DE1619277A1 - Impermeable sheet material and process for making same - Google Patents

Description

Impermeable sheet material and method of manufacturing the same

The invention relates to a flexible impermeable sheet material having excellent wear and tear resistance. This material can be used to make clay seals, Packings, diaphragms, shoe soles and other products are used that are flexible, impermeable to liquids and gases and highly wear and abrasion resistant must be »

Filling and sealing material is usually made of special Leather cuts made. To improve these packings and seals, the leather has been coated with compounds such as waxes to reduce its porosity and its

BAD ORfQIMAL

109823/2081

FFD-843

To enable use with higher bruoc differences. Man also has other connections for treating this specialty. leather designed to be wear and tear resistant as well as increasing their tensile strength * reducing their coefficient of friction or the temperature range of their application to expand. One of the main difficulties with these treated leathers is that they are damaged by the treatment agents become stiff »what the production» especially the deformation, to seals and the sealing ability as well as its durability reduced, untreated and treated Leather also has a tendency to swell or shrink Treatment with a wide variety of petroleum products »when used with certain liquids, such as gasoline or alkaline liquids, they disintegrate completely and at high temperatures over 80 to 100 ° 0 and they are unusable.

A planar material has now been found which an excellent combination of flexibility »tensile strength» impermeability »wear and tear resistance» · good volume stability in the presence of most petroleum products and has a good service life as a sealing material at temperatures up to 150 ° 0 »Dieees material consists of j

(A) a microporous plastic carrier with an effective j Permeability value of about 5000 to 25,000, the one with

(B) an essentially linear polymer passes through j is, which consists of organic diisooyanate units 'polyether-'

103823/2081 BADORtG ₁ NAL

. i

a having a molecular weight up to about 10,000 and units of measurement.

r "opacity" herein is the ability to understand the surface material to prevent the passage van liquids and gases, weim this -one at pressure differentials% uindestens 2 _t 8 kg / cm ein® 1.145 ram thick Prote of the material according to the method the ASEM Prüfnoria D 751-60T for B.3 £ itiiniBung the hydrostatic resistance ZIW action are brought. This fixed to wirö cantilevered samples äureingeführt, Imae the ErgebJiisse not give AEA tatsäehliche

of the largest msterial according to the

again, which bsi pressure over 350 kg / cm for HorBtelltmg of waterproofing can be used if there is is supported.

Under "Burelisetsen" - or "Durchdidngen" here is the practieofc-e Fillings of both the surface pores and the inner, in connection with each other on pores or cavities of the microporous plastic carrier used in accordance with the invention

The materials used to produce the impermeable planar material 3 micro-eyelet 3-carrier disposable according to the invention consist of evenly microporous, permeable surfaces adhesive plastic material, and awiir made of a fiber mat, that

- 3 ~
109823/2081

is impregnated with a polymer which is able to form a structure of interconnected micropores see below. This ffii? 4xoporösen Eräger "besitssen eiaen practically gleichiaässigenj microporous cross-section. For the production of sheet-like material undurehlässigen geiaäea of the invention" one makes use of a Sränlcvorgangea MUI, a / 38 Burchdringungsvqrganges. First, a microporous support is? Aseriaatte prepared by Iränken one, and then this is microporous support with a Polirmerieat durc3idrungen> is woduroh the impermeable sheet-like material "forms. Zuu ^r £ '% Imken. And euh penetration" bsw ™ By setting can gleicslie polymer be used?; this is not absolutely necessary.

I am more microporous! 483 manufactured. The erfindimgsgemässe microporous support is voraugsvsia © out of einor by about 30 to 90 ^ their original surface shrunk, bonded Paeeratoffmatte in place _l S * t: 3lle vcridirzten synthetißchen Faßenn, ÖIE with a raikrcporösen polymer which strength at 5 ^ elongation at a tensile stress Voe _f O 55 to 10.5 kg / CSSI comprises, in amounts of about 10 ids 70 wt. ~ # _f based on the total fläcbenhafte material "soaked if? t. Yorssugweise the fiber mat made of PolyatAylentec ^ aphtLelatfasen, and

- 4 -109823/2081

soak SNCA a polymer of organic Uxethanainheiten, Polyalkylenätherglykoleinheiten and Dianinsiriheiten or © is preferably used in mixture of such a polymer with polyvinyl chloride, as described in US Patent No. 3,067,483 * Polyäthylenäthergiykoleiriheiten having molecular weights of about 900 special to 3000 »PoIytstraaaethylenathergXykoisinheiten and Polypropylenätherglyfeoleinheiten Ityiok * are available with this molecular weight range and provide a particularly solid, impermeable, flat material,

