DE2025616A1 - Process for the production of microporous flat structures by coagulating polyurethane solutions - Google Patents

Description

Process for the production of microporous fabrics through coagulation of polyurethane solutions

It is known, water-vapor-permeable sheet-like structures or coatings from solutions of polyurethanes (e.g. dimethylformamide) by coagulation in nonsolvents (e.g. water). manufactured by a series of processes in which the desired, Microporous structure of the polymers through compliance with very specific and defined conditions during coagulation should be achieved. If the special conditions are not complied with, macropores, i.e. coarse, can easily develop Holes in the film visible to the naked eye, or the structure becomes unusable, the surfaces are uneven are uneven, or the microporous structure disappears again in the critical phase of drying with the formation of a non-porous, transparent see-through film.

The use of solutions of polyurethanes or polyurethane ureas in highly polar solvents such as dimethylformamide or dimethylacetamide (possibly with the use of other Polymers such as polyvinyl chloride or polyacrylonitrile) for the production of films, coatings on fabrics or as binders for nonwovens with removal of the solvent by treatment (e.g. immersion) with water, glycerine or other liquids, which are miscible with the highly polar solvents mentioned, but are incompatible with the polyurethanes, is already described in German patent specification 888 766. The use of common solution

Le A 13 028 - 1 -

109850/1756

medium (are soft nonsolvents for the polyurethane), e.g. Me-. ethylene chloride, acetone or benzene. ^ , ..

In a large number of later property rights, special.ver- _r . : ■ driving steps indicated in order to arrive at the desired microporous structure with more or less improved safety. For example, German patent specification 1 110 607 proposes for the coagulation of polyether-based polyurethanes to expose hygroscopic polyurethane solutions (e.g. dimethylformamide serves as a solvent) to the action of an atmosphere containing water vapor, possibly in circulation, which has a relative humidity of 15 to 10096 at one temperature of the dry thermometer from 10 to 3B ⁰ C. Through the absorption of the water by the hygroscopic solvent, the polyurethane is precipitated to a greater or lesser extent from the surface, probably with a pre-formation of the microporous structure. Leg. When the pregelled films or coatings are placed in water, the hygroscopic solvent is completely removed from the film with coagulation. If the pre-gelation by exposure to the above-mentioned humid atmosphere is omitted, the result is mostly transparent, non-permeable films or coarse-pored, inhomogeneous films which are unusable for the intended purpose.

In the German Offenlegungsschrift 1 444 163 a modified one is used Method indicated where by adding minor proportions of nonsolvents (e.g. water) to the polyurethane solution this is brought into a slightly cloudy, dispersion-like form, which - if necessary after heating - after Spread directly on the surface (i.e. without pre-gelling in humid atmosphere) coagulated in a non-solvent such as water can be.

In German Offenlegungsschrift 1 444 165, another Process specified, according to which, without pre-gelation, by direct coagulation in a mixture of nonsolvent and solvent

Le A 13 028 - 2 -

: 109850/1756

medium (ζ..B. dimethylformamide / i ^ O 10:90 to 95: 5) microporous Should receive slides. ;

According to another variant, which is in the Belgian patent specification 624 250 is described, the. Polyurdhan solution .... so much nonsolvent to separate the gel from the polymer can and first spreads this gel onto the substrate and coagulates in non-solvent (water) to form a microporous structure.

In this last way of working, it is technically difficult that Separate the gel and process it into a homogeneous coating. The procedure according to DOS 1 444 165 requires extended coagulation times, especially for baths with a lot of solvents because the polyurethane only coagulates slowly. So it becomes the capacity of a given production facility. In addition, microporous structures can only be used with this method with low certainty and apparently on selected polyurethane compositions limited to be preserved.

When working according to DOS 1 444 163, it is difficult to find the right one Amount of non-solvent for making the colloidal To meet dispersions. The process uses raw materials in an unstable state; because the properties of the dispersion change over time and as a function of temperature and moisture, the elastomer dispersions changing into a pasty, no longer smoothly deformable state.

The working method according to DAS 1 110 607 requires an atmosphere with precisely conditioned humidity and a long exposure time in this humid atmosphere. The results are, however, hardly reproducible. Apparently only polyether urethanes can do this are processed. Here, too, there is a relatively low productivity with a low level of security and range of applications achieved.

Le A 13 028 - 3 -

109350/1756

According to the proposal of the German Offenlegungssehrift 1 803 021, a dry or moist gas stream acts at a certain flow rate over a flat layer of a polyurethane solution until a dense, gelled layer is formed on the surface of the solution due to moisture or evaporation of the solvent. It is then coagulated in water, for example. As will be explained in detail, it is appropriate and desirable over the temperatures not higher than 50 ⁰ C, preferably not more than 30 ⁰ C.

In the German Auslegeschrift 1238206 it is stated that a direct coagulation of elastomers leads to microporous structures, if coagulated in baths, which are heated in .the near the boiling point of the bath liquid, for example in hot "water at 95 ⁰ C.

Furthermore, German Auslegeschrift 1 270 276 teaches the polyurethane solutions 10 to 30 to be coagulated % By weight of a cationic containing quaternary ammonium nitrogen atoms Polyurethane dispersion, up to 7% by weight of water and optionally to add up to 2.5% by weight of anionic, synthetic tanning agents.

After this procedure you can after treatment of the spread Polyurethane solutions with moist air and subsequent coagulation in water or aqueous solvent mixtures water- ^ Vapor-permeable polyurethane top layers can be produced much more safely than in the processes described above.

When pretreating with moist air, use this procedure Dwell times necessary that

a) when adding commercially available tanning agents to the coagulable Polyurethane solution with the use of 10 to 30% by weight cationic polyurethane dispersion not less than 10 minutes,

b) for post-treatment of the coagulated polyurethane top layers in aqueous neutralized tannin solutions not under

20 minutes and

Le A 13 028 -A-

109850/1756

c) not less than 50 minutes without the use of tanning agents. ■

The object of this invention is an economical process for the production of microporous polyurethane top layers without these complex measures and without additional chemical aids provide that can be carried out continuously.

With increased production reliability and, in particular, increased production speed and with little outlay in terms of equipment, this process provides improved microporous sheet-like structures _f , it advantageously also being possible to dispense with the use of the cationic polyurethane dispersion.

The invention relates to a process for the production of microporous sheet-like structures from polyurethanes by pretreating thin layers of polyurethane solutions in a moist atmosphere, coagulation in aqueous precipitation baths and subsequent drying, characterized in that a thin layer of the polyurethane solution, optionally mixed with an aqueous cationic -Polyurethane dispersion; exposed to a steam atmosphere of at least 50% relative humidity at temperatures above 65 ⁰ G for 0.1 to 60 minutes, then the majority of the polyurethane solvent is removed in water or aqueous coagulation baths, the microporous polyurethane optionally with an aliphatic alcohol for 0.2 to 20 minutes treated for a long time and then dries.

Solvent for polyurethane, which can be used for implementing the method of the invention are preferably highly polar _f hygroscopic water-soluble organic solvent having amide, urea or Sulfoxydgruppen, particularly preferably with boiling points above IJCPc, you must be soluble in water or aqueous coagulation baths. Dimethylformamide, dimethylacetamide, tetramethylurea, dimethyl sulfoxide, diethylformamide, formylmorpholine, hexamethylphosphoramide or, for example, are suitable

Le A 13 028. - 5 -.

109850/17 56

Mixtures of these. These solvents are below ground "Solvent" or "Solvent" understood. : '■ "' -i

These “solvents” can also be admixed with “nonsolvents” or “nonsolvents”. Liquids are included here Understand that the polyurethanes do not dissolve (and preferably swell only slightly) or are inert to polyurethanes. Preferred The nonsolvent is water. But there are also, for example, hydrocarbons such as benzene, chlorobenzene, aliphatic Alcohols such as methanol, ethanol, ethers such as dioxane, tetrahydrofuran and esters such as ethyl acetate are possible.

The coagulation bath preferably consists of water. However, baths can also contain a (water-miscible) Containing non-solvents (as defined above) should be used. In special cases, pure alcohol baths are also used, preferably from aliphatic alcohols such as methanol or ethanol. Mixtures of water and one are also suitable "Solvent" as defined above.

It was surprising that a reliable, uniform and fine-pored pre-gelation is achieved at high temperatures and intensive exposure to concentrated water vapor, which leads to well microporous coagulated sheet-like structures with a good surface with considerably greater process reliability than in the above-described processes. The previous methods used relatively low water vapor pressures (e.g. DAS 1 110 067 at 10 to 38 C and 15 to 100% relative humidity, corresponding to a maximum of about 50 Torr) and indicate that the temperature should not be higher than 50 ⁰ C, preferably not higher than 30 ⁰ C (See. DAS 1,803,021, p.6 / 7) when the gelation of the solution is carried out in large panels spread.

The water vapor atmosphere for performing the method according to the invention should preferably at least 50%, 80 - contained 100 ⁰ C - 100% relative humidity at temperatures over 65 ⁰ C, preferably 75 miles. It is best to work at the specified temperature

Le A 13 028

109850/1756

temperature range with as saturated a water vapor atmosphere as possible, e.g. with saturated steam or a steam atmosphere over boiling water. For a continuous manufacturing process is here the additional presence of an inert transport gas, in the simplest case air, for technical control the flow conditions in the gas phase are important. In practice you can get the desired gas mixture that is almost saturated with water vapor before contact with the applied polyurethane solution Generate mixing of superheated steam and transport gas. The water vapor atmosphere should be brought into contact with the polyurethane solution in general at a negative pressure of a few mm of water column will. However, you can also use a slight overpressure work. -

The optimal exposure time to the steam atmosphere can be for Polyurethane mixtures of different compositions can be determined in simple preliminary tests. It is generally 0.1 to 30 minutes, preferably 0.5 to 3 minutes.

When exposed to the concentrated water vapor atmosphere at high temperatures, it forms on the surface in a very short time the polyurethane solution or mixture forms a gelled polyurethane layer, which then further coagulates the solution controls with the formation of micropores. Therefore, in general, the outermost layer of the resulting microporous film is something denser than the inside. However, this is desirable because it is the Application of the foils facilitated.

If the polyurethane solution painted on, for example, glass plates is heated in dry air at about 80 to 100 ^° C. and then immersed in water, the desired result is not achieved concrete points of contact of the fine water droplets with the solvent surface discrete, visible macropores with the formation of an inhomogeneous surface.

Le A 13 028 - 7 -

109 850/1756

The process can be carried out batchwise or continuously in different

different embodiments can be carried out. For development or testing purposes, a polyurethane solution, if necessary heated, painted on glass plates, can be carried over a container with hot or boiling water, in an enclosed space * - gel. (Discontinuous procedure) You can also use saturated or superheated steam in a room of the appropriate temperature in which the solution to be gelled is located »No condensate drops must be allowed on the gelling Polyurethane fall. This can be done by appropriate design of the ceiling of the gelation room or e.g. by heating the ceiling and / or the coagulation pad can be prevented.

The polyurethane mixture can be used for continuous implementation pour continuously onto a permanent support in the usual way, e.g. with doctor blades or slot pourers, then if necessary To even out the applied solution, convey a short piece without the action of steam or one from the underside exposed to the acting vacuum (for direct coating and impregnation of textiles such as woven, knitted and non-woven or felt-like materials) and then through the treatment room containing hot water vapor. Possibly the carrier material can also be heated.

Water and aqueous solutions are used as coagulating liquids of the polyurethane solvent, e.g. water, dimethylformamide, Mixtures up to a mixing ratio of 1: 1. One can have a coagulating bath or several different coagulating baths Composition in a row · νοΓ3 ^ ιβι. The bath temperatures are preferably from 20 to 35 ° C .; however, higher and lower temperatures can also be used or when using several bands Temperatures and concentrations can be varied.

If a concentrated alcohol solution is used as the last wash bath, preferably methanol, the microporous structure is stabilized and the subsequent drying is made much easier. The drying can, after squeezing off excess liquid, in usual

Le A 13 028. - 8th -

1 0 9 8!; 0/1 7 S 6

hot air dryers.

Polyurethanes suitable for producing the solutions are in particular Polyurethane elastomers. In principle, all polyurethanes can be used, but their tendency to Formation of the microporous structure is different. You can Significantly facilitate the formation of microporosity by adding cationic polyurethane dispersions to the polyurethane solution, but with it occasionally takes a deterioration in the mechanical Strength of the microporous film in purchase. The amount of cationic polyurethane dispersion should generally be 35% by weight do not exceed. It is preferred to take 0.5-20% by weight and particularly advantageously 0.5-10% by weight. Relate percentages ■ each on solids in the polyurethane solution and the dispersion. .. ■.

The cationic polyurethane dispersions are particularly effective with continuous Manufacture of the microporous fabrics regulating and stabilizing when treated with steam and during the subsequent coagulation. You thus improve production reliability and increase production speed. ■

Furthermore, one can without impairment of the coagulation behavior Add additives e.g. polyvinyl chloride and its copolymers, polyacrylonitrile and its copolymers, commercially available anionic tannins, carboxymethyl cellulose, polyalkyl (meth) acrylates, Emulsifiers, optical brighteners, antioxidants, special ones Light stabilizers such as Ν, Ν-dialkylhydraaide, crosslinking active substances such as paraformaldehyde, melamine hexamethylol ether or other formaldehyde derivatives, polyisocyanates, quaternizing agents or polyaziridine ureas and dyes, suitably insoluble pigments.

