DE2244231A1 - STEAM PERMEABLE COMPOSITIONS AND METHOD FOR MANUFACTURING THEM - Google Patents

Description

DR. MÜLLER-BORE DIPL-PHYS. DR. MANITZ DIPL-CHEM. ΟΠ. DE ¹ JFEL

DiPL-ING. FINSTERWALD dipl.-ing. GRÄMKOV /

PATENT LAWYERS

^r * Sep.

Wt / My - C 2605

CPC INTERNATIONAL INC., ENGLEWOOD CLIFFS, New Jersey / USA

Breathable compositions and methods for their

Manufacturing

The invention relates to novel polymeric compositions that are water vapor permeable and absorbent. The invention relates in particular to compositions which are permeable to water vapor with good physical properties that are valuable in the manufacture of a wide variety of coatings, films, and sheet materials are.

A large number of synthetic, vapor permeable or vapor permeable. Materials has been manufactured over the past decade with the aim of imitating leather and increasing comfort Increase wearing clothes that were made from synthetic polymeric materials. During earlier development Synthetic, vapor-permeable materials, such products were made by placing polymeric coatings on porous Applied substrates and then perforated the coatings with an embossing roller. With this procedure, remain visible Holes in the cover and this affects the appearance of the manufactured products that replace the leather should.

3000 ^ / 1018

Dr. Müller-Bor * Dr. Manitz Dr. Deiriel - Dlpl.-Irifl. F insterwald Dlpl.-Ing. Grimkov Braunschweig, Am BOrgerpark 8 8 Mönchen 22, Robert-Koch-StraB'e 1 7 Stuttgart-Bad Cannitatt, MarktatraB 3 Telephone (0631) 73887 Telephone (0811) 293845, T «lex 5-22050 mbpat Telephone (0711) 597281

__ I / .IL.L.-I -

22U231

Other work has involved making porous structures in which blowing agent and air were incorporated into the compositions to form a foam. In addition, volatile liquids were incorporated into the composition which, when blown, gave a porous structure such as water in poly (vinyl chloride) diastisols. Compositions containing soluble particles such as salt, ureas, starches and sugars were leached with chemicals capable of dissolving and decomposing the particles, leaving a permeable, porous matrix. A further development of this process used soluble fibers which, when leached from the composition, resulted in a network of holes that were the size of the fibers. Another modification of this process involved incorporating fine, fragile, hollow spheres into the coating composition, which were then reduced in size by machining the composition, leaving a permeable network.

Various other methods of making vapor permeable Coatings were developed. For example, polymer solutions such as those containing cellulose nitrate, cellulose acetate, urethane or nylon, slowly precipitated in the presence of non-solvent liquids or vapors and wherein microporous structures have been formed. Poly (vinyl alcohol) can be reacted with formaldehyde to form gel, creating a fine-pored sponge. Dry powders made from hard polymers such as poly (vinyl chloride) can be sintered being structures with a variety of pore sizes are formed.

It can be seen that in all of the methods described above for making vapor permeable films or coatings, actual there are open passages through which the moisture is transported through the permeable substance.

30ÖSI4 / 1016 _3_

Another approach has also been taken to impart vapor permeability to polymer coatings. In doing so, moisture-sensitive chemical groups were built into the various polymer backbones. In addition, moisture-sensitive polymers were dispersed in a matrix of hydrophobic polymer, compositions being obtained in which the water vapor transmission takes place by diffusion through hydrophilic parts. Most of these coatings show water vapor permeation. However, they tend to lose some of their physical properties when exposed to water for long periods of time. In many cases these films swell _$ they become sticky and lose their tensile strength »

It has now been found that water vapor permeable or water vapor permeable and absorbent films, coatings and sheet materials can easily be made which are good. have physical properties, even when exposed to water for long periods of time. In contrast to the mixtures _p in which the moisture-sensitive polymers are only dispersed within the hydrophobic matrix, in the composition according to the invention the hydrophilic materials are fused with the hydrophobic material, a homogeneous mixture being obtained which results in completely clear films on rolling » since the blends are thermoplastic in all materials and remain so, they can thin too much, clear, smooth films are processed, the uniformly swell when exposed to moisture, but wiedergewinnen- their original shape and properties during the subsequent drying. In most of the aforementioned mixtures, only the hydrophobic phase swells, which results in a rough surface and a loss of strength.

The present invention is a water-vapor composition containing

3000 * 4/101

-4- 22U231

(a) a hydrophilic linear thermoplastic polymeric material containing from about 10 to about 60 parts by weight of a homopolymer, copolymer or graft copolymer an unsaturated amide of the formula

R ¹ OR ²

I If

CH ₂ = C-C -'N

where R is hydrogen and / or alkyl with up to 4 carbon

P it.

atoms, R and R ^ mean alkyl with up to 4 carbon atoms, and

(b) a hydrophobic polymeric material containing from about 90 to about 40 parts by weight of a polymer such as Vinyl chloride, polyurethane, poly (methyl methacrylate), polyamide, polypropylene and / or polyester.

The term "linear" as used herein is intended to be both straight-chain and branched, as well as grafted or branched Graft polymers include, but include uncrosslinked and thermoset materials.

The hydrophilic thermoplastic polymeric materials of an α, β-unsaturated amide described above are known.

Alpha, beta-unsaturated amides can be obtained by many known methods, for example by pyrolysis of the reaction product of beta-propiolactone and an alkylamine, as described in US Pat. No. 2,548,155. The preferred polymers of α, β-unsaturated amides are obtained from N ₁ N-dimethylacrylamide.

3006 * 4/1011 - 5 -

The homopolymers and copolymers of the unsaturated amides described above can be prepared in solution systems by combining the monomers and a free radical catalyst such as benzoyl peroxide into one. Polymerization bottle or flask containing hexane, heptane or a similar liquid transfer medium and equipped with devices for temperature control, for stirring and for condensation of reaction vapors. If the mixture is heated for several hours and stirred at 50 to 70 ^° C., a polymer or copolymer is obtained which can be filtered, washed and dried ^{at 40 to 50 ° C. in vacuo.}

The comonomers that are used to prepare the copolymers of the <x, unsaturated Amides are suitable can be any polymerizable monomer, the polymer of which has a glass transition temperature below that of the homopolymer of the α, β-unsaturated Amids lies. Examples of, monomers include butyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, vinyl acetate, polymerizable esters of polyalkylene oxides such as acrylic acid, Methacrylic acid and maleic acid half esters of polyethylene or polypropylene oxides. Such esters are for example in U.S. Patent 3,277,157.

Graft copolymers or graft copolymers of α, ß-unsaturated Amides used as hydrophilic thermoplastic polymeric materials * are suitable can be prepared by known methods. In a preferred method, the α, β-unsaturated Amide is grafted onto a polymer backbone that has the appropriate glass transition temperature, as explained above. For example, N, NrDimethylacrylamid can be added to the backbone grafted on by butyl acrylate using benzyl peroxide will. Alternatively, the polymerizable monomers mentioned above, especially the polymerizable esters, can be used the polyalkylene oxides, on the basic structure of the α, β-unsaturated

303034/1015

Amides, for example of Ν, Ν-dimethylacrylamide, grafted on will.

The hydrophobic polymeric materials of the invention, Polyblends are well known and readily available. Examples suitable hydrophobic polymeric materials include polymers of vinyl chloride, polyurethane, poly (methyl methacrylate), Polyamide and polyester.

The polymers of vinyl chloride include poly (vinyl chloride), copolymers of vinyl chloride with vinyl acetate, vinylidene chloride or acrylonitrile as well as plasticized polymers and copolymers of vinyl chloride that are at least approximately Contain 85% by weight of poly (vinyl chloride).

The polyurethane polymers necessary for the water vapor permeable composition Can vary widely and include both the reaction products of isocyanates with Polyether as well as polyester. Examples of isocyanates useful in making the polyurethane polymers used for the vapor permeable compositions of the invention that can be used include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Tolidine diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate and the like.

Examples of polyethers for making the polyurethane polymers include poly (oxypropylene) glycols, poly (oxypropylene) adducts of glycerine, poly (oxypropylene) adducts of tri-methylolpropane, poly (oxypropylene) adducts of 1,2,6-hexane

tnric triol, poly (oxypropylene) adducts of pentaacrylthritol, pentaery / Poly (oxypropylene) adducts of sorbitol, polytetrahydrofuran polyether, those with methylene-bis-phenyl diisocyanate and hydrazine were extended, and the like.

The polyesters for the urethane polymers of the present invention include the reaction products of adipic acid or phthalic anhydride with any ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, diethylene glycol, 1,2,6 = Hexanetriol trimethylolpropane or 1,1,1-trimethylolethane.

Polyamides useful in the present invention include, for example, 6-nylon, 6,6-nylon, 6,10-nylon, and theirs Copolymers.

Poly (methyl methacrylate) polymers useful in the present invention useful are the well-known, commercially available products.

The polyesters that make up the water vapor permeable composition can be used are the fiber-forming reaction products of aromatic dicarboxylic acids with polyhydroxy compounds and include poly (ethylene) terephthalate and poly (cyclohexanedimethanol) terephthalate.

In addition to the essential ingredients, which are the polymers described above, it may be preferred in some cases * to incorporate additional ingredients into the water vapor permeable compositions according to the invention. In some Cases may include a plasticizer for either or both of the polymeric materials in an amount from about 5 to about 100 parts by weight per 100 parts by weight of the mixture of hydrophilic and hydrophobic polymeric materials may be desirable. The particular amount of plasticizer that is used is made up of the hydrophobic polymer used and the ratio of hydrophilic to hydrophobic polymer! Material and the Depend on the end use of the product. For example, when using poly (vinyl chloride) as the hydrophobic polymeric material, a plasticizer can be used to make the resulting composition flexible as well as elastomeric.

