DE1619249C - - Google Patents

Description

Case is. In the case of natural leather, there is essentially no stiff adhesive substance between the fibers. Instead, the fibers are separated by a relatively soft, resilient fatty substance which keeps the fibers apart but does not prevent their restricted mobility within the leather body. In this way the fibers retain their flexibility so that the natural product is flexible. Since the fibers are able to move in the fat-like matrix * they can react to an applied voltage themselves, whereby the tension is distributed over some fibers.
. Porosity is a particularly important property of natural leather with regard to the manufacture of shoe tops. The natural product has good breathability, since 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 empty spaces. These pure pores are responsible for a low bulk density and good thermal insulation. They allow water vapor to permeate through the leather and, being so small, offer considerable resistance to the permeability of liquid water.

One 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 plays an important role. As far as artificial leather for production used by shoe tops, this shows the disadvantage that the shoes are uncomfortable to wear because the synthetic leather does not adapt exactly to the shape of the foot. But after a long time If the shoe is adapted to the foot, the shoes return to their original position after wearing Shape a.

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

From the German Auslegeschrtft 1159 898 is a Process for the production of a synthetic fiber leather containing polyurethane as a binder with leather-like Properties known, in which a loose fleece is impregnated with a solution, which a Contains crosslinkable polyurethane and a blowing agent. The product is then under pressure at increased Temperature solidified, ur * d at a temperature that already before the decomposition of the propellant Polyurethane is so strong that small stable cells can form when gas is generated. The product obtained in this way can then be given a finish. Since this subsequent Finishing barely penetrates the synthetic leather, what has been given a finish Product a layered structure.

US Pat. No. 2,832,997 discloses a two-component system made from a latex with therein distributed fibers described, wherein the latex forms a porous substance after gelling. An artificial leather on the basis of impregnated fibrous substrates is the Belgian patent 660,733 refer to. There it is an essentially laminar product. The French Z.isatzpatcntschrift 84,412 to patent 1,316,434 describes a laminar product in which two layers of one

Layer carrier are connected to one another by needling. Finally, the Japanese interpretative document concerns 3560/66 / a breathable, fiber-like film material in which a three-component system

is used. The product described there is produced by / on a foam oil Fiber fleece on needles and then the surface of the needled fiber fleece is impregnated with a solution of a synthetic, fiber-forming polymer.

ίο After the fibrous binder has coagulated you then get an artificial leather, in which the fiber fleece and the plastic film coagulate by means of the, fiber-forming material are interconnected. This product is built laminar.

»5 The invention relates to a breathable, flexible, fiber-like film material based on Polyurethane foam, fiber material and elastomeric binder, which is characterized in that the sheet material has a non-layered structure

so that is made up of the three-component combination

a) 10 to 60 ° / "of a flexible polyurethane foam,

b) 5 to 55% fibers in the foam over the entire cross-section through an interlocking network, the fibers to a limited movement are able, are distributed, and

c) 25 to 75% of a soft, resilient elastomer, which covers the empty spaces between the Fibers and the foam substantially, but not completely, and which, if applicable contains interconnected micropores,

consists, the percentages being based on the total weight of the three-component combination.

The new materials of the invention are breathable composite structures made up of consist of an interlocking network of fibers and a foam, with a soft, resilient, elastomeric filler material is distributed through the network, but which is not completely fills the empty spaces between the fibers and the foam. The materials are similar to hers Structure of natural leather insofar as they are not laminates, but made of one piece Structures in which the fiber content is distributed over the entire cross-section. As in Natural leather are the fibers in a soft, resilient body made from a cellular product as well as embedded in a filler so that the fibers are not completely restricted in their movement,

but rather in a limited way in the event of a stress load in a free way be able to move.

The breathable, flexible, fibrous sheet material according to the invention can thereby be produced be that one

(1) a fiber fleece with a density of about 102 to 815 g / m ^a on a sheet of flexible polyurethane foam with a thickness of about 0.8

up to 38 mm and a density of about 13 to 97 kg / m ³ ,

(2) a plurality of the fibers one-rubs in-the Polyurethänschaum by needling with a Eindringdichte of about 77 to 230 penetrations / cm ^a, where at least 50 ° / ₀ of the invading fibers in a film thickness of at least about 75 ° / ₀ and at least 10% the fibers completely penetrate the film,

