WO2008068192A1 - Soil-repellent composition for leather - Google Patents

Soil-repellent composition for leather Download PDF

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Publication number
WO2008068192A1
WO2008068192A1 PCT/EP2007/063050 EP2007063050W WO2008068192A1 WO 2008068192 A1 WO2008068192 A1 WO 2008068192A1 EP 2007063050 W EP2007063050 W EP 2007063050W WO 2008068192 A1 WO2008068192 A1 WO 2008068192A1
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Prior art keywords
carbon atoms
radical
hydrogen
leather
use according
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PCT/EP2007/063050
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French (fr)
Inventor
Thomas Fischer
Hartmut Huber
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Clariant International Ltd
Clariant Finance (Bvi) Limited
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Publication of WO2008068192A1 publication Critical patent/WO2008068192A1/en

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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Definitions

  • the present invention relates to the use of amino -functional organopolysiloxanes for improving the soiling behaviour of leather.
  • a finish usually composed of a plurality of layers and containing binder and additives is applied for protecting the sensitive leather surface. In some cases, however, crusts are also finished only with oils or waxes. If a system composed of a plurality of layers and containing a binder is employed, the uppermost layer referred to as a topcoat has a stronger influence on the physical properties and therefore also on the soiling behaviour than the underlying layers. Additives for reducing the soiling may be introduced into all layers of the finish, but preferably in the topcoat.
  • Aqueous compositions which use amino -functional organopolysiloxanes are known. Such compositions are used, for example, for water-repellent treatment of textile fibres or building materials or as a constituent of cosmetic formulations or care compositions.
  • Aqueous compositions of amino -functional organopolysiloxanes are known to the person skilled in the art in the form of oil- in- water or water-in-oil emulsions. These emulsions may be present in the form of so-called micro- or macroemulsions which as a rule are stabilized by nonionogenic, cationic or amphoteric emulsif ⁇ ers or silicone- polyether copolymer emulsif ⁇ ers.
  • DE 43 28 917 Al describes a process for the preparation of microemulsions based on amino -functional organopolysiloxanes, in which the Case 2006CH001
  • organopolysiloxane 1,3-bis(trimethyl)-2-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butane, 1,3-diol, 1,3-diol, 1,3-dioe, 1,3-butane, 1,3-butanethyl, 1,3-butanethyl, 1,3-butanethyl, 1,3-butanethyl, 1,3-butanethyl, 1,3-butanethyl, 1,3-butanethyl, 1,3-butanethyl, 1,3-butanethyl, 1,3-butanethyl, 1,3-butanethyl
  • Dirt may comprise different compositions having ingredients such as carbon black, oils, ketchup, soft drinks, dyes or cosmetics, depending on the type of substrate considered and the respective sector.
  • ingredients such as carbon black, oils, ketchup, soft drinks, dyes or cosmetics, depending on the type of substrate considered and the respective sector.
  • carbon black, oil and/or dyes are often applied to the leather surface for test purposes.
  • Organo polysiloxanes comprising perfluoro alkyl side chains or perfluoro side groups are known as well their use on different substrates like leather. This described e.g. in DE 196 49 953 Al. DE 196 49 953 Al emphasizes the hydrophobic and the oleophobic effect of the disclosed compounds. However, the hydrophobic thus water repellent effect or the oleophobic thus oil repellent effect may not be regarded as a soil repellent effect which means this treatment does not impart soil repellence. Tests performed regarding to soil release showed no or no substantial improvement of the soil repellence when the leather is finished with those fluorinated compounds and polymers.
  • fluorine chemicals are generally also popularly used but have an undesired hand as a disadvantage and do not meet all requirements of the leather customers in their efficiency. Moreover, fluorine chemicals may not be safe owing to accumulation in animal tissue and harmful effects on health.
  • amino silo xanes amino -functional organopolysiloxanes
  • the invention therefore relates to the use of amino silo xanes for the soil-repellent treatment of leather surfaces wherein the amino siloxanes are linear or branched organopolysiloxanes corresponding to the general formula (I)
  • R ⁇ independently of one another, represent monovalent, saturated and/or unsaturated linear or cyclic hydrocarbon radicals having 1 to 20 carbon.
  • hydrocarbon-oxy groups correspond inter alia to the formulae (-OC2H4-); or (-OC3H5-); or combinations thereof, it being possible for j to assume values between 1 and 50, as in the case of polyethylene glycol or polypropylene glycol groups.
