The method of processing tanned skin

 

(57) Abstract:

The inventive tanned skin is impregnated with the aqueous dispersion of amphiphilic copolymer average mol.m.2000-100000 containing from more than 50 to 90 wt. % of at least one hydrophobic monomer selected from the group consisting of (C8-C22) alkyl/meth/acrylate, (C8-C22) alkoxy or (C12-C22) alkylphenoxy /polyethylene oxide/meth/acrylate, (C12-C22) primary alkenes, minilateral (C12-C22) alkylcarboxylic acids and mixtures thereof, and from 10 to less than 50 wt.% at least one vodorastvorimogo acidic or basic hydrophilic comonomer with ethylene unsaturated bonds. 11 table.

The invention concerns a skin treatment selected amphiphilic copolymers.

Processing of skins to get the skin includes a number of interdependent on each chemical and mechanical operations. These operations can be divided into a series of separate wet stages, which is the serial number of dry stages. A method of manufacturing a skin consists of the following sequence of separate wet stages: pruning and sorting, soaking, meskene, obespechivanie, processing fat emulsion and stabilization. These wet end stages followed by dry stages: drying, conditioning, styling in the foot, Cherkovna, dressing, coating, measuring and sorting. A description of each of these operations is given in Leather Facts, New England Tanney, 1972.

The invention covers a separate wet transactions that occur after the initial tanning, namely: re-tanning and processing of fat emulsion. The primary goal of tanning is to make skins or skin into a stable non-perishable material. This is due to the transformation of raw collagen fibers in the skin or skin into a stable product that does not undergo decomposition, i.e. which does not deteriorate. In addition, tanning improves several properties of the skins or leather, such as dimensional stability, resistance to abrasion resistance, resistance to chemicals and heat, increased elasticity and ability to withstand repeated cycles of wetting and drying. The main method used for the tanning of hides and skins, known as chrome tanning.

This method requires the use of basic chromium sulfate, often referred to simply as chrome, which is obtained in the result is sachivalya in the skin, resulting in a bluish-green color. This color change is used to determine the degree of penetration or the degree of tanning. In addition, to measure the speed and degree of tanning is used, the shrinkage temperature. Not tanned leather gives considerable shrinkage when exposed to hot water, for example water with a temperature of 140 (60aboutC), while subjected to the chrome tanned leather can withstand exposure to water with higher temperatures, for example, water with a temperature of 212 f (100about(C) without shrinkage (U.S. patent N a-4 327997). Hides and skins can be tanned with plant extracts, such as extracts from trees and bushes, such as quebracho tree, locust, sumac, Hemlock, oak and spruce.

After tanning the skin is re-tanning, dyeing and processing of fat emulsion. This three-step operation is often regarded as one stage, since all three operations can be performed sequentially in a single drum. Subjected to the chrome tanning of raw materials, called blue Miriam, retains to a large extent heterogeneous fibrous structure, such as on the skin of the animal. Some of wasdirectly may be desirable thin paper type. Because Tanner wants to obtain a homogeneous sample of the skin, it carries out the second stage of tanning, known as re-tanning to improve the physical and aesthetic characteristics. These characteristics include, for example, improving the volume of skin density and uniformity of the structure, characteristics razvivaemosti, the uniformity and intensity of the shades of staining of more uniform rasstegivaemoy or elasticity, better wettability and additional resistance to water and wypadaniu. Re-tanning can be carried out using various kinds of materials of natural origin, including plant extracts, and synthetic tanning agents, known as synteny, or combinations thereof. Historically, extracts from trees and bushes of the specified types are used as agents for re-tanning. Over the last 50 years developed many artificially get centany, which are widely used at present, especially for the manufacture of soft skin and white or pastel colors. Re-tanning is usually carried out at temperatures of from about 80 (27) to 120 f (49aboutC) using about 3-20 wt.% everhot re the chrome tanning to regularly carry out the step of re-tanning full tanning any previously nezadelannyh areas and to align chromium, especially in the areas of grain for a more uniform coloring. Re-tanning is usually done within 1-2 hours, while the entire sequence of operations to re-tanning, dyeing and processing fat emulsion usually takes about 2-6 hours After surgery, re-tanning of the skin is painted using either natural dye type or dye penetrant. Typically, acid dyes penetrates through the skin, while the basic dyes are used for dyeing only the surface.

After re-tanning and dyeing the skin is processed by a fat emulsion. Processing the fat emulsion according the desired characteristics of strength and elasticity of the skin. Fat emulsion lubricates the fibers of the skin so that after drying, the fibers are able to slide on one another. In addition to the regulatory flexibility of the skin, handling a fat emulsion has a significant impact on the tear resistance of the skin. Processing the fat emulsion may also affect the tension at break or on the pattern of folding, when the exposed area (grain) curves inward.

The goal is to get the skin that does Shemini in the processing of fat emulsion, are insoluble in water, oils and fatty substances, such as crude (unrefined) oil and sulphonated and sulfotyrosine oil. Typically, the liquid fat content (by weight of the skin) is 3-10%. The method of distribution of oil on the skin affects the character of the skin and subsequent finishing operations. For a homogeneous body covering large parts of the fibers of the skin should dilute these fats organic solvent or preferably dispergirovany of these fats in aqueous system using emulsifiers.

Although the ways to regulate the degree of penetration of the emulsion into the skin to rupture and deposition in the form of fat on the fibers is carried out to give the skin softness and greater elasticity, the characteristics of long-term resistance to water and characteristics of vodoottalkivayuschie not good enough when used alone fat emulsions.

There are various copolymers for skin treatment in the process of tanning and re-tanning, especially copolymers serving as substitutes for natural tanning agents and sintanol derived from phenol-formaldehyde resins.

In U.S. patent N A-2205882 and 2202883 describes the use to which polimery of maleic anhydride and styrene, the copolymers of methacrylic acid and styrene, hydrolyzed methyl methacrylate.

From U.S. patent N a-2 475 886 and 2452536 known from sulphonated water-soluble copolymers of styrene-Malei - new anhydride for tanning and re-tanning of the skin.