A special influence on the coagulability of the polyurethane solutions can be exercised by adding a weight solvent, preferably water, to the coagulable polyurethane systems

Le A 13 028 --9 -. "'

.., ..,. -.,., 109850/1756

will. The. highest possible. Nonsolvent amount is _; reached when ... ^ the polyurethane begins to precipitate. -Also, by using it. ^. _{! o0!} ^v of the cationic polyurethane dispersion may Nichtlösungsmittf.l ,,., (water) be introduced into the system. In this., ..... case you can also add nonsolvents .... In general, nonsolvents are not added in, purer. Form but in a mixture with solvent, so uses, for example, a dimethylformamide / water mixture. Of the. The total content of non-dissolving agent in the coagulable mixture, 1, should generally not exceed 9%. ... _; . , ■, ...-

Another influencing the coagulability siqh obtained by a thermal Vorbehandlungx the evt ... non-solvent-containing polyurethane mixtures, such brief heating, for example, to "to 2 hours at 70 ⁰ C bis.100 or 2 to 20 hours at 40 to 70 ⁰ C) or by letting such polyurethane mixtures stand for a long time at room temperature, especially if they contain lower proportions of non-solvents.

The solids content of the ready-to-use polyurethane mixtures should be between 5 and 40% by weight, preferably between 10 and 30% by weight lie.

To prepare the polyurethane solutions for the inventive These processes are in themselves a multitude of different methods accessible products, which, however, all contain the typical urethane grouping (cf. Ulimann, Enzyklopädie der technical chemistry, 4, edition, volume 14, pp. 338 to 363). It can, for example, be polyurethanes in the narrower sense act, which are made of higher molecular weight polyhydroxy! compounds, Dialcohols and diisocyanates are accessible by single or multi-stage processes (via NC0 pre-adducts). For example, polyester or polyethers reacted with an excess of diisocyanates to form NCO pre-adducts and these then with Diol-Ver ™ bonds such as 1,4-butanediol, N-methyl-diethanolamine, hydrochi-

Le A 13 028 ■ - 10.-

1 09 8507-1 75B

non-bis (hydroxyethyl ether), bis-hydroxyethyl terephthalate be implemented in equivalent or slightly lower amounts, both in the melt and in Solvents can work. However, the above components can also be converted into an elastomer in a classification process then dissolve in highly polar solvents.

However, polyurethane ureas as described as "components a" in German Auslegeschrift 1 270 276 are particularly suitable. For their preparation, higher molecular weight, essentially linear polyhydroxy compounds with terminal hydroxyl groups with a molecular weight between 40Ö and 5000 and optionally other low molecular weight dialcohols, amino alcohols or diamines with an excess of diisocyanates are first reacted to a pre-adduct with terminal isocyanate groups and this is then reacted with water or with bifunctional Compounds containing at least one of their isocyanate-reactive hydrogen atoms bonded to nitrogen atoms, reacted. Because of the material compared with diols and higher reactivity Umsetzurigsgeschwindigkeit this chain extension agent, this reaction is preferably in highly polar, water-soluble solvents, carried out with a boiling point of about ⁰ C 1OQ.

The manufacture of such polyurethane urea and their solutions is for example in the German patents 888 766, 1 123 467, 1 150 517, .1 154 937, the German AuslegeSchriften 1161 007, 1 183 196, 1 186 618, the Belgian patents 649 619, 646 637, 658 363, 664 344, 664 346, 666 208, the French U.S. Patents 1,380,082, 1,371,391, 1,383,077 and U.S. Patents 2,929,803, 2,929,804, 3,040,003.

Higher molecular weight, essentially linear polyhydroxy compounds with terminal hydroxyl groups, which are used for the production of

Le A 13 028 - 11 -

1.0 9850/175 G

elastomeric polyurethanes are suitable, for example, polyesters, polyesteramides, polyethers, polyacetals, polycarbonates or poly-N-alkyl urethanes or mixtures thereof, including those with ester, ether, amide, urethane, N-alkyl urethane groups with molecular weights between 400 and 50,000 and melting points of preferably +60 to -50 C, expediently below 45 ° C. (Polyhydroxy compounds with higher melting points can cause the finished products to harden too much ^{at temperatures around or 0 ° C.)}

Particular mention may be made of polyesters made from adipic acid and dialcohols or mixtures of dialcohols, for example ethylene glycol, propylene glycol, butane-1,4, 2,2-dimethylpropanediol-1,3, hexanediol-1,6 or bishydroxy methylcyclohexane. Diols or mixtures of diols having five or more carbon atoms are preferred because of the good hydrolysis resistance of the polyester produced from them. Polyesters obtained by condensation of caprolactone and diols or amines such as 1,6-hexanediol with a narrow molecular weight distribution are also suitable. Particularly good microporous films with excellent surface properties and good water vapor permeability are derived from mixed polyesters made from 90 - 60 weight. -% adipic acid and 10 to 40 wt .-% terephthalic acid and a diol, preferably ethylene glycol, 1,4-butanediol, neopentylglycol and / or 1,6-hexanediol have been produced.

Polyurethane ureas with excellent hydrolysis resistance can also be obtained from polyethers, preferably from polytetramethylene ether diols, which can optionally also be used as mixed polyethers.

Suitable diisocyanates, if appropriate in a mixture, are aliphatic, cycloaliphatic, araliphatic, aromatic diisocyanates or heterocyclic diisocyanates. Special mention should be made of diisocyanates with a symmetrical structure, e.g. diphenylmethane-4,4'-diisocyanate, Diphenyldimethylmethane-4,4'-diisocyanate, 2,2'-6,6'-tetramethyldiphenylmethane diisocyanate, diphenyl-4,4'-

Le A 13 028 - 12 -

109850/1756

diisocyanate, diphenyl ether 4,4'-diisocyanate or their alkyl, Alkoxyl- or halogen-substituted derivatives, also toluylene 2,4- or 2,6-diisocyanate or their technical mixtures, diisopropylphenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate or a, a, a'a'-tetramethyl-p-xylylene diisocyanate or their other alkyl or halogen substitution products, dimeric toluene-2,4-diisocyanate, bis (3-methyl-4-isocyanatophenyl) urea or naphthylene-1,5-diisocyanate. Aliphatic Diisocyanates, such as hexamethylene diisocyanate, cyclohexane-1,4-diisb-

cyanate, dicyclohexylmethane-4,4'-diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane or 2,2,4-trimethylhexane-1,6-diisocyanate, can be used and produce very little discolouring products when exposed to light.

Diphenylmethane-4,4'diisocyanate, the isomeric Tolylene diisocyanate, p-phenylene diisocyanate and - optionally partially - hexamethylene diisocyanate or dicyclohexylmethane-4,4'-diisocyanate used.

The higher molecular weight polyhydroxyl compounds are mixed with the diisocyanates in about a molar ratio of 1: 1.25 to 1: 4.0, if necessary in several stages in the melt or in solvents inert to isocyanates, such as tetrahydrofuran, dioxane or chlorobenzene or dimethylformamide, at temperatures of about 20 to 130 ⁰ C, preferably 40 to 100 ⁰ C implemented.

Such reaction times are observed that an essentially linear pre-adduct with terminal NCO groups is obtained, that in the implementation with approximately equivalent amounts of bifunctional Chain extenders a substantially linear, in polar solvents soluble elastomeric polyurethane resp. yields a polyurethane urea.

It can be used together with higher molecular weight polyhydroxy compounds also low molecular weight diols (molecular weight preferably below 250), e.g. ethylene glycol, 1,4-butanediol, bis-N, N- (ß-hydroxyethyl) diethylamine, Bis-N, N- (ß-hydroxypropyl) -methylamine, N, N'-

Le A 13 028 - 13 -

10 9 8 5 0/1756

Bis-hydroxyethylpiperazine or hydroquinone bis ^ ß-hydroxyethyl ether) can also be used. The amount of low molecular weight diols

can e.g. be dimensioned so that per mole of OH groups of the higher molecular weight Polyhydroxyl compound 0.1 to 3 mol OH groups of the low molecular weight diol are present. -Tertiary diols Nitrogen increase the colorability, improve the light resistance and create the point of attack for further post-treatment, e.g. cross-linking with strongly alkylating compounds.

The NCO group content of the pre-adducts (calculated on solvent-free Pre-adduct) is of crucial importance for t the properties of the polyurethane ureas obtained from it. It must be at least 0.75 percent by weight and should preferably be between about 1.00 and about 7 »6 percent by weight, especially between 1.5 and 5.5 percent by weight, so that the polyurethane ureas have sufficiently high melting points, tensile strengths, Have elongations at break and stress values. In the case of the chain extension reaction with water, the NCO content is lower preferably higher, e.g. between 3.5 and 7.6 percent by weight, as part of the NCO groups. first saponified to amino groups will.

The chain extenders should and can have a molecular weight of from 18 to about 500, preferably from 32 to 350 optionally used in a mixture or stepwise reaction. In addition to water, there are for example ethylenediamine, 1,2- or 1,3-propylenediamine, 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, 2,2,4-trimethylhexanediamine-1,6, 1-methylcyclohexane-2,4-diamine, 4,4'-diaminodicyclohexylmethane, Bis (-aminopropyl) -diethylamine, N, N-bis (-eminopropyl) -piperazine, araliphatic diamines such as 1,5-tetrahydronahthalene, or aromatic diprimary amines such as 4,4-diaminodiphenylanthan, 4,4'-diaminodiphenyl ether, 1-methyl-2,4-diaminobenzene or araliphatic diprimary diamines, such as m-xylylenediamine, p-xylylenediamine, a, a, a ', a'-tetramethyl-p-xylylenediamine or 1,3-bis- (ß-aminoiso-

Le A 13 028 -14 -

109850/1756

propyl) benzene, sulfosäuregruppenhaltige further diamines such as 4,4'-diaminostilbene-2,2'-disulfonic acid or 4,4 ^f -Diaminodiphenyläthan-2,2-disuifonsäure, 1,6-hexamethylenediamine-N-butylsulfonic acid, 1,6 -hexamethylene-3-sulfonic acid or their alkali metal salts, hydrazide compounds, such as Carbddihydrazid, adipic, succinic, glutaric, Pimelinsäuredihydrazid, Hydr acrylsäuredihydrazid, terephthalic acid dihydrazide, isophthalic acid dihydrazide _f ß-SemjParbasLdo-ethane-carbazinester, .beta.-aminoethyl-semicarbazide, .beta.-semicarbazido-propionic acid hydrazide, 4-semicarbazido-benzoic acid hydrazide or hydrazine hydrate, or Ν, Ν'-diaminopiperazine. These chain extenders can be used individually, in a mixture or together with water. Secondary diamines, preferably with a symmetrical structure, such as piperazine or 2,5-dimethylpiperazine, can also be used (but expediently less than 30 mol percent).

If chain extension mixtures are used, the solubility of the polyurethane ureas and the melting point generally increase the elastomer decreases. Preferred chain extenders are ethylenediamine, nu-xylylenediamine, hydrazine, carbodihydrazide, aliphatic dicarboxylic acid hydrazides such as glutaric acid dihydrazide and water are used. These are chain extenders used together with others, their amount should be at least 50 mole percent, preferably more than 80 mole percent of the total.

The reaction of the NCO prepolymers with the chain lengthening agents is carried out in highly polar water-soluble over 130 ⁰ C boiling solvents. Mention should be made of solvents containing amide or sulfoxide groups with the ability to form strong hydrogen bonds, for example dimethylformamide, N-methylpyrrolidone, diethylfprmamide, dimethylacetamide, formylmorpholine, hexamethylphosphoramide, dimethylsulphoxide, tetramethylurea or their mixtures. The technically preferred solvent is dimethylformamide. Up to a certain proportion, which is about 35 percent by weight of the amount of solvent, can be less

Le A 13 028 - 15 -

10 9850/1756

polar solvents, which alone cannot dissolve the polyurethane ureas, are added to the highly polar amide solvents e.g. tetrahydrofuran, dioxane, acetone or glycol monomethyl ether acetate. The concentration of the elastomer solutions should preferably be about 5 Ms 33 percent by weight, especially 15 to 27 percent by weight, the viscosities are preferably between 1 and 1000 poise, especially between 50 to 800 poise / 25 ° C.

Further suitable polyurethane elastomers are also those obtained by reacting bis-chlorocarbonic acid esters and diamines or from bis-carboxylic acid chlorides and diamines (with one of the components preferably having a higher molar

»Cellular compound with a molecular weight of about 400 to -

5000 is). Reaction products of higher molecular weight may be mentioned by way of example Bis-chloroformic acid esters of polyhydroxyl compounds with diamines and reaction products of higher molecular weight Compounds with amino end groups (made e.g. from polyhydroxy ! compounds, diisocyanates and chain extension with noticeably excess amounts of chain extenders containing NEL end groups) and bis-acid chlorides or bis-chloroformic acid esters. Such compounds are shown, for example, in U.S. Patents 2,929,801, 2,929,802, 2,962,470, 2,957,852. Segmented polyester or polyether elastomers, such as those in the French patents, are also suitable 1,354,553 and 1,359,090 and in Belgian patent 574,385.

Mechanical strength values can be measured on solid films produced from these polyurethane elastomer solutions by drying the solutions or elastic properties, e.g. after cutting the film into strips or threads. Solid foils Polyurethanes particularly suitable for the process according to the invention have the following properties:

Le A 13 028 - 16 -

1098ÜQ / 17 56

1. Melting point on the Kofler bench at least 180 ° C, preferably above 200 ⁰ C,

2. Tear strength of at least 200 kg / cm, preferably 300 to 800 kg / cm,

3. Elongation at break at least 200%, preferably 400 to 800%,

4. Tension forces during the * first expansion to 20%: At least

ο 'ο

5.0 kg / cm, preferably 10 to 30 kg / cm j in the expansion

2 2

to 100%: at least 20 kg / cm, preferably 45 to 75 kg / cm, "with the first extension to 300%: at least 60 kg / cm, preferably 80-580 kg / cm ² .

