DE2040335C3 - Natural looking leather-like material and process for its manufacture - Google Patents

Description

The present invention relates to a natural-looking, leather-like material made from a non-woven fabric Substrate bonded with a synthetic butadiene rubber, a fabric layer and a uniform microporous surface layer with a granular structure formed by wet coagulation made of polyurethane, the polyurethane also connecting the fabric layer to the substrate. the The invention also relates to a method for producing such natural-looking, leather-like material made from a nonwoven substrate.

There are already various natural-looking, leather-like materials and methods of making them known, for example the following:

1. A method which is characterized in that a polyurethane solution is applied directly to a Applying substrate for artificial leather, like a material obtained by using a non-woven Make processed with a binder, such as with a synthetic resin or natural or synthetic rubber latex, and films formed by the so-called wet Coagulation process, d. H. a method of coagulating and regenerating the applied Polymers by placing the coated substrate in a liquid that is suitable for the polymer Is nonsolvent and which is miscible with the solvent of the polymer solution, thereafter it is washed and dried (Japanese Patent Application No. 4673/1968).

2. A method which is characterized in that a synthetic polymer solution is used applies a woven fabric that coagulates the polymers through what is known as dry coagulation and regenerated, d. H. a method in which the solvent is removed by drying with hot Air is removed, or a moist coagulation procedure as above, one being first forms a granular layer and then the granular layer thus formed with an adhesive applied to a substrate of non-woven fabric.

3. A method which consists in making a pile fabric or fluff with a synthetic polymer solution impregnated, the impregnated fabric of a moist coagulation treatment subordinates and the resulting product to a non-woven product that was previously made with a synthetic polymer solution was impregnated, placed on top without drying and immediately thereafter the combined fabrics subjected to a moist coagulation and regeneration treatment and then washes and dries (Japanese Patent Application No. 3718/1966).

4. A process that consists in getting a. Substrate of a non-woven fabric woven fabric lays a dispersion through the woven fabric on the inner part of the fabric The substrate can penetrate by suction from the lower side of the substrate and then the Polymers coagulate and regenerate according to a wet process followed by washing and drying (U.S. Patent 34 18 198).

However, the product obtained by the method 1 is poor in tear strength and poor dimensional stability, which leads to a setback in the deformation of the product.

In the above-described method 2, there are various disadvantages when the substrate connects to the woven fabric or product. The choice of adhesives that can be used is very limited because of the properties of the structure at low temperature and its flexibility and because of the destructive effect of the solvent of the adhesive on the granular layer formed what result in a decrease in moisture permeability and roughening of the granular surface layer makes noticeable.

The above method 3 has the disadvantage that it is difficult to obtain a product with a softer and smoother Surface as the surface of the nonwoven fabric covered with the granular polymer is rough, and it is therefore necessary to have a relatively thick granular layer around a to maintain a smooth surface.

In the method 4 described above, there arises a problem with regard to the surface rits of the granular Layer on. The amount of polyacre solution that is drawn into the substrate by suction device differs at the various points because of the different pore sizes that are located on the surface of the substrate. Farther the artificial leather thus obtained is not always satisfactory because there are no leather-like cracks or Contains wrinkles, which is due to the fact that the polymers contained in the granular layer and the Adhesive layer used are the same.

The object of the present invention is to address the major disadvantage of conventional artificial leather eliminate, which consists in the fact that the known artificial leathers do not give breaks that the natural Resemble leather.

Surprisingly, there has now been a method for producing natural-looking, leather-like Material made from a nonwoven substrate has been found to have the various disadvantages mentioned above overcomes.

The invention relates to a natural-looking, leather-like material made from a non-woven A substrate bonded with a synthetic butadiene rubber, a fabric layer and a uniform microporous surface layer with a granular structure formed by wet coagulation made of polyurethane, the polyurethane also being the

each layer connects to the substrate, the quence of 11 Hz, from 3.0-10 ⁸ to 1.0 · 10 ⁹ Dynjcw?

is characterized by the fact that the microporous upper has, the dynamic modulus of elasticity the

Smile layer with a granular structure made of one with ses polyurethane for the adhesive layer by at least

Polyurethane terminated in an alcoholic residue 1.0 · 10 ⁸ dynes / cm ² lower than that of the poly-

consists that is free of ether bonds and must be of 5 urethane for the granular surface layer.

sinem polyester polyol without ether bonds as the process according to the invention

Polyol component is formed, uud the one dynamic - a natural-looking, any kind, artificial

mix modulus of elasticity, measured at 30 ° C 'and leather material to produce cracks and wrinkles

at a frequency of 11 Hz, from 4.0 · 10 ^B to and that in its appearance very strongly

1.5 · 10 ⁹ dynes / cm ² , and that the weave of natural leather is similar when bent. To-

layer with the substrate layer through a micro- in addition to the many properties mentioned above

porous co-shaped polyurethane adhesive layer-composite, this leather material is an improved film material-

is made of a polyurethane with hydroxyl end group, which is used for shoes, bags, belts, clothing,

pen made of a polyol with at least one of accessories, interior decoration, upholstered furniture, such as

Ether bond is formed in the molecular chain and chair covers and the like are suitable. It owns

which has a dynamic modulus of elasticity, measured excellent moisture permeability, wear and tear

at 30 ° C and a frequency *. of 11 Hz, of tongue resistance, flexural strength, dimensional stability

3.0 10 ⁸ to 1.0-10 ⁹ dynes / cm *, with the dynamics, surface smoothness, homogeneity and none

mix modulus of elasticity of these polyurethane adhesive layer splitting properties.

layer by at least 1.0-10 ⁸ dynes / cm ² lower than 20 It is surprising that according to the invention a

is that of the polyurethane of the surface layer. natural-looking, leather-like material for

Another important subject matter that can be presented is that of the natural

The invention is a method to closely resemble the above mate leather, and in particular fractures

rial through simple process steps in industry and wrinkles like natural leather. This

len scale easy to maintain. 25 properties are only available through a special selection

The natural-looking, leather-based polyurethane resins according to the invention according to the present invention like material made from a nonwoven substrate, the method available. It must be admitted that bound with a synthetic butdiene rubber the use of various polyurethanes for the herist, a fabric layer and one by wet coagulation of artificial leather is already known, but The person skilled in the art from the prior art can use the surface layer made of polyurethane formed lation the fabric layer with the substrate also do not expect that by selecting special polydurch Polyurethane is connected, is thereby produced urethane with the elastic defined according to the invention, that on a surface of a non-modulus one can obtain a product that is naturally woven Substrates that so closely resemble a synthetic leather.

