A method of obtaining a composition for the fatliquoring of leather
(57) Abstract:Use: dyeing-fatliquoring of leather. The inventive mixture of natural fats, synthetic fats and oils UNDER oxidized by air heated to 65-105oC in the presence of copper-chromium-barium catalyst and then adding to oxidate to 35 wt.% ink compositions composition, wt.%: 35 black pigment, 30 organic acids, 25 kerosene. The resulting mixture was treated with an aqueous solution of sodium sulfite to obtain a self emulsifiable in water product. As the black pigment used indulin, nigrosine, technical carbon (soot) and their mixture, and as an organic acid, a saturated or unsaturated carboxylic acids of the series C8-C20and mixtures thereof. 3 C.p. f-crystals, 4 PL. The invention relates to the field of leather industry, namely the production of chemical materials for dyeing and greasing processes in the production of black leather.Black leather prefabricated receive, as a rule, through the progressive implementation of the following technological operations: dyeing semi direct or acid black dye, fatliquoring, filling, retanning and growing is complex dyes [1, 2] the Disadvantages of this method are the large number of technological operations, increased consumption of auxiliary chemicals per unit area produced by the skin, a large amount of wastewater.More optimal is the realization of technological processes in monomane ("CD")  this reduces the volume of wastewater, improving the development of reagents used, however, the number of technological operations continues to be high. In addition, the conduction processes in manouane requires careful selection of used chemical materials in terms of their compatibility, failure of which leads to a significant deterioration in the quality of the leather.Significantly reduce the number of technological operations and to improve the quality of finished leather can, by applying chemical materials with multifunctional purpose, such as "Pansitan MN" (tool for retanning and alignment in the production of particularly high-quality leather)  "Immergas A" (oil tanning agent, he is also a component of fattening mixes)  etc.Closest to the invention is a method of obtaining a composition for the fatliquoring of leather by air oxidation of a mixture of natural fats, synthetic fats, complex adresowania cyclohexanol, polycondensation of cyclohexanone in the number of 4-19% by weight of the initial reaction mixture and catalyst mixture of copper, chromium and barium chloride salts of fatty acids when the mass ratio of the metals in the catalyst 10:10:1 and the amount of the catalyst is 0.001 to 0.01% by weight of the initial reaction mixture at a temperature of 65-105oC for 0.5-1 h followed by treatment of oxidate 20% aqueous solution of sodium sulfate at a temperature of 20oC and the mass ratio oxidat: a solution of sodium sulfate 10:4  the Disadvantage of this method is the product monofunctional destination.The aim of the invention is the creation of a product for the fatliquoring of leather, allowing simultaneously with creasing to carry out the filling of the skin and superficial staining black.This objective is achieved in that the receiving part is carried out by passing air for 2-7 h through heated to 65-105oC mixture of natural and synthetic fats, oil based on a mixture of high-boiling oxidation products of cyclohexane, dehydrogenation of cyclohexanol, polycondensation of cyclohexanone in the number of 4-19% by weight of the initial reaction mixture and catalyst mixture of copper, chromium and barium chloride salts fat is similar to the reaction mixture, followed by processing of the received oxidate 20% aqueous solution of sodium sulfite at a mass ratio oxidat: a solution of sodium sulfite 10:4, and before handling oxidate solution of sodium sulfite in it enter the ink composition in an amount of 3-35% by weight of oxidate of the following composition:
black pigment 35%
organic acid 40%