3ÖÖÖ34 / 101S

Examples of plasticizers that can be used are dioctyl phthalate, tricresyl phosphate, trioctyl phosphate, esters of adipic acid, azelaic acid and sebacic acid, trioctyl maleate ester and polyester such as the Paraplex products from Rohm and Haas, polyalkylene oxides including polyethylene and polypropylene oxide, known as Carbowaxe. Particularly advantageous Results are obtained using more than one plasticizer such as dioctyl phthalate together with polyethylene oxide.

Other ingredients included in the vapor permeable compositions may be incorporated include pigments for coloring, fillers, heat stabilizers, UV absorbers The use of these additives is familiar to the person skilled in the art and does not require any further explanation.

As mentioned above, the invention contain water vapor permeable Compositions of about 10 to 60 parts by weight of the hydrophilic thermoplastic polymeric material and 90 to 40 parts by weight of the hydrophobic polymeric material as before described. In a preferred embodiment of the invention the composition contains from about 25 to about 50 parts by weight of the hydrophilic thermoplastic polymer Materials and from about 75 to about 50 parts by weight of the hydrophobic polymeric material. In general, the best results are obtained when using a mixture of the same Weight of the hydrophilic polymeric material and the hydrophobic material used. In general, an increase in the proportion of the first polymer in comparison with the second polymer an increase in the water vapor permeability and Absorbency and a decrease in the tensile strength of the Films or foils made from it. As a result, the corresponding proportions of the Polymers can be varied, taking into account the properties of the finished product Can adjust the product accordingly.

3ÖÖÖ34 / 101S

The vapor-permeable compositions according to the invention can be made by physically mixing the individual ingredients in various ways, for example the mixing can take place with solvents or as an emulsion, the medium can then be evaporated or you can dry mix at elevated temperatures using the shear forces.

Mixing with a solvent dissolves the thermoplastic hydrophilic and hydrophobic polymeric materials in a suitable solvent, pour the solution onto the desired substrate and evaporates the solvent, leaving the vapor permeable composition as a film or coating remains on the substrate. This film can either remain on the substrate or, if desired, it can be replaced by suitable means Measures are deducted. This process for the preparation of the composition according to the invention is valuable, when thin films or coatings are desired, or when maximum penetration into a porous or woven substrate it is asked for.

In many cases the hydrophobic polymeric material described in the present application is in the form of an emulsion to disposal. Since the polymers made from the unsaturated amides described are water soluble are, aqueous solutions of these polymers can easily be dispersed in the emulsion of the second polymer, whereby one receives homogeneous mixtures. The resulting mixtures can then be used to coat the desired substrate then the water can be evaporated to obtain the vapor permeable composition. The mixing the aqueous solutions of the first polymer with emulsions of the second polymer has the advantage that this process is safer and avoid the risk of using volatile solvents.

- 10-

The preferred method of making the invention Water vapor permeable compositions consists in that you get the polymers in the dry state and without the use mixed by solvents. This can be achieved by first typing the required components into granular or powder form mixed and then mixed the mixture with moderately high shear forces at temperatures close to the softening point exposed to the mixture. All of the additives that should be present in the finished composition can be used at the beginning can be added to the mixture. A variety of processing devices are available with which one can take Use of shear forces can mix intimately. One can use two roller mills such as those used in the rubber industry Sigma mixing devices or Pfleider mixers, Use a banburry mixer and screw extruder. These devices are examples of mixing devices. The temperature at which the polymeric mixture is processed will vary depending on the individual components. However, one will choose a temperature which is close to the softening point of the polymers used. However, care must be taken not to look at the decomposition temperature of any of the Constituents approaching. Thermal stabilizers for the polymers can be used when the polymer decomposes Causes trouble. In many cases, the use of a plasticizer will set the temperature at which a particular one Polymer mixture processed on the device described above can become, humiliate.

The water vapor permeable and absorbent according to the invention Compositions and their preparation are described in more detail in the following examples. These examples explain the invention without, however, limiting it.

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309034/1015

example 1

Production of a vapor-permeable film from a polyvinyl chloride-poly (N, N-dimethylacrylamide) -polyblend

Powdered polyvinyl chloride (50 g, Vygen, a product of General Tire and Rubber Co.) Powdered poly (N, N-dimethylacrylamide) (50 g) and barium cadmium stearate heat stabilizer (3 g) were mixed in a paper cup. Dioctyl phthalate (60 g) was added to the polymer mixture and then stirred until a uniform mixture was obtained. The mixture was then processed on a two -'Walzenmühle at a temperature of about 149 ° C (300 ⁰ F) until it was melted. After this time, the molten mixture was further milled for about 5 to 10 minutes until a uniform plastic mass was obtained. This mass was then removed from the roller and ^{pressed at a temperature of approximately 149 0} C (300 ⁰ F) between two chrome steel plates, which were separated by suitable spacer frames, so that thin foils with a thickness of 0.25 mm and 0, 5 mm (10 and 20 mils). The films were then cooled to room temperature. The desired product was obtained.

Example 2

Production of a vapor-permeable film from a polyvinyl chloride-poly (N, N-dimethylacrylamide) -poly mixture

Powdered polyvinyl chloride (60 g, Vygen, a product of General Tire and Rubber Co.), powdered poly (N, N-dimethylacrylamide) (40 g), and barium cadmium stearate heat stabilizer (3 g) were mixed in a paper cup. Dioctyl phthalate (60 g) was added to the polymer mixture and then stirred until a uniform mixture was obtained. The mixture was then processed on a two-roll mill at a temperature 'of about 149 ° C (300 ⁰ F) until melted. After this time, the molten mixture became an additional 5 to 10

Mill for minutes to ensure that a uniform plastic mass was obtained. This mass was then removed from the mill and ^{pressed at a temperature of approximately 149 0} C (30O ⁰ F) between two chrome steel plates, which were separated by suitable spacer frames, using foils with a thickness of 0.25 mm and 0.5 mm (10 and 20 mils). The films were then cooled to room temperature, thereby obtaining the desired product.

Example 3

Production of a vapor-permeable film from a polyvinyl chloride po Iy- (N, N-dimethy! Acrylamide) poly blend

Powdered polyvinyl chloride (67 g, Vygen, a product of General Tire and Rubber Co.), powdered poly (N, N-dimethylacrylamide) (33 g), and barium cadmium stearate heat stabilizer (3 g) were mixed in a paper cup. Dioctyl phthalate (60 g) was added to the polymer mixture and then stirred until a uniform mixture was obtained. The mixture was then processed on a two roll mill at a temperature of approximately 149 ^° C (300 ^° F) until it melted. After this time, the molten mixture was milled for an additional 5 to 10 minutes to ensure that a uniform plastic mass was obtained. This mass was then removed from the mill and ^{pressed at a temperature of approximately 149 0} C (300 ⁰ F) between two chrome steel plates, which were separated by suitable spacer frames, using thin foils with a thickness of 0.25 mm and 0.5 mm (10 and 20 mils). The films were then cooled to room temperature to give the desired product.

Example 4

Production of a vapor-permeable film from a polyvinyl chloride-poly (N, N-dimethylacrylamide) -poly mixture

309834/1016

- 13 -

Powdered polyvinyl chloride (75 g, Vygen, a product of General Tire and Rubber Co.) "Powdered poly (N, N-dimethylacrylamide) (25 g) and barium cadmium stearate heat stabilizer (3g) were mixed in a paper cup", dioctyl phthalate (60 g) was added to the polymer mixture and then stirred until a uniform mixture was obtained. The mixture was then processed on a two roll mill at a temperature of approximately 149 ° C (300 ° F) until it melted. After this time, the molten mixture was milled for an additional time of about 5 to 10 minutes to ensure that a uniform plastic mass was obtained. This hasse was then removed from the mill and kept at a temperature of about 149 C (300 ^° F ) between two chrome steel plates separated by suitable spacer frames to give thin sheets 0.25 mm and 0.5 mm (10 and 20 mils) thick. The films were then cooled to room temperature to give the desired product.

Example 5

Production of a vapor-permeable film from a polyvinyl chloride po Iy (N, N-dimethylacrylamide) poly blend

Powdered polyvinyl chloride (86 g, Vygen _s a product of General Tire and Rubber Co.), powdered poly (N, N-dimethylacrylamide) (14 g) and barium cadmium stearate heat stabilizer (3 g) were mixed in a paper cup. Dioctyl phthalate (60 g) was added to the polymer mixture and then stirring, until a uniform mixture was ■> The mixture was then processed on a two-roll mill at a temperature of about 149 ° C (300 ⁰ F) until melted . After this time, the molten mixture became another. Mill for about 5 to 10 minutes to ensure that a uniform plastic mass is obtained. This mass was then removed from the mill and stored at a temperature

309834/1016 " ¹⁴ ~

.14-22U231

of approximately 149 ^° C (300 ^° F) between two chrome steel plates separated by suitable spacer frames to give thin sheets 0.25 mm and 0.5 mm (10 and 20 mils) thick. The films were then cooled to room temperature to give the desired product.

Example 6

Production of a vapor-permeable film from a polyvinyl chloride-poly (Ν, Ν-dimethylacrylamide) -poly mixture

Powdered polyvinyl chloride (60 g, Vygen, a product of General Tire and Rubber Co.), powdered poly (Ν, Ν-dimethylacrylamide) (40 g), and barium cadmium stearate heat stabilizer (3 g) were mixed in a paper cup. A low molecular weight polyester plasticizer (60 g, Paraplex G-33 »a product of Rohm and Haas Co.) was added to the polymer mixture and then stirred until a uniform mixture was obtained. The mixture was then processed on a two roll mill at a temperature of approximately 149 ^° C (300 ^° F) until it melted. After this time, the molten mixture was milled for an additional time of about 5 to 10 minutes to ensure that a uniform plastic mass was obtained. This mass was then removed from the mill and ^{pressed at a temperature of approximately 149 0} C (300 ⁰ F) between two chrome steel plates, which were separated by suitable spacer frames, using thin foils with a thickness of 0.25 mm and 0, 5 mm (10 and 20 mils). The films were then cooled to room temperature to obtain the desired product.