5. Molecular weight corresponding to an intrinsic viscosity of at least 0.6, preferably 0.90 to 1.9

with C = concentration in g / 100 ml, 07 _R = Viskosi-C '

did a 1% by weight solution of the polyurethane in phosphoric acid trisdimethylamide at 25 ° C)

6. Insolubility in weakly polar solvents such as tetrahydrofuran, Dioxane or glycol monomethyl ether acetate: solubility in highly polar solvents such as dimethylformamide.

To convert the strength and module information from kg / cm into g / dtex or mg / dtex (cf. e.g. Table 1 or Table 8) the following relationship applies:

x = j>. y. 10 ³

ο where χ is the measure of the tensile strength or the module in kg / cm _f y the measure of the tensile strength or the module in g / dtex f the measure of the density in g / cm.

If you express the tensile strength or modulus values y in mg / dtex off, then the relation χ = j> applies. y, where χ and / has the above meaning to have.

Le A 13 028 - 17 -

109850/1756

20256 7 6

Solid polyurethane films generally have the following density: Polyester polyurethanes: j> = approx. 1.2 g / cm " ⁵

Polyether polyurethanes: ^ = approx. 1.0 - 1.05 g / cm "*" The density of microporous films is generally between 0.5 and 1.0 g / cm ³ .

In a particular embodiment of the method of the invention, the polyurethane solution koagulierfähigen cationic aqueous polyurethane dispersions can be added in amounts up to 35 wt -.% (In each case based on solid polyurethane). These are, in particular, polyurethanes containing quaternary ammonium groups

with a certain hydrophilic character, which in water or aqueous liquids e.g. water / dimethylformamide mixtures, preferably in a mixing ratio of 1: i "without the aid of Emulsifiers or wetting agents are dispersed or dissolved colloidally.

Cationic polyurethanes suitable for this are e.g.

DAS 1 270 276 obtained if at least when building up the polyurethane a component with one or more basic tertiary nitrogen atoms is also used and the basic tertiary Nitrogen atoms of the polyurethane with alkylating agents

or inorganic or organic acids are reacted.

It is basically irrelevant at which point of the Polyurethane macromolecules are the basic nitrogen atoms. You can also use polyurethanes with reactive ^ to quaternize capable halogen atoms with tertiary amines »Furthermore, one can also use polyurethanes under chain-building Produce quaternization by e.g. Diols and isocyanates with reactive halogen atoms or diisocyanates and halogen alcohols dihalo urethanes and converts these with ditertiary amines. Conversely, one can choose from compounds with two isocyanate groups and terti-r, ary amino alcohols to produce ditertiary diaminourethanes. and react these with reactive dihalogen compounds. Of course, the cationic polyurethane composition can also

Le A 13 028 - 18 -. ■

109850/1756

from a cationic salt-like starting component, for example a quaternized basic polyether or an isocyanate containing quaternary nitrogen. These manufacturing methods are e.g. in the German exit fonts 1,184,946, 1,178,586, 1,179,363 and the Belgian patents 653 223, 658 026, 636 799. The starting materials suitable for the synthesis of the salt-like polyurethanes can also be found there listed.

In addition to the urethane groups, the polyurethane composition can also contain urea groups contain.

In order to obtain a satisfactory set of properties in the end product, the content of urethane and optionally urea groups should be 8 to 35 percent by weight of the polyurethane composition. The content of quaternary ammonium groups should be approximately 0.5 to 2.0 percent by weight, preferably 0.8 to 1.8 percent by weight, the polyurethane mass.

The aqueous dispersions or colloidal solutions of these cationic Poly urethanes have particle sizes between approximately 10 and 1000 m / U. You can also use organic solvents in amounts up to about 50%, for example acetone or dimethylformamide. So you need that to make the dispersion according to the German Auslegeschriften 1 184 946, 1178586 and the Belgian patent 653 223 used solvents cannot be removed from the dispersion formed and, moreover, can also use high-boiling solvents such as dimethylformamide in the preparation of the dispersion.

Cationic polyurethanes composed of higher molecular weight polyhydroxyl compounds are preferred for the process according to the invention

from molecular weight 500 to 5000, polyisocyanates, a basic one Chain extenders with tertiary, preferably aliphatically substituted nitrogen atoms, such as N-methyl diethanolamine, N, N-bis (aminopropyl) methylamine, and optionally other non-basic chain extenders, such as

Le A 13 028 - 19 -

1098 50/17 5 G. '

are preferably dialcohols or diamines, water, hydrazine or substituted hydrazines. Preferably contains the predominantly linear polyurethane compound, which is soluble in organic solvents such as dimethylformamide, cold 5 to 12% N-methyl diethanolamine. From this into the polyurethane mass built-in tertiary nitrogen are 10 to 60% with an alkylating agent, such as dimethyl sulfate, methyl chlorine ethyl ether, diethyl sulfate or bromoethanol, quaternized and 30 to 70% neutralized with an acid such as hydrochloric acid, lactic acid, acetic acid, in the presence of water. 10 to 20% of the tertiary nitrogen is generally not converted into the salt.

It is preferable to find, at least in part, bi- or trifuriktionel-Ie Alkylating agents such as dibromobutane, p-xylyenedichloride, 1,3-P Dimethyl-4,6-bis-chloromethylbenzene, methylen-tois-bromoacetamide, Trimethylolpropane-tris-chloroacetic acid ester or bi- or trifunctional Acids with pH values below 4, such as phosphoric acid, oxylic acid or sulfuric acid, each used as an aqueous solution, these react predominantly monofunctional and then exert a crosslinking function in the finished microporous planar structure.

These cationic polyurethanes are then dispersed in water. For later crosslinking, the dispersed polyurethanes can of course also be incorporated, for example, methylolethyl groups contain.

" The mechanical strength values and elastic properties of the microporous fabrics are determined in the same way as the corresponding values for the solid film made from the polyurethane elastomer components. Naturally, the higher the water vapor permeability of the materials, the lower the microporous films.

The determination of the water vapor permeability is carried out according to the Method of I UP 15, given in "Das Leder", 1961, pp. 86 - 88,

Le A 13 028 - 20 -

1 0 98 50/17 56

which provides the water vapor permeability in mg (measurement

2 ι 'ii.cm

solution at normal pressure and a relative humidity of 65% 20 ° C) or according to a new method, which allows much faster determinations and the so-called Permeation coefficient provides, which is the water vapor permeability describes by a film of normalized thickness. The measurement or the evaluation of the measurement results is how is carried out as follows:

A circular film sample with a diameter of 2 cm is loaded with saturated water vapor from one side in an apparatus previously evacuated to 0.1 Torr. The amount of water permeating due to the effect of the saturation vapor pressure of 18.7 Torr at 21 ° C. is frozen in a cold trap and then determined by thawing the cold trap and measuring the vapor pressure established in the known measuring volume. The permeation coefficient PK in * is obtained, which indicates the amount of water in grams which passes through a film with an area of 1 cm ² and 1 cm thick at a differential pressure of 1 Torr. (Dimension: g / h.cm.Torr). The numerical values of the PK value are given in the following, each multiplied ^{by 10 8.} (For literature see; Lax d'Ans, Springer-Verlag, 19 ^ 5 * S.1118.) The determination of the tear strength, elongation at break as well as the modulus and other elasticity values. The microporous foils are carried out as described for the solid files.

The strength values of the microporous films are naturally lower, the greater the water vapor, permeability or the PK value. Even with the same water vapor permeability, the respective strength properties still depend crucially on the quality and uniformity of the. microporous structure, which is caused by the applied coagulation process is determined. It is a particular value of the method according to the invention that uniformly microporous

Le A 13 028 _ 21 -

109850/1756

Films with a good surface with increased strength values compared to other processes, reduced thermoplasticity, improved * Serten abrasion properties can be achieved with high permeabilities, while at the same time the process is shortened in terms of time can be.

For the continuous production of microporous fabrics bring the polyurethane solution or a mixture of polyurethane solution and cationic dispersion on a porous or non-porous substrate, e.g. by brushing, pouring or knife coating, on, allows the applied layer to pass through a treatment room with steam, whereby gelation occurs at an ebb and then bathes the material in coagulation and water odor ^ - and aftertreatment baths, the last of which can be an alcohol bath. The microporous material is then dried.

The applied layer thickness depends on the desired final thickness of the microporous surface structure. Usually will Layer thicknesses of the applied polyurethane mixtures of 0.5 up to 1.5 mm will be sufficient. A porous substrate will be chosen if this is to be coated directly with the polyurethane compound. Examples of porous substrates are fabrics, Knitted fabrics, fleeces or felts.

A non-porous substrate, e.g. glass plates, metal strips (optionally with a structural surface) or fabric sheets coated with plastics, e.g. perfluoropolyethylene, are used when porous polyurethane films are required that are to be removed and transferred, e.g. glued, to other e.g. porous substrates. Suitable substrates are, for example, wood, split leather, cardboard, paper or woven and non-woven textile fabrics, masonry and metal.

Le A 13 028 - 22 -

109850/175 6

A) Tests without using a cationic polyurethane dispersion

A1) Manufacturing instructions for the polyurethane elastomer solutions

Polyurethane a)

6000 parts of an adipic acid mixed polyester (1,6-hexanediol and 2,2-dimethylpropanediol-1,3 in the molar ratio 65:35) with an OH number of 66.3 are mixed with 1550 parts of diphenylmethane-4,4 * -diisocyanate and 1895 parts of dimethylformamide heated to 50 ° for 170 minutes until the NCO content of the pre-adduct solution 2 is> 35 $ (corresponds to 2.93 % NCO in the pesticide). In a 70 ° hot solution of 190 parts of carbodihydrazide in 16010 parts of dimethylformamide

7525 parts of the above NCO adduct solution will flow in with stirring leaving a clear, homogeneous elastomer solution with a viscosity of 506 poise.

Polyurethane b)

1000 parts of an adipic acid mixed polyester (ethylene glycol / 1,4-butanediol in a molar ratio of 1: 1) with an OH number of 54.8 are heated to 50 ° for 80 minutes with 233 parts of diphenylmethane-4,4'-diisocyanate and 310 parts of dimethylformamide, until the NCO content of the solution is 2.26 % (corresponds to 2.84 % NCO in the powder substance). 1290 parts of the above NCO pre-adduct solution are stirred into a solution of 31.15 parts of carbodihydrazide in 2730 parts of dimethylformamide at 70 °, a highly viscous elastomer solution: (270 poise / 20 ° C.) being formed. After stirring in 2.35 parts of 1,6-hexane diisocyanate, a clear, homogeneous elastomer solution with a viscosity of 530 poises is obtained.

Polyurethane 6)

800 parts of an adipic acid / butanediol polyester with an OH number of 119

Le A 13 028 -.23 - ■ '

10 ate SO / 17 5.6, -

are reacted with 314 parts of diphenylmethane-4,4 * -diisocyanate and 280 parts of dimethylformamide for 25 minutes at 55 ° until the NCO content is 2.93 % (based on the powder substance). 421 parts of this solution are mixed with a solution of 10.8.2 parts of carbodihydrazide in 910 parts of dimethylformamide to give a clear, homogeneous elastomer solution (750 poise / 20 ° C). . /

Polyurethane d)

800 parts of a butanediol / Adipinsäüre-polyester of OH number diisocyanate with 305 parts of ^{diphenylmethane-4,4'-J} and 277 parts of dimethylformamide is heated 25 minutes at 50 ⁰ C until the NCO content has fallen to 2.98%. 413 parts of the NCO pre-adducts are stirred into a solution of 11 parts of carbodihydrazide in 910 parts of dimethylformamide, a homogeneous elastomer solution of 650 poise being obtained.

Polyurethane e)

800 parts of a 1,4-butanediol / Aätipinsäure-polyester of OH number 69.3 are diisocyanate with 217 parts of ^{diphenylmethane-4,4'-J} and 253 parts of dimethylformamide, reacted for 25 minutes at 55 C to ^P NCO preadduct. 413 parts of this NCO pre-adduct are reacted with 11.0 parts of carbodihydrazide and 9IO parts of dimethylformamide to give the elastomer solution (400 poise).

Polyurethane

1000 parts of the polyester described in a.) (OH number 66, -9) are mixed with 50 parts of 2> 2-dimethylpropanediol-1,3, 373 parts of diphenylmethane-4,4'-diisocyanate and 356 parts of dimethylformamide for 50 minutes implemented at 6O ⁰ C to the NCO pre-adduct (2.39 t NCO in the solid). (600 poise) to form a homogeneous elastomer solution was added, η ^ β 1.26 · - · ^{^;;} ■ _ν: - 316 parts thereof are in a solution of 6.6 parts of carbodihydrazide in 68I parts of dimethyl formamide _"...: , ",, .- ■

Le A 13 028 - 24 -

109850/1756

Polyurethane g)

1000 parts of the polyester from a), 239 parts of diphenylmethane. '4,4'-diisocyanate and 310 parts of dimethylformamide 57 minutes at 45 to 50 ⁰ C Ziirn NCO preadduct implemented and 212 parts of the same in a solution of 4.42 parts of carbodihydrazide in 452 parts of dimethylformamide to form a Elastornerlösung viscosity 1010 poise entered . "

Polyurethane h)

1000 parts of an adipic acid-hexanediol-1,6 / 2,2-dimethylpropanediol-1,3-mixed polyester (di-oil ratio 65:35) with an OH number of 65.9 are mixed with 250 parts of diphenylmethane-4,4 ^J -diisocyanate and 313 parts of dimethylformamide heated to 45 to 50 ° for 125 minutes until the NCO content is 2.6 % (based on solids).

269 parts of the NCO pre-adduct solution are prepared by throwing 5 parts of solid carbonic acid into a suspension Solution of 3.56 parts of 94.2 # hydrazine hydrate in 562 parts Dimethylformamide, added to form a homogeneous elastomer solution (565 poise / 20 ° C).

