JP2006188645A - Adhesive clay film and method of using the same - Google Patents
Adhesive clay film and method of using the same Download PDFInfo
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- JP2006188645A JP2006188645A JP2005046325A JP2005046325A JP2006188645A JP 2006188645 A JP2006188645 A JP 2006188645A JP 2005046325 A JP2005046325 A JP 2005046325A JP 2005046325 A JP2005046325 A JP 2005046325A JP 2006188645 A JP2006188645 A JP 2006188645A
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- 239000004927 clay Substances 0.000 title claims abstract description 254
- 239000000853 adhesive Substances 0.000 title claims abstract description 124
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims description 32
- 230000004888 barrier function Effects 0.000 claims abstract description 55
- 239000010410 layer Substances 0.000 claims abstract description 51
- 239000012790 adhesive layer Substances 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims description 49
- 239000000654 additive Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 230000000996 additive effect Effects 0.000 claims description 26
- 239000012779 reinforcing material Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000010292 electrical insulation Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 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
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 10
- 230000035699 permeability Effects 0.000 claims description 10
- -1 stevensite Inorganic materials 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229920000620 organic polymer Polymers 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
- 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
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000005871 repellent Substances 0.000 claims description 6
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 229920001353 Dextrin Polymers 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 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
- 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
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 235000019425 dextrin Nutrition 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 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
- 239000011491 glass wool 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
- 239000002557 mineral fiber Substances 0.000 claims description 4
- 229910000273 nontronite Inorganic materials 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 238000007747 plating Methods 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
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000002940 repellent Effects 0.000 claims description 2
- 239000002356 single layer Substances 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
- 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
- 239000000463 material Substances 0.000 abstract description 46
- 239000010408 film Substances 0.000 description 206
- 239000006185 dispersion Substances 0.000 description 29
- 239000007788 liquid Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000012856 packing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 239000002734 clay mineral Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
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- 239000002245 particle Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229910021647 smectite Inorganic materials 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000005856 abnormality Effects 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
- 238000005341 cation exchange Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001308 poly(aminoacid) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004830 Super Glue Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 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
- 238000003618 dip coating Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000945 filler Substances 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
- 238000007731 hot pressing Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 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
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 239000002114 nanocomposite Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) 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
- 230000002265 prevention Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing 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
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- 238000003466 welding Methods 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、粘土膜に接着層が存在する粘着粘土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、高いガスバリア性を有し、かつ優れたフレキシビリティーを有し、それ自身を重ね合わせて、厚膜化することが容易に、均一、かつ確実にでき、異種材料表面との接着が容易に、均一かつ確実にできる新しい単層又は多層構造の粘着粘土膜に関するものである。ガスバリア膜及び絶縁膜の作製技術及びその製品の技術分野においては、従来、粘土膜には接着面が存在せず、他材料との多層化のために、接着剤を均一に塗り、乾燥させるための手順を必要とした。しかし、一般には、均一に接着剤を塗ることは困難であり、接着を確実、強固にすることも困難であった。本発明は、粘土膜に接着面を形成した、容易に、均一、かつ確実に他材料との接着ができる粘着粘土膜を提供するものである。 The present invention relates to an adhesive clay film in which an adhesive layer is present in the clay film. More specifically, the present invention has mechanical strength that can be used as a self-supporting film, high gas barrier properties, and excellent flexibility. The present invention relates to a new single-layered or multi-layered adhesive clay film that can be laminated and thickened easily, uniformly and reliably, and can be easily and uniformly adhered to the surface of different materials. Is. In the technical field of gas barrier films and insulating films and in the technical field of their products, conventionally, there is no adhesive surface on clay films, and in order to apply an adhesive uniformly and to dry it for multilayering with other materials. Needed the procedure. However, in general, it has been difficult to uniformly apply an adhesive, and it has also been difficult to ensure and secure adhesion. The present invention provides an adhesive clay film in which an adhesive surface is formed on a clay film and can be easily and uniformly adhered to other materials with certainty.
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部及び配管連結部などでは、例えば、配管をガスバリア加工する、あるいは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などの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ガスバリア材料は、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、金属製ガスバリア材を用いなければならないが、その金属製部材は、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、絶縁とす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 piping part and the pipe connecting part of these production lines, for example, measures such as gas barrier processing of the pipe or prevention of liquid or gas leakage by packing or welding are taken. Until now, for example, a gas barrier material 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 that, a metal gas barrier material must be used, but the metal member is compared with that of an organic polymer material. There was a problem that it was inferior in flexibility. Metal packing made of aluminum, copper, or the like needs to be strongly tightened in order to obtain complete gas barrier properties, 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、ガラス板から粘着粘土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 left to dry to form a film with uniform particle orientation. For example, in this method, A fixed orientation sample for X-ray diffraction has been prepared (Non-Patent Document 1). However, when a film is formed on a glass plate, it is difficult to peel the adhesive clay film from the glass plate, and there is a problem that it is difficult to obtain a self-supporting film, for example, a crack occurs in the film. 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、柔軟性に優れた粘土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 clay film having mechanical strength that can be used as a self-supporting film and excellent in flexibility.
