DE1444056A1 - Water impermeable, but water vapor permeable material - Google Patents

Description

Impermeable to water, but permeable to water vapor Material. ,

The invention relates to a water-impermeable, but water-vapor-permeable; ümaterial _o In particular, the invention relates to waterproof textile materials which are suitable for the production of waterproof rainwear, protective tarpaulins, etc. *

The invention was based on the task of finding a fibrous material such as textile material, paper, leather and the like. to be waterproof in such a way that it is permeable to water vapor at the same time.

This task was solved by developing a material which is characterized in that it is formed from a thread or fiber, with a discontinuous Layer of a water-swellable elastomer covered, flat structure.

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The watertight, permeable to water vapor, Zib _o textile material of the invention can be obtained by ^ that, for example, swells in contact with water / Etoe a Gev or coated working portion with a non-continuous layer of an elastomer or ;, impregnates and in most cases swells in such a way that the interstices of the woven or knitted fabric are closed when exposed to high relative humidity. The elastomers must swell with water, but also be able to be applied to the textile material at the same time. The elastomers should be flexible, wear-resistant and adhere well to the fabric.

The waterproof textile material according to the invention can be manufactured practically by two methods. Either a water-swellable elastomer is produced from a copolymer of 2 or more monomers, of which at least a monomer is a polar, hydrophilic component or it becomes an elastomer which is not hydrophilic or swells insufficiently with water, modified with another polymer or copolymer that is attacked by water and with the elastomer through primary chemical Bonds, or physical, sufficiently strong, intermolecular forces connected "is so that the two Polymers are practically inseparable. The textile material is then treated with one of the elastomers «

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The elastomers suitable according to the invention consist of Polymers, copolymers and interpolymers or from mixtures of those polymers which, when cured, can provide a single graft polymer containing the polymer in question makes it swellable in water.

The water swellability of the elastomers can be achieved by copolymers, Terpolymers, etc., any combination of monomers having water-sensitive groups with monomers, containing conjugated unsaturated bonds can be achieved. Or else, for this purpose it becomes the elastomer forming monomers with monomers: copolymerized, whereby water swellability is obtained. Examples of such polymers are copolymers of diene monomers with acrylonitrile, Acrylic acid esters and acrylamides; Methacrylic acid esters and methacrylic acid amides and maleic anhydride. These copolymers can also be hydrolyzed, whereby Copolymers are obtained which contain unsaturated former units and contain carboxyl groups. Other processes for the production of suitable elastomers are for example: Hydrolysis of copolymers of vinyl acetate (whereby hydroxyl groups are released), ammonolysis of ester to amide groups, and sulfonation with the formation of elastomers with sulfonic acid groups. The hydrophilic groups can be made part of the final elastomer by adding certain Polymers are added. These polymers are those that, after the elastomer has been applied to the

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-4- Η44Ό56

appropriate tissue has been applied, by, a Curing reaction are chemically bound. Such polymers are, for example, those that have some unsaturated Monomer units and at the same time larger ones

units
Can contain amounts of hydrophilic Sa »g» 3a «a ± eK.

These include copolymers of open-chain diene monomers having 4 to 8 carbon atoms with one or more of the hydrophilic monomers listed above. In this embodiment Copolymers having 40 to 99 hydrophilic monomer units can be used in the invention. As As described above, it is usually desirable that the hydrophilic monomer react with elastomeric polymers or is grafted onto it. The two polymers are said to be bonded together to prevent that hydrophilic polymer, which is water-soluble before being incorporated into the elastomer, from the elastomer during whose contact with water is extracted. The grafting reaction can also take place in a hardening or crosslinking reaction exist for the entire matrix. If the networking is done at this point, it is necessary that this Eeaction is made after the elastomer hits the Textile material would be applied or treated with this.

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In certain cases it may be desirable to use an uncured elastomer, but it has often proven useful to cure the elastomer which reduces the water sensitivity. The curing agents, accelerators and curing conditions for these elastomers are similar to those known for the vulcanization of rubber. In addition, curing can also be carried out using organic peroxides as catalysts. Apart from curing the elastomer, it can sometimes be advantageous to add water-repellent agents such as silicone resins or silicone waxes and the like. This ensures that the textile material in question is water-repellent from the start, so that no water can penetrate into the interstices of the textile material before the elastomer has swelled in contact with water.

According to the invention, water-swellable elastomers from Condensation type, such as polyester, copolyester, Block copolyesters, polyurethanes, polyureas, polyamides and polysulfides can be used.

Polymers that are useful modifying agents for condensation-type elastomers are those that do

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of the following, for making addition's- ' polymeric monomers used: acrylic, methacrylic, Iumaric, maleic and crotonic acids, including their amides, nitrogen-substituted amides, ammonium and metal salts, Oxyethyl ester, anhydrides and acid chlorides. Interpolymers of the abovementioned monomers are also suitable other polymerizable monomers. Such monomers are for example: vinyl chloride, acrylonitrile, vinyl acetate, Styrene, acrylic and methacrylic acid esters as well as polymerisieroare, unsaturated hydrocarbons.

Also polymerizable monomers are one or more hydrophilic groups, such as a sulfon, phosphon, sulfate, Contain phosphate, hydroxyl or pyridinium lactam groups, as well as polymers that are converted into hydrophilic products such as vinyl acetate, acrylonitrile, esters of acrylic and methacrylic acid, which are polymers during hydrolysis with hydroxyl or carboxyl groups can be used. Sulfonatable polymers such as polystyrene and cellulose are also suitable.

Pur the modification of the condensation type elastomers Hydrophilic condensation polymers can also be used. These hydrophilic elastomers can contain hydrophilic groups, such as sulfate, sulfonic acid, phosphate or phosphonic acid

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contain groups or consist of salts of the corresponding acids. You can also use long-chain polyether segments, which are derived from ethylene or propylene oxide, have as side chains or as part of the main polymer chain.

In some cases, the hydrophilic nature can be attributed to hydroxyl

groups, while in other cases the hydrophilic nature of the polymer is inherent in the polymer itself Can be a property, namely as a result of a large number of amide groups present in the main chain or as a side chain. The invention is therefore not restricted to a few polymer combinations. Rather, all poly

merenzusammenstellungen suitable which are insoluble in water, but are sensitive to water, preferably in an extent such that the polymer swells in water) (50 to 500 i. " Incidentally, the water-swellable product should exhibit an elongation of preferably 200 # and an elastic recovery of at least $ 30 .

The polymers described can be applied to textile material in a wide variety of ways, for example from solutions or suspensions, with the aid of mixed systems, such as an emulsion of a water-soluble polymer which is contained in a Polymer dissolved containing solution of an organic solvent is suspended. Examples of suspensions are the so-called "organosols"

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or "plastisole". In most cases, the water-swellable elastomer is applied to the fabric in question from a solution of the elastomer in an organic solvent. DIE concentration of the elastomer in the solvent may have any value, but the usual concentrations are in the range of 10 to 50 $> solids. The choice of solvent will depend on the particular elastomer being used. For example, in the event that a modified polyamide resin is used, the solvent could be low molecular weight organic acids or mixtures of alcohol

• and water exist. On the other hand, that would be the case for a polyester required solvents generally from chlorinated hydrocarbons, alcohols, esters, ketones

• and mixtures of these solvents with other organic solvents Liquids or water. As the invention in particular the use of water-swellable materials is concerned, in many cases it is advantageous to use water in the solvent systems that are used for the application these elastomers are used on the fabric in question.

