Method of producing hydrophobic leather

FIELD: chemistry.

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

 

The invention relates to chemical treatment of skins, in particular to methods for production of special kinds of skin and can be used in the formulation of hydrophobic leather for Shoe upper with a sustainable and long-term anti musty effect.

A known method of manufacture of hydrophobic leather, including retanning, dyeing, greasing, filling and hydrophobic dispersion consisting of silicone drugs siloxane and elementooxanes patterns, individual water-soluble dyes, and mixtures thereof, poly(alkoxy) (acyloxy)silsesquioxanes or polyorgano(acyloxy)silsesquioxane mixed with surfactants in amounts of, respectively, 0.5-5, 2-8 and 4-8% by weight of cement, the concentration of 8-15 g/l, pH 4-8 when treatment duration 6-10 h (EN 2036974 C1, CL C14C 9/00, 09.06.95).

The closest analogue of the proposed technical solution is the way we produce hydrophobic skin, including retanning semi-finished chrome tanning agent, neutralizing to waste after chrome retanning tub, washing, dyeing with LCD 1,0-1,2, retanning polymer tanning agent, retanning with a mixture of synthetic and vegetable tanning agent in the same tub, gidrofobiziruyuschey greasing, processing organic acid, re-retanning chrome tanning agent, drying and finishing (EN 2039835 1, CL C.14C 13/00, 3/08, 11/00, 20.07.95).

The disadvantages of the known methods are relatively low hygienic properties of the obtained hydrophobic skin, as well as a low pressestelle skin when stored in conditions of high humidity and temperature.

The technical result of the invention is to improve the hygienic properties of hydrophobic leather, as well as ensuring long-term sustainability of the skin against the mold under conditions of high humidity and temperature.

This result is achieved in that in the method of manufacture of hydrophobic leather, including retanning semi-finished chrome tanning agent, neutralizing, washing, dyeing, double retanning organic tanning agent first polymer; tanning agent, the second is a mixture of synthetic and vegetable tanning agent, gidrofobiziruyuschey greasing, processing of organic acid and re-retanning chrome tanning agent, before neutralization is carried out additional washing, dyeing is performed after the second retanning, while neutralization, double retanning and dyeing is carried out at liquid ratio of 0.5-0.7, and gidrofobiziruyuschey greasing is performed in presence of a 20%aqueous solution of the product of the interaction of amerosport with fatty acids vegetable oils of fractions of C12-C22and boric acid when the molar ratio is attachment 2:1:1 mineral oil (hereinafter - the product of the interaction) in an amount of 0.5 to 1.5% by weight of the semifinished product.

A distinctive feature of the proposed method is that the leaching after retanning chrome tanning agent allows you to more efficiently conduct subsequent neutralization process that allows doublelayer compounds, dyes and greasing substances fuller and deeper understanding of the structure of the skin, is uniformly distributed on its layers. The implementation processes of neutralization, double retanning and dyeing with LCD 0,5-0,7 enhances the penetration of reagents into the skin, which in combination with water-repellent creasing in the presence of the product of the interaction in the amount of 0.5 to 1.5% by weight of the semifinished product causes a synergistic effect of increasing the hygienic properties of the skin and its pressestelle.

Conducting processes of neutralization, retanning organic tanning agent and dyeing in LCD less than 0.5 can lead to deterioration of the quality of the skin due to wear of the semi-finished product. Carrying out these processes in LCD more than 0.7 will slow down the speed of penetration of the reagents into the skin. Consumption reduction product of the interaction of less than 0.5% by weight of semi-finished product will not lead to a synergistic effect of improving hygiene and plasmasonic properties of the skin, and increase consumption of this product more than 1.5% of netsales is figuratively, as further improvement of these properties does not occur.

The method of obtaining the product of the interaction of amerosport with fatty acids of vegetable oils fraction C12-C22and boric acid is as follows:

In a reactor equipped with a mixer nozzle Dean-stark, reflux condenser and thermometer, load 1 mol of fatty acids of vegetable oils fraction C12-C22and 2 mol of amerosport. The reaction mass is heated under stirring up to 60-80C, then enter 1 mol of boric acid and raise the temperature of the reaction mixture to 160-180C, maintaining it at this temperature for 1-2 h until a homogeneous product with an amine number of 50-60 mg HCI/year

As fatty acids of vegetable oils fraction C12-C22use palmitic (TU 6-09-4132-75), stearic (GOST 6484-96), oleic (GOST 7580-91), linoleic, linolenic, ricinoleic (TU 6-09-4821-80) and other acids, and mixtures thereof.

