PL103078B1 - METHOD OF MAKING FINISHED SKIN OR SKIN SUBSTITUTES - Google Patents

Description

The invention relates to a manufacturing process made hides or leather substitutes. Spo this method can be used for finishing splits, horse high-quality hides and pelts made of pellets face, for non-woven and other materials artificial materials applicable for the manufacture of synthetic leather, especially intended for the tops of shoes, pigskins, sheep and other leather-like materials.

This method produces a final product one that meets the aesthetic requirements by the leather industry with a significant reduction the number of steps required to obtain the product final product. Moreover, the obtained product contained retains or shows better properties as required from leather and leather-like materials used for the manufacture of footwear, leather goods, clothing ties, belts, upholstery, etc. These properties include flexibility, abrasion resistance, grip, trans water vapor permeability, resistance to scuffing Aug, a good grip and aesthetic qualities what to do the skin sags. This property set is hard to come by obtained by coating with other known methods give me. The invention is particularly suitable for the implementation of cutting of leather and leather substitutes, irregular surface or sagging defects those that do not resemble their original appearance art of trimmed leather as this process gives a solid artificial surface similar to a face skin on the substrates in question.

In the field of leather finishing and materials, steppe skin ways to raise the quality of low high-quality or damaged materials are always present wanted. The search for an attraction is also in progress cheap, cheap materials replacing microprocess grooved urethane laminate currently being applied to surfaces of substantially non-woven materials with a porous structure.

Woven fabrics have been successfully covered with composite polymeric positions or compositions high-impact polymers that were applied to the fabric in the form of a foam, e.g. according to US Pat.

US No. 3,527,654. This method cannot be can be used with good effect for non-woven fabrics bearings, found in the field of finishing skins, because the property complex required from skin or skin substitutes is different and more difficult to obtain than with woven fabrics.

Crushable foam coating as it is now used in the textile industry is applied in the form of mechanically generated foam, which then, in a knife manner, it is applied to the slide continuously woven fabric on the roller. Knife coating is not a suitable method to perform because it causes excessive losses covering substance, and also can not be a hundred suitable for the skin, as the skin usually has no uniform thickness. Mechanically produced foam can be applied by spraying, but not foam during spraying and long 103 078 103 078 make volumetric low-density foam required to obtain adequate coverage, it makes this fabric tode not very attractive. This method is therefore exhausted completely different from the method of the invention. Nakla¬ the spray dish of the unfoamed mixture gives inadequate surface coverage and gaps right.

As mentioned previously, it has not yet stopped Leather covers and substitutes for bedskins were used from foamed polymers, and thus until obtaining half in dragging materials of this type, no substances were used containing foaming agents. So, yes equally the use of foaming agents as coating layer components and method their imposition discussed below are new.

Depends on the nature of the foam frother on may arise directly on application the coating from the sprayer as it can it is possible to use a solvent-borne agent foam concentrate with a boiling point below ambient temperature. Foam may also develop soak while drying the coated substrate in the oven cu. As the penetration of the coating will normally be given better grip, but stiffer grip, therefore the regulation of the ultimate properties of the coverage can be made by the selection of foam concentrates with the desired characteristics.

It is known that a stable cell can be made a foam structure made of latex-copolymers acrylic, for example by the method described in the patent specification st. US Of America No. '3640916. It was found however, the knowledge of only solvent aviation Nika is not enough to describe quality and structure foam. You should also take into account mutual interaction of the solvent with the polymer, because the vase exists; direct relationship between the degree with no foaming and solvent allow cym, foaming the polymer. By using the soluble for which a foaming factor falls-in the value range you want, possible is now getting adequate foaming.

It is a solvent (dissolves in the polymer, then it cannot be used for foaming la¬ text.

It was found that the properties of the crushed foam were broken covering split leather on the side of the front or on the side of the inside inner skin, producing them according to the principles of the method of the invention are significant better than those made by conventional methods to me. The softness of the grip of leather and leather substitutes is improved produced by the method of the invention is significant no better than conventionally processed materials by other methods of finishing.

In the method according to the invention, the meaning is obtained good coating in one coating operation, while in conventional methods, Fluid coverage usually does not provide adequate coverage masking the imperfections or texture of the substrate.

Moreover, the method of the invention eliminates multistage of conventional processes and steady state a new economical way to improve the quality of leather and skin substitutes. A further advantage is controllable The course of the coating is therefore eliminated There is a shine through effect of the covered substrate.

The method in question also enables use as a substitute for ordinary leather, also for leather quality that has not previously been used for Kanczania. Leather with distinct handbags hair or other undesirable features, such as weakness foot traffic, surface damage, signs important, etc., can now be carried out the way according to the invention into a useful and desirable little terial. For example, tanned pigskin mo¬ It is known to cover the yield by the method according to the invention jacquard with perfectly finished leather. The process as per exc the invention is particularly useful in its application for splits. The method according to the invention can be to make leather splits much better physical properties and aesthetic level than it is hitherto possible with the use of 'convention other methods of finishing the split.

The method in question also eliminates the need for them impregnation of leather, although it was found well, in some cases thanks to impregnation you can get a product of higher quality.

The total properties of a layout depend on the properties > foamable latex that allows you to obtain soft, pliable and water-permeable trawls and together with a durable vein finish They enable obtaining adequate resistance wears abrasion without loss of flexibility and allows it to pass water capacity The ideal layer of latex that introduced as a foam coating. Za¬ both the foam coating and the finish which determines the final properties and parameters of the output robu.

The method according to the invention also includes the preparation of nc washing the coating on substitutes for skin giving a material that competes with high-quality leather.

