DE2030703A1 - Laminate suitable as synthetic leather - Google Patents

Description

BI. YOU. PONiE DE NEMORS AND COMPANY 10th and Market Streets, Wilmington, Delaware 19 898, V.St.A.

Laminate suitable as synthetic leather

The invention relates to a new and improved, water vapor permeable Laminate made by covering a porous fiber base layer with a microporous polymer layer will be produced. The preferred embodiments of the invention relate to the manufacture of a flexible one Artificial leather «, which consists of an adhesive coating of a microporous Layer made of a durable elastomer on a patterned base layer made of a nonwoven made of highly intertwined fibers.

There are many important uses for vapor permeable Laminates with a microporous polymer layer, which are in the form of a self-supporting film or in the form of a porous, reinforced G-round layer adhering coating. For example, shoe uppers, upholstery and Garments are made from pliable, vapor-permeable laminates, which are made up of a microporous layer an elastic polymer with a woven or nonwoven fabric

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is connected to a whole. It is well known that such laminates are on a par with leather in terms of their durability, their pleasing appearance and their comfort.

It is known that vapor-permeable microporous fabrics by covering certain nonwovens with a flexible polymer layer, the one structure of communicating with each other Has micropores, produced v / ground «The Manufacture of such products is covered in US patents 3,000,757, 3,238,055 and 3,067,483 '. Ba it often happens that the weave pattern of fabrics through the microporous If the covering shows through, use the basic layers io general nonwovens »

The usual methods for the production of microporous products include the known processes of impregnating, coating and / or lamination of woven and nonwovens with various polymers. The permanent varieties of these microporous .Products be a verhältnisiaässig dense with ", but it still porous, made by interlocking of the fibers held together Sextilstoff, - in which the locking of the fibers by lladelnj, Heisspressen.und Odei ¹ storage is achieved from porous binders /.

Many methods of making such fabrics, while generally quite satisfactory, have “certain” limitations. For example, the Einleistens place in the process in the manufacture of shoes of synthetic leather which is produced by impregnating and coating einer'Faserstoffbahn ISFE "often roughening at the locations instead, where the material is more stretched b, especially in the Yorderkappe, the heel area and in the Upper part »As a result of the roughening, the fibers of the base layer can be recognized by giving the surface covering an unevenly textured appearance. This unfortunate and unsightly mess is known as roughening and usually coarses with it

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sweets (including needle patterns) hand in hand that make the have known nonwovens prior to impregnation.

Although nan has improved resistance to the Roughening such material can be achieved by using a multi-layer fabric that has an intermediate layer show the products according to the invention an improved palte and an improved break, as well as a high degree of suppleness.

The invention provides a moisture-permeable, soft and supple laminate with a leather-like feel and appearance. see available. This new and improved laminate is made by making a patterned nonwoven base layer made from various fibers available in Hasse and coated them with a microporous polymer coating coated. If necessary, a polymeric binder can be incorporated into the base layer. The base layer is produced by treating a layer of fiber material in the form of staple fibers, continuous filaments or mixtures of continuous filaments and staple fibers with jets of liquid, that a nonwoven fabric with a repeating pattern of closely spaced fiber entanglement lines arises. The patterned base layer can be characterized by having repeating parallel surfaces of "fiber entanglement", which differs in their areal density differ from one another and extend linearly on one or more axes or in some other orderly manner and result in an even sexton that is about 4.65 to

2 2

1550 holes per cm and preferably 62 to 620 holes per cm having. This base layer can be applied by various methods, e.g. according to US patents 3 100 721 and 3 208 875, be coated with a microporous coating.

A polymeric binder can also be used in the base layer store in order to ensure their strength, abrasion resistance, flexural rigidity and to improve other related properties.

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The new laminates according to the invention are produced by first creating a nonwoven base layer, which is created by an ordered pattern of three-dimensional fiber interlacing is characterized, made from a fiber material and applies a microporous coating to the base layer. The base layer is made by making a Layer made of fiber material in the form of staple fibers, continuous filaments or mixtures of continuous filaments and staple fibers Treated jets of liquid that penetrate the fiber material, and then the fibers into a continuous nonwoven fabric condensed. The patterned base layer can be characterized by having repeating parallel surfaces of "fiber entanglement", which differ from one another in areal density and are linear on one or multiple axes or in any other orderly manner and result in a uniform pattern that is about 4.65

2
to 1550 openings or holes per cm and preferably 62 to

620 holes per cm. The areas of "fiber entanglement" can be referred to as "seams".

Before the treatment, the fibrous material layer is arranged on a carrier organ. The jets of liquid are fed under a pressure of at least 14 atmospheres from openings of less than about 0.38 mm in diameter. Fine jets of liquid are formed which, at the distance from the openings in which the treatment is carried out, have an energy flux density of more than 23,000 foot pounds / 6 ₁ 4.5 cm »second. The jets of liquid are allowed to penetrate through the fibrous material layer on the carrier in such a way that their center-to-center spacing is less than about 2.54 mm, so that a treatment energy of at least 0.1 PS-hours / 453.6 g of plastic product is applied ,.

The fine jets of liquid are usually created by drawing water from openings 0.05 to 0.76 mm in diameter ejected, which are fed by a manifold

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and in a density of 2 to 39.4, preferably 7.9 "to 15.7 openings per cm are arranged.

The speed at which the fiber material is removed from the liquid jets is penetrated, and the number of treatment processes provide a total treatment energy of at least 0.1 horsepower hour / 453.6 grams of fabric. The individual jets of liquid must be so fine that they create the desired interlacing of the thread. In general, the jets of liquid occur from openings with diameters from -0.05 to 0.38 mm. The size of the openings can vary depending on the material to be treated and the desired effect. To the Treatment of loose fiber fleeces varies the size of the opening preferably depending on the weight per unit area of the fibrous material layer and the titer of their fibers. Preferably be for Fabrics with a low basis weight and a low fiber denier Openings of small diameter and for higher basis weights or fiber titre openings of larger diameter are used.

By making columnar jets of a liquid, like water, from the outlet openings directly onto the pulp layer is sprayed on parallel, contiguous paths, which can be straight, curved or zigzag, the result is a nonwoven base layer with the lines of the Fiber entanglement a straight, curved or zigzag shape Have pattern that is determined by the paths of the liquid jets and in terms of number and frequency of Number and frequency of the jet nozzles corresponds. This kind of Line-wise matted base layer shows a pronounced Ray trace pattern that can be enhanced by performing the treatment so that parallel rays are repeated several times cover the same routes one after the other. The fiber entanglement and strength of such base layers can be achieved through repeated treatment or increased by prolonged treatment e.g. by slowly moving the liquid

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radiate over the base layer. The patterned non-woven fabric - '"■" " Base layers usually have at least two seams each cm up. The fibers of the base layer are entangled, intertwined and intertwined with one another, whereby the fiber entanglement extends in all dimensions, while the fiber parts between the seams are randomly oriented and in the throughout the rest of the nonwoven fabric are distributed. The above procedure is usually carried out by first making a pulp treated layer, which is on a large-mesh sieve (with for example 5.5 to 11.8 meshes per cm). The second stage of the process is that you get the fiber layer on a fine-mesh sieve (finer than 31.5 meshes per cm) so that very few fibers get into the holes of the Sieves are driven in and the jets of liquid form clear traces on the base layer. In this treatment Base layers with alternating surfaces are formed with strong and weak fiber entanglements, which clearly show the traces of the liquid jets.