Example 7

Production of a vapor-permeable film from a polyvinyl chloride-poly (Ν, Ν-dimethylacrylamide) -poly mixture

Powdered polyvinyl chloride (60 g, Vygen, a product of

309834 / 1Ö16 - 15 -

General Tire and Rubber Co.) Powdered poly (N, N-dimethylacrylamide) (40 g) and barium cadmium stearate heat stabilizer ("3 g) were mixed in a paper cup. Dioctyl phthalate (100 g) was added to the polymer mixture and then stirring until obtaining a uniform mixture * the mixture was then placed on a two-roll mill (F 300 ⁰⁾ processed at a temperature of about 149 ⁰ C, until it. jSehmolz. After this time, the molten mixture was added a ^ more time ground of about 5 to 10 minutes to ensure that erhiisit a uniform plastic mass. This mass was then removed from the mill and suitable at a -temperature of about 149 ° C (300 ⁰ F) between two stainless steel plates separated by Spacer frames were weighed separately and pressed to give thin films 0.25 mm and 0.5 mm (10 and 20 mils) thick, and the films were cooled to room temperature to give the desired product.

Example 8 -_ ■, - .-. L ·

Production of a vapor-permeable film from a polyurethane-poly (N, N-dimethylacrylamide) poly ^{mixture ίν}

Granular polyurethane rubber (60 g, Estane, v; a product of BFGoodrich Co.) and powdered poly (N, N-diethylacrylamide) (40 g) were mixed in a paper cup. The mixture was then processed on a two roll mill at a jty temperature of about 149 to about 163 ° C (300 to 3SIf ⁰ F) until it melted. After this time, the molten mixture was milled for an additional time of about 5 to 19 minutes to ensure that a uniform plastic mass was obtained. The mass was then removed from the mill and pressed at a temperature of about 14 ° C (30O ⁰ F) between two chrome steel plates separated by suitable spacer frames, using thin sheets 0.25 mm thick and 10 and 20 mils (0.5 mm). The films were cooled to room temperature and the desired product was obtained.

3098U / 101S -16-

ORJGtNALlNSPECTED

-16- 22U231

Example 9

Production of a vapor-permeable film from a poly (methyl methacrylate) -poly (N, N-dimethylacrylamide) -poly mixture

Granulated poly (methyl methacrylate) (75 g), powdered poly (N, N-dimethylacrylamide) (25 g) were mixed in a paper cup. The mixture was then processed on a two roll mill at a temperature of approximately 149 to 163 ^° C (300 to 325 ^° F) until it melted. After this time, the molten mixture was milled for an additional time of about 5 to 10 minutes to ensure that a uniform plastic mass was obtained. This mass was then removed from the mill and ^{pressed at a temperature of approximately 149 0} C (300 ^o F) between two chrome steel plates, which were separated by suitable spacer frames, using thin foils with a thickness of 0.25 mm and 0, 5 mm (10 and 20 mils). The films were cooled to room temperature, thereby obtaining the desired product.

Example 10

Production of a vapor-permeable film from a polyamide-poly (N, N-dimethylacrylamide) poly mixture

Granular polyamide (75 g, nylon 6,6) and powdered poly (N, N-dimethylacrylamide (25 g) were mixed together. The mixture was ineinen small laboratory-screw extruder at a temperature of about 260 ⁰ C (500 ⁰ F), where The product was then deformed by pressing at a temperature of approximately 260 ^° C. (500 ^° F.) between two chrome steel plates separated by suitable spacer frames to form thin sheets of 0.25 mm and 0.5 mm (10 and 20 mils) The films were then cooled to room temperature to give the desired vapor permeable product.

309Ö34 / 1Ö1S - ¹⁷ -

Example 11

Production of a vapor-permeable film from a polyester-poly (N, N-dimethylacrylamide) poly mixture

Powdered polyester, a reaction product of phthalic acid and a diol (75 g, Vituf, a product of Goodyear Corp.), and powdered poly (N, N-dimethylacrylamide) (25 g) were mixed into a uniform mixture. The mixture was then placed in a laboratory extruder at a temperature of about 288 ° C (550 ^o F) and extruded to obtain a homogeneous product. The product was (500 F ⁰⁾ is then deformed by pressing at a temperature of about 26O ⁰ C between two stainless steel plates that were separated by appropriate spacer frame to yield thin films having a thickness of 0.25 mm and 0.5 mm (10 and 20 mils). The films were cooled to room temperature to obtain the desired vapor permeable product.

Example 12

Production of a vapor-permeable film from a. Polyvinyl chloride Poly (N, N-dimethylacrylamide) poly blend

Powdered polyvinyl chloride (40 g, Vygen, a product of General Tire and Rubber Co.), powdered poly (N, N-dimethylacrylamide) (60 g), and barium cadmium stearate heat stabilizer (3 g) were mixed in a paper cup. Tricresyl phosphate (60 g) was added to the polymer mixture and then stirred until a uniform mixture was obtained. The mixture was then processed on a two-roll mill at a temperature of about 149 ° C (300 ⁰ F) until melted. After this time, the molten mixture was milled for an additional time of approximately 5 to 10 minutes to ensure that a uniform mass was obtained. This mass was then removed from the mill and placed at a temperature of approximately 149 ⁰ C (30O ⁰ F) between two chrome

- 18 -

steel plates, which were separated by suitable spacer frames, pressed, using thin foils with a thickness of 0.25 mm and 0.5 mm (10 and 20 mils). The films were then cooled to room temperature, whereby the desired Product received.

The properties of the water vapor permeable according to the invention Compositions were determined according to various standard testing procedures.

The ability of the compositions to absorb water at both room temperature and the boiling temperature of water was determined by determining the change in weight of a sample after immersion over a period of time. The test samples were in the form of a rod 12.7 cm (5 inches) long, 1.27 cm (1/2 inch) wide, and 0.5 mm (20 mils) thick. After the samples were weighed, they were immersed in distilled water for 1 hour and 18 hours at room temperature and in boiling water for 1 hour. The test samples were then wiped off and immediately weighed to determine the water absorption capacity of the composition. After this initial weighing, the samples were ^{dried at a temperature of 70 °} C. for a period of 2 hours and then weighed again in order to determine the amount of material which had been leached from the composition during the immersion period. The results of these tests are given in the following tables. Table I shows the weight change of the samples. This value corresponds to the water absorption of the compositions according to the invention after various immersion times both in water at room temperature and in boiling water. Table II shows the weight change of the dry samples after the water absorption test has been carried out. These values correspond to the loss

309834 / 1Ö1S - ¹ 9 -

Product due to the leaching of hydrophilic material the composition. The results in Tables I to III are expressed in percent by weight.

Table I. Water absorption of the test compositions

Immersion time

Test sample V .E.g 1
b .1 Hours.
Room temp. 18 hours
b.Room temp. II , 9 V .E.g . 1 1 H.
b.Room temp Immersion time Oil 1 H.
at 100 ^° C , 0 -1.5 product V Il 2 31 44 Λ V Il
• 2 18th
• bi 44 , 7 -0.6 product V Il 3 19th 21 V Il 3 not examined 19th , 07 -0.3 product V Il 4th 1.9 9 V Il 4th -0.7 12th , 13 -0.2 product V Il
• 5. 1.1 6th V Il 5 -0.1 10 , 06 +0.1 product V Il 6th 0.5 3 V Il 6th -0.1 6th Λ -1.8 ' product V Il 7th 15th 23 V Il 7th 0.0 33 , 3 -0.15 product V Il
• 8th 13th 18th V Il
• 8th 11 , 0 decomposition product V Il 9 107 205 V Il 9 decomposition , 0 +0.6 product V Il 10 • 2.9 7, V It
• 10 19th , 17th +2.1 product 6.8 15, 15.7 Tabel not examined -0.2 after leaving Weight change of dry compositions
sorption attempt not examined Hour 1 hour
Room temp. at 100 C -1 ? -1 +1.2 -0 Test sample 3Ö9Ö34 / 1 -0 product -0 product -0 product -1 product -0 product -3 product -1 product +0 product product product

- .20 -

-20. 22.U231

The water absorption properties of the second polymer used in the compositions of the examples was intended for control purposes. These experiments followed exactly the same procedures as were used for the compositions described in Table I were used. Furthermore, the second polymer was identical to that in the compositions used in the examples. The results of these tests are given in Table III.

Table III Water absorption of the control samples

Immersion time

1 hour 18 hours 1 hour test samples at room temp. b.Room temp. at 100 C

Polyvinyl chloride " ¹ " 0.04 0.1 1.5

Polyurethane rubber 1.0 1.0 melted

Poly (methyl methacrylate) 0.2 1.0 2.2

Polyamide 1.3 6.2 7.0

+ The sample contained 60 parts by weight of dioctyl phthalate Weiclmacher per 100 parts by weight of polyvinyl chloride.