(3) the product produced in this way by needles has ηοΛνοη or closed pores, with open pores of the other sites with 31 to 233 penetrations / pores being preferred. Is intended by the term "open" nadsU and bsi dsr first Nadslung "porous understood wsrds-i, daö least ungevollständig in the foue penetrated fibers ferry 53 ⁹ / o of the pores miteuiandir in combination in the film repels by Nadsln, which are 5 and free of separating membranes, the Farär-Foam-FoHen-Combination of uns. Open-pore cellular polyurethanes can be made with about 10 to 80 percent by weight fibers with about 20 to 93 percent by weight foam. Furthermore, the pores of a foam can exist in relation to the total weight, whereby with closed pores only a few fiber ends are opened chemically or explosively from the film,
protrude, ~ A for the practical implementation of the

(4) the obtained fiber-foam film combination lying invention particularly preferred poly, at 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? jlymensat dider Fibers or polyurethane foam, granulated, which is at least about 25 weights primed, contains percent chlorine, the total chlorine content

(5) the resulting compressed fiber Schaumfolien- soft, ferry 10% "" ^{3, the} Erweichungstempsratur about resilient elastomeric filler is Sihaums of the polymer plus at least unge-Komhination with a solution of a solu- 15O ⁰ C. The foams are impregnated by solvents and the filler is released from an organic polyisocyanate with a compound that contains active hydrogen atoms, neither by evaporation of the solvent nor deposited as a cellular product with micropores connected to one another, such as a polyether or a poly, by ester, in the presence of a gas-generating agent, one treats the impregnated fiber-foam film com- such as water, and the chlorine enlhalbination with a liquid containing »5 border polymer, which essentially with the solvent for the elastomeric filler urethane forming components of the mixture is miscible, in which, however, the elastomer is incompatible, produced. The amount of the ztgenicht does not dissolve significantly, and mm finally put chlorine-containing polymer should d.zu

(6) the fiber-foam film combination sufficient with the that the composition ultimately obtained werigdann deposited Elastomsren at about 18 to 30 least 10 weight percent chlorine, based on the 120 ⁰ C under elevated pressure permanently comparable total weight of composition, comprises of simplicity Forms Or if the surface is smooth, these foams are hereinafter referred to as

The foam used is called foams containing polyurethane halogen. A special foam, Since this is available in a simple manner, the advantage of this foam is that the

stands, is easy to work with and is tough, and 35 fiber-foam combinations in which they are

is resistant to abrasion, an essentially permanent fit

A flexible polyurethane is one that has less severe pressure conditions and that at room temperature has an elongation at break of at least about 103 ^J / _o than is the case with other fiber-foam combinations. The combinations are therefore easily deformed under load. Typical foams, which are of uniform density and can be foams, which are suitable for practical implementation in the manner described below for the thread invention, are such foams, now | can be impregnated with a highly satisfactory sub-soft of about 0.2 to 7.0 kg pressure.

per 323 cm * required to produce a 25 ⁹ / igi deflection Oe ver t / s list fiber mats are those in which the measurements with a 53.8 mm 45 weave the single fibers sufficient bend thickness sample up to 25 ⁰ C g -jmI3 dsr ASTM-Test- leeway, so that you in ds.n S: haum to the method 1554-53T for a bend "nter eh- achievejn | di? gawünsshtei degree of penetration of impressing load caused by wjrdsn. The gitriebin · wjrd; i körnen. Non-woven mats Foam film preferably has a tensile strength with a visibly looser construction between about 0.3 and 2.5 kg / cn *, a gross weight of 50% is preferred. In all'JHJinen they have a density elongation between about 103 and 4D3% and between 102 and 815 g / m *. The preferred fiber tear strength of about 0.15-0.98 kg / cm. The preferred foams also have between goods with a density of about 2D4 to about 10 and 40 cells per linear centimeter 5Φ3 g / m *. Two or more superimposed and a density on the order of about 55 yellow centers can be used.
13 to 97 kg / m ³ . The fiber center can be made from any usual natural

The pliable cellular polyurethane, which are made with or synthetic fibers, for example

the practical "implementation of the invention refer to fibers made of polyesters, acrylic compounds,

is used, is made by reacting an organic polyamide, vinyl compound, cellulose compound

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

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

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

preferably the original compound with polyamides, such as polyhexamethylan

at least two reactive hydrogen atoms adipimide (nylon-6,6) or polydaproimide (nylon-6).

a molecular weight of at least 233.65 polyesters such as polyethylene terephthalate

