DE1470918A1 - Process for the production of microporous, flat structures - Google Patents

Description

Patent attorney 1 A 7 Π 9 1 ft DR.-ING. WALTER ABITZ Monks May 16, 1961

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EI DU PONT DE NEMOURS AND COMPANY 10th and Market Streets, Wilmington 98, Delaware, V.St.A.

Process for the production of microporous, flat-like structures

The invention relates to new, water-permeable, surface · adhesive structures made of polymeric material and their production, in particular polymer foils and films, in the form of linerless Laenbrunartiger films or in the form of coatings that adhesively connected to fiber substrates, which is a very verbose combination of properties, including Have durability, flexibility and microporosity. Preferred embodiments of the invention; are on the making an exchange material for leather of the upper parts of the eyelet and reference bL «. Upholstery purposes used / ended type directed » '.

The technology that makes products such as uppers, upholstery and upholstery materials, and clothing from genuine leather has long been trying to overcome certain problems associated with leather. Like most product "natural origin, the leather properties change from post to post and ütück to ütück ₀ Ausaerdem is the

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Oröeee the available ütüoke on the size of the animals limited what the buildings deliver «Die ^ rseu £ uo great perturbation problems often at night on the lake Ueiss an expensive chopping and fitting together potnendig. The usefulness of large utilities often means that Presence of imperfections and hang-ups, such as softening, spots, flesh and scars.

There are many unsuccessful * attempts. nt emonsen "order, create a synthetic leather or a leopard hoodie, with the limitations of the natural product over » sore and trotsäet * a similar permanence, a similar look and a similar conformity in the oebrauoh is obtained. To previous Ycrouohen to produce such an Itatsrial belong methods in which overriding polya.ercr masses applied to porous fiber layers; the coatings through needles in a Hadslotuhl, duroh dissolving in the coating, contained lüslichor feilohen, duroh Drying and shrinking contained in the coating, duroh Solvent by swollen particles or by activation a swelling agent contained in the coating porous ge ^ • get night. In many cases they were the suggested ones Methods for the tea "little use too slow or su complicated,

Some of the well-known leather exchanges have one

bad quality, especially those for that

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unarmed eyes "payable loher included, d. H. are "makroporue". The fabric with additional flexibility tend to have a lower level of abrasion and abrasion, in particular Type of abrasion that gives oiota at the corners and edges (in Beieplel 1 explained in more detail) and ala "ItanteoTeTeohleiea" can be rewarded. Those substances "the ta de" for 0ohuhoboiteile necessary degrees weaaerdanpfdurehlftasl £ elnd, ceigen a tenders,? aaaer selbot at kursseltigea Wear at naeaea tfaaeer su etark to record.

The invention provides flexible «waeetrdaapfdtirohlle ige, sheet-like fabrics made of polymeric material sttr Xerfttgtfng «you maoht a new and improved * Lederauetaueohaaterlal has the aikroporuee AueeenfULohe bat * · one has microporous coating, which is not only permeable and flexible, but rather averaoweiäend and abrasion-resistant solder · More tortelle and tweoltengabea the Ir « Findings result from the following specification.

These utoffees are grounded by making oikroporttaer pilae and ObereUge from the essential WäeeerunlOuliohen pol * · fabrics through the formation of a film or cover a solution of the polymeric substance in a solvent, - not let the liquid used in the following bathing treatment be oilable, bathing the files or cover in an inert liquid, in particular water,

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with removal of solvent and coagulation of the Polymerisates and hardening and / or drying of the product obtained recovered, especially the invention

(1) αϊ β polymer lit off a copolymer which contains carboxyl groups in the polymer chain, preferably a Copolymer of two or more monomers, of which at least one each a ionomcres of a conjugated diene Bit 4 to 8 carbon atoms and a monomeric one Is a carboxylic acid that contains a polymerizable, ethylene-unsaturated component, in particular .ein monomer, which is simply ethylene unsaturated, and

(2) a solution of the polymeric substance which is an oxide of a polyvalent metal, possibly also containing sulfur »,

is used"

The copolymer is preferably a chewy terpolymer of a butadiene-1 ^ carbon hydrogen, of an acrylonitrile and one that is copolymerizable therewith Acrylic compound such as acrylic acid or a homologue or a product of the same substituted in o-position is used.

When the layer is coagulated by bathing in an inert liquid, such as water, it turns into a gelatinous one Polymer layer transferred, which has a cell structure of interconnected micropores

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preferably essentially all of the organic Solvent removed from the cell layer by further bath treatment with an inert liquid. In some cases the polymer is partially hardened in the cell layer after further bathing with an inert liquid and thereby the cell structure of the layer sweeping collapse stabilized.

