TWI290941B - Membranes with fluid barrier properties and articles containing such membranes - Google Patents

Abstract

A membrane comprise at least one elastomeric material, at least one polymeric fluid barrier material, and a laminar nano-filler having an average platelet thickness of up to about 10 nanometers and an average aspect ratio of at least about 200 provides desirable appearance and low gas transmission characteristics. The membrane may be a single layer, but preferably the membrane includes at least one layer of an elastomeric material and at least one layer of a polymeric barrier material, in which the elastomeric material layer and/or the polymeric barrier material layer comprises the laminar nano-filler.

Description

1290941 Case No. · 93123224 August 28, 2006 Amendment IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a film having a filler that meets the barrier and bendability requirements, particularly for use in preparation for inflation An expansion of the article and the cushioning device. The invention further relates to articles that are inflated and have an inflatable element. [Prior Art] The barrier film and the inflated product formed by such a film have been diversified for use in inflatable trcr and cushioning articles, including tires for vehicles, balls, accumulators for heavy machinery, and footwear. Especially sports shoes. It is generally desirable to use thermoplastic polymeric materials to form films because thermoplastic materials can be recycled and remanufactured into new articles, reducing waste during manufacturing and improving reuse after the life of the article. However, the thermal plastic barrier film is very thin and may shrink to a certain extent. Generally, the plastic barrier film only has a barrier material layer, and in many applications, there is not enough flexibility, especially when applied to withstand high tension. Inflatable expansion. In order to solve these problems, the barrier material uses an elastic material that has been bent or multi-layered. Elastomeric materials or elastomers can essentially return to their original shape and size after removal of the deforming force, even if part of it has been deformed. Elastomeric materials are important on many filled swell surfaces, including footwear, moving balls, and inflatable swells of accumulators. An important characteristic of the film for producing a gas-filled expander is its "gas transmission rate". - Method used in the manufacturing process to measure the relative penetration (_eanee) and permeability of different thin rides, marked as astmd-1434|^. The gas swell is expected to remain available during its life cycle. 4HDP/04002TW/NIKE-Replacement Page 5 1290941 Case No. 93132224 Modified on August 28, 2006 without periodically reintroducing the inflation gas, thus inflating The expansion is permanently sealed and does not require refilling. A method of achieving a low gas diffusion rate required for such a sturdy, permanent expansion, in order to increase the thickness of the barrier layer of the film of the swell, however, due to the increased hardness, a thicker barrier material is formed. Not an attractive choice. From the standpoint of maintaining film elasticity, it is preferred to reduce the gas diffusion rate by a method which does not substantially increase the hardness of the film. In applications such as footwear or ball swells, the "style" is an expansion, another consideration, the style attracts the buyer's vision, and makes the item attractive. Recently, a reform of the footwear style has a surface appearance. The transparent component, y expects the transparent component to be clear, smooth, and "high-tech". The inflatable expansion contained in the shoe to provide cushioning may also have the function of this transparent element, however, the expansion must maintain its elasticity and gas-barrier characteristics to accomplish its primary function of providing a cushioning foot. Therefore, it is expected that the appearance of the film is not opaque (〇pa (jUe) or non-hazy), and the gas diffusion rate is reduced by the film. The layer has a plurality of layers of flexible material and a multilayer fluid barrier layer. The film layer has been described, for example, the U.S. Patent No. 6,082,025 approved on July 4, 2000, and the U.S. Patent No. 6,013,340 approved on January 1, 2000. U.S. Patent No. 5, 952, 065, issued on Sep. 14, 1999, and U.S. Patent No. 5,713, issued to "Permanently" sealed, gas filled _ and still expected to improve its elasticity. ..., 4HDP/04002TW/NIKE-Replacement Page 1129941 Case No.: 93 1 23224 Modified August 28, 2006 Modified mica and other large appearance An aspect ratio of the plate filler has been used to reduce the gas diffusion rate of the aerated film. U.S. Patent No. 5,221,566 to the entire disclosure of the teachings of the present invention, which is incorporated herein by reference. EV0H) and the first layer of 5-50% inorganic filler, as well as A second layer of a wet-impedance thermoplastic resin of an alkene having an average sheet thickness of no greater than 50 microns, an apparent ratio of at least 3, and a whiteness of at least 80 (measured by a Kett spectrophotometer) The material of Tokoh et al. does not have the resilience required for cushioning devices and other inflated articles. Therefore, a composition of a fluid barrier material having a high impermeability to the inflation gas is still required. SUMMARY OF THE INVENTION The present invention provides a At least one film comprising at least one elastic material and at least one polymer fluid barrier material, wherein the film has a laminar nano-fi ler, and the layer is The nanofiller has an average sheet thickness of up to about 10 nanometers and an average aspect ratio of at least about 200. The film preferably comprises at least one elastic layer of elastic material and at least one polymer fluid. A barrier layer that resists the early material of the material. The elastic material provides the elastic and dimensional stability of the film of the present invention, and the fluid barrier material allows the thin The membrane prevents the fluid from moving from thin to the other side. The layered nanofiller avoids fluid from one of the other sides of the film, does not significantly increase the non-transparency and enthalpy of the film, and does not reduce the elasticity of the film. The flexible barrier film can be used to inflate the inflated material. 4HDP/04002TW/NIKE-Replacement Page 7 1290941 Case No.: 93 1 23224 * , August 28, 2006 Amendment "Durable" means that the film has excellent resistance The elasticity is fatigued, and in particular, the film of the present invention can withstand repeated shrinkage and/or repetitive manufacture and recovery without stretching the interlayer of the film, preferably to withstand a wide range of temperatures. For the purposes of the present invention, the term "film" is used to mean a free-standing layer for the exchange of fluids, especially gases, preferably at about atmospheric pressure, with another fluid (liquid or gas) or with low pressure. The gas is separated. A film that is layered or embossed on another article other than the purpose of separating the fluids' is excluded from the film defined by the present invention. Another aspect of the present invention provides a film comprising a microlayer polymer composite layer having a microlayer comprising at least one polymer fluid barrier material and comprising at least one elastomer A microlayer, any layer having one or more other materials, all of which are regularly arranged in the composite layer. The polymeric fluid barrier material and/or elastomeric layer further comprises a shaped nanofiller having an average sheet thickness of up to about 1 nanometer and an average appearance ratio of at least about 200. The invention further provides an enclosure formed from a film of the invention, including but not limited to a permanently sealed, inflated, inflated