DE1619249B - - Google Patents

Description

'' alI is. With natural) leather comes in the washable no stiff adhesive substance between the fibers or. Instead, the fibers are by means of a relative soft resilient fat absorption, which separates the - keeps fibers away from each other, but not their - »restricted moveable wedge within the leather body prevented. In this way, the fibers retain their flexibility, so the natural product is flexible. Since the fibers are able to move in the fat-like matrix, they can move on by themselves respond to an applied voltage, the tension being distributed over some fibers.

Porosity is a particularly important property of natural leather with a view to the manufacture of shoe uppers. The natural one The product is breathable because practically half of its volume is taken up by air which is distributed in extremely fine pores between the fibers so that there are no large gaps or there are empty spaces. These pure pores are for a low bulk density and good thermal Isolation responsible. They allow water vapor to pass through the Leather and, because they are so small, offer permeability of liquid water has considerable resistance.

Fine of the most outstanding properties of natural leather is its ability to apply to be deformable by pressure and to maintain the shaped shape. This is particularly important the use for the production of shoe uppers has a large RoIL. As far as artificial leather for production from Schuhotv! share 'was used, this shows the Disadvantage that the suiuhe uncomfortable when wearing because the synthetic leather does not exactly match the shape of the foot adapts. But if the shoe has adapted to the foot after being worn for a long time, take it the shoes return to their original shape after wearing them.

It is an object of the present invention to provide new flexible sheet materials as well in processes for making the same.

From the German Auslegesclirift 1 150 898 is a Process for the production of a synthetic fiber leather containing polyurethane as a binder and having leather-like finishes Properties known, in which a loose fleece is impregnated with a solution, which a crosslinkable polyurethane and a blowing agent enihäh. The product is then solidified under pressure at an elevated temperature, and / was at a temperature that even before the decomposition of the propellant mill, the polyurethane has such a high strength that see can form small stable / rushes during gas formation. The product thus obtained can then with be stranded with a finish. Since this post-1 the finish hardly in i'a. I aserkim leather penetrates, it has a finish with a finish Product a layered slrukliir.

Iu of the LSΛ. Patent specification 2,832 <) ') 7 is a two-component system made of a latex with it distributed fibers described, wherein the latex forms a porous substance after gelling. An artificial leather based on impregnated fibrous substrates is Belgian patent 660 733 refer to. There it is an essentially laminar product. The French additional patent specification 84,412 to patent 1,316,434 describes a laminar product in which two layers of one Support :; connected to each other by leveling will. Finally, the Japanese interpretative document applies 3560/66 a breathable, fibrous film material, in which a three component system is used. The product described there is made by laying on a foam sheet Needled fiber fleece and then the surface of the needled fiber fleece with the solution of a impregnated with synthetic, fiber-forming polymers.

ίο After coagulation of the fa ^ like binder you then get an artificial leather, in which the fiber fleece and the plastic film medium! = of the coagulated, fiber-forming material are interconnected. This product is built laminar.

The invention relates to a breathable, flexible, fiber-like film material based on Polyurethane foam, thread material and elastomeric binder, which is characterized in that the film material has a non-layered structure made up of the three-component combination

a) 10 to 60 "/ _{0 of} a pliable polyurethane foam,

b) 5 to 55 "J ₀ fibers of time other cross-ineir. in the foam over the entire cross-section through a network, wherein the fibers to a limited movement in the location are distributed, and

c) 25 to 75 "/" of a soft, resilient elastomer, welciies the empty spaces between the

_ ₀ fibers and the foam essentially, however

not completely filled out and which may contain interconnected micropores,

consists, the percentages being based on the total weight of the three-component combination.
The new materials according to the invention are breathable composite structures which consist of an interlocking network of lasers and a foam, with a soft, resilient, elastomeric filler material being distributed through the network. we'.j! however, it does not completely fill the empty spaces / wipe the fibers and the foam. The structure of the materials is similar to that of natural leather insofar as they are not laminates, but structures consisting of one piece in which the fiber content is vcrtcill across the entire cross-section. As with natural bait, the fibers are embedded in a soft, resilient body made of a cellular product and in a filler, so that the movement of the lasers is not completely restricted, but rather can be freely moved in a restricted manner when stressed able to move.

Da> eiTiiiilimgsgcmaKe. atinmigable. flexible. Γ). ") Faserariigc I olienniaterial can thereby be produced ν earth that one

(!) cm Fascrvlie 'with a density \.>! i about 102 to 8IiM! 111- on a lohe made of a flexible PoK iirclhaiv-chamn with a thickness of about OK to 38 min and a density of ctv.a 13 bib 97 kg / m ^a .

(2) a plurality of the fibers into the polyurethane foam by needling with a F.indringdichte of about 77-230 penetrations cm one rubs ² wherein at least 50 ⁿ / _n of the invading fibers in a film thickness of at least about 75 _^0/0, and at least 10 " / “The fibers penetrate completely into the film.

