材を、粘土分散液に加え、均一な分散液を調製する。補強材として、鉱物繊維、グラスウール、炭素繊維、セラミックス繊維、植物繊維、有機高分子繊維樹脂、のうちの１種以上を用いることができる。補強材の全固体に対する重量割合は、３０パーセント以下であり、好ましくは１パーセントから１０パーセントである。このとき、補強材の割合が低過ぎる場合、添加の効果が現れず、補強材の割合が高すぎる場合、調製した膜中で補強材と粘土の分布が不均一になり、結果として得られる粘土膜の均一性が低下し、やはり添加効果が薄れる。なお、補強材と添加物の添加順序はどちらが先と決まっているわけではなく、どちらを先に加えてもよい。 Next, the weighed reinforcing material is added to the clay dispersion to prepare a uniform dispersion. As the reinforcing material, one or more of mineral fiber, glass wool, carbon fiber, ceramic fiber, vegetable fiber, and organic polymer fiber resin can be used. The weight ratio of the reinforcing material to the total solid is 30% or less, preferably 1 to 10%. At this time, if the proportion of the reinforcing material is too low, the effect of addition does not appear, and if the proportion of the reinforcing material is too high, the distribution of the reinforcing material and the clay becomes uneven in the prepared film, and the resulting clay The uniformity of the film is lowered and the effect of addition is also diminished. Note that the order of adding the reinforcing material and the additive is not determined first, and either may be added first.
次に、この分散液を、布を敷いた容器に流し込むあるいは布を接するように広げた支持体表面に塗布したのち、分散媒である液体を乾燥除去し、布と粘土層からなる多層膜を作製する。このとき、布として、有機高分子繊維、シリカ繊維、アルミナ繊維、ガラス繊維、セラミックス繊維又はそれらの中間組成物、あるいはこれら二種以上からなる複合体が例示される。布の材料については、３００℃以上の耐熱性が必要となる場合には無機系のものを用いるのが好ましい。ただし、３００℃程度までの耐熱性であれば十分である場合には、使用条件に応じてアラミド繊維、フッ素系樹脂、アミド樹脂、イミド樹脂などの耐熱性有機高分子を用いた布を用いることが可能である。このとき、布を支持膜として利用する場合には、布を物体に接着・溶着などして固定してから分散液を流し込むあるいは塗布することが考えられる。布と粘土膜の中に気泡が入り込まないように分散液層を形成させ、布の目の中に粘土の微結晶が入り込み、ピンホールやクラックがない緻密な多層膜を得る。 Next, this dispersion is poured into a cloth-covered container or coated on the surface of a support spread so as to contact the cloth, and then the liquid as a dispersion medium is dried and removed to form a multilayer film composed of the cloth and the clay layer. Make it. At this time, examples of the cloth include organic polymer fibers, silica fibers, alumina fibers, glass fibers, ceramic fibers, an intermediate composition thereof, or a composite composed of two or more of these. As for the material of the cloth, it is preferable to use an inorganic material when heat resistance of 300 ° C. or higher is required. However, if heat resistance up to about 300 ° C is sufficient, a cloth using a heat-resistant organic polymer such as aramid fiber, fluororesin, amide resin, or imide resin should be used depending on the conditions of use. Is possible. At this time, when the cloth is used as a support film, it is conceivable that the dispersion is poured or applied after the cloth is fixed to the object by adhesion or welding. A dispersion layer is formed so that air bubbles do not enter between the cloth and the clay film, and the fine crystal of clay enters into the eyes of the cloth to obtain a dense multilayer film free from pinholes and cracks.