where as the black pigment used indulin, nigrosine, technical carbon (soot) or their mixture, and as the organic acid is any saturated or unsaturated acid from a number C8-C20or their mixture.Characteristics of the raw materials used.Technical fish oil 1-3 grades according to GOST 1304-76 "Fats of fish and marine mammals."Animal fats 1-3 grades according to GOST 1045-73 "technical animal Fat".The methyl esters, THE 243516-003-10-408818-94 "Methyl esters fraction C10-C20obtained from technical fat".Oil, THE 113-03-476-82 "Oil (a mixture of high-boiling oxidation products of cyclohexane, dehydrogenation of cyclohexanol, polycondensation cyclohexanone)".Technical sodium sulfite according to GOST 5644-75 "sodium Sulfite anhydrous".The catalyst mixture of copper salts of formula CuA2(Mcf=673), chrome salt CrA3(Mcf= 967) and barium salts BaA2(Mcf=747), where A Ani is I in organic media. The mass ratio of the metals in the catalyst is Cu:Cr:Ba 10:10:1.Indulin fat-soluble GOST 4770-77.Nigrosine water soluble GOST 4014-75.Carbon black according to THE 38-11551-77E "technical Carbon (soot) PM-15 RVDM".Stearic acid according to GOST 6484-65.Oleic acid according to GOST 7580-55.Synthetic fatty acids according to GOST 23239-89 "fatty Acid synthetic fractions of C5-C6C7-C9C5-C9C10-C13C10-C16C17-C20".Tall oil acid according to GOST 18845-79 "fatty Acids, tall".Waste of FLC on THE-38-1071231-89 "bottoms products production FLC".Kerosene according to GOST 28577.2-90, ISO 8217-87.Obtaining a composition for the fatliquoring of leather by the claimed method consists in the following.The mixture of fats, oil and catalyst in the desired weight ratio of load in oxidator with shirt and bubbler air supply, after which produce heating of the reaction mixture. Upon reaching the operating temperature served in oxidator current of air and conduct the oxidation at a given temperature for 2-7 h, controlling the depth of oxidation through the t in the autoclave with stirrer and add the required amount of pre-prepared ink compositions of a given composition. The resulting mixture is stirred until homogeneous, then add 20% aqueous solution of sodium sulfite and continue mixing until obtaining a self emulsifiable in hot water product.Example 1. 600 kg of fish oil, 100 kg technical animal fat, 80 kg of oil UNDER and 0.05 kg of catalyst loaded into oxidator with shirt and bubbler air supply, and start heating up the reaction mixture. When the temperature reaches 85oC served in oxidator current of air and oxidize the mixture at the specified temperature for 4 h the resulting oxidate pumped into the autoclave, equipped with a mechanical stirrer, and then add to it 100 kg ink composition having a proportion of its constituent components:
carbon black 20%
synthetic fatty acid fraction C17-C2040%
The resulting mixture is stirred until homogeneous, then add 200 kg of 20% aqueous solution of sodium sulfite and continue stirring for 20 min to obtain the product, spontaneously mulgirigala adding hot water.Example 2. 600 kg of fish oil, 100 kg technical animal fat, 80 kg of oil BY heating the reaction mixture. When the temperature reaches 85oC served in oxidator current of air and oxidize the mixture at the specified temperature for 4 h the resulting oxidate pumped into the autoclave, equipped with a mechanical stirrer, and then add 200 kg of 20% aqueous solution of sodium sulfite and continue stirring for 20 min to obtain the product, spontaneously mulgirigala adding hot water. Then, while continuing the stirring, add in the autoclave 100 kg ink composition having the following proportions of components:
carbon black 20%
synthetic fatty acid fraction C17-C2040%
and mixed components to obtain a homogeneous product. The properties of the final product and giovannoli them leather semi-finished product is shown in table. 1.Examples 3-7. The dependence of the properties of products obtained in example 1, the duration of the oxidation of mixtures of fats and evaluation giovannoli these products semi-finished leather are shown in table. 2.Examples 8-11. The dependence of the properties of the product and giovannoli them leather semi-finished product from the mass ratio oxidat:ink composition is given in table the motion properties of the final product and giovannoli them semi-finished leather to the nature of the pigment when used as acid synthetic fatty acid fraction C17-C20(examples 12-17) and on the nature of the acid when used as a pigment mixture of indoline and soot, taken in a mass ratio of 1:1 (examples 18-22) (table. 