Composition for skin treatment and method of treatment

 

(57) Abstract:

Usage: in the leather industry, in particular in methods of treatment of the skin in a certain composition. The inventive method provides for the treatment of skin under fatliquoring or after this composition, including at least one of fattening agent, selected from the group of ester phosphate, a derivative of phosphonic acid containing alkyl fluoride, florenceville group or a group of simple Ftorafur, their ammonium salts, salts of alkaline, alkaline-earth metals and the reaction products of the specified complex ether phosphate, a derivative of phosphonic or phosphinic acid with a compound of the metal, with the exception of alkaline and alkaline-earth metals, and at least one fluorine-containing oil is selected from the group: parfocality with duplicate links of f-crystals: parfocality with duplicate links of f-crystals: where p, g, r are integers, the sum of which is not less than 2 and not more than 200; simple poliferation with duplicate links of f-crystals: where a, b, c, d, e, f are zero or an integer long number satisfying the equation: 2 (a+B+c+d+e+f < 200 and a+c+d+f > I, and connections with duplicate links of f-crystals: -(CF2CFCl)n. 2 C. and 7 C. p. F.-ly, 1 table.

In order to improve the structure and elasticity iravani and tanned skin, use a natural or synthetic oil together with oiling agent under fatliquoring of leather. However, the products obtained from the thus treated leather, such as leather dresses, lose color or fade with dry cleaning using perchloroethylene (Perlen) or petroleum solvent. The reason for this may be the extraction of oil, which was introduced at the stage of processing fat.

There is a method of skin treatment, comprising impregnating her on stage fatliquoring or after fatliquoring composition containing at least one greasing agent and at least one fluorine oil.

The purpose of the invention is to provide a skin treatment that gives your skin with a good structure, the resistance with water and malatjalian and resistance to washing.

The purpose of the invention is also to propose a method of skin treatment using the above-mentioned processing.

In accordance with the first aspect of the invention is proposed treatment is the SPECTA of the invention proposes a method of skin treatment, including the processing of its composition, which contains greasing agent and oil, fluorine, under fatliquoring.

In accordance with a third aspect of the invention proposes a method of skin treatment, which includes the creasing of the skin and then processing iravani skin oil containing fluorine.

Oil containing fluorine, should be stable oil and it includes parfocality comprising recurring units of the formula:

(F2O)- (for example, KRYTOX trade name, manufactured by E. I. DuPont), parfocality comprising recurring units of the formula:

(F2O)p-(CF2O)qin which, p, q and r are integers whose sum is not less than 2 and not more than 200 (for example, FOMBLIN trade name, manufactured by Montedison), simple formality containing the repeating unit of the formula:

-(CH2CF2CF2O)a-(CHClCF2CF2O)b-

-(CCl2CF2CF2O)c-(CHFCF2CF2O)d-

-(CFClCF2CF2O)e- (CF2CF2CF2)fin which a, b, c, d, e and f are zero or positive integers and satisfy the equations:

2 a + b + c + d + e + f 200 and a + c + d + f 1 (Ie the repeating unit of the formula:

-(CF2CFCl)n(e.g., DIPLOID trade name, manufactured by Daikin industries limited). Among them, the connection end of the molecule which modified carboxyl group, or a phosphate group, is preferred.

Greasing agent used in accordance with the invention, can be any greasing agent. Greasing agents in accordance with the coarse classification is divided into agents of emulsion type and emulsioning type; greasing agents, emulsion type include agents of the anionic type such as sulfated oil, sulfite oil, sulfonated oil, soap, phosphated oil and oil based on the condensation of aliphatic acids, cationic type, such as oil-based aliphatic amine acids, amphoteric type such as oil-based aminocarbonyl acid and betainovuyu compounds and non-ionic type, such as derivatives of polyethylene oxide. To greasing agents emulsioning type include natural oils such as fish oil, butter, beef fat, vegetable oil (e.g. olive oil), animal oils (e.g., beef tallow, pork and mutton fat), wool fat, mineral oil, wasactive oil. As modified oils, examples of oxidative polymerized oil and moellon deglass.

