DE2425553A1 - METHOD OF EQUIPMENT OF MATERIALS MADE OF LEATHER AND LEATHER REPLACEMENT - Google Patents

Description

DR. MÜLLER-BORE dipl.-ing. GROENING DIPL.-CHEM. dr. DEUFEL DIPL.-CHEM. DR. SCHÖN DIPL.-PHYS. HERTEL

PATENTANWÄLTE l · 4 2 0 ü 0 3

S / R 14-93

Rohm and Haas Company, Philadelphia, Pa. / UNITED STATES

Process for finishing materials made from leather and leather substitutes

The invention relates to the finishing of raw hides, which are made for use as split leather as well as cheap flawless ones as well as fully grained leather, as well as other substrates used as leather substitutes are, for example, textiles, nonwoven webs and other webs that are suitable for the production of leather imitations are. It is also possible to finish pore-containing materials, other plastic materials and other leather-like materials Materials that result in products that have the aesthetic characteristics expected from leather. The invention also applies to the finished products. They can improve the properties of a leather or leather-like Materials used to make shoes, purses, clothing, ribbons, upholstery, wallets or the like is used. The improvements

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may refer to one or more of the following Properties related to: flexibility, abrasion resistance, adhesion, Water vapor permeability, wear resistance, Grip or hardness or other leather-like aesthetic properties.

The invention is particularly suitable for finishing leather and leather replacements with irregular surface defects or with an unsatisfactory appearance, as this process can be used by a single Coating a uniform artificial and covering leather-like Apply scar surface to the substrate. Furthermore, a controlled application of the coating has the consequence that the reproduction of the substrate ("photographing") is kept to a minimum.

When finishing leather and leather substitutes, one is constantly looking for methods, cheap or destroyed Improve materials. Fener is looking for cheap alternative materials for the microporous urethane laminates heretofore used for this purpose are essentially nonwoven webs to cover pore-containing materials.

Textile fabrics have already been successful with polymeric preparations or coated deformable polymeric preparations which foam on the fabric (see US Pat. No. 3,527,654). This method however, it cannot be successfully applied to nonwoven substrates, as they are used, for example, for leather equipment, due to the fact that the coordination of the Properties expected of leather and leather substitutes are more difficult than in the case of conventional textile goods is to achieve. Examples of leather with an initially unsatisfactory appearance that can be successfully improved are leathers that have pronounced hair follicles or other undesirable skin features, such as burn marks,

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Scars as well as protrusions. For example, a tanned pig skin can be coated according to this method, with a leather with an excellent finish is obtained. This method is particularly applicable to split leather. Under application this process gives split leather an excellent aesthetic appearance as well as good physical properties, . and to a greater extent than was previously the case with the application the usual split leather finishing methods is possible.

The process also eliminates the need for the leather substrate to impregnate, although in certain cases it has been found that a better product can be obtained if one Impregnation is carried out.

The invention provides a method for finishing a substrate made of leather or any other material that can be used as a leather substitute, the consists in

a) to apply a coating of a polymer latex to the substrate which contains a blowing agent which 1) consists of a solvent with a boiling point of -46 to 104 ° C (-50 to 220 ^° F), in which the non-crosslinked polymer Has a swelling ratio of 1 to 7, or 2) consists of a chemical blowing agent,

b) foaming the latex on the substrate and drying the coated substrate, preferably at a temperature of 49 to 204 ⁰ C (120 to 400 ⁰ F),

c) pressing and curing the coated substrate at such a temperature and pressure that the pressed foam adheres to the substrate, preferably at a temperature of 66 to 204 ⁰ C (150 to 40O ⁰ F) and below a pressure of 0.35 to 175 kg / cm ² (5 to 2500 psi) and

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d) a coating of equipment on the compressed foam surface to raise.

The properties of the coated substrate depend to a considerable extent on the properties of the foamable latex, which makes it possible to produce a soft, flexible and water-vapor-permeable coating. Becomes an equipment cover made of a durable resin, then a high resistance to abrasion and wear is achieved, without sacrificing flexibility or water vapor permeability of the foam coating are lost. Sowb & l the foam over-eye as well as the equipment coating determine the final properties and the mode of operation of the system.

With regard to the term “leather substitute”, refer to the definitions pointed out, as described in U.S. Patents 3,537,883, 3,110,721 and 3 000 757 can be found.

A compressed foam cover means a cover which is compressed after a cellular structure is obtained, and either by even pressing together or selectively by embossing.

A preferred embodiment of the invention consists in

a) to apply a coating of a polymer latex to the substrate and foaming the latex on the substrate using a blowing agent that expands

1) a solvent having a boiling point of 24-104 ⁰ C (220 ° F comprising 75 bis) in which the non-cross-linked polymers swelling ratio of 1 to 7, or

2) consists of ammonium bicarbonate,

b) drying and foaming the substrate coated with the latex at a temperature of 66 to 199 ⁰ C (150 to 390 ^{0 F),}

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c) the foam coated substrate under a pressure of 0.35 to 175 kg / cm (5 to 2500 psi) and at a temperature crimping, embossing, and hardening from 66 to 163 ° C (150 to 325 ° F), and

d) as an equipment coating on the pressed substrate covered with the foam, one or more of the following specified Preparations to apply: Preparations that contain maleic resins, urea / formaldehyde condensates, nitrocellulose, urethanes, Polyvinyl chlorides, acrylic compounds, cellulose acetate butyrates, Nitrocellulose or modified urethanes.

As a result of the differences between leather and leather substitutes Slight variations of the preferred methods of finishing these respective substrates are contemplated. For example, if the leather substrate is a full grain leather, a split leather or a reconstituted leather, then the preferred method is to perform the following stages:

a) the spraying of a coating of a polymer latex on the leather and in its foaming on the leather using a solvent foaming agent with a boiling point of 24 to 104 ⁰ C (75 to 220 ⁰ F), in which the non-crosslinked polymer has a swelling ratio of 1 to 6,

b) in the drying and foaming of the leather coated with the latex at a temperature of 82 to 163 ° C (180 to 325 ⁰ F),

c) in a uniform pressing and / or embossing as well as in a curing of the leather covered with the foam under a pressure of 1.0 to 84.0 kg / cm (15 to 1200 psi), usually at a temperature of 66 to 149 ° C and especially 82 to 132 ° C (180 to 270 ⁰ F), and *

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d) in the application of a preparation, the nitrocellulose and an isocyanate-terminated prepolymer from an organic Contains polyisocyanate with a polyester or polyether polyol or cellulose acetate butyrate as a finish on the leather covered with the pressed foam.