4). Oxidat ratio oxidat:ink composition similar to example 1.Examples 1 and 2 show that the mixture of ink compositions with oxidation to the reaction of sulfonation is crucial to obtain fattening product with the claimed properties. A simple mechanical mixture of the ink compositions prepared emulgirujushchie composition does not allow to obtain a product which would provide the normal course of dyeing and greasing processes and quality leather material (example 2).Example 3-7 follows that the duration of the oxidation mixture of fat with oil must be located within 2-7 p.m. With a smaller duration of the oxidation stability of the aqueous emulsion of the product is low, resulting in creasing the bulk of the fat together with the ink composition is deposited directly on the outer layers of the skin, without penetrating inside (skin hard and ocalenie). On the other hand, when the oxidation of the mixture of fat over 7 hours due to thermal-oxidative reactions of polymerization in the ACS is a, despite good emulgiruet in the water hardly penetrates the inner layers of the skin, which increases its stiffness (example 7).Example 8-11 follows that the minimum number to be added to oxidate ink composition is 3% by weight of oxidate, then the properties of the obtained product cannot provide the claimed result, namely a sufficient degree of blackness of the leather surface of the semi-finished product with a good level of pozirovanii. On the other hand, increasing the number of ink compositions more than 35% by weight of oxidate leads to deterioration of emuliruemogo the final product in water. In the practical use of such a product is strong osal the surface of the skin, dramatically reducing viviremos dyes from the bath, and so on, as a Consequence, obtaining high-quality leather semi-finished product is simply impossible.Examples 12-22 illustrate the properties of the obtained products, in particular the sustainability of their water emulsions and quality giovannoli these products semi-finished leather. You can see that the use of any pigment and acid from the claimed range of stability of the aqueous emulsion of the product corresponds to the examples, has good and excellent quality.The positive effect of the invention is as follows.Using the product obtained by the claimed method, in the technology of manufacture of the leather allows for a 25% reduction in the number of technological operations, to reduce the volume of wastewater, pollution, decrease the value of the skin by eliminating the use of expensive metal complex dyes.Improving commodity form of the finished product due to use as pigments substances, commonly known as grease thickeners. As a result of increasing the viscosity of the product decreases the speed of its stratification into separate components, which increases the warranty period of storage.Using the proposed method allows you to quickly set up production of a colored product on the basis of already existing production of fattening materials by way of the prototype, which is impossible for the organization of production of metal-complex and other dyes.In contrast to the production of dyes manufacture of the product by the claimed method virtually waste-free.The sources of information.1. Chemistry and technology of leather and fur. / S="ptx2">3. Tanning, dyeing, finishing of leather. Bayer AG, 51368 Leverkusen, GK 765 r, may 1994, 393 S.4. Technical information. Product of BASF for the leather industry. TI/P 2582 r, July 1982, 16 S.5. RF patent N 2039087, class C 14C 9/02. 1. A method of obtaining a composition for the fatliquoring of leather by passing air through the heated to 65 105oWith the mixture of natural and synthetic fats, oil based on a mixture of high-boiling oxidation products of cyclohexane, dehydrogenation of cyclohexanol, polycondensation of cyclohexanone in an amount of 4 to 19% by weight of the initial reaction mixture and catalyst mixture of copper, chromium and barium chloride salts of fatty acids when the mass ratio of the metals in the catalyst 10 10 1 and the amount of the catalyst is 0.001 to 0.01% by weight of the initial reaction mixture, followed by processing of the received oxidate 20% aqueous solution of sodium sulfite at a mass ratio oxidat solution of sodium sulfite 10 to 4, characterized in that oxidation of the mixture of fats and oils are within 2 to 7 h, after which the resulting oxidate enter the ink composition in an amount of 3 to 35% by weight of oxidate, the resulting mixture is stirred until a homogeneous mass which is then treated with a solution of sodium sulfite.2. I acid 40% kerosene 25%
3. The method according to p. 1, wherein the black pigment used indulin, nigrosine, technical carbon (soot) or their mixture.4. The method according to p. 1, wherein the organic acid is used any saturated or unsaturated carboxylic acid of the series WITH8C20or their mixture.
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.
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: process engineering.