Microporous embossing two production of the impermeable sheet-like material according to the invention are described in && xl USA-Pateiitachriften 2,723,935 and 3,067,482. Instead of the bound, non-woven fleeces described in these patents, it is also possible to use interwoven fabrics such as woven or knitted mats or other non-woven fibers.

eel: Penetration of the microporous carrier with effective penetration values of about 10,000 to 15,000 with the retention in the "& i © imdusohläesigsicQn imu. festesten? lägemäsa ä © x ^s invention ♦ Di © given here effec-

Viokörs in "^ oi? ^ AaX of" fe & @! »© aishex? öfeesists Äsgs ^ Qiatioa ¹ * «

"* ⁵ ■ * · BAD ORiGINAL

10S82I / 2081

FKD-843

Volume 45 (April 19, 1950), pages 211-242 a »1.27 mm thick samples in g / h / 100 in.

Microporous carriers with thicknesses from 0.4572 to 7.62 mm are am best suited and easiest to use with the polymers (B) penetrate j but you can also use carriers Use thicknesses outside this range. By penetrating or penetrating with the polymer (B), the The thickness of the support usually does not increase significantly.

Penetrating thick (more than about 3-8 aim thick) microporous supports (A) with polymers (B) for producing the sheet-like material according to the invention are carried out by Use of external pressure to drive the polymer (B) intermittently or continuously into the carrier (A). Typical intermittent processes are the yakuum table process, where the microporous support is on a vacuum table clamped and the solution dea polymer (B) on the carrier is poured while applying a vacuum from below is applied to the carrier; the Eintottiohinethode, in which Layers of the embossing in a solution of the polymer (B) while a vacuum is applied to the whole system will be until .the solution no longer develops} and the Zweottiohraethoteg liei'äer der-porters in an empty vat exposed to a vacuum for about f $ minutes, and then - a solution

10982372081 _BAD

1 & 19277

of the polymer (B) through a tube from a second vat ** is introduced for thick milling cutters, calibration is also possible operate a continuous process in which the Duroh

with squeeze rollers into the inner pores of the ! Prägers is driven here ",

E carriers (tron less than 3.8 µm thick) can be dtafölisat dtafölisat after the fee-operated Yakuumjnethoden or after a continuous IXdiwn T & xichme- blioae. Durclitoingimg becomes this continual κ metfcode by repeatedly adding one

e-approved after-treatment of 6 minutes at 82 ° C and 6 Mträitesi "is 115 to 127 ° C between the individual passages Terljessert «The penetration of the microporous IrSger im Simae of the invention can also be achieved by using longer immersion '" Ride instead of external means for driving in the polymer solution. carried out into the inner pores or cavities wsreeaj for most modern plants, wad procedures However, aieeo belly sides are au for economic reasons

"Essentially linear ¹¹ bind here polymers with ho- * Iekülstr? i] rtix2? en to understand, which have a length, but in relation to this length no substantial thickness (no crosslinking or ^ side chains). An essential rope of the constituents or Units of this essentially 11-

near polymer is bifunctional.

Typical, essentially linear polymers for the production of impermeable sheet-like material according to the invention can be produced by reacting a polyether glycol with a molar excess of an organic diisocyanate to form a prepolymer of polyether glycol units and organic diisooyanate units and then blocking the terminal xsooyanate groups of this prepolymer with a volatile ketoxime a stable prepolymer is obtained. This stable prepolymer is mixed with a chain-lengthening diamine (which provides the diamine units of the polymer (B)), and the mixture is used to penetrate the microporous embossing (A). Then the carrier permeated by the polymer is heated in order to evaporate the ketoxime and to allow the chain extension reaction to take place * so that an essentially linear polymer is formed, which consists of organic diisocyanate units, polyether glycol units and diamine units.

The polyether glycols which can be used for the preparation of the prepolymers for the polymers (B) include polyalkylene ether glycols of the general formula ΗΟ (ΕΟ) _η Η, in which R is an alkylene reet and η is a sufficiently large whole number «

- 8 109823/2081

BATH

so that the polyalkylene ether glycol has a molecular weight of at least 750. The alkylene radicals (R) in a single polyalkylene ether glycol can all have the same anis number of carbon atoms, or the polyalkylene ether glycol can contain mixed (RO) groups, in which the radicals R have different chain lengths, such as the compound HOCCH ₂ OC ₂ E ₄ O) _n H, Polyalkylenilether-thloäthtrglykole and Polyalkylenäther-arylenätherglykole (for the particular examples in the work "Polyurethanes" by Sanders and Jrisoh, Verlag Wiley & Sone, Hew York, 1962, are given) can likewise for the Polyätherglykoleinneiten of the PoXymtriaats (B. ) be used"