The term "Leather substitutes" is to be understood in Polish as defined in US Pat. US

Nos. 3,537,883, 3,100,721, and 3000,757, i.e. as all materials that replace natural leather. 40 The term "crushed foam coating" means the coating, which after the formation of the cell structure the input has been pressed by squeezing or by pressing owl. " The present invention relates to a new production process finished leather and finished substitutes leather, which involves the processing of various types of leather lenghts covering leather to the grain, tops, two leather, composition leather, leather substitutes, ma¬ non-woven fabrics with stretch and stretch properties recovery and other properties resembling leather as well as other materials, by (a) application to the skin or skin substitute polymer latex coating containing sro- 55 foam decks and foaming on the substrate by the action of a foaming agent such as (1) a solvent with a boiling point in the range of (-10) - (104) ° C, which causes foaming of the volume qualitatively non-cross-linked polymer 1 to 7 times 60 (foaming factor 1-7) or (2) chemical foaming agents, (b) drying and foaming applied on a latex base at a temperature of 49- —204 ° C, (c) crushing, pressing and cross-linking the covered substrate under a pressure of 0.35-175 atm 65 at 66-204 ° C and the finisher on a substrate covered with crushed half foam drag.

A preferred variant of the process according to the invention is consists in: (a) applying a polymer coating of la¬ text that can be foamed on the base, by the use of a foaming agent, such as as (1) boiling point solvents in the range of 24-104 ° C, which causes the foaming of cross-linked polymer 1-7 times by volume and (2) ammonium bicarbonate, (b) drying and foaming latex coating on the substrate at temperature 66-190 ° C (c) crushing, pressing and crosslinking foam coating under a pressure of 0.35-175 atm at a temperature of 66 ° -163 ° C and (d) overcoating squatting on the coated surface crushed foam, the finishing coat being a composite entry containing melamine resins, condensation urea-formaldehyde, nitrocellulose, ure- tans, polyvinyl chloride, acrylic resins, acetate cellulose maslains, modified nitrocellulose, ure- tans or mixtures of these compounds. , e Due to significant differences between leather and sub leather, there is a difference in the preferred different ways of finishing these different substrates.

For example, if the skin is full skin grain, split leather or regenerated leather, then the most preferred method is: (a) na¬ squirting the polymer latex coating onto the leather re, the coating of these foams on the skin later use of a solvent-borne foam creative with a boiling point in the range of 24- -104 ° C, where the agent causes foaming of a non-cross-linked polymer 1 to 6 times by volume, (b) drying and foaming latex-coated leather at a temperature in the range 82 ° -163 ° C. (c) compresses for pressing, pressing and cross-linking the foam-coated leather rice under a pressure of 1-85 atm at a temperature usually 66-149 ° C, most preferably at temperature 82-132 ° C, and (d) applying to the cover of the crushed skin foam topcoat forming compositions of nitrocellulose and the terminated group of iso- organic cyanate prepolymer isocyanate nu with a polyester or polyether polyol or also from cellulose acetate-butyrate.

If a cover is to be applied to leather substitutes For example, the preferred method is: (a) a spray stripping the polymer latex coating onto the sub a kind of leather, with the coating foaming into a sub skin handling, using a solvent boiling foaming agent in the range of 24 ° -104 ° C., this agent increasing causes the non-cross-linked polymer to expand 1 to 6 times, (b) drying the foam-coated skin substitute at a temperature of 49-204 ° C, (c) crushing, pressing netting and cross-linking of the crushed foam coating on skin substitute under a pressure of 0.35-175 atm, and most preferably at a pressure of 1.4 to 70 atm and at 66 ° C to 204 ° C, and most preferably at temperature 135-163 ° C and (d) applying to the foam substitute for leather and a solid finish new composition of nitrocellulose and finished the isocyanate groups of the organic prepolymer it polyisocyanate with polyester polyol or with cellulose acetateomasate. b Use of lower pressures and higher temperatures ratur is preferred in the case of leather substitutes rice because it gives better adhesion to the coating to the substrate.

Many synthetic and artificial leather materials similar does not require such high temperatures and can be made at lower temperatures and under lower pressures. These temperatures and pressures They refer to ironing with flat panels hydraulic or mechanical presses in which contact time with the ground is easy to do terms. In the case of rotary ironing real-time ironing devices, in which the material contacts with the rollers and the pressure at the time of contact are significantly more difficult to define. Therefore, you should expect nodding slight deviations from the given values, including pressing temperatures. Time op ration and crushing, pressing and cross-linking of the polymer it is usually within 0.5 ^ 10 sec. For of the skin, this time is preferably within 2–6 seconds, and for leather substitutes in the game threads 0.5-2 sec.

The solvent may be foamable of the polymer, if it is still present in the polymer after draining off the water and adding more warm. There is a difference between the foaming of la text and foaming the polymer. Manufacturing process cellular structure through internal production the gas or vapor is in the continuous phase of the polymer completely different and requires different production conditions foam dissipation than in the case of latex, where the phase water is still present, and the structure is formed during foaming The foam re should be fixed in the form of a network of cells of the polymer, the latex particles being found they will be on the surface of the bubbles, creating layers or baffles that will remain after evaporation continuous phase.

Solvents matching a narrow range of foaming factors they give products with a smooth surface of crushed foam, which, when crushed, is capable of masking undesirable defects of the substrate. Factor the foaming is referred to as the volume of the foamed structure polymeric phase for a given solvent divided by the volume of the polymer sample before exposure to a solvent.

The numerical values of this factor can be easily obtained in the laboratory using numerous methods, the best of which is the gravimetric method tric. In this method, the polyrrier is weighted before and after equilibrium treatment with solvents, and na step by step measuring the appropriate polymer densities and solutions solvent, you can define the volumetric joint foaming factor.

Examples of suitable solvents are dichlorodifluoroethane, carbon tetrafluoride, tri- chlorotrifluoroethane, pentane, hexane, cyclohexane, trichlorofluoromethane, monpchlorotrifluoromethane, monobromotrifluoromethane, monochlorodifluoromethane methane, octafluorocyclobutane and their isomers.

The amount of solvent used as an agent The foaming agent may be 3-20% by weight of the entire composition. Usually solvent 40 45 50 55 60 103 078 8 Nickel is used in an amount of 7-12% by weight of the total composition position.