Butadiene rubber is bound, homogeneously an organic 35 The substrate, which can be used in the present invention niche solvent solution of a linear poly, can be applied in the following way urethane, a fabric layer on which can be adhered: by interweaving any layer on top , homogeneously an organic one or more types of fibers, such as synthetic solvent solution of a linear polyurethane for table fibers, such as polyamide, polyester or poly the granular surface layer on the fabric * o acrylonitrile fibers, or natural fibers, such as tree layer, after a Part of the adhesive wool fibers, and regenerated fibers, such as viscose solutions, the surface of the fabric layer made of rayon staple fibers and the like; the so formed flows, whereby a coagulation of the adhesive layer Random fabric is then needled or provided with needles because of the evaporation of the solvent with holes, whereby a non-woven fiber is formed, and thus a four-layer laminate is formed, and that so obtained will not. After that, the laminate is dipped into a liquid woven fabric and then subjected to the finishing treatment, which for the linear polyurethanes is a treatment with the binder made from a synthetic nonsolvent and which is miscible with the organic polymers or a natural or synthetic solvent of the two solutions, rubber latex. A substrate added particularly before the polyurethanes in the adhesive is obtained, if the non-layer and woven fabric in the granular surface layer are simultaneously coagulated with 50 to 350 percent by weight and the solvent is washed off - preferably 100 to 250 percent by weight, calculated, and dried. This process is inventively impregnated on the product, a liquid which is characterized according to the fact that for an aqueous dispersion of synthetic butadiene formation of the microporous surface layer with rubber, such as styrene-butadiene copolymer of granular structure, a solution of a with an aiko - and similar, a vulcanizing agent and a VuI-holischen residue terminated polyurethane used, contains canization accelerator, the impregnated that is free of ether bonds and vulcanized with a poly product by heating with steam, ester polyol without ether bonds as polyol grain> o washes and warms and the surface of the de-duck is formed and a dynamic elasticity- 60 standing film material, so that it becomes smooth, with a modulus of 4.0 · 10 ⁸ to 1.5 · 10 ⁹ dynes / cm ² , measured by a belt grinder,
at 30 ° C and a frequency of 11 Hz, as a woven product or fabric that can be used in the and that can be used to form the adhesive layer between the invention, such heGewebe and substrate a solution of a polyurethane should be imagined that are cut from Staple fibers with hydroxyl end groups are used, which is formed from a 65 or filament, yarn from synthetic fibers, polyol with at least one ether bond in the molecular chain such as polyamides, polyesters, polyacrylonitrile fibers and which is a dynamic or similar, measured from natural fibers, such as tree's modulus of elasticity at 30 ° C and a wool, or regenerated fibers, such as viscose rayon

Staple fibers, are woven. The main reason woven fabrics are used is in that the articles obtained from the natural-looking leather-like structure have dimensional stability want to lend. Otherwise, there are no restrictions on their physical properties.

The linear polyurethane used for the granular surface layer in the invention includes Polyurethane segment elastomers, d. H. Elastomers, which are divided into sections and terminal alcoholic Have groups, and which consist of three components, i. H. an organic diisocyanate, a Polyester with hydroxyl groups at both ends, which is composed of a polymethylene glycol and a organic dicarboxylic acid is obtained, and a GIykol exist as a chain extender. The polyurethane can either be produced by the prepolymer process, which is characterized by that you first have a prepolymer with isocyanate groups at its ends by reacting 1 mol a polyester with terminal hydroxyl groups with 3 to 6 moles of an organic diisocyanate, the prepolymer dispersed in a solvent for polyurethanes and 2 to 5 moles of a glycol added to cause further polymerization, or by a one-step process that thereby is characterized by the fact that the above-mentioned three components are dissolved in a solvent for polyurethanes and polymerizes them immediately. In this case, the polymerization is achieved in that one stoichiometrically fewer hydroxyl groups than isocyanate groups used in order to achieve a predetermined Viscosity can be achieved by stopping the polymerization reaction by adding a polymerization terminator or inhibitor containing active hydrogen atoms associated with the isocyanate groups can react, quits. As an organic diisocyanate compound, which is a component of the polyurethanes preferably aromatic and cycloaliphatic diisocyanate compounds should be mentioned such as tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,5-naphthylene diisocyanate, paraxylene diisocyanate, 4,4'-methylene-bis (cyclohexyl isocyanate) and the like, among which diphenylmethane-4,4'-diisocyanate is most preferred. As a polyester with terminal hydroxyl groups, which is one of the A polycondensation product is said to be the main constituent of the granular surface layer of the polyurethanes a polymethylene glycol and an organic dicarboxylic acid. As an example one Glycols should include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, or the like which can be used alone or together. Most preferred glycol is ethylene glycol alone or a mixture of ethylene glycol and propylene glycol. Examples of organic Dicarboxylic acids include succinic acid, adipic acid, sebacic acid, terephthalic acid and the like, among which adipic acid is most preferred. A desirable average Molecular weight of the ester with terminal hydroxyl groups, which is produced by the polycondensation of the glycol and the organic dicarboxylic acid is formed is in the range of 1,000 to 3,000, more preferably 1,500 up to 2500. As a glycol that can be used as a chain extender and which is also a polyurethane component of the granular layer, either ethylene glycol or tetramethylene glycol is suitable.

Furthermore, every monofunctional compound, which contains active hydrogen atoms, from the theoretical point of view, serve to facilitate the polymerization To quit, however, studies have shown that the polymeric solutions are in their Behaviors vary widely, depending on the end groups of the agent that one used to quit the Polymerization used. For example, if an alcohol is used as a polymerization terminator, thus, the resulting resin solution exhibits excellent anti-foaming properties, thereby forming a grain layer with a smooth surface and a film with luster can be formed after coagulation and regeneration. In this case, however, the redissolving speed is not very high. If an amine is used, in order to terminate the polymerization, a polyurethane solution is obtained which is remarkable dissolves again quickly, but does not show a good antifoam effect, so that it is difficult to get out of it make a film with a smooth surface as required for the granular layer.

In the case of a solution that is mainly a polyurthane with terminal hydroxyl groups, the solution itself shows properties similar to one Solution that contains a polymer with terminal alcoholic residues, but a coating solution that is made by incorporating further compounds or additives into it, shows, compared with the latter, a decrease in the redissolution rate.

As previously described, the properties of a polymer solution depend mainly on polyurethane contains, depends strongly on the type of end groups of the polyurethane. Since it is believed that the properties by the presence of an excess amount of the agent that terminates the polymerization, are influenced, a comparison of the properties of a polymer solution prepared by Adding an amine to the polymer prepared using an alcohol as the polymerization terminator had been prepared, and a polymer solution, in which you add an alcohol a polymer added using an amine as a polymerization terminating agent had been prepared, and it was found that the properties of both polymer solutions were only affected by the polymerization terminator used in the first Stage had inflicted. This confirms the assumption that the properties of the polymerization solution of the Depending on the type of end groups of the polymer. From the above studies it can be seen that a Monoalcohol is important as a polymerization terminator for the polyurethanes for the granular layers is.

The average molecular weight of the above-mentioned polyurethane elastomer is preferably as high as possible as the redissolution rate of the polymer solution allows. Since the granular bodies require the article high fatigue strength, the viscosity of a polyurethane solution having a content of 35 weight percent solids should suitably in the range from 50,000 to 200 000cps at 30 ⁰ C, preferably from 70,000 to 150,000 cps at 30 ° C lie.

609639/124

The polyester polyol, ie the one component for the granular layered resin according to the invention, should, without reducing the coagulation and regeneration rate of the polymer solution, provide a granular point which has the necessary properties such as high modulus of elasticity and resistance to scratching or scratching.

The elastic modulus required for the above-mentioned polymer was found to be a dynamic modulus of elasticity determined at 30 ° C. and at a frequency of 11 cycles using a Vibron-DI) -VII-type tester with respect to one Film of 0.1 mm thick formed according to the so-called dry coagulation method, preferably in a range of 4.0 x 10 ⁸ to 1.5 x 10 ⁹ dynes / cm ² , more preferably 4.7 x 10 ⁸ to 1, 0 · 10 ⁹ dynes / cm ² , most preferably 5.0 · 10 ⁸ to 7.5 · 10 ⁸ dynes / cm ² . If the dynamic elastic modulus is less than 4.0 · 10 ⁶¹ dynes / cm ² , the resulting polymer is too soft and easily damaged, and therefore it is not; always suitable for the granular layers. If the dynamic elastic modulus is higher than 1.5 x 10 6 "dynes / cm ² , the resulting polymer becomes hard and its fatigue strength (flexural strength) is remarkably lowered, so that it sometimes cannot be used for leather-like structures.

