RU2553652C1 - Composition for protection of products from natural and artificial smooth and pile leather against action of water and water solutions of de-icing reagents - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: composition for the protection of materials against the action of water and/or a water solution, contains: a) organic solvent; b) reactionable bifunctional aminosiloxane, which has the general structural formula I: (I) R1-O[-Si(CH3)2O-]n[-Si(OR2)(R10)O-]mR3; c) fluoropolymer, which represents a polymer and/or a copolymer of monomers, which have the general structural formula (II)-(VI), with the following content of monomers counted per the total weight of the polymer and/or copolymer (wt %): (II) R4-O(CH2)2R6 40÷97, (III) R4-OR7 3÷35, (IV) R4-OR8 0÷25, (V) R4-NHCH2OH 0÷15, (VI) CH2-C(R9)Cl 0÷40, where: R1 and R3 independently on each other represent CH3-Si(OCH3)O-[-Si(CH3)(OR2)O-]x, or methyl, R2 represents an alkyl, which contains one, two, three or four carbon atoms, R4 represents a group CH2=C(R5)C(O)-, R5 represents H or methyl, R6 represents an alkyl, which contains, at least, 4 carbon atoms, substituted with one or two fluorine atoms, R7 represents a C1-C40 alkyl with a straight or branched chain, R8 represents hydroxy(C2-C4)alkyl, R9 represents H or C1, R10 represents -R11-NH-R11-NH2, R11 represents an alkylene, which contains two, four or five carbon atoms, x represents an integer number from 10 to 500, m represents an integer number from 1 to 50.EFFECT: composition possesses high protective activity due to the combination of bifunctional polyogranosiloxanes and fluoropolymers in one means for leather protection.12 cl, 2 dwg, 4 tbl, 3 ex

Description

FIELD OF THE INVENTION

The invention relates to household chemicals used for hydrophobization of products from natural smooth and pile skin and their protection from the negative effects of electrolyte solutions.

BACKGROUND

To impart water-repellent properties to various types of leathers in the leather industry and in everyday life, compositions based on two large groups of chemicals are used: organosilicon compounds and fluorine-containing compounds.

In the simplest case, chemically inert non-functional groups containing polydimethylsiloxanes (PDMS) and polydimethylphenylsiloxanes can be used, however, their protective effect is short-lived (since chemical bonds between the molecules of the active substance and the substrate do not form), moreover, they are of little use for pile skins, since they form oily film spoiling the appearance of suede and velor products.

Organosilicon compounds containing functional groups (Si-OAlk, Si-OH, amino groups) possess better protective properties compared to unmodified polydimethylsiloxanes [1-7]. These functional groups provide adhesion of the entire macromolecule of the organosilicon compound to the surface of the substrate (skin). An example of amino-functional organosilicon polymers of this type is a polymer with the general structural formula (VII):

An example of α, ω-dihydroxypolydimethylsiloxane is a polymer having the general structural formula (VIII):

Hydrophobization of the surface can be achieved by treatment with fluorine-containing compounds [8, 9].

Modern chemistry of water, oil and dirt repellents is mainly based on formulations containing fluorine-containing polymers such as polyperfluoroalkyl acrylates and polyperfluoroalkyl methacrylates, with the number of fluorinated carbon atoms in the side chain of the polyacrylate being 4, 5, 6, 7, 8 or more [8 -12].

Polymers based on vinyl esters of perfluorocarboxylic acids, urethanes, and some other fluorine-containing polymers can serve as alternatives to polyperfluoroalkyl acrylates and polyperfluoroalkyl methacrylates [9].

Water and oil repellent compositions are known, including:

(a) an agent containing an aliphatic fluoroalkyl radical;

(b) polysiloxane having cyclic carboxylic acid anhydride as a substituent;

(c) filler and / or plasticizer [13].

Composition [13] gives the material water and oil repellent properties.

Fluoroalkyl radical-containing agents that can be used in such compositions include condensation polymers such as polyesters, polyamides, and vinyl polymers such as acrylates, methacrylates or polyvinyl esters. Such agents are described, for example, in US Pat. substituents, supplied as a 40% solution in ethyl acetate).

A known composition for the treatment of washable skin, giving high rates of oleophobicity and hydrophobicity, containing:

(a) at least one fluorinated urethane component,

(b) at least one fluorinated ether, and

(c) at least one fluorinated urethane derivative of citric acid [14].

A known composition based on a nonaqueous solvent containing polyperfluoroalkylmethacrylate [17]. Examples are given of the preparation and testing of a polymer proposed as a repellent for treating leather and other types of hard surfaces.

