EP1506336A2 - Softening silicone formulations for textile finishing - Google Patents

Softening silicone formulations for textile finishing

Info

Publication number
EP1506336A2
EP1506336A2 EP03749889A EP03749889A EP1506336A2 EP 1506336 A2 EP1506336 A2 EP 1506336A2 EP 03749889 A EP03749889 A EP 03749889A EP 03749889 A EP03749889 A EP 03749889A EP 1506336 A2 EP1506336 A2 EP 1506336A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
chain
stands
sum
independently
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP03749889A
Other languages
German (de)
French (fr)
Other versions
EP1506336B1 (en
Inventor
Winfried Guth
Rainer Idel
Detlev Kierspe
Friedrich Koch
Peter Landenberger
Helmut-Martin Meier
Horst Lange
Roland Wagner
Jürgen Krott
Annette MÖLLER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Momentive Performance Materials GmbH
Original Assignee
GE Bayer Silicones GmbH and Co KG
Bayer Chemicals AG
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 GE Bayer Silicones GmbH and Co KG, Bayer Chemicals AG filed Critical GE Bayer Silicones GmbH and Co KG
Publication of EP1506336A2 publication Critical patent/EP1506336A2/en
Application granted granted Critical
Publication of EP1506336B1 publication Critical patent/EP1506336B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01B—PERMANENT WAY; PERMANENT-WAY TOOLS; MACHINES FOR MAKING RAILWAYS OF ALL KINDS
    • E01B37/00—Making, maintaining, renewing, or taking-up the ballastway or the track, not provided for in a single one of groups E01B27/00 - E01B35/00
    • 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
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/17—Halides of elements of Groups 3 or 13 of the Periodic Table
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71—Salts of phosphoric acids
    • 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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • 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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • 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
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C19/00—Machines, tools or auxiliary devices for preparing or distributing paving materials, for working the placed materials, or for forming, consolidating, or finishing the paving
    • E01C19/12—Machines, tools or auxiliary devices for preparing or distributing paving materials, for working the placed materials, or for forming, consolidating, or finishing the paving for distributing granular or liquid materials
    • E01C19/18—Devices for distributing road-metals mixed with binders, e.g. cement, bitumen, without consolidating or ironing effect
    • E01C19/185—Devices for distributing road-metals mixed with binders, e.g. cement, bitumen, without consolidating or ironing effect for both depositing and spreading-out or striking-off the deposited mixture
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01B—PERMANENT WAY; PERMANENT-WAY TOOLS; MACHINES FOR MAKING RAILWAYS OF ALL KINDS
    • E01B21/00—Track superstructure adapted for tramways in paved streets
    • 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 invention relates to new formulations based on quaternized aminoalkyl silicones or siloxanes, processes for the preparation of these formulations and their use as textile auxiliaries for finishing textile materials.
  • Silicone plasticizers are used in a variety of ways to finish textile materials.
  • requirements such as storage stability, temperature stability, resistance to whitening agents and other anionic textile auxiliaries, resistance to pH changes and salt addition and to the effects of mechanical energy are of central importance.
  • stability against the action of mechanical energy shear stability or jet stability often causes great difficulties in silicone emulsifier emulsions under practical conditions (cf. R. Zyschka, Melliand Textile Reports 6/2001, 497).
  • Microemulsions basically offer the advantage of thermodynamic stability.
  • the equilibrium phase behavior depending on the structure of the oil to be emulsified and the surfactant (s) has been dealt with in a large number of publications.
  • the addition of inorganic salts has also been studied systematically (see M. Kahlweit et.al., Langmuir 11 [1995], 3382; M. Kahlweit et.al., Langmuir 11 [1995]).
  • the equilibrium phase behavior of microemulsions of low molecular weight silicones has also been investigated (EP-A 774482; H. von Berlepsch et.al, Progr. Colloid Polymer Science 111 [1998], 107).
  • Fine-particle microemulsions of aminoalkylsiloxanes are said to be accessible in a two-stage process by preparing a concentrate from aminoalkylsiloxane, silicone-insoluble surfactant and a little water with subsequent rapid stirring into water (US Pat. No. 4,620,878).
  • aminosiloxane emulsions are said to be mechanically stable through the use of water-soluble nonionic emulsifiers.
  • extreme shear loads such as are achieved on modern jet systems, it was found that the inventions disclosed in DE-A 3723697 are not sufficient to prevent failures in the jet systems and on the textiles to be treated.
  • amino-functional organosilicon compounds should also be mechanically stable in jet dyeing machines without the use of water-soluble nonionic emulsifiers. It was found that the measures disclosed in WO 02/10501 are also still not sufficient to reliably prevent the precipitation on differently pretreated textiles.
  • salts of strong acids for example Al 2 (SO4) 3 x 18 HO, ensure the protonation of cationic dyes in thermal transfer printing pastes, but at the same time impair their stability (cf. US-A 5925701).
  • this object can be achieved by combining quaternized ammoalkylsiloxanes with highly hydrophilic nonionic surface-active compounds (surfactants) and / or highly hydrophilic dispersants and / or salts of polyvalent cations and, if appropriate, other customary formulation agents.
  • surfactants highly hydrophilic nonionic surface-active compounds
  • dispersants and / or salts of polyvalent cations and, if appropriate, other customary formulation agents.
  • the present invention therefore relates to formulations comprising at least one quaternized aminoalkylsiloxane and at least one compound from the series
  • hydrophilic, nonionic surface-active compounds b) the hydrophilic dispersant and c) the salts of divalent or trivalent metals with inorganic acids.
  • Preferred hydrophilic, nonionic surface-active compounds (a) for the purposes of the invention are substances which reduce the surface tension of water to below 45 mN / m. It is particularly ethylene propylene oxide (EO / PO) modified compounds, optionally unsaturated and / or branched, from the group of fatty alcohols, fatty acids, alcohols, acids, alkylaryl derivatives, fatty amines, glycerides and sorbitan esters, in which the number of EO / PO Units is between 15 and 150, the ratio of PO units to EO units being 0.25 or less than 0.25, and in which the number of ethylene oxide units (EO part) is greater than or equal to the number of carbon atoms in the non- EO is part, and around alkyl polyglycosides, ethylene oxide / propylene oxide copolymers and polyether siloxanes.
  • Hydrophilic dispersants (b) in the sense of the invention are substances whose addition to water lowers the surface tension to a
  • the preferred compounds (b) are water-soluble polysaccharides such as carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose or compounds of the formula
  • x stands for 1.5 to 20, preferably 1.5 to 10.
  • the salts (c) are divalent or higher metal salts, preferably calcium, magnesium and aluminum salts, optionally in the form of their hydrates, with inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid.
  • the counterions should be selected so that, given the stability of the salt, sufficient water or formulation solubility is guaranteed. Examples of such salts are Ca (Cl) 2 , Mg (Cl) 2 and Al 2 (S ⁇ 4) 3 , optionally in the form of their hydrates.