The water-miscible solution of a polyurethane in a solvent thus obtained can be one or more types of different polymers that are soluble in the solvent, such as polyvinyl chloride, Add polyacrylonitrile, polyacrylic acid and their copolymers as a secondary component.

In the process according to the invention, the polymer or the polymers, which are mainly polyurethane, as described above, included, in the form applied to a solution in an organic solvent. As examples of such solvents that Can be used alone or together in combination, such as N, N'-dimethylformamide, Ν, Ν'-Diinethylacetamid, Dimethylsulfoxyd or similar. A diluent or an extender such as acetone, methyl ethyl ketone, Tetrahydrofuran, dioxzm, and the like can also be used when making the polymer do not coagulate.

The coating solution used to form the granular layer is a viscous solution in the above-described solvent of a polymer mainly containing the aforementioned polyurethane or, if desired, urea or thiourea, a coloring agent such as a dye or contains a pigment, a light stabilizer, fillers such as talc and which is in a liquid state ^{at a temperature below 30 ° C.}

In order to facilitate the application of the solution to the woven fabric connected to the substrate , the viscosity of the coating solution should suitably be in the range of 5000 to 150,000 cps at 30 ^° C., preferably 20,000 to 100,000 cps at 30 ^° C. .

The linear polyurethane used as an adhesive layer to the nonwoven fabric substrate and the woven fabric must have the following three properties:

1. The ability to form a film according to the so-called wet coagulation process and the ability to form an adhesive layer with a microporous structure under the same coagulation

forming conditions such as those required for the granular layer;

2. Good adhesive strength with respect to the substrate, in particular with respect to its binding agent;

ίο 3. The dynamic modulus of elasticity of the polyurethane must be lower than that of the polyurethane for the granular surface layer.

The aforementioned property 1. is therefore

t5 desirable so that the moisture permeability, which is required for artificial leather is not reduced, and the property 2. is used to bond between the substrate and the woven fabric, which is an object of

ao ing invention. Property 3 is a requirement in order to form cracks on the surface of the articles when they are bent, which are similar to natural leather.
Since the non-woven fabric used according to the invention is bound with a butadiene rubber binder, it is necessary to pay particular attention to which linear polyurethane is used as the adhesive layer so that the property mentioned under 2. is satisfactory, since polyurethane is generally poor with butadiene rubbers glued.

A polyurethane for the adhesive layer having the above properties is suitably a polymeric compound having two terminal hydroxyl groups prepared from an organic diisocyanate, a polyol having terminal hydroxyl groups having at least one ether bond in its main molecular chain, and a glycol.
As an organic diisocyanate compound, ie as

a component of the polyurethane for the invention Adhesive layer, aromatic and cycloaliphatic diisocyanates such as tolylene-2,4-diisocyanate, Tolylene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,5-naphthylene diisocyanate, paraxy

lendiisocyanat, dicyclohexyM ^ '- diisocyanate and similar are mentioned.

As a polyol with terminal hydroxyl groups and at least one ether bond in its main molecular chain mention should be made of a polyester polyol which

obtained by polycondensation of a glycol with a ether bond and an organic dicarboxylic acid, and a polyether polyol. Examples of glycols used above are diethylene glycol and dipropylene glycol. Examples of dicarbon

acids are succinic acid, sebacic acid and adipic acid. Examples of the latter are polyethylene glycol Polypropylene glycol or polytetramethylene glycol, their preferred average molecular weight in the range from 1000 to 3000, preferred!

in the range from 1500 to 2500.

Many of the well-known man-made leathers own the disadvantage that they do not have natural leather-like cracks or wrinkles or crimps when bent exhibit. In other words, natural leather egg

6s can be easily distinguished from artificial loaders by the appearance of the cracks formed when bending. Natural leather shows many fine cracks " in a direction perpendicular to the bending direction, while

rend artificial leather only forms thick cracks. Accordingly, the former will stress distributed by tension or pressure over the bent part, while the latter the stress concentrates on one spot. As a result, there are great differences in the flexural strength between the two on. Many attempts have therefore been made to produce structures that are natural provide looking leather-like cracks from both an appearance and a mechanical standpoint Property off.

Surprisingly, it has been found that natural-looking leather-like cracks appear on the surface the article can produce if the elastic moduli of the polyurethane for the granular layer and the polyurethane for the adhesive layer is precisely differentiated. If one uses a polyurethane for the former with excellent re-dissolution properties and a slightly higher modulus of elasticity than the latter, an article is obtained which exhibits similar behavior when bent like natural leather.

For the adhesive layer, a polyurethane which has a modulus of elasticity which is lower can be used than that of polyurethane for the granular layer, can be created by making a polyurethane, which has a low content of organic diisocyanate. However, the coagulation and Regeneration rate is very lowered when the diisocyanate content is reduced, which consequently in the production of a natural-looking leather-like structure poses problems, so that Washing is necessary for long periods of time, and if washing is insufficient, the surface of the grainy Layer becomes rough as it dries. Hence, the method described above is for degradation of the modulus of elasticity of the polyurethane for the adhesive layer are not suitable, and moreover does not meet the requirements mentioned under 1 above.

To obtain a polyurethane for the adhesive layer that has the same or a higher coagulation and regeneration speed compared to that for the granular layer, it is necessary to to keep the organic diisocyanate content equal to or higher than that in the polyurethane for the granular Layer. Under such conditions, a polyurethane can have a comparably low modulus of elasticity can be obtained by using a polyol as a raw material which is at least has an ether bond in its main molecular chain

A polyurethane with terminal hydroxyl groups, which is made from a polyol that contains ether bonds, has better adhesiveness compared to synthetic butadienic rubber ■ as a polyurethane that has no ether bond in its main molecular chain

Accordingly, if one obtains a polyol that has an ether bond in its main molecular chain possesses, used as a raw material, a polyurethane which has a relatively low modulus of elasticity together with excellent adhesiveness to the rubber binder of the of non-woven fabric without reducing the rate of coagulation and regeneration will.

The only means that can be used as raw material the chain of the polyurethane used for the adhesive layer in the method according to the invention is 1,4-tetramethylene glycol, that meets the desired requirements. The physical properties of a polymer are greatly influenced by its end groups, in other words, by the class of agents that is used to terminate the polymerization. Seen from this point of view, a poly-

urethane with terminal hydroxyl groups has excellent adhesiveness compared to the synthetic one butadiene rubber, which is used as a binder of the substrate. Therefore, as a polymerization terminating agent glycols are used for the polyurethane. The termination or stopping agents provide hydroxyl groups for both ends of the polymer, Examples thereof are ethylene glycol, propylene glycol, 1,4-tetramethylene glycol and 1,6-hexamethylene glycol. Of these, the most preferred are

ao added propylene glycol and 1,4-tetramethylene glycol, which react easily with the isocyanate groups.

Although a bifunctional glycol as a chain extender in the polymerization reaction it can also be used as an inhibitor

* 5 den to stop the polymerization when it is in excess amount is added all at once into the polymerization system, thereby reducing the stoichiometric Equivalence relationship between the isocyanate groups and the hydroxyl groups is lost.

The larger the number of terminal groups per unit weight, the better the adhesiveness of the polyurethane described above. As previously described, the polyurethane is in solution in an organic solvent is used as the adhesive layer, and there should be a coagulation speed as large as possible, with the coagulation speed from the average Molecular weight depends, with the former being higher and the latter being smaller. this fact is in accordance with the requirements for adhesiveness, where it is preferred that the content of terminal groups in the polymer is higher. Accordingly, it is preferable that dei Degree of polymerization is as low as possible and as is the various physical properties allow.

The average molecular weight of the polyurethane for the adhesive layer, which is determined by the viscosity at 30 ° C from a 35% solution is advantageously in the range of 8000 bii 130000cps, more preferably in the range of 20000 bii 100,000 cps.