1 6) 9 249

(3) the product thus produced by NKlein still has pores closed by the closed pores, with open pores on the other side with 31 to 233 penetrations / pores being preferred. The term "open ² needles and the name of the first layer of pores" is to be understood as meaning that fibers at least incompletely penetrated into the film are about 53 ^: "the pores are connected to each other in the film through N. uleln drives back, after which 5 stand and free of porciHrcnnonde :! The membranes of the fuser-foam combination are not made. O-pary cellular polyurethanes can be made from about 10 to 83 percent by weight fibers with about 23 to 93 percent by weight foam using suitable foaming tools. Furthermore, the pores of a foam can be based on the total weight, with closed pores being opened chemically, mechanically few fiber ends out of the film - ionically or explosively,
protrude, a for the practical presentation of the

(4) the fiber-foam film combination obtained is particularly preferred in the invention a temperature between about 110 urethane foam is a polyurethane foam in which and 190 ° C, but below the flow temperature, a thermoplastic vinylidene chloride polymer dider Fibers or polyurethane foam, granulated, which is at least about 25% by weight, percent contains chlorine, the total chlorine content

(5) the resulting compressed fiber-foam film of the foam plus the polymer at least in combination with a solution of a soft, approximately 10 ^IJ / "and the softening temperature of approximately resilient elastomeric filler in a solution is 153 ° C. The foams are impregnated with solvents and the filler is removed from an organic polyisocyanate with a compound that contains active hydrogen atoms, either by evaporation of the solvent, or as a cellular product with micropores connected to it, such as a polisher or a polyciiv.inder precipitates out by ester, in the presence of a Gau-generating agent, one treats the impregnated fiber-foam roll-like water, and the chlorine enthalination with a liquid, which with 25 border polymer, which essentially with the solvent for the elastomer Filler urethane-forming components of the mixture is miscible, in which, however, the elastomer is incompatible, produced. The amount of the added chlorine-containing polymer should not dissolve significantly, and should also be added

(6) the fiber-foam sheet combination with the sufficient that the mass ultimately obtained has little in it deposited elastomers at <about 18 to 30 percent by weight of chlorine, based on the 123'C under increased pressure permanently contained. Total weight of the mass. Formed from simplicity or smooth the surface. these foams are hereinafter referred to as

The foam used is called foams containing polyurethane halogen. A bcson-

■ cliauni, since this is available in a simple manner, the advantage of these foams is that the

■ divides, is easy to work with and is tough and has 35 fiber-hemostatic combinations in which it is

is resistant to abrasion. hold an essentially permanent fit

A small amount of polyurethane is one which, under less severe pressure conditions, has an elongation at break of greater than that of; with other fiber-foam combinations at least about 10.VV ₀ and is below the case. The combinations are therefore in the Belaslum ^: ι simply deform la '. !!. Typical 40 wcscitlichei a uniform density and can ichä'ni. ·. which are suitable for practical implementation in the manner described below for winners are those sehä'.im, ·, nanz von in ho'ie: n M i! .Vj satisfactory subjects a ·; Prints; vo 1 about 0.2 to 7.0 kg stratcn iniorag ii; rl will i.

firo 323 c 11 ² be.l.irfe 1. um ein: 25 '/ "iiz; D.irchbieg.ing the ver.ve i.le'.e 1 fibers! Uten s ^; nd such, in

Iu ergo 1. where the M: ssu: rz-: n with a 53, sense 45 welehei the eii'clive.i fibers yiagnd movement

dliekei I .vöc b; i 25 C ίΐ; τΓ. '. ⁽ the ASTM-ICt margin b;, iUei. so d t'.i them in dei:>e'num / 111

iiiet'i i.le 15> I-5) T for a Direhbier.ini unier ei 1- Achieve .in 5 el. ·; <z: .va i; chl'C 1 intruder zr.idcs a

ilriicke 1 l: r load is darchzcuihrt. The gitricbM w.vdei köiici. Not woven malls

tchannifolie has before / .1 z ^ .v; is; a V:. \ zl'cti'zkeit nvt void i'.veis: Io; '<:;' cr K> islruktion werder

! .wipe irvz: drive 0.1 and 2Λ k'z ^; c.rr. ei ve Ts-u; h- 50 be / or / nz ·. They are here in all »: 11 -'a dichk

<le! m: ri'z /'.vi^chei un;. * fäir 103 ui.l 4i).) '' · ■ ',, and a / wisehen 102 un.l S 1 5 lz in ^; . The famous: i laser

Hi!

l) ie! vjvorzMzt-en S: h: iume be.it/e-i further /wis.-'ien ^ '. i: en with a density of ungcfilir 2) 4 bi-

About 10 in. ¹ , 43 / rush 1 per running / enlim; ter 51) g'm ^! . E-. kii.ine-.i two or more on top of each other

\ v \ i \ a density in the Gröl.ie.iorJ, 111 \ vi of about Γι5: 'ele; te MiUe-. use; been.