After further discharge, the polymer solution, in particular terpolymer solution, also other polymers are etched and / or the polymer solution is pre-treated brought the üchichtbilduni * biu to the hand of gel formation, by gradually becoming essentially ule maximal A lot of water or another inert liquid is mixed that can be added without actually leading to oiling.

Bine essential component of the preferred Polyaerisatlösunc is a rubber artigee Terpolyir.erisat a · butadiene-l, 3-l'-ohlerivyaGserstoffe _t a AcryleäurenitrilB and in o-stellL-nc simply äthylenungeoättigten Oarboneäure such as methacrylic acid, acrylic acid or the like, or in α-position substituted product of the same. A Terpolynerisat of about 40 to 80 wt. ^£ / i butadiene, acrylonitrile and 10 to 50 Gew.vi 2 bie 25 wt. '/ 5 üethacrylsäure v / ill be particularly preferred. Suitable kautechukartice Terpolynerieate and their · production eied

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in the USA patents 2,395,017 and 2,724,707 describe a preferred process for their preparation lot in an essay by H. F. Brown and CJ. Gibis, "Carboxylic jälaotoirere", in Rubber Chemistry and Technology, 28, U. 937 (1955).

Typical butadiene l _t 3 kohlenvfauseratoffe fl'r the llerutellunc such Terpol..nerlsate are ßutadien-1,3 (usually easy genunnt butadiene) and Hoaologe thereof with 5 bi ~ carbon atoms, isoprene v.ie "2, i-Dioethylbutadien- 1.3 »Pentanediene-1,3t Hexnndiene-1,3 and Gecieche the same.

The acrylonitrile is allgeoeinen the preferred acrylonitrile for Terpolynerisat but auc ^v methacrylonitrile, Athacrylnitril, α-butyl acrylonitrile, a-Phen _v lacrylnitril, a-Chl> RACR ^_tf: lnitril, A üethoxnethylacrylnitril unl de are the same

The third essential ingredient in the manufacture of the Terpolycerisatee »ought to be an acrylic compound, the for polymerization with the other two components and incorporation of carboxyl groups into the terpolymerioate is felt. Organic acrylic compounds include the Acrylic acid and you · Hoaologen uni in a-litolltn>; Substituted products of the same, more valuable of them, or the in a-iitellunc simply ethylsnarti_ and esUttic lioecarbonic acids der alleeceinen Forael dig "C-C- OH, in which HH, Cl,

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C ₂ Hc and let. Han works as a precautionary measure with methacrylic acid, acrylic acid or geoisols of the same. The presence of carboxyl groups in the terpolymer enables it to be partially hardened in the presence of Jeseer.

One smells old ο en polymer a cenlieende L'enge de · Oxydes of surplus value eat l'etallu so that it may be widespread in the Vaeeerbadbehandlunc; v.-ird that the Sellutruk'ur dee Movies or over it is sustained · Usually about 5 to 10 parts of the oxide and 100 parts of the oxide range Polymers «from. Zinc oxide is preferred, but & an Jtann also with CaleiuD ", Magneeiua, dibutyltin, lead", barium, Cobalt, tin or utrontium oxide work

In order to achieve maximum moisture resistance and abrasion resistance of the product, a hardener for olefin alumina tones known from the past, presulfur-free sulfur, is usually added to the terpolymer. You set one cenUtjende amount of this auxiliary hardenera su to harden the partially hardened terpolymeric acid during the removal the inert liquid and exposure to hardening temperatures to drive in a TroekenwürmejBone su end.

The Hürter can with dec polymer on a customary KautdebttkaU Ie, a hißeher of the type Banbury or ao-

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their herkömclic! cn chewable knuckles are venaisoht You can ban the hardener from a solution of the polymer Other known types of kit can also be used Additives for rubber, such as pigments, fillers, stabilizers, plasticizers and antioxidants, mixed which is preferably done before the hardener is added

The hardener-containing polyamide is sufficient "'!! close orgcniochen solvent dissolved to make a solution the viscosity of which is suitable for the method to be used for the application of tiuf dao üubotrat. The solvent should, preferably completely »be miscible with the water or the other inert liquid» which is used in bath treatment. Ν, Ν-DiDetnylformanid is a preferred solvent · Other suitable solvents include dimethyloulfoxide, tetrahydrofuran, tetramethylurea, Η, Η-dimethylaoctamide, H-ethyl-2-pyrrolidone and γ-butyrolactone. Deletions of this too Solvent with various liquids that can be mixed with old water, such as B. Ketones, which are only bad solvents for the terpolymer, can be used. A mixture of blue ethyl formamide and methyl ethyl ketone is particularly valuable.