In cases where suspensions, including use of organosols or plastisols, the organic liquids in question contain about 20 to 80 suspended i> solids. Such suspensions can by means of

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the usual coating techniques on the textile materials or by first forming a film of the suspension on a metal knife or metal cylinder which is then applied to the textile material by calendering. Again, it may be desirable be to use different amounts of water to suspend the elastomer in the organic liquid to support, or to achieve, that the elastomer is deposited in its water-swollen state (in the tissue) will. It may therefore be desirable in some cases to have a particular one in a suspended state in water Mix to rhyme. The preferred according to the invention Elastomers have "mixed behavior" with solvent systems and in some cases it is necessary can be to first reduce the particle size of the polymer by mechanical means, followed by the smaller Particles are suspended in a water.

The elastomers can be coated onto the textile material from solutions or suspensions, by & alandrating by means of Impregnation process, or by spraying solutions or suspensions. That in every special one The method used depends on the nature of the elastomer and the nature of the solvent chosen.

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- ι ο -

Although any fabric, paper, leather or other porous material can be made waterproof and permeable to water vapor by applying these water-swellable elastomers, the most suitable materials for the process according to the invention are those fabrics, papers and leather that have a sufficient thickness - * - ^! 'so that the elastomer in question can be deposited inside the porous material. For example, fabrics that are relatively tightly woven and weigh more than 50.9 g / m 2 are preferred. Similar considerations are taken into account when applying the elastomer to paper, leather and the like. The amount of elastomer to be applied depends on the original porosity of the material and its weight. For example, a fabric that weighs 50.9 g / m requires a larger amount of the elastomer

more than a fabric that weighs 101.8 g / m 2. on the other hand

is the weight of the coating, in turn, reduced with a fabric which weighs more than 101.8 g / m. The following table I summarizes the coating weights of water-swellable elastomers used for variously heavy fabrics with the corresponding values for the air and water vapor permeability achieved.

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tissue
weight
g / m ² Medium
Air flow
nonchalance
of the unconcerned
acted
Tissue
νάΡ = 11.58 mm
Hg.G./m ² / hour Medium
Steam
permeable
speed
AP = 11.5mm
Hg.G./mVStd. Table I. upper limit
of the elastome * -
renweight
g / m (pretty
Tt, r .U1 _H TI7 ι ι T ι ■ ii I ^ Medium
Air flow
nonchalance
of the inventor
appropriately
treated
Tissue
P = 11.58 mm
Hg.G./m2/h 50.85 300 200 lower limit
of the elastome * -
renweight B.
g / m (density
Advertising) KXElt «advertising ) 150 67.8 275 190 33.9 loose
67.8 160 84.7
101.8 250
225 170
150 27.1 84.7 170
180 118.7 200 '135 23.7
20.3 84.7
84.7 190 8098 135.6
152.5 175
125 120
100 17.0 67.8 150
125 ο
<ο 169.5 125 100 17.0
13.5 59.4
67.8 125 O
K) 186.4 13.5 84.7 203.5 17.0 101.8 237.1 17.0 118.7 > 339 17.0 118.7 17.0 11 (8.7

Average water vapor permeability of the treated according to the invention
Tissue

P = 11.58 mm Hg.G./m2/h,

65 67 70 72 77 78 80 83

ο cn cn

Preferably the fabric with the elastomer is as follows treated or impregnated!

1. Dae queli'öare copolymers in a suitable solvent such as. B. toluene or mixtures of toluene dissolved with solvents such as ethyl acetate. The special nature of the solvent is not essential to the invention; rather, the solvent can consist of any organic liquid or liquid mixture which dissolves the elastomer. The proportion of the elastomeric mixture in the solvents can vary between 5 and 70% and is usually in the range from 20 to 35 %, '

2. Then the hardeners, pigments, plasticizers or inhibitors to the elastomer solution using those in the rubber and coating industry usual. Techniques added.

3. The final mix of hardeners and others Additions with the hydrophilic elastomers is applied to the ßswtbe in such a way that the elastomers under the Surface of the tissue in question is deposited.

The (common) procedure used for this is by using a standard coating device • ine eogexi & nnte "dense adherence * to provide. The Strength of the

BATH

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The coating applied to the fabric depends on the nature of the fabric to be treated, the nature of the sandals to be applied and the desired degree of water tightness or the degree of air permeability. Beer is useful for a significant number of coating applications and a high degree of air permeability can be obtained if the end use does not require a high degree of water tightness. The exact amount of elastomers applied to the fabric is best described as the amount required to produce a certain degree of water tightness in a beetiaatea fabric that is able to reach a water column of 12.7 to 127 cm wummm ± mniam & mt *. to resist · «. For example, if an 84.7 g cotton fabric ait "Kor * webu & g * old of an elaatoa is treated or impregnated because it swells 100 J *, the fabric of a Druok ron resists 76 om water column, if the elaatomere in an amount of 30» 5 g / m 2 was deposited in the tissue. Ea it is clear that changes in the slastomere adhesion, the composition of the tissue, the fabric structure, the fabric weight and the patiMafeB *

Pressure resistance «• ■« bBMbIwW desired hydrostatic / teab ·: Tielerlei Tariatioaen are possible, and since almost any fabric can be made waterproof and at the same time permeable to water vapor, in order to achieve almost any desired end use au correspond.

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4. The step in the production of the invention-specific tissue consists of hardening the relevant Ilaatoaeren, the exact time for hardening and the hardening conditions depend of course on the type and type of tissue «R dea llaatsaeren iced hardener * b. On the other hand, the shepherding conditions and the type of hardening also depend on the type of fabric . While, for example, it may be desirable, sin old one «fssssr% t £ * llbar * n flastoawsn iaprftgniertea Sauwollstoff 45 minutes at 150 ° 0 iu harden, kaasä it his "nderereeit * necessary" any ei 'other impregnated fabric with a lower Teaperatur and also prolonged period su cure · The usual HiIiM il 11 lirifliiiifliin HIr lt ^ tlBB * P * ffiitill ■■ oopolyser © · «bear 145 ° δ and 45 stole · These «conditions provide for good curing, which makes the elastomer insoluble, but in no way prevents it from swelling» / when old water is touched. Of course, the exact hardness conditions also depend on the amount of hardness agents and others! Additions and the conditions can be adjusted individually by adding larger or smaller amounts of such hardening agents.

In the isolated applications of the invention, the water-swellable El & stonere from solutions of the elastomer in

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" ¹⁵ " U44056

organic liquids or mixtures of organic liquids applied to the tissue. For example, a butadiene copolymer that contains less than 10 " acrylic acid or" aliueacrylate units is easily applied from a solution in foluene, whereas if the polymer in question contains more than 10 # of such units, a mixture of toluene and some polar liquid such as . S. lower alcohols, ketones or acids may be required. In some cases it may be desirable to add small amounts of water which will be dissolved or emulsified in the coating mixture. The use of water in the coating odor is also required when the elastomer has more than about 15 # metal salts

Proportions of acidic lfftrf ¹ * ^{such as} * ^B salts of carboxylic acids,

Sulphonic acids or phosphonic acids or Imiu acidÄ sulfur • contains lure «or phosphoric acid esteiji. In some cases Can aas elastomers from suspensions dee elastomers in

in organic liquids or / mixtures of organic Liquids and water are applied. This procedure is particularly valuable because it is proportionate discontinuous layer of the elastomer is desired, »• nn / a suspension of the water-swellable elastomer the tissue is applied, the hardening leads to a ^ r etest structure of particles that are sintered together. Xa this trap shows the film because of the discontinuities Fibers of the fabric 4 are incompletely impregnated, and »Part that contains elastomeric microscopic extinguishers. Both

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compared to water vapor ft greYjftt Twggwrfraft? permeable

and are, if the elastomer is swollen by water, sealed against liquid water. Regardless of the solvent or suspending agent used, the nature of the process according to the invention requires that volatile liquids are used. The practical implementation is based on the use of water and limited to those organic liquids that can be removed by evaporation. That is, solvents can be used or liquids boiling below 160 ° 0 are used. Also, some higher boiling materials can be used when in the final coating

• Plast

may remain to be used as a qualification or To serve plasticizers. -

/ »He practice of the invention is for one The specific use fabric type used is important in that the fabric and the elastomer are a suitable combination.

of swelling due to the elastomer and / density of the weave of the

Fabric must be provided which allows that - "wiping spaces or gaps in the fabric are closed, " when the elastomer has swelled by about 100%. Any fabric that does not interfere with the curing of the elastomer can be used. Examples of suitable fabrics are those made from cotton, polyamides, cellulose esters, regenerated cellulose and polyeteiii such. B. poly (äthy lent er ephthalat) and poly (1,4-ßyclohexyleniatxmethylenterephthalat). Also useful

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are mixtures of the fabrics mentioned above, such as a fabric composed of 50 Ί · Bauan roll and 50 6 polyester. While any tissue structure can be used, it is usually important to have a relatively

A moderately dense fabric, such as poplin or a body-like fabric Tissue * to be used.