13 to ') 7 kz'in'. The F.ivermUle can be made from any conventional natural egg

The biezsime / elifi'innize l'olyurethane. welelie-. at or synthetic lasers are produced, for example

<ler practical D.irchfü'iru vi of Erlinduim comparable as au; Cisers from l'olyeslers. Aerylverbint'imuen

If we use! Cellulose prevention

Polyisocyanate with an organic compound 60 gene, wool, silk or the like. The preferred lasers

with at least two isocyanate-reactive hydrogen fibers are organic fibers, with synthetic organic fibers

atoms produced in a manner known per se. Pre-fibers are most preferred. You can

preferably the organic compound has from polyamides, such as polyhexamethylane

at least two reactive hydrogen atoms adipamid (NyIon-6,6) or polycaproamid (nylon-6)

a molecular weight of at least 203.65 polyesters, such as polyethylene tetrachloride

The preferred cellular polyurethanes are or polydimethylcyclohxyltcrcphthalate, acrylic

flexible? cellular polyether or polyester compounds, such as, for example, polyacrylonitrile, vinyl

fhane. You can create a structure of open pore compounds, such as polyvinylchloride.

or polyvinyl alcohol, cellulose compounds. such as rayon or the like, and wool are made. Mixtures of two or more fiber types are particularly suitable, for example mixtures, which contain wool and polyester as well as polyamides and polyester.

The term "fiber" should be understood to mean tow, stacks, endless threads and similar fiber shapes. The fibers can be present as yarns. They can be curled (possibly heat set) or uncrimped . The lasers used generally have a denier between approximately 0.5 and 6 and preferably between 0.5 and 3.

The individual lasers should have a length. which is at least sufficient that they are able to penetrate the cellular polyurethane film to the desired extent under the action of pressure. Fiber lengths of at least about 12 mm are desirable. Fibers in <- \ c \\ customary 2ηextile lengths are generally suitable for the present frame.

Elastomeric binders are soft, resilient, thermoplastic or thermosetting materials, for example polyurethanes or copolymers of butadiene and acrylonitrile. Polyirethane elastomers. from a large number of polyethers or polyesters by reaction with poly-Mmktionelle; ' Isocyanates are especially preferred. They are made using the same basic rules as they are for! Li-sLe '.;,; .-, g \ o; -i PoK uiv.'. I ^ i-.chäimu.i in the same manner as above may be used, but maintaining conditions such that foaming does not occur. These substances represent a known class of polymeric materials that are readily available in the marketplace. Usually they are placed on the market in organic liquids such as dimethylformamide. ,\O

According to the preferred method according to the invention, the new materials are produced in that a fiber mat is placed on a flexible, uncompressed cellular polyurethane foam sheet, whereupon the fibers of the mat are driven into the sheet to obtain a fiber-foam combination in the form of a unit. This fiber-foam combination is then compressed at a temperature and under a pressure which are sufficient for this. that the combination essentially retains its dimensions when compressed. On top of this, the compressed product is impregnated with an elastonized binder, this binder being introduced into the substrate by means of a solution, from which it is either heated or coagulated by adding a miscible liquid in which the elastomer is not soluble to any appreciable extent is. is deposited, whereupon it is compressed again to obtain an essentially permanently veroimten Pro product of the desired dimensions. When using thin foam sheets, for example with a thickness of up to 4.7 mm, the initial compression stage can often be omitted. because the physical process of vibrating the fibers into the foam sheet delivers the desired result.

In this way a three component system is formed in which interlocking networks made of fibers and foam, with a resilient, soft filler distributed in the networks is present. The filler does not completely fill all the empty spaces between the fibers and the Foam off. so that the material is breathable.

Hs can use any suitable method used to propel the fibers through the foam. The preferred method is to drive the fibers into the foam by means of needles by driving a plurality of needles through the fiber pins and then into the cellular polyethanololic, a convenient and quick method, which is a keeps physical damage to the foam to a minimum. Usual needles. such as needling chairs, can use! will. Preferably, relatively thin needles with a number of barbs are used which grip the fibers and drive them through the foam.

/.ur Kr / ielimg the desired overall sirukiur the fibers are preferably mostly from one Side driven into the foam with a penetration density of approximately 77 to 230 quarters per cm. The product produced in this way is then from the other side with an intruder density from 31 to 230 i penetrations per cm- sienadeii.

In order to achieve the desired (ic-amistniktur muli a sufficient intruder is ensured .sciii. The ^ - is generally achieved when at least 5i>"" of the penetrating fibers penetrate into a thickness of at least about 75 " ₀ and at least 10 "Of the fibers completely into the 1 olie emdnr.jen. A product is obtained from which only very few fiber ends protrude from one of the two sides of the four foil drive in both ropes.

