CN101563218A - Laminates of acid polysaccharide films - Google Patents

Abstract

The present invention relates to a laminate prepared in part from a continuous acid polysaccharide film. In various embodiments, the laminate is useful for fabrication as a protective article as it typically is largely impermeable to hazardous chemical and biological agents, but is sufficiently permeable to water vapor that, if worn as protective apparel, it is both protective and comfortable to wear.

Description

The layered product that comprises acid polysaccharide films

Invention field

The present invention relates to partly layered product by the continuous film preparation that comprises acidic polysaccharose.In a plurality of embodiments, described layered product can be used for making protective article, and the preferred chemistry and the biological reagent of impermeable danger basically, but can fully permeate steam.If as the protective garment dress, then wearing not only has protectiveness but also have comfortableness.

Background of invention

For providing individual's protection in case the needs of the structure of virose chemistry and biological reagent are increasing always.The structure that designs impermeable poisonous chemical gas and liquid is known, but when using as clothes, is wearing this type of structure and also can feel sultry, heavy and uncomfortable usually.

Be subjected to the appreciable impact of the vapour quantity of the permeable fabric of going into to form clothes by the comfort level that clothes provided as protective suit dress.The continuous perspire of human body is as the method for control body temperature.When armored fabric hinders steam when human body runs off, the sweating cooling procedure is hindered, and this causes the individual uncomfortable.When protective suit is allowed few or do not have steam to run off, can in very short a period of time, produce great heat stress or thermoplegia.Therefore, wish that except the protection to poisonous chemicals and liquid that highest level is provided, practical chemistry and biological protection suit also should have higher steam transfer rate.Wish that also suitable safeguard structure body weight is lighter, and same high level long-term protection is provided.

The layered product that comprises continuous chitosan films of alternative infiltration is provided in common unsettled U.S. Patent Application Serial Number 11/593,598.Described layered product allows that steam sees through, and provides barrier to the chemistry that is detrimental to health and the infiltration of biological substance simultaneously.

The invention provides the layered product of alternative infiltration, described layered product comprises the continuous film of acidic polysaccharose and can be used on the goods that are used for personal protection.Compare with impermeable goods, it provides the snugness of fit of improvement.

Summary of the invention

One aspect of the present invention is by the method that comprises in layered product that continuous acid polysaccharide films suppresses chemically or harmful reagent passes layered product or structure or permeated by the clothing that it is made on the biology.

Another aspect of the present invention is the safeguard structure body that comprises continuous acid polysaccharide films.In some embodiments, described structure is also to comprise the layered product of one deck fabric at least.

Another aspect of the present invention is the finished product that comprises layered product, and described layered product comprises continuous acid polysaccharide films and one deck fabric at least.Finished product comprises clothing, veil and protective cover.

Another aspect of the present invention is the method that is used to make the alternative layered product that permeates, and described method comprises:

(a) solution of formation acidic polysaccharose;

(b) deposition is enough to form the acidic polysaccharose solution of film amount in substrate, and wherein said substrate is not higher than on base plane substantially expects the outstanding of thickness with the chitosan coating that is transformed into film;

(c) the acidic polysaccharose solution that deposits in the dry substrate, thus continuous acid polysaccharide films formed;

(d) randomly, extra play is deposited on the acid polysaccharide films; And

(e) form and to comprise substrate and acid polysaccharide films and the layered product of one deck fabric at least.

Another aspect of the present invention is the method that is used to make the alternative layered product that permeates, and described method comprises:

(a) solution of formation acidic polysaccharose;

(b) on equipment, deposit this solution that is enough to form the film amount;

(c) deposition of the acidic polysaccharose solution on the dry equipment, thus continuous acid polysaccharide films formed;

(d) randomly, extra play is deposited on the acid polysaccharide films;

(e) remove film from equipment; And

(f) form and to comprise the film and the layered product of one deck fabric at least.

To one skilled in the art, according to following specification and additional claims, these and other aspect of the present invention will be apparent.

The accompanying drawing summary

Fig. 1 is the schematic diagram that shows the structure of the layered product that permeates according to one type the alternative of one embodiment of the invention.

Detailed Description Of The Invention

In context of the present disclosure, will use many terms.

As used herein, term " film " refers to thin and loose structure body, and described structure body can be regulated the material that is in contact with it such as the transmission of gas, steam, aerosol, liquid and/or particulate. Film can be for chemically or physically uniform or heterogeneous. It is thick less than about 0.25mm that film generally is understood to.

As used herein, term " thin slice " or " in flakes " refer at least thick film of 0.25mm.

As used herein, term " acid polysaccharide " both referred to that (1) comprises the polysaccharide of ionizable acidic functionality, also referred to the salt of (2) this kind polysaccharide.

As used herein, term " acid polysaccharide films " refers to comprise by weight the film of at least 50% at least a acid polysaccharide component.

As used herein, term " atresia " expression material or surface only allow that air passes through through molecular diffusion.

As used herein, term " continuous functionalized polysaccharide films " refers to have at least one without the polysaccharide films of hole surface.

As used herein, term " permeable " refers to allow that liquid or gas pass through.

As used herein, term " alternative infiltration " refers to allow that some kind material is by still playing the barrier effect to other kind material.

As used herein, term " layered product " refers to comprise two or more at least in part materials of the parallel material layer of mutual bonding.

As used herein, term " substrate " refers to be formed by solution the material of film thereon.

As used herein, term " equipment " expression only is used to form film and does not become subsequently the substrate of the part of layered product.

As used herein, when being illustrated in and mixing with designated solvent, term " solubilized " forms the visually material of transparent solution. For example, water-soluble material forms transparent solution when mixing with water, and the insoluble material of water can not.

As used herein, at least a acid polysaccharide component of term " acid polysaccharide solution " expression is dissolved in the indication solvent. Yet the material that is insoluble to the indication solvent also can exist.

As used herein, term " makes (no) dissolving " and refers to cause material (no) to be dissolved in designated solvent.

As used herein, term " crosslinked " refers to generate key between the polymer chain, and is namely crosslinked. Crosslinkedly can be ionic bond, covalent bond or hydrogen bond.

As used herein, term " chitosan " comprises the composition based on chitosan, comprises chitosan itself, chitosan salts and chitosan derivative.

As used herein, term " harmful to health " is meant by skin contact, picked-up or breathes result as acute or chronic exposure and causes injury to the people.

In preferred embodiments, acid polysaccharide films and by impermeable basically some biology of its layered product of making and/or chemical reagent.Usually wish that film and layered product are impermeable to some reagent at least 99%, even maximum 100% is impermeable.

In one embodiment, the invention provides the safeguard structure body, described safeguard structure body is made by continuous acid polysaccharide films or the layered product that comprises the alternative infiltration of continuous acid polysaccharide films.Used for the structure of being made by continuous acid polysaccharide films as this paper, " structure " comprises individual layer and the continuous acid polysaccharide films of multilayer.Acid polysaccharide films can be used for making layered product.Described structure can be used in the goods and clothing that the chemistry that is detrimental to health of opposing and biological reagent expose.Specific embodiment comprises by continuous acid polysaccharide films or comprises the finished product that the layered product of the alternative infiltration of continuous acid polysaccharide films is made, comprises clothes product.

In other embodiments, the invention provides by comprise in the layered product of alternative infiltration that continuous acid polysaccharide films suppresses chemically or on the biology harmful reagent pass the layered product of alternative infiltration or pass method by its goods of making or clothing infiltration.

In other embodiments, the invention provides by the layered product manufacturing that in structure or clothing, combines the alternative infiltration that comprises acid polysaccharide films and prevent the method for structure that the harmful chemistry of health and biological reagent are exposed and make the method for clothing.

Because described layered product is alternative infiltration; therefore we find; when this layered product is used to make clothing; provide protective barrier by its structure of making; thereby described barrier can suppress may be harmful chemistry and biological reagent pass layered product and pass the structure infiltration, keep enough water vapor permeable rate to keep the individual comfortable simultaneously.

The layered product of alternative infiltration as herein described comprises continuous acid polysaccharide films.In one embodiment, layered product is to deposit to suprabasil acid polysaccharide films by solution.In another embodiment, layered product is to adhere on the layer acid polysaccharide films on the polyurethane film for example by hot adhesion.In another embodiment, be poured into suprabasil continuous acid polysaccharide films or acid polysaccharide films, or be thermally bonded to the acid polysaccharide films on another layer, by adhesives to one or more layers fabric.Adhesive can adopt the form of bar or preferred point that discontinuous adhesive phase is provided, so that barrier gas and/or the liquid layered product that passes alternative infiltration does not pass through.Fig. 1 shows and can be used for a for example embodiment of the layered product of the alternative infiltration of clothes product.In the embodiment illustrated, described layered product comprises following part: continuous acid polysaccharide films (1); The continuous acid polysaccharide films of confession adheres to the substrate (2) on it; Extra play (3,3 '); Liner (4); Shell (5) and adhesive.Yet the embodiment that is not the layered product of all alternative infiltrations comprises whole part shown in Figure 1.

Continuous acid polysaccharide films

It is distinguishing being used in acidic polysaccharose in the film and the simple polysaccharide of cellulose and dextrin (starch) and so on, because except having relevant with polysaccharide traditionally hydroxyl and acetal group, acidic polysaccharose also have can the acidic functionality of water intermediate ionization (for example-COOH and-SO ₃H).Limiting examples comprises: pectin, alginic acid, propylene glycol alginate, carboxymethyl cellulose, xanthans, gum arabic, karaya, plantain seed, xylan, arabic acid, bassora gum acid, khava natural gum, linseed acid, celluronic acid, lichenin uronic acid, gellan gum, rhamsan gum, welan gum, carrageenan, glycosaminoglycan (for example hyaluronic acid, chondroitin-4-suleate, 6-chondroitin sulfate, dermatan sulfate, keratan sulfate and heparin); And the alkali of these materials, alkaline earth and alkyl (ammonium) salt.Usually, have can be up to about 10,000,000 or higher at least about 3,000 molecular weight and molecular weight for acidic polysaccharose.