Other base coats suitable for the purposes of the invention show a recurring pattern of fiber entanglement areas, which have a higher surface density (weight per unit area) than the average density of the textile fabric, and connecting fibers between the tight entanglement areas extend and are randomly intertwined in the dense, matted areas, local intertwining areas may be interconnected by fibers extending between adjacent entanglement areas extend and form areas of lower surface density than that of the adjacent fabric. The dense intertwining areas and the fibers connecting them can define a pattern of openings that is free of fibers. at In other basic layers, the tightly intertwined areas are arranged in a regular pattern and ordered by © Groups of fibers are connected in such a way that the nonwoven looks similar to a conventional woven fabric, but the fibers

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which randomly through the textile material from a looping run rich to the other. The lines of an ordered group can be substantially parallel or random to one another to be arranged «

The fiber entanglement regions of higher surface density than that of the nonwoven fabric can have any shape or size. A fiber entanglement area may be quite long in one direction or have a compact shape in which the diameter of the inscribed circle is at least 50 µl of the diameter of a circle circumscribed around the periphery of the area. The fiber entanglement areas can extend continuously in straight or undulating paths, or they can be separate, intertwined masses of fibers of circular, square, or rectangular appearance. They can be connected to one another by groups of fibers and, together with these, delimit a pattern of openings. By "opening" is a hole in the nonwoven fabric to be understood that _t be practically free of parsers are or relatively few fibers can contain. The ordered fiber groups can hold the dense fiber looping areas together so tightly that the openings only become visible when the nonwoven is stretched and / or that they are only visible when enlarged. The term "ordered" refers to the coarse appearance of the groups of fibers. The groups may be bundles or ribbons of yarn-like or strip-like appearance. The individual strands can be substantially parallel or assume parallel directions as the nonwoven fabric is tensioned, or the fibers can be randomly intertwined or otherwise arranged in a manner capable of collectively distributing the tension in the nonwoven fabric.

The repeating pattern of fiber arrangements can be regular be by making essentially similar arrangements periodically in one or more directions in the plane of the

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Nonwoven, or the 'repeating pattern can be irregular. Depending on the fineness of the pattern, on your patterned organ or after a follow-up treatment, such as the shrinkage generated, the formation of a fiber crimp or the like, the fiber arrangement being the Forms, be easily recognizable with the naked eye or not. However, when enlarged, these patterns are easy to close recognize. When viewed in transmitted light, the more densely entwined areas appear as dark areas in the Textile fabric. If there are shrunken or curled fibers, you can see when the fabric is slightly stretched ^ the difference between the dense entanglement areas and the ordered fiber groups.

The term "apertured patterning member" includes Sieves, perforated or grooved plates or the like on which the starting material lies during the treatment, and due to their openings and / or surface contours, the displacement of the fibers to form a pattern under the action caused by jets of liquid with a high energy flux density. The patterning element can be a flat or uneven surface or have a combination of flat and uneven areas.

In order to produce base layers with an ordered pattern of holes, the fiber layers are treated on a sieve with 4 to 31.5 stitches per cm and preferably from 7.9 to 15.7 stitches per cm. The jets of liquid force the fibers to follow the pattern of the carrier screen. Depending on the amount of energy that is applied to the fibrous material layer, holes can form in the resulting base layer at the wire crossing points of the screen.

However, the base layers according to the invention can also first on a coarse-mesh sieve (4 to 15 _t 7 stitches per cm) slightly felted and then (straining 15.7 to 39 per cm) will be permanently entangled on a fine mesh screen. With this one

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The process requires less energy to achieve an equivalent amount of fiber entanglement, and it gets through it also improves the uniformity of the base layer

These base layers normally have a fiber entanglement 3 completeness (c) of at least 0.5 and an entanglement frequency (f) of at least 25, determined in the bondless state. (Under "bondless ¹¹ is meant that the fibers of the nonwoven are not bound to each other by a binding agent or mutual fusing. In other words: the nonwoven is examined to determine strength and other properties that are exclusively due to the mutual interlacing .)

Particularly strong, patterned nonwoven base layers are produced by jets of liquid through the fibrous web can penetrate from openings with diameters from 0.05 to 0.25 mm, which have linear intervals of 7.8 to 23.6 openings per cm, are injected, the be fed with water at pressures of 35 to 140 atmospheres.

The excellent strength of the base layers used according to the invention is based on the mutual paserving, those without the use of feltable fibers or conventional ones Needles is achieved.

The fibrous materials used according to the invention include cellulose fibers and synthetic textile fibers such as fibers made from acrylic polymers, polyesters *, polyolefins and polyamides. Any desired ones are suitable for producing the base layers Layers of fibrous material made up of fiber elements in Form of staple fibers or filaments and in the form of Wadding, fleece, webs, laminates or mixtures of such forms is present. Fiber webs with weights per unit area between 34 and 340 g / m 2 are preferred for making the base layers. ■ .-

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Characterized by a base layer of intertwined fibers through a textile structure in which the pasers tangled, intertwined, intertwined, or otherwise connected in such a way that they become practical can not be separated from each other. The treatment process can be selected points of the fiber layer of any Large, but also the entire layer of fiber material, subjected will. If one looks at the treated sheet in cross-section, one notices that a number of fiber sections has been rearranged by the action of the liquid jets in a direction perpendicular to the plane of the nonwoven fabric.

To the nonwoven base layers used according to the invention To obtain high strength ^ it is desirable that the fiber material be exposed to rays from a non-compressible Liquid is subjected to such a high energy flux density and to such a high degree of treatment, that the fibers intertwine. The initial one

Energy flux density in foot poundals per 6.45 cm per second can easily be according to the equation

EP ₁ = 77 PG / a

in which the symbols have the following meanings:

P = liquid pressure in units of 0.07 kg / cm, G = volumetric flow of the liquid in units of 0.0283 m ⁵ / min. and

a = initial cross-sectional area of the liquid jet

■ ρ
in units of 6.45 cm.

The value of G in the above equation is obtained by determining the flow velocity of the liquid jet. The initial cross-sectional area (a) that is in the nozzle can be determined by measuring the nozzle area and multiplying it by the discharge coefficient (usually 0.64), or it can be calculated from measured flow rates. Since the area (a) corresponds to the flow of the massive jet, the above equation gives the

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Maximum value for the energy flux density that can be achieved at the relevant pressure and the relevant flow velocity. Usually, the energy flux density decreases rapidly with increasing distance of the beam from the exit orifice, even if carefully shaped exit orifices are used. Before it hits the fibrous web, the liquid jet diverges up to an area (A), and the kinetic energy of the jet is distributed over this larger area. The cross-sectional area (A) can be estimated from photographs of the beam when the fibrous web has been removed, or it can be measured with micrometer probes. The energy flux density is then equal to the product of the initial energy flux density and the radiance ratio (a / A). From this, the equation EF ₁₁ = 77 PG / A foot-poundal / 6.45 cm ² sec.

The value of (A) increases with the distance from the nozzle opening and depends on the for a given treatment distance Nozzle device and the pressure of the liquid supplied to the nozzles away.

