JP5652672B2 - Surface treated clay film - Google Patents
Surface treated clay film Download PDFInfo
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- JP5652672B2 JP5652672B2 JP2012252325A JP2012252325A JP5652672B2 JP 5652672 B2 JP5652672 B2 JP 5652672B2 JP 2012252325 A JP2012252325 A JP 2012252325A JP 2012252325 A JP2012252325 A JP 2012252325A JP 5652672 B2 JP5652672 B2 JP 5652672B2
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- clay
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- dispersion
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- 239000004927 clay Substances 0.000 title claims description 175
- 239000006185 dispersion Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000654 additive Substances 0.000 claims description 29
- 230000000996 additive effect Effects 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 20
- 239000012779 reinforcing material Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 230000035699 permeability Effects 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- -1 polysiloxane Polymers 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000002612 dispersion medium Substances 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 229920005749 polyurethane resin Polymers 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 239000005871 repellent Substances 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 229920001817 Agar Polymers 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 102000053602 DNA Human genes 0.000 claims description 3
- 108020004414 DNA Proteins 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 108010068370 Glutens Proteins 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000008272 agar Substances 0.000 claims description 3
- 235000010419 agar Nutrition 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 3
- 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 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 235000013312 flour Nutrition 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000011491 glass wool Substances 0.000 claims description 3
- 235000021312 gluten Nutrition 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229910000271 hectorite Inorganic materials 0.000 claims description 3
- 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 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000113 methacrylic resin Substances 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000002557 mineral fiber Substances 0.000 claims description 3
- 229910000273 nontronite Inorganic materials 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920006122 polyamide resin Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000009719 polyimide resin Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 235000018102 proteins Nutrition 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 229920002477 rna polymer Polymers 0.000 claims description 3
- 229910000275 saponite Inorganic materials 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 238000006116 polymerization reaction Methods 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
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 239000010408 film Substances 0.000 description 143
- 239000000463 material Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 20
- 239000010409 thin film Substances 0.000 description 15
- 239000011247 coating layer Substances 0.000 description 13
- 230000004888 barrier function Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000011810 insulating material Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
- 238000012856 packing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000002734 clay mineral Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000615 nonconductor Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910021647 smectite Inorganic materials 0.000 description 3
- 239000000243 solution Substances 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 230000005856 abnormality Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001875 compounds Chemical class 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
- 238000001914 filtration Methods 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
- 239000010410 layer Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012461 cellulose resin Substances 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
- 238000007796 conventional method Methods 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
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 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
- 238000010292 electrical insulation Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 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
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 239000011164 primary particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
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- 230000002940 repellent Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Description
本発明は、粘土膜及びその製造方法等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、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、耐水性に優れる、新規粘土膜、その製造方法及びその製品に関するものである。
本発明は、粘土薄膜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、柔軟性が高く、耐熱性が高く、電気絶縁体であり、熱伝導率が低く、膜内部に種々の化学物質を内包することが可能な、粘土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、自立膜として利用可能な機械的強度を有し、しかも、優れた柔軟性、熱安定性、多孔性を併せ持つ粘土膜及びその製造技術、及び電気絶縁性部材、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 clay film and a method for producing the same, and more specifically, has mechanical strength that can be used as a self-supporting film, is highly flexible, has high heat resistance, is an electrical insulator, and is insulated. The present invention relates to a novel clay film having excellent properties and water resistance, a production method thereof, and a product thereof.
The present invention has a mechanical strength that can be used as a self-supporting film in a conventional technique in the technical field of clay thin film production technology and products thereof, and has high flexibility, high heat resistance, and an electrical insulator. It is difficult to produce a clay film that has low thermal conductivity and can contain various chemical substances inside the film, and it can be used as a self-supporting film based on the strong demand for its development. Useful as a clay film that has mechanical strength and has excellent flexibility, thermal stability, and porosity, and its manufacturing technology, as well as new technologies and new materials such as electrical insulating materials and heat insulating materials. It is.
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。アルミホイルあるいはアルミ蒸着膜は、高いガスバリア性を有しているが、透明ではない。また、アルミホイルは、金属であるため、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、透明で、ガスバリア性に優れたシリカ蒸着膜もあるが、このシリカ蒸着膜は、ベースとなる材料は有機化合物フィルムであるため、やはり３５０℃を超える高温条件下で使用することができない。 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. An aluminum foil or an aluminum vapor deposition film has a high gas barrier property but is not transparent. Moreover, since aluminum foil is a metal, it cannot be used as a sealing material wound around the screw portion. In addition, there is a silica vapor deposition film that is transparent and excellent in gas barrier properties. However, since the base material of the silica vapor deposition film is an organic compound film, it cannot be used under high temperature conditions exceeding 350 ° C.