  • aliphatically unsaturated compounds are vinylene, propenyl, butenyl or hexenyl radicals
  • aromatic hydrocarbon radicals are the phenyl radical, alkaryl groups, such as the tolyl radical, or aralkyl radicals, such as the benzyl group.
  • n-alkyl radicals are the methyl, ethyl, butyl and hexyl radical.
  • cycloaliphatic hydrocarbons are the cyclopentyl or cyclohexyl radical
  • isoalkyl radicals are isopropyl or amyl radicals
  • alkyl radicals having tertiary carbon atoms are the tert-butyl and tert-pentyl radical.
  • Short-chain alkyl radicals having 1 to 5 carbon atoms are preferred, particularly preferably methyl or ethyl radicals.
  • R z represents hydrogen, methyl, ethyl or an -OX group, it being possible for X to represent a radical such as, for example, hydrogen, methyl, ethyl, propyl, butyl, amyl and methoxyethyl; methyl and ethyl groups are preferred.
  • R z may also have a nitrogen- containing group having the same meaning as R ⁇ , and w may assume a value between 1 and 3.
  • RN represents a radical of the formula (II)
  • the group or NR 3 ⁇ group it also being possible for the group or NR 3 ⁇ group to be a saturated or partly saturated heterocycle having a ring size of 5 to 10 atoms,
  • n and n independently of one another, may be 1 to 10, and p may assume values of 0, 1 or 2.
  • R3 independently of one another, may be saturated and/or unsaturated, linear and/or cyclic hydrocarbon radicals having 1 to 30 carbon atoms or hydrogen, preferably hydrogen or methyl.
  • R4 may denote hydrogen or hydrocarbon radicals, e.g. n-alkyl radicals having 1 to 20 carbon atoms, such as methyl, ethyl, butyl or hexyl radicals; cycloalkyl radicals; isoalkyl radicals having 3 to 20 carbon atoms, such as isopropyl and amyl radicals, and alkyl radicals having tertiary carbon atoms with a total number of 4 to 20 carbon atoms, such as the tert-butyl and tert-pentyl radical. Hydrogen or an alkyl radical having 1 to 4 carbon atoms is preferred, and hydrogen is very particularly preferred.
  • n-alkyl radicals having 1 to 20 carbon atoms such as methyl, ethyl, butyl or hexyl radicals
  • cycloalkyl radicals isoalkyl radicals having 3 to 20 carbon atoms, such as isopropyl and amyl radicals
  • R N are -(CH 2 )3-NH 2 , -(CH 2 )SNH-C 2 H 4 -NH 2 , -(CH 2 ) 2 -NH 2 , -(CH 2 ) 2 -NH- CH 3 , -(CH 2 ) 4 -NH 2 , -(CH 2 ) 2 -NH- (CH 2 ) 2 -NH-C 4 H 9 , -(CH 2 ) 2 -CH-(CH 3 )-NH-(CH 2 ) 2 - NH 2 , (CH 2 ) 4 -NH-(CH 2 ) 3 -NH-C 2 H 5 , -(CH 2 ) 3 -N(CH 3 )-(CH 2 ) 2 -N(CH 3 ) 2 ,
  • nitrogen-containing radicals can, however, also be those of the following formulae:
  • Preferred radicals are -(CH 2 )SNH-C 2 H 4 -NH 2 , -CH 2 -CH-(CH 3 )-NH-(CH 2 ) 2 -NH 2 and
  • R_5 represents a divalent hydrocarbon radical free of aliphatic multiple bonds and having one to four carbon atoms per radical.
  • amine groups of the aminosiloxanes may be present as amido or imido groups, for example by reacting primary or secondary amines with acid anhydrides or acid chlorides. Furthermore, the aminosiloxanes may be partly quaternized in a suitable manner. For the use according to the invention, the amino -functional groups in the aminosiloxanes can be reacted with organic or inorganic acids in the sense of a protonation to give the corresponding ammonium salts.
  • Organic acids such as acetic acid, oxalic acid, benzoic acid, formic acid, acrylic acid, caproic acid, lauric acid, cyclohexanecarboxylic acid, bromobenzoic acid, nitrobenzoic acid, phthalic acid, maleic acid, oleic acid and phenylacetic acid may be mentioned by way of example for these.
  • inorganic acids which can be used are hydrochloric acid, hydrofluoric acid, sulphuric acid, phosphoric acid, diethyl phosphate and others.
  • Organic acids are preferred, and formic acid and acetic acid are very particularly preferred.
  • aminosiloxanes used according to the invention may also be mixtures of different compounds of the general formula (I), which may also be reactive components which can form a chemical bond with further components.
