WO2011147959A2 - Hydrophobizing of fibrous materials with polyorganosiloxanes - Google Patents

Hydrophobizing of fibrous materials with polyorganosiloxanes Download PDF

Info

Publication number
WO2011147959A2
WO2011147959A2 PCT/EP2011/058720 EP2011058720W WO2011147959A2 WO 2011147959 A2 WO2011147959 A2 WO 2011147959A2 EP 2011058720 W EP2011058720 W EP 2011058720W WO 2011147959 A2 WO2011147959 A2 WO 2011147959A2
Authority
WO
WIPO (PCT)
Prior art keywords
polyorganosiloxane
group
use according
composition
leather
Prior art date
Application number
PCT/EP2011/058720
Other languages
French (fr)
Other versions
WO2011147959A3 (en
Inventor
John Huggins
Roland Wagner
Karl-Heinz Sockel
Original Assignee
Momentive Performance Materials Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Momentive Performance Materials Gmbh filed Critical Momentive Performance Materials Gmbh
Priority to CN201180036896.3A priority Critical patent/CN103038274B/en
Priority to KR1020127033940A priority patent/KR101875237B1/en
Priority to EP20110721556 priority patent/EP2576660B1/en
Priority to US13/699,051 priority patent/US8778457B2/en
Publication of WO2011147959A2 publication Critical patent/WO2011147959A2/en
Publication of WO2011147959A3 publication Critical patent/WO2011147959A3/en