U.S. patent N A-3103447 relates to aqueous solutions of ammonium or amine salts of acidic copolymers for impregnation of leather with the purpose of obtaining the desired properties subjected to the re-tanning of the skin, such as improved performance gap, the resistance to abrasive action and the best finish. These copolymers are water-insoluble acid form, but water-soluble salt form, in which they practically used. These copolymers derived from polymerizable acids monoethylene unsaturated bonds, such as acrylic or methacrylic acid esters, such as esters of a saturated monohydroxy aliphatic alcohol and acrylic or methacrylic acid, obtained from cyclohexanol and alkanols containing 1 to 18 carbon atoms, or vinyl esters of fatty acids containing 1-18 carbon atoms, such as vinyl acetate, vanillaware and ministart. The preferred copolymers of the Ira. The most specific copolymers include those which are formed from 85 wt.% ethyl acrylate, 15 wt.% methacrylic acid, 66 wt.% of butyl acrylate, 34 wt.% of acrylic acid, 60 wt.% of methyl acrylate, 25 wt.% 2-ethylhexyl acrylate and 15 wt.% methacrylic acid.

U.S. patent N A-3231420 relates to a method of impregnation of the skin water-insoluble copolymers to obtain a skin for the ultimate finish. This method improves the characteristics of the gap, provides a higher density of finish, improves resistance to abrasion impact and abrasion properties, which are usually achieved by re-tanning. Used copolymers derived from (a) to 3.5 to 18.5 mol.% acid selected from acrylic acid, methacrylic acid and basis of itaconic acid, (b) 1.5 to 8 mol.% at least one of ester (meth)acrylic acid and a saturated polyhydric alcohol containing 8-18 carbon atoms) 10.5-43 mol.% methyl, ethyl or isobutylacetate, g) from about 47-84,5 mol.% of ester of acrylic acid and d) a saturated polyhydric alcohol containing 1-14 carbon atoms; and the total concentration of a) plus b) of 15-45 mol. %, and the ratio of b) to C) is(1 : 3,3) - (1 : 6,7). Copolymer having all four basis is torodi, chlorinated hydrocarbons or mixtures thereof, with preference being given hydrophobic hydrocarbons and halogenated hydrocarbons, which do not moisten the skin and which allow impregnation.

U.S. patent N A-3945792 relates to a method of filling tanned skin with the use of unsubstituted or substituted Homo - or copolymers of acrylic acid, which is soluble in water mixed with protein glue when the ratio of polymer to protein glue, equal(1 : 12) - (12 : 1).

In U.S. patent N A-4314802 describes a multistep process of tanning. In the first step uses an aqueous solution or dispersion of a polymer containing at least 50% of acrylic or methacrylic acid, with not necessarily used to a very limited number of complex Olkiluoto ether (meth)acrylic acid or sulfonated unsaturated dried oil. In the second stage uses zirconium tanning substance.

U.S. patent N A-4345006 relates to methods of processing tanned skin hydrophilic acrylic resin in water dispersion. Hydrophilic acrylate is a film-forming copolymer derived from 60 to 80 wt.% of ester (meth)acrylate, keylong ether (meth)acrylic acid, 1-10 wt.% capable of polymerization, anionic compounds, such as taconova acid, maleic acid, fumaric acid, crotonic acid, acrylic acid or methacrylic acid, preferably in the form of a water-soluble salt of an alkali metal or ammonium, 0.2 to 2.5 wt.% at least one transverse cross-linkable monomer, 0-2,5 wt.% (meth)acrylamide.

The dominant (meth)acrylate component having a low value of Tdusually described as a complex ether alcohols, preferably alkanols containing 2-18 carbon atoms. These songs are hydrophilic film-forming coatings with low content of acid-functional monomers (for example, with the content of 10-20 wt.% oxygenbinding monomer) used as agents re-tanning, but they are not substitutes fat emulsion and is not used for processing in order to give vodootlivnye.

Patent N A-4526581 relates to a method of tanning or re-tanning with the use of copolymers of methacrylic acid with a narrow range of molecular weights. These copolymers contain not less than 5 mol.% esters of the alcohol with a short carbon chain (1-4 atom (C) and acrylic acid. seen the results, for example, ensures a high resistance to cracking sections of the protrusions (grains) and removal of tannins.

Known methods of manufacturing of leather, which has a higher resistance to water and/or full vodoottalkivayuschie, for the more hydrophilic the surface of the skin due to chemical reactions with chromium or other mineral tanning agents or due to multiple treatments with the use of acids and salts of multivalent metals.

In U.S. patent N A-2968580 describes impregnating the leather with an aqueous solution of acid ether salts containing at least two salt-forming acyl groups, drying the skin and then the chemical interaction of the acid with miscible with water complex salt of the multivalent metal.

According to the U.S. patent N A-3010780 used mineral tanning agent which forms a complex with polimernymi dragonanime or more polybasic acid derivative containing a hydrophobic group, such as boric acid, phosphoric acid, arsenic acid, citric acid, trimesterly acid, malletova acid, atanderson acid, etc.

According to the U.S. patent N A-3276891 are used Nepal is about acid, aminolevulinic polycarboxylic acids containing 4 to 10 carbon atoms, or phenyl, or oxyphenylbutazone acids containing 2 to 6 carboxylic acid groups, partial esters of (simple or complex) polyhydric alcohols containing 2 to 10 carbon atoms, and at least two free hydroxyl groups and lipophilic radicals with the content of 8-22 carbon atoms with one unsaturated bond in the quality of impregnating in an organic solvent.

From the patent of the USSR N 265063 known hydrophobic treatment, including the use of high molecular weight hydrophobic product, which is the reaction product of the alkali metal glycolate with a styrene-maleic anhydride or acrylic acid to enhance vodoottalkivayuschie.

C. E. Retzche in the publication "Water system" designed to produce skin dry cleaning, which is no longer wetted " (Rev. ech. Ind. Cir, 69, 1977) describes the difficulty of imparting resistance to water skins, which were processed hydrophilic Centanni and fat emulsions. It is proposed to use some containing phosphate polymers in combination with a chromium compound.

U.S. patent N A-4527992 concerns FPIC among oxidized aliphatic hydrocarbons content 18-26 carbon atoms, oxidized and partially from sulphonated aliphatic hydrocarbons content 18-26 carbon atoms, oxidized paraffin hydrocarbon content 32-40 carbon atoms and oxidized and partially from sulphonated hydrocarbon content 32-40 carbon atoms. After such processing is processed with the use of impregnating agents in the form of copolymers of salts of an alkali metal, or ammonium, or lower alkyl with the content of 60-95 mol.% unsaturated acid selected from acrylic acid and methacrylic acid, and 5-40 mol.% monomer selected from methyl acrylate, ethyl acrylate, propylacetate, butyl acrylate, acrylamide, Acrylonitrile, methyl methacrylate, edelmetall - Lata, prophylatically, butyl methacrylate, methacrylamide and Methacrylonitrile, where the copolymer has a mole.m. 800-10000. Next are acidification, consolidation and finishing.

