DE1952464A1 - Fiber-reinforced synthetic resin film - Google Patents

Description

DR. ING. F. WUESTIIOFF DIPL. ING. G. PULS DR.ETPECHMANN

DR. ING. D. BEHRENS

PATENTANIViLTE

8 MUNICH 9O

6CEiVEIOERSTHASSE 2 TCIKFOX 2208 31

TKX ₁ XOIIAMHASRESSSs

hCxciu

IA-36 931

Description of the patent application

-PAK, Inc., 2 North Riverside Plaza Chicago, Illinois 60606, U.S.A.

concerning

Fiber-reinforced synthetic resin film

Natural sausage casings are made from the intestines in a variety of ways Animals for slaughter, mainly produced by obstacles, pigs and sheep. The intestines are slaughtered from the Cattle taken out and in the usual manner

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cleaned and then with various sausage masses. fills and becomes individual. ⁷ sausages tied, which can then be cooked.

Up until around 1925, practically all sausage casings were natural, made from the intestines of slaughtered animals Sheaths. Since then, various types of synthetic sausage casings have been developed. Some artificial casings are made produced by breaking down animal skin fibers and processing them into a tubular, tough collagen film will. The majority of the artificial sausage casings, however, are made from regenerated cellulose, preferably according to the viscose process, but also according to the copper ammonium process and also by denitrating extruded cellulose nitrate tubing.

Sausage products cut into slices have already met with strong approval from consumers, e.g. 3. Bolognese sausages, salami, etc., which are dispensed in the form of relatively small appropriately sized packs, each pack containing a small predetermined amount of sausage in Σ ^γ όπώ a given number of slices. The reason for this is that the slicing of the sausages is carried out mechanically so that a uniformly thick product is obtained which is easy to pack. In order to obtain a predetermined number of slices in a package of a given weight, the diameter of the sausages must be carefully controlled. During sausage production, a sausage emulsion is poured into the sausage casing, which is then tied off at each end and boiled or boiled and smoked. To make sure that the sausage slices are of the same size, casings are used in the meat product industry

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used known as fiber casings. Fiber casings consist of cellulosic fibers, preferably in the form of a saturating tissue paper, which is soaked with regenerated cellulose and held together by this will. A long-fiber hemp paper is preferably used as the paper, this is also used Soaked in viscose, formed into a tube and treated in a coagulating and regenerating bath, with and forms regenerated cellulose on the paper. The finished product is a regenerated cellulose casing reinforced with fibers, which has a relatively high strength and a relatively low ductility.

For many years, despite the development of competing cheaper plastics, the cellulose casings remained the most frequently used and generally also the most economical casings because cellulose has the properties required in the processing of sausage products, namely good wet and dry strength, low elongation and / or permeability to water vapor and smoke . Some plastics, for example polyethylene, polyvinyl chloride, etc. can be easily processed on foils, but never gave satisfactory sausage casings because they are insufficiently permeable to smoke or water vapor. Most of the other plastics used for packaging purposes, including polyvinyl alcohol, can be easily processed into films with high vapor and smoke permeability, but are too stretchable, especially when wet, to be used as sausage casings. For polyvinyl alcohol films, for example, an elongation of up to 700 % at breaking load in the wet state is characteristic.

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The invention aims at new and improved casings for food, in particular sausage casings, those made of fiber-reinforced polyvinyl alcohol resin sheets; exist and have high strength and low ductility have in · re-moistened state.

It has been shown that the new casings can be produced in a simple manner by using a saturating fibrous web material with an aqueous or organic solution of a polyvinyl alcohol resin or with a melt-extruded film of a polyvinyl alcohol resin impregnated and then makes the impregnating resin in and on the material insoluble and hardens. Long-fiber hemp paper is preferably used as the fiber material; it is either made into a hose * forms and then soaked and post-treated or first soaked and post-treated and then into a tube ' shaped.

The invention now relates to new and improved casings for food, in particular V.'ursthüllen and their manufacturing process. A web of saturating fibrous material, preferably a long fibrous one Hemp paper-comes with either a watery or organic look Polyvinyl alcohol solution or with a heat softened melt-extruded film of a film-forming polyvinyl alcohol resin impregnated and coated and then post-treated to make the polyvinyl alcohol resin in the form of a to make continuous film insoluble, to harden and, if necessary, to dry it. Another insolubilization of the deposited resin by reaction with a

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Crosslinking agents such as formaldehyde are also preferably carried out. The crosslinking agent can Impregnating resin solution or melt can be added or in a further treatment stage with the impregnated Material are brought into contact. The material, which is saturated with polyvinyl alcohol, is either directly from the Impregnation produced in the form of a hose or as a flat sheet material, which is then cut to size in the desired manner and is processed into tubular casings. the finished tubular casings can then be hardened for the last time or with moisture To be subjected to treatment. The required and optional process steps are in the attached The flow diagram in FIG. 1 is indicated by solid or dashed lines.

Fig. 1 is a flow chart showing the characteristic shows successive stages of the method according to the invention schematically; . ■

Fig. 2 is a schematic representation of the production process in the continuous coating of a Continuous web and forming the same into a casing using a polyvinyl alcohol resin solution j

Fig. 3 shows schematically another embodiment of the inventive method for continuous Coating of a fibrous web material and immediate deformation into a tubular casing underneath Use of a polyvinyl alcohol resin solution;

Figures k - 9 show the different application options for a polyvinyl alcohol resin solution on a

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continuous paserbahn material namely

FIG. K shows a doctor blade over an applicator roller; FIG. ■

Pig. 5 a coating machine with an air knife;

Pig. 6 a blanket coater;

7 eTne "roller application machine running in the same direction;

Fig. 8 shows a so-called Gontracoater, i.e. one usual in the same direction ^ roller application machine and

9 shows a three-roll application machine with direct Assignment;

Fig. 10 shows schematically how a fibrous web material with melt-extruded polyvinyl alcohol resin is continuous is coated and impregnated and formed directly into a shell;

Fig. 11 shows schematically another embodiment) form of the method according to the invention, in which a flat fiber web material ,! initially with melt-extruded Polyvinyl alcohol resin is coated and impregnated and only then shaped into a tubular casing.

Monaural ethanol is available as a free compound not known. All attempts to produce free vinyl alcohol resulted in a rearrangement of the compound to acetaldehyde. Technically, polyvinyl alcohol resins are usually obtained by hydrolysis of polyvinyl compounds

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produced which contain aliphatic or aromatic vinyl esters, including vinyl polymers such as polyvinyl ester homopolymers, for example polyvinyl acetate, polyvinyl propionate, polyvinyl benzoate and others; and also carboxylated polyvinyl ester polymers, for example the compounds obtained by copolymerizing a vinyl ester such as vinyl acetate, vinyl propionate and vinyl benzoate with an ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid and shark acid. The extent of hydrolysis is controlled in order to obtain products with the desired degree of OH group substitution. Vinyl alcohols prepared in this way and usable for the invention have a degree of substitution of at least about 20 %, based on the OH group content; The degree of substitution is usually in the range from about ho to about 99 »99 #, the latter number indicating the maximum hydrolysis effectiveness that can be achieved in industrial production. Among the resins containing carboxyl groups, the resins with a degree of substitution of up to about 25 %, preferably in the range of about 0.1-10%, based on the carboxyl groups, can be used for the Zitfecke according to the invention.

The polyvinyl alcohol resins to be used according to the invention must be reshaping resins, ie have a degree of polymerization of at least about 800. Such resins are known in and by a viscosity of at least b cP, for example in the range of about 65 cP to about k- about intended for k- wt .- # aqueous solutions at 20 ⁰ C, usually in an Ostwald-Fenske Viskoneter . These properties are necessary so that * the saturating fiber material is sufficiently soaked and the insolubilized dried film has the desired strength and wet strength. In general, the molecular weight and OH group content of the increase

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Polyvinyl alcohol, its solubility, but its film strength and melting point to _e For example, resins with an OH-group substitution degree above about 95 $ less soluble and melt at higher temperatures and form films which are very wet strength even without crosslinking. The crosslinking, however, makes these and other resins even stronger and less sensitive to water and accordingly, according to the invention, the resin in the film is preferably crosslinked

In the embodiments of the method according to the invention, in which the fibrous web material with a polyvinyl alcohol resin solution is brought into contact and soaked with it, the solvent of the resin solutions used be any aqueous or organic liquid in which the respective Polyvinyl alcohol resin used is soluble (e.g. with the formation of viscous solutions containing 1-40 wt .- ^ Polyvinyl alcohol resin. Which solvents are preferred in individual cases for certain uses depends primarily depends on the particular polyvinyl alcohol resin used.

. For example, polyvinyl alcohol resins dissolve

* with a lower degree of OH group substitution

(SG) of, for example, not over $ 80, by a wide margin Range in organic solvents, including the different solubility in anhydrous organic solvents Liquids fall, for example in alcohols such as methanol, ethanol and isopropanol; Ethers like that Monomethyl, monoethyl, monobutyl and diethyl ethers of ethylene glycol and diethylene glycol; Ketones such as acetone, methyl ethyl ketone, diacetone alcohol, methyl isobutyl ketone and cyclohexanone; Esters such as ethyl acetate,

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'952464. ,.

Methyl acetate, and n-butyl acetate; chlorinated compounds such as carbon tetrachloride and ethylene dichloride; Hydrocarbons such as benzene and toluene; Nitro compounds such as nitrobenzene and heterocyclic compounds such as dioxane and tetrahydrofuran and water-miscible liquid mixtures which contain any of the organic solvents mentioned. In this context it should be pointed out that the term "organic solvent" encompasses miscible mixtures of water and organic solvents which contain sufficient organic solvent to change the solubility properties of water alone, for example if at least 10 percent by volume of the total solvent is organic . In addition, polyvinyl alcohol resins with a degree of substitution of up to about 80 % are soluble in aqueous alkaline media. Preferred embodiments of such alkali-soluble resins, which are used according to the invention due to the improved overall properties of the films formed from them, are the resins with a degree of OH group substitution of at least about 10 %.