article comprising a gemstone closure and an intumescent article. The swell may be sealed by a body such as nitrogen, which may be used to inflate or cushion, for example, to inflate a sports ball or provide cushioning for footwear that may be combined with other materials such as clothing or foam ( F〇am) outer layer to form a buffer device. The barrier film preferably has a relatively low gas diffusion rate and can be used for a 4HDP/04002TW/NIKE-replacement page 1129941. Case number: 93132224 Modified on August 28, 2006, the bulge is maintained "permanently" Sealing, that is, maintaining a useful internal pressure for the useful life of the article containing the expansion. One acceptable method for measuring the relative penetration, permeability, and diffusion of different film materials is ASTM D-1434-82-V. The gas diffusion rate of the film is expressed as the amount of gas diffused through the film per unit area and unit time. The gas diffusion rate may be expressed under standard temperature and pressure in units of (cc) (mil/(m2) (24hour), the present invention. The barrier film is preferably less than 1 (cc) (mil/(m2) (24hour). [Embodiment] The following description is merely a preferred embodiment and is not intended to limit the invention and its application. The invention provides a film having at least one layer, the film comprising at least one elastic material and at least one polymer fluid barrier layer, wherein the film has at least one layer of a layer of nano filler, the layered nano filler Having an average thickness of one of up to about 10 nanometers, and an average appearance ratio of at least about one. The film may be a single layer comprising an elastomeric material, a fluid barrier IV layer, and a layered nanoparticle. a filler, but the film preferably has at least two layers. The film preferably comprises at least one layer of an elastomeric material, and at least one layer of a barrier material, wherein the layer of elastomeric material and/or the layer of polymer barrier comprises layered naphthalene Meter a filler having a layered nanofiller having an average thickness of at least about 2 GG and an average appearance ratio. The layered nanofiller is preferably combined with a fluid barrier material, such as a fluid barrier material or The fluid barrier layer of the multilayer film. The elastic material can be - thermoplastic elastomer or rubber, thermoplastic elastomer 4HDP / 04002TW / NIKE - replacement page 1129942 Case number: 93132224 2 〇 August 28, 曰 Correction generally has One or more soft or easy, segmental segments to provide translatability properties and having a hard or rigid segment as a thermoreversible physical crosslink, allowing the polymer to be treated as a thermoplastic material, while in the chamber The elastic behavior is maintained at a temperature. For example, a thermoplastic elastomer has a soft or rubbery polymer segment like a polyester or polyether segment, and a hard or glass-like segment like a polyurethane segment. An ABA block copolymer such as styrene/butadiene/styrene has a similar structure, and the middle of the polymer chain is always a soft or elastic segment (ie, rubber-like) Polybutylene ), and its tail end is a glass-like section (ie polystyrene). Another suitable class of thermoplastic elastomer is dynamic vulcanizate, rubbery phase in the melted thermoplastic phase (rubbery phase) An embodiment of an elastomer suitable for forming an elastic layer, comprising not limited to a polyurethane elastomer, having an aromatic- and aliphatic-based elastomer, a homopolymer having a flexible polyethylene and a polypropylene (homopolymer) And copolymers (cop〇iymer) flexible olefins, styrene thermoplastic elastomers with block copolymers of styrene (ethylene-butadiene) styrene, polyamine elastomers, polyamine-ether elasticity Body, ester-ether and ester-ester elastomers, flexible ionics, thermoplastic hard rubber, flexible polyvinyl chloride homopolymers and copolymers, elastomeric acrylic polymers, and blends thereof Alloys such as polyvinyl chloride and polyvinyl chloride-polyurethane alloys. Rubber which may be extruded prior to crosslinking may be used, with crosslinking after extrusion of the film. The rubber inclusion is not limited to nitrile rubber and butyl rubber. Different elastomeric materials may be combined into a mixture in the same layer, or may be included in separate layers of the film. Particularly suitable are thermoplastic polyester-polyurethane, polyether-polyurethane and 10 4HDP/〇4〇〇2Tvv/nikE-replacement page 1290941. Case number: 93 1 23224 • August 2006 · 28曰 Modified polycarbonate-polyurethane, Including polytetrahydrofuran which is not limited to polyurethane and diol reagent (0〇17七六仕81^(11'(^1^811), polyester, polylactone polyester (especially poly-self) a polycaprolactone diol, or a polycarboxylic acid having a hydroxy group, a polyether or a ring of ethylene oxide and propylene oxide. a polyester prepared from a copolymer of oxyethylene and propylene oxide. These polymer diol-based polyurethanes are composed of polymer diols (polyester diol, polyether diol, polycaprolactone II). Alcohol, polytetrahydrofuran diol or polycarbonate diol), one or more polyisocyanates, and optionally reacted with a chain extension compound. Chain extension as referred to herein The compound has two or more functional groups, preferably two The functional group is reactive with the polyisocyanate group, and the polymer glycol polyurethane is preferably substantially linear (meaning that substantially all of the reactants are di-functional). The present invention is used to form a preferred thermoplastic polyurethane. Polyester diols are generally prepared by polyacids (including their anhydrides and their esters) and polycondensates, which are more condensed and condensed. It is preferred to have a dual functional group, that is, a diacid compound (an anhydrate containing a dibasic acid compound) and a diol (diol) for preparing a substantially linear polyester diol, although it may contain a small amount of a single Mono-functional, trifunctional, and more functional based materials (possibly up to 5 mole percent). Suitable dicarboxylic acids include, but are not limited to, glutaric acid, Succinic acid, malonic acid, oxalic acid, citric acid (phthalic 4HDP/04002TW/NIKE-replacement page 11 1290941 Case number: 93 1 23224 August 28, 2006 Correction Acid), hexahydrophthalic acid, adipic acid, maleic acid, and anhydrate thereof. Suitable polyols are not limited, and the extensions are selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and pentanediol. Glycol), dipropylene glycol ((^口1:€^716116忌17(:〇1), tripropylene glycol (1:140): (^7161^ glycol), tetrapropylene glycol, cyclohexanol (cyclohexanedimethanol), 2-ethyl-1,6-propanediol, 1,4-butanediol, 1,5-butanediol (1) , 5-pentanediol), 1,3-propanediol, butylene glycol, neopentyl glycol, and mixtures thereof. Sometimes there is a small amount of ternary An alcohol or a higher functional polyol such as trimethyl propyl alcohol or pentaerythritol. In a preferred embodiment, the dicarboxylic acid comprises adipic acid and the diol comprises hydrazine. Butylene glycol, a catalyst generally used for esterification polymerization is protonic acid, Lewis acid, titanium And dialkyltin oxides. Polymerization of hydroxydicarboxylic acid compounds also produces polyesters, which may or may not contain a starting polyol. ' ~ Polyether or polylactone diol can be used for preparation. The thermoplastic oxime, 1 ether or t-s-sterol can be made from a starting diol initiator, a glycol such as ethylene glycol or propylene glycol, and an internal vinegar or alkenyl oxide or (Oxirane) chain extension reagent. Suitable chain for the preparation of polylactone = 4HDP/04002TW/NIKE-Replacement page 12 1290941 Case number: 93132224 Modified activating hydrogenate lactone on August 28, 2006. For example, appropriate Inside, the bag, but not limited ε-hexa vinegar inside the vinegar, 10,000 _ ding;:

(butyrolactone) ^ Sl(propriolactone) ^ r-T

Tl\a'J^~6'T^m ' ^ γ-Α 曰 valerolactone, valinolactone, decanolactone, 3 - vinegar, ^ —壬: lactone, R-octanolactone (及其ctan〇ic lact〇ne) and its group can be used in the following chemical formulas for the cyclic lactones of the present invention.

R

Ο 〇 where η is a positive number from 1 to 7, and R is one or more hydrogen atoms or an unsubstituted fluorenyl group ’ contains 7 carbon atoms. The catalyst which can be used comprises a catalyst which synthesizes the above polyester, and the reaction can also be carried out on the molecule which will produce a ring of lactone. The diol starting agent and the epoxide containing poly(10) ethanol are used to carry out the polymerization of the polyurethane, and the compound containing oxirane is preferably a hydrocarbyl oxide. (alkylene oxide) or cyciic ether, especially styrene, propylene oxide, butylene oxide, tetrahydrofuran; The section of the polymer of the extended hydrocarbon-based oxide includes, but is not limited to, propane, 1:2-epoxyhexane, 1-butylene oxide, 2-epoxybutane, "oxygenated, second" Epoxy Ethylene Baked, Glycidyl Ether Glycerin_(Oil_Glycidyl Ether), 1-Epoxy Oxide, Epoxy Isobutyl Osmium, 4HDP/04002TW/NIKE-Replacement Page 13 1290941 Case No.: 93322324 A product obtained by polymerization of a modified oxide), cyclipetene oxide, 1-epoxypentane and a combination thereof, preferably Ethylene Ethylene, Epoxy-C-Athene, and In the composition, the polymerization of the hydrocarbyl oxide is generally basic catalysis, and the reaction is carried out, for example, by adding a hydroxyl initiator, a catalytic amount of caustic, such as sodium bismuth oxide, methanol. Sodium (meth) methoxide or sodium p-butoxide (t〇tassium tert-butoxide), and a sufficient rate of addition of a hydrocarbyl oxide to maintain a sufficient amount of monomer, two or more different hydrocarbyl groups Oxide monomers may be arbitrarily copolymerized because of the coincidental addition and The sequential addition results in a bulk polymerization, preferably a homopolymer or a copolymer of ethylene bromide or propylene oxide. The tetrahydrofuran is polymerized under known conditions to form the following repeating units: —^CH2CH2CH2CH2〇J_4 The terpene is a tertiary oxonium formed by using a counterion such as SbFe-, AsF6-, PF6_, SbCl6-, BF4-, CF3SO3, FS〇3, Cl〇4 for the cationic open % reaction. The polytetrahydrofuran is prepared as a living polymer' and the reaction is terminated when the aforementioned diol having a hydroxyl group is added. The preparation of an aliphatic polycarbonate diol can be carried out by using a diol and a diol. Dialkyl carbonate (such as diethyl carbonate), diphenyl carbonate, dioxane (diox〇lan〇ne) (such as a cyclic carbonate having a five-ring and a six-ring), The reaction is carried out in the presence of an alkali metal catalyst, a tin catalyst or a titanium catalyst. The diol 4HDP/04002TW/NIKE-replacement page 14 1290941 can be used. Case number: 93132224 August 28, 2006 Amendment includes but not limited to Any on Compounds. Aromatic polycarbonates are generally obtained by the genus 纷^?1^11〇1), such as 2,2-phenol decane 〇 0 ^0 [^11〇18), with phosgene or Diphenyl carbonate is prepared. Preferred are polyglycols for the synthesis of polyurethanes, such as the aforementioned polyester diols, having an average molecular weight of from about 300 to about 4,000 (samples as determined by ASTM D-4274), preferably from about 400 to about 30,000. More preferably, it is from about 500 to about 2,000. The polyglycol typically forms the soft segment of the elastomeric polyurethane. The elastomeric polyurethane can be synthesized by one or more of the above polyhydric alcohols, one or more compounds having at least two isocyanate groups, and optionally one or more chain extending agents. The elastic polyurethane is preferably linear, and therefore the isocyanate compound preferably has substantially a difunctional group. Useful isocyanate compounds for the preparation of the thermoplastic polyurethane of the present invention include, but are not limited to, isophorone diisocyanate (IPDI), diterpene bis-4-cyclohexyl enoic acid Methylene bis-4-cyclohexyl isocynate, cyclohexylene diisocyanate (CHDI), m-tetramethyl xylyene diisocyanate (m-TMXDI), p-four Methyl lysine diisocyanate (P-TMXDI), ethyl diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanate, 1,6 - Hexane diisocyanate (hexamethyl diisocyanate or HDI), 1,4-butylene diisocyanate, isopropyl acetonate, 1,4-decyl biscyclohexyl isocyanate (1,4-methylene bis(cyclohexyl isocynate)), various isomers of toluene diisocyanate, separation 15 4HDP/04002TW/NIKE-Replacement Page 1129941 Case No.: 93322224 August 28, 2006曰 氨酸 二 二 diisocyanate and lysine diisocyanate, 4-chloro-1,3-phenylene monoisoester ( 4-chloro-1,3-phenylene diisocyanate), 1,5-tetranaphthalene diisocyanate, 4,4-diphenyldiisocyanate and 1,2,4-triisocyanate Esters, lysine diisocyanates (xdi) and combinations thereof, particularly suitable for diphenylenemethane diisocyanate MDI. Suitable active hydrogen (hydrogen-contained ng) chain extension reagents generally comprise two active hydrogen groups, such as diols, dithiols, diamines, or, for example, alkanolamines, alkylamine thiols (aminoaikyi) A compound having a hydroxyl group, a thiol group and an amine group, such as mercaptan), such as a hydroxymercaptothiol, has a molecular weight of from about 60 to about 400, preferably an alcohol and an amine. Suitable diols typically as extensions of the polyurethane chain include, but are not limited to, 1,6-hexanediol, cyclohexyldidecyl alcohol (CHDM sold by Eastman Chemical Company), 2-ethyl-1,6-hexanediol, Esterdiol 204 (sold by Eastman Chemical Company), 1,4-butanediol, ethylene glycol; and lower oligomer of ethylene glycol, including ethylene glycol, glycerol, Ethylene glycol, pentanediol; and lower oligomeric polymer of propylene glycol, including propylene glycol, glycerol and propylene glycol; 1,3-propanediol, 1,4-butanediol, neopentyl glycol; Aromatic compounds such as hydroquinone and resorcinol (bis(2-hydroxyethyl)ether); lysine-α -α,-diol; bis(2-ethyl)-ethyl phthalate-α-α'-diol; m-amino acid-α-α'-diol and its bis(2-hydroxyl) Ethyl)ether, and combinations thereof. Suitable diamine chain extensions include, but are not limited to, p-phenylenediamine, meta-phenylenediamine, benzidine, ethylenediamine, and their group 16 4HDP/04002TW/NIKE-Replacement Page • 1129094 No. · 93123224 August 28, 2006 correction compound. Other typical chain extensions are diethylenedipropanol, tripropylene glycol, tetrakiol: and butyl groups, preferred extensions 、^, isopropyl, butanediol, pentanediol, such as Mn extensions may also appear - small amounts: a 6-hexanediol and a trifunctional group of glycerol and a monofunctional active hydrogen-containing compound of m butanol or dimethylamine, ίϊ:1: The extender and the monofunctional group compound are preferably 5. The equivalent weight percentage or less based on the total weight of the reaction product and the hydrogen-containing compound used. The reaction is generally carried out by heating the compound to effect the reaction of a polyisocyanate, a polyglycol, and a selective chain extender, such as by a dissolution reaction in a twin-screw extruder. The catalyst comprises an organotin such as stannous 〇ct〇ate or dibutyl tin dilaurate. In general, such as polyglycols of polyester diols, the ratio of the diols to the extensions can vary over a relatively wide range, depending primarily on the hardness desired for the final polyurethane elastomer, for example, polyester diols and extensions. The equivalent ratio may be from 1 ··〇 to 1:12, and preferably from 1··1 to 1:8. Preferably, the diisocyanate is used in a suitable ratio such that the ratio of the total equivalent ratio of the isocyanate to the active hydrogen-containing material is between 0.95:1 and 1·10:1, preferably 〇·98:1 to 1. 04 : 1. The polyglycol segment is typically formed from about 35% to about 65% by weight of the polyurethane polymer, preferably from about 35% to about 50% by weight of the polyurethane polymer. 4HDP/04002TW/NIKE-Replacement Page 17.1290941 Case No.: 93 1 23224 2006 _ August 28曰 Revised in some specific applications, the elastic layer of the film or some layers with a polyurethane mixture is expected, for example when sensitive to hydrolysis This is especially important. For example, the polyurethane comprises a soft segment of a polyether diol or a polyester diol, wherein the repeating unit of the reaction product has more than eight carbon atoms, and can be combined with a polyester diol having eight or fewer carbon atoms or two Mixtures of alcoholic branches, preferably those which do not contain a polyester diol having eight or fewer carbon atoms, or an oxygen atom contacting a repeating unit of tertiary f, up to 30% in the mixture Weight percent soft section. (That is to say based on the polyurethane based on the weight percentage of polyethylene glycol adipate g, and based on the amount of liquid phthalic acid polyester diol). An example of a polyester diol is a polyester diol wherein the reaction product has more than eight carbon atoms, including polyethylene glycol phthalate, poly 1,4-butanediol phthalate, and poly-1,6- Hexanediol phthalate. It is possible to use a single polyurethane with multiple soft sections instead of a mixture of multiple thermoplastic polyurethanes. In one embodiment, the soft section may comprise a soft section of polyester; or a soft section with polyester a polyether polyol that is combined and has a repeating unit of a total of eight or fewer carbon atoms; or a polyether polyol having a repeating unit of f total of more than eight carbon atoms. Preferably, φ is the total number of soft segments having a repeating unit having a total carbon number of more than eight, and is a weight percent of the soft segment contained in the polyurethane of about 3% by weight. In another preferred embodiment, a soft segment comprising at least about 7 percent by number of repeating units of a total of eight or fewer carbon atoms. Examples of suitable commercial elastomers include Elf At〇chem, Polyamines sold by Shangxin PEMAX®, 曰, the self-twisting ether elastomer sold by the trademark jjytrel®, DSM Engineering, Trademark y\ 4HDP/04002TW/NIKE-Replacement Page for sale by RNITEL®18.1290941 Case No.: 93 1 23 224, August 28, 2006 p Modified vinegar-vinegar and S-mystery elastomer, Advanced Elastomeric System, trademark SANT0PRENE® Thermoplastic hard plastics sold, EMS-Chmie, Sumter, SC, elastomeric polyamines sold under the trademark GRILAMID®, flexible polyurethanes sold by Dow Chemical Company, Midland, Ml, trademark PELLETHANE®, and trademarks sold by Bayer TEX IN® And DESTHPAN's polyurethane 'Huntsman' sold by MORTHANE, Noveon sold by ESTANE® polyurethane. The film may also comprise a polymeric barrier material which may be a mixture of elastomeric materials, for example a single layer film, or a multilayer film as a single layer. In this case, a small amount of the polymer barrier material and a large amount of the elastic material are preferred, so that the elastic material is a continuous matrix. Preferably, however, the polymeric barrier material is separated from the layer comprising the elastomeric material as a separate layer. Typically, the polymeric barrier material layer is thinner than the elastomeric material layer such that the film will be pliable and durable. Suitable polymeric barrier materials include, but are not limited to, ethyl ethoxylate, polyglycol, polyvinylidene halide polymers and copolymers, including polyethylene fork gas; polyamine, including non-stereo Polyamide; acrylonitrile, including acrylonitrile-methyl decanoate; polyurethane engineering plastics; polymethyl pentylene resin; ethylene-oxygen oxyethylene copolymer; liquid crystal polymer; polyacetic acid, such as U acid glycol; A quinone imine comprising a polyether quinone imine and a polypropylene quinone imine; and, he is known to have a polymer material having a low gas diffusion rate. Mixtures and grafts of these materials are also suitable materials, and combinations of imines and crystalline polymers such as liquid crystal polymers 4HDP/〇4〇〇2TW/N|KE_ Replacement Page 1129941 Case No.: 93322324 Aug. 28, 2006 revised a composition of decanoic acid glycol and a polyamidamine having styrene. The film may have a layer of one or more fluid barrier materials, or different fluid barrier materials may be included in the film in separate layers. Fortunately, the father-in-law is a polyethylene-ethylene glycol copolymer, especially those having a molar percentage of 25 to 50 having a ethylene-accumulated precursor, and the most preferred molar percentage is 25 to 50. The acetamethylene-vinyl alcohol copolymer is prepared from a known hydrolyzed ethylene-vinyl acetate copolymer. Examples of suitable specific articles include BAREX® as supplied by BP Chemical Inc.; such as Dow Chemical Corp., Midland, Ml.