While the technique of applying the water-swellable Elastomer is important to the fabric, this is not the case for the device. Any device with which a coating compound distributed and incorporated into a textile material is suitable for the inventive method. An "air knife" is particularly suitable. But in

some cases a three roll coater, a combination of Roller and a coating knife assigned to the roller or a combination of two rollers and arranged one above the other one of the coating knives assigned to a roller can be used with advantage.

Although the type of process used is unimportant, it is essential that the deposition of the elastomer in the Inside the fabric. It is desirable if the elastomer protrudes in a thin layer over the center plane of the fabric. Maximum flexibility and

* a twill-j type weave

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only then will the impregnated fabric get a good grip obtained when the elastomer is essentially in the space between the midplane of the fabric and a plane that is halfway between the median plane and the top surface of the fabric. if for example an air knife is used, these results can be obtained using the coating knife has an open angle of about 8 ° and a thickness of about 63 mm. Of course, other angles and

smooths

Thick can be used. The open angle aSfc / the uncoated Tissue and serves to force the coating solution under the surface of the tissue. The voltage

Likewise
of the fabric, jettmoBC is adjusted so that it has a be

correct pressure of the fabric during the coating operation

causes. The pressure of the fabric against the coating """'"

included
knife supports / the deposition of the elastomer in the

correct position. Finally, each layer of the elastomer is applied from alternating directions so that the interstices of the tissue in more

or less evenly filled, taking them however, cannot be completely closed during the coating operation itself.

After the elastomer has been applied to the fabric in a suitable solvent, the curing process takes place accomplished by applying heat. The heating can be carried out in autoclaves, hanging ovens or continuous roller ovens

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take place. The exact time and temperature necessary for reasonable If hardening is required, it depends, as already indicated, on the elastomer, the fabric and the hardening system away. In most cases, the elastomer is deposited beneath the surface of the fabric, with what is in the relevant technique known as "tight hardening", is not as important as it is for a rubber coating "deposited on the surface. However, when peroxides in a

the elastomer

Amount of about 0.5 to 5 parts, based on sxaatxflknano :, used hardening conditions of 100 to 200 ° C and hardening times between 1 minute and 2 hours can be used will. Sulfur cures can be achieved using 0.5 to 8 parts of sulfur or sulfur-containing compounds be carried out, the usual temperature ranges between 100 and 200 ° C and the curing times between 10 Out and about 2 hours. Other hardening systems use metal oxides and sulfur, as used in hardening systems for chlorinated elastomers such as B. neoprene are known.

For the practical implementation of the invention, copolymer · are used, the water-swellable elastomers provide the 50 56-95 ° i of a monomer, such as butadiene, Chloxpren, isoprene or the like. The monomers, the homopolymers of which are water-soluble or significantly swell in water, are used in an amount of 5 to 50 #. The following examples explain the invention in detail

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example 1

An elastomer based on 75 $> butadiene and 25 # acrylic acid was dissolved in a mixture of 75 $> toluene and 25 # ethyl acetate. Based on the dissolved elastomers were then 5 $> finely divided zinc oxide, 1 # sulfur and 0.5 i> Teiocarbanilid, and based on the weight elastomers, 2 <$> 2,6- (1-methylheptadecyl) -p-cresol as Stabilizer added. This mixture was applied to a 84.7 g / m cotton fabric by passing the fabric between a roller and a doctor blade, with 26 g of elastomer

In each case ρ solid constituents (as a solution) / were deposited on 1 m.

The coating device was adjusted so that the fabric was tensioned and that the angle of the hook with the fabric caused the elastomer to be forced through the surface of the fabric and deposited beneath it, but the elastomer solution did not fully permeate the fabric. It was then cured by placing the fabric in an oven heated to 150 ° C. After 45 minutes, the tissue was then removed from the oian again. The fabric treated as described was found to withstand a 76 cm column of water (liquid water). Other samples of the fabric were then tested for water vapor permeability and found that the fabric was capable of / 65 g / m / hr. at 50 it> relative humidity on one side of the fabric and 100 # relative humidity on deyanderen side of

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To let through tissue. The temperature during the water vapor permeability test was 26 ° C. The fabric had otherwise good looks and feel.

Example 2

10Og of a blastomer based on 60 £ ^ butadiene and 40 56 Η, Η-Dimethy! Acrylamide were in 250 g of toluene, the 150 g Ethanol were added, dissolved. As in Example 1, hardeners and accelerators were added to the solution. A water-repellent silicone resin was also added to the solution. With the mixture obtained, an 81.5 g / m

ρ impregnated heavy polyamide fabric. 30.5 g (dry) sizing was applied to the fabric per m. After curing, the fabric withstood a water column of 584 cm and Hess 72 g / m ² / hr. Water vapor at 50% relative humidity on one side of the fabric and 100% on the other side of the same at a temperature of 26 ° C. The air permeability was 165 g / m / h. or 66? fc that of the untreated fabric.

Example 5

10og a blastomeres from 60 i »butadiene and 40 i" N-isopropyl acrylamide were dissolved in 25 g of toluene with 150 g of ethanol: was mixed, dissolved. To the solution was 5 g

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finely divided zinc oxide, 1 g sulfur and 0.5 g 2-mercaptoimidazoline. added. A water-repellent silicone resin was again added to the solution. A cotton fabric weighing 101.8 g / m 2 was impregnated with the mixture obtained. The dry weight of the coating on the fabric was 42.5 g / m 2. The impregnated fabric was then cured for 45 minutes at 15O ⁰ G. The fabric resistance to a water column of 1,067 cm and left under the same test conditions as described in Example 2, 65 g / m / hour. Water vapor through.

Similar results were obtained using elastomers made from 70-6 butadiene-30% acrylamide; $ 70> butadiene-30 % beta-oxyethyl acrylate; $ 70> butadiene- $ 30> vinyl pyridine; 70 # butadiene-30 5 & methacrylic acid; 70 i "Butadieh-30 fo methacrylamide; 70 $> chloroprene 30 fi methacrylamide and 70% isoprene-30 received i> acrylic acid. A wide variety of fabrics, such as cotton and polyester, namely poly (1,4-cyclohexylenedimethylene terephthalate) and polyethylene terephthalate) and fabrics made from mixtures of such polyesters with cotton, could be impregnated in an excellent manner with these elastomers.