The preferred cellular polyurethanes are or Polydimethylcyclohexylterephthalat, Acrylver-

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

thanc. They can have an open-pore structure such as polyvinyl chloride

or polyvinyl alcohol, cellulose compounds, such as In this way becomes a three-component system For example, rayon or the like, and wool are made. formed in which interlocking mesh mixtures two or more types of fibers are made of fibers and foam, with in are particularly suitable, for example mixtures, the networks a resilient, soft filler welchc Wool and polyester as well as polyamides and 5 parts are present. The filler does not fill completely Contains polyester. any empty spaces between the fibers and the

The term "fiber" is used to denote tow, foam, so that the material can be used for alpine use.

Stacks, continuous filaments, as well as similar fiber shapes Any suitable method can be used

be understood. The fibers can be used as yarns to drive the fibers through the foam. the

are present. They can be curled (if necessary, _Jo's preferred method is to put the fibers in

heat cured) or uncrimped. Use needles to drive in the foam by pulling a

The fibers generally have a denier of a plurality of needles through the batt and

between about 0.5 and 6 and preferably subsequently into the cellular polyurethane film

between 0.5 and 3 is driven. The needling is a convenient and

The individual fibers should have a length _"l5 quick method which is sufficient physical Schädidie least that keeps them in the overall supply of the foam to a minimum. Conventionally desired degrees of pressure penetration into the cellular polyurethane needling devices such as needle sheet needle punch may be used. Preferably fortune. Fiber lengths of at least approximately will be relatively thin needles 12 mm in number are useful. Fibers used in the usual 20 barbs that grasp the fibers, textile lengths are generally used for the present and propel through the foam.
Invention suitable. To achieve the overall structure you want

The elastomeric binders used are soft, flexible fibers, preferably mostly from one

Different, thermoplastic or thermosetting material side in the foam with a penetration density

materials in question, for example polyurethanes or 35 of approximately 77 to 230 penetrations per cm ²

Copolymers of butadiene and acrylonitrile. Poly-driven. The product made in this way

urethane elastomer, which is made from a variety of poly- is then from the other side with a single

ethers or polyesters through conversion with a poly-penetration density of 31 to 230 penetrations

functional isocyanates are needled per cm *.

particularly preferred. You will be using 30 to achieve the overall structure you want

the same basic connections are made, as they must ensure sufficient penetration

for the production of Polyurethanschäumc.i in the perform. This is generally achieved

manner described above, wherein if at least 50% of the penetrating fibers in

however, such conditions are met, a film thickness of at least about 75% no foaming occurs. These substances make up 35 penetrate and at least 10% of the fibers completely

represent a known class of polymeric materials that penetrate the film. You get such a product

which are readily available on the market. from which very few fiber ends from one

Usually, in organic liquids, they will stick out from both sides of the slide. One can

such as dimethylformamide, the polyurethane foam sheet between two fibers is also commercially available. Place 40 mats and put the fibers in the foil of both

Drive in according to the preferred method according to the invention.

The new materials are produced by the fact that the unified fiber-foam combination is made by placing a fiber mat on a flexible nation, which is formed by not physically compressed cellular polyurethane kaiischem way fibers from the fiber mat into the Foam film is placed, whereupon the fibers of the 45 cellular polyurethane film are driven Mat in the film to obtain a shape at about 110 to 190 ° C, under a pressure and a unit of fiber-foam-combina- tion pressed together during such a period of time, tion are driven. Then this fiber - that a product is obtained which, although it Foam combination must remain deformed at one temperature and not necessarily permanently, pressed under a pressure sufficient to show only a limited tendency to return to its original state the combination will essentially return to its dimensional lent thickness, if so sings in the compressed state. in fact, occurs very slowly. This is followed by the compressed compression devices such as Product with an elastomeric binder imprä- holding rollers, rotary presses, plate presses or the like., gnosed, this binder in the substrate 55 can be used. The exactly selected by means of a solution is introduced, from which there are compression parameters depend on the type and either by heating or by coagulation the properties of the respective cellular poly Addition of a miscible liquid, in which urethane and the selected fibers as well as in one the elastomer is not soluble to a significant extent to a high degree from the particular plant used is, is deposited, whereupon again for recovery 60 from. The temperature used should be one essentially permanently glued profiles, a compression of the fiber-foam duct The substrate is compressed to the desired dimensions under the pressure and time applied. When using thin foam sheets, under- conditions allow the temperature for example with a thickness of up to 4.7 mm, but it cannot be so high that a thermal the initial compression stage can often be omitted 65 decomposition of one of the components takes place. the ilen, since the physical process of constraining temperature should be lower than the temperature <! he fibers in the foam sheet the desired result in which the fiber or the polyurethane underneath nis supplies the applied pressure and / or conditions