In the polymer solution from which the microporous products are formed according to the invention, one or several other polymers than dai> The main polymer described above is present. That

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The purpose is often obtained from a polymer solution which also contains a vinyl chloride polymer and / or a polyurethane atom. The abrasion resistance of the products tends to reach its maximum when the products contain a vinyl chloride polymer, ie either polyvinyl chloride or a copolymer which has a larger proportion, preferably at least 80, v, vinyl chloride and a minor proportion of another ethylene-like unsaturated monomer , s · B «vinyl acetate, vinylidene chloride or diethyloaleate, contains ·

Particularly valuable polyurethane atoms for the polymer solution are obtained by chain extension of the reaction product of a polyalkylene ether and an organic diisocyanate with a compound which contains two active - »water atoms bonded to amino nitrogen atoms. When one of these elastomers is present, the resistance of the products to damage from repeated bending has the best value. To produce these elastomers, a prepolymer (or "capped" dimer) can first be formed by mixing the glycol with the diisocyanate and heating to about 50 to 120 ° C. until a prepolymer has formed, the terminal -NCO groups having. On the other hand, Ltan can react the diisocyanate with a molar excess of the glycols and "cap" the product by reacting with further diisocyanate.

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Glycols usually have a molecular weight of etY / a 300 to 5000 and preferably 400 bio 3000. B. Polyäthyleniither ;; lycol, polypropylene ether glycol, polytotraethylene ether glycol, polyhexane ethylene ether ^ l ^ .col, polyoctacethylene ether glycol, polynonamethyl ether glycol, polydecane ethylene ether glycol and mixtures thereof. Po ^ glycols, which contain several different residues in the molecular chain, such as z. B. the compound HO (CHpOC ₂ H ^ O) H, where η is an integer greater than alu 1, can also be used.

Aromatic, aliphatic and cycloaliphatic diisocyanates or mixtures thereof can be used to form the prepolymers. Such diisocyanates oind z. B. Toluylene-2,6- and toluylene-2,4-dÜ6Ocyanat, m-phenyl diisocyanate, diphenylene-4,4'-diisocyanate, methylene-bie- (4-phenyl-isocyanate), 4-chloro-1,3-phenylene -diisocyanate, Naphthalene-l ^ -diisocyanate, tetranethylene-l, 4- <iiisocyanate, Hexamethylene-lfS-diisocyanate, decamethylene-ljlO-diisocyanate, Cyclohexylene-l ^ -diisocyanate, methylene-bis- (4-cyclohexylene isocyanate) and tetrahydronaphthalene diisocyanate; Arylene diisocyanates, d. H. Isocyanates, in which the isocyanate groups are attached and attached to the aromatic ring are preferred. I3ie generally react faster than alkylene diisocyanates.

Dao prepolymer is chain-lengthened with at least one compound that contains two active hydrogen atoms on anino-stick Contains £ toffatone gebunaen, z. B. hydrazine, substituted

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Hydrazines and diamines, including both primary ones as well as secondary diamines. Examples of such chain-extending compounds are hydrazine, monosubstituted hydrazines, dinethylpiperazine, 4-ifethyl-ni-phenylenediamine, m-phenylenedianine, 4,4'-diaminodiphenylmethane or mixtures the same. Hydrazine is a preferred chain extender.

The "capped" prepolymer, which has terminal isocyanate groups (-NCO) and is the reaction product of a glycol and an isocyanate, contains urethane bridges (-OCONH-). If this "capped" prepolyester with hydrazine or a dianine, the two active 'hydrogen atoms on Λ; Inostickotoffatucien contains, chain-lengthened, a polymer is obtained that has urea bridges (-HNOONH-), sometimes referred to as polyuratoff. The chain-lengthened polymers are also labeled as ale -Polyurethane, i.e. a ± e represent chain-lengthened polyurethanes.

The Kettenverlängcrungen v / usually earthed at a temperature below 120 ⁰ C and often, especially at hydrazinverlunrerten polymers in etv / a room temperature. The chain extensions can be carried out without solvents in a high-performance collector or in homogeneous solutions. If the implementation takes place in solution,

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One can conveniently use one of the organic solvents as the solvent Use solvents that help in the formation of the microporous Coatings are used. The chain lengthener described above; usually provides an essentially linear polymer with a molecular weight of about 5000 to 300,000.