The extent of the treatment must be sufficient and is measured by the energy that is expended per unit weight of the fabric produced. The energy (E ₁ ) that is expended in the manufacture of a given nonwoven fabric in one pass under the distribution line is expressed in PS-hours. measured 453.6 g of fabric and from the equation

E ₁ = 0.125 (YPG / sb) calculated in the

Y = number of openings per unit length of 25.4 mm of the

Distribution line, P = pressure of the liquid in the distribution line in units of 0.07 kg / cm,

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• ζ

G β volumetric flow in units of 0.0283 nr / min. / Du-. mouth opening,

s «speed of advance of the fiber web under the liquid jets, expressed in units of 0.3048 m / min., And

b = weight per unit area of the nonwoven fabric produced in units of 33.91 g / m ² .

If the fibrous web is treated several times with the liquid jets, the total amount is that in the treatment The energy used is equal to the sum of the individual energy values for each passage under the distribution line.

The energy flux density of the liquid jets depends on the nozzle device used, the pressure under which the liquid is applied is fed to the nozzles, and the distance between the nozzle openings and the fibrous web during the treatment. Initially, the liquid forms "massive" jets, i.e. «uninterrupted, homogeneous liquid jets. Such rays are preferably obtained by using a suitable liquid, like water, squirting out under high pressure under such conditions through an orifice of small diameter, that the exiting rays remain essentially columnar, at least until they hit the fiber material hit. Substantially columnar rays have an overall angle of divergence of less than about 5 °. Particularly solid and surface-resistant base layers are obtained with high-pressure liquid jets that have an angle of divergence less than about 3 °. If necessary, the fibrous layer can first be treated with a wetting agent or treat surfactants to facilitate processing. Such means can also be the jet fluid can be added. An example of a particularly suitable means that increases the penetration of the rays, is high molecular weight polyethylene oxide.

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Depending on the nature of the initial fiber layer of the to The nonwoven base producing the nonwoven material can reduce the energy flux density brought about by the liquid jets, can be controlled by adjusting the size of the openings which the jets emerge, the pressure under which the liquid is fed to the nozzles, and the distance of the path from the openings varied. Other procedural variables that changed ν can be changed in order to obtain the desired nonwoven fabric is the speed at which the fibrous layer advances, the number of passages of the fibrous layer under the liquid jets and / or the directions in which the fibrous material layer intersects the path of the liquid jets.

Wherever columnar rays act on the layer, individual fibers of the layer are inevitably intertwined in all dimensions of the layer brought. One can have a single jet of liquid or several jets of liquid that are spaced apart from one another stand, continuously or discontinuously to act on the fibrous material layer in a direction perpendicular or inclined to the surface of the layer. Further the fiber layer can be on one or both sides be treated.

Particularly suitable for the production of twisted lines Base layers according to the invention are the method and device according to Canadian patent 739 652.

The base layers or base layers provided with a screen pattern, which have openings or holes can be produced according to British patent specification 1-088,376.

Although it is not necessary to impregnate the Grundsohichtmaterial with a polymeric binder, you can use this measure to the strength of the base layer to increase and improve their grip · When used in prägniermittel, the signal is fed preferably in

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the base layer in the form of a solution or an aqueous dispersion a. The impregnating agent is a polymer with a low modulus of elasticity, i.e. that which is distributed in the base layer The binder must be in a form without the fibers in which there is a tensile strength of at least 0.35, but less than 10.5 kg / cm and, preferably, at 5 percent elongation

of less than 7 kg / cm. A particularly preferred one Impregnation agent has a tensile strength at 5 percent elongation

strength of less than 3.5 kg / cm.

By using the patterned nonwoven base layer in the microporous synthetic leather according to the invention, the The development of roughness is suppressed in those parts of the artificial leather that are stretched without one Need to apply intermediate layer to distribute the stretch. This synthetic leather is "non-roughening" in the sense that that irregularities in the base layer do not shine through the surface of the artificial leather when the Base layer provided with a base layer is stretched, as in the case of the molding of the toe cap and the upper part in the manufacture of Shoes. The use of patterned base layers leads to an artificial leather that resists roughening, and which cannot be produced with the previously known nonwoven base layers.

Usually such an amount of impregnating agent and topcoat is used on the base layer that any patterns that might become visible when the synthetic leather is stretched are covered. It has been found that it is possible to get by with less top covering in order to make the artificial leather according to the invention "non-roughening ¹¹ if the method for treating the patterned nonwoven base layer is varied.

A method of reducing the amount of decking that is required is to hide the patterned base layer and to improve resistance to roughening; consists of the patterned non-woven base

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layer of area shrinkage, whereby the sexton is downsized. Shrinkage of the base layer can be achieved by treating the base layer with hot water or some other agent capable of causing the fibers to contract without melting or damaging the fibers. If shrinkage is to be undertaken, the fibrous materials used in the base layer should be able to contract when properly treated, for example with heat or a swelling agent. The contraction can be due to a simple change in length (ie shrinkage) or to a distortion of the threads into an irregular shape (ie, crimping or curling), or both. The contractibility or degree of contraction relates to a free thread under the treatment conditions and is conveniently expressed as the percentage decrease (based on the original value) of the shortest distance between two points on a single thread; If both shrinkage and curling take place, the contraction is the sum of the effect caused by the reduction in length and the formation of a more irregular path between the two measuring points. Fibers that cannot contract under the treatment conditions and are therefore unsuitable as the only component when the nonwoven fabric is to be shrunk can be mixed or wrapped with contractible synthetic threads in order to achieve special effects. At least three methods can be used to treat the base layer according to the invention:

(1) One of a single, contractible type of fiber existing base layer can be subjected to area shrinkage?

(2) one of contractible and non-contractible Fibers existing base layer can be subjected to a shrinkage area in which only the

: contractible fibers shrink:

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(3) a base layer consisting of only one type of fiber, in which the fibers are able to curl or to lengthen, can be subjected to the surface ear sump. This effect is called spontaneous in technology Denotes crimp or spontaneous elongation;

(4) You can do any combination of methods Operate (1), (2) and / or (3). ·

If the patterned base layer consists of only a single type of fiber that has the ability to contract, the artificial leather produced with this base layer has an improved resistance to roughening and requires less top coat than if the patterned base layer had not been shrunk. When you get one out together tensile and non-contractible fibers; If the existing base layer is used to produce the artificial leather according to the invention, a more supple, high-grade one is obtained drapable synthetic leather that is even more resilient against roughening has as an artificial leather in which the base layer consists of only one type of fiber and has been shrunk. It is believed that this increased resistance to roughening on the The fact is, that initially a lower percentage the fiber in the base layer is stretched when the synthetic leather is stretched.

The use of a base layer made of fibers that can be crinkled or lengthened spontaneously when heated results in the formation of an artificial leather which has a higher resistance to roughening than an artificial leather in which the base layer consists of only one type of fiber and has been shrunk in the normal way . These synthetic leather also have an improved fracture and improved Palte ·

Practically all synthetic, fiber-forming polymers can be produced in such a way that they have the required combination

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Have attraction, and can therefore according to the invention treated in such a way that they provide valuable products. Except for the polymers described in the examples below The fibers can be made from polyamides (e.g. polyhexamethylene sebacic acid amide, poly- ε-caproic acid amide and mixed polyamides of these and other polyamides), polyesters (e.g. polyethylene sebacate), polyester amides, polyureas, polyurethanes, acrylonitrile polymers (including the copolymers of acrylonitrile, especially with others Ethylene-unsaturated monomers such as vinyl chloride, vinyl acetate, methyl acrylate and vinyl pyridine include), vinyl polymers general (e.g. polyvinyl acetate, polyvinyl chloride and polystyrene), polymerized hydrocarbons (e.g. polyethylene) and halogenated derivatives thereof, synthetic proteinaceous polymers and cellulose derivatives (including esters, ethers and similar cellulose derivatives) exist.