ISOPLAST® is a engineering plastic; such as the EVAL Company of America (EVALCA), the trademark EVAL®, Nippon Goshei Co., Ltd (USA) of New York, NY, Lisle Illinois, S0ARN0L®, Solvay's CLARENE ®, DuPont's SEALR®0H ethylene-vinyl alcohol copolymer; such as Dow Chemical, trademark SARAN® 2K7, Solvay, trademark IXAN® vinylidene chloride; such as Hoechst Celanese's VECTRA, such as Amoco Chemicals' XYDAR® liquid crystal polymer Mitsubishi Gas Chemical Co., Ltd, Solvay, and Toyobo's MXD6 nylon; such as Mitsubishi's N0VAMID® X21, PA DuPont's SELAR®, General Electric Company's GEL0N A-100 amorphous nylon; Rohm & Haas' KAMAX® Propylene quinone copolymer; polyethyl phthalimide sold by General Electric under the trademark ULTEM®; VINEX polyethylene-vinyl alcohol supplied by Air Product; Phi 1 ips 66 Company supplied, trademark CRYSTALOR, from Mitsui Petrochemical Industries, trademark TPX ® Polymethylpentene Resin. The best commercial ethylene-vinyl alcohol copolymer, for example, EVALCA 4HDP/04002TW/NIKE-Replacement Page 20 1290941 Case No.: 93 1 23224 August 28, 2006 Correction = should have 'approximately 25 mole percentages to a percentage of 48 moles of ethylene, at least a layer of the film or at least a layer of fineness - a polymeric material comprising two f-type nanofillers' layered nanofillers having a di-nano-second degree and at least about - Average appearance ratio. The film comprises a layer of elastic layer and a layer of elastic barrier material of the barrier material layer or both of which have a layer of nano filler, having an average thickness of about 1 〇, and an average thickness of the layer. And an average appearance ratio of at least about 200, the father's hash material is about 丨 nanometer to about 1 () nanometer thickness, respectively, from G. 1 micron to 丨. 5 micron. The average appearance is better than that of the recorded stone soil to about 5 - in the case of the film - the preferred embodiment, the single layer comprises the rubber, the polyurethane polyurethane, the small amount of the (3) amine and the total weight of the composition The percentage is about (10). In the preferred embodiment, the elastomer is in the thermoplastic material, in the other-hybrid or in the elastomer-transferred rubber and the hybrid material. Covalent bonds between the elastomers can be used to promote adhesion of the interface. The n-type nanofiller can be used together with a hydrophilic copolymer to modify it to increase the affinity of the polymeric layered na[iota] (e.g., to facilitate stripping of the layered nanofiller and new stacking. In a better modification, it is the eighteen yards of the top three winds, she is inclined, eight silks, three nails, and the paper layered nano-materials 4HDP/04002TW/NIKE-replacement page 21 1290941 Case number: 93 1 23224 August 2006 28 曰 correction material, and after drying the nano material fine g really wet, adding processing material -, ΐΓΐ ί ί ί 使 秘 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ) a capture (about 4 to about the body barrier properties, this pass f will not affect (four) the film through the moon::,,,,, using traditional materials such as talc or mica, Jiang Zang

St: Translucent;, the degree is increased enough = dimming fish j#, concentric with traditional fillers, lower layered nanofillers and lesser-produced flakes, will improve the modulus of the film =. In the example, the layered nanofiller is incorporated into the polymer to retard the crystallinity of the barrier material. The layered nano-village provides a layer of gas _ scatter rate, no layered nai is not filled, the financial quality does not (four) axis mirror material contribution. The nano-filler can be incorporated into the layer material, for example by knowing that j = (comp〇unding meth〇d). The incorporation of the layered nanofiller can also be used to form layered nanofillers and monomers, or other reagents used for the formation prior to polymerization. As noted, the layered nanofiller can be suitably treated to aid dispersion in the layer material. The extra material used for the month b or the layer of the layer contains a modifier. Such modifiers and additives are, for example, not limited to plasticizers, light stabilizers, hydrolysis stabilizers, heat stabilizers, gloss agents, antioxidants, rheology modifiers, organic anti-blocking (anti-block) Compounds, fungicides, antimicrobial agents (including bactericidal 4HDP/04002TW/NIKE-replacement page 22 1290941 case number: 93322224 August 28, 2006 amendments and the like), 脱,如Μ_η转二剂和Its composition. (4) __ can be formed by transparent coloring such as radiation. Special iridescent inks (mdeSCene) in transparent films can be achieved with pigments of specific effects. Stone"f solution, a formulation, for example, comprises two commercial diammonium-carbohydrate-based hydrolysis stabilizers, as known by