多層膜の作製方法としては、例えば、分散液である液体をゆっくりと蒸発させ、膜状に成形する。分散液を支持体表面に塗布し、分散媒である液体を乾燥除去する、などの方法がある。分散媒である液体の乾燥除去法としては、例えば、種々の固液分離方法、例えば、遠心分離、ろ過、真空乾燥、凍結真空乾燥、加熱蒸発法の何れか、あるいはこれらの方法の組み合わせが可能である。これらの方法のうち、例えば、分散液を容器に流し込み加熱蒸発法を用いる場合、平坦なトレイ、好ましくはプラスチック製あるいは金属製のトレイ等の支持体に布を敷き、粘土の濃度を０．５〜３重量パーセントに調整し、事前に脱気処理した分散液を布の上から注ぎ、水平を保った状態で、強制送風式オーブン中で３０から７０℃の温度条件下、好ましくは３０から５０℃の温度条件下で、３時間から半日間程度、好ましくは３時間から５時間、乾燥して二層の多層膜を得る。 As a method for producing a multilayer film, for example, a liquid that is a dispersion liquid is slowly evaporated to form a film. There is a method of applying a dispersion liquid on the surface of a support and drying and removing a liquid as a dispersion medium. As a method for drying and removing the liquid as the dispersion medium, for example, various solid-liquid separation methods such as centrifugation, filtration, vacuum drying, freeze vacuum drying, heat evaporation method, or a combination of these methods are possible. It is. Among these methods, for example, when the dispersion is poured into a container and the heating evaporation method is used, cloth is laid on a support such as a flat tray, preferably a plastic or metal tray, and the clay concentration is 0.5. A dispersion adjusted to ˜3 weight percent and pre-degassed in advance is poured over the cloth and kept in a horizontal condition in a forced air oven at a temperature of 30 to 70 ° C., preferably 30 to 50 Under a temperature condition of 0 ° C., it is dried for about 3 hours to half a day, preferably 3 hours to 5 hours to obtain a two-layer multilayer film.
また、別の例として、固液比の比較的高いゲル状分散液を物体に塗布し、加熱蒸発法を用いる場合、平坦な金属板の上に布を敷き、粘土の濃度を４〜７重量パーセントに調整し、事前に脱気処理した分散液を布の上に２ｍｍの厚さに塗布し、強制送風式オーブン中で３０から１００℃の温度条件下、好ましくは３０から８０℃の温度条件下で、１０分間から２時間程度、好ましくは２０分間から１時間、乾燥して二層の多層膜を得る。これらの場合布の上面に粘土層が形成される。 As another example, when a gel-like dispersion having a relatively high solid-liquid ratio is applied to an object and the heating evaporation method is used, a cloth is laid on a flat metal plate, and the clay concentration is 4 to 7 weights. Apply a dispersion adjusted to percent and pre-degassed to a thickness of 2 mm on the cloth, and in a forced air oven at a temperature of 30 to 100 ° C., preferably 30 to 80 ° C. Then, drying is performed for about 10 minutes to 2 hours, preferably for 20 minutes to 1 hour to obtain a two-layered multilayer film. In these cases, a clay layer is formed on the upper surface of the fabric.
二層の多層膜を裏返し、粘土層を形成される上記の処理をすることによって布の両面に粘土層が形成された三層からなる多層膜を得ることができる。また、二層の多層膜を作製する過程で、粘土層が完全に乾燥する前にお互いを張り合わせるなどすることにより、粘土層を布でサンドイッチした三層からなる多層膜を得ることができる。更に、これらの手順の繰り返しによって、三層以上からなる多層膜を作製することができる。三層以上からなる多層膜を作製する場合に、接着剤を用いることが可能である。 By turning the two-layer multilayer film upside down and performing the above-described treatment for forming a clay layer, a multilayer film composed of three layers in which the clay layers are formed on both sides of the cloth can be obtained. Further, in the process of producing a two-layer multilayer film, a multilayer film composed of three layers in which the clay layer is sandwiched with a cloth can be obtained by pasting each other before the clay layer is completely dried. Furthermore, by repeating these procedures, a multilayer film composed of three or more layers can be produced. An adhesive can be used when producing a multilayer film composed of three or more layers.