There are patents where siloxane and fluorinated blocks are combined in one polymer molecule [15], general structural formula (IX), or low molecular weight substance [16] of general structural formula (X):

Thus, the analysis of the prior art shows that:

(a) monocomponent skin protection agents based on siloxanes with fluorinated alkyl radicals and based on acrylates with fluorinated alkyl radicals have been developed;

(c) multicomponent skin protection products containing fluorinated derivatives of esters and urethanes, as well as protective products containing an agent with long perfluoroalkyl chains and polysiloxane, have been developed.

SUMMARY OF THE INVENTION

The objective of the present invention is to provide a new tool for protecting leather products from water and aqueous solutions of electrolytes, which has a higher protective activity than its components with the same type of activity, taken in the same amount.

The technical result achieved in the present invention is that due to the combination of bifunctional polyorganosiloxanes and fluoropolymers in one skin protection agent, a higher protective activity is achieved than would be expected from the action of the taken amount of components. High synergism of the components of the composition is achieved not only when used to protect the skin from the action of water and neutral aqueous solutions with low ionic strength, but also from the action of anti-icing reagents. It should be emphasized that the effect on the skin and the protective coating of solutions of anti-icing reagents is different from the action of water, because aqueous solutions of anti-icing reagents have alkaline pH (see Fig. 1) and greater ionic strength compared to pure water.

The problem was solved due to the fact that the invented composition for protecting materials from the action of water and / or aqueous solutions contains:

a) an organic solvent

b) reactive bifunctional aminosiloxane of formula I

(I) R1-O [-Si (CH ₃ ) ₂ O-] _n [-Si (OR2) (- R11-NH-R11-NH ₂ ) O-] _m R3,

c) a fluoropolymer, which is a polymer and / or copolymer of monomers having the general structural formula (II) to (VI), with the following monomer content based on the total weight of the polymer and / or monomer (wt.%):

(II) R4-O (CH ₂ ) ₂ R6 40 ÷ 97 (III) R4-OR7 3 ÷ 35 (IV) R4-OR8 0 ÷ 25 (V) R4-NHCH ₂ OH 0 ÷ 15 (VI) CH ₂ = C (R9) Cl 0 ÷ 40

Where

R1 and R3 independently from each other are CH ₃ —Si (OCH ₃ ) O - [- Si (CH ₃ ) (OR2) O—] _x , or methyl,

R2 is an alkyl containing one, two, three or four carbon atoms,

R4 represents a group CH ₂ = C (R5) C (O) -,

R5 represents H or methyl,

R6 is alkyl containing at least four perfluorinated carbon atoms,

R7 is a straight chain or branched C1-C40 alkyl

R8 is hydroxy (C2-C4) alkyl,

R9 represents H or Cl,

R11 is alkylene containing two, three, four or five carbon atoms,

x is an integer from 1 to 10,

n is an integer from 10 to 500,

m is an integer from 1 to 50.

Said reactive bifunctional aminosiloxane may have a viscosity (without limitation) of from about 10 to about 100 centistokes.

Said reactive bifunctional aminosiloxane may have (without limitation) a number average molecular weight of from about 1000 to about 50,000 daltons.

R6 may be alkyl containing at least eight carbon atoms substituted by fluorine.

The total content of the aforementioned aminosiloxane and fluoropolymer can be (without limitation) from 1 to 24 wt.%, The rest is an organic solvent and, optionally, functional additives.

An organic solvent may be (without limitation):

an aliphatic hydrocarbon with a carbon number of 6 to 14,

aromatic hydrocarbon with a number of carbon atoms from 6 to 14,

monohydric alcohol with a number of carbon atoms from 2 to 5,

ester with the number of carbon atoms from 3 to 10,

ether with the number of carbon atoms from 4 to 6,

ketone with a carbon number of 3 to 6

or a mixture of these substances.

In accordance with another aspect of the present invention, it is proposed the use of the above composition for protecting the skin from the action of water and / or aqueous solutions.

The skin may be (without limitation) natural smooth skin and / or pile skin.

Aqueous solutions can be (without limitation) solutions of anti-icing reagents.

In accordance with another aspect of the present invention, there is provided a method of using the composition described above, characterized in that it is applied to the skin with a tampon, roller, brush or spray.

Spraying the composition can (without limitation) produce sprayer.

Preferably, the spray application is carried out by means of an aerosol can in which the propellant gas is propane, butane and mixtures thereof, or dimethyl ether, or compressed nitrogen, or compressed air.

BRIEF DESCRIPTION OF THE DRAWINGS AND OTHER MATERIALS

In FIG. 1 shows the specification of the anti-icing agent used in the tests.

In FIG. 2 is a photograph of the samples used in the tests.