™ Except for the above-described polyether urethanes, too Polyether urethanes suitable, d. H. the products of the implementation of a polyester, e.g. B. neopentyl glycol adipate, with a organic diisocyanate and hydrazine or a diamine of above Art.

The weight ratio of the vinyl chloride polymer to the rubber-like mixed polymer in the polymer solution (and in the product) can be as high as about 50:50 in the production of exchangeable lumber, and in other cases even greater. The weight ratio of polyurethane elastomers to chewable terpolymer can be as high as about 99: 1. The polymer solution, various "in the überzugetec ^l" nik common Zusutzstoffe as V.'eichraacher, viecositätümodifizjxer, Füllatoffe and league duck, are added.

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According to a preferred embodiment, the polymer is »

solution brought to the brink of gelling before m & n apply it to a substrate. For this purpose, water is gradually mixed with the solution, preferably the inaxinule or almost maximum amount of water or an equivalent inert liquid which can be added without gelling. The inert liquid is z. B. in a narrow area that is 0.1 to 2D> J below the length required for "gelation" of the solution, ie for coa ulation and thereby converting the same into a gelatinous | dough or gelatinous sols. In other words, "on hands of gelling" refers to the point in which water or another inert liquid is gradually added to the polymer solution, at which point the solution contains 0.1 to about 20> less water or other inert liquid than sit · Is necessary for the solution to gel. This ^ rbeitsv / else is particularly advantageous if the Zollntruktur the product ao fine and gleichmäs: ig to Vin as possible. It is also recommended if the changes that occur in the layer in the subsequent harvesting stage of the bath treatment are to be carried out as quickly as possible.

The amount of inert liquid needed to make a The given approach to bring polymer solution to the verge of gelling can be predetermined by measuring the amount of breath of inert liquid which is necessary for gelling small sample of the approach is required and about 80 to 99.9 $ dea received .. selects as a basis for the to calculate the appropriate amount of liquid to be added to the batch. jjajj ORlQfMAl. 909832/1343

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Before the ..water or the other inert liquid of the poly merisate solution is added, it is preferably mixed with a substantial proportion, e.g. B. about the 2 to 5faohen weight of an organic solvent of the type such as it is used in the production of the polymer clay The addition of the inert liquid to the solution should close up and with stirring to prevent local coagulation.

w'aseer is usually preferred as an inert liquid, but there are also other liquids suitable for this Main polymer ioat solver and with desj organic Solvent in which it is dissolved are miscible, e.g. B. ethylene glycol, glycerine, GIykolmonoäthylather, Oxyäthylncetat and alcohols which are miscible with .'aaaer, such as tert-butyl alcohol.

Unexpectedly, polymer solutions can be produced, "that is enough called Hauptpolymerieat contain, better with an inert FlUeoigkcit to the hand of gelling than solutions, in which do not contain int, in particular main polymer-free solutions of a vinyl chloride polymer tea and / or a Polyurethane elastomers · The latter solutions have been used for the production of microporous films by adding '..aoee

Q and coagulation similar to the I. method described above as

oo proved suitable, but it is difficult to cn such solutions

to bring the edge of the gelation "without the occasional

^ Solution gelled prematurely. Ba which the Hauptpolymerisat entw holding solutions in Besag the Kcnge inert liquid, which is required to bring m ei · on the fa "id CUS &eLi'erens*""

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set lower requirements, the risk is smaller, that the desired end point is exceeded and the solution is gelled as a result. When the amount of inert liquid, dl « is added, less than about 90 to 95 / * that for gelation of the required amount of solution, the tendency is to one subsequent occurrence of the cells alo in the case of the above-mentioned polymer-free polymerizate · » löaunjcn.

A layer of polymer solution that what from the applied Depending on the method, it can be on the verge of gelling ^, but is not required, is applied to a surface using any coating or application method. Suitable application methods are, for example, knife coating, extrusion, dipping, .Valzcn and brushes.

Leather substitutes and other reinforced microporous Flat composite products are obtained by clicking on one or both sides of a flexible porous fiber substrate, z. B. a nonwoven fabric, a sheet or fabric deposited from an aqueous slurry or the like, a · Applying layer of polymer solution. The fiber of the substrate can be a natural or artificial, straight or crimped, organic or inorganic staple or endless fiber or the fiber used in paper manufacture Have lance. When bathing, drying and hardening after the procedure According to the invention, the solution does not go into a nikropo-

rose polymer layer over, the bit dec fiber substrate su one

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Unity is united.