On the other hand, as stated above, the solubility of the resin in general and in hydrophobic liquids in particular decreases with increasing OII group content. Resins with a higher degree of OH group substitution, for example over about 80 %, are less soluble in the organic solvents described above, but can advantageously be dissolved in aqueous solvents and the more hydrophilic organic solvents, for example alcohols and mixtures thereof. V / ater is a particularly preferred one

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Solvents for such resins with a degree of OH group substitution of at least about 98 %. Particularly useful organic solvents for these and other resins with a high degree of substitution are alcohol-water mixtures having a volume ratio of alcohol to water of at least 0.1: 1, wherein the alcohol is a lower alkanol such as methanol or ethanol.

The heat sensitivity of polyvinyl alcohol resins is another factor that influences the choice of solvent. During the final drying of the impregnated webs produced according to the invention, the highest possible temperatures and / or reduced pressures should of course be avoided. Therefore, in which a solvent carrier used to impregnate the Paserbahn, in the embodiments of the process, preferably a solvent which is volatile under Normalbedingung'en, 'for example, a solvent whose boiling point is not (at 760 mm Hg) over 10O ⁰ G .

In the embodiments which use Provide a solvent, the polyvinyl alcohol resin solution is in any known manner on the Web material applied. In general, a web material becomes continuous (e.g. upwards, downwards or horizontally) past a corresponding application device for the resin and. with this brought into contact. The soaked and coated

As already mentioned, Paserbahn can already be closed

tubular casings be deformed or the obtained flat material will be added at a later date Envelopes that have a seam, joined together, in both cases the applied polyvinyl

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alcohol copolymer from the fibrous web material through a Corresponding treatment made insoluble and can then optionally and will also be preferred by Reaction made further insoluble with an appropriate crosslinking agent.

The polyvinyl alcohol resin on the saturated fiber web materials coated with resin solutions according to the invention can be converted to the insoluble state with the help of all suitable measures. The modes of operation that outweigh these transfers to an insoluble state are preferred act by removing the solvent from the resin solution impregnated web. According to a Embodiment is the solvent from the with Solution-impregnated web is removed by passing the impregnated web material through a coagulating bath before the polyvinyl alcohol resin is regenerated. The composition of preferred coagulating baths varies depending on the resin and solvent used but generally either aqueous or organic solutions x of acids, salts and their mixtures, for example sulfuric acid, ammonium sulfate and their mixtures or organic liquids (i.e. non-soluble diluents) in which the resin used is only partially soluble or completely insoluble and which cause the resin to coagulate. For example, acidic highly concentrated te aqueous salt solutions, for example those containing sulfuric acid concentrated ammonium sulfate solutions are particularly suitable to remove polyvinyl alcohol resins from their aqueous To regenerate solutions. Particularly useful for coagulating polyvinyl alcohol resins from organic Solutions, for example from aqueous-alcoholic

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Solutions are regeneration baths that are non-dissolving Contain diluents, for example acetone or benzene, which are more organophilic than organic Solvent.

* According to other preferred embodiments in which the web material is impregnated with a resin solution, the insolubility of the resin is effected by evaporation of the solvent, especially if volatile solvents are used for the resin solution under normal conditions. Polyvinyl alcohol resin films containing volatile solvents will bubble at elevated temperatures. Accordingly, the solvent is preferably carried out at moderate temperatures, for example in the range of 100 - 120 ⁰ C evaporated, obxvohl higher temperatures may be used if the contact time is short. Reduced prints can also be applied if this appears necessary or desirable. However, by choosing a suitable volatile solvent, the use of a vacuum can be avoided. The resin-impregnated sheet material is heated directly or indirectly by conical flow, irradiation, or in any other suitable manner. It is very useful if the web material is brought into contact with a hot inert gas, for example air.

When applying the polyvinyl alcohol resin to the fiber web material from solutions, a crosslinking agent is preferably also provided which reacts with the deposited polyvinyl alcohol during drying and curing in the heat, so that a film is produced on and in the fiber web that is insoluble in water and is relatively insensitive to this. According to a preferred procedure, a soluble crosslinking agent is added and the _{Tränkharζlösung:} then in drying the impregnated haterials

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activated. The polyvinyl alcohol resin solution can also be applied first and then the resinous material in a further operation with a solution of the crosslinking agent sprayed, soaked in or otherwise treated with it, using the same or a different solvent than is used in the resin solution. As a crosslinking agent, the usual agents come into question Form crosslinks between the polyvinyl alcohol molecules. Examples of such substances that one or several reactive functional groups per molecule contains aldehydes such as formaldehyde, glutaraldehyde, glyoxal and others; Polymethyl oil compounds such as water-soluble Formaldehyde-amine and formaldehyde-amide condensation products, for example dimethylolurea, trimethylolmelamine and liquid urea-formaldehyde resins; Diisocyanates such as the diisocyanate of dimerized linoleic acid; ', ^ f-, V-methylenebis (cyclohexyl isocyanate) and others; Polyepoxides such as uterine diepoxide and others; Polyamide epichlorohydrin resin; Acid halides such as adipic acid chloride, Sebacic acid chloride and others as well as polymeric ketenes e.g. 3. the diketene of dimerized linoleic acid. . The less responsive Crosslinking agents can be applied in a mixture with the impregnating resin solution. When more responsive Crosslinking agents are used, so * d.rd first of all Fiber web material soaked with the resin solution and then treated with the crosslinking agent in a further operation, preferably before drying and curing. If necessary or desired, a catalyst for the Crosslinking agents are added, either in the Resin solution, into the crosslinking agent solution, or separately from both.

In the embodiments of the method according to the invention, the fiber web material with a multiple marriage

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melt-extruded (melt-cast) polyvinyl alcohol resin is impregnated and coated, the film-forming polyvinyl alcohol resins are preferably those with a degree of OH group substitution of at least

about 60 % used. If the melt-castable

If resins contain carboxyl groups, a maximum degree of substitution with respect to the fully ionic carboxyl groups of about 5 % is preferred, in particular about 0.5 %. These resins can easily be extruded into film-like coatings on the saturating fibrous web material which penetrate the material and ultimately form films in and on the web material which have the desired strength and wet strength. As already indicated, with increasing molecular weight and OH group content, the solubility decreases and the film strength increases. Film-forming resins with a degree of QH group substitution above about 95 %, for example, if they are appropriately softened, can be extruded into films which are quite resistant to moisture even without crosslinking. As in the case of the films applied from solutions, however, these or other hot-melt-extruded resins become stronger and less sensitive to water as a result of the crosslinking, and accordingly the hot-melt-extruded resin films are also preferably crosslinked.

On the other hand, very high molecular weight polyvinyl alcohol resins can present difficulties because the melting point of the resin increases with molecular weight. The polyvinyl alcohol resins are preferably used to melt below about 220 ⁰ G, such as in the range of about 180 to 215 C. etvia Such resins are characterized by a degree of polymerization in the range of about 1 000 to about

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5 000 marked and.-have a viscosity in ur faiger aqueous solution, measured as indicated above, of less than about ^ 5 c? on. The particularly preferred resins are, moreover, practically uniform polymers which melt completely ^{within a temperature range of 10 ° C.}

In order for the polyvinyl alcohol resins to be able to be extruded into films according to the invention, they must be effectively softened. The softening allows the resins to be extruded at temperatures at which they are not yet thermally decomposed (which occurs, for example, above about 2 ^ 0 ⁰ C) and that the molten resin has such a viscosity that self-supporting and yet impregnating the tape material extruded films are produced. The best results in impregnation are achieved when the polyvinyl alcohol resin is so plasticized that its melt viscosity is in the range of about 100 to about 1000 P at normal shear rate.

In general, all compounds or mixtures of compounds which have a plasticizing effect on polyvinyl alcohol resins are used as a plasticizer component. suitable in the resins extruded according to the invention. The more effective plasticizers for polyvinyl alcohol resins are moisturizing water-soluble monomers or '..'. polymeric alcohols, amines or amides. Individual examples are glycerine, ethylene glycol, propylene glycol, polyethylene glycols and polypropylene glycols with a molecular weight of up to about 1,000 (triethylene glycol, tripropylene glycol, garbowax 200, carbowax / K) O ₁ carbowax 600, etc.) trimethylolpropane, sorbitol, formamide, urea Polyoxyethylene ethers and esters containing

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about 2-20 moles of ethylene oxide units per molecule ■ for example, monophenyl ether of polyoxyethylene containing 2 - 7 ethylene oxide units per molecule (zBPycals) Purfurylalkoholäther of polyoxyethylene containing 3-12 mol ethylene oxide units per molecule and similar ethoxylated urea derivatives (Nopco GS-5), Diraethylolformamid, trimethylolpropane and others. in particular, such a plasticizer, for example, preferably, the polyoxyethylene compounds described, whose boiling point (at? 6o mm Hg) is above about 220 ⁰ C.

How much plasticizer is added in each individual case depends primarily on the resin and the extrusion conditions. In general, as the molecular weight of the resin increases and at lower extrusion temperatures and pressures, higher amounts of plasticizer are required. In order that the suitable melt viscosities are achieved in the above range, the plasticizer content in the range of about 5 to about 4o must% _t preferably from about 15 to about 30%, based on the weight of the polyvinyl alcohol resin. The proportion of plasticizer can also be above or below the specified values, provided that the plasticized resin can be extruded into self-supporting, practically non-tacky films.