  • the soiled leather piece is also treated with a cleaning solution, and the effectiveness of the cleaning is once again assessed using the grey scale.
  • the exact mode of action of the aminosiloxanes is not known.
  • the siloxane can form a layer between finish and test fabric, which layer firstly changes the coefficient of friction and secondly prevents direct contact of the soil with the leather surface so that there is no migration of the soil into the surface of the finish.
  • an amino -functionalized siloxane shows an improvement with regard to non-soiling through a possible interaction of the amino functionality with the soil or the surface of the finished leather.
  • incorporación of the aminosiloxane into the finish, preferably the topcoat results in a certain permanence, so that the incorporated silicone offers long-term protection for the leather end product.
  • a part of the aminosiloxane is also chemically bonded by the crosslinking agents usually used in the topcoat, so that furthermore, a more or less significant amount of aminosiloxane may be present on the leather even after the leather has been used for a certain time or after a cleaning step.
  • the use, according to the invention, of the silicones or silicone emulsions and particularly the aminosiloxanes or emulsions thereof can be effected by adding an aminosiloxane formulation to a formulation corresponding to the prior art, particularly a topcoat formulation.
  • the aminosiloxane can be used in the form of a compound which is water-soluble or soluble in a cosolvent (for example as alkoxylated aminosiloxane), in a form dispersible in water with or without cosolvent or in the form of a micro- or macroemulsion.
  • the amount used depends on the concentration in the chosen form for use, the requirements which the leather end product has to meet and the method of application.
  • the aminosiloxane is added in an amount of 1 to 500, in particular 5 to 300 and very particularly 20 to 200 parts by weight, based on a formulation with 1000 parts by weight. It is known to the person skilled in the art that the addition of the aminosiloxane to the topcoat leads to a change in the properties of Case 2006CH001
  • the topcoat and hence of the finish which change may be limited by a corresponding variation of the formulation.
  • the aminosiloxane can also be used as a so-called overspray solution in the abovementioned application forms.
  • a further layer which is characterized in its function in particular by a high content of aminosiloxane is applied to the finish in addition to the topcoat.
  • the aminosiloxane can be used alone in its various application forms, diluted with water or as a mixture with binders, matting agents, crosslinking agents or further additives customary in finishing.
  • the hand of the leather is influenced compared with an identically finished leather. Since the assessment of the hand is a very subjective matter, this change may be rated as being positive or negative depending on the assessment.
  • the aminosiloxane can also be changed by chemical modification.
  • the emulsif ⁇ ability and the antisoiling properties also change as a result of the chemical modification. Reactive groups such as, for example, compounds having epoxy, isocyanate, acid anhydride and acid chloride groups are to be regarded as groups suitable for the chemical modification. Depending on the conversion of the amino groups between 0 and 1, the properties of the aminosiloxane can be changed in a targeted manner.
  • the invention relates therefore also to a process characterized in that leather is treated with the aminosiloxane formulation according to the invention wherein the appliocation parameters are given above and wherein the leather is rendered soil repellent.
  • the amino silo xanes and comparative compounds were tested on leather by mixing the substances to be tested either additionally in the topcoat or as an overspray solution or both on a leather bottomed in a pale shade.
  • For the topcoat 200 parts of Aqualen® Top D-2018.A, 90 parts of Aqualen® Top 2007.A, 30 parts of Melio® LV-03, 340 parts of water and 60 parts of Aqualen® IW-80.A are mixed.
  • This topcoat formulation (Topi) serves, without addition of further additives, as a reference for soiling tests.
  • silicone emulsions aminosiloxanes or fluorocarbons (table 1), topcoats with reduced soiling are obtained (table 2).
  • Suparex® DE05 is an aqueous silicone oil emulsion
  • Melio® 09-F-20 is an aqueous mixture of polyurethane and siloxane
  • Melio® 09-F-41 is an aqueous aminosiloxane emulsion
  • Bavon® Oil WR-600 is an organic mixture based on an aminosiloxane.
  • Nuva® 2110 and Nuva® HPC are aqueous solutions of a resins with perfluoro alkyl groups.
  • the leathers thus finished were tested for their soiling behaviour on a Martindale tester with standardized test fabric 104 of the Eidgen ⁇ ssische Materialpruf GmbH (EMPA,
  • the degree of soiling can be substantially reduced by the use of amino silo xanes in Top4 and Top5, whereas a silicone emulsion free of amino functionality, as in Top2, leads only to a slight improvement.