Links

Classifications

    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-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
    • 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
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6433—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing carboxylic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to waterproofing agents based on specific polyorganosiloxanes with polar functional groups for the treatment of materials having a fibrous structure, in particular natural fibers, such as found in leather, furs, textiles and paper.
  • the invention further relates to a process for treating fibrous materials with waterproofing agents containing specific polyorganosiloxanes with polar functional groups. Owing to the durable fixation of polyorganosiloxanes with specific polar functional groups to natural fibers, the inventive waterproofing agents provide long-lasting hydrophobic treatment desired in uses such a shoewear, clothing or furnishings.
  • GB 1005475 discloses a fatliquoring salt composition of a hydroxylated
  • WO 95/30028 propose the use of organofunctional polyorganosiloxanes having OH, SH, NH groups for leather treatment. They disclose compositions of polydimethylsiloxanes and C18-alkyl-polyethers having carboxylic groups neutralized with sodium hydroxide.
  • WO 03/64707 discloses compositions comprising polycarboxylic acids, carboxy functional polysiloxanes, N-olelysarcosine, oleylether carboxylic acids and others.
  • EP213480 discloses compositions of emulsions for leather waterproofing wherein siloxanes have mercapto functional groups and emuisifiers are selected from the group of alkylacyl-aminoacids and its salts.
  • the organofunctional siloxanes claimed comprise amino, sulfido and carboxy functional groups.
  • EP638128 describes leather waterproofing with siloxanes with organofunctional sulfosuccinate groups.
  • EP745141 describes leather waterproofing with emulsions of siloxanes with
  • organofunctional carboxy groups whereby the carboxy groups are separated from the siloxane backbone by a C5 - C25 organic spacer group.
  • EP 938590 describes leather waterproofing with carboxyamid-functional
  • EP1087021 describes leather waterproofing with an organic oil or wax, a
  • EP1 108765 describes leather waterproofing with emulsions of specific organofunctional siloxanes with carboxy groups.
  • EP1470258 describes leather waterproofing with an organic oil, an organofunctional siloxane, an anionic surfactant and an organic acid.
  • EP 1416057 describes Chromium-free tanning and fatliquoring of leather with organofunctional siloxanes, including carboxyfunctional siloxanes.
  • EP 0356963 discloses siloxane compounds terminated with the diol at one end thereof. These siloxane compounds are used as comonomers where the hydroxy groups react for example with isocyanate or carboxylic groups to obtain siloxane modified
  • hydroxyalkyloxyalkylsiloxanes useful as stabiliser of polyurethane foams.
  • EP 101 0748 discloses diesel fuel defoamer compositions, comprising mixtures of silicons, including hydrosilation reaction product of SiH silicon and trimethylol propane monoallylether.
  • waterproofing leather need allow for uniform dyeing, little loss of firmness, and good water vapor permeability.
  • Leather used in footwear needs to exhibit dynamic water resistance as tested by the method of Maeser.
  • Many of the proposed agents leave an oily film on the leather surface or lead to significant loss of firmness or a too soft hand.
  • many of the proposed agents form emulsions with marginal stability, often leading to a non-uniform treatment of the substrate and other problems in the application of these materials. It is particularly desirable in the field that waterproofing agents be stable to heat and freezing.
  • processes for treatment of fibrous materials involve aqueous treatment baths or floats that have a pH of 4 to 7, in particular a pH of 5 to 6.
  • the preferred waterproofing agent should be stable to dilution in excess water in this pH range.
  • polyorganosiloxanes with 1 ,3-dihydroxyalkyl functional groups on Si-C-bonded hydrocarbon radicals are especially effective waterproofing agents for fibers, pulps, leather and a wide variety of other fibrous materials.
  • these polyorganosiloxanes could be formulated to give emulsions that are highly stable to heat, freezing and dilution in water at pH 5 to 6.
  • combining the inventive polyorganosiloxane with 1 ,3-dihydroxyalkyl functional groups with even minor proportions of polyorganosiloxanes with specific polar functional groups can produce hydrophobic articles with highly durable waterproofing in fiber, pulp, or leather treatment processes.
  • the present invention provides a novel use of ac polyorganosiloxane a) comprising at least one 1 ,3-dihydroxy alkyl moiety in the treatment of fibrous substrates.
  • said polyorganosiloxane a) is used in an aqueous composition, in particular, in an aqueous emulsion.
  • the fibrous substrates are preferably selected from leather, furs or leather substitutes, for example, natural or artificial leather, alcantara (ultrasuede).
  • the polyorganosiloxane a) may have the formula:
  • R is an organic group, with the requirement that R comprises at least one group R 1 comprising dihydroxy alkyl moiety.
  • the 1 ,3-dihydroxy alkyl moiety is in particular a group shown by of the formula:
  • the dotted line is the free valence of the group to the rest of molecule
  • the group R* may represent one or more organic substituent groups, preferably with up to 20 carbon atoms, and optionally comprising one or more hetero atoms, attached to any carbon atom of said 1 ,3-dihydroxy alkyl moiety.
  • the 1 ,3-dihydroxy alkyl moiety according to the invention usually does not include alkyl moieties having an additional hydroxyl substituent at the ⁇ -carbon atom, that is, at the carbon atom between the 1 ,3-position, i.e. having an 1 ,2,3-trihydroxyalkyl moiety.
  • R d to C 2 2-alkyl, fluoroalkyl or aryl
  • R 1 is an organic group bound via a carbon atom to the silicon atom, comprising dihydroxy alkyl moiety
  • polysiloxanes having linear polydiorganosiloxane backbones formed of D units that is, preferred are polysiloxanes having linear polydiorganosiloxane backbones formed of D units.
  • polyorganosiloxane a) is selected from polyorganosiloxanes having pendant and/or terminal 1 ,3-dihydroxy alkyl moieties. This means that the 1 ,3-dihydroxy alkyl moieties are attached either to the terminal units M or chain-forming units D and T, preferably D.
  • the polyorganosiloxane a) is selected from linear polyorganosiloxanes having terminal ,3-dihydroxy alkyl moieties.
  • the 1 ,3-dihydroxy alkyl moiety is preferably a group of the formula:
  • A is a di- or trivalent organic residue having up to 30, preferably up to 20 carbon atoms bound to a silicon atom of the polyorganosiloxane moiety via a carbon atom
  • B is an optionally substituted 1 ,3-dihydroxypropanyl moiety bound to the group A having the above indicated formula: , wherein R * is as defined above.
  • R* includes preferably an optionally substituted alkyl group with 1 to 6 carbon atoms, wherein optional substituents include in particular 1 to 3 three groups, selected for example from hydroxy, for example R * is methyl, ethyl, hydroxymethyl etc..
  • the di- or trivalent, preferably trivalent organic residue having up to 20 carbon atoms A includes linear, branched and/or cyclic, saturated, unsaturated and/or aromatic organic residues which may comprise one or more hetero atoms, selected from N, O, S, and P.
  • linking groups A include saturated hydrocarbon groups, optionally comprising one to three ether groups (-0-) for example -CH z O-CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 -0-CH 2 - -CH 2 CH 2 CH 2 NH-CH 2 -, or
  • Preferred 1 ,3-dialkyl moieties B include for example:
  • linking groups A include for example:
  • ** indicates the bond to the silicone atom of the polyorganosiloxane backbone and * denotes the bond to the 1 ,3-dihydroxy alkyl moiety B.
  • a is 0 to 3, preferably 0 or 1 , x is 0 to 1000, preferably 10 to 1000, y is O to 100, x+y is 0 to 1 100, preferably 10 to 1000, a + y is > 1 ,
  • a and B are as defined above,
  • R is an organic group having up to 25 carbon atoms.
  • polyorganosiloxane a) is of the general formula:
  • R 3-a A. 3-a wherein a is 0 or 1 ,
  • x 10 to 1000
  • y is 0 to 100
  • x+y is 10 to 1 100
  • A is a divalent optionally substituted organic radical with up to 20 carbon atoms that can contain one or more groups such as, optionally substituted aromatic moieties, such as optionally alkoxy and/or hydroxy substituted phenylene, -0-, -NR'-, -CH 2 -CH(OH)-CH 2 -, -C(0)NR'-, -0-C(0)NR'-, -C(O)-, -C(0)0-, and the like, and R' is hydrogen, an alkyl or alkylaryl group with up to 18 carbon atoms,
  • B radical is any organic radical with two or more hydroxy groups wherein at least two such hydroxy groups are positioned 1 ,3 to another, as explained above,
  • R is an organic group having up to 25 carbon atoms.
  • Preferred examples of -A-(B), are:
  • polyorganosiloxanes with pendant and/or terminal quaternary ammonium functional groups are also preferred.
  • the Si-C-bonded hydrocarbon radicals with quaternary ammonium functional groups in component b) preferable include organic groups with up to 40 carbon atoms, containing at least one quaternary ammonium group and optionally containing one or more heteroatoms selected from N, S, O and P.
  • R is an organic group having up to 25 carbon atoms, preferably methyl.
  • An is a organic or inorganic anion, like a carboxylate anion, halogen anion, preferably Cl “ , Br " , sulfate anion, sulfonate anion, phosphate, nitrate, perchlorate, and x and y are as defined above.
  • polyorganosiloxanes b) with polar functional groups wherein the functional groups are amide, carboxy or sulfosuccinate groups, including by reference the functional polyorganosiloxanes cited in US 7,250,456 (pg. 2, line 56 to pg. 3, line 55), EP1 108765 (pg. 4, line 38 to pg. 23, line 56), W01998021369 (pg. 7, line 18 to pg. 9, line 25), EP 745141 (pg. 2, line 24 to pg. 3, line 43), EP0095676 and EP638128 (pg. 3, line 11 to line 33).
  • x and y are as defined above, and X is a carboxy and/or carboxy amide group containing organic group with up to 60 carbon atoms bond to a silicon atom via a Si-C- bond, such as: organic groups containing at least one group of the formulas:
  • Optional component d) is any of a number of polar surfactants different from
  • component a) to c) is no polysiloxane, does not have a carboxylic acid group or a salt thereof, except for zwitter ionic compounds).
  • component d is no polysiloxane, does not have a carboxylic acid group or a salt thereof, except for zwitter ionic compounds.
  • polar surfactants selected from the group of amino acids, amino sulfonic acids, commonly known as sarcosines and taurides, quaternary amido carboxylates and sulfates, sulfosuccinates, and, including by reference the surfactants cited in US 2964425 (pg. 3, lines 1 1-32), US 7,250,456 (pg. 3, line 56 through pg. 5, line 2), EP 1 108765 (pg. 25, lines 8-22) and WO 98/021369 (pg 21 , lines 17-29).
  • component d) with the general formula:
  • sarcosines such as N-oleylsarcosine, N-stearylsarcosine and N-lauroylsarcosine and N-isononanoylsarcosine and their respective salts.
  • betaines such as cocoalkylamidopropylbetaine, N-lauryldimethyl- betaine, cocoalkylamidopropylsulfobetaine, 3-(dodecyldimethylamonio)propansulfonate and their salts.
  • the inventive waterproofing compositions may include hydrophobic oils or waxes e), whereby said oils and waxes can be any natural or synthetic oils and waxes such as mineral oils, white oils, alkyl esters of fatty acids or hydrogenated fatty acids, vegetable or animal oils, including fish oils, paraffin waxes, oxidized paraffins or chloroparaffins, and included by reference those oils and waxes cited in US 7,250,456 (pg. 2, line 44-55), EP 1 108765 (pg. 25, lines 3-7) and WO 98/021369 (pg. 19, lines 7- 15).
  • hydrophobic non-polar polyorganosiloxanes such as polydimethylsiloxanes.
  • the optional oils and waxes can be added to the waterproofing liquor as separate aqueous emulsions.
