CN107101587A - 薄膜扩散阻挡层 - Google Patents
薄膜扩散阻挡层 Download PDFInfo
- Publication number
- CN107101587A CN107101587A CN201611014114.7A CN201611014114A CN107101587A CN 107101587 A CN107101587 A CN 107101587A CN 201611014114 A CN201611014114 A CN 201611014114A CN 107101587 A CN107101587 A CN 107101587A
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- CN
- China
- Prior art keywords
- layer
- diffusion impervious
- cationic
- material diffusion
- anion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 125000002091 cationic group Chemical group 0.000 claims abstract description 137
- 150000001450 anions Chemical class 0.000 claims abstract description 111
- 229920001971 elastomer Polymers 0.000 claims abstract description 102
- 239000000806 elastomer Substances 0.000 claims abstract description 97
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920006318 anionic polymer Polymers 0.000 claims description 6
- 229910001853 inorganic hydroxide Inorganic materials 0.000 claims description 6
- -1 anion Compound Chemical class 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229920000083 poly(allylamine) Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 101000598921 Homo sapiens Orexin Proteins 0.000 claims description 3
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 229920001456 poly(acrylic acid sodium salt) Polymers 0.000 claims description 3
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 2
- 239000008119 colloidal silica Substances 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 2
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- PHXKQKZYWQUGLW-UHFFFAOYSA-N 1h-pyrrole;pyrrolidin-2-one Chemical compound C=1C=CNC=1.O=C1CCCN1 PHXKQKZYWQUGLW-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
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- 229910021647 smectite Inorganic materials 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 230000005611 electricity Effects 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- 239000000654 additive Substances 0.000 description 15
- 230000000996 additive effect Effects 0.000 description 14
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- 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 description 14
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- 239000012046 mixed solvent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 241000252506 Characiformes Species 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 238000002242 deionisation method 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