粘土膜を実用化する場合、多くの場合、粘土膜は、他種材料でできた部材に接するように用いられる。このとき、粘土膜と、他種材料でできた部材との固定、接合などが容易に、均一かつ確実に行われることが要求される。粘土膜同士を接着する場合、粘土膜との接着力が高い接着剤を用いることが考えられる。また、粘土膜と、金属、ガラス、紙、プラスチック、ゴムなどの他種材料を接着する場合、粘土膜と他種材料の両者を接着できる接着剤を用いることが考えられる。これらの接着剤は、比較的容易に入手可能であり、粘土膜同士、あるいは粘土膜と他種材料を接着剤により接着することが可能である。しかしながら、この接着剤を均一に粘土膜に塗布し、均一で、確実な接着をすることは、従来、成功していなかった。特に、極性溶媒を用いる接着剤では、粘土膜が膨潤しやすいという問題点がある。また、粘土膜自身が高いガスバリア性を有しているため、乾燥に時間がかかり、厚い膜を作ることが難しいという問題点がある。 When a clay film is put into practical use, in many cases, the clay film is used in contact with a member made of another kind of material. At this time, it is required that the clay film and the member made of another kind of material are easily and uniformly fixed. When adhering clay films, it is conceivable to use an adhesive having high adhesive strength with the clay film. In addition, when bonding a clay film and other types of materials such as metal, glass, paper, plastic, and rubber, it is conceivable to use an adhesive that can bond both the clay film and other types of materials. These adhesives can be obtained relatively easily, and clay films can be bonded to each other, or clay films and other kinds of materials can be bonded with an adhesive. However, it has heretofore been unsuccessful to apply this adhesive uniformly to a clay film to achieve uniform and reliable adhesion. In particular, an adhesive using a polar solvent has a problem that the clay film tends to swell. Further, since the clay film itself has a high gas barrier property, there is a problem that it takes time to dry and it is difficult to form a thick film.
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、電気絶縁性、及びフレキシビリティーを有する粘土膜と、他材料が接着・複合化した、新規ガスバリア材料、あるいは電気絶縁材料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、粘土膜の表面に接着層を形成させ、粘土膜同士を接着し、多層化することで、厚い粘土層を得、ガスバリア性及び電気絶縁性を更に高めた膜が容易に、均一に、かつ確実にできることを見出した。また、粘土膜表面に接着層を形成させることにより、他材料との接着・複合化が容易に、均一に、かつ確実にできることを見出した。本発明者らは、これらの事実に注目し、粘土膜への接着層の形成のさせ方、接着剤の選定など更に研究を重ねて、自身の積層、あるいは他材料との接着が容易に、均一に、また確実にできる、接着層が存在する粘着粘土膜を得ることに成功して、本発明を完成するに至った。 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 excellent gas barrier properties, electrical insulation properties, and flexibility. In the process of intensive research aimed at developing new gas barrier materials or electrical insulating materials in which other materials are bonded and combined with other clay films, an adhesive layer is formed on the surface of the clay film, It was found that a thick clay layer can be obtained by bonding and multilayering, and a film with further improved gas barrier properties and electrical insulation can be easily, uniformly and reliably. Further, it has been found that by forming an adhesive layer on the surface of the clay film, adhesion / combination with other materials can be easily, uniformly and reliably performed. The present inventors pay attention to these facts, and further research on how to form an adhesive layer on the clay film, selection of an adhesive, etc., makes it easy to laminate itself or adhere to other materials, The present invention has been completed by successfully obtaining a clay clay film having an adhesive layer which can be uniformly and reliably.
本発明は、容易に、自身、あるいは他材料との接着・多層化ができる粘着粘土膜を提供することを目的とするものである。また、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、電気絶縁性、及び柔軟性を併せ持つ多層化粘土膜を提供することを目的とするものである。更に、本発明は、本粘着粘土膜を貼り付けることにより、ガスバリア性、水蒸気バリア性、及び電気絶縁性のいずれかを付与したフィルム、シート、パイプ、容器、あるいは本粘着粘土膜を貼り付けることにより、フィルム、シート、パイプ、容器にガスバリア性、水蒸気バリア性、電気絶縁性のいずれかを付与する方法、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。 An object of the present invention is to provide an adhesive clay film that can be easily bonded or multilayered with itself or other materials. Another object of the present invention is to provide a multilayered clay film having mechanical strength and toughness that can be used as a self-supporting film, and having both excellent gas barrier properties, electrical insulation properties, and flexibility. It is. Furthermore, the present invention attaches a film, sheet, pipe, container, or the present adhesive clay film to which any of gas barrier property, water vapor barrier property, and electrical insulation is imparted by attaching the present adhesive clay film. Accordingly, it is an object of the present invention to provide new technologies and new materials such as a method for imparting any of gas barrier properties, water vapor barrier properties, and electrical insulation properties to films, sheets, pipes, and containers.
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）粘土を主成分とし、柔軟性を有し、自立膜として利用可能であり、ガスバリア性を有する粘土膜に、接着層が存在する単層又は多層の構造を有することを特徴とする粘着粘土膜。
（２）接着層が、粘土膜の片面又は両面に存在する前記（１）に記載の粘着粘土膜。
（３）粘土膜が、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）に記載の粘着粘土膜。
（４）粘土膜の主要構成成分が、天然粘土又は合成粘土である前記（１）に記載の粘着粘土膜。
（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）に記載の粘着粘土膜。
（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、及びシリコン樹脂からなる群のうちから選択される一種以上である前記（１）に記載の粘着粘土膜。
（７）補強材が鉱物繊維、グラスウール、セラミックス繊維、植物繊維、及び有機高分子繊維の群のうちの一種以上である前記（３）に記載の粘着粘土膜。
（８）接着層が、接着剤、又は接着剤とベース層により構成される前記（１）に記載の粘着粘土膜。
（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、及び接着層の成分同士、又は成分間において、新たな化学結合を生じさせて、耐水性、ガスバリア性、及び／又は機械的強度を改善させた前記（１）から（８）のいずれかに記載の粘着粘土膜。
（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）に記載の粘着粘土膜。
（１１）円、正方形、又は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）に記載の粘着粘土膜。
（１２）粘土膜の厚さが、１ｍｍよりも薄く、粘着粘土膜の面積が、１ｃｍ２よりも大きい前記（１）に記載の粘着粘土膜。
（１３）添加物の、粘土膜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）に記載の粘着粘土膜。
（１４）補強材の、粘土膜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）に記載の粘着粘土膜。
（１５）粘土膜に表面処理を施して、撥水、防水、補強、及び／又は表面平坦化をした前記（１）に記載の粘着粘土膜。
（１６）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（１５）に記載の粘着粘土膜。
（１７）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）に記載の粘着粘土膜。
（１８）前記（１）から（１７）のいずれかに記載の粘着粘土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。
（１９）前記（１）から（１７）のいずれかに記載の粘着粘土膜を、フィルム、シート、パイプ、容器などの部材に貼り付けることにより、ガスバリア性、水蒸気バリア性、及び電気絶縁性のいずれかを付与したことを特徴とする部材。
（２０）前記（１）から（１７）のいずれかに記載の粘着粘土膜を貼り付けることにより、フィルム、シート、パイプ、容器などの部材に、ガスバリア性、水蒸気バリア性、及び電気絶縁性のいずれかを付与する方法。
The present invention for solving the above-described problems comprises the following technical means.