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Example 4

An elastomer based on 70 i> butadiene and 30 i> Hatriumacrylat was dissolved in a group consisting of 80? 6 of toluene and 20 $ methyl ethyl ketone solvent mixture. The polymer was contained in the solution in a concentration of 26 % . Based on the dissolved polymer, 1 "f» of a water-repellent silicone resin was then added. As in Example 1, curing agent and accelerator were added and the resulting elastomer solution was used to impregnate a 118.7 g / cotton fabric. After evaporation of the solvent contained the fabric 35 »6 g / m 2 of the elastomer deposited in the fabric. Finally, the elastomer was cured by oven heating as in Example 1. After curing, the fabric was tested to find that it had a hydrostatic pressure of 119 cm The test conditions during the water vapor permeability test were 50 56 RH on one side and 100 56 RH on the other side of the fabric at a temperature of 26 ° C .

Example 5

150 g of a copolymer based on 68 % butadiene and 32 % acrylonitrile were dissolved in 650 g of toluene. This solution

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was stirred at 80 ° C αη ± χ4 & and 45 g of potassium hydroxide, which was dissolved in 250 g of ethanol, added. Stirring was continued for 1 hour after which time 36 g of water were added. An additional 36 grams of water was added while stirring was continued for an additional 12 hours. After 24 hours analysis indicated that 90 # of the acrylonitrile units of the original copolymer had been converted to potassium acrylate units. The final polymers consisted of $ 67> butadiene, 29.8 fi ijaliumacrylat and 3.2 9 & acrylonitrile. Films cast from this mixture showed a swelling of up to 400 # in the presence of water. Cured films obtained by adding $ 1.5 dicumyl peroxide, based on "Kauteeh.uk ¹¹ , and

Warming up to 110 ° C for 45 minutes,

Presence of showed a swelling in / waters of about 300? 6.

This elastomer was used to impregnate 152 g / m 2 poplin fabric obtained from a fiber blend. Before the elastomer was used for the impregnation, it was modified with 1.5% dicumyl peroxide, based on the solids content in the coating solution. The fibers consisted of a mixture of 55 f * poly (I, 4-cyelohexylendimethylenterephthalat) and 45 fi one of Courtaulds Limited under the name "Topel". cellulose fiber placed on the market ». This fabric has been so

impregnated that 30.5 g of the elastomer kaaen to 1 m, wherein

the impregnation was carried out in such a way that actually no elastomer on the surface of the fabric

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was present. The impregnation was carried out in a laxt exne * manner known in the relevant art as the air knife process, a coating knife being pressed against the "strapless" fabric and the impregnation being carried out in two passages over the fabric in opposite directions. "The fabric impregnated as indicated was finally hardened by heating in an oven at 110 ° C. for 45 minutes. After hardening, the fabric was

always

be tested, and it was found that / the elastomer was air-permeable but waterproof. As a result of the hydrophilic nature of the elastomer, the fabric swelled in contact with water _Y wherein it was not long after swelling air permeable "Next was leicht.feucht the impregnated fabric due to the hydrophilic Hatur of the elastomer, wesahalb the surface of the tissue to this for use to make usable as a waterproof material,

was

after-treatment with a silicone resin, which is done using an aqueous emulsion of the silicone resin in question · * ■

After the surface had been treated with the silicone resin, the fabric was tested again and found that it did not become wet in contact with water, provided there were no water columns above the fabric. It was also found that under these conditions the elastomer swelled and that as a result it stuck to a water column 55 cm high.

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held, respectively this trugjbal. The water vapor permeability became 65 g / m ² / hour. at 25 ° with a steam

.- ■ ":. From...
difference in pressure / corresponding to 11.5 mm Hg determined.

Example 6 '· ■■■■■ ;.

Using the technique described in Example 5, a copolymer of butadiene and methacrylate was hydrolyzed and then coated with a fabric. The original copolymer consisted of 65 % butadiene and 35% methacrylate. The physical properties of this polymer were similar to those of the hydrolyzed polymer of Example 5. A fabric impregnated as in Example 5 showed the same "water column resistance ^11" and the same air permeability. The water vapor permeability was measured to be 65 g / m / h at 25 ° with a vapor pressure difference of 11.5 mm Hg.

Example 7 .

100 g of a copolymer based on 70 $ 'isoprene and 30 # Acrylonitrile was dissolved in 200 g of toluene and 40 g of Sali »avon Potassium hydroxide dissolved or suspended in 100 g of ithanol was added. This mixture would be heated stirred at 70 ° C for 36 hours. During this time ammonia evolved and the end product consisted of a copolymer of isoprene and aluminum acrylate. This

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Copolymers were made on a 118.7 g / m cotton fabric like this

2 K

plotted that 37 »3 g / m dry" JgfiEttautsehuk ¹¹ "was deposited behind the surface of the fabric

and
Impregnation was permeable to air and water vapor, but impervious to liquid water at a pressure height of 66 cm. Under test conditions of 50 $ relative Peuchtigkeit at 75 C, the fabric 70 g / m / h had. Water vapor through.

Example 8

100 g of a copolymer consisting of 70 # isoprene and 30 % sodium acrylate were dissolved in 200 g of toluene + 100 g of ethanol, 2.5 g of senzoyl peroxide were added and the mixture was applied to a fabric made from polyalkylene terephthalate. This fabric weighed 95 gg / m. The coating was carried out by an air knife process which caused the coating to be deposited as a discontinuous film in the spaces or voids of the fabric. The solvent was then evaporated and the fabric / heated to 145 ° C. The final product consisted of a fabric that had a discontinuous layer of

contained hardened, swellable elastomers, welthes 65 g / m / Hours water vapor to a »water vapor pressure difference of 11.5 ma Hg let through,, -.......,

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Example 9

The elastomer described in Example 8 was in 1 part Dissolved toluene + 2 parts of methyl ethyl ketone. Based on the elastomer, there was 1.0 part of sulfur and 1.5 parts of 2-mereaptoimidazoline and 5 parts of zinc oxide added. This mixture was applied to a fabric which weighed 271 g / m 2. The weight of the dry elastomer after coating was 71 g / m. As in Example 8, the elastomer deposited beneath the surface of the fabric in the form of a discontinuous layer, which is subsequently heated by heating was cured to 14-5 ° C for 45 minutes. The received Fabric was permeable to water vapor, but waterproof. The tissue was then further treated by putting it through an aqueous suspension containing 1.6% silicone resin, was passed through. The fabric was then dried and tested. When cherishing it during a restricted When exposed for a period of time, the finally obtained product was found to be waterproof while fortriBDC

exposed or prolonged exposure to a thickness of 2.5 cm / hour. it was found that the silicone water resistance of the fabric surface was destroyed. However, the fabric remained waterproof (against Hegen) because the water-swellable elastomer had swollen and closed the gaps between the tissue.

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- ²⁹ - U44056

Example 10

100 g of a copolymer consisting of 95% isobutylene and 5 i ° butadiene were dissolved in 200 g of toluene. Next, 33 g of a Polyäthylenoxyds a molecular weight of 2400, which was esterified in the end groups with acrylic acid, dissolved in 33 g methyl ethyl ketone. This solution was then mixed with the solution of the copolymer and 3t0 g of sulfur, 5 g of zinc oxide, 3.0 g of stearic acid and 1 g of aETetramethylthiuram disulfide were added to the mixture in the form of a fine dispersion in toluene. This mixture was used to coat or impregnate a cotton poplin fabric, which weighed 118 g / m 2, by means of a knife suspended over a reindeer drum. In detail, 3 observation walks or passages were carried out. After this

part ρ

Evaporation of the solvent was / asxx 30.5 g / m 2 of the elastomer deposited within the fabric and on the surface of the fabric. This fabric-elastomer combination was then heated to 145 ° C. for 1 hour in order to crosslink or cure the elastomer. When the impregnated fabric was treated with methyl ethyl ketone, it was found that the polyethylene oxide was chemically bonded to the elastomer because , although the modified elastomer swelled very strongly, no resin could be extracted from the fabric. The fabric treated as indicated was further exposed to water, causing the polymer to swell again, tests in which the fabric was exposed to a column of water 50.8 cm high,

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631

shows / that the elastomer in the swollen state is water constantly held.