DETAILED DESCRIPTION OF THE INVENTION

For testing:

- use leather goods Verona 2.3, 9000-N black, grade 2; velor (Leather goods Velor split 3010-Y30R, grade 2, production of Russian Leather JSC);

- deicing agent (Bashkhimprom LLC), corresponding to the specification depicted in FIG. one;

- component A is a bifunctional aminosiloxane of formula (I) in the form of a concentrate solution from a commercially available product sold under the brands BRB 869, WACKER® L 655, XIAMETER OFX-0536, DOW CORNING® 536 FLUID; also, this aminosiloxane is available under the number CAS 69430-37-1;

- component B - the aforementioned fluoropolymer in the form of 19-35 wt.% solution-concentrate in an organic solvent from commercially available products sold under the brands RUCO 1006 ,. RUCO 1016, RUCO 1026, RUCO 1000, RUCO 1010, RUCO 1020, Capstone® LP A, HEXAFOR 6280, HEXAFOR 6282, HEXAFOR 6380, LINEPLUS PDM 180, LINEPLUS PDM 280; the preparation of fluoropolymers of this type is described in US patent No. 3459696, 3491169, 3547856, 3637614, 4100340, 4742140, 5344903, 6479605 and in US applications published under the numbers 20100227173 A1 and 20110200829 A1.

A solution of the anti-icing agent for testing is prepared as follows: 5 grams of anti-icing agent is mixed in 95 milliliters of water at 40 ° C for 1 hour, then filtered and the resulting solution is used in subsequent experiments.

EXAMPLE No. 1

A protective solution is prepared containing 98.5% heptane, 1.5% component B (concentrate solution with a fluoropolymer concentration of 24%, isopropyl acetate solvent) (all percent by weight). A solution of 10 milliliters is placed in a spray made of polyethylene.

Pieces of skin 6 × 6 centimeters in size are treated with a solution from a sprayer by 10-fold (10 taps) spraying from a distance of 10 centimeters.

Treated skin pieces are left for 1 hour at room temperature until the free solvent is completely evaporated, after which the skin pieces are weighed for the first time (m ₀ ).

The surface of a glass plate 18 × 11 centimeters in size, laid horizontally on two supports, which allows you to visually fix the through leakage, is covered with a piece of filter paper, on which a processed piece of skin is placed on top.

A Teflon ring is placed in the center of this skin piece (if necessary, the ring is pressed against the skin surface with a small load for full contact). Inside the ring, as shown in FIG. 2, pour the prepared solution of a salt deicing agent with a volume of 3 milliliters.

Watch the bottom surface of the sample for 2.5 hours, fixing the through-flow time (darkening of the filter paper) - t ₁ (minutes).

The solution remaining on the skin surface is carefully removed using a syringe or pipette, the ring is removed, and if drops of saline remain on the skin surface, they are carefully removed with filter paper, if possible without touching the skin surface.

Following this, a repeated measurement of the mass of a piece of skin is performed (m ₁ ).

The relative weight gain W of the _{saline solution} (in%) is calculated by the formula (1)

The test results are presented in tables No. 1 and 2.

EXAMPLE No. 2

The experiment is carried out in accordance with the method according to example No. 1.

In this case, a protective solution containing (wt.%) Is used:

petroleum ether (T _bale 80 ÷ 400 ° C) 98.5 component B 1,0 component a 0.5

The test results are presented in tables No. 1 and 2.

EXAMPLE No. 3

The experiment is carried out in accordance with the method according to example No. 1.

In this case, a protective solution containing (wt.%) Is used:

petroleum ether (T _bale 80 ÷ 100 ° C) 98.5 component a 1,5

The test results are presented in tables No. 1 and 2.

Solutions containing components A and / or B with the content of these components 3-24% were prepared and tested in a similar way.

Also, for a concentration of 3%, the effect of the ratio of the components of the composition on the protective effect was determined (tables 3 and 4).

Thus, the experimental results show that the combination of components A and B in the composition of the protective composition allows to achieve a better protective effect for leather materials than would be expected from a simple sum of the effects of the individual components taken in the same amount.

LITERATURE

1. Schlicht V. New trends in leather care. // SOFW Journal (2005). V. 131, No. 11, pp. 74-77.

2. Rajeckas V. Leather coatings. In: Coatings Technology Handbook, 3rd Edn., Boca Raton: CRC / Taylor & Francis, 2006, pp. 100-1-100-7.

3. Mallen L., Godefroid L. The benefits of silicones in leather finishing. // World Leather (2004), Feb./March, pp. 31-34.