Ρ ΐΓ〇ί J-611'011 f STABAX〇LP STABAX〇L l 1 may be useful for the fc carbon or poly-competition carbon hydrolyzed soybean oil, the total enthalpy of the hydrolytic stabilizer may be less than the layer The total weight is 5%. Plasticization can be included to increase the flexibility and usability of the final product, as well as to enhance the material from the resin form to the film or sheet, for example, but not to define those based on tetraphenyl decyl ester. The plasticizer was confirmed to be useful. Regardless of the mixture of plasticizer or plasticizer, the total amount of plasticizer will generally be less than 20% by weight of all layers, preferably less than 5% by weight of the total layer weight. The inventive film may comprise a microlayer polymer composite layer having at least alternating microlayers of fluid barrier materials as previously described and elastomeric materials as previously described. It is also contemplated that the microlayer polymer composite layer comprises microlayers of different fluid barrier materials and/or microlayers comprising different elastomeric materials, the different layers being arranged in a regular repeat. It is also possible to include layers other than the elastic layer and the fluid barrier layer, and the elastic layer and the fluid barrier layer are alternately arranged in a regular pattern. The microlayer polymer composite layer should have at least about 10 microlayers, and the microlayer polymer composite layer preferably has at least 23 4 HDP/04002 TW/NIKE-replacement page '1290941, . Case number 93122324, August 4, 2006 The modification has about 20 microlayers, and the microlayer polymer composite layer preferably has at least about 3 layers, and the microlayer polymer composite layer preferably has at least about 5 microlayers, and the microlayer polymer composite layer can have A thousand microlayers, as can be understood by those skilled in the art, the number of microlayers depends on a number of factors, such as the particular material selected, the thickness of each layer, the preparation conditions of the multilayer, and the composite of the microlayer polymer. application. The layered layer preferably has from about 1 to about 10 microlayers, more preferably from about 30 to about 1 microlayer, and more preferably from about 5 to about 500 microlayers. The average thickness of each layer of the fluid barrier layer of the microlayer polymer composite layer may be as low as several nanometers (nm), as high as several mils to about 1 micron (micron), and each layer preferably has a 〇.lmil (average thickness of about 2.5 microns), each layer preferably has an average thickness of about 4 mils (about ·i microns) to about 0·lmil (about 2.5 microns), for example, each resistance The barrier material may have an average thickness of about 5 mils (about 1.2 microns) on average. A microlayer having a thinner fluid barrier material can increase the durability of the film. The microlayer polymer composite layer has an average thickness of about 2525 mil (about 6.35 microns) to about i 〇 2 mil (about 2600 microns). The average thickness 'preferably has an average thickness of from about 3 mils (about 75 microns) to about 200 mils (about 0.5 cm), preferably having an average thickness of from about 3 mils (about 75 microns) to about 40 mils (about 〇·lcm). The alternating layers of the structural polymer and the fluid barrier polymer have a major surface 'substantially aligned parallel to the major surface of the composite, and the fluid barrier polymer has a sufficient number of layers such that the microlayer composite has a desired fluid diffusion rate. . 24 4HDP/04002TW/NIKE-Replacement Page 1290941 Case No.: 93322224 2^) August 28, 2006 Correction of this microlayer polymer composite layer can be achieved by using a two, three or five layer feed block. The layered stream becomes a static mixture or layers, the static mixture having a plurality of mixing elements, preferably at least five, geometrically increasing the number of layers, preferably forming a microlayer polymer composite layer The method is approved by Schrenk, et al., U.S. Patent No. 5,094, 793, issued Mar. 10, 1992, the disclosure of which is incorporated herein by reference in its entirety in The method approved on December 14, 1993, which is incorporated herein by reference. The protective layer protects the elastomer and fluid barrier from instability and disintegration during layer formation and multiplication, the protective layer being provided by a softened thermoplastic material to support the exterior 'surface of the composite stream to Forming a protective boundary layer on the wall of the co-extrusion mechanism, this protection & can add specific light or physical properties to the micro-layer polymer composite layer, such as a specific color, including by having a metal or other flake pigment The metal dye obtained in the boundary layer. % Appreciate that the microlayer polymer composite layer is not – it must be a complete layer, the basin is in the plane of the extension, but expects most of it;