After drying, the fabric was against air and water vapor permeable. The fabric was then further treated by adding a solution of silicone resin DC-ZÖ18, as used by the Dow Corning Corporation is manufactured on-the-surface of the fabric was sprayed. -After the solvent has evaporated The surface of the fabric was found to be water-repellent and the fabric to be waterproof and water-permeable was.

Example T1

100 g of a copolymer consisting of 5 piperylene and 95 ° C. isobutylene were dissolved in 300 g of toluene. In addition, 33 g of a copolymer consisting of 10 "A- butadiene and 90 ° / ° lithium acrylate were dissolved and 100 g of water were added. This mixture was stirred until a smooth, viscous 2-phase dispersion was obtained. This was followed by 2.0 g tert-butyl hydroperoxide was added and the mixture was applied to a fabric made of poly (1,4-cyclohexylenedimethylene terephthalate).

carried. This fabric weighed 123 g / m and was made of poplin. The application of the coating mix was done using an air doctor technique carried out in such a way that after the subsequent evaporation of the solvent 50.9 g / m of the elastomer were deposited under the surface of the fabric. The fabric was then heated to 160 ° C /

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heated to cure the elastomer. Try the butadiene-lithium acrylate copolymer Extraction with water was unsuccessful, although the elastomer through the The water welled up. The fabric was waterproof up to a water column of 1,041 cm, but air and water vapor through casual. The water vapor permeability was 58 g / m / h. with a water vapor pressure difference of accordingly 11.5 now ed.

Example 12

100 g of polybutadiene were dissolved in 200 g of toluene. For this purpose, 20 g of maleic anhydride and 0.5 g of benzoyl peroxide / added and the mixture was heated at 50 ° C. for 24 hours in a reaction vessel equipped with a stirrer. Afterward

o the mixture was cooled and 3 more 2 g of benzene peroxide

added. This mixture was then made as in Example 11

Likewise
applied to the fabric described in Example 11.

After evaporation of the solvent, the elastomer was made by heating the Göwebes to 145 ° C for 20 minutes hardened. The tissue was then passed through an aqueous solution of sodium hydroxide, laughing Upon drying this fabric it was found that it was coated with a water-swellable elastomer that was water-resistant but opposed .Water vapor was permeable, was impregnated. By passing through of the fabric by an emulsion of a fluorocarbon became the fabric impregnated as described

8 09809/1024

³² "U44056

after / treated. The end product consisted of a porous fabric with a water-repellent surface, but was also waterproof because the polybutadiene, modified by the sodium salt of maleic acid, swelled on contact with extensively liquid water. This fabric resistor 61 cm water column hydrostatic pressure of MndbapttJEObBnä but allowed water vapor at a rate by which 65 i> of the water vapor found for the untreated fabric transmission rate corresponded.

Example 13

The copolymer described in Example 12 was converted into the sodium salt of the maleic acid-butadiene copolymer, before it was used to impregnate the fabric by adding sodium hydroxide dissolved in ethanol to the toluene solution of the Copolymers was added. After applying the modified elastomer and then evaporating the solvent and hardening, the fabric showed identical properties as the fabric obtained according to Example 12.

Example 14-

33 g of a copolymer consisting of styrene and maleic anhydride in a molar ratio of 1: 1 were dissolved in 50 g of acetone and 50 g of toluene dissolved. To this, 5 g of allyl alcohol was added and the mixture was heated to cause the alcohol

809309/1024,.

esterified with part of the anhydride. Afterward 5 g of water was added to hydrolyze the remainder of the maleic anhydride. The polymer obtained passed from a copolymer of styrene and maleic acid, some of which was esterified with allyl alcohol. That is still in solution

to
Sensitive polymers were then added / 100 g of natural rubber dissolved in 200 g of toluene, finally 2 g of acetyl peroxide was added to the mixture and this was applied to a cotton fabric that weighed 135.6 g / m2

a "knife * over roller technology" is used, which causes »»,

that the openings in the tissue are incomplete with the egg

p
stomers were closed, with 23.7 g of des

dry elastomers came. This elastomer was then cured by heating at 125 ° for 1 hour. the Analysis showed that the maleic acid-styrene copolymer chemically adapts to the natural rubber by reaction of the allyl ester groups was grafted on. The elastomer was swellable in water and therefore tended to be continuous Form a barrier against water when the fabric was damp. Otherwise, the fabric was in a dry state air and water vapor permeable.

Example 15

The maleic acid-styrene copolymer described in Example 14, which contained some allyl alcohol ester groups, was tested by

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high

Addition of a molar amount, based on the free carboxyl groups, of atrium hydroxide converted into the sodium salt. This conversion occurred before the polymer was added to a solution of rubber as in Example H. It was here a similar fabric treated as in Example 14, with otherwise similar results being obtained.

Example 16

100 g of a ^{copolymer consisting of 80 σ} / Ό butadiene and 20 f> liatrium allyl sulfonate were prepared according to the following recipe:

80 parts 1,3-butadiene
10 "180 ⁿ liatriumallylsulfonat water

3 ^M polyethylene oxide

2 "potassium persulfate

0.5 "sodium bisulfite

The mixture was stirred and heated to 50 ° C. for 24 hours. No attempt was made to prevent networking. The polymer was in the form of suspended particles obtain. 300 g of toluene was added to the reaction mixture and the water was removed by azeotropic distillation. After the water had been separated off, the product consisted of an organosol of the particles of the original emulsion. These

80 980 9/10 24

Particles were swollen by the toluene into a semi-rigid, gel-like structure. Two parts of dicumyl peroxide, based on the polymer, were then mixed into the mixture. This organosol was then applied to a cotton fabric weighing 344 g / m 2 using a doctor blade suspended between and below 2 rollers so that the fabric was pressed below the connection line formed by the two upper roller surfaces. The angle made by the ⁿ V ^{n of} the depressed tissue was about 160 ° C. The coating was carried out in 3 passes. The total weight of the elastomer after evaporation of the solvent was 81 g / m 2. It was hardened by heating to 175 ^{° C. for 1/2 hour.} Almost all of the cured elastomer was deposited in the interstices of the fabric. The elastomer was microporous. Bies resulted from an experiment in which a film was cast on a metal plate. A material was obtained which was porous to air under a slight excess pressure. In the present case, the air and water vapor permeability was based on the fact that the elastomer between the fibers was micro-. porous and the incompletely impregnated fiber bundles were permeable. Both types of micropores were closed by swelling when the elastomer came into contact with water. That after this

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U44056

Technique made fabric was waterproof to a water column of 147 cm and let water vapor with a 50 g /

m / h corresponding speed with a vapor pressure difference of 11.5rHg?

Example 17

10og dissolved in 200 g of toluene polybutadiene wurdei with 75 g of a 50 $ aqueous solution of an interpolymer that the 36.8 f> of styrene, 53.0 # of sodium maleate and 10.0% of a mixed allyl-Fatriumsalz Maleic acid, mixed. 1.75 g of benzoyl peroxide were then added to the mixture and this mixture was then added

a ρ the manner described in Example 1 on / 108 g / m cotton

so
tissue applied. The treated or impregnated fabric let water vapor at a rate of 65 g / m / h. at 25 C and a vapor pressure of 11.58 mm Hg. It also withstood a water column of 89 cm. The air permeability was 183 g / m / h. or 68% of that of the untreated fabric.