分散液を事前に脱気処理しない場合、粘土層に気泡に由来する孔ができ易くなるという問題がある場合がある。また、乾燥条件は、液体分を乾燥除去するのに十分であるように設定される。このとき、乾燥速度が遅すぎると、乾燥に時間がかかるという問題がある。また、乾燥速度が速すぎると、分散液の対流が起こり、多層膜の均一性が低下するという問題がある。粘土層の厚さは、分散液に用いる固体量を調整することによって、任意の厚さの膜を得ることができる。 If the dispersion is not degassed in advance, there may be a problem that pores derived from bubbles are easily formed in the clay layer. The drying conditions are set so as to be sufficient to dry and remove the liquid component. At this time, if the drying speed is too slow, there is a problem that it takes time to dry. Further, when the drying rate is too high, there is a problem that convection of the dispersion occurs and the uniformity of the multilayer film is lowered. As for the thickness of the clay layer, a film having an arbitrary thickness can be obtained by adjusting the amount of solid used in the dispersion.
多層膜を自立膜として用いる場合は、多層膜を容器あるいは物体表面から剥離し、粘土自立膜を得る。粘土薄膜が容器等の支持体から自然に剥離しない場合は、好適には、真空引きにより剥離を促進させ自立膜を得る。また剥離の別の方法として、好適には、約１１０から２００℃の温度条件下で乾燥し、剥離を容易にして自立膜を得る。このとき、温度が低すぎる場合には、剥離が起こりにくいという問題がある。温度が高すぎる場合には、添加物が劣化しやすくなるという問題がある。添加物を含まない場合には、更に、高温の処理により剥離を促進させることができる。このときの高温の処理は、７００℃までの温度条件が可能である。 When the multilayer film is used as a self-supporting film, the multilayer film is peeled off from the container or the object surface to obtain a clay self-supporting film. In the case where the clay thin film does not naturally peel from a support such as a container, the peeling is preferably promoted by evacuation to obtain a self-supporting film. As another method of peeling, it is preferably dried under a temperature condition of about 110 to 200 ° C. to facilitate peeling and obtain a self-supporting film. At this time, if the temperature is too low, there is a problem that peeling does not easily occur. When the temperature is too high, there is a problem that the additive tends to deteriorate. When an additive is not included, peeling can be further promoted by a high temperature treatment. The high temperature treatment at this time can be performed at a temperature condition up to 700 ° C.
以上のようにして得られた粘土膜あるいは粘土自立膜は、基本的には、親水性であり、そのため、プラスチックフィルムや金属箔に比較して耐水性に劣る。そのため、結露する条件下、あるいは水に接する条件下では、膨潤し、脆弱になるという問題点がある。また、高い遮湿性を持たせることが困難である。ここで、粘土膜の表面を処理することにより、親水性から疎水性に変え、耐水性・高遮湿性を付与することが可能である。表面処理としては、粘土膜あるいは粘土自立膜表面を疎水化するものであれば、特に限定されるものではないが、例えば、被覆層作製法がある。 The clay film or the clay self-supporting film obtained as described above is basically hydrophilic and therefore inferior in water resistance as compared with plastic films and metal foils. For this reason, there is a problem in that it swells and becomes brittle under conditions of condensation or in contact with water. In addition, it is difficult to provide high moisture barrier properties. Here, by treating the surface of the clay film, it is possible to change from hydrophilic to hydrophobic and to impart water resistance and high moisture barrier properties. The surface treatment is not particularly limited as long as the surface of the clay film or the clay free-standing film is hydrophobized. For example, there is a coating layer preparation method.