The polyurethane used as the adhesive layer in the present invention can be if obtained either by the prepolymer process or by the one-step process under the same conditions as those used for the granular layer polyurethane here before were written.

The composition of the linear polyurethane for the adhesive layer should be chosen so that it is in a suitable relationship to the: polyurethane of the granular layer used, in such a way that the dynamic modulus of elasticity of this polyurethane for the adhesive layer to a range of 3, 0 · 10 ⁸ to 1.0-10 »dynes / cm ⁸ , preferably 3.5 · ΙΟ ⁸ to 8.0 · 10 ⁸ dynes / cm ^l . The best results are obtained when the polyurethane

the adhesive layer has a dynamic modulus of elasticity of ^{3.7-10 8} to 5.0-10 ⁸ dynes / cm ² and if it is lower than that of the polyurethane for the granular layer by at least 1.0 · 10 ⁸ dynes / cm ² that you use together with it.

Examples of organic solvents used in the invention for the polyurethane for the adhesive Layer that can be used include N, N '-dimethylformamide, N, N' -dimethylacetamide, Dimethyl sulfoxide and the like. A diluent or an extender such as acetone, methyl ethyl ketone, Tetrahydrofuran, dioxane and the like can also be added to the solvent, if they do not cause the polymer to coagulate.

The coating solution that is applied to the substrate is made by simply adding a Dissolving the polyurethane in the organic solvent with the aforementioned solvent diluted or by adding urea, thiourea, a filler such as talc, a neutral to the solution Salt, such as sodium sulfate, sodium chloride, calcium carbonate or the like, incorporated and also a Pigment or dye admixed in a given case. Such solutions are preferred at a temperature below 30 ° C for a long time in the liquid state; about that To facilitate applying the aqueous solution to the substrate, it is desirable that it be at 30 ° C have a viscosity in the range of 5,000 to 50,000 cps, more preferably 8,000 to 30,000 cps. It is preferred that the polymer solution for the adhesive layer has a polymer content of 10 to 40 percent by weight owns.

The coagulation bath used in the method according to the invention is a liquid which is a nonsolvent for the linear polyurethane and that with the organic Solvent is miscible, for example water, an aqueous solution of an inorganic salt and an organic solvent that is a nonsolvent for the polyurethane and that with the Solvent of the polyurethane solution is miscible.

As inorganic salts can be used sodium chloride, aluminum chloride, ammonium chloride, Sodium sulfate, ammonium sulfate, aluminum sulfate or the like, and if desired, can urea or thiourea can also be added.

The optimal concentrations of the salts in the aqueous solutions used in the coagulation bath are in the following areas:

Sodium chloride 200 to 300 g / l

Aluminum chloride 200 to 450 g / l

Ammonium chloride 100 to 250 g / l

Sodium sulfate 200 to 300 g / l

Ammonium sulfate 150 to 350 g / l

Aluminum sulfate 100 to 200 g / l

In case when urea or thiourea together is used with the saline solution, the concentration of the aqueous solution becomes appropriate chosen so that it is in the range of 100 to 350 g / l, depending on the type of concentration of the inorganic salt in the coagulation bath. As a suitable organic solvent to be used in the coagulation bath, mention should be made of alcohols such as methanol, propanol and the like, and ketones such as acetone, methyl ethyl ketone and the like ..

As described above, various kinds of compositions can be used as the coagulation bath and a particularly preferred composition is an aqueous solution of an inorganic Salt or a combination of this aqueous solution with urea or thiourea. The bath temperature for the coagulation and regeneration is advantageously in the range from 25 to 55 ° C and especially at 30 to 40 ° C.

For the implementation of the method according to the invention, a device is described whose Execution is explained in more detail below. First, a coating solution of the polyurethane for the

ao adhesive layer on a substrate in such a Amount applied so that the final thickness is approximately 0.05 to 0.2 mm, taking into account that the amount of the coating solution depends on the solids content in the solution. After that, a woven Make applied to it. A coating solution for the granular layer is then applied at a time when part of the coating solution for the adhesive layer through the surface of the woven fabric exudes. The amount of coating depends on the solids content in the solution and it is therefore adjusted so that the final thickness of the granular layer is in the range of 0.2 up to 0.5 mm. At this stage of manufacture it is not beneficial if the woven product is made with the Polyurethane solution for the granular layer is coated before the polymer of the adhesive layer through the surface of the woven fabric sweats because air is in the texture of the woven Make is present, rises into the granular layer and creates macropores or small holes are formed therein.

Preferred ranges of elastic moduli of the polyurethane for the granular layer of the polyurethane for the adhesive layer have been described above

♦ 5 den. The modulus of elasticity of the polyurethane for the granular layer must be at least 1.0 · 10 ⁸ dynes / cm ² greater than that of the adhesive polyurethane.
After coagulation and regeneration it will

washed repeatedly and then dried

A device which is suitable for carrying out the method according to the invention contains a device for applying the polymer solution for the adhesive layer to the substrate, a

Apparatus for placing the woven fabric on top of it, an apparatus doing a polymer solution for to apply the granular layer to the woven fabric because it is on the substrate, unc a device to transform the structure into a coagula

tion bath to conduct so that simultaneous coagulation of the adhesive and granular polymer occurs If the method according to the invention is carried out by using such a device, s < Problems arise as to which apparatus or equipment should be used to make the adhesive and to use the granular polymer, and wi these devices should be roped against each other.

Coating devices that are suitable for carrying out the method according to the invention, include all known t, covering devices, for example a reverse roll coater that is loaded from above, a reverse roll coater, which is fed from below, a doctor roller application machine, an ink roller application machine, a direct three-roll coater, a micro-jet coater, doctor blade or knife application machine, hot dipping of coatings, flotation coating with a doctor blade, counter-rotating coating with a doctor blade, inverted coating with a doctor blade, coating with a slot die coater, and among these is coating with a reverse roll coater preferably. Neither application with a micro-jet application machine nor application with a printing press is very suitable, since the former is subject to dirt, gelled urethane, etc. sometimes accumulates at the tip of the missile, and as a result, longitudinal stripes are formed on the coated surface, and in the latter, the amount of applied solution is too small.

In the present invention, the coating apparatus should be chosen or designed so that the woven fabric is not pressed too hard onto the substrate by the adhesive is, but that it floats on the adhesive or is freely movable on it, so that the adhesive can sweat through the top surface of the woven fabric. For this reason is a Roller coater for the granular layer with two reversing rollers more preferred than one with three reversing rollers, because the latter is the woven product that does not yet match the substrate is connected, because of the shear forces between the application roller and the counter-pressure roller do not sweat what creates tension in the woven fabric. With the squeegee or knife application machine it is difficult to create a smooth surface. On the other hand, if the adhesive layer, which has been applied to the substrate contains uneven thicknesses, are supplied by the roller application machines with two reversing rollers a non-smooth coating, which is a partial separation between the woven fabric and the substrate, and then an applicator with three Un.-control rollers suitably used.

The leather-like material obtained according to the invention contains four layers, a substrate layer, an adhesive layer, a fabric layer and a granular surface layer, where the modulus of elasticity the adhesive layer is relatively lower than that of the granular layer and wherein the material very closely resembles natural leather in its appearance when bent, and it is the same exquisite Has properties like natural leather, so it can be used in the same way as this one can.