The fiber-foam combination that forms a single unit. which is formed by physically driving fibers out of the fiber mole into the cellular- ¹ polyurethane film, is compressed at between 10 and 100 ° C. under a pressure and for such a period of time that a product is obtained which, although not necessarily permanently deformed. shows only a limited tendency to return to its original thickness, and if d ^ is indeed the case, it does so very slowly. Compression devices: such as, for example, platen rollers. Rotary presses. Plate presses or the like. The precisely selected compression parameters depend on the type and properties of the particular cellular polyurethane and the selected fibers and, to a large extent, on the particular one used The temperature used should be sufficient to allow the fiber-foam substrate to compress under the pressure and time conditions used, but the temperature must not be so high that thermal decomposition of one of the components takes place Temperature should be lower than the temperature at which the fiber or polyurethane is exposed to the pressure and time conditions applied

1C9 584 39

1976

begins to flow so that the fibers are not significantly deformed and the pore structure of the polyurethane is not lost. Temperatures that are too low do not allow the desired compression. Excessive temperatures cause the combination to decompose or lose it its fiber or pore properties.

The pressure applied must be sufficient to cause the desired compression of the substrate under the conditions maintained, but it must not be so high that the pore structure of the polyurethane / is destroyed. The creation of compressed fiber-Sehaiim-Itombinations with the desired density. Thickness Κ η ti dem aiu; estrcblen Percentage of compression required may vary depending on the system used. When using bed presses, pressures from 1.0 to 28.1 kg cm ^{2 are} suitable, with pressures from 17.6 to 22.9 kg cm 2 being preferred. The timespan. during which the fiber-eye combination is compressed must be sufficient for this. to achieve the desired degree of compression and the desired physical properties. Compression times of about 30 set hours to 15 minutes are generally satisfactory when using flat presses. Significantly shorter germination times are able to achieve the desired degree of compression. To 'eye compression times result in a loss of the desired structure. If an alternative device is used, the compression time can be varied to achieve equivalent compression conditions. For example, equivalent compression times for a Rotalion press have generally turned out to be somewhat less than the compression times. which are adhered to when using a flat bed press. The product obtained after compression is a flexible, one-piece fiber-foam combination. which contains a large number of voids, the fibers being separate from (the foam. The composition of the l'ascr-foam combination depends on the original thickness and density of the cellular polyurethane film and the thickness and weight of the fiberboard. In Typically, the fiber-foam combination can be laser-cut about 10 to 80 percent by weight and contain about 20 to 90 percent by weight foam based on total weight, and then the one-piece fiber-foam combination is impregnated with the selected elastomeric binder Any impregnation method can be used for this purpose. The substrate can simply be immersed in a solution of the elastomer. Alternatively, the substrate can be passed through a set of pressure rollers in a bath of the elastomer. Furthermore, a vacuum method can be used in which the solution of the elastomer on the substrate by means of a doctor blade or the like Similar device is applied and then sucked into the substrate under vacuum, with an essentially complete intrusion takes place.

The elastomer can be in the substrate by treatment with a liquid containing the liquid carrier for the elastomer is miscible. in which, however, the elastomer does not materially Measures is soluble. for example by treatment with water. this has a precipitation of the elastomer from the solution result. The precipitation can be carried out in a convenient manner by causing the impregnated product to be immersed in water by treating it with Wassci sprayed or exposed to a humid atmosphere. Optionally, the elastomer clurcli

ίο heating the impregnated product, for example by heating it in an oven, to remove the solvent / w may be deposited. The storage temperature used should be high enough to remove the solvent! can be, but it should not be so high that the elastomer begins to be called !. In every 1 all the product is breathable. ie. it \ crmages to let water vapor through. In the washing method, a product is produced because what is more breathable than the product which is retained in the linback method, the filler produced in the product according to the former process itself has a porous structure, composed of one another \ crbonded rows of micropores. The fact that.

the product is breathable regardless of the method used. clearly shows that in the fiber Scliaum-Kombina'.ion empty sites are present and that these sites are not completely in the substrate are filled. Substrates that have been manufactured according to the water washing method have in generally better aesthetic properties, such as handle. Fracture. Adaptability or the like. This method is then preferred to whom such qualities for end-use purposes of the product are important.

The amount of dry elastomer egg added is about 25 to 75 percent by weight. The fiber content of the material can range from approximately 5 to: 55 weight percent fluctuate while the foam

4 "content between approximately 10 and 60 percent by weight where all percentages relate to the total refer to the weight of the material.

In the last stage of the process for the preparation of the new materials according to the invention, wirel dit The fiber-foam combination with the deposited elastomer increases again under such conditions squeezed. that the product is permanently deformed and the surface is smoothed. Under the The term "permanently deformed" should be understood to mean that the product does not return to its original form lumen returns, but essentially there: maintains volume, which it assumes when di < Exposure to heat and pressure ceases.

The processing conditions, which are carried out in the same manner as in the above assembly; describe with the initial compression level! are adhered to are: time: approximately 5 seconds to 3 minutes: temperature: ineffective 18 to 120X: pressure: 3.5 to 12.3 kg / cm ² .