In a preferred embodiment of the invention uses oiling agent containing a functional group which is reactive to the connection of the metal included in the tanned skin and forms a complex or double salt (for example, carboxyl group, the group of complex phosphate ester, group, phosphonic acid group, phosphinic acid group, sulfuric acid group sulphurous acid group (mono) sulfonic acids, amino group, and so on).

In a more preferred embodiment of the invention as greasing agent can be used ester phosphate, a derivative of phosphonic acid derivatives of phosphinic acid containing alkyl fluoride group, florenceville group or a group of simple Ftorafur, or ammonium salt, alkali metal salts or salts of alkaline earth metals, the reaction products of the above mentioned compounds containing fluorine phosphoric Foundation (mentioned ester phosphate, a derivative of phosphonic acid derivatives of phosphinic acid) with a compound of the metal, with the exception of alkaline mi.

In addition, in the preferred embodiment, as greasing agents use fluorine carboxylic acids or their salts, as well as containing fluorine surface-active agents.

Metal connection that communicates with the connection based on the phosphorus may be any compound of the metal, which can interact with a group of phosphonic acid with the formation of the complex or double salt, and includes all compounds of metals, excluding compounds of alkali metals and alkaline-earth metals, for example compounds of chromium, zirconium, titanium, aluminum, thallium, zinc, etc., such as salts, oxides, sulfides, halide and hydroxides that are soluble in organic and inorganic solvents.

Ester phosphate, having an alkyl fluoride group, florenceville group or a group of simple Ftorafur, or its salt, ammonium salt, alkali metal salt, alkaline-earth metal or salt with a compound of the metal can be represented by the following formula:

(RfR2O)(OR)k(OH)y(OM)t(1)

(RfSO2NR3R4O)(OR)k(OH)y(OM)t(2) in which Rf is a C3-C21-perakyla,3-C21-florenceville or other metal, such as chromium, zirconium, titanium, aluminum, thallium, or zinc, ammonium group or a substituted ammonium group (examples of the substituents are C1-C5an alkyl group or1-C5alkoxy group), R1is1-C5alkyl group; R2C1-C10alkalinous group or a group of the formula:

-CH2CH(OR5)CH2-, in which R5is a hydrogen or C1-C10-Alloway group

-CH2CH(OH)-, -CONR6in which R6is1-C5alkyl group,

-CH= CHCH2- or-CH2CHXCH2in which Y is a halogen atom; R3an atom of hydrogen or C1-C5alkyl group; R4C1-C10alkalinous group; j is 1,2 or 3, y is 0,1 or 2, but not more than (j-1), K is equal to 0,1 or 2, but not more than 3-(j+Y), a t is 3-(j+y+K).

Specific examples of the compounds (1) and (2) are the following:

CF3CF2(CF2CF2)3CH2CH2O(OH)2< / BR>
C8F17SOCH2O(ONH4)2< / BR>
(C8F17SOCH2O)ONH4< / BR>
CF3CF2(CF2CF2)3CH2CH2O(CH2)xPO(OR)m(OH)n(OMO no more than (2-m), a n = 2-(m+n).

Specific examples of compounds of the formula (3) and (4) are the following:

CF3CF2(CF2CF2)2-8CHCH(OH)2< / BR>
(CF3)2CF(CF2CF2)2-4CH2CHCH

C8FCH(OH)2< / BR>
Derived phosphinic acid containing alkyl fluoride group, florenceville group or a group of simple Ftorafur, and its reaction product with a compound of the metal is represented by the following formula:

(RfR2)p(H)qP(OR')r(OH)s(OM)v(5)

RfOCH(H)qP(OR)r(OH)s(OM)v(6) where Rf, R1, R2and M have already been defined above; p is 1 or 2; q 2 p; s is 0 or 1; r is 0 or 1, but not more than (1-r) a v 1-(s+r).