The tensile strength in kg / cm (pounds per square inch) of the various vapor permeable compositions according to the invention was determined under various conditions, which are referred to below as conditions A, B, C or D. Tensile properties were measured according to the method corresponding to ASTM Method D638-64T. Condition A means the condition of the product immediately after manufacture. Condition B means the state of the product after immersion in boiling water for a period of 1 hour and subsequent drying at a temperature of 70 ^° C. for a period of 2 hours. Condition C means the condition of the product after it has been exposed to a relative humidity of 85% at room temperature for 18 hours. Condition D means the condition of the product after it is in water

309Ö34 / 101S - ²¹ *

Room temperature was immersed for a period of 18 hours and then ^{dried at 70 0} C for a period of 2 hours. The results of these tests are expressed in kg / cm (pounds per square inch) and are reported in Table IV. '·

Table IV Tensile Strength

Test sample

condition

Product v.Bps.1 87.9 (1250)

Product v. »2 127 (1800)

Product v. «3 142.5 (2020)

Product v. »4 141 (2000)

Product v. "5 166 (2370)

Product v. "6 75 (1070)

Product v. »7 35.2 (500)

Product v. »8 336 (5200)

Product v. »9 408 (5800)

86 (1220) not investigated

133 (1890) 88 (1250) 143 (2040) 95 (1360) 149 (2110) 89 (1270) 162 (2300) 141 (2000) 84 (1200) not under.

35.2 (500) 26.7 (380) decomposition 32.3 (460) 471 (6700) 478 (6800)

91.4 (1300) 120 (1700) 118 (1680) 127 (1800) 143 (2040) 73.8 (1050) 33.7 (480) 73.8 (1050) 619 (8800)

The value of the compositions of the invention as vapor permeable materials was shown in tests in which the water vapor transmission of foils with a thickness of 0.25 mm (.10 mils) was determined. ASTM test method E96-63T (B) was used in this experiment. In this procedure the amount of water vapor is measured in g that passes through a sample that is on one side of a 100% relative humidity and on the other hand is exposed to 50% relative humidity. The results this procedure are in grams of water that in 24 hours

2
penetrate per m of surface, 'expressed. The results

are listed in Table V.

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309034/1016

- 22 Table V

22U231

Water vapor transmission

g / 24h / m ²

Product of Example 1 550

Product of Example 2 380

Product of Example 3 48

Product of example k 28

Product of Example 5 16

Product of Example 6 280

Product of Example 7 300

Product of Example 8 472

The water vapor transmission of polyvinyl chloride with dioctyl phthalate was plasticized in a 100 to 60 weight ratio was also determined for control purposes and man found that the water vapor transmission was 9 g / 24 h / m.

It has been found that films made from poly-hybrids hydrophobic polymers such as polyvinyl chloride and various modified polymers of unsaturated amides were made, have excellent physical properties and, in some cases, the modified polymers give superior ones Properties compared to the poly blends in which homopolymers of unsaturated amides are used. It has been found, for example, that copolymers of unsaturated amides with polymers with a lower Glass transition temperature have a strong influence on the strength of films made from the poly blend. Others modified Polymers of the unsaturated amides include graft copolymers of unsaturated amides such as the graft copolymers of N, N-dimethylacrylamide and butyl acrylate prepared by placing the former on a poly (butyl acrylate) backbone grafted with a free radical catalyst, for example benzoyl peroxide, or by converting a maleate half ester

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Polyethylene oxide (with a molecular weight of 600 to 1500) grafted onto a basic structure of Ν, Ν-dimethylacrylamide. For example, Ν, Ν-dimethylacrylamide can be used with the maleate half ester in the presence of azobisisobutyronitrile catalyst react in a benzene solvent.

Example 15

Production of a vapor-permeable film from a polyvinylchloride-poly (Ν, Ν-dimethylacrylamide) / butyl acrylate copolymer polymer mixture

The mixed polymer of Ν, Ν-dimethylacrylamide / butyl acrylate was in a non-aqueous teterogenic polymerization system using heptane as a transfer medium and a stearate salt as a surfactant. the Polymerization was initiated with azobis (isobutyronitrile), with a copolymer in the form of a suspension or unstable emulsion with an average particle size between a conventional aqueous suspension and emulsion polymers received. The copolymer was collected by filtration and analyzed. It was found to have the following composition had: 90/10 poly (Ν, Ν-dimethylacrylamide) / butyl acrylate copolymer.

Powdered polyvinyl chloride (45 g, Vygen 110, a product of General Tire and Rubber Co), powdered interpolymer of Ν, Ν-dimethylacrylamide and butyl acrylate, prepared as described above, (55 g) and barium cadmium stearate heat stabilizer (3 g ) were mixed in a paper cup. Dioctyl phthalate (60 g) was added to the polymer mixture and then stirred until a uniform mixture was obtained. The mixture was then processed on a two-roll mill at a temperature of about 149 ° C (300 ⁰ F) until melted. After this time, the molten mixture was milled for an additional time of approximately 5 to 10 minutes to ensure that

30983-4 / 1015

a uniform plastic mass was obtained. The mass was then removed from the mill and ^{pressed at a temperature of approximately 149 0} C (30O ⁰ F) between two chrome steel plates, which were separated by suitable spacer frames, using thin foils with a thickness of 0.25 mm and 0, 5 mm (10 and 20 mils). The films were then cooled to room temperature to give the desired product.

Example 14 '

Manufacture of a vapor-permeable film from a polyvinyl chloride-poly (N, N-dimethylacrylamide) / butyl acrylate-mischpoly merisat-polymischunff

Powdered polyvinyl chloride (50 g, Vygen 110, a product of General Tire and Rubber Co.), powdered copolymer of poly (N, N-dimethylacrylamide) and butyl acrylate, prepared as described in Example 13, (50 g) and barium cadmium stearate - Heat stabilizer (^ were mixed in a paper cup, dioctyl phthalate (60 g) was added to the polymer mixture and then stirred until a uniform mixture was obtained. The mixture was then processed on a two-roll mill at a temperature of approximately 149 ^° C ( 300 ^° F) until it melted, after which time the molten mixture was milled for an additional time of about 5 to 10 minutes to ensure that a uniform plastic mass was obtained Temperature of about 149 ⁰ C (300 ⁰ F) between two chrome steel plates, which were separated by suitable spacer frames, pressed, using thin foils with a thickness of 0.25 mm un d received 10 and 20 mils (0.5 mm). The films were then cooled to room temperature to give the desired product,

Example 15

Production of a vapor-permeable film from a polyvinyl chloride-poly- (Ν, Ν-dimethylacrylamide) / butyl acrylate-mischpolymeri sat-polymi research

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Powdered polyvinyl chloride (55 g, Vygen 110, a product of General Tire and Rubber Co.), powdered copolymer of poly (N, N-dimethylacrylamide) / butyl acrylate, prepared as described in Example 13 above, (45 g) and barium Cadmium stearate heat stabilizer (3 g) was mixed in a paper cup. Dioctyl phthalate (60 g) was added to the polymer mixture, followed by stirring to ensure that the mixture was uniform. The mixture was then processed on a two-roll mill at a temperature of about 149 ° C (300 ⁰ F) until melted. After this time, the molten mixture was milled for an additional time of about 5 to 10 minutes to ensure that a uniform plastic mass was obtained. The mass was then removed from the mill and (300 ⁰ F) between two stainless steel plates that were separated by appropriate spacer frame, pressed at a temperature of about 149 ° C to obtain thin films having a thickness of 0.25 mm and 0, 5 mm (10 and 20 mils). The films were then cooled to room temperature to give the desired product.

Example 16

Production of a vapor-permeable film from a polyvinyl chloride-poly (N, N-dimethylacrylamide) / butyl acrylate-mixed polymer-poly mixture «-________« _____

Powdered polyvinyl chloride (60 g, Vygen 110, a product of General Tire and Rubber Co.), powdered copolymer from Poly (N, N-dimethylacrylamide) / butyl acrylate (40 g) and barium cadmium stearate heat stabilizer (3 g) were mixed in a paper cup. Dioctyl phthalate (60 g) was added to the polymer blend and then stirred until a uniform mixture was obtained. The mixture was then on a Two roll mill operated at a temperature of about 149 ° C (300 ° F) until it melted. After this time, the melted Mix for a further time of about 5 to 10 minutes

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grooves ground to ensure that a uniform plastic mass was obtained. This mass was then removed from the mill and pressed at a temperature of approximately 149 ° C (30O ⁰ F) between two chrome steel plates, which were separated by suitable spacer frames, using thin foils with a thickness of 0.25 mm and 0, 5 mm (10 and 20 mils). The films were then cooled to room temperature to give the desired product.

Example 17

Production of a vapor-permeable film from a polyvinyl chloride-poly (N, N-dimethylacrylamide) / butyl acrylate-mixed polymer-polymer mixture

Powdered polyvinyl chloride (65 g, Vygen 110, a product of General Tire and Rubber Co.), powdered copolymer of poly (N, N-dimethylacrylamide) / butyl acrylate, prepared according to Example 13, (35 g) and barium cadmium stearate heat stabilizer (3 g) were mixed in a paper cup. Dioctyl phthalate (60 g) was added to the polymer mixture and then stirred until a uniform mixture was obtained. The mixture was then processed on a two roll mill at a temperature of approximately 149 ^° C (300 ^° F) until it melted. After this time, the molten mixture was milled for an additional time of about 5 to 10 minutes to ensure that the mass was uniform. This mass was then removed from the mill and ^{pressed at a temperature of approximately 149 0} C (30O ⁰ F) between two chrome steel plates, which were separated by suitable spacer frames, using thin foils with a thickness of 0.25 mm and 0, 5 mm (10 and 20 mils). The films were then cooled to room temperature to give the desired product.

The properties of the water vapor permeable compositions, obtained in Examples 13 to 17 were made according to

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Standard test procedures as described in "Examples 1 Ms 10 are examined. The results of these tests are summarized in Table VI below.

WVT

Test samples

Table VI 18 hours
- RT ^c the test- 39 b. 1 H,
b 100 ° C % Water absorption
composition 33 43.5 n ² '18 hours b *
85% RH ^D 27 35.7 8.8 24 23.8 7.9 14th 14.2 7.4 13.2 6.4 5.3

Product v.Bps 13 450

Product v. »14 370

Product v. »15 270

Product v. "16 150

Product v. "17 50

^a water vapor transmission

relative humidity ^c room temperature

The results in Table VI show that the polyblends of polyvinyl chloride and the copolymers of N, .N-dimethylacrylamide and butyl acrylate excellent water vapor transmission and have water vapor absorption properties. It is also from the properties given in Table VI it can be seen that these properties are improved as increasing amounts of the hydrophilic polymer are employed. Different expressed, the water vapor permeability of the films reduced when the relative amount of acrylamide polymer in the composition is reduced.