  • inventive waterproofing compositions may include other auxiliaries f), like organic solvents such as glycols, glycolethers or alcohols, such as hexyleneglycol, butylglycol, 1 ,2-propandiol, 1 ,2-ethandiol, 1-butanol, 2-ethylhexanol and the like, pH- adjusting agents (acids, bases), buffers, preservatives, biocides, perfumes, dies, pigments, thickeners or fillers.
  • auxiliaries f like organic solvents such as glycols, glycolethers or alcohols, such as hexyleneglycol, butylglycol, 1 ,2-propandiol, 1 ,2-ethandiol, 1-butanol, 2-ethylhexanol and the like, pH- adjusting agents (acids, bases), buffers, preservatives, biocides, perfumes, dies, pigments, thickeners or fillers
  • the polyorganosiloxane a) is used preferably in an aqueous composition, preferably in aqueous emulsions, comprising for example 0,1 to 60 weight-% of the
  • inventive waterproofing compositions thus may be preferably formulated with water and appropriate pH adjusting agents to aqueous compositions, preferably aqueous emulsions.
  • aqueous compositions including emulsions, containing 3 and 70 wt-%, preferably 5 to 60, more preferably 10 and 50% of the inventive components a) - e) the remainder being water and optionally organic solvents.
  • aqueous emulsions with between 3 and 50 % of the inventive components a) and b) .
  • Most especially preferred are emulsions with between 5 and 40 % of the
  • the preferred waterproofing emulsions have a pH value of greater than 7. Especially preferred is a pH of 8 - 11.
  • Appropriate pH adjusting agents are any typical water- soluble acid or base.
  • bases such as sodium or potassium hydroxide, sodium carbonate, sodium formate, sodium acetate, and ammonia or a primary, secondary or tertiary amine or alcohol amine such as trimethylamine, triethylamine, morpholine, pyridine, triethanolamine, diethanolamine, or ethanolamine.
  • bases such as sodium or potassium hydroxide, sodium carbonate, sodium formate, sodium acetate, and ammonia or a primary, secondary or tertiary amine or alcohol amine such as trimethylamine, triethylamine, morpholine, pyridine, triethanolamine, diethanolamine, or ethanolamine.
  • WO 1998/021369 page 18, line 23 through page 19, line 2
  • EP 324345 page 2, line 15 to 32.
  • waterproofing emulsions with a pH of greater than 7 comprising as base sodium hydroxide, triethylamine, diethanolamine, triethanolamine or morpholine.
  • a particularly preferred composition comprises: 10-90 (preferable 20-80) parts per weight of at least one polyorganosiloxane a) as defined above,
  • auxiliaries f 0-20 (preferable 1 -10) auxiliaries f),
  • the resulting solid contents (components a) to f)) of the aqueous compositions according to the invention is preferably in the range of 10 to 70 %, preferably 15 to 60 by weight based on the total composition.
  • the inventive waterproofing emulsions can be prepared according to the state-of-the- art by mixing the components with water and pH adjusting agents using moderate to high shear and then if desired diluting with more water and adjusting the pH with acids or bases. Common biocides can be added as storage preservatives.
  • a particular advantage of the inventive waterproofing emulsions is that they can be formulated to highly stable emulsions that are stable to both heat and freezing and dilution to a pH between 4 and 7.
  • waterproofing emulsions comprising the component b) can be formulated as microemulsions with a volume average d 50 size of less than 120 nm, preferably less than 100 nm, measured by laser scattering method preferably performed by using a Beckman Coulter Particle Sizer Model LS 13320 preferably according to the Mie-Theory of light scattering applying the method ISO 13320-1 (1990): Particle size analysis - Laser diffraction methods. See also I .
  • waterproofing microemulsions comprising component b) selected from the group of polyorganosiloxanes with one or more polar carboxy, carboxy amide or quaternary ammonium functional groups, or combinations of such polyorganosiloxanes.
  • component b) selected from the group of polyorganosiloxanes with one or more polar carboxy, carboxy amide or quaternary ammonium functional groups, or combinations of such polyorganosiloxanes.
  • microemulsions that comprise between 2 and 30 % of the selected component b) with one or more polar carboxy, amide or quaternary
  • ammmonium functional groups or combinations of such polyorganosiloxanes.
  • inventive waterproofing compositions are suited for the hydrophobic treatment of fibrous materials, in particular those materials composed of at least in part of natural fibers.
  • inventive compositions and emulsions can be used to treat textiles and fabrics to make them water repellant.
  • the hydrophobic treatment can occur before, during or after dyeing the textile or fabric.
  • the inventive compositions and emulsions are particularly suited for the hydrophobic treatment of leather, furs and leather substitutes.
  • the hydrophobic treatment can occur in one or more steps before, during or after retanning and fatliquoring. Included by reference are the methods described in WO 1998/021369 (page 20 , line 21 through page 21 , line 12), EP1 108705 (pg. 39, line 15 to pg. 41 , line 13), EP 1087021 (pg. 8, line 46 to pg. 9, line 58) and WO2003/064707 (pg. 16-17).
  • Preferred embodiments of the invention comprise the following: A use of a polyorganosiloxane a) or a composition comprising the same of the invention, wherein the fibrous substrate to be treated is selected from leather, furs or leather substitutes.
  • A is a di- or trivalent organic residue having up to 30 carbon atoms bound to a silicon atom of the polyorganosiloxane moiety via a carbon atom
  • a is 0 to 3
  • x is 0 to 1100, preferably 10 to 1000
  • y is 0 to 100
  • x+y is 0 to 1000, preferably 10 to 1 100
  • a + y is > 1
  • a and B are as defined above,
  • R is an organic group having up to 25 carbon atoms.
  • polyorganosiloxane a) or a composition comprising the same, wherein polyorganosiloxane a) has the formula:
  • a further preferred embodiment relates to a composition of the invention comprising: a) at least one polyorganosiloxane a) as defined above,
  • the functional groups in the polyorganosiloxane b) are preferably selected from the group consisting of
  • composition of the invention comprises preferably:
  • composition of the invention comprises component c), an organic silicon-free compound having at least one carboxy group or a salt thereof.
  • the composition of the invention comprises component d), at least one surfactant, different from component a) to c).
  • the composition of the invention is an aqueous composition, preferably an aqueous emulsion.
  • aqueous compositions in particular, aqueous emulsions are preferably applied before, during or after tanning of the leather.
  • the aqueous compositions are applied to wet leathers obtained after the aqueous tanning process.
  • the aqueous compositions of the invention comprises 40 to 97 % by weight water.
  • the aqueous compositions of the invention has a pH value at 20 °C of more than 7.
  • the composition of the invention comprises 3 to 60 % by weight of the components a) and b).
  • the composition of the invention is an aqueous emulsion having a pH value at 20 °C of more than 7 comprising 40 to 97 % by weight water.
  • the polyorganosiloxane a) or a composition comprising the same according to the invention is for use for the treatment of fibrous substrates to make them hydrophobic.
  • the invention relates to a process for the treatment of fibrous substrates, which comprises the contacting of the composition of the invention with fibrous substrates.
  • the invention relates to a process for the treatment of fibrous substrates, wherein the fibrous substrate is selected from tanned, dried leather, and the composition according to the invention as defined above comprises a volatile organic solvent, which process further comprises the step of drying the leather to remove the volatile organic solvent.
  • this embodiment of the invention relates to the treatment of tanned, dried leather, after completion of the water-based tanning and fatliquoring processes and drying, with a composition according to the invention comprising one or more of the above defined polyorganosiloxanes a) and preferably one or more polyorganosiloxanes b) in at least one volatile organic solvent, having preferably a boiling point of less than 250 °C, preferably less than 100 °C.
  • tanned leathers such as described in EP1702991 (page 2, lines 1 1-14) and W01996/15276 (page 3, lines 18-39) are treated with a composition according to the invention as defined above after tanning and drying.
  • Vegetative tanned leather is commonly used in shoe sole leather and similar articles where a very dense and stiff leather is required.
  • Vegetative tanning in general is carried out in an aqueous bath of natural or synthetic organic tanning agents at a pH of 4 or below. At this pH the aqueous polyorganosiloxane emulsions are less stable, making them less preferred for those already tanned dried leathers.
  • the invention relates to a process for the treatment of tanned, dried leathers, which process involves the step of contacting the leather with a solution of one or more polyorganosiloxanes a) as defined above, and/or one or more polyorganosiloxanes b) in a volatile organic solvent. After this step the treated leather is then dried to remove the organic solvent.
  • solutions that contain 10 to 60 % per weight of the said polysiloxanes, based on the total weight of the composition.
  • Preferred is contacting the leather with the polysiloxane solution by immersion for between 30 minutes and 24 hours at ambient temperature (25° C).
  • the leather can also be treated at temperatures above ambient but below the boiling point of the organic solvent.
  • Preferred is also repeated treatment by further immersion after drying.
  • the preferred organic solvents are volatile at temperatures of below 100 °C.
  • Examples of the preferred organic solvents are aliphatic or aromatic hydrocarbons, alcohols, polyalcohols, ethers, polyethers, ketones and esters, such as Isopar G or Exxsol D100 (sold by ExxonMobil Chemicals), isopropanol, isobutanol, 1 ,3-butandiol, 1 -pentanol, 2- ethylhexanol, 1 -decanol, 2-butanone, and ethyl acetate.
  • Isopar G or Exxsol D100 sold by ExxonMobil Chemicals
  • isopropanol isobutanol, 1 ,3-butandiol, 1 -pentanol, 2- ethylhexanol, 1 -decanol, 2-butanone, and ethyl acetate.
  • organic alcohols such as isopropanol, isobutanol, 1 ,3-butandiol, 1 -pentanol, 2- ethylhexanol, and 1 -decanol.
  • Q is a quaternary ammonium or an amino functional organic group and x and is as defined above.
  • the invention relates to a fibrous product treated with the composition of the invention, which contains preferably 0,2 to 20 % by weight silicon per 100 % by weight of the fibrous product.
  • the invention relates to a fibrous product, which is a leather product that is treated before, after or during retanning and dyeing of leather with the composition of the invention.
  • the product was a clear microemulsion with a particle size of less than 0, 1 microns.
  • the emulsion was stable to 1 :50 dilution in a pH 5,5 aqueous buffer solution.
  • the microemulsion was stable to storage at 50 °C for in excess of 9 weeks.
  • the emulsion could be subjected to freezing at -8 °C, remaining a stable emulsion upon thawing.
  • the emulsion was found to yield a highly durable
  • the final emulsion had a solids content of 31 ,0 %, a viscosity of 1 1 mPa*s at 23 °C and a pH value of 1 1 .
  • the emulsion was stable to 1 :50 dilution in a pH 5,5 aqueous buffer solution. The emulsion was found to yield a highly durable hydrophobation of leather.
  • component d This mixture was then combined with deionized water and 13,5 parts of a 40% solution of sodium hydroxide (component f)) in water using moderate shear to obtain a homogeneous emulsion.
  • the final emulsion had a solids content of 31 , 1 %, a viscosity of 15 mPa*s at 23 °C and a pH value of 9.
  • the emulsion was stable to 1 :50 dilution in a pH 5,5 aqueous buffer solution, but failed to yield leather with a durable hydrophobation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates on the use of 1,3-dihydroxyalkyl functionalized polyorganosiloxanes in compositions for the treatment of materials having a fibrous structure, such as leather, furs, textiles and paper. The invention further relates to a process for treating fibrous materials with waterproofing.