When the sour form of acidic polysaccharose when water insoluble (as under the situation of alginic acid and carboxymethyl cellulose), can for example alkali salt (for example mosanom) or (alkyl) ammonium salts be come casting film by the soluble salt of acidic polysaccharose.

Acidic polysaccharose will depend at the suitable concn of cast in the solution how solution will be used and change, and also depend on the molecular weight of acidic polysaccharose, because may need lower concentration for the acidic polysaccharose of higher molecular weight.Different application processes plays best effect to the solution of different viscosities, but normally, solution will comprise about 0.5% acidic polysaccharose to about 15% weight.

Except acidic polysaccharose, also can comprise inorganic filler by its solution for preparing film, its limiting examples comprises glass marble, glass envelope, clay (for example sepiolite, attapulgite and montmorillonite) etc.A spot of this type of filler preferably is less than 10% weight, can be used for strengthening the heat endurance and the modulus of acid polysaccharide films when needed.

Acidic polysaccharose solution by its preparation film can comprise such as additives such as natural polymer, synthetic polymer, crosslinking agent, filler, fire retardant, plasticizer, flexibilizer and stabilizing agents, to strengthen the multifrequency nature of acid polysaccharide films, shrinkage, fire resistance and stability during as intensity, pliability, drying.The typical additive of natural polymer is a chitosan.Chitosan is the common first names of poly-[1-4]-β-D-aminoglucose.It is commercially available acquisition, and chemically derived from chitin, it is poly-[1-4]-β-N-acetyl group-D-aminoglucose.Chitin is then derived from the cell membrane of fungi, the shell of insect (especially shell-fish).Be suitable for and do that the composition based on chitosan of additive comprises chitosan itself, chitosan salts and chitosan derivative among the present invention.The representative example that can be used for chitosan derivative of the present invention comprises N-and O-carboxyalkyl chitosan.

The amount that additive exists adds that based on acidic polysaccharose the gross weight meter of additive is less than 50% weight.

Examples of such additives dissolves in solution, and perhaps they can be used as the insoluble material existence of dispersion.Solution can comprise one or more water-soluble polymers as additive strengthening desired characteristics, as comprise that polyvinyl alcohol is to strengthen pliability.Can add polymer such as chitosan or polymine with basic functionality reacts to form undissolved salt with the sour form of acidic polysaccharose.

Can prepare acid polysaccharide films in the substrate by acidic polysaccharose solution directly is poured into, described substrate will be incorporated in the layered product with film.Alternatively, can be with the acidic polysaccharose solution casting to equipment such as smooth surface for example on glass or the thin polymer film (for example polyester film).If film is poured on the equipment, make film drying so subsequently, take off, in independent step, be attached in the layered product then.

Can solution be administered in the substrate by in the several different methods known in the art any one.For the small-scale production method,, use usually and be coated with the cutter Treatment Solution as the laboratory test sample.The non-limiting of method that can be used to be coated with the plane surface with irregular surface comprises that spraying, dip-coating and rotation are coated with.In commercial scale process, can use the method that includes but not limited to following example that solution for example is administered to movably on the net width of cloth: contrary roller, coiling or Mayer bar, directly and skew intaglio printing, slot die, blade, heat fusing, curtain, be coated with the cutter applicator roll, extrude, air knife, spraying, rotary screen, multilayer slide plate, coextrusion, meniscus, comma and the coating of nick version.These and other proper method is described in " Coating Processes " [the John Wiley ﹠amp of Cohen and Gutoff on the theKirk-Othmer Encyclopedia of Chemical Technology; Sons, the 5th edition (2004), the 7th volume, the 1st to 35 page.] selected method will depend on Several Factors, as treat the speed of the rheology of solution application, the wet film thickness of expectation, mobile substrate and the coating accuracy that requires as gross thickness percentage.

Make applied solution drying by any suitable way known in the art then, as it is dry (in general, referring to Cohen and Gutoff, op.cit.) to be exposed to hot air cabinet, Tad or radiation (for example infrared or microwave).The result of this stage drying is a continuous film.After drying, this type of film still can be water miscible.Water-soluble film provides good water vapour to transmit, but is fit to for the another kind of form of many final uses (as making the layered product of protective garment by it) not as it.Can be by means of by ionomer water-soluble casting film not being dissolved in the solution that film is immersed at least a divalence or trivalent salt.The example of suitable divalence and trivalent salt includes but not limited to CaCl ₂, SrCl ₂, BaCl ₂, ZrOCl ₂, FeCl ₃Deng.Salting liquid is generally about 1% weight in the water to the salt of about 40% weight.To depend on the concentration of concrete acidic polysaccharose kind, salting liquid and the temperature of salting liquid for making film not dissolve required Immersion time, and can under the situation of not cancelling experiment, easily determine by those of ordinary skill in the art.Typical Immersion time at about 1 minute to about 2 hours scope.

Also can pass through covalent cross-linking, for example by the diamines of use carbodiimide-mediated and the coupling of the COOH group on the acidic polysaccharose; Or by the polysaccharide derivates handling film with activating agent (for example 2-chloro-1-picoline iodide) and make the gained intermediate activated through being heated or shining (as United States Patent (USP) 5,676,964 in disclosed), film is made undissolved.

For water-fast acidic polysaccharose, prepare film by the water soluble salt form of acidic polysaccharose and can make water-insolublely by washing then then with sour contact membrane, this is converted into sour form with film from salt form.If stand-by acid-treated film is connected in the substrate, so Suan composition and concentration will be subjected to the influence of base property (for example it is to the reactivity of acid) and treatment conditions (for example temperature and time of contact, still batch methods) continuously.Compare with the pKa of the acidic polysaccharose for the treatment of insoluble processing, suitable acid has low pKa.Usually, acid is 1% to 10% hydrochloric acid or aqueous formic acid by weight.Be following 30 seconds to 3 hours of environment temperature typical time of contact.

Base material

Although the self-supporting acid polysaccharide films can be attached in the protective article, if desired, it can be adhered in the substrate.Depend on substrate and desired use, can use or not use adhesive.Therefore, term " adhesion " comprises by the application such as methods such as gluing, suction or fusions.Referring to Fig. 1, can prepare acid polysaccharide films 1 in the substrate 2 by acidic polysaccharose solution directly is poured into, described substrate will be incorporated in the layered product with film.Also it can be poured into as on the working surface of PETG (PET) film and remove and abandon working surface before or after apply with extra play.In some cases, the substrate itself that can prepare acid polysaccharide films on it can be serialgram or film, and precondition is that substrate enough is used for specific final use to the permeability of steam under service condition.For example, clothes will need higher water vapor permeable rate than tent or oil skin.

Suitable substrate will have at least one smooth surface, promptly not be higher than substantially the acidic polysaccharose coating that is transformed into film is expected the outstanding of thickness on base plane.Therefore, when the expectation thickness of acidic polysaccharose coating is 25 microns than when it is 100 microns, need more smooth substrate surface.

Suitable substrate can be for for example enough being used for the film, thin slice, microporous barrier (promptly wherein typical aperture is about 0.1 to 10 micron the sort of of diameter) of specific final use to the permeability of steam or by the goods of aforementioned any preparation under service condition.The substrate surface that preferably will contact acid polysaccharide films is smooth but also atresia not only.

Suitable base material comprises thin polymer film, comprises elastomer, glassy polymers and those semi-crystalline materials.The substrate characteristics of expectation is that pliability, durability, good moisture transmit and the contraction in water or swelling are minimum or does not have.The example of suitable base material includes but not limited to ionomer, polyolefin and fluoropolymer polymer.

As used herein, term " polyolefin " is meant derived from wherein at least a and is the polymer of monomers of alkene.The suitable non-limiting polypropylene that comprises of polyolefinic example; Polyethylene, for example polyethylene of high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), metallocene catalysis, ultra-low density polyethylene (VLDPE), ultra-high molecular weight polyethylene (UHMWPE), high-performance polyethylene (HPPE); The copolymer of ethene and propylene; The copolymer of derived from ethylene or propylene and at least a monomer, described monomer is selected from propylene, methyl acrylate, ethyl acrylate, n-butyl acrylate, methylmethacrylate, acrylic acid, methacrylic acid and carbon monoxide; And the copolymer of alkene and diene, copolymer as ethene or propylene or ethene and other alkene and following other diene: the linear aliphatic non-conjugated dienes that contains six carbon atom at least is (as 1, the 4-hexadiene) and other conjugation or non-conjugated dienes, as norbornadiene, bicyclopentadiene, ethylidene norbornene, butadiene etc.

Suitable other polymer as base material is an ionomer.As used herein, term " ionomer " be meant inorganic salts group wherein be connected to polymer on the polymer chain (Encyclopedia ofPolymer Science and Technology, the 2nd edition, H.F.Mark and J.I.Kroschwitz edit, the 8th volume, the 393rd to 396 page).Below two kinds of typical ionomer structure bodies are shown in:

Wherein the ratio of m and n is typically about 10 to 100; Promptly only about repetitive of 1% to 9% comprises ionic group usually.Ion M is generally the metal ion such as lithium, sodium, lithium or zinc, but also can be other cation, for example ammonium.Usually, at first make the sour form of polymer, then with comprising the degree that the alkali of expecting metal ion is neutralized to expectation.Poly-(ethene is the methacrylic acid altogether) of part neutralization and poly-(ethylene-co-acrylic) of part neutralization are ionomeric examples, also have sulfonated polystyrene and sulfonated phenylethylene-polyolefin diblock and triblock copolymer equally.Business-like more ionomeric examples are

Thermoplastic resin derives from E.I.du Pont de Nemours ﹠amp; Co., and Inc. (Wilmington, Delaware);

The perfluorinated sulfonic acid TFE copolymer also derives from DuPont;

Perfluorocarboxylic acid salt ionomer is developed in Japan by Asahi Glass Company; And sulfonated ethylene-propylene terpolymers, derive from Exxon.With the sulfonation and copolymerization monomer polymerization of low content with the polyester that strengthens the yarn fabric stainability and polyamide (referring to for example United States Patent (USP) 5,559,205,5,607,765 and 3,389,549) and the sulfonated aromatic polyamide (referring to for example United States Patent (USP) 3,567,632 and 4,595,708), as be used in reverse osmosis membrane and other to select in diffusion barrier those also be to be used for suitable substrate of the present invention.