The subject of this invention is a method of treatment of tanned skin to improve properties came under the tanned skin or improved method of processing tanned skin.

These publications describing the use of various combinations of hydrophilic and hydrophobin the skin in one step so this provides the desired properties to be achieved by a separate wet stages of re-tanning, processing fat emulsion and make the skin vodootlivnye.

As the subject of this invention is a copolymer, which may find a good use for treatment of tanned skin in one step, so that this provides the desired combination of properties achieved in a normal individual stages of the re-tanning and processing fat emulsion.

The next subject of invention is a copolymer, which may also improve the resistance of the skin.

The next subject of invention is a copolymer, which can improve the intensity of the colour tone, the resistance to solvent extraction, the ability to wash and videofilmfest skin and which reduces drying time and energy required for each stage of processing.

According to this invention provides a method of processing tanned skin to improve its aesthetic properties, strength and elasticity. This method includes the use of dispersible in water selected amphiphilic copolymers formed from preobladanie hydrophilic copolymerizable monomer. Selected amphiphilic copolymer is effective in the processing stage, replacing the usual stages of re-tanning and processing fat emulsion, and improves the water resistance of the treated skin.

Aqueous dispersions of water-insoluble amphiphilic copolymers formed from a predominant amount of at least one hydrophobic monomer and minor amounts of at least one copolymerizes hydrophilic co monomer, find useful application for processing tanned skin during wet processes, allowing you to achieve a number of desirable aesthetic and physical characteristics, such as enhanced intensity of the colour tone and dynamic resistance, preferably in excess of 1500 bends ser.

Amphiphilic copolymer contains both hydrophilic and hydrophobic groups. This copolymer is obtained from more than 10 wt.% to less than 50 wt.%, preferably 15-45 wt. % , even more preferably 20-40 wt.%, at least one hydrophilic monomer and from more than 50 wt.% to less than 90 wt.%, preferably 55-85 wt.%, most preferably 60-80 wt. % of at least one hydrophobic co monomer. This copolymer has srednevekovogo monomers to obtain amphiphilic copolymers is the result of the empirical research data copolymers in comparison with the control using the selected control criteria process. Experimental examples presented below, clearly demonstrate that the comparative amphiphilic copolymers obtained from 10 wt.% hydrophilic monomer and 90 wt.% hydrophobic co monomer do not meet the specified end properties, particularly in respect of compliance and resistance. Similarly, upon receipt of a copolymer of an equal (50/50) weight concentrations of hydrophilic and hydrophobic monomer these final objectives were not attained.

The hydrophilic monomer used to obtain amphiphilic copolymer is at least one monomer selected from among water-soluble acidic or basic monomers of ethylene with unsaturated bonds, preferably with monoethanol link, or mixtures thereof. Examples of suitable hydrophilic monomers that can be used individually or as mixtures, are acrylic acid, methacrylic acid, taconova acid, fumaric acid, maleic acid, anhydrides of these acids, collocazione (meth)acrylates, such as Postretirement and sulphadimethoxine, collocazione (meth)acrylamide, such as 2-acrylamide-2-methylpropanesulfonate, and the main substituted (meth)acrylates and (meth) is kilat, tertiary butylmethacrylate and dimethylaminoethylmethacrylate. Preferred water-soluble hydro - faceted monomer used to obtain amphiphilic copolymer is acrylic acid.

The choice of the nature and concentration of the hydrophilic monomer is carried out in such a way as to give the amphiphilic copolymer ability to good dispersion in aqueous solution. For this purpose it is prepared from high polymer solids, providing the ability to process and shear viscosity without the reverse effect on the ability of the copolymer to the penetration through the skin by making it superior aesthetic characteristics, strength, elasticity and water resistance.

Hydrophobic comonomer used to obtain amphiphilic copolymer is at least one monomer selected from long chain alkyl(meth)acrylates, long-chain alkoxy/polyethylene oxide/meth/acrylate, alkylphenoxy/polyethylene oxide/meth/acrylate, primary alkenes, and vinyl esters of long-chain alkylcarboxylic acids and mixtures thereof. Examples of suitable hydrophobic monomers that can be used individually or as mixtures with each other and/polyethylene oxide /meth/acrylate, 1-alkenes (C12-C22and complex vinyl esters of alkyl (C12-C22) carboxylic acids. Examples of these hydrophobic monomers are dodecyl/meth/acrylate, pentadecyl/meth/acrylate, cetyl/meth/acrylate, stearyl/meth/acrylate, eicosyl/meth/acrylate, Isodecyl/ meth/acrylate, ministart,nonylphenoxy/ethylene oxide/meth/acrylate, octadecyl, hexadecan, tetradecene, dodecene and mixtures of any of them.

Preferred hydrophobic monomers providing the amphiphilic copolymer with the best performance, especially the characteristics of water resistance, are long-chain alkyl (C12-C20)/meth/acrylate and their mixtures, such as mixtures of alkyl(C16-C20)methacrylates, which are hereafter referred to as "SEM" for tetracaprylate. Meth - acrylate or acrylamide - refers to both acrylates and acrylamides and methacrylates or methacrylamide respectively.

Minor amounts of other copolymerizate monomers with ethylene unsaturated bonds in concentrations equal to or less than 50 wt.% of the total concentration of hydrophobic co monomer may be used in combination with the predominant number (more than 50 wt.%) at least on the thinners for other hydrophobic comonomers without negative impact on the ability to re-tanning - processing fat emulsion, which is achieved when the skin treatment amphiphilic copolymer. The use of such diluents hydrophobic monomer may be justified to achieve the economic effect; however, this use of such hydrophobic diluents may be to the detriment of those improvements characteristics of water resistance, which is achieved using the dominant hydrophobic monomer. Examples of such useful copolymerizate hydrophobic comonomers, which diluents are the lower alkyl (C1- C7) /meth/acrylate, styrene, alpha-methylsterol, vinyl acetate, and /met/Acrylonitrile and olefins. When using such hydrophobic comonomers as diluents preferably use misfunctioning (without functional groups) monomers other than the monomers with functional groups, for example, monomers with hydroxyl and amide functional groups.

An effective amount of amphiphilic copolymer that is present in the aqueous dispersion is not less than 1 wt.% from the tanned skin. This is not a maximum limit on the number of amphiphilic copolymer, which may be present in the dispersion, the village is to reuse or removed after the termination of the process. Generally, the amount of amphiphilic copolymer that is present in the aqueous dispersion, should not exceed 20 wt.% from the tanned skin. The amount of amphiphilic copolymer used in this way is about 1-10 wt.% from the tanned skin, most preferably this amount is 3-7 wt.% from the tanned skin.