Examples of compounds of the formulas (5) and (6) are the following:

[CF3CF2(CF2CF2)2-8CH2CH2]C8F17OCH-OH

C6FCH-ONa

Examples of fluorine-free carboxylic acids are carboxylic acids of the formula:

Rf(CH2)nCOOH in which Rf has already been defined above; n is a number from 0 to 10, or their salts such as ammonium salt, salts of alkali metals, salts of alkaline-earth metals and salts of other metals (e.g. chromium, zirconium, titanium is ASS="ptx2">

As the fluorine surface-active agent can be used compounds of the following formulas:

RfCHCHCOOK

RfCHCHCH2CH2OH)2I-< / BR>
RfCHCH2NH(CH2)3-CH2O(CH2CH2O)9CH3< / BR>
RfCHCH2O(CH2CH2O)9H

RfCHCH2O(CH2CH2O)8COCH2O(CH2CH2O)8SON2< / BR>
When the skin treatment in accordance with the invention, the weight ratio oiling agent for fluorine oil in General varies from 10:1 to 1:2, in the preferred embodiment, from 5:1 to 1:1.

In accordance with the method of the invention oiling agent is used in an amount of from 1 to 30 wt. in a preferred embodiment, from 2 to 10 wt. in terms of the mass of the skin, and containing fluorine oil is used in an amount of from 1 to 10 wt. in a preferred embodiment, from 2 to 4 wt. in terms of the mass of the skin.

When tanned skin is treated with the agent for skin treatment containing oiling agent, and oil containing fluorine, which are present in emulsion form, processed hides the shape of the skin has an extremely high performance to the touch and elasticity, while it does not lose curiouser agent, and then treated with fluorine oil, for example, by spray coating or dipping in the oil will have the same effects.

In accordance with the invention as to the touch, water resistance, water - and oil-repellency, for a long time and durability when washing is improved, and the effect of deep color is achieved with a low refractive index fluorine oil. In addition, tanned skin does not lose color and appearance when dry cleaning, improves elasticity, pjatnovyvoditel, resistance to contraction and swelling.

P R I m e R 1. Getting the feel of the song.

Phosphate containing alkyl fluoride group, and parfocality as oil emulsiable as follows:

the pH value of a predetermined number containing alkyl fluoride group, phosphate provided at the level of 6.5 using 28% aqueous ammonia solution with stirring. It was added a predetermined amount of parfocality and thoroughly mixed. Then the mixture was emulsiable by adding (slow) water to obtain an emulsion (50 ml).

P R I m m e R 2. Skin treatment.

Tanned skin was treated with p is I wet processing, i.e. the stage below was carried out in a rotating drum. Stage of leaching was carried out carefully under running water. At the stages of neutralization in the drum was loaded aqueous solution of at least one neutralizing agent in excess of about two times the amount of tanned skin, and then the drum was rotated at a temperature of about 30aboutC for 60 min, to provide a pH in the bath at the level of 5.5 to 6.0. Used neutralizing agents include sodium formate and sodium bicarbonate. The dyeing was carried out by loading solution 6% (calculated on the weight of the skin) dye Luganil black HT (manufactured by BASF) and 100% of the water in the drum, rotating the drum at a temperature of 50aboutC for 60 min by adding 2% aqueous solution of formic acid, and then, rotating the drum for 10 minutes to provide a pH at 3.5. Then added 3% Luganil black HT and the drum was rotated for 30 minutes After dripping the liquid, the skin was rinsed with water and again dobili.

Re-tanning was carried out by rotating the drum containing the skin and a solution of 2% Bichrome F. and 100% of water at a temperature of 30aboutWith over 90 min, subsequent storage during the night. Next, the skin was rinsed with water Ghent.

At the stage of fatliquoring, the emulsion obtained in example 1 was used in the same way that when processing using a greasing agent. Namely, a predetermined amount of the test compounds and known oiling agent was added to water (100%) and were loaded into the drum. After rotation of the drum at a temperature of 50aboutC for 60 min was added to a 1.5% aqueous solution of formic acid and the drums are rotated within 30 minutes After dripping the liquid, the skin was rinsed with water, kept overnight, and dried in the air, beat off, and then hung.

Used the following connections:

The invention

Sample 1

5% R f-OPO(OH)2+ 1% of Demnum s-200 (parfocality produced by the firm Daikin industries Ltd).