The polymer blends made in Examples 13-17 were clear thermoplastics with an unexpectedly improved one Compatibility with polyvinyl chloride, compared with the poly blend from the homopolymer of Ν, Ν-dimethylacryl-

-ZB-

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amide. The copolymer results in stronger films that are free from defects such as "fish eyes". The loss of copolymer after extended immersion times in water at room temperature, or at 10O ⁰ C does not exceed 1%. This indicates the unusual stability of this poly blend.

It was also not to be expected that the addition of acrylamide polymers to the plasticizer-containing polyvinyl chloride polymi loops according to the invention would not bring about a reduction in the abrasion resistance and that the properties of the polyvinyl chloride would not change at low temperatures. It has surprisingly also been found that, depending (-20 ⁰ F) occurs from the plasticizer used, no embrittlement -28.9 to ⁰ C.

Similar favorable properties with regard to the water vapor permeability are obtained if the copolymer is made from Ν, Ν-dimethylacrylamide and butyl acrylate with other hydrophobic Polymers such as polypropylene, poly (methyl methacrylate), polyamide (nylon), polyurethane and polyacrylonitrile mixed. Movies from these poly-mixes adsorb and perspire moisture similar to leather.

Copolymers of Ν, Ν-dimethylacrylamide with other monomers, which have a glass transition temperature (Tg) which is lower than that of poly- (N, N-dimethylacrylamide), also have similar water vapor permeable properties, when mixed with polyvinyl chloride. For example, it has been found that 2-ethylhexyl acrylate, acrylonitrile, vinyl acetate and polymerizable esters of polyalkylene oxide copolymers with Ν, Ν-dimethylacrylamide, which form stable polymi loops with polyvinyl chloride.

The unsaturated polymers have been found to be opposite Effect on the resulting ground films

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can exercise «. For example, if the polymer is an unsaturated Amides such as poly (N, N-dimethylacrylemide) hard particles contains, these particles often do not melt with the polyvinyl chloride and dioctyl phthalate during the milling process. The resulting films will therefore contain numerous small spots that will become even more noticeable when the films are stretched or when exposed to moisture. If pigments are used to color the films, these parts become in addition, the pigments do not absorb, which makes the film appear speckled. The water vapor transmission those films containing the infusible particles are also greatly reduced, as is the tensile strength.

One way to turn off the previously mentioned problem, is to increase the shear forces on the mill, i.e. to grind the material without the use of a plasticizer and then after the mixture of polyvinyl chloride and Poly (N, N-dimethylacrylamide) is melted to add the plasticizer. However, this method is sometimes not practical and brings with it a certain degradation, due to the harsh conditions in the first stage

It has now been found that the presence of these particles can be completely avoided and that one becomes more uniform Results obtained when the polymer from the unsaturated amide such as from poly (N, N-dimethylacrylamide) treated with water It looks like the water softens the polymer and lowers the Tg enough that the polymer is smooth with it the hydrophobic polymer, the polyvinyl chloride and the plasticizer, Dioctyl phthalate can be milled using normal, relatively mild conditions «,

The following examples illustrate the good results obtained when using the polymer from the unsaturated amide used together with moisture.

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Example 18

Production of a water-permeable film from a poly vinyl chloride-poly (N, N-dimethylacrylamide) -poly mixture

Powdered polyvinyl chloride (90 g, Vygen 110, a product of General Tire and Rubber Co.), poly (N, N-dimethylacrylamide) containing hard particles (60 g), and barium cadmium stearate heat stabilizer (3 g) were used mixed in a paper cup. Dioctyl phthalate (90 g) was added to the polymer mixture and then stirred until a uniform mixture was obtained. The mixture was then processed on a two roll mill at a temperature of approximately 149 ^° C (300 ^° F) until it melted. After this time, the molten mixture was milled for an additional time of about 5 to 10 minutes to ensure that a uniform plastic mass was obtained. This mass was then removed from the mill and ^{pressed at a temperature of approximately 149 0} C (300 ⁰ F) between two chrome steel plates, which were separated by suitable spacer frames, using thin foils with a thickness of 0.25 mm and 0, 5 mm (10 and 20 mils). The films were cooled to room temperature to obtain the desired product.

Example 19

Production of a vapor-permeable film from a polyvinyl chloride-Foly (NN-dimethylacrylamide) -poly mixture

Powdered polyvinyl chloride (90 g, Vygen 110, a product of General Tire and Rubber Co.), poly (N, N-dimethylacrylamide) (60 g) that had been mixed with 60 g of water and stored overnight at room temperature , and barium cadmium stearate heat stabilizer (3 g) were mixed in a paper cup. Dioctyl phthalate (90 g) was added to this polymer mixture and then stirred until a uniform mixture was obtained. The mixture was processed on a two-roll mill at a temperature of approximately 149 ⁰ C (300 ⁰ F).

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22A4231

tet until it melted. After this time, the molten mixture was milled for an additional time of approximately 5 msec. 10 minutes to ensure that a uniform plastic mass was obtained. This mass was then removed from the mill, " ^{pressed at a temperature of approximately 149 0} C (300 ⁰ F) between two chrome steel plates, which were separated by suitable spacer frames, with thin foils with a thickness of 0.25 and 0.5 mm (10 and 20 mils) The films were then cooled to room temperature to give the desired product.

The water was observed to drain off during the first few minutes of the milling process. In contrast to the Films obtained in Example 18 that were slightly hazy and showed many spots when stretched were the films made from the poly (N, N-dimethylacrylamide) immersed in water were glossy and clear and remained even so after stretching.

Example 20

Production of a vapor-permeable film from a polyvinyl chloride-poly (NN-dimethylacrylamide) -poly mixture

The procedure of Example 18 was repeated with the exception that the poly (Ν, Ν-dimethylacrylamide) polymer was exposed to the ambient conditions of the relative humidity for 6 days. During this time, the water content of the polymer increased from an initial 1.3% to 5% _f 0 determined by the Karl Fischer method, too.

Example 21

Manufacture of a vapor-permeable film from a polyvinyl. chloride-poly (NN-dimethylacrylamide) -ftoly mixture

The procedure of Example 18 was repeated today with the Exception that the poly (N, N-dimethylacrylamide) used

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6 days exposed to a relative humidity of 85% became. The water content of the polymer increased; from 1.3% at the beginning to 12.2%, determined according to the Karl Fischer method.

The films made from the mixed polyols described in Examples 18-21 were overlaid on the above described way investigated. The results of these studies are given below.

Table VII

Water absorption of the .18 Bps, . 18th 1 Ö-td.
at RT Test composition Table VIII Immersion time V hrs.
at 10O ⁰ C 19th η 19th 3.9 Immersion time the dry composition
Absorption test 18 hours
at RT 14.6 Test samples 20th H 20th 15th 18 hrs.
at RT -1.2 16.1 Product of E.g. 21 η 21 13.3 13.4 i "ύ'ϊά,
at RT -0.3 13.7 Product of η 15.1 23 -0.6 -1.2 13.1 Product of η Weight change 21.7 -0.7 -1.5 Product of η 22.1 -1.5 after this Test samples -1.4 Product of 1 H. _
at 100 ^° C Product of -0.1 Product of -0.6 Product of -1.3 -1.2

R.T. = Room temperature

The tensile strengths in kg / cm (pounds per square inch) of the various vapor permeable compositions are prepared

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according to Examples 18, Ms 21, were determined under various conditions, hereinafter referred to as Conditions A, B, C or D. The tensile properties were determined according to ASTM method D638-64T. Condition A means the condition of the product after production, as described in Examples 18 to 21. The denotation B denotes the state. _v '.'"of the product after immersion in boiling water for a period of 1 hour and subsequent drying at a temperature of 70 ^° C. for 2 hours. Condition C means the state of the product after it was exposed for 18 hours at room temperature to a relative humidity of 85%. Condition D means the state of the product after it was immersed in water at room temperature during a time was immersed for 18 hours, and was then dried at 70 ⁰ C for 2 hours. The results of these experiments are in kg / cm (poui
and given in Table IX.

Tests are expressed in kg / cm (pounds per square inch)

Table IX tensile strenght

condition

Test sample A B

Product of bps. 18 105 (1500) 89 (1270). 77 (1100) 108 (1540)

Product of "19 153 (2180) 168 (2390) 94 (1340) 184 (2620)

Product of "20 152 (2160) 136 (1920) 84 (1200) 184 (2620)

Product of »21 126 (1790) 153 (2180) 92 (1320) 148 (2090)

The effectiveness of the compositions prepared in Examples 18 to 21 as vapor-permeable materials was shown in Tests compared in which the water vapor transmission of 0.25 mm (10 mils) thick films. ASTM test method E 96-63 $ (B) was used in this attempt. This method then consists of the

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Measures the amount of water vapor, in grams, that passes through a sample that is on a relative humidity page of IOO56 and on the other hand a relative humidity exposed out of 5096 1st. The results of this procedure are expressed in g of water vapor in 24 hours per square meter of surface. The results are given in Table X.

Table X Water vapor transmission Test samples g / 24 h / m

Product of Example 18 64

Product of Example 19 280

Product of Example 20 175

Product of Example 21 240

From the results given in the tables above, particularly from the results in Table X, where the water vapor transmission of the films is compared, it can be seen that the moisture content in the Ν, Ν-dimethylacrylamide polymer plays an essential role. It can therefore be assumed that polyblends made by blending N ₁ N-dimethylacrylamide containing greater than 3% moisture will provide improved results, especially when these polymers contain hard bits which are difficult to grind in the blending process are.