  • the use of additives with perfluoro alkyl groups leads only to a small improvement of soil resistance.

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  • Organic Chemistry (AREA)
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  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

The present invent ion relates to the use of amino-funct ional organopolysilo xanes for improving the so iling behaviour of leather, the active substance preferably being used in the topcoat or as an overspray so lut ion. By chemical modificat ion with react ive groups, the properties o f the amino-funct ional organopolysilo xane can be adjusted in a targeted manner.

Description

SOIL-REPELLENT COMPOSITION FOR LEATHER
The present invention relates to the use of amino -functional organopolysiloxanes for improving the soiling behaviour of leather.
The soiling of leather and leather articles is highly dependent on the colouring. While no problems with soiling occur in the case of black leather, as leather is predominantly finished, this becomes an increasingly great problem in the case of lighter shades. Improvements in this respect can be achieved by a special choice of the polymeric binders and matting components used for the finishing, as is sufficiently well known to the person skilled in the art. A further improvement of the formulation can be achieved by the addition of additives.
In the finishing of crusts (tanned leathers), a finish usually composed of a plurality of layers and containing binder and additives is applied for protecting the sensitive leather surface. In some cases, however, crusts are also finished only with oils or waxes. If a system composed of a plurality of layers and containing a binder is employed, the uppermost layer referred to as a topcoat has a stronger influence on the physical properties and therefore also on the soiling behaviour than the underlying layers. Additives for reducing the soiling may be introduced into all layers of the finish, but preferably in the topcoat.
Aqueous compositions which use amino -functional organopolysiloxanes are known. Such compositions are used, for example, for water-repellent treatment of textile fibres or building materials or as a constituent of cosmetic formulations or care compositions. Aqueous compositions of amino -functional organopolysiloxanes are known to the person skilled in the art in the form of oil- in- water or water-in-oil emulsions. These emulsions may be present in the form of so-called micro- or macroemulsions which as a rule are stabilized by nonionogenic, cationic or amphoteric emulsifϊers or silicone- polyether copolymer emulsifϊers.
Thus, for example, DE 43 28 917 Al describes a process for the preparation of microemulsions based on amino -functional organopolysiloxanes, in which the Case 2006CH001
2 components organopolysiloxane, emulsifier, water, optionally co-surfactant and optionally acid are combined in any desired sequence and mixed.
The use of such emulsions of amino -functional organopolysiloxanes on leather is also described, as, for example, in DE 10 2004 040 266 Al. Here, however, only the use of amino -functional organopolysiloxanes with regard to hydrophobing of the leather surface for prolonging the time taken for a water drop applied to the surface to penetrate into the interior of the leather is investigated. The hydrophobing is the water-repellent property of a surface, so that said surface or substrate is not moistened. In comparison, the property of non-soiling relates to the ability of a surface to prevent soil from adhering or to avoid being stained or otherwise impaired by the soil. Dirt may comprise different compositions having ingredients such as carbon black, oils, ketchup, soft drinks, dyes or cosmetics, depending on the type of substrate considered and the respective sector. In the leather sector, carbon black, oil and/or dyes are often applied to the leather surface for test purposes.
Organo polysiloxanes comprising perfluoro alkyl side chains or perfluoro side groups are known as well their use on different substrates like leather. This described e.g. in DE 196 49 953 Al. DE 196 49 953 Al emphasizes the hydrophobic and the oleophobic effect of the disclosed compounds. However, the hydrophobic thus water repellent effect or the oleophobic thus oil repellent effect may not be regarded as a soil repellent effect which means this treatment does not impart soil repellence. Tests performed regarding to soil release showed no or no substantial improvement of the soil repellence when the leather is finished with those fluorinated compounds and polymers. Additionally, also in other technical areas the hydrophobic or oleophobic treatment is not imparting soil repellence. Facade elements with hydrophobic treatment are soiled more easily and the water repellence additives were identified causing this problem by causing more stickyness of the surface (see E. Bagda, A. Ulgen; Farbe und Lack, 112 (2006) S. 36-42). No correlation between the oil repellence and soil repellence was shown for textiles as well (see T. F. Cooke, Textile Chemist and Colorist, 19 (1987), S. 31-41). This missing correlation between the hydrophobic and/or oleophobic effect compared with the soil repellence is also shown in this application (see the examples Top6 and Top7). Case 2006CH001
In the soil-repellent finish, fluorine chemicals are generally also popularly used but have an undesired hand as a disadvantage and do not meet all requirements of the leather customers in their efficiency. Moreover, fluorine chemicals may not be safe owing to accumulation in animal tissue and harmful effects on health.