  • E for a radical R 1 hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 8 -alkyl, which is optionally substituted mono- or melirfach by -OH, CC / ralkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl is, or is C 5 -C ⁇ o-cycloalkyl, which is optionally substituted one or more times by -C-C 4 alkyl, -OH, -C-C 4 alkoxy, C ⁇ -C 4 alkoxycarbonyl or carbonyl,
  • R 1 represents straight-chain or branched, saturated or unsaturated C 8 -C 4 o-alkyl, the alkyl chain of which is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which is optionally one or more times by -OH, -C-C 4 -alkoxy, -C-C 4 -alkoxycarb- onyl or carbonyl, amino, mono- or di- CrC -alkylamino is substituted, or represents C 5 -C ⁇ o-cycloalkyl, the alkyl chain of which may be one or more times by oxygen and / or nitrogen atoms is interrupted and which is optionally substituted one or more times by C 1 -C 4 -alkyl, -OH, - C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl, amino, mono- or di-Ci- C 4 -alkylamino is
  • R 2 stands for straight-chain or branched, saturated or mono- to polyunsaturated C 8 -C 4 o-alkyl, which is optionally substituted one or more times by -OH, -CC 4 alkoxy, -C 4 -alkoxycarbonyl or carbonyl is
  • R 3 represents straight-chain or branched C 1 -C 26 alkyl or C 6 -C 8 aryl, -CH 2 CH 2 -O- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E,
  • Z is a straight-chain or branched alkyl or cycloalkyl radical, which can in each case be interrupted by -O- and / or -CO- and optionally substituted by at least one OH group
  • ql and q2 are independently 0 to 150
  • r 0 to 50
  • rl and r2 independently of one another represent 0 to 50
  • r3, r4, r5 and r6 independently of one another represent 0 to 50
  • n 1 to 50
  • n and m.8 independently of one another represent 1 to 50
  • the compounds (a) are also those of the formulas (1 ') to (9')
  • bracketed expressions " ⁇ " and " ⁇ " shown in the formulas (1 ') - (8') mean that the ethylene oxide or propylene oxide units contained within these bracketed expressions can either be arranged in blocks as shown or else randomly can be arranged
  • R 1 hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 8 -alkyl which may be mono- or poly-optionally by -OH, -C-C 4 alkoxy, C 1 -C 4 alkoxycarbonyl or carbonyl groups, or is Cs-Cio-cycloalkyl, which is optionally monosubstituted or polysubstituted in each case by C ⁇ -C 4 - substituted alkyl, -OH, C ⁇ -C 4 -alkoxy, C 4 alkoxycarbonyl, or carbonyl,
  • R 1 represents straight-chain or branched, saturated or unsaturated C 8 -C 4 o -alkyl, the alkyl chain of which is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which is substituted one or more times by -OH, Ci-C -alkoxy, -C-C 4 -alkoxycarb- onyl or carbonyl, amino, mono- or di- -CC 4 -alkylamino, or for C 5 -C ⁇ o-cycloalkyl stands, whose alkyl chain is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which optionally one or more times by C 1 -C 4 -alkyl, -OH, d- C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or Carbonyl, amino, mono- or di-Ci-C 4 alkylamino is substituted, or stands for C 6 -C ⁇ o aryl, which is optionally
  • R 2 represents straight-chain or branched, saturated or mono- to polyunsaturated C 8 -C 4 o-alkyl, which is optionally substituted one or more times by -OH, -CC 4 -alkoxy, -C-C 4 alkoxycarbonyl or carbonyl is
  • R 3 represents straight-chain or branched C 6 -C 6 alkyl or C 6 -C 6 aryl
  • Z is a straight-chain or branched alkyl or cycloalkyl radical which is interrupted in each case by -O- and / or -CO- and is optionally substituted by at least one OH group or
  • parentheses “ ⁇ ” and “ ⁇ ” shown in the aforementioned formulas in turn mean that the ethylene oxide or propylene oxide units within these parentheses are either arranged in blocks as shown. can be or can also be randomly arranged as desired,
  • ql and q2 are independently 0 to 150
  • q3, q4, q5 and q6 independently of one another represent 0 to 150
  • r 0 to 50
  • rl and r2 independently of one another represent 0 to 50
  • n 1 to 50
  • n and m8 independently of one another represent 1 to 50
  • s represents 5 to 150, preferably 15-150
  • t represents 0 to 150, preferably 5 to 150 and in particular 5 to 20,
  • E represents hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C ⁇ -C 4 - alkyl which is substituted 4 alkoxycarbonyl or carbonyl optionally having 1 to disubstituted by -OH, -C 4 -alkoxy, C, or C 5 -C 6 cycloalkyl, which is in each case optionally substituted one to more times by C 1 -C 4 alkyl, -OH, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl or carbonyl,
  • R 1 represents straight-chain or branched, saturated or unsaturated C 1 -C 36 -alkyl, the alkyl chain of which is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which may be one or more times by -OH, -C-C 4 - Alkoxy, -CC 4 -alkoxycarb- onyl or carbonyl, amino, mono- or di -CC-C 4 alkylamino is substituted, or stands for Cs-C ö cycloalkyl, the alkyl chain of which may be one or more times by oxygen and / or nitrogen atoms is interrupted and which is optionally one or more times by -CC 4 -Al yl, -OH, -C-C 4 -alkoxy, -C-C 4 -alkoxycarbonyl or carbonyl, amino, mono- or di-Ci- C 4 -alkylamino is substituted,
  • R represents straight-chain or branched, saturated or mono- to polyunsaturated C 1 -C 36 -alkyl, which is optionally substituted one or more times by -OH, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl,
  • R 3 represents straight-chain or branched C 1 -C 8 alkyl or C 6 -C 8 aryl
  • R 4 for a radical R 3 or for a radical of the formulas or
  • ql and q2 independently represent 20 to 100
  • q3, ⁇ 5 and q6 independently represent 20 to 100
  • rl and r2 independently of one another represent 0 to 20,
  • r3, r4, r5 and r6 independently of one another represent 0 to 20,
  • n 1 to 7 m7 and m8 are independently from 1 to 7,
  • the compounds (a) are also those of the formulas (1 ') to (9'), in which
  • C 1 -C 4 -alkyl which is optionally 1 to 2 times substituted by -OH, -CC 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl, or for C 5 -C 5 cycloalkyl, which in each case optionally up to is substituted several times by C 1 -C 4 -alkyl, -OH, CrC 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl,
  • R 1 represents straight-chain or branched, saturated or unsaturated C 1 -C 36 -alkyl, the alkyl chain of which is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which may be one or more times by -OH, -C-C 4 - Alkoxy, -CC -alkoxycarb- onyl or carbonyl, amino, mono- or di- C 1 -C 4 alkylamino is substituted, or represents Cs-C ⁇ -cycloalkyl, the alkyl chain of which may be one or more times by oxygen and / or nitrogen atoms and which is optionally one or more times by C] .
  • R represents straight-chain or branched, saturated or mono- to polyunsaturated C 1 -C 36 -alkyl, which is optionally substituted one or more times by -OH, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl,
  • R for straight-chain or branched C] . -C 18 alkyl or C 6 -Cio aryl,
  • ql and q2 independently represent 20 to 100
  • q3, q4, q5 and q ⁇ independently represent 20 to 100
  • rl and r2 independently of one another represent 0 to 20,
  • r3, r4, r5 and r6 independently of one another represent 0 to 20,
  • n 1 to 7
  • n 1 to 7
  • the ratio of q: m> 4 s represents 5 to 100, preferably 15 to 100,
  • t represents 5 to 100, preferably 5 to 20,
  • the compounds (a) are particularly preferably those of the formulas (1) to (9), in which
  • n3 0 to 18,
  • n5 3 to 15,
  • n6 8 to to 28,
  • R 3 represents -C 8 -alkyl or C 6 -C 10 -aryl
  • R 4 for a radical R 3 or for a radical of the formulas
  • ql and q2 independently represent 25 to 60
  • q3, q4, q5 and q6 independently represent 25 to 60
  • r 0 to 10
  • rl and r2 are independently 0 to 10,
  • r3, r4, r5 and r6 independently of one another represent 0 to 10,
  • the compounds (a) are also particularly preferably those of the formulas (1 ') to (9'), in which
  • n2 3 to 23, preferably 6 to 23
  • n3 0 to 18, preferably n2 + n3 ⁇ 31,
  • n5 3 to 15,
  • n6 8 to to 28,
  • R 3 represents Ci-Cis-alkyl or C 6 -C ⁇ 0 -aryl
  • ql and q2 independently represent 25 to 60
  • q3, q4, q5 and q6 independently represent 25 to 60
  • r 0 to 10
  • rl and r2 are independently 0 to 10,
  • r3, r4, r5 and r6 independently of one another represent 0 to 10,
  • Formulations according to the invention which contain the ester of stearic acid and 40 mol of EO as compound (a) are very particularly preferred.
  • the formulations according to the invention contain at least one ammoalkylsiloxane compound (silicone quat) quaternized on nitrogen.
  • ammoalkylsiloxane compound silicone quat
  • Such compounds and their preparation are known, e.g. from WO 02/10 256, WO 02/10 257, WO 02/10 259, EP 282 720, EP 17 121, DE-A 100 36 533, DE-A 100 36 539, DE-A 100 36 532, DE- A 100 36 522 and DE -A 102 12 470.
  • the quaternized ammoalkylsiloxane compounds contained in the formulations according to the invention preferably correspond to linear or cyclic poly- siloxane polymers of WO 02-10259 with repeating essential structural units of the formulas (10) and (11)
  • X is a divalent hydrocarbon radical with at least 4 carbon atoms, which may have a hydroxyl group and preferably has a hydroxyl group and which may be interrupted by an oxygen atom, and the groups X in the repeating units may be the same or different,
  • Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by one or more oxygen or nitrogen atoms,
  • R 11 , R 12 , R 13 and R 1 "* are identical or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals or the radicals R 11 and R 13 or R 12 and R 14 can each be constituents of a bridging alkylene radical, R 16 is H or an alkyl radical with 1 to 20 carbon atoms, which may be oxygen-substituted,
  • EOx is an ethylene oxide unit and POx is a propylene oxide unit
  • n 2 to 1000 in which the n in the repeating units can be the same or different, and
  • A- means an inorganic or organic anion.
  • the formulations according to the invention optionally also contain any mixtures of the above-mentioned quaternized aminoalkylsiloxane compounds with the corresponding non-quaternized compounds.
  • one of the radicals R 11 or R 12 or R 13 or R 14 is therefore missing in the formula (10) on the nitrogen atoms in the main chain
  • the quaternized aminoalkylsiloxane compounds preferred according to the invention are the subject of WO 02/10 259 and are described there generally and specifically.