As amerosport - monoethanolamine (TU 2423-065-05807977-2004), diethanolamine (TU 2423-054-05807977-2000) or triethanolamine (TU 2423-061-05807977-2002).

As mineral oil use spun or industrial oil brands AND 8A, AND 12A, AND-20A according to GOST 20799-88.

The method is as follows:

Semi-finished leather for Shoe upper, obtained by standard methods from raw material big horn the cattle, doublenaut chrome tanning agent, washed at a temperature of 30-35C for 10-15 min and neutralized with formate and bicarbonate of sodium in the LCD of 0.5-0.7. After washing at a temperature of 30-35C prefabricated doublenaut when LCD 0.5 to 0.7 during the first 20-30 min of polymer tanning agent (Relugan RE, Relugan RV, Relugan RF, Ecolas M, YOU on THE other 2294-076-00302267-2002 and others) when the flow rate of 3-4% by weight of cement, and then for 20-30 min with a mixture of synthetic (Relugan D, Relugan S, Basyntan SL, DFPM on THE 17-06-164-95, PCA on THE 13-7308001-389-85, and others) and plant (Mimosa, quebracho, chestnut) tannins in their consumption accordingly 5-7% and 2-3% by weight of the semifinished product. Then produce a dyeing within 30-40 minutes After that in the same bath add 75% water at a temperature of 50-60C and hold gidrofobiziruyuschey greasing within 60-90 min in the presence of 20%solution of the product of the interaction of amerosport with fatty acids of vegetable oils fraction C12-C22and boric acid when a molar ratio of 2:1:1 mineral oil in the amount of 0.5 to 1.5% by weight of prefabricated Consumption of fattening materials 3-4%, hydrophobic - 7-8% by weight of the semifinished product. As greasing materials used ready oiling composition based on natural and synthetic fats, for example Universal S, Universal, Extra, Tramal N TU 2484-052-00302267-2000, SMX-e on THE other 2484-013-222-84-995-99 etc. as hydrophobe is atarov use silicones brand PENTA-812 on THE other 2251-054-40245042-2003, Hydrophob A synthetic fatty acids, wool grease or lanolin, Silor-hydrophob on THE 5772-085-05015207-2005 etc. Then in the same bath add 1-2% organic acids and handling are within 20-25 minutes After washing produce re retanning chrome tanning agent for 60-90 min at the rate of 2-3%" by weight of the semifinished product. Further processes and operations carried out by known techniques.

Example 1. The semi-finished product obtained by standard methods from raw materials rawhide average, after retanning chrome tanning agent is washed at a temperature of 35C and neutralized with 2% of sodium formate and 0.8% sodium bicarbonate when LCD 0,5 within 90 minutes After washing at a temperature of 35C hold first retanning polymer tanning agent Relugan RV in the amount of 3% by weight of the semifinished product in LCD 0.5 and a temperature of 30C for 20 min, and then for 20 min with a mixture of tannins Basyntan SL 5% and Mimosa 3% by weight of the semifinished product. Dyeing produced in the same bath for 40 min at a flow rate of dyes of 2.5%. After that, the drum add 75% of water at 60C and produce gidrofobiziruyuschey greasing for 60 min with a mixture of 3% Extras and 7% of hydrophobe PENTA-812 in the presence of 20%solution of the product of the interaction of triethanolamine, oleic acid and boric acid in their molar ratio 2:1:1 in spun oil in the amount of 0.5% by weight of the floor is of apicata. Then in the same tub to impose 2% formic acid and the treatment continued for another 20 minutes After washing at a temperature of 35C produce re retanning chrome tanning agent at the rate of 3% by weight of the semifinished product. After 90 min the semi-finished product is washed at a temperature of 20C, subjected to aging, bussing, drying and finishing according to the Method of production of leather, chrome tanning of different thicknesses and range for the uppers and lining of the hides of cattle.