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 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 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
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- 229960001545 hydrotalcite Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B11/00—Measuring arrangements characterised by the use of optical techniques
- G01B11/02—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness
- G01B11/06—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material
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- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/548—No curing step for the last layer
- B05D7/5483—No curing step for any layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/588—No curing step for the last layer
- B05D7/5883—No curing step for any layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
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- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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Abstract
本发明涉及薄膜扩散阻挡层。本发明提供了一种弹性体基材及其制备方法,所述弹性体基材具有材料扩散阻挡层。在一个实施例中,一种用于在弹性体基材上制备材料扩散阻挡层的方法包括将弹性体基材暴露于阳离子溶液,以在弹性体基材上产生阳离子层。所述方法也包括将所述阳离子层暴露于阴离子溶液,以在阳离子层上产生阴离子层。层包括所述阳离子层和所述阴离子层。所述层包括材料扩散阻挡层。
Description
本申请是申请号为201280068500.8,申请日为2012年12月28日,发明名称为“薄膜扩散阻挡层”的中国专利申请的分案申请。
技术领域
本发明涉及扩散阻挡层的领域,更具体地涉及对抗材料扩散的薄膜阻挡层的领域。
背景技术
对气体和蒸气的扩散阻挡层是多种应用(如食品包装和柔性电子)中的关键部件。例如,持续需要用于食品包装的改进的对抗材料扩散的阻挡层性能。常规包装的缺点包括包装的气体和液体渗透性。这种缺点可导致对包含于包装内的食品的损坏。已开发用于常规包装的涂层和衬层,以降低气体和液体渗透性。开发的涂层和衬层的缺点包括包装的增加的厚度和刚性。增加的厚度可导致包装的不希望的重量增加。另外,这种增加的刚性可导致对包装的不希望的损坏。
因此,需要改进的扩散阻挡层。也进一步需要对抗流体和固体扩散的改进的薄膜阻挡层。
发明内容
本领域的这些和其他需要通过用于在弹性体基材上制备材料扩散阻挡层的方法在一个实施例中得以解决。所述方法包括将弹性体基材暴露于阳离子溶液,以在弹性体基材上产生阳离子层。所述方法也包括将所述阳离子层暴露于阴离子溶液,以在阳离子层上产生阴离子层。另外,所述方法包括具有阳离子层和阴离子层的层。所述层包括材料扩散阻挡层。
本领域的这些和其他需要通过用于在弹性体基材上制备材料扩散阻挡层的方法的另一实施例得以解决。所述方法包括将弹性体基材暴露于阴离子溶液,以在弹性体基材上产生阴离子层。所述方法也包括将所述阴离子层暴露于阳离子溶液,以在阴离子层上产生阳离子层。另外,所述方法包括具有阴离子层和阳离子层的层。所述层包括材料扩散阻挡层。
前述相当广泛地概述了本发明的特征和技术优点,以可更好地理解之后的具体实施方式。本发明的另外的特征和优点将在形成本发明的权利要求书的主题的下文描述。本领域技术人员应了解,所公开的概念和具体实施例可易于用作用于实施本发明的相同目的的改变或设计其他实施例的基础。本领域技术人员也应该认识到,这种等同的实施例不偏离如所附权利要求书中所述的本发明的精神和范围。
附图说明
对于本发明的优选实施例的详细描述,现在参照所附附图,其中:
图1示出了弹性体基材上的四层的一个实施例;
图2示出了四层、弹性体基材和底漆层的一个实施例;
图3示出了三个四层和弹性体基材的一个实施例;
图4示出了随四层的数量而变化的厚度;
图5示出了随四层的数量而变化的氧气传输速率;
图6示出了涂层的弹性的图像;
图7示出了弹性体基材上的双层的一个实施例;
图8示出了可成层材料和添加剂的双层的一个实施例;
图9示出了具有可成层材料和添加剂的交替层的双层的一个实施例;且
图10示出了具有可成层材料和添加剂的双层的一个实施例。
具体实施方式