The top of the shell is the entire layer and extends to all edges of the dragonfly. Possible unfilled film, suitable long-distance of the expansion. This phase may be a gas-forming formation. The film of the present invention may contain one or more = number of microlayers available for the film, = layer to = material = layer. Preferably, the film comprises at least another layer, which is a layer of 4HDP/04002TW/N|KE_. Replacement page 25 丄290941 Case No.: 93322224 2〇〇6年28月28曰 Correction is a thermoplastic polyurethane. The present polyurethane layer A, and at least the film comprises at least a layer of elastic layer or two A = ammonia vinegar elastomer and two materials. The third material comprises at least a thermoplastic polymer, and the thin material is broken, and has ί, 岐The layered nano-enrichment of this (4)- or a variety of materials tends to 'the axis of the micro-layer system is more flat than the thin county mosquitoes, and the nano-frequency is expected to be drunk. Another feature is that there is an enhanced bond, which is caused by the contact of the material with the _, and the fluid layer of the microlayer polymer composite layer is between the early material layers, and the enhanced bond is generally used by using the material. Appropriate functional groups in adjacent layers may participate in hydrogen bonding. For example, the nitrogen atom or the ruthenium atom in the secret chain is attached to the nitrogen atom of the poly-n-type, which can participate in different hydrogen-bonding groups. Oxygen atoms in the group, silk oxygen and esters in the polyurethane, and chlorine atoms such as PVDC. For example, it is believed that the 氲 bond occurs when the elastic material comprises a polyester diol-based polyurethane, and the fluid barrier material comprises a polymer selected from the group consisting of copolymers of ethylene and ethylene glycol, polyethylene forks Copolymers of chlorine, acrylonitrile and guanamine methyl ester, poly(p-citric acid oxalic acid), aliphatic and aromatic polyamines, crystalline polymers and polyurethane engineering thermoplastics. In addition to the 氲 key, there may be a certain amount of covalent 4HDP/04002TW/NIKE-replacement page 26 1290941 Case number··93123224 ' On August 28, 2006, the key is between the layers, there are still other factors, such as orientation And inducing forces, other known as van der Waals, are believed to originate from the presence of any two molecules of & Dun force, and the dipole-dipole force between the two polar molecules, providing the bond strength of the adjacent layer. It is believed that in addition to these physical forces and chemical forces, the interface structure also contributes significantly to bond strength. Referring now to the drawings, Figure 1 discloses that film 1 () has layers 12, 14, 18 and 20 of elastomeric material, and a polymeric fluid barrier layer 16, layers 12 and 2 are thicker, such as 12-14 mils, having polymer elasticity. The elastomeric material comprised of the body is a thermoplastic polyurethane elastomer, but it may contain traces of other polymeric Lu materials, such as layer 16 of polymeric fluid barrier material. Layers 14 and 18 are more specialized, such as 1-3 mi 1, as the outer layers 12 and 20 and the inner layer, the barrier layer 16 (the phantom layer. The polymer material of layer 14 and layer 18, for example, must be The thermoplastic polyurethane elastomer is composed of a thermoplastic polyurethane elastomer which can condense the human fluid, and the layer 16 of the barrier material has a hydrogen bond, preferably an ethylene-ethylene glycol dimer. The urethane which is formed by the polyglycol ester Between the alcohol group of the ethyl vinegar and the ethylene-ethylene glycol copolymer. At least the layer has a layered nanofiller, preferably the layer 16 〇10, FIG. 2 illustrates that the film has a microlayer polymerization as a core and a barrier layer. Composite 124, the microlayer polymer composite crucible 24 may be 5-7 mm thick, and has alternating layers of polymer barrier layer and elastic material. Layer 112 and 丨^ such as 25-27 mil, the elastic material is mainly polymerized. a composition of a plastid, such as a thermoplastic polyurethane elastomer, but which may have a small amount of other polymeric materials, such as polymeric fluid barrier materials. The layers 114 and 118 are relatively thin, such as a polymer material of a thermoplastic polyurethane elastomer. This film 11〇 has an outer layer (outerskin layer) 122 & 126, Bu 2mil 4HDP/04002TW/NIKE-Replacement page 27 1290941 Case No. · 93 1 23224 August 28, 2006 Revision of Thermoplastic Polyurethane This layered nanofiller is preferably thick and has substantially the same thermoplastic Elastomeric body. At least one layer has a layered nanofiller comprising one or more layers 112, 124 and 120. Figure 3 is a side elevational view of the multilayer film of Figure 2, partially enclosing the microlayer composite layer m - (d), the microlayer polymer composite layer is disclosed as having a thick layer comprising a polymer fluid enthalpy material and an elastomeric material. The polymer fluid barrier material is preferably a copolymer of ethylene and acetylene, such as The layer 140, the thick layer of the elastic material is preferably a thermoplastic polyurethane elastomer, such as layer 142. The layered nanofiller may have two layers, but preferably the layered nanofiller comprises at least a layer of polymer fluid barrier material. The invention further comprises an intumescent, in particular an aerated, inflated material, prepared from a film of the invention or other article comprising an intumescent material. The film of the invention provides for the diffusion of a flexible and resistive fluid, such as an inflation gas. These films may be inflated by a gas such as nitrogen, preferably providing a gas diffusion rate of about 1 〇 cc / m 2 · a ^ n · jay or less. The durable, elastic film of this aerated product can be used in many applications, especially It is an application of an inflator or a cushion. "Durable" means that the film is excellent for resisting fatigue failure, that is, the film is subjected to repeated varicose and/or deformation and recovery without cracking or other failure, and is preferably overcome. Environmental conditions, such as temperature and phase humidity. For the purposes of the present invention, the word "membrane" is used to mean a separate film that separates a fluid, whether a gas or a liquid, from another fluid. A film that is layered or embossed on another article other than the purpose of separating the fluids' is excluded from the film defined by the present invention. The film may be thin or thick, and the film should be thick enough to provide sufficient 28 4HDP/04002TW/NIKE- Replacement Page 1129941 • Case No.: 93322224, August 28, 2006 Correct wall strength, thin enough to provide adequate bending Sex. Preferably, the film has a thickness of from about 20 mils to about 70 mils, more preferably from about 2 mils to about 4 mils, and is a five-layer structure of a car-family, for the intermediate fluid barrier material layer. The edge of the elastic material layer, respectively, is from 0 to 4 mil thick, preferably at least about 〇 5 mil thick, particularly preferably at least about 6 mil thick, and more preferably at least about 1 mil thick; and up to 3 mii thick, preferably Dayo & 5mil thick, especially good for about 2mil thick, better about L 6mil thick. Preferably, the outermost layer is predominantly an elastomeric material having a small amount of fluid barrier material, preferably at least about 7 mils thicker, more preferably at least about 8 mils thick, more preferably up to $9 mils thick; and preferably up to about 2 mils. Thick, especially good for about 丨^丨丨 thick. In particular, the present invention provides an inflated article for use in a footwear, a battery, or a device such as a sports ball, the expansion having a film comprising at least one elastomeric material, at least one polymer stream The bulk barrier material is preferably a separate layer wherein the layered nanofiller has an average sheet thickness of up to about 10 minutes and an average aspect ratio of at least about 200 is present in at least one of the film layers. The film of the present invention has an elastic mechanism characteristic such that it can be overwhelmed and surely absorbed by the intended high force without gradual deterioration or fatigue failure. This film is particularly important in such applications with excellent stability in circulating loads. The barrier material also has a low gas diffusion rate that keeps it inflated, thus providing cushioning and & gas, without periodically refilling and repressurizing the expansion body, the article substantially has a desired life span, thus Permanently sealed. The % bulge can be welded by RF (radio frequency production) to two thin layers of material or a film containing microlayers, especially when the layer is a bipolar material. Non-polar materials such as polyolefins can be used with ultrasonic or heat sealing technology. 4 H D P/04002TW/N | KE-Replacement Page 29 1290941 Case No.: 9332224 Modified on August 28, 2006 Welding. Other known welding techniques can also be used. (10) The ruthenium film can be formed into an expansion by a blow molding process. In general, the second can be formed by first forming a flat film or tube after first pressing the second layer of the flat wire shape, and then, for example, the multi-layered molten material may be co-extruded. Take f as an embryo. , there is a general expectation of the full shape of the expansion and the structure of the

And package _ Guanwei. The mold base is attached to the edge mold position of the mold. Above the model, the opening part of the embryo is Ϊ 人: person, through the pressure of gas or other gases, such as nitrogen / ΐ and t air pressing the mold next to the inner surface of the mold, this thing 吹 _, into _ thin Cooling and hardening in the embryo from the mold, about 30. F to I F, at the same time ^

Moved to the lower part of the mold which has been cut by the first die - L* to =====Bu: The shape of fr may be borrowed