被覆層作製による方法としては、フッ素系膜、シリコン系膜、ポリシロキサン膜、フッ素含有オルガノポリシロキサン膜、アクリル樹脂膜、塩化ビニル樹脂膜、ポリウレタン樹脂膜、高撥水メッキ膜、金属蒸着膜、カーボン蒸着膜などを表面に形成するものがある。この場合、膜作成法として湿式法、乾式法、蒸着法、噴霧法等の方法がある。表面に作製された被覆層は疎水性であり、そのため、結果として粘土膜表面の撥水性が実現する。この処理は、用途に応じて、粘土膜の片面のみ、あるいは両面とも行うことができる。表面処理法としては、他に、シリル化、イオン交換などの化学処理によって表面改質を行う方法がある。 As a method by coating layer production, fluorine film, silicon film, polysiloxane film, fluorine-containing organopolysiloxane film, acrylic resin film, vinyl chloride resin film, polyurethane resin film, highly water-repellent plating film, metal vapor deposition film, Some have a carbon deposition film or the like formed on the surface. In this case, there are methods such as a wet method, a dry method, a vapor deposition method, and a spray method as a film forming method. The coating layer formed on the surface is hydrophobic, and as a result, water repellency on the surface of the clay film is realized. This treatment can be performed on only one side or both sides of the clay film depending on the application. As another surface treatment method, there is a method of modifying the surface by chemical treatment such as silylation or ion exchange.
この表面処理により、以上述べた撥水性、防水性の付与の他に、膜強度を高める補強効果、表面における光散乱を押さえ、光沢を与え外見を美麗にする効果が期待できる。一方、被覆層を有機高分子とする場合、粘土膜の常用温度範囲が被覆層の材料の常用温度範囲によって規定される場合がある。そのため、用途によって表面処理に用いる材料の選定や膜厚が注意深く選択されることになる。 By this surface treatment, in addition to the above-described water repellency and waterproofness, the effect of reinforcing the film strength, the effect of suppressing the light scattering on the surface, giving gloss and making the appearance beautiful can be expected. On the other hand, when the coating layer is an organic polymer, the normal temperature range of the clay film may be defined by the normal temperature range of the material of the coating layer. For this reason, the material used for the surface treatment and the film thickness are carefully selected depending on the application.
本発明の複合膜は、例えば、はさみ、カッター等で容易に円、正方形、長方形などの任意の大きさ、形状に切り取ることができる。本発明の複合膜は、好適には、厚さは１ｍｍよりも薄く、面積は１ｃｍ２ よりも大きい。また、本発明の多層膜は、自立膜として利用可能な機械的強度を有し、柔軟性が高く、耐熱性が高く、電気絶縁体であり、熱伝導率が低いといった特徴を有する。 The composite film of the present invention can be easily cut into an arbitrary size and shape such as a circle, a square, and a rectangle with a scissor, a cutter, or the like. The composite membrane of the present invention preferably has a thickness of less than 1 mm and an area of greater than 1 cm 2 . In addition, the multilayer film of the present invention has mechanical strength that can be used as a self-supporting film, has high flexibility, high heat resistance, is an electrical insulator, and has low heat conductivity.
耐熱性の高い多層膜を作製する場合に、粘土に比較して耐熱性に劣る添加物の添加量を少なくすることは重要である。この場合、添加物の総固体に対する重量比は１０％以下であることが好適である。特に耐熱性を要求されない場合はこの限りではない。本発明の多層膜は、粘土が主成分であることから、絶縁性に優れ、耐熱性絶縁膜として広範に使用することができる。また、本発明の多層膜は、断熱性に優れ、断熱膜として広範に使用することができる。 When producing a multilayer film having high heat resistance, it is important to reduce the amount of an additive inferior in heat resistance compared to clay. In this case, the weight ratio of the additive to the total solid is preferably 10% or less. This is not the case when heat resistance is not particularly required. Since the multilayer film of the present invention is mainly composed of clay, it has excellent insulating properties and can be widely used as a heat-resistant insulating film. Moreover, the multilayer film of the present invention is excellent in heat insulating properties and can be widely used as a heat insulating film.
本発明により、（１）自立膜として利用可能な機械的強度と靭性を有し、しかも、優れた柔軟性、熱安定性、優れたガスバリア性、優れた水蒸気バリア性を併せ持つ多層膜の新技術・新素材を提供できる、（２）耐熱性及び柔軟性を併せ持つパッキンあるいは固体電解質燃料電池隔膜、電気絶縁材、断熱材として使用可能な部材等の新技術・新素材を提供できる、という効果が奏される。 According to the present invention, (1) a new multilayer film technology that has mechanical strength and toughness that can be used as a free-standing film, and also has excellent flexibility, thermal stability, excellent gas barrier properties, and excellent water vapor barrier properties・ Providing new materials, (2) Providing new technologies and materials such as packing that has both heat resistance and flexibility, solid electrolyte fuel cell membranes, electrical insulating materials, and materials that can be used as heat insulating materials Played.