4. Owen M.J. Why Silicones Behave Funny, Booklet No. 01-3078-01.-USA: Dow Corning Corporation, 2005. - 11 pp.

5. Textiles, Leather & Nonwovens. - Munich (Ger.): Wacker Chemie, 2009 .-- 16 pp.

6. Household Care, Catalog of Products. - Hanau (Ger.): Degussa GmbH, 2007. - 16 pp.

7. Shin-Etsu Silicone Fluids, Booklet. - Tokyo: Shin-Etsu, 2010 .-- 16 pp.

8. New in the technology of fluorine compounds (trans. From Japanese.) ./ Ed. N. Ishikawa. - M .: Mir, 1984, p. 394-422.

9. Kissa E. Fluorinated repellents, in: Fluorinated Surfactants and Repellents (Surfactant Sci. Ser., V. 98), 2nd Edn. -New York: Marcel Dekker, 2001, pp. 516-553.

10. Walters A., Santillo D. Uses of Perfluorinated Substances, Technical Note 06. — Greenpeace Research Laboratories, September 2006. — 20 pp.

11. A new generation of high performance leather protectors. // Leather Intl. (2003) July 15; http://www.leathermag.com.

12. Technologies in Fluorochemical Specialties. Leather, Textile and Carpet Protector Technical Data. - Castelli Calepio, Italy: Maflon / Guarniflon, 2012 .-- 3 pp.

13. US patent No. 5536304 A.

14. European application 1859065 A1.

15. US application published under the number 2011/0287678 A1.

16. Patent of the Russian Federation No. 2390567.

17. WO 2011100546 A1.

Claims (12)

1. A composition for protecting materials from the action of water and / or aqueous solutions, comprising:
a) an organic solvent
b) reactive bifunctional aminosiloxane of formula I
(I) R1-O [-Si (CH ₃ ) ₂ O-] _n [-Si (OR2) (- R11-NH-R11-NH ₂ ) O-] _m R3,
c) a fluoropolymer, which is a polymer and / or copolymer of monomers having the general structural formula (II) to (VI), with the following monomer content based on the total weight of the polymer and / or copolymer (wt.%):
(II) R4-O (CH ₂ ) ₂ R6 40 ÷ 97 (III) R4-OR7 3 ÷ 35 (IV) R4-OR8 0 ÷ 25 (V) R4-NHCH ₂ OH 0 ÷ 15 (VI) CH ₂ = C (R9) Cl 0 ÷ 40,
Where
R1 and R3 independently from each other are CH ₃ —Si (OCH ₃ ) O - [- Si (CH ₃ ) (OR2) O—] _x or methyl,
R2 is an alkyl containing one, two, three or four carbon atoms,
R4 represents a group CH ₂ = C (R5) C (O) -,
R5 represents H or methyl,
R6 is an alkyl containing at least four carbon atoms substituted with one or two fluorine atoms,
R7 represents a straight chain or branched C1-C40 alkyl,
R8 is hydroxy (C2-C4) alkyl,
R9 represents H or Cl,
R11 is alkylene containing two, three, four or five carbon atoms,
x is an integer from 1 to 10,
n is an integer from 10 to 500,
m is an integer from 1 to 50. 2. The composition of claim 1, wherein said reactive bifunctional aminosiloxane has a viscosity of from about 10 to about 100 centistokes. 3. The composition of claim 1, wherein said reactive bifunctional aminosiloxane has a number average molecular weight of from about 1000 to about 50,000 daltons. 4. The composition according to claim 1, in which R6 is an alkyl containing at least eight carbon atoms substituted by fluorine. 5. The composition according to p. 1, in which the total content of the above aminosiloxane and fluoropolymer is from 1 to 24 wt.%, The rest is an organic solvent and, optionally, functional additives. 6. The composition according to claim 1, in which the organic solvent is:
an aliphatic hydrocarbon with a carbon number of 6 to 14,
aromatic hydrocarbon with a number of carbon atoms from 6 to 14,
monohydric alcohol with a number of carbon atoms from 2 to 5,
ester with the number of carbon atoms from 3 to 10,
ether with the number of carbon atoms from 4 to 6,
ketone with a carbon number of 3 to 6
or a mixture of these substances. 7. The use of a composition according to any one of paragraphs. 1-6 to protect the skin from the action of water and / or aqueous solutions. 8. The use of a composition according to claim 7, wherein said skin is natural leather, artificial leather, smooth skin and / or pile skin. 9. The use of a composition according to claim 7, wherein said aqueous solutions are anti-ice reagent solutions. 10. The method of applying the composition according to any one of paragraphs. 1-6, characterized in that it is applied to the skin with a swab, roller, brush or by spraying. 11. The method according to p. 10, in which the spray application is carried out by a sprayer. 12. The method according to p. 10, in which the spray application is carried out by means of an aerosol can, in which the propellant gas is propane, butane and mixtures thereof, or dimethyl ether, or compressed nitrogen or compressed air.

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