The disadvantages exhibited by the known artificial solvents are absent; i.e. that the Material according to the invention provides natural-looking, leather-like breaks when bent, so that the Pressure is distributed by tension and compression, and the flexural strength is greatly improved. The The characteristic feature of the present invention is that the adhesive polyurethane, that between the substrate and the ge

wove make is applied, a polyurethane is used that has a relatively low average Has molecular weight and contains at least one ether bond in its main molecular chain and two

has terminal end groups, so that it has good adhesive properties compared to synthetic butadinischera rubber has, and that it also has a lower elasticity and greater coagulation and Has regeneration speed than the poly-

urethane for the granular layer For the granular layer one uses a polyurethane with relative high average molecular weight that does not contain an ether bond in its main molecular chain and that two terminal alcoholic residues

holds so that it has a good anti-foam effect, which after coagulation and regeneration provides a smooth surface, and still has this Polyurethane has a relatively higher elasticity than adhesive polyurethane.

ao Before the invention is explained by means of examples will be, will be in the manufacturing process 1 to 7 the production of polyurethane solutions for the granular layer and for the adhesive layer should be used, described in more detail.

»5 The examples then deal with the production of! natural-looking, leather-like structures in which solutions are used, their production is described in this manufacturing process. The term "part" describes in the manufacturing

examples and in the following examples "parts by weight".

The determinations were made according to the following test procedures:

1. The peel strength of a substrate from a woven fabric is determined in the following manner using an Instron TM-M type pilot machine (manufactured by Instron Co. Ltd.) definitely. A sample that is 2.5 inches wide and

15 cm long, 5 cm is forcibly lifted or peeled off on the examination device at a distance of 5 cm from the Holding device placed and at a speed of 10 cm / min. Pulled away 10 cm

gen. The separation force is determined by an average value of three maxima and three Minimum specified.

2. The moisture permeability is determined as follows and is given by the amount of water (mg) that passes through a sample of 1 cm ^{2 in} one hour: A sample is placed in an aluminum dish containing calcium chloride, sealed well with paraffin and placed in an atmosphere of 80 ⁰ zo

relative humidity at 30 ° C for three hours. The amount of water taken by the Calcium chloride is absorbed is determined.

3. Dynamic modulus of elasticity:

A 20%, Ν'-dimethylformamide solution of Polyurethane is made, a film 1.5 mm thick is cast on a glass plate, one Heated hour at 60 ° C and further at an elevated temperature of 80 ° C for three hours Sucking heated with a water jet pump, leaving a clear dry film of a thickness of about 0.1 mm. This film is made on a Vibron DD-VII type experimental device appropriate, and then would

Curves recorded showing the dependence of the dynamic modulus of elasticity at 30 ° C.

4. The formation of cracks is observed with the naked eye by bending the specimen.

5. Flexural strength was measured using a flexiometer (manufactured by Yasuda Seüa Seisakusho Co.) by bending the sample at 90 cycles per minute

Manufacturing process 1

In a polymerization reactor equipped with a device for the passage of nitrogen gas was, 72.9 TeUe of polyethylene glycol reaction were a further 4 hours 25 minutes at 60 ° C away. After the viscosity of the solution reached 69,000 cps, 2.5 parts became ethano added to terminate the polymerization. The polymer solution obtained was viscous and transparent having a viscosity of 105,000 cps at 30 ° C

Manufacturing process 4

39 parts of diethylene glycol adipate (DEGA) with an average molecular weight of 2000 µm two terminal hydroxyl groups were mixed with 23, (parts of 4,4'-diphenylethane diisocyanate with stirring and introducing a stream of nitrogen gas by heating at 80 ° C. for two hours. The

adipate (EGA) with an average molecule 15 nien at 80 ^u C wä

lar weight of 2056 and two terminal hydroxyl reaction product was in 130 parts Ν, Ν'-di

ao

large weight - -

groups and 44.1 parts of 4,4'-diphenylmethanednsocyanate flakes reacted for three hours at 80 ° C., a prepolymer being obtained. After cooling to 30 ° C., this was dissolved in 194.6 parts of Ν, Ν'-dimethylformamide containing 0.012% water, and 44.9 parts of 1,4-tetramethylene glycol were then added with stirring. The reaction was carried out at 30 ° C for one hour, and then the temperature was raised to 60 ° C, which took 30 minutes. 3 hours 10 minutes after they had raised the temperature to 6O ⁰ C, achieved ": solved the viscosity of the polymerization methylformamide and gefcühlt on Zimmertemperatui. 6.4 parts of 1.4 · tetramethylene glycol were added to this solution, and the mixture was then heated at 60 ° C. for a further 4 hours. After the reaction solution reached a viscosity of 70,000 cps at 30 ° C, 1.7 TeUe of ethanol was added to terminate the polymerization. The resulting polymer solution was a transparent solution with a viscosity of 97,000 cps at 30 ° C.

Manufacturing process 5
73 parts of EGA with an average mol-

a value of 68,000 cps if you have 46.3 parts 73 parts EUA with a

Ν, Ν'-Dimethylformamide, which was previously obtained with 2.4 parts by weight of 2056, was 26.7 parts

4,4'-diphenylmethane diisocyanate reacted at 8O ⁰ C for two hours in a nitrogen gas stream, where '.in prepolymer was obtained. The prepolymer was dissolved in 194 parts of N, N'-dimethylformamide containing 0.012% water, and after cooling to room temperature 6.2 parts of 1,4-tetramethylene glycol were added as a chain extender. The reaction was continued at room temperature for 30 minutes with stirring

The polymerization reaction was continued to the similar 40, and then the temperature within- ' heated half of 30 minutes to 70 ° C. The Um

Settlement was continued for 3 hours 40 minutes at this elevated temperature. After the viscosity the reaction solution had reached 63,000 cps,

len methanol mixed into the polymerization reaction mixture added to stop the polymerization. The N, N'-dimethylformamide solution thus obtained of the polyurethane resin was a viscous, clear solution having a viscosity of 98,000 cps at 30 ° C.

Manufacturing process 2

Manner as described in the preparation process I and was terminated by a) a dispersion of 3.9 parts of 1,4-tetramethylene glycol in 46.3 parts of N, N'-E> imethylformamide or b)

a dispersion of 2.2 parts of p-toluidine in 46.3 parts of 1.7 parts of ethanol was added to the polymerisation N, N'-dimethylformamide (to terminate the excess ion. This gave a transparent

Amino groups were after the end of the polymerization by adding 3 parts of acetic acid neutralized) as a polymerization terminating agent added to the reaction solution, the viscosity of the so Solution at 30 ° C was 70,000 cfw. The received Polyurethane solutions were viscous, clear solutions with viscosities of 95,000 cps at 30 ° C im Case of a) and of 95 500 cps at 30 ° C in case of b).

55

Manufacturing process 3

45 parts of EGA with an average molecular weight of 1,500 and z: \ vei terminal hydroxyl groups were 4,4'-diphenylmethane diisocyanate flakes with 37.5 parts reacted with stirring in a nitrogen gas stream by heating for two hours at 80 ° C. The prepoly

mere was in 192 parts of N, N'-dimethyll: ormamid, 65 parts of Ν, Ν'-dimethylformamide, as the polymerization Contained 0.012% water, dissolved and added to six fractions of the reaction temperature chilled. Solution was added to this solution when each fraction was a Viskosi-10.2 Parts 1,4-tetramethylene glycol and performed the fact reached of a) 2700 cps, b) 3500 cps,

viscous polyurethane solution with a viscosity of 112,000 cps at 3O ⁰ C.