The resin is preferred because of the relatively high temperatures used in extrusion contain practically no water and other volatile substances. Are such substances in noticeable quantities is present, the water and similar volatile substances suddenly evaporate when the resin mass emerges from the Nozzle and thus cause defects in the surface of the

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extruded film. In the preferred embodiments, therefore, the resin, plasticizer (s) etc. are selected or pretreated in such a way that the moisture content in the resin mixture fed into the extruder remains below about 0.5 % , based on the total weight.

The plasticized polyvinyl alcohol resin can be used in the present invention heated in any conventional manner and extruded into a film and the film onto a reinforcing fiber web be applied. The type of extrusion molding machine is not critical and any one for injection molding can be used Thermoplastic devices can be used. In general, work is carried out continuously and obtaining a flat or tubular resin film, the temperature of which is higher than the transition point of the resin and which is brought into intimate contact with a saturating fiber material, whereupon the temperature of the impregnated piaterials is reduced, so that one impregnated with a continuous enveloping resin film and coated fibrous web material. The fiber material is first formed into a tube and accordingly If the polyvinyl alcohol resin is extruded as a tubular film, tubular film is obtained immediately Sheaths. In other cases, a flat fibrous sheet material with a flat-extruded polyvinyl alcohol resin film is first used coated and soaked. The flat fiber webs obtained then become tubular casings deformed, with the seam-like meeting edges glued with an adhesive for polyvinyl alcohol resins , for example with aqueous or organic solutions of polyvinyl alcohol resins, diisocyanates, Epoxides and others

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The fiber web material is impregnated with the injection-molded polyvinyl alcohol because the extruded polyvinyl alcohol resin film is kept above the softening point of the respective resin (for example 5-1O ⁰ C above the melting temperature) until it has enveloped the fiber web material in the desired manner. A certain cooling of the extruded film, for example by bringing it into contact with cooler flowable substances (for example air) or cooler surfaces (for example cooled plates or rollers) is, however, also provided and preferably carried out in embodiments in which extrusion takes place at higher temperatures .

The extruded film must be fed into and onto the fibrous web material, and this is done in several ways possible. According to one embodiment, an endless fiber web resting on a support device becomes direct passed the spray nozzle from which the resin film exit. The polyvinyl alcohol resin is' pressurized enough to allow it to penetrate in the desired manner, extruded directly onto the web. This working method is used, for example, to work on already tubular parts To impregnate and coat fiber material, the tubular casing then being obtained immediately.

In another embodiment, the polyvinyl resin occurs at a certain distance from the 'fibrous web material, fibrous web material and softened resin film become then brought together so that their surfaces come into contact with each other, whereupon sufficient pressure is then applied to both is exercised by, for example, the sheet and film in contact with one another by a corresponding narrow opening between two rigid bodies (for example through the gap of two counter-rotating rollers) is to the resin film in and through the fibrous web material

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to press through. This procedure is generally used for the production of sheet material that then formed into a tubular shape, but can also be used directly for wrapping and packaging food can.

In performing the procedures just described, a US Pat. No. 2,958,364 described procedure can be modified. After that / will. a fiber web material is deformed into a tube and in a supported, open-ended, generally cylindrical rigid mold was introduced. Inside this The hose is made with the help of conventional combined injection-blow molding processes formed a tubular film made of polyvinyl alcohol resin. The penetration of the resin filament in the fibrous web material is effected by applying pressure, for example by the internal pressure of the blow molded Resin bubble is kept sufficiently high by compressed air, the pressure of which can be varied.

After a fiber material has been impregnated with the injection molded resin according to this process, it becomes Polyvinyl alcohol resin is cooled to temperatures below the glass transition temperature of the resin to make it in the form of a to solidify (i.e. make insoluble) a continuous film enveloping the reinforcing material. The speed·, with which that in and. Resin applied to the fiber material is cooled, can fluctuate. But it must be sufficiently large and it must be quick enough after the web material has been brought into contact be cooled with the hot resin in order to avoid an undesirable thermal change in the web material.

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The deposited resin can be cooled directly or indirectly in any way, for example with inert Coolants such as air or water, cooled surfaces the web material itself as well as through combinations of these measures. The cooling of the soaked fiber material can take place in the same zone in which the material is impregnated with the extruded film or in another. According to a preferred mode of operation, “cooled surfaces are used to protect the fibrous web material during . the impregnation with the resin film to support or to press, so that the cooling of the resin simultaneously with the Impregnation of the fiber material with the resin film takes place.

As already stated above, the fiber web materials soaked in accordance with the invention with polyvinyl alcohol resin are treated with a crosslinking agent which reacts with the polyvinyl alcohol resin during autogenous or heat curing of the coated and soaked material and crosslinks it so that the film on and in the fiber web material is even more insoluble and becomes less sensitive to water and other solvents. The optionally used crosslinking agent can be applied in any desired manner. Very convenient is the use of an aqueous or organic solution of the crosslinking agent that is before or after the impregnation with the resin and w before or after cooling of the resin film by spraying, dipping or else applied to other suitable V /. A slowly reacting crosslinking agent, for example an epoxy resin, can also be added to the resin charge of the injection molding machine and activated after the fiber web material has been impregnated with the resin compound by bringing the impregnated fiber material into contact with an appropriate catalyst or accelerator (e.g. ammonia for an epoxy). .

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In these embodiments, the crosslinking agent used is injection-molded resin onto the fiber web material is applied, all M or polyfunctional parts Means the crosslinks between the molecules of the polyvinyl alcohol resin can train, in question, already mentioned above in connection with the application of the resin from a solution described xtfurden. As far as necessary or if desired, a catalyst, accelerator, or the like can be used. for the crosslinking agent are added, and either directly to the "^ Hargschmelze, the crosslinking agent or independently of both. After applying the crosslinking agent and optionally the Accelerator on the resin film or after activating the combination of crosslinking agent and accelerator the product is cured to introduce the crosslinks and render the resin insoluble. Although often can can be effectively cured even at room temperature, but preferably heat is applied to this operation To shorten. The heating is also useful to harden a seam adhesive, if this is used for Was used, or to remove solvents in connection with adhesives, crosslinking agents, etc. were used.

For the production of the casings according to the invention Preferably, filling webs made of long hemp fibers with a corresponding fritter to increase the wet strength, for example Hegenerate cellulose or an insolubilized polyvinyl alcohol resin used with a high degree of substitution of e.g. over about 80/3 /. Other non-woven sannen such as Xoshino Paper, hot paper, paper made from polyvinyl alcohol resin fibers, Hemp, rayon, cotton and nylon as well as woven products such as gauze, marquisette, ... Organdy and Voile can be used. Of course, all of these j / aserbahn materials are in

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Commercially available. The long fiber hemp paper (Dexstar pa.per) is generally preferred for its high strength, easy handling and for economic reasons.

Fig. 2 of the accompanying drawing / schematics shows a

Device with which, according to the invention, a fibrous web material with a solution of a polyvinyl ronol resin coated and / or impregnated and this can be formed directly into a fiber sheath.

^. A paper web 11, preferably of the type such as

it is described in U.S. Patent 2 0 ^ 5 3 ^ 9, namely a long fiber hemp paper, depending on the desired size and weight of the

Sheath 20, ^{weighing 1} 1/2 to 27.2 g / m 2, is sucked off from the supply roll 12 via guide rollers 13 and 1 and around templates 15 and 10, which bring the paper into the desired tube shape. The paper tube is then drawn down over a rigid mold 17. This rigid form 17, preferably a hollow metal tube, for example a steel tube with an outside diameter of 5-17.8 cm (2-7 inches), depending on the desired diameter of the casing to be produced, can be of any desired size

"be suitably long, purposefully about 9.15 m (30 feetj_ and hang down from a suitable support, for example an I-beam 18 or the like, as shown. The now tubular one Paper web 11 is over the rigid form 17 after pulled down, by a shaping ring 19 ,, which is preferably is a metal ring, the inner diameter of which is only is a little wider than the diameter of a tube

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shaped paper web that is pulled through and the has the task of keeping the paper in this tubular shape until it reaches the coating device 20. This is a hollow, annular body made of metal or a similar material with an annular Opening 21 arranged concentrically to the inner diameter, through which one in the chamber of the device 20 below Aqueous or organic polyvinyl alcohol solution maintained under pressure is applied to the outer surface of the downward moving paper tube to make it even to soak and coat. The polyvinyl alcohol solution is prepared in a mixing tank and in a Holding tank from which it is fed to the device 20, as indicated schematically.

A sleeve 33 made of metal or the like Material is drawn onto the rigid form 17 and causes the polyvinyl alcohol solution to be applied more evenly through the opening 21 while the paper tube 11 slides down past it. A number of slip rings 22, which on the rigid form 1? at suitable distances, for example 90 cm (3 feet) are drawn and made of metal or the like, cause the inside of the with "polyvinyl alcohol resin coated and soaked paper tube does not come into contact with the outside of the rigid mold 17, while the hose is pulled downwards.

In this embodiment shown in FIG. The rigid form 17 stretches through a drying chamber The drying chamber 23 has an inlet 24 for hot air on, through the air from the air heater 25 with the help of a

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strong fan or a strong pump 26 is pressed. In the drying chamber 23, the polyvinyl alcohol resin coated and impregnated fiber cover is quickly predried. '

At the lower end of the drying chamber 23, the dried fiber casing collapses and is arranged at the entrance 28 and passed into the dryer 29. At the exit 30 of the dryer 29 there is another pair of rollers Jl. The roller pairs 2? and 31 act so that an air bubble is trapped in the envelope so that it is dried in the inflated state and thereby prevented from shrinking. The dryer 29, the hot air from a

ρ not shown two-chamber air preheater or from the Air preheater 25, as indicated by the dashed line, are fed. In the manufacture of the casings according to this embodiment, the one with polyvinyl alcohol resin The soaked fiber tube is dried thoroughly in the drying chamber and hardened in the dryer 29 '. The shell will then re-moistened to the desired moisture content either by feuclite at the exit of the dryer 29 Air is supplied or the casing is stored after exiting the dryer 29 under the moisture-balancing conditions. That in drying chambers 23 and 29 Solvent evaporated from the shell can, if necessary, in the schematically indicated solvent recovery

"The system can be condensed and recirculated.