  • the content of WO 02/10 259 is hereby fully encompassed by the present application.
  • ⁇ only represents the ratio of the total amount of components (a) to (c) to the amount of silicone quat. If the amounts of additive (a) and / or (b) and / or (c) used are too small, the effective stabilization in the fiber equipment is exhausted, that is to say, for example, that the shear stability may not always be the case under strong mechanical shear, high temperatures, and long equipment cycles can be maintained. Very large additional quantities are uneconomical and can undesirably change the soft feel of the textile.
  • the additives a) to c) described can be added in two ways. On the one hand, it is possible for the additives according to the invention to be introduced directly into the formulations. On the other hand, it may be preferred under practical conditions to first dilute the formulations to the application concentration and then to add the additives according to the invention to the prepared liquor.
  • the formulations according to the invention can also contain further surface-active components (f) which enable emulsification or microemulsification.
  • components (f) are customary formulation agents known to those skilled in the art for the preparation of the silicone (micro) emulsions, but these alone are not stable against high energy input.
  • examples of such preferred components are f1 to f6): (f1) oxyalkylation products which can be obtained by alkoxylation with ethylene oxide or propylene oxide from condensation products of phenolic OH group-containing aromatics with formaldehyde and NH-functional groups.
  • non-ionic or ionically modified compounds from the group of alkoxylates, alkylolamides, esters, amine oxides and alkyl poly- glycosides, in particular reaction products of alkylene oxides with alkylatable compounds, such as, for example, fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, carboxamides and resin acids.
  • ethylene oxide ethers from the class of the reaction products of ethylene oxide with saturated and / or unsaturated fatty alcohols with 6 to 25 C atoms (commercially available, for example in the form of the Renex® product series) or alkylphenols with 4 to 12 C atoms in the alkyl radical or saturated and / or unsaturated fatty amines with 14 to 20 carbon atoms or saturated and / or unsaturated fatty acids with 14 to 22 carbon atoms or esterification and / or arylation products prepared from natural or modified, optionally hydrogenated castor oil fatty substances, which may be by esterification with Dicarboxylic acids are linked to recurring structural units.
  • Ionic or non-ionic compounds from the group of the reaction products of alkylene oxide with sorbitan esters [Tween, ICI], oxalkylated acetylenediols and glycols, oxalkylated phenols, in particular phenol / styrene polyglycol ethers.
  • ionic or nonionic polymeric surface-active agents from the group of homopolymers and copolymers, graft and graft copolymers and statistical and linear block copolymers.
  • anionic surfactants such as alkyl sulfates, ether sulfates, ether carboxylates, phosphate esters, sulfosuccinatamides, paraffin sulfonates, olefin sulfonates, sarcosinates, isothionates and taurates f6) amphoteric surfactants such as betaines and ampholytes, especially glycinates, propionates and imidazolines.
  • Particularly preferred formulation constituents (f) are alkoxylated fatty alcohols, branched fatty alcohols and fatty acids with 4 to 14 alkoxide units, very particularly preferred formulation constituents (f) are alkoxylated fatty alcohols, branched fatty alcohols with 6 to 12 alkoxide units, especially formulations which contain the ether of tridecyl alcohol with 12 mol EO, the ether of tridecyl alcohol containing 6 mol EO.
  • the formulation constituents are generally added to the formulation according to the invention in customary amounts.
  • Components (f) are preferably added in amounts of 1 to 200% by weight, preferably 10 to 80% by weight, particularly preferably 10-50% by weight, based on the quaternized aminoalkylsiloxane.
  • the formulations may in each case, alone or in combination, and additives (f) also contain other auxiliaries in the amounts customary for these auxiliaries.
  • Usual aids in the sense of the invention include Leveling agents, wetting agents, gloss finishes, fiber protection agents, anti-slip agents and other auxiliaries according to the prior art.
  • a good overview of the auxiliaries according to the invention can be found in Chwala / Anger, Handbuch der Textilosstoff, Verlag Chemie, Weinhein 1977.
  • buffer systems can be incorporated to adjust an optimal pH during the finishing.
  • the quaternized aminoalkylsiloxane compounds can be mixed with components (a), (b) and / or (c), if appropriate with the addition of further components mentioned above, preferably in the temperature range from 20 to 90 ° C. particularly preferably at 25 to 70 ° C, very particularly preferably at 30 to 60 ° C.
  • the quaternized aminoalkylsiloxanes are preferably added to the compound (s) (a), (b) and / or (c);
  • the quaternized aminoalkylsiloxane (silicone quat) is particularly preferably introduced and the emulsion formation is completed by adding the compound (s) (a), (b) and / or (c) and, if appropriate, further additives.
  • the formulations according to the invention are outstandingly suitable as textile softeners when finishing textile fabrics, in particular those made of cotton, keratin fibers, preferably wool, silk or synthetic fibers or for example, very good for finishing textile fabrics made from blends of cotton with polyester, polyamide, polyacrylonitrile, wool or silk. Excellent results are also achieved when finishing textile fabrics made of synthetic fibers, especially polyester, polyamide, polypropylene or mixtures thereof
  • Textile fabrics are preferably fabrics, knitted fabrics, knitwear and nonwovens.
  • the equipment is generally carried out by the continuous process (padding or lisseuse process) or by the exhaust process (jet process).
  • the formulations according to the invention using one of these finishing methods, it has proven to be advantageous to comply with the following technological parameters:
  • Drying temperature 75-105 ° C in a convection oven or
  • Equipment temperature 30-60 ° C, preferably 35-50 ° C and especially 35-45 ° C
  • Heating rate 2-4 ° C / minute 4. Finishing time: 15-25 minutes 5.
  • Fleet ratio 1: 5 to 1:50, especially 1:10 to 1:30 6. Drying temperature 75-105 ° C in a circulating air oven or 10-60 sec on the stenter at 150 ° C, especially 30-45 sec
  • microemulsion concentrates (about 40% based on SQ) are uniformly diluted with water to 11% silicone quat content.
  • 6 g (absolute silicone quat quantity 0.66 g) of each of these 11% transparent microemulsions are taken, mixed intensively with 6000 ml of water and any additives and used for jet equipment under the following boundary conditions: Jet type: Mathis Laboratory Jumbo-Jet jet pump: Level 6 ( highest possible shear) Water volume in the jet: 6000 ml Equipment: 15 minutes at 40 ° C drying: 80 ° C
  • Renex® 36 trade name of ICI surfactants Tridecyl Alcohol- (EO) 12 -OH Renex® 30 trade name of the ICI surfactants; Tridecyl alcohol- (EO) 6 -OH Crodet® S40 trade name of Croda GmbH; Stearic acid (EO) 4 o-OH
  • Experiment 1 describes the unacceptable result of an experiment according to the prior art which is not according to the invention. A doubling of the amount of surfactant of both Renex types does not prevent the failure (test 2, not according to the invention).
  • Experiments 3 and 4 prove that precipitation can be reliably prevented by adding salts of polyvalent cations according to the invention. Aluminum salts are more effective than magnesium compounds.
  • Experiment 5 shows that by incorporating hydrophilic surface-active compounds directly into the formulation, precipitation is reliably prevented. This also applies to a partial subsequent addition (experiment 6) or complete addition (experiment 7) according to the invention of this hydrophilic surface-active compound.

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Abstract

The invention concerns novel formulations containing at least one quaternized aminoalkylsiloxane and at least one compound selected among: a) non-ionic hydrophilic surfactant compounds, b) hydrophilic dispersants and c) divalent of trivalent metal salts with inorganic acids. Said formulations are excellent textile softeners for finishing textile structures in accordance with continuous or drawing process and are characterized by particular shearing stability.

Description

Formulierungen von Silikonweichmachern für die textile AusrüstungFormulations of silicone softeners for textile finishing
Die Erfindung betrifft neue Formulierungen auf Basis von quaternierten Amino- alkylsiliconen bzw. -siloxanen, Verfahren zur Herstellung dieser Formulierungen und deren Verwendung als Textilhilfsmittel zur Ausrüstung von Textilmaterialien.The invention relates to new formulations based on quaternized aminoalkyl silicones or siloxanes, processes for the preparation of these formulations and their use as textile auxiliaries for finishing textile materials.