Manufacturing process 6

89.1 parts of diethylene glycol adipate (DEGA) with two terminal hydroxyl groups and an average one Molecular weight of 2038 and 14.5 parts of 1,4-tetramethylene glycol 1,4-TMG were 236.4 Share Ν, Ν'-dimethylfonmamide, which is 0.015% water contained, dissolved, and 54.1 parts were added thereto with stirring and introduction of a stream of nitrogen gas 4,4'-Diphenymethane diisocyanate flakes (MDI) too. After the dissolution of the 4,4'-diphenylmethane diisocyanate has ended the temperature was increased to 60 ° C. within 30 minutes. Proceeded with stirring the polymerization reaction, and then there were 4.8 parts of 1,4-tetramethylene glycol. solved in 53.5

:) 10500q> s, d) 22,000 cps, e) 31,000 cps or E) 61,000 cps. Thus, one transparent polyurethane resin solutions was 6300 cps / 30 ⁰ C and the viscosities of a), b) from 8 500 cps / 30 ° C, c) 25 000 cps / 30 ⁰ C, d) 53 000 cps / 30 ° C ₅ s) 78,000 cps / 30 ⁰ C or f) 103,000 cps / 30 ⁰ C.

Manufacturing process 7

Similar to the manufacturing process described under 6 Polyurethane solutions were prepared having the compositions as shown in Table 1 are shown.

Table 1

Polyol class

MW

Amount in divide

MDI

Amount in parts 1 !, 4 TMG

Amount in divide

Polymerization

termination

medium

Resin solution

Viscosity (cps / 30 ⁰ C)

a EGA 2056 39.8 24.1 6.4 1,4-TMG 38 500 b DPGA 2036 50.0 31.2 8.7 1,4-TMG 70 500 C. PTMG 1500 50.0 31.3 7.77 1,4-TMG 71800 d PTMG 2473 62.0 18.8 4.98 1,4-TMG 48,000 e PTMG 1500 50.0 37.5 10.6 1,4-TMG 51300

Note: DPGA - dipropylene glycol adipate. PTMG - polytetramethylene glycol. MW - molecular weight.

example 1

35

To 100 parts of the polyurethane solution obtained in Production Method 1 was added 5.25 parts of urea, 3.5 parts of calcium carbonate, 0.7 parts of carbon black and 10 parts of Ν, Ν'-dimethylformamide and mixed the mixture well in a kneading machine at 60 ° C. for two hours to obtain a coating solution for the granular layer with a viscosity of 75,000 cps at 30 ° C. ·

100 parts of the polymer solution, prepared according to the preparation process 6 f), were mixed with 7 parts Calcium carbonate and 44 parts of Ν, Ν'-dimethylformamide in a kneader or mixer at 60 ° C Mix well for one hour, using a coating solution for the adhesive layer having a viscosity of 14,000 cps at 30 ° C.

On the nonwoven fabric used as a substrate and containing nylon and polyester fibers in a ratio of 30:70 and bonded with 150% styrene-butadiene copolymer, the coating solution for the adhesive layer was applied with a three-roller applicator resulting in a final thickness of 0.05 mm. Then, cotton shirt fabric made of polyester fiber / cotton blended spun yarn was subsequently laid thereon, and at the time when the coating solution for the adhesive layer sweated through the surface of the shirt cloth, the coating solution for the granular layer thereon became homogeneous applied by a coater with two rollers so that a final thickness of 0.3 mm was obtained. Immediately thereafter, the laminated material was immersed or bathed in an aqueous solution of 250 g / l sodium sulfate and 200 g / l urea for 10 minutes to achieve the simultaneous coagulation and regeneration of the adhesive layer and the granular layer. Then it was washed with hot water, dried, pressed and a cover was applied to produce a natural-looking, leather-like material. Ilen. When bent, this material forms breaks that are very similar to those of natural leather. It has a peel strength of the substrate from the woven fabric of 1.9 kg in the warp direction and 1.81 kg in the weft direction, a moisture permeability of 3.7 mg / cm * / hour. The values of the dynamic elastic modulus at 30 ° C (frequency: 11 cycles) of the granular resin and the adhesive resin were 6.1 x 10 ⁸ dynes / cm ² and 4.2 x 10 dynes / cm ^2, respectively.

Example 2

To 100 parts each of the polyurethane resin solution obtained in accordance with production processes 1, 2 a), 2 b) and 4 7 parts of freshly precipitated calcium carbonate were added, and a suitable one Amount of Ν, Ν'-dimethylformamide to make the solution viscosity at 30 ° C of approximately 15,000 cps Achieve, the reaction mixture was mixed in a kneader at 60 ° C. Each of the so obtained Solutions have been used to form the adhesive layer in the manufacture of synthetic leather, as in Example 1 described, used. The natural-looking leather-like material obtained had the properties in Table 2 given physical properties.

./ft Table 2 20 40 335 22nd 2 B) 4th EGA DEGA Shark Solution No. -NH ~ <3-CH, -OE, Polyol 1 2a) 95 500 97000 End groups EGA EGA Viscosity of the original resin -OE, -OH 6.1 108 4.2-108 solution (cps / 30 ° C) 98000 95,000 Dynamic modulus of elasticity of the 1 > 1 Adhesive layer (Dyn / cm * at 30 ° C) 6.1 108 6.2-1O ⁸ Dynamic elasticity ratio module of the granular layer to the 1 1 Adhesive layer 1.10 1.49 ^; Separation strength (kg / 2.5 cm *): 0.98 1.43 Chain are not formed will Shot 1.18 1.43 educated Natural looking leather-like breaks 1.04 1.32 not broken not
Broken will not will not Flexural strength at 300,000 cycles educated educated Broken Broken

Moisture Permeability (mg / cmVh) 2.4

2.7

3.2

3.8

From Examples 1 and 2 above, it can be seen that terminal hydroxyl groups contain, and whole

that the adhesive strength between the substrate and especially when using a polyurethane

the woven fabric is higher if one turns than kle 30, which fulfills both conditions. In a sol-

The resin used is a polyurethane which, from a case in point, has a synergistic

a polyol made with an ether bond kung in terms of adhesive strength,
or if you use a polyurethane,

Example 3

For every 100 parts of the solution of approximately 8,000 cps to be produced according to the 30 ° C production

procedure 6 a), 6 b), 6 c), 6 d), 6 e) and 7 a). The solution thus obtained was used as a coating

made polyurethane solutions, 7 parts of the solution were used to form the adhesive layer,

Precipitated calcium carbonate and other necessary and natural-looking leather-like materials were

if N, N'-dimethylformamide, while in a 40 the method described in Example 1 is produced

Kneader heated at 60 ° C to a viscosity of represents. The results are given in Table 3.

Table 3

Resin solution no. 6 b) 6 c) 6d) 6e) 7 a) > 1.52 6 a) DEGA DEGA DEGA DEGA EGA 1.33 Polyol DEGA -OH- -OH -OH -OH -OH will End groups (resin) -OH 8 500 25,000 53,000 78,000 38,000 not
educated Viscosity of the original resin 6,300 breaks solution (cps / 30 ⁰ C) 4.1 · 108 3.9 ♦ 108 3.8 · 108 4.1 ⁸ 6.3 · 108 Dynamic modulus of elasticity of the 4.0 · 108 Adhesive layer (Dyn / cm * at 30 ° C) > 1 > 1 > 1 > 1 1 Dynamic elasticity ratio > 1 moduli of the granular to the Adhesive layer Separation strength (kg / 2.5 cm): 1.68 2.45 2.78 2.41 Chain 1.40 1.62 2.66 2.61 2.37 Shot 1.21 will will will will Natural looking leather-like breaks will educated educated educated educated educated breaks breaks breaks breaks Flexural strength at 300,000 cycles breaks not not not not not

Moisture Permeability (mg / cmVh) 4.3

4.1

4.1

4.2

3.9

3.9

It can be seen from Table 3 that excellent adhesive strength is obtained when the polyols that are used to make the polyurethanes for the adhesive layer, ether bonds have and if their viscosity at 5 30 ° C of a 35% solution is within the range from 8,000 to 130,000 cps [(see example 6 b), 6 c), 6 d) and 6 e)] or especially in the range from 20,000 to 100,000 cps [cf. Example 6c), 6d), 6e)]. A polyurethane that has no ether bond in the polyol component, as described in Example 7 a), does not give high adhesive strength, even if the original viscosity of the 35% solution is in the above area.