If a leather substitute is to be coated, the preferred method is to perform the following steps:

a) spraying a coating from the polymer latex onto the leather substitute and foaming the covering onto the leather substitute using a solvent blowing agent with a boiling point of 24 to 104 ^° C. (75 to 220 ^° F), in which the non-crosslinked polymer has a swelling ratio of 1 to 6,

b) in the drying of the leather substitute coated with the foam at a temperature of 49 to 204 ⁰ C (120 to 400 ⁰ F),

c) in the uniform pressing and / or embossing and hardening of the leather substitute coated with the pressed foam at a pressure of 0.35 to 175 kg / cm and preferably under a pressure of 3.5 to 70 kg / cm (5 to 2500 psi or 50 to 1000 psi) and at a temperature of 66 to 204 ⁰ C (150 to 400 ⁰ F) and preferably at a temperature of 135 to 163 ° C (275 to 325 ° F), and

d) in the application of a mass, the nitrocellulose and an isocyanate-terminated prepolymer made from an organic polyisocyanate with a polyester or polyether polyol or cellulose acetate butyrate as a finish on the with the pressed foam cover provided leather substitute.

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The use of lower pressures as well as higher temperatures is preferable in the case of leather substitutes as this improves the adhesion of the coating to the substrate. Many of the synthetic and man-made leather-like materials do not require the stated high temperatures to be achieved sufficient adhesion so that at their Use can be carried out at lower temperatures and in compliance with lower pressures.

These temperatures and pressures apply to pressing using a flat hydraulic or mechanical press, when used, the period of time during which contact is made with the bed can easily be determined. at The use of a rotary device to carry out the pressing is the length of time during which the material is is in contact with the roll and the contact pressure is more difficult to determine. Therefore there are some deviations from to these conditions, including the embossing temperature expect. The pressing, embossing and curing times usually vary from 0.5 to 10 seconds. In the case of leather the time is preferably between 2 and 6 seconds. When processing leather substitutes, the time spans lie delayed between 0.5 and 2 seconds.

For the production of pressed foam coatings, as they are currently used in the textile industry, one uses one mechanically generated foam that is knife-coated onto an endless web of fabric. The squeegee is used to finish leather not possible because too large an amount of the coating material is lost, and furthermore there is no uniform coating on the Leather can be applied, which often has a varying thickness. A mechanically generated foam can be sprayed on can be applied, but the foam may collapse during spraying. Furthermore, the high volume throughput makes of the low density foam required to

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To apply a satisfactory coating, such a process is unsuitable. A spray on of the non-foamed mixture often results in inadequate coverage of the surface as well as inadequate coverage.

Depending on the volatility of the blowing agent, foaming can occur as the coating exits the spray gun as it it is possible to use solvent blowing agents with a boiling point that is below ambient temperature. Furthermore, this can Foaming take place only when the coated substrate is dried in an oven. As the penetration of the coating is generally a resulting in better adhesion, but providing a stiffer feel, control of the final properties of the coating is now possible through a selection of blowing agents which have the desired properties, as explained in more detail below will be.

It is known a stable cellular foam structure from one To produce latex acrylic copolymers (see, for example, US Pat. No. 3,640,916). It was found, however, to be a mere knowledge the volatility of the solvent is insufficient to control the quality and structure of the foam. It is also the interaction of the solvent with the polymer must be taken into account, as there is a direct relationship between the swelling ratio as well as the solvent available to foam the polymer. Using solvents, at whose use the swelling ratio falls within the specified limits, it is now possible in a reproducible manner to carry out desired foaming. Once the solvent is dissolved in the polymer, it is no longer able to foam of latex available.

Of course, the solvent would be able to do the polymer to foam if it is still in the polymer after the

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Water has been driven off and further heat is added. You have to choose between foaming the latex and foaming of the polymer differ. The process of creating a cellular structure by internal gas or steam generation runs differently than the generation of a foam from a latex, since in this case the continuous phase (water) is the expanded structure, which is stabilized as a cellular network by the fact that latex particles on the surface the bubbles form films or supports which remain after the continuous phase has evaporated.

It has been found that solvents are in a narrow swelling ratio range fall, capable of delivering products, -which have a uniform coating of a compressed Have foam which, when compressed, is able to mask many undesirable defects. The swelling ratio is taken as the volume of swollen polymer network in a given solvent divided by the volume of the polymer sample before solvent treatment. The corresponding numerical values can be easily found in the laboratory using a variety of simple test methods, with the the fastest, a gravimetric method, is when performing it the polymer is weighed before and after the equilibrium treatment with the solvents in question. Under Taking into account the corresponding densities of the polymer and the solvent, the volumetric swelling ratio can be determined determine . Examples of these solvents are dichlorodifluoromethane, Carbon tetrachloride, trichlorotrifluoroethane, pentane, hexane, cyclohexane, trichlorofluoromethane, monochlorofluoromethane, Monobromotrifluoromethane, monochlorodifluoromethane, Octafluoroyclobutane and isomers thereof.

The amount of blowing agent used varies preferably from 3 to 20% by weight, based on the total weight of the Formulation. In general, the amount of the selected

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Solvent between 7 and 12% by weight, based on the Weight of the formulation.

In addition to the solvent-type blowing agents, chemical blowing agents can also be used, which can be both organic and inorganic in nature. Examples of organic chemical blowing agents are azo compounds such as azobisformamide, azobisisobutyronitrile, diazoaminobenzene, N-nitrose compounds such as N, N ^f -dimethyl-N, N'-dinitrosoterephthalamide and N, N ¹ -dinitrosopentamethylene tetramine, such as sulfonyl hydrazide, for example , p-toluenesulfonylhydrazide and 4,4'-oxybis (benzenesulfonylhydrazide). Examples of inorganic chemical blowing agents are ammonium bicarbonate, sodium bicarbonate, sodium carbonate, hydrogen peroxide, ammonium nitrate and malonic acid, with ammonium bicarbonate being the preferred chemical blowing agent.

The amount of foam applied depends on the type of substrate as well as the desired appearance. An application of 15 to 30 g / 0.09 m (sq.ft.), in a moist state, is recommended for a finely polished, impregnated split leather with hair cell printing, as the impregnation helps to seal the surface and keep the foam system out . A damp application in an amount of 30 to 60 g / 0.09 m may be necessary if it is a non-impregnated rough split leather with a deep lizard-like pattern. Jobs in the 60g range should generally be avoided unless the samples are unusually deep. The wet applications described above relate to a foam which is applied from a formulation which contains approximately 50 to 55 % of the polymer, the applications varying with the polymer content.

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The drying step can be carried out at a temperature of 49 to 204 ⁰ C (120 to 400 ⁰ F). A certain degree of crosslinking takes place during this stage, but this should be kept to a minimum, as excessive crosslinking can affect the embossing ability. In general, the drying temperature and the drying time are determined by simple experiments and by error calculation, these parameters being changed until the desired properties have been achieved.