在一个实施例中,多层薄膜涂布方法通过在基材上交替沉积带正电和带负电的层而提供了具有扩散阻滞涂层的弹性体基材。每一对正电层和负电层构成一层。在实施例中,多层薄膜涂布方法在基材上产生任意数量的所需层,如双层、三层、四层、五层、六层、七层、八层和增加的层。不限制地,一个或多个层可提供所需的产率。此外,不限制地,多个层可提供对材料传输通过弹性体基材的所需阻滞。材料可为任何可扩散材料。不限制地,可扩散材料可为固体、流体或它们的任意组合。流体可为任何可扩散流体,如液体、气体或它们的任意组合。在一个实施例中,可扩散流体为气体。
正电层和负电层可具有任何所需的厚度。在实施例中,每个层为约0.5纳米至约100纳米之间厚,或者约1纳米至约100纳米之间厚,或者约0.5纳米至约10纳米之间厚。在多层薄膜涂布方法的一些实施例中,正电层中的一个或多个为中性的而非带正电的。
弹性体基材包括具有粘弹性的材料。可使用多层薄膜涂布方法涂布任何所需的弹性体基材。不限制地,合适的弹性体基材的例子包括聚异戊二烯、聚氯丁烯、丁二烯-苯乙烯共聚物、丙烯腈丁二烯共聚物、乙烯丙烯-二烯橡胶、聚硫橡胶、腈橡胶、有机硅、聚氨酯、丁基橡胶,或它们的任意组合。
带负电(阴离子)层包括可成层材料。可成层材料包括阴离子聚合物、胶体粒子,或它们的任意组合。不限制地,合适的阴离子聚合物的例子包括聚苯乙烯磺酸酯、聚甲基丙烯酸、聚丙烯酸、聚(丙烯酸钠盐)、聚茴香脑磺酸钠盐、聚(乙烯基磺酸钠盐),或它们的任意组合。另外,不限制地,胶体粒子包括有机和/或无机材料。此外,不限制地,胶体粒子的例子包括粘土、胶体二氧化硅、无机氢氧化物、硅基聚合物、低聚硅倍半氧烷、碳纳米管、石墨烯,或它们的任意组合。可使用适合用于阴离子溶液中的任意类型的粘土。不限制地,合适的粘土包括钠蒙脱石、水辉石、皂石、怀俄明膨润土、蛭石、埃洛石,或它们的任意组合。在一个实施例中,粘土为钠蒙脱石。可使用可提供对气体或蒸气传输的阻滞性的任意无机氢氧化物。在一个实施例中,无机氢氧化物包括氢氧化铝、氢氧化镁,或它们的任意组合。
带正电(阳离子)层包括阳离子材料。在一些实施例中,一个或多个阳离子层为中性的。阳离子材料包括聚合物、胶体粒子、纳米粒子,或它们的任意组合。聚合物包括阳离子聚合物、具有氢键的聚合物,或它们的任意组合。不限制地,合适的阳离子聚合物的例子包括支链聚乙烯亚胺、直链聚乙烯亚胺、阳离子聚丙烯酰胺、阳离子聚二烯丙基二甲基氯化铵、聚(烯丙胺)、聚(烯丙胺)盐酸盐、聚(乙烯基胺)、聚(丙烯酰胺-共-二烯丙基二甲基氯化铵),或它们的任意组合。不限制地,合适的具有氢键的聚合物包括聚环氧乙烷、聚缩水甘油、聚环氧丙烷、聚(乙烯基甲基醚)、聚乙烯醇、聚乙烯基吡咯烷酮、聚烯丙胺、支链聚乙烯亚胺、直链聚乙烯亚胺、聚(丙烯酸)、聚(甲基丙烯酸)、它们的共聚物,或它们的任意组合。在实施例中,具有氢键的聚合物为中性聚合物。另外,不限制地,胶体粒子包括有机和/或无机材料。此外,不限制地,胶体粒子的例子包括粘土、层状双氢氧化物、无机氢氧化物、硅基聚合物、低聚硅倍半氧烷、碳纳米管、石墨烯,或它们的任意组合。不限制地,合适的层状双氢氧化物的例子包括水滑石、镁LDH、铝LDH,或它们的任意组合。
在实施例中,通过任何合适的方法将正电(或中性)层和负电层沉积于弹性体基材上。实施例包括通过任何合适的液体沉积方法将正电(或中性)层和负电层沉积于弹性体基材上。不限制地,合适的方法的例子包括浴涂布(bath coating)、喷涂、槽缝式涂布、旋涂、幕式涂布、凹版式涂布、逆向辊涂布、罗拉刮刀(即间隙)涂布、计量(Meyer)杆涂布、气刀涂布,或它们的任意组合。浴涂布包括浸渍或浸入。在一个实施例中,通过浴沉积正电(或中性)层和负电层。在其他实施例中,通过喷雾沉积正电层和负电层。
在实施例中,多层薄膜涂布方法提供了两对正电层和负电层,所述两对构成四层。实施例包括在弹性体基材上产生多个四层的多层薄膜涂布方法。图1示出了具有四层10的涂层65的弹性体基材5的一个实施例。在制备图1所示的经涂布的弹性体基材5的一个实施例中,多层薄膜涂布方法包括将弹性体基材5暴露于阳离子混合物中的阳离子分子,以在弹性体基材5上产生第一阳离子层25。阳离子混合物含有第一层阳离子材料20。在一个实施例中,第一层阳离子材料20为带正电的或中性的。在实施例中,第一层阳离子材料20为中性的。在一些实施例中,第一层阳离子材料20为具有中性电荷的具有氢键的聚合物。实施例包括包含环氧乙烷的第一层阳离子材料20。不限制地,包含中性材料(即环氧乙烷)的第一层阳离子材料20可提供所需的产率。在这种实施例中,弹性体基材5为带负电的或中性的。实施例包括具有负电荷的弹性体基材5。不限制地,带负电的弹性体基材5提供所需的粘附力。阳离子混合物包括第一层阳离子材料20的水溶液。水溶液可通过任何合适的方法制得。在实施例中,水溶液包含第一层阳离子材料20和水。在其他实施例中,第一层阳离子材料20可溶解于混合溶剂中,其中溶剂中的一者为水,另一溶剂可与水溶混(例如水、甲醇等)。溶液也可含有与聚合物组合的胶体粒子,或单独的胶体粒子,如果带正电的话。可使用任何合适的水。在实施例中,水为去离子水。在一些实施例中,水溶液可包含约0.05wt.%第一层阳离子材料20至约1.50wt.%第一层阳离子材料20,或者约0.01wt.%第一层阳离子材料20至约2.00wt.%第一层阳离子材料20,还或者约0.001wt.%第一层阳离子材料20至约20.0wt.%第一层阳离子材料20。在实施例中,可将弹性体基材5暴露于阳离子混合物达到任何合适的时间段,以产生第一阳离子层25。在实施例中,将弹性体基材5暴露于阳离子混合物达到约1秒至约20分钟,或者约1秒至约200秒,或者约10秒至约200秒,还或者约瞬间至约1,200秒。不限制地,弹性体基材5对阳离子混合物的暴露时间和第一层阳离子材料20在阳离子混合物中的浓度影响第一阳离子层25的厚度。例如,第一层阳离子材料20的浓度越高,暴露时间越长,则通过多层薄膜涂布方法产生的第一阳离子层25越厚。