In addition to using solvents as a medium, foamers, you can also use chemistry numerous blowing agents, organic or inorganic nothing. Examples of organic chemical agents foaming compounds are azo compounds such as azo di-formamide, azodiisobutyroniitrile, diazoamine- nobenzene, etc., N-nitroso compounds such as N, N'- terephthalate dimethyl-N, N'-dinitrosamide ue, N, N'-dinitropomethylene tetramine, etc. and sulfonyl hydrazides such as benzene phonylhydrazide, p-toluenesulfonylhydrazide, 4,4'- -oxybis- (benzenesulfonylhydrazide), etc. Ex with inorganic foam chemicals creative are ammonium bicarbonate, bicarbonate sodium, sodium carbonate, hydrogen peroxide, ammonium nitrate nu, malonic acid, etc., with the most preferred Another chemical foaming agent is water ammonium hydroxide.

The foam is applied to the skin or to the skin substitute slow way, such as the spraying technique or similar.

The amount of foam applied depends on the nature of the surface base and the type of embossed pattern you want.

An amount of 160-320 g / m2 is recommended for exactly half of the varnished impregnated splits when used not embossing the pattern of the hair bag, because impregnation helps to seal the surface surface and strong bonding of the foam. Quantity 320— —640 g / m2 wet may be desired when applied on unimpregnated velor split "for deep embossing lizard skin pattern. Quantities about 640 g usually It is avoided except for particularly deep extrusion patterns. The above-mentioned amounts of foam in condition when moist, it is applied in the form of a composition containing about 50-55% of polymer and they depend on the polymer content of the composition.

The drying step is carried out at a temperature of 49- ^ 204 ° C. Partially crosslinking occurs at this stage not and necessary, it is necessary to prevent significantly due to the fact that this process takes place su too much at this stage affects the ironability of the product. Usually temp perature and drying time are determined by change these parameters until you get the desired ones product properties.

The drying time depends on many factors, but usually the residence time in the oven is included within 2-8 minutes. Great importance during drying is attached to the appropriate selection of the shaft drying rounds in order to prevent excessive foam spreading, which gives inferior results, and results in poor results considerably longer drying times due to a lot to isolate and cut off the lower layers foam. Parameters that play an important role in the drying process there are temperature and time spent the thickness of the applied foam and the flow rate it airy in the stove.

The air flow in the oven is a significant steam by subway and can be adjusted by setting partitions in most furnaces and in others by changing the speed of the blower. It is recommended that, to make the air faster, giving favorable the acceleration of the drying process did not strike me without it indirectly into the foam as this can lead to too much turbulence and increased intrusion.

The exact degree of drying is judged by the subject efficiently. The foam should be dried sufficiently, yes so that when you slide your finger on its surface, no There was a feeling of sticking, but it can't be too dry, otherwise the material is not good adopts an embossed pattern.

Laboratory dish indicates occurrence a wide range of drying time between drying and overdrying. For example, if you are assessing I believe that the time of 3 minutes. is the best time for sewing in special conditions, then 1.5 min. probably will give satisfactory results with this food Pumpkins the drawback that there may be some difficulties when removing from the hob after ironing, for example cities 5 mim. the drying period will probably which reduced the expressiveness of extrusion, but outside this will give you the best results. Accuracy of stampings pattern is extremely important because without finishing on it will not give an authentic look skin.

The next stage consists of a single stage crushing, pressing and cross-linking coated foam backing, by subjecting covered with pebble the substrate is subjected to the action of a pressure in the range of 0.35-175 atm, and most preferably 1.05-84 atm at temperature 66-204 ° C, most preferably 66-163 ° C. Wyelimino the need for separate operations was important crushing, pressing and cross-linking of polymers.

After the drying stage, the covered substrate can be treated under a slight pressure, for example 0.35 atm, if it is necessary from the ope point of view tears covered with substrate. At this stage of the process su the coating is slightly adhesive and may peel off jack if the coating is in contact with other materials lami or is contacted by an outside party with 40 outside of other, foam-covered backing zy. Nevertheless, even a slight back pressure ensures adequate adhesion of the coating to the floor osier.

The final stage of the manufacturing process of the workpiece skins and prepared skins substitutes consists on dabbing on a skin substitute covered with crushed the foam of the composition to form the coating is finished czajacej, which is flexible and stretchable and contains one of the following ingredients: nitrocellulose, urethanes, polyvinylchlorides, acrylic polymers, The cellulose acetate butyrates or compositions also contain jace nitrocellulose and terminated in isocyanate groups- new organic polyisocyanate prepolymer with polyester or polyether polyol, or Also mix them mixed or unmixed with plasticizers.

Preferred finish coats are half strings made of compositions containing low 60 trocellulose and terminated with isocyanate groups organic polyisocyanate prepolymer with a polyester or polyether polyol or the same containing cellulose acetate butyrates. The beneficial ones the coating compositions provide a finishing coat 65 on the skin or skin suits, characterizing 50 55 103 078 9 improved flexibility and greater wear resistance life than the coatings hitherto obtained with the use of other finishing methods. Octano- Cellulose butyrates are described in US Patent No.

US No. 3,574,154, hereafter referred to as was called.

The amount of nitrocellulose present in one of the cells The preferred compositions are most preferably included in the range of 15-55% of the total the amount of solids included in the composition.

These preferred coating compositions are described in more particularly in U.S. Patent No. US America no.3763061.

The finishing coat can be applied in amounts is approximately 10.7 g / m2 solid in the coating in order obtaining the best set of physical properties ensuring adequate flexibility and resistance on abrasion. The thickness of the finishing coat may be regulated by the solids content in the composition position, parameters of the imposing machine, the speed of movement of the substrate and the number of applied layers. The outer shell should be formed made from a mixture of urethane polymers with nitro cellulose in a 55:45 ratio giving the best team properties in terms of flexibility, abrasion resistance not and sticky. The ratio of uretah polymers to nitrocellulose can be changed, if it is a horse not necessary, within 50: 50—65: 35 to obtain best results on individual types skins, but when changing this ratio it changes flexibility, abrasion resistance and adhesiveness the essence of the shell. Usually used in accordance with the method or, according to the invention, latex coatings should contain latex polymer, aluminum, titanium dioxide nu or other inert fillers and stabilizer foam and may also contain causing additives cross-linking the polymer.