Example 18

100 g Polychlonspren, which was dissolved in 200 g of toluene was charged with 100 g of a Toluolsuispension that 50 g of a 33.8 styrene $, 53 ° f ^ potassium maleate and xax 13.5% asausxxlaaBJB mixed "allyl ester of maleic acid potassium salt existing

809809/1024.

contained
Copolymers / mixed. To the mixture was added 1.75 grams of cumene hydroperoxide and the final mixture

on a polyamide fabric weighing 186 g / m, according to the example 1 described technique applied. The fabric obtained in this way was permeable to water vapor, but it resisted a hydrostatic pressure corresponding to a height of 183 cm.

The air permeability of the sample was 130 g / m / hour or $ 78 that of the untreated fabric.

Example 19

100 g of a copolymer which consisted to 68% of butadiene and 32 f> acrylonitrile as monomeric components, wurdeiin 200 g of toluene and treated with 100 g of a copolymer of composition 70 io butadiene and 30 $ acrylic acid, which was previously dissolved in 200 g MethyläHthylketon , mixed. To the mixture was added 2.5 g of dicumyl peroxide and using the method and similar conditions

like that described in Example 1, a 339 g / m weighing cotton canvas fabric, with treated. This The fabric was then permeable to air and water vapor, but waterproof to all types of natural precipitation. The fabric pretreated as indicated was particularly suitable for use as tent material and for Covers or canvas.

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Example 20

100 g of a copolymer containing 95 1 ° isobutylene and butadiene containing 5 $, were dissolved in 200 g of toluene. This solution was mixed with a solution of 25 g · polyvinyl alcohol which had previously been reacted with 10 g of acrylic anhydride in order to esterify part of the hydroxyl groups of the polyvinyl alcohol. 2.5 g of dicumyl peroxide were added to the mixture and the coating mixture consisting of an emulsion of the aqueous phase in the toluene phase was finally applied to a fabric using the technique described in Example 1

applied. This fabric weighed 156 g / m and was made of a polyester fiber. The final fabric allowed water vapor and air to pass through at a rate 66 % that of the untreated fabric. The fabric pretreated as described was waterproof to a water column of 127 cm. This fabric was suitable for use as rainwear.

Example 21

100 g of a copolymer consisting of 95% isobutylene and 5 % butadiene were dissolved in 250 g of toluene. Next, 40 g of a 60 i of "Oxyäthylacrylat and 40 $ chloroprene copolymers existing in 150 g of a 1: 1 mixture of isopropyl alcohol and toluene dissolved. The two solutions were then mixed together and then another 1.25 g

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Cumene hydroperoxide added. The final solution was made

2 ^w
Applied to a 118.7 g / m 2 Hanging cotton fabric as described in Example 1. After curing, the fabric was permeable to water vapor and waterproof to liquid water. It was useful for making sports and hunting jackets, as well as other sports apparel.

Example 22

100 g of polychloroprene were dissolved in 250 g of toluene. 50 g of a copolymer consisting of 85% acrylamide and 15 1 ° chloroprene were also dissolved in water. The two solutions were then mixed with one another, 1.25 g of dicumyl peroxide were added to the mixture and the aqueous solution was emulsified in the toluene solution by vigorous stirring. After a smooth dispersion had been obtained, the mixture was applied to a cotton fabric weighing% 390 g / m 2 as described in Example 1. After curing, the ^{surface of the fabric was treated with an M} fluorocarbon type resin. The final fabric was permeable to water vapor, but waterproof to liquid water.

Example 23

100 g of a copolymer consisting of 91 # butadiene and 9 % acrylamide were dissolved in 300 g of toluene. Next were

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50 g of a 90 i »sodium acrylate and 10 ^ acrylamide copolymers existing in 65 g of water dissolved. The two solutions were mixed with one another, an emulsion of the water phase in the toluene phase being formed. 2 g of potassium carbonate and 10 g of formaldehyde were added to the emulsion, and this mixture was heated to 70 ° C. for 0.5 hour. The mixture was then cooled and acidified by adding 2.0 g of acetic acid. This mixture was finally used to impregnate a poplin fabric weighing 157 g / m. After impregnation, the fabric contained 37.2 g / m 2 of the elastomer deposited under the surface of the fabric. The coating itself was carried out in 3 coating passes using an air knife. After the solvent had evaporated, the fabric impregnated with the elastomer was heated in an oven at 150 ° C. for 1/2 hour. The end product consisted of a fabric which contained an elastomer which was insoluble in all solvents because it was crosslinked. The elastomer swelled in water and the fabric was waterproof, although the layer of elastomer in the fabric after drying was a continuous or discontinuous layer.

The fabric was finally treated with a silicone resin so that its surface became water-repellent. The end product was air and water vapor permeable, but waterproof against liquid water.

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Example 24

100 g polyethylene, previously modified by chlorosulfonation was dissolved in 250 g of toluene. Further

K and 50 g of a copolymer which consisted of 50 φ £ aluminum acrylate / 50 io butadiene and was suspended in 100 g of a 1: 1 mixture of toluene-methyl ethyl ketone were added to the solution. After finally O ₅ 75 g cumene hydroperoxide had been added, this mixture was used to produce a

To treat cotton fabric weighing 142 g / m. To

about ρ of the treatment or impregnation was / 54 g / m of the dry elastomer is deposited in the gaps in the fabric. After curing as in Example 1, this left

Fabric 38 g / m / h Water vapor through when the water vapor pressure difference 11.6 mm Hg was equivalent. The fabric withstood a water column of 150 cm after the elastomer was swollen by water. This fabric was

to plan
suitable for tent material, canvas, Kamamr and the like.

Example 25

A polyester containing polyethylene oxide segments was made using polyethylene oxide attached to the end groups Containing hydroxyl groups and having a molecular weight of 500. Lie's exact composition was 1 mole of adipic acid, 0.5 mole of ethylene glycol and 0.5 mole of polyethylene oxide This polymer possessed for the implementation

80 980 "/ 1024

of the invention had sufficient elastomeric properties and swelled to about $ 300 in water. The polymer was dissolved in a mixture of toluene and ethyl alcohol · produce a viscous solution containing 33 ° f solids was obtained. The polymer was then applied to a fabric weighing 118.7 g / m 2 using a so-called "roller doctor blade technique" within three passes. 27 g / m 2 of the elastomer was deposited in the fabric. After the solvent had evaporated, the fabric was checked for water vapor permeability. With a water vapor pressure gradient corresponding to 11.58 mm Hg, the fabric left 80 g / m / h. Water vapor through. The untreated fabric left 105 g / m / h under the same conditions. Water vapor through. The impregnated fabric was also tested for its water retention capacity. It withstood a water column 81 cm high. The impregnated fabric had excellent flexibility and abrasion resistance properties. It let air through at a rate 757 of the value obtained for the untreated fabric.