(accumulator-type)^^. ^Γΐ;Γα 'head), X^fBm^(intermittent)^ ; Blowing tube or diligent. Other blowing ii{ silk money method includes ^ forming, vacuum forming, transfer forming, compression into ten ❹ J town t hot melt casting, radio frequency welding and so on. The seals, the seals, and the joints are strong, and the single lifts are aimed at 仏2~., the flattened film can cut t; irr〇 r ^ is the expected outer shape, the two parts of the flat film: the expansion. The film can also be rolled up, recorded, and edged to form a joint to shape the bulk. And in its miscellaneous electric welding 4HDP/04002TW/NIKE- replacement page 30 1290941 Case number: 93 1 23224 Modified on August 28, 2006 ^ This expansion can be sealed with fluid and permanently sealed, the fluid is preferably gas. For example, this expanded, durable, elastic film can be incorporated into the bottom of the footwear. "Durable" means that the film is excellent for resisting fatigue failure, that is, the film is subjected to repeated varicose and/or deformation and recovery without peeling off the interface of the mixed barrier film, preferably across a width. The temperature of the area. Footwear, especially shoes, typically consists of two main masters: the shoe upper and the bottom. The purpose of the upper portion of the shoe is to fit the foot snugly and comfortably, and the upper portion of the shoe is desirably made of a combination of attractive, very durable, comfortable materials and materials. The upper part of the shoe may be made of a typical material, including but not limited to leather black, nylon, and other textile materials. This bottom is constructed of financial materials' designed to provide friction and protect the feet during use. This bottom is also typical of 底部 运 运 运 犹 犹 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 崎 崎 崎 崎 崎 崎 崎 崎 崎 , , , , , , The friction generated by the force. In the running activity produces = force, 2 or 3 times the weight of the wearer, the activity 'playing basketball can produce _ force, for the wearer's weight 1 ° if for these functions, the bottom typically has a cushioned bottom clip ; On, e or inner bottom (inSQle), and an outsole with a friction surface. The swell is preferably applied to the inner bottom of the shoe, i.e., generally transparent. The swell may form at least a portion of the outer surface of the shoe. Preferably, the film is a conventional technique for accommodating a bundle of shoes for a relatively long period of time. _surface. The secret of the Ϊ ί 奈 填料 填料 具有 具有 具有 具有 具有 具有 具有 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 body. In a preferred embodiment, for example, the film will not lose more than about 20% of the initial inflation gas pressure over a period of about 2 years. In other words, the inflated product is initially in a steady state, at about 20 〇 to 22.0 pSi, and should remain at least for a period of about 2 〇 to 18 〇 psi for about 2 years: The cushioning device may be inflated with air, or air or supergas, such as nitrogen. When using a cushioning device in footwear, such as shoes, the inflated material may be inflated, preferably with nitrogen, to an internal pressure of 3 psi. Preferably at least about 5 psi to about 50 psi. Preferably, the expanded material is inflated to an internal pressure of from about 5 psi to about 35 psi, more preferably from about 5 psi to about 30 psi, particularly preferably from about 1 psi to about 3 Torr, but preferably from about 10 psi to about 25 psi. Those skilled in the art should be aware of other non-shoes applications, and the expected and preferred pressures can vary widely, as determined by those skilled in the art. For example, battery pressures can range from approximately 1000 psi. The battery pressure is preferably about 500 psi, and a preferred range of battery applications is from about 200 psi to about 1 psi, but the pressure is as low as about 25 psi. Depending on the design of the battery, the typical pressure of the expander used in sports balls is from about 8 to about 40 psi. After inflation, the inflated portion can be sealed by radio frequency welding to become a permanently sealed and inflated expansion. In order for the expansion to remain permanently inflated, the rate of gas diffusion must be suitably low. In a preferred embodiment, the film of the expanded material has a gas which expands the tendency gas, preferably air or nitrogen, and should be less than 15 cc/m2 · atln · day ' preferably less than about 6 cc/m2·atm·day, In particular, less than about 4 cc/m2 · atm · day 'more preferably less than about 2 · 5 cc / m 2 · atm · day, especially less than about 1.5 cc / m 2 · atm · day, particularly preferably less than about 1 cc / m 2 · atm · day. 32 4HDP/04002TW/NIKE-Replacement Page 1290941 Case No.: 93 1 23224 2006, August 28, 2008 A correction can be used to measure the penetration, penetration and diffusion associated with different layers, called ASTM D-143, which is set in the process. Among them. According to ASTM D-143, nitrogen is the preferred bound gas for many embodiments and as a reference for the analysis of gases and diffusion rates, the film can contain a variety of different gases and/or liquids: batteries 'especially hydraulic batteries It is used in vehicle suspension systems, vehicle brake systems, industrial hydraulic batteries, or other applications where the stress is poorer than the two potentially different bending media. The membrane separates the water cell into two chambers or compartments, one of which contains gas and one of which contains liquid. 〃 In addition to the cushioning devices used in footwear and batteries, it is understood that the films of the present invention have a wide range of applications, including but not limited to expansions for inflatable objects, including such as American football, basketball, and football. ; an inner tube; an elastic floating device such as a test tube or a sputum; as a component of medical equipment such as a catheter balloon; as part of a household item, such as a chair seat, as part of a protective device, including a climbing brace and steel; a support element for a household item, and in particular a support for worn furniture; a part of a vehicle tire, in particular an outer layer of the tire; and as part of a particular device, such as a wheel portion for coaxial or wheeled skates, The invention is further described by the following examples. These examples are for illustrative purposes only and are not intended to limit the scope and scope of the invention. Example 1 Preparation of a thin layer of two single-layer ethylene-vinyl alcohol copolymer [EV0H] comprising a layered nanofiller having a percentage of 5% by weight, replaced by = 4HDP/04002TW/NIKE-page 33 1290941 93 1 23224 Amendment of August 28, 2006

Kuraray/Evaica's ETC_133, with Ab, • soil and two (hardening to the United States C=e treatment) and Cl〇isite 30 a (nano, concentrated and then diluted as follows: y preparation for correction. & some In the high clay, the sample is re-extruded by _/ t, and the sample is re-extruded to reach 5% by weight, and the percentage of clay is reduced. From the second extrusion, the pellets are made. 'The stalking 133 clay naphtha pellets. The barrier properties of the mm are determined in the following manner. The weaved ETC-133 clay nanocomposite pellets are cast (cast film) for gas supply. , go, 玄, 々, a = group W sub-layer rate, · two expansion ϊ: ίτ^ ΐ 2: the gas diffusion rate of the nano-composite layer is compared with the diffusion rate of the iiZ gas, which is recorded by the manufacturer. The results are summarized in Table 1. Sample - mi 1/m2-day-atm) 95 wt· ETC-133/5 wt% Cloisite 15A 5.16 95 wt· ETC-133/5 wt% Cloisite 30A 4.07 ETC-133 (eg Kuraray Institute Report) 5. 76 挤压 Extrusion of ETC-133 Clay Nanocomposite Pills and Thermoplastic Poly 4HDP/04002TW/NIKE-Replacement Page 34 1290941 1290941 Case No.: 93 1 23224 200 6, August 28 曰 corrected, the film is formed into a dense, bulging, and inflated with a milk, such as U.S. Patent No. 5,952, which is incorporated into the bottom of the shoe, as described in U.S. Patent No. 5,952. Example 2 is ^ί^=ΐ^ΕΤ(Η33耻奈钱合丸压,微朴复合复合,妖根#Bc)nket α J^8.2, 〇21^ 1 ? 1 ETC-133 # tsSii~ , LCF1G1 material in the patent example. The micro-layered, "in", inflated, and inflated material is then included in the bottom of the shoe as described in Example 1. The present invention has been described with reference to the preferred embodiments. It will be understood that regardless of Any changes and modifications thereof fall within the spirit and scope of the present invention and the following patent claims. OBJECTIVES OF THE INVENTION The present invention can be illustrated by the following detailed description and the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a multilayer film of the present invention; Figure 2 shows a film; and a multilayer of a microlayer polymer composite layer of the present invention. Figure 3 shows a partial enlarged view of the multilayer film of Figure 2. [Main component symbol description] 10 film 4HDP/04002TW/NIKE-replacement page 35 1290941 Case number: 9 3 1 2 3 2 2 4 August 28, 2006 Revision 12, 14, 18, 20 elastic material layer 16 polymer fluid Barrier layer 110 film 112, 114, 118, 120 elastic material layer 122, 126 outer layer 124 microlayer polymer composite 140, 142 polymer fluid barrier and thick layer of elastic material 4HDP/04002TW/NIKE-replacement page 36

Claims (1)