Latex compositions from which they are made foam used in the method according to the invention, is being prepared from at least two of the results the monomers mentioned below, at least less one monomer has a functional group crosslinkable: (a) unsaturated acids which A double bond of the ethylene type has occurred puje in position a, fi, including the following acids: acrylic, methacrylic, ethacrylic, itacone, aconite, croton, citraconic, maleic, fumaric, a-chloroacrylate, cinnamon and meso horse, etc, and can also be used mixtures of these acids, (b) monomer of formula 1, wherein R represents a hydrogen atom or an alkyl group a lower, for example lower alkyl group contains has 1 to 4 carbon atoms and R 1 is straight, dil branched or cyclic alkyl group, alkoxy kilo or alkoxyalkyl containing 1-20 carbon atoms or the cycloalkyl group also contains with 5 to 6 carbon atoms, such as a methyl group wa, ethyl, propyl, n-butyl, 2-ethylhexy- low, heptyl, hexyl, octyl, 2-methylbutyl rear, 1-methylbutyl, butoxybutyl, 2-me- tylopentyl, methoxymethyl, ethoxyethyl, cyclopentyl, cyclohexyl, isobutyl, ethyl lotioethyl, methyltdoethyl, ethylthiopropyl, 6-methylmonyl, decyl, dodecyl, tetrade- cylindrical, pentadecyl, etc .; R1 can also mean non-ureido group, lower hydroxyalkyl- steel containing 1-5 carbon atoms, such as hydro xymethyl, hydroxyethyl, hydroxypropyl wa, hydroxybutyl, hydroxypentyl, etc., 2,3-epoxypropyl group, lower aminoalkyl group a single or alkyl group substituted with one or two lower alkyl or lower radicals with the hydroxyalkyl radical, substituted with a sixth alkylamino group, (c) a monomer of formula 2, wherein R2 is a hydrogen atom or a meta group rear, and R3 is halogen such as chlorine and the like, lower alkanoyloxy group such as ace- toxins, etc. cyano, formyl, fanyl groups, carbamyl, N-hydroxymethyl, tolyl, metal toxymethyl, 2,4-diamido-s-tariaazinylalkyl and epoxy i R4 is a hydrogen atom or a methyl group, while R5 and R6 are lower alkoxy groups, such as as methoxy, ethoxy, etc>. or lower groups alkanoyloxy such as acetoxy, etc.

Examples of monomers mentioned in the (b), (c) and (d) points that may be used are na¬ steppe compounds: methyl methacrylate, methacrylate ethyl, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, meta Krylane II-order. butyl, tertiary-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, methacrylate cyclohexylate, 2-ethylbutyl methacrylate, meta 2-ethylhexyl acrylate, octyl methacrylate, methacrylate decyl lan, lauryl methacrylate, myristic methacrylate- lu, cetyl methacrylate, stearyl methacrylate, acrylic methyl lan, ethyl acrylate, propyl acrylate, acrylate isopropyl polyamide, butyl acrylate, isobutyl acrylate, tert-butyl-acrylate, tert-butyl-acrylate, amyl acrylate, isoamyl acrylate, acrylate-III-order- amyl, hexyl acrylate, octyl acrylate, acrylate 2-ethoxyhexyl, vinyl acetate, tetradecyl acrylate, acrylamide, pantadecyl acrylate, styrene, methacrylate pentadecyl lan, vinyl toluene, methacrylamide, N- -methylacrylamide, etc., glycidyl methacrylate, meth methylaminoethyl tacrylate, methacrylate-III-order- butylaminoethyl, 6- (3-butylene) -2,4-diamino-s- triazine, hydroxypropyl methacrylate, methacrylate hydroxyethyl, methacrylonitrile, methoxymethylmeth- tacrylamide, N-methylmethacrylamide, acrolein, me- tacrolein, 3,4-epoxy-butene-1, diethyl acetal - acrolein, acrolein dimethyl acetal, diacetate allylidene, metallylidene diacetate, analogous to of the above methacrylic acid derivatives from others unsaturated acids such as acid acrylic and itaconic acid, these acids as such, dicarboxylic acids such as maleic acid you and their half-esters and half-amides, vinyl glycol ethers coli such as ethylene glycol.

As can be seen, constituting an addition to the network what unsaturated monomers with polymeric capability of the reaction have reactive polar groups such as group: -OH, -SH,> NH, group of formula 4, -N = C = = O,> CHCN, -CHO, -COOH and the group of formula 5.

Such groups cause mutual networking or self- brass plating, or you can add a separate one cross-linking compounds such as resin triazinoformaldehyde.

Of course, you cannot use it in ox systems water-sensitive substances that are 40 45 50 55 60 103 078 11 12 such as isocyanates, as long as they are not protected baked as a result of reactions with phenolic groups, which protect the isocyanate groups up to the moment of heating. You can also use others reaction methods, such as using conventional normally used catalysts of the compound type calcium, zinc or tin.

Preferred copolymers have a molecular weight 70,000-20,000,000, and most preferably 250,000-10,000,000 and are produced by copolymerization of the emulsion of a series of monomers in the corresponding stages portions. Conventional copolymerization methods emulsion is described in US Pat.

US Nos. 2,754,280 and 2,795,654. So mono mers can be emulsified using anionic, cationic or non-ionic dispersants used in amounts of 0.05-10% by weight in relation to the total amount of monomers. Mono acid units and many monomers of other groups functional armpits or those containing polar groups, can be soluble in water, so that the measure dispersant serves to emulsify another mono mer or monomers.

A type polymerization initiator may be used a free radical such as ammonium persulfate or potassium, alone or in combination with an accelerator, ta kim such as potassium metabisulphite or thiosulphate sodium. They are also useful as organic initiators ne peroxides such as benzolyte peroxide or tertiary butyl hydroperoxide. Initial thorium and accelerator, usually called a catalyst, can be used in amounts of 0.1-10% of each ingredients in relation to the total amount of polymerized monomers. The quantity shown is off the lower can be chosen to obtain the appropriate the viscosity index of the polymer. Temperature and polymerization may vary by temperature room temperature to around 760 ° C.