Mixtures of different polymers can also be used; Furthermore, the individual threads can be used as hollow threads, as sheath core threads or as other multi-component threads. If necessary, in the same product Layers of these and other thread-like materials combined will; the selection of nonwoven components from a wide variety of synthetic thread materials that can be used made in such a way that they have the ability to contract, depends not only on the known properties of each fiber material itself, but also according to the behavior of the same in the process and according to the desired use of the product.

Particularly advantageous results in the production of the base layers according to the invention are obtained with threads made of polyethylene terephthalate obtained according to U.S. Patents 2-6o4,639 and 2,758,903. If those Threads in water to the boiling point or close to the boiling point

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point or in hot air to temperatures of about 95 to about 180-200 ° C heated, they suffer a spontaneous ripple, and such threads not only have a superficial wool-like appearance, but stand out against the wool also characterized by their elasticity and other properties. Good results are also obtained according to the invention with threads, which contract but not pucker when heated; the production of such threads from polyethylene terephthalate is described in U.S. Patent 2,465,319.

Another type of spontaneously crimpable thread that uses the invention gives the desired properties, regenerated cellulose is of the type described in the United States patent 2,515,834; at room temperature this material will curl in a swelling agent such as aqueous alkali or liquid ammonia, spontaneously. Liquid ammonia also causes contraction (not by rippling, but by Shrinkage) of fibers made of ordinary viscose rayon, which are also used to manufacture the felt-like products according to the Methods according to the invention can be used. Hot aqueous solutions of dimethylformamide or γ-butyrolactone are the used to constrict polyacrylonitrile fibers bring about.

In order to achieve the contraction of the fibers can be in different ways heat, z _o Bo with water, oil, steam, air or another flowing · media, the relatively indifferent behave towards the thread material, or can be the material to be in addition to or instead of the heat treatment treat with a swelling agent. A combination of chemical and physical treatment can be used, ζ.Β «with the help of mild acidic or alkaline baths. Each method for contracting Let the fiber material from ■ one end to the other, which does not affect the fiber structure tw strong, is acceptable. If the base layer is placed in a liquid bath instead of by heating. Contraction

I ι

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hen is to be brought, the nonwoven fabric can be placed on a conveyor belt be passed through a container, where it enters the Contraction inducing liquid immersed in or with it is padded or sprayed. The liquid can then be removed, e.g. by means of squeeze rollers and a dryer. The duration of treatment can vary from a few seconds to a few hours; however, for the sake of simplicity Treatment times on the order of minutes or less preferred.

The next stage in making the roughening resistant Artificial leather according to the invention is the application of a microporous polymer coating on the base layer. For the production and for the application of the microporous coating one can use various methods for the production of Use artificial leather. Particularly valuable for the production of the laminates according to the invention are, for example, those in USA patents 3 100 721 and 3 208 875 described polymer dispersions * Also the substances described in U.S. Patents 3,190,766, 3,284,274, and 3,364,098 Methods can be used to create a microporous polymer layer to be applied to the base layers according to the invention.

The first step in making and applying the microporous coating is the preparation of a solution, which is essential Contains constituents of a polymer component and a solvent for the polymer component. This solution can be used directly as a coating dispersion will; however, it is preferable to add a liquid to the solution, which is miscible with the solvent, the polymer component however, does not dissolve, in amounts up to and including that Kenge at which the polymer solution in a to pass into an essentially colloidal polymer dispersion begins. If a colloidal dispersion is used, it should have a viscosity greater than about 1 poise and a polymer

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Have risat concentration greater than about 7 percent by weight. (For the purposes of the invention, the term "dispersion" includes the above-described mixtures of polymer and solvent, in the form of solutions, as mixtures of polymer in solvents and non-solvents in the form of solutions or as colloidal dispersions of polymers in Mixtures of solvent and nonsolvent may be present.) The polymer dispersion is then applied to the base layer applied and the latter treated with an inert liquid, which is a non-solvent for the Polymerisatkorcponente and is miscible with the solvent. The product is then dried.

For the production of microporous synthetic leather for shoe upper leather, however, there is an additional requirement that the polymer component in the entire manufacturing process, i.e. from the point in time at which the polymer component becomes a microporous one Structure is coagulated to dryness with a tensile modulus of secant at 5 percent elongation of more than about 42 kg / cm must have. A microporous structure made with a polymer that is in contiguous form has a secant tensile modulus of less than about 42 kg / cm, collapses during or after the removal of the liquid from the micropores of the structure, so that a relatively impermeable product receives. Preferably the secant modulus of the 3 polymer at 5 percent elongation during the entire manufacturing process is about 42 to

2 2

1758 kg / cm and especially about 56 to 211 kg / cm. The secant pulling module is the ratio of the tension of the specimen to its elongation at 5 percent elongation, determined from the Stress-strain curve, and is expressed as the force per unit area, e.g. kg / cm. The secant tensile modulus is determined in accordance with ASTM test standard D-882-64-T with the following described modification. - ·. ■

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The secant tensile modulus of the polymer suitable for the purposes of the invention is "determined by producing a 0.13 to 0.51 mm thick, continuous, void-free polymer film from the polymer solution used in the process for the production of the microporous artificial leather according to the invention. The The film is produced by pouring the polymer solution onto a glass plate and drying the solution, for example within 90 minutes at 105.degree.

The stress-strain curve required to obtain the secant tensile modulus to calculate the polymer used according to the invention at 5 percent elongation is preferably with obtained on an Instron tensile tester using a 12.7 mm wide sample made from the polymer film described has been cut out, with a gripper jaw spacing of 25f4 mm used. It is preferable to provide the Instron tester To obtain the stress-strain curve, enter the following values: Recording sheet speed 2514 cm / Min., Sliding jaw speed 2.54 cm / min., Load with full deflection 0.9 to 2.27 kg.

The secant train module is obtained from the curve of the relationship between force and elongation by looking at 5 percent sample elongation (Elongation) draws a line parallel to the force coordinate of the diagram "The point at which this line the Force-elongation curve, indicates the force in kilograms that is required to stretch the sample by 5 #. This Force value we, d by the initial cross-sectional area of the

Sample divided by the corresponding tension value in kg / cm to obtain. If you compare this voltage value with the relative Dividing elongation (0.05) gives the secant tensile modulus at 5 percent elongation. ■

• To select the beginning for use according to the invention suitable "polymers, passing the Untex'suchung usually at! 'Room temperature, about 23 dureh" have peraiur ° C. At this 2em- polymers "possibly for Terwen-

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according to the invention come into embossing, a secant pull module at 5 percent elongation of more than about 42 kg / cm. As already mentioned, for the purposes of the invention suitable polymers but a secant tensile modulus at 5 percent elongation throughout the manufacturing process greater than about 42 kg / cm. Therefore, the test is carried out at the highest temperature used during manufacture of the microporous product occurs. If at the Process e.g. the drying temperature of 110 C is the highest temperature, the secant tensile modulus is intended for the purposes polymer suitable for the invention at 110.degree can be determined and at this temperature have a value of more than about 42 kg / cm.