Polyurethane i)

269 parts of the NCO pre-adduct solution prepared according to the previous example are in a suspension, prepared by throwing solid carbonic acid into a solution of 4.10 parts of ethylenediamine in 562 parts of dimethylacetamide, stirred in to form a clear, homogeneous elastomer solution of 315 poise.

Polyurethane k)

1000 parts of a polytetramethylene ether diol of molecular weight 1020 with 21.2 parts of N-methyl-bis- (ß-hydroxypropyl)

Le A 13 028 - 25 -

109850/1756

amine, 368 parts of diphenylmethane-4,4 * -diisocyanate and 346 parts Dimethylformamide heated for 80 minutes at 45 ° until the NCO content of $ 2.12 (based on solids) is reached.

100 parts of the above NCO-Voradduktlcsung are stirred into a warm solution of 1.95 parts of carbodihydrazide in 226 parts of dimethylformamide, and the homogeneous, highly viscous solution (Looo poise / 20 ⁰ C) then diluted with dimethylformamide to 23 percent by weight (530 poise / 20 ° C ).

Polyurethane l)

^w 245 parts of the NCQ pre-adduct solution described for polyurethane K 'are stirred into a finely divided suspension, prepared by introducing 5 parts of solid carbonic acid into a solution of 2.87 parts of hydrazine hydrate in 559 parts of dimethylformamide, with a homogeneous _{C0 a evolution} Elastomer solution (290 poise / 20 ° C.) is obtained, the viscosity of which increases to 470 poise after the addition of 0.2 part of 1,6-hexane diisocyanate.

Polyurethane m)

257 parts of the NCO pre-adduct solution described for polyurethane K are placed in a suspension, prepared by throwing it in of 8 parts of solid carbonic acid in a solution of 3 * 32 parts Ethylenediamine in 600 parts of dimethylformamide, stirred in to form a viscous elastomer solution, the viscosity of which after the addition of 0.4 part of hexane-1,6-diisocyanate on 506 poise / 20 ° C.

Polyurethane n)

800 parts of an adipic acid-hexanediol-1,6 / 2,2-dimethylpropanediol-1,3-mixed polyester (Di-oil ratio 65:35), OH number 65.9, and 98 parts of 2,2-dimethyl-propanediol-1,3 with a solution of 451 parts of diphenylmethane-4,4'-diisocyanate and 339 parts of Le A 1 3 028 - 26 -

109850/1756

len dimethylformamide mixed at 50 °, the temperature rising briefly to 88 °. A reaction temperature of about 55-60 ° is maintained by cooling. After 60 minutes the NCO content of the NCO pre-adduct is 2.36 i (based on the pesticide content). -

266 parts of the NGO pre-adduct are converted into a solution of 9.72 Parts of ß-semicarbazido-propionic acid hydrazide in 19 parts of water and 561 parts of dimethylformamide were stirred in to form an elastomer solution with a viscosity of 410 poise.

Polyurethane o)

800 parts of an adipic acid-ethylene glycol / butanediol-l ^ mixed polyester (OH number 54.8) are combined with 35 * 2 parts of 1,4-butanediol with a solution of 297 parts of diphenylmethane-4,4 * - diisocyanate in 286 parts Dimethylformamide is added at 50 ° C., the reaction temperature rising briefly to 71 ° C., brought to 50 ° C. by cooling and held at this temperature for 30 minutes. The cloudy NCO pre-adduct mixture has an NCO content of 2.86 4 NCO (in the pesticide).

10.58 parts of carbodihydrazide are in 910 parts at 60 to 70 ° C Dissolved dimethylformamide and mixed with 430 parts of the above NCO pre-adduct solution stirred. The homogeneous, clear solution (180 poise / 20 ° C.) rises after the addition of 0.5 part of diphenylmethane-4,4 * -diisocyanate to a viscosity of 630 poise.

Polyurethane p)

800 parts of an adipic acid-ethylene glycol / 1,4-butanediol mixed polyester (OH number 54.8) and 70.4 parts of 1,4-butanediol are mixed with a solution of 407 parts of diphenylmethane-4,4 * -diisocyanate in 694 parts dimethylformamide, mixed at 40 ° C with the reaction temperature is increased to 83 ⁰ C, is brought by cooling but rapidly increased to 50 ⁰ C. After about 50 minutes at 40 ° -50 ° C., a relatively viscous, cloudy NCO pre-adduct mixture is obtained which contains 2.4 g ^ NCO (based on solid substance).

Le A 13 028 - 27 - ■ .- ■■■■ ... ·. _y

109850/1756

815 parts of the NCO pre-adduct are in a solution of 14, Q Parts of carbodihydrazide added to 1325 parts of dimethylformamide to form a clear elastomer solution of 670 poise.

Polyurethane q ^

14.9 parts carbodihydrazide are dissolved in 1325 parts of dimethylformamide at 70 ⁰ C and mixed with stirring with 8L5 parts described in p) NCO Voradduktlösung, wherein a kla.re, homogeneous, viscous solution was obtained (670 poises / 20 ° C) will.

Polyurethane r)

A polyester with an OH number of 77.9 is prepared by esterifying 1752 parts of adipic acid, 762 parts of bishydroxyethyl terephthalate and 698 parts of ethylene glycol. 600 parts of the same are reacted with 173.5 parts of diphenylmethane-4,4 ^J -diisocyanate and 194 parts of dimethylformamide to give the NCO pre-adduct. 537 * 5 parts of the NCO pre-adduct solution are reacted with a solution of 12.3 parts of carbodihydrazide in 1136 parts of dimethylformamide to form an elastomer solution with a viscosity of 880 poise.

Polyurethane s)

A polyester with an OH number of 67 is prepared by esterifying 1752 parts of adipic acid, 762 parts of bisydroxyethyl terephthalate and 1328 parts of 1,6-hexanediol. 600 parts of the polyester are used with 157. » 5 parts of diphenylmethane-4,4 ^J -diisocyanate and 1QO parts of dimethylformamide reacted at 55 ° C. for 40 minutes. 535 parts of the NCO pre-adduct formed are stirred into a solution of 12.95 parts of carbodihydrazide in 1142 parts of dimethylformamide to form an elastomer solution with a viscosity of 660 poise.

Le A 13 028

- 28 -

109850/1756

A polyester of the composition as In r) with the OH number 47 becomes 600 parts with 128 parts of diphenylmethane-4,4 * -diisocyanate and 183 parts of dimethylformamide for 45 minutes at 50 ° C. to give the NCO pre-adduct implemented, of which 543 parts in a solution of 13.24 parts of carbodihydrazide in 1139 parts of dimethylformamide is added to form an elastomer solution of viscosity 500 poise.

Polyurethane u)

600 parts of an adipic acid-butanediol-1,4-polyester with a molecular weight of 1695 are heated with 155 *} parts of diphenylmethane-4,4'-diisocyanate and 189 parts of dimethylformamide at 50 ° C for 100 minutes until the NCO content is 2.855 ° ( based on plague substance). 532 parts of the NCO pre-adduct solution are stirred with a solution of 13.15 parts of carbodihydrazide in 1139 parts of dimethylformamide at 65 ° C., a homogeneous elastomer gap with a viscosity of 700 poise / 20 ° C. being formed.

Polyurethane v)

1100 parts of a mixed polyester with 1,6-hexanediol and 2,2-dimethylpropanediol-1,3 in a molar ratio of 65:35 (OH number 65.9) are mixed with 659 g of a solution of 331 parts of 4,4 * -diphenylmethane diisocyanate in 373 parts of dimethylformamide, the 30 minutes after standing an NCO öehalt of 8.35 ^ exhibited, reacted for 5 hours between 50 and 60 ⁰ C. The NCO content of preadduct then lies at 3.32 $ with respect to Pestsubstanz.

162 parts of the above MCO pre-adduct are made into a solution 326 parts of dimethylformamide and 4.6 parts of carbodihydrazide are stirred in at 50 to 60 ° C. The solution then has a temperature of 2 ° C. Viscosity of 855 poise.

Le A 13 U2ü - - 29

109850/1758

160 parts of the above NCO pre-adduct are stirred into a solution of> 340 parts of dimethylformamide and 9.55 parts of pimelic acid dihydrazide at 60 to 80.degree. The solution has a viscosity of 800 poise ^{at 20 ° C.}

Polyurethane x)

150 parts of the NCO pre-adduct described in regulation v) are stirred into a solution of 150 parts of dimethylformamide and 10.3 parts of suberic acid dihydrazide at 70 to 80.degree. The solution has a viscosity of 630 poise at 20 ^° C. after cooling

Polyurethane y)

158 parts of the described inyorsdnift v) NCO preadduct be * 7 parts of sebacic stirred into a solution of 343 parts of dimethylformamide and 11 at 80 to 90 ⁰ C. After cooling, the viscosity of the polyurethane solution is 675 poise at 20 ^° C.

Polyurethane ζ)

150 parts of adipic acid / l “4-butanediol polyester (molecular weight approx. 950) are mixed with 133 g of a solution of 90 parts of 4,4 * -diphenylmethanedilsocyanate in 67 parts of dimethylformamide, which after standing for 30 minutes has an NCO content of 19 , 1 $, reacted at 50 to 54 ° C for 120 minutes. The NCO content of the pre-adduct is then 5> 29 io based on the solid substance.

212 parts of the above MCO pre-adduct are stirred into a solution of 425 parts of dimethylformamide and 9.75 parts of carbodihydrazide, which was dissolved in 10.5 parts of hot water, at 30.degree. To 40.degree. After the reaction has ended, the 26 percent strength solution has a viscosity of 655 poise ^{at 20 ° C.}

Ls A 13 028 - 30 -

109850/1756

Polyurethane aa) 3

170 parts of adipic acid / 1,4-butanediol polyester (molecular weight about 950) are mixed with 412 g of a solution of I80 parts 4,4 ^J -i> iphenylmethan diisocyanate in 26? Parts of dimethylformamide, which after standing for 30 minutes had an NCO content of 13.55 ^, reacted ^{at about 40 to 45 ° C.} After 5 minutes it will be within

20 minutes 32.3 parts of 1,4-butanediol and 4θ between .45 ⁰ C was added dropwise. The NCO content of the pre-adduct is 2.73 i> NCO based on the solid substance after 90 minutes.

500 parts of the above NCO-preadduct are stirred into a solution of 1016 parts of dimethylformamide and 9.44 parts of carbodihydrazide, which was dissolved in hot l8,9 parts of water at about 30 ⁰ C. After the reaction has ended, the 20 percent solution has a viscosity of 175 poise ^{at 20 ° C.}

Polyurethane bb)

1000 g of an adipic acid / ethylene glycol-butanediol mixed polyester (molar ratio of the glycols 1: 1; OH number 55.0; acid number 0.70; water content 0.01 <g) are mixed with 93.0 g of 1,4-butanediol, 14.4 g of titanium dioxide (rutile) and mixed at 6O ⁰ C with 0.31 g of iron (III) acetylacetonate and displaced quickly g of diphenylmethane-4,4'-diisocyanate with stirring 400th After a mixing time of about three minutes, the melt is poured into shallow dishes and reheated for 15 minutes in an ^{oven heated to 110 °} C., after which the already solidified polyurethane mass is removed and granulated after cooling.

To prepare a solution 250 g of granulated polyurethane having a rji value of 0, 10 partly added to 75Og of dimethylformamide at 50 to 6O ⁰ C with stirring, until after about 8 hours complete solution has occurred. The viscosity of the solution is 35 poise / 20 ° C.

LeA 13 028 - 31 -

109850/1756

Polyurethane cc)

200 parts of an adipic acid / 1,4-butanediol polyester (molecular weight about 950) are ^{mixed with 431 parts of a solution of 175 parts of 4,4 i} -diphenylmethane diisocyanate in 286.1 parts of dimethylformamide, which has an NCO content of after standing for 30 minutes 12.8% had reacted at 40 to 50 ⁰ C. After 5 minutes, 38 parts of 1,4-butanediol are added dropwise over 25 minutes at the same reaction temperature. The solution becomes more viscous as the reaction time progresses. It is gradually diluted to £ 26 with dimethylformamide. It has a viscosity of 1260 poise after 24 hours. "

Polyurethane dd)

200 parts of an adipic acid / 1,4-butanediol polyester (molecular weight 400) are mixed with 355 parts of a solution of 200 parts of 4,4 * -diphenylmethane diisocyanate in 177.2 parts of dimethylformamide, which has an NCO content after standing for 30 minutes of 17.8%, had reacted at 35 to 45 ⁰ C. The NCO content of the pre-adduct after 190 minutes is 5 * 4 % NCO based on the particulate matter.

485 parts of the above pre-adduct are in a solution of 781 parts of dimethylformamide and 19.75 parts of carbodihydrazide, the is dissolved in 39.5 parts of hot water, stirred in between 30 to 35 ° C. The approx. 26 percent solution has a viscosity of 54 poise.

>. : '"■" ■■■■ ■, ■', ■■ ^: ■ -

Polyurethane ee)

210 parts of a polyester of 1,6-hexanediol and ε-caprolactone with an OH number of 70.5, freed of volatile constituents at 130 ° C./12 Torr, are mixed with 50.5 parts of 1,6-hexamethylene dilocyanate while stirring Brought irin temperature of 75 to 78 ⁰ C and held for 20 minutes. The hot pre-adduct melt (NCO content 4.62 4>) is cooled and diluted with 112 parts of dimethylformamide to give a solution with a 70% pesticide content.

Le A 13 028 ■ - 32 -. ^. :.

1 09850/1756.

198 parts of this NCO pre-adduct solution are in a 50 to 55 ° - hot solution of 7.41 parts of carbodihydrazide, 14.82 parts of water and 368 parts of dimethylformamide stirred in as quickly as possible, whereby an elastomer solution of 320 poise at 25 ° C is obtained. The pesticide content of the solution is 25 ^.