The drying time depends on many factors, but generally an oven dwell time is from 2 to 8 minutes sufficient. When drying, it is essential to control the drying conditions to prevent excessive skin formation Foam is avoided, which has poorer results, in which case longer drying times are necessary because a skin insulates and seals the moist foam underneath. The main variables The factors that play a role in drying are the temperature, the dwell time, the amount of foam applied and the in amount of air flowing through the oven. The amount of air flowing in the oven is an important variable that is created by adjusting the baffles can be controlled in most ovens, although in certain ovens it is possible to change the fan speed is. It is expedient that not at high speed flowing air currents, although they are favorable for a quick drying, impinge directly on the foam, since this too serious turbulence and skin formation. The exact extent of drying is determined by keys. Of the Foam should be dry enough that it isn't sticky to the touch, but not so dry that the material doesn't Embossing pattern can accept more. Laboratory readings show that there is a considerable amount of time during drying between a too small and excessive drying is available. Become at-

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for example, 3 minutes was determined to be the best drying time in the case of a particular installation, then 1.5 minutes likely to give an acceptable result, the only downside being the material quality after embossing can be lifted slightly worse from the plate, while drying for a period of 5 minutes there is likely to be only a slight decrease in the embossing pattern, but otherwise acceptable results are obtained will. Reproduction of the pattern is extremely important because without this pattern the equipment will not look authentic of leather.

The next stage consists of pressing as well as curing the substrate coated with the foam and is carried out as a single stage. The substrate coated with the foam coating is subjected to a pressure of 0.35 to 175 kg / cm (5 to 2500 psi) and preferably a pressure of 1.0 to 84.0 kg / cm (15 to 1200 psi) at a temperature of 66 psi subjected to 204 ⁰ C (150 to 40O ⁰ F) and preferably from 66 to 163 ° C (150 to 325 ° F). The compression can be carried out in the form of an embossing, different compression pressures being exerted on different parts of the foam. The need to carry out pressing, embossing and hardening separately is no longer necessary, but these stages can be carried out separately.

After drying and before pressing and curing, the coated substrate can be exposed to minimal pressure (e.g. 0.35 kg / cm (5 psi), if necessary, in order to better handle the coated substrates can. At this point in the process the coating is slightly tacky and may tend to delaminate when the coating is removed is brought into contact with another material, or if the substrate with the coated side facing other with Foam coated substrate is laid. However, a mini

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Apply pressure to ensure that the coatings adhere sufficiently.

The final stage in the implementation of the process according to the invention consists in applying one or more finishing coating compositions to the pressed foam surface. The equipment or The finish coat is preferably one that is stretchable, bendable and contains one or more of the following ingredients: Nitrocellulose, urethanes, polyvinylchloride, acrylic compounds, Cellulose acetate butyrate or a preparation, the nitrocellulose and an isocyanate-terminated prepolymer from an organic Contains polyisocyanate and a polyester or polyether polyol or mixtures thereof with or without plasticizers. The preferred Finishing coatings are those coating preparations that contain nitrocellulose and an isocyanate-terminated prepolymer from an organic polyisocyanate and a polyester or polyether polyol or cellulose acetate butyrate. These preferred Coating preparations provide finishing coatings on leather as well as leather substitutes that are well balanced against one another Have flexibility and wear properties. The cellulose acetate butyrates are described in U.S. Patents 3,57 & 154.

The amount of nitrocellulose present in one of the preferred finishing preparations is preferably between 15 and 55%, based on the total solids content of the preparation. These preferred coating formulations are described in more detail in US Pat. No. 3,763,061. The equipment coating can be applied in an amount such that approximately 1 g of the solid coating falls per 0.09 m (sq. Ft.) Of the substrate. In this way the best balance of the physical properties in terms of flexibility and abrasion resistance is achieved. The amount of equipment coating applied can be controlled by the solids content of the formulation, machine settings, conveyor speeds, and the number of coatings applied. The coating should

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preferably while maintaining a urethane / nitrocellulose ratio 55/45 should be formulated so that the best balance of the properties in terms of flexibility and abrasion resistance and tackiness is achieved. This urethane / nitrocellulose ratio can optionally be varied from 50/50 to 65/35 to get a special result on a specific To achieve leather, however, if changes are made, then the flexibility, the abrasion resistance as well as the Stickiness can be observed. In general, the latex coatings used according to the invention should be a latex polymer, Clay, titanium dioxide or other inert fillers and a foam stabilizer contain, and they may also have an additive for crosslinking the polymer.

The latex preparations suitable according to the invention can be made from at least two of the following monomers can be prepared, at least one of which is a monomer, the functional Contains groups that are able to form a network:

a) An α, β-ethylenically unsaturated acid, such as Acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, Aconitic acid, crotonic acid, citraconic acid, maleic acid, fumaric acid, α-chloroacrylic acid, cinnamic acid and mesaconic acid,

b) a monomer of the formula

R 0

f Il

CH ₂ = CC-OR ₁

where R is hydrogen or alkyl, for example lower alkyl having 1 to 4 carbon atoms, and R * is a straight-chain, branched or cyclic alkyl, alkoxyalkyldder alkylthioalkyl radical having 1 to 20 carbon atoms or a cycloalkyl radical having 5 to 6 carbon atoms, as in

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for example methyl, ethyl, propyl, η-butyl, 2-ethylhexyl, heptyl, hexyl, octyl, 2-methylbutyl, 1-methylbutyl, butoxybutyl, 2-methylpentyl, methoxymethyl, ethoxyethyl, cyclopentyl, cyclohexyl, isobutyl, ethylthioethyl, methyl , 6-methylnonyl, decyl, dodecyl, tetradecyl, pentadecyl or the like. R ₁ can also represent ureido, hydroxy-lower alkyl with 1 to 5 carbon atoms, for example hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl and hydroxypentyl, 2,3-epoxypropyl, amino-lower-alkyl or mono- or di-lower-alkyl or hydroxy lower-alkyl-substituted amino-lower-alkyl.

c) A monomer of the formula

CH ₀ = C

where Rp is hydrogen or methyl, and R ^ is a halogen, for example chlorine, lower alkanoyloxy, for example acetoxy, Cyano, formyl, phenyl, carbamoyl, N-hydroxymethyl, tolyl, Methoxyethyl, 2,4-diamino-s-triazinyl-lower-alkyl or epoxy is,

d) a monomer of the formula

₀ -CCR ^ -
2 _t b

where R 1 is hydrogen or methyl, and R _{1 and R 6 are} lower alkoxy, for example methoxy and ethoxy, or lower alkanoyloxy, for example acetoxy.