One preferred for making microporous synthetic leather The main polymer component is an elastomeric polyurethane, which is produced by combining a diisocyanate with a polymer containing reactive hydrogen atoms, such as a polyalkylene ether glycol or a terminal hydroxyl-containing polyester, to a polyurethane prepolymer with terminal isocyanate groups and this Can prepolymer react with a chain extender in which two reactive hydrogen atoms on amino nitrogen atoms are bound. A preferred chain extender is a mixture of hydrazine and N-methylaminobis-propylamine; However, you can also use other chain extenders, such as dimethylpiperazine, 4-methyl-m-phenylenediamine, m-phenylenediamine, 1,4-diaminopiperazine, ethylenediamine and mixtures same, use.

The polyurethane can be made by first a molar excess of diisocyanate is mixed with the polymer containing the reactive hydrogen atoms and that Mixture heated to about 50 to 1.20 ° C until the prepolymer has formed. One can also use the diisocyanate with a molar excess of the reactive hydrogen atoms

- 22 -.

009 883/19 07

PPD-3118 '■' ■

React containing polymer and the reaction product by reaction with further isocyanate to form a prepolymer Capping.

To produce the prepolymer, aromatic, aliphatic, cycloaliphatic diisocyanates or mixtures thereof can be used. Such diisocyanates are e.g. Toluylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, m-phenylene diisocyanate, Biphenylene-4,4'-diisocyanate, methylene-bis- (4-phenyl isocyanate), 4-chloro-i, 3-phenylene diisocyanate, naphthylene-1,5-diisocyanate, Tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, Decamethylene-1,10-diisocyanate, cyclohexylene-1,4-diisocyanate, Methylene bis (4-cyclohexyl isocyanate) and tetranydronuphethylene diisocyanate. Arylene diisocyanates, so those Isocyanates in which the isocyanate groups are attached to an aromatic ring are preferred. they react generally lighter than the alkylene diisocyanates.

The for. Production of the prepolymer preferred polymers containing reactive hydrogen atoms are polyalkylene ether glycols. The most advantageous polyglycols have molecular weights from 300 to 5000, preferably from 400 to 2000; they include eg Polyäthylenätherglykol, PoIypropylenätherglykol, Polytetramethylenätherglykol, Polyhexamethylenätherglykol, Polyoctamethylenätherglykol, Polynonamethylenätherglykol, Polydecacethylenätherglykol, Polydodecamethylenätherglj ^r kol, and mixtures thereof. Polyglycols which have several different radicals in the molecular chain, such as the compound HO (CHpOC ₂ H,) H, where η is an integer greater than 1, can also be used.

Polyesters instead of the polyalkylene ether glycols or together that can be used with them are, for example, those obtained by reacting acids, esters or acid halides can be obtained with glycols. Suitable glycols are polymethylene glycols, such as ethylene, propylene, tetramethylene, Decamethylene glycol, substituted polymethylene glycols, such as

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BATH ORIGINAL

3118

2,2-dimethylpropanediol-1,3, cyclic glycols such as cyclohexanediol, and aromatic glycols such as xylylene glycol. When maximum flexibility in the product is desired, aliphatic Glycols generally preferred. These glycols are mixed with aliphatic, cycloaliphatic or aromatic Dicarboxylic acids or lower alkyl esters or ester-forming derivatives thereof to polyesters of relatively low Molecular weight implemented, which preferably have a melting point of less than about 70 ° C and molecular weights similar to those of the polyalkylene ether glycols. Dicarboxylic acids for making such polyesters are. e.g. succinic acid, Adipic acid, suberonic acid, sebacic acid, terephthalic acid, hexahydroterephthalic acid and the alkyl and halogen substituted Derivatives of the same.

The chain extension reaction is usually carried out at temperatures below 120 ° C and often at around room temperature, especially when using hydrazine as a chain extender. During this reaction, polymer molecules are added a substantially linear polyurethane molecule, the molecular weight of which is usually at least 5000 and sometimes is even 300,000. The reaction can be carried out without a solvent in a high-performance mixer or in a homogeneous solution be performed. In the latter case, it is advisable to use one of the organic solvents as the solvent that are also used in the polymer solution.

Since the polyurethane thus obtained has a rubber-like elasticity, it is referred to as "elastomer" although the Degree of rubber-like elasticity depending on the chemical structure of the polymer and that in combination with the same applied substances from one product to another within further limits can fluctuate.

Another suitable component of the polymer solution bei.der Manufacture of artificial leather is a polymer of vinyl chloride. Obtains products with excellent abrasion resistance

L 24 -009883/1907

if you use a vinyl chloride polymer together with an elastomer, such as the polyurethane described above. In the preparation of material for shoe upper leather or the like from a mixture of an elastomeric polyurethane and a vinyl chloride polymer, this polymer mixture preferably contains more than 30 percent by weight, in particular 75 ia polyurethane, while the balance being polyvinyl chloride.

Suitable polymers of vinyl chloride are polyvinyl chloride and copolymers from a larger proportion, preferably at least $ 80, vinyl chloride and a smaller portion of one other ethylene-unsaturated monomers such as vinyl acetate, vinylidene chloride or maleic acid diethyl ester.

With the proviso that the secant pull module in the above Range, the polymer component of the solution from which the coating is produced, the most varied Contain types of polymers, e.g. polyurethanes, vinyl halide polymers, polyamides, polyester amides, polyesters, Polyvinyl butyral, poly-a-methylstyrene, polyvinylidene chloride, Alkyl esters of acrylic acid and methacrylic acid, chlorosulfonated polyethylene, copolymers of butadiene and acrylonitrile, cellulose esters and ethers, polystyrene and other polymers made from monomers containing vinyl groups. Synthetic organic polymers are generally preferred, and relatively high molecular weight elastomers are particularly preferred.

If a polymer is used that is compatible with plasticizers, for example a vinyl chloride polymer, it can be mixed with known plasticizers in any amount, which, however, must not be so large that the secant tensile modulus at 5 percent elongation is less than 42 kg / cm falls. Other known additives for polymers, such as pigments, .3? Üllstof £ e. _s stabilizers and antioxidants, can also ssix der; Polymer components are added,

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FFD-3118 Ib

The polymer component is dissolved in so much solvent that a solution of the desired solids content is obtained and the desired viscosity. For application with the doctor blade, a solution is usually preferred that is after Addition of nonsolvent, if one is used, a polymer content of about 10 "to 30 percent by weight and has a viscosity of about 10 to 500 poise. The organic one used in the solution as well as during coagulation Solvent should be miscible with the nonsolvent, preferably completely miscible. A preferred one Solvent for polymers soluble in it is N, N-dimethylformamide, since it has a high solubility for many of the preferred polymers and a high degree of miscibility with the im generally preferred nonsolvents including water. Other suitable solvents are diethyl sulfoxide, Tetrahydrofuran, tetramethylurea, N, N-dimethylacetaniid, N-methyl-2-pyrrolidone, ethyl acetate, dioxane, butylcarbinol, Phenol, chloroform and γ-butyrolactone. Can also be used are mixtures of these solvents with various water-miscible liquids, such as ketones and alcohols, which by themselves are often poor solvents for the polymer. A very beneficial mixture exists from dimethylformamide and methyl ethyl ketone.

When the solvent is from the applied layer only is to be removed by drying, it should be more volatile than the nonsolvent used in the process.