The following is a list of the copolymers that may be to use in a way according to invention. Copolymers these have the following composition, with the definitions of the abbreviations used are given in the following description su: 96BA / 3, 5 AM/O, 5AA, 96EA / 4MOA, 94EA / 5, 5ALAC AC / O, 5AA, 94, 5EA / 5HEMA / 0.5AA, 66EA / 32, 7MMA / 1.3MAA, 100EA, 83EA / 15MMA / 2AA / Na /, 5IA. 86EA, 10AN / 4MOA 83BA / 14AM / 1AC / 2AA, 97EA / 1AC / 2AA, 68BA / 28MMA / 2Au / 2Ac / 2AN, 30BA / / 55EA / 10MMA / 3,5AN / 0,5Ac / AA, 45BA / 10AN / 40 / EA / / 4HEMA / 1AA, etc.

Use of a water-soluble agent surfactant or combinations thereof Agents improve the dispersion of the emulsion latex and acts as a foam aid and foam stabilizer. These measures active ingredients include alkali metal salts, salts ammonium or amine salts such as mono-, di-, triethanolamine and aliphatic carboxylic acids with 16-20 carbon atoms in the total phials such as oleic acid, stearic acid, etc., for example sodium, potassium or ammonium stearate sodium, potassium, ammonium oleate etc. With those described above surfactants can be used Wac at the same time other surfactants active, including alkali metal salts, ali fatty or alkylaryl sulfonic acids such as sodium lauryl sulfate, dodecylben- zenesulfonate, sodium, etc. as well as non-ionic surfactants such as products condensation of ethylene oxide with alkylphenols or higher fatty alcohols, for example tertiary octylphenol condensed with 5 to 40 monos ethylene oxide, condensed lauryl alcohol containing 5 to 50 units of ethylene oxide or polyethylene similar products of ethylene oxide condensation with long chain mercaptans, fatty acids amines, etc.

Although it is used in the method according to the invention both thermoplastic resins and ther- multi-sclerotic, however, the latter are more advantageous because the foam formed therefrom produces articles leather and leather-like, more suitable for processing bu, and also more convenient to use.

For cross-linking, acrolein resins or methacrolein, dibasic amines, for example diethylenetriamine, hydrazine, etc. Resins type melamine is used to cross-link polymers containing functional hydroxyl groups and amine. You can also use other well cross-linking agents known to those skilled in the art.

The finishing compositions may be transparent These or may also contain matting agents, pills ments or dyes depending on the particular items great aesthetic values. Examples pigments that can be used are clay, double titanium oxide, calcium carbonate, barite white, doped finely divided metals such as aluminum etc., color lakes and oxides which are dyes. Other¬ and conventional additives that can be used words are fillers, lubricants and agents suitable slipperiness. Composition to be made The finishing layers preferably also includes a silicone rubber polymer, such as a product commercial Dow Corning marked * as DC-160, 40 FC227, Syl-Off-29i with catalyst type an organic metal salt, for example bis laurate butyltin, zinc salt of heptanecarboxylic acid etc. The last two additions are intended to further six improvement in wear resistance and value 45 aesthetic.

Finishing Compositions The hot tub can be applied to the covered crushed foam the substrate using one of the methods well known to those skilled in the art: brush, brush, spray, drench or 50 by dipping. Among these methods are also the methods described in US Pat. US

Nos. 2,126,321 and 2,884,340. If desired one or more coatings may be applied.

The coating thickness may vary depending on the 55 specific purposes it is intended to serve.

The amount of finishing coat depends on the type of finish covered metal and desired finish.

Usually the top coat forms a layer thickness 0.0025-0.2 mm in the form of a dry layer, 60 and most preferably 0.0076-0.013 mm. After putting on the the wool can be hardened by drying to condition non-sticky at room temperature for a period from 30 min. up to 1 hour or by heating to temperature up to about 100 ° C, until the 65 provides adequate hardening. 103 078 13 14 The advantage of the nitracellulose finishing composition vourethane is the fact that it forms a shell with excellent pliable properties and ability to returning to the previous state, and at the same time it is strong enough to be used as an outer layer on the skin or as a substitute tachts of leather intended for suitcases or upholstery and in applications such as shoes, coats, etc. These properties of flexibility and the ability to return to previous state makes compositions ready for use making nitrocellulose-finishing coatings -urethane is a particularly valuable raw material for dragging thick, pliable surfaces, especially substrates with a thickness of 0.76-2.54 mm, if these substrates are subjected to multiple bending actions for example as coverings for skin or as a substitute heats of leather used for suitcases, upholstery, shoes and other fancy goods.

While emulsion polymers are the most preferred, however, the polymers produced can also be used in organic solvents, for example clade in ethylene glycol, ether, xylene, mono- ethylene glycol methyl ether and the like are known m and by conventional methods, using to initiation, benzolithium peroxide, etc. The polymers are prepared in a solution that can be used in it of the present invention most preferably have a shadow molecular weight 10,000 to 10,000,000.

Composition for making a crushed lid The foam body can be very varied composition. Table 1 shows the content of the individual ingredients of the composition as you can use.

Table 1 Typical ingredients of the composition Resin (40-60% solids) Foam stabilizer Surfactants Fillers Coloring substances Waxes and other auxiliary substances Ammonia (28%) Dibasic amines Melamine resins Parts by weight 500-1000 —80 0-150 —200 0-150 0 ^ 100 0 ^ 15 0—25 0—25 It should be understood that the composition for the production of the foam coating can be made Today also other ingredients. Especially fillers, coloring substances and waxes can be added to composition in various amounts to obtain products with the desired characteristics. Exact There are several types of fillers that can be used clays, mica, calcium carbonate, bentonite, silica, etc. Examples of a coloring matter that can used in the composition are the dyes produced from inorganic and organic pigments, and in particular dispersions of pigments in used water with a dispersant and protective colloid him. Carbon black may be examples of these pigments carbon, iron oxides, anthanase, titanium dioxide etc. Waxes are used in the composition to facilitate the process of removing the laminate from the ironing plates.

Such waxes are well known to those skilled in the art and include the following: I polyethylene waxes, etc.