Fig. 3 schematically shows another embodiment for coating and impregnating a fiber web material with a polyvinyl alcohol solution and direct deformation to a fiber sheath. The system shown here is the same with regard to the deformation of the paper web into a tube and the coating and impregnation with resin solution of the device shown in Fig. 2 and accordingly

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the same components of the two devices are denoted by the same numerals.

In Fig. 3, as in Fig. 2, a paper web is shown 11, preferably a long fiber initial paper peeled off from the supply roll 12, around the templates 15 and 16 formed into a tube, drawn down over a rigid mold 17 and through the coating yor /. 2Ό iiind.by, in which an aqueous or organic polyvinyl alcohol solution is applied to the outer surface of the downward sliding paper tube is applied and this coated evenly.

In Fig. 3, the rigid mold 17 extends into a container 123 which houses a coagulating bath 124, for example an aqueous or organic bath liquid in the concentration required for coagulation an acid, a salt or an organic liquid that does not dissolve the resin, so that in and a polyvinyl alcohol resin film on the fibrous web material is regenerated and solidified. The rigid form 17 can be connected to an inlet pipe or line 125 and to an outlet pipe or line 126, so that the coagulating fluid can circulate inside the tubular casing formed. The flow rate inside the shell is dimensioned so that the liquid level inside the formed The envelope is approximately equal to the level of the bath liquid 124 in the container 123.

A hollow 127 is arranged at the bottom of the container 123. The casing collapses in the lower part of the container 123 and is coagulated around the roller 127 from the ICoagulier- and Regeneration bath led out. The shell 128 (in difference

- 26 -

009820/1885 bad original '

135.2464 - ²⁶ - iÄ-36 931;

to the untreated paper 11 at the beginning of the process) xtfird is guided and run through a series of pulleys a range of treatment baths. The containers I30 and 1 ^ 0, through which the envelope is initially passed, -contained additional coagulating bath liquid I3I and 1 ^ i, to make the resin completely insoluble in the shell. The envelope enters the container from a container 3Λθ 150, which contains washing liquid 15I. And in the coagulating bath ~ liquid and any by-products present washed out of the envelope, in the container 160 brought the shell into contact with a bath 16I that a plasticizer, for example glycerine, and a ^ wetting agents such as formaldehyde for the Poly-P contains vinyl alcohol resin film. The casing is then moved over pulleys from the container 160 to the entrance of the dryer 15 ^ out, where they are between a pair of rollers 155 and 156 passes through, which together with the pair of rollers 158 and 159 at the exit of the dryer in the envelope a large air bubble trapped so that it is enveloped in the inflated state without excessively shrinking, can be dried »In the dryer 15 ^ the casing will be with Hot air dried out from the air preheater 170 with the Pump 172 is pushed through line '17I. The ones from the Dryer -1.5 ^ peeled envelope is then not shown on Rolls wound up. '

The devices shown in FIGS. 2 and 3 for the production of casings by impregnation and coating with a polyvinyl alcohol resin solution offer the advantage that the apparatuses and arrangements customary for the production of cellulose fiber casings can be used. The devices and modes of operation shown in FIGS. K - 9, on the other hand, offer the advantage that work can be carried out more quickly. The Fig. ^ - 9 show different ex

- 27 -

ORfGJfMAL

009820/1885

- 2? - ΊΑ-36- 931

Guide forms of application machines for flat web material, with which a saturating fiber web material is coated with a polyvinyl alcohol resin solution and soaked and then dried. In any case vilrd. the coated web material immediately after drying or after a certain storage time cut to size rnicjizu tubular casings processed using a conventional "device for shaping and closing the longitudinal seam. Any conventional adhesive for polyvinyl alcohol resin films can be used for this purpose. Such adhesives are melted, plasticized polyvinyl alcohol resins with high degree of OH group substitution of, for example, over about 80 %, * aqueous or organic solutions of polyvinyl alcohol resins or reactive adhesives such as isocyanates, epoxy resins or similar adhesives in the form of aqueous or organic solutions of di- or polyfunctional substances, as already stated many times above, crosslink the polyvinyl alcohol resins.

U shows a device with the doctor blade over an applicator roller. A fiber web material 235, preferably a long-fiber hemp paper or some other saturating material, is drawn over the applicator roller 236. A viscous polyvinyl alcohol solution is applied to the outer surface of the web, as shown at 238, and dispensed with doctor blade 237 and metered. The coated and impregnated web thus obtained passes through the dryer 239 _} in which the polyvinyl alcohol resin is thoroughly predried and cured. For the establishment of the moisture equilibrium. For example, moisture can be introduced into a certain part of the exit end, or the coated, dried and cured sheet material after exiting the dryer 239 is treated with moisture in a further operation before it

00982G / 188S "■■

BATH ORIGINAL

- 28— ■ ■; IA-36 931

then wound up ..

Fig. 5 shows a coating machine with / air knife.

The fiber web material "2 ^ 0 is over a support 241 and the guide roller 242 out. An air knife 2 ^ 3 is located between the support 2 ^ -1 and the guide roller 2 ^ 2 and doses the viscous polyvinyl alcohol resin solution- ~ 244 the web material 2 ^ 0. The finished coated and soaked Web material 2 ^ 0 is then passed through dryer 2A-5 out, in which the resin is thoroughly dried into a film, hardened and preferably its moisture equilibrium is restored. If necessary, the restoration of the moisture equilibrium can be achieved in a separate operation after leaving the dryer. The air knife can be used for non-woven Railway materials are operated slowly, we-. gen the relatively low wet strength of the web material. This spreading device is therefore more suitable for woven products or for non-woven materials which previously with an additive to increase wet strength. have been complained.

B ¹ Ig. Figure 6 shows a modified form of the air knife known as a blanket coater. With this device, nonwoven materials can be coated and soaked at a higher speed, since the web material is supported at the point where the coating material is applied and spread with the air knife. In Fig. 6 the non-woven saturating web material 2kh is fed via the guide roller 2W ( . The device comprises a guide roller 2 ^ 3 and a drive roller 2 ^ -9 over which a continuous cloth 250 runs, on which the web material to be coated lies. The .uahnmaterial ZhG is supported by the cloth 250 at the point at which a viscous polyvinyl alcohol resin solution 252 is applied and dosed with the doctor knife 251. The coated unc \ soaked

■ '■ - 29- ":,'

009820/1885 - ^{/ left}

Web material is then fed through dryer 253, Before it is dried, hardened and preferably its moisture balance will be produced. If necessary, the restoration of the moisture equilibrium can be achieved take place in a separate operation after leaving the dryer ..

Fig. 7 shows a conventional rotary roller application machine, rollers running in the same direction are used here to apply a polyvinyl alcohol resin solution to a fiber web material to raise. In this application machine, the fiber web material 25 ^ is guided over a support roller 255, which provides vertical adjustment to control the thickness of the applied coating. Close-fitting to the support or guide roller 255 are the transmission or distributing roller 256 and the applicator roller 257, which are arranged at a variable speed to run; the applicator roller 257 is preferably with a Micrometer alignment is provided to match the thickness of the Control the film. In addition, the application roller 257 and the transfer roller 256 with a pick-up knife 259 are provided and 260 provided. The viscous coating solution becomes added between rollers 256 and 257, as at 258 shown. In this device the coating material 258 is applied in a certain thickness to the transfer roller 2 * 1-6. The thickness is determined by the Application roller 257 controlled. From the transfer roller 256 gets the coating material on the cream 25 ^ 1-, which is then fed into the dryer 26l. Here will that coated and impregnated. Web material is thoroughly dried and cured and preferably is used here as well the moisture balance is restored. If necessary, however, the moisture equilibrium can

- 30 -v

BAD ORiGjNAL

009820/1885 ^:

also in another downstream of the dryer: i-work gear he follows.

8 shows a conventional, co-rotating four-cylinder application machine ^{known as 'Contracoater 1} ', "with which polyvinyl alcohol resin solutions can also be applied to fiber web materials according to the invention. The fiber web material 262 is guided over a guide roller 263 and around the transfer roller 26h. The device comprises a container 265 for the coating solution 266, for example a viscous aqueous or organic polyvinyl alcohol resin solution

267 picks up the coating solution 266 and transfers it jfc on the transfer roller 25S * "Adjacent to the transfer roller .268 a metering roller 269 is arranged, which determines the thickness of the film layer on the transfer roller 268, which arrives at the fibrous web material 262 controls. The surface of the metering roller 269 is

. Knife 270 cleaned. That by the transfer roller ..

268 coated sheet material is then put into the dryer 271 where it is thoroughly dried and hardened

and preferably also its moisture balance again will be produced. If necessary, the restoration of the moisture equilibrium in the hardened Polyvinyl alcohol resin impregnated and coated Railway material also in its own downstream work P to take place.

Fig. -9 shows a three-roll application machine with direct. Assignment. Here the fibrous web material 272 is over the guide roller 273 and guided around the conveyor roller 27 ^. The device comprises a container 275 in which the Coating solution 276, for example a viscous aqueous one

BATH ORIGiMAL

O 0 9 820/18 8 p

-: .3.l - lA-36 931

or organic polyvinyl alcohol resin solution. The applicator roller 277 is immersed in the coating solution 276 and, as it rotates, transfers the coating solution to the transfer roller 278, from where it reaches the surface of the web material 272 as it runs around the conveyor roller 278. The coated and impregnated web material obtained is passed through a dryer 279, "where it is thoroughly dried and cured and preferably also its moisture equilibrium is restored. If necessary, the moisture equilibrium can be restored in a separate, downstream operation.