Silikonweichmacher werden vielfältig zur Ausrüstung von Textilmaterialien eingesetzt. Für den praktischen Einsatz der Silikonweichmacheremulsionen sind Anforderungen wie Lagerstabilität, Temperaturstabilität, Resistenz gegenüber Weißtönern und anderen anionischen Textilhilfsmitteln, Resistenz gegen pH- Wert Änderungen und Salzzusatz und gegen die Einwirkung mechanischer Energie von zentraler Bedeutung. Besonders die Stabilität gegen die Einwirkung mechanischer Energie, die Scherstabilität oder Jetstabilität, bereitet Silikonweichmacheremulsionen unter Praxisbedingungen oftmals große Schwierigkeiten (vgl. R. Zyschka, Melliand Textil- berichte 6/2001, 497).Silicone plasticizers are used in a variety of ways to finish textile materials. For practical use of silicone softening emulsions, requirements such as storage stability, temperature stability, resistance to whitening agents and other anionic textile auxiliaries, resistance to pH changes and salt addition and to the effects of mechanical energy are of central importance. In particular, stability against the action of mechanical energy, shear stability or jet stability often causes great difficulties in silicone emulsifier emulsions under practical conditions (cf. R. Zyschka, Melliand Textile Reports 6/2001, 497).
Microemulsionen bieten grundsätzlich den Vorteil der thermodynamischen Stabilität. In einer Vielzahl von Veröffentlichungen ist das Gleichgewichtsphasenverhalten in Abhängigkeit von der Struktur des zu emulgierenden Öls und der/des Tenside/s behandelt worden. Systematisch ist ebenfalls der Zusatz von anorganischen Salzen studiert worden (vgl. M. Kahlweit et.al., Langmuir 11 [1995], 3382; M. Kahlweit et.al., Langmuir 11 [1995]). Das Gleichgewichtsphasenverhalten von Microemulsionen niedermolekularer Silikone ist ebenfalls untersucht worden (EP-A 774482; H. von Berlepsch et.al, Progr. Colloid Polymer Science 111 [1998], 107).Microemulsions basically offer the advantage of thermodynamic stability. The equilibrium phase behavior depending on the structure of the oil to be emulsified and the surfactant (s) has been dealt with in a large number of publications. The addition of inorganic salts has also been studied systematically (see M. Kahlweit et.al., Langmuir 11 [1995], 3382; M. Kahlweit et.al., Langmuir 11 [1995]). The equilibrium phase behavior of microemulsions of low molecular weight silicones has also been investigated (EP-A 774482; H. von Berlepsch et.al, Progr. Colloid Polymer Science 111 [1998], 107).
Hinsichtlich der weichmachenden Komponenten sind Kombinationen von kohlenwasserstoffbasierten Quats mit Silikonquats (GB-A 1549180) oder auch Siliconpoly- ethern mit Siliconquats (US-A 4921895) vorgeschlagen worden. Zur Verbesserung der Hydrophilie werden die weithin benutzten Aminoalkylsiloxan- öle zunehmend durch polyethermodifizierte Aminoalkylsiloxanöle ersetzt (vgl. EP-A 578144).With regard to the softening components, combinations of hydrocarbon-based quats with silicone quats (GB-A 1549180) or also silicone polyethers with silicone quats (US-A 4921895) have been proposed. To improve the hydrophilicity, the widely used aminoalkylsiloxane oils are increasingly being replaced by polyether-modified aminoalkylsiloxane oils (cf. EP-A 578144).
Eine zusätzliche Einführung von Alkoxysilylstrukturen in polyether- und a ino- substituierte Silikone ist ebenfalls vorgeschlagen worden (US-A 20020028900).An additional introduction of alkoxysilyl structures into polyether- and a inosubstituted silicones has also been proposed (US-A 20020028900).
Echte permanent-hydrophile Textilweichmacher auf Silikonquatbasis sind schließlich in WO 02/10256, WO 02/10257 und WO 02/10259 offenbart worden.Real permanent hydrophilic fabric softeners based on silicone quat have finally been disclosed in WO 02/10256, WO 02/10257 and WO 02/10259.
Feinteilige Microemulsionen von Aminoalkylsiloxanen sollen in einem Zweistufen- prozess durch Herstellung eines Konzentrates aus Aminoalkylsiloxan, silikonunlöslichem Tensid und wenig Wasser mit anschließendem schnellen Einrühren in Wasser zugänglich sein (US-A 4620878).Fine-particle microemulsions of aminoalkylsiloxanes are said to be accessible in a two-stage process by preparing a concentrate from aminoalkylsiloxane, silicone-insoluble surfactant and a little water with subsequent rapid stirring into water (US Pat. No. 4,620,878).
Gemäß DE-A 3723697 sollen Aminosiloxanemulsionen durch die Verwendung wasserlöslicher nichtionogener Emulgatoren mechanisch stabil werden. Für extreme Scherbelastungen, wie sie auf modernen Jetanlagen erreicht werden, wurde festgestellt, dass die in DE-A 3723697 offenbarten Erfindungen nicht ausreichen, Ausfallungen in den Jetanlagen und auf den zu behandelnden Textilien zu verhindern.According to DE-A 3723697, aminosiloxane emulsions are said to be mechanically stable through the use of water-soluble nonionic emulsifiers. For extreme shear loads, such as are achieved on modern jet systems, it was found that the inventions disclosed in DE-A 3723697 are not sufficient to prevent failures in the jet systems and on the textiles to be treated.
Gemäß WO 02/10501 sollen aminofunktionelle Organosiliciumverbindungen ohne Verwendung wasserlöslicher nichtionogener Emulgatoren auch in Düsenfärbe- maschinen mechanisch stabil werden. Es wurde festgestellt, daß die in WO 02/10501 offenbarten Maßnahmen ebenfalls noch nicht ausreichen, die Ausfällungen auf verschieden vorbehandelten Textilien sicher zu verhindern.According to WO 02/10501, amino-functional organosilicon compounds should also be mechanically stable in jet dyeing machines without the use of water-soluble nonionic emulsifiers. It was found that the measures disclosed in WO 02/10501 are also still not sufficient to reliably prevent the precipitation on differently pretreated textiles.
Mechanische Stabilität von Aminosiloxanmicroemulsionen soll auch durch Anwendung von Betainen ggf. in Kombination mit nichtionogenen Tensiden des HLB Bereiches 5 bis 16 erreicht werden können (vgl. US-A 5573694; US-A 5520827). In der Färbetechnik ist bekannt, komplexe Mischungen, die sulfonierte Alkyl- naphthylderivate und halogenierte Kohlenwasserstoffe enthalten, als jetstabile Anfär- bebeschleunigerformulierungen zu benutzen (US-A 4080166).Mechanical stability of aminosiloxane microemulsions should also be achieved by using betaines, possibly in combination with non-ionic surfactants in the HLB range 5 to 16 (cf. US-A 5573694; US-A 5520827). It is known in dyeing technology to use complex mixtures which contain sulfonated alkylnaphthyl derivatives and halogenated hydrocarbons as jet-stable dyeing accelerator formulations (US Pat. No. 4,080,166).
Derartige sulfonierte Naphthylderivate in Kombination mit Fettalkoholethoxylaten sind ebenfalls zur Stabilisierung von tintenstrahltauglichen Formulierungen vorgeschlagen worden (US-A 6302948). Die Kombination von Fettalkoholethoxylaten mit Pigmenten bestimmter Größe soll ebenfalls zu tintenstrahltauglichen Systemen führen (US-A 6099627).Such sulfonated naphthyl derivatives in combination with fatty alcohol ethoxylates have also been proposed for the stabilization of inkjet-compatible formulations (US-A 6302948). The combination of fatty alcohol ethoxylates with pigments of a certain size should also lead to systems suitable for ink jet (US-A 6099627).
Schließlich ist noch bekannt, dass Salze starker Säuren, z.B. Al2(SO4)3 x 18 H O, die Protonierung kationischer Farbstoffe in Thermotransferdruckpasten sichern, gleichzeitig aber deren Stabilität beeinträchtigen (vgl.US-A 5925701).Finally, it is also known that salts of strong acids, for example Al 2 (SO4) 3 x 18 HO, ensure the protonation of cationic dyes in thermal transfer printing pastes, but at the same time impair their stability (cf. US-A 5925701).
Allen zitierten Vorschlägen ist gemein, dass sie keine Hinweise auf Maßnahmen enthalten, wie Emulsionen bzw. Microemulsionen von silikonbasierten Textilweich- machern, vorzugsweise Aminosiloxanen und quaternierten Ammoalkylsiloxanen (Silikonquats), gegen die Einwirkung von hohem mechanischem Energieeintrag der modernen Jetsysteme in Kombination mit stark schwankenden Flottenverhältnissen und den Einfluss variierender Vorbehandlungspräparationen der Fasern sicher stabilisiert werden können. Weiterhin sind aus dem Stand der Technik keine Maßnahmen bekannt, wie die gleichzeitig auftretende hohe Schaumneigung (zieht Fleckenbildung nach sich) von Textilweichmacher-Formulierungen bei hohem mechanischem Energieeintrag begrenzt werden kann.All the quoted proposals have in common that they do not contain any indications of measures such as emulsions or microemulsions of silicone-based fabric softeners, preferably aminosiloxanes and quaternized ammoalkylsiloxanes (silicone quats), against the effects of high mechanical energy input in modern jet systems in combination with strongly fluctuating fleet ratios and the influence of varying pretreatment preparations of the fibers can be safely stabilized. Furthermore, no measures are known from the prior art on how the simultaneously occurring high tendency to foam (which leads to the formation of stains) of textile softener formulations with high mechanical energy input can be limited.