Solvents other than water or agents containing water containing the unsaturated amide polymer such as Ν, Ν-dimethyiacrylamide soften, give similar results. Examples of such solvents are methanol, glycol, glycerin and urea.

The following examples explain the production of vapor-permeable films from a poly mixture of a hydrophobic polymer and a polymer of an unsaturated amide, where ¹ the corresponding polymers are first dissolved in a suitable solution.

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medium and then the homogeneous solution to one Film is shed. ■

Example 22

Production of a vapor-permeable film from a polyvinyl chloride-poly (Ν, Ν-dimethylacrylamide) -poly mixture

A composition of 100 parts by weight of polyvinyl chloride and 50 parts by weight of poly (N, N-dimethylacrylamide) and 50 parts by weight Dioctyl phthalate became a film from a tetrahydrofuran solution poured »The resulting film was clear. After immersing the film in water for a short time of about 10 minutes after the film had dried, a very opaque white film was obtained. The opacity was temporarily lost when the film was moistened with water was, 'but the opacity returned when the film was dried. When to the opaque film one strong pressure was applied like a fingernail or typewriter, this part of the film became clear The vapor-permeable films also gave a clearly legible film with a pencil or typewriter Pressure.

Example 25

Production of a vapor-permeable film from a polyvinyl chloride-poly (N «N-dimethylacrylamide) -poly mixture

A composition of 100 parts by weight of polyvinyl chloride and 100 parts by weight of poly (N, N-dimethylacrylamide) was cast into a film from a tetrahydrofuran solution. The clear film was highly opaque when it was treated with water, it had a good strength and flexibility and a good ink receptivity and ^v ink. The film treated with water appeared to have a reticulated structure as determined by an optical microscope. These cavities scatter the light and cause the opaque

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activity of the film. The combination of voids and the poly (N, N-dimethylacrylamide) gives films that are both breathable are as well. ' improved water vapor transport properties exhibit.

The films prepared according to Examples 22 and 23 are also of value in the production of synthetic ^v paper or non-pigmented paper coatings which are excellent in absorption capacity, Naßreibbeständigkeit and for paints and coatings have a good absorption capacity for a long time. If desired, the films produced in this way can be made water-resistant with a shielding coating which is applied from hydrocarbon solvents such as toluene.

If desired, solvents other than tetrahydrofuran can be used as a solvent for making the film as described in Examples 22 and 23 can be used. The person skilled in the art can easily select the solvents using solubility tables, the only requirement being that is, the solvent used is both the hydrophobic polymer and the polymer of the unsaturated Amides sufficiently dissolves. Examples of solvents in addition to tetrahydrofuran, the polyvinyl chloride and N, N-dimethylacrylamide polymers solve are methyl isobutyl ketone and dimethylformamide.

In addition to the leaching process used in the present invention If filming voids are obtained, excellent physical properties are obtained if one is in that beforehand The solvent system mentioned is a mutually miscible non-solvent for one of the polymers in the polymer mixture according to the invention wJLe an aliphatic or aromatic Adds hydrocarbon. Depending on the amount of nonsolvent used, you can either use a closed

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.37- 2 2 4 A 2 31

Cell structure or an open cell structure. If for example about 50 parts by weight of a relatively low volatility nonsolvent for one of the polymers in of the mixture used, the solvent being such as tetrahydrofuran at a much faster rate than the nonsolvent evaporates, the nonsolvent falls in the form of fine droplets into the polymeric film structure and evaporates then from the film structure by diffusion. A large number of small, closed cells are left behind. Films made this way are very opaque, but not porous. However, due to the structure of the films that contain internal voids have them Films have the inherent property of being water vapor permeable. The presence of both the hydrophilic polymer in the poly blend as well as the presence of internal voids in the film complement each other and one obtains particularly useful films, This process is described in detail in U.S. Patents 3,654,193, 3,655,591, and 3,661,807.

An open-cell structure film can be easily obtained by using a nonsolvent, which Non-solvent is used in copious amounts. In such cases, the presence causes during film formation large amounts of a nonsolvent cause the polymers to precipitate and the nonsolvent subsequently evaporates out of the precipitated matrix, leaving open-cell empty spaces behind. Various modifications to this procedure are familiar to the person skilled in the art. However, the use of this system has been made with a combination of hydrophilic and hydrophobic Polymers that are compatible with one another have not yet been described, and so far the surprising properties have been these systems have not yet been recognized.

The present invention also relates to a method for the production of breathing vinyl films according to a modified

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adorned plastisol process. Most of the polyvinyl chloride plasticizers do not soften the poly (N, N-dimethylacrylamide). The known plastisol methods can be used with the inventive Poly hybrids are not used.

The plastisol process for making flexible polyvinyl chloride films and coatings is well known in the art and is widely practiced in industry. The system includes a specific plastisolquality of polyvinyl chloride, which is mixed with a softener at room temperature to a paste-like slurry and then casting onto a release paper · and curing at 16O ° C (32O ⁰ F) for about 5 to 10 minutes without any pressure in a film is transferred. Organosols are plastisols to which a solvent has been added in order to reduce the viscosity of the plastisol. They are used in a similar manner to plastisols, with the solvent being removed during the curing step. Because poly (N, N-dimethylacrylamide) is insoluble in dioctyl phthalate or other common plasticizers, previous attempts to make films by simply adding poly (N, N-dimethylacrylamide) to polyvinyl chloride plastisols have been unsuccessful.

It has now been found that stable plastisol-like mixtures of a desired viscosity can be prepared by dissolving the poly (N, N-dimethylacrylamide) in a solvent prior to adding the material to the polyvinyl chloride / dioctyl phthalate plastisol. The solvent requirements for the Ν, Ν-dimethylacrylamide polymer are as follows: (1) It must be compatible with the polyvinyl chloride / dioctyl phthalate plastisol; (2) the solvent must be a nonsolvent for the polyvinyl chloride itself in order to prevent the viscosity from increasing sharply, and (3) the boiling point of the solvent must be in the range of 60 to 150 ^° C. so that it does not foam during excessively

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_ 39 - 22U231

the formation of the film can be easily removed. Examples of solvents include alcohols, many aromatic compounds, ketones, etc .; n-butanol is the preferred solvent. The following example illustrates this embodiment of the invention.

Example 24

50 g of poly (N, N-dimethylacrylamide) were dissolved in 150 g of n-butanol with stirring at room temperature. This solution was added to a slurry containing 50 g of polyvinyl chloride and 60 g of dioctyl phthalate and mixed by stirring at room temperature for ½ s. The resulting 'paste is stable for at least a week'. Various films were made by pouring the paste onto glass plates using a Gardner doctor blade. After evaporation of the butanol at room temperature for 24 hours, the films were cured for 5 minutes at 150 C. The resulting films were somewhat cloudy, but smooth and homogeneous. The films showed a water vapor transmission, determined according to ASTM method E96 condition B, of 700 g / m ^2/24 hr.

Using the procedure described above, a series of experiments were carried out using varying amounts of poly (N, N-dimethylacrylamide) (P-NNDMA) in polyvinyl chloride (PVC) and then the water vapor transmission of each of the films was determined (WVT) ₀ The results of these tests are given in Table XI.

1 PVC NNDMA Table VI DOP WT 573 2 50 50 Butanol 60 708 408 Test sample 3 60 40 150 60 536 - 297 Attempt no. 4th 70 30th 120 60 432 - Attempt no. 80 20th 90 60 252 - Attempt no. 60 Attempt no.

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From the table above it can be seen that the water vapor transmission gradually with decreasing amount of poly- (N, N-dimethylacrylamide) decreases. It is very surprising, however, that the water vapor transmission is an average of high has a higher value than mixtures made with similar ratios, but only as before described, ground.

The plastisol technique described above has great advantages with himself. In particular, the surfaces can very easily be precisely defined and permanently printed, whereby it is possible also show details. The technique described above, which is the subject of the present invention, is different differs from the known organosol system not only in that the resulting polymers have breathability, but also because the added solvent only a Solvent for the hydrophilic polymer, i.e. the poly- (Ν, Ν-dimethylacrylamide) and for polyvinyl chloride, a nonsolvent. As a result, a homogeneous one is obtained Film without reducing the viscosity of the plastisol. As previously mentioned, it has also been found that the addition of a Polyalkylene oxide having a molecular weight in the range of about 600 to 1500 provides the "grip" or "handling" of the films, made from a mixture of NjN-dimethylacrylamide / butyl acrylate-polyvinyl chloride were made, improved. The improved grip of these new blends that adds the extra Containing plasticizers is especially noteworthy after these were subjected to extremely different relative humidities. Blends, the polyethylene oxide polymer contain, retain their soft, pliable texture while blends change without the polyethylene oxide polymer. When the humidity is very high they are very soft and when the humidity is low they are very soft Moisture, they are stiff and hard. In addition, water vapor transmission and water absorption are also much improved.

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The following examples illustrate the advantageous results obtained when adding polyalkylene oxide Plasticizers incorporated into the mixtures according to the invention,

Example 25

Powdered polyvinyl chloride (55 g, Vygen 110, a product of General Tire and Rubber Co.) »powdered mixed polymer of poly (N, N-dimethylacrylamide) / bu^ aacrylate, prepared as described in Example 13 above, (45 g;. 90/10 copolymer of !!, N-dimethyl acrylamide / butyl acrylate with a _(glass transition temperature of 104-105 ⁰ C) and barium Cadmiurastearat heat stabilizer (3 g) were mixed in a paper cup of dioctyl phthalate (60 g) was added to the Polymer mixture was added and then stirred until a uniform mixture was obtained Various amounts of polyethylene oxide having a molecular weight of 600 to 1500 (Carbowax) were added to the mixture described above and then stirred until a uniform mixture was obtained then processed on a two roll mill at a temperature of about 149 ° C (300 ° F) until it melted, at which time the molten mixture was milled for an additional time of about 5 to 10 minutes en to ensure that a uniform plastic mass was obtained. This mass was removed from the roller and pressed at a temperature of approximately 149 C (300 F) between two chrome steel plates, which were separated by suitable spacer frames, using foils with a thickness of 0.25 mm and 0.5 ram (10 and 20 mils). The films were then cooled to room temperature to give the desired product.