在实施例中,在形成第一阳离子层25之后,多层薄膜涂布方法包括从阳离子混合物中移出具有产生的第一阳离子层25的弹性体基材5,然后将具有第一阳离子层25的弹性体基材5暴露于阴离子混合物中的阴离子分子,以在第一阳离子层25上产生第一阴离子层30。阴离子混合物含有第一层可成层材料15。不限制地,正电或中性第一阳离子层25吸引阴离子分子,以形成第一阳离子层25和第一阴离子层30的阳离子(或中性)-阴离子对。阴离子混合物包括第一层可成层材料15的水溶液。在一个实施例中,第一层可成层材料15包括聚丙烯酸。水溶液可通过任何合适的方法制得。在实施例中,水溶液包含第一层可成层材料15和水。第一层可成层材料15也可溶解于混合溶剂中,其中溶剂中的一者为水,另一溶剂可与水溶混(例如乙醇、甲醇等)。阴离子聚合物和胶体粒子的组合可存在于水溶液中。可使用任何合适的水。在实施例中,水为去离子水。在一些实施例中,水溶液可包含约0.05wt.%第一层可成层材料15至约1.50wt.%第一层可成层材料15,或者约0.01wt.%第一层可成层材料15至约2.00wt.%第一层可成层材料15,还或者约0.001wt.%第一层可成层材料15至约20.0wt.%第一层可成层材料15。在实施例中,可将具有第一阳离子层25的弹性体基材5暴露于阴离子混合物达到任何合适的时间段,以产生第一阴离子层30。在实施例中,将具有第一阳离子层25的弹性体基材5暴露于阴离子混合物达到约1秒至约20分钟,或者约1秒至约200秒,或者约10秒至约200秒,还或者约瞬间至约1,200秒。不限制地,具有第一阳离子层25的弹性体基材5对阴离子混合物的暴露时间和第一层可成层材料15在阴离子混合物中的浓度影响第一阴离子层30的厚度。例如,第一层可成层材料15的浓度越高,暴露时间越长,则通过多层薄膜涂布方法产生的第一阴离子层30越厚。
在如图1进一步显示的实施例中,在形成第一阴离子层30之后,多层薄膜涂布方法包括从阴离子混合物中移出具有产生的第一阳离子层25和第一阴离子层30的弹性体基材5,然后将具有第一阳离子层25和第一阴离子层30的弹性体基材5暴露于阳离子混合物中的阳离子分子,以在第一阴离子层30上产生第二阳离子层35。阳离子混合物含有第二层阳离子材料75。在一个实施例中,第二层阳离子材料75为带正电的或中性的。在实施例中,第二层阳离子材料75为正电的。在一些实施例中,第二层阳离子材料75包含聚乙烯亚胺。阳离子混合物包括第二层阳离子材料75的水溶液。水溶液可通过任何合适的方法制得。在实施例中,水溶液包含第二层阳离子材料75和水。在其他实施例中,第二层阳离子材料75可溶解于混合溶剂中,其中溶剂中的一者为水,另一溶剂可与水溶混(例如水、甲醇等)。溶液也可含有与聚合物组合的胶体粒子,或单独的胶体粒子,如果带正电的话。可使用任何合适的水。在实施例中,水为去离子水。在一些实施例中,水溶液可包含约0.05wt.%第二层阳离子材料75至约1.50wt.%第二层阳离子材料75,或者约0.01wt.%第二层阳离子材料75至约2.00wt.%第二层阳离子材料75,还或者约0.001wt.%第二层阳离子材料75至约20.0wt.%第二层阳离子材料75。在实施例中,可将弹性体基材5暴露于阳离子混合物达到任何合适的时间段,以产生第二阳离子层35。在实施例中,将弹性体基材5暴露于阳离子混合物达到约1秒至约20分钟,或者约1秒至约200秒,或者约10秒至约200秒,还或者约瞬间至约1,200秒。
在实施例中,在形成第二阳离子层35之后,多层薄膜涂布方法包括从阳离子混合物中移出具有产生的第一阳离子层25、第一阴离子层30和第二阳离子层35的弹性体基材5,然后将具有第一阳离子层25、第一阴离子层30和第二阳离子层35的弹性体基材5暴露于阴离子混合物中的阴离子分子,以在第二阳离子层35上产生第二阴离子层40。阴离子混合物含有第二层可成层材料70。不限制地,正电或中性第二阳离子层35吸引阴离子分子,以形成第二阳离子层35和第二阴离子层40的阳离子(或中性)-阴离子对。阴离子混合物包括第二层成层材料70的水溶液。在一个实施例中,第二层可成层材料70包括粘土。实施例包括包含钠蒙脱石的粘土。水溶液可通过任何合适的方法制得。在实施例中,水溶液包含第二层可成层材料70和水。第二层可成层材料70也可溶解于混合溶剂中,其中溶剂中的一者为水,另一溶剂可与水溶混(例如乙醇、甲醇等)。阴离子聚合物和胶体粒子的组合可存在于水溶液中。可使用任何合适的水。在实施例中,水为去离子水。在一些实施例中,水溶液可包含约0.05wt.%第二层可成层材料70至约1.50wt.%第二层可成层材料70,或者约0.01wt.%第二层可成层材料70至约2.00wt.%第二层可成层材料70,还或者约0.001wt.%第二层可成层材料70至约20.0wt.%第二层可成层材料70。在实施例中,可将具有第一阳离子层25、第一阴离子层30和第二阳离子层35的弹性体基材5暴露于阴离子混合物达到任何合适的时间段,以产生第二阴离子层40。在实施例中,将具有第一阳离子层25、第一阴离子层30和第二阳离子层35的弹性体基材5暴露于阴离子混合物达到约1秒至约20分钟,或者约1秒至约200秒,或者约10秒至约200秒,还或者约瞬间至约1,200秒。因此,四层10在弹性体基材5上产生。在其中弹性体基材5具有一个四层10的如图1所示的实施例中,涂层65包括四层10。在实施例中,四层10包括第一阳离子层25、第一阴离子层30、第二阳离子层35和第二阴离子层40。