Special, EUR manufacturing the Vorpolyraerieate suitable iolyalkylenätherglykole are Pölyätßyienätnerglykoi, Polypropyleaätherglykol, Polytetraraethyleaä1 h _"rglykol? Polyhesfiiaethylene ether glycol, Polyuctarosthylenätherglykol, Polynonaffletnylenätherglykol, Polydecamethylenätherglykoi, Polydodeeajoethylenätherglykol and mixtures dorse1Den. Polyalkylene ether glycol® with molecular weights of up to about 10,000 can be used to produce the polymers (B). Bolyelfylene ether glycols with molecular weight of about 1000 to 3000 deliver Polymerisat® (B) from aueg @ g @ iclmeter f "Btigk @ ifc and Biegea" - no, are easy to obtain & ^ let it be done - <andrors are therefore 'bcnugt * ~ '

.BADOFBQINAL

Polyether glycols with lower molecular weights can be added to these polyether glycols with higher molecular weights in order to obtain prepolymers which are suitable for the production of polymers (S) according to the invention whose polymer chain contains both polyether units of lower molecular weight and polyether units of higher molecular weight the lower molecular weight polyether glycol units to the higher molecular weight polyether glycol units in these blends can range from about 0.5 to 3 depending on the physical properties desired in the impermeable sheet material. (A higher proportion of polyether glycol units of low molecular weight reduces the flexibility of the impermeable sheet material). Suitable low molecular weight glycols can have molecular weights up to about 750. They include ethylene glycol, propanediol (1 * 2) _r propanediol »(1,3), butanediol (t» 2}, butanediol (1 _? 3), butanediol (1,4), pentanediol (1 , 5) "Beoandiol- (1 _K 10)" Oyclohexanedimethanol- (1 * 1)? Öyclohexen "(3) -dimethanol- (1,1), diethylene glycol ^ uropropylene glycol, 2-kydro36yetho3Eypropenol -» (1) _t

etc.

For the Miaocyanateinliöiten in ßim the production of the Poly-Ktrieat * (B) used »YorpQlyjaeria & ten 1mm . di # Uaae-fesung with aroJER-feiaoiisii-, aliph * tiBCii «n or oyoloalipiiÄtiBohaiß Ui-

.BATH

Isocyanates or mixtures thereof are carried out. Typical suitable diisocyanates are toluene-2 _> 4-diisocyanate, toluylene-2,6-diisocyanate, m-phenylene diisocyanate, biphenylene-4,4'-diisocyanate, mathylenebie- (4-plieayli8OOyanate), 4 -Chlorophenylene-1,3-diisocyanate, Hapbthylen-1,5-diisocyanate, T · tjramethyl8n-1 _f 4-diiBOoyanat, Eexaisetliylen-1,6-dÜBOoyaaat, decamethylene-f, 10-aiisocyanat, CyoIohea ^ len-i ^ - dÜBOcyanat, Methylen-bie * (4-c * ycloiie3 ^ iieooyanat) laid Tetrahydronaphthylendii eocyanat, Aromatic Diisooyanat ", ie Uiisooyanat" with at least one EessonanB-containing cbocyolieohen

Ring, are more reactive imd be deehiab

In the preparation of the prepolymer for the polymers (B) according to the SrfiMimg about the use of organic diisocyanate in molar oil content. Polymers (B), which eioh aw ¥ "ß © a irert ^^ eitim lasien" are obtained with a molar ratio "en voti Biieocyaaat" u & ly & ol of about 1.2! 1 Ms 5 s 1 · Valuable polymers (B) can also be used with molar ratios of Siisocyanat au Qiykol tifeea? 5 ί 1 are divided up. Di "Uaeetsung Bwiechen de · fflykol and DÜBocyanat is performed indoB the Beitiusdttil · are mixed and dae Gsaiach optionally heated to 70 ble 12O ⁰ C, accelerate the ubbe &solution" α. Are optionally also possible catalysts are EUgesetzt _not like egg "in the United States Patent 2,929,800 ^ to accelerate Beaktion described. >

to "te. ζ a? /« i V

FFD-343

Baa acting as a blocking agent ketoxime must be present in the prepolymer in a slight molar excess, usually of about 5 #, over the terminal isocyanate groups, so that the prepolymer is stable. Molar excesses of ketoxime of more than 5 ft may indeed applied w ^f erd © n, however, provide any additional Torteil. The concentration of terminal isocyanate groups in the reaction can be determined by using a known overshoe on a secondary amine, which reacts quickly with the free isocyanate groups in the solution, whereupon the unreacted secondary amine is reacted with hydrochloric acid. To the completeness of the reaction between the diisocyanate. and the polyether glycol and to prevent waste of material, loan usually uses prepolymers with a concentration of free isocyanate groups between 2 and 10? S. The blocking reaction is carried out by simply mixing the ketoxime with the prepolymer at room temperature or above room temperature.