The properties of the improved water vapor permeable compositions, obtained according to the procedure of Example 25 were as in the previous examples described determined. In Table XII the values for the

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Water absorption in percent and the water vapor transmission of the new poly blends containing various amounts of a polyethylene oxide polymer included (Carbowax 600 and Carbowax 1500).

310 1500 400 Table XII 18 hours b,
85% RH ^D Test together 410 470 7.2 18 hours
hRT 580 580 % Water absorption of
settlement 8.1 29 660 1 hour
100 ⁰ C 9.7 30th Parts by weight WVT ^a _o
Carbowax 600 g / 24 h / m * " 22nd 10.5 37 0. 31 44 5 32 8.6 10 33 9.5 32 20th 9.7 39 Parts by weight
Carbowax 27 43 VJl 29 10 35 20th

Water vapor transmission, method ASTM E96-B Velative Humidity
'Room temperature

From Table XII it can be seen that the water vapor transmission and the percentage of water absorption can be increased significantly by adding the polyethylene oxide plasticizer. For example, it is clear that the water vapor transmission of the Polymix more than double by adding 20 wt. Parts of Carbowax 600 is enlarged compared to the sample that does not contain Carbowax 600. Furthermore, the water absorption in percent by adding a polyalkylene oxide plasticizer to the new poly mixture also increased.

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The tensile strength properties and elongation of the mixtures containing the polyethylene oxide in amounts of 5 or 10 parts by weight, did not change compared to those mixtures which did not contain polyethylene oxide. Became the polyethylene oxide used in an amount of 20 parts by weight, so "observed one has a drop in tensile strength. This amount exceeds the tolerable amount, and therefore the usefulness decreases of the polyethylene oxide.

In addition to the polyethylene oxides as plasticizers for the NjN-dimethylacrylamide-polyvinylchloride films, some Polyols derived from polypropylene oxide are a notable one Improvement in the "handle" of the coated articles when these are used as co-calibrators in the mixtures according to the invention be used.

The following polyols, which are derived from polypropylene oxide, have been used or manufactured with success:

1. Cord 500 (a methyl glucoside that is different from polypropylene glycol and has a molecular weight of approximately 450);

2. Cord 300 (the same as above, with a molecular weight of 750);

3. Voranol RS 450 (a polypropylene oxide polyol which is derived from sucrose and has a molecular weight of owns about 600), and

4. Voranol RQ 490 (a polypropylene oxide polyol derived from sorbitol and having a molecular weight of approximately 700 owns).

Each of the above polyols derived from polypropylene oxide were made with 55 parts by weight of polyvinyl chloride, 45 parts by weight a copolymer of Ν, Ν-dimethylacrylamide and butyl acrylate, prepared as in Example 13, -60 parts by weight of dioctyl

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phthalate plasticizer and 10 parts by weight of the test samples Above specified polypropylene oxide polyols and 3 parts by weight Blended barium cadmium stearate stabilizer.

All of the films made from the above formulations give very strong, clear sheets with a much improved one "Handle" compared to films that do not contain the polyols.

The addition of the polyols, which are derived from polypropylene oxides, does not change the water vapor transmission compared to the polyols, which are derived from polyethylene oxide, which greatly improve the transmission of water vapor.

From the results of the comparative experiments, which are given in Example 25 and Table XII, as well as from the experiments with The polyols derived from polypropylene oxides seem to be the products derived from polyethylene oxide and having a moderately low molecular weight, i.e. below about 6000, the "handle" in addition to water vapor transmission to improve in the novel mixtures according to the invention. The polyols derived from polypropylene oxide and one Having high functionality and low molecular weight also improve "feel", but they appear to have water vapor transmission the films do not improve.

As will be described below, the polyalkylene oxide polymers also in the form of copolymers or graft copolymers can be used with the α, β-unsaturated amides, valuable vapor permeable film compositions being obtained. The following examples illustrate this embodiment of the invention .

Example 26

A copolymer of Ν, Ν-dimethylacrylamide and a maleate

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half ester of a polyethylene oxide with a molecular weight of 750 and with a terminal methyl group ("capped with a methyl group ") was prepared in the following manner, The maleate half ester of polyethylene oxide was prepared, by · maleic anhydride with polyethylene oxide monomethyl ether condensed according to the following equation:

CH C ^

yO + HO (-CH ₂ CH ₂ O -) ^ - OCH ₃

CH C

Il

CH-C-OH
ti

CH - CO (-CH ₀ CH ₀ O OCH ^

\\ 2 ά 'η 3

15 parts by weight of Ν, Ν-dimethylacrylamide / butyl acrylate copolymer as none (NNDMA / BA, 90/10 copolymer), 0.75 parts by weight of calcium stearate (1.5 parts by weight including the nuclei) and 250 were placed in a reaction vessel Parts by weight heptane. The reactor was heated to 70 ° C. while purging with nitrogen and then a monomer mixture was added over 4 1/2 hours. The monomer mixture contained the following components: 135 parts by weight of N, N-dimethylacrylamide, 15 parts by weight of the maleate diester of polyethylene oxide monomethyl ether, as described above (Malox 750), 7.5 parts of Ν, Ν-dimethylacrylamide / lauryl methacrylate copolymer (an NNDMA / IMA copolymer, ratio 50/50), 0.3 part by weight of azobisisobutyronitrile and 0.3 part by weight of t-dodecyl mercaptan. After all the material had been added, the temperature was ^{heated to 85 °} C. over 1 hour. At this point the stirrer was

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turned off and the vessel cooled and opened. The polymer was obtained in the form of discrete large particles, useful for making the blends of the invention, particularly blending with polyvinyl chloride.

Example 27

55 g of polyvinyl chloride, 45 g of the copolymer of poly (N, N-dimethylacrylamide) / maleate half ester of monomethyl ether of polyethylene oxide with a molecular weight of 750 and 3 g of barium cadmium stearate heat stabilizer were mixed in a paper cup. 60 g of dioctyl phthalate was added to the polymer mixture, followed by stirring until a uniform mixture was obtained. The mixture was then processed on a two roll mill at a temperature of about 149 ° C (300 ° F) until it melted. After this time, the molten mixture was milled for an additional time of approximately 5 to 20 minutes to ensure that a uniform plastic mass was obtained. The mass was then removed from the mill and pressed between two chrome steel plates, which were separated by suitable spacer frames, ^{at a temperature above 149 0} C (300 ^{0 F), using thin foils with a thickness of 0.25 mm and 0.5 mm} (10 and 20 mils). The films were cooled to room temperature to obtain the desired product.

Example 28

A graft copolymer made of Ν, Ν-Dimethylacrylaraid with a Monomethyl ether of polyethylene oxide with a molecular weight of about 750 is prepared as follows: 90 parts by weight of N, N-dimethylacrylamide, 10 parts by weight of a monomethyl ether of polyethylene oxide with a molecular weight of 750 (Carbowax 750) and 40 parts by weight of benzene. 0.5 part by weight of azobisisobutyronitrile polymerization catalyst is added to this reaction mixture

- 47 -309834/1015

22U231

at a temperature of 7O ⁰ C. The reaction further 18 hours was conducted under a nitrogen purge. The product was obtained by precipitation in hexane and drying under reduced pressure. The resulting N / N-dimethylacrylamide / polyethylene oxide copolymer is a graft copolymer of the two polymers.

In order to determine the usefulness of the above graft copolymer in the new mixtures according to the invention, the following mixture was prepared: 55 g of powdered polyvinyl chloride, 45 g of NjN-dimethylacrylamide graft copolymer, prepared as above, and 3 g of barium cadmium stearate heat stabilizer were mixed in a paper cup. 60 g of dioctyl-. phthalate was added to the polymer mixture and then stirred until a uniform mixture was obtained. The mixture was then processed on a two-roll mill at a temperature of about 149 ° C (300 ⁰ F) until melted. After this time, the molten mixture was milled for an additional time of about 5 to 10 minutes to ensure that a uniform plastic mass was obtained. This mass was then removed from the mill and ^{pressed at a temperature of approximately 149 0} C (300 ⁰ F) between two chrome steel plates, which were separated by suitable spacer frames, using thin foils with a thickness of 0.25 mm and 0, 5 mm (10 and 20 mils). The films were cooled to room temperature to obtain the desired product.

The properties of the water vapor permeable compositions, those in Examples 27 and. 28 were obtained by various standard testing procedures, as detailed in Examples 1 to 10 are described, measured. The results of these experiments are as follows Table XIII summarized.

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- 48 Table XIII

Test samples

g / 24 h / m '

% Water absorption of the test composition

1 hour 18 hours 10O ⁰ C

18 hours RT ^C

Product v. Example 27

Product v. Example 28

330

304

27.0 23.0

7.2
7.0

33.6 25.5

Water vapor transmission, ASTM EI96-B method

^ relative humidity room temperature

The results in Table XIII show that the polyblends of polyvinyl chloride and the copolymer of N, N-dimethylacrylamide and the maleate half ester of the monomethyl ether of polyethylene oxide, very satisfactory water vapor transmission and have water vapor absorption properties. In addition, the products produced by the process of Examples 25 and 26 have a very good "feel" and are tough films that are valuable as coatings for fabrics.