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Examples of suitable monomers of classes b), c) and d) are the following: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, Isopentyl methacrylate, tert-pentyl methacrylate, hexyl methacrylate, Cyclohexyl methacrylate, 2-ethylbutyl methacrylate, 2-Ä + ethylhexyl methacrylate, Octyl methacrylate, decyl methacrylate, lauryl methacrylate, Myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, Methyl arylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, Butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, tert-amyl acrylate, Hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, vinyl acetate, Tetradecyl acrylate, acrylamide, pentadecyl acrylate, styrene, pentadecyl methacrylate, vinyl toluene, methacrylamide, N-methylolacrylamide, Glycidyl methacrylate, methylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, 6- (3-butenyl) -2,4-diamino-striazine, Hydroxypropyl methacrylate, hydroxyethyl methacrylate, methacrylonitrile, methoxymethyl methacrylamide, N-methylol methacrylamide, Acrolein, methacrolein, 3> 4-epoxy-1 - "butene, acrolein diethylacetal, Acrolein dimethyl acetal, allylidene diacetate, methallylidene diacetate, the analogs of the methacrylic acid derivatives given above with other unsaturated acids, such as acrylic acid and itaconic acid, the acids themselves, Qicarboxylic acids, such as maleic acid and half-esters and half-amides thereof, vinyl ethers of glycols, such as, for example, ethylene glycol Etc.

The crosslinkable unsaturated polymerizable addition monomers have reactive polar groups that can be represented by the following formulas:

It

-OH, -SH,> NH, -C-N <, -N = C = O, > CHCN, -CHO, -COOH and -C C.

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In addition, groups that can be networked with one another or with themselves come into question; Compounds are added, such as triazine / formaldehyde resins.

Of course, no water sensitive materials like Isocyanates are used in aqueous systems, provided they are not blocked by a reaction with a phenol group, which protects the isocyanate groups until the subsequent heating. In addition, other reaction mechanisms are possible, for example, one can fall back on the usual calcium, zinc or tin compounds, which are known as catalysts.

The preferred emulsion copolymers have a molecular weight of from 70,000 to 2,000,000 and preferably from 250,000 to 1,000,000 and are prepared by emulsion copolymerization of the various monomers in the appropriate proportions. Common emulsion polymerization techniques are described in U.S. Patents 2,754,280 and 2,795,654. The monomers can be emulsified with an anionic, cationic, or non-ionic dispersant, about 0.05 to 10 percent usually being employed based on the weight of the total monomers. The acidic monomer, as well as many of the other functional or polar monomers, can be soluble in water so that the dispersant serves to emulsify the other monomer or monomers. A free radical polymerization initiator such as ammonium or potassium persulfate can be used alone or in conjunction with an accelerator such as potassium metablsulfite or sodium thiosulfate. Organic peroxides, such as benzoyl peroxide and tert-butyl hydroperoxide, are also suitable initiators. The initiator and accelerator, often referred to as a catalyst, can be used in amounts of 0.1 to 10 %, each based on the weight of the mono-

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mers, can be used. The amount can be adjusted, as indicated above, to control the intrinsic viscosity of the polymer. The temperature may vary from room temperature to about 60 ⁰ C (14O ⁰ F).

The following is a list of the copolymers which can be used according to the invention: The copolymers possess the following monomer compositions: 96EA / 3.5AM / O, 5AA; 96EA / 4M0A; 94EA / 5.5ALAC / AC / 0.5AA; 94.5EA / 5HEMA / 0.5AA; 66ΞΑ / 32.7MMA / 1.3MAA; 100EA; 83EA / i5MMA / 2AA (Na); 83BA / 15AN / 1AC / 1 AA; 65EA / 25.5BA / 4.5AN / 3.5AM / 1.51A; 86EA / 10AN / 4MOA; 83BA / i4AN / 1Ac / 2AA; 97EA / 1Ac / 2AA; 68BA / 28MMA / 2Ac / 2AN; 3OBA / 55EA / 1OMMA / 3.5AN / 0.5Ac / 1AA; 45BA / 10AN / 40EA / 4HEMA / iAA or the like. (The explanation of the Abbreviations will follow later)

The use of a water-soluble surfactant or a combination of surfactants increases the dispersion of the latex emulsion and acts as a foaming aid as well as foam stabilizers.

These surface-active agents consist, for example, of alkali metal, ammonium or amine salts, for example the Mono-, di- or triethanolamines of aliphatic carboxylic acids having 16 to 20 carbon atoms, such as oleic acid and Stearic acid, sodium, potassium or ammonium stearate, sodium, Potassium or ammonium oleate. Other surfactants which can be used according to the present invention together with those described above can be used, for example, the alkali metal salts of aliphatic sulfonic acids or alkylarylsulfonic acids, for example sodium lauryl sulfate, sodium dodecylbenzenesulfonate etc., and nonionic surfactants are also included Question, such as the polyethylene oxide condensates of alkylphenols or higher fatty alcohols, such as tert.-octylphenol, that with 5 to about 40 ethylene oxide units

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Is condensed, lauryl alcohol, which has 5 "to 50 ethylene oxide units is condensed. or similar ethylene oxide condensates of long-chain mercaptans, fatty acids or amines.

Even if thermosetting or thermoplastic resins are used in carrying out the process according to the invention However, the preferred resins are thermosetting resins since the foam produced provides products that are more suitable for the production and subsequent use of leather and leather-like materials.

To crosslink acrolein or methacrolein containing resins, a dibasic amine such as diethylenetriamine or hydrazine can be used. The melamine-like resins can are used to crosslink polymers that contain hydroxyl and amino functions. Other known crosslinking agents can also be used.

The finishing preparations can be clear, but they can also contain matting agents, pigments or dyes, and depending on the intended use or depending on the desired aesthetic properties. Examples of pigments, which can be used according to the invention are clay, titanium dioxide, potassium carbonate, barite white, fine metals, such as aluminum or the like, lacquers or coloring oxides, other common additives that are used are, for example, fillers, lubricants and lubricants. The finish coating compositions preferably also contain a silicone rubber polymer, for example that available from Dow Corning under the designations DC-160, FC227 and SyI-Off-291 sold polymers, together with an organometallic salt catalyst, for example dibutyltin laurate and Zinc octoate.

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These two chemicals help improve abrasion resistance as well as the handle.