(1) Adhesive comprising clay as a main component, having flexibility, usable as a self-supporting film, and having a single-layer or multi-layer structure in which an adhesive layer exists on a clay film having gas barrier properties Clay film.
(2) The adhesive clay film according to (1), wherein the adhesive layer is present on one side or both sides of the clay film.
(3) The adhesive clay film according to (1), wherein the clay film 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 adhesive clay film according to (1), wherein the main component of the clay film 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. Adhesive clay 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 Group consisting of resin, polyamide resin, polyester resin, polyimide resin, polyvinyl resin, polyethylene glycol, polyacrylamide, polyethylene oxide, protein, deoxyribonucleic acid, ribonucleic acid and polyamino acid, phenols, benzoic acid compounds, and silicon resin The adhesive clay film according to (1), wherein the adhesive clay film is one or more selected from among the above.
(7) The adhesive clay film according to (3), wherein the reinforcing material is one or more members selected from the group consisting of mineral fibers, glass wool, ceramic fibers, plant fibers, and organic polymer fibers.
(8) The adhesive clay film according to (1), wherein the adhesive layer is composed of an adhesive or an adhesive and a base layer.
(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 chemistry is performed between the components of the clay, the additive, and the adhesive layer or between the components. The adhesive clay film according to any one of (1) to (8), wherein bonding is caused to improve water resistance, gas barrier property, and / or mechanical strength.
(10) The adhesive clay according to (1), wherein a permeability coefficient for 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. film.
(11) The adhesive clay 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.
(12) The adhesive clay film according to (1), wherein the clay film is thinner than 1 mm and the area of the adhesive clay film is larger than 1 cm 2 .
(13) The adhesive clay film according to (1), wherein the weight ratio of the additive to the total solid of the clay film is 30% or less.
(14) The adhesive clay film according to (1), wherein the weight ratio of the reinforcing material to the total solid of the clay film is 30% or less.
(15) The adhesive clay film according to (1), wherein the clay film is subjected to surface treatment to be water repellent, waterproof, reinforced, and / or surface flattened.
(16) 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 adhesion clay film | membrane as described in said (15) which is forming a carbon vapor deposition film | membrane on the surface.
(17) The adhesive clay film according to (1), wherein a direct current electric resistance in a direction perpendicular to the film is 1 megaΩ or more.
(18) A member having a gas barrier property, a water vapor barrier property, and / or an electrical insulating property, comprising the adhesive clay film according to any one of (1) to (17).
(19) By adhering the adhesive clay film according to any one of (1) to (17) to a member such as a film, a sheet, a pipe, or a container, a gas barrier property, a water vapor barrier property, and an electrical insulating property A member having any one of them.
(20) By sticking the adhesive clay film according to any one of (1) to (17) above, a gas barrier property, a water vapor barrier property, and an electrical insulating property are applied to members such as a film, a sheet, a pipe, and a container. How to grant one.
次に本発明について、更に詳細に説明する。
本発明は、粘土膜に接着層が存在する粘着粘土膜であり、粘土を主成分とし、柔軟性を有し、自立膜として利用可能であり、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に接着層が存在することを特徴とするものであり、本粘土層の室温における、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未満であることを特徴とするものである。
Next, the present invention will be described in more detail.
The present invention is an adhesive clay film in which an adhesive layer is present in the clay film, which is mainly composed of clay, has flexibility, can be used as a self-supporting film, has no cracks or pinholes, and has a gas barrier property. The clay layer has an adhesive layer, and the permeability coefficient of the clay layer with respect to air, oxygen gas, nitrogen gas, hydrogen gas, or helium gas at room temperature is 1 × 10 −12 cm. It is less than 2 s −1 cmHg −1 .
本発明の粘着粘土膜は、接着層が、粘土膜の片面あるいは両面に存在する。本発明の粘着粘土膜の粘土層は、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。前記粘土層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 adhesive clay film of the present invention has an adhesive layer on one side or both sides of the clay film. The clay layer of the adhesive clay 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 main components of the clay layer 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、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。また、前記接着層としては、接着剤、あるいは接着剤とベース層から構成されるものが例示される。本発明では、例えば、加熱、光照射等の任意の方法、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粘着粘土膜も対象とされる。 Examples of the reinforcing material include one or more of mineral fibers, glass wool, ceramic fibers, plant fibers, and organic polymer fibers. Examples of the adhesive layer include an adhesive, or an adhesive layer composed of an adhesive and a base layer. In the present invention, for example, chemical reaction such as addition reaction, condensation reaction, polymerization reaction, etc. is carried out by any method or means such as heating, light irradiation, etc. In the above, an adhesive clay 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、ヘリウムガスに対する透過係数は、１×１０−１２ｃｍ２ｓ−１ｃｍＨｇ−１未満である粘着粘土膜を提供できる。また、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よりも大きい粘着粘土膜を提供できる。 In the present invention, for example, an adhesive clay 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, and helium gas at room temperature can be provided. In the present invention, for example, it has an arbitrary two-dimensional planar shape represented by a circle, a square, a rectangle, etc., or an arbitrary three-dimensional planar shape that is a flat plate, tube, cylinder, cone, sphere, or a combination thereof, It can be used as a self-supporting film, and can provide an adhesive clay film having a thickness smaller than 1 mm and an area larger than 1 cm 2 .