Example 26

One using 0.5 moles of adipic acid, 0.5 moles of succinic acid, 0.5 moles of 1,4-butenediol and 0.5 moles of polyethylene

809809/1 024

oiyd (with hydroxyl groups as end groups and a molecular weight of 1,200) produced Oopolymeres was dissolved in a mixture of methyl ethyl ketone and toluene, the Quantities were chosen such that a solution containing 40% solids was obtained. With the The solution was a 118.7 g / m cotton fabric with a simple poplin weave in 4 passes using one Prank eater coated. This knife was made by means of two rollers, which refer to the direction in which the Tissue was passed under the knife, in front of and behind the cutter, so with the tissue brought into contact that the tissue'of the doctor blade was depressed. In addition, intimate contact of the tissue with the knife was achieved by the Tissue was passed under the knife in a stretched state, This special doctor knife was. at the front edge beveled by 20 ° and arranged in such a way that it depressed the tissue, with that of the tissue The angle formed by the back of the knife was 75 °. A microscopic examination performed after coating of the fabric showed that the elastomer deposited between the two surfaces of the fabric in a discontinuous layer had been. As a result of these discontinuities, the fabric was below that in Example 1 with respect to water vapor conditions described permeable, and withstood one Water column of 114 cm high. The air permeability became 190 g / m / hr, or 73 # that of the untreated

809809/1 024

'would be

Tissue found. Example 27

A block polymer was produced from two prepolymers A and B by mixing the prepolymers with one another and polymerizing them by heating in vacuo to form a high molecular weight polymer, which consisted of alternating blocks or segments of prepolymer A and prepolymer B, respectively. Pas prepolymers A £ i & mkUaär \ XB 0.25 mole adipic acid and 0.3 mol of polypropylene oxide, 4The at the ends

Carried hydroxyl groups and a molecular weight of 2,500
₀ / £ as prepolymers Bjeutadate using 0.3 mol

was

Succinic acid and 0.25 Mbl Polyäthylenoxyt produced / the hydroxyl groups at the ends Ata bore and having a molecular weight of 3 000th The final polymer was thinly dissolved in a mixture of acetone and toluene in a ratio of 60 40. Me solution containing 15 $> Feet components and was used to produce a Baumwollgewtbe to impregnate the 203 g / m weighed, so that the fabric after evaporation of the solvent 50.9 m g / contained the block polyester. This polyester was swellable in water and the coated fabric withstood a water column of 73.5 cm. Height, although the layer of elastomer in the fabric was discontinuous and therefore water vapor permeable. The impregnated fabric was tested and found to be 76 grams. Waestr- »steam / m / hour under the same conditions wl® in example 1

8 0 9 8 0 b / 1 0 2 4 ■ "- ■■ BAD

- 45 - U44056

described below, let through. The air permeability xadsbc under the same test conditions was 145 g / m / h. or 63 I / o that of the untreated tissue was found.

Example 28

A polyurethane was produced from toluene diisocyanate and a polyethylene oxide which had hydroxyl groups as terminal groups and a molecular weight of 3,000. This polymer was prepared in a mixed solvent of toluene and methyl ethyl ketone. -The solution contained 26 % solids and consisted of a viscous liquid,

which was applied to a fabric weighing 157 g / m 2 made of a mixture of a polyester and a cellulose fiber. The fabric was impregnated in three passes so that a discontinuous film formed between the two Surface was deposited, was provided. This discontinuous film, which weighed 30.5 g / m 2, was in water swellable. However, due to the discontinuous nature of this film, the impregnated fabric was resistant to water vapor

i.e.

permeable / the fabric was described in example 1

P.
under conditions 73 g water vapor / m / h. by. The impregnated

held ^r

ned sample msuBcaaüsiaui. a water column of 145 cm high /.

The air permeability was checked and found to be 125 g / nr / hour. or 76 # of those of the untreated fabric found.

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Example 29

Polymer that
On / off toluene diisocyanate, 1,4- £ utes-2-diol and a polyethylene oxide having a molecular weight of 500 and with hydroxyl end groups was prepared as was dissolved in a mixture of toluene and methyl alcohol to a solution containing 30 ° / o solid component dissolved. The polymer was swellable in water and could be used for coating or impregnating fabrics, paper or leather. Such coated or impregnated materials could, depending on how much polymer aaacfic the porous material in question was deposited, be made resistant to water columns at a height of 12.7 to 254 cm. When the elastomer is deposited as a discontinuous layer as described in the previous examples

and otherwise became porous, the impregnated / material was permeable to water vapor.

This polymer had the additional characteristic that it Was olefinically unsaturated and therefore could be cured or crosslinked. The hardening or crosslinking was carried out through

from
Addition of peroxides, / certain metal-containing dryers, such as. B. cobalt naphthenate or by adding sulfur or certain sulfur-containing organic compounds to the elastomer before it was applied to the fabric. For example wurde4u a part of the above elastomers dissolved 1.5 ° f dicumyl peroxide, based on the weight of the elastomer is added. This portion of the elastomeric solution was then used to impregnate various fabrics

8 * 0 930 S / 1024

or charged in order to produce waterproof, water-vapor-permeable materials. After the solvent had evaporated, the elastomer was cured or replaced by heating the sample in question at 150 ° in an oven for 45 minutes. The elastomer could not then be very detached from the fabric by means of solution ducts, as is common for dry cleaning operations. Because "curing or crosslinking impaired Incidentally * ¹ * in no way affect the usefulness of the impregnated fabric with respect to its hydrostatic resistance or its water vapor permeability. Another portion of the elastomer solution was made curable by adding 1.5 # manganese naphthenate based on the weight of the dissolved polymer. This solution was used to impregnate a fabric, whereupon the fabric was hardened or crosslinked after the solution had evaporated by heating it in an oven at 110 ° for an hour. Another part of the elastomer solution w received additions of 1 part of sulfur and one part of 2-mercaptoimidoline, based on the dissolved polymer, as a catalyst. After impregnation and evaporation of the solvent, the elastomer was cured by heating in an oven at 145 ° C. for 45 minutes.

Example 30

Am polyester based on 0.25 moles of terephthalic acid, 0.25

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Moles of maleic acid and 0.5 moles of polyethylene oxide (with hydroxyl groups as end groups and a molecular weight of 1,200) were dissolved in a mixture of methyl ethyl ketone and alcohol and a solution containing 36% of solid polymer. Based on the dissolved polymer ₃ , i <> benzoyl peroxide was added to the solution 2 ₉ and the mixture obtained was added to it

used to apply a 118.7 g / m cotton fabric in two passes of the fabric under a coating knife such ^ tKksatSdrkaörtSMCxacilas: to impregnate that 31 ^ 5 g / m of the elastomer were deposited in the fabric, Kach dem Evaporation of the solvent, the coated fabric was heated to 120 ° 0 for 30 minutes in the oven. That coated Fabric has been tested and found to be water vapor permeable

found. Ss left 62 g / yd. /Hours. Water vapor at 15 ° 0

5
- with / 5 % relative humidity on one side of the fabric and 100 % relative humidity on the other side of the same. The coated fabric was also tested for resistance to liquid water and was found to withstand a water column of 124 cm. The fabric was further tested by soaking samples in various organic liquids which dissolved the original polymer. Although these solvents swelled the elastomer, it was not dissolved by it, weatting the crosslinks formed during the curing process.

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Example 31

A polyamide made from equal molar parts of hexamethylenediamine and adipic acid was reacted with ethylene oxide to form a polyamide which had polymeric ether chains attached to the nitrogen atom. The reaction was carried out so that 75 i> contained the weight of the final polymer Polyäthylenoxydsegmente. This polymer swelled easily in water and was soluble in mixtures of water and methyl alcohol. A solution of the polymer was prepared containing 25% solids. One such solution Oatgx. jerisaoduaajac a viscous mass and could be applied to a fabric using a doctor blade or a roller application process. A polyester fabric weighing 135.6 g / m was impregnated with it in three passes or layering passes in such a way that 37.2 g / m 2 of dry elastomer was deposited in the spaces or gaps in the fabric. The amount of elastomer deposited in this particular way consisted of a discontinuous layer which was embedded in the fabric in such a way that it formed a porous layer which was permeable to water vapor. Since the elastomer swelled slightly in water, the gaps or spaces in the tissue concerned were closed when it came into contact with water. The combination of fabrics - elastomer was »» therefore waterproof in the swollen state, it means "f * n ry water column ^ on 107 cm height / The water vapor

permeability was 67 g / m / hour with a steam

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like that
kdifc, & «κ 11.58 mm Hg was equivalent, found

Raincoats made from the impregnated fabric and sports jackets provide excellent protection from rain and meadows due to their permeability to water vapor, they are more comfortable to wear.