The product produced in this way is similar in structure to natural leather. It has a lot the physical and aesthetic property ^ of natural leather, such as the handle, there Adaptability. Drapability or the like. To improve its appearance, it can be on a or be polished on both sides. For technical use, especially for use as material for shoe tops. becomes the product

1976

generally coated on at least one side with a flexible polymeric coating. This coating is referred to as the base coat, although the product coated with the top coat is suitable for is suitable for many purposes without further coatings. It serves as the basis for further coatings, which to increase the functional properties or the aesthetic properties of the finished Serve product. Optionally, the flexible polymeric base coat itself can be desired final coating. The flexible polymer can be applied to the substrate in the form of a solution. (an aqueous or not powerful dispersion, a IPlastisols. Organosols with or without a carrier (i.e. in a 100 "strength, non-liquid form) or the like. to be fcufaebreht.

Anyone can use flexible Polyrnerisatiner / ug lOlymerisatziisanimensätze order which in sufficient Dimensions is flexible and elastic. so that it is compatible with the substrate. The main / wake of the coating consist of. ; an upgradeable surface to create and. according to preferred alligator shapes. Fibers that tie a in the surface Foam can stick out to bind. The coating should also have the ability to have a strong

To form bond with the substrate. Preferably it has high toughness and abrasion resistance.

The flexible polymer can be a polyurethane. a polyacrylate, a vinyl polymer, such as, for example Polyvinyl chloride or polyvinylidene chloride, a polyester, a polyamide, an epoxy resin or the like. Be. The flexible polymer is preferably a flexible polyurethane elastomer, since these materials

ίο generally the most favorable physical properties have, especially in terms of abrasion resistance.

The coatings are preferably porous, so that they prevent the products according to the invention from being absorbed not affect.

Examples 1 to 2 ^l >

These examples show embodiments of the ν 01-lying Invention in which various foams, lasers and elastomers are used to manufacture a number of different products can be used within the scope of the present invention.

The following table shows the foams used and their properties:

foam flee in 2.5 "" ILD Φ 47.7 1.69 Tensile strength type © kg ιn ^{: 1} 19.5 50 "" 40.0 ability i
kg cn Λ PES 26-10 32.5 24.8 45.5 1.08 B. PES 23! ¹ O 40.5 2.14 1.16 C. PESS 28VO ■>"> ι 40.0 2.10 2.88 D. PEH 24 «: 0 19.0 32.0 2.02 0.60 E. PEH 2610 22.5 26.7 1.76 0.75 I · ' PEH 2155 23 D 31.0 2.0 0.80 G PEII 21 (5th 20.0 28.4 0.71 H PEH 22ü 0 27.5 0.77

OeIiHUiIg

in " "

275
229
367
156
186
195
173
198

I ¹ PIiS is a polyether polyurotin with a high silicone content. PFSS is a polyester-polyurethane with a high SiI'congchalt. PtM is a halogen containing; Polyetherpolv urethane.

I Deflection under compressive loads.

The following fibers are used:

1. A 1: 1 blend of 12 month old Texas wool (Degrees 64 to 70) with an average staple length of 63. :: mm together with a combed full of AA skin (grade 64 to 70) with an average;: !! Stack length of 50.8 mm. This becomes one: crossed Fiber mat made of 255.1 g.

2. A 170.1 g fiber mat au; 1 with an underlying 56.7 g Fascn read from polyethylene terephthalate fibers having an average denier per filament \ on ^li: mm and an average fiber length of 38th

3. A 170.1 g fiber mat au; 1 with an underlying 106.3 g non-woven fabric made of polyethylene terephthalate fibers with an average denier per thread of L5 and an average Fiber length of 38 mm.

4. A 170.1 g fiber mat from 1 with an underlying 70.8 g non-woven fabric am. Nylon with an average denier per thread of 1.5 and an average length of 38 mm.

5. Line 241.0 g fiber mattc made of nylon with an average denier per thread of 1.5 and an average fiber length of 38 mm.

6. A 170.1 g nonwoven nylon fiber with an average Denier per thread of 3.0 and an average fiber length of 3S mm and an underlying 70.8 g non-woven nylon fabric of average denier per thread of 1.5 and an average fiber length of 38 mm.

In any case, the nonwovens are made of a film with a thickness of 3.2 mm from the selected polyurethane and stitching the structure through a laboratory needling machine four times. which is set for complete penetration. needled. The sewn product is then turned over and twice passed through the same machine with the needles set to the same depth. The product is turned over again and passed through the machine twice, with the needles on an incomplete one Intruder (64.8 mm) are set. the

1976

1 61

Penetration density per diaphragm is 34 penetrations per cm ² . The fiber-foam combination is then placed in a rotary press with a dwell time of. 3 minutes and 11 seconds under a hand pressure of 318 kg and a roller pressure of 544 kg at a temperature of 156 "C. The comparable values for foams D, E, F and G are: time: 42 seconds; tape pressure: 318 kg : Roller pressure: 90 kg: Temperature: 93C.