From table 2 and from table 3 it is also possible to

It is obvious that leather-like breaks appearing naturally are formed when the ratio of the dynamic The elastic modulus of the granular resin to the adhesive resin is greater than 1.

Example 4

The polyurethane solutions produced in each case by production process 7 c), 7 d) and 7 c) were with Ν, Ν'-dimethylformamide to a viscosity diluted at 30 ° C from 20,000 cps, using coating solutions to form the adhesive layer received. Natural-looking, leather-like material was made according to the procedure described in Example 1 manufactured. The results are given in the table.

Table 4

Resin solution no. 7c) 7 «

7 c)

Polyol

End groups _o

Viscosity of the original resin solution (cps / 30 C)

Dynamic modulus of elasticity of the adhesive layer (Dyn / cm * at 30 ° C)

Ratio of the dynamic moduli of elasticity

Polyurethane of the granular layer to the adhesive

Polyurethane

Separation Strength (kg / 2.5 cm)
Chain
Shot

Natural-looking leather-like fractures. Flexural strength at 200,000 cycles

Moisture permeability (mg / cm * / hour) Note: PTMG - polytetramethylene glycol.

PTMG PTMG PTMG -OH -OH -OH 71800 48,000 51300 3,6 · ΙΟ « 2.4 · 108 1.3 109

> 1

2.25
2.49

will
educated

not
Broken

3.3

> 1

1.72
1.58

will
educated

not
Broken

0.7

<1

4.10 3.76 are formed

broken (from the grainy to the adhesive layer)

3.4

"Clearly is that who * the dynamic Elasüatatemodul of the adhesive _g material-polyurethane / located in the area of W"> dyne / cn, as a result of a bad keitspermeabilität occurs even if the 'dynamic modulus of elasticity from the results of Table 4 P of the granular layer ™ ***** is greater than 1 This fact Reutet, Sn to obtain a polyurethane with a modulus of elasticity L in the region of 2.5 30 ° C, the content of J "" J must be, since in In such a case the speed of dissolution is so rapid that the effectiveness of the article is strong

& it can also be seen that in the substance-polyorethane with a
modulus of elasticity in the range of, J flexural strength decreases sharply, since that itself is flat, and «upper limit of dynamic

man, adhesive polyurethane considerably below 2.2 · 10 »dynes / cm ² .

Example 5

To 100 parts each of polyurethane solutions, which according to the manufacturing process 2 a), 2 b), 3, 4 and 5 were prepared, 10.5 parts of thiourea and 10.5 parts of precipitated calcium carbonate were added and mixed in a kneader at 60 ° C. It was diluted with N, N'-dimethylformamide to Prepare coating solutions for the granular layer that have a viscosity of approximately 70 0 () 0 cps possessed at room temperature.

To 100 parts of the polyurethane solutions, prepared according to the preparation process 7 b), were 3.5 Parts of calcium carbonate were added, and the mixture was mixed in a kneader at 60 ° C and mixed with NJi'-dimethylformamide diluted to make a coating solution for the adhesive layer with a viscosity of about 15,000 cps at room temperature to manufacture.

609.439 / 124

On a substrate of a non-woven fabric, the viscose staple fibers and polyester fibers in a ratio of 30:70 and with 200 weight percent, calculated on the fibers, of a styrene-butadiene copolymer was bound, the coating solution for the adhesive layer with a Three-roll coating machine applied to a finished thickness of 0.05 mm. Immidiatly after nylon gauze was placed on it, and when the adhesive solution through the surface of the woven Make sweat, became the coating solution

for the granular layer thereon with a two roll coater Applied in a finished thickness of 0.3 mm. The thus laminated material was in an aqueous solution containing 200 g / l of sodium chloride and contained 400 g / l urea, bathed at 45 ° C for 5 minutes, around the granular layer and the adhesive layer to coagulate and regenerate, after which it was washed with hot water, pressed and provided with a coating. In this way, natural-looking leather-like materials were obtained. The results are given in Table 5.

Table 5

Resin solution no. 2 a) 2b)

Granular layer:
Polyol
End groups

Viscosity of the original
Resin solution (cps / 30 ° C)

Dynamic modulus of elasticity
(Dyn / cm * at 30 ° C)

EGA EGA > CH ₃ EGA EGA EGA -OH —NH- / ~ -OE, -OE, -OE, 95,000 95 500 105,000 97,000 112,000

6.5 · 108 6.4 · 10 »1.7 · 10» 4.1 · ΙΟ «3.1 · ΙΟ ⁸

Adhesive layer: DPGA Polyol -OH End groups 70 500 Viscosity of the original Resin solution (cps / 30 ° C) 3,6-IC Dynamic modulus of flux (Dyn / cm * at 30 ° C) J. i Resin solution No. 7 b)

Article:

Ratio of dynamic
Modulus of elasticity of the surface layer to the adhesive layer

> 1

> 1> 1

> 1

<1

Separation Strength (kg / 2.5 cm) 2.23 2.34 Chain 2.10 2.39 Shot educated educated Natural looking leather strings Fractions no no Flexural strength (200,000 cycles) Break Break 1.5 3.4 Moisture retention (mg / cmVh.) I. Π Condition of the granular surface

2.31 2.29 2.18 2.47 2.18 2.35 educated not not educated educated breaks no no Break Break 1.5 3.1 0.9

IV

Remarks: I = a little bad.

Π = poor antifoam effect of the resin layer solution. ΠΙ = easily cracks when scratched. IV = low.

From Table 5 it can be seen that when the poly-65 is made hard and very poor urethane the granular layer has a dynamic fatigue strength and that a product of Modulus of elasticity in the region of 1.7-10 · Polyurethane with a dynamic modulus of elasticity Dyn / cm *, it is almost plastic, and that this is in the region of 3.1 · 1QeDyn / cm * because of the

bad re-resolution speed none shows good surface conditions. From this one can conclude that the dynamic modulus of elasticity is the granular layer must be in a narrower area than the area between the two corresponds to the above values.

It can also be seen that, in the case of a polyurethane for the granular layer with therminal hydroxyl groups, the moisture permeability is increased 55.0 parts Ν, Ν'-dimethylformamide with stirring at 60 ° C for two hours, was mixed in a kneader and produced a solution for the KlebstoSschicht having a viscosity at 3O ⁰ C 15 000th In a manner similar to that described in Example 1

ring and that the grainy surface is not so much a natural-looking leather-like material because of its poor redissolution, good is made by adding an aqueous solution of

40 ° C, the 200 g / l ammonium sulfate and 250 g / l sodium chloride contained, used as bath liquid for coagulation. The results are in Table 6 is specified.

Table 6 also gives values for a comparative article, which according to the prior art Technique by bonding a substrate and a woven fabric with an adhesive, covering

no natural-looking leather-like breaks formed with a granular resin and coagulation after be det. The experiments have also shown so-called wet process was established. the

Comparative article was made with a polyurethane that was made using a polyol was, although in the invention, specified as viscosity range of a 35% solution of the polyol which, however, does not contain any ether bonds in the polyol. The values that were used in the manufacture of the comparative article, are obtained in particular in terms of tensile strength and elongation at break,

added 17.5 parts of thiourea, 7.0 parts of CaI- 3 ° those clearly inferior in their production cium carbonate and 0.3 parts of carbon black, microporous surface layers with a granular structure were also used Parts of Ν, Ν'-dimethylformamide were added, and the door made of such a polyurethane was used who-mix was in a kneader for 3 hours at 60 ° C, but as an adhesive layer, polyurethane, in their mixed. A coating solution was obtained in this way. Use for polyols with hydroxyl end groups the granular layer with a viscosity of 35 det, these polyols at least one 64,000 cps at 30 ° C. Ether bonds contained in the molecular chain.

speed, and further it is practically impossible to use an amine as a polymerization terminating agent to be used because of the poor anti-foaming effect of the coating solution.