Polyurethane ff)

265 parts of a polyester of the composition as described under regulation ee) and an OH number of 106 are heated with 84.1 parts of 1,6-hexamethylene diisocyanate to an internal temperature of 70 to 75 ° C. for 45 minutes. The NCO content of the melt is then $ 5.69. After cooling to 40 ° to 45 ° C. and adding 150 parts of dimethylformamide, an NCO content of 3.94% is obtained . The viscosity of the 70 percent pre-adduct solution is 12.3 poise / 25 ° C.

194 parts of the NCO pre-adduct solution are stirred with a 50 to 55 ° - hot solution of 9 * 29 parts of carbodihydrazide, 13.94 parts of water and 375 parts of dimethylformamide. An elastomer solution of 162 poise at 25 ^° C. is obtained. .

Polyurethane g g)

180 parts of a polycaprolactone ester according to Example ee) with the OH number 185 are mixed with 88.2 parts of 1,6-hexamethylene diisocyanate and 115 parts of dimethylformamide reacted at 40 to 45 ° C for 20 minutes. The NCO content of the pre-adduct is 4.90 <£.

199 parts of the above preadduct be reacted in the solution of 371 parts of dimethylformamide, 11.7 parts of carbodihydrazide and 23.4 parts of water at 50 ⁰ C. The resulting 25 percent elastomer solution has a viscosity of 216 poise at 25 ^° C.

Iß A 13 028 - 33 -

OBtQlNAL INSPECTED

109850/1756

T a b e 1 1 β 1

Properties of solid films ^X ' Polyurethane « speed strain the one for the microporous Module bl. Dhg « turning curve Yo - Coagulation used > · g / dtex ■> 150 * 300 <$>) Polyurethane Tear Resistant- Break- module mg / dt ex (3 »Hück- mg / at ex HDT ^XX ^ 300 fo 16 - 14th 23 ⁰ C 0.66 480 7th 23 0.56 486 285 18th 28 0.53 511 214 18th 12th C. 0.67. 546 203 20th 14th 1700 d 0.78 628 165 16 15th 1680 e 0.50 520 103 22nd 29 1680 f 0.54 586 108 231 15th I630 S. 0.57 536 81 20th 17th 1600 H 0-48 588 137 20th 27 - - i 0.52 566 105 19th 27 k 0.69 424 101 17th 17th 1 0.63 653 414 18th 28 0 m 0.64 490 132 20th 26th η 0.69 529 25O 18th 13th 178 O 0.72 619 241 14th 14th 170 ° P. 0.73 603 170 20th 11 I83O q. 0.62 763 134 18th 16 169 ° Γ 0.82 681 103 18th 18th 164 ° a 0.71 622 97 17th 21st 1670 t 0.66 515 131 16 22nd 26 3 ° U 0.51 463 137 16 23 I620 V 0.53 4741 150 "<+ B * ^ - lnllrelative . _ _emi 51 1650 W. 0.82 529 162 »+ VittT t \ Vu I650 X ■ »• 4 ·. A AU VS sirrti 410 140 ° y 137 ° Z 1810 "Π a · * ·« ι - (_Ua r »a-nVi rti» o tn · 5 Α

is for the above polyurethanes within the limits of 0.7 The 1.5 » All polyurethane melting points (measured on the Kofler bench) are above 220 ° C »

x) Solutions in a drying cabinet at 100 ° C to »solid film dried up,

xx) HDT Heat Distortion Temperature measurement specification, Belgian patent 734 189, the preload being 1.8 mg / dtex and the heating rate 2.1 0 / min. is chosen.

Iß A 13 028

109850/1756

A2 Production of the microporous films Example 1

A 26% dimethylformamide solution of the polyurethane a) is diluted to 25% with a dimethylformamide / water mixture, so that the total solution contains 1.5% by weight of water. The solution is stirred for 2 hours at 100 ^° C. and then applied evenly to glass plates using a doctor blade. The films are pregelatinized at 75 ° C. and 90 % relative humidity.

The films are then placed in water at room temperature for 50 minutes coagulated and then left to dry at room temperature.

If the steam gelation times ti are varied, films with are obtained extraordinary difference in microporosity, surface. and appearance. Films with t ^ = ο minutes are completely transparent,

with tj = 5 still predominantly transparent, with white spots and edges, a rough surface and a strong tendency to curl. Smooth, uniformly microporous films are obtained with tj = 20 minutes. A smooth film with _an excellent surface and good grip is obtained with tj = 30 minutes. While the quality of the surface decreases somewhat with increasing time t ^, the PK value reaches a maximum at about t ^ = 40 minutes. The measured values are shown in Figure 1. When the exposure to the hot steam atmosphere was extended for over 2 hours, the films became completely transparent and water vapor impermeable again. They then resemble films. which are obtained by evaporating the solvent in a drying cabinet.

(See Figure 1).

If the steam temperature in the pre-gelation phase is increased to 100 ° C. at 100 4> relative humidity, the maximum microporosity of the films is reached more quickly (after about 20 to 50 minutes) and begins after only 1 hour of exposure to the steam

le A 13 028 -.35 -

109850/1756

the films are again less permeable to vapor or partly transparent to become.

It can be seen from the example that for a certain

Substance when exposed to steam of a certain temperature and humidity, a maximum range exists in each case in time, which provides the desired microporosity, (see Figure 1.)

Comparative experiment 1 .1

If you leave the same solution as in Example 1) over a period of 1 to 120 minutes in a humid atmosphere (about 22 ° C / k 60 ^ relative humidity) to pre-gel and proceed then as indicated in Example 1), only transparent or predominantly transparent films with a rough surface are obtained Surface and strong tendency to curl.

Comparative experiment 1.2 (according to DAS 1 238 206, analogous to example 1)

A 23 ° strength dimethylformamide solution of the polyurethane a) is applied evenly to a glass plate using a doctor blade, so that a film about 1.2 mm thick is formed. It appeared this film directly for 2 minutes in water of 95 ° C and then in water of about 20 ⁰ C and dried in air at 6O ⁰ C. It transparent after drying, shrunk film is obtained with a high tendency of curling that no Has microporosity and has an extremely low coefficient of permeability (<200).

Comparison test i.5 (analogous to DAS 1 110 60?)

A dimethylformamide solution of the polyurethane a) is evenly spread with a doctor blade onto a glass plate in a thickness of about 1.2 mm , left to pregelatinize for 0 minutes in air with 62 ^ relative humidity at 2 ° C and then in cold water 3 hours of coagulation and

Le A 13 028 - 36 - "" Vt - ■

1098 5Jfff7§§ z _{k <:. C} i BATH

then air-dried. The result is a coarsely structured film, which is about 80 % transparent and has scattered, white islands of a somewhat microporous structure, is also white at the edge in a small width of about 5 mm, but here too has a partially coarse-pored structure. The film in this form is far from being sufficient for practical purposes.

Comparative experiment Λ .4 (according to DOS 1 444 165)

A dimethylformamide solution of the polyurethane a) is evenly applied with a doctor blade to a glass plate approx. 1.2 mm thick, and then placed in a coagulating bath with the composition 50 $ dimethylformamide and 50 4 water for 20 minutes, several hours in cold water to remove the dimethylformamide coagulated from the film and air-dried * The result is a transparent, non-microporous, strongly curling film which dries up transparently; which has only a very, low permeation coefficient.

Man, diluted: the solution of the polyurethane b) with aqueous dimethylformamide to a solid content of 23 <& vpn at a water content 1.5 percent by weight in the total solution. The solution _ is heated for 1 hour at IQO ⁰ C with stirring and coated onto glass plates ■ ·. These spreads are pregelled for 30 minutes in a steam temperature of 70 ° / 100 % relative humidity or 100 ° C / 100% relative humidity, then 30 minutes in flowing .. ■

The water is freed from the solvent, immersed in methanol for 5 minutes and then dried in warm air. It will be _; . · Films with an excellent, "drawn, even surface, high water vapor permeability and, for this permeability, high strength (see table 3). · ■. · ■■

Le A 13 028 ■ - ■ 37 -

Comparative experiment 2. 1 τ

The procedure described in Example 2), but only used humid air instead of steam (23 ° C / 55% relative humidity) for Vorgelierüng, they are transparent, highly shrunk elastomeric films with insufficient water vapor permeabilities PK. 10 f500).

Example 3

A dimethylformamide solution of the polyurethane 1) is ^{stirred for 2 hours at 100 °} C. and then applied uniformly with a doctor blade to a thickness of 1 mm on glass plates. The mixture is allowed a film for 30 minutes at 100 ⁰ C in water vapor (lOO 4> relative humidity) and another film for comparison 30 minutes at Elmmertemperak door and 65 i> RH-gelling and coagulation in water leads (30 minutes) and then Immerse in methanol (5 minutes).

After drying, both films show a microporous structure. ßie The measured values compiled in Table 3 show that with comparable Water vapor permeability, the tensile strength and modulus 300 of the film pregelled in the steam according to the invention considerably above the values of the comparison test (according to DAS 1 110 60?) lies, which is attributed to the more uniform structure of the first film must become. Accordingly, the surface of the first film is smooth and even * during the second film Has a spongy structure with small bubbles on the underside b.

The example and the comparative experiment show that even with the (few) polyurethane solutions, which are already after pre-gelation Allow to coagulate microporous with moist air at room temperature when carrying out the pre-gelation according to the invention with hot steam microporous films of improved,

Iß A 13 028 - 38 -

BAD ORfGJNAL

109d5Q / i7S6

more uniform structure with improved surface properties and significantly improved strengths can be achieved. .

Le A 13 028 - 39 -

109850/175 6

β Φ 43 <Η Approx

CJ CQ β Φ,

5 *

• Π

H Φ

43

ω Fh Φ M.

β Φ

• Η

cn : θ Fh

Fh • Η

U II tu

φ <n Λ fi

co A α ro 43 λ,
(QS Fh CQ · Η g>
ce ct> pi: αί « ^B

■■ fc · ■■ ■

r-f

• Η ·

Φ («0

H ' , P

Ό O ^ -S.

Ji 2

Fh Φ. ^ PP Ό β

() 0 43 H I. • Η • Η O CEL 43 4 * • Η W. "G* Ό Φ
« Φ
«Η O I. IO
fit I. CQ
β Ό • δ, O
• Η ' Ή α) 43. · '
fr ..

I Φ P *

U W

Φ β U

rH Hi-O

Φ Co

Fh ό β

O Φ · Η

■■ 'ρ tJ

Γ Ph β "

Fh cn

O ^ Φ: Ο

Φ H

U β

<Ö H ^

N -., Μ

43 ■: ο

: cd H

co U I

pt 3 ρ

N N Ph

I 1 N

> ί I β I β

H Φ cd ^ o α)

O Fh & g 4s

Ph S 43 CO 03

H Φ • Η P < CQ

• Η · Φ Fh

m te

Φ Ό ^; jH.

, O β -Η-Ό

O φ -f *, β

Φ O (B + »43

43: oä 4J »CQ -rl

3 rH -ΕΙ..Φ φ

ITv ο VO

• k · »« b

H «Μ CVI

CNf CVJ CM

O O O

O O O

ο σ ο

OO O

ITk να cm

CU CM N>

co co σν

I It

rH- ^ J- ΙΤΛ

ιο -sr IPv

VO, -; ro (Γ \ H H H-.

O O O

ο, ο ■ -. ο

OQO OOO HHH

O O

. ο O

OO O

O O O

C ~ - rH rH

OOO ro ro, ro

O ο. ο

O O 'O

O O.,. O

H H. H

CM

O OO

10 OK

H. H IfN

H tvl CM CM

10

β φ ι Fh φ 43 β; 3 t Λ
ο φ 43 Fh :CD υ Ä M. Φ rH Φ
H- O H , α ad O O rH 43 Φ CQ «Η
γΗ CQ 43 Φ 0 rO O

ν «H:

10

CM CVi

VO

IO

CO

CM O

CVJ

ιο ιο

CVl

POJO 10 O cm

O O

CM

Λ CVI

ro

k ρ, Ε -p jü | o

φ; ■■■ ·

m
φ

C ^

W:

xi co ο ^ cti to.

φ
E.

■ cvj-

Ό CVJ,

Ä; - γη ^, - ■. .'ho --- *. ■ • η evr .. ■ ρ

WH · ■: Φ .ο >>;.

CQ. Pt ¹ .

• η ω. '

Φ Ή. i-

t (Φ ^: "

U: PQ, Φ

■ Ρ ■: ■ '■ -

• Η Φ

• Η -.

ex"

CM

; .κν

ORIGINAL INSPECTED

I. ti "ΠΙ • Η
rH TJ O φ U H ti φ δ οβ
: θ ti U φ Qi P- ,O ti O • Η fa α Ό M.
t B * • ΓΙ
θ

rH

03

M Fi

^> η

te!

JKN S

U Φ PP Ό

t -rl φ

00. 4 »4» 4 ^s • rl 03 · Η Ό '

Φ Φ Φ ^> ^

ti I ^ * S

N 09

4>: ο.

.3 4 »

4 »to η

U ^

k U φ

«Φ ti

Ό> 4 »Φ

«W φ Φ Ό O

Vi «Η α Λ U

• Η «Η CQ O · Η ί-Ι

fl O Φ -rf ^ f

UN ITN IfN

ω on - *

U.N.

O O

VO CVJ CD CO KN KN il rH rH rH

ITN O

t - ITN UN

O UN

■ ^ t- KN

UN UN KN rH

O O O O O O O O VO

U.N.