Description

Hydrophobizing of Fibrous Materials with Polyorganosiloxanes
The present invention relates to waterproofing agents based on specific polyorganosiloxanes with polar functional groups for the treatment of materials having a fibrous structure, in particular natural fibers, such as found in leather, furs, textiles and paper. The invention further relates to a process for treating fibrous materials with waterproofing agents containing specific polyorganosiloxanes with polar functional groups. Owing to the durable fixation of polyorganosiloxanes with specific polar functional groups to natural fibers, the inventive waterproofing agents provide long-lasting hydrophobic treatment desired in uses such a shoewear, clothing or furnishings.
The treatment of leather, furs, textiles and other fibrous materials to impart
hydrophobicity, often referred to as waterproofing, is common. In particular
waterproofing leather is desirable in the manufacture of high quality footwear, clothing or furnishings. Also waterproofing textiles and fabrics is common in outerwear. A durable waterproofing is difficult to achieve and a number of approaches to this problem have been proposed.
US 2964425 describes the use of organic sarcosines in leather waterproofing.
GB 1005475 discloses a fatliquoring salt composition of a hydroxylated
polydimethylsiloxanes , aminoalkyltrialkoxysilane, glacial acetic acid and isoproylalco- hol in the treatment of making the leather soft and hydrophobic.
The inventors of WO 95/30028 propose the use of organofunctional polyorganosiloxanes having OH, SH, NH groups for leather treatment. They disclose compositions of polydimethylsiloxanes and C18-alkyl-polyethers having carboxylic groups neutralized with sodium hydroxide.
WO 03/64707 discloses compositions comprising polycarboxylic acids, carboxy functional polysiloxanes, N-olelysarcosine, oleylether carboxylic acids and others. EP213480 discloses compositions of emulsions for leather waterproofing wherein siloxanes have mercapto functional groups and emuisifiers are selected from the group of alkylacyl-aminoacids and its salts. The organofunctional siloxanes claimed comprise amino, sulfido and carboxy functional groups.
EP 324345 describes leather waterproofing with emulsions of siloxanes having organofunctional carboxy groups, whereby the carboxy groups are neutralized by an appropriate nitrogen base.
EP638128 describes leather waterproofing with siloxanes with organofunctional sulfosuccinate groups.
EP745141 describes leather waterproofing with emulsions of siloxanes with
organofunctional carboxy groups, whereby the carboxy groups are separated from the siloxane backbone by a C5 - C25 organic spacer group.
EP757108 describes leather waterproofing with polyorganosiloxanes in combination with specific acrylic copolymers. Described are siloxanes with organofunctional amino, thio or carboxy groups and MQ resins.
EP 938590 describes leather waterproofing with carboxyamid-functional
polyorganosiloxanes.
EP1087021 describes leather waterproofing with an organic oil or wax, a
carboxyfunctional siloxane and an anionic surfactant.
EP1 108765 describes leather waterproofing with emulsions of specific organofunctional siloxanes with carboxy groups.
EP1470258 describes leather waterproofing with an organic oil, an organofunctional siloxane, an anionic surfactant and an organic acid.
EP 1416057 describes Chromium-free tanning and fatliquoring of leather with organofunctional siloxanes, including carboxyfunctional siloxanes.
EP 0356963 discloses siloxane compounds terminated with the diol at one end thereof. These siloxane compounds are used as comonomers where the hydroxy groups react for example with isocyanate or carboxylic groups to obtain siloxane modified
polyurethanes or polyesters that might be used for example to improve surface characteristics like water repellency of certain substrates. As the terminal diol group reacts in the copolymerisation reaction, it is no longer contained in the final product. Thus there is no clue in this document to use siloxane compounds as such in the treatment of fibrous substrates. US 3538137 discloses hydrolyzable organosillanes derived from silicon hydrogen compounds and trimethylol alkane derivatives. These silanes are taught to be useful as glassfibre sizing agents. However, there is no clue to the use of polysiloxanes in the treatment of leather etc.
DE 1283238 discloses as a method for the manufacture of the
hydroxyalkyloxyalkylsiloxanes useful as stabiliser of polyurethane foams.
* EP 101 0748 discloses diesel fuel defoamer compositions, comprising mixtures of silicons, including hydrosilation reaction product of SiH silicon and trimethylol propane monoallylether.
None of these proposed waterproofing agents meet all of the requirements for durable waterproofing of fibrous materials. For example waterproofing leather need allow for uniform dyeing, little loss of firmness, and good water vapor permeability. Leather used in footwear needs to exhibit dynamic water resistance as tested by the method of Maeser. Many of the proposed agents leave an oily film on the leather surface or lead to significant loss of firmness or a too soft hand. In particular many of the proposed agents form emulsions with marginal stability, often leading to a non-uniform treatment of the substrate and other problems in the application of these materials. It is particularly desirable in the field that waterproofing agents be stable to heat and freezing. Also many processes for treatment of fibrous materials involve aqueous treatment baths or floats that have a pH of 4 to 7, in particular a pH of 5 to 6. The preferred waterproofing agent should be stable to dilution in excess water in this pH range.
It was surprisingly found that polyorganosiloxanes with 1 ,3-dihydroxyalkyl functional groups on Si-C-bonded hydrocarbon radicals are especially effective waterproofing agents for fibers, pulps, leather and a wide variety of other fibrous materials. In particular, it was found that these polyorganosiloxanes could be formulated to give emulsions that are highly stable to heat, freezing and dilution in water at pH 5 to 6. In another aspect of the present invention it was found that combining the inventive polyorganosiloxane with 1 ,3-dihydroxyalkyl functional groups with even minor proportions of polyorganosiloxanes with specific polar functional groups can produce hydrophobic articles with highly durable waterproofing in fiber, pulp, or leather treatment processes. Thus the present invention provides a novel use of ac polyorganosiloxane a) comprising at least one 1 ,3-dihydroxy alkyl moiety in the treatment of fibrous substrates. In a preferred embodiment said polyorganosiloxane a) is used in an aqueous composition, in particular, in an aqueous emulsion. The fibrous substrates are preferably selected from leather, furs or leather substitutes, for example, natural or artificial leather, alcantara (ultrasuede).
By using polyorganosiloxane a) a hydrophobic treatment of the fibrous substrate is performed.
The polyorganosiloxane a) may have the formula:
[MaDbTcQd]e (I) wherein M = R3Si01/2,
Figure imgf000005_0001
T = RSi03/2) Q = S1O4/2, with a = 1-10 b = 0-1000 wherein
R = is an organic group, with the requirement that R comprises at least one group R1 comprising dihydroxy alkyl moiety.
The 1 ,3-dihydroxy alkyl moiety is in particular a group shown by of the formula:
Figure imgf000006_0001
wherein the dotted line is the free valence of the group to the rest of molecule, and wherein the group R* may represent one or more organic substituent groups, preferably with up to 20 carbon atoms, and optionally comprising one or more hetero atoms, attached to any carbon atom of said 1 ,3-dihydroxy alkyl moiety. The 1 ,3-dihydroxy alkyl moiety according to the invention usually does not include alkyl moieties having an additional hydroxyl substituent at the β-carbon atom, that is, at the carbon atom between the 1 ,3-position, i.e. having an 1 ,2,3-trihydroxyalkyl moiety.
In a preferred embodiment the polysiloxane compounds according to the invention comprise siloxy structural elements selected from the following formulas:
Figure imgf000007_0001
wherein R = d to C22-alkyl, fluoroalkyl or aryl, and
R1 is an organic group bound via a carbon atom to the silicon atom, comprising dihydroxy alkyl moiety,
f = 0 - 600,
Figure imgf000007_0002
wherein the groups R is as defined above, and g = 0 - 700,
Figure imgf000007_0003
wherein R is as defined above, and h = 0 - 10,
Figure imgf000008_0001
wherein R1 is as defined above, and i = 0 - 10,
Figure imgf000008_0002
wherein R and R1 are as defined above, and j = 0-30,
Figure imgf000008_0003
wherein R is as defined above, and k = 0-30,
Figure imgf000009_0001
wherein 1 = 0 - 10, f+g+h+i+j+k+l = 12 to 1100.
In preferred embodiments l=i=h = 0, that is, preferred are polysiloxanes having linear polydiorganosiloxane backbones formed of D units. In a further preferred embodiment the polyorganosiloxane a) is selected from polyorganosiloxanes having pendant and/or terminal 1 ,3-dihydroxy alkyl moieties. This means that the 1 ,3-dihydroxy alkyl moieties are attached either to the terminal units M or chain-forming units D and T, preferably D. Preferably the polyorganosiloxane a) is selected from linear polyorganosiloxanes having terminal ,3-dihydroxy alkyl moieties.
The 1 ,3-dihydroxy alkyl moiety is preferably a group of the formula:
-A-(B), wherein v = 1 or 2, preferably 1 , A is a di- or trivalent organic residue having up to 30, preferably up to 20 carbon atoms bound to a silicon atom of the polyorganosiloxane moiety via a carbon atom, B is an optionally substituted 1 ,3-dihydroxypropanyl moiety bound to the group A having the above indicated formula:
Figure imgf000010_0001
, wherein R* is as defined above.
R* includes preferably an optionally substituted alkyl group with 1 to 6 carbon atoms, wherein optional substituents include in particular 1 to 3 three groups, selected for example from hydroxy, for example R* is methyl, ethyl, hydroxymethyl etc..
The di- or trivalent, preferably trivalent organic residue having up to 20 carbon atoms A includes linear, branched and/or cyclic, saturated, unsaturated and/or aromatic organic residues which may comprise one or more hetero atoms, selected from N, O, S, and P. Examples of such linking groups A include saturated hydrocarbon groups, optionally comprising one to three ether groups (-0-) for example -CHzO-CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2-0-CH2- -CH2CH2CH2NH-CH2-, or
-CH2CH2CH2-0-CH2CH(OH)CH2-NH-CH2-. Preferred 1 ,3-dialkyl moieties B include for example:
Figure imgf000010_0002
Figure imgf000011_0001
wherein * indicates the bond to the linking group A. Preferred linking groups A include for example:
Figure imgf000011_0002
wherein ** indicates the bond to the silicone atom of the polyorganosiloxane backbone and * denotes the bond to the 1 ,3-dihydroxy alkyl moiety B.
A preferred polyorganosiloxane a) has the formula:
a
Figure imgf000011_0003
wherein a is 0 to 3, preferably 0 or 1 , x is 0 to 1000, preferably 10 to 1000, y is O to 100, x+y is 0 to 1 100, preferably 10 to 1000, a + y is > 1 ,
A and B are as defined above,
R is an organic group having up to 25 carbon atoms. l a preferred embodiment polyorganosiloxane a) is of the general formula:
R R
B-AY~Si— O- ■Si— O -Si— 0- -Si A-B)
>a I I
R 3-a A. 3-a wherein a is 0 or 1 ,
x is 10 to 1000
y is 0 to 100,
x+y is 10 to 1 100
a + y is > 1 ,
A is a divalent optionally substituted organic radical with up to 20 carbon atoms that can contain one or more groups such as, optionally substituted aromatic moieties, such as optionally alkoxy and/or hydroxy substituted phenylene, -0-, -NR'-, -CH2-CH(OH)-CH2-, -C(0)NR'-, -0-C(0)NR'-, -C(O)-, -C(0)0-, and the like, and R' is hydrogen, an alkyl or alkylaryl group with up to 18 carbon atoms,
B radical is any organic radical with two or more hydroxy groups wherein at least two such hydroxy groups are positioned 1 ,3 to another, as explained above,
R is an organic group having up to 25 carbon atoms.
Preferred examples of -A-(B), are:
-CH2CH2CH20-CH2C(CH2CH3)(CH2OH)2,
-CH2CH2CH20-CH2C(CH2CH3 )(CH2OH)(CH2OCH2C(CH2CH3 )(CH2OH)2), -CH2CH2CH20-CH2C(CH3 )(CH2OH)2 ,
-CH2CH2CH20-CH2C(CH3 )(CH2OH)(CH2OCH2C(CH3)(CH2OH)2), -CH2CH2CH20-CH2C(CH2OH)3 ,
-CH2CH2CH20-CH2C(CH2OH)2(CH2OCH2C(CH2OH)3),
-CH2CH2CH20-CH2CH(OH)CH2NHCH2C(CH2OH)3 ,
-CH;.CH2(CH2 )„C(CH,OH);( , n = 1 -18,
Figure imgf000013_0001
Figure imgf000013_0002
and the like.
The general synthesis of such polyhydroxy functional polyorganosiloxanes is described for example in US 3381019 and US 4640940. Especially preferred are polyorganosiloxanes a) with the formula:
Figure imgf000014_0001
wherein x and y are as defined above.
Preferred are compositions for the treatment of fibrous materials comprising a) at least one polyorganosiloxane with 1 ,3-dihydroxyalkyl functional groups as defined above,
b) at least one polyorganosiloxane - different from polyorganosiloxane a) - having one or more organic groups bound to the polyorganosiloxane backbone via an Si-C-bond, said organic group comprises at least one, preferably 1 to 3 polar functional group, or salts thereof.
In such polyorganosiloxane b) the polar functional groups are preferably selected from the group consisting of: ether, polyether, sulfido, epoxy, polyetherester, amide, amine N-oxide, sulfate, quaternary ammonium, zwitter ionic, sulfonate, carboxyl, acid anhydride, phosphonate, phosphate, hydroxyl and sulfosuccinate groups.
Most preferred are compositions with polyorganosiloxanes b) with at least one polar functional group on Si-C bonded hydrocarbon radicals selected from the groups consisting of: amino, epoxy, amide, carboxy, quaternary ammonium and zwitter ionic groups.
Most especially preferred are compositions with polyorganosiloxanes b) with one or more polar carboxy, amide and/or quaternary ammonium functional groups, or combinations of such polyorganosiloxanes.
Also preferred are compositions for the treatment of fibrous materials comprising in addition to a), the polyorganosiloxanes with 1 ,3,-dihydroxyalkyl functional groups and b), the polyorganosiloxanes with polar functional groups, also c), an organic silicone- free compound, e.g. a synthetic or natural organic compound, with at least one carboxy group or an organic polymer with at least one carboxy group, each free of silicon (i.e. different from a) and b)) or salts thereof, and optionally d) a surfactant different from any of the components a) to c). The preferred compositions may also comprise optionally e) hydrophobic oils and waxes, again each different from component a) to d).