10 shows an apparatus for coating and impregnating a fibrous web material with melt-extruded material (Injection molded} polyvinyl alcohol resin and directly deforming the same into a fiber casing according to the invention.

In FIG. 10, as in some of the previously described embodiments, a paper web 11 is pulled off the supply roll 12 via the deflection rollers 13 and Ik and guided around the stencils 15 and 16, which cooperate and deform the paper web into a tube. The paper tube then runs downwards and is supported and guided in its interior by a rigid "form 17". The rigid form I? 8 cm (2 - 7 in.). The length of the rigid mold 17 is dimensioned, for example, 3 - ^, (10 - 15 feet) so that the casing does not orient itself during the molding operations and while the resin in the film is orienting itself undesirably coincides and

009 8 20 / 1-8-8 8 bad original

shrinks. The rigid form 17 is expediently of held by a carrier, in the present case by an I-carrier 18. The paper sheet 11 also runs downwards over the rigid mold 17 through an annular body 19 and through the injection molding device 320. The outside diameter of the 'annular body 19, the usual price of metal. is a little larger than the diameter of the paper tube and its job is to keep the paper web in the tubular shape until it enters the injection molding machine 320 arrives.

The injection molding device 320 generally consists of a body, indicated here only schematically, in which the plasticized introduced resin with corresponding Means, for example, a rotating single-flight screw with constant pitch and promoted in one or several stages is heated above its melting temperature. At the end adjacent to the paper tube is the nozzle part of the spray device 320 as Sing formed through which the paper tube runs. A continuous tubular resin film occurs from one on the inside 321 of the bing of the injection molding machine 320 circumferential annular opening 322 the end. In some cases the temperature of the exiting resin can be regulated more precisely by additional Heating or cooling of the resin directly at the nozzle opening 322, for example at the annular surface 321, with the aid of conventional heat exchange media, e.g. embedded coils. len and the like, which are not shown here. The injection molded resin is fluid, i.e. its temperature is above the freezing or glass transition temperature and it occurs from injection molding apparatus 320 under sufficient pressure

'- 33

BATH ORIGINAL

009820/1885

on the surface of the paper tube to get the Fibrous web material appears as a continuous film Soak and coat polyvinyl alcohol resin.

The impregnation and coating process is still through this supports that the tubular material in the area the immediate vicinity of the injection molding device 320 from the inside additionally by an., ring-shaped Cuff 339 is underlaid, the diameter of which is slightly larger than the desired diameter of the sleeve and the one around the rigid form 1? shrunk around or is firmly connected to it in another way. A series of slip rings 323, which at appropriate intervals, e.g. 90 cm (3 feet) also on the rigid form 17 attached, for example shrunk, cause the inside of the soaked and coated tubular web does not come into contact with the rigid mold 17 until the resin has set sufficiently.

The hose web soaked and coated with polyvinyl alcohol resin is then cooled in a cooling chamber 32 ^. ■ The cooling medium used is air that comes from an air cooler 326 through line 325 under the action of the fan 327 enters the cooling chamber 32 * 1-. Cooling down in the Chamber 32 ^ - does two things: On the one hand it prevents the fibrous web material is destroyed by the heat escaping from the applied resin. The second will the temperature of the applied resin film is lowered below the .Einfrier- or glass transition temperature, so that the applied resin becomes hard.

The rigid form 17 extends into a container 328, which contains a solution 329 of a crosslinking agent such as formaldehyde. In the container 328 the hose '

0 0 9 8 2 0/1885 ^BAD

shaped web material - sufficient crosslinking agent, ■ -.- around the resin in the shell during subsequent curing is sufficient to make insoluble. Solution 329 can optionally additionally contain other substances with which the resin film is to be impregnated, for example accelerators, for the crosslinking agent, additional amounts of Plasticizers, dyes, antioxidants, etc.

The tubular casing then flattens out around a hollow

330 ^a ro bottom of container 323 and the now flat track

331 via a series of guide rollers into the drying and Curing chamber 333 out. In the drying chamber 333 is

fc the envelope re-inflated and with the help of the roller. pairs 33 ^ 'and 335 at the entrance and 337 and 338 at the exit the drying chamber kept inflated so that . it hardens evenly and does not shrink. By doing Dryer 333 is the casing either directly e.g. with hot air or indirectly e.g. by irradiation. heats so that the polyvinyl alcohol resin film is crosslinked and insoluble and thus the finished product is created.

■ '..:. "When in Fig apparatus and shown 11 operation' is a film-forming and injection-moldable polyvinyl holharz with a plasticizer, mixed and then in a conventional manner to a virtually flat Earzfolie 3 ^ 2 sprayable W poured A web of. saturating paper fibers 3 ^ + 1. "are unwound from a supply roll 3 ^ K) and in flat contact with the ■ resin film 3 ^ 2. brought. The resin film 3 ^ -2 has already cooled down somewhat at this point, but its temperature is still above the freezing or glass temperature of the resin framework and the film is therefore still malleable. The reinforcing sheet material 3 ^ 1 and the resin film 342 are ".then passed together between two rollers 3 ^ 3 and 3 ^ 4, which apply sufficient pressure to the web-film laminate

■ .. '■■ "- Λ. Λ ■■■' .- 35 - - .. ■■■:

. . 'BAD ORiGiNAL

0098 20 / 18S5

1352484 - 35 - iA-3- 931

Exercise to let the polyvinyl alcohol resin get into your pores of the reinforcing fiber material penetrates, so that in of the web 3 * K5 emerging from the gap is the reinforcing one Fiber core completely and continuously with polyvinyl alcohol resin is impregnated and coated. One of the two reels 3 ^ 3 and 3 ^ · or both are with usual, not Cooled means shown, so that the desired cooling of the -Folyvinylalkoholharzes simultaneously with the impregnation takes place in order to protect the fibrous sheet material and to solidify the penetrated resin film.

The resin reinforced film 3 * 2-5 is then covered with a Cutting device in the one desired for the manufacture of the casing Cut to width; the waste will be with appropriate Gowns removed, in the present case when guiding over a pair of deflecting guide rollers 3 ^ 9 and 350. The cut resin reinforced sheet 3 ^ 8 is then passed through the container 351, the one-bath 352 with a Crosslinking agents and other additives used in the finished Sheath should be included.

The fiber reinforced film 3 ^ 8 is made with the help of the guide rollers 353 and 35 ^ J- out of the bed and over the Guide out template 355, which is designed in the usual way to fold the film 3 ^ 8 into a tube and to shape. On the top of the template 355 there is an application device 357 of a conventional type Glue with which the ICleber 356 is attached overlapping edges of the film deformed into a tube is applied. In this operation it becomes so a sleeve 358 is formed which has a longitudinally extending seam sealed with adhesive.

J) Ie final treatment of the shell takes place in the dryer 359 in which the cover of a heat setting treatment is subjected., during which the "poly-

- 36 -

009820/1885

ORSGINAL

vinyl alcohol resin completely cross-linked and the adhesive hardens. In order to achieve maximum effectiveness and uniform results, the casing can be kept in the inflated state during the passage through the heat hardener 359, with the cooperation of the roller pairs 36O and 3 & 1 before entry and 363 and 36 ^ after the exit from the chamber an air bubble is kept trapped in the envelope. If a slow-marking adhesive 356 is used to close the envelope seam, the envelope should of course not be inflated so that the seam does not open. In addition to using fast-acting ICLs, this difficulty can also be avoided by first curing the adhesive in a separate operation after shaping and closing the seam and only then is the crosslinking agent applied and / or cured.

The various embodiments of the invention are now explained in more detail using the following examples.

example 1

This example shows the production of a fiber casing by impregnating and coating a fiber paper tube with an aqueous one. Polyvinyl alcohol resin solution and then evaporating the water described from the soaked material.

An aqueous 10% solution of a polyvinyl alcohol-polyvinyl acetate copolymer with an OH group of 99> 5 % and a polymerisation was used

009820/1885 BADORiGfNAL

1A-36,931 - 37 -,.

degree of about 1600 produced. The copolymer was in the. Solvent mixture dissolved at about 90 Ms 95 ° G. After cooling, 2.25 % glycerol as a plasticizer, 0.4% formaldehyde as a crosslinking agent and 0.22% lactic acid as a catalyst for the crosslinking agent were added to this viscous solution.

A sheet of long fiber hemp paper (Dexstar), weight 25.5 s / m j. was pulled from a supply roll and ' passed through the device shown in lig, 2. the The paper web was formed into a tube and the paper tube with the viscous polyvinyl alcohol resin solution from ' the annular nozzle 20 soaked and coated. the Application speed of the resin solution 'corresponded to a Wet tube thickness of about 1.27 mm (50 mils). In the dryer 23 was. The moist hose with hot air dried by 120 g. The air containing water vapor was withdrawn from the dryer 23 and the water in a Solvent recovery system as shown above, recovered. The tubing was then cured in the 29 "oven at 140 ° C., with thorough crosslinking of the film and the formation of hydrogen bonds between the substituents on the polyvinyl alcohol copolymer molecules

took place. After curing, the casing was in a moist .. ■ wocLurcn

Atmosphere after-treated, -i-lo & em · it absorbed moisture and became pliable and easy to use.