An unsupported, flexible microporous film can be obtained "by placing the layer of the solution on a removable sheet Base, preferably a smooth, impermeable base, such as polished glass, rust-free steel, aluminum foil, Plastic film or a faeeroubotrut coated with a release agent, applies and then carries out the necessary bathing, drying, hardening and scraping work.

The polymer solution layer supported by an underlay v. is preferably bathed in water or a mixture of ae & er and another liquid which, in relation to the main polymer i; inen is non-solvent and with v / aseer and the organic solvent in which the polymer g 1 dissolves is, like ethylene glycol, glycerin and the like, is miscible. The solution layer is preferably immediately in water immersed and soaked. The bath treatment can, however, also be done Indian, spraying or spraying on the layer Steam of the bath fluid act läant or these and others known bathing methods combined. Under "bath treatment" is here /, to understand dasa ruan Y / asoer or an equivalent inert Liquid, in liquid or Daripfform, with the Polyraerisatuehicht getting together

With regard to the processes in the applied to the pad to one layer, the bath treatment can be viewed as a three-stage

^ den: In the first stage, coagulation takes place, which is carried out by the ^ Formation of a cell structure from interrelated oteher

% d ^f

is accompanied by the uricropores in the entire layer.

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In the second stage, looseness is removed. In the third layer, the terpolymer is partially cured, with the resulting stabilization of the cell structure. In the first stage, coagulation usually takes about 1/2 to 1. Min. Essentially complete. The coagulated, gelatinous layer has a microporous cell structure over its entire thickness and is already sufficiently tough to withstand considerable forces during handling. Mun can e.g. B. when producing a linerless microporous film, strip the coagulated layer from the removable backing at this point. The process can also be used to produce a microporous film of unlimited length.

In the second stage of the bath treatment, the removal of solvents, the gelatinous cellular polymer is removed. atschioht bathed long enough with enough water to remove all or practically all of the organic solvent from it. If substantial solvent concentrations are left in the layer, they can lead to a substantial or complete loss of porosity by collapsing the cell structure in the following stages.

The water coil used in the first two stages of the bath treatment is around room temperature, preferably around 10 to 22 ° C. The third stage of bath treatment, the partial cure is carried out, on the other hand most effectively with water heiseen · For example, when using water of about 80 to 100 ⁰ C, the parti elle curing in a few minutes completely, while the

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Hardness times with water from about 18 to 22 ⁰ C in typical

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V / ei se etv / a 10 ble 20 hours.

Eu is assumed that the partial curing of the main polymer there is also one in the solvent-washed cellulose Interaction between the carboxyl groups of the main polymer and the mixed oxide yields the polyvalent Ifetallo. Partial hardening takes place more quickly in the presence of '.'aaser. Surprisingly, the reaction is not unique to the microporous cell; structure harmless, but it stabilizes it even to such an extent that it is retained after drying and oven curing.

A satisfactory Teilhärtungograd is present if the subject of the Badbehandlun £ layer can withstand curing stages the drying and Oi-en · without determined under a Kikros · LAD or in a ftasaerdacipfdurchlässigkeiteprüfung, a being coincident ¹ Licher part of the cell structure. Partial hardening can be controlled by forming a sample, drying and hardening and any excessive collapse of cells that may occur by using hotterera ./aaser during partial hardening or by longer partial hardening and / or by increasing the proportion of oleic oxide in the Polyraerisatmaese corrected.

Then the partially hardened layer is dried, preferably in a warm zone with air circulation.

- ** The dried, partially hardened. Foil, as received, works for some purposes, but the best durability

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is usually obtained in that the polymer changes, preferably fully cures. This can be done by heating in an oven or another zone to the hardening temperature up to the reaction of the polymer with Aera in it existing I.tetalloxyd and / or sulfur (or other auxiliary hardener) takes place

The process of the invention and the products obtained v / have important advantages that are readily understood by those skilled in the art of manufacturing microporous films, leatherette replacements, and leather products. The process is useful for the rapid and economical manufacture of unlimited quantities and sizes of microporous sheet-like products suitable.