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、表面処理を行うことが可能であり、表面処理により、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り、前記補強材の、全固体に対する重量割合も、好適には、３０パーセント以下である。 In the present invention, for example, surface treatment can be performed for the purpose of water repellency, waterproofing, reinforcement, and surface flattening. By the surface treatment, a fluorine-based film, a silicon-based film, a polysiloxane film, a fluorine-containing organopolysiloxane can be used. A siloxane 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 a carbon vapor deposition film can be formed on the surface. The weight ratio of the additive to the total solid is preferably 30% or less, and the weight ratio of the reinforcing material to the total solid is also preferably 30% or less.
本粘着粘土膜は、自立膜、柔軟、加工容易、機能化容易であり、粘土層の厚さは、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。本粘着粘土膜は、ＪＩＳ Ｋ７１２７による引っ張り強度は、１０ＭＰａ以上という特徴を有する。本粘着粘土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）、引っ張り強さは１０ＭＰａ以上である。本粘着粘土膜では、特に、主要成分の粘土の割合を高め、耐熱性が高い材料を接着層として選ぶことで高い耐熱性が得られる。 This adhesive clay film is a self-supporting film, flexible, easy to process, and easy to functionalize. The thickness of the clay layer is, for example, 3 to 100 μm, the orientation is micrometer, and the nano-order is highly oriented. Have. This adhesive clay film is characterized by a tensile strength according to JIS K7127 of 10 MPa or more. Regarding the basic performance of the present adhesive clay film, the gas barrier property is less than the measurement limit value (corresponding to aluminum foil) with helium, and the tensile strength is 10 MPa or more. In the present adhesive clay film, in particular, high heat resistance can be obtained by increasing the ratio of clay as a main component and selecting a material having high heat resistance as an adhesive layer.
本発明の粘着粘土膜を構成する粘土層は、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。この粘着粘土膜は、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。得られた粘着粘土膜は、粘土層の膜厚が３〜１００μｍであり、ガスバリア性能は、粘土層の厚さ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、膜に対して、垂直方向の直流電気抵抗は１メガΩ以上である。 The clay layer constituting the adhesive clay film of the present invention uses clay as a main raw material (90% by weight or more), and preferably has a basic structure of, for example, a layer thickness of about 1 nm, a particle diameter of about 1 μm, and an aspect ratio of about 300. For example, a natural or synthetic swellable clay having a degree 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 10% by weight or less. This adhesive clay film is produced, for example, by densely laminating layered crystals having a thickness of about 1 nm, oriented in the same direction. The resultant pressure-sensitive clay film is a film thickness of the clay layer is 3 to 100 m, the gas barrier performance, the oxygen permeability at a thickness 30μm of the clay layer 0.00001cc / m 2 / 24hr / atm under a hydrogen permeability 0 .002cc / m 2 / 24hr / less than atm, the area is capable of large area over 100 × 40 cm, with respect to the film, a DC electrical resistivity in the vertical direction is 1 or more mega Omega.
本発明は、容易に、自身、あるいは他材料との接着・多層化ができる粘着粘土膜を提供するものであり、また、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、電気絶縁性、柔軟性、を併せ持つ多層化粘土膜を提供するものである。また、本発明は、本粘着粘土膜を貼り付けることにより、ガスバリア性、水蒸気バリア性、電気絶縁性のいずれかを付与したフィルム、シート、パイプ、容器などの部材を提供するものである。また、本発明は、本粘着粘土膜を貼り付けることにより、フィルム、シート、パイプ、容器にガスバリア性、水蒸気バリア性、電気絶縁性のいずれかを付与する方法を提供するものである。 The present invention provides an adhesive clay film that can be easily bonded or multilayered with itself or with other materials, and has mechanical strength and toughness that can be used as a self-supporting film. The present invention provides a multilayered clay film having gas barrier properties, electrical insulation properties, and flexibility. Moreover, this invention provides members, such as a film, a sheet | seat, a pipe, a container, etc. which gave any of gas barrier property, water vapor | steam barrier property, and electrical insulation by sticking this adhesion clay film | membrane. The present invention also provides a method for imparting any of gas barrier properties, water vapor barrier properties, and electrical insulation properties to films, sheets, pipes, and containers by attaching the present adhesive clay film.
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可能性がある。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可能性がある。 In the present invention, as clay, natural or synthetic material, preferably, natural smectite and synthetic smectite, or a mixture thereof is added to water or a liquid containing water as a main component, and diluted and uniform. A simple dispersion is prepared. 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, drying may take too long. In addition, when the concentration of the clay dispersion is too high, clay does not disperse well, so the orientation of the clay particles is poor and it may be 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、粘着粘土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粘着粘土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、粘着粘土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 can be mixed with clay to improve the flexibility or mechanical strength of the adhesive clay film. For example, 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, poly One or more of acrylic amide, 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 the clay becomes uneven in the prepared film, resulting in the resulting adhesive The uniformity of the clay film is reduced, and the effect of addition is also diminished. Moreover, when the ratio of an additive is too high, the heat resistance of an adhesive clay 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.
粘土層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を水平に置き、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、乾燥して粘土層を得る。また、別の例として、固液比の比較的高いゲル状分散液を支持体となる物体に塗布し、加熱蒸発法を用いる場合、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金属板などの物体の上に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、乾燥して粘土層を得る。 As a method for producing the clay layer, for example, a liquid that is a dispersion 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, a flat tray, preferably a plastic or metal tray is placed horizontally, and the clay concentration is 0.5 to 3 weight percent. In a forced air oven, the dispersion was poured into a pre-degassed dispersion and maintained in a horizontal position, and the temperature was 30 to 70 ° C., preferably 30 to 50 ° C. The clay layer is obtained by drying for about half a day, preferably 3 to 5 hours. As another example, when a gel-like dispersion having a relatively high solid-liquid ratio is applied to an object serving as a support and the heating evaporation method is used, the clay concentration is adjusted to 4 to 7 weight percent, The degassed dispersion is applied to a thickness of 2 mm on an object such as a metal plate, and is subjected to a temperature condition of 30 to 100 ° C., preferably 30 to 80 ° C. in a forced air oven. Dry for about 10 minutes to 2 hours, preferably 20 minutes to 1 hour to obtain a clay layer.