Sample 2

5% R f OPO(OH)2+ 1% of Demnum s-200

Sample 3

5% R f OPO(OH)2+ 1% of Demnum, the ends of which are modified with the help of carboxyl groups

4 sample

5% R f OPO(OH)2+ 1% of Demnum, the ends of which are modified with the use of phosphate groups

Sample 5

5% R f OPO(OH)2+ 1% of Diploma 10 (manufactured by Daikin industries Ltd).

Sample 6

5% R f OPO(OH)2+ 1% fomalin 25, it is th modified using carboxyl groups.

Compare connection

Sample 8

5% R f OPO(OH)2+ 1% H2F (manufactured by Hoechst, oil)

Sample 9

5% R f OPO(OH)2+ 1% H2F

Sample 10

15% Sycolin L (manufactured by Ishikawa Forces manufacturing To. Co., Ltd.).

Sample 11

5% R f OPO(OH)2only

Sample 12

5% R f OPO(OH)2only

In the above formulas, R f is

(CF3)2CF(CF2CF2)3-CH2CH(OH)CH2-, a R"f is CF3CF2(CF2CF2)nCH2CH2- Processing stage (%, calculated on the weight of haired skin).

Thorough rinsing in running water; neutralization: formate, sodium of 1.5% sodium bicarbonate and 1.5% water 100% pH 6, the drum was rotated for 60 min; thorough rinsing in running water; color: Luganil black HT (firm BASF) 6% water to 100% at a temperature of 50aboutWith, the drum was rotated for 60 min, was added 3% Luganil black HT and the drum rotated for 30 minutes Thorough rinsing under running water; re-tanning: Bahram f (Bayer AG) 2% water 100% drum rotated at 30aboutWith over 90 min (kept during the night). Washing with water, neutralization using the same procedure as above.

Rinse wlsa at 50aboutC for 60 min, was added to 1.5% of formic acid, the drum was rotated for 30 minutes Then rinse with water, removing the water and drying by hanging.

P R I m e R 3. Skin texture was evaluated by 10 people (five men and five women) in accordance with the following criteria:

5: much softer than the skin of treated sample 10;

4: softer than skin treated sample 10;

3: the same soft, like the skin is processed by the sample 10;

2: tougher than leather that has been treated sample 10;

1: much tougher than leather processed by the sample 10.

The results are shown below.

Sample Assessment to the touch (average) 1 4,3 2 4,9 3 4,9 4 4,9 8 3,9 9 3,8 10 3,0 11 3,7 12 3,1

P R I m e R 4. Static test resistance.

In accordance with JIS K 6550, hydraulic pressure of a column of water high in 150 cm was applied to the skin and recorded the time after which the opposite surface appeared three drops of water (the time of appearance of water droplets). The same test was carried out in six different locations. The results are presented in the table.

P R I m e R 5. The depth of the colour before and after dry cleaning.

In accordance with JIS K 6552, each piece of skin amrabat the d and after dry cleaning scale bleaching JIS and using the depth of coloration of the skin, the treated sample 8 and 9, before dry cleaning as standard (scale 5).

The results are shown in the table.

1. The composition for treatment of skin, including greasing agent and at least one fluorine oil, characterized in that the fluorine oil selected from the group consisting of parfocality comprising recurring units of the formula

< / BR>
parfocality comprising recurring units of the formula

< / BR>
where p, q and r are integers whose sum is not less than 2 and not more than 200,

simple poliferation comprising recurring units of the formula

-(CH2CF2CF2O)A(CHClCF2CF2O)B(CCl2CF2CF2O)c-;

(CHFCF2CF2O)d(CFClCF2CF2O)e- (CF2CF2CF2)f-,

where a, b, c, d, e and f are 0 or positive integers and satisfy the equations: 2 a + b + c + d + e + f 200 and a + c + d + f 1,

and compounds comprising recurring units of the formula

(CF2CFCl)n-,

as greasing agent selected from the group consisting of complex ether phosphate, a derivative of phosphonic acid and a derivative of phosphinic acid containing peralkaline alkaline earth metals, and reaction products of the specified complex ether phosphate, a derivative of phosphonic acid derivatives of phosphinic acid with a compound of the metal, excluding alkali and alkaline earth metals.