After drying and re- moisture equilibrium (to about 12%) under controlled humidity conditions, the peck of the casing was about 101 to 152 / U (4 to 6 mils). If the shell was immersed in water,

- 38 -

009820/1885

"ganges

■■ "- ■ '.' 1JL-36 931

- 38 -

so it swelled to a thickness of about 152 to 203 / u- (6 to 8 mils). The sheath had a larger tensile strength and a lower elongation at break than a shell of fiber-reinforced RegeneratcelluloseT the · tensile strength of the sleeve was 304 to 375 kg / m ^ against (1 ?. to 21 lbs / inch) and its ultimate elongation from about 15 to _30%% about 60 to 70 % of a fiber-reinforced regenerated cellulose casing. - ·

One as above made from a polyvinyl alcohol copolymer and The casing made of fiber material was first soaked in hot water and then with an emulsion for Bolognese Stuffed sausages. The cover was tied at one end with a string and, after it was thoroughly stuffed, at the other end closed with a clip .. The casing stuffed with sausage mixture was cooked and smoked. The shell did not crack anywhere and the vapor and smoke permeability was about the same as with a standard cellulose fiber casing. The scope of the Originally 38 cm (15 inch) envelope fluctuated less than 4.76 in (3/16 inch) over the course of the entire working period

B is ρ i el 2 "■

This example describes the production of a synthetic sausage casing, with a filling first Fiber material with an aqueous polyvinyl alcohol resin solution impregnated and coated and the coated web obtained then into a tube having a seam is deformed. ·

χ or elongation at break -q

009 820 / 18S5

1A-36,931

- 39 -

A 10% solution of a polyvinyl alcohol / polyvinyl acetate polymer with an OH group content SG of 98 ° / ° and a PG of about 1400, which contained 2.25 % glycerol, 0.4% formaldehyde and 0.22 % lactic acid was produced according to example 1. The viscous solution obtained was applied with the help of a knife over an applicator roller according to FIG. 4 to a web of long fiber hemp paper (Dexstar), weight 25.5 g / m ^; the "coated and impregnated paper web had a thickness of about 1.27 mm in the wet state and was dried under the same conditions as in Example The dry coated web was about 10 1 to 152 / u. thick. The re-moistened paper was about 152 up to 203 / U and in terms of tensile strength, when re-moistened and elongation at break, superior to paper soaked and coated with cellulose.

The soaked, dried and hardened paper was passed through a humid atmosphere in order to restore its moisture balance and to make it pliable. The impregnated paper was then cut to size in the desired manner and processed into a tube with a longitudinal seam on a conventional closing machine. During the production of this tubular casing, a 10% aqueous solution of a polyvinyl alcohol / polyvinyl acetate copolymer (OH groups JB.G. about 99.5% ) _{9 was} softened with glycerine and containing formaldehyde and lactic acid in the same ratio as an adhesive for the IT seam like the impregnating resin solution. After the tapes were glued together, the sleeve was heated in order to dry the glue and to create continuous wetting both in the glue and in the surfaces connected to each other

- 40 -

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• '1A-36 931

. cause. This case does not burst open along the seam ^7, when "were -üblichen tensile tests done with her.

The fiber casing obtained balanced the casing in terms of its strength and its processing properties Example 1.

Example 3 to 10.

These examples illustrate further embodiments of the Manufacture of synthetic casings by impregnating and coating a flat sheet of a saturating material Material with an aqueous solution of a polyvinyl alcohol resin, Drying the treated material and forming the resin-impregnated sheet material into one Hose in one closing operation.

According to Example 2, 10% strength aqueous solutions of film-forming polyvinyl alcohol resins containing glycerin and crosslinking agents and applied to flat

2 strips of long fiber hemp paper (Dexstar), weight 25.5 s / ^{m were} applied. The resin-impregnated paper webs were dried, then formed into tubes in a step that closed the seam; the adhesives used for the seam are given in Table I below.

TABLE I:

_ 41 _ 009820/1885

TABEL

CSO CO

At- impregnating resin solution

game polyvinyl alcohol resin

-7a PVA / PVac. (OH SG,

88 ^; P..G.,

I5OO)

PVA / PVAc (OH S.G-, %; P..G-, 17OO;

PVA / PVAc '(OH S. G., 99%; P-G., 1800)

dto.

dto.

crosslinking agent

0.4% formaldehyde 0.22% lactic acid

dto.

0.4% formaldehyde 0.3% malic acid

1.25% trimethylol

melamine,

0.2% citric acid

0.5% polyamide epichlorohydrin. (Eymene 557) Applicator glue for? seam

Air knife (Fig. 5)

Blanket coating machine (Pig. 6)

3 'roller application machine with rollers running in the same direction (Pig. 7)

3-roller application machine with direct order (Pig. 9)

4-roller application machine with rollers running in the same direction (Pig. 8)

like impregnating resin solution

dto.

30% 2,4-toluene diisocyanate in acetone

30.%. Cyano acrylic ester in acetone

30 % butadiene diepoxide

in acetone

Ports. TABLE I:

ro 1

Forts, too. TABEL

Tränkhar zTö solution

At- '

game polyvinyl crosslinking alcohol resin medium

10

PVA / PVAc 1.0 % Dimethylolur-COH ö. &",",. Stoff, 99 % i P.JS .., 0.2% lactic acid 1800)

dt o.

.dto.

5% glyoxal 0.3 # malic acid

5.5% glutaraldehyde 0.2% malic acid Order machine

Glue for seam

4-whale cleaning machine like impregnation solution with rollers running in the same direction (Fig. 8)

dto.

dto.

dto,

dto.

/ a polyvinyl alcohol / polyvinyl acetate copolymer

1A-36 931 • - 4-3 -

The strength and processing properties of this with Seam, .ifed covers made of fiber-reinforced polyvinyl alcohol resin were similar to those of the casings from Example 1 and

In all of the above examples, glycerine was used as a plasticizer for the polyvinyl alcohol resin film of the casings produced. Obviously, superior casings can be produced if, instead of glycerine, any one; Another of the water-soluble monomers or polymers mentioned in the description, hydroxyl, amino or amide group-containing plasticizers for polyvinyl alcohols is used in an effective amount of, for example, 0.5 to about 4 % . . '·

Example 1 * 1

In this example, a tubular web is made from a saturating fiber material impregnated with an organic solution of a polyvinyl alcohol resin and coated the solvent evaporates from the coated material. . -

The procedure of Example 1 was repeated with the Exception that instead of water as the solvent for the impregnating resin solution, a methanol-water mixture 30:70 (V / V) was chosen. The fiber-reinforced polyvinyl alcohol resin casings obtained immediately had the same strength and processing properties like the casings of the previous examples.

_ 44 _

009820 / 188S

1A-36,931

Examples 12 to 16

Following the general procedure of Example 2, 100% organic solutions of f i ImTDiI d end en polyvinyl alcohol resins were prepared containing glycerine and crosslinking agents and on flat long fiber paper webs (Dexstar), weight 22.5 g / m 2; the Resin-soaked sheets were then dried and formed into tubes. In the following Table II are the application devices used, the adhesives used for the seams, the polyvinyl alcohol resins, Crosslinking agents and solvents specified in the impregnating resin solutions.

TABLE II:

- 4-5 -

009 820 / 186S

TABLE II

ο ο «ο

example

12th

• 13

Drinking solution

Polyvinyl crosslinking solution alcohol resin medium medium application machine

Glue for seam

PVA / PVAc 0.4 % form methanol / water air knife

(OH SG, aldehyde, 50:70 (Y / V) (E ¹ Ig. 5)

88; e; PG, 0.22 % dairy

1200 acid

Aqueous PVA / PVAc solution (Example 2)

PVA / PVAc

(OH S.G., .70 «tojP.G. I5OO)

dto,

PVA / PVAc / 0.4 % form

PPlA / Λ aldehyde,

(OH SG, 0.3 % apple

50%; P.G., acid

1400)

PVA / PVAc 1-, 25 Tri- (OH S.G.,. Methylol-99.5 / ö; P.-G. , melamine, 1000) 0.2% citric acid

Methyl ethyl ketone

Methyl acetate blanket coater (Fig. 6)

dto,

3 ~ ¥ salt application 30% 2,4-toluene machine with the same diisocyanate in acetone running rollers sensibly (Fig. 7). \

Methanol / water, 3-roll application 30:70 (V / V) machine with direct application (Fig. 9)

Continued TABLE II:

30% diketene from dimerized linoleic acid in acetone

ι -.

Ports, too, Q? CHART II

example

Impregnating resin solution

16

Polyvinyl crosslinking solution alcohol resin medium medium Application machine

PVA / PVAc 0.5% glutar benzene

(OH S.G., aldehyde,

30%; P.G., 0.2% apple

1800) acid

Glue for seam

4-roll application machine with rollers running in the same direction

30 % butadiene diepoxide in acetone

CD <JD ISJ '

ZsL CD
~ ö
ΓΓϊ

/ a Terpolymer with carboxyl group SG approx. 5%, obtained by hydrolyzing a polyvinyl acetate / polymethacrylic acid copolymerB ..

1A-36,931

- 47 -

The fiber-reinforced casings made of ilalrfc The polyvinyl alcohol resins of Examples 12 "to 16 were similar in terms of their strength and processing properties the covers of the previous examples.

Again in these examples, the plasticizer used was glycerine, which was replaced by any of the others The plasticizers specified above can be replaced, in which case casings with comparable properties are obtained will.

Example 17

In this example the immediate production of a synthetic shell using an aqueous solution of a polyvinyl alcohol resin and an ifoagulierbades described.

It became a 10% aqueous solution of a polyvinyl alcohol resin with an OH group S.G. of 99.5% and one P.G. made by about Ί1ΟΟ; from the previous ones Examples of this preparation differed in that the addition of a plasticizer and a crosslinking agent was omitted.