1290941 Case No.: 9323224 Amendment of August 28, 2006, the scope of application for patents: 1·- kinds of elastic thin purchase (four) Cong), including - elastic material (elast 〇 mate matenal), a polymer fluid barrier material (p〇 The lymericfluidbarrier material) and the layered nanofiller Gan^nar nan〇—fHier), the layered nanofiller has a platelet thickness of up to 1G nanometer, and an average appearance ratio of less than 200 (aSpectrati) 〇) and one of its height and width are from 〇 1 μm to h 5 μm. The film of claim 1, comprising a mixture of the polymer fluid barrier material and the layered nanofiller. 3. The film of claim 2, wherein the mixture is dispersed in a continuous matrix of the elastomeric material. The film of claim 1, comprising at least one elastic layer and at least one barrier layer, the elastic layer comprising the elastic material, the barrier layer comprising the polymer fluid barrier material, wherein at least one layer of the film Further comprising a layered nanofiller having an average thickness of one of up to 10 nanometers and an average appearance ratio of at least 2 (9) and at least one of the height and width of the sub-meter to 1.5 microns. The film according to any one of claims 1 to 4, wherein the elastic material is selected from the group consisting of a polyester elastomer (p〇lyUre廿 along this eiast〇mer), a flexible polyolefin , styrene thermoplastic elastomer, p〇iyamide elastomer, polyamide-ether elastomer, ester-ether and ester-ester -ester) Elastomer, flexible ion (i〇n〇mer), 4HDP/04002TW/NIKE-Replacement page 37 1290941 Case No.: 9332224 Modified a vulcanizate, flexible aggregate on August 28, 2006 A group of poly(vinyl chloride) homopolymers and copolymers, flexible acrylic polymers, and combinations thereof. The film according to any one of claims 1 to 4, wherein the elastic material is selected from the group consisting of thermoplastic polyester-polyurethane, thermoplastic polyether-polyurethane, thermoplastic polycarbonate-polyurethane, and the combination thereof. Group. The film according to any one of claims 1 to 4, wherein the polymer fluid barrier material is selected from the group consisting of ethylene-vinyl alcohol copolymer, polyvinyl chloride, and polyvinylidene. (poly vinylidene) polymers and copolymers, polyamides, acryl〇nitrile polymers, engineering plastics, poly(methy 1 pentene resin), ethylene - A group of carbon monoxide copolymers, liquid crystal polymers, polyesters, P〇lyimides, and combinations of the foregoing. The film of any one of claims 1 to 4, wherein the polymer fluid barrier material comprises an ethylene-ethylene glycol copolymer. The film according to any one of claims 1 to 4, wherein the layered nanofiller has an average thickness of one of from 1 nm to 10 nm, and one of from 2 to 1 Average appearance ratio. The film of any one of items 1 to 4, wherein the layered nanofiller is a montmorillonite clay. 4HDP/04002TW/NIKE-Replacement Page 1129941 Case No.: 93 1 23224 Aug. 28, 2006. The film of claim 1 to 4, wherein the film is 4°/〇 to 10% Weight percent of the layered nanofiller. </ RTI> A permanently sealed, inflated swell (1) 1 &amp; (1), which is a film according to any one of 1 to 11. An swell, wherein the swell is inflated by a gas. 14. An swell comprising the elastic film of claim 1, wherein: the film comprises a microlayer polymer layer a composite layer) having at least 10 microlayers each having a thickness of up to 100 micrometers, the microlayer being alternately between the polymer fluid barrier material and the elastic barrier material; Further, the microlayer or both of the microlayer or elastomeric material of the polymer fluid barrier material comprises the layered nanofiller. The expander of claim 14, wherein the polymer fluid barrier The microlayer of the material comprises the layered nanofiller. The expandable material of claim 14, wherein the elastic material comprises a film selected from the group consisting of polyurethane elastomers, flexible polyolefins, and styrene. Thermoplastic elastomer, polyamine bomb Sexual, polyamine-ether elastomers, ester-ether and ester-ester elastomers, flexible ionics, thermoplastic vulcanizates, flexible polyvinyl chloride homopolymers and copolymers, flexible C: !: 酸酸聚合物, and 4HDP/04002TW/NIKE-Replacement Page 39 1290941 Case No.: 93 1 23224 A group consisting of the above-mentioned compositions was modified on August 28, 2006. A polyarene 7 as claimed in claim 14 The swellable material, wherein the elastic material comprises a sputum body, wherein the swellable material according to claim 14, wherein the elastic material comprises a bismuth, the film is selected from the group consisting of thermoplastic polyester diol polyurethanes, Thermoplastic polyether 1 alcoholic polyurethane, thermoplastic polyether glycol polyurethane, thermoplastic polycaprolactone glycol polyurethane, thermoplastic polytetrahydrofurandiol polyurethane, thermoplastic copolymerized polyurethane, and the above composition The swelling material according to claim 18, wherein the elastic material comprises a swellable polyester diol polyurethane, wherein the swell of the item 19, wherein the polyurethane The gathering The ester diol is a reaction product, and the reaction product is a mixture comprising at least a dicarboxylic acid-anhydride selected from the group consisting of adipic acid and glutaric acid. And succinic acid, malonic acid, oxalic acid, anhydrate of these acids and mixtures thereof, and at least one diol selected from the group consisting of ethylene glycol ( Ethylene glycol), diethylene glycol diethylene glycol, propylene glycol (triethyleneglycol), tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol Glycol), 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-butyl 2HDP/04002TW/ NIKE-Replacement Page 40, 1129094 Case No.: 93 1 23224 Modified on August 28, 2006, an alcohol (1,5-pentanediol), 1,6-hexanediol (1,6-hexanediol) and a mixture thereof Group. The expansion product of claim 14, wherein the fluid barrier material comprises a film selected from the group consisting of ethylene-vinyl alcohol copolymer, polyvinyl chloride, acrylonitrile copolymer, and poly(terephthalic acid). A vinyl ester (p〇lyethyiene terephthalate), a polyamidamine, a crystalline polymer, a polyurethane engineering thermoplastic, and the above composition. The swell of claim 14, wherein the fluid barrier material comprises an ethylene-vinyl alcohol copolymer. The swell of claim 14, wherein the microlayer polymer composite layer comprises at least 50 microlayers. The swell of claim 14, wherein the microlayer polymer composite layer comprises from 10 microlayers to 1000 microlayers. The swell of claim 14, wherein the microlayer polymer composite layer comprises from 50 microlayers to 500 microlayers. The thickness of the micro-layer of the fluid-blocking material is from 0.01 μm to 2.5 μm thick, respectively. The swell of claim 14, wherein the microlayer polymer composite layer has an average thickness of from 75 micrometers to 0.5 centimeters, respectively. 41 4HDP/04002TW/NIKE-Replacement Page 1290941 Case No.: 9332224 Amendment of August 28, 2006 • The expanded material described in Item 14 has a layer of elastic polyurethane. The m film further comprises at least one y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y ^•. The swell of the item 14, wherein the swell is a swell of the id 14 of a gas, wherein the swell is comprised of - including the nitrogen, the expansion of the item The inflation gas is at a pressure of 3 psig (PS1). 33. The swell of claim 14, wherein the swell is permanently sealed. The hull of item 15, wherein the layered nanofiller has an average thickness of one of 10 10 m and an average outer ratio of 2 (8) to 诵. The expansion product described in claim 15 is a ten-layered nano-filler. The swell of claim 15, wherein the film comprises _ 1 〇% by weight of the layered nanofiller. 4 H D P/04002TW/N 丨 KE-Replacement Page 42 1290941 Case No.: 93 1 23224 August 28, 2006 Amendment 37. A shoe comprising at least one of the expansions as claimed in claim 14. 38. The shoe of claim 37, wherein the swell is a portion of the shoe. 39. The shoe of claim 37, wherein the swell forms an outer surface of the shoe. 40. A bulb comprising one of the expandables as claimed in claim 14. 4HDP/04002TW/NIKE-Replacement Page 43 1290941 Case No.: 93 1 23224 August 28, 2006 Amendment VII. Designation of Representative Representatives (1) The representative representative of the case is as shown in Figure 1. (2) Brief description of the symbol of the representative figure: 10 film 12, 14, 18, 20 elastic material layer 16 polymer fluid barrier layer 8. If there is a chemical formula in this case, please show the chemical formula that best shows the characteristics of the invention: none 4HDP/04002TW/NIKE-Replacement page 4