8 8

O 00 ON UN VO VO

■ «J- -tj- VO rH ri rH

OO OO OO OO rH "SJ- CVJ. CVJ

OO

ON ON rH fH

αο
VO rH
C- CVl
C- Oi. C- VO
VO C-
C- U.N.
C- O
GO KN
ω UN UN
H ON
UN> 3- O
ON
U.N. U.N.
O
VO U.N.
ω
U.N. GO
GO
U.N. 590 620 U.N.
O
VO KN.
νο 655 U.N.
VO
U.N. ^ O KN
H γΗ U.N.
CVi t—
CVI VO
CV) et U.N.
cvj cvj C-
cvj ON
CVJ C-
■ cvj KN
CVJ O O O Ö O O O O O O O O

ooooo ο ο ■ o "oooo

OOOOO ooooo rH pH rH rH rH

O O

ο ο .ο

ο O

O

• ο ο

ON

O O §

ir U.N.

C-O C-O C-C-O

rH

O O

■ I I ■

O

ti

■ Η

KN

ITN

O ri

CO CvI O

10985 0 / 17S6

Example 4 \ ^; '·· ^^''s^^;.': ■■ - ^·;

Dissolve in the polyurethane solution b) additionally "jewelIS ^J 1 $ * '3 '<#«, · '■ 5 ^ o or 10 percent by weight (based on the solid substance) - of a polyacrylonitrile copolymer made of 95 # acrylonitrile and $ 4 , Methacrylic acid methyl ester and carries out the pre-gelation or coagulation by varying the test conditions (see table, then with increasing amounts of polyacrylonitrile copolymer (PAN) a reduction in the water vapor permeability and an improvement in the surface and the feel of the Microporous layer. In this way, an optimization of water permeability, strength and surface properties can be achieved from a polyurethane elastomer. Neither too high nor too low a water vapor permeability is desired. The polymer additives bring about an even out of the microporous structure under the conditions of steam pre-gelation with an improvement in the strength values of the films (for results, see Table 4).

Example 5

The following are a large number of different polyurethane solutions the formation of microporous films is carried out in compliance with the following "standard conditions". The most important Properties of the microporous films are reported (see

"Table 5).

Standard condition for the test series;

The elastomer solution in dimethylformamide (approx. 23%) with additions of 0 to 5 percent by weight of water (based on the solution) is optionally "aged" by stirring the solution at 50 to 100 ° C. for up to two hours. The optionally warm (40-95 ⁰ C) solution is coated on warmed mm glass plates in thicknesses of about 0.5 to 1.5. The "gelation" is carried out for about 30 minutes in substantially saturated with water vapor at 75 to 100 ⁰ C. The "coagulation" of the film will

Le A 13 028 - 42 -

10 9850/1756

in water at room temperature with dimethylformamide contents of

0 to 20% done. (Duration approx. 30 minutes). A post-treatment of the white, microporous film takes place by subsequent bathing: the film - .. in methanol (up to 50 .. minutes. Dwell time) * .... The drying of the films is done by lying for 2 to 15 hours 'Films at room temperature, followed by drying for 5 hours at 11 Q ° a .: ^. ; . ·.; ■ - ■ ■ ·. · ■,. · ..: ..: /. ,, -; ' ,. -. _?

AiTerTiölyurethäniösungen were under thinking andärdbedingun · * - .. genes! but ^; under pre-control In air at room temperature and; relative humidity voh $ 0 bis 65 $ '(^ ^ .45 exposure time ■ 30.Minuten) - coagulated films - instead of eriindungsgemäßen Vdrgelierungsbedingungen. All of these 'films (except polyurethane

1 and ,, ζX were completely or partially transparent, severely shrunk, had a sloping surface and were not microporous. .

Example 6 .

The solution of the polyurethane ζ is mixed with aqueous dimethylformamide to a solution containing 23 percent by weight of solids and 3 percent by weight of water, stirred at 50 ° for 2 hours and left to stand for 48 hours. The solution is heated to 90 ° C before pouring and immediately painted onto a hot glass plate (approx. 90 ° C). After pre-gelation in a steam atmosphere of _: 78 ° ^C and 95.9 ^ relative humidity for only a short period of 1 minute, the film is then. Coagulated in water at 60 ° C. for 30 minutes, then treated in methanol for 10 minutes and then dried. A microporous film with "smooth, homogeneous surfaces and" good tear resistance is obtained. (0.245mg / dtex). . _ '. .., -...

If one proceeds as obön, but does-the 'pre-gelation .an ^ μΐΐ of 25 ^Q 6' / 50 ^: - '% ·· relative humidity, · then · one obtains a .microporous film, which however- ^ has a rough surface and only reduced strength «(Ο / 1 · 9 ^ mg / dtex). '■ - -' - - ■ »■■ · ^·:.. - · "

- ⁴³ - ORIGINALINSPECTED 109850/175 6 '^ "''*''''*

Example 7

A water-containing solution prepared as in Example 6) Polyurethane ζ is heated to 80 ° C and placed on a rotating,.

Preheated steel strip (70 to 80 ° C) is knuckled on and after approx. 5 to 6 seconds it is brought into a steam room with water vapor of approx. 75 ° C and approx. 90 to 95% relative humidity. After a running time of 5 minutes is allowed to run the film in a coagulation bath at 70 ⁰ C. The film is then placed in a second, unheated water bath where the remaining solvent is extracted. The total residence time in the coagulation baths is about 20 to 25 minutes. The dimethylformamide concentration in baths is kept below 5% by constant renewal of the water. t The hot Vorgelierbades on the polyurethane film cover is maintained at 90 to 100 ⁰ C, in order to avoid drop formation on the ceiling. The film web runs through after Ab-. squeeze 10 minutes a methanol bath of room temperature, is then squeezed again and is anschlißend in a drying oven for 20 minutes at 110 ⁰ C..getrocknet.

A uniformly microporous film web with a smooth surface and good tear resistance is obtained. \ -

Ii £ ■ - ■

Le A 13 12:28 Γ ί ^"Γ:

98 5 0/1756

"Ht

β I Ή

I ·

ί KN

IfN

KN

CM

\ ο

ο ο

CQ CQ KN OS CM H rt ri CsI

8th ο

ο ο ο

i I 8

O CV O O CM IfN

η νο β η H »

O O CM IfN

β η H ι »

H KN

H β \ M) N Q ΰ CNf »Η | «I CM IS CV |

IiN CM VO QE) VO No.

. IA O O

• 3 rj -ft

t- Q VQ «0 OQ VO VO ft «(F KN ΚΛ iSt

CO 03 «N« M Tf O Ο

CT \ t "CM KN VO t- * CNi Hr-J CM r + H CM CM

QQOO i $; ' Q- Q

Ö Ö O O O O O

Q Q Q Q-OQQ

O Q Q Q- "O ON CTN

q ο

Q he ο

O Q O Q

OOOO rf H; * -i ri

O Q Q Q

Cl

^ "^ CM

C3 C3 O Ό H H

c »

• I ti * ^ I ϊ

trv

it, α ο

^ f SO

KN CVt

CM CM

KN CM

VO

P)

ΙΛ VO tfi

t- CM ti vfl

QOO O

SS 8 8 8 8 8

vo φ σ \ «ir \ ο ο \

VO r4 CQ KN CM H Κ \

■ Η ""

H IT »CM ι-Ι H H OQ CM CM CM KS ■ <* CM KN

rl in

(Q O

in

H KN

OB tfN

· ** ■ -rf «π o on oo on vo ο M α? tt \ ο

C iN T KN

ο M ? t

ICl IiN (TN KN:

VQ ^ ft e- * Q Q Q

VO ^ φ O CQ KN CO Q H CM CM CM. KN H * φ "

α α ο'- <a c? c? c?

Q IfN

Q Q

QQ ₁ QQQ

ca Q ft crv ο

H H

O Q H HI

OQO QQO

Q H

IfN

OQ

tfN IfS

η ί |

M% tf \ 'Ό tf \ ITv ΙΓ \ ΙΟ, UNIfNIfNlTkIfNUTNIfN

la b al 1 * 5 (continuation) production requirements tmcl property »n microporous r foils

example

No.

*· Additive·

to. ■■■■. ·.> tamn »PÜ ^ Solution Substance»

Yorbe «act of PU exercise

Yergelier- Koägu »Tearing · Breaking Äodul stay * FK» ΙΟ ⁸

Conditions latio »e-> firm« · d «h» JGO Jt Dhg. G

⁰ C / rel. bad keit nung ag / dtex $ h.cm.Taar Feucnt · Τ · ϋ · g / dt * ac jt "'/

Water-

läeaigkeit g-tigk, ( _n , ag Graves) kp / cn

5.15 5.16 5.17 5.18 5.19 5.20 5.21 5.22 5.23 5.24 5.25 5.26 5.27 5.28 5.29

Ar

• r

• Β β B

1 ^: 1000 IQOO / $ 100

lppo / ipoji
75 ° /

l ^h. 1000 2 ^h 1000

■ * '^v;' t

/ Q

, 100,. / $

/ 10

u ν

loo ⁰

100 °

Le A A3 -

0.270

/ 10.
90/10

/ 10
90/10
/ OK
100/0
1Θ0 / 0
/ 0

0.170
0 * 190
0.220

0.250
0.290
0.180
Ö * 23ö

443
475
525
473
531
423

452
575
515
517

501

143

Λ37

96

97

107

'96
87
76

m ns

15th
: 95

31 32 10

13th

14 14 15 14 14 15 IT 17 19, 22

140,000

29

17th

100 55'jOO

: 77

84

, 72

43

6 θ

54

15th

69 oo;

20 50 JOOO

11.5

6.5

16.0

3.6

.4.5

16.5

15.0

11.9 14.7

4;, 4

7.4 ■ 8.5

5 »l / 7,: 5

2.1 / 2.0.

E * ball e 5 (continued)

.30 Poly »
ur ·· » Additive·
to the Vorb ·· *
plot Conditions of manufacture «unj? En and properties microporous films By-
'firm » Fracture modulus
deh- $ 300 mg / dtex stay
Dhg. .PK
"K • 108 water
steam through h.cm ² Further-
r «ißf · - ί 1.8 / 2.1 .31 than »
Sub · » PtJ solution the PU
Solution Vergelier »Koagu»
Conditions lational k * it
g / dtex tion
1 ° Jt-- H. cmi leaves ssigke it
mg 11.0 stigk. (n.
Graves) .32 punch » oc / rel. bath
Wet part 85 6.5 kp / cm .33 ■. w 5 * H ₂ O l ^h 1000 0.180 472 89 25th 36 000 11.0 example
No. 34 χ 5JiH ₈ O l ^h 1000 780/95 $ 90 / ίο 0.190 481 102 28 15th 000 14.7 y 5 $ H ₈ O l ^h 1000 780/95 $ 90/10 0.220 466 194 27 38 000 7.5 Z έ !, 9 ^ H ₈ O 78 ° /? ^ | 90 /..XO 0.190 311 275 25th 83 000 , V.5. CC 3 $ H ₂ O 2 ^h 1000 75 ° / 9ρ | XPO / _:? 0 0.340 361 87 12th 000 780/90 $ IQO / «? Q VJl : '5 · 5.

The films listed in the table were white due to the "microporosity" of the films and showed good, smooth surfaces · The microporous films showed no damage or damage after 200,000 kinks Impairment of the surface

If the methanol bath aftertreatment is dispensed with, some of the previously microporous Films at least partially transparent (cf. 5.01, 5 · 6, 5 * H) · In addition, the methanol aftertreatment improves the raw tone of the films and greatly facilitates the drying of the microporous films *

Le A 13 028

- 47 -

cn cn

Example 8

A solution of the polyurethane aa bb, or dd-containing solution is diluted in aqueous dimethylformamide optionally in a 23 percent by weight, stirred for one hour at 100 ⁰ G and then, at 80 ⁰ C on preheated GElaaiplattenaufgeatiriehen. After different gelation times (see table 6) in hot steam or in humid air at room temperature, the films are coagulated for JO minutes in a water at 25 °, bathed in methanol for 20 minutes and then ^{dried at HO 0} C for up to 5 hours.

Uniformly microporous films with smooth surfaces are obtained. The measured values (Table 6) show that the water vapor permeability of the films can be controlled via the gelation times in hot steam, with hot steam treatment from 1 to Minutes a significant improvement in properties compared to (elimination in moist air at room temperature can be achieved.

Example 9

A 22 percent dimethylformamide solution of polyurethane ee, ff or gg _t which still contains about 3 ^ water is evenly applied to a glass plate 1.35 mm thick with a squeegee. The film is allowed to ^{gel for a few minutes at 75 °} C. in saturated steam and then coagulation is carried out in water (15 minutes on the plate, 30 minutes without a plate) at room temperature. After drying one hour at 70 ° to 80 ⁰ G, the films exhibit a uniformly. ' microporous structure (measured values in Table 7).