次に、実施例に基づいて本発明を具体的に説明するが、本発明は、これらの実施例によって何ら限定されるものではない。 Next, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
（１）多層膜の製造
長さ約３０ｃｍ、幅２０ｃｍの真鍮製板に、それよりも一回り小さなガラス製平織り布（株式会社ソーラー製ガラスクロス）を敷いた。グラス製布の厚さは約０．１ｍｍである。次に、粘土として、２グラムの天然モンモリロナイト（クニピアＰ、クニミネ工業株式会社製）を、６０ｃｍ３の蒸留水に加え、プラスチック製密封容器に、テフロン（登録商標）製回転子とともに入れ、激しく振とうし、均一な分散液を得た。この分散液を、ガラス平織り布の上に塗布し、これを水平に静置し、強制送風式オーブン中で６０℃の温度条件下で３０分乾燥して、厚さ約０．２ｍｍの多層膜を得た。
(1) Manufacture of multilayer film A glass plain woven fabric (Solar Glass Cloth Co., Ltd.) that was slightly smaller than that was laid on a brass plate having a length of about 30 cm and a width of 20 cm. The thickness of the glass cloth is about 0.1 mm. Next, 2 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) as clay is added to 60 cm 3 of distilled water, placed in a plastic sealed container with a Teflon (registered trademark) rotor, and vigorously shaken. Finally, a uniform dispersion was obtained. This dispersion is applied onto a glass plain weave cloth, left to stand horizontally, and dried in a forced air oven at 60 ° C. for 30 minutes to obtain a multilayer film having a thickness of about 0.2 mm. Got.
（２）多層膜の特性
本多層膜の室温における、空気、酸素ガス、窒素ガス、水素ガス、又はヘリウムガスに対する透過係数は、１×１０−１２ｃｍ２ｓ−１ｃｍＨｇ−１未満であった。本多層膜の熱重量測定から、２００℃から６００℃にかけての加熱による重量減少は、わずかに０．２３％であった。走査型電子顕微鏡写真（図１、図２）より、ガラス製平織り布の片面に粘土層が密に製膜されている様子が分かる。また、本多層膜を６００℃で２４時間過熱処理後もガス透過係数は１×１０−１２ｃｍ２ｓ−１ｃｍＨｇ−１未満であった。以上のことから、本多層膜は、耐熱性が高いことが示された。膜に対して、垂直方向の直流電気抵抗を交流二端子法で測定した結果，１メガΩ以上であった。
(2) Characteristics of Multilayer Film The permeability coefficient of this multilayer film with respect to air, oxygen gas, nitrogen gas, hydrogen gas, or helium gas at room temperature was less than 1 × 10 −12 cm 2 s −1 cmHg −1 . . From the thermogravimetric measurement of this multilayer film, the weight loss due to heating from 200 ° C. to 600 ° C. was only 0.23%. It can be seen from the scanning electron micrographs (FIGS. 1 and 2) that the clay layer is densely formed on one side of the glass plain weave fabric. Moreover, the gas permeability coefficient was less than 1 × 10 −12 cm 2 s −1 cmHg −1 even after the multi-layer film was overheated at 600 ° C. for 24 hours. From the above, it was shown that this multilayer film has high heat resistance. As a result of measuring the direct current electric resistance in the vertical direction with respect to the film by the alternating current two-terminal method, it was 1 megaΩ or more.