The viscous 10> jige copolymer solution was in a device according to Pig. 3 on a sheet of long fiber hemp paper (Dexstar), weight 25.5 g / m? upset. The paper web was drawn over the stencils and the tube obtained was drawn through the annular coating device 20; the thickness of the coated wet tube was about 1.27 ram (50 mils). The polyvinyl alcohol resin was made insoluble in the coagulating baths 124- and '".1 / \ , these were aqueous

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009820/1885

_BATH

1A-36 931 -MB-

Solutions containing 5 % concentrated (100 %) sulfuric acid and 15 % sodium sulfate. The coagulated hose was then passed through water baths 141 and 15I and thoroughly rinsed and then through bath 161, which consisted of an aqueous solution containing 30 % glycerol, 1 % formaldehyde and 0.2 % lactic acid. From the bath the hose was passed through the dryer 154- where it was crosslinked and completely dried.

h The approximately 101 to 152.4 / U thick casing has been treated with sufficient moisture to restore its moisture balance and make it flexible and easy to handle. When immersed again in water, the shell swelled to a thickness of 152 to 203 / U. Its tensile strength and heat resistance were greater, its elongation at break was lower than that of conventional fiber-reinforced cellulose casings, and it was easy to stuff, cook and smoke, as described in Example 1.

Example 18

This example illustrates the direct manufacture of a "synthetic shell using an organic one." Solution of a polyvinyl alcohol resin and subsequent treatment of the resin-soaked material in a regeneration bath.

It was worked according to Example I7 - with the difference that

(A) a methanol-water mixture as the solvent for the impregnating resin solution 50:70 (V / V). used and

(b) Acetone was used instead of coagulating baths 124 and 131 became.

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009820/1885 _BAD original

1Δ-36,931 - 49 -

The shell obtained showed signs of failure, as did the previous ones Examples, a higher strength and lower elongation at break than the usual fiber-reinforced cellulose casings and could be stuffed, cooked and / or smoked as described in Example 1 with good results.

Example 19

This example illustrates the on-site manufacture of synthetic casings using an aqueous alkaline solution of an alkali-soluble, film-forming polyvinyl alcohol resin.

The procedure was as in Example 17 with the difference that

(a) To produce the 10% impregnating resin solution, a polyvinyl alcohol / polyvinyl acetate copolymer with an OH group content of about 5> 0 % and a P..G. from about 1600 and as a solvent for this an aqueous 4% sodium hydroxide solution and

(b) Bath 141 with dilute (1 / fig) aqueous sulfuric acid was replaced.

The fiber-reinforced polyvinyl alcohol resin solution obtained had the same strength and processing properties as the casings of the previous ones Examples.

Examples 20 to 27

These examples illustrate many other embodiments

- 50 -

009820/1885

I952A64

1A-J6 951

■ - 50 -

Much more about the production of the synthetic sausage casings aqueous alkaline solutions of polyvinyl alcohol resins be used.

In all examples, ver travel; the composition of the 10% impregnating resin solutions and the plasticizer bath 161 containing glycerin summarized in the following Table III.

TABLE III:

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TABLE III

at Impregnating resin solution Networking Networking • - _ 0.2% methylol game middle melanin Plasticizer _ - _ Polyvinyl FaOH • alcohol conc. % _ _ 20th resin - "- PVA / PVAc 1% trimethylol (OH S.G., 50%; melamine,
0.3% malic acid 21 P.G. , 1600) 3 PVA / PVAc (OH S.G., 40%; _ _ 22nd P.G., 1700) 8 PVA / PVAc / PA ^ (OH S.G., 50%; 1% trimethylol 23 P.G., 1300) 4 melamine, PVA / PVAc / PA ^ 0.3% apple (OH S.G., 30%; acid 24 P.G., 1800) " dto. " 25th PVA / PVAc / PMA ^ ⁰ - (OH S.G., 50%; 26th P.G., I300) " PVA / PVAc (OH S.G., 40%; PG, I7OO) » 27 Il Il

Terpolymer containing 0.5% acrylate obtained by hydrolyzing a polyvinyl acetate / polyacrylic acid copolymer;

Terpolymer containing 8% acrylate obtained by hydrolyzing polyvinyl / polyacrylic acid copolymers;

Terpolymer with a carboxylate content of approximately 3% by hydrolyzing a polyvinyl acetate / dialeic acid copolymer.

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All the casings received were like the casings in the previous ones Examples, in terms of their processing. and elongation properties of the common fiber-reinforced Superior to cellulose casings.

Example 28

κ This example illustrates the production of synthetic Envelopes by placing a flat paserbahn material with an aqueous soaked in an alkaline solution of a polyvinyl alcohol resin and coated, the resin regenerated on the flat sheet material, and the resin impregnated and coated Fiber web material in a further operation Closure of a seam is deformed into a shell.

There was a 10% aqueous alkaline solution of a PoIyvinylalkohol / polyvinyl acetate copolymers prepared with an OH-SG 50% as in Example 20, and in a 4-roll coater with co-rotating rollers of FIG. 8 on a flat web of long fiber hemp paper \ (Dexstar), weight 25? 5 g / m? applied. The impregnated and coated paper web was then passed through a series of coagulating, washing and softening baths of the same composition as in Example 20. The finished, resin-coated and impregnated paper web was then shaped in a sealing machine into a tube with a longitudinal seam; An aqueous polyvinyl alcohol resin solution as in Example 2 was used as an adhesive for the seam. The casing obtained resembled the casing of the previous examples in terms of its strength and processing properties.

In the above examples, the alkaline

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soluble polyvanyl alcohol resins 5 to 8% sodium hydroxide solution. Of course, effective amounts of aqueous solutions of other alkaline substances such as EOH, MLOH and (CH ^) JiTOH can be used instead; in all cases, casings with comparable properties are obtained. Generally, the alkali concentration in these aqueous solutions will vary from about 1 to about 20 percent. In the same way, the coagulating baths can also contain other acids and salts, as indicated above. In general, those coagulating and regenerating baths are effective whose pH value and salt content are equivalent to aqueous solutions containing 1 to 20 % sulfuric acid and KapSO ^ or (NEL) pSO ^ in an amount of about 5% to saturation (e.g. 40%) %) contain.

Example 29

This example illustrates the use of injection molded Polyvinyl alcohol resin for immediate manufacture of synthetic casings.

100 parts by weight of a dry polyvinyl alcohol / polyvinyl acetate copolymer with an OH group S.G. of about 71% and a viscosity in 4% aqueous solution of about 11 cP / 20 ° C were uniformly with 20 parts by weight of a Polyoxyalkylenphenoläthers mixed, which contained an average of five iithylenoxideinheit per molecule and below the trade name Pycal 94 as a polymeric plasticizer for Polyvinyl alcohol is known. The moisture content of the mixture was less than 0.1 wt.

A long-facer hemp paper web (Dexstar), weight 25.5 g / m,

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1A-36 931 - 54- - '

was withdrawn from a supply roll and passed through the device shown in FIG. The paper web was deformed into a tube and the copolymer was injection molded through the annular nozzle 320 (Ai ^ strittgtemperature about 175 ° C) ' _? to soak and coat the paper tube. The application rate was adjusted so that the thickness of the soaked and coated tubing was about 127 to 254yU (5 to 10 mils). The coated tube was pulled down and immediately thereafter cooled in the cooler 324 with air at about 15 ° C. The tube in container 328 was then brought into contact with an aqueous solution containing 1 % formaldehyde and 0.2% lactic acid, the latter being the catalyst for the crosslinking agent formaldehyde. Then the tube was passed through the dryer 333 and the resin film up to 140 ⁰ G thoroughly crosslinked here at temperatures and insolubilized. After curing, the casing obtained was post-treated in a humid atmosphere to increase its moisture content to, for example, 10 to 15% by weight, thereby improving flexibility and handling

The finished casing had a higher tensile strength and a v / es, lower elongation at break than corresponding ones fiber-reinforced casings made from regenerated cellulose.

The finished casing was soaked in hot water and then stuffed with a Bolognese sausage emulsion and in usually cooked and smoked. The shell did not burst and the vapor and smoke permeability were about the same as conventional fiber-reinforced cellulose casings.

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- 55 -

Examples 30 "to 4-1

These examples illustrate further embodiments of the direct production of casings with melt-cast Polyvinyl alcohol resin.

The general procedure of Example 29 was repeated; the various polyvinyl alcohol resins and Plasticizers are summarized in Table IV below.

TABLE XV ":

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TAB ELLE •OH- Visc. ^ IV added Triethylene 5 Exit Polyvinyl alcohol resin SG y ^C / ■ o cPs te amount glycol 15th temp. ⁰ C Plasticizers Weight Pycal 94 30th at formula share Glycerin 20th game 99.5 10 - Duration 20th Pycal 9 ^ H Il part. 10 Il Il 15th 200 32 PVA / PVAc 205 33 Il 98.0 12th Pycal 94- 15 · 200 34 Il Il Il It 25th Carbowax 195 35 PVA / PVAc 95 9 400 / Ά • 10 195 36 Il M. Il Pycal 94- 10 Carbowax 200 37 PVA / PVAc 300 Zs. 38 Il 85 11th Pycal 94- 190 70 12th Pycal 94- 95 15th 185 39. PVA / PVAc 175 40 PVA / PVAc 190 41 PVA / PVAc / PIlAA ^

As a 4 % aqueous solution at 20 ^° C .;

Polyethylene glycol with an average molecular weight of approx.

400. _ .. ■; ■

Z £

Polyethylene glycol with an average molecular weight of approx.

3OO.

- Terpolymer with carboxyl groups-S.G. of approx. 1 _% produced by hydrolyzing a polyvinyl acetate / polymethacrylic acid copolymer " up to the given OH-S, G.