Examples are given below to illustrate the typical compositions of compositions which can be used in a manner according to the invention: Example I - Composition 1 40 45 50 60 Components Copolymer composed of 83BA / 14AN / / 1AC / 2AA China clay Ammonium stearate (33%) Diethylene triamine Ammonium hydroxide (26%) Primal red dye Parts by weight 100 7.0 0.6 2.0 , 0 Example II - Composition 2 Copolymer composed of 825BA / 14AN / / 1.5Ac / 2AA Clay Ammonium stearate Diethylene triamine _ Ammonia (28%) Primal brown dye Water ^ ¦ 500.0 75.0 .35.0 3.5 , 0 75.0 65.5 Example III - Composition 3 Copolymer composed of 86EA / 10AN / / 4MOA Clay Ammonium stearate An aqueous suspension of melamine resin wo-formaldehyde Ammonia (28%) White color 264 565.5 75.0 , 0 11.5 , 0 75.0 Example IV - Composition 4 H20 NH3 (28%) Clay Czern Primal 110 copolymer composed of 96EA / 3MOA / / 0.5AA Ammonium stearate 65.5 , 0 75.0 75.0 500.0 , 0103 078 Example V - Composition 5 Czern Primal 110 NH8 (28%) Clay Copolymer composed of 96EA / 3MOA / / 0.5AA Ammonium stearate Water suspension of melami resin- new-formaldehyde 75.0 , 0 75.0 565.5 , 0 11.5 Example W - Composition 6 Pcimal ocular yellow NH8 (28%) Clay Copolymer composed of 96EA / 3MOA / / 0.5AA Melamine 75.0 1> 0, 75.0 \\ , 0 11.5 The ingredients of the compositions in Examples 1-6 are added while stirring in the order shown (amo¬ The tray is divided into two batches, half of them introduced only after the addition of the resin melted Aerotex MW mine) and mixes thoroughly (in the city Lightning, Talboys or Cowles). You can also use other types of melamine resins, such as vidce available under the name: Aerotex M-3, melamine-formaldehyde-methanol, methoxy- important melamine-formaldehyde resin. After While stirring, the resulting mixture is washed tightly to avoid scum formation.

Example VII - Composition 7 1 Ingredients Copolymer composed of 83BA / 14AN / 1AC / 2AA Ammonium stearate Octylphenoxy polyethoxy ethanol Clay Acme WW Czern Primal 110 NH, (25%) Polyethylene wax Diethylene triamine parts by weight 420.5 , 8 21.5 57.5 41.7 7.0 23.9 2.1 600.0 Latex and non-ionic surfactants ^ the active ingredients are added to the Cowles mixer and slowly mixes. Then ammonium stearate is added.

The mixing speed is increased and the mixture is mixed at the same time prefers to add the other ingredients in the order given carriers. After obtaining a homogeneous suspension of the 16 The items are filtered through the cheese cloth or a sieve with a mesh size of 40 mesh. Substance yes is obtained and is ready for use with a suitable foam concentrate. By replacing no coloring agent, black Primal 110, other a suitable coloring agent can be prepared make other compositions in substantially the same way.

Example VIII - Spraying in form aerosol Compositions of Example III (70 g), trichloroflu- oromethane (60 g) and dichlorofluoromethane (40 g) was placed in an aerosol canister with nozzles with a valve. The container was shaken and the contents sprayed onto: (1) leather split and (2) paper.

The material being sprayed began to bubble without directly after leaving the nozzle of the aerosol can because the boiling point of the propellant of the frother was below the temperature the surrounding rounds and the foaming of the coating took place further on the ground. Coating on the skin after drying was simultaneously crushed, pressed and on the Watson Stillman press (temperature 88 ° C, pressure 30 t, time 3 sec). Sprayed density the foam was approximately 0.0007 g / cm3.

When using a charge of 70 g of the composition for example clade III, 50 g of trichloromethane and 50 g of dichloromethane of difluoromethane, the foam had approximately 0.012 g / cm3 after crushing and pressing in the manner described above.

Example IX - Spraying with a gun The composition according to Example VII remained at the same time at room temperature with trichlorotrifluoroethane.

The mixture was placed in a pressure vessel (vacuum charging, line pressure 4.2 atm, pressure in the tank 1.05 atm). Mixture was sprayed on the skin in an amount of approximately 39.5 up to 45.6 g / m2. The mixture was slightly foaming at the At room temperature, but drying at room temperature At 138 ° C, the coating foamed very well. Rotten cheap, pressing and cross-linking were performed in one go tuition fees on the Watson Stilman press at temperature 88 ° C, with a pressure of 30 t, for a period of 3 sec. 45 Example X - Spray gun The experiment described in the example was repeated IX with trichlorotrifluoroethane with this rose There is no need to use split leather that is warmer it was heated for a few minutes at 138 ° C before applying the coating. Coating applied to the heater on the skin it foamed immediately and foamed the draglines lasted while drying. Crushing, ironing no and cross-linking as described in the example IX gave a leather with a perfect coating. 55 Example XI - Foaming properties of an emulsion of acrylic polymers using trichloro trifluoroethane The foaming properties of various emulsions were investigated 60 acrylic polymers by the use of composite items with the following composition: latex 307.5 g; NH8 (28%) 5.0 g; 537.5 g coloring agent and trichloro trifluoroethane 35 g. The compositions were sprayed with the spray a pressure vessel working under pressure 65 1.05 atm., At a pressure 5.6 atm. In the conduit. 103 078 17 18 The substrate used was a white cardboard size 36.8 cm x 29.2 cm. After spraying, the coating air dried for 1 minute, then oven dried under forced circulation temperature at 138 ° C for 5 minutes.