9 10

begins to flow so that the fibers are not significantly deformed, however the elastomer is not deformed in any way and the pore structure of the polyester is soluble, for example by polyurethane is not lost. Too low a temperature treatment with water can be deposited. this has Doors do not allow the desired coalescence - a precipitation of the elastomer from the solution depression. Temperatures that are too high result in a 5. The precipitation can be carried out in a convenient manner Decomposition of the combination or loss caused by the impregnated protein Fiber or pore properties. Dukt is immersed in water that it is with water

The pressure applied must be sufficient for this. sprayed or exposed to a humid atmosphere desired compression of the substrate is set. Optionally, the elastomer can through to effect under the conditions met. io heating the impregnated product, for example However, it must not be so high that the pores can be removed by heating in an oven to remove the solvent structure of the polyurethane is destroyed. To be removed, to be deposited. The applied Making compressed fiber-foam caking temperature should be high enough so Combinations with the desired density, thickness the solvent can be removed, they should be J

and the desired percentage of the aggregate should not, however, be so high that the elastomer can be> ψ pressurized pressure required, depending on the pressure to be met. In any case, the product _i system used is fluctuating. Breathable when used, ie water vapor can pass through. Flatbed presses allow pressures of approximately. In the water washing method, a 7.0 to 28.1 kg / cm ^s suitable, with pressures of product produced, which is something atimingsfähiger be preferred than ¹ ^ about 17.6 to 22.9 kg / cm ^2. 20 the product obtained with the baking method \

The period of time during which the fiber becomes foam as that in the product after the former is consumed

Combination is squeezed together, muli to drive generated filler itself a pore-shaped sufficient to possess the desired degree of compression as well as structure made up of interconnected the desired physical properties consists of rows of micropores. The fact that

achieve. Compression times of approximately .10 Se- 25 the product regardless of the method used hours up to 15 minutes are generally breathable, clearly shows that in the fiber f

use of flatbed presses satisfactory. Foam combination, empty spots are present, significantly shorter compression times are possible and these spots in the substrate are not completely filled and cannot be filled with the desired degree of compression. Substrate, depending on the water. Too long compression times have resulted in a washing method, resulting in the desired structure. If a generally better aesthetic properties, such as other devices are used, then the grain, for example handle, break, adaptability, compression time to achieve equivalent compression or the like. This method is preferred when conditions are varied. For example, such qualities for the end use have equivalent compression times for a rota- 35 of the product are important,
The amount of dry elastomer added is generally somewhat lower

exhibited as the compression times, which is approximately 25 to 75 percent by weight of the Use of a flatbed press must be adhered to. Fiber content of the material can be from about 5 to

The percent obtained after compression fluctuates, while the foam duct is a flexible, one-piece content between about 10 and 60 percent by weight fiber-foam combination, which is a large number, with all percentages on the total emptiness Contains places where the fibers relate separately to the weight of the material,
the foam. The composition of the In the last stage of the process of manufacture

The fiber-foam combination depends on the origin- the new materials according to the invention will be the borrowed the thickness and density of the cellular polyurethane 45 fiber-foam combination with the deposited film as well as the thickness and weight of the fiber elastomers again under such conditions away. Typically, the fiber-foam can be compressed so that the product is permanently combined about 10 to 80 percent by weight is formed and the surface is smoothed. Under the Fibers and approximately 20 to 90 percent by weight of the term "permanently deformed" are intended to be understood. Foam, based on the total weight, included. 50 that the product does not return to its original

Then the one-piece lumen is returned, but essentially the fiber-foam combination with the selected volume is retained, which it assumes when the elastomeric binder is impregnated. To this end, exposure to heat and pressure ceases
any impregnation method can be used

the. The substrate can easily be immersed in a solution of the elastomeric solution similar to that described above. Optionally - as described with the initial compression stage, the substrate can be maintained by a set of pressure - are the following: Time: approximately rolling in a bath made of the elastomer passed 5 seconds to 3 minutes; Temperature: to be approx. A vacuum method can also be used - 18 to 120 "C; pressure: 3.5 to 12.3 kg / cm *,
in which the solution of the elastomer 60 The product produced in this way resembles in several ways on the substrate by means of a doctor blade or its structure natural leather. It has many of a similar device applied and other physical and aesthetic properties, including being sucked under vacuum into the substrate of natural leather, for example the handle that is, with an essentially complete adaptability, drapability or the like. To improve its appearance it can be done on a ^{6 S urgent}