Example 2. The semi-finished product obtained by standard methods from raw materials byczyna easy process as in example 1, but the neutralization, the first polymeric retanning tanning agent Allans M to 3.5%, the second retanning with a mixture of synthetic tanning agent PCA 6%, quebracho of 2.5%, and the dyeing is carried out at the LCD to 0.6. Gidrofobiziruyuschey greasing is carried out at the expense of fattening composition Tramal H 3,5% and hydrophobe A 7.5% in the presence of 20%solution of the product of the interaction of diethanolamine, linoleic acid and boric acid in their molar ratio 2:1:1 in the industrial oil AND 12A in the amount of 1.0% by weight of the semifinished product.

Example 3. The semi-finished product obtained by standard methods from raw materials byczyna heavy, treated as in example 1, but the neutralization, the first polymeric retanning tanning agent YOU 4%, the second retanning with a mixture of synthetic tanning agent Relugan D 7%, quebracho 2%, and Alenia produce LCD 0,7. Gidrofobiziruyuschey greasing is carried out at the expense of fattening composition Wagon-N 4% and 8% of hydrophobe PENTA-812 in the presence of 20%solution of the product of the interaction of monoethanolamine, palmitic and boric acid in their molar ratio 2:1:1 in the industrial oil I-20A in the amount of 1.5% by weight of the semifinished product.

Example 4. The semi-finished product obtained by standard methods from raw materials rawhide average, treated as in example 1, but the neutralization, the first polymeric retanning tanning agent Relugan RE, the second doubleValue mixture of synthetic tanning agent Relugan S and plant Mimosa, and dyeing is carried out at the LCD of 0.4. Gidrofobiziruyuschey greasing is carried out in the presence of 20%solution of the product of the interaction of triethanolamine, oleic acid and boric acid in their molar ratio 2:1:1 in spun oil in an amount of 0.4% by weight of the semifinished product.

Example 5. The semi-finished product obtained by standard methods from raw materials byczyna easy process as in example 1, but the neutralization, the first polymeric retanning tanning agent YOU second retanning with a mixture of synthetic tanning agent DFPM and plant quebracho, and dyeing is carried out at the LCD to 0.8. Gidrofobiziruyuschey greasing is carried out in the presence of 20%solution of the product of the interaction of diethanolamine, linoleic acid, and boric acid when the molar ratio is attachment 2:1:1 in the industrial oil AND 12A in the amount of 2% by weight of the semifinished product.

Indicators of hygiene and hydrophobic properties of the skin and skin of the prototype are presented in table 1. Tests conducted on the device HPH-2 according to GOST 938.22-71.

Pressestelle skin is determined according to GOST 9.048-85. The indices of the skin samples in the scores are: 0 - total absence of mold; 1, 2, 3, 4, 5 - the defeat of the mold surface of the sample, respectively, %: 5, 25, 50, 75 100. The test results presented in table 2.

Using the proposed method allows to obtain hydrophobic leather for the uppers with high hygienic properties and long planetology in conditions of high humidity and temperature.

The relative permeability, %
Table 1
Name of indicatorValues for the examplesThe placeholder
12345
Vodopronitsaemosti in dynamic conditions min606265506048
303335253524
Proencode, mg/cm2hour789675
Hygroscopicity, %171819201921
Lagoudaki, the amount of absorbed moisture, %939596919590
Table 2
Name of indicatorValues for the examplesThe placeholder
12345
Pressestelle through 30/60 days, scores, when the holding temperature
5-8C0/00/00/00/00/00/0
10-15C0/00/00/00/00/00/0
15-20C0/00/00/00/00/00/0
20-25C0/00/00/00/00/00/1
25-30C0/00/00/00/10/01/2
30-35C0/00/00/00/20/02/3

The way we produce hydrophobic skin, including retanning semi-finished chrome tanning agent, neutralizing, washing, dyeing, double retanning organic tanning agent: first polymeric tanning agent, the second is a mixture of synthetic and vegetable tanning agent, gidrofobiziruyuschey greasing, processing of organic acid and re-retanning chrome tanning agent, characterized in that before the neutralization is carried out additional washing, dyeing is performed after the second retanning, while neutralization, double retanning and dyeing is carried out at liquid ratio of 0.5-0.7, and gidrofobiziruyuschey greasing is performed in presence of a 20%aqueous solution of the product of the interaction of amerosport with fatty acids of vegetable oils fractions With12-C22and boric acid when a molar ratio of 2:1:1 mineral oil in the amount of 0.5 to 1.5% by weight of the semifinished product.



 

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EFFECT: simplified process and increased product discharge degree.

1 tbl, 19 ex

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