Es war somit Aufgabe der vorliegenden Erfindung, Maßnahmen zu beschreiben, wie Emulsionen bzw. Microemulsionen von silikonbasierten Textilweichmachern, vorzugsweise quaternierten Ammoalkylsiloxanen (Silikonquats), bei Einwirkung von hohem Energieeintrag (extrem hoher Scherkräfte bei modernen Jetsystemen) in Kombination mit stark schwankenden Flottenverhältnissen und dem Einfluss variierender Vorbehandlungspräparationen sicher stabilisiert werden können und gleichzeitig die Schaumneigung begrenzt werden kann.It was therefore an object of the present invention to describe measures such as emulsions or microemulsions of silicone-based textile softeners, preferably quaternized ammoalkylsiloxanes (silicone quats), when exposed to high energy input (extremely high shear forces in modern jet systems) in combination with strongly fluctuating fleet ratios and the influence Varying pre-treatment preparations can be safely stabilized and the tendency to foam can be limited at the same time.
Es wurde überraschend gefunden, dass durch die Kombination von quaternierten Ammoalkylsiloxanen mit stark hydrophilen nichtionogenen grenzflächenaktiven Verbindungen (Tensiden) und/oder stark hydrophilen Dispergiermitteln und/oder Salzen mehrwertiger Kationen und gegebenenfalls weiteren üblichen Formulierungsagenzien, diese Aufgabe gelöst werden kann.It has surprisingly been found that this object can be achieved by combining quaternized ammoalkylsiloxanes with highly hydrophilic nonionic surface-active compounds (surfactants) and / or highly hydrophilic dispersants and / or salts of polyvalent cations and, if appropriate, other customary formulation agents.
Die vorliegende Erfindung betrifft daher Formulierungen enthaltend mindestens ein quaterniertes Aminoalkylsiloxan und mindestens eine Verbindung aus der ReiheThe present invention therefore relates to formulations comprising at least one quaternized aminoalkylsiloxane and at least one compound from the series
a) der hydrophilen, nichtionogenen grenzflächenaktiven Verbindungen b) der hydrophilen Dispergiermittel und c) der Salze von zwei- oder dreiwertigen Metallen mit anorganischen Säuren.a) the hydrophilic, nonionic surface-active compounds b) the hydrophilic dispersant and c) the salts of divalent or trivalent metals with inorganic acids.
Bevorzugte hydrophile, nichtionogene grenzflächenaktive Verbindungen (a) im Sinne der Erfindung sind Substanzen, die die Oberflächenspannung von Wasser auf unter 45 mN/m absenken. Es handelt sich insbesondere um Ethylen Propylenoxid (EO/PO) modifizierte Verbindungen, gegebenenfalls ungesättigt und/oder verzweigt, aus der Gruppe der Fettalkohole, Fettsäuren, Alkohole, Säuren, Alkylarylderivate, Fettamine, Glyceride und Sorbitanester, bei denen die Anzahl der EO/PO Einheiten zwischen 15 und 150 liegt, wobei das Verhältnis von PO Einheiten zu EO-Einheiten bei 0,25 oder unter 0,25 liegt, und bei denen die Anzahl der Ethylenoxideinheiten (EO-Teil) größer oder gleich der Anzahl der Kohlenstoffatome im Nicht-EO Teil ist, und um Alkylpolyglykoside, Ethylenoxid/Propylenoxid Copolymere und Polyethersiloxane . Hydrophile Dispergiermittel (b) im Sinne der Erfindung sind Substanzen, bei deren Zugaben zu Wasser die Oberflächenspannung auf einen Wert zwischen 72 bis 45 mN/m abgesenkt wird.Preferred hydrophilic, nonionic surface-active compounds (a) for the purposes of the invention are substances which reduce the surface tension of water to below 45 mN / m. It is particularly ethylene propylene oxide (EO / PO) modified compounds, optionally unsaturated and / or branched, from the group of fatty alcohols, fatty acids, alcohols, acids, alkylaryl derivatives, fatty amines, glycerides and sorbitan esters, in which the number of EO / PO Units is between 15 and 150, the ratio of PO units to EO units being 0.25 or less than 0.25, and in which the number of ethylene oxide units (EO part) is greater than or equal to the number of carbon atoms in the non- EO is part, and around alkyl polyglycosides, ethylene oxide / propylene oxide copolymers and polyether siloxanes. Hydrophilic dispersants (b) in the sense of the invention are substances whose addition to water lowers the surface tension to a value between 72 to 45 mN / m.
Bei den bevorzugten Verbindungen (b) handelt es sich um wasserlösliche Polysacca- ride wie Carboxymethylcellulose, Hydroxyethylcellulose, Methylhydroxypropyl- cellulose oder um Verbindungen der FormelThe preferred compounds (b) are water-soluble polysaccharides such as carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose or compounds of the formula
worinwherein
x für 1,5 bis 20, bevorzugt 1,5 bis 10, steht.x stands for 1.5 to 20, preferably 1.5 to 10.
Bei den Salzen (c) handelt es sich um zwei- oder höherwertige Metallsalze, vorzugsweise um Calcium-, Magnesium- und Aluminiumsalze, gegebenenfalls in Form ihrer Hydrate, mit anorganischen Säuren wie Salzsäure, Schwefelsäure, Phosphorsäure. Die Gegenionen sind so auszuwählen, dass bei gegebener Stabilität des Salzes eine hinreichende Wasser- bzw. Formulierungslöslichkeit gewährleistet ist. Beispiele derartiger Salze sind Ca(Cl)2, Mg(Cl)2 und Al2(Sθ4)3, gegebenenfalls in Form ihrer Hydrate.The salts (c) are divalent or higher metal salts, preferably calcium, magnesium and aluminum salts, optionally in the form of their hydrates, with inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid. The counterions should be selected so that, given the stability of the salt, sufficient water or formulation solubility is guaranteed. Examples of such salts are Ca (Cl) 2 , Mg (Cl) 2 and Al 2 (Sθ4) 3 , optionally in the form of their hydrates.