The elastomer can be polished through or on both sides of the substrate. For a tech treat with a liquid which is related to the niche use, especially for a use liquid carrier for the elastomer is miscible in as a material for shoe upper, the product becomes

generally coated on at least one side with a flexible polymeric coating. This coating is referred to as a basecoat, although the product coated with the basecoat is suitable for many uses without additional coatings. It serves as the basis for further coatings, which serve to increase the functional properties or the aesthetic properties of the finished product. Optionally, the pliable polymeric base coat itself can be the desired hand coat. The flexible polymer can be applied to the substrate in the form of a solution, an aqueous or non-aqueous dispersion, a plastisol, organosol with or without a carrier (ie in a 100 ° / _o by weight, non-volatile form) od. Like. Be applied.

The flexible polymer coating can consist of any polymer composition which is sufficient Dimensions flexible and elastic so that it is compatible with the substrate. The main purposes of the coating consist in creating a surface that can be finished and, according to preferred embodiments, To bind fibers that may protrude from the surface of the foam.-The coating should also have the ability to form a strong 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 generally have the most favorable physical properties, particularly with regard to abrasion resistance.

Preferably the coatings are porous so that they enhance the breathability of the products of the invention not affect.

Examples IbU 29

These examples illustrate embodiments of the present invention, some of which are various Foams, fibers and elastomers used to make a number of different products in frames of the present invention can be used.

The following table shows the foams used and their properties:

foam
type © Density in
kg / m ³ 25 "/" 1LD ©
50 »/. J 65 »/. 65/25 module Tensile strength
speed in
kg / cm * strain
in */. A. PES 2640 19.5 24.8 33 1.69 1.08 275 B. PES 2390 32.5 1.16 229 C. PESS 2870 2.88 367 D. PEH 2490 22.2 32; o 47.7 2.14 0.60 156 E. PEH 2610 19.0 26.7 40.0 2.10 0.75 186 F. PEH 2195 22.5 31.0 45.5 2.02 0.80 195 G PEH 2105 23.0 28.4 40.5 1.76 0.71 173 H PEH 2290 20.0 27.5 40.0 2.0 0.77 198

© PES is a high silicone polyether polyurethane, PESS is a high silicone polyester polyurethane, PEH is a halogen-containing polyether polyurethane.

© Deflection under impressive load.

The following fibers are used:

1. A 1: 1 blend of 12 month old Texas wool (Degree 64 to 70) with an average staple length of 63.5 mm along with a combed AA hide wool (grade 64 to 70) with an average stack length of 50.8 mm. This becomes a crossed one Fiber mat made of 255.1 g.

2. A 170.1 g fiber mat from 1 with a dar- underlying 56.7 g nonwoven made of polyethylene terephthalate fibers with an average denier per thread of 1.5 and an average Fiber length of 38 mm.

3. A 170.1 g fiber mat from 1 with an underlying 106.3 g nonwoven fabric made from polyethylene terephthalate fibers with an average denier per thread of 1.5 and an average Fiber length of 38 mm.

4. A 170.1 g fiber mat from 1 with an underlying 70.8 g nonwoven fabric made of nylon with an average denier per thread of 1.5 and an average length of 38 mm.

5. A 241.0 g fiber mat made of nylon with a 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 38 mm and an underlying 70.8 g nonwoven fabric made of nylon with an average denier per thread of 1.5 and an average Fiber length of 38 mm.

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

13 14

Eindringungsdichte per passage amounts to 34 The composition of Check-in of the water washing

pressure per cm ² . The fiber-foam combination method of elastomers used is as follows:

is then placed in a rotary press at a weight scale

Weil7.cil of 3 minutes and 11 seconds under a [-'hstomeres A 'SO

Tape pressure of 318 kg and a roller pressure of 5 sulfinamide alkyl estersV '.'. '.'. '.'. '.'. '.'. '.'. '.'. '.'. ". '." 5

544 kg at a temperature of 156 C together - molecular sieve (powder

pressed. The comparable values for the foams, _{3 χ T} aluminosilicate) 2

D, E, F and G are: time: 42 seconds; Tape printing: silica powder ~>

318 kg; Roller pressure: 90 kg; Temperature: 93 C.