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、粘土層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、任意の厚さに調製することができる。 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 clay layer is lowered. The thickness of the clay layer can be adjusted to an arbitrary thickness by adjusting the amount of solid used in the dispersion.
次に、粘土層を容器あるいは物体表面から剥離する。粘土層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。 Next, the clay layer is peeled off from the container or the object surface. When the clay layer does not naturally peel from a support such as a container, the peeling is preferably promoted by evacuation. Further, as another method of peeling, it is preferably dried at a temperature 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 promoted by a higher 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層は、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、粘土層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、粘土層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。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、粘着層を形成させない側の表面に行う。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。 The clay layer obtained as described above is basically hydrophilic, and therefore has poor water resistance compared to 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 layer, 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 layer is hydrophobized. For example, there is a coating layer preparation method. 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 is performed on the surface on the side where the adhesive layer is not formed. 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.
次に、粘土層の少なくとも片面に接着層を形成させる。接着層形成前に、必要に応じて粘土層の清浄化を行う。また、必要に応じて粘土層と接着層の間にプライマーを塗布する。プライマーの塗布目的としては、粘土層と接着層の親和性改良、被着体表面の補強、接着界面の保護などがあり、プライマーとしては、例えば、エチレン−酢酸ビニル樹脂系接着剤などがあげられる。粘土層は、高いガスバリア性を有し、接着剤の乾燥を遅くすることから、無用剤タイプの接着剤を用いることが推奨される。粘土層への接着層の形成法としては、塗布、噴霧、ディップコーティング、などがある。接着剤としては、天然物接着剤、無機接着剤、熱可塑性接着剤、熱硬化性接着剤、ゴム系接着剤、シアノアクリレート系接着剤、耐熱性接着剤などがある。また、接着層がフィルム状になっており、熱プレスで粘土層へコートする方法もある。更に、これらの接着層を基材両面に塗布した、両面粘着シートを用いることも可能である。両面粘着シートの片側の離型シートを剥がして粘土層に接着することで、粘土層の片側に接着面を形成することができる。 Next, an adhesive layer is formed on at least one side of the clay layer. Before forming the adhesive layer, the clay layer is cleaned as necessary. Moreover, a primer is apply | coated between a clay layer and an adhesive layer as needed. The purpose of applying the primer is to improve the affinity between the clay layer and the adhesive layer, to reinforce the adherend surface, and to protect the adhesive interface. Examples of the primer include an ethylene-vinyl acetate resin adhesive. . Since the clay layer has a high gas barrier property and slows the drying of the adhesive, it is recommended to use a useless type adhesive. Examples of the method for forming the adhesive layer on the clay layer include coating, spraying, and dip coating. Examples of the adhesive include natural product adhesives, inorganic adhesives, thermoplastic adhesives, thermosetting adhesives, rubber adhesives, cyanoacrylate adhesives, and heat resistant adhesives. There is also a method in which the adhesive layer is in the form of a film and the clay layer is coated by hot pressing. Furthermore, it is also possible to use a double-sided pressure-sensitive adhesive sheet in which these adhesive layers are applied to both sides of the substrate. An adhesive surface can be formed on one side of the clay layer by peeling off the release sheet on one side of the double-sided PSA sheet and bonding it to the clay layer.
また、基材を有する両面粘着シートを用いた場合、基材が粘土層を補強する役割を果たすという効果をもたらす。このとき、基材は、有機ポリマーフィルムであったり、不織布であったりする。粘着粘土膜の耐熱性を高めるためには、接着層の耐熱性を高める必要がある。そのためには、アクリル製材料をベースにするなどで耐熱性を確保することができる。また、熱硬化性接着層を熱ラミネーションで仮着後、オーブンキュアで本硬化させるタイプの接着層をコートする方法を採用することで耐熱性を確保することができる。 Moreover, when the double-sided adhesive sheet which has a base material is used, it brings about the effect that a base material plays the role which reinforces a clay layer. At this time, the substrate may be an organic polymer film or a non-woven fabric. In order to increase the heat resistance of the adhesive clay film, it is necessary to increase the heat resistance of the adhesive layer. For this purpose, heat resistance can be ensured by using an acrylic material as a base. Moreover, heat resistance can be ensured by adopting a method in which a thermosetting adhesive layer is temporarily attached by thermal lamination and then an adhesive layer of a type that is cured by oven curing is applied.
本発明の粘着粘土膜は、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。本発明の粘着粘土膜は、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、本発明の粘着粘土膜は、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、ガスバリア性が高く、電気絶縁体であり、容易に、均一に、かつ確実に粘土膜同士あるいは他材料との複合部材を形成可能、といった特徴を有する。 The adhesive clay 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, for example, scissors and a cutter. The adhesive clay film of the present invention preferably has a thickness of less than 1 mm and an area of greater than 1 cm 2 . The adhesive clay film of the present invention has mechanical strength that can be used as a self-supporting film, is highly flexible, has a high gas barrier property, is an electrical insulator, and is easily, uniformly and reliably clay film. It has a feature that a composite member of each other or other materials can be formed.
耐熱性の高い粘着粘土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。本発明の粘着粘土膜の粘土層は、粘土が主成分であることから、電気絶縁性に優れ、絶縁膜として広範に使用することができる。また、本発明の粘着粘土膜は、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 an adhesive clay film with high heat resistance, it is important to reduce the amount of 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 particularly the case when heat resistance is not required. Since the clay layer of the adhesive clay film of the present invention is mainly composed of clay, it is excellent in electrical insulation and can be used widely as an insulating film. Moreover, the adhesive clay film of the present invention is excellent in heat insulating properties and can be widely used as a heat insulating film.