Suitable fluoropolymer polymer as base material is non-limiting to be comprised by trifluoro-ethylene, hexafluoropropene, a chlorotrifluoroethylene, dichloro difluoroethylene, tetrafluoroethene, vinylidene fluoride, vinyl and fluoridizes those of the polymer of thing or the like and copolymer.For example, fluoropolymer can be the ethylene/propene copolymer of fluoridizing (being commonly referred to as the FEP resin); The dimer of the copolymer of the copolymer of ethene and chlorotrifluoroethylene, ethene and tetrafluoroethene, perfluorovinyl ether/TFE copolymer (" PFA "), vinylidene fluoride/hexafluoropropylene copolymer, vinylidene fluoride/perfluoro (alkyl vinyl ether) and with the terpolymer of tetrafluoroethene; The blend of polyvinylidene fluoride homopolymer (PVDF) or Kynoar and acrylic polymer; Or polyvinyl fluoride homopolymers (PVF), or the like.

If expectation is poured on the hydrophobic surface of micropore, may need or not need surfactant (for example fluorine-containing surfactant) to strengthen wettable so.The example of the hydrophobic substrate of suitable micropore is non-limiting to comprise that microporous polypropylene membrane (for example

2500 and 3400 films, derive from Celgard LLC, Charlotte, North Carolina, USA), (for example PorexLateral Flow Membrane derives from Porex Corporation, Fairburn to microporous polyethylene film, Georgia, USA) and micropore or the expansion PTFE film (Mupor of micropore for example ^TMThe PM9P film derives from Porex Corporation, Fairburn, Georgia, USA; Expanded ptfe (PTFE) porous membrane derives from Yeu Ming Tai Chemical Industrial Co., LTD, Taiwan, Republic of China).

Extra play

Protection layered product as herein described comprises continuous acid polysaccharide films and one deck fabric at least.In due course; extra play (for example second tissue layer or microporous barrier) can be used in the layered product for following purpose: (a) produce the complex structure body that the protection acid polysaccharide films avoids reducing the environment of its performance; and/or (b) produce layered product; and may therefore produce its complex structure body; described structure has except those features that provided by acid polysaccharide films and described at least one tissue layer and also has further feature, and/or (c) improves the performance of final structure body.For example; can additional film or microporous barrier be administered on the outer surface of acid polysaccharide films and substrate (when existing) by coating, heat lamination and alternate manner known in the art; (3,3 ') as shown in Figure 1, avoid dust and liquid or physical hazard with protection acidic polysaccharose and substrate film.The impact and the protection wearer that can use one or more layers ballistic fabric to absorb emitter exempt from injury.

In many final uses especially clothes, continuous acid polysaccharide films (and at the bottom of dependency basis, when existing) is attached in the structure that comprises the material outer layer (" shell " 5 among Fig. 1) that is exposed to environment and/or liner 4.

Can be according to such as rugosity, impact resistance and wear-resisting or tear and give function reasons such as comfort and popular outward appearance to clothes and select outside and internal material respectively.Painted and material patterning also can be used as outer to introduce the camouflage feature in Military Application.Shell and inner lining material be fabric or microporous barrier normally.

Fabric can for woven material or non-woven material (for example by rotation bonding/melt-blown process or the non-woven sheets structure by the electrostatic spinning generation, as be described in for example people's such as Z.-M.Huang Composites Science and Technology (2003), the 63rd phase, the 2223rd to 2253 page).Can prepare fabric by any synthetic or natural fiber that is applicable to the concrete final use of considering.Preferred fabric can and comprise any blend in these by aromatic polyamides, nylon, polyester, cotton, prepares such as but not limited to the blend of nylon and cotton fiber (" NYCO ").As used herein, term " nylon " is meant the polyamide except aromatic polyamides.Aromatic polyamides be wherein at least 85% acylamino-(CONH-) key is directly connected to two aromatic polyamides on the aromatic ring.The fire resistance fibre that comprises aromatic polyamides (preferred maximum 40%) can exert an influence with hot property and comfort level to fabric with the aromatic polyamides blend.Suitable aromatic polyamides can be taked the form of copolymer, and described copolymer can contain nearly other diamines or muriatic other binary acid chloride of binary acid of 10 replacement aromatic polyamides nearly of the diamines of 10 replacement aromatic polyamides.In the fabric of As used herein, be will be, and poly-(poly P phenylene diamine terephthalamide) be preferably to aromatic polyamides (PPD-T) for preferred to aromatic polyamides.Between aromatic polyamides also can use in the present invention, and poly-(metaphenylene isophthaloyl amine) (MPD-I) be preferred between aromatic polyamides.Being particularly useful for of the present invention is respectively with trade mark to aromatic polyamides and an aramid fibre and yarn

With

(E.I.du Pont de Nemours and Company, Wilmington Delaware, USA) and

With

(Teijin Ltd., Osaka, Japan) those of Chu Shouing, and the equivalent product that provides by other company.Usually, although an aromatic polyamides can be used as the part of liner and is used to improve fire resistance, aromatic poly-amide fabric will be used in the shell, and liner will more likely comprise fabric, as polyester, nylon, cotton or their blend.

Film and microporous barrier can be prepared by any synthetic or natural material that is applicable to its concrete final use.Can be used as the film of part of liner or shell and non-limiting poly-(tetrafluoroethene) film that expands that comprises of example of microporous barrier, as with trade mark GORE-

(W.L.Gore ﹠amp; Associates, Inc., Newark, Delaware, USA) those of Chu Shouing; Hydrophobicity microporous polyurethane film is (referring to for example S.

Deng the people, Fibres ﹠amp; Textiles in Eastern Europe, in January, 2005/December, the 13rd (6) phase, the 53rd to 58 page); Micropore (gathering) propylene, for example derive from 3M (St.Paul, Minnesota, USA) or Celgard LLC (Charlotte, NC, USA); Thermoplastic polyurethane film is as with trade mark

Brand Film is by Omniflex (Greenfield, Massachusetts, USA) those of Chu Shouing;

Polyether block amide, (Paris France) sells by Arkema; And DuPont ^TMActive Layer derives from E.I.du Pont de Nemours and Company (Wilmington, Delaware, polyester film USA).

Make

The layered product of alternative infiltration as herein described can use in the following operation known in the art any to assemble: sewing, roll extrusion, the net dress is fixing or the bonding operation, as hot pressing.

Referring to Fig. 1, layer to be assembled comprises acid polysaccharide films 1 and at least one other layer.For example, if acid polysaccharide films is poured on the equipment, just makes film drying so subsequently and take off as the self-supporting film.Can before or after taking off, add other layer from equipment.Can use adhesive such as urethane based adhesives to be connected on another layer (for example substrate, add a cover film, shell, liner) then.Adhesive can be used as following form and exists: pantostrat, precondition are the expection final uses that its moisture permeable enough is used for layered product; The adhesive spots of an array; Or take many alternative forms, as straight line or curve.Applied adhesives comprises spraying or gravure roll in many ways.

In order to come manufacturing structure body or other goods such as clothing by layered product of the present invention, layered product can be clipped between (adding) weaven goods.Can be for example with bounding point or film make between membrane structure and the fabric be bonded as continuous or semi-continuous.Alternatively, can make by for example the edge being stitched together to be bonded as discontinuously, this is the arrangement that is commonly referred to " outstanding lining ".Other discontinuous bonding mode can comprise use

Band or zip.

Purposes

Layered product and continuous acid polysaccharide films itself are alternative infiltrations, have 2kg/m at least ²The moisture transmission of/24h (" MVTR "), and to the transmitance of health harmful substance enough low with prevent to injure, disease or dead generation.Essential concrete transmitance will depend on concrete harmful substance necessarily; For example, NFPA 1994,2006 revised editions require: for mustard gas＜4.0 μ g/cm ²With for Suo Man＜1.25 μ g/cm ²Accumulation infiltration in a hour, two requirements are all satisfied by the continuous acid polysaccharide films that described layered product and they comprise.Therefore, described layered product and continuously acid polysaccharide films itself can be used for making various products or as a part in the various products.These goods comprise that protective garment goods, in particular for clothes, coat or be intended to other article of protecting wearer or user to escape injury.Described injury causes by being exposed to poisonous chemistry and/or biological reagent.The non-limiting material that comprises those reagent that may be used in combatant's environment and be denoted as " poisonous industrial chemistry medicine (TIC) " or " the poisonous raw material of industry (TIM) " of described reagent; Referring to for example Guide for the Selection of Chemical and BiologicalDecontamination Equipment for Emergency First Responders, NIJGuide 103-00, the I volume, by National Institute of Justice, U.S.Department of Justice (October calendar year 2001) publishes, and incorporates this paper into way of reference.Several examples of TIC are phosgene, chlorine, ammonia, parathion and acrylonitrile.Layer in layered product or the layered product can be determined by several different methods the permeability of concrete material, the limiting examples of these methods comprises ASTMF739-91, those that describe in " Standard Test Method for Resistance of ProtectiveClothing Materials to Permeation by Liquids or Gases UnderConditions of Continuous Contact. ".