The product obtained is impregnated with 25 percent by weight, based on the total weight of the impregnated product of a polyester polyurethane elastomer A. dissolved in dimethylformamide, by applying a uniform coating of the elastomer solution to the combination using a doctor blade and by applying a vacuum. l) as impregnated product is then on after a \ "two MeIh (Hl treated ¹¹ H, which referred to in the table as Mehenden naeli-B" or -W Wc

With the! Wthode WVV. as the water-washing method the product is immersed in water for 16 hours and dried at 93 ° C. After drying it is put in an Ilachen press bruised together for 1 minute at 93 C under a pressure of 10.5 kg cm.

With tier method B or four baking metals the product is baked in a (> IVn at about 99 C. 1 s is then used to wash excess food Silicone soaked in water and dried at 93 C. Eventually it will be at 93 C and compressed under a pressure of 10.5 kg cm- 1 minute.

249 6

The composition of the elastomer used in the water washing method is as follows:

Parts by weight

Elastomer A 150

Sulfinamide alkyl esters 5

Molecular sieve (powder,

13 χ type aluminosilicate) 2

Silica powder 2

ίο The composition of the Einbackmct '^ ode elastomers used is like folet:,. ,

Components

1.lastomeric A 2 (1

SuH'inamidalkylestcr 1

Dimethylformamide 5

' ^J methyl ethyl ketone 5

Molecular Sieve I.

Kiesderdepiilvcr 0.4

Polyurethane elastomer based on polyether in a 20 weight percent solution in

Dimethylformamide 10

The surfactants. Molecular sieves and silica are used as a means of regulating the Viscosity added to aid impregnation.

The table shows the properties of the products obtained in the various examples. From the table it can be seen that it is possible by varying the components, the s \ vienis and the 1 performance mode. Manufacture products which have the desired coordination of physical properties. \\ k it is a natural leather to one.

abellc

foam I ascr Dry
Irlastoineies'L
B WAV 97 79 I Oi 96 126 69 HerstfesiiskeiiiJ ' ¹
in kv; Vcrrornum ^ nod
mm in k'z cm '
¹¹ "I ·. ·" ReUI'estigkcit ■ \1\ A. Ί 94 42 63 57.6 25.3 1.5 22.2
54 8th ; o4 A. 1 28 55 47.6 35.4 1.2 23.0
Sl S. 155 A. 1 100 ^: 28.6 0.8 A. ■) 98.0 31.9 1.3 68.9
42 12th Λ ~> 86.2 32.3 1.2 63.3
49 11th A. 3 32.5 1.0 A. 3 96.1 31.9 1.3 71.6
41 18th 111 A. 3 86.2 32.3 ^ ■>
.1 . i. 58.7
51 13th A. 4th 23.4 A. 4th 103.4 24.2 1.3 72.6
44 15th 97 A. 5 209.0 18.4 1.4 169.0
43 A. 5 197.0 27.2 1.6 151.0 22nd 99

Koten at the end of the table

1976

(Continuation of the Tiihdle)

Φ Percentage by weight of impregnating agent. based on tlas weight tier I • i'-or-Sch.iiini-Kiinihin.itiiiii.

U) I agree with ASTM H 22IO-f4.

Cv In ",". Determined according to the SATR Λ-Te ·.!. Which subsequently he; chneivii wiiil.

iT> Hestimml according to ASTM D 22 (W-W.

■ ΐ; Heslimiiil according to ASTM Π 2211-04.

'<"> Ueslimmes according to ASTM Π 2212-W.

f ^; Hestimml to the following! iiimoiiehenen test.

foam Tasor Dry
Elastomeres ©
B WW 103 119 67 116 67 107 106 110 100 79 113 113 108 72 103 Resistance l)
in kg Deformation!) D ic ki '
mm Tensile strength ©
in kg / cm ⁵
"To E® Tear Resistance® MVTa- 14th A. 6th 9 « 110 30.4 1.1 Λ 6th 161 22.8 1.4 149.6
51 82.7 17th B. 6th 171.6 27.6 1.5 141
47 25th 19th B. 6th 23.8 1.2 16 B. 6th 150.4 25.8 1.2 155
50 19th C. 6th 1.1 C. 6th 159.9 23.1 1.5 144
49 23 D. 6th 24.0 1.2 D. 6th 109 24.2 1.1 150.5
46 E. 6th 25.7 1.2 16 F. 6th 142.3 25.0 1.4 172.5
48 is F. 6th 120.0 23.3 1.2 122.8
42 17th 1- 6th 144.3 23.1 1.2 125.6
45 G 6th 24.2 1.3 G 6th 150.9 28.2 ! .5 152.4
41 Il f. 156 17.9 1.2 133.4
42 Il 6th 150.9 22.S 1.3 117.6
45

The under << ■. Hi and. '■;ineet; chenen values are the values which are in \ iei values as the average crmitt'. 'Ll, and / was /v.ei in one chain and two in the weft line !.