The finishing coating preparations can be applied to the substrates coated with the pressed foam by known methods, for example by brushing on, sponging on, spraying on, flowing on or by dipping. Suitable methods are described in U.S. Patents 2,126,321 and 2,884,340. One or more coatings can optionally be applied. The thickness of the coating can be varied depending on the intended purposes for which the coating is to serve. The amount of equipment coating applied will vary depending on the type of material being coated as well as the type of equipment being finished. In general, the equipment coating is applied in an amount such that it is in the dry state as a film having a thickness from 2.5 to 203 u ⁽⁰ ^ ^b i ^{s 8} mils), wherein the film thickness is preferably about 7.6 to about 12 .7 u (0.3 to 0.5 mils). After application, the coating can be cured by drying to a tack-free state at room temperature for a period of 30 minutes to 1 hour or by heating to a temperature of up to 100 ^° C. until the desired degree of curing has been achieved.

There is one advantage to the nitrocellulose / urethane finish coating in the fact that he has an excellent elastic recovery ability and very good flexibility and yet is tough enough to be used as an abrasion layer when applied to leather or leather substitutes, which are used to manufacture luggage, upholstery or items of clothing such as shoes and jackets. It is this flexibility, as well as this resilient recovery capacity, that makes the nitrocellulose / urethane finish coating formulations extremely valuable for covering thick ones

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flexible substrates, especially those substrates that have a thickness of about 762 to about 2540 µ (30 to 100 mils). Such substrates will bend sharply exposed, for example in the case of leather or leather substitutes used in the manufacture of luggage, upholstery, Shoes and other items of clothing are used.

Even if emulsion polymers are preferred, polymers that are produced in organic solutions can also be used. for example in ethylene glycol, ether, xylene, ethylene glycol monomethyl ether etc., in compliance with the usual measures, such as using an over free Radical initiation with benzoyl peroxide can be used. According to the invention have suitable solution polymers preferably a molecular weight between 10,000 and 1,000,000.

The formulation of the pressed foam cover allows many variations. The following table shows the quantities of the components that can be used in typical formulations:

Table I.

Parts by weight

Resin (with a solids content of

40 to 60 %) 500-1000

Foam stabilizers 5-80

Surfactant 0-150

Fillers 25-200

Colorant 0-150

Waxes and other auxiliaries 0-100

Ammonia (28%) 0-15

Dibasic amines 0-25

Melamine resins 0-25

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Other ingredients can of course finish the foam cover finishes be added. In particular, fillers, colorants and waxes can be used in the formulation in various proportions can be added to obtain products with specific desired properties. Examples of fillers, which can be used according to the invention are clays, mica, Potassium carbonate, bentonite and silica. Examples of colorants that can be used are dyes, which are produced from inorganic and organic pigments, in particular dispersions of the pigments in water with a dispersing agent and a protective colloid such as carbon black, iron oxide pigments, anatase (titanium dioxide) or like that. Waxes are used to prevent the release of the To facilitate pressing plate. These waxes are known. For example, polyethylene waxes may be mentioned.

Preferred embodiments of the invention are described below with reference to the examples, which only illustrate the invention should. "Primal" is a registered trademark.

Example 1 - Formulation 1

Batch parts by weight

Copolymer

83BA / 14AN / 1Ac / 2AA 100

China Clay 15 ammonium stearate (33 %) 7.0

Diethylenetriamine 0.6

Ammonium hydroxide (26%) 2.0

Primal, non-bleeding red dye 15 »0

Example 2 - formulation 2

Copolymer

825BA / 14AN / 1,5Ac / 2AA 500.0

Tone 75.0

Ammonium stearate 35.0

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Diethylenetriamine 3.5

Ammonia (28%) 10.0

Primal, brown dye 75.0

Water 65.5

Example 3 - Formulation 3

Copolymer

86EA / 10AN / 4M0A 565.5

Tone 75.0

Ammonium stearate 35.0

Aqueous melamine / formaldehyde resin 11.5

Ammonia (28 % ± g) 10.0

Primal, 264 white dye 75.0

Example 4 - Formulation 4

H ₂ O 65.5

NH ₃ (28%) 10.0 '

Tone 75.0 Primal BIk. 110

Copolymer

96EA / 3MOA / O, 5AA 500.0

Ammonium stearate 35.0

75.0 10.0 75.0

565.5

Ammonium stearate 35.0

Aqueous melamine / formaldehyde resin 11.5

Example 5 - Formulation 5 Primal BIk. 110 NH ₃ (28 years old) volume Copolymer the end 96EA / 3M0A / 0, 5AA

509813/1135

Example 6 - Formulation 6

Primal, yellow ocher 75.0

NH ₃ (28 #ig) 10.0

Tone 75.0

Copolymer

96EA / 3MOA / O, 5AA 565.0

Ammonium stearate 35.0

Melamine 11.5

The components of Examples 1 to 6 are added to the mixture in the order shown (with the ammonia in two Feeds is divided. Half of it is saved until the melamine resin, Aerotex MW, has been added). Then stir vigorously (using a flash mixer, Talboys mixer, or Cowles device). It Other melamine resins can also be used, for example those available under the trademarks indicated below used: Aerotex M-3 (melamine / formaldehyde / Methanol, methoxylated melamine / formaldehyde). After mixing, the formulated mixture is covered to form a skin avoid.

Example 7 - Formulation 7

Batch parts by weight

Copolymer

83BA / 14AN / 1Ac / 2AA 420.5

Ammonium stearate 25.8

Octylphenoxypolyethoxyethanol 21.5

Acme WW tone 57.5

Primal Black 110 41, 7

NH ₃ (25 % ± g) 7.0

Polyethylene wax 23.9

Diethylenetriamine 2.1

600.0

509813/1 135

The latex as well as the nonionic surfactants are added to a Cowles device and slowly stirred. Then the ammonium stearate is added. The stirring is increased, slowly adding the remaining ingredients in the order given. Having an even Suspension is obtained, the formulation is filtered through a cheesecloth or sieve (40 mesh). This Material can now be used in conjunction with a suitable blowing agent. Instead of the dye Primal Black 110 other suitable colorants can be used, as can other formulations in substantially the same Way to be made.

Example 8 - Spraying from an aerosol can

70 g of the formulation of Example 3, 60 g of tridhlorofluoromethane and 40 g of dichlorodifluoromethane are poured into a 123 mm can with a non-breakable nozzle. The tin is shaken, whereupon the contents are sprayed 1) onto split leather and 2) onto paper. The sprayed material begins to foam after leaving the nozzle of the spray can, since the boiling point of the blowing agent, which also serves as a propellant, is below Ambient temperature. The foaming continues on the substrate. After drying, the coating is placed on the Leather pressed, embossed and hardened at the same time using a Watson Stillman press (88 ° C, 30 tons, 3 seconds) . The density of the foam sprayed is approximately 0.007 g / cc.

If a batch of 70 g of the formulation according to Example 3, 50 g of trichloromethane and 50 g of dichlorodifluoromethane is used, then the foam has a density of approximately 0.012 g / cc after compression and embossing in that described above Way.