The product obtained is 25% by weight. The composition of the paving method

percent, based on the total weight of the elastomer used, is as follows: _

gnated product of a polyester polyurethane elasto- ucwicnisteiie

merenA, dissolved in dimethylformamide, by Auf- , ΤΤιΓι,

brings about a uniform coating of the elastosulfinamide alkyl esters 1

meren solution on the combination by means of a squeegee 15 μ ΤιΓν-, κη? ¹ ? f

and impregnated by applying a vacuum. Metnyiatnyiketon 5

The impregnated product is then after a molecular sieve 1

treated by two methods, which in the after- Κ-ieseierdepuiver 0,4

table as "B" öder, WW. refers to polyurethane elastomers on Poiyäiheroas.s

_{are 20} in a 20 weight percent solution in

In the WW method, which uses dimethylformamide 10 as the water washing method

The product is referred to for 16 hours. The surfactants, molecular sieves and

immersed in water and dried at 93 ° C. Silicas are used as a means of regulating the

After drying, it is added in a flat viscosity press to make the impregnation

convey at 93 ° C under a pressure of 10.5 kg / cm ^{2 for} 1 minute 25,

long compressed. ! n the table are the properties of the

In method B or the baking method, various examples of the products obtained are added.

put the product in an oven at about 99 ° C. The table shows that

bake. It is then used to wash off over- it by varying the components of the system

Schüssige silicone soaked in water and at 30 and the manufacturing method is possible to produce products

93 ° C dried. Eventually it will be at 93 ° C and establish whichever vote you want

have the physical properties as they are under a pressure of 10.5 kg / cm ^{2 for 1 minute}

compressed. is inherent in a natural leather.

table

foam fiber Dry
Elastomeres® WW Burst strength wedge ©
in kg Deformation® thickness Zuefestigkeit ©
in kg / cm ¹ Tear strength © MVT © B. 94 mm 7oE® A. 1 28 57.6 25.3. 1.5 22.2
54 8th 104 A. 1 47.6 35.4 1.2 23.0
81 8th 155.7 A. 2 97 79 28.6 0.8 A. 2 42 98.0 31.9 1.3 · 68.9
42 12th A. 2 86.2 32.3 1.2 63.3
49 11th A. 3 101 32.5 1.0 A. 3 63 96.1 31.9 . 1.3 71.6 18th 111.4 A. 3 55 86.2 32.3 1.2 41 13th A. 4th 100 96 23.4 58.7
51 A. 4th 103.4 24.2 1.3 15th 97.5 A. 5 126 69 209.0 18.4 1.4 72.6
44 22nd A. 5 ■ «7.0 27.2 1.6 169.0
43 22nd 99.6 151.0

Notes at the end of the table

(Continuation of the table)

foam fiber Trod
Blaston
B. cenes
leres ©
WW Burst Resistance®
ir »kg Deformation® thickness
mm · "■■ Tensile strength ©
.in kg / cm *
• / .E® > 155 Tear Resistance® MVT © • A. 6th 98 30.4 1.1 50 ^; ''.'Ά. ■ '· ■ ■ ON 103 161 22.8 1.4 149.6 22nd 82.7 ' B. 6th 119 vr 171.6 27.6 1
1.5 . 51 144 25th B. 6th 110 ■ 23.8 1.2 141 49 B. 6th 67 150.4 25.8 1.2 47 19th C. 6th 116 1.1 150.5 C. 6th 67 159.9 23.1 1.5 46 23 D. 6th 107 24.0 1.2 D. 6th 106 109 24.2 1.1 172.5 14th E. 6th 110 25.7 1.2 48 E. 6th 100 142.3 25.0 1.4 122.8 17th F. 6th 79 120.0 23.3 1.2 42 19th F. 6th 113 144.3 23.1 1.2 125.6 16 G 6th 113 24.2 1.3 45 G 6th 108 150.9 ■ 28.2 1.5 16 H 6th 72 156 17.9 1.2 152.4 18th H 6th 103 150.9 22.8 1.3 41 17th 133.4 42 117.6 45

© Weight percent impregnation agent, based on the weight of the fiber-foam combination.