The strapless, microporous Polymcrisutfollen that comes with the Ver uhren are not only durable, flexible and waterproof, but also from overheads and hangings essentially f.ei. As the product is free from lactopores structure of interconnected ilicropores (pores that not easily visible to the naked eye) due to its substantial thickness, it is strong for vapors

and relatively little permeable to liquids · It CD

* y? can thus "breathe", but is still water-repellent · ^ Typical for the products for which aich diu linerless film

> *. suitable are filter media, raincoats, battery separators, ^w ./ roll sleeves and special glove types. to

If these new microporous films during or after

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their formation combined with fiber substrates to form a unit are leather-like surfaces can _t: be ebilde get that s for many purposes over previous leather substitute as well as the genuine leather significant advantages have "Z * B" is a shoe upper leather Austauachstoff achieved, the appearance, durability and confort of the leather with your absence the wide periodic price fluctuations and fluctuations in the properties that are characteristic of genuine leather. In addition, the availability of the product in infinite form and any desired Width with an essentially identical and defect-free quality of the product for purposes such as cover material, items of luggage, table and valance covers, pressure rollers and sports jackets a clear advantage over leather.

The new microporous films and coated substrates can the softness of a chamois or suede or the hardness the stiffest, most abrasion-resistant leathers are as good as eggs Type and amount of the modifying polymer and others Additives depends.

The following examples serve to further explain the Invention. Lengon specifications are, unless otherwise specified, based on weight.

Example 1 The following mixture is made on a two-roller rubber grinder

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made ι

Parts

Rubber-like terpolymer 100.0 (obtained by polymerizing 69 parts of butadiene, 26.5 parts of acrylonitrile and 4.5 parts of methacrylic acid)

Zinc oxide 5.0

sulfur 0.5

Accelerator CTetramethyl-1.5

thiuramldfisulfid)

Antioxidant 2.0

(2,2-diethylcn-bis- (4-ynethyl-

6-tert-butylphenol)

109.0

By mixing a liquid solution of this mixture in dimethylformamide and a solution of polyvinyl chloride in dimethylformamide, a polyamide solution is formed which contains the terpolymer and the polyvinyl chloride in a weight ratio of 65 s 35.

Then, with stirring, 21 parts of a solution of 20% Si / ajeer and 80% dimethylformamide are added slowly to 100 parts of the polymer solution. The solution is brought to the edge of the gellerene by adding about the maximum amount of water that can be added to the solution without actually gelling it.

Most of the trapped bubbles are removed from the polymeric acid solution by the action of negative pressure in a Vukuuakamaer. Depending on the large particles that may be present, such as gelled polymer particles, are obtained from the

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Solution filtered off through coarse tree gauze

A layer of a porous fiber substrate (non-woven fabric impregnated with a polyurethane elastomer:!, As in Example 1 of the USA patent coated to a Naasdicke of about 1.7 am, what in a zone of 21 ⁰ C and 20? » relative humidity takes place.

The applied layer of solution is coagulated, but the coated material with the coated side down can vibrate for 30 seconds on water at 16 ° C and then for 30 seconds. completely into the van.; it dips to remove most of the dinethylformaraide. The resulting, bath-treated, gelatinous polynuclear layer has a structure of interconnected, microporous cells .

The terpolymer in the gelatinous layer is partially hardened, without damaging the cell structure, by applying the coated material for 20 Hin. in './as β he dives from 80 to 90 ° C. The coated material is then immersed in water at 16 ^° C. for 1 hour

dipped to a substantially complete removal co
ο of the dimethylforaamides to ensure.

^ The coated material, the coating of which is solvent-free c *> and a cell structure stabilized against collapse, has dried ** Vitra in a heat zone of 100 ^{° C.} Hin by 30 · • heating the coated material in an oven at 15O ° C

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the curing of the terpolymer atea in the coating ends felt.

Dae product, a porous fiber substrate with which a hardened, tough and flexible, microporous polymer coating of about 0.3 am thick is connected to form a unit, has a .. 'asse. vapor permeability value of over 10,000 (after examination by Kanagy and Vickero, described in Journal of the Leather Chemists Association, 45, pp. 211-242, April 19, 1950, determined).

The product is suitable as a leather substitute for shoe tops, covers or upholstery corners, handbags, uakkos, Caps, hats and bearings.

Particularly important properties of the product in terms of its marketability as ο shoe upper material are (a) his Comfort, such as flexibility, "consistency" on the fiber substrate side in contact with the foot, breathability and ability for water repulsion when worn in the rain, (b) his appearance and its surface properties, including the lack of macro pores on the {, esanten thickness of the coating include what surface treatments such as roughening, buffing, polishing, coloring and embossing, allowed without the risk of exposing unsightly holes, and (c) its durability, including resistance to tearing, repeated Bending and abrasion.

The type of abrasion known as "edge wear resistance"

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Abrasion resistance is very important in shoe uppers, and a convenient method of measuring this property is to pluck an edge of a sample obtained by splitting under a load of 4.54 kg with 50 reciprocating strokes (the ho ₁ ift each Movement is about 15 cm) per minute on a rough construction (canvas) No. 10, failure in a given number of cycles is expressed in considerable abrasion and a noticeable roughening of the folded edge. When the coated area of the product in this example is tested for this level, a value of more than 2,000 is obtained Cellular Dlaetoraeruassen, say well below 2,000, usually even below 1,000.