在如图2所示的一个实施例中,涂层65也包括底漆层45。底漆层45设置于弹性体基材5与四层10的第一阳离子层25之间。底漆层45可具有任意数量的层。邻近弹性体基材5的底漆层45的层具有吸引至弹性体基材5的电荷,邻近第一阳离子层25的底漆层45的层具有吸引至第一阳离子层25的电荷。在如图2所示的实施例中,底漆层45为具有第一底漆层80和第二底漆层85的双层。在这种实施例中,第一底漆层80为包括第一底漆层材料60的阳离子层(或者中性),第二底漆层85为包括第二底漆层材料90的阴离子层。第一底漆层材料60包括阳离子材料。在一个实施例中,第一底漆层材料60包括聚乙烯亚胺。第二底漆层材料90包括可成层材料。在一个实施例中,第二底漆层材料90包括聚丙烯酸。在其他实施例中(未显示),底漆层45具有超过一个双层。
在如图2所示的另外的实施例中,多层薄膜涂布方法包括将弹性体基材5暴露于阳离子混合物中的阳离子分子,以在弹性体基材5上产生第一底漆层80。阳离子混合物含有第一底漆层材料60。在一个实施例中,第一底漆层材料60为带正电的或中性的。在实施例中,阳离子混合物包括第一底漆层材料60的水溶液。水溶液可通过任何合适的方法制得。在实施例中,水溶液包含第一底漆层材料60和水。在其他实施例中,第一底漆层材料60可溶解于混合溶剂中,其中溶剂中的一者为水,另一溶剂可与水溶混(例如水、甲醇等)。溶液也可含有与聚合物组合的胶体粒子,或单独的胶体粒子,如果带正电的话。可使用任何合适的水。在实施例中,水为去离子水。在一些实施例中,水溶液可包含约0.05wt.%第一底漆层材料60至约1.50wt.%第一底漆层材料60,或者约0.01wt.%第一底漆层材料60至约2.00wt.%第一底漆层材料60,还或者约0.001wt.%第一底漆层材料60至约20.0wt.%第一底漆层材料60。在实施例中,可将弹性体基材5暴露于阳离子混合物达到任何合适的时间段,以产生第一底漆层80。在实施例中,将弹性体基材5暴露于阳离子混合物达到约1秒至约20分钟,或者约1秒至约200秒,或者约10秒至约200秒,还或者约瞬间至约1,200秒。
在如图2所示的实施例中,在形成第一底漆层80之后,多层薄膜涂布方法包括从阳离子混合物中移出具有产生的第一底漆层80的弹性体基材5,然后将具有第一底漆层80的弹性体基材5暴露于阴离子混合物中的阴离子分子,以在第一底漆层80上产生第二底漆层85。阴离子混合物含有第二底漆层材料90。阴离子混合物包括第二底漆层材料90的水溶液。水溶液可通过任何合适的方法制得。在实施例中,水溶液包含第二底漆层材料90和水。第二底漆层材料90也可溶解于混合溶剂中,其中溶剂中的一者为水,另一溶剂可与水溶混(例如乙醇、甲醇等)。阴离子聚合物和胶体粒子的组合可存在于水溶液中。可使用任何合适的水。在实施例中,水为去离子水。在一些实施例中,水溶液可包含约0.05wt.%第二底漆层材料90至约1.50wt.%第二底漆层材料90,或者约0.01wt.%第二底漆层材料90至约2.00wt.%第二底漆层材料90,还或者约0.001wt.%第二底漆层材料90至约20.0wt.%第二底漆层材料90。在实施例中,可将具有第一底漆层80的弹性体基材5暴露于阴离子混合物达到任何合适的时间段,以产生第二底漆层85。在实施例中,将具有第一底漆层80的弹性体基材5暴露于阴离子混合物达到约1秒至约20分钟,或者约1秒至约200秒,或者约10秒至约200秒,还或者约瞬间至约1,200秒。然后从阴离子混合物中移出具有底漆层45的弹性体基材5,随后进行多层薄膜涂布方法以产生四层10。
在如图3所示的实施例中,重复暴露步骤,具有四层10的基材5持续暴露于阳离子混合物和随后的阴离子混合物,以产生具有多个四层10的涂层65。对阳离子混合物和随后的阴离子混合物的重复暴露可持续,直至产生所需数量的四层10。涂层65可具有任何足够数量的四层10,以提供给弹性体基材5所需的对气体或蒸气传输的阻滞。在一个实施例中,涂层65具有约1个四层10至约40个四层10之间,或者约1个四层10至约1,000个四层10之间。
在一个实施例中,多层薄膜涂布方法以约0.1%至约100%之间,或者约1%至约10%之间的产率提供经涂布的弹性体基材5(例如包括涂层65)。另外,实施例包括提供经涂布的弹性体基材5的多层薄膜涂布方法,所述经涂布的弹性体基材5具有约0.03cc/(m2*天*atm)至约100cc/(m2*天*atm)之间,或者约0.3cc/(m2*天*atm)至约100cc/(m2*天*atm)之间,或者约3cc/(m2*天*atm)至约30cc/(m2*天*atm)之间的气体传输速率。
应了解,多层薄膜涂布方法不限于暴露于阳离子混合物,之后暴露于阴离子混合物。在其中弹性体基材5带正电的实施例中,多层薄膜涂布方法包括将弹性体基材5暴露于阴离子混合物,之后暴露于阳离子混合物。在这种实施例(未显示)中,将第一阴离子层30沉积于弹性体基材5上,且第一阳离子层25沉积于第一阴离子层30上,将第二阴离子层40沉积于第一阳离子层25上,之后将第二阳离子层35沉积于第二阴离子层40上以产生四层10,重复所述步骤直至涂层65具有所需厚度。在其中弹性体基材5具有中性电荷的实施例中,多层薄膜涂布方法可包括起始于暴露于阳离子混合物,之后暴露于阴离子混合物,或者可包括起始于暴露于阴离子混合物,之后暴露于阳离子混合物。
在实施例(未显示)中,四层10可具有一个或超过一个阳离子层(即第一阳离子层25、第二阳离子层35、底漆层45中的阳离子层),所述一个或超过一个阳离子层由超过一种类型的阳离子材料组成。在一个实施例(未显示)中,四层10可具有一个或超过一个阴离子层(即第一阴离子层30、第二阴离子层40、底漆层45中的阴离子层),所述一个或超过一个阴离子层由超过一种类型的阴离子材料组成。在一些实施例中,一个或多个阳离子层由相同的材料组成,和/或阴离子层中的一个或多个由相同的阴离子材料组成。应了解,涂层65不限于一种可成层材料,而是可包括超过一种可成层材料和/或超过一种阳离子材料。