After the polymer dispersion has been prepared, it is optionally possible (this method is generally preferred) mix the solution with a non-solvent for the polymer, being used as a nonsolvent a liquid which with the organic solvent in the solution at least is partially miscible. Non-solvents that can be mixed with the polymer solution according to this method, ' are water, ethylene glycol, glycerine, glycol monoethyl ether,

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FFD-3118 Π

Hydroxyethyl acetate, tert-butyl alcohol, 1,1,1-trimethylolpropane, Methanol, ethanol, hexane, benzene, gasoline, toluene, tetrachlorethylene, chloroform and the like. If this is possible, it is usually preferred to use water and Mixtures of the same with liquids miscible with water.

The finished synthetic leather shows a high degree of suppleness, strength and resistance to roughening.

In the following examples, parts and percentages are by weight unless otherwise specified. at According to the specifications of the product characteristics in the examples, M means in the machine direction and Q in the cross direction.

example 1

A homogeneous mixture of equal parts of polyacrylonitrile fibers and rayon fibers with staple lengths of 38 mm and titers of 1.5 denier is produced. A fiber fleece with a weight per unit area of 95 g / m 2 is produced from the fiber mixture by randomly depositing it from an air stream and then treated with columnar water jets in accordance with Canadian patent 739 652. The jets of liquid are sprayed out of openings 0.18 mm in diameter, which are drilled out of a distribution line at intervals of 1.5 »75 holes per cm. When cleaning and drilling out the openings, special care is taken to ensure that the liquid enters the openings sharply so that the liquid jets are prevented from breaking up after leaving the openings as far as possible. A cylindrical filter is arranged coaxially within the distribution line so that the water is evenly distributed over the openings. The filter is a fine-meshed wire net with 39 »4 x 39» 4 meshes per cm and an open area of 30 * £.

The fiber fleece is placed on a wire netting with 9.5 9.5 meshes per cm and 20 pounds of open area and placed under three

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FFD-3118 ^<σ

Lenförinigen water jets of 30 ° C passed through. For the For the first jet, the liquid pressure in the distribution line is 14 atm, for the last two jets 70 atm. Of the The distance between the distribution line and the fiber fleece is 2.5 cm.

Thickness, mm 0.48

Density, g / cra ⁵ . 0.203

Tensile strength, kg / cm ² (M / Q) 34.4 / 28.8

5 ^ -secant modulus, kg / cm ² (M / Q). 9.14 / 7.73

Puncture tear strength, kg / cm (M / Q) 37.7 / 33.4

Link completeness 0.91

Link Frequency 72

Basis weight, g / m 98.3

The nonwoven is then soaked for 5 minutes with a 40 percent aqueous solution of butyrolactone at 100 C, whereby an area shrinkage of $ 65 occurs. The acrylonitrile fibers tend to shrink here. The characteristics of the shrunken Nonwoven fabric are the following:

Thickness, mm 0.77

Density, g / cm ⁵ 0.291

Tensile strength, kg / cm ² (M / Q) 30.3 / 27.2

5 # edge module, kg / cm ² (M / Q) 7.94 / 6.75

Puncture tear strength, kg / cm (M / Q) 34.1 / 30.2

Link completeness 0.88

Link Frequency 73

Basis weight, g / m 227

According to Example 1 of US Pat. No. 3,100,721, a 12 1/2 percent dispersion of polyvinyl chloride and polyurea in dimethylformamide is prepared with the difference that the ratio of polyvinyl chloride to polyurea is not 65:35, but 75:25 and is used as a chain extender not 50 parts of hydrazine hydrate, but 40 parts of hydrazine

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FFD-3118 43

zinc hydrate and 10 parts of N-methyl-dipropylamine can be used. The nonwoven is saturated with this solution and leached in water and then dried.

A solution of 20% water and 80% fo Ν, Ν-dimethylformamide is slowly added to 60 parts of the initial solution, and the solution begins to iridescent. At this point, colloidal polymer particles are dispersed in the solution.

The dispersion is applied in a wet film thickness of 1.78 mm dried, impregnated base coat applied. The coated The base layer is then treated in accordance with Example 1 of US Pat. No. 3,100,721 with steam, then in water, and heat-treated. A coating is obtained from one Thickness of 0.4 mm.

The synthetic leather of this example is soft and pliable and is suitable for the production of clothing, shoes, boots and the like. The physical properties are the following:

Thickness, mm 1 »17

Basis weight, g / m '573

Density, g / cm ^ 0.55

Tensile strength, kg / cm ² (M / Q) 63 / 54.9

Water vapor permeability, g / h / 100 m 3416

5 ^ edge modulus, kg / cm ² (M / Q) 128.7 / 114.7

Visible roughening at -. - ■

15 percent elongation none

Example 2

The procedure is as in Example 1, but using the two

serarten a fiber fleece of 227 g / m surface weight of roughly the same type is produced. The fiber fleece is in one passage with a water pressure in the distribution line of 1 * 4 atm and 14 passages with a water pressure of 105 atü passed under the jets of water. The property

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FED-3118 ' ■ $ 0

ten dee non-woven fabric are the following:

Thickness, mm 0.77

Density, g / cm ³ 0.292

Tensile strength, kg / cm ² (M / Q) 33.9 / 28.3

5 jS secant modulus, kg / cm ² (M / Q) 8.5 / 8.0

Puncture resistance, kg / cm (M / Q) 32.9 / 27

Entanglement completeness. 0.84

Link Frequency 67

Basis weight, g / m 227

After the sample has been impregnated and coated according to Example 1, the product has the following properties:

Thickness, mm ■ 1.17

Basis weight, g / m 570, density, g / cm ⁵ 0.55

Tensile strength, kg / cm ² (M / Q) 60.5 / 52

Via water vapor permeability, g / h / 100 m 3297 5 ^ -secant modulus, kg / cm ² (M / Q) 254 / 239.4

Visible roughening at) Acceptable, however

15 percent elongation} the sieve

pattern through

example

You work according to Example 2, but with a nonwoven fabric a basis weight of 227 g / m made of spontaneously crimpable polyester fibers with a staple length of 63.5 mm and a Titer of 4.5 den. The properties of the nonwoven fabric are as follows: -

Thickness, mm - 30 - 0.88 Density, g / cm 009883/190 7 0.258 Tensile strength, kg / cm ² (M / Q). 33.4 / 30 5 ^ edge module, kg / cm (M / Q) 36.3 / 24 Puncture tear strength, kg / cm (M / Q) 30/28 Entanglement completeness. 0.91 , Basis weight, g / m 227

FFD-3118 * ^

The nonwoven is then grooved 5 times between stationary panels heated to 100 ° C, so that there is a micro-pucker in the fibers developed and a more dashing one, against roughening A permanent fiber web is created.