509813/1135

- 26 Example 9 - Spraying Using a Spray Gun

The formulation according to Example 7 is made with trichlorotrifluoroethane mixed at room temperature. The mixture is poured into a pressure vessel (vacuum charging, line pressure

27 kg, vessel pressure 6.8 kg). The mixture is sprayed on leather, in an amount of about 36.9 to 42.6 g / 0.09 m (square foot) when wet.

The mixture foamed slightly at room temperature at a heating to a temperature of 138 ⁰ C, the coating foams good. The pressing, embossing and curing are carried out simultaneously using a Watson Stillman press (88 ° C, 30 tons, 3 seconds).

Example 10 - Spray Gun

The experiment of Example 9 is repeated, using trichlorotrifluoroethane is used, with the exception that the split leather used is used for a period of a few minutes heated to it-38 ° C before applying the coating. Will the coating is applied to the heated leather then it foams immediately, with foaming continuing as it dries. The pressing, embossing and hardening are carried out as in Example 9. A leather with an excellent one is obtained Template.

Example 11 - Foaming Properties of Acrylic Emulsion Polymers when using trxchlorotrifluoroethane

Testing the foaming properties of various acrylic emulsions is carried out using a formulation having the following composition: 307.5 g of latex, 5.0 g of one

28 % ± gen NH, 537.5 g of a coloring agent and 35 g of trichlorotrene

509813/113 5

fluoroethane. The formulations are under vascular pressure of 6.8 kg and sprayed under a line pressure of 36 kg. The substrate used is a white cardboard plate with dimensions of 368 χ 292 mm. After spraying, the coating air dried for 1 minute, then dried for 5 minutes in an air circulation oven at a temperature of 138 ° C.

The polymers used are made from monomers in the following proportions:

1. 96EA / 3.5AM / O, 5AA

2. 96EA / 4MOA

3. 94EA / 5,5ALACAC / O, 5AA

4. 94.5EA / 5HEMA / O, 5AA

5. 66EA / 32.7MMA / 1.3MAA

6.100EA

7. 83EA / 15MMA / 2AA (Na)

8. 83BA / 15AN / TAC / 1AA

9. 65EA / 25.5BA / 4.5AN / 3.5AM / 1.5IA

10. 86EA / 10AN / 4M0A

11. Butadiene rubber (Hycar 1571)

EA = ethyl acrylate, BA = butyl acrylate, MMA = methyl methacrylate, AA = asrylic acid, MAA = methacrylic acid, IA = itaconic acid, HEMA = hydroxyethyl methacrylate, AN = acrylonitrile, Ac = acrolein, ALACAC = allylacetoacetate, MOA = acrylamide / methylolacrylamide (1: 1) and AM = acrylamide.

509813/1 1 35

Results

Polymer Foambe
evaluation Added
Amount, ₀
g / 0.09 vT Up
broke
the festival
fabric
stop 1 Well - 44.3 2 quite
Well 14.4 44.3 3 quite
Well 14.4 44.3 4 ■ quite
Well 21.6 44.3 5 Well -
very good 14.4 43.5 6th quite
Well 16.2 44.3 7th quite
Well 10.8 37.5 8th quite
Well 12.1 44.3 9 Well 14.0 44.3 10 Well 19.8 44.3 11 very good 8.5 38.3

field viscosity,
(cps)

9.4 tall bluish black 9.9 336 bluish black

8.6 286 bluish black 9.8 648 bluish black

10.1 660 bluish black

10.0 48 greenish ge

colors

10.2 1636 bluish black

9.7 88 green

9.7 11300 green
9.4 860 bluish

10.1 40 bluish black

Example 12 - Investigation of the solvent blowing agents

A large number of solvent blowing agents are being investigated, an acrylic polymer with the composition 96 ethyl acrylate / 3.5 acrylamide / 0.5 acrylic acid (87.8 parts by weight) is used. The dye consists of Primal Black 110 (10.7 parts by weight) It also contains ammonia (28%), 1.5 parts by weight). The formulation is sprayed onto poster board and kept at 138 ° C dried over a period of 5 minutes. The quality of the foam and the swelling ratio in each case The following table shows the solvent used:

509813/1 135

CH ₂ Cl ₂ Kp.,
⁰ C - 29 - 2425553 H 39.7 % of the solution
means in 100
Share the For
mulation CHCl, II 5 % Foam swelling
relationship Il 62.1 10 % no foam 19.61 solvent CCl ₃ CF ₃ Il 5 ° / o Il It Il 1. Il 47.3 10 % no foam 44.74 CCl ₃ F Il 5% low "
Amount of foam 2. Il 23.8 10 % evenly - 2.53
deep foam Pentane It 5% Il Il Il 3. Il 36.1 10% evenly - 5.57
deep foam Hexane Il 5 % Il Il It 4th 68.7 10% evenly- 1.21
deep foam 5% It Il Il 5. evenly - 1.07
deep foam 6th

10 %

Example 13 - Equipment Coating and Application

Stage A - Preparation of the prepolymer

500.5 g of a polyether triol (molecular weight 1540) are poured into a 2 liter three-necked flask equipped with a mechanical stirrer, a thermometer, a distillation head, a condenser, a nitrogen inlet valve and a vacuum source. The pressure is reduced to 51 mmHg, whereupon the temperature is increased to 70 ^° C. while the mixture is stirred. 45.5 g of the distillate are collected, whereupon the temperature is reduced to 30 ° C. while the pressure is brought to 760 mmHg with the addition of nitrogen. 305 g of toluene diisocyanate are added to the reaction mixture, whereupon the temperature is increased to 75 ^° C. over a period of 16 hours. The isocyanate content is determined, whereupon the product

5 0 9 8 13/1135

temperature is cooled. The prepolymer has the following properties: 74.21 % solids, meq. NCO / g solution - 0.834, GH viscosity - T +, remainder TDI value - 1.17.

Stage B - Preparation of the finishing coating

The equipment coating composition is prepared in such a way that the following ingredients (parts by weight) are mixed: A prepolymer (110), nitrocellulose (177), nitrocellulose plus a matting agent (100), black pigment, Plasticizers and nitrocellulose (200), butyl acetate, xylene and 2-ethoxyethyl acetate (413 parts in a ratio of 50:40:10), silicone rubber polymer (25, "Dow Corning - 160") and dibutyltin laurate (50).

Stage C - Application

The preparation of stage B is based on leather or a leather substitute applied using standard spray equipment, for example in an amount of 1.0 g solids

ρ
per 0.09 m of the substrate.

If other prepolymers are used instead of those according to Example 12 prepolymers used to carry out stage B and other pigments or dyes instead of the carbon black pigment used as well as another silicone rubber as well as other prepolymers and catalysts, then similar finish coating formulations will be used obtain.