（１）多層膜の製造
長さ約３０ｃｍ、幅２０ｃｍの真鍮製板に、それよりも一回り小さなガラス製平織り布（株式会社ソーラー製ガラスクロス）を敷いた。グラス製布の厚さは約０．１ｍｍである。次に粘土として、１．８２グラムの天然モンモリロナイト（クニピアＰ、クニミネ工業株式会社製）を、６０ｃｍ３の蒸留水に加え、プラスチック製密封容器に、テフロン（登録商標）製回転子とともに入れ、激しく振とうし、均一な分散液を得た。この分散液に、添加剤として、イプシロン−カプロラクタム（和光純薬工業株式会社製）を０．１８グラム含む水溶液を加え、得られた分散液を、ガラス平織り布の上に塗布し、これを水平に静置し、強制送風式オーブン中で６０℃の温度条件下で３０分乾燥して、厚さ約０．２ｍｍの多層膜を得た。次に、生成した多層膜をトレイから剥離して自立多層膜を得た。次に、この多層膜を２５０℃で所定時間加熱して、イプシロンカプロラクタムが重合したナイロン６を含む多層膜を得た。
(1) Manufacture of multilayer film A glass plain woven fabric (Solar Glass Cloth Co., Ltd.) that was slightly smaller than that was laid on a brass plate having a length of about 30 cm and a width of 20 cm. The thickness of the glass cloth is about 0.1 mm. Next, 1.82 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) as clay was added to 60 cm 3 of distilled water and placed in a plastic sealed container with a Teflon (registered trademark) rotor. Shake to obtain a uniform dispersion. To this dispersion, an aqueous solution containing 0.18 g of epsilon-caprolactam (manufactured by Wako Pure Chemical Industries, Ltd.) as an additive was added, and the resulting dispersion was applied onto a glass plain weave fabric, And dried in a forced air oven at 60 ° C. for 30 minutes to obtain a multilayer film having a thickness of about 0.2 mm. Next, the produced multilayer film was peeled from the tray to obtain a self-supporting multilayer film. Next, this multilayer film was heated at 250 ° C. for a predetermined time to obtain a multilayer film containing nylon 6 polymerized with epsilon caprolactam.
（２）多層膜の特性
本多層膜の室温における、空気、酸素ガス、窒素ガス、水素ガス、又はヘリウムガスに対する透過係数は、１×１０−１２ｃｍ２ｓ−１ｃｍＨｇ−１未満であった。また、本多層膜を６００℃で２４時間過熱処理後もガス透過係数は、１×１０−１２ｃｍ２ｓ−１ｃｍＨｇ−１未満であった。以上のことから、本多層膜は、耐熱性が高いことが示された。膜に対して、垂直方向の直流電気抵抗を交流二端子法で測定した結果，１メガΩ以上であった。
(2) Characteristics of Multilayer Film The permeability coefficient of this multilayer film with respect to air, oxygen gas, nitrogen gas, hydrogen gas, or helium gas at room temperature was less than 1 × 10 −12 cm 2 s −1 cmHg −1 . . Moreover, the gas permeability coefficient was less than 1 × 10 −12 cm 2 s −1 cmHg −1 even after the multi-layer film was overheated at 600 ° C. for 24 hours. From the above, it was shown that this multilayer film has high heat resistance. As a result of measuring the direct current electric resistance in the vertical direction with respect to the film by the alternating current two-terminal method, it was 1 megaΩ or more.
以上詳述したように、本発明は、多層膜、その製造方法及びその用途に係るものであり、自立膜として利用可能な機械的強度を有し、しかも、優れたフレキシビリティーを有し、高温条件下で使用できる新しい多層膜、その製造技術及びその製品を提供することができる。本発明は、耐熱性に優れた膜を提供することを可能とする。また、本発明の粘土薄膜は、自立膜として使用可能であり、耐熱性及びフレキシビリティーに優れ、ガスバリア性に優れることから、例えば、化学産業分野の配管の接続部分に用いられるパッキン材、電子・電機機器などに用いられる絶縁膜、断熱材として使用可能である。 As described above in detail, the present invention relates to a multilayer film, a method for producing the same, and its application, has mechanical strength that can be used as a self-supporting film, and has excellent flexibility, It is possible to provide a new multilayer film that can be used under high temperature conditions, a manufacturing technique thereof, and a product thereof. The present invention makes it possible to provide a film having excellent heat resistance. Further, the clay thin film of the present invention can be used as a self-supporting film, and has excellent heat resistance and flexibility, and excellent gas barrier properties. -It can be used as an insulating film and heat insulating material used in electrical equipment.