Ketcsiae with molecular weights up to about 200 are used as blocking agents best suited for the prepolymers from which the polymers (B) are produced. Ketoxime The lowest molecular weights are preferred because they are more volatile and therefore used in the chain extension reaction escape better customary, suitable according to the invention

BATH ORIGINAL

FJ? D ~ 843

Nets Kstoxime are acetone oxime, methyl ethyl ketone oxime, methyl isolnutylkötonoxira, cyclohexanone oxime, acetophenone oxime, benzo- UBW.

Su dan aur chain extension of the duroh dae ketone oxime blocked Vorpolymeriaate sur preparation of the polymers (B) of the invention gsffiäas suitable diamines include aromatigche or aliphatisohe primary Diaiaine such as m-Phenylendianin, 4,4'-methylenedianiline, 2,4-Soluylendiamin _t Hydrajsin, Äthylendian In, 1,3-propanediamine, 1,4-butanediainine, 1,5-pentanaiainine, 1 ₅ 6'HsxandiaiDin, etc. Aroraatieohe diamines, especially the more reactive aromatic diamines such as m-phenylenediamine and 4 ₅ 4'-Msi; hyXendianilin, are preferred because they provide the best surface material. As used herein, the term "aromatic" refers to diamines having at least one resonance on an earboyclic ring. The oil ratio of diamine. to diisocyanate in the polymer (B) is about 1 *

Sheet-like material according to the invention, in which about 70 up to 150% by weight of polymer (B) on the microporous carrier (A) omitted, show the best combination of non-permanent Strength, flexibility and wear resistance. The percentage by weight of the polymer (B) in the ratio to the amount of the microporous carrier (A) can with dt »fläohenhaft Material was measured according to the invention the time of immersion of the support (A) in the bath

1O9823 ¹ / Vo81. bad owqwal

PFD-843

The polymer solution (B) ₉ by measuring the percentage of the pesticide content of the solution of the polymer (B), that is, passing through the solution (B). etc. t * 4? il »rt be. For the continuous thermosetting of the microporous »» forlgsr according to the invention with the polymer, you can use an ¹¹ oil system, over sewing the rope without changing the length of the fauob vessel *

In general, the time of immersion can be aÜoiöporöeen Carrier (A) into the solution of the polymer »(B) for production of the impermeable sheet-like material of the invention depending on the thickness of the support, the desired degree of penetration and the viacoaity of the permeability τοη vary between less than 30 seconds and more than every 30 minutes The best efficiency of the penetration receives aan nit solutions with fuel contents τοη about 20 to 70

The hydrostatic resistance and the tensile strength of the sheet-like material according to the invention can be increased by the density of the material at pressures of 17-5 kg / cm in lengths of about 10 to 30 minutes at temperatures of about 177 ° C. The hydrostatic resistance and tensile strength of the planar material can also be determined using the AJ3TM test standard D 751-60T. The Berntfeatigkelt is determined according to this method as the force: it _P of a self-supporting Jcreisförnige sample from the surface-related material with a

109823/2011

Area of 6.45 cm can withstand »without au fail. This value is a measure of the tensile strength, which is of particular importance for sealing material * The hydrostatic Pressure (a rabbit for impermeability) is after determined by this method as the water pressure that is on

a circular sample of 6.45 µm in area for action. can be brought without water penetrating through the material. The values of the burst strengths and the hydrostatic Resistance for 3.175 mm thick products according to of the invention can provide up to 52.7 and 28 kg / cm, respectively the material for 10 minutes at 165 ° C under a pressure of

2.

1.76 kg / cm has been compacted. If the two-dimensional material used according to the invention with mechanical support becomes, as is usually the case with sealing, more mechanical Parts of the pail is, holds © s hytiteaulleoh · Drüeko of more than 350 kg / cm without a hydraulic leakage or failure of the structure occurs.

The impermeable sheet material according to the invention can become laminates under the action of heat and pressure of exceptionally good wear resistance will. Such laminates are suitable for the production of shoe soles, surfaces that are exposed to wear and tear and certain seals and packings where good wear resistance is important and a certain amount of leakage

- 15 -

BATH

109823/2081

FPD-843

As a result of the stiffness bow! β a corresponding reduction in the ability of the Sohiohtetoffes to be sealed can be accepted. The laminate production is based on these Flat material usually takes place at temperatures From about 135 to 177 ° 0 and printing from about V76 to 17 »6 kg / cm. These pressures and temperatures are usually around 3 paused for 30 minutes, whereupon the Sohiohtetoff, beror it is removed from the Presee «cooled to below about 82 ° C will.