SUBSTANCE: oil, fat or polymer is applied on leather in amount of less that 20%, preferably, less than 15%, particularly preferably less than 10%, per leather weight. Then leather is treated by compressed air. Carbon dioxide is used as compressed air, treatment if carried out at pressure below 70 bar and temperature below 25°C. Leather is processed by compressed air unless leather weight is at least 1% smaller than its weight prior to applying oil, fat or polymer.
EFFECT: improved leather structure due to increased non-blocking property of molecules.
SUBSTANCE: method involves chrome tanning and post-tanning a semi-finished product through chrome tanning in the presence of a product of reaction of 3-aminopropyltriethoxysilane and glycidylmethacrylate in molar ratio of 1:2 and consumption of the chrome tanning agent and reaction product of 3-4% and 2-3% of the weight of the semi-finished product respectively. Neutralisation and hydrophobisation with a polymer tanning agent are then carried out for 30-40 minutes with consumption of the tanning agent equal to 8-10% of the weight of the semi-finished product. After that dyeing is carried out in the presence of a synthetic tanning agent in amount of 3-4% of the weight of the semi-finished product. Post-tanning is carried out with a plant-material tanning agent and the semi-finished product is also treated for 20-30 minutes with a product of reacting hexamethylenediamine with phosphoric acid and urea in the presence of glycerin in molar ratio of 1:3:3:0.5 respectively, in amount of 3-4% of the weight of the semi-finished product and for 20-30 minutes with organic acid in amount of 0.5-1.0% of the weight of the semi-finished product. Further, the semi-finished product undergoes greasing and re-treated for 40-50 minutes with a product of reacting hexamethylenediamine with phosphoric acid and urea in the presence of glycerin in molar ratio of 1:3:3:0.5 and consumption of 7-8% of the weight of the semi-finished product, volume ratio of 0.8-1.0 and temperature of 20-22°C. Hydrophobisation with a polymer tanning agent, dyeing in the presence of a synthetic tanning agent, post-tanning with a plant-material tanning agent, further treatment with a product of reacting hexamethylenediamine with phoshoric acid and urea in the presence of glycerin in the said molar ratio and with organic acid is carried out in one bath. Separation and drying are carried out after all operations.
EFFECT: higher water-, fungus- and heat-resistance of leather under high moisture and temperature conditions, and wide range of special types of leather.
2 cl, 3 tbl, 5 ex
SUBSTANCE: method involves tanning a semi-finished product with a chrome tanning agent, neutralisation, washing, dyeing and tanning with organic tanning agents twice. The first tanning is carried out with a polymeric tanning agent, while the second is carried out with a mixture of synthetic and vegetable tanning agents. Hydrophobicising greasing, treatment with an organic acid and re-tanning with a chrome tanning agent are then carried out. Additional washing is carried out before neutralisation. Dyeing is carried out after the second tanning. Neutralisation, tanning twice and dyeing are carried out at water-to-goods ratio of 0.5-0.7. Hydrophobicising greasing is carried out in the presence of a 20% solution of the product of reacting amino alcohol with fatty acids of vegetable oils of the C12-C22 fraction and boric acid in molar ratio of 2:1:1 in mineral oil in amount of 0.5-1.5% of the weight of the semi-finished product.
EFFECT: good hygienic properties of hydrophobic leather and prolonged fungus resistance of the leather in high humidity and temperature conditions.
2 tbl, 5 ex
FIELD: leather industry.
SUBSTANCE: invention relates to leather industry in production of leather of various assortment, in particular, to methods of drumming leather in presence of fungicide, and can be used in skin processing for improving operational properties. Method of drumming leather is implemented with drumming composition in presence of an effective antifungal inhibitor, the latter is represented by 6.0 % solution of N1-chloro-methylbenzimidazole fungicide. Fungicide is dissolved in ethyl alcohol taken in the amount of 0.2-0.5 % of squeezed leather weight at the drumming composition consumption of 20-22 % of the squeezed leather weight in terms of 100 % fat. Drumming time is 1.5-2.5 hours at the temperature of 70-80 °C.
EFFECT: proposed method of drumming leather provides effective antifungal inhibition at high quality of finished skin.
1 cl, 2 tbl, 3 ex