Amphiphilic copolymer can be obtained by way of polymerization of hydrophilic and hydrophobic monomers by any known method. Preferably the implementation of polymerization is mixed with water, alcohol such as tert-butanol or butylcellosolve (Union Carbide Corp.), using the water-insoluble free radical initiator, reaction concentration of about 0.2 to 5 wt.% from the total amount of monomers. Examples of suitable free radical initiators that can be used in this case are the esters of nagkalat azo compounds. The polymerization is carried out preferably at a temperature in the range 60-150aboutC, preferably at a temperature of 85-120aboutC. To regulate the molecular weight can be used by agents, chain transfer. The polymerization may be carried out by polymerization of visasia not fully stops the conversion of more than about 98%). As a result of polymerization is achieved, the concentration of the amphiphilic polymer solids in the solvent 20-75% with viscosity Brookfield from about 100 to 1000000 SP.

The copolymers formed using hydrophobic olefinic monomers, can be obtained according to the procedure described in U.S. patent N A-3968148 and 4009195.

After contacting tanned skin with amphiphilic copolymer of this skin can be treated mineral tanning agent to improve the characteristics of elasticity and water resistance of the skin. Thus treated, the skin has a dynamic water resistance of more than 15,000 curves eser. Preferred mineral tanning agents are chromium, aluminum and zirconium tanning agents.

The present invention encompasses an improved method of skin treatment, which includes tanning skins or untreated normal skin tanning agent, and drawing on this tanned hide or skin with water dispersion containing an effective amount, preferably at least 1 wt.% from the mass of tanned skins or leather, not soluble in water dispersed amphiphilic copolymer, abrashev, comprising long-chain alkyl/meth/acrylate, long-chain alkoxy - or alkylphenoxy/polyethylene oxide/metal/acrylates, primary alkenes, complex, vinyl esters of long-chain alkalicarbonate acid and mixtures thereof with a minor amount of at least one copolymerizes water-soluble acidic or basic co monomer ethylene with unsaturated bonds.

This method improves the subsequent drying of the treated skin or skins and includes one stage, replacing the usual stages of re-tanning and processing fat emulsion.

With this invention are skin, which may have desirable characteristics, such as industry themselves and/or the ability to dry cleaning.

The invention comprises an amphiphilic copolymer. Amphiphilic copolymers is to obtain one way (a-D).

Method A. All components are based on 1000 g of the monomer.

Illustrates the method of producing a copolymer of 40 wt.% acrylic acid/ 60 wt.% SEMA. In chetyrehosnuju three-liter round-bottom flask equipped with stirrer, thermometer, reflux condenser and blanketed with nitrogen, is injected 900 g of tertiary butanol. Then the flask is heated to 85th is injected with a constant speed following monomers: 400 g of acrylic acid, 600 g of tetracaprylate together with 10 g of a free radical initiator Vazo 67 (company E. I Du Pout de Nemours and Co.) and 20 g of 3-mercaptopropionic acid in 165 g of deionized water as the agent of the transfer chain (one HUNDRED). After that enter 1 g of Vazo 67, and 5 g of tertiary butanol, the temperature of the reaction mixture support 85aboutWith in an hour. Then the reaction vessel is cooled and the obtained copolymer is poured into the vessel. This obtained copolymer with a theoretical solids content of 48.1 wt.% has a real solid content of 51.2 wt.%, srednevekovoy molecular weight 10600 and srednecenovogo molecular weight of 6500.

Method C. All components are based on 200 g of monomer.

Illustrates the method of producing a copolymer of 70 wt.% SAM and 30 wt.% 2-sulfonethylmethane. The reaction flask is the same as in method A, with the difference that its volume is 1 L. In this flask is introduced 150 g of isopropanol and the flask is heated to 82aboutC. In a heated flask (82aboutC) for 2 h uniformly impose the following monomer mixture, initiator and agent of the transfer chain. This monomer mixture contains 200 g of isopropanol, 140 g SEMA, 60 g of 2-sulfonethylmethane and 2 g of initiator Vazo 67, a HUNDRED mA is operating the vessel administered 1 g of Vazo 67, and 10 g of isopropanol, then the temperature in the vessel is maintained 82aboutC for one hour. Next, the reaction mixture is cooled and the product is poured into the container. The obtained copolymer with a theoretical solids content of 34.7 wt.% has the actual solids content of 34.3 wt.%. Srednevekovaja molecular weight is 13000 and Brednikova molecular weight - 9660.

Method C. This method is carried out according to U.S. patent N A-3968148 and 4009195. Illustrates the obtaining of a copolymer of 35 wt.% acrylic acid and 65 wt.% hexadecane. In one litre round bottom chetyrehosnuju flask equipped with stirrer, thermometer, reflux condenser and a blanket of nitrogen, is injected 450 g hexadecane. Then the flask is heated to 130aboutC. Next, evenly for 5 h with a linear velocity with temperature 130aboutWith injected into the flask to 120 g of acrylic acid, 30 g hexadecane and 3 g of tert-butylbenzoate as the initiator of the polymerization reaction. The temperature of the flask is supported 130aboutWith in an hour and then starts cooling and a diluent - 150 g butylcellosolve (2-butoxyethanol). The resulting copolymer has a total solids content in butylcellosolve of 46.2 wt.% and nebelspalter copolymer paired with stair structure (example 5), prepared according to method a with the difference that the number of 3-mercaptopropionic acid (Yunis Emre) - agent transfer circuit or a HUNDRED - changed as follows. Monomers, G. M. wt. AA SEMA, SMRA Middleweight. Shredneck.

mol.m.(MW) mol.m(MM) 300 700 0 69 000 24 200 300 700 2,5 25 100 16 500 300 700 6 16 650 11 300 300 700 20 10 000 6 500 300 700 40 4 500 3 400 300 700 60 3 000 2 400

The method of this invention includes the processing of skin selected amphiphilic copolymers. Amphiphilic copolymers are estimated by matching the aesthetic characteristics of strength, elasticity, elasticity and water resistance of the leather treated with the amphiphilic copolymers, with the characteristics of leather treated with conventional sinanovi tanning agents and fat emulsions. The strength of such treated skin was determined by elongation at cracking the grain and elongation at break of the skin of the ball. This method is commonly used technique for evaluating the effectiveness of conventional fat emulsion for lubrication of the skin. This test is carried out in such a way that reproduces the stretching of the skin over a Shoe pad in the process of making shoes by using a tool called lactometer. A strip of processed leather is clamped in place and then zo is when it starts to be a crack in the grain (cracked grain) and at the point where the skin is broken (open ball). The more the tensile cracking in the grain and at break of the ball, the greater the tear resistance of the skin. To evaluate the effectiveness of amphiphilic copolymers have been established criteria stretching when cracking the grain to break the bead 142 g for cowhide, constituting more than or equal to 13 mm and greater than or equal to 15 mm, respectively, as the minimum value to increase the strength in the specified handle.