The spatial stability and chemical resistance of the sheet-like material according to the invention when immersed in petroleum products or other chemicals is considerably higher than that of the materials currently used for seals. The percentage change in volume of the sheet material according to the invention is on average less than 10 i * after 168 hours of immersion in an automatic transfer fluid, in an unalloyed engine oil and in a heavily alloyed engine oil at 100 ° C. Typical changes in volume of the sheet material in accordance with the invention in other fluids the following are about 6 to 7 1 · after 168 hours in ASTM oil ITr. 1 at 100 ° Oj 13 to 16 + after 168 hours in ASTM oil Ir. 3 at 100 ° 0; 1.0 to 1.5 t after 168 hours in 20% salic acid at room temperature) 11 to 14.1 i » after 168 hours in Benein at room temperature and 14 to 19 ^, after 168 hours in turpentine at room temperature,

- 16 -109823/2011

_BATH

The sealing capacity of the sheet-like material according to the invention is determined by deforming the material on oil shells, which in an oil shell test stand a periodic oil pressure of 211 kg / cm with a frequency of 86 periods per minute at an average surface speed of 3 m / min , are exposed »At the beginning, the surface of the carbon steel running surface of the test stand has a 0.457 to 0.559 μ (BMS) thick layer« ASiH-Öl Hr. 2. The test is started with a break-in period in which the oil pressure is slowly increased to 70 kg / cm ² . At this pressure, 1000 partial periods are carried out. Then the oil pressure is set to 211; kg / cm and the test continued, but an occasional re-digging check is carried out until the leakage flow of the oil past the cup is 50 l / h. achieved. During the periodic re-sealing checks (about every 50,000 psi), the system is stopped, the pressure is released for 1 hour, and the pots to be examined are then checked for their ability to seal when the initial pressure is slowly restored.

3lsohalen, those from the sheet-like material according to the Erung are shaped, last over 16 times more tea periods a commercially available polyurethane treated one

- 17 109823/2081

BATH

PFD-843

leather and show less than 1/5 after 1,000,000 test periods the wear and tear of a commercially available polysulfide treated leather. You static and kinetic friction τοη Seals which are made from the material according to the invention have favorable values in comparison with commercially available seals.

Flat material according to the invention, in which the amount of polymer (B) is 70% by weight of the microporous carrier (A), can be compressed to less than 50 Jt of its free volume, which means that there is a great deal of variability in the production of Gasket and packing parts enable · {"The treated leathers currently used for gaskets generally cannot be compressed by more than 30% 1.-9») »

In the following examples eich refer to rope · »if not · otherwise stated, aaengen on weight »

example 1 Bin fiber fleece is made from Polyäthyleriterephthalatfasesn from

, 25 den and 3.8 oa length made, dl «10 curls on j · 25.4 mm "by opening the fibers in a roller card and removing them from a suspension in air" and a loose, f-2,? mm thick fleece with a? läohengewloht from 4-4-0.8 to

- 18 -

109823/2011 bad original

FFD-843

508.6 g / n are deposited «Sas loose fleece is placed on a Thickness from about 12j7 to 19 now compacted and with two Hadelstühlen to a uniform, dense, felt-like structure needled.

The first needle hole has an average needle density of 20.2 needles each 6.45 cm and works with 140 to 150 diameters

perforations per back · With the first needle loom, the

ρ total number of needle sticks per 6.45 cm 816, and that on The fiber fleece produced in this needle loom has a bead of 14 am and a density of 0.034 g / car *, the sweit © needle chair

has a mean pin count of 9.53 needles each. 6.45 om and work with 350 loops per minute »The fleece runs three times through iea sw @ it © m tfadeletuhl _s where © s mainly

2 total 1396 diameter, © otea§ © s 3 © 6 ^ 45 es © sfeilto Hern ¥ liee Enmuehr has a thickness of 1ö ii tuaä @ ia @ SiQkts ¥ © a © ₉ 045 g / eas ₀

The shrinkage of the? Li®ses is achieved "- iadem dE @ tliee is led through two successive baths, of which the first is 64 to 65 ° C and the second is 71 to 72 ° G, whereby the total area of the fleece shrinks by about 67 to 71 pounds. The immersion tent in each bath is 3 minutes. The meant included water is removed from the fleece by leading the fleece over a vacuum box, whereupon the drying of the fleece in a heated to 143 ° C

- 19 109823/2081

PPD-843

ten Palmer dryer is completed. The fleece obtained in this way is about 5 to 6.3 mm thick and has a thickness of about 0.17 to 0.23 g / cm ³ (the weight is 1187 g / m ² *).