Thus, there was still a need for providing leather with a dirt-repellent finish without disadvantageous effects on the performance characteristics.
It has now been found that a surprisingly substantial reduction in soiling is achieved by the use of amino -functional organopolysiloxanes (referred to below as amino silo xanes), particularly if they are used in the topcoat or in an additional layer.
The invention therefore relates to the use of amino silo xanes for the soil-repellent treatment of leather surfaces wherein the amino siloxanes are linear or branched organopolysiloxanes corresponding to the general formula (I)
R2wRl3-wSi-O-[SiR12-O]x[SiR1RNθ]y-[SiR1QO]z-SiR1 3-wR2 w (I)
Here, R^, independently of one another, represent monovalent, saturated and/or unsaturated linear or cyclic hydrocarbon radicals having 1 to 20 carbon. Examples of hydrocarbon-oxy groups correspond inter alia to the formulae (-OC2H4-); or (-OC3H5-); or combinations thereof, it being possible for j to assume values between 1 and 50, as in the case of polyethylene glycol or polypropylene glycol groups. Examples of aliphatically unsaturated compounds are vinylene, propenyl, butenyl or hexenyl radicals, and examples of aromatic hydrocarbon radicals are the phenyl radical, alkaryl groups, such as the tolyl radical, or aralkyl radicals, such as the benzyl group. Examples of n-alkyl radicals are the methyl, ethyl, butyl and hexyl radical. Examples of cycloaliphatic hydrocarbons are the cyclopentyl or cyclohexyl radical, examples of isoalkyl radicals are isopropyl or amyl radicals and examples of alkyl radicals having tertiary carbon atoms are the tert-butyl and tert-pentyl radical. Case 2006CH001
4
Short-chain alkyl radicals having 1 to 5 carbon atoms are preferred, particularly preferably methyl or ethyl radicals.
Rz represents hydrogen, methyl, ethyl or an -OX group, it being possible for X to represent a radical such as, for example, hydrogen, methyl, ethyl, propyl, butyl, amyl and methoxyethyl; methyl and ethyl groups are preferred. Rz may also have a nitrogen- containing group having the same meaning as R^, and w may assume a value between 1 and 3.
RN represents a radical of the formula (II)
-(CR32)m - [NR3k - (CR32)n]p - NR3 jR4 (II)
it also being possible for the
Figure imgf000005_0001
group or NR3 \ group to be a saturated or partly saturated heterocycle having a ring size of 5 to 10 atoms,
and Q represents a radical of the formula (III)
-(CR32)m " [NR3 - (CR32)n]p - NR3 - (CR3 2)m-*Si (III)
or of the formula (IV)
-(CR3 2)m - N[ - (CR32)n - NR3]p -*Si (IV)
*Si representing an intermolecular or intramolecular linkage point to a molecule of the general formula (I). Examples of Q are -(CH2)3-NH-(CH2)2-NH-(CH2)3- and
CH2CH(CH3)CH2-NH-(CH2^-NH-CH2CH(CH3)CH2-. The values for x, y and z are chosen so that the amine content is 0.01 to 20 meq/g (milliequivalent per g of aminosiloxane), i.e. 1 g of aminosiloxane consumes 0.01 to 20 ml of 1 molar hydrochloric acid in an acid/base titration, and the viscosity at 250C is in the range of 20 to 1 000 000 mPa-s. The value for z is either 0 or so great that on average less than one Case 2006CH001
5 linkage point is present per aminosiloxane molecule. The values for k and 1, independently of one another, may be 0, 1 or 2.
The values for m and n, independently of one another, may be 1 to 10, and p may assume values of 0, 1 or 2.
R3, independently of one another, may be saturated and/or unsaturated, linear and/or cyclic hydrocarbon radicals having 1 to 30 carbon atoms or hydrogen, preferably hydrogen or methyl.
R4 may denote hydrogen or hydrocarbon radicals, e.g. n-alkyl radicals having 1 to 20 carbon atoms, such as methyl, ethyl, butyl or hexyl radicals; cycloalkyl radicals; isoalkyl radicals having 3 to 20 carbon atoms, such as isopropyl and amyl radicals, and alkyl radicals having tertiary carbon atoms with a total number of 4 to 20 carbon atoms, such as the tert-butyl and tert-pentyl radical. Hydrogen or an alkyl radical having 1 to 4 carbon atoms is preferred, and hydrogen is very particularly preferred.