Example 14 - Equipment Coating and Application of Cellulose Acetate Butyrates

5098 13/1135

Level a

97.5 parts of poly (1,3-butylene adipate) which has been prepared by a conventional method and has a molecular weight of 5000 and a hydroxyl number of 20 are thoroughly dehydrated by passing nitrogen through them at a temperature of 130 to 140.degree. The polyester is then ^{cooled to 106 to 108 °} C., whereupon 4.6 parts of methylenebis (4-phenyl isocyanate) are added over a period of 15 minutes. The temperature of the reaction mixture is increased to 110-115 ° C and mixing is continued under positive nitrogen pressure for a period of 30 hours. The cooled product has a viscosity of approximately 1 million poise and is a pale colored stiff gum. A 50% solution in xylene has a Gardner Holdt viscosity of Zg.

Stage B - Formulation of a clear plasticized cellulose acetate butyrate solution

A solvent mixture is prepared in such a way that 510 parts of toluene, 170 parts of methyl ethyl ketone and 320 parts Ethyl alcohol are mixed. To 69 parts of this solvent mixture are 15.1 parts of a cellulose acetate butyrate (Viscosity 3 seconds) with a 20% butyryl uride added with a 25% acetyl content, whereupon the addition of 3.8 parts of a linear polyester followed, namely propylene glycol sebacate with a molecular weight of 8000. In addition, 12.1 parts of a 50% solution of the stretched Polyester from Example A in xylene added. The mixture is stirred until a homogeneous solution is obtained has been. The mixture is light straw yellow in color and has a viscosity of 2,100 centipoise.

509813/1 1 35

- 32 Level C - Deposition

20 parts of the clear equipment, from level B to 80 parts Methyl ethyl ketone mixed, whereupon 1 part of a red dye which is soluble in alcohol is added. The mix will on a piece of a leather substitute with a pressed

p th foam coating at a rate of 1.0 g solids per 0.09 m sprayed on. The equipment is air dried and then under a pressure of 1.4 kg / cm and at a temperature of 160 ° C for 60 seconds with a sandblown Pressed plate. The equipment obtained has a warm brown color and excellent resistance against cracking or dulling when bending.

509813/1 135

Claims (22)