Le A 13 028 - 48 -

Ί 0 9 8 5 0/1: 7 S $ κ V ■: ° ^RiGfNAL

Yellow = Tabel 6th = Jmodule prio ⁸ Water vapor = Poly = conditions ! Tear = I fracture $ 100 permeable urethane min / ° C / rel strength deh = img / dtex
I. h-cm'Torr speed - ^ - ρ
h- cm ² substance 30'78 ° 95 <£ , Pig / dtex
ι tion ^ 131 160000 18.4 a a 2 »7709596 0.27 246 110 59OOO 10.5 a a 1 * $ 76095 0.14 178 110 4OOOO 9.5 a a -1Ο · 25 ° 65 ^ 0.14 172 110 5800. 2.2 a a 30 * 78 ° 95 $ 0.11 137 23 380000 25th b b 4 ^f 90 ° 35 $ 0.13 604 21st 28000 9.8 b b , 10 * 250 65 ^ 0.11 528 17th I7OOO 6.4 b b 30 * 78 ° 9 59ε 0.05 427 145 84000 11.4 there 4'9G ° 95 $ 0.18 148 160 11000 6.0 d d 10 * 25 ° 65 $ 0.22 155 160 1600 0.5 d d 0.17 119

Le A 13 028

- 49 -

10 9 8 5 0/1756

ORIGINAL INSPECTED

Tabel Example polyurethane; additives for Gielier == ptOagulations =

Polyurethane.! conditions jbad Tei le • Solution fflia / ° c '[Ejo / DMP

substance

• ipfeetig =! Speed. Ip / cni ⁸ anga / quer ^

Fraction = continue = elongation tear =

jfestig-

! speed

jKp / cm

IWaeaerdampf = ! permeability

hem?

lengthways / crossways j

7.1 e e 3.3 H 5/75 100 / 0 91.6 / 51.4 495 7, 8/5, 0 4.9 7.2 f f 2.8 1, 5/75 100 / 0 102/85 625 10, 8/7, 8th 5.3 7.3 ' S. e 3.9 ■ It 3/75 100 / 0 78.9 / 54.9 485 2, 0/1, 8th 6.9 fa H ₂ O # H ₂ O

to the direction of the winding up of the films

Le A 13 028

CT) CD "

B) Experiments «with the use of a cationic polyurethane dispersion

B1) Manufacturing instructions for the polyurethane ureas a) Polyurethane urea a / 1

4470 parts (parts by weight are always given) of a polyester made of adipic acid and 1,4-butanediol with an OH number of 50.2 and dehydrated for 1 hour at 130 ° C./12 Torr are mixed with 674 parts of hexamethylene diisocyanate (molar ratio Polyester to diisocyanate = 1: 2) brought to an internal temperature of 89 91 ⁰ C with stirring and held for 25 minutes. The hot NCO preadduct-.schmelze (NCO content 3.82%) is added after cooling to 55 ⁰ C with 2206 parts of dimethylformamide. The NCO content of the pre-adduct solution is 2.55%.

5980 parts of the above Voradduktlömxng rerden in an approximately 50 - 55 ⁰ C hot solution of 173 parts of carbodihydrazide, 346 parts of water, and added to 11040 parts of dimethylformamide to form a homogeneous elastomer solution having a viscosity of 196 P / 25 ° C 24.9 % solids concentration arises. The properties of the elastomeric substance (measured at about 0.2 mm thick films which are obtained by Aufräkeln of the elastomer solution on glass plates and evaporating the solvent at 100 ⁰ C) are listed in Table 1 below. The films show excellent resistance to yellowing and mechanical degradation.

Polyurethane urea a / 2

3,440 parts of a polyester described in regulation a / 1 with an OH number of 52.2 and 47.6 parts of N-methyldiethan <8amine (molar ratio of polyester to aminol = 0.8: 0.2) are mixed with 952 parts of diphenylmethane-4 , 4'-diisocyanate and 2550 parts of dimethylformamide were ^{stirred at 30 °} C. for 15 minutes.

Le A 13 028 - 51 -.

10 3 8 5 0 / ■ 1 7 5 6 ORIGINAL INSPECTED

3,880 parts of this NCO pre-adduct solution (NCQ content .1.49%) .wer- ,; in the ^{heated to 55 0} C solution of 70.6 parts of carbodinydrazide, 141 parts of water and 4070 parts of dimethylformamide, stirred. The 24.6% elastomer solution has a viscosity of.190 P / 25 ° C. '_ ". ■ __: ..

Polyurethane urea / 3

3,930 parts of a polyester made from adipic acid and diethylene glycol with an OH number of 42.9 are stirred at 60 ° with 7 parts of a 35% solution of SOp in dioxane for 15 minutes and then at 12 torr / 120 ° 30 Devolatilized for minutes. The so vortoehandelte polyester is 4,4'-diphenylmethane diisocyanate with 750 parts and 2010 parts of dimethylformamide for 15 minutes at 35 - 40 ⁰ C heated. 4050 parts of the NCO pre-adduct solution (NCO content 1.70%) are combined with 76 parts. Carbodihydrazide, dissolved in 152 parts of water and 7,272 parts of dimethylformamide, converted to a clear elastomer solution with a viscosity of 162 P / 25 ° C. Solids content 25.2%.

Polyurethane urea a / 4

3940 parts of a treated according to procedure a / 2 mixed polyester of adipic acid and ethylene glycol 1,4-butanediol (Molverhältöis 1: 1) with an OH number of 57 are reacted with 640 parts Hexämethylen-1, 6> diisocyanate 30 minutes at 92 ⁰ C. , cooled and with. 1960 parts of dimethylformamide to the NCO pre-adduct solution (2.1% NCO | diluted.

1,990 parts of this solution are added to the mixture of 44; 7 "' Carbodihydrazide, 67.1 parts of water and 3,678 parts. Diet & yl * - * "

formamide stoved. The 25 ₁ of 1% has a Eistomerlösung, viscosity of 276 P / 25 ° C. ^; '""'"'"'""'.'"'"

Le A 13 028 - 32 -

10 9850/176 6 'original inspected

Polyurethane urea a / 5

7,200 parts of a polyester made from adipic acid and 1,4-butanediol (OH number 62.4) are reacted with 1280 parts of 1,6-hexamethylene diisocyanate ^{at 85 ° C. for 40 minutes.} The melt, which has been cooled to 60 ^° C., is stirred with 3568 parts of dimethylformamide.

3,950 parts of the NCO pre-adduct solution (2.29 % NCO) give, with 105.4 parts of carbodihydrazide dissolved in 210 parts of water and 7304 parts of dimethylformamide, an elastomer solution with a viscosity of 157 P / 25 ° C. solids content 24.3 %.

Polyurethane urea a / 6

450 parts of the polyester described in regulation a / 5 with 1253 parts of diphenylmethane diisocyanate and 2,477 parts of dimethylformamide Heated to 40 ° for 10 minutes.

6,250 parts of the NCO pre-adduct solution (NCO content 2.28 %) are introduced into the solution of 161.3 parts of carbodihydrazide, 322.6 parts of water and 10,966 parts of dimethylformamide to form an elastomer solution of 225 P (25.4 %) Solid).

Polyurethane urea a / 7

1,500 parts of the polyester from regulation a / 5 with the OH number 66.7 and 25.9 parts of N-methyldiethanolamine are combined with 529 parts

Brought diphenylmethane diisocyanate in 2,280 parts of dimethylformamide at 25 ⁰ C to react. After 10 minutes the NCO content of the pre-adduct solution is 1.2396.

In a solution of 82.5 parts of carbodihydrazide and 1.65 parts of water and 4,080 parts of dimethylformamide become 3,998 parts of the above NCO pre-adduct solution is stirred in, a solution (2590 with a Viscosity of 143 P / 25 ° C arises.

Le A 13 028 - 93 -

109860/1756

Polyurethane urea a / 8 . '

4,160 parts of a polyester made from adipic acid and diethylene glycol with an OH number of 54.0 are reacted with 673 parts of 1,6-hexamethylene diisocyanate at 92 ° for 25 minutes. After the melt has cooled to 60 ^° C., 2075 parts of dimethylformamide are added.

3980 parts of this NCO pre-adduct (-2.24 % NCO) are mixed with a solution of 107.6 parts of carbodihydrazide, 215.2 parts of water and 7118 parts of dimethylformamide to form an elastomer solution of

133 P / 25 ° C converted. The solids content of the solution is 24.9 %.

Polyurethane urea a / 9

5000 parts of an adipic acid, ethylene glycol-1,4-butanediol mixed polyester (molar ratio of the glycols 1: 1) with an OH number of 57.2 are mixed with 1,205 parts of diphenylmethane-4,4'-diisocyanate and 2,650 parts of dimethylformamide . The temperature is maintained at 40 ° during the 55 minute stirring. The NCO pre-adduct solution has an NCO pre-adduct solution has an NCO content of 2.06 %.

2050 parts of this NCO-preadduct methylformamide be given to a solution of 45 parts of carbodihydrazide, 90 parts of water and 3640 parts of di-W. The elastomer solution obtained has a viscosity of 330 P / 25 ° and a solids content of 25.1 %.

Polyurethane urea a / 10

3,400 parts of a mixed polyester of adipic acid and 1,6-hexanediol-2 _f 2-3) imethylpropanediol-1,3 (molar ratio of the glycol mixture 65 * 35) with the OH number and 1001 parts of diphenylmethane diisocyanate 1, treated according to regulation a / 1 884 parts of dimethylformamide reacted ^{for 40 minutes at 35 °} C. to an NCO content of 2.38 %.

Le A 13 028 - 54 -

100850/1756

4030 parts of NCO pre-adduct react with 109.6 parts of carbodihydrazide, 219.2 parts of water and 7312 parts of dimethylformamide to give a clear elastomer solution at 272 ° C./25 ° C. with 25.2% solids content.

Polyurethane urea a / 11 -

2100 parts of a polyester made from caprolactone and 1,6-hexanediol with a molecular weight of 1410 are reacted at 74 ° -76 ° with 505 parts of hexamethylene diisocyanate for 35 minutes. After cooling and the addition of 1120 parts of dimethylformamide, an NCO pre-adduct solution containing 3.1 % NCO is obtained. . .

1980 parts of this NCO pre-adduct are stirred into the solution of 71.5 parts of carbodihydrazide, 107.3 parts of water and 3721 parts of dimethylformamide. The viscosity of the resulting homogeneous elastomer solution is 183 P / 25 ° C (24.9 % solids).

Polyurethane urea a / 12 ,

2640 parts of a polycaprolactone ester as described in regulation a / 11 with an OH number of 107.5 are 1252 parts Diphenylmethane diisocyanate reacted in 1680 parts of dimethylformamide for 10 minutes at 35-40 ° C.

1960 parts of this NCO pre-adduct solution (3.41 % NCO) are stirred into 80.4 parts of carbodihydrazide, 160.8 parts of water and 3641 parts of dimethylformamide to form an elastomer solution at 160 P / 25 ° C. (24.7 % pesticide).

Polyurethane urea a / 13 ..-. . ,

4120 parts, of an adipic acid-hexanediol polyester ^ with the OH -....... number .136 are at 30 - SS ^ C'ji ^ t.SSIO ^ Ieilw.p ^ .e ^ lmetha ^ aiisopyanat in 6 330 parts of dimethylformamide are stirred. After 10 minutes this is _; NCO content of, Jiösuiig 2.11>;",, .- ■■ _,,; . . : ■. ■■■■■

Le A 13 028 - 55 - _

109

ORIGINALINSPECTED

To 152 parts of carbodihydrazide in 304 parts of water and 6,134 parts of dimethylformamide are 5920 parts of the NCO pre-adduct solution
added with stirring. The viscosity of the clear elastomer solution increases within a few minutes to 232 P / 25 ° C (24.8 %
Solid).

Polyurethane urea a / 14

4120 parts of the polyester from regulation a / 13 are mixed with 2025 parts of dimethylformamide with 625 parts of diphenylmethane diisocyanate
extended. After stirring for 10 minutes at 30-40 ^° C., the goes
NCO content around 0. In this solution, 74.5 parts of N-methyldiethanolamine, 1495 parts of diphenylmethane diisocyanate and
Stir in 4110 parts of dimethylformamide. After 12 minutes the NCO content is 1.75%.

6030 parts of this NCO pre-adduct solution are stirred into the solution, heated to 55 °, of 124 parts of carbodihydrazide, 248 parts of water and 6,228 parts of dimethylformamide, an elastomer solution with a viscosity of 186 P / 25 ° C being formed (25.1%
Solid).

Polyurethane urea a / 15

1800 parts of a polyester made from caprolactone and 1,6-hexanediol
with a molecular weight of 600 are 8 minutes ^{at 65 0 C}
^ long reacted with 960 parts of hexamethylene 1,6-diisocyanate. 1180 parts of dimethylformamide are added to the melt. The NCO content of the pre-adduct is 4.93%.

1,998 parts of this pre-adduct solution are stirred into 117 parts of carbodihydrazide dissolved in 234 parts of water and 3710 parts of dimethylformamide. The solution viscosity is 216 P / 25 ⁰ C, the solids content 25%.

Le A 13 028 - '' - 56 -

10 9850/1756

Properties of polyurethane urea solutions and films (Table 8)

Polyurethane $ NCO in Viscosity of the Solid Testing of elastomer foils on rod samples according to DIN 535o4 Elongation at break
in % Moving on
speed in kg / cm ureas a NCO pre-adduct Elastomeric'sung
in P / 25 ° C salary tensile strenght
in kg / cm ^e.g. 965 58.O a / l 2.55 196 24.9 54o 9o5 69.0 a / 2 1.49 190 24.6 565 89o 62.0 * / 3 l, 7o 162 25.2 57o 92o 56, o a / 4 2, Io 276 25.1 545 92o 74.4 a / 5 2.29 157 24.3 515 89o Si, 7 a / 6 2.28 225 25.4 575 860 68.5 Ϊ0 a / 7 1.23 143 25, o 520 875 54.2 a / 8 2.24 133 24.9 46o Io85 47.2 a / 9 2, o6 33o 25.1 55o 855 42.6 a / lo 2.38 272 25.2 545 795 6 *, o a / 11 3.1 183 24.9 598 62o 52.1 a / 12 3.41 I60 24.7 57o 582 41.1 a / 13 2.15 232 24.8 558 555 36.7 a / 14 1.75 186 25.1 755 560 39.4
I. a / 15 4.93 216 25, o 6io

Le A 13 028

- 57 -

O NJ cn

Manufacturing instructions for the cationic polyurethanes b Cationic polyurethane b / 1

1000 parts of a polyester with an OH number of 62 and a water content of less than 0.1 % produced from phthalic acid, adipic acid and ethylene glycol (molar ratio 1 s 1: 2.2)
257 parts of tolylene diisocyanate (mixture of isomers 65; 35)
Implemented at 70 ⁰ C for 120 minutes. 840 parts of dimethylformamide and are successively added to the viscous pre-adduct obtained
107 parts of N-methyl-diethanolamine and stirred at 50 ° until the viscosity is 60 P. A solution of 6.5 parts of dibutylamine in 60 parts of dimethylformamide is then added in succession
a solution of 30 parts of 1,3-dimethyl-4,6-bis-chloromethylben- w zene in 193 parts of dimethylformamide was added. The mixture is stirred at 50.degree
until a viscosity of 45 P is reached. You then follow
successively a solution of 29 parts of phosphoric acid in 120 parts of water, 1065 parts of dimethylformamide and 1300 parts of water
at 50 ⁰ C added. After cooling, a 28.5 % strength is obtained
white dispersion.