Examples of RN are -(CH2)3-NH2, -(CH2)SNH-C2H4-NH2, -(CH2)2-NH2, -(CH2)2-NH- CH3, -(CH2)4-NH2, -(CH2)2-NH- (CH2)2-NH-C4H9, -(CH2)2-CH-(CH3)-NH-(CH2)2- NH2, (CH2)4-NH-(CH2)3-NH-C2H5, -(CH2)3-N(CH3)-(CH2)2-N(CH3)2,
-(CH2)2CH(CH3)-NH-(CH2)4-NH2, -(CH2)2CH(CH3)-NH-(CH2)2-NH-C4H9, -CH2- CH-(CH3)-NH-(CH2)2-NH2.
Examples of nitrogen-containing radicals can, however, also be those of the following formulae:
O N-R5- N-R5-
Figure imgf000006_0001
Case 2006CH001
O NH
HC
Preferred radicals are -(CH2)SNH-C2H4-NH2, -CH2-CH-(CH3)-NH-(CH2)2-NH2 and
Figure imgf000007_0001
R_5 represents a divalent hydrocarbon radical free of aliphatic multiple bonds and having one to four carbon atoms per radical.
Some of the amine groups of the aminosiloxanes may be present as amido or imido groups, for example by reacting primary or secondary amines with acid anhydrides or acid chlorides. Furthermore, the aminosiloxanes may be partly quaternized in a suitable manner. For the use according to the invention, the amino -functional groups in the aminosiloxanes can be reacted with organic or inorganic acids in the sense of a protonation to give the corresponding ammonium salts. Organic acids, such as acetic acid, oxalic acid, benzoic acid, formic acid, acrylic acid, caproic acid, lauric acid, cyclohexanecarboxylic acid, bromobenzoic acid, nitrobenzoic acid, phthalic acid, maleic acid, oleic acid and phenylacetic acid may be mentioned by way of example for these. Examples of inorganic acids which can be used are hydrochloric acid, hydrofluoric acid, sulphuric acid, phosphoric acid, diethyl phosphate and others.
Organic acids are preferred, and formic acid and acetic acid are very particularly preferred.
The aminosiloxanes used according to the invention may also be mixtures of different compounds of the general formula (I), which may also be reactive components which can form a chemical bond with further components.
There is no uniform standard for the soiling of a leather. Especially in the automotive Case 2006CH001
7 sector, there are numerous standards of various automobile manufacturers from which the respective specifications can be taken. In many cases, test fabrics with a standardized amount of soil are moved on a special test machine, the so-called Martindale, over the leather surface. By comparison with a greyscale, the degree of soiling compared with an unsoiled surface of the leather is rated on a scale from 1
(strongly soiled) to 5 (no soiling). In some cases, the soiled leather piece is also treated with a cleaning solution, and the effectiveness of the cleaning is once again assessed using the grey scale. The exact mode of action of the aminosiloxanes is not known. Possibly, the siloxane can form a layer between finish and test fabric, which layer firstly changes the coefficient of friction and secondly prevents direct contact of the soil with the leather surface so that there is no migration of the soil into the surface of the finish. Compared with a non-functionalized siloxane, an amino -functionalized siloxane shows an improvement with regard to non-soiling through a possible interaction of the amino functionality with the soil or the surface of the finished leather. Incorporation of the aminosiloxane into the finish, preferably the topcoat, results in a certain permanence, so that the incorporated silicone offers long-term protection for the leather end product. A part of the aminosiloxane is also chemically bonded by the crosslinking agents usually used in the topcoat, so that furthermore, a more or less significant amount of aminosiloxane may be present on the leather even after the leather has been used for a certain time or after a cleaning step.
The use, according to the invention, of the silicones or silicone emulsions and particularly the aminosiloxanes or emulsions thereof can be effected by adding an aminosiloxane formulation to a formulation corresponding to the prior art, particularly a topcoat formulation. The aminosiloxane can be used in the form of a compound which is water-soluble or soluble in a cosolvent (for example as alkoxylated aminosiloxane), in a form dispersible in water with or without cosolvent or in the form of a micro- or macroemulsion. The amount used depends on the concentration in the chosen form for use, the requirements which the leather end product has to meet and the method of application. In general, the aminosiloxane is added in an amount of 1 to 500, in particular 5 to 300 and very particularly 20 to 200 parts by weight, based on a formulation with 1000 parts by weight. It is known to the person skilled in the art that the addition of the aminosiloxane to the topcoat leads to a change in the properties of Case 2006CH001
8 the topcoat and hence of the finish, which change may be limited by a corresponding variation of the formulation. In addition to or instead of a use in the topcoat, the aminosiloxane can also be used as a so-called overspray solution in the abovementioned application forms. A further layer which is characterized in its function in particular by a high content of aminosiloxane is applied to the finish in addition to the topcoat. Here, the aminosiloxane can be used alone in its various application forms, diluted with water or as a mixture with binders, matting agents, crosslinking agents or further additives customary in finishing.