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 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 the 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、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１）、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２）、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３）、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 a clay thin film having strength as a self-supporting film cannot 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 (Patent Document 1) comprising forming an aqueous dispersion of a hydrotalcite-based intercalation compound into a film and drying, and performing a heat treatment for promoting the reaction between the layered clay mineral and phosphoric acid or a phosphate group 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 2), an aqueous composition for film treatment containing a complex compound of a smectite clay mineral and a divalent or higher metal (Patent Document 2) There are many cases including literature 3). 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.
一般的に、粘土、特に可塑性に優れた粘土は水によく分散し、均一な膜を作りやすい。また、このような粘土は親水性化学物質との親和性に優れ複合体を作り安い。このような利点を有する粘土は、一方で、耐水性に劣り、浸水すると、膨潤し、脆弱になり、ついにはその形態を保てなくなる。 In general, clay, particularly clay having excellent plasticity, is well dispersed in water and can easily form a uniform film. In addition, such clays have excellent affinity with hydrophilic chemicals and are cheap to make composites. On the other hand, a clay having such advantages is inferior in water resistance, and when immersed, it swells and becomes brittle, and finally cannot maintain its form.
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、優れたフレキシビリティーを有し、高温度条件下で使用でき、耐水性に優れる新しい粘土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を含む均一な分散液を調製し、この分散液を容器に流し込む、あるいは支持体の表面に塗布した後、分散媒である液体を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、又は加熱蒸発法で分離し、粘土膜を得た後、これを必要に応じて容器あるいは支持体から剥離し、粘土自立膜を得られることを見出した。更に、この製造方法において、特に表面処理を行うことにより、粘土膜の撥水性、防水性、靭性、光透過性を向上させることが可能であることに注目し、更に研究を重ねて、好ましい原料の組成及び作製法を見出し、本発明を完成するに至った。 Under such circumstances, in view of the above prior art, the present inventors have mechanical strength that can be used as a self-supporting film, and have excellent flexibility under high temperature conditions. Uniform dispersion including clay or clay and a small amount of additive, or clay and a small amount of additive and a small amount of reinforcing material in the process of intensive research aimed at developing a new clay film that can be used and has excellent water resistance After preparing the liquid and pouring the dispersion into a container or coating it on the surface of the support, the liquid as the dispersion medium is subjected to various solid-liquid separation methods, such as centrifugation, filtration, vacuum drying, freeze vacuum drying, Or it isolate | separated with the heating evaporation method, and after obtaining the clay film | membrane, this was peeled from the container or the support body as needed, and it discovered that a clay self-supporting film | membrane could be obtained. Furthermore, in this manufacturing method, it is possible to improve the water repellency, waterproofness, toughness, and light transmittance of the clay film, particularly by performing surface treatment. As a result, the present inventors have found the composition and production method of the present invention and have completed the present invention.
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、優れた柔軟性、熱安定性を併せ持つ粘土膜及びその製造技術、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。 The present invention has a mechanical strength that can be used as a self-supporting film, and also has excellent flexibility, thermal stability, a manufacturing technique thereof, an electrical insulating material, a member that can be used as a heat insulating material, etc. The purpose is to provide new technologies and 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］粘土、又は添加物を含有する粘土、又は添加物及び補強材を含有する粘土から構成され、かつ粘土の含有量が９０重量％以上である自立膜であって、少なくとも一方の表面が樹脂膜により撥水処理及び／又は耐水処理されていることを特徴とする粘土膜。
［２］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［１］に記載の粘土膜。
［３］前記樹脂膜が、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、及びポリウレタン樹脂膜からなる群のうちのいずれかである［１］又は［２］に記載の粘土膜。
［４］前記粘土が、天然粘土又は合成粘土である［１］〜［３］のいずれかに記載の粘土膜。
［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［４］に記載の粘土膜。
［６］前記添加物が、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、及び安息香酸類化合物からなる群うちの一種以上である［１］〜［５］のいずれかに記載の粘土膜。
［７］前記補強材が、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、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［１］〜［６］のいずれかに記載の粘土膜。
［８］［１］〜［７］のいずれかに記載の粘土膜の製造方法であって、
粘土、又は添加物を含有する粘土、又は添加物及び補強材を含有する粘土の分散液を調製し、この分散液を容器に流し込むか又は支持体の表面に塗布した後、分散媒である液体を分離して粘土膜とし、これを必要に応じて容器あるいは支持体から剥離して、自立膜を得た後、更に、樹脂を用いて表面処理を行うことを特徴とする粘土膜の製造方法。
［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ることを特徴とする［８］に記載の粘土膜の製造方法。
The present invention for solving the above-described problems comprises the following technical means.