After impregnation and coating according to Example 1 the product has the following properties:

Thickness, ηώ '1.27

Basis weight, g / m 607

Density, ß / cra. 0.535

Tensile strength, kg / cm ² (K / Q.) 60 / 50.5 water vapor permeability, g / h / 10Q m 3128

5 '/ o secant modulus, kg / cm ² (K / Q) 206.5 / 159

No roughening at 15 percent elongation

Example 4

Bin fleece with a weight per unit area of 95 g / m made of randomly arranged, heat-shrinkable polyester fibers of 38 ns staple length and 1 1/2 den becomes through random filing from eir.e ~ Air flow produced and then wet according to Example 1 with columnar Treated water jets. The product is then steamed treated until the area shrinkage is $ 35. The sample is dried and a nonwoven fabric is obtained with the following properties:

Thickness, mm 0.69

Density, g / cm ³ 0.212

Tensile strength, kg / cm ² (K / Q) 51.2 / 45.5

5 5 ^ -secant module, kg / cm ² (M / Q) 65.3 / 17.4

Puncture tear strength, kg / cm (K / Q) 35 / 24.8

Entanglement completeness. 0.82

Loop Frequency 78

Surface weight, g / m 146

Impregnation and coating according to Example 1 give a, product with the following characteristics:

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BATH ORIGINAL

FFD-3118 3i

Thickness, mm 1.07

Basis weight, g / m 512

. Density, g / cm ⁵ . 0.535 tensile strength, kg / cm ² (M / Q) 80 / 68.5

5 fo secant module, kg / cm ² (M / Q) 154.4 / 100.9 Visible roughening at

15 percent elongation is very low

Example 5

To explain the roughening that can be found in some unpatterned Makes artificial leather products noticeable, the procedure of Example 2 is carried out with a nonwoven fabric made of polyester fibers of 38 mm staple length and 1.5 denier, which, however, is produced using the usual machine needling process has been. This nonwoven is smooth, dense and shows no pattern. It has the following characteristics:

Thickness, mm 0.9

Density, g / cm ⁵ 0.25

Tensile strength, kg / cm ² (M / Q) 48.9 / 44.9

5 # edge module, kg / cm ² (M / Q) 34.9 / 33.3

Puncture tear strength, kg / cm (M / Q) 35.3 / 33.6

Basis weight, g / m 227

By impregnating and coating this base layer according to Example 1, a product is obtained with the following properties:

Thickness, mm 1.14

ο
Basis weight, g / m 607

Density, g / cm ⁵ 0.530

Tensile strength, kg / cm ² (M / Q) 77 / 74.6

Water vapor permeability, g / hour / 100 m ² 3021 5 ^ -secant modulus, kg / cm ² (M / Q) .. 264.3 / 243.4

Roughening at 15 percent ) outspoken. Stretching } orange peel

) leneffekt

- 32 -009883/1907

FFD-3118 33

Although the artificial leather produced by this process is excellent Having overall properties, pronounced roughening occurs when the material is stretched.

Example 6

The procedure is as in Example 4, but with a mixture equal parts heat-shrinkable polyester fiber and poly ■ amide fibers. After treating the fiber fleece with steam a 25 percent area shrinkage is obtained. The properties of this base layer are as follows:

Thickness, mm 0.69

Density, g / cnr 0.18

Tensile strength, kg / cm ² (M / Q). 30.8 / 20.9 5 # edge modulus, kg / cm ² (M / Q) 3.7 / 2.3

Puncture tear strength, kg / cm (M / Q). 22.3 / 18.4 basis weight, g / m 146

Obtained after impregnation and coating according to Example 1 a product with the following properties:

Thickness, mm 1.09

Basis weight, g / m 509

Density, g / cm ⁵ 0.55

Tensile strength, kg / cm ² (M / Q) 167.7 / 87.9

5 ^ -secant modulus, kg / cm ² (M / Q) 16 / 10.7

Visible roughening at -. - ^:

15 percent elongation is very low

Example 7

The randomly deposited fiber fleece according to Example 6 is after the treatment with water jets according to Example 1 on a .Drahtnetz with 15.75 x 15.75 meshes each om and 36 # open Area passed under three water jets of 30 ° 0, which are injected under a pressure of 70 atmospheres. the Liquid jets are created from nozzle openings with a diameter

- 33 -0 0 9883/190 7

PPD-31'.Θ 5 "

cores of 0.18 mm, coming from a distribution line have been drilled at intervals of 15.75 holes per cm.

After impregnation and coating, the product has similar properties to the synthetic leather according to Example 6, however an even better resistance to roughening, because the base layer has a fine-meshed screen pattern with a minimal energy has been impressed.

Examination of the completeness and freeness of the entanglement

The nonwovens according to the invention can by the extent ' Their fiber entanglement can be identified by the entanglement completeness (c) and the entanglement frequency (f) 'des IDextilstoffs' determined. Both values are sent to the Nonwovens in the "unbonded state" on the Instron tester determined according to a special method to investigate the breaking strength. Under a "bond free state" it is to be understood that the experiment is carried out with nonwovens, the fibers of which are neither bound by a binding agent nor by a binding agent are bound to one another by mutual fusion. In other words: The specified values may only apply to the fiber loop be due.

The entanglement completeness (c) is a measure of the proportion of pasers that are used when examining a long and break a wide strip (and not slide away from each other). This value is related to the development of the strength of the nonwoven fabric.

The interlocking frequency (f) is a measure of the frequency with entanglements occurring along the length of individual fibers in the nonwoven fabric. The higher the value for the link frequency is, the higher the surface resistance of the nonwoven, i.e. its resistance to the formation of pilling effects and fraying with repeated washing.

- 34 - ■ ' 009883/1907

FFD-3118 S *.

Durable nonwovens exhibit resistance to entanglement (c) of at least 0.5, nonwovens with satisfactory surface resistance for normal textile purposes, e.g. as textiles for clothing, have a looping frequency (f) of at least 20 per 25.4 mm, preferably of at least 40 per 25.4 mm. For textile uses, which do not require a good surface appearance to be obtained after multiple washes remains, can products with a complete intertwining (c) of at least 0.5 and an interlacing frequency (f) of less than 20 can be used.

The link completion (c) and the link frequency (f) are calculated from the values of the strip tensile strength using strips of the following sizes:

Symbol of the stripe width ^w q ^w i ^w 2 stripe width in units

from 25.4 ma 0.8 0.3 2 w _Q + w-

<2.0

"In8tron" measuring length in
Units of 25.4 mm 0 1.5 1 »5

Expansion rates
in units of
25.4 Ott / min · 0.5 5 5

When cutting strips of nonwovens that have a recurring pattern, e.g. a pattern of furrows or lines of high and low basis weight, the strip width must contain whole numbers of such recurring units, always cutting through the part with low basis weight and trying to in all cases as close as possible to the desired widths for w _Q and W ₁ . However, so that W _{2 is} less than 2.0 (ie less than 50.8 mm), w _Q can be reduced somewhat. The width of the narrowest part of a W ₁ strip is critical. It must not go from the middle width of all W _{1 stripes}

- 35 - · ..- ■■. 009883 / T907

FFD-3118 **

than - 0.51 mm.

Aue patterned fabrics will streak in two directions cut out: (a) in the direction of the pattern furrows or lines from the highest basis weight (i.e. weight per unit area) and (b) in the direction perpendicular thereto. In the case of non-patterned nonwovens, you can choose any two, one on top of the other choose vertical directions.

In each selected fabric direction, ten or more strips for inspection at w .., five or more strips for inspection at W _2, and five or more strips for inspection at w _{Q are} cut out. In order to suppress the effect of localized weak points as far as possible, all strips of every size should not be cut out of successive, adjacent surfaces of the textile material. It is therefore preferable to cut all of the strips from a small section of fabric and alternate them in the following order: w., W ₂ , w ^, w _Q , etc.