If relatively large amounts of an aminosiloxane formulation are used in the topcoat or especially as an overspray solution, the hand of the leather is influenced compared with an identically finished leather. Since the assessment of the hand is a very subjective matter, this change may be rated as being positive or negative depending on the assessment. In addition to the addition of further additives influencing the hand (so- called hand agents) the aminosiloxane can also be changed by chemical modification. In addition to the hand, the emulsifϊability and the antisoiling properties also change as a result of the chemical modification. Reactive groups such as, for example, compounds having epoxy, isocyanate, acid anhydride and acid chloride groups are to be regarded as groups suitable for the chemical modification. Depending on the conversion of the amino groups between 0 and 1, the properties of the aminosiloxane can be changed in a targeted manner.
The invention relates therefore also to a process characterized in that leather is treated with the aminosiloxane formulation according to the invention wherein the appliocation parameters are given above and wherein the leather is rendered soil repellent.
The following examples are intended to explain the present invention in more detail. Unless stated otherwise, "parts" are to be understood as meaning "parts by weight". Case 2006CH001
EXAMPLES
The amino silo xanes and comparative compounds were tested on leather by mixing the substances to be tested either additionally in the topcoat or as an overspray solution or both on a leather bottomed in a pale shade. For the topcoat, 200 parts of Aqualen® Top D-2018.A, 90 parts of Aqualen® Top 2007.A, 30 parts of Melio® LV-03, 340 parts of water and 60 parts of Aqualen® IW-80.A are mixed. This topcoat formulation (Topi) serves, without addition of further additives, as a reference for soiling tests. By addition of silicone emulsions, aminosiloxanes or fluorocarbons (table 1), topcoats with reduced soiling are obtained (table 2).
Table 1:
Figure imgf000010_0001
Suparex® DE05 is an aqueous silicone oil emulsion, Melio® 09-F-20 is an aqueous mixture of polyurethane and siloxane, and Melio® 09-F-41 is an aqueous aminosiloxane emulsion. Bavon® Oil WR-600 is an organic mixture based on an aminosiloxane. Nuva® 2110 and Nuva® HPC are aqueous solutions of a resins with perfluoro alkyl groups.
The leathers thus finished were tested for their soiling behaviour on a Martindale tester with standardized test fabric 104 of the Eidgenόssische Materialprufanstalt (EMPA,
Swiss Federal Laboratories for Materials Testing and Research). On the Martindale the finished leather to be tested and the test fabric are each clamped in a holder and the holder with the test fabric is then moved in a defined manner on the leather test specimen (1000 cycles). By comparison with a greyscale, the degree of soiling compared with an unsoiled surface of the leather is rated on a scale from 1 (strongly Case 2006CH001
10 soiled) to 5 (no soiling) (table 2).
Table 2:
Figure imgf000011_0001
As can be seen in table 2, the degree of soiling can be substantially reduced by the use of amino silo xanes in Top4 and Top5, whereas a silicone emulsion free of amino functionality, as in Top2, leads only to a slight improvement. The use of additives with perfluoro alkyl groups leads only to a small improvement of soil resistance.