The polymers used were prepared as follows monomers in the following proportions: , 1. 96EA / 3.5 / 0.5AA 2. 96EA / 4MOA 3. 94EA / 5.5LACAC / 0.5AA 4. 94.5EA / 5HEMA / 0.5AA . 66EA / 32.7MMA / 1.3MAA 6.100EA 7. 83EA / 15MMA / 2AA / Na / 8. 83BA / 15AN / 1AC / 1AA 9. 65EA / 25.5BA / 4.5AN / 3.5AM / 1.5IA . Butadiene rubber (Hycar 1571) The individual abbreviations mean: EA - acrylate ethyl, BA - butyl acrylate, MMA - methacrylate methyl, AA - acrylic acid, MAA - meta acid krillic, IA - itaconic acid, HEMA - meta hydroxyethyl acrylate, AN - acrylonitrile, Ac - ak- rolin, ALACAC - allyl acetoacetate, MOA - acry- lamide / methylol acrylamide (1: 1) and AM - acrylamide.

The results are given in Table 2.

Example XII - Solvent Assessment foaming agents and a variety of solvent-borne foaming agents The tests were assessed using an acrylic polymer 96 parts of ethyl acrylate (3.5 parts acrylamide) 0.5 parts of acrylic acid (87.8 parts by weight) with pigment black 110 Primal (10.7 weight) and ammonia (28%, 1.5 parts by weight out). The compositions were sprayed onto the screen and dried at the temperature of 138 ° C for 5 minutes. Quality foams and the foaming factor for each individual the solvents tested are listed in table 3.

Polymer .1 2 3 4 6 7 ' 8 9 '10 1.1 Quality created foam Okay sufficient-good sufficient-good sufficient-good good-very good sufficient-good sufficient-good sufficient-good Okay Okay good bardiza Quantity na¬ carried composition g / m2 - 155 155 232 155 174 116 130 150 213 91 Blackboard Carry on the quantity of a sown body la permanent - 44.3 44.3 44.3 44.3 43.5 44.3 37.5 44.3 44.3 44.3 38.3 2 pH 9.4 9.9 8.6 9.8 , 1 , 1 , 2 9.7 9.7 9.4 , 1 Viscosity according Brook- field cP high 336 268 648 660 48 1636 88 11300 860 40 Hue bluish-black bluish-black bluish-black bluish-black bluish-black greenish bluish-black 1 green green bluish bluish-black Table 3 Solvent Temperature boiling Percentage of cannons in 100 parts composition Foam condition Factor foaming 1. 2. 3. 4.

CH2Cl2 CHClg CHCl3 CC18CF3 CC18CF8 CC1SF CCI3F pentane pentane hexane hexane 39.7 39.7 62.1 62.1 47.3 47.3 23.8 23.8 36.1 36.1 68.7 68.7 -10 no foam no foam no foam poor foam homogeneous homogeneous homogeneous homogeneous homogeneous homogeneous homogeneous homogeneous foam foam foam foam foam foam foam foam 19.61 19.61 44.74 44.74 2.53 2.53 , 57 , 57 1.21 1.21 1.07 1.07103 078 19 20 Example XIII - Finish and its application Step A - Preparation of the prepolymer A 2 liter three-necked flask is supplied with a mechanical stirrer, thermometer, and an attachment distillation, coolers, nitrogen supply valve and connection to the vacuum pump charged 500.5 g of polyetherthiol (molecular weight 1540). Ci¬ the dream was lowered to 51 mm Hg and the lower temperature raised to 70 ° C while mixing the contents flasks. 45.5 g of distillate was collected and the temperature was lowered z oo to 30 ° C, increasing the pressure to 760 mm Hg by introducing nitrogen.

Then 305 g was added to the reaction mixture toluene diisocyanate and the temperature was raised up to 75 ° C for 16 hours Isocyanate content was determined and the product was cooled to room temperature peace. The resulting prepolymer has the following properties: percentage of solids - 74.21; milirówno- NCO group vats / g solution -0.834; viscosity in Cardner-Holdt-T ^ debt; unreacted tolu- enodiisocyanate - 1.17.

Stage B - Preparation of coating compositions finishing Finish coating compositions were prepared by mixing the following ingredients (weight parts are given in brackets); prepolymer from step A (110), nitrocellulose (177), nitrocellulose with matting agent (100), pigment black, plastic ficator and nitrocellulose (200), butyl acetate, xylene and 2-ethoxyethyl acetate (413 parts in the ratio 50: 40.10), silicone rubber polymer (25,>, Dow Corning - 160 ") and dibutyltin laurate (50).

StageC- Application Stage B compositions were applied to the skin or skin substitute using standard equipment by spraying, applying approximately 35.2 g of solid per m2 of substrate.

By replacing the prepolymers they use no in example XII, step B, with other prepolymer- m and by using other pigments or dyes incl instead of the black pigment used in this example day and by using other silicone and pre- polymers and catalysts similar prepared finishing compositions.

Przyiclao; XIV - Finishing and finishing coat cladation of cellulose acetateomaslate 97.5 parts of poly (1,3-butylene adipines) were obtained conventional methods, time weight with a molecular weight of 5000 and a hydroxyl number of 20, constant the wounded man was dehydrated by flushing with nitrogen at a temperature of 130-140 + C. The polyester was cooled down step to 106-108 ° C and added into the liquid 15 min. 4.6 parts methylene bis (4-phenylisocyanide- nanny). The temperature of the reaction mixture increased It was sieved to H1-15 ° C and stirring was continued at overpressure of nitrogen for a period of 30 hours. Chilled the product had a viscosity of about a million poises and a figure slightly colored sticky rubber. 50% solution in xix The sloth had a viscosity according to Gardner-Holdt ZB.

Stage B - The composition of the clear solution of plasticized cellulose acetate-butyrate.

Prepared solvent mixture by mixing 510 parts of toluene, 170 parts of metabolic ketone Tylo-ethyl and 320 parts of ethyl alcohol. Down 69 parts of this solvent mixture were added 1 part of cellulose acetatebutyrate with a viscosity of 3 sec, containing 20% of butyryl groups and 25% of groups acetyl followed by 3.8 parts linear polyester, namely propylene glycol succinate new with a molecular weight of 8000. Then 12.1 parts of a 50% solution of xylene are added of the polyester from step A. The mixture was thoroughly mixed until io until a homogeneous solution is obtained. Obtained the mixture had a light straw color and a sticky color bone 2,100 cP.