[1] Clay or clay containing additive, or additives, and is composed of clay containing a reinforcing material, and the content of clay is a self-supporting film is 90 wt% or more, least be of one A clay film characterized in that the surface is water-repellent and / or water-resistant treated with a resin film.
[2] The clay film 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 .
[3] The resin film is any one selected from the group consisting of 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, and a polyurethane resin film. The clay film according to [1] or [2].
[4] The clay is clay film according to any one of a natural clay or synthetic clay [1] to [3].
[5] The natural clay or synthetic clay is one or more members selected from the group consisting of mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, and nontronite. Clay film.
[6] The additive is ethylene glycol, glycerin, epsilon caprolactam, dextrin, starch, cellulosic resin, gelatin, agar, flour, gluten, alkyd resin, polyurethane resin, epoxy resin, fluororesin, acrylic resin, methacrylic resin, Of the group consisting of phenol resin, polyamide resin, polyester resin, polyimide resin, polyvinyl resin, polyethylene glycol, polyacrylamide, polyethylene oxide, protein, deoxyribonucleic acid, ribonucleic acid and polyamino acid, phenols, and benzoic acid compounds The clay film according to any one of [1] to [5], which is one or more.
[7] The reinforcing material according to any one of [1] to [6], wherein the reinforcing material is one or more members selected from the group consisting of mineral fiber, glass wool, carbon fiber, ceramic fiber, plant fiber, and organic polymer fiber. Clay film.
[8] A method for producing a clay film according to any one of [1] to [7],
After preparing a dispersion liquid of clay, or clay containing an additive, or clay containing an additive and a reinforcing material, the dispersion is poured into a container or applied to the surface of a support, and then a liquid which is a dispersion medium A clay film is produced by separating the film from a container or a support as necessary to obtain a self-supporting film, and then performing a surface treatment using a resin. .
[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 reinforcing material or between the components. The method for producing a clay film according to [8], wherein bonding is generated.
本発明により、（１）表面が撥水性、親水性であり、自立膜として利用可能な機械的強度を有し、しかも、優れた柔軟性、優れたガスバリア性、優れた水蒸気バリア性、優れた熱安定性を併せ持つ粘土膜及びその製造技術を提供できる、（２）電気絶縁性、断熱性を有する新技術・新素材を提供できる、（３）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) the surface is water-repellent and hydrophilic, has mechanical strength that can be used as a self-supporting film, and has excellent flexibility, excellent gas barrier properties, excellent water vapor barrier properties, Can provide clay film with thermal stability and its manufacturing technology, (2) Can provide new technology and new materials with electrical insulation and heat insulation properties, (3) Packing or solid electrolyte fuel with both heat resistance and flexibility The effect of providing new technologies and new materials such as battery diaphragms, electrical insulating materials, and members that can be used as heat insulating materials is achieved.
次に、本発明について、更に詳細に説明する。
本発明は、粘土のみ、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、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、ガスバリア性を有し、表面処理が行われていることを特徴とする粘土膜、であり、粘土膜の主要構成成分が、天然粘土又は合成粘土である請求項１に記載の粘土膜であること、表面処理が、撥水処理、防水処理、補強処理、及び表面平坦化処理のうちの一種以上であること、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未満であること、を特徴とするものである。また、本発明は、粘土膜の製造方法であって、粘土を主成分とする固体原料を、水あるいは水を主成分とする分散媒である液体に分散させ、均一な粘土分散液を調製し、この分散液を容器に流し込むあるいは物体表面に塗布したのち、分散媒である液体を除去し、粘土膜を作製し、更に、任意に、粘土膜を容器あるいは物体表面から剥離し、次に、粘土膜の表面処理をすることにより、粘土自立膜を得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 composed only of clay, clay and a small amount of reinforcing material, or clay and a small amount of additive and a small amount of reinforcing material, has flexibility, can be used as a self-supporting film, has heat resistance, The clay layer is a clay film characterized by being free from cracks and pinholes, having a gas barrier property, and being subjected to a surface treatment. The main component of the clay film is natural clay or synthetic clay. The clay film according to claim 1, wherein the surface treatment is at least one of water repellent treatment, waterproof treatment, reinforcement treatment, and surface flattening treatment, air, oxygen gas, nitrogen at room temperature The permeability coefficient for gas, hydrogen gas, or helium gas is less than 1 × 10 −12 cm 2 s −1 cmHg −1 . The present invention also relates to a method for producing a clay film, in which a solid raw material mainly composed of clay is dispersed in water or a liquid which is a dispersion medium mainly composed of water to prepare a uniform clay dispersion. Then, after pouring this dispersion into the container or applying it to the object surface, the liquid as the dispersion medium is removed to produce a clay film, and optionally, the clay film is peeled off from the container or object surface, A clay self-supporting film is obtained by surface treatment of the 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、均一な膜ができないという問題がある。 In the present invention, as clay, natural or synthetic material, preferably natural smectite, synthetic smectite, or a mixture thereof is used, and this is added to water or a liquid mainly composed of water, and diluted and uniformly dispersed. Prepare the solution. 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 a uniform film cannot be formed.