Claims

Case 2006CH00111 CLAIMS
1. Use of amino silo xanes for the soil-repellent treatment of leather surfaces characterized in that the amino silo xanes are linear or branched organopolysiloxanes of the general formula (I)
R2wRl3-wSi-O-[SiR12-O]x[SiR1RNθ]y-[SiR1QO]z-SiR1 3-wR2 w (I)
in which Rl, independently of one another, denote monovalent, saturated and/or unsaturated linear or cyclic hydrocarbon radicals having 1 to 20 carbon atoms or aryl radicals having 6 to 20 carbon atoms or hydrocarbon-oxy groups
R% independently of one another, denote R^, hydrogen or an -OX group, X being hydrogen, methyl, ethyl, propyl, butyl, amyl or methoxyethyl,
RN, independently of one another, are a radical of the formula (II)
-(CR32)m - [NR3k - (CR32)n]p - NR3 jR4 (II)
it also being possible for the
Figure imgf000012_0001
group or NR3 \ group to be a saturated or partly saturated heterocycle having a ring size of 5 to 10 atoms,
R3, independently of one another, are saturated and/or unsaturated, linear and/or cyclic hydrocarbon radicals having 1 to 30 carbon atoms or hydrogen,
R4 is hydrogen, an alkyl radical having 1 to 20 carbon atoms, an isoalkyl radical having 3 to 20 carbon atoms or an alkyl radical having tertiary carbon atoms with a total number of 4 to 20 carbon atoms,
Q is a radical of the formula (III)
-(CR32)m - [NR3 - (CR32)n]D - NR3 - (CR3 2)m-*Si (III) Case 2006CH001
12
or of the formula (IV)
-(CR32)m - N[ - (CR32)n - NR3]p -*Si (IV)
*Si representing an intermolecular or intramolecular linkage point to a molecule of the general formula (I), k, 1 and p, independently of one another, are 0, 1 or 2, m and n, independently of one another, are a number from 1 to 10, w has a value of 1 to 3, and x, y and z are chosen so that the amine content is 0.01 to 20 meq/g of aminosiloxane.
2. Use according to Claim 1, characterized in that
RI is an alkyl radical having 1 to 5 carbon atoms,
R^ is a methyl or ethyl radical,
RN is -(CH2)SNH-C2H4-NH2, -CH2-CH-(CH3)-NH-(CH2)2-NH2 or
Figure imgf000013_0001
R^ is hydrogen or a methyl radical, and
R^ is hydrogen or an alkyl radical having 1 to 4 carbon atoms.
3. Use according to Claim 2, characterized in that RI is a methyl or ethyl radical,
Rz is a methyl or ethyl radical, RN is -(CH2)3NH-C2H4-NH2, -CH2-CH-(CH3)-NH-(CH2)2-NH2 or Case 2006CH001
13
Figure imgf000014_0001
R^ is hydrogen and R4 is hydrogen.
4. Use according to Claims 1 to 3, characterized in that the amino silo xanes are chemically modified with reactive groups selected from epoxy, isocyanate, acid anhydride and acid chloride groups.
5. Use according to Claims 1 to 4, characterized in that the use of the aminosiloxanes takes place in the topcoat or as an overspray solution.
6. Use according to Claims 1 to 5, characterized in that the aminosiloxanes are used in the form of a compound which is water-soluble or soluble in a cosolvent or as an aqueous dispersion or emulsion.
7. Use according to Claims 1 to 6, characterized in that the aminosiloxanes are used in a concentration of 2 to 20% by weight, based on the total formulation, in the topcoat formulation or up to 100% by weight in the overspray solution.
8. Use according to Claims 1 to 7, characterized in that further additives from the group consisting of the hand agents, matting agents and other additives are used in addition to the aminosiloxanes.
PCT/EP2007/063050 2006-12-04 2007-11-30 Soil-repellent composition for leather WO2008068192A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111349382A (en) * 2018-12-24 2020-06-30 贝内克-长顺汽车内饰材料（张家港）有限公司 Artificial leather treatment agent and artificial leather obtained therefrom

Citations (3)

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Publication number Priority date Publication date Assignee Title
DE4240274A1 (en) * 1992-12-01 1994-06-09 Minnesota Mining & Mfg Polysiloxanes with fluoroaliphatic and carboxyl-containing terminal groups, their preparation and their use in the treatment of fibrous substrates
DE19649953A1 (en) * 1996-12-03 1998-06-04 Huels Chemische Werke Ag Fluoroalkyl-functional organopolysiloxane-containing water-based compositions, processes for their preparation and their use
DE102004040266A1 (en) * 2004-08-19 2006-02-23 Wacker-Chemie Gmbh Oil-in-water emulsions of aminosiloxanes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4240274A1 (en) * 1992-12-01 1994-06-09 Minnesota Mining & Mfg Polysiloxanes with fluoroaliphatic and carboxyl-containing terminal groups, their preparation and their use in the treatment of fibrous substrates
DE19649953A1 (en) * 1996-12-03 1998-06-04 Huels Chemische Werke Ag Fluoroalkyl-functional organopolysiloxane-containing water-based compositions, processes for their preparation and their use
DE102004040266A1 (en) * 2004-08-19 2006-02-23 Wacker-Chemie Gmbh Oil-in-water emulsions of aminosiloxanes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111349382A (en) * 2018-12-24 2020-06-30 贝内克-长顺汽车内饰材料（张家港）有限公司 Artificial leather treatment agent and artificial leather obtained therefrom

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