StageC - Application parts of the clear composition from step B were changed shano with 80 parts methyl ethyl ketone and 1 part alcohol-soluble color was added Nika red. The mixture was applied by the method of nailing squirt on a piece of covered leather substitute Crushed foam coating in the amount of 1.0 g per m2 skin substitute. The finishing layer was dry It is cut in the air and then pressed under cut sleep 1.4 atm at a temperature of 160 ° C for a period of 60 seconds when using a sandblasted plate. Received the finishing layer had a brown heat dyeing and had excellent la¬ resistance mania or tarnishing when bending.

It is obvious to a person skilled in the art that it is described above the process is illustrative only and it is possible many variants and modifications of the housing method falling within the scope of the method according to the invention.

Claims (12)

Patent claims A method for the production of finished leathers and leather substitutes by coating leather with a polymer, characterized in that the leather or leather substitutes are covered with a polymeric acrylic latex coating, the polymer of which contains at least one monomer having a functional group capable of cross-linking after application. latex on leather or leather substitutes, these coatings are foamed with a solvent having a boiling point of (-10) - (104) ° C, in which the non-cross-linked polymer contained in latex has a foaming factor of 1 to 7 times, the latex-coated substrate is dried It is formed and formed at a temperature of 49-204 ° C, and then the covered substrate is compressed, pressed and hardened under a pressure of 0.35-175 dtm. at a temperature of 65-204 ° C and a finishing coat is applied to the coated substrate of the crushed foam. 2. The method according to claim The process of claim 1, wherein the solvent has a boiling point of 23-93 ° C, in which the non-cross-linked polymer contained in the latex causes the non-cross-linked polymer 1-7 to expand by volume. 3. The method according to p. The process of claim 1 or 2, characterized in that compositions containing nitrocellulose, urethanes, polyvinylchloride, acrylic polymers, cellulose acetobutyrate, urethane-modified nitrocellulose or mixtures thereof are used as the finishing coat. 4. The method according to p. The method of claim 1, wherein the polymer latex is a latex containing at least two monomers, of which at least one of which has cross-linkable functional groups, vaporized with these monomers. are either unsaturated acids with an ethylene bond in the α, 0 position, or monomers of formula I, where R is hydrogen or an alkyl group and R1 is a straight, branched or cyclic alkyl, alkoxyalkyl or alkylthioalkyl radical or monomers of formula II, where R2 is hydrogen or methyl, and R3 is halogen, alkanoyloxy, cyano, phenyl, formyl, carbamyl, epoxy, N-hydroxyethylcarbamyl, tolyl, methoxymethyl or 2 , 4-diamino-s-thiazinoalkyl, or monomers of formula III wherein R4 is hydrogen or methyl and R5 and R6 are lower alkoxy or lower alkanoyloxy groups. 5. The method according to p. The method of claim 1, wherein the polymer latex is a latex containing fillers such as clay, mica, calcium carbonate and silica, a foam stabilizer, a colorant, and a crosslinker such as ammonia, diamine, alkaline and melamine resin. 6. A method for the manufacture of finished hides and leather substitutes by coating leather; polymer, characterized in that the skin or skin substitutes is coated with a polymeric acrylic latex, the polymer of which contains at least one monomer having a functional group capable of cross-linking when the latex is applied to the skin or skin substitutes , the coating is foamed with a chemical foaming agent, the latex coated substrate is dried and formed at a temperature of 49-204 ° C, and then the covered substrate is compressed, pressed and hardened under a pressure of 0.35-177 atm, at a temperature of 65 -204 ° C and a finishing coat is applied to the coated substrate with crushed foam. 7. The method according to p. The process of claim 6, wherein the chemical foaming agent is an azo compound, N-nitroso compound, sulfonyl hydroxide, ammonium bicarbonate, sodium bicarbonate, sodium carbonate, hydrogen peroxide, ammonium nitrate or malonic acid. 8. The method according to p. The process according to claim 6 or 7, characterized in that compositions containing nitrocellulose, urethates, polyvinyl chloride, acrylic polymers, cellulose acetate butylate, urethane modified nitrocellulose or mixtures thereof are used as the finishing coat. 5 9. The method according to p. 6. The method of claim 6, wherein the topcoat composition is a composition comprising nitrocellulose and a polymer terminated with organic isocyanate lysocyanate groups with a polyester or polyether polyol or cellulose acetate butyrate. 10. The method according to p. 6. A method according to claim 6, characterized in that the polymer latex is a latex containing at least two monomers, at least one of which has determinable functional groups, the monomers being the same or with unsaturated acids a bond of the ethylene type in the position α, 1, or monomers of formula I, wherein R is hydrogen or an alkyl group, and R1 is a straight, branched or cyclic 2e alkyl radical, an alkoxyalkyl or an alkylthioalkyl radical, or monomers of Formula 2, wherein R2 is hydrogen or methyl, and R3 is halogen, alkanoyloxy, cyano, phenyl, formyl, carbamyl, epoxy, 25- [beta] -hydroxymethylcarbamyl, toluyl, methoxymethyl, or 2 , 4-diamino-s-triazinoalkyl or monomers of formula III where R 4 is hydrogen or methyl and R 5 and R 6 are lower alkoxy or lower alkanoyloxy groups. 11. The method according to p. The method of claim 10, wherein the polymer latex is a latex containing a monomer selected from at least three of the four groups consisting of ethyl acrylate and butyl acrylate in the first group, acrylamide, methyl acrylamide, allyl acetoacetate, hydroxyethyl methacrylate. , methyl methacrylate, acroleine and methacrylate in the second group, acrylic and methacrylic acids in the third group and acrylonitrile in the fourth group. 12. The method according to p. The method of claim 6, wherein the polymerase latex is a latex containing fillers such as clay, mica, calcium carbonate and silica, a foam stabilizer, a colorant and a crosslinker such as ammonia, dibasic amine, and melamine resin. 103 078 R 9 and ii. CHj-C-C-OR1 Formula 7 ** CH2 = C R5 Formula 2 R4R5 CH. = C-C-RB and H Formula 3 -C-N <Formula A Formula 5 LDA - Acc. 2 - Order 1032/80 - 100 pcs. Price PLN 45