Along with the assessment of increasing the strength of the skin is achieved through the use of amphiphilic copolymers was also made qualitative assessment of the elasticity of the skin, which was associated with indicators of compliance was obtained in the processing of conventional agents re-tanning and fat emulsion. Compliance is a measure of the firmness and elasticity of the skin: the higher the compliance, the better the measure of the firmness and elasticity of the skin. Measurements of elongation of the treated skin samples using a compression tester strain Gunther-Spring, modified according to Stubbing: Stubbings and E. Senfeldn, JALCF, volume 58, No. 1, jap. 1963. As a minimum criterion was set indicator compliance nextwindow assessment discontinuous characteristics of the treated skin. In addition, the estimated intensity of shade staining of the usual processed and subjected to the chrome tanning samples of skin against skin, subjected to the chrome tanning, processed amphiphilic copolymers. The higher the intensity of the color of the dye, the higher the intensity of the tone coloring for a given weight percentage of dye. It is noted that the skin treated with the amphiphilic copolymers are dried faster during subsequent operations. This reduction of the drying time along with the possibility of excluding at least the step of wet processing provides an additional economic effect and save energy costs in the implementation of the proposed method.

Processing of leather selected amphiphilic copolymers not only improves the mentioned physical and aesthetic characteristics of the skin, but also provides the possibility of improving the characteristics of the water resistance of the treated skin. In addition, we discovered that if the skin is treated with the amphiphilic copolymer, further processed mineral tanning agent, the resulting skin meets the requirements of vodootlivnye. Under the used C the hen should not leak water under all conditions; implies a higher degree of water resistance.

The resistance of the skin treated with the amphiphilic copolymer, and control skins, is determined by two separate tests. The first is called dynamic test for resistance to salt water. This test uses a test device topenetrate ser corresponding to the ASTM D-20009-70. Registered number of bends Maeser, which are necessary in order to cause water infiltration into the skin. Because this test is used the salt water, desire - tion to predict the resistance of the skin to damage not only from water but also from sweating. The number of bends Maeser more than 15,000 t is the minimum criterion established in the U.S. military for skin boots.

Treated skin is also evaluated by static tests on the absorptivity of water, whereby the skin samples treated with the amphiphilic copolymer, immersed in water for 2 h at room temperature, then this skin is again weighed to determine the percentage of absorbed this water skin. The lower the percentage of water absorption, the greater the resistance of the skin to water. According to specifications, developed by the US military, on the absorption istia amphiphilic copolymers in the processing of tanned leather (procedure F) were compared with the control process, used for normal agents re-tanning and fat emulsions (procedure E). All of the skin, unless otherwise stated, were made with 142 g (weight of the feedstock) cow hides, tanned with chromium. However, these procedures are applicable to other types of hides and skins such as subjected to the chrome tanned pigskin and sheepskin, tanned with plant extracts sheepskin etc.

Procedure E. The Control.

All components taken from weight blue raw weight, i.e. 100% means mass equal to the mass of raw material in the drum.

1). All raw materials runs in the danger of water washing for 10 min in an open place at the 32aboutC.

2). This product adds 200% floating mass (under a floating mass mean water; 200% floating mass input means twice the amount of water to the original weight of raw materials) at the 32aboutAnd then added 1% of a neutralizing agent and 1% ammonium bicarbonate. The mixture is mixed in the drum within 120 minutes

3) Then the raw material is unloaded from the drum for 10 min. washed with water temperature 55aboutIn the open room.

4) To the weight of the raw material is added to 100% floating mass at 46-54aboutAI solids, equivalent to 2% of active lakatan), diluted with an equal weight of water and is introduced into the drum mix through the tail hole (the hole of the drum). The mixture was stirred in the dryer for 60 minutes

6) Then is introduced into the drum of acid dye (0.5% of orange der 2 R, previously dissolved in hot water), and the mixture is stirred in the dryer for 20 minutes

7) Introduces a 1% formic acid, previously diluted to obtain 10% solution for fixing the colored raw material.

8) the Drum is emptied, the raw material is washed with water for 10 min in an open space at the 35aboutC.

9) In the raw material is introduced 100% floating mass at 55aboutC, then added to the fat emulsion, sulphonated 6% Morita, 6-82 (fat emulsion 70% active ingredient), dispersed in 20% of water at 55aboutS, after which the mixture is mixed in the dryer for 40 minutes

10) are Then introduced with 0.5% formic acid for fastening, raw materials are mixed in the dryer for 10 minutes and then unloaded from the drum.

11) This step is an arbitrary phase, which consists in post-processing mineral tanning agent.th acid, for 0.5-4 h before it is used, is introduced into the raw mass and mixing in the dryer for 60 minutes at 35aboutC.

12) Raw material is washed for 10 min in an open place at the 27aboutC.

13) Then raw vylivaetsya collected in the stack during the night.

14) Then it hung (to smooth and remove excess moisture) and subjected to vacuum drying for 2 minutes at 70aboutC.

15) Next, the raw material is dispersed (hang to dry) overnight and cooled within 1-7 days at room temperature 72 f (22aboutC), relative humidity of 60%, and then stretched on the hare or Machida (mechanical abating).

Procedure F.

This procedure is performed when a one-step process of re-tanning and processing the fatty emulsion of amphiphilic copolymers. All weight measurements are taken of the weight of raw blue mass or other tanned skins.

1) Raw material is subjected to water washing at 40aboutC for 15 min in an open room.

2) To this raw material is added to 200% floating mass at 40aboutWith, after which is added 1% of a neutralizing agent and 1% of bicarbona is subjected to water washing for 15 min in an open space at the 50aboutC.