In one embodiment, clothing can be used to protect the army personnel in case skin is exposed to the chemistry and the biological reagent that may run in combatant's environment.The non-limiting never poison that comprises of examples of such agents, as sarin (" GB; " methyl fluophosphonic acid isopropyl ester), Suo Man (" GD; " the own ester of first fluorinated phosphonic acid uncle), tabun (" GA, " dimethylamino cyanogen phosphinic acid ethyl ester) and VX (O-ethyl-S-[2-(diisopropylaminoethyl) ethyl] methyl thiophosphate); Vesicant agent is as sulfur mustard gas (for example two (2-chloroethyl) sulfide and two (2-chloroethyl sulfo-) methane); Lewisite is as the 2-chlorovinyldichloroarsine; Nitrogen mustard is as two (2-chloroethyl) ethamine (" HN1 "); Teargas and riot control reagent are as bromvbenzy lcyanide (" CA ") and phenyl acid chloride (" CN "); The human disease bacterium is as virus (for example encephalitis viruses, Ebola virus), bacterium (for example rickettsia rickettsii, bacillus anthracis, clostridium botulinum) and toxin (for example ricin (WA), cholera toxin).The human disease bacterium is the microorganism that causes human diseases.

In another embodiment, clothing can be used to protect first response personnel in case the known or unknown chemistry or the biological reagent that may run under the emergency response situation.In another embodiment, article are intended to protect the cleaning personnel to exempt from chemistry or biological reagent injury during the harmful substance response case.Except listed those above, the example of dangerous substance also comprises some pesticide, especially organic phosphate insecticide.

Non-limiting protective garment, rain gear, ski trousers, gloves, socks, boots, footwear and boots cover, trousers, scarf, cap, mask and the shirt that comprises coveralls, protective suit, overcoat, jacket, limited use of this type of clothes, coat or other article.

In another embodiment, described layered product can be used to make protective cover, as oil skin or collective cover, as tent, exempts from the injury of chemistry and/or biological war reagent with protection.

In addition, described layered product can be used in the multiple medical applications as the protection of guarding against poisonous chemistry and/or biological reagent.In one embodiment, described layered product can be used to make and is used to keep healthy workman's clothing, as medical or operation robe, gloves, slippers, footwear or boots cover and headgear.

Embodiment

Specific embodiments of the present invention is shown in following examples.These embodiment based on embodiment of the present invention only be illustrative, and do not limit the scope of claims.

Implication with in an embodiment abbreviation is as follows: " mi n " is meant minute, and " h " is meant hour, and " kg " is meant kilogram, " g " is meant gram, and " mg " is meant milligram, and " μ g " is meant microgram, " oz " is meant ounce, and " yd " is meant sign indicating number, and " mol " is meant mole, " mmol " is meant mM, and " m " is meant rice, and " cm " is meant centimetre, " mm " is meant millimeter, and " μ m " is meant micron, and " mL " is meant milliliter, " μ L " is meant microlitre, and " % weight " is meant percentage by weight, " M _w" be meant weight average molecular weight, " Pa " is meant Pascal, and " mPa " is meant the milli handkerchief, and " cP " is meant centipoise, and " ePTFE " is meant expanded ptfe.Except as otherwise noted, used water is distilled water or deionized water.

Raw material

All raw materials use all when receiving.Snow algin (" mosanom "), from alginic acid and sodium carboxymethylcellulose (mean molecule quantity=700,000 of brown algae; 0.9mol every mole of cellulose of carboxymethyl) derive from Aldrich Chemical Company (Milwaukee, Wisconsin, USA).Propylene glycol alginate (PGA) is with trade mark

Derive from FMC BioPolymer (Philadelphia, Pennsylvania, USA).According to manufacturer's explanation,

GP7530 is by by forming with the alginic acid biopolymer of propane diols reaction 80% esterification.It has 3.8 pH and the viscosity of 135mPa.s in 1% aqueous solution.Carrageenan is with trade mark

Also derive from FMC BioPolymer.According to manufacturer's explanation,

GP 359 Hes

GP 379 is ι-carrageenan, but GP 379 is more flexible than GP 359;

GP 812 is kappa carrageenan.Chitosan is with trade mark

Derive from Primex Ingredients ASA (Norway).According to manufacturer's explanation, Primex

TM-656 has the Brookfield viscosity of 26cP (0.026Pa.s, 1% chitosan is in 1% acetic acid aqueous solution).

The polyester nonwoven substrate

8004 derive from E.I.du Pont de Nemours ﹠amp; Company (Wilmington, Delaware, USA), its for (non-commercial) 0.75mil (19 microns) of experiment usefulness thick take sour form

Perfluorinated sulfonic acid/polytetrafluoroethylene (PTFE) copolymer film.

The microporous polypropylene membrane of 2500,25 micron thickness (55% porosity, 0.054 micron of aperture 0.209x) and

3400, scribble the microporous polypropylene membrane (37% porosity, 0.042 micron of aperture 0.117x) of 25 micron thickness of wetting agent, derive from Celgard LLC (Charlotte, North Carolina, USA).Mupor ^TMPM9P, the micropore PTFE film that 2mil (51 microns) is thick (30% porosity, 1 micron pore size), with PorexLateral Flow film, the microporous polyethylene film that 10mil (0.25mm) is thick (6 to 10 micron pore size) derives from PorexCorporation (Fairburn, Georgia, USA).The expansion PTFE porous membrane that (0.7mil 18 microns) are thick, 2101 types derive from Yeu Ming Tai Chemical Industrial Co., LTD (Taiwan, Republic of China).

Method

The preparation of normal glass plate

All films are poured into

On the glass plate, the surface of described glass plate is water and the strict cleaning of washing agent, alcohol, highly basic and strong acid before using.Following cleaning procedure can be used for embodiment, but other thorough cleaning program is also applicable.Solution washing with Micro-90 laboratory glass wares cleaning agent Glass plate, the water flushing is dried with paper handkerchief then.Cleaning this plate with isopropyl alcohol then opens and dries.Then, the NaOH aqueous solution of 10% weight is coated onto on the plate, it was stopped five minutes, use distilled water flushing, then that blackboard eraser is dried.At last, red fuming nitric acid (RFNA) is coated onto on the plate, it was stopped one minute, wash out with distilled water then.After drying, think that plate is ready to cast with distilled water flushing at last and with soft tissue.

Moisture transmission (MVTR)

Method by the inverted cup method [ASTM E 96 Procedure BW, Standard Test Methods for Water Vapor Transmission of Fabrics (ASTM 1999)] measured derived from MVTR is measured MVTR.For each test, give open-topped container filled with water, earlier with moisture permeable (liquid non-permeate) expansion PTFE film (" ePTFE ") layer, use the sample of MVTR to be determined then, and use woven at last then

Fabric cover layer [5.6oz/yd ²(0.19kg/m ²), handle with durable waterproof final lacquer] the covering opening.With in position three-layer sealed, reverse 30 minutes to regulate these layers, be weighed into immediate 0.001g magnitude, then contact drying nitrogen stream in reversing.After official hour, the sample of weighing again also calculates MVTR (kg/m by following formula ²/ 24h):

MVTR＝1/[(1/MVTR _obs.)(1/MVTR _mb)]

MVTR wherein _ObsBe the observation MVTR of experiment, and MVTR _MbBe the MVTR (measuring respectively) of ePTFE moisture barrier.The value of being reported is the mean value from the result of four repeated sample.

Dimethyl methyl phosphonate (" DMMP ") infiltration

DMMP is as the nontoxic relatively simulation of chemical warfare G-class never poison.Following the carrying out of DMMP infiltration that is used for embodiment hereinafter described: for each measurement, that gives that open-topped container loads onto measured amount comprises the water of 0.100% propane diols as inner GC standard.With sample film and

Weave cover layer [5.6oz/yd ²(0.19kg/m ²), handled with durable waterproof final lacquer] the covering opening.Each layer sealing handled fabric face in position and with the DMMP (2.3mg) of one 2 μ L.Container is put into box 17h that nitrogen the purged DMMP concentration by GC assay determination water then.DMMP with the μ g that measures in water after the 17h reports the result, and the result is the mean value of five repeated sample.DMMP derive from Aldrich Chemical Company and when receiving use.

Embodiment 1

This embodiment shows the preparation of protective mosanom film, not dissolving and ionomer.

Preheating food blending machine cup in the water-bath of boiling place it on the motor of mixer, and the 95g that packs into has been preheated to 80 ℃ distilled water.Add 5g mosanom powder, dissolve (2 to 5min) with the high-speed stirred mixture up to solid then.Then the shallow golden yellow brown solution pressure filtration of thickness is passed Whatman 514 filter paper (20 to 25 micron pore size).Before casting film, make solution at room temperature standing over night to eliminate bubble.This cast solution contains the mosanom of 5% weight and has 6.85 pH.

By using 50mil (1.27mm) 4 square inches (10 square centimeters) to be coated with cutter solution casting is arrived On the glass plate and at room temperature dried overnight prepares the film of two 4 " x 8 " (10cm x20cm).By raising the edge film is mentioned from glass plate with sharp razor blade.Then every film is cut into three onesize pieces, to provide six 4 " x2.6 " (10cm x 6.6cm) films that are designated as 1A to 1F.

Film 1A does not further handle and keeps water-soluble.By dipping 1.5h in 10% hydrochloric acid (1B) or formic acid (1C) aqueous solution film 1B and 1C are not dissolved.Acid treatment is to estimating to make the water-soluble sodium salt of alginic acid change water-insoluble alginic acid polymer into.By dipping 1.5h in the aqueous solution of the following divalent metal salt of 10% weight film 1D to 1F is not dissolved and ionomer: calcium chloride (CaCl ₂, 1D), barium chloride (BaCl ₂, 1E) or zirconyl chloride (ZrOCl ₂, 1F).After the dipping, film 1B to 1F is lain on the glass plate in handle bathing, Jiang Gejiao forces down in case during drying crispatura and shrink, then dried overnight at room temperature.The film 1B to 1F that handled is no longer water-soluble.