图7示出了具有多个双层50的涂层65的弹性体基材5的一个实施例。应了解,多层薄膜涂布方法通过上述和图1-3所示的实施例制备经涂布的弹性体基材5。如图7所示,每个双层50具有阳离子层95和阴离子层100。在所示的实施例中,阳离子层95具有阳离子材料105,阴离子层100具有可成层材料110。在所示的实施例中,多层薄膜涂布方法根据如上实施例通过暴露于阳离子混合物,之后暴露于阴离子混合物,从而制备涂层65。在一个实施例中,双层50具有包括聚环氧乙烷或聚缩水甘油的阳离子材料105,且可成层材料110包括粘土。在一些实施例中,双层50具有包括聚环氧乙烷或聚缩水甘油的阳离子材料105,且可成层材料110包括聚丙烯酸或聚甲基丙烯酸。
应了解,用于制备具有涂层65(所述涂层65具有双层50)的弹性体基材5的多层薄膜涂布方法不限于暴露于阳离子混合物,之后暴露于阴离子混合物。在其中弹性体基材5带正电的实施例中,多层薄膜涂布方法包括将弹性体基材5暴露于阴离子混合物,之后暴露于阳离子混合物。在这种实施例(未显示)中,将阴离子层100沉积于弹性体基材5上,将阳离子层95沉积于阴离子层100上,以产生双层50,重复所述步骤直至涂层65具有所需厚度。在其中弹性体基材5具有中性电荷的实施例中,多层薄膜涂布方法可包括起始于暴露于阳离子混合物,之后暴露于阴离子混合物,或者可包括起始于暴露于阴离子混合物,之后暴露于阳离子混合物。
还应了解,涂层65不限于一种可成层材料110和/或一种阳离子材料105,而是可包括超过一种可成层材料110和/或超过一种阳离子材料105。不同的可成层材料110可设置于同一阴离子层100上、交替的阴离子层100上,或双层50的层中(即,或三层或增加的层的层中)。不同的阳离子材料105可设置于同一阳离子层95上、交替的阳离子层95上,或双层50的层中(即,或三层或增加的层的层中)。例如,在图8-10所示的实施例中,涂层65包括两种类型的可成层材料110、110’(即钠蒙脱石为可成层材料110,氢氧化铝为可成层材料110’)。应了解,在图8-10中仅为了说明的目的,未显示弹性体基材5。图8示出了其中可成层材料110,110’在双层50的不同层中的一个实施例。例如,如图8所示,在可成层材料110沉积于弹性体基材5(未显示)之后,将可成层材料110’沉积于顶部双层50中。图9示出了其中涂层65在交替的双层50中具有可成层材料110,110’的一个实施例。应了解,在图9中仅为了说明的目的,未显示阳离子材料105。图10示出了其中存在两种类型的双层50的一个实施例,所述两种类型的双层50由粒子(可成层材料110,110’)和阳离子材料105,105’(例如聚合物)组成。
图7-10未显示具有底漆层45的涂层65。应了解,具有双层50的涂层65的实施例也可具有底漆层45。具有三层、五层等的涂层65的实施例(未显示)也可具有底漆层45。
应了解,多层薄膜涂布方法通过用于双层50和四层10的如上公开的实施例制备三层、五层和增加的层的涂层65。应了解,涂层65不限于仅多个双层50、三层、四层10、五层、六层、七层、八层或增加的层。在实施例中,涂层65可具有这种层的任意组合。
在其中涂层65包括三层的一些实施例中,三层包括第一阳离子层、第二阳离子层和阴离子层,所述第一阳离子层包括聚乙烯亚胺,所述第二阳离子层包括聚环氧乙烷或聚缩水甘油,所述阴离子层包括粘土。在这种实施例中,第二阳离子层设置于第一阳离子层与阴离子层之间。在其中涂层65包括三层的另一实施例中,三层包括第一阳离子层、阴离子层和第二阳离子层,所述第一阳离子层包括聚乙烯亚胺,所述阴离子层包括粘土,所述第二阳离子层包括聚环氧乙烷或聚缩水甘油。在这种实施例中,阴离子层设置于第一阳离子层与第二阳离子层之间。在其中涂层65包括三层的一些实施例中,三层包括阳离子层、第一阴离子层和第二阴离子层,所述阳离子层包括聚环氧乙烷或聚缩水甘油,所述第一阴离子层包括聚丙烯酸或聚甲基丙烯酸,所述第二阴离子层包括钠蒙脱石。在这种实施例中,第一阴离子层设置于阳离子层与第二阴离子层之间。
在一些实施例中,多层薄膜涂布方法包括在每个(或者超过一个)暴露步骤(即暴露于阳离子混合物的步骤或暴露于阴离子混合物的步骤)之间冲洗弹性体基材5。例如,在弹性体基材5从暴露于阳离子混合物中移出之后,冲洗具有第一阳离子层25的弹性体基材5,然后将所述弹性体基材5暴露于阴离子混合物。在一些实施例中,在暴露于相同或另一阳离子和/或阴离子混合物之前,冲洗四层10。在一个实施例中,冲洗涂层65。通过适用于从弹性体基材5和任意层去除离子液体中的全部或一部分的任意冲洗液体完成冲洗。在实施例中,冲洗液体包括去离子水、甲醇或它们的任意组合。在一个实施例中,冲洗液体为去离子水。可冲洗层达到任何合适的时间段,以去除离子液体中的全部或一部分。在一个实施例中,冲洗层达到约5秒至约5分钟的时间段。在一些实施例中,在暴露步骤中的一部分之后冲洗层。
在实施例中,多层薄膜涂布方法包括在每个(或者超过一个)暴露步骤(即暴露于阳离子混合物的步骤或暴露于阴离子混合物的步骤)之间干燥弹性体基材5。例如,在弹性体基材5从暴露于阳离子混合物中移出之后,干燥具有第一阳离子层25的弹性体基材5,然后将所述弹性体基材5暴露于阴离子混合物。在一些实施例中,在暴露于相同或另一阳离子和/或阴离子混合物之前,干燥四层10。在一个实施例中,干燥涂层65。通过将干燥气体应用于弹性体基材5而完成干燥。干燥气体可包括适用于从弹性体基材5去除液体中的全部或一部分的任何气体。在实施例中,干燥气体包括空气、氮气,或它们的任意组合。在一个实施例中,干燥气体为空气。在一些实施例中,空气为经过滤的空气。干燥可进行任何合适的时间段,以从层(即四层10)和/或涂层65去除液体中的全部或一部分。在一个实施例中,干燥约5秒至约500秒的时间段。在其中多层薄膜涂布方法包括在暴露步骤之后冲洗的一个实施例中,在冲洗之后并在暴露于下一暴露步骤之前干燥层。在可选择的实施例中,干燥包括将热源应用于层(即四层10)和/或涂层65。例如,在一个实施例中,将弹性体基材5设置于烘箱中达到足以从层去除液体中的全部或一部分的时间。在一些实施例中,直至已沉积所有的层时才进行干燥作为使用前的最终步骤。