If Example 1 is repeated with the modification that there is no coagulated coating instead of 20 Hin. 2 here Jtunden immersed in water of 80 to 9O ⁰ C in water of 16 ⁰ C, a unporöset · and therefore do not obtain breathable product. The 2-hour immersion in cold water does not stabilize the cell structure of the coating against collapse during the subsequent heating stages.

At-BPiel 2

A leather substitute with similar ISi _v s economy and s

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Similar digestibility as in Example 1 is indicated by ', / repetition des Beiepielü I hergectelltι with the following modification The terpolymer in the coagulate coating is instead immersing the cover in hot water for 20 hours Materials partially hardened in V / aucer of 16 ° C. By the 20-hour immersion in cold ..water becomes the terpolymer partially hardened to the degree of :: ur! stabilization the cell structure of the coating against collapse the following heating levels is necessary.

Bet game 3

üs v / ird a Ι ^, 'Λζν Löcuno of the ground Terpolyrnej described in Example 1. Isati mixture produced. With this solution, one side of a cotton web is coated which, at 152 1/2 cm wide, has a weight per unit area of 215 gA *. The solution layer (Na8:> about 3/4 mm thick) is coagulated, bathed, partially hardened, dried and hardened as in Example 1.

The product, a porous fabric substrate covered with a flexible, but tough, microporous elastomeric coating to form a unit connected, has a water vapor permeability of more than 10,000. üo is suitable as a leather replacement material in general and especially as a remedy and reference "* or Padding material *

Example 4 For the production of a 20 ^ iJeH solution of a polyurethane adhesive

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do

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U70918 U

mers are first 3343 parts of polytetramethylene ether glycol (molecular weight about 1000) mixed with 291 parts of toluene-2,4-diioocyanate and the mixture 3 ütd. heated to 90 ⁰ C. 248 parts of the resulting dimer containing hydroxyl end groups are mixed with 570 parts of ethylene bis (4-phenyl isocyanate). The mixture is heated for 1 hr. At 80 ⁰ C to give an isocyanate-terminated Vorpolymerisit obtained. The prepolymer is dissolved in 10,000 parts of dimethylformamide and the resulting solution is slowly added to a solution of 50 parts of hydrazine hydrate and 0.5 part of dibutylanine in 1,710 parts of dimethylformamide.

By mixing this 20 # Lgen solution of the chain-extended Polyurethane with the 25% solution of the ground terpolymer mixture and the loose solution of the polyvinyl chloride β According to Example 1, a polymer solution is prepared «the Terpolymer, polyvinyl chloride and polyurethane la weight ratio of 35:30; 35 contains.

Bann are slowly added to 19 parts of a solution while stirring out of 20? » Water and 80 # .dimethylformamide to 100 parts of the Polymer solution added, making this dee to the edge Vulture is brought.

By repeating example 1 but using the

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FFD-693

Polymeric acid solution prepared above, a leather exchange material with similar properties and similar usability as the product of Example 1 is made «

The product obtained has an even better strength under repeated bending stress than the product according to Example 1

Example 5

From the mixed Iolymerieatlösung ^ ernäse Example 1 becomes A carrierless »membranformi« e, microporous film is produced, which can be used as a battery separator or filter material suitable. One pours this on one side of a polished one Stainless steel sheets apply a layer of the solution (wet thickness about 3/4 mm). You layer will, as in example 1, coagulated, bath treated, partially cured, dried and cured, whereupon the cured, microporous film is removed from the Sheet area decreases. The film is simply lifted or pulled off for this purpose.

In a modification of the above procedure, the partially cured film is removed from the steel base and then dried and hardened.