Use

Cover layer is measured the MVTR and the DMMP infiltration of passing film 1A to 1F.The results are given in the table 1.

Table 1: mosanom thin film data

Sample	Handle	Thickness (mil (μ m))	MVTR (kg/m 2/24h)	Average DMMP (μ g is in the time of 17h)	DMMP value (μ g is in the time of 17h)
						1A	Do not have	1.2(30)	31.7	3	0、0、13、0、0
1B	HCl	1.2(30)	24.1	23	69、30、14、0、0
						1C	HCOOH	1.6(41)	23.0	12	36、8、14、0、0
1D	CaCl 2	1.6(41)	21.0	0	0、0、0、0、0
						1E	BaCl 2	1.2(30)	24.5	0	0、0、0、0、0
1F	ZrOCl 2	2.0(51)	18.0	0	0、0、0、0、0

Embodiment 2

This embodiment 1) show the comparatively simpler method and 2 for preparing the solution of sodium alginate that is used to pour into a mould) show that thin alginates film can provide better moisture permeable to keep simultaneously the superior of DMMP stopped.

5g mosanom and 95g distilled water at room temperature stirred to spend the night dissolve up to all solids.The solution of sodium alginate of gained 5% weight be thickness but do not have bubble, and color is shallow golden yellow brown.

By using 40mil (1.02mm) to be coated with cutter solution casting is arrived

On the glass plate and at room temperature dried overnight prepares film 2.By raising the edge film is mentioned from glass plate with sharp razor blade.By barium chloride (BaCl in 10% weight ₂) dipping 5min does not dissolve and ionomer free film in the aqueous solution.Film is lain on the glass plate, and Jiang Gejiao forces down in case during drying crispatura and shrink, then dried overnight at room temperature.The film of handling is that 0.8mil (20 μ m) is thick and be insoluble in water.

Use

Cover layer to the measurement result of film 2 is: MVTR=28.1kg/m ²/ 24h and DMMP infiltration=0 μ g in the time of 17h (following five values average: 0,0,0,0,0).But film 2 is than film 1E (table 1) thin 1/3 and have higher MVTR have same superior DMMP resistance.

Embodiment 3

This embodiment has illustrated that it is that initiation material prepares that protection film can replace the sodium salt of alginic acid by alginic acid itself.By adding alkali the alginic acid biopolymer is dissolved in the water.

At room temperature 6.1g (34.9mmol COOH) alginic acid is joined in the water of 94.2g vigorous stirring.Most of solid does not dissolve, and the pH of solution is 2.45.(" TMEDA, " Aldrich Chemical Company, Milwaukee, Wisconsin, USA, as use when receiving) adds up to whole alginic acid dissolvings so that 0.2mL is a with tetramethylethylenediamine.(1.54g, 13.3mmol) TMEDA obtains the thickness pale yellow solution of pH=4.23 afterwards adding 2mL altogether.Agitating solution 10min is so that the bubble effusion.This cast solution contains the alginic acid of 6.0% weight.

By using 30mil (0.76mm) to be coated with cutter solution casting is arrived

Prepare film 3 in 150 ℃ of dry 30min on the glass plate and in filling the baking oven of nitrogen.Dry film is that 1.2mil (30 microns) is thick, and mentions from glass plate by raising the edge with sharp razor blade.Film is not further handled and is kept water-soluble.

Use

Cover layer to the measurement result of film 3 is: MVTR=27.4kg/m ²/ 24h and DMMP infiltration=4 μ g in the time of 17h (following five values average: 0,0,0,0,18).

Embodiment 4

This embodiment has illustrated that protection film can replace the sodium salt of alginic acid or alginic acid to begin to prepare by propylene glycol alginate (PGA).

(PA is USA) by by forming with the alginic acid biopolymer of propane diols reaction 80% esterification (promptly 80% hydroxy-acid group is replaced by propylene glycol ester functional group) for FMC BioPolymer, Philadelphia for ester GP 7530.By adding alkali the PGA ester is dissolved in the water.

Load onto 200g distilled water for the mixer food cup.Add 13g Ester GP 7530 pale powders add the globular solid sodium hydroxide of about 0.2g (NaOH) simultaneously.2min dissolves up to all solids with the high-speed stirred mixture, measures the pH of solution then.The NaOH that adds more parts then stirs 2min behind each the interpolation, reaches 5.9 up to the pH of solution.Gained solution contains the PGA of 6.1% weight and does not at room temperature have bubble basically after the standing over night.Notice that the viscosity of PGA/NaOH solution changes with pH: the solution of pH＜6.5 has the viscosity that is applicable to casting film, and the solution of pH=6.5 to 7.0 shows the viscosity and the not enough cutter that is coated with of viscosity that reduce and drags into film.

By using 50mil (1.27mm) to be coated with cutter solution casting is arrived

On the glass plate and at room temperature dried overnight prepares the film of 4 " x 8 " (10cm x 20cm).By raising the edge film is mentioned from glass plate, be cut into three onesize pieces then, to provide three 4 " x 2.6 " (10cm x 6.6cm) films that are designated as 4A to 4C with sharp razor blade.

Film 4A does not further handle and keeps water-soluble.By respectively at the barium chloride (BaCl of 10% weight ₂) and zirconyl chloride (ZrOCl ₂) the aqueous solution in dipping 1.5h make free (no esterification) carboxylate base ionomer of film 4B and 4C.Film 4B and 4C are insoluble in water after these are handled.

Use

Cover layer is measured the MVTR and the DMMP infiltration of passing film 4A to 4C.The results are given in the table 2.

Table 2: propylene glycol alginate thin film data

Sample	Handle	Thickness (mil (μ m))	MVTR (kg/m 2/24h)	Average DMMP (μ g is in the time of 17h)	DMMP value (μ g is in the time of 17h)
						4A	Do not have	1.2(30)	27.9	18	0、22、52、0、16
4B	BaCl 2	2.0(51)	20.5	3	0、0、0、0、15
						4C	ZrOCl 2	1.6(41)	14.7	9	45、0、0、0、0

Comparative examples A

This comparative example has shown that handling the macropore fabric in the mode that does not produce continuous film can not provide the material with gratifying protective characteristic, as indicated by the DMMP osmotic value.

With adhesive tape with the polyester nonwoven substrate

8004 (E.I.du Pont de Nemoursand Company) adhere to open and flatly

On the surface of glass plate.Using 40mil (1.02mm) to be coated with cutter is poured into the solution of sodium alginate of 5% weight of preparation among the embodiment 2 on the fixed fabric substrate.The solution of cast makes substrate wetting, soaks into fabric, and makes and not only adhere to the downside of fabric but also adhere to film on the glass plate below the fabric.At room temperature after the dried overnight, film/substrate composite is mentioned from glass plate by raising the edge with sharp razor blade.By barium chloride (BaCl in 10% weight ₂) dipping 5min does not dissolve and ionomer the film of support in the aqueous solution.Wash it then with water to remove excessive BaCl ₂, it is lain on the glass plate, Jiang Gejiao forces down in case during drying crispatura and shrink, then dried overnight at room temperature.Film adheres in the substrate and when immersing composite in the water and does not dissolve.

Use

Cover layer to the measurement result that compares film A is: MVTR=26.1kg/m ²/ 24h and DMMP infiltration=262 μ g in the time of 17h (following five values average: 278,229,241,289,273).Relatively SEM (SEM) microphoto of film A confirms that the mosanom polymer is not in porous

Form continuous film in the substrate.On the contrary, in film, observe crack, hole and slit (size be ten to hundreds of micron).

Embodiment 5

This embodiment has illustrated that continuous protection film can prepare in the ventilative substrate of micropore or atresia.

The mosanom cast solution for preparing 5% weight as in Example 2.By using 40mil (1.01mm) to be coated with cutter solution casting is prepared 5A to 5E to the substrate of micropore or atresia, described substrate is adhered to adhesive tape open and flatly On the surface of glass plate.Used substrate is:

2500,25 uncoated micron thickness capillary polypropylenes (5A); Celgard

Scribble surfactant to improve 25 wetting micron thickness capillary polypropylenes (5B); PorexLateral Flow film has the thick microporous polyethylene film of 10mil (5C) in 6 to 10 microns holes; Thick with 0.75mil Film (5D).Under all scenario, mosanom cast solution rests on the top that microporous polymer supports basically, rather than passes completely through the hole infiltration of substrate as in the Comparative examples A.

The film composite material that makes support is dried overnight at room temperature, removes from glass plate then.By barium chloride (BaCl in 10% weight ₂) dipping 5min does not dissolve and ionomer the film of support in the aqueous solution.At last, composite is lain on the glass plate, Jiang Gejiao forces down in case during drying crispatura and shrink, then dried overnight at room temperature.At BaCl ₂After the processing, film sticks in the substrate and when immersing composite in the water and does not dissolve or layering.

Use Cover layer is measured the MVTR and the DMMP infiltration of passing film 5A to 5D.The results are given in the table 3.

Table 3: the mosanom thin film data of support

^*Support member adds the gross thickness of mosanom film coating

Embodiment 6

This embodiment has illustrated that continuous protection film can use and has contained fluorine-containing surfactant and prepare in the substrate of micropore or atresia to improve the wetting cast solution of substrate surface.

Prepare the mosanom cast solution of 5% weight as in Example 2, and in solution, add 0.2g (0.2% weight)

The FSA fluorine-containing surfactant (E.I.du Pont deNemours and Company, Wilmington, DE, USA).Surfactant does not mix fully with cast solution, but seems to form microemulsion.Before cast, make emulsion be divided into two-phase, and use and to contain water and come casting film.