An impregnating agent for producing a microporous carrier from this fleece is produced by mixing 334-3 parts of polytetramethylene ether glycol with a molecular weight of 1000 with 291 parts of toluene-2,4-diisocyanate and heating the mixture to 90 ° C. for 3 hours. 2483 parts of the hydroxyl-terminated dinate obtained in this way are mixed with 570 ropes of methylene bis (4-phenyl isocyanate), and the mixture is heated to 80 ° C. for 1 hour. This produces a torpolymer with terminal isocyanate groups. This torpolymer is dissolved in 10,000 parts of Ν, Ν-diaethylformamide and the solution is slowly added to a solution of 50 parts of hydraainhydrate and 0.5 part of dibutylamine in 1710 parts of Ν, Η-diaethylformamide. Finally diesee Heaktionsgenisch 40 is heated Hinuten to 80 ° C, wherein a polymer solution is formed with a Yiscosität of 115 poise and a Feetetoffgehalt 20 i ".

10.85 parts of this polymer solution are bit 1.80 parts of a copolymer of vinyl chloride and vinyl acetate, 0.65 parts of a misoh polymer modified by hydroxyl groups from vinyl chloride and vinyl acetate, 1.20 parts

- 20 - 109823/2081

, hydrated silica, as it is commonly used tn ier Kxmatkau-tackukinduatrie, do feoprene-: ratr; sehu] s: land Jfitril & autschuk to give strength * and 74.-7 ropes E, II ~ DiBi9thyXformaaaia. mixed. 10.83 parts einee ieMsches aua 70 parts JT _f IT "DiiBethylforBjainid and 30 parts of U & .Bf.isr be su this mixture eye with a fine Bispsrsion from Polymerisatieilcivan arises · Dispersion A & föält drip t _f * 14.5 56 solids has at innd 24 ° 0 a Brookfield of about 15 to 20 poise »

Has fleece produced according to the above specification is made with this polymer dispersion is soaked by pouring it into the ; 56 ° 0 heated dispersion is immersed to saturation The saturated fleece is passed over a doctor blade to remove the remove excess solution from the bottom.

Then a microporous carrier is made from this saturated fleece by letting the fleece float on a 24 to 27 ° C water bath and letting it sink into the water bath Vacuum of 13 to 33 mm Hg bit more water leached out to wash out all N, H-bioel ^ ylforznamid, and then by moving around "in"? Row of sachs dried on drums with the lowest oil temperature. Bas flexible _f microporous fläohenhafte material which forms this rivet, besltsst a tfläohengewieht of 2374 g / m ^2.

- 21 109823/1081

PFD-843

The polymer in the microporous material has at 5 ^ iger Elongation means a tensile stress of about 0.35 to 10.5 kg / am.

Flat material with thicknesses of 1.145 aa is used, 1.905 mm and 3 »175 mm are produced by splitting the material obtained by the above process with the leather splitting machine will.

The prepolymer for the polymer (B) is divided by reacting 1000 parts of polytetramethylene ether glycol with an average molecular weight of 1C00 with 348 parts of 2,48-toluene-2,4-isocyanate over a period of 1 to 4 hours, bia the Sehalt fell to 6.3 isocyanate groups errolohb fi determined by reaction with dibutylamine and Zurüoktitrieren with hydrochloric acid.

100 parts of this prepolymer are 13.7 parts Methyl ethyl ketone oxime reacted su a blocked prepolymer, which in the form of a clear Flüeelgktit old of a viscosity at 50 ° 0 of 10 000 oP.

4 * 3 parts of this blocked prepolymer are mixed with 43 »3 parts of methyl ethyl ketone, whereupon 1.7 parts of a 50% solution of 4,4'-methylenedianiline in ethyl ethyl ketone are stirred into this solution, keeping the solution under vacuum is used to expel air and dissolved las ©. With aie-

109823/2061

FFD-843

A container is filled with the solution and becomes a microporous carrier with the three thicknesses given above are separately by this vessel was carried down at such speeds, that the residence times are 30 seconds, 55 seconds and 110 seconds, respectively. After they have escaped from the solution container run the carrier between doctor blades to remove the excess Remove the polymer solution, after which it is passed through a vertical oven in which there are three successive hot zones with temperatures of 82 ° O, 127 ° C. 149 ° C. They run through every zone in this furnace Porter about 6 minutes hindu. ! laughed at the exit from the third zone, the planar ifeterial is cooled and ssu Rolls wound up. The approximate weight gain on this one

Penetrating the microporous Trtjer with the three different, is angegebenen'Blaken above 70 $ ₉ 73% and '75 # · From this planar material l> ei 1 ₉ 76 kg / oa and 150 ° C in the course of 10 Mixmtesi shaped T-Baeknagen have good flexibility and non-permeability.

example 2

The sheet-like material produced according to Example 1 is again passed through the penetration solution from the blocked prepolymer and polyhydric polymerized according to Example 1. The burst strength and the hydroetatic resistance and dea öc preserved impermeable planar material