在一些实施例(未显示)中,可将添加剂添加至涂层65中的弹性体基材5中。在实施例中,添加剂可与可成层材料一起在阴离子混合物中混合。在其他实施例中,添加剂可设置于不包含可成层材料的阴离子混合物中。在一些实施例中,涂层65具有一个或多个添加剂的层。在实施例中,添加剂为阴离子材料。添加剂可用于任何所需目的。例如,添加剂可用于保护弹性体基材5免于紫外光或用于耐磨性。对于紫外光保护,可使用适用于防护紫外光和用于涂层65中的任何带负电的材料。在一个实施例中,用于紫外保护的合适的添加剂的例子包括二氧化钛或它们的任意组合。在实施例中,添加剂为二氧化钛。对于耐磨性,可使用适用于耐磨性和用于涂层65中的任何添加剂。在实施例中,用于耐磨性的合适的添加剂的例子包括交联剂。可使用适于与弹性体一起使用的任何交联剂。在一个实施例中,交联剂包括二醛。交联剂的例子包括戊二醛、溴代烷烃,或它们的任意组合。交联剂可用于交联阴离子层和/或阳离子层(即第一阳离子层25和第一阴离子层30)。在一个实施例中,将具有涂层65的弹性体基材5暴露于阴离子混合物中的添加剂。
在一些实施例中,调节阴离子和/或阳离子溶液的pH。不希望受限于理论,降低阳离子溶液的pH会降低涂层65的生长。此外,不希望受限于理论,由于阳离子溶液在降低的pH值下可具有高的电荷密度,这可导致聚合物主链排斥自身而成为平直状态,因此可降低涂层65生长。在一些实施例中,增加pH以增加涂层65生长并产生更厚的涂层65。不受限于理论,阳离子混合物中更低的电荷密度提供了增加的卷曲聚合物。可通过任何合适的方式调节pH,例如通过添加酸或碱。在一个实施例中,阴离子溶液的pH为约0至约14之间,或者约1至约7之间。实施例包括约0至约14之间,或者约3至约12之间的阳离子溶液的pH。
阴离子和阳离子混合物中的暴露步骤可在任何合适的温度下发生。在一个实施例中,暴露步骤在环境温度下发生。在一些实施例中,涂层65为光学透明的。
为了进一步说明本发明的各种示例性实施例,提供如下实例。
实例1
材料。天然钠蒙脱石(MMT)(NA+,其为南部粘土产品公司(SouthernClay Products,Inc.)的注册商标)粘土按原样使用。单独的MMT薄片具有在去离子水中的负表面电荷、2.86g/cm3的报道密度、1nm的厚度和≥200的标称纵横比(l/d)。支链聚乙烯亚胺(PEI)(Mw=25,000g/mol和Mn=10,000g/mol)、聚环氧乙烷(PEO)(Mw=4,000,000g/mol)和聚丙烯酸(PAA)(在水中35wt.%,Mw=100,000g/mol)购自西格玛-奥德里奇公司(威斯康辛州密尔沃基)(Sigma-Aldrich(Milwaukee,WI)),并按原样使用。500μm厚的单面抛光的硅晶片购自大学晶片公司(马萨诸塞州南波士顿)(University Wafer(South Boston,MA)),并用作用于经由椭圆光度法的膜生长表征的反射基材。
膜制备。所有的膜沉积混合物使用来自5超纯水系统的18.2MΩ去离子水制得,并滚动一天(24h)以获得均匀性。为密理博公司(MilliporeCorporation)的注册商标。在沉积之前,使用1.0M HCl将PEI的0.1wt.%水溶液的pH改变至10或3,使用1.0M HCl将PEO的0.1wt.%水溶液的pH改变至3,使用1.0M HCl将PAA的0.2wt.%水溶液的pH改变至3,使用1.0M HCl将MMT的2.0wt.%水悬浮体的pH改变至3。在用水、丙酮和再一次水冲洗晶片之前,将硅晶片piranha处理30分钟,并在沉积之前最终用过滤空气干燥硅晶片。弹性体基材用去离子水冲洗,浸入在40℃下的在水浴中的40wt.%丙醇达5分钟,用RT的在水中的40wt.%丙醇冲洗,用去离子水冲洗,用过滤空气干燥,并在每一面上等离子体清洁达5分钟。然后将每个经适当处理的基材浸入pH 10下的PEI溶液中达5分钟,用去离子水冲洗,并用过滤空气干燥。当接下来将基材浸入PAA溶液中时,遵循相同的工序。一旦沉积所述初始双层,当将基材浸入PEO溶液,随后浸入PAA溶液、随后浸入pH 3下的PEI溶液和最后浸入MMT悬浮体中时,重复如上工序(对于聚合物溶液,使用5秒浸入时间,对于MMT悬浮体,使用1分钟浸入时间),直至获得所需数量的PEO/PAA/PEI/MMT的四层。使用自制机械浸入系统制备所有的膜。
膜表征。使用椭偏仪测量每一个至每五个四层(在硅晶片上)的膜厚度。为J.A.伍拉姆公司(J.A.Woollam Co.,Inc.)的注册商标。在0%RH下使用Oxtran 2/21ML仪器,根据ASTM D-3985由膜康公司(Mocon,Inc.)进行OTR测试。
根据结果,图4示出了当沉积于硅晶片上并经由椭圆光度法测量时,厚度随四层PEO/PAA/PEI/MMT的数量的变化。图5示出了当沉积于1mm厚的橡胶板上时,氧气传输速率(OTR)随PEO/PAA/PEI/MMT的四层的数量的变化的结果。图6示出了涂层的弹性,左边的图像为在橡胶上10QL,右边的图像为以20英寸/分钟拉伸至30%应变的同一涂层。该右边图像未显示大龟裂的迹象,并揭示了涂层对拉伸橡胶表面的适形性。
尽管已详细描述本发明及其优点,但应了解,在不偏离如所附权利要求书所限定的本发明的精神和范围的情况下,可在本文进行各种改变、替换和变化。
Claims (20)
1.一种在弹性体基材上的材料扩散阻挡层,其中所述材料扩散阻挡层包括:
第一阳离子层,其中所述第一阳离子层包含聚环氧乙烷;
第一阴离子层,其中所述第一阴离子层包含聚丙烯酸;和
第二阳离子层,其中所述第二阳离子层包含聚乙烯亚胺。
2.根据权利要求1所述的材料扩散阻挡层,所述材料扩散阻挡层还包括第二阴离子层,其中所述第二阴离子层包含粘土。