In another preferred embodiment of the invention Polyblends can be the monomethyl ethers of the polyethylene oxide polymers with polymerizable compounds with the free hydroxyl groups of the polyethylene oxide ether react, are implemented. These reaction products can act as plasticizers for the poly (N, N-dimethylacrylamide) homopolymers when blended with the polyvinyl chloride monomers will. Examples of compounds that can be reacted with the monoalkyl ethers of the polyalkylene oxides include Polyisocyanates such as toluene diisocyanate. The isocyanate adducts mo-

- 49 -

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differentiate the polyethylene oxide in such a way that groups for possible hydrogen bonds are introduced and · that this prevents leaching of the polyethylene oxide polymer from the film of the polymer mixture. Of course other adducts with the polyalkylene oxide polymers which can easily be selected by the person skilled in the art can be used,

The invention also relates to a process for producing a foamable composition from the polymer blends according to the invention. These compositions are made by incorporating into the polyblend a propellant which decomposes to form a gas at a temperature close to the softening point of the vapor permeable composition. The propellants which do not leave a residue upon decomposition to adversely affect the vapor permeable composition and those which do not exhibit any adverse physiological effects are preferred. The amount of blowing agent to be used in the field can be up to about 10 wt.%. It is preferably in the range from about 0.2 to about 8 wt. Activators for the blowing agents can be used if desired.

Examples of useful propellants are azodicarbonamide, N, N ^I -dime'thyl-N, N'-dinitrosoterphthalamide, 4,4'-oxy-bis (benzenesulfonylhydrazide), dinitrosopentamethylene tetramine, and others. Water vapor permeable films can also be prepared by using the composition Propellants such as air, nitrogen or hydrocarbon gases or / also with chlorine and fluorocarbon gases such as with the freons foams.

The vapor-permeable compositions according to the invention can can be used for a variety of different applications. They can be used in the manufacture of leather substitutes, Use upholstery fabrics, rainwear, etc. at

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for many of these applications it is desirable to have foamed, flexible films are obtained that are resistant to touch. The polymer blends according to the invention, the hydrophilic polymer are also useful as plastics that accept dyes. The invention Films are useful in coated fabrics because they almost don't build up static, and besides, they can for many Special textile fibers are used.

It should be emphasized that the present invention also encompasses all modifications that do not substantially change it will. For example, the poly (N, N-dimethylacrylamide) can be mixed with urethane rubbers or to form a polyester prepolymer, which was made from polybutylene adipate can be added before curing and then this mixture can be used Apply to a textile base. Furthermore, the poly (N, N-dimethylacrylamide) be mixed with polymeric binders such as acrylic compounds and polyacrylonitriles, wherein breathable, nonwoven textile films are obtained.

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Claims (30)

- 51 claims 1. Water vapor permeable, film-forming composition, characterized by a mixture of polymers (a) a hydrophilic thermoplastic polymeric material containing from about 10 to about 60 parts by weight a homopolymer, copolymer or graft copolymer unsaturated amide of the formula ¹ Ro R ¹ 0 CH ₂ = C - C - N where R is hydrogen or an alkyl group with up to 4 carbon p -z fuel atoms, R and R alkyl groups with up to 4 carbon atoms mean, and (b) a hydrophobic polymeric material containing from about 90 to about 40 parts by weight of a polymer such as Vinyl chloride, polyurethane, poly (methyl methacrylate), polyamide, Polypropylene and / or polyester. 2. Composition according to claim 1, characterized in that the hydrophilic thermoplastic polymeric material a copolymer (a) the unsaturated amide and . (b) A monomer capable of forming a polymer with to give a glass transition temperature which is lower than that of the homopolymer of the unsaturated amide, used. 3 · Composition according to claim 1, characterized in that the hydrophilic thermoplastic polymeric material a copolymer of - 52 - 30983471015 (a) the unsaturated amide and (b) a monomer such as butyl acrylate, 2-ethylhexyl acrylate, Acrylonitrile, vinyl acetate or polymerizable esters of polyalkylene oxides used. 4. Composition according to claim 1 or 2, characterized in that the hydrophilic thermoplastic polymeric material a copolymer of N, N-dimethylacrylamide and butyl acrylate are used. 5. Composition according to claims 1, 2 or 3 »characterized in that one is called hydrophilic thermoplastic polymeric material a copolymer of N, N-dimethylacrylamide and a polymerizable ester of a polyalkylene oxide such as an acrylic acid, methacrylic acid or maleate half ester of polyalkylene oxides. 6. Composition according to any one of claims 1 to 5, characterized in that it is also of about 5 to about 100 parts by weight of at least one plasticizer capable of softening the hydrophobic polymer. 7. Composition according to claim 6, characterized in that the plasticizer used is dioctyl phthalate, polyethylene oxide and / or polypropylene oxide or mixtures thereof. _/ 8. Composition according to any one of claims 1 to 7, characterized in that it is also a mutual solvent for both the hydrophilic thermoplastic polymeric material and the hydrophobic contains polymeric material. - 53 309834/1015 9. Composition according to claim. 8, characterized in that one is used as the mutual solvent Tetrahydrofuran, methyl isobutyl ketone or dimethylformamide used. 10. Composition according to claim 8, characterized in that it contains a nonsolvent contains lower volatility than the mutual solvent for at least one of the polymeric materials. 11. The composition according to claim 10, characterized in that the nonsolvent is aliphatic or aromatic hydrocarbons are used. 12. Composition according to any one of claims 1 to 11, characterized in that the hydrophilic thermoplastic polymeric material also at least contains about 3% by weight of water. 13 · Composition according to any one of claims 1 to 12, characterized in that it also contains a Contains propellant. 14.. Composition according to Claim 13, characterized in that the propellant is a compound capable of gas formation at a temperature close to the softening point of the vapor-permeable composition to decompose. 15. Composition according to claim 14, characterized in that one is used as a foaming agent or blowing agent Azodicarbonamide, NjN'-dimethyl-NjN'-dinitrosoterphthalamide, 4,4'-oxy-bis (benzenesulfonylhydrazide) or dinitrosopentamethylene tetramine used. - 54 309834 / 1015- 16. A method for producing a vapor-permeable film, characterized in that one (a) the composition of any one of claims 1 to 5 mixed in the dry state and (b) the blended composition in a dry state in the absence of a solvent and at a temperature close to the softening point of the composition is high Subjected to shear forces. 17. The method according to claim 16, characterized in that the composition is mixed thoroughly by squeezing the composition of claims 1 to 5 between pressing parts. 18. Process for the preparation of a vapor-permeable composition, characterized in that the solution according to claim 8 is poured onto a substrate and that Solvent evaporates. 19. A method for producing a vapor-permeable film from the composition according to any one of claims 1 to 15, characterized in that one (a) Preparing a mixture by adding an aqueous solution of the hydrophilic thermoplastic polymeric material dispersed in an emulsion of the hydrophobic polymeric material, (b) coating a substrate with the mixture and (c) the water evaporates from the mixture. 20. A method for producing a cellular, vapor-permeable film, characterized in that man - 55 -309834/1015 - .55 - (a) pouring the composition of claim 10 onto a substrate and (b) evaporating the solvents from the composition. 21. Vapor-permeable laminate, characterized in that it contains a fiber base which associated with a mechanically well mixed, essentially present in a homogeneous dry state mixture is, from: ' (a) a hydrophilic thermoplastic polymeric material containing from about 10 to about 60 parts by weight co of a homopolymer, copolymer or graft polymer unsaturated amide of the formula ■ R ¹ 0 R ² 1 Il CH ₂ = C - C - N wherein R is a hydrogen atom and an alkyl group with up to p ^ 4 carbon atoms, R and R alkyl groups with up to 4 carbon atoms mean, and (b) a hydrophobic polymeric material containing from about 90 to about 40 parts by weight of a polymer such as Vinyl chloride, polyurethane, poly (methyl methacrylate), polyamide and polyester, being the thoroughly mixed homogeneous mixture was deformed to a structure or a layer, which has vapor permeability, due to the · thorough Mixing the two polymeric materials. 22. Laminate according to claim 21, characterized in that the mixture is from about 25 to about 50 parts by weight of hydrophilic thermoplastic polymer - 56 309834/1015 Material and from about 75 to about 50 parts by weight contains hydrophobic polymeric material. 23. Laminate according to claim 22, characterized in that the unsaturated amide is N, N-dimethylacrylamide used. 24. Structure of synthetic plastic material that is permeable to water vapor, characterized in that it is an intimate physical mixture contains from (a) a hydrophilic thermoplastic polymeric material containing from about 10 to about 60 parts by weight a homopolymer, copolymer or graft copolymer unsaturated amide of the formula R ¹ 0 R ² I Il CH ₂ = C - C - N , 3 1
wherein R is a hydrogen atom or an alkyl group with up to 2 "5 4 carbon atoms, R and R ^ alkyl groups with up to 4 carbon atoms mean, (b) a hydrophobic polymeric material containing from about 90 to about 40 weight percent of a polymer such as one Polymers of vinyl chloride, polyurethane, poly (methyl methacrylate), polyamide and polyester. 25 · Structure according to claim 24, characterized in that the mixture is from about 25 to about 50 parts by weight of hydrophilic thermoplastic polymeric material and from about 75 to about 50 parts by weight of hydrophobic contains polymeric material. - 57 - 3 05834/1015 26. Structure according to claim 25, characterized in that the unsaturated amide is N, N-dimethyl acrylamide used. 27. Structure according to claim 26, 'characterized in that the physical mixture is pressed out will. 28.. Structure according to claim 27, characterized in that the physical mixture is formed by deposition of the solvent is squeezed out. 29. Vapor-permeable membrane, marked by the composition of any one of claims 1 to 30. Substrate coated with the composition of any one of claims 1 to 15. OBiGINAL INSPECTED 30-9834 / .1O 15