Each strip is examined for tensile strength at break, whereby one Instron tester with normal, rubber-coated flat jaw surfaces and the above specified gauge lengths and strain rates are used · For a given Sample should cover the entire investigation from the time the strip is cut out to the investigation of the tensile properties can be carried out in a few hours "

The mean tensile breaking forces for each width (w _Qt, w- and W ₂ ) are for each. Direction specified as T _Q , T ₁ or T ₂ to three places after the decimal point. One observes that for each direction the relationship

W ₁ w ₂ W ₀ exists. The above inequalities exist because

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FFD-3118. *

(1) a border zone of width (D) at the cutting edges of the Samples with the long gauge length exist that have no tension can accommodate, and '

(2) at zero measuring length, the gripper jaws holding the pastes butt against each other and ideally all fibers Absorb tension up to their breaking point, while at the long measuring length some are insufficiently tangled Fibers slide past each other without breaking.

A measure of the proportion of stress-absorbing fibers in the examined textile direction is derived from the following Equations calculated and labeled (c).

Provided that (D) is less than 1/2 w «, then applies;

W ₂ - 2Ü φ -W ₂ T ^fJ? O W ₁ - 2D D = W ₁ ί Π? ^w o c = 2 (I ₂ -T ₁ ) ^W 0 (w ₂ - W ₁ ; V

In certain cases, (D) can be close to zero and even a small experimental error will result in a negative (D) value.

The values (c) and (D) become special for each fabric direction is determined, and the arithmetic mean of the values is calculated for both directions and denoted by (c) or (D).

The value (c) is referred to as the entanglement of the fabric. When (c) is larger than 0.5, (D) is a measure for the mean distance the fibers in the fabric must have to be so completely entwined that they cannot be separated without breaking. if (δ) / is less than 0.5, (D) may be due to factors other than

- 37 - ^: 009883/1907

the fiber entanglement can be influenced. Accordingly it can happen that the calculation of (D) if (c) is smaller than 0.5 is meaningless by the above method.

By examining various samples, it was observed that the surface resistance of a nonwoven fabric increased with Product of (1 / D) and the square root of the pasertiter (d) increases. Because pasers with a titer of 1.5 denier are often used all titers are normalized to 1.5 den, and the entanglement frequency (f) per unit length is 25 »4 mm then defined by the following equation:

f = (1 / D) v / d / 1.5

If the nonwoven has fibers of several different titers contains, the weight average of the titre is used for (d). If the measured value (D) is zero or negative, it can be assumed that the actual value (D) is less than 0.25 mm and (f) therefore greater than 100 / d / 1.5 per unit of length of 25.4 mm.

Paser lock attempt

The paser lock value is the maximum force in grams per each Unit of fabric weight required to pull a given sample apart between two hooks.

► Samples of 12.7 mm 25t4 mm are cut and weighed, and two points are marked on each sample, symmetrically spaced along the center line of the fabric 12.7 mm apart so that each point is 6.35 mm from the sides near one end of the fabric away.

The eyelet end of a hook (Carlisle-6 fishhook with ground Barb or a hook of a similar wire diameter and size) is attached to the upper jaw Instron tester so that the hook hangs vertically from the cheek. This hook is through

- 38 009883/1907

FFD-3118 35 ^BC

inserted the one marked point in the fabric sample.

A second tick is marked by the other point of the Specimen is inserted and the loop end of this hook is clamped into the lower jaw of the Instron. Now the two hooks are in one line, but in opposite directions Positions, and hold the specimen 12.7 mm between the hooks.

The Instron tester is set to scan the sample at a speed of 12.7 mm / min. (100 i » elongation / min.) And the force in grams that is required to pull the sample apart is recorded. The maximum load in grams divided by the basis weight of the fabric in g / m is the individual fiber lock value. The mean of three determinations in the machine direction and three determinations in the transverse direction is reported to within two decimal places of the fiber lock value.

- 39 - 00988371907

Claims (18)

EGG. du Pont de Nemours June 22nd I97O and Company FPD-3118 Claims Laminate suitable as synthetic leather and made of a nonwoven made of intertwined fibers as a base layer and one or one layer of a uniformly microporous one Polymer that adheres to one or both surfaces of the base layer, characterized in that that the fibers of the base layer in recurring coughs from locally dense areas of intertwined fibers, located between adjacent areas of intertwined fibers that are less dense than the neighboring textile areas are intertwined with one another in a random manner. 2. Laminate according to claim 1, characterized in that some of the fibers of the base layer are made of shrunk synthetic Staple fiber is made up, while the rest of the fibers of the base layer are made of unshrunk synthetic Staple fibers ". 3. Laminate according to claim 1, characterized in that ρ the base layer has about 4.65 to 1550 holes per cm. 4. Laminate according to claim 1, characterized in thatthe Base layer has about 62 to 620 holes per cm - 40 009883/1907 PFD-3118 HA 5. Laminate according to claim 1, characterized in that the fibers of the base layer are shrunk synthetic staple fibers are. 6. Laminate according to claim 5 »characterized in that the polymer is a polyurethane. 7. Laminate according to claim 5, characterized in that the polymer is a mixture of a polymer of the 'vinyl chloride and a polyurethane, which is at least Contains 30 percent by weight polyurethane. 8. Laminate according to claim 5, characterized in that the fibers of the base layer are polyacrylic fibers, cellulose fibers, Polyester fibers, polyamide fibers and / or polyolefin fibers are. · 9. Laminate according to claim 1, characterized in that the fibers of the base layer have an irregular shape are extended. 10. Laminate according to claim 1 to 3, characterized in that the base layer has recurring, parallel fiber loop areas which differ from one another in their surface density and which extend linearly on one or more axes, and that the entire base layer has a fiber loop perfection (c) of at least 0.5 and a fiber entanglement frequency (f) of
at least 25 each 25> 4 mm, determined in the bond-free state. 11. Laminate according to claim 10, characterized in that
that the fibers of the base layer are at least 50 % off
made of shrunk synthetic staple fibers 12 · Laminate according to claim 10, characterized in that that the base layer is a mixed textile, its , / a piping component consists of shrunk piping. ι ■. - 41 - ■■■■ ' 009883/1907 FFD-3118 ^ C 13. Laminate according to claim 10, characterized in that the strands of the base layer are irregular Shape are elongated. 14. Laminate according to claim 10, 12 or 13, characterized in that the polymer is a polyurethane with a tensile modulus of secant at 5 percent elongation of about 56 to kg / cm ² . 15. Laminate according to claim 10, characterized in that the polymer is a mixture of a polymer of the | Vinyl chloride and a polyurethane which contains at least 30 weight percent polyurethane. 16. Laminate according to claim 10, characterized in that the base layer has a weight per unit area of about 34 bi3 g / m. 17. A process for the production of laminates according to claim 1 to 16, characterized in that one (1) jets of liquid that are closely spaced from one another, those made up of openings from 0.05 to 0.76 mm Diameter to which the liquid is under pressure 2
of at least 14 kg / cm are injected with an energy flux density which, at the distance at which the treatment takes place, is more than 23,000 foot-poundals per 6.45 cm "sec. is, through the base layer material along continuous parallel lines, 'which have a frequency of at least two lines per cm, - with a treatment energy of at least 0.1 PS-hour. Each 453y6 g of textile material can penetrate and (2) at least one surface of the base layer treated in this way covered with a layer of a microporous polymer. - 42 -00 9883/190 7 FFD.-3i.18 IV 18..Verfahren according to claim 17i characterized in that the base layer consists of at least 50 i "of shrinkable synthetic staple fibers, prior to coating with the microporous polymer by a shrinking treatment, which can shrink the shrinkable fibers without melting them bring, condensed. 19 · The method according to claim 17, characterized in that the base layer is subjected to a treatment which elongates the fibers into an irregular shape will. - 43 009883/1907