Example 52

100 g of an elastomer made from 0.5 mol of adipic acid, 0.5 mol of maleic acid, 0.5 mol of 1,4-butanediol and 0.5 mol of polyethylene oxide (with hydroxyl groups as end groups and a molecular weight of 500) was prepared in Dissolved 100 g of toluene and 100 g of isopropanol. Next, 50 g of methacrylic acid and dissolved from 60 fo 40% butadiene copolymers existing in 50 g of water + 10og isopropanol. The two solutions were mixed together and 2.5 g of dicumyl peroxide were added to the mixture, whereupon the mixture was applied to a fabric weighing 84.7 g / m 2 as described in Example 1. After curing, the impregnated fabric was tested to find that it passed 63 g of water vapor / m / hour at a vapor pressure difference or gradient equivalent to 11.58 mm Hg. The fabric was also waterproof, meaning it withstood a water column of 107 cm. This fabric was for use as rainwear and et & a? Protective covers suitable for sensitive instruments.

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Example 33

10Og poly (deoamethylene urea) in the form of a fine Powders were suspended in dimethylformamide. The mixture was placed in an autoclave and injected with 50 g of ethylene oxide. The mixture was then heated with stirring to cause the ethylene oxide to have polymeric side chains,

ⁿ en

which were linked to the nitrogen atom / the polyurea chain formed. The polymer finally obtained weighed 135 g and was in solvents such as. B. methyl ethyl ketone, 1,4-dioxane and mixtures of these solvents with toluene are soluble. 100 g of this polymer were dissolved in 200 g of methyl ethyl ketone and 50 g of a 80 $> Ν, ΐί-Diinethylacrylamid and 20% acrylamide added to existing copolymer. After the second copolymer was dissolved, 5 g of a melamine-formaldehyde resin containing reactive methylol groups were added. This mixture became this

used to produce a cotton fabric weighing 108.4 g / m

kind of layering that 37.2 g / m 2 of the dry elastomer came. The impregnated fabric was then heated, to cause the elastomeric polyurea, the hydrophilic, Acrylamide-containing polymers and the methylol-containing resin crosslink. The impregnated fabric was against

tight

Liquid water was water-vapor-permeable, but water vapor was permeable.

Example 34

100 g of poly (hexamethylene tetrasulfide) were dissolved in 200 ml of toluene

809809 / 102Λ

+ 100 ml of methylene chloride dissolved. For this purpose 50 g of a copolymer consisting of 45% butadiene and 55% acrylic acid and dissolved in methyl ethyl ketone were added. This mixture was used to treat a 161 g / m 2 fabric according to the technique described in Example 1. After heating in the oven at 145 ° C for 45 minutes, the final fabric withstood a water column of 81.3 cm in height, but was air and water vapor permeable, ie it let 68 % of the water vapor through under the same conditions,

how the untreated fabric let through.

An important aspect of the present invention is the storage or spatial arrangement of the elastomer with respect to the fabric structure. The greater part of the Elastomer is forced under the tissue surface while only a small part, if any, of that Elastomer is visible on the fabric. The fabric therefore retains its original texture, i.e. H. it doesn't get any smooth or shiny appearance. This is a very important advantage or advantage over the known ones "coated" fabrics. As is known, the application of a continuous layer to the surface of a textile fabric two undesirable iolgenj a) The appearance of the fabric is completely changed, d. H. the fabric then resembles a film or an I-foil rather than a textile

full product, · b) the fabric or cloth qualities have arrived

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-55- 1444OiS

got lost, d. H. the tissue now feels stiff at. In contrast to this, textile fabrics treated or impregnated by the method according to the invention are in appearance not changed. Furthermore, the quality of the fabric, in particular the handle, has not changed significantly because that Elastomer is present in the form of a discontinuous structure and therefore only has a minimal stiffening effect exercises. It is all the more surprising that the invention treated fabrics are highly resistant to penetration by liquid water. This valuable Combination of (unchanged) appearance and functional properties is somewhat complete in the relevant technology New.

The simultaneous use of a water-repellent "finish" together with the elastomers is desirable in order to giving the elastomer time to swell after it has come into contact with water. The exact nature of this "finish" is not valid. However, it should be like that be that it can be applied to the fabric,

Fabric after the elastomer has been applied to the £ ia »± sin« r «, namely before hardening or after hardening. In some cases the "finish" can also be used together with the elastomer be applied. "Finishes" that are applied from an emulsion in water can be applied to the fabric after the elastomer has been applied, either before or after curing. Water-repellent materials,

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which are soluble in the same solvents as the elastomer can be applied together with the elastomer by dissolving the water repellent in the solvent for the elastomer. This material can can also be applied after the elastomer is applied became. In detail, the materials in question can be applied by dipping, brushing or spraying onto the material to be coated Tissue are applied. The amount of water-repellent material to be used depends on 1. the effectiveness the material in question and 2. the working technique used to apply the material. If ζ. B. that

water-repellent material is added to the solvent,

s
since & contains dissolved elastomer, the material can make up, or amount to, any part of the total Pest Ingredients from $ 0.001 to $ 20. From the table showing the fabric and elastomer weights, it can be calculated that the weight range of the water-repellent finish is from 0.0135 to

ο
25 »7 g / m, based on the weight of the fabric, varies.

When the water repellent (fin * ih) is applied from an aqueous emulsion or from a solution after the elastomer has already been applied to the fabric, the amount of the water repellent to be used can be any value from 0.0135 to 33.9 g / m ² have. This amount can

treatment »* / 1

in one treatment or in several treatments / on the Tissue are applied. The water repellent finishes that are suitable for this application are hydrophobic

809809/102 k

Waxes, oils, metallic soaps and the like. Paraffin waxes are particularly valuable; Silicone oils, silicone waxes and other silicone polymers; fluorinated oils, waxes and polymers; and certain pyridinium compounds. The way how these are applied to the finishes according to the invention treated with the elastomers tissue changes,

depending on the type of finish, dsx tu syy of the fabric »and $ s ssLcia instructed

■ tea / used synergistic combinations of water drainage

m butting »finish and organic resins.

809Ö0S / 1024

Claims (1)

Claims 1. Impermeable to water, but permeable to water vapor Material, characterized in that it is formed from threads or fibers, with a discontinuous one Layer of an I-flat structure covered with water-swellable elastomer 2. Material according to claim 1, characterized in that the fabric consists of a textile fabric. «3. Material according to Claims 1 and 2, characterized in that the elastomer consists of a copolymer of 90 to 50 % of a hydrophobic monomer and 10 to 50% of a hydrophilic monomer. 4. Material according to claim 3, characterized in that the hydrophobic components of the elastomer consist of conjugated, Dienes with 4 to 8 0 atoms which are optionally substituted by alkyl groups or halogen atoms. b * Material according to Claims 1 to 4, characterized in that the water-swellable elastomer is embedded essentially below the surface of the material. 80980S / 1024 6. Material according to claim 5 »characterized in that the water-swellable elastomer is essentially below the surface of the material, but above the Center line of the material is stored. 7. Material according to claims 1 to 6, characterized in that the elastomer in contact with water by 50 to 500 i> of its original volume swells. 8. Material according to claims 1 to 7, characterized in that that the elastomer contains a vinyl polymer. 9. Material according to claims 1 to 8, characterized in that the elastomer contains a condensation polymer. 10. Material according to claim 4, characterized in that the hydrophobic components of the elastomer made of butadiene, Isoprene or chloroprene exist. 11. A method for producing a material according to claims 1 to 10, characterized in that a water vapor permeable sheet structure with a copolymer, composed of 90 to 50 wt. 5ε hydrophobic and 10 to G-ew.-ji hydrophilic monomers, impregnated. 12. The method according to claim 11, characterized in that the elastomer is pressed into the interstices of the textile material by means of a coating knife or doctor blade. öübdü ₃ / lü24