Speziell handelt es sich bei den Verbindungen (a) um solche der FormelnCompounds (a) are specifically those of the formulas
R1-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E (1), R 1 -O- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E (1),
R2-NH-[CH2CH(CH3)O]r-[CH2CH2O]q-E (3),R 2 -NH- [CH 2 CH (CH 3 ) O] r - [CH 2 CH 2 O] q -E (3),
(5),(5)
R2-NH-CH(CH3)CH2-[OCH2CH(CH3)]m-[OCH2CH2]q-O-E (6),R 2 -NH-CH (CH 3 ) CH 2 - [OCH 2 CH (CH 3 )] m - [OCH 2 CH 2 ] q -OE (6),
R2-NH-CH(CH3)CH2-[OCH2CH(CH3)]ra7-[OCH2CH2]q-[OCH2CH(CH3)]m8-NH-R2 R 2 -NH-CH (CH 3 ) CH 2 - [OCH 2 CH (CH 3 )] ra7 - [OCH 2 CH 2 ] q - [OCH 2 CH (CH 3 )] m8 -NH-R 2
(7),(7)
E-O-[CH2CH2O]s-[CH2CH(CH3)O]rE (8),EO- [CH 2 CH 2 O] s - [CH 2 CH (CH 3 ) O] r E (8),
oder ein Polyethersiloxan (9) or a polyether siloxane (9)
worinwherein
E für einen Rest R1, Wasserstoff, geradkettiges oder verzweigtes, gesättigtes oder ein- oder mehrfach ungesättigtes Cι-Cι8-Alkyl, welches gegebenenfalls ein- oder melirfach durch -OH, C C/rAlkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist, oder für C5-Cιo-Cycloalkyl steht, welches gegebenenfalls ein- oder mehrfach durch Cι-C4-Alkyl, -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,E for a radical R 1 , hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 8 -alkyl, which is optionally substituted mono- or melirfach by -OH, CC / ralkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl is, or is C 5 -Cιo-cycloalkyl, which is optionally substituted one or more times by -C-C 4 alkyl, -OH, -C-C 4 alkoxy, Cι-C 4 alkoxycarbonyl or carbonyl,
R1 für geradkettiges oder verzweigtes, gesättigtes oder ungesättigtes C8-C4o- Alkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarb- onyl oder Carbonyl, Amino, mono- oder di- CrC -Alkylamino substituiert ist, oder für C5-Cιo-Cycloalkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch Cι-C - Alkyl, -OH, - C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl, Amino, mono- oder di-Ci- C4-Alkylamino substituiert ist,R 1 represents straight-chain or branched, saturated or unsaturated C 8 -C 4 o-alkyl, the alkyl chain of which is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which is optionally one or more times by -OH, -C-C 4 -alkoxy, -C-C 4 -alkoxycarb- onyl or carbonyl, amino, mono- or di- CrC -alkylamino is substituted, or represents C 5 -Cιo-cycloalkyl, the alkyl chain of which may be one or more times by oxygen and / or nitrogen atoms is interrupted and which is optionally substituted one or more times by C 1 -C 4 -alkyl, -OH, - C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl, amino, mono- or di-Ci- C 4 -alkylamino is
R2 für geradkettiges oder verzweigtes, gesättigtes oder ein- bis mehrfach ungesättigtes C8-C4o- Alkyl steht, welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,R 2 stands for straight-chain or branched, saturated or mono- to polyunsaturated C 8 -C 4 o-alkyl, which is optionally substituted one or more times by -OH, -CC 4 alkoxy, -C 4 -alkoxycarbonyl or carbonyl is
R3 für geradkettiges oder verzweigtes Cι-C26 Alkyl oder C6-Cιo-Aryl steht, -CH2CH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E ,R 3 represents straight-chain or branched C 1 -C 26 alkyl or C 6 -C 8 aryl, -CH 2 CH 2 -O- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E,
-CH2CH2CH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E-CH 2 CH 2 CH 2 -O- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E
-CH2CH2CH2-0-CH2CHOHCH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E-CH 2 CH 2 CH 2 -0-CH 2 CHOHCH 2 -O- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E
-Z-[CH2CH2O]q-[CH2CH(CH3)O]r-E-Z- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E
wobeiin which
Z ein geradkettiger oder verzweigter Alkyl- oder Cycloalkylrest ist, der jeweils durch -O- und /oder -CO- unterbrochen und gegebenenfalls durch mindestens eine OH-Gruppe substituiert sein kannZ is a straight-chain or branched alkyl or cycloalkyl radical, which can in each case be interrupted by -O- and / or -CO- and optionally substituted by at least one OH group
oderor
steht, stands,
q für 15 bis 150 steht,q represents 15 to 150,
ql und q2 unabhängig voneinander für 0 bis 150 stehen,ql and q2 are independently 0 to 150,
wobei die Summe von ql + q2 = q ist,where the sum of ql + q2 = q,
q3, q4, q5 und q6 unabhängig voneinander für 0 bis 150 stehen, wobei die Summe von q3 + q4 + q5 + q6 = q ist,q3, q4, q5 and q6 independently of one another represent 0 to 150, where the sum of q3 + q4 + q5 + q6 = q,
r für 0 bis 50 steht,r represents 0 to 50,
rl und r2 unabhängig voneinander für 0 bis 50 stehen,rl and r2 independently of one another represent 0 to 50,
wobei die Summe von rl + r2 = r ist,where the sum of rl + r2 = r,
r3, r4, r5 und r6 unabhängig voneinander für 0 bis 50 stehen,r3, r4, r5 and r6 independently of one another represent 0 to 50,
wobei die Summe von r3 + r4 + r5 + r6 = r ist, undwhere the sum of r3 + r4 + r5 + r6 = r, and
das Verhältnis von r : q < 0.25 ist,the ratio of r: q <0.25,
m für 1 bis 50 steht,m represents 1 to 50,
m7 und m.8 unabhängig voneinander für 1 bis 50 stehen,m7 and m.8 independently of one another represent 1 to 50,
wobei 2 < m7+m8, und die Summe von m7 + m8 = m+1 ist, undwhere 2 <m7 + m8, and the sum of m7 + m8 = m + 1, and
das Verhältnis von q : m > 4 ist,the ratio of q: m> 4,
s für 5 bis 150 steht,s stands for 5 to 150,
t für 5 bis 150 steht,t stands for 5 to 150,
wobei 0.05 < s : t < 20,where 0.05 <s: t <20,
0 < zl < 2000 mindestens ein R4 ≠ R3 , und0 <zl <2000 at least one R4 ≠ R3, and
0,01 < Σ Alkylreste R3 : Σ q+r < 1.0.01 <Σ alkyl radicals R 3 : Σ q + r <1.
Speziell handelt es sich bei den Verbindungen (a) auch um solche der Formeln (1') bis (9')Specifically, the compounds (a) are also those of the formulas (1 ') to (9')
R1-O CH2CH2O]q-[CH2CH(CH3)O]1 -E (i' R 1 -O CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] 1 -E (i '
R-NH-f CH2CH(CH3)O]r-[CH2CH2O] E (3 '),R-NH-f CH 2 CH (CH 3 ) O] r - [CH 2 CH 2 O] E (3 '),
R2-NH-CH(CH3)CH2. OCH2CH(CH3)]m-[OCH2CH2]q- -E (6r), R 2 -NH-CH (CH 3 ) CH 2 . OCH 2 CH (CH 3 )] m - [OCH 2 CH 2 ] q - -E (6 r ),
E-O CH2CH2O]s-[CH2CH(CH3 ) }xk (80.EO CH 2 CH 2 O] s - [CH 2 CH (CH 3 )} xk (80.
oder ein Polyethersiloxan (9')or a polyether siloxane (9 ')
worin die in den Formeln (l ')-(8') dargestellten Klammerausdrücke „{" und „}" bedeuten, dass die innerhalb dieser Klammerausdrücke stehenden Ethylenoxid- bzw. Propylenoxid-Einheiten entweder wie dargestellt blockweise angeordnet sein können oder aber auch beliebig statistisch angeordnet sein können,wherein the bracketed expressions "{" and "}" shown in the formulas (1 ') - (8') mean that the ethylene oxide or propylene oxide units contained within these bracketed expressions can either be arranged in blocks as shown or else randomly can be arranged
E für einen Rest R1, Wasserstoff, geradkettiges oder verzweigtes, gesättigtes oder ein- oder mehrfach ungesättigtes Cι-Cι8-Alkyl welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist, oder für Cs-Cio-Cycloalkyl steht, welches jeweils gegebenenfalls ein- oder mehrfach durch Cι-C4- Alkyl, -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,E for a radical R 1 , hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 8 -alkyl which may be mono- or poly-optionally by -OH, -C-C 4 alkoxy, C 1 -C 4 alkoxycarbonyl or carbonyl groups, or is Cs-Cio-cycloalkyl, which is optionally monosubstituted or polysubstituted in each case by Cι-C 4 - substituted alkyl, -OH, Cι-C 4 -alkoxy, C 4 alkoxycarbonyl, or carbonyl,
R1 für geradkettiges oder verzweigtes, gesättigtes oder ungesättigtes C8-C4o- Alkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebe- nenfalls ein- oder mehrfach durch -OH, Ci-C -Alkoxy, Cι-C4-Alkoxycarb- onyl oder Carbonyl, Amino, mono- oder di- Cι-C4-Alkylamino substituiert ist, oder für C5-Cιo-Cycloalkyl steht, dessen Alkylkette gegebenenfalls ein- oder melirfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder melirfach durch Cι-C4-Alkyl, -OH, d- C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl, Amino, mono- oder di-Ci- C4-Alkylamino substituiert ist, oder für C6-Cιo Aryl steht, welches gegebenfalls substituiert, insbesondere durch C3-Cι5.Alkyl substituiert ist.R 1 represents straight-chain or branched, saturated or unsaturated C 8 -C 4 o -alkyl, the alkyl chain of which is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which is substituted one or more times by -OH, Ci-C -alkoxy, -C-C 4 -alkoxycarb- onyl or carbonyl, amino, mono- or di- -CC 4 -alkylamino, or for C 5 -Cιo-cycloalkyl stands, whose alkyl chain is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which optionally one or more times by C 1 -C 4 -alkyl, -OH, d- C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or Carbonyl, amino, mono- or di-Ci-C 4 alkylamino is substituted, or stands for C 6 -Cιo aryl, which is optionally substituted, in particular substituted by C 3 -Cι 5 .Alkyl.