粘土層は、容易に層厚を厚くすることが困難である。それは、粘土層のガスバリア性が高いために、層が厚い場合、溶媒を乾燥除去することが難しくなるためである。本粘着粘土膜を重ねて貼り付けることにより、厚い粘土膜を容易に、均一に、かつ確実に作製することができる。これにより、厚みを必要とするパッキン、高い電気絶縁性を必要とする電気絶縁膜、高いガスバリア性を必要とするガスバリア膜が容易に提供できる。 It is difficult to increase the thickness of the clay layer easily. This is because, since the gas barrier property of the clay layer is high, when the layer is thick, it is difficult to dry and remove the solvent. By laminating and sticking this adhesive clay film, a thick clay film can be easily, uniformly and reliably produced. Thereby, it is possible to easily provide a packing that requires thickness, an electrical insulating film that requires high electrical insulation, and a gas barrier film that requires high gas barrier properties.
次に、本発明の材料（基材）の特性値について説明する。
（１）密度
従来材料は、下表に示されるようにプラスチック・フィラーナノコンポジット製品において、その密度が最も高いものでも１．５１である。これに対して、本発明の材料は、１．５１を上回る密度を有し、２．０以上、例えば、２．１０程度の密度の測定値を示す。このように、本発明の材料は、１．５１を上回る密度、特に、１．６０から２．５０程度の高密度を有する。
Next, the characteristic value of the material (base material) of this invention is demonstrated.
(1) Density As shown in the table below, the conventional material has a highest density of 1.51 in the plastic-filler nanocomposite product. On the other hand, the material of the present invention has a density exceeding 1.51 and exhibits a measured value of density of 2.0 or more, for example, about 2.10. Thus, the material of the present invention has a density greater than 1.51, in particular a high density on the order of 1.60 to 2.50.
（２）柔軟性
従来材料で最も柔らかいものは、粘土とパルプ繊維からできている市販のシートであり、その剛軟度は、曲げ反発性試験の値として、ＪＩＳ Ｌ１０９６：１９９９「一般織物試験方法」Ａ法に準拠して測定された値は、８．０（ｍＮ）である。一方、粘土膜で最も硬いものは、ＨＲ５０／５−８０Ｈであり、表面が５．３（ｍＮ）、裏面が１７．１（ｍＮ）である。これに対して、本発明の材料は、曲げ反発性試験の値が２．０ｍＮ程度であり、少なくとも、８．０ｍＮを下回る値を有するものである。従来材料と本発明の材料の剛軟度の閾値は８．０ｍＮであると言えることから、この値をもって、本発明の材料を従来材料と区別（識別）することができる。
(2) Flexibility The softest material in the past is a commercially available sheet made of clay and pulp fiber, and its bending resistance is JIS L1096: 1999 “General Textile Test Method” as the value of the bending resilience test. The value measured according to method A is 8.0 (mN). On the other hand, the hardest clay film is HR50 / 5-80H, the front surface is 5.3 (mN), and the back surface is 17.1 (mN). On the other hand, the material of the present invention has a bending rebound test value of about 2.0 mN and at least a value lower than 8.0 mN. Since it can be said that the bending resistance threshold of the conventional material and the material of the present invention is 8.0 mN, the material of the present invention can be distinguished (identified) from the conventional material by this value.
（３）原料粘土の特性
本発明では、原料粘土として、好適には、例えば、１次粒子のアスペクト比（粒子数基準）が３２０程度のもので、特に、メチレンブルー吸着量、陽イオン交換容量が高いものが使用される。具体例として、例えば、メチレンブルー吸着量が１３０ｍｍｏｌ／１００ｇ、陽イオン交換容量が１１０ｍｅｑ／１００ｇ、２％水分散液ｐＨが１０．２、４％水分散液粘度が３５０ｍＰａ・ｓ、水分散メジアン径が１．１３μｍの諸物性を有するものが例示される。しかし、これらに制限されるものではなく、これらを標準値として、これらと同等もしくは均等の物性を有するものであれば同様に使用することができる。これらの原料粘土として、山形県月布産粘土及びこれを主原料とする材料が好適に用いられる。
(3) Properties of raw clay In the present invention, the raw clay preferably has, for example, an aspect ratio (based on the number of particles) of primary particles of about 320, and particularly has a methylene blue adsorption amount and a cation exchange capacity. Higher ones are used. As a specific example, for example, methylene blue adsorption amount is 130 mmol / 100 g, cation exchange capacity is 110 meq / 100 g, 2% aqueous dispersion pH is 10.2, 4% aqueous dispersion viscosity is 350 mPa · s, and aqueous dispersion median diameter is Those having various physical properties of 1.13 μm are exemplified. However, it is not limited to these, and these can be used in the same manner as long as they have the same or equivalent physical properties as standard values. As these raw clays, clay from Tsukiyama, Yamagata Prefecture and materials using this as the main raw material are preferably used.