- 33 claims ik / method for finishing a substrate made of leather or another material which is used as a leather substitute or in a leather substitute, characterized in that, that a) a coating of a polymer latex is applied to the substrate, which contains a blowing agent from 1) a solvent with a boiling point of -46 to 104 ⁰ C (-50 to 220 ⁰ F), in which the non-crosslinkable polymer has a swelling ratio of 1 to 7, or 2) contains a chemical blowing agent, b) the latex is foamed on the substrate and the coated substrate is dried, c) the coated substrate at such a temperature is pressed and cured under such a pressure that the pressed foam adheres to the substrate, and d) a finish coating is applied to the pressed foam surface. 2. The method according to claim 1, characterized in that the drying b) at a temperature of 49 to 204 ⁰ C (120 to 400 ⁰ F) and stage c) at a temperature of 66 to 204 ⁰ C (150 to 400 ⁰ F) as well as under a pressure of 0.35 to 176 kg / cm (5 to 2500 psi). 3. The method according to claim 2, characterized in that the solvent blowing agent used to carry out step a) has a boiling point of 24 to 93 ° C (75 to 200 ⁰ F) or consists of one or more of the chemical blowing agents specified below: azo compounds, N-nitrosover- 509813/1 135 bonds, sulfonyl hydroxide, ammonium bicarbonate, sodium bicarbonate, sodium carbonate, hydrogen peroxide, ammonium nitrate and malonic acid, and to carry out step b) a temperature of 77 to 199 ° C (170 to 390 ⁰ F) is maintained, and to carry out step c) the pressure (psi 5-1200) to 0.35 to 84.0 kg / cm and the temperature are set to 66 to 16O ° C (150 to 320 ⁰ F), and for carrying out step d) coating equipment used consists of one or more The following ingredients: Preparations containing nitrocellulose, urethane, polyvinyl chloride, acrylic compounds, cellulose acetate butyrate or nitrocellulose-modified urethanes. 4. The method according to claim 2 for finishing leather, characterized in that, to carry out step a), the application latex is sprayed onto the leather, the blowing agent used being composed of a solvent with a boiling point of 24 to 93 ° C (-75 to 200 ⁰ F), and in which the non-crosslinked polymer has a swelling ratio of 1 to 6.0, to carry out step c) the pressure to 1.0 to 84.0 kg / cm (15 to 1200 psi) and the temperature to 66 to 149 ⁰ C (150 to 300 ⁰ F), and the finishing coating preparation used to carry out stage d) contains nitrocellulose and an isocyanate-terminated polymer of an organic polyisocyanate with a polyester or polyether polyol or cellulose acetate butyrate. 5. The method according to claim 4, characterized in that to carry out step c) the temperature is set to 82 to 132 ° C (180 to 270 ⁰ F). 6. The method according to claim 2 for finishing a leather substitute, characterized in that, to carry out stage a), the coating is sprayed onto the substrate and the one used A solvent blowing agent with a boiling point 50981 3/1135 from 24 to 104 ⁰ C (75 to 220 ⁰ F), the non-crosslinked polymer having a swelling ratio of 1 to 6.0 in this solvent. 7. The method according to claim 6, characterized in that for Carrying out stage c) the pressure to 3.5 to 70.0 kg / cm (50 to 1000 psi) and the temperature is maintained between 135 and 163 ° C (275 to 325 ° F). 8. The method according to any one of the preceding claims, characterized in that the polymer latex used is a polymer contains, the polymer units of two or more monomers of the following groups, wherein at least one of the monomers a functionally crosslinkable group contains: a) a $ -ethylenically unsaturated acids, b) monomers of the formula: R 0 I Il CH ₂ = CC-OR ₁ wherein R is hydrogen or alkyl, and R _{1 is} a straight-chain, branched or cyclic alkyl, alkoxyalkyl or alkylthioalkyl radical, and c) monomers of the formula: CH ₂ = C ^ ² where Rp is hydrogen or methyl, and R- * halogen, Alkanoyloxy, cyano, phenyl, formyl, carbamoyl, epoxy, N-hydroxymethylcarbamoyl, Tolyl, methoxymethyl, 2,4-diamino-s-triazinyl-lower alkyl means or d) monomers of the formula: 509813/1135 CH ₅ = CC-IL-2, 6 where R ^ is hydrogen or methyl, and Rc and Rg are lower-alkoxy or lower alkanoyloxy. 9. The method according to claim 8, characterized in that the polymer used contains units of monomers from at least three of the following groups: a) ethyl acrylate, butyl acrylate, methyl methacrylate, b) acrylonitrile, c) acrylamide, methylolacrylamide, allylacetoacetate, hydroxyethyl methacrylate, Acrolein and methanrolein, d) acrylic acid and methacrylic acid. 10. The method according to claim 9, characterized in that the polymer also contains one or more of the following fillers: clay, mica, potassium carbonate or silicon dioxide, a foam stabilizer, a colorant "as well as one or more of the following crosslinking agents: ammonia, dibasic amines or melamine resins. 11. The method according to claim 3, characterized in that the solvent blowing agent is selected from one or more of the following Compounds consists of: dichlorodifluoromethane, carbon tetrachloride, trichlorotrifluoroethane, trichlorofluoromethane, monochlorotrifluoromethane, Monobromotrifluoromethane, monochlorodifluoromethane, Octafluorocyclobutane, pentane, hexane and cyclohexane. 12. The method according to claim 4, characterized in that the blowing agent used from trichlorofluoromethane and / or tri- 509813/1135 - 37 chlorotrifluoroethane or consists of ammonium bicarbonate. 13. Leather coated with a compressed foam or leather substitute coated with such a foam, thereby characterized in that it is obtainable by a process according to claims 1 to 7 and 11 to 12. 14. Leather covered with a compressed foam or with a leather substitute coated with such a foam, characterized in that it or he according to the method according to Claim 8 is available. 15. Leather covered with a compressed foam or with a leather substitute coated with such a foam, characterized in that it or he according to the method according to Claim 9 is available. 16. Leather coated with a compressed foam or leather substitute coated with such a foam, thereby marked that it or he according to the procedure according to Claim 10 is available. 17. Product according to claim 16, characterized in that the pressed foam cover is made from one or more of the following copolymers: 96 ethyl acrylate / 3.5 acrylamide / 0.5 Acrylic acid, 96 ethyl acrylate / 4 acrylamide / methylol acrylamide, 94 ethyl acrylate / 5.5 allylacetoacetate / 0.5 acrylic acid, 94.5 ethyl acrylate / 5 Hydroxyethyl methacrylate / 0.5 acrylic acid, 66 ethyl acrylate / 32.7 Methyl methacrylate / 1,3 methacrylic acid, 83 ethyl acrylate / 15 Methyl methacrylate / 2 acrylic acid (Na), 83 butyl acrylate / 15 acrylonitrile / 1 Acrolein / 1 acrylic acid, 65 ethyl acrylate / 25.5 butyl acrylate / 4.5 Acrylonitrile / 3.5 acrylamide / 1.5 itaconic acid, 86 ethyl acrylate / OK Acrylonitrile / 4 acrylamide methylol acrylamide, 83 butyl acrylate / 14 acrylonitrile / l acrolein / 2 acrylic acid, 97 ethyl acrylate / 1 acrolein / 2 Acrylic acid, 68 butyl acrylate / 28 methyl methacrylate / 2 acrylic 509813> / 1 135 lin / 2 acrylonitrile, 30 butyl acrylate / 55 ethyl acrylate / 10 methyl methacrylate / 3.5 Acrylonitrile / 0.5 acrolein / 1 acrylic acid or 45 butyl acrylate / OK acrylonitrile / 40 ethyl acrylate / 4 hydroxyethyl methacrylate / i Acrylic acid, the numbers being the percentages by weight of the monomers in the monomer mixtures which one Polymerization to form the copolymers are subjected. 18. Upper material, characterized in that it is made of a leather covered with a pressed foam or made of a leather substitute, which is covered with a compressed foam, consists .and according to a method according to claims 1, 2 and 8, wherein the equipment coating contains one or more of the following components: Nitrocellulose, urethanes, polyvinylchloride, acrylic bonds, Cellulose acetate butyrate and preparations, the nitrocellulose and an isocyanate-terminated prepolymer from an organic Contain polyisocyanate and a polyester or polyether polyol. 19. Upper material, characterized in that it is made of a leather covered with a pressed foam or made of a leather substitute, which is covered with a compressed foam, and according to a method according to claims 3 and 9, wherein the finish coating is cellulose acetate butyrate, nitrocellulose and / or an isocyanate-terminated one Contains prepolymer of an organic polyisocyanate with a polyester or polyether polyol. 20. Upper material, characterized in that it is made of a leather covered with a pressed foam or made of a leather substitute, which is covered with a compressed foam, and according to a method according to claims 3 and 10, wherein the finish coating contains 15 to 55% by weight nitrocellulose. 509813/1135 21. Shoe upper material, characterized in that it consists of a leather covered with a pressed foam or of a leather substitute which is covered with a pressed foam, and is obtainable by a method according to claim 4, wherein the pressed foam cover consists of one or more of the The following copolymers are produced: 96 ethyl acrylate / 3.5 acrylamide / 0.5 acrylic acid, 96 ethyl acrylate / 4 acrylamide / methylol acrylamide, 94 ethyl acrylate / 5.5 allylacetoacetate / 0.5 acrylic acid, 94.5 ethyl acrylate / 5 hydroxyethyl methacrylate / 0.5 Acrylic acid, 66 ethyl acrylate / 32.7 methyl methacrylate / 1.3 methacrylic acid, 83 ethyl acrylate / 15 methyl methacrylate / 2 acrylic acid (Na), 83 butyl acrylate / 15 acrylonitrile / 1 acrolein / 1 acrylic acid, 65 ethyl acrylate / 25.5 butyl acrylate / 4.5 Acrylonitrile / 3.5 ^ acrylamide / 1.5 itaconic acid, 86 ethyl acrylate / 10 acrylonitrile / 4 acrylamide methylol acrylamide, 83 butyl acrylate / 14 acrylonitrile / 1 acrolein / 2 acrylic acid, 97 ethyl acrylate / 1 acrolein / 2 acrylic acid, 68 butyl acrylic at / 28 methyl methacrylate / 2 acrolein / 2 acrylonitrile, 30 butyl acrylate / 55 ethyl acrylate / 10 methyl methacrylate / 3j5 acrylonitrile / 0.5 acrolein / 1 acrylic acid or 45 butyl acrylate / 10 acrylonitrile / 40 ethyl acrylate / 4 hydroxyethyl methacrylate / i acrylic acid, the numbers being Denotes weight percentages of the monomers in the monomer mixtures which undergo polymerization to form the copolymers and a finish coating is provided which, in the form of a dry film, is 2.5 to 203 } i (0.1 to 8 mils) thick and consists of a preparation containing 15 to 55% by weight nitrocellulose. 22. Upper material according to claim 19, characterized in that that the dry film thickness of the equipment coating is 7.6 to 12.7 µm (0.3 to 0.5 mils). 509813/1135