3.根据权利要求1所述的材料扩散阻挡层,其中所述第一阳离子层还包含聚合物、胶体粒子、纳米粒子,或它们的任意组合。
4.根据权利要求3所述的材料扩散阻挡层,其中所述聚合物包括具有氢键的聚合物,其中所述具有氢键的聚合物包括聚缩水甘油、聚环氧丙烷、聚(乙烯基甲基醚)、聚乙烯醇、聚乙烯基吡咯烷酮、聚烯丙胺、支链聚乙烯亚胺、直链聚乙烯亚胺、聚(丙烯酸)、聚(甲基丙烯酸)、它们的共聚物,或它们的任意组合。
5.根据权利要求1所述的材料扩散阻挡层,其中所述第一阴离子层还包含阴离子聚合物、胶体粒子,或它们的任意组合。
6.根据权利要求5所述的材料扩散阻挡层,其中所述第一阴离子层还包含聚苯乙烯磺酸酯、聚甲基丙烯酸、聚丙烯酸、聚(丙烯酸钠盐)、聚茴香脑磺酸钠盐、聚(乙烯基磺酸钠盐),或它们的任意组合。
7.根据权利要求5所述的材料扩散阻挡层,其中所述胶体粒子包括粘土、胶体二氧化硅、无机氢氧化物、硅基聚合物、低聚硅倍半氧烷、碳纳米管、石墨烯,或它们的任意组合。
8.根据权利要求1所述的材料扩散阻挡层,其中所述弹性体基材包括设置于所述弹性体基材与所述第一阳离子层之间的底漆层。
9.根据权利要求1所述的材料扩散阻挡层,所述材料扩散阻挡层还包括多个层。
10.一种在弹性体基材上的材料扩散阻挡层,其中所述材料扩散阻挡层包括:
第一阳离子层,其中所述第一阳离子层包含聚环氧乙烷;
第一阴离子层,其中所述第一阴离子层包含钠蒙脱石粘土;和
第二阳离子层,其中所述第二阳离子层包含聚乙烯亚胺。
11.根据权利要求10所述的材料扩散阻挡层,其中所述第一阳离子层还包含聚合物、胶体粒子、纳米粒子,或它们的任意组合。
12.根据权利要求11所述的材料扩散阻挡层,其中所述聚合物包括具有氢键的聚合物,其中所述聚合物包括聚缩水甘油、聚环氧丙烷、聚(乙烯基甲基醚)、聚乙烯醇、聚乙烯基吡咯烷酮、聚烯丙胺、支链聚乙烯亚胺、直链聚乙烯亚胺、聚(丙烯酸)、聚(甲基丙烯酸)、它们的共聚物,或它们的任意组合。
13.根据权利要求10所述的材料扩散阻挡层,其中所述第一阴离子层还包含阴离子聚合物、胶体粒子,或它们的任意组合。
14.根据权利要求13所述的材料扩散阻挡层,其中所述阴离子聚合物包括聚苯乙烯磺酸酯、聚甲基丙烯酸、聚丙烯酸、聚(丙烯酸钠盐)、聚茴香脑磺酸钠盐、聚(乙烯基磺酸钠盐),或它们的任意组合。
15.根据权利要求13所述的材料扩散阻挡层,其中所述胶体粒子包括粘土、胶体二氧化硅、无机氢氧化物、硅基聚合物、低聚硅倍半氧烷、碳纳米管、石墨烯,或它们的任意组合。
16.根据权利要求10所述的材料扩散阻挡层,其中所述弹性体基材包括设置于所述弹性体基材与所述第一阳离子层之间的底漆层。
17.根据权利要求10所述的材料扩散阻挡层,所述材料扩散阻挡层还包括多个层。
18.根据权利要求10所述的材料扩散阻挡层,所述材料扩散阻挡层还包括在0.03cc/(m2*天*atm)至100cc/(m2*天*atm)之间的气体传输速率。
19.根据权利要求10所述的材料扩散阻挡层,所述材料扩散阻挡层还包括二氧化钛。
20.根据权利要求10所述的材料扩散阻挡层,所述材料扩散阻挡层还包括交联剂,其中所述交联剂包括二醛。
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EP3521057A1 (en) | 2019-08-07 |
EP2797699A4 (en) | 2015-05-27 |
JP6556275B2 (ja) | 2019-08-07 |
CN104114286A (zh) | 2014-10-22 |
JP2015509043A (ja) | 2015-03-26 |
BR112014016330A8 (pt) | 2017-12-26 |
CN104093530A (zh) | 2014-10-08 |
CN108480155A (zh) | 2018-09-04 |
CN104114286B (zh) | 2016-12-14 |
JP6110876B2 (ja) | 2017-04-05 |
US10195642B2 (en) | 2019-02-05 |
JP6423388B2 (ja) | 2018-11-14 |
EP2797699B1 (en) | 2019-05-01 |
US20140363579A1 (en) | 2014-12-11 |
WO2013101975A1 (en) | 2013-07-04 |
US20140363689A1 (en) | 2014-12-11 |
WO2013101976A1 (en) | 2013-07-04 |
BR112014016332A2 (pt) | 2017-08-22 |
BR112014016330A2 (pt) | 2017-08-22 |
JP2019037976A (ja) | 2019-03-14 |
JP2017100135A (ja) | 2017-06-08 |
EP3385093A1 (en) | 2018-10-10 |
EP2797699A1 (en) | 2014-11-05 |
EP2797724A4 (en) | 2015-06-03 |
JP2015510444A (ja) | 2015-04-09 |
JP6286081B2 (ja) | 2018-02-28 |
EP2797724A1 (en) | 2014-11-05 |
JP2018065139A (ja) | 2018-04-26 |
JP2016175084A (ja) | 2016-10-06 |
BR112014016332A8 (pt) | 2018-01-02 |
EP2797724B1 (en) | 2018-07-04 |
JP5960283B2 (ja) | 2016-08-02 |
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