The one for Hestimmunj! des l'n> / enNat / e < tier deformation of the cründungsgcmLÜJe.11 products carried out Test is provided in the Shoe and Filled Trades Research Association information sheet (Ref. No. HOURS. 110 of December 1961). This test uses a circular disc of the to be tested product clamped around its perimeter, whereupon the product in a predetermined Way by prying a hemispherical shaped die against its lower surface is expanded. The sample is held in a certain position for a certain period of time, whereupon the Gcv.-nk is removed. The chest is then cmc certain / eitkmu left, whereupon d> in Asis-

. ",, j measured at the elongation κην ^ ΜΉ retained. From these values the pro / enls.it / deformation is calculated, for these examples the initial spinning time is 5 minutes and the elongation retained is measured after 5 minutes.

In the case of the determination of the moisture vapor permeability For the applied test, place 10 ml of water in a flanged cup known as the Payne Permeability Cup is given. The / ti examining sample is placed over the beaker and clamped between a circular ring and the flange of the cup held in place. The mug is then in a

E \ siccator over anhydrous calcium chloride at im kept at a substantially constant temperature. At the end of 24 hours, the ikcher is reweighed, to determine the weight of water which passed through the test sample and thus escaped from the cup. This value is called the fire vapor permeability (in indicated in the table as MVP).

U e ι s ρ ι e I M

In this example a 6.3 mm thick sheet of polyurethane foam of the type identified as B in the previous examples is used. Separate nonwovens, each weighing 155.9 g and produced by placing heavily crimped nylon threads with a titer of 3 denier and a length of 38 mm in air, are placed on one side of the film. The structure is pierced four times through a laboratory needling machine with barbed needles 40 in thickness which are adjusted to allow complete intrusion to occur. guided. The product is turned over and passed four times through the device with the same needle setting. It is then turned around again and passed through device j: once more. the needles being adjusted in this way. tlal.i incomplete penetration takes place. The penetration density for each pass is 34 intruders per cm Roller pressure of 544 kg and a Temper.itlit of about 156 C pressed together. The product obtained is then impregnated with an equal weight of a Polvester-based polyurethane elastomer in a weight percent solution of dimethylformamide. The impregnated product is washed with water in the manner described in the introductory examples, using an aiMiahme. that the final compression in emei rotation pulses at a temperature \> n lld (. ". ei'icr YerweilzeU '.on IS seconds 'nl'. 'l. The recovered material ι.ί is covered with a Yinsl ^ ilorid-I'ia, tisol. with a l'nulu' -. l .vhalien, which such ai when u \\ <. \ such physical I roperties bjsit / t d;.. 'ß e> is suitable for Eederpolster.

I in fiS (). 4 - '.: - \! :> made of wool of the type as it is idcniili / iert iinU-r I iu den \ ors | i: hot examples. wir.l on a 'S nini thick lohe from Pol;, - urethane des in d'. 'n vorsiehein.i./n examples under C bcschncbuncn I > pus gclegl. Uic btruklur is once passed through a laboratory needling device provided with fine needles, the needles of which are adjusted in such a way that complete penetration takes place. The penetration density is 38 penetrations per cm ^a . The product is turned over and glued again six times through the same device with the same needle setting. It is then turned over again and passed once through a needling device, the needles of which are set in such a way that an incomplete intruder occurs at a penetration density of 15 penetrations per cm ³ . The fiber-foam combination is pressed in a flat press at a temperature of HOC and under a pressure of 7.0 kg / cm ^{2 for} 15 minutes. It is then with the _Z weifachen their weight of a polyether-polyurethane elastomer in a solution in dimethylformamide 25gewichtsprozeiuigen impregnated by the combination is passed through a bath of the elastomer, which is provided with Abquetschspaken. The impregnated product is baked in the manner described in the preceding examples and pressed in a flat press for 5 seconds at a temperature of 121 ° C. and under a pressure of 21.1 kg cm. Then the product is lightly polished on both sides. Separate parts of the product thus made are covered with a variety of base coats, finishing coats, and sanitary napkins. as they are generally used for natural leather, coated. When the products obtained are examined, it turns out that they have physical properties which are within the ranges which are generally determined for natural leather. The products have an excellent grip, while their draping, their breakage, their hardness and flexibility come close to the corresponding ligaments of a natural leather.

<. 1 s ρ ι l. _

An X5.0-gl ^: L-er \ read of the class specified under 4 in the above examples is placed on a 4.7 mm thick film made of polyurethane of the type described in the above examples. The structure is drawn six times on each side by a laboratory needle. device guide !, animals needles set in this way> iiul. dai 'euu \ <>!, - constant intruder occurs, whereby the Gc-imteindrmgungsdichtc on each rope is 230 penetrations per cm-. The structure> mk1 then once passed through a needle device, the needles are set in such a way, "let ep e incomplete penetration takes place, with the density I? Penetration per cm- Ivtri'.gl. The product obtained is then impregnated with 75% of its weight, 25% by weight, and then impregnated with a polyester-based polyester-based dimethane, imide, and afterwards in the manner described in the preceding examples with water "ewasdicu. It is then in an Ilachen I're.se at an Ecnip? ral iir of 121 ( The product is then coated with a polyvinylchloride ore coating and then coated with a patent leather finishing coating The product obtained has the physical properties and appearance of patent leather and is also suitable for use as such.