By using 40mil (1.01mm) to be coated with cutter solution casting is prepared 6A to 6D to the substrate of micropore or atresia, described substrate is adhered to adhesive tape open and flatly

On the surface of glass plate.Used substrate is: 2500,25 uncoated micron thickness capillary polypropylenes (6A); (0.75mil 19 microns)

Film (6B); The thick Mupor of 2mil (51 microns) ^TMPM9P PTFE film (6C); And the thick ePTFE film (6D) of 0.7mil (18 microns).Note preceding two kinds of substrate (Mupor ^TMAnd ePTFE) be not implemented the cast solution-wet that lacks fluorine-containing surfactant of example 5, but the cast solution that comprises surfactant that is implemented example 6 is fully wetting.Under all scenario, mosanom cast solution rests on the top of polymer support basically, rather than passes completely through its infiltration as in the Comparative examples A.

The film composite material that makes support is dried overnight at room temperature, removes from glass plate then.By barium chloride (BaCl in 10% weight ₂) dipping 5min does not dissolve and ionomer support film in the aqueous solution.At last, composite is lain on the glass plate, Jiang Gejiao forces down in case during drying crispatura and shrink, then dried overnight at room temperature.At BaCl ₂After the processing, film sticks in the substrate and when immersing composite in the water and does not dissolve or layering.

Use

Cover layer is measured the MVTR and the DMMP infiltration of passing film 6A to 6D.The results are given in the table 4.

Table 4: the mosanom of support member/fluorine-containing surfactant thin film data

^*Support member adds the gross thickness of mosanom film coating

Also scribbling surfactant to improve 25 wetting micron thickness capillary polypropylenes

3400 (6E) and have on the microporous polyethylene film Porex Lateral FlowMembrane (6F) in 6 to 10 microns holes and poured into a mould film.Because the substrate moistening badness all is formed with the inhomogeneous film of particulate under two kinds of situations, for film 6E, MVTR is high in actual measurement, and the DMMP infiltration is also high, thereby indication has formed the film of discontinuous unshielded property.Under the situation of 6F, the difference of MVTR in film is variable, and the DMMP infiltration is very high.

Embodiment 7

This embodiment shows protection film and can be prepared by the cast solution of the mixture that comprises mosanom and chitosan formates polyelectrolyte.Although add not dissolving reagent of acid, divalent metal salt or other, it is water insoluble to be heated to 150 ℃ of films that spend the night.

The mosanom cast solution for preparing 5% weight as in Example 2.Described in the solution of the chitosan of formates such as U.S. Patent Application Serial Number 11/593,598, being prepared as follows of 5% weight:

Preheating food blending machine cup in the water-bath of boiling places it on the mixer motor, and pack into 564g hot water and 36g chitosan (Primex

TM-656) (0.22 mole-NH ₂).In vigorous stirring, and the formic acid of adding 11.5g (0.25 mole) 98% purity (Aldrich Chemical Company, Milwaukee, Wiscons in, USA).Viscosity increases immediately.After stirring three minutes, gained thickness piece is poured into

Heat 1h in the vial and in the water-bath of boiling.Then, coarse filter paper is passed in its pressure filtration.Leave standstill at room temperature after three days that solution is limpid not to have a bubble.

In order to make alginates-chitosan cast solution, give the solution of sodium alginate of 100g5% weight on the food mixer cup and the chitosan soln of above-mentioned 5% weight of 100g.At ambient temperature with the described solution 10min of high-speed stirred.The gained mixed solution is thickness and somewhat inhomogeneous very, because two kinds of polymer are separated and/or form small amount of precipitate.Cast solution contains the mosanom of 2.5% weight and the chitosan formates of 2.5% weight.

By using 40mil (1.01mm) to be coated with cutter solution casting is arrived

On the glass plate and at room temperature dried overnight prepares 4 " x 8 " (10cm x 20cm) film.By raising the edge film is mentioned from glass plate, be cut into three pieces that are designated as 4 " x2.6 " (10cm x 6.6cm) of 7A to 7C then with sharp razor blade.

Film 7A does not further handle and keeps water-soluble.By barium chloride (BaCl in 10% weight ₂) flooding the mosanom component ionomer that makes film 7B yesterday in the aqueous solution, this makes the film of handling water insoluble.By under nitrogen atmosphere, film 7C not being dissolved in 150 ℃ of heated overnight.Heat treatment makes film 7C become dark golden yellow brown from shallow milky white brown.Reaction between the carboxylate base of alginate polymer and the amino of chitosan polymer can be 150 ℃ of generations to form the covalency amido link between polymer molecule.

Use

Cover layer is measured the MVTR and the DMMP infiltration of passing film 7A to 7C.The results are given in the table 5.

Table 5: mosanom/chitosan formates thin film data

Sample	Handle	Thickness (mil (μ m))	MVTR (kg/m 2/24h)	Average DMMP (μ g is in the time of 17h)	DMMP value (μ g is in the time of 17h)
						7A	Do not have	0.6(15)	38.6	0	0、0、0、0
7B	BaCl 2	0.6(15)	32.0	21	22、0、49、7、0
						7C	150℃	0.2(5)	31.3	0	0、0、0、0、0

Embodiment 8

This embodiment shows the preparation of protective carrageenan film, not dissolving and ionomer.

In glass jar, 50g distilled water is heated to 75 ℃.Add 2.5g

GP359 ι-carrageenan pale powder, and stir the mixture up to solid dissolving (16h).The golden yellow brown solution of gained thickness is the carrageenan of 4.8% weight and has 8.49 pH.When making solution be cooled to room temperature, it forms the Thermoreversibly clear gel, dissolves when reheating to 80 ℃ again.The solution storage at room temperature and in the baking oven that is filling nitrogen before the cast soon is heated to 80 ℃.Prepare with the same manner

The solution of GP 379 ι-carrageenan (4.8% weight, pH 8.43) and

The solution of GP 812 kappa carrageenan (4.8% weight, pH8.24).

By before using, carrageenan poured into a mould solution, with and top-pour annotate film

Glass plate and be used for the cutter that is coated with of casting film and in filling the baking oven of nitrogen, place and be heated to 80 ℃ in several hours.Be coated with cutter by the 50mil (1.27mm) that uses preheating hot solution is poured into preheating On the glass plate by every kind of carrageenan formulations prepared from solutions 4 " x 8 " 10cm x 20cm) film.Make film dried overnight at room temperature then.By raising the edge film is mentioned from glass plate, and each film is cut into two onesize pieces, to provide six 4 " x4 " (10cm x 10cm) films that are designated as 8A to 8F with sharp razor blade.

Film 8A (GP 359 ι-carrageenan), 8C (GP 379 ι-carrageenan) and 8E (GP 812 kappa carrageenan) further do not handle and keep water-soluble.By zirconyl chloride (ZrOC l in 40% weight ₂) dipping 1.5h does not dissolve film 8B (GP 359 ι-carrageenan), 8D (GP 379 ι-carrageenan) and 8F (GP 812 kappa carrageenan) in the aqueous solution.At ZrOCl ₂After the dipping, film 8B, 8D and 8F are lain on the glass plate in the bath, Jiang Gejiao forces down in case during drying crispatura and shrink, then dried overnight at room temperature.Film 8B, the 8D and the 8F that handled are no longer water-soluble.

Use

Cover layer is measured the MVTR and the DMMP infiltration of passing film 8A to 8F.The results are given in the table 6.Find not use ZrOCl ₂The carrageenan film of handling (8A, 8C and 8E) is the bad barrier of DMMP and therefore is not useable for security application, and uses ZrOCl ₂The film of handling (8B, 8D and 8F) is proved to be the superior barrier of DMMP infiltration.

Table 6: carrageenan thin film data

Sample	Handle	Thickness (mil (μ m))	MVTR (kg/m 2/24h)	Average DMMP (μ g is in the time of 17h)	DMMP value (μ g is in the time of 17h)
						8A	Do not have	1.4(36)	31.1	92	41、108、79、47、186
8B	ZrOCl 2	2.8(71)	25.7	6	0、31、0、0、0
						8C	Do not have	1.2(30)	26.2	80	90、74、58、110、66
8D	ZrOCl 2	2.4(61)	34.5	0	0、0、0、0、0
						8E	Do not have	1.4(36)	40.8	169	146、189、195、209、 107
8F	ZrOCl 2	1.4(36)	32.9	8	18、0、0、21、0

Embodiment 9

This embodiment shows the preparation of protective carboxymethyl cellulose film and dissolving not.

By rapid mixing 4g sodium carboxymethylcellulose (mean molecule quantity=700,000; AldrichChemical Company, Milwaukee, Wisconsin USA) prepares the cast solution of 4% weight of thickness with 96g water.Be placed on mixture in the bottle and on roller mill, roll and spend the night, up to the solution that obtains not having gel particle.Filtering solution and it is left standstill up to limpid do not have a bubble.

By using 30mil (0.76mm) to be coated with cutter carboxymethylcellulose sodium solution is poured into

The film for preparing 4 " x 8 " (10cm x 20cm) on the glass plate.Make film the pressing plate (pressing off) of heating go up in 100 ℃ at air drying 4 to 8min.Then by raise with sharp razor blade the edge with film from glass plate mention 1/2nd, and remove from glass.This film that is designated as 9A is not further handled and the maintenance water soluble.

Second half of film stayed on the glass plate and is designated as 9B.When still supporting onboard, film 9B is immersed in 10min in 5% hydrochloric acid (HCl) aqueous solution of room temperature.Form weak gel by film; Acid treatment is to estimating that the water-soluble sodium salt with carboxymethyl cellulose changes the water-insoluble polymer that comprises carboxylic acid into.Washing film 9B with water to remove excessive HCl and NaCl salt, is neutral up to the pH of cleaning solution.Make film the pressing plate (pressing off) of heating go up in 100 ℃ at air drying 4 to 8min, mention from glass plate by raising the edge then with sharp razor blade.The colorless film 9B that gained is transparent is water insoluble.

Use

Cover layer is measured the MVTR and the DMMP infiltration of passing film 9A and 9B.The results are shown in the table 7.