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、多価フェノール、安息香酸類化合物のうちの一種以上を用いることができる。 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 clay 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 acid, polyhydric phenol, and benzoic acid compound can be used.
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、粘土膜の耐熱性が低下する。 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, and the resulting clay 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 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一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、この分散液を容器に流し込む、あるいは物体表面に塗布したのち、分散媒である液体を乾燥除去し、粘土膜を作製する。粘土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を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、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、乾燥して粘土薄膜を得る。 Next, after pouring this dispersion into a container or applying it to the surface of an object, the liquid as a dispersion medium is removed by drying to produce a clay film. As a method for producing a clay film, for example, a liquid that is a dispersion is slowly evaporated to form a film, a dispersion is applied to a support surface, and a liquid that is a dispersion medium is dried and removed. There is. As a method for drying and removing the liquid as a dispersion medium, for example, various solid-liquid separation methods such as centrifugation, filtration, vacuum drying, freeze vacuum drying, heat evaporation, or a combination of these methods can be used. It is. Among these methods, for example, when the dispersion is poured into a vessel and the heating evaporation method is used, the clay concentration is adjusted to 0.5 to 3% by weight, and the dispersion deaerated in advance is preferably a flat tray, preferably Is poured onto a support such as a plastic or metal tray and kept in a horizontal state in a forced air oven at a temperature of 30 to 70 ° C., preferably 30 to 50 ° C. A clay thin film is obtained by drying for about half a day from time, preferably for 3 hours to 5 hours.
また、別の例として、分散液を物体に塗布し、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平坦な金属板の上に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、乾燥して粘土膜を得る。 As another example, when the dispersion is applied to an object and the heating evaporation method is used, the clay concentration is adjusted to 4 to 7 weight percent, and the dispersion deaerated in advance is placed on a flat metal plate. To a thickness of 2 mm, and for 10 to 2 hours, preferably from 20 minutes under a temperature condition of 30 ° C. to 100 ° C., preferably 30 ° C. to 80 ° C. in a forced air oven. Dry for 1 hour to obtain a clay film.
分散液を事前に脱気処理しない場合、粘土薄膜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、粘土膜の均一性が低下するという問題がある。本粘土膜の厚さは、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 thin film. 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 film is lowered. The thickness of the clay film can be obtained by adjusting the amount of solid used in the dispersion liquid.
粘土膜を自立膜として用いる場合は、粘土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。 When the clay film is used as a self-supporting film, the clay 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. Further, as another method of peeling, it is preferably dried under a temperature condition of about 110 ° C. 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.
本発明の表面処理粘土膜を構成する粘土膜自体は、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。得られた粘土膜は、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 clay film itself constituting the surface-treated clay film of the present invention uses clay as a main raw material (90% by weight or more), and preferably has, for example, a layer thickness of about 1 nm, a particle diameter of about 1 μm, and an aspect ratio. Examples include a structure in which about 300% by weight of natural or synthetic swellable clay of about 300 and 10% by weight or less of natural or synthetic low-molecular / high-molecular additives having a molecular size of several nm or less. . This clay film is produced, for example, by densely laminating layered crystals having a thickness of about 1 nm, oriented in the same direction. The resulting clay 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.