Cationic polyurethane b / 2

Proceed as in regulation b / 1, but using 48 parts of acetic acid instead of phosphoric acid. The 28.5% dispersion obtained is more coarse.

Cationic polyurethane b / 3

The procedure of Vorsclii & ft% / Λ, but using 87 parts of conc. Hydrochloric acid. A 28.5% strength, opaque, viscous polyurethane solution is obtained.

Cationic polyurethane b / 4

Proceed as in regulation b / 1, but using 33 parts of 2,5-dichlorobenzoyl chloride instead of bischloromethylbenzene. After cooling down, you get a bluish shimmering

Le A 13 028 - 58 -

109850/1756

; ; 2025S16

mering dispersion, which is 28.5%. Cationic polyurethane b / 5

Man. Proceeds as in regulation b / 1, but using 30 parts of benzyl chloride instead of 1,3-dimethyl- · 4,6-bis-chloromethylbenzene and receives a 28.5% dispersion of the corresponding polyurethane.

Cationic polyurethane b / 6

Proceed as in regulation b / 1, but using 23 parts of dimethyl sulfate. It results in a 28.4% opaque Polyurethane solution.

Cationic polyurethane b / 7

The procedure is as in regulation b / 1, but using 30 parts of terephthalic acid dichloride instead of 1,3-dimethyl-4,6-bis-chloromethylbenzene and receives an opaque, viscous, 28.5% solution of the polyurethane.

Cationic polyurethane b / 8

The procedure is as in regulation b / 1, but phthalic acid dichloride is used in place of 1,3-dimethyl-4,6-bis-chloromethylbenzene. A less viscous, opaque solution results of polyurethane than in b / 7.

Cationic polyurethane b / 9

Proceed as in regulation b / 1, but using 30 parts of 1,4-dichloromethylbenzene instead of 1,3-dimethyl-4,6-bis-chloromethylbenzene. A thin, 28.5% dispersion is obtained.

Le A 13 028 - 59 -

109850/1756

B2) Production of Microporous Films Example 10

400 parts by weight of the solution of the polyurethane urea according to regulation a / 2 in dimethylformamide, which is 24.6 % , are mixed with a solution of 38.4 parts of the cationic polyurethane solution according to regulation b / 1, to which a further 7.6 parts of dimethylformamide are added are stirred intensively at room temperature. The mixture is 22 % ± g and has a viscosity of 116 Ρ / 25 °, the water content is 3.6 %.

200 parts by weight of this solution are deaerated in vacuo and then brushed onto a 460 cm glass plate in a 1.3 mm thick layer with a doctor blade. This is then placed in a 90 ⁰ C warm box which is filled with expanded steam, and maintained for 5 minutes in the atmosphere of steam, after which the solution is gelled. The plate is then placed in a water bath where the dimethylformamide is washed. The resulting porous film is peeled off the base after 15 minutes, left in the water bath for a further 30 minutes and then squeezed off five times and soaked again with water in between. After the fifth squeezing, the white, smooth film is ^{dried at 60 °} C. in flowing air. It has a water vapor permeability (according to I UP 15, "Das Leder", 1961, pp. 86-88) of

16.1 mg / cm. Example 11

300 parts of a 25.1% strength solution of the polyurethaneurea a / 9 in dimethylformamide are intensively mixed with 46.6 parts of a cationic polyurethane solution in dimethylformamide (28.5% strength according to specification b / 1 with 56 parts of dimethylformamide. The solution is 22% strength of solids and 4.5% of water.The viscosity is 214 P / 25 ⁰ · The solution is slowly stirred for 1 hour at 70 °, degassed in vacuo and, as shown in Example 10, spread on /2 minutes

Le A 13 028 - 60 -

109850/1756

left in the steam atmosphere for a long time and then in a water bath ■ further treated as in example 1. The film produced in this way

■ ■ ■ ■ - ρ there is a water vapor permeability of 18.9 mg / em h.

Example 12

300 parts of the polyurethane urea solution a / 12 (in dimethylformamide, 24.7%) are mixed intensively at room temperature with the amounts of polyurethane urea b / 1 given in Table 9 and the parts of dimethylformamide necessary to obtain a 22% solution. The samples, as applied in Example lobe written on a glass plate in a uniform layer, (rel 90 ⁰ C, 100%. Humidity) in the steam box treated for the indicated time in the table, and then treated in a water bath to an end. After drying, the porous films have the properties listed.

Le A 13 028 - 61 -

109850/1756

Table 9 (example 12)

Weight reduction
ratios of
PU according to regulation
a / 12 : b / 1 viscosity
in P / 25 ° concentration
the solution
% water
salary
% Steam
permeable
ability «
mg / cm h Gelation
Time
Min. Examination of
Tear-resistant
speed
kp / cm microporous
fracture
strain
% loops
Tear on
strength
kp / cm 80: 2o 185 22nd 6.7 23.3 o, 5 51 395 5, ο 85:15 172 22nd 6.1 19.1 o, 7 59 41o 6.1 9o: Io 158 22nd 5, ο 16.4 o, 8 66 442 6.7 95: 5 139 22nd 3.97 12.1 1.3 82 43o 8, ο 98: 2 128 22nd 3.2 9.8 2, o 94 58o

Le A 13

- 62 -

Example 15 ,

400 parts of a 24.3% solution of the polyurethane urea a / 5 in dimethylformamide are mixed with 38 parts of a cationic polyurethane solution in dimethylformamide according to regulation b / i (ratio a: b = 90:10), 53 parts of dimethylformamide and with increasing amounts (0, 5 - 5 %, based on the solids; Table 10) polyacrylonitrile polymer added. The approximately 22% strength solutions are degassed and applied using the method given in Example 1, treated for 5 minutes in a steam atmosphere (90 °; 100 % relative humidity) and then treated in water. The microporous films show a decrease in water vapor permeability with increasing amounts of polyacrylonitrile polymer, but an improvement in handle and surface and an increase in strength values. The polymer additives thus enable optimization with regard to water vapor permeability, strength and surface.

Le A 13 028 - 63 -

1098S0 / 1756

Table -jQ Comparison of the properties of microporous films with PAN additives according to Example 13

00 cn ο

4Π

co

Polyurethane
substance b / 1 Additions to
PU solution PAN Pre-gelation
B ^ conditions
° C / RH Tear resistance
ο
kp / cm Elongation at break Tear on
strength
kp / cm Water vapor through
nonchalance
mg / cm ^z h a / 5 b / 1 no ί PAN 9o ° / 53 5oo lo, 5 19.8 a / 5 b / 1 o, 5? 6 PAN 9o ° j 66 530 14.7 15.2 a / 5 b / 1 l.o? % PAN 9o °, 95 455 lo, 7 9.7 a / 5 b / 1 1.5 ί ί PAN 9o ° / Io6 48o 14.1 6.4 a / 5 bi 2, ο 5 ί PAN 9o ° / 98 525 io, 2 5.8 a / 5 b / 1 3, ο ί i PAN 9o ° / 115 38o 16.5 2.9 a / 5 b / 1 4, ο J έ PAN 9o ° / Io9 545 13.9 4.2 a / 5 5, ο ί 9o ° / 112 575 9.4 3.8 'loo % ' iOO io ' loo % ' lOO <fo ' loo % ' loo % ' loo % ' loo%

Le A 13 028

- 64 -

N)

Ql cn

CD

Example 14 ■ tb ■

The solution of the polyurethane urea a / 10 is mixed with the cationic polyurethane solution b / 1 (a: b = 9: 1) and further dimethylformamide to form a solution with a solids content of 22% and a water content of 5.2 %. The solution is degassed and painted on glass plates. This is treated for 10 minutes in a steam atmosphere of 80 ° / 100 % relative humidity and the dimethylformamide is then rinsed out with water. The film is then dipped in methanol and dried in warm air. The films are characterized by good surfaces, water vapor permeability values and strengths.

Example 15

According to Example 10, the polyurethane urea solutions given in the table below are mixed with those given cationic polyurethane dispersions mixed with dimethyl. formamide diluted to the concentration of 22%. These solutions are doctored onto glass plates and exposed to the steam atmosphere. After the specified times, they are treated further in the water as in Example 1. After drying, the result water vapor permeability listed in Table 11.

Le A 13 028 - 65 -

109850/1756

Tabel

Polyurethane urea
solutions and advantages
fonts cation. Polyurethane
Regulation b relationship
PU a: b Io Water content
% Gel time
Min. Permeable to water vapor
ability ο
mg / h cm a / l b / l 9o Io 4, ο Io 14.8 a / 3 bi 9o Io 3.3 15th 16, i a / 4 b / 1 9o Io 3.2 5 18.3 a / 6 b / 1 9o Io 3.8 4th 12.6 a / 7 b / 2 9o Io 4, O 3 13.5 a / 7 b / 9 9o Io 4, o 3 11.9 a / 7 b / 7 9o Io 4, o 5 oil a / 11 b / 2 9o Io • 3.8 3 7.8 0 * a / 13 b / 6 9o Io 4.4 ok 4.3 a / 14 b / 9 9o . Io 4, ο 8th . 9.6 a / 15 b / 4 9o : Io 5.6 2 5.8 a / 15 b / 5 9o 5.6 2.5 4.7

Le A 13

- 66 -

Claims (14)

Claims * »■? Process for the production of microporous sheet-like structures from polyurethanes by pretreating thin layers of polyurethane solutions in a moist atmosphere, coagulation in aqueous ones Precipitation baths and subsequent drying, characterized in that a thin layer of the polyurethane solution is optionally applied in a mixture with an aqueous cationic polyurethane dispersion in a steam atmosphere with a relative humidity of at least 50% at temperatures of at least 65 for 0.1 to 60 minutes, then in water or aqueous Coagulation baths removed most of the polyurethane solvent, the microporous polyurethane optionally with a treated with aliphatic alcohol for 0.2 to 30 minutes and then dried. 2. The method according to claim 1, characterized in that one other polymers are also used. 3. The method according to claim 1, characterized in that one uses a solution of an elastomeric polyurethane in a water-soluble, highly polar solvent. 4. The method according to claim 1, characterized in that one a mixture of a solution of an elastomeric polyurethane and up to 35 wt .-% (weight based on solids) one aqueous cationic polyurethane dispersion or colloidal solution is used. 5. The method according to claim 1, characterized in that a water vapor atmosphere with a relative humidity of 80-100 % and a temperature of 75-100 ⁰ C 0.1 to Leave on for 30 minutes. 6. The method according to claim 1, characterized in that saturated water vapor is applied at the boiling point of the water. ■ Le A 13 028 - 67 - 109850/1756 7. The method according to claim 1 to 6, characterized in that a solvent-containing polyurethane mixture of a polyurethane elastomer, and optionally a cationic polyurithan .andispersion with a Gesamtkonaentration from 5 to 40 wt.% And used a viscosity of 10 to 1000 poise. 8. The method according to claim 1 to 7, characterized in that the polyurethane elastomers used are those which are obtained by reacting NCO pre-adducts with. 1.0 to 7.6 wt. # »NGO consisting essentially of polyhydroxy compounds with molecular weights between 400 and 5000 and melting points below 60 ° C, optionally 10 to 300 mol% of the OH content of the polyhydroxyl compounds in low molecular weight diols, and organic diisocyanates ¹¹ can be obtained with essentially bifunctional chain extenders. 9. The method according to claim 1, 2 and 4-8, characterized in that as cationic polyurethane dispersions, which have a stabilizing and regulating influence for the desired formation of the microporous structures in terms of production safety and production speed, those used with a high molecular weight structure 8 to 35% by weight of urethane and optionally urea groups, and 0.5 -.? 2.0 wt .- contain 6 quaternary ammonium nitrogen atoms and as a dispersion or colloidal solutions in water or are present water-dimethylformamide mixtures. 10. The method according to claim 1, 2 and 4-9, characterized in that the solvent-containing polyurethane mixtures, based on solids, composed of 80-99.5 parts by weight of polyurethane elastomers and 0.5 to 20 parts by weight of cationic polyurethane dispersion. 11. The method according to claim 1 to 10, characterized in that the solvent-containing polyurethanes or polyurethane mixtures up to 9% by weight of non-solvent added * Le A 13 028 - 68 - 109850/1756 12. The method according to claim 1 to 11, characterized in that
that one artificially ages the solvent-based polyurethanes or polyurethane mixtures by heating. 13. The method according to claim 1 to 12, characterized in that
that the solvent-containing polyurethanes or polyurethane mixtures are exposed to the treatment with the steam atmosphere on a heated surface. ■ 14. The method according to claim 1 to 13, characterized in that
that one applies the solvent-containing polyurethanes or polyurethane mixtures in a continuous process on a manufacturing scale on a base, through a treatment room with a humidity of at least 50 % at a temperature above 65 C with a residence time of 0.1 to 30 minutes, then in aqueous coagulation baths removed most of the solvent and, if necessary, after squeezing off and after passing through a methanol bath with a residence time of Q, 2 to 30 minutes, dried in heated air. Le A 13 028 - 69 - 109850/1756 Blank page