- 23 -109823 / 2D81

Vi

teriäls are according to the ASTM test standard D 751-60T with the following Results determined:

Microporous backing thickness, mm 1.143 1.905 3.175

Weight per unit area of the microporous! Embossing, g / m2 430.6 746.0. 1425.7

3 areal weight of the impermeable sheet-like material, g / m2 986.7 1546.2 2370

Burst strength, kg / cm ² 19.69 22.85 38.67

Hydrostatic resistance, kg / cm ² 2.81 3.16 4 »57

After a deformation pressure of 1.76 kg / cm ^{2 at} 163 ° C for 10 minutes, the impermeable, flat material has the following properties:

Thickness of the beam, mm

before compaction after compaction

Burst strength *! kg / cm

Hydrostatic resistance *, kg / cm ²

* Determined in accordance with ASTM test standard D 751-60T.

1.143 1.905 3.175 0.813 1.575 2.838 1.1 25.3 52.7 2.3 16.2 28.1

- 24 -

BATH OFKGINAL

109823/2081

EE & -843

Piesa's shaped sheet material shows a linear shrinkage wagon 4 # and after 72 hours of aging at 149 ° 0 the Shore Α hardness increases from about 85 to 95t. The aged samples do not jump if they are exposed to a temperature for 4 hours be bent from «54 ° Ö flaoh.

B a ia ρ ie I 3

Eas densely compacted, impermeable, sheetlike material according to example 2 is again passed through the burglar penetration exercise O.oB blocked gate polynieriaats and the oven according to example 1, which is accessible from several zones. This results in a total weight reduction of the original fflikrosoxtfjsen charges of 130 jS, 115 $ or 135? 4 for the (Eräger xait idoksn of 1.143 mm, 1.905 mm or »3» 175

For Yaz purposes, a sheet-like material is produced by producing a needled, sumped, but not impregnated fiber fleece according to Example 1 and processing it directly into a non-woven material simply by soaking it with the solution of the bare polymerizate described in Example 1 instead sunäohst cut out the microporous carrier and then use the polymerisable buh g liu öurohdringen. Bar hydrostatic Wideretand these "impermeable material immediately fläohenhaften prepared is uai about 20 fi under the resistance hydroetatieohen

'»25 - SAD

10982372081

stood the impermeable sheet-like material produced according to the invention according to this example, although the directly produced material contains over 9 $> more polymer than the total amount of impregnating agent and penetrant corresponds to the impermeable sheet-like material according to the invention. This sheet-like material produced immediately is also less elastic and is more difficult to deform into a sealing material with a smooth surface than the impermeable sheet-like material produced according to Examples 1 to 3 «

Tests of coating shells made from the flat material As in this example, it was molded under a pressure of 1.76 kg / om in the course of 10 minutes at 165.degree are, in the oil pan test rig after 1 000 000 Periods (= 35j66 km conveying distance) with an oil pressure of 211 kg / cm (AS'J? M-Ö1 Hr. 2) and room temperature without failure of the material canceled. Here the oil pans are in the Test stand with a 0.127 mm interferenasita in a bowl diameter of 69.85 mm.

Bin commercially available, treated with polyurethane leather fails in the same Teat after 55 000 cycles (average).

- 26 -

BAD ORiCIlNAL

109823/2081

FFD-843

At i BPl el 4

Three layers of impermeable, sheet-like material, which is made from the microporous carrier as described in Example 1, by penetration with 110 wt , which is produced from the 1.145 mm thick microporous carrier according to example 1 by penetrating it »it 125 Öew.-flS polymer solution similar to Example 1, based on the carrier, are in the course of 15 minutes under a pressure of 7 kg / om ² at 163 ° C to a thickness of 4 "compacted 445 mm" After cooling under pressure, the laminate is removed from the press.

In Srag exams with shoes where the soles «and the Heels are cut from this laminate, compared with shoes. whose soles and heels are made of good leather, the soles and heels made from the laminate produced according to the present example last three times longer than the soles and heels made of leather.

Kaoh the same process, but made from two layers of dee 3.175 mn thick microporous backing with 115 weight- £ des Impregnating agent is soaked according to Example 1, and swei Layers of the 1.9 mm thick microporous carrier according to the two

BATH

- 27 -109823/2081

FJKD-84-3

game 1, which with 110 wt .- ^ of the polymer according to Example 1 is soaked, 6.35 mm thick laminates are produced, by including 20 minutes? feg / cm and 120 ° 0 compressed These laminates are also suitable for the manufacture of shoe soles.