Claims (4)

ρ .., impregnated in a solvent and the laiemanspruciie: filler either by evaporation of the 1. Breathable, pliable, fibrous fo-solvent deposits or as a cellular ienmaterial based on polyurethane foam, product with interconnected microfiber ■ material and elastomeric binder that precipitates pores by impregnating the characterized in that the film-fiber-foam film combination with a naterial has a non-layered structure, treats liquid with the solute Mixable from the three-component combination of medium for the elastomeric filler ν ia u- Ann / u- η ι ι is, in which, however, the elastomer a 10 to 60'V _{n of} a flexible polyurethane · ,,, ·,, .. ■., ■ _m ·, hiuns ^l0 essentially lost, and finally you . . ί Λ. üVoj c A-Aoi. η ( ^fi > the fiber-foam film combination with the b) 5 to 35 ^u / o fibers in the foam ■ · ,,. _ni u ■. , _o . _{,, Λ} L UU- ju then aged astomers at about 18 across the entire cross-section through, ·,., _A o £ ^fc . . ..., ~, • ■. _{,, XI,,} ^6,. Permanent up to 120 C under increased pressure an interlocking network, where _r . ■ · ~, "~ , ... ' , - _c ii-i r, deformed or the surface ti attet.
the fibers to a restricted movement are able to are distributed, and c) 25 to 75 ° / n of a soft, resilient elastomer meren, which the empty spaces between the fibers and the foam essentially, however, does not completely fill and which _{2o B bes (EHL ejn Bcdiirfni nal} Q _r, he _{ichcs Led} by possibly interconnected m, - an _{artificial leather> which is} largely the good Contains kroporen, has to replace the properties of natural leather. consists, the percentages based on the total weight Among the good properties of natural leather <ler three-component combination are related. its ability to pass moisture vapors 2. Foil material according to claim 1, characterized in that its breathability, flexibility, characterized in that the material in addition to the adaptability, the tensile strength, tear at least one side with a pliable poly- strength and plasticity and the abrasion resistance, rnerisauiberzii! is less than the thickness of the material. share what is due to it being 3. Material according to claim 2, characterized in that it is a natural product with regard to its It also means that the polymer coating is porous. Quality, size and the like. Considerable fluctuations 4. Method of making a breathable subject. Furthermore, natural leather is often sufficient Capable, flexible, fiber-like film material does not meet the requirements that one against chemical according to claim I. characterized in that and biological attacks and damage by heat or abrasion and the like are provided. It is already numerous synthetic film materials as art (1) A non-woven fabric with a density of about 102 leather has been proposed. This is up to 15 g / m ² on a film made of a flexible, in most cases laminates made of two or more polyurethane foam with a thickness of several layers of different substances. If about 0.X to 38 mm and a density of 40 these materials are also leather-like, then about 13 to ⁽ ) 7 kg m 'are missing. they still have a number of properties. Into the- (2) a large number of the fibers in the polyurethane special, these materials do not have the crumbled foam through needles with a penetration-coordination of the physical and chemical density of about 77 to 230 penetration properties, which natural leather / u own per cm- penetrates, where at least 50 "/" 45. Even if artificial leather in one or the other of the penetrating fibers may be equal to or even greater than at least about 75 "/" and at least in thickness relation to natural leather, other properties are often lacking. 1 () ". ■ '" of the fibers completely into the low as well as breathability, the wet strength and the like. When penetrating the laminates occurs at the interfaces .icr layers (3) the product thus produced by needling, and in addition, often cracking cm. On the other hand with 31 to 230 one-tier main reasons for these disadvantages of the dr.ii! i; n; icn per cm-needles and those with synthetic products that they do not have a needle size ¹ completely in the foil the structure of natural leather, which is not a single layer: η fibers in the lohe through fabric. own. Natural feather consists of a needle pushing back the fiber. ",:"Ineinani'.ei"maturing system of fibers or fiber-sheath foil combination of about 10 dogs, which extend over its entire thickness, up to SO Weight percent I r-ern only about The lasers are so free to fit; in 20 hi ¹ M) weight percent foam, based on the total weight in each direction to absorb stresses, exists, with only being able to move because of the three-dimensional few Fiber ends protrude from the film, 60 interweaving, in contrast to the layered ones (4) the obtained fiber-foam film combination structures of synthetic products are present tion at a temperature between approximately natural leather essentially no weak 110 and 190 "C. But below the flow layers. For these reasons leather has a temperature of the fibers or of the polyurethane good tensile strength and splitting strength. foams. compressed. 65 In natural leather, most of the fibers are long, (5) the obtained compressed fiber foam- thin and highly flexible. This flexibility in combination with a solution of a film is lost if a stiff adhesive is present between the soft, resilient elastomeric filler and the fibers, as is the case with wood