Component b) is any polyorganosiloxane with one or more polar groups, i.e. heteroatom-containing groups, bound to the polymer backbone via Si-C-bonded hydrocarbon radicals, wherein the functional groups are selected from the group consisting of: ether, sulfido, epoxy, polyetherester, amide, amine N-oxide, sulfate, quaternary ammonium, zwitter ionic, sulfonate, carboxy, phosphonate, phosphate, hydroxyl or sulfosuccinate groups.
Component b) is preferably a polyorganosiloxane with one or more polar functional groups on Si-C-bonded hydrocarbon radicals, wherein said polar functional groups consist of one or more quaternary ammonium functional groups.
Especially preferred are also polyorganosiloxanes with pendant and/or terminal quaternary ammonium functional groups.
The Si-C-bonded hydrocarbon radicals with quaternary ammonium functional groups in component b) preferable include organic groups with up to 40 carbon atoms, containing at least one quaternary ammonium group and optionally containing one or more heteroatoms selected from N, S, O and P.
In a preferred embodiment polyorganosiloxane b) is of the general formula:
Figure imgf000016_0001
wherein a is 0 to 3,
x is 1 to 1000, preferably 10 to 1000
y is 0 to 100,
x+y is 1 to 1 100
a + y is > 1 ,
Z is an organic radical with up to 60 carbon atoms comprising at least one polar group preferably selected from
- an ether group, - a polyether group,
- a sulfido group,
- an epoxy group,
- a polyetherester group,
- an amine group,
- an amide group,
- a carboxy amide group,
- an amine N-oxide group,
- a sulfate group,
- a quaternary ammonium group,
- a zwitter ionic group,
- a sulfonate group,
- a carboxyl group,
- an acid anhydride group,
- a phosphonate group,
- a phosphate group,
- a hydroxyl group,
- a sulfosuccinate group.
and which organic radical is bonded via a carbon atom to the silicon atom, and
R is an organic group having up to 25 carbon atoms, preferably methyl.
Preferred are polyorganosiloxanes b) comprising a quaternary ammonium group and/or a carboxyl group, or salts thereof with suitable anions or cations. Especially preferred are polyorganosiloxanes b) with quaternary ammonium functional groups of the formula:
Figure imgf000018_0001
and Q =
quaternary ammonium group containing organic group with up to 60 carbon atoms, such as:
Figure imgf000018_0002
Figure imgf000019_0001
wherein An is a organic or inorganic anion, like a carboxylate anion, halogen anion, preferably Cl", Br", sulfate anion, sulfonate anion, phosphate, nitrate, perchlorate, and x and y are as defined above.
Also preferred are polyorganosiloxanes b) with polar functional groups, wherein the functional groups are amide, carboxy or sulfosuccinate groups, including by reference the functional polyorganosiloxanes cited in US 7,250,456 (pg. 2, line 56 to pg. 3, line 55), EP1 108765 (pg. 4, line 38 to pg. 23, line 56), W01998021369 (pg. 7, line 18 to pg. 9, line 25), EP 745141 (pg. 2, line 24 to pg. 3, line 43), EP0095676 and EP638128 (pg. 3, line 11 to line 33).
Especially preferred are polyorganosiloxanes b) with carboxy and/or amide functional groups of the general formula: CH CH CH,
I I I
H3C-Si— -O- Si- Si -Si— CH,
I CH3 CH CH-?
X or
Figure imgf000020_0001
wherein x and y are as defined above, and X is a carboxy and/or carboxy amide group containing organic group with up to 60 carbon atoms bond to a silicon atom via a Si-C- bond, such as: organic groups containing at least one group of the formulas:
-(CH2)p-0-E,
-NH-E,
-NH(CH2)q-NH-E,
-N(E)(CH2)q-NH-E,
-0-CH2-CH(OH)-CH2-NH-(CH2)q-NH-E,
-0-CH2-CH(OH)-CH2-N(E)-(CH2)q-NH-E, -0-CH2-CH(OH)-CH2-NH(CH2CH2-0-E), -0-CH2-CH(OH)-CH2-N(CH2CH2-0-P)2,
Figure imgf000020_0002
Figure imgf000021_0001
or the like, wherein E is independently selected from groups such as:
-C(0)CH2CH2C(0)OH,
-C(0)CH=CHC(0)OH,
-C(0)CH(R2)CH2C(0)OH,
-C(0)(CH2)nOC(0)CH2CH2C(0)OH,
-C(0)(CH2)nOC(0)CH=CHC(0)OH,
-C(0)(CH2)nOC(0)CH(R2)CH2C(0)OH ,
wherein R2 is a saturated or unsaturated organic group with up to 25 carbon atoms and n = as defined above, preferably 2- 2, or E is
Figure imgf000022_0001
and the like.
Especially preferred are combinations of polyorganosiloxanes a) with polyhydroxy functional groups with one or more polyorganosiloxanes b) with quaternary ammonium, carboxy or carboxy amide functional groups.
The inventive polyorganosiloxanes a) and b) may also have additional groups bonded to the polymer backbone by either Si-O-C or Si-C linkages taken from the group consisting of alkyl, aryl, alkoxy, alkylaryl, alkylphenolic or carbinol. Especially preferred are also waterproofing agents that comprise both polyorganosiloxanes b) with at least one Si-C bonded quaternary ammonium group and polyorganosiloxane polymers b) with at least one Si-C bonded carboxy and/or amide group. Component c) is an organic silicon-free compound having at least one carboxy group such as a synthetic or natural organic compound with at least one carboxy group or an organic polymer with at least one carboxy group or a salt thereof. Suitable salts include for example alkaline (sodium, potassium) or alkaline-earth salts (calcium) or ammonium salts.
Preferred are natural fatty acids derived from tallow, palm oil, fish oils, or seed oils and their mixtures.
Especially preferred are fatty acids and hydrogenated fatty acids such as oleic acid, linoleic acid, ricinoleic acid, lauric acid, myristic acid, palmitic acid, stearic acid and their mixtures.
Also preferred are synthetic carboxy-functional molecules such as those derived from paraffins and the like, such as oxidized paraffins. Also preferred are polyacrylates that contain at least one acrylic acid group per molecule. Included by reference are the copolymers cited in EP 372746 (pg. 4 line 52 to page. 6 line 40) and EP 757108 (pg.2 line 19 to page. 3 line 44). Included by reference are also the polycarboxylic acids and carboxy polymers cited in US 7,250,456 (page. 5, line 1 to page. 0, line 16).
Furthermore are included alkylacylamidocarboxylic acids, alkylether carboxylic acids. Component c) does not include zwitter ionic molecules, which shall belong to the class of surfactants d) as defined below.
Optional component d) is any of a number of polar surfactants different from
component a) to c) (i.e. component d) is no polysiloxane, does not have a carboxylic acid group or a salt thereof, except for zwitter ionic compounds). Preferred are those polar surfactants selected from the group of amino acids, amino sulfonic acids, commonly known as sarcosines and taurides, quaternary amido carboxylates and sulfates, sulfosuccinates, and, including by reference the surfactants cited in US 2964425 (pg. 3, lines 1 1-32), US 7,250,456 (pg. 3, line 56 through pg. 5, line 2), EP 1 108765 (pg. 25, lines 8-22) and WO 98/021369 (pg 21 , lines 17-29). Preferred are component d) with the general formula:
Figure imgf000024_0001
or
O
II
o
CH3 ONa
or
Figure imgf000024_0002
or other substituted taurins,
or
Figure imgf000024_0003
wherein R is as defined above.
Especially preferred are sarcosines such as N-oleylsarcosine, N-stearylsarcosine and N-lauroylsarcosine and N-isononanoylsarcosine and their respective salts.
Also preferred are taurides such as oleic acid methyl tauride and its salts.
Also preferred are betaines such as cocoalkylamidopropylbetaine, N-lauryldimethyl- betaine, cocoalkylamidopropylsulfobetaine, 3-(dodecyldimethylamonio)propansulfonate and their salts.
Optionally the inventive waterproofing compositions may include hydrophobic oils or waxes e), whereby said oils and waxes can be any natural or synthetic oils and waxes such as mineral oils, white oils, alkyl esters of fatty acids or hydrogenated fatty acids, vegetable or animal oils, including fish oils, paraffin waxes, oxidized paraffins or chloroparaffins, and included by reference those oils and waxes cited in US 7,250,456 (pg. 2, line 44-55), EP 1 108765 (pg. 25, lines 3-7) and WO 98/021369 (pg. 19, lines 7- 15). Also included in the inventive oils and waxes are hydrophobic non-polar polyorganosiloxanes such as polydimethylsiloxanes. Alternatively, the optional oils and waxes can be added to the waterproofing liquor as separate aqueous emulsions.
Optionally the inventive waterproofing compositions may include other auxiliaries f), like organic solvents such as glycols, glycolethers or alcohols, such as hexyleneglycol, butylglycol, 1 ,2-propandiol, 1 ,2-ethandiol, 1-butanol, 2-ethylhexanol and the like, pH- adjusting agents (acids, bases), buffers, preservatives, biocides, perfumes, dies, pigments, thickeners or fillers.
The polyorganosiloxane a) is used preferably in an aqueous composition, preferably in aqueous emulsions, comprising for example 0,1 to 60 weight-% of the
polyorganosiloxane a).
The inventive waterproofing compositions thus may be preferably formulated with water and appropriate pH adjusting agents to aqueous compositions, preferably aqueous emulsions. Preferred are aqueous compositions, including emulsions, containing 3 and 70 wt-%, preferably 5 to 60, more preferably 10 and 50% of the inventive components a) - e) the remainder being water and optionally organic solvents. Especially preferred are aqueous emulsions with between 3 and 50 % of the inventive components a) and b) . Most especially preferred are emulsions with between 5 and 40 % of the
components a) and b).
The preferred waterproofing emulsions have a pH value of greater than 7. Especially preferred is a pH of 8 - 11. Appropriate pH adjusting agents are any typical water- soluble acid or base. Preferred is the use of bases such as sodium or potassium hydroxide, sodium carbonate, sodium formate, sodium acetate, and ammonia or a primary, secondary or tertiary amine or alcohol amine such as trimethylamine, triethylamine, morpholine, pyridine, triethanolamine, diethanolamine, or ethanolamine. Included by reference are the bases cited in WO 1998/021369 (page 18, line 23 through page 19, line 2) and EP 324345 (page 2, line 15 to 32).
Especially preferred are waterproofing emulsions with a pH of greater than 7 comprising as base sodium hydroxide, triethylamine, diethanolamine, triethanolamine or morpholine.
A particularly preferred composition comprises: 10-90 (preferable 20-80) parts per weight of at least one polyorganosiloxane a) as defined above,
1 -50 (preferable 5-40) parts per weight at least one polyorganosiloxane b) as defined above,
0-60 (preferable 10-50) parts per weight organic silicon-free compound c) as defined above
0-40 (preferable 1 -30) parts per weight surfactant component d) as defined above, 0-40 (preferable 0-30) hydrophobic oils or waxes e),
0-20 (preferable 1 -10) auxiliaries f),
and 50- 4000 parts water per 100 parts of the total of the components a) to f).
The resulting solid contents (components a) to f)) of the aqueous compositions according to the invention is preferably in the range of 10 to 70 %, preferably 15 to 60 by weight based on the total composition. The inventive waterproofing emulsions can be prepared according to the state-of-the- art by mixing the components with water and pH adjusting agents using moderate to high shear and then if desired diluting with more water and adjusting the pH with acids or bases. Common biocides can be added as storage preservatives. A particular advantage of the inventive waterproofing emulsions is that they can be formulated to highly stable emulsions that are stable to both heat and freezing and dilution to a pH between 4 and 7. In particular waterproofing emulsions comprising the component b) can be formulated as microemulsions with a volume average d50 size of less than 120 nm, preferably less than 100 nm, measured by laser scattering method preferably performed by using a Beckman Coulter Particle Sizer Model LS 13320 preferably according to the Mie-Theory of light scattering applying the method ISO 13320-1 (1990): Particle size analysis - Laser diffraction methods. See also I .
Zimmermann Ingenieur Technik 68 (1996) Nr. 4.
Preferred are waterproofing microemulsions comprising component b) selected from the group of polyorganosiloxanes with one or more polar carboxy, carboxy amide or quaternary ammonium functional groups, or combinations of such polyorganosiloxanes. Especially preferred are microemulsions that comprise between 2 and 30 % of the selected component b) with one or more polar carboxy, amide or quaternary
ammmonium functional groups, or combinations of such polyorganosiloxanes.
The inventive waterproofing compositions are suited for the hydrophobic treatment of fibrous materials, in particular those materials composed of at least in part of natural fibers. The inventive compositions and emulsions can be used to treat textiles and fabrics to make them water repellant. The hydrophobic treatment can occur before, during or after dyeing the textile or fabric.
The inventive compositions and emulsions are particularly suited for the hydrophobic treatment of leather, furs and leather substitutes. The hydrophobic treatment can occur in one or more steps before, during or after retanning and fatliquoring. Included by reference are the methods described in WO 1998/021369 (page 20 , line 21 through page 21 , line 12), EP1 108705 (pg. 39, line 15 to pg. 41 , line 13), EP 1087021 (pg. 8, line 46 to pg. 9, line 58) and WO2003/064707 (pg. 16-17).
Preferred embodiments of the invention comprise the following: A use of a polyorganosiloxane a) or a composition comprising the same of the invention, wherein the fibrous substrate to be treated is selected from leather, furs or leather substitutes.
A use of a polyorganosiloxane a) or a composition comprising the same in the hydrophobic treatment of the fibrous substrate.
A use of a polyorganosiloxane a) or a composition comprising the same, wherein the polyorganosiloxane a) is selected from polyorganosiloxanes having pendant and/or terminal 1 ,3-dihydroxy alkyl moieties.
A use of a polyorganosiloxane a) or a composition comprising the same, wherein the polyorganosiloxane a) is selected from polyorganosiloxanes having terminal 1 ,3- dihydroxy alkyl moieties.
A use of a polyorganosiloxane a) or a composition comprising the same, wherein 1 ,3- dihydroxy alkyl moieties are bound to a silicon atom of the polyorganosiloxane moiety via a carbon atom.
A use of a polyorganosiloxane a) or a composition comprising the same, wherein the polyorganosiloxane a) has a 1 ,3-dihydroxy alkyl moiety of the formula:
-A-(B), wherein A is a di- or trivalent organic residue having up to 30 carbon atoms bound to a silicon atom of the polyorganosiloxane moiety via a carbon atom, B is an optionally substituted 1 ,3-dihydroxypropanyl moiety bound to the group A and v = 1 or 2.
A use of a polyorganosiloxane a) or a composition comprising the same, wherein the polyorganosiloxane a) has the formula:
Figure imgf000028_0001
wherein a is 0 to 3, x is 0 to 1100, preferably 10 to 1000, y is 0 to 100, x+y is 0 to 1000, preferably 10 to 1 100, a + y is > 1 ,
A and B are as defined above,
R is an organic group having up to 25 carbon atoms.
A use of a polyorganosiloxane a) or a composition comprising the same, wherein polyorganosiloxane a) has the formula:
Figure imgf000029_0001
or
Figure imgf000029_0002
wherein x and y are as defined above. A further preferred embodiment relates to a composition of the invention comprising: a) at least one polyorganosiloxane a) as defined above,
b) at least one polyorganosiloxane b) - different from polyorganosiloxane a) - having one or more organic groups bound to the polyorganosiloxane backbone via an Si-C-bond, said organic group comprises at least one polar functional group, or salts thereof.
In a further preferred embodiment of the invention the functional groups in the polyorganosiloxane b) are preferably selected from the group consisting of
- an ether group,
- a polyether group,
- a sulfido group,
- an epoxy group,
- a polyetherester group,
- an amine group,
- an amide group,
- a carboxy amide group,
- an amine N-oxide group,
- a sulfate group,
- a quaternary ammonium group,
- a zwitter ionic group,
- a sulfonate group,
- a carboxyl group,
- an acid anhydride group,
- a phosphonate group,
- a phosphate group,
- a hydroxyl group,
- a sulfosuccinate group. In a further preferred embodiment the composition of the invention comprises preferably:
per 100 parts by weight of the component a),
1 to 200 parts by weight of the component b).
In a further preferred embodiment the composition of the invention comprises component c), an organic silicon-free compound having at least one carboxy group or a salt thereof. In a further preferred embodiment the composition of the invention comprises component d), at least one surfactant, different from component a) to c).
In a further preferred embodiment the composition of the invention is an aqueous composition, preferably an aqueous emulsion. Such aqueous compositions, in particular, aqueous emulsions are preferably applied before, during or after tanning of the leather. Preferably the aqueous compositions are applied to wet leathers obtained after the aqueous tanning process.
In a further preferred embodiment the aqueous compositions of the invention comprises 40 to 97 % by weight water.
In a further preferred embodiment the aqueous compositions of the invention has a pH value at 20 °C of more than 7. In a further preferred embodiment the composition of the invention comprises 3 to 60 % by weight of the components a) and b).
In a further preferred embodiment the composition of the invention is an aqueous emulsion having a pH value at 20 °C of more than 7 comprising 40 to 97 % by weight water. ln a further preferred embodiment the polyorganosiloxane a) or a composition comprising the same according to the invention is for use for the treatment of fibrous substrates to make them hydrophobic. In a further preferred embodiment the invention relates to a process for the treatment of fibrous substrates, which comprises the contacting of the composition of the invention with fibrous substrates.
In a further preferred embodiment the invention relates to a process for the treatment of fibrous substrates, wherein the fibrous substrate is selected from tanned, dried leather, and the composition according to the invention as defined above comprises a volatile organic solvent, which process further comprises the step of drying the leather to remove the volatile organic solvent. In particular, this embodiment of the invention relates to the treatment of tanned, dried leather, after completion of the water-based tanning and fatliquoring processes and drying, with a composition according to the invention comprising one or more of the above defined polyorganosiloxanes a) and preferably one or more polyorganosiloxanes b) in at least one volatile organic solvent, having preferably a boiling point of less than 250 °C, preferably less than 100 °C. In particular, preferably vegetative or synthetic (preferably without use of chromium salts) tanned leathers such as described in EP1702991 (page 2, lines 1 1-14) and W01996/15276 (page 3, lines 18-39) are treated with a composition according to the invention as defined above after tanning and drying. Vegetative tanned leather is commonly used in shoe sole leather and similar articles where a very dense and stiff leather is required. Vegetative tanning in general is carried out in an aqueous bath of natural or synthetic organic tanning agents at a pH of 4 or below. At this pH the aqueous polyorganosiloxane emulsions are less stable, making them less preferred for those already tanned dried leathers. In a preferred embodiment the invention relates to a process for the treatment of tanned, dried leathers, which process involves the step of contacting the leather with a solution of one or more polyorganosiloxanes a) as defined above, and/or one or more polyorganosiloxanes b) in a volatile organic solvent. After this step the treated leather is then dried to remove the organic solvent. Preferred in this embodiment are solutions that contain 10 to 60 % per weight of the said polysiloxanes, based on the total weight of the composition. Especially preferred are solutions that contain 30 to 40 % per weight of the said polysiloxanes, based on the total weight of the composition.
Preferred is contacting the leather with the polysiloxane solution by immersion for between 30 minutes and 24 hours at ambient temperature (25° C). The leather can also be treated at temperatures above ambient but below the boiling point of the organic solvent. Preferred is also repeated treatment by further immersion after drying. The preferred organic solvents are volatile at temperatures of below 100 °C. Examples of the preferred organic solvents are aliphatic or aromatic hydrocarbons, alcohols, polyalcohols, ethers, polyethers, ketones and esters, such as Isopar G or Exxsol D100 (sold by ExxonMobil Chemicals), isopropanol, isobutanol, 1 ,3-butandiol, 1 -pentanol, 2- ethylhexanol, 1 -decanol, 2-butanone, and ethyl acetate. Especially preferred are organic alcohols such as isopropanol, isobutanol, 1 ,3-butandiol, 1 -pentanol, 2- ethylhexanol, and 1 -decanol.
Preferred is the treatment of tanned, dried leather with solutions comprising at least one polyorganosiloxane a). Also preferred is the treatment with solutions comprising at least one polyorganosiloxane b) having one or more organic groups bound to the polyorganosiloxane backbone via an Si-C-bond, said organic group comprising at least one polar functional group, wherein the functional group is an amino or a quaternary ammonium group. Especially preferred in the treatment of tanned, dried leather with polyorganosiloxanes b) with the general structure
Figure imgf000034_0001
or
Figure imgf000034_0002
wherein Q is a quaternary ammonium or an amino functional organic group and x and is as defined above. Most especially preferrred are polyorganosiloxanes b) wherein Q is a group with the general structure
Figure imgf000034_0003
or
Figure imgf000035_0001
wherein An is a organic or inorganic anion. In a further preferred embodiment the invention relates to a fibrous product treated with the composition of the invention, which contains preferably 0,2 to 20 % by weight silicon per 100 % by weight of the fibrous product.
In a further preferred embodiment the invention relates to a fibrous product, which is a leather product that is treated before, after or during retanning and dyeing of leather with the composition of the invention.
Examples:
Testmethods: Dynamic water resistance according to Maeser, method ASTM D 2099- 70 or ISO/DIN 5403-2.
Static water absorption after immersion for 4 hours according to ASTM D1815 or ISO 2417:2002
Water vapour permeability according to ASTM D5052 or ISO 14268:2002.
Materials:
Dihvdroxy-functional Siloxan a1 )
A polydimethylsiloxane with terminal 1 ,3-dihydroxy functional groups with a number average molecular wt. of 10.000 g/mol and on average 0,4 mmol/g of hydroxy groups, a viscosity of 550 mPa*s at 23 °C and a refractive index of 1.408 at 20 °C of the formula:
Figure imgf000036_0001
Dihydroxy-functional Siloxan a2) (Comparison)
A polydimethylsiloxane with terminal 1 ,2-dihydroxy functional groups with an average molecular wt. of 10.000 g/mol and on average 0,4 mmol/g of hydroxy groups, a
Figure imgf000036_0002
Quaternary-ammonium-functional Siloxan b1 )
A poiydimethylsiloxane with terminal quaternary ammonium functional groups of the general structure
Figure imgf000037_0001
where Q =
Figure imgf000037_0002
with an average molecular weight of 3800 g/mol and on average 0,49 mmol/g quaternary ammonium groups.
Carboxy-functional Siloxan b2)
A poiydimethylsiloxane with pendant carboxy functional groups with an average molecular weigth of 30000 g/mol and on average 0,375 mmol/g Si-C-bonded hydrocarbon radicals that contain on average two carboxy amide groups.
Figure imgf000038_0001
where x = 300 and y = 10 and E has the formula
-C(0)CH2CH2C(0)OH , and -C(0)(CH2)50C(0)CH2CH2C(0)OH. Example 1 )
69 parts of the dihydroxy-functional polyorganosiloxane a1 ) were thoroughly mixed with 19,5 parts of oleic acid (component c) and 1 1 ,5 parts of oleoylsarcosine (commerically available as Crodasinic O from Croda GmbH - component d)). This mixture was then combined with 245 parts of deionized water and 5 parts of a 40% solution of sodium hydroxide (component f) in water using moderate shear to obtain a homogeneous emulsion. The final emulsion had a solids content of 28,8 %, a viscosity of 43 mPa*s at 23 °C, a pH value of 7,5 and an average particle size of 0,77 microns. The emulsion was stable to 1 :50 dilution in a pH 5,5 aqueous buffer solution. The emulsion was found to be effective in the hydrophobation of leather.
Example 2)
54 parts of the dihydroxy-functional polyorganosiloxane a1 ), 15 parts of the quaternary- ammonium-functional siloxane b1 ) were thoroughly mixed with 19,5 parts of oleic acid (component c)) and 11 ,5 parts of oleoylsarcosine (component d)). This mixture was then combined with deionized water and 9 parts of a 40% solution of sodium hydroxide (component f)) in water using moderate shear to obtain a homogeneous emulsion. The final emulsion had a solids content of 35,9 %, a viscosity of 485 mPa*s at 23 °C, a pH value of 9 and an average particle size of less than 0, 1 microns. The emulsion was stable to 1 :50 dilution in a pH 5,5 aqueous buffer solution. The emulsion was stable to storage at 50 °C for in excess of 9 weeks. The emulsion could be subjected to freezing at -8 °C, remaining a stable emulsion upon thawing. The emulsion was found to yield a highly durable hydrophobation of leather.
Example 3)
30,5 parts of the dihydroxy-functional siloxane a1 ) and 30,5 parts of the quaternary- ammonium-functional siloxane b1 ) were thoroughly mixed with 34 parts of oleic acid (component c)) and 5,0 parts of oleoylsarcosine (component d)). This mixture was then combined with deionized water and 14 parts of a 40% solution of sodium hydroxide (component f)) in water using moderate shear to obtain a homogeneous emulsion. The final emulsion had a solids content of 31 , 1 %, a viscosity of 1 17 mPa*s at 23 °C and a pH value of 9. The product was a clear microemulsion with a particle size of less than 0, 1 microns. The emulsion was stable to 1 :50 dilution in a pH 5,5 aqueous buffer solution. The microemulsion was stable to storage at 50 °C for in excess of 9 weeks. The emulsion could be subjected to freezing at -8 °C, remaining a stable emulsion upon thawing. The emulsion was found to yield a highly durable
' hydrophobation of leather.
Example 4)
28 parts of the dihydroxy-functional siloxane a1 ) and 28 parts of a carboxy-functional siloxane b2) were thoroughly mixed with 31 parts of oleic acid (component c)) and 13 parts of oleoylsarcosine (component d)). This mixture was then combined with deionized water and 14 parts of a 40% solution of sodium hydroxide (component f))in water using moderate shear to obtain a homogeneous emulsion. The final emulsion had a solids content of 33,7 %, a viscosity of 28 mPa*s at 23 °C and a pH value of 1 1. The emulsion was stable to 1 :50 dilution in a pH 5,5 aqueous buffer solution. The emulsion was found to be particularly effective in the hydrophobation of leather. Example 5)
1 Q parts of the dihydroxy-functional siloxane a1 ) and 17 parts of of the quaternary- ammonium-functional siloxane b1 ) and 29 parts of a carboxy-functional siloxane b2) were thoroughly mixed with 29 parts of oleic acid (component c)) and 6 parts of oleoyisarcosine (component d)). This mixture was then combined with deionized water and 16 parts of a 40% solution of sodium hydroxide (component f))in water using moderate shear to obtain a homogeneous emulsion. The final emulsion had a solids content of 31 ,0 %, a viscosity of 1 1 mPa*s at 23 °C and a pH value of 1 1 . The emulsion was stable to 1 :50 dilution in a pH 5,5 aqueous buffer solution. The emulsion was found to yield a highly durable hydrophobation of leather.
Example 6)
53 parts of the dihydroxy-functional siloxane a1 ), 6,5 parts of the quaternary- ammonium-functional siloxane b1 ) were thoroughly mixed with 33 parts of oleic acid (component c) and 7,5 parts of oleoylmethyltauride (commerically available as
Arkonpon T8015 from Clariant GmbH - (component d)). This mixture was then combined with deionized water and 1 1 parts of a 40% solution of sodium hydroxide (component f)) in water using moderate shear to obtain a homogeneous emulsion. The final emulsion had a solids content of 36,8 %, a viscosity of 1 mPa*s at 23 °C, a pH value of 9,5 and an average particle size of 1 ,15 microns. The emulsion was stable to 1 :50 dilution in a pH 5,5 aqueous buffer solution. The emulsion was found to be particularly effective in the hydrophobation of leather.
Comparative Example 1 )
31 parts of the dihydroxy-functional siloxane a2), with 1 ,2-dihydroxy functional groups, and 31 parts of the quaternary-ammonium-functional siloxane b1 ) were thoroughly mixed with 33 parts of oleic acid (component c)) and 5 parts of oleoyisarcosine
(component d)). This mixture was then combined with deionized water and 13,5 parts of a 40% solution of sodium hydroxide (component f)) in water using moderate shear to obtain a homogeneous emulsion. The final emulsion had a solids content of 31 , 1 %, a viscosity of 15 mPa*s at 23 °C and a pH value of 9. The emulsion was stable to 1 :50 dilution in a pH 5,5 aqueous buffer solution, but failed to yield leather with a durable hydrophobation.