® Determined according to ASTM D 2210-64. ,

© In ° / o, determined according to the SATRA test, which is described below.

© Determined according to ASTM D 2209-64.

® Determined according to ASTM D 2211-64.

® Determined according to ASTM D 2212-64.

® Determined after the test given below.

The values given under ©, © and ® are "the values obtained from four values as an average can be determined, namely two in the warp and two in the weft direction.

The one carried out to determine the percentage deformation of the products according to the invention 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 die is removed. The sample is then left to stand for a certain period of time, whereupon the extent the elongation retained is measured. These values become the percentage of deformation calculated. In these examples, the initial voltage period is 5 minutes during the expansion retained is measured after 5 minutes.

In the test used to determine moisture vapor transmission rate, 10 ml Water into a flanged cup known as a Payne Permeability Cup is given. The sample to be examined 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

209 636/185

Desiccator stored over anhydrous calcium chloride at essentially constant temperature. To At the end of 24 hours, the beaker is reweighed to determine the weight of water, which passed through the test sample and thus escaped from the cup. This Value is referred to as moisture vapor permeability (indicated as MVP in the table).

Example 30

IO

In this example a 6.3 mm thick sheet of polyurethane foam is used as in the preceding Examples of the type identified as B. Separate nonwovens, each weighing 155.9 g and by placing heavily crimped nylon threads with a titer of 3 denier and a length of 38 mm are placed on each side of the film. The structure is made four times through a laboratory barbed needle punching machine yours with a thickness of 40, which are adjusted so that there is complete penetration, Passed, the product is turned over and another four times through the device with the same Needle setting guided. It is then turned over again and through the device one more time guided with the needles adjusted so that incomplete penetration occurs. the Penetration density for each passage is 34 penetrations per cm *. The fiber-foam combination is then given a dwell time of 3 minutes and 11 seconds with a belt pressure of 318 kg and a roller pressure of 544 kg and a temperature of about 156 ° C. The product obtained is then with an equal weight of a polyester-based polyurethane elastomer in a 5 weight percent Impregnated solution of dimethylformamide. The impregnated product is treated with water in the manner described in the preceding examples washed, except that the final compression in a rotary press at one temperature of 116 ° C, a dwell time of 18 seconds, a belt pressure of 318 kg and a roller pressure of 90 kg. The material obtained is coated with a vinyl chloride elastisol to give a product which has such an appearance and physical properties that it is suitable for leather upholstery.

50 Example 31

A 680.4 g wool yarn of the type identified under 1 in the preceding examples is placed on a 38 mm thick sheet of polyurethane of the type described under C in the preceding examples. The structure is passed once through a laboratory needling device fitted with fine needles, the needles of which are adjusted so that complete penetration occurs. The penetration density is 38 penetrations per cm ² . The product is turned over and 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 incomplete penetration takes place at a penetration density of 15 penetrations per cm ^a . The fiber-foam combination is compressed for 15 minutes in a flat press at a temperature of 110 ⁰ C and under a pressure of 7.0 kg / cm *. It is then impregnated with twice its weight of a polyether-polyurethane elastomer in a 25 weight percent solution in dimethylformamide by passing the combination through a bath of the elastomer which is provided with pinch gaps. The impregnated product is baked a-J according to the procedure described in the preceding examples and in a flat press 5 seconds) at a temperature of 121 ⁰ C and unte a pressure of 21.1 kg / cm ^a pressed. Then the product is lightly polished on both sides. Separate parts of the product thus produced are coated with a variety of base coats, finish coats and tie coats such as are commonly used for natural leather. Upon examination of the products obtained, it is found that they have physical properties which are within the ranges which are generally determined for natural leather. The products have an excellent grip, while in terms of their draping, their breakage, their hardness and flexibility they come close to the corresponding properties of natural leather. :

Example 32

An 85.0 g nonwoven of the class specified under 4 in the preceding examples is placed on a 4.7 mm thick polyurethane film of the type described in the preceding examples. The structure is passed six times on each side through a laboratory needling device, the needles of which are set in such a way that complete penetration occurs, the total penetration density on each side being 230 penetrations per cm ² . The structure is then once! passed through a needling device, whose; Needles are set in such a way that an incomplete; Penetration takes place, the density being 15 penetrations per cm *. The product received will! then impregnated with 75% of its weight of a 25% by weight solution of a polyurethane elastomer, based on polyester, in dimethylformamide: and washed with water in the manner described in the preceding examples. It is then pressed in a flat press at a temperature of 121 ° C. and under a pressure of 21.2 kg / cm ² for a period of 3 minutes. The product is then coated with a polyvinyl chloride base coat and then coated with a patent leather finishing coat. The product obtained has the physical properties and appearance of patent leather and is also for use as such