2. The composition according to p. 1, characterized in that the ester phosphate, having an alkyl fluoride group, florenceville group or a group of simple Ftorafur, or its salt, ammonium salt, alkali metal salt, alkaline earth metal or salt with a compound of the metal is a compound of formula

< / BR>
< / BR>
where Rf3WITH21foralkyl,3- C21florangela group or3WITH21the group of simple Ftorafur;

M is alkali metal, alkaline earth metal or other metal, an ammonium group or a substituted ammonium group;

R1WITH5is an alkyl group;

R2WITH1WITH10-Allenova group, or a group of the formula

-CH2SN (OR SIG5) CH2,

where R5hydrogen or C1WITH10-acyl group-CH2CH (OH)-, NR6,

where R6WITH1WITH5is an alkyl group, -CH=SNSN2- or-CH2NHSN2-, where X is halogen,

R3bodoro and 3;

y is 0,1 or 2, but not more than (3-j);

to 0,1 or 2, but not more than 3- (j + y); t 3-(j + y + k).

3. The composition according to p. 2, characterized in that the complex ether phosphate or its salt is

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
4. The composition according to p. 1, characterized in that said derivative of phosphonic acid having alkyl fluoride group, florenceville group or a group of simple Ftorafur and its reaction product with a compound of the metal, is a compound of the formula

RfR2PO(OR)m(OH)n(OM)u;

< / BR>
where Rf, R1, R2and M have the above meanings; w is 1 or 2;

x is 1 or 2;

m is 0,1 or 2;

n is 0,1 or 2, but not more than (2 m);

u 2-(m + n).

5. The composition according to p. 4, characterized in that the derivative of phosphonic acid or its salt is a

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
6. The composition according to p. 1, characterized in that said derivatives of phosphinic acid containing alkyl fluoride group, florenceville group or a group of simple Ftorafur, and its reaction product with a compound of the metal is a compound of the formula

(RfR2)p(H)qP(OR)r(OH)sOM)v;

< / BR>
where Rf, R1, R2and M have the above snakesize by p. 6, characterized in that said derivatives of phosphinic acid or its salt is

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
8. The composition according to p. 1, characterized in that said oiling agent is a fluorine-free carboxylic acid of the formula

Rf (CH2)nCOOH,

where Rf is the specified value;

n 0 10,

or its salt.

9. The method of skin treatment, comprising impregnating her on stage fatliquoring or after fatliquoring composition containing at least one greasing agent and at least one fluorine oil, characterized in that the fluorine oil selected from the group consisting of parfocality comprising recurring units of the formula

< / BR>
parfocality comprising recurring units of the formula

< / BR>
where p, q and r are integers whose sum is not less than 2 and not more than 200 simple poliferation comprising recurring units of the formula

-(CH2CF2CF2O)a(CHClCF2CF2O)b(CCl2CF2CF2)c-;

(CHFCF2CF2O)d(CFClCF2CF2O)e- (CF2CF2CF2)f-,

where a, b, c, d, e and f are 0 or positive integers and satisfy SUB>CFCl)n-,

as greasing agent selected from the group consisting of complex ether phosphate, a derivative of phosphonic acid and a derivative of phosphinic acid containing alkyl fluoride group, florenceville group or a group of simple Ftorafur, and their ammonium salts, alkali metal salts and alkaline earth salts of metals, and the reaction products of the specified complex ether phosphate, a derivative of phosphonic acid derivatives of phosphinic acid with a compound of the metal, excluding alkali and alkaline earth metals.

 

Same patents:

The invention relates to leather production, namely the production of fattening materials and emulsifiers for the leather industry

The invention relates to fur and leather industries and can be used by enterprises engaged in the production of fattening compositions

The invention relates to light industry and can be used in the leather and fur industries

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

The invention relates to chemical treatment of skins and can be used in leather industry

The invention relates to leather production, in particular to the production technology of natural leather to get a fashionable color effect

The invention relates to leather production, namely the production of fattening materials and emulsifiers for the leather industry

The invention relates to leather and fur industry and can be used for processing of leather and fur

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

Up!