Table 7: sodium carboxymethylcellulose thin film data

Sample	Handle	Thickness (mil (μ m))	MVTR (kg/m 2/24h)	Average DMMP (μ g is in the time of 17h)	DMMP value (μ g is in the time of 17h)
						9A	Do not have	About 1 (about 25)	32.1	4	9、0、0、10、0
9B	HCl	About 1 (about 25)	32.9	1	6、0、0、0、0

Embodiment 10

This embodiment shows the preparation of protective pectin films and dissolving not.

By in 200g distilled water, adding the pectin solution that 7g pectin prepares 3.4% weight.At room temperature this solution of vigorous stirring is 3 days.Make then muddy light orange solution at room temperature standing over night to eliminate bubble.

By using 50mil (1.27mm) 4 square inches (10 square centimeters) to be coated with cutter solution casting is arrived

On the glass plate and at room temperature dried overnight prepares two 4 " x 8 " (10cm x20cm) films.Remove the thick dry film of 1mil (25 microns) by raise the edge with sharp razor blade from glass plate.Then film is cut into two onesize pieces, to provide two 4 " x 4 " (10cm x 10cm) films that are designated as 10A and 10B.

Film 10A does not further handle and keeps water-soluble.By at 40% zirconyl chloride (ZrOCl ₂) dipping 5min does not dissolve and ionomer film 10B in the aqueous solution.After the dipping, film 10B is lain on the towel in handle bathing, Jiang Gejiao forces down to minimize crispaturaing and shrink during drying, then dried overnight at room temperature.Film 10B is no longer water-soluble.

Use

Cover layer is measured the MVTR and the DMMP infiltration of passing film 10A and 10B.The results are given in the table 8.

Table 8: pectin films data

Sample	Handle	Thickness (mil (μ m))	MVTR (kg/m 2/24h)	Average DMMP (μ g is in the time of 17h)	DMMP value (μ g is in the time of 17h)
						10A	Do not have	1.0(25)	21.9	0	0、0、0、0、0
10B	ZrOCl 2	1.1(28)	26.7	0	0、0、0、0、0

Embodiment 11

The protective capacities that this embodiment shows pectin films is not subjected to the influence of pectin esterification degree.

Three pectin films (11A, 11B and 11C) are prepared as follows:

Film 11A: at room temperature in the water of 77.2g vigorous stirring, add 2.8g 30% esterify pectin to provide the esterify pectin solution of 3.5% weight.Solution becomes gets muddy and is light orange.By using 50mil (1.27mm) to be coated with cutter 30% esterify pectin solution casting is arrived

The film for preparing 4 " x 8 " (10cm x 20cm) on the glass plate.Make film dried overnight at room temperature.By raising the edge film is mentioned from glass plate then, and remove from glass with sharp razor blade.This film is not further handled and the maintenance water soluble.

Film 11B: at room temperature in the water of 76g vigorous stirring, add 4g 60% esterify pectin to provide the esterify pectin solution of 5.0% weight.Solution becomes gets muddy and is light orange.The same manner that is used to prepare film 11A with description prepares this film.

Film 11C: in the water of 72g vigorous stirring, add 5g 90% esterify pectin to provide the esterify pectin solution of 6.5% weight.Solution be it seems the solution thickness and opaquer more not that is used for film 11A and 11B than preparation.Therefore, the sodium hydrate aqueous solution that in 5mL cast solution, adds 150 μ L, 10% weight.Solution becomes limpider and thickness a little fast.By using 50mil (1.27mm) to be coated with cutter solution casting is arrived

Prepare film on the glass plate.Make film dried overnight at room temperature.By raising the edge film is mentioned from glass plate then, and remove from glass with sharp razor blade.This film is not further handled and the maintenance water soluble.

Use

Cover layer is measured the MVTR and the DMMP infiltration of passing film 11A, 11B and 11C.The results are given in the table 9.

Table 9: esterify pectin thin film data

Sample	The % pectin esterification	Thickness (mil (μ m))	MVTR (kg/m 2/24h)	Average DMMP (μ g is in the time of 17h)	DMMP value (μ g is in the time of 17h)
						11A	30	1.0(25)	29.8	4	21、0、0、0、0
11B	60	1.0(25)	27.1	2	0、0、9、0、0
						11C	90	1.0(25)	25.2	3	0、0、0、0、17

Embodiment 12

This embodiment shows water insensitive protection film can be by the mixture preparation of pectin and chitosan.

With 2g chitosan (Primex

TM-656) be dissolved in the hydrochloric acid (0.1N) of 200g vigorous stirring.With the 2g pectolysis in the water of 50g vigorous stirring.Two kinds of solution are merged and vigorous stirring 1 hour.With solution be heated to 85 ℃ 10 hours up to 56g water evaporation, provide the final cast solution that comprises 1.0% weight chitosan and 1.0% weight pectin.Solution left standstill is spent the night to eliminate bubble.

By using 50mil (1.27mm) to be coated with cutter solution casting is arrived Prepare film 12 on the glass plate.Make the thick film of 0.7mil (18 μ m) dried overnight at room temperature.By raising the edge film is mentioned from glass plate then, and remove from glass with sharp razor blade.This film is not further handled.Soaking 72 hours rear films in water does not dissolve; Yet, it become not only soft but also a little less than.Use

Cover layer to the measurement result of film 12 is: MVTR=42.7kg/m ²/ 24h and DMMP infiltration=0 μ g in the time of 17h (following five values average: 0,0,0,0,0).

Embodiment 13

This embodiment shows the influence of multiple additives to the protective characteristic of pectin films.

Film 13A: under vigorous stirring, in the 3.5% pectin aqueous solution of 50g, add the 0.19mL 50% glyoxylic acid aqueous solution.By using 50mil (1.27mm) 4 square inches (10 square centimeters) to be coated with cutter solution casting is arrived

On the glass plate and at room temperature dried overnight prepares film.Remove the thick film of 1mil (25 microns) by raise the edge with sharp razor blade from glass plate.With membranes submerged 15min in the 40% zirconyl chloride aqueous solution, the water flushing, and dry.

Film 13B: under vigorous stirring, in the 30g 3.5% pectin aqueous solution, add 0.01g polymine (PEI).By using 50mil (1.27mm) 4 square inches to be coated with cutter solution casting is arrived

On the glass plate and at room temperature dried overnight prepares film.Film is heated to 150 ℃ of 2min.Remove the thick film of 1mil (25 microns) by raise the edge with sharp razor blade from glass plate.With membranes submerged 15min in the 40% zirconyl chloride aqueous solution, the water flushing, and dry.

Film 13C: under vigorous stirring with 0.35g glucose and 7.2g pectolysis in 113g water.Solution left standstill is spent the night to eliminate bubble.The same manner that is used for casting film 13A with description comes casting film.With membranes submerged 5min in the 40% zirconyl chloride aqueous solution, the water flushing, and dry.

Film 13D: four (methylol) phosphorus chloride (TK) the fire retardant aqueous solution that under vigorous stirring, in the 30g 3.5% pectin aqueous solution, adds 10 μ L 80%.The same manner that is used for casting film 13A with description comes casting film.With membranes submerged 15min in the 40% zirconyl chloride aqueous solution, the water flushing, and dry.

Use

MVTR and DMMP that cover layer carries out film 13A to D measure.

Table 10: the data that are used to contain the pectin films of additive

Sample	Additive	Thickness (mil (μ m))	MVTR (kg/m 2/24h)	Average DMMP (μ g is in the time of 17h)	DMMP value (μ g is in the time of 17h)
						13A	Glyoxylic acid	1.0(25)	26.0	0	0、0、0
13B	PEI	1.0(25)	30.8	21	75、0、0、30、0
						13C	Glucose	1.0(25)	18.7	13	0、0、0、0、67
13D	TK	1.0(25)	26.0	0	0、0、0

Embodiment 14

BaCl is used in preparation as in Example 2 ₂Carry out the thick alginates film of 1mil (25 μ m) of ionomer.With the polyurethane side of its heat lamination to the preform layered product.Described layered product is made up of the melt polyurethane adhesive and the thick polyurethane film of 9 μ m of nylon-cotton blend fabric, dot matrix style.The MVTR of gained layered product is satisfactory, and does not observe detectable DMMP infiltration after 17h.

Embodiment 15

Two kinds of laminate structure 15A and 15B are prepared as follows:

15A: will with viscoelastic polyurethane chalaza (25% covers)

Nightwear grid (pajamacheck) fabric is bonded on monolithic polyurethane (PU) film (5 to 10 μ m are thick).

15B: will with polyurethane binder point (25% covers)

Braided fabric is bonded on polyurethane (PU) film (5 to 10 μ m are thick).

BaCl is used in preparation as in Example 2 ₂Carry out the thick alginates film of 1mil (25 μ m) of ionomer.Between laminate structure 15A and 15B, under every kind of situation, all make the PU pellicular front film heat lamination to the alginates film.Then with the anti-polybenzimidazoles (" PBI ") that breaks/(derive from Southern Mills with the Gemini trade mark, shell Inc.) covers these samples, and wherein layered product 15A is orientation upwards to aramid fiber blends.

The sample of cutting from the resulting structures body has all passed through the requirement of NFPA 1994,2006 revised editions: for sulfur mustard gas [S (CH ₂CH ₂Cl) ₂]＜4.0 μ g/cm ²With for never poison Suo Man＜1.25 μ g/cm ²Accumulation infiltration in a hour.The MVTR of each sample is 2kg/m at least ²/ 24h.