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方法が例示される。この場合、膜作製法として、湿式法、乾式法、蒸着法、噴霧法等の方法があげられる。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げられる。 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, The method of forming a carbon vapor deposition film etc. on the surface is illustrated. In this case, examples of the film production method include a wet method, a dry method, a vapor deposition method, and a spray 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. Other examples of the surface treatment method include 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、外見を美麗にするとともに、透明度を高める表面平坦化効果が期待できる。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。 In addition to the water repellency and waterproofness described above, this surface treatment provides a reinforcing effect that increases film strength, suppresses light scattering on the surface, gives gloss, makes the appearance beautiful, and makes the surface flatter to increase transparency. The effect 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. Therefore, the selection of the material used for the surface treatment and the film thickness are carefully selected depending on the application.
本発明の粘土自立膜は、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。本発明の粘土自立膜は、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、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 clay self-supporting 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 clay free-standing film of the present invention preferably has a thickness of less than 1 mm and an area of more than 1 cm 2 . The clay 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。本発明の粘土膜は、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 a clay 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 clay film of the present invention is mainly composed of clay, it is excellent in insulation and can be widely used as a heat-resistant insulation film. Moreover, the clay film of this invention is excellent in heat insulation, and can be widely used as a heat insulation film.
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. In contrast, the material of the present invention has a density greater than 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, especially 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 repulsion 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 the 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.
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.
［実施例１］
（１）粘土膜の製造
粘土として、０.９５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、２０ｃｍ3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０.０９グラム含む水溶液を加え、均一な分散液を得た。得られた分散液を、長さ約３０ｃｍ、幅約２０ｃｍの真鍮製板に塗布し、板の水平を保った状態で、強制送風式オーブン中で６０℃の温度条件下で１時間乾燥して、厚さ約６０マイクロメートルの均一な水溶性高分子複合粘土薄膜を得た。生成した粘土薄膜をトレイから剥離して粘土膜を得た。次に、粘土膜の撥水性及び水蒸気バリア性を高めるため、粘土膜両面にフッ素系ウレタン樹脂とシリコン樹脂のアセトン、イソプロピルアルコール溶液を噴霧し、室温で乾燥することにより、フッ素系ウレタン樹脂とシリコン樹脂の被覆層を形成した。被覆層の厚さは約１マイクロメートルであった。
[Example 1]
(1) Manufacture of clay film As clay, 0.95 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) is added to 20 cm 3 of distilled water. It was put together with the child and shaken vigorously to obtain a uniform dispersion. An aqueous solution containing 0.09 g of epsilon-caprolactam (manufactured by Wako Pure Chemical Industries, Ltd.) as an additive was added to this dispersion to obtain a uniform dispersion. The obtained dispersion was applied to a brass plate having a length of about 30 cm and a width of about 20 cm, and dried for 1 hour in a forced air oven at 60 ° C. with the plate kept horizontal. A uniform water-soluble polymer composite clay thin film having a thickness of about 60 micrometers was obtained. The produced clay thin film was peeled from the tray to obtain a clay film. Next, in order to improve the water repellency and water vapor barrier properties of the clay film, the fluorine-based urethane resin and silicon are sprayed on both sides of the clay film by spraying acetone and isopropyl alcohol solution of fluorine-based urethane resin and silicon resin and drying at room temperature. A resin coating layer was formed. The coating layer thickness was about 1 micrometer.
（２）粘土膜の特性
粘土膜の室温における、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。このように、両面に被覆層を作製することにより、引っ張り強度の高い粘土膜が得られた。粘土膜の４０℃、相対湿度９０％における透湿度をカップ法（ＪＩＳ Ｚ０２０８）により測定した結果、被覆前の三分の一と測定された。また、水平に静置した粘土膜に水を滴下した場合、水はじきは良好であり、撥水性の付与が確認された。このように、両面に被覆層を作製することにより、ガス透過性、透湿度共に低く、表面撥水性の粘土膜が得られた。
(2) Characteristics of clay film The permeability coefficient of the clay film for 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 . Thus, the clay film with high tensile strength was obtained by producing a coating layer on both sides. The moisture permeability of the clay film at 40 ° C. and relative humidity of 90% was measured by the cup method (JIS Z0208), and was measured as one-third before coating. Moreover, when water was dripped at the clay film set still horizontally, water repelling was favorable and the provision of water repellency was confirmed. Thus, by producing a coating layer on both sides, a clay film having low gas permeability and moisture permeability and having a surface water repellency was obtained.