4) are pre-dispersion of the copolymer by the initial input is a floating mass or hydrate of sodium oxide, (if the copolymer is obtained from acidic hydrophilic monomer) or formic acid (when the copolymer is formed from the primary hydrophilic monomer) in a quantity sufficient to neutralize at least 50% of a polymeric acid or a polymeric base, depending on the circumstances. Then the copolymer is dispersed in 100% floating mass by intensive mixing or magnetic stirrer or paddle mixer. Then introduced into the mass of this amphiphilic copolymer, pre-dispersed thus 100% of the floating mass, and the mixture is stirred in the dryer for 60 minutes at 50aboutC. This amphiphilic copolymer is introduced in the amount of 6 wt.% from the mass of raw materials, unless a different value.

5) In this mass is injected acid dye (0.5% of orange dermis 2 R, previously dissolved in hot water) and stirring in the dryer for 20 min at 50aboutC.

6) In the case of acidic hydrophilic co monomer is injected with 1% formic acid (10% rastel mixed in drum for 10 min. at 50aboutC.

7) the Drum is emptied, the raw material is washed for 15 min in an open space at the 35aboutC.

8) This step (and step 11 in the procedure E) is an arbitrary phase, which consists in post-processing mineral tanning agent, in this case chromium. A solution prepared from 100% floating mass, 3% Carolina M-1 and 0.5% formic acid (prepared for 0.5-4 h before use) into raw mass and mixed in the dryer for 60 minutes at 35aboutC.

9) Then this raw material is washed for 15 min in an open space at the 35aboutC.

10) Raw materials vylivaetsya during the night.

11) Then raw hung out and subjected to vacuum drying for 2 minutes at 70aboutC.

12) Then the raw material is dispersed throughout the night and cooled within 1-7 days at a constant room temperature of 72 f (22about(C) at a relative humidity of 60% and is abating.

It should be emphasized that the procedure F, which serves to re-tanning and processing fat emulsion tanned skins using amphiphilic copolymers requires only 12 stages compared with 15 stages required for a normal p is she.

P R I m e R 1. Skin treatment.

In this example, given the mapping method of processing leather amphiphilic copolymer with skins obtained using conventional tanning funds and fat emulsions (see table. 1). In each case, as the substrate was used 142 g blue raw weight, tanned. Skin treated with effective amounts of amphiphilic copolymer, meet or even surpass the required final characteristics, including density (density), razvivaemosti, stretchability and strength (elongation at break of the ball and cracked grain) and the intensity of the shade of coloring, in addition, they are superior to processed in the usual way the skin against water resistance. In addition, the procedure F has the advantage that it requires fewer steps than the procedure that is

P R I m m e R 2. Amphiphilic copolymer composition.

This example illustrates processing using amphiphilic copolymers prepared from different ratios of hydrophobic (SEMA) and hydrophilic (AA) monomers to achieve the desired properties: elasticity, strength and water resistance (see tab. 2).

All floor the procedure F using 6 wt.% solid copolymer of substances from the weight amount of the blue mass of raw materials and the implementation of the optional subsequent processing stage chrome.

This example illustrates the surprising benefits of copolymer compositions containing from more than 10 to less than 50 wt.% hydrophilic monomer and from more than 50 wt.% to less than 90 wt.% hydrophobic monomer.

P R I m e R 3. Other hydrophobic monomers.

This example illustrates the results of processing of hides selected amphiphilic polymer compositions prepared using various selected hydrophobic monomers. All of the following materials: 30% by weight AA and 70 wt.% selected hydrophobic monomer. In table. 3 shows the various selected hydrophobic monomers that can be used, and the advantages of the method of this invention using such polymer compositions over conventional compositions (for example, styrene/acid or MMA/acid). Compared to the same polymer compositions compositions conforming to the present invention, exhibit improved strength characteristics of the skin (the elongation and stretching when cracking the grain and breaking ball), as well as the improvement of the characteristics of the water resistance of the skin.

P R I m e R 4. Additional copolymers-thinners.

This example is displayed is exactly compositions containing at least one additional dilution monomer (butyl acrylate). These compositions contain more than 10% and less than 50% of the selected hydrophilic monomer, with at least half of the remaining monomer is one selected gidrofilnyh monomers (table. 4), and the remainder is other defunctionalizing, i.e. not containing functional groups, ethylenedeamine monomer (diluent) butyl acrylate (BA). All the skin was made according to procedure F using the optional further processing chromium (stage 8).

P R I m e R 5. Amphiphilic copolymers with different molecular weights.

In the practical implementation of this invention can be used amphiphilic polymers with a wide range of values of molecular weight (table. 5). The polymers are presented in table. 5, turned out according to method D. the Skin was treated according to method F, including optional post-processing step chromium (step 8). All polymers provide improved characteristics of resistance and strength of the skin.

P R I m e R 6. Other hydrophilic monomers.

In table. 6 illustrates the process of ionomerov. As shown by the strength parameters obtained skin, these copolymers have demonstrated their efficiency in one treatment: re-tanning - processing fat emulsions. All the skin was treated according to procedure F, and subjected to an optional subsequent processing stage chromium (step 8).

P R I m e R 7. Flushed skin.

In table. 7 and 8 demonstrate the advantages achieved by the use of amphiphilic polymers, in comparison with the conventional fat emulsions for the production of washed leather. Skin washed in an automatic washing machine top loading, using detergent Tiole (Proctor and Gamle). As the skin is subjected to processing conventional sulfated fatty emulsion (comparative processing), and the skin treated with the amphiphilic copolymers retain a significant degree of softness and strength, as shown by the data of elongation and elongation at cracking the grain and breaking ball. Unlike the other two skins skin obtained with the use of amphiphilic copolymers, which was subjected to subsequent treatment with chromium (step 8), shows the improvement in softness and durability. The skin treated amfit is romawki. These skin was subjected to air drying, which plays drying on the line fabric, as it usually is recommended to wash fine particles.

P R I m e R 8. Subsequent processing of mineral tanning agent already tanned skin.

In table. 9 shows the effect of subsequent processing of mineral tanning agents on the resistance of the leather to be treated is selected amphiphilic copolymers. Securing conventional fat emulsion by further processing of the tanning metal, such as aluminum (Al), zirconium (Zr), chromium (Cr) or iron (Fe), is a known method of improving the water resistance of the skin.

All leather is processed according to procedure F, which includes an optional post-processing (stage 8), as described above. Even in the absence of further processing of the skin treated with the amphiphilic copolymer, much more water resistant than normal skin (see table. 1). Amphiphilic copolymer in this example is a 30 AA/70 SEMA used with a concentration of 6%.

P R I m e R 9. Resistance to solvent extraction.