R2 für geradkettiges oder verzweigtes, gesättigtes oder ein- bis mehrfach ungesättigtes C8-C4o-Alkyl steht, welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,R 2 represents straight-chain or branched, saturated or mono- to polyunsaturated C 8 -C 4 o-alkyl, which is optionally substituted one or more times by -OH, -CC 4 -alkoxy, -C-C 4 alkoxycarbonyl or carbonyl is
R3 für geradkettiges oder verzweigtes Cι-C 6 Alkyl oder C6-Cιo-Aryl steht,R 3 represents straight-chain or branched C 6 -C 6 alkyl or C 6 -C 6 aryl,
R4 für R3 oder für einen Rest der FormelnR 4 for R 3 or for a rest of the formulas
-CH2CH2-θ [CH2CH20]q-[CH2CH(CH3)O]r-t ,-CH 2 CH 2 -θ [CH 2 CH 2 0] q - [CH 2 CH (CH 3 ) O] r -t,
CH2CH2CH2-θ CH2CH2O]q-[CH2CH(CH3)O]>-ECH 2 CH 2 CH 2 -θ CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O]> - E
-CH2CH2CH2-O-CH2CHOHCH2-O [CH2CH2O]q-[CH2CH(CH3)O]r]-CH 2 CH 2 CH 2 -O-CH 2 CHOHCH 2 -O [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r ]
-ZJ[CH2CH2O]q-[CH2CH(CH3)O¥-E-ZJ [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O ¥ -E
wobeiin which
Z ein geradkettiger oder verzweigter Alkyl- oder Cycloalklyrest ist, der jeweils durch -O- und /oder -CO- unterbrochen und gegebenenfalls durch mindestens eine OH-Gruppe subsituiert oderZ is a straight-chain or branched alkyl or cycloalkyl radical which is interrupted in each case by -O- and / or -CO- and is optionally substituted by at least one OH group or
steht, wobei die in den vorgenannten Formeln dargestellten Klammerausdrücke „{" und „}" wiederum bedeuten, dass die innerhalb dieser Klammerausdrücke stehenden Ethylenoxid- bzw. Propylenoxid- Einheiten entweder wie dargestellt blockweise angeordnet. sein können oder aber auch beliebig statistisch angeordnet sein können, stands, the parentheses "{" and "}" shown in the aforementioned formulas in turn mean that the ethylene oxide or propylene oxide units within these parentheses are either arranged in blocks as shown. can be or can also be randomly arranged as desired,
q für 15 bis 150 steht,q represents 15 to 150,
ql und q2 unabhängig voneinander für 0 bis 150 stehen,ql and q2 are independently 0 to 150,
wobei die Summe von ql + q2 = q ist,where the sum of ql + q2 = q,
q3, q4, q5 und q6 unabhängig voneinander für 0 bis 150 stehen,q3, q4, q5 and q6 independently of one another represent 0 to 150,
wobei die Summe von q3 + q4 + q5 + q6 = q ist,where the sum of q3 + q4 + q5 + q6 = q,
r für 0 bis 50 steht,r represents 0 to 50,
rl und r2 unabhängig voneinander für 0 bis 50 stehen,rl and r2 independently of one another represent 0 to 50,
wobei die Summe von rl + r2 = r ist, wobei die Summe von r3 + r4 + r5 + r6 = r ist, undwhere the sum of rl + r2 = r, where the sum of r3 + r4 + r5 + r6 = r, and
das Verhältnis von r : q < 0.25 ist,the ratio of r: q <0.25,
m für 1 bis 50 steht,m represents 1 to 50,
m7 und m8 unabhängig voneinander für 1 bis 50 stehen,m7 and m8 independently of one another represent 1 to 50,
wobei 2 < m7+m8, undwhere 2 <m7 + m8, and
das Verhältnis von q : m > 4 ist,the ratio of q: m> 4,
s für 5 bis 150, bevorzugt 15-150 steht,s represents 5 to 150, preferably 15-150,
t für 0 bis 150, bevorzugt 5 bis 150 und insbesondere 5 bis 20 steht,t represents 0 to 150, preferably 5 to 150 and in particular 5 to 20,
wobei t : s < 0,25where t: s <0.25
0 < zl < 20000 <zl <2000
0 < z2 20000 <z2 2000
mindestens ein R4 ≠ R3 , und für Formel (9') gilt:at least one R4 ≠ R3, and the following applies to formula (9 '):
0,01 < Σ Alkylreste R3 : Σ q < 1. Insbesondere handelt es sich bei den Verbindungen (a) um solche der Formeln (1) bis (9), worin0.01 <Σ alkyl radicals R 3 : Σ q <1. In particular, the compounds (a) are those of the formulas (1) to (9), in which
E für Wasserstoff, geradkettiges oder verzweigtes, gesättigtes oder ein- oder mehrfach ungesättigtes Cι-C4- Alkyl welches gegebenenfalls 1 bis zweifach durch -OH, CrC4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist, oder für C5-C6 -Cycloalkyl steht, welches jeweils gegebenenfalls ein- bis mehrfach durch Cι-C4-Alkyl, -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,E represents hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated Cι-C 4 - alkyl which is substituted 4 alkoxycarbonyl or carbonyl optionally having 1 to disubstituted by -OH, -C 4 -alkoxy, C, or C 5 -C 6 cycloalkyl, which is in each case optionally substituted one to more times by C 1 -C 4 alkyl, -OH, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl or carbonyl,
R1 für geradkettiges oder verzweigtes, gesättigtes oder ungesättigtes Cιo-C36- Alkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarb- onyl oder Carbonyl, Amino, mono- oder di- Cι-C4-Alkylamino substituiert ist, oder für Cs-Cö-Cycloalkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch Cι-C4-Al yl, -OH, Ci- C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl, Amino, mono- oder di-Ci- C4-Alkylamino substituiert ist,R 1 represents straight-chain or branched, saturated or unsaturated C 1 -C 36 -alkyl, the alkyl chain of which is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which may be one or more times by -OH, -C-C 4 - Alkoxy, -CC 4 -alkoxycarb- onyl or carbonyl, amino, mono- or di -CC-C 4 alkylamino is substituted, or stands for Cs-C ö cycloalkyl, the alkyl chain of which may be one or more times by oxygen and / or nitrogen atoms is interrupted and which is optionally one or more times by -CC 4 -Al yl, -OH, -C-C 4 -alkoxy, -C-C 4 -alkoxycarbonyl or carbonyl, amino, mono- or di-Ci- C 4 -alkylamino is substituted,
R für geradkettiges oder verzweigtes, gesättigtes oder ein- bis mehrfach ungesättigtes Cιo-C36-Alkyl steht, welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,R represents straight-chain or branched, saturated or mono- to polyunsaturated C 1 -C 36 -alkyl, which is optionally substituted one or more times by -OH, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl,
R3 für geradkettiges oder verzweigtes Cι-Cι8 -Alkyl oder C6-Cιo-Aryl steht,R 3 represents straight-chain or branched C 1 -C 8 alkyl or C 6 -C 8 aryl,
R4 für einen Rest R3 oder für einen Rest der Formeln oderR 4 for a radical R 3 or for a radical of the formulas or
-CH2CH2CH2-0-[CH2CH2O]q-[CH2CH(CH3)O]r-E-CH 2 CH 2 CH 2 -0- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E
steht,stands,
q für 20 bis 100 steht,q stands for 20 to 100,
ql und q2 unabhängig voneinander für 20 bis 100 stehen,ql and q2 independently represent 20 to 100,
wobei die Summe von ql + q2 = q ist,where the sum of ql + q2 = q,
q3, < 5 und q6 unabhängig voneinander für 20 bis 100 stehen,q3, <5 and q6 independently represent 20 to 100,
wobei die Summe von q3 + q4 + q5 + q6 = q ist,where the sum of q3 + q4 + q5 + q6 = q,
r für 0 bis 20 steht,r stands for 0 to 20,
rl und r2 unabhängig voneinander für 0 bis 20 stehen,rl and r2 independently of one another represent 0 to 20,
wobei die Summe von rl + r2 - r ist,where the sum of rl + r2 - r is
r3, r4, r5 und r6 unabhängig voneinander für 0 bis 20 stehen,r3, r4, r5 and r6 independently of one another represent 0 to 20,
wobei die Summe von r3 + r4 + r5 + r6 = r ist, undwhere the sum of r3 + r4 + r5 + r6 = r, and
das Verhältnis von r : q < 0.25 ist,the ratio of r: q <0.25,
m für 1 bis 7 steht m7 und m8 unabhängig voneinander fürl bis 7 stehen,m represents 1 to 7 m7 and m8 are independently from 1 to 7,
wobei 2 < m7+m8, und die Summe von m7 + m8 = m +1 ist, undwhere 2 <m7 + m8, and the sum of m7 + m8 = m +1, and
das Verhältnis von q : m ≥ 4 ist,the ratio of q: m ≥ 4,
s für 5 bis 100 steht,s stands for 5 to 100,
t für 5 bis 100 steht,t stands for 5 to 100,
wobei 0.05 < s : t < 20,where 0.05 <s: t <20,
0 < zl < 20000 <zl <2000
0 < z2 < 20000 <z2 <2000
mindestens ein R4 ≠ R3at least one R4 ≠ R3
undand
0,01 < Σ Alkylreste R3: Σ q+r < 0,5.0.01 <Σ alkyl radicals R 3 : Σ q + r <0.5.