Claims (36)

1. By comprise in layered product that continuous acid polysaccharide films suppresses chemically or on the biology harmful reagent pass layered product or structure or by the method for its clothing of making infiltration.
2. 2. the safeguard structure body of alternative infiltration, described structure comprise continuous film and one deck fabric at least, and described continuous film comprises by weight at least one acidic polysaccharose composition of at least 50% amount.
3. 3. the structure of the alternative of claim 2 infiltration, wherein said at least one acidic polysaccharose composition comprises one or more following members: pectin, alginic acid, propylene glycol alginate, carboxymethyl cellulose, xanthans, gum arabic, karaya, plantain seed, xylan, arabic acid, bassora gum acid, khava natural gum, linseed acid, celluronic acid, lichenin uronic acid, gellan gum, rhamsan gum, welan gum, carrageenan, glycosaminoglycan; And the alkali of these materials, alkaline earth and (alkyl) ammonium salt.
4. 4. the structure of the alternative of claim 3 infiltration, wherein said at least one acidic polysaccharose composition comprises that one or more are selected from following glycosaminoglycan: hyaluronic acid, chondroitin-4-suleate, 6-chondroitin sulfate, dermatan sulfate, keratan sulfate, heparin; And the alkali of these materials, alkaline earth and (alkyl) ammonium salt.
5. 5. the structure of the alternative of claim 2 infiltration, wherein said structure are to comprise the continuous acid polysaccharide films and the layered product of one deck fabric at least.
6. 6. the structure of the alternative of claim 2 infiltration, wherein said acid polysaccharide films also comprises one or more following members that are selected from: natural polymer, synthetic polymer, crosslinking agent, filler, fire retardant, plasticizer, flexibilizer and stabilizing agent, and wherein said film comprises at least 50% acidic polysaccharose by weight.
7. 7. the structure of the alternative of claim 2 infiltration, described structure also comprises substrate, to this substrate, wherein said substrate is not higher than on base plane and will be transformed into expectation thickness outstanding of the acidic polysaccharose coating of described film described acid polysaccharide films substantially by solution casting.
8. 8. the structure of the alternative of claim 7 infiltration, wherein said substrate is selected from: film, thin slice and microporous barrier.
9. 9. the structure of the alternative of claim 7 infiltration, wherein said substrate is film, thin slice or microporous barrier, and comprises at least a following polymer that is selected from: elastomer, glassy polymers and those semi-crystalline materials.
10. 10. the structure of the alternative of claim 9 infiltration, wherein said at least a polymer is selected from: ionomer, polyolefin and fluoropolymer.
11. 11. the structure of the alternative of claim 10 infiltration, wherein said ionomer is selected from the ionomer of following material: ethylene/acrylic acid copolymer or ethylene/methacrylic acid; Perfluorinated sulfonic acid or carboxylate polymer; Sulfonated polystyrene; Sulfonated ethylene-propylene terpolymers; Sulfonated phenylethylene-polyolefin diblock and triblock copolymer; Sulfonated polyester; And sulfonated polyamide.
12. 12. the structure of the alternative of claim 11 infiltration, wherein said perfluorinated sulfonic acid polymer is the perfluorosulfonic acid TFE copolymer.
13. 13. the structure of the alternative of claim 10 infiltration, wherein said polyolefin is selected from: polypropylene; The polyethylene of high density polyethylene (HDPE), low density polyethylene (LDPE), LLDPE, metallocene catalysis, ultra-low density polyethylene, ultra-high molecular weight polyethylene, high-performance polyethylene; The copolymer of ethene and propylene;

    The copolymer of derived from ethylene or propylene and at least a monomer, described monomer is selected from propylene, methyl acrylate, ethyl acrylate, n-butyl acrylate, methylmethacrylate, acrylic acid, methacrylic acid and carbon monoxide; And the copolymer of alkene and at least a diene.
14. 14. the structure of the alternative of claim 13 infiltration, wherein said and copolymer diene is selected from: the copolymer of ethene or propylene or ethene and other alkene and following other diene: contain linear aliphatic non-conjugated dienes and other conjugation or the non-conjugated dienes of six carbon atom at least, as norbornadiene, bicyclopentadiene, ethylidene norbornene and butadiene.
15. 15. the structure of the alternative of claim 10 infiltration, wherein said fluoropolymer is selected from: trifluoro-ethylene, hexafluoropropene, a chlorotrifluoroethylene, dichloro difluoroethylene, tetrafluoroethene, vinylidene fluoride and vinyl are fluoridized the polymer and the copolymer of thing.
16. 16. the structure of the alternative of claim 15 infiltration, wherein said fluoropolymer is selected from: the copolymer of the copolymer of ethylene fluoride/propylene copolymer, ethene and chlorotrifluoroethylene, ethene and tetrafluoroethene, perfluorovinyl ether/TFE copolymer, vinylidene fluoride/hexafluoropropylene copolymer, vinylidene fluoride/perfluor (alkyl vinyl ether) dimer and with terpolymer, polyvinylidene fluoride homopolymer or the Kynoar of tetrafluoroethene and the blend and the polyvinyl fluoride homopolymers of acrylic polymer.
17. 17. the structure of the alternative of claim 9 infiltration, wherein said substrate is a hydrophobic microporous membrane.
18. 18. the structure of the alternative of claim 18 infiltration, wherein said weave or supatex fabric comprises one or more following members that are selected from: aromatic polyamides, polybenzimidazoles, nylon and cotton.
19. 19. the structure of the alternative of claim 2 infiltration, wherein said moisture transmission is 2kg/m at least ²/ 24h, and at least a transmitance to harmful chemistry of health or biological reagent is enough low to prevent the generation by described chemistry or the caused injury of biological reagent, disease or death.
20. 20. the structure of the alternative of claim 19 infiltration, wherein said chemistry or biological reagent are selected from: never poison, vesicant agent, lewisite, nitrogen mustard, teargas and anti-riot reagent, poisonous industrial chemistry medicine and the poisonous raw material of industry, pesticide, phosgene, chlorine, parathion, acrylonitrile, virus, bacterium and toxin.
21. 21. the structure of the alternative of claim 5 infiltration, described structure also comprises at least one extra play.
22. 22. combine the finished product of structure of the alternative infiltration of claim 2.
23. 23. the finished product of claim 22, described finished product also combine shell and optional liner, described shell and liner comprise at least one following member respectively independently: weaven goods, supatex fabric, film and microporous barrier.
24. 24. the finished product of claim 22, wherein said finished product is selected from: clothing, veil and protective cover.
25. 25. the clothing of claim 24, wherein said clothing is selected from: the protective garment of coveralls, protective suit, overcoat, jacket, limited use, rain gear, ski trousers, gloves, socks, boots, footwear or boots cover, trousers, scarf, cap, face shield, shirt and medical garment.
26. 26. the medical garment of claim 25, wherein said medical garment is selected from: medical or operation robe, gloves, slippers, footwear or boots cover and headgear.
27. 27. the process of claim 1 wherein that described method provides the protection to the army personnel, be exposed to the chemistry and the biological reagent that may run in combatant's environment to prevent skin; To the protection of first response personnel, in case chemistry under the emergency response situation or biological reagent; Or to clearing up personnel's protection, in case chemistry under the harmful substance response case or biological reagent.
28. 28. also comprising, the structure of the alternative of claim 6 infiltration, wherein said acid polysaccharide films be selected from following natural polymer: chitosan itself, chitosan salts and chitosan derivative.
29. 29. be used to make the method for the alternative layered product that permeates, described method comprises:

    (a) solution of formation acidic polysaccharose,

    (b) deposition is enough to the described acidic polysaccharose solution of film forming amount in substrate, and wherein said substrate is not higher than substantially on base plane and will be transformed into expectation thickness outstanding of the acidic polysaccharose coating of film;

    (c) the acidic polysaccharose solution that deposits in the dry described substrate, thus acid polysaccharide films formed;

    (d) randomly, extra play is deposited on the described acid polysaccharide films; With

    (e) form and to comprise described substrate and described acid polysaccharide films and the layered product of one deck fabric at least.
30. 30. be used to make the method for the alternative layered product that permeates, described method comprises:

    (a) solution of formation acidic polysaccharose,

    (b) on equipment, deposit this solution that is enough to film forming amount;

    (c) deposition of acidic polysaccharose solution on the dry described equipment, thus acid polysaccharide films formed;

    (d) randomly, extra play is deposited on the described acid polysaccharide films;

    (e) remove described film from described equipment; And

    (f) form and to comprise the described film and the layered product of one deck fabric at least.
31. 31. the method for claim 29 or 30, wherein said substrate is selected from: film, thin slice and microporous barrier.
32. 32. the method for claim 29 or 30, described method comprise that also being selected from following method by one or more does not dissolve described continuous film: heating; By means of carrying out ionomer in the solution that described film is immersed at least a divalence or trivalent salt; Covalent cross-linking; And contact acid, described acid has the low pKa of pKa than the acidic polysaccharose of waiting not dissolve change.
33. 33. the method for claim 32, described method comprise that described divalence or trivalent salt are selected from: CaCl by means of by ionomer described continuous film not being dissolved in the solution that described film is immersed in divalence or trivalent salt ₂, SrCl ₂, BaCl ₂, ZrOCl ₂And FeCl ₃
34. 34. the method for claim 29 or 30, the concentration of the acidic polysaccharose in the wherein said acidic polysaccharose solution (a) are about 0.5% to about 15 weight %.
35. 35. the method for claim 29 or 30 is wherein used to be coated with cutter coating, spraying, dip-coating or to rotate coating described acidic polysaccharose solution is deposited on the described equipment; Or use following method that described acidic polysaccharose solution is administered in the mobile network width of cloth or the substrate: contrary roller, coiling or Mayer bar, directly and skew intaglio printing, slot die, blade, heat fusing, curtain, be coated with the cutter applicator roll, extrude, air knife, spraying, rotary screen, multilayer slide plate, coextrusion, meniscus, comma or nick version coating process.
36. 36. the method for claim 29 or 30, wherein said acidic polysaccharose solution also comprises and is selected from following any one or a plurality of member: natural polymer, synthetic polymer, crosslinking agent, filler, fire retardant, plasticizer, flexibilizer and stabilizing agent, and wherein described by weight gained film at least 50% be acidic polysaccharose.