Claims (4)

1 βΐ9 249 $ K \ _t 1 '^:;_; ■ '■ · ^v 2 . , '" « _''- t · impregnated in a solvent and the Claims: filler either by [evaporating the 1. Breathable, pliable, fibrous fo-solvent deposits or as zeUförraiges lien material based on polyurethane foam, product with interconnected ^ micro- Fiber material and elastomeric binder, the pores precipitate by impregnating the characterized in that the film-fiber-foam film combination with ^ a material has a non-layered structure, treats liquid that is exposed to the solvent those from the three-component combination of medium for the elastomeric filler are miscible λ m u: axw · ν οι »κ ^is » ⁱⁿ which, however, the elastomer a) 10 to 60 · /. of a flexible polyurethane _M ^ substantially dissolves, and finally μ Γ ^ ™ "^ · / c AA cu ♦» (Θ the fiber-foam sheet combination with the b) 5 to 55 · / "fibers across the permanent m dariV the foam deposited elastomer at about 18 over the entire cross-section through _{BJS 120} ^ _u * _ter elevated pressure a memandCTgrafendes network wob" ^ _{erfonnt the} surface glätteL the fibers to a limited motion are able to are distributed, and c) 25 to 75 · / _{β of} a soft, resilient elastomer _____ meren, which the empty spaces between the fibers and the foam essentially, however not completely filled out and which _{ao it} ^^ _{a BeaMaiSt} natural leather through possibly connected to one another, _{a Kunsüeder} , _we | _c hes but largely the good ones Contains kroporen, properties of natural leather has to replace. consists, the percentages based on the total weight Among the good properties of natural leather the three-component combination. its ability to pass moisture vapors 2. Foil material according to claim 1, thereby allowing its breathability, flexibility, characterized in that the material is additionally adaptable, tensile strength, tearing at least one side with a flexible poly- strength and plasticity and abrasion resistance On the other hand, natural leather has a large number of properties that are 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 shows 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, fibrous sheet material does not meet the requirements that can be met against chemical according to claim 1, characterized in that and biological attacks and damage by you put 35 heat or abrasion and the like. They are 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 815 g / m * on a sheet of flexible, in most cases laminates of two or more polyurethane foam with a thickness of several layers of different substances. If about 0.8 to 38 mm and a density of 40 these materials are also leather-like, then about 13 to 97 kg / m ^s are missing, but they still lack a number of properties. Into the- (2) a large number of the fibers in the polyurethane special, these materials do not have the desired foam through needles with a penetration coordination of the physical and chemical density of about 77 to 230 penetrations properties, which natural leather drives in per cm *, whereby is at least 50 ° / "45. Even if artificial leather natural in one or the other of the invading fibers in a film thickness relationship leather Obervon may be the same or even lay at least about 75%, and at least, frequently other missing properties, 10 ° / ₀ of the fibers completely in the film such as breathability, the Wet strength, etc. In the event of penetration, laminates occur at the interfaces of the layers (3) the product thus produced by needling still 50 and, moreover, often breaks. from the other side with 31 to 230 a. One of the main reasons for these disadvantages of the penetration per cm * needles and that of the synthetic products is that they are not first needling completely into the foil, the structure of natural leather, which does not have any layer-penetrated fibers into the foil through fabric is own. Natural leather consists of a needle pushing back, after which the fiber 55 interlocking system of fibers or fiber-foam film combination of about 10 bundles that extend over its entire thickness, up to 80 percent by weight fibers with about The fibers are so free to move slightly in 20 to 90 percent by weight foam, based on each direction to absorb stresses on the total weight, exists, with only being able to move. Because of the three-dimensional few fiber ends sticking out of the film, 60 interweaving, in contrast to the layered ones (4) The resulting fiber-foam film combination structures of synthetic products have essentially no weak 110 and 190 "C at a temperature between approximately natural leather, but below the flow layers. For these reasons, leather has a temperature of Fibers or polyurethane good tensile strength and tensile strength. foam, 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 is lost when a stiff adhesive is present between the soft, resilient elastomeric filler and the fibers, as is the case with wood