［実施例２］
（１）粘土膜の製造
粘土として、０.９５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、２０ｃｍ3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０.０９グラム含む水溶液を加え、均一な分散液を得た。得られた分散液を、長さ約３０ｃｍ、幅約２０ｃｍの真鍮製板に塗布し、板の水平を保った状態で、強制送風式オーブン中で６０℃の温度条件下で１時間乾燥して、厚さ約６０マイクロメートルの均一な水溶性高分子複合粘土薄膜を得た。生成した粘土薄膜をトレイから剥離して粘土膜を得た。次に、粘土膜の機械的強度を向上させるために、粘土膜両面にアクリル樹脂とメチルフェニルポリシロキサンのエタノール溶液を噴霧し、室温で乾燥することにより、アクリル樹脂とメチルフェニルポリシロキサンの被覆層を形成した。被覆層の厚さは約１マイクロメートルであった。
[Example 2]
(1) Manufacture of clay film As clay, 0.95 grams of natural montmorillonite (Kunipia P, manufactured by Kunimine Kogyo Co., Ltd.) is added to 20 cm 3 of distilled water. It was put together with the child and shaken vigorously to obtain a uniform dispersion. An aqueous solution containing 0.09 g of epsilon-caprolactam (manufactured by Wako Pure Chemical Industries, Ltd.) as an additive was added to this dispersion to obtain a uniform dispersion. The obtained dispersion was applied to a brass plate having a length of about 30 cm and a width of about 20 cm, and dried for 1 hour in a forced air oven at 60 ° C. with the plate kept horizontal. A uniform water-soluble polymer composite clay thin film having a thickness of about 60 micrometers was obtained. The produced clay thin film was peeled from the tray to obtain a clay film. Next, in order to improve the mechanical strength of the clay film, the acrylic resin and the methylphenyl polysiloxane coating layer are sprayed on both sides of the clay film by spraying an ethanol solution of acrylic resin and methylphenyl polysiloxane and drying at room temperature. Formed. The coating layer thickness was about 1 micrometer.
（２）粘土膜の特性
粘土膜の室温における、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が１×１０-12ｃｍ2ｓ-1ｃｍＨｇ-1未満であった。粘土膜の引っ張り強度は２１.６ＭＰａ（ＪＩＳ Ｋ７１２７）であり、被覆前の値である１８.９ＭＰａよりも高い値を示した。このように、両面に被覆層を作製することにより、引っ張り強度の高い粘土膜が得られた。このように、両面に被覆層を作製することにより、ガス透過性が極めて低く、より強化された粘土膜が得られた。
(2) Characteristics of clay film The permeability coefficient of the clay 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 . The tensile strength of the clay film was 21.6 MPa (JIS K7127), which was higher than the pre-coating value of 18.9 MPa. Thus, the clay film with high tensile strength was obtained by producing a coating layer on both sides. Thus, by producing a coating layer on both sides, a clay film having a very low gas permeability and a stronger strength was obtained.
以上詳述したように、本発明は、粘土膜及びその製造方法等に係るものであり、透湿度とガス透過性が低く、表面が撥水性、耐水性であり、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粘土膜、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、耐水性、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、耐水性、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としても使用可能である。また、本発明により、上記粘土膜を、廃液を出さない簡便な工程で製造する方法を提供することができる。 As described above in detail, the present invention relates to a clay film and a method for producing the same, a machine having low moisture permeability and gas permeability, a surface having water repellency and water resistance, and usable as a self-supporting film. It is possible to provide a new clay film, a manufacturing technique thereof, and a product thereof which have high strength and excellent flexibility and can be used under high temperature conditions. The present invention makes it possible to provide a film excellent in water resistance and heat resistance. In addition, the clay thin film of the present invention can be used as a self-supporting film, has excellent water resistance, heat resistance and flexibility, and excellent gas barrier properties. It can also be used as a material. In addition, the present invention can provide a method for producing the clay film in a simple process that does not generate waste liquid.
Claims (9)
粘土、又は添加物を含有する粘土、又は添加物及び補強材を含有する粘土の分散液を調製し、この分散液を容器に流し込むか又は支持体の表面に塗布した後、分散媒である液体を分離して粘土膜とし、これを必要に応じて容器あるいは支持体から剥離して、自立膜を得た後、更に、樹脂を用いて表面処理を行うことを特徴とする粘土膜の製造方法。 A method for producing a clay film according to any one of claims 1 to 7,
After preparing a dispersion liquid of clay, or clay containing an additive, or clay containing an additive and a reinforcing material, the dispersion is poured into a container or applied to the surface of a support, and then a liquid which is a dispersion medium A clay film is produced by separating the film from a container or a support as necessary to obtain a self-supporting film, and then performing a surface treatment using a resin. .
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