The finished casings of Examples 32 to 41 were similar to these

ORIGINAL BATHROOM

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1A-36 931 - 57 - '

from Example 29. The best results were with resins with an SG-. (OH) achieved by at least 95 % »

B e i s ρ ie I 42

This example illustrates the manufacture of synthetic Covering by coating a flat sheet material Fiber paper with melt-cast polyvinyl alcohol resin and then formed into a tube in one Closing process. . -

A sample of the calibrated polyvinyl alcohol resin mixture according to Example 30 became a at about 200 G flat soft, about 508 / U_ (20 mils) thick film extruded and this ITiIm. then as shown in Fig. '11 on and through a flat sheet of long fiber hemp paper (Dexstar),

ο
Weight 25.5 g / m% pressed. The pair of rolls were passed through the nip of the resin film and the web of paper, cooled (10 ⁰ C) had Ghromflachen. The coated and soaked material was about 254- / U (10 mils) thick. It was cut 15.24 cm (6 inches) wide and then passed through bath 352

led, which as a crosslinking agent is an aqueous solution, de-oil /

containing 1 % dimethyl urea and 0.2% lactic acid. The treated film was then shaped into a continuous tube, an aqueous 10 ^ solution of a polyvinyl alcohol / polyvinyl acetate copolymer containing 2 % glycerol, 1 % formaldehyde and 0.2 % lactic acid being used as the adhesive for the seam. Each time the seam adhesive hardened, the resin in the shell was fully cured and crosslinked in the dryer 359 at a temperature of up to 140 ° C.

The casing obtained did not tend to open along the seam.

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. 1Α-36 931 '

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burst when subjected to the usual tests became; their other properties resembled those the covers from the previous examples.

Examples 43 "to 45 - ■ '

The procedure of Example 42 was repeated with with the exception that a 30 / aige k acetone solution of toluene diisocyanate, butadiene diepoxide and ν- the diketene of dimerized linoleic acid was used I

The casings obtained corresponded in their strength and their brewing properties to the casings from Example 42.

In the above examples ^: A long fiber hemp paper was used as the paper in each case. In general, however, the same results are obtained if some other saturating material, "p ^ v / ebt / nonwoven", of adequate strength is chosen instead. In some cases the web material can be pretreated with a surfactant or crosslinking agent therewith the polyvinyl alcohol resin penetrates the material more easily. '-

In the general examples above only one was limited The number of compounds given as crosslinking agents for the polyvinyl alcohol resin filiae formed. However, the same results will be obtained with any other of the achieved crosslinking agents listed in the description. Of course, it can also be used without a crosslinking agent. be working; generally .become, but then less preferred cases received.

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The casings made according to the invention are essentially clear. However, the same processes can also be used for the production of colored casings. Such colored ones Cases are obtained, for example, xtfeim approved Pigments or dyes of the impregnating resin solution or the resin melt and / or the aftertreatment baths are added. "-

It should also be noted that in addition to Polyvinyl alcohol resin minor amounts, for example up to about 20 wt .- / o of other film-forming resins such as Polyvinyl acetate, amylose etc. can be used that usually added to the impregnating resin solution or the melt v / ground provided that these resins are compatible with the polyvinyl alcohol resin and the application conditions are compatible and the characteristic advantages in terms of strength does not affect the properties of the resin films.

It should also be pointed out that the casings produced according to the invention can additionally be coated, impregnated or chemically reacted with other monomeric or polymeric substances during or after the production process described in order to change the outer and / or inner surface of the polyvinyl alcohol resin film of the casing and the covers & ΰ. to adapt to certain special purposes. In general, the agents used as auxiliary agents of this type are those which are usually used in the case of cellulose casings, in order to give them a certain desired gloss, flexibility, strength, shrinkage, adhesive or non-adhesive properties, and wet strength. Water permeability, vapor permeability,

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• 1A-36 951

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Abriet », abrasion resistance, fungus resistance and other properties to rent. Particularly useful tools are, in addition to those described above, inside and outside applicable lubricants and release agents, for example oils, such as silicone oils and polymethylhydrοgensiloxane, fats, such as acetylated monoglycerides, Cj ^ -C ^ g fatty acid ketendimers, Cetyl alcohol or other compounds such as aluminum sulfate, lactic acid, inositol, methyl cellulose and garboxyjk methyl cellulose; shrinkage and adhesive coating agents to be applied to the inside; these can be proteinaceous Substances, e.g. mixtures of gelatine and acetylated monoglycerine as well as gelatine hardened with dialdehydes such as Glutaraldehyde and liquid smoke; continue to be applied to the outside coating substances that the. Reduce water and vapor permeability, for example vinylidene chloride homopolymers and copolymers (saran) as well polymeric mixtures of a paraffin wax and a dimerized ester of an epichlorohydrin-bis-phenol reaction product.

The tubular casings W produced according to the invention are primarily suitable for processing and packaging sausages, such as Bolognese sausages, etc. They can also be used for wrapping and packaging food and other products. The covers are also suitable as semipermeable membranes for purifying water by reverse osmosis and as fjaemodialysis membranes in artificial animals.

'"PATENT CLAIMS:

BAO ORiQIMAL

0098 20/18 85

Claims (1)

⁽ Iy fiber-reinforced synthetic resin film, preferably in the form of a tube, optionally with a longitudinal seam, characterized in that the synthetic resin is a film-forming, optionally crosslinked polyvinyl alcohol resin with a degree of substitution of at least about 2%, based on the OH groups. 2. Synthetic resin film according to claim. 1, characterized in that the polyvinyl alcohol resin has a degree of substitution with respect to the OH groups of about 25 to about 99.99 % and a degree of polymerization of at least about 800 and a polyvinyl alcohol / polyvinyl ester polymer or a carboxylated polyvinyl alcohol / polyvinyl ester resin with a degree of substitution With respect to the carboxyl groups up to about 25 ■ -> is. 3. Synthetic resin film according to claim 1 or 2, characterized characterized in that the polyvinyl alcohol resin additionally contains a plasticizer. ί \ ·. Synthetic resin film according to Claim 3, characterized in that the weight ratio of polyvinyl alcohol resin to plasticizer is 100 to approximately kO . 0 0 9 8 20/1885 bad original - • 2 "62, lA-36 931 5. synthetic resin film according to claim "! To U-, ciaaurclr g e k e η η ζ ei c h η e t that. the fiber core eats filling long fiber hemp paper. 6. A method for producing the fiber-reinforced synthetic resin film according to claim 1 "to 5, wherein a fiber web material impregnated with resin and coated, the resin solidifies and the film, if necessary, into a tube deformed, characterized in that one in and on the fibrous web material a continuous Film made from a film-forming polyvinyl alcohol which a degree of substitution with respect to UH groups of at least about 20; -5 has, separates and makes insoluble. 7, · The method of claim 6, characterized GEK e η η - ζ ei c Ii η et that - 'impregnating the FaserbeJinraaterial with a solution of Olyvinylalkoliolharzes uiiri "coated and Hegenerierunp. Of Polyvinylalkoholiiar ^ is the resin-impregnated sheet material with a The coagulating bath comes into contact or it evaporates the solvent from the resin-impregnated tooth material. 8. The method according to claim 7, dadur ..ι geke η η ζ eich η et that an organic solution of a polyvinyl alcohol resin is used as an organic solution of a polyvinyl alcohol resin, which has a degree of substitution rait he train on ütl groups of about 25 to about 99, 99 >'and a Poljnaerisationsgi ^ ad of at least about 800 and a polyvinyl alcohol / polyvinyl ester copolymer or a carboxylated polyvinyl alcohol / polyvinyl ester resin with a substitution gray with respect to carboxyl groups up to about 25 /. 9. A method according to claim 7, characterized GEK en η ze ic h η _.et that "man as Tränlcha.rzlösun £; verviendet a Polyvinylalkoholiiarses a w £ tssri-galkal is before solution having a Substitubionsgrad with reference to UH-Ginxppen from '' BAD ORIGINAL 009820/1885 -C3 - IA-3ό 931 comprising about 25 about 80 Dis> and a PolymerisationsgracL of at least about 800 and a PolyvinyIaI-alcohol / Polyvinylestercopolyrner or a carboxylated polyvinyl alcohol / polyvinyl ester resin with a substitution ie gracl with ^s;? ug of the carboxyl groups is up to about 25 · &,. 10. The method according to claim 7, characterized in that g e k e 11 11 - ζ eic Ii η et that the impregnating resin solution is an aqueous solution; an i-olvinylalkoliolharzes with a substitution graph with respect to OH groups of about BO to et about 99.99 7 * and a degree of polymerization of at least about 80 ° used. 11. The method according to claim 6, characterized in that the fiber web material with a plasticized, melt-cast film-forming Polyvinyl alcohol resin soaks and coats, the one Degree of substitution with reference to uE groups of at least 60; ö has. 12. The method according to claim 11, characterized in that a scimelzgeschossenes Holyvinyl alcohol resin is used, which contains up to about ^{1 part by} weight of plasticizer, ie 10 parts by weight of resin, free of i'-euc-aticity and practically melts evenly 220 ⁰ C at a temperature below etv \ ra. 13 · Method according to claim 6 to 12, characterized TTl Ώ Vl marked that / the synthetic resin film treated with a crosslinking agent 1 * 1 · .. The method according to claim 6 to 13, characterized in that one already becomes one 009820/1885 BATH ORIGINAL -Cb'- IA-36,931 'Tubing deformed fibrous web material soaks and. coated. 15. The method according to claim 6 to 13, characterized that you have a flat paserbahn material soaked and coated and then the resin-soaked and coated flat material obtained formed into a tube with a longitudinal seam closed with an adhesive. 7223 BATH ORIGINAL 009 820/18 85