（４）その他の特性
本発明の材料は、熱サイクルテスト（１００−６００℃、３０サイクル）で異状がなく（高耐熱性）、電気抵抗は、体積抵抗率（５００Ｖ）が２．３×１０７Ωｍ（ＪＩＳ Ｋ６９１１：１９９５）であり（高絶縁性）、例えば、フレキシブル基板材料として使用される。本発明の材料は、他の特性として、例えば、以下のような特性値を有する。酸素透過度：＜０．００００８ｃｍ３／２０μｍ・ｍ２ ｄａｙ・ａｔｍ、水素透過度：０．００２ｃｍ３／２０μｍ・ｍ２ ｄａｙ・ａｔｍ、破断延び：２．２％、引裂試験（ＪＩＳＫ６２５２：２００１）：３３．４Ｎ／ｍｍ、酸素指数（ＪＩＳ Ｋ７２０１：１９９５）：＞９４．０、比熱：１．１９Ｊ／ｇ・Ｋ、熱拡散率：１．１２×１０−７ｍ２／ｓ、熱伝導率：０．２７Ｗ／ｍ・Ｋ、熱膨張係数（−１００〜１００℃）：０．１×１０−４Ｋ−１、熱膨張係数（１００〜２００℃）：−０．０６×１０−４Ｋ−１、耐ガス腐食試験：異状なし。これらの値は、本発明の材料の好適な特性値を示すものであり、本発明は、これらに制限されるものではなく、これらを標準値として、これらと同等もしくは均等のものであれば、本発明の範囲に含まれる。
(4) Other characteristics The material of the present invention has no abnormality in the thermal cycle test (100-600 ° C., 30 cycles) (high heat resistance), and the electrical resistance has a volume resistivity (500 V) of 2.3 × 10. 7 Ωm (JIS K6911: 1995) (high insulation), for example, used as a flexible substrate material. The material of the present invention has, for example, the following characteristic values as other characteristics. Oxygen permeability: <0.00008cm 3 / 20μm · m 2 day · atm, hydrogen permeability: 0.002cm 3 / 20μm · m 2 day · atm, fracture extends: 2.2%, tear test (JISK6252: 2001) : 33.4 N / mm, oxygen index (JIS K7201: 1995):> 94.0, specific heat: 1.19 J / g · K, thermal diffusivity: 1.12 × 10 −7 m 2 / s, thermal conductivity : 0.27 W / m · K, thermal expansion coefficient (−100 to 100 ° C.): 0.1 × 10 −4 K −1 , thermal expansion coefficient (100 to 200 ° C.): −0.06 × 10 −4 K -1 , Gas corrosion resistance test: No abnormality. These values show suitable characteristic values of the material of the present invention, and the present invention is not limited to these values. If these are standard values, these are equivalent or equivalent, It is included in the scope of the present invention.
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粘着粘土膜の新技術・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 adhesive clay film having mechanical strength and toughness that can be used as a self-supporting film, and also having excellent flexibility, thermal stability, excellent gas barrier properties, and excellent water vapor barrier properties. Technology and new materials can be provided. (2) New technology and new 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. Is 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）粘着粘土膜の製造
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、長さ約３０ｃｍ、幅２０ｃｍの真鍮製板の上に、厚さ約２ミリメートル塗布し、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、剥離し、厚さ約０．０４ミリメートルの粘土層を得た。次に、両面粘着シート（日東電工株式会社製）の片方の粘着面を上記粘土層に接着し、粘着粘土膜を作製した。上記粘着シートの厚みは０．１５ミリメートル、接着剤は無溶剤型アクリル系粘土膜であり、ベース層は不織布である。
(1) Manufacture of adhesive clay film As a clay, 2 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Industries Co., Ltd.) is added to 60 cm 3 of distilled water, and a Teflon (registered trademark) rotor is placed in a plastic sealed container. And shaken vigorously to obtain a uniform dispersion. This dispersion was applied on a brass plate having a length of about 30 cm and a width of 20 cm, and about 2 millimeters in thickness. The dispersion was allowed to stand horizontally, and was subjected to a temperature of 60 ° C. in a forced air oven at 30 ° C. It was partially dried and peeled to obtain a clay layer having a thickness of about 0.04 mm. Next, one adhesive surface of a double-sided pressure-sensitive adhesive sheet (manufactured by Nitto Denko Corporation) was adhered to the clay layer to produce an adhesive clay film. The pressure-sensitive adhesive sheet has a thickness of 0.15 mm, the adhesive is a solventless acrylic clay film, and the base layer is a nonwoven fabric.
（２）多層粘土膜の製造
上記（１）で作製した粘着粘土膜の粘着面に、厚さ約０．０４ミリメートルの粘土層を貼り付けることによって、多層粘土膜を作製した。本多層粘土膜の全体の厚みは、約０．２３ミリメートルであった。
(2) Manufacture of multilayer clay film A multilayer clay film was prepared by sticking a clay layer having a thickness of about 0.04 mm to the adhesive surface of the adhesive clay film prepared in (1) above. The overall thickness of the multilayer clay film was about 0.23 millimeters.
（３）多層粘土膜の特性
本多層粘土膜の室温における、ヘリウムガスに対する透過係数は、１×１０−１２ｃｍ２ ｓ−１ｃｍＨｇ−１未満であった。走査型電子顕微鏡写真（図１）より、両面粘着シートと粘土層は、均一に、かつ強固に接着して、密に製膜されている様子が分かる。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。
(3) Properties of the multilayer clay film The permeability coefficient of the multilayer clay film with respect to helium gas at room temperature was less than 1 × 10 −12 cm 2 s −1 cmHg −1 . From the scanning electron micrograph (FIG. 1), it can be seen that the double-sided PSA sheet and the clay layer are uniformly and firmly bonded to form a dense film. 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）粘着粘土膜の製造
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、長さ約３０ｃｍ、幅２０ｃｍの真鍮製板の上に、厚さ約２ミリメートル塗布し、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、剥離し、厚さ約０．０４ミリメートルの粘土層を得た。次に、両面粘着シート（日東電工株式会社製）の片方の粘着面を粘土層に接着し、粘着粘土膜を作製した。上記粘着シートの厚みは０．１５ミリメートル、接着剤は無溶剤型アクリル系粘土膜であり、ベース層は不織布である。
(1) Manufacture of adhesive clay film As a clay, 2 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Industries Co., Ltd.) is added to 60 cm 3 of distilled water, and a Teflon (registered trademark) rotor is placed in a plastic sealed container. And shaken vigorously to obtain a uniform dispersion. This dispersion was applied on a brass plate having a length of about 30 cm and a width of 20 cm, and about 2 millimeters in thickness. The dispersion was allowed to stand horizontally, and was subjected to a temperature of 60 ° C. in a forced air oven at 30 ° C. It was partially dried and peeled to obtain a clay layer having a thickness of about 0.04 mm. Next, one adhesive surface of a double-sided pressure-sensitive adhesive sheet (manufactured by Nitto Denko Corporation) was adhered to the clay layer to prepare an adhesive clay film. The pressure-sensitive adhesive sheet has a thickness of 0.15 mm, the adhesive is a solventless acrylic clay film, and the base layer is a nonwoven fabric.