Claims

Claims
1. Use of a polyorganosiloxane a) comprising at least one 1 ,3-dihydroxy alkyl
moiety in the treatment of fibrous substrates.
2. Use according to any of the preceding claims, wherein the fibrous substrate is leather, furs or leather substitutes.
3. Use according to any of the preceding claims in the hydrophobic treatment of the fibrous substrate.
4. Use according to any of the preceding claims, wherein the polyorganosiloxane a) is selected from polyorganosiloxanes having pendant and/or terminal 1 ,3- dihydroxy alkyl moieties.
5. Use according to any of the preceding claims, wherein 1 ,3-dihydroxy alkyl
moieties are bound to a silicon atom of the polyorganosiloxane moiety via a carbon atom.
6. Use according to any of the preceding claims, wherein the polyorganosiloxane a) has a 1 ,3-dihydroxy alkyl moiety of the formula:
-A-(B)V, wherein A is a di- or trivalent organic residue having up to 30 carbon atoms bound to a silicon atom of the polyorganosiloxane moiety via a carbon atom, B is an optionally substituted 1 ,3-dihydroxypropanyl moiety bound to the group A and v = 1 or 2.
7. Use according to any of the preceding claims, wherein the polyorganosiloxane a) has the formula: R R
I
B-Aj-Si— O- -Si- -O- -Si— o- -Si-fA-B) a
R R 3-a
3-a A. wherein a is 0 to 3, x is 0 to 1100, preferably 10 to 1000, y is 0 to 100, x+y is 0 to 1000, preferably 10 to 1 100, a + y is > 1 ,
A and B are as defined above,
R is an organic group having up to 25 carbon atoms.
8. Use according to any of the preceding claims, wherein the polyorganosiloxane a) has the formula:
Figure imgf000043_0001
or
Figure imgf000044_0001
wherein x and y are as defined above.
9. Use according to any of claims 1 to 8, wherein the polyorganosiloxane a) is used in a composition comprising at least one solvent, selected from the group consisting of water and organic solvents.
10. Use according to any of claims 1 to 9, wherein a composition comprising: a) at least one polyorganosiloxane a) as defined in any of the preceding claims,
b) at least one polyorganosiloxane b) - different from polyorganosiloxane a) - having one or more organic groups bound to the polyorganosiloxane backbone via an Si-C-bond, said organic group comprises at least one polar functional group, or salts thereof, is used.
11 . Use according to claim 10, wherein the composition comprises
per 100 parts by weight of the component a),
1 to 200 parts by weight of the component b).
12. Use according to claims 9 or 10, wherein the composition further comprises at least one component selected from component c), an organic silicon-free compound having at least one carboxy group or a salt thereof, and
component d), at least one surfactant, different from component a) to c).
13. Use according to in any of the claims 9 to 12, wherein the composition is an aqueous emulsion.
14. Use according to in any of the claims 9 to 12, wherein the composition is a
solution of at least one organic solvent.
15. A process for the treatment of fibrous substrates, which comprises the
contacting of the composition as defined in any of the claims 9 to 13 with fibrous substrates.
16. A process for the treatment of fibrous substrates according to claim 15, wherein the fibrous substrate is selected from tanned, dried leather, and the composition comprises a volatile organic solvent, which process further comprises the step of drying the leather to remove the volatile organic solvent.
17. A fibrous product treated with the composition as defined in any of the 9 to 12 claims.
PCT/EP2011/058720 2010-05-28 2011-05-27 Hydrophobizing of fibrous materials with polyorganosiloxanes WO2011147959A2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201180036896.3A CN103038274B (en) 2010-05-28 2011-05-27 Hydrophobizing of fibrous materials with polyorganosiloxanes
KR1020127033940A KR101875237B1 (en) 2010-05-28 2011-05-27 Hydrophobizing of fibrous materials with polyorganosiloxanes
EP20110721556 EP2576660B1 (en) 2010-05-28 2011-05-27 Hydrophobizing of fibrous materials with polyorganosiloxanes
US13/699,051 US8778457B2 (en) 2010-05-28 2011-05-27 Hydrophobizing of fibrous materials with polyorganosiloxanes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10164322 2010-05-28
EP10164322.9 2010-05-28

Publications (2)

Publication Number Publication Date
WO2011147959A2 true WO2011147959A2 (en) 2011-12-01
WO2011147959A3 WO2011147959A3 (en) 2012-01-19

Family

ID=43303916

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/058720 WO2011147959A2 (en) 2010-05-28 2011-05-27 Hydrophobizing of fibrous materials with polyorganosiloxanes

Country Status (5)

Country Link
US (1) US8778457B2 (en)
EP (1) EP2576660B1 (en)
KR (1) KR101875237B1 (en)
CN (1) CN103038274B (en)
WO (1) WO2011147959A2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150073069A1 (en) * 2013-09-11 2015-03-12 Evonik Industries Ag Coating composition comprising polysiloxane quats
WO2016111225A1 (en) * 2015-01-09 2016-07-14 信越化学工業株式会社 Polyoxyalkylene-modified diorganopolysiloxane compound, method for producing same, and organopolysiloxane emulsion composition
EP3336202A1 (en) 2016-12-13 2018-06-20 LANXESS Deutschland GmbH Process for preparing leather treating agents having hydrophobic effect
EP3501488A1 (en) 2017-12-21 2019-06-26 Momentive Performance Materials GmbH Aqueous silicone polymer compositions
EP3744175A1 (en) * 2019-05-31 2020-12-02 Rolex S.A. Composition for impregnating a substrate, in particular a watchstrap

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11179312B2 (en) 2017-06-05 2021-11-23 Momentive Performance Materials Inc. Aqueous compositions for the treatment of hair
JP6882236B2 (en) * 2017-10-10 2021-06-02 信越化学工業株式会社 Silicon-containing compounds, urethane resins, elastic films, and methods for forming them
JP7045766B2 (en) * 2017-10-13 2022-04-01 信越化学工業株式会社 Urethane resin, elastic membrane and its forming method
CN108085806A (en) * 2017-12-13 2018-05-29 武汉纺织大学 A kind of online preparation method of hydrophobic yarn for matching network composite spinning
CN108035023A (en) * 2017-12-13 2018-05-15 武汉纺织大学 A kind of hydrophobic yarn online preparation method of Seluofle composite spinning
CN107938052B (en) * 2017-12-13 2020-08-07 武汉纺织大学 Online preparation method of hydrophobic yarn of embedded composite spinning
US11090255B2 (en) 2018-12-04 2021-08-17 Momentive Performance Materials Inc. Use of polycarboxylic acid compounds for the treatment of fibrious amino acid based substrates, especially hair
CN112011657A (en) * 2019-05-31 2020-12-01 劳力士有限公司 Composition for impregnating substrates, in particular watch straps
NL2027334B1 (en) 2021-01-18 2022-07-25 Stahl Int B V Composition and process for waterproofing leather

Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2964425A (en) 1958-04-29 1960-12-13 Socony Mobil Oil Co Inc Waterproofing of leathers
GB1005475A (en) 1963-01-21 1965-09-22 Dow Corning Improvements in or relating to the treatment of leather
US3381019A (en) 1963-08-27 1968-04-30 Union Carbide Corp Siloxane-alcohol ethers
US3538137A (en) 1967-10-30 1970-11-03 Gen Electric Hydrolyzable organosilanes derived from silicon hydrogen compounds and trimethylol alkane derivatives
EP0095676A2 (en) 1982-05-21 1983-12-07 SWS Silicones Corporation Carboxylic acid-functional polysiloxane polymers, process for preparing the same and use thereof
US4640940A (en) 1985-08-13 1987-02-03 Loctite Corporation Polyol terminated silicones and derivatives thereof
EP0213480A2 (en) 1985-08-21 1987-03-11 BASF Aktiengesellschaft Method of water-proofing leather and furs
EP0324345A1 (en) 1988-01-12 1989-07-19 BASF Aktiengesellschaft Method for water-proofing leather, furs and synthetic leathers
EP0356963A2 (en) 1988-08-29 1990-03-07 Shin-Etsu Chemical Co., Ltd. Novel siloxane compounds terminated with a diol at one end thereof
EP0372746A2 (en) 1988-12-02 1990-06-13 Rohm And Haas Company The use of selected amphiphilic copolymers in the treatment of leather
EP0638128A1 (en) 1992-04-29 1995-02-15 Stockhausen Chem Fab Gmbh Process and agents for waterproofing materials having a fibrous structure.
WO1995030028A1 (en) 1994-04-29 1995-11-09 Stockhausen Gmbh & Co. Kg Agents and process for waterproofing leather and hides
WO1996015276A1 (en) 1994-11-15 1996-05-23 Basf Aktiengesellschaft Process for preparing leather and furs using polymer tanning agents
EP0745141A1 (en) 1994-02-16 1996-12-04 Basf Aktiengesellschaft Water-proofing process for leathers and pelts by comb-like carboxylated polysiloxanes
EP0757108A2 (en) 1995-08-03 1997-02-05 Rohm And Haas Company Method for waterproofing leather
WO1998021369A1 (en) 1996-11-13 1998-05-22 Basf Aktiengesellschaft Use of carboxyamide-polysiloxanes for water-proofing leather
EP1010748A1 (en) 1998-12-15 2000-06-21 Ck Witco Corporation Diesel fuel antifoam composition
EP1087021A1 (en) 1999-09-18 2001-03-28 Trumpler GmbH & Co. Chemische Fabrik Leather-treatment agent
EP1108765A2 (en) 1999-12-13 2001-06-20 Bayer Ag Hydrophobisation with carboxyl group containing polysiloxanes
EP1108705A1 (en) 1999-12-15 2001-06-20 Sumitomo Chemical Company, Limited Process for alkylation on the aromatic ring of phenols or of ethers of phenols
WO2003064707A1 (en) 2002-01-31 2003-08-07 Tfl Ledertechnik Gmbh Compositions and its use for imparting water repellency to leather or furskins, textiles and other fibrous materials
EP1416057A1 (en) 2002-10-28 2004-05-06 Bayer Chemicals AG Chrome free waterproof leather
EP1702991A2 (en) 2005-03-17 2006-09-20 Lanxess Deutschland GmbH Process for hydrophobing leather using alkylalkoxysilanes and hydrophobic leather obtained therewith