- 28 "

109823/2081

Claims (1)

$ 196 1st Indurable, fluid material _s dedu £ ofe net that it consists of (A) @ ln @ m microporous »K \ ffist @ t @ f £ lazy £ with an effective oosohläeeigkeiteiievtr would be 25,000" b © @ t © 1at _? d @ i? (B) τοπ eisen lsi w@inahmatlihabenl.®a PoljiBes'isat öns © te © @ t © t igt, w @ XeM @ i ®ii © © sgiaig @ k @ a 9Ü @ ® «cyaaat @ inli @ it © 2i ₉ Poly larg © wi © ht fei® @fe? a 10 © C äsi I% lv © gIiSl ^ aä © voa lilK VÖü 0iÄ © ä ^ © a sä S0I9® g sharp ^ s © st lim a® © im © ^ m§B ^r § @ BM \ m§ "bot I ^ om mm oiaos ⁵ ®s © © ig it © twa IQ Mq 7 © 60 ^ 0 * = ^? tes @@ dsa amf äea §Q0QB ^ i ^ mMk% φο SsG, = BATH FFD-843 3. Flat material according to claim 2, characterized in that that the fibers consist of polyalkylene terephthalate. 4 · Planar material according to claim 3 »characterized in that that the microporous plastic carrier has a permeability value of about 10,000 to 15,000. 5. Fläehenhaft © s material according to claim 4 »characterized in that that the polymer with which the microporous! Polyalkylene ether glycol units and siamine units osting polymer and polyvinyl chloride is 6 * Eläcshenfeaftee liatesial aach Anepruoli 3 t- characterized by j äs @@ which have Bolyätfeesglykol @ inlieii * © a in the microporous s (Aj i3öl © lo.CLi »g © w £ -eMi © -WQm. ®im & 900 to 3000 « 7. fiieiisn! Sf'ö @ © Ife-feesiel üseli Äs®pi? Ii6lL C ₉ marked thereby- n & t * t Sas © äi © löl ^ tli &s'glyiEol ^ lislieitssi in iea » microporous is (Xt) l ^ lfiiQtgSKeiii ^ eiiS -Eia ^ jiglj ^ lciylteiten odsr Poly- 8th". flifcfeiiAis £ i; Q £ ifeissoial & fse? i Anepauss :. 7 _e iMf 10S823 / 2081 BAD ORiGlHAL c Pliiohenhaftea material sack according to claim 8, characterized y that the polyethylene glycol units dee polymers (B) Are polyalkylene ether glycol units, 10. Flat material according to claim 9 »thereby known without, that the polyalkylene ether glycol units of the polymer (B) Polytetramethylene ether glycol units or polypropylene ether glycol units are· 11. Flacheiibaftes material according to claim 10, characterized in that that the diisoeyanate units of the polymer (B) aroiaatisohe Diitsoayänatelriheiten are. 12 '.'iläohoniiaftes material according to claim 11, characterized gekenneeich-CGT ₁ that the ManiB INAE @ @ th of the polymer (B) Aromatis siad before Maraineinheiten " 13 ° i ⁷ läclieiilia.ftes material according to claim 12, characterized in that the molar ratio of the diisocyanate units to the polyether glycol units in the polymer (B) is in the range, tone 1j2: 1 to 3 s 1, 14. Flat material according to claim 13 «characterized, that the weight ratio of the polymer (B) to the nikx'Oporösen carrier (A) is about 0.7 to 1.5. - 31 - 109823/2081 15. Flat material according to claim 1, characterized in that that the microporous support has an effective permeability value from about 10,000 to 15,000. 1o. Planar material according to claim 1, characterized in that that the Polyätherglykoleiruieiten in the polymer (B) have a molecular weight of about 1030 to 3000. 17 «Flat material according to claim 1, characterized in that that the biisocyanate units and the diamine units in the polymer (B) are aromatic units. 18. Surface adhesive material according to claim 1, characterized in that the molar ratio of the Dilsooyanateinheitan to the polyether glycol units in the polymer (B) is in the range from 1.2 i 1 to 3: 1. 19 * sheet-like material according to claim 1, characterized in that that the weight ratio of the poly (B) to dea microporous! rager (A) is in the range from 0.7 to 1.5. 20. Laminate, characterized in that it consists of at least two layers of the fluffy material according to claim 1 consists. - 32 r 109823/2081 21. A process for the production of flat material according to claim 1, characterized in that a polyether glycol with a molar excess of an organic diisocyanate is reacted with a torpolymer of polyether glycol units and organic diisocyanate units, by blocking the terminal isocyanate groups of the torpolymer with a ketoxime, a stable prepolymer manufactures the latter. mixed with the Kettenterlängerung effecting this mixture diamine _t sum penetration of a microporous plastic Slower used and the erhitat durchseteten with AEM Torpolymerisat microporous support .zwecks evaporation of Ketozias from the Torpolymerisat and course of the chain extension reaction. BATH 109823/2081