（２）多層粘土膜の製造
上記（１）で作製した粘着粘土膜の粘着面に、厚さ約０．０４ミリメートルのポリエチレンフィルムを貼り付けることによって、多層膜を作製した。本多層膜の全体の厚みは、約０．２３ミリメートルであった。
(2) Production of Multilayer Clay Film A multilayer film was produced by attaching a polyethylene film having a thickness of about 0.04 mm to the adhesive surface of the adhesive clay film produced in (1) above. The overall thickness of the multilayer film was about 0.23 millimeters.
（３）多層膜の特性
本多層膜の室温における、ヘリウムガスに対する透過係数は、３．７×１０−１２ｃｍ２ ｓ−１ｃｍＨｇ−１以下であった。この値は、厚さ約０．０４ミリメートルのポリエチレンフィルムのみの値６．６×１０−１０ｃｍ２ｓ−１ｃｍＨｇ−１に対して、非常に小さく、粘土層によるガスバリア性の付与が確認された。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。
(3) Characteristics of Multilayer Film The permeability coefficient of this multilayer film with respect to helium gas at room temperature was 3.7 × 10 −12 cm 2 s −1 cmHg −1 or less. This value is very small with respect to the value of 6.6 × 10 −10 cm 2 s −1 cmHg −1 only for the polyethylene film having a thickness of about 0.04 mm, and it was confirmed that the gas barrier property was imparted by the clay layer. It was. 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、粘着粘土膜に係るものであり、自立膜として利用可能な機械的強度を有し、高いガスバリア性を有し、優れたフレキシビリティーを有し、それ自身を重ね合わせて、厚膜化することが容易、均一、かつ確実にでき、他材料表面との接着が容易、均一、かつ確実にできる新しい粘着粘土膜を提供することができる。本発明は、ガスバリア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 an adhesive clay film, has mechanical strength that can be used as a self-supporting film, has high gas barrier properties, and has excellent flexibility. It is possible to provide a new adhesive clay film that can be easily and uniformly and reliably thickened by superimposing itself, and can be easily, uniformly and reliably adhered to the surface of other materials. The present invention makes it possible to provide a film having excellent gas barrier properties. 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.
Claims (20)
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| JP2005046325A JP4836166B2 (en) | 2004-12-10 | 2005-02-22 | Adhesive clay film and method of using the same |
| EP05814763.8A EP1832553B1 (en) | 2004-12-10 | 2005-12-11 | Clay film product |
| 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 |
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Cited By (10)
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| JP2008035679A (en) * | 2006-07-31 | 2008-02-14 | Furukawa Electric Co Ltd:The | Normal temperature shrunk tube unit and cable connection structure |
| JP2008104331A (en) * | 2006-10-20 | 2008-05-01 | Furukawa Electric Co Ltd:The | Cold shrink tube unit, and cable connection structure |
| JP2008137161A (en) * | 2006-11-30 | 2008-06-19 | National Institute Of Advanced Industrial & Technology | Laminated clay film and its manufacturing method |
| WO2008096610A1 (en) * | 2007-02-07 | 2008-08-14 | Nitto Denko Corporation | Adhesive tape |
| WO2008108157A1 (en) * | 2007-03-06 | 2008-09-12 | Nitto Denko Corporation | Pressure-sensitive adhesive tape |
| WO2009060747A1 (en) * | 2007-11-10 | 2009-05-14 | Kyushu Institute Of Technology | Carbon fiber reinforced prepreg having gas barrier properties and carbon fiber reinforced plastic, and processes for producing them |
| JP2009136832A (en) * | 2007-12-10 | 2009-06-25 | National Institute Of Advanced Industrial & Technology | Natural mineral membrane |
| JP2010169185A (en) * | 2009-01-22 | 2010-08-05 | Kawasaki Heavy Ind Ltd | Vacuum heat insulation pipe for low-temperature liquefied gas |
| JP2011057912A (en) * | 2009-09-14 | 2011-03-24 | Toppan Printing Co Ltd | Composition for forming gas barrier layer, method for producing the same, and gas barrier film |
| US7935738B2 (en) | 2007-12-05 | 2011-05-03 | Industrial Technology Research Institute | Transparent flexible film and fabrication method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008035679A (en) * | 2006-07-31 | 2008-02-14 | Furukawa Electric Co Ltd:The | Normal temperature shrunk tube unit and cable connection structure |
| JP2008104331A (en) * | 2006-10-20 | 2008-05-01 | Furukawa Electric Co Ltd:The | Cold shrink tube unit, and cable connection structure |
| JP2008137161A (en) * | 2006-11-30 | 2008-06-19 | National Institute Of Advanced Industrial & Technology | Laminated clay film and its manufacturing method |
| WO2008096610A1 (en) * | 2007-02-07 | 2008-08-14 | Nitto Denko Corporation | Adhesive tape |
| WO2008108157A1 (en) * | 2007-03-06 | 2008-09-12 | Nitto Denko Corporation | Pressure-sensitive adhesive tape |
| WO2009060747A1 (en) * | 2007-11-10 | 2009-05-14 | Kyushu Institute Of Technology | Carbon fiber reinforced prepreg having gas barrier properties and carbon fiber reinforced plastic, and processes for producing them |
| US7981500B2 (en) | 2007-11-10 | 2011-07-19 | Kyushu Institute Of Technology | Carbon fiber reinforced prepreg of gas barrier properties, carbon fiber reinforced plastic and methods of producing the same |
| US7935738B2 (en) | 2007-12-05 | 2011-05-03 | Industrial Technology Research Institute | Transparent flexible film and fabrication method thereof |
| JP2009136832A (en) * | 2007-12-10 | 2009-06-25 | National Institute Of Advanced Industrial & Technology | Natural mineral membrane |
| JP2010169185A (en) * | 2009-01-22 | 2010-08-05 | Kawasaki Heavy Ind Ltd | Vacuum heat insulation pipe for low-temperature liquefied gas |
| JP2011057912A (en) * | 2009-09-14 | 2011-03-24 | Toppan Printing Co Ltd | Composition for forming gas barrier layer, method for producing the same, and gas barrier film |
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