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| PCT/JP2005/022702 WO2006062209A1 (en) | 2004-12-10 | 2005-12-11 | Clay film product |
| US11/721,403 US8178194B2 (en) | 2004-12-10 | 2005-12-11 | Clay film product |
| EP05814763.8A EP1832553B1 (en) | 2004-12-10 | 2005-12-11 | Clay film product |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006188645A (en) * | 2004-12-10 | 2006-07-20 | National Institute Of Advanced Industrial & Technology | Adhesive clay film and method of using the same |
| JP2008137161A (en) * | 2006-11-30 | 2008-06-19 | National Institute Of Advanced Industrial & Technology | Laminated clay film and manufacturing method thereof |
| WO2011152500A1 (en) * | 2010-06-03 | 2011-12-08 | 独立行政法人産業技術総合研究所 | Water vapor barrier film and method for producing same |
| JP2012016875A (en) * | 2010-07-07 | 2012-01-26 | National Institute Of Advanced Industrial Science & Technology | Transparent incombustible material and method for manufacturing the same |
| WO2012137559A1 (en) * | 2011-04-04 | 2012-10-11 | 株式会社村田製作所 | Flexible clay film and method for producing same, and flexible substrate using same |
| WO2013035538A1 (en) * | 2011-09-09 | 2013-03-14 | 独立行政法人産業技術総合研究所 | Composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05131586A (en) * | 1991-11-14 | 1993-05-28 | Japan Vilene Co Ltd | Heat resisting sheet |
| JPH0532514Y2 (en) * | 1986-03-27 | 1993-08-19 | ||
| JP2001096656A (en) * | 1999-09-30 | 2001-04-10 | Dainippon Printing Co Ltd | Decorative board for interior finish work |
-
2004
- 2004-12-10 JP JP2004358627A patent/JP4691721B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0532514Y2 (en) * | 1986-03-27 | 1993-08-19 | ||
| JPH05131586A (en) * | 1991-11-14 | 1993-05-28 | Japan Vilene Co Ltd | Heat resisting sheet |
| JP2001096656A (en) * | 1999-09-30 | 2001-04-10 | Dainippon Printing Co Ltd | Decorative board for interior finish work |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006188645A (en) * | 2004-12-10 | 2006-07-20 | National Institute Of Advanced Industrial & Technology | Adhesive clay film and method of using the same |
| JP2008137161A (en) * | 2006-11-30 | 2008-06-19 | National Institute Of Advanced Industrial & Technology | Laminated clay film and manufacturing method thereof |
| WO2011152500A1 (en) * | 2010-06-03 | 2011-12-08 | 独立行政法人産業技術総合研究所 | Water vapor barrier film and method for producing same |
| JPWO2011152500A1 (en) * | 2010-06-03 | 2013-08-01 | 独立行政法人産業技術総合研究所 | Water vapor barrier film and method for producing the same |
| US9228113B2 (en) | 2010-06-03 | 2016-01-05 | National Institute Of Advanced Industrial Science And Technology | Water vapor barrier film and method for producing same |
| JP2012016875A (en) * | 2010-07-07 | 2012-01-26 | National Institute Of Advanced Industrial Science & Technology | Transparent incombustible material and method for manufacturing the same |
| WO2012137559A1 (en) * | 2011-04-04 | 2012-10-11 | 株式会社村田製作所 | Flexible clay film and method for producing same, and flexible substrate using same |
| WO2013035538A1 (en) * | 2011-09-09 | 2013-03-14 | 独立行政法人産業技術総合研究所 | Composite material |
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| JP4691721B2 (en) | 2011-06-01 |
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