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Claims (1)

FFD-693 Claims ο Process for the production of microporous films and coatings, in particular in the form of a water-vapor-permeable one Leather substitute3, made up of essentially water-insoluble polymeric substances, with the formation of a film or a coating from a solution of the polymeric substance in one L Solvent miscible with an inert liquid » Bathing the film or the coating in an inert liquid and thereby removing the solvent and coagulation of the polymer and curing and / or drying the obtained products, characterized in that (1) as a polymeric substance a copolymer containing carboxyl groups in the polymer chain, and (2) a solution of polymeric substance that is an oxide of a contains polyvalent metal, is used" 2ο Method according to claim 1, characterized in that water is used as the inert liquid. 3. Method according to claim 1 or 2, characterized in that daee a copolymer of two or more monomers, of at least one of which contains a conjugated diene with 4 to 8 carbon atoms and one of which contains a carboxylic acid, a polymerizable, ethylene-unsaturated portion, in particular a mono-ethylene-unsaturated monomer, is, «Earth. -28-9098 3 2/1343 BATH ORIGINAL U70918 PFD-695 4 · The method according to claim 3 »characterized in that as a copolymer, a terpolymer of a 1,3-butadiene hydrocarbon, an acrylonitrile and acrylic acid or homologues or products thereof substituted in α-3 division as an acrylic compound which can be copolymerized therewith, is used. 5 « Method according to claim 4», characterized in that a Terpolymer of about 40 to 80 Gew.jG butadiene, 10 to 50% by weight of acrylonitrile and 2 to 25% by weight of methacrylic baw. Acrylic acid is used., ? "■>■> A method according to any one of claims 1 to 5, characterized gekenni; i HNET, \ ass in dsr Pol ^ ii-risatlösung additionally _t Viny 1-CO ^ ridpolymeris .- 'irt ·> 5 \ ν. .? λ 3lyurt th .n3lastoaere, especially ± \ a Msnge ^up;. · $ 100 beiiogrn the Mischpolyaerieat, be translated * '; verden. 7 * Method according to one of claims 1 to 6, characterized in that the layer coagulates by bathing » by further bathing the organic solvent, in particular, it is essentially completely removed from the splint and the mixed polyacrylate is partially cured by further bathing treatment - 29 - 909832/1343 ORIGINAL BATHROOM H70918 FFD-693 8 · The method according to any one of claims 1 to 7 »characterized in that, prior to application to a base, the polymer solution is essentially used to raise the pole mixed with an inert liquid that can be added without actual gel formation, the inert liquid represents a non-solvent for the copolymer and is miscible with the organic solvent, and thereby brings to the edge of gel formation. 9 · The method according to any one of claims 1 to 8, characterized in that in the Folytserisatlösung additionally sulfur is used » 10. The method according to claim 3, characterized in that the Inert liquid l * i the partial hardening of the copolymer with a \ voaent: .i: .h temperature above room temperature is used. 11. The method according to claim 9 or 10, characterized in that the partially hardened layer is heated until the copolymer has completely hardened. 12. The method according to any one of claims 1 to It, characterized in that the copolymer solution is based on a flexible, porous, in particular flat, fiber base is applied and the resulting layer is connected to it to form a unit. " ³⁰ " 909832/1343 . . BADORKäfe " H70918 PPD-693 3 / 13 «Method according to one of Claims 1 to 11, characterized in that the mixed polymer solution is reduced to a smooth Applied surface having impermeable material and then removed the film formed on this will· 14 »Flexible, water vapor permeable, flat material, characterized by a microporous polymer film, that of a cured, chewable terpolymer of a butadiene-1,3-kohlenwaeeerstoffe, an acrylonitrile and an aoryl compound that is miso-polymerizable with it, namely acrylic acid or homologues or α-substituted Products of the same, is formed and on their whole Sink a structure of interconnected micropores having. 15ο Product according to claim 14, characterized in that « the terpolymer is a terpolymer clay about 40 to 80 OvW) Butadiene, 10 to 50% by weight of acrylonitrile and 2 to 25% by weight of C. Is methacrylic or acrylic acid. 16. Product according to claim 14, characterized in that the polymer film also contains a polyurethane elastomer. * 31 - 909832/1343 BAD _{; f:} U70918 FFD-693 17. Product naoh claim 14 »gekennselohnet by Aase dl · polymeric film also contains a Vinylchloridpolymerieat. 1Θ. A product according to claim 17, characterized gekennselohnet, the polymer film daββ a Kantenvereohleisefestigkeit ron min destene 2000 »beetimiat Reibbeanepruohung by a folded edge of the material under 4" 54 kg load at ■ 50 cycles / min, to dry Baunwolldruok Mr. 10, comprising · 19 · Product according to claim 14 »characterized in that the polymer film is connected to a flexible, porous, flähenhaft fiber material to form a unit . 20. The product of claim 19, gekennselohnet in that the fiber material is a nonwoven fabric 1st · ο Product according to claim 19 »is worthwhile in that the · fiber material is a fabric · 22. Product according to claim 19, characterized in that ·· has a water vapor permeability of more than 10,000 and the microporous polymer film is essentially free of macropores over its entire thickness » - 32 - 909832 / 13A3