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MXPA05004805A (en) * 2002-11-04 2005-07-22 Procter & Gamble Fabric treatment compositions comprising oppositely charged polymers.
DE102006042869A1 (en) * 2006-09-13 2008-03-27 Evonik Goldschmidt Gmbh Novel polycarboxy-functional organosiloxanyl derivatives and their use for the treatment of leather
DE102007030642A1 (en) * 2007-07-02 2009-01-08 Momentive Performance Materials Gmbh Process for the preparation of polyorganosiloxanes having (C6-C60) -alkylmethylsiloxy groups and dimethylsiloxy groups
JP5042807B2 (en) * 2007-12-27 2012-10-03 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 Hair cosmetic composition
KR101627304B1 (en) * 2009-11-24 2016-06-03 모멘티브 퍼포먼스 머티리얼즈 게엠베하 Hydrophilic/lipophilic modified polysiloxanes as emulsifiers

Patent Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2964425A (en) 1958-04-29 1960-12-13 Socony Mobil Oil Co Inc Waterproofing of leathers
GB1005475A (en) 1963-01-21 1965-09-22 Dow Corning Improvements in or relating to the treatment of leather
US3381019A (en) 1963-08-27 1968-04-30 Union Carbide Corp Siloxane-alcohol ethers
DE1283238B (en) 1963-08-27 1968-11-21 Union Carbide Corp Process for the preparation of hydroxyalkyloxyalkylsiloxanes
US3538137A (en) 1967-10-30 1970-11-03 Gen Electric Hydrolyzable organosilanes derived from silicon hydrogen compounds and trimethylol alkane derivatives
EP0095676A2 (en) 1982-05-21 1983-12-07 SWS Silicones Corporation Carboxylic acid-functional polysiloxane polymers, process for preparing the same and use thereof
US4640940A (en) 1985-08-13 1987-02-03 Loctite Corporation Polyol terminated silicones and derivatives thereof
EP0213480A2 (en) 1985-08-21 1987-03-11 BASF Aktiengesellschaft Method of water-proofing leather and furs
EP0324345A1 (en) 1988-01-12 1989-07-19 BASF Aktiengesellschaft Method for water-proofing leather, furs and synthetic leathers
EP0356963A2 (en) 1988-08-29 1990-03-07 Shin-Etsu Chemical Co., Ltd. Novel siloxane compounds terminated with a diol at one end thereof
EP0372746A2 (en) 1988-12-02 1990-06-13 Rohm And Haas Company The use of selected amphiphilic copolymers in the treatment of leather
EP0638128A1 (en) 1992-04-29 1995-02-15 Stockhausen Chem Fab Gmbh Process and agents for waterproofing materials having a fibrous structure.
EP0745141A1 (en) 1994-02-16 1996-12-04 Basf Aktiengesellschaft Water-proofing process for leathers and pelts by comb-like carboxylated polysiloxanes
WO1995030028A1 (en) 1994-04-29 1995-11-09 Stockhausen Gmbh & Co. Kg Agents and process for waterproofing leather and hides
WO1996015276A1 (en) 1994-11-15 1996-05-23 Basf Aktiengesellschaft Process for preparing leather and furs using polymer tanning agents
EP0757108A2 (en) 1995-08-03 1997-02-05 Rohm And Haas Company Method for waterproofing leather
WO1998021369A1 (en) 1996-11-13 1998-05-22 Basf Aktiengesellschaft Use of carboxyamide-polysiloxanes for water-proofing leather
EP0938590A1 (en) 1996-11-13 1999-09-01 Basf Aktiengesellschaft Use of carboxyamide-polysiloxanes for water-proofing leather
EP1010748A1 (en) 1998-12-15 2000-06-21 Ck Witco Corporation Diesel fuel antifoam composition
EP1087021A1 (en) 1999-09-18 2001-03-28 Trumpler GmbH & Co. Chemische Fabrik Leather-treatment agent
EP1108765A2 (en) 1999-12-13 2001-06-20 Bayer Ag Hydrophobisation with carboxyl group containing polysiloxanes
EP1108705A1 (en) 1999-12-15 2001-06-20 Sumitomo Chemical Company, Limited Process for alkylation on the aromatic ring of phenols or of ethers of phenols
WO2003064707A1 (en) 2002-01-31 2003-08-07 Tfl Ledertechnik Gmbh Compositions and its use for imparting water repellency to leather or furskins, textiles and other fibrous materials
EP1470258A1 (en) 2002-01-31 2004-10-27 TFL Ledertechnik GmbH Composition and its use for imparting water repellency to leather or furskins, textiles and other fibrous materials
US7250456B2 (en) 2002-01-31 2007-07-31 Tfl Ledertechnik Gmbh Composition and its use for imparting water repellency to leather or furskins, textiles and other fibrous materials
EP1416057A1 (en) 2002-10-28 2004-05-06 Bayer Chemicals AG Chrome free waterproof leather
EP1702991A2 (en) 2005-03-17 2006-09-20 Lanxess Deutschland GmbH Process for hydrophobing leather using alkylalkoxysilanes and hydrophobic leather obtained therewith

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZIMMERMANN INGENIEUR TECHNIK, vol. 68, no. 4, 1996

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150073069A1 (en) * 2013-09-11 2015-03-12 Evonik Industries Ag Coating composition comprising polysiloxane quats
US9353289B2 (en) * 2013-09-11 2016-05-31 Evonik Degussa Gmbh Coating composition comprising polysiloxane quats
WO2016111225A1 (en) * 2015-01-09 2016-07-14 信越化学工業株式会社 Polyoxyalkylene-modified diorganopolysiloxane compound, method for producing same, and organopolysiloxane emulsion composition
JP2016128538A (en) * 2015-01-09 2016-07-14 信越化学工業株式会社 Polyoxyalkylene-modified diorganopolysiloxane compound, method of producing the same, and organopolysiloxane emulsion composition
EP3336202A1 (en) 2016-12-13 2018-06-20 LANXESS Deutschland GmbH Process for preparing leather treating agents having hydrophobic effect
WO2018108595A1 (en) 2016-12-13 2018-06-21 Lanxess Deutschland Gmbh Method for producing hydrophobising leather treatment agents
EP3501488A1 (en) 2017-12-21 2019-06-26 Momentive Performance Materials GmbH Aqueous silicone polymer compositions
EP3744175A1 (en) * 2019-05-31 2020-12-02 Rolex S.A. Composition for impregnating a substrate, in particular a watchstrap

Also Published As

Publication number Publication date
EP2576660A2 (en) 2013-04-10
US20130130040A1 (en) 2013-05-23
EP2576660B1 (en) 2014-04-02
CN103038274A (en) 2013-04-10
US8778457B2 (en) 2014-07-15
KR20130109020A (en) 2013-10-07
WO2011147959A3 (en) 2012-01-19
CN103038274B (en) 2015-03-25
KR101875237B1 (en) 2018-07-05

Similar Documents

Publication Publication Date Title
EP2576660B1 (en) Hydrophobizing of fibrous materials with polyorganosiloxanes
JP4510721B2 (en) Aminosiloxane oil-in-water emulsion and use thereof
DE102007020790B4 (en) Fluorocarbon polymer-free preparations based on water and / or organic solvents and their use as a finish on fabrics and textile substrates obtained therefrom
US5925469A (en) Organopolysiloxane emulsions
DE69312956T2 (en) FLUORALIPHATIC END GROUPS AND CARBOXYL END GROUPS CONTAINING POLYSILOXANS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN THE TREATMENT OF FIBROUS SUBSTRATES
JP5449179B2 (en) Fabric with improved wet strength treated with a copolymer of epoxy compound and aminosilane
CN102159605B (en) Aqueous polymer dispersion composition and surface treatment agent
CA2149958A1 (en) Self-crosslinking preparations, production and use thereof
CN101952350B (en) Polydiorganosiloxane bearing carbamate functions, their preparation and their use as softeners in the textile industry
JP2513979B2 (en) Process for the preparation of emulsions containing acylated amino-functional organopolysiloxanes
JP2007525604A (en) Treatment of fabrics with emulsions containing silicone resins.
JP2002537434A (en) Shear stable amino silicone emulsion
JP3403217B2 (en) Organosilicon compound emulsion composition
KR101854906B1 (en) Compositions of aminosiloxanes, alkoxysilicon compounds and metal carboxylates
KR101495689B1 (en) Mixtures comprising aminoalkyl-containing polyorganosiloxanes and silicone resins
DE4240274A1 (en) Polysiloxanes with fluoroaliphatic and carboxyl-containing terminal groups, their preparation and their use in the treatment of fibrous substrates
JP6978323B2 (en) Polyurethane organic polysiloxane
US5514418A (en) Fiber treatment compositions and methods for the preparation thereof
CN101443372B (en) Silicone polymers crosslinkable via methylol groups
JP6149788B2 (en) Film-forming silicone emulsion composition and film
CN107163208B (en) Durable environment-friendly fluorine-containing nano three-proofing finishing agent and preparation method and application thereof
TW202222921A (en) Silicone emulsion composition and fiber treatment agent
JPS5950179B2 (en) Silicone emulsion composition
JP7414079B2 (en) Water absorption inhibitor and paperboard
RU2114881C1 (en) Aqueous emulsion composition on the base of polyorganosiloxane for treatment of fibrous materials

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180036896.3

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11721556

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 10152/DELNP/2012

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 2011721556

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20127033940

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 13699051

Country of ref document: US

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112012030079

Country of ref document: BR

REG Reference to national code

Ref country code: BR

Ref legal event code: B01E

Ref document number: 112012030079

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112012030079

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20121126