In table. 10 illustrates the improved resistance to solvent extraction skins, processed amphiphilic solvent is an indicator of the ability to dry cleaning. Amphiphilic copolymer in this example is a 70 SEMA/30 AA used with a concentration of 6%. Conventional fat emulsion is a Morite G-82, sulfated oil, used with a concentration of 4.2%. Optional post-processing of chromium is carried out where indicated. The skin is first dried for 4 h at 100aboutWith, then it is weighed and the weight of the dried skin is taken as the initial one. The skin is placed in a flask extraction vessel socket and extracted for 10-12 h in methylene chloride. Methylene chloride is then evaporated and is determined by the mass of solids extracted from the skin. The quantity of material extracted from the skin, is considered as a mass percentage of the original mass.

P R I m e R 10. Improved drying.

At the end of operation of wet processing the skin is dried. Skin treated with the amphiphilic copolymers are dried faster than skin treated with conventional fat emulsions. It provides both time savings and the reduction of energy required for drying of the skin. Faster drying of the skin treated by a fat emulsion together with the amphiphilic copolymer is illustrated in the A. After the final washing the skin vylivaetsya overnight and then dried in air at room temperature. In table. 11 shows the mass percentage of moisture in the skin depending on the time of air drying. Leather is regarded as dry and ready to be abating, when the content of moisture reaches 18%. Extrapolation of data from table. 11 shows the time air drying 12 h for the usual way of processed leather, while this time is 8 hours for skin treated with the amphiphilic copolymer.

1. The METHOD of PROCESSING TANNED SKIN, including impregnation its aqueous dispersion containing water-insoluble amphiphilic copolymer, characterized in that the use of a copolymer containing 50-90 wt.% at least one hydrophobic monomer selected from the group consisting of C8- C22the alkyl(meth)acrylates, C8- C22- alkoxy or C12- C22- alkylphenoxy(polyethylene oxide) (meth)acrylates, C12- C22primary alkenes, vinylation C12- C22- alkylcarboxylic acids and their mixtures and 10-50 wt.% at least one water-soluble acid or a basic hydrophilic co monomer with ethylene unsaturated bonds, and when casesy hydrophilic comonomer except (meth)acrylic acid.

2. The method according to p. 1, characterized in that alkylacrylate contain at least 12 carbon atoms.

3. The method according to PP.1 and 2, characterized in that the co monomer is acrylic acid.

4. The method according to PP.1-3, characterized in that the amphiphilic copolymer has an average molecular weight 2000-100000.

5. The method according to PP.1-4, characterized in that after the treatment the skin amphiphilic copolymer her further treated mineral tanning agent.

 

Same patents:

The invention relates to a method of fatliquoring fibrous pulp and Shoe Board single layer of shimmer and can be used in light industry in the manufacture of artificial leather

FIELD: tannery industry, in particular method for syntan (synthetic tanning material) production.

SUBSTANCE: claimed method includes diphenolepropane sulgation and condensation with formaldehyde followed by acidifying with sulfuric acid. Formed product is dispersed in lignosulfates containing 0.5-1.5 % of aluminum sulfate as calculated to aluminum oxide.

EFFECT: syntans with stable content of tanned materials: environmentally friendly and economical process.

1 ex

FIELD: chemistry of polymers, leather industry, chemical technology.

SUBSTANCE: invention relates to a method for preparing polymeric products that are used in processes for dressing leather or fur, in treatment and disinfection of natural and sewage waters. Method for preparing polymeric products involves the hydroxymethylation reaction of polyhexamethylene guanidine chloride with formaldehyde and arylation reaction of prepared product with aromatic compound comprising o-amino- or o-hydroxy-groups. The hydroxymethylation reaction is carried out in the presence of acetic acid or formic acid up to formation of trimethylol derivative of polyhexamethylene guanidine chloride. In some cases the arylation product is subjected for complex formation with transient metal salt or azo-coupling reaction with diazonium salt taken among group including sulfanilic acid, naphthionic acid, j-naphthyls, p-nitroaniline, 2,6-dichloro-4-nitroaniline. Invention provides simplifying, accelerating and enhancing the effectiveness of process in dressing leathers with derivatives of polyhexamethylene guanidine showing tanning effect, staining properties, flocculating capacity and high antibacterial activity.

EFFECT: improved preparing method.

3 cl, 1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to graft polymers based on polysaccharides and polypeptides. Graft polymer based on polysaccharides and polypeptides or respective derivatives thereof are obtained by free-radical polymerisation of A) a monomer selected from following, or a mixture of following monomers: (a) from 20 to 100 wt% acrylic acid or methacrylic acid, or mixture thereof, or salts thereof with an alkali metal, alkali-earth metal or ammonium, (b) from 0 to 80 wt% other monoethylenically unsaturated monomers, which can be copolymerised with monomer (a) and (c) from 0 to 5 wt% monomers containing per molecule at least 2 ethylenically unsaturated unconjugated double bonds in presence of B1) polysaccharides subjected to oxidative, hydrolytic or enzymatic decomposition, oxidised polysaccharides subjected to hydrolytic decomposition or subjected to enzymatic decomposition, or chemically modified decomposed products, chemically modified mono-, oligo-or polysaccharides, or mixtures of said compounds and B2) polypeptides subjected to hydrolytic or enzymatic decomposition and optionally chemically modified polypeptides, or mixtures of said compounds, with weight ratio A:(B1+B2) ranging from 60:40 to 1:99 and B1:B2 from 97:3 to 3:97. Also disclosed is a method of producing graft polymers, method of tanning leather, and tanned leather.

EFFECT: wider range of polymers for various types of tanning.

7 cl, 18 ex

FIELD: leather industry.

SUBSTANCE: semifinished product is degreased, neutralized, dyed, and lubricated. Dyeing is performed in two washing-interrupted steps with anionic black dye consumed in amount 0.5-0.6% of the weight of semifinished product in each dyeing step. Lubrication is followed by retannage with chrome tanner in amount 0.6-1.0% of the weight of semifinished product (calculated for chromium oxide) and treatment with 0.8-1.0% of spindle oil.

EFFECT: achieved deep black color and high performance characteristics.

1 tbl, 5 ex

FIELD: tannery or furry production.

SUBSTANCE: the invention is pertaining to the field of tannery or furry production and may be used for a piece by piece treatment of a tanning, furry semi-finished product with emulsions of "water in oil" type. The device for impregnation of sheets contains a mounted on the frame bath with a working compound, in which a corrugated roller is dipped, and also a feeding and auxiliary conveyers and a smoothing roller, a supporting means with a resilient counterbody, an actuator, a tool for removal of a finished semi-product, a device for creation of a hydrodynamic wedge and a pinch roller for engagement of the ribbed roller with the feeding conveyor. The problem of the presented invention is - development of the device simple in its servicing with a high reliability allowing to realize the process of impregnation more efficiently with a possibility of its installation in an automatic production line.