It can be seen that when the difference in the dynamic elastic moduli between the polyurethane of the granular layer and the adhesive polyurethane is more than about 0.5 dynes / cm ² ,

that articles are easily scratched by scratching on the granular surface when the polyurethane the surface layer contains ether bonds in its main molecular chain.

Example 6

To 100 parts of a polyurethane solution prepared according to Preparation Method 1,

Table 6

Chain Comparison item Shot Chain According to the invention
article Shot Thickness (mm)
Weight (g / m ² )
Apparent specific weight (g / cm ³ )
Surface hardness 1.54
1013
0.66
72 1.43
805
0.56
60

Strength (kg / mm «) 0.97

Elongation to break ( ^e / o) 25.3

Modulus at 10% elongation (kg / cm ² ) 16.8

Elastic recovery at 5% 92.3 elongation (° / o)

Tensile strength (kg) 4.0 G ar 1 ey stiffness (cm · g) 89.7 Young modulus (kg / mm *) 5.55 Moisture Permeability (mg / cm ² / hr) 1.5

0.77 32.5 9.5 92.8

5.5

59.2

2.39

1.5

0.95 29.9 14.2 91.0

7.1

59.7

3.31

4.2

0.70 34.8 6.6 95.0

8.0

43.0

1.02

4.2

Claims (12)

'L ; Patent claims: I. Natural-looking leather-like material made of a non-woven substrate which is bound with a synthetic butadiene rubber, a fabric layer and a uniform microporous surface layer formed by wet coagulation with a granular structure made of polyurethane, the polyurethane also connecting the "> fabric layer to the substrate characterized in that the microporous surface layer with a granular structure consists of a polyurethane terminated with an alcoholic radical, which is free from ether binding and is formed from a polyester polyol without ether binding as a polyol component and which has a dynamic modulus of elasticity, measured at 30 ° C and at a frequency of 11 Hz, from 4.0 · 10 ⁸ to 1.5 · 10 ⁹ dynes, »o cm ² , and that the fabric layer is connected to the substrate layer by a microporous coagulated polyurethane adhesive layer made of a polyurethane with hydroxyl end groups that is made from a polyol with at least one eth bond is formed in the molecular chain and has a dynamic modulus of elasticity, measured at 30 C and a frequency of 11 Hz, of 3.0 · 10 * to 1.0 · 10 ⁹ Dyn'crn *, the dynamic modulus of elasticity of this polyurethane Adhesive layer is at least 1.0 · 10 ⁸ dynes / cm ² lower than that of the polyurethane of the surface layer. 2. Naturally working leather-like material according to claim 1, characterized in that the dynamic modulus of elasticity of the polyurethane of the adhesive layer is in the range of 3 ;; · 10 ^s to 8.0 · 10 ⁸ dynes / cm «and that of the polyurethane of the granular surface layer is in the range from 4.7 · 10 ⁸ to 1.0 ^{· 10 9} dynes / cm ² . 3. Of course, acting leather-like material according to claim 1, characterized in that the dynamic modulus of the polyurethane of the adhesive layer is in the range of 3.7 -10 5.0-10 ⁸ to ⁸ dyne / cm ² and the grained surface layer in the calculation of 5 , 0 · 10 ^a to 7.5 · 10 ⁸ dynes / αη ² . 4. Naturally acting leather-like material according to claim 1, characterized in that the nonwoven substrate with a styrene-butadiene copolymer or an acrylonitrile-butadiene copolymer is bound. 5. The method for producing a natural-looking leather-like material according to claim 1, wherein a solution of an adhesive resin in an organic solvent is homogeneously applied to a surface of a nonwoven substrate bonded with a synthetic butadiene rubber, on the surface of the substrate, a The fabric layer is applied, a solution of a polyurethane in an organic solvent is applied homogeneously to the surface of the fabric layer after part of the adhesive solution has flowed out to the surface of the fabric layer, and the laminate obtained is immersed in a liquid which is a non-solvent for the adhesive resin and the polyurethane of the surface layer is and is miscible with organic solvents of the two solutions, whereby the polymers are coagulated and the solvent is washed out and dried, characterized in that, in order to form the microporous surface layer with a granular structure, ei ne solution of a polyurethane terminated with an alcoholic radical, which is free of ether bonds and is formed with a polyester polyol without ether bonds as a polyol component and has a dynamic modulus of elasticity of 4.0 · 10 ⁸ to 1.5-10 «dynes / cm«, measured at 30 ° C and a frequency of 11 Hz, and that a solution of a polyurethane with hydroxyl end groups is used to form the adhesive layer between tissue and substrate, which is formed from a polyol with at least one ether bond in the molecular chain and which has a dynamic modulus of elasticity , measured at 30 ° C. and a frequency of 11 Hz, from 3.0 · 10 ⁸ to 1.0-10 »dyne / cm ² , the dynamic modulus of elasticity of this polyurethane for the adhesive layer being at least 1.0-10 ⁸ Dyn / cm ^{2 must be} lower than that of the polyurethane for the granular surface layer. 6. The method according to claim 5, characterized in that the nonwoven substrate with a styrene-butadiene copolymer or an acrylonitrile-butadiene copolymer is. 7. The method according to claim 5, characterized in that the polyurethane for the adhesive ^{layer has a dynamic modulus of elasticity of 3.7 ■ 10 8} to 5.0 · 10 ⁸ dynes / cm ² , the polyurethane for the granular surface layer has a dynamic modulus of elasticity of 5 .0 · 10 ⁸ to 7.5 10 ⁸ dynes / cm ² , the difference between these values being at least 1.0 · 10 ⁸ dynes / cm ² . 8. The method according to claim 5, characterized in that the adhesive solution has a viscosity at 30 ° C, calculated to a concentration of 35%, from 8,000 to 130,000 cps, preferably from 20,000 to 100,000 cps, and the polyurethane solution for the granular surface layer a viscosity at 30 ° C, calculated to a concentration of 35%, from 50,000 to 200,000 cps, preferably from 70,000 to 150,000 cps. 9. The method according to claim 5, characterized in that for the formation of the microporous granular surface layer a polyurethane is used, which is made by reacting a polyester glycol with a medium Molecular weight from 1000 to 3000, made from ethylene glycol or ethylene glycol / propylene glycol and adipic acid, an organic diisocyanate and ethylene glycol or tetramethylene glycol, wherein the polymerization reaction has been terminated by a monoalcohol has been. 10. The method according to claim 5, characterized in that for the formation of the adhesive layer a polyurethane is used which is prepared by reacting a polyether polyol and / or a polyester polyol produced by polycondensation of a glycol with at least one ether bond with an organic dicarboxylic acid, with an organic diisocyanate and 1,4-tetramethylene glycol, the Implementation is terminated by a glycol. 11. The method according to claim 5, characterized in that that the liquid for coagulating the polyurethanes is an aqueous inorganic salt solution or an aqueous solution of an inorganic one Salt and urea or thiourea. ίο 12. The method according to claim 5, characterized in that the formation of the adhesive layer solution of the linear polyurethane used in addition urea, thiourea, Contains sodium sulfate or sodium chloride.