EFFECT: the invention presents a device simple in its servicing, having a high reliability, more efficient realization of the process of impregnation, a possibility of its usage in an automatic production line.

2 dwg

FIELD: tannery industry.

SUBSTANCE: claimed method includes treatment of chrome-tanned semi-finished product with antiseptic such as polymineral obtained from natural non-metal fossils (minerol), which is used in amount of 5-10 mass % based on semi-finished product. Minerol is also used as filler being introduced in retanning step with chrome compounds in amount of 5-10 mass % based on semi-finished product.

EFFECT: effective biological leather conservation after chrome tanning.

3 cl, 1 tbl

FIELD: chemical technology.

SUBSTANCE: invention relates to greasing and emulsifying substances used in fur, leather and other branches of industry. Invention describes a method for deep sulfonation of oxidized vegetable oils, fats and their mixtures, and oxidized mixtures with the nominal viscosity value in the range 33-75 by viscosimeter VZ-4 at 20°C in their treatment with sodium sulfite. The process is carried out in system consisting of oxidized component or mixture of oxidized components, sodium sulfite, water and soap additives, carboxylic acid, phenol and copper (II) salt as a catalyst in bead mill of vertical type at temperature of environment up to practically complete ceasing or quantitative consumption of sodium sulfite and charge of the latter is calculated by the following formula: mNA2SO3 = 0.006 x mOX x (I.N.)OX wherein mOX and (I.N.)OX mean mass and iodine number of oxidized component or mixture of oxidized components, respectively. The mass ratio of oxidized component and water varies in the range from 1:4 to 1:2.5. Dosing additives with respect to oxidized component are following: soap, 2%; carboxylic acid, 4%; phenol, 2.5%. Oxidized flax, sunflower, soybean and cotton oils, oxidized fish oil and mixtures of vegetable oils with fish oil or pig fat are subjected for sulfonation reaction with air in regimen of intensive bubble bubbling at 105 ± 5°. Soaps in indicated system are represented by sodium stearate and sodium oleate and by reaction mixtures of practically quantitative alkaline hydrolysis of fats and vegetable oils also. Benzoic, oxalic, malonic and citric acids are used as acid, and sulfate, acetate and other water-soluble salts of copper (II) are sued as a catalyst dosed in the amount (2-7.5) x 10-4 mole/kg of the parent charge. The sulfonation reaction degree is 33-40%.

EFFECT: improved preparing method.

5 cl, 1 tbl, 16 ex

FIELD: tanning industry.

SUBSTANCE: process is conducted in vertical mill to which soot, induline, kerosene and diesel fuel are introduced. Then components are mixed and slow heating the apparatus and its content is started after which mixing is switched off and slow heating of mill content is continued. Upon expiration of said time, acids or their compositions, white spirit and fatty additive are introduced and chemical mass-exchange process is performed at spontaneously fixed temperature due to thermal effects of this process and natural cooling at the beginning and at the end, as well as due to forced cooling at intermediate stage characterized by high rates of temperature at maximum of 140-150°C. At the moment when forced cooling is discontinued, 0.5-1.5 h before discontinuation of mixing and beginning of withdrawal at temperature of 80-115°C, 43-52-% solution of aluminum salts and C10-C20 of carboxylic acids is introduced into product being prepared.

EFFECT: facilitated procedure; increased amount of product.

1 tbl, 15 ex

FIELD: leather industry.

SUBSTANCE: preparation of composition is conducted on vertical-type bead mill. Induline, kerosene, and diesel fuel are consecutively charged into mill before stirring mechanism is energized, after which apparatus and contents thereof are slowly heated. Stirring is then stopped for 1 h while slow heating of mill contents is continued. When specified time expires, carboxylic acid or acid mixture, white spirit, fat additive, and aluminum oxide or hydroxide are added. Mechanic stirring is then switched on and contents of the bead mill are ground and the process is carried out at spontaneously fixed temperature caused by heat effects of the processes and natural cooling. When temperature is lowered to 85-120°C, desired product is discharged.

EFFECT: simplified process and increased product discharge degree.

1 tbl, 19 ex

FIELD: leather industry.

SUBSTANCE: method, which is suitable for finishing chrome leathers, comprises consecutively applying coating layers followed by action with low-temperature plasma at generator lamp anodic current intensity 0.2-0.6 A. Action of low-temperature plasma is effected for 180-240 sec at pressure 13.3-26.6 Pa in discharge chamber and consumption of plasma-forming gas (argon) 0.035-0.04 g/sec. Method is implemented on high-frequency plasma installation.

EFFECT: increased adhesion of coating to dry and wet leather, dye penetration depth, resistance to repetitive bends, and strength at better quality of leather.

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to copolymers consisting of monomers comprising acid groups with double bond and other hydrophobic monomeric component used in prophylaxis of inorganic and organic deposits in water-bearing systems. Invention describes a water-soluble copolymer comprising: (a) monoethylene-unsaturated monomers chosen from group consisting of monocarboxylic acids, dicarboxylic acids and sulfoacids that can be neutralized; (b) at least copolymerizable hydrophobic acrylic, monocyclic and/or bicyclic terpene comprising unsaturated double bond wherein terpene hydrocarbon is preferable, and copolymer is prepared by free-radical copolymerization of components (a) and (b) in an aqueous phase. Also, invention describes a method for synthesis of abovementioned copolymer and methods for its using. Invention provides synthesis of nontoxic copolymer used for prevention of deposits in water-bearing systems that can be easily prepared from available components and able to store for a long time without loss of activity.

EFFECT: improved preparing method, valuable properties of copolymers.

22 cl, 6 tbl, 6 ex

FIELD: individual and household supplies.

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EFFECT: enhanced shoe shape stability and adhesion durability in the wearing process.

1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: modified leather is meant for making internal components of shoes with good biocidal properties and relates to light industry. The modified leather includes a collagenic base with a multilayer structure, tanning, retan, oiling compounds and a biocidal additive, the later being in form of silver nanoparticles and alkyldimethylbenzyl ammonium chloride in ratio of 1-:-0-1.5 respectively. Content of silver nanoparticles is 710-5 - 6.410-3 wt %.

EFFECT: wide range of lining leather while cutting on number of biocidal agents used on the leather and stabilisation of deformation-strength characteristics of the leather during its use, as well as improved environmental friendliness of the process of manufacturing said leather.

2 tbl

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