Insbesondere handelt es sich bei den Verbindungen (a) auch um solche der Formeln (l ') bis (9'), worinIn particular, the compounds (a) are also those of the formulas (1 ') to (9'), in which
E für Wasserstoff, geradkettiges oder verzweigtes, gesättigtes oder ein- oder mehrfach ungesättigtes Cι-C4-Alkyl welches gegebenenfalls 1 bis zweifach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist, oder für C5-C5 -Cycloalkyl steht, welches jeweils gegebenenfalls ein- bis mehrfach durch Ci-C4-Alkyl, -OH, CrC4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,E for hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 4 -alkyl which is optionally 1 to 2 times substituted by -OH, -CC 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl, or for C 5 -C 5 cycloalkyl, which in each case optionally up to is substituted several times by C 1 -C 4 -alkyl, -OH, CrC 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl,
R1 für geradkettiges oder verzweigtes, gesättigtes oder ungesättigtes Cιo-C36- Alkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C -Alkoxycarb- onyl oder Carbonyl, Amino, mono- oder di- C1-C4-Alkylamino substituiert ist, oder für Cs-Cβ-Cycloalkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch C].-C -Alkyl, -OH, Ci- C4-Alkoxy, Cι-C4-AlkoxycarbonyI oder Carbonyl, Amino, mono- oder di-Ci- C4-Alkylamino substituiert ist, oder für C6-Cιo Aryl steht, welches gegebenfalls substituiert, insbesondere durch C3-Ci5_Alkyl substituiert ist.R 1 represents straight-chain or branched, saturated or unsaturated C 1 -C 36 -alkyl, the alkyl chain of which is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which may be one or more times by -OH, -C-C 4 - Alkoxy, -CC -alkoxycarb- onyl or carbonyl, amino, mono- or di- C 1 -C 4 alkylamino is substituted, or represents Cs-Cβ-cycloalkyl, the alkyl chain of which may be one or more times by oxygen and / or nitrogen atoms and which is optionally one or more times by C] . -C alkyl, -OH, Ci- C 4 -alkoxy, C 4 -AlkoxycarbonyI or carbonyl, amino, mono- or di-Ci- C 4 alkylamino groups, or C 6 -Cιo aryl, which optionally substituted, in particular substituted by C 3 -Ci 5 _alkyl.
R für geradkettiges oder verzweigtes, gesättigtes oder ein- bis mehrfach ungesättigtes Cιo-C36-Alkyl steht, welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,R represents straight-chain or branched, saturated or mono- to polyunsaturated C 1 -C 36 -alkyl, which is optionally substituted one or more times by -OH, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl,
R für geradkettiges oder verzweigtes C].-C18 -Alkyl oder C6-Cio-Aryl steht,R for straight-chain or branched C] . -C 18 alkyl or C 6 -Cio aryl,
R für einen Rest R oder für einen Rest der FormelnR for a radical R or for a radical of the formulas
-CH2CH2-O-iCH2CH2O]q-[CH2CH(CH3)0]riE ,-CH 2 CH 2 -O-iCH 2 CH 2 O] q - [CH 2 CH (CH 3 ) 0] r iE,
oderor
-CH2CH2CH2-O-iCH2CH2O]q-[CH2CH(CH3)O]rJE q für 20 bis 100 steht,-CH 2 CH 2 CH 2 -O-iCH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r JE q stands for 20 to 100,
ql und q2 unabhängig voneinander für 20 bis 100 stehen,ql and q2 independently represent 20 to 100,
wobei die Summe von ql + q2 = q ist,where the sum of ql + q2 = q,
q3, q4, q5 und qό unabhängig voneinander für 20 bis 100 stehen,q3, q4, q5 and qό independently represent 20 to 100,
wobei die Summe von q3 + q4 + q5 + q6 = q ist,where the sum of q3 + q4 + q5 + q6 = q,
r für 0 bis 20 steht,r stands for 0 to 20,
rl und r2 unabhängig voneinander für 0 bis 20 stehen,rl and r2 independently of one another represent 0 to 20,
wobei die Summe von rl + r2 = r ist,where the sum of rl + r2 = r,
r3, r4, r5 und r6 unabhängig voneinander für 0 bis 20 stehen,r3, r4, r5 and r6 independently of one another represent 0 to 20,
wobei die Summe von r3 + r4 + r5 + r6 = r ist, undwhere the sum of r3 + r4 + r5 + r6 = r, and
das Verhältnis von r : q < 0.25 ist,the ratio of r: q <0.25,
m für 1 bis 7 steht,m represents 1 to 7,
m7 und m8 unabhängig voneinander fürl bis 7 stehen,m7 and m8 are independently from 1 to 7,
wobei 2 < m7+m8, undwhere 2 <m7 + m8, and
das Verhältnis von q : m > 4 ist, s für 5 bis 100, bevorzugt 15 bis 100 steht,the ratio of q: m> 4, s represents 5 to 100, preferably 15 to 100,
t für 5 bis 100, bevorzugt 5 bis 20 steht,t represents 5 to 100, preferably 5 to 20,
wobei t: s < 0,25where t: s <0.25
0 < zl < 20000 <zl <2000
0 < z2 < 20000 <z2 <2000
mindestens ein R4 ≠ R3 ,at least one R4 ≠ R3,
undand
für die Formel (9') gilt:the following applies to formula (9 '):
0,01 < Σ Alkylreste R3: Σ q < 0,5.0.01 <Σ alkyl radicals R 3 : Σ q <0.5.
Besonders bevorzugt handelt es sich bei den Verbindungen (a) um solche der Formeln (1) bis (9), worinThe compounds (a) are particularly preferably those of the formulas (1) to (9), in which
E für H-, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2- oder CH3C(O)-E for H-, CH 3 -, CH 3 CH 2 -, CH 3 CH 2 CH 2 -, (CH 3 ) 2 CH-, CH 3 CH 2 CH 2 CH 2 - or CH 3 C (O) -
steht,stands,
R1 für einen Rest der Formeln CH3(CH2)nl-R 1 for a remainder of the formulas CH 3 (CH 2 ) nl-
CH3(CH2)n2CHCH2- CH3(CH2)n3CH2 CH3 (CH2) n2CHCH 2 - CH3 (CH 2 ) n3CH 2
CH3(CH2)7CH=CH(CH2)8-CH3 (CH 2 ) 7CH = CH (CH 2 ) 8-
mitWith
nl = 9 bis 23,nl = 9 to 23,
n2 = 3 bis 23,n2 = 3 to 23,
n3 = 0 bis 18,n3 = 0 to 18,
n4 = 7 bis 23,n4 = 7 to 23,
n5 = 3 bis 15,n5 = 3 to 15,
steht,stands,
für einen Rest der Formeln for a rest of the formulas
mitWith
n6 = 8 bis bis 28,n6 = 8 to to 28,
steht,stands,
R3 für Cι-Cι8 -Alkyl oder C6-C10-Aryl steht,R 3 represents -C 8 -alkyl or C 6 -C 10 -aryl,
R4 für einen Rest R3 oder für einen Rest der FormelnR 4 for a radical R 3 or for a radical of the formulas
-CH2CH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E ,-CH 2 CH 2 -O- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E,
oderor
-CH2CH2CH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E-CH 2 CH 2 CH 2 -O- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E
steht,stands,
q für 25 bis 60 steht,q represents 25 to 60,
ql und q2 unabhängig voneinander für 25 bis 60 stehen, q3, q4, q5 und q6 unabhängig voneinander für 25 bis 60 stehen,ql and q2 independently represent 25 to 60, q3, q4, q5 and q6 independently represent 25 to 60,
wobei die Summe von q3 + q4 + q5 + q6 = q ist,where the sum of q3 + q4 + q5 + q6 = q,
r für 0 bis 10 steht,r represents 0 to 10,
rl und r2 unabhängig voneinander für 0 bis 10 stehen,rl and r2 are independently 0 to 10,
wobei die Summe von rl + r2 = r ist,where the sum of rl + r2 = r,
r3, r4, r5 und r6 unabhängig voneinander für 0 bis 10 stehen,r3, r4, r5 and r6 independently of one another represent 0 to 10,
wobei die Summe von r3 + r4 + r5 + r6 = r ist, undwhere the sum of r3 + r4 + r5 + r6 = r, and
das Verhältnis von r : q < 0.25 ist, undthe ratio of r: q is <0.25, and
0,01 < Σ Alkylreste R3: Σ q+r < 0,10.01 <Σ alkyl radicals R 3 : Σ q + r <0.1
Besonders bevorzugt handelt es sich bei den Verbindungen (a) auch um solche der Formeln (1 ') bis (9'), worinThe compounds (a) are also particularly preferably those of the formulas (1 ') to (9'), in which
E für H-, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2- oder CH3C(O)-E for H-, CH 3 -, CH 3 CH 2 -, CH 3 CH 2 CH 2 -, (CH 3 ) 2 CH-, CH 3 CH 2 CH 2 CH 2 - or CH 3 C (O) -
steht,stands,
R1 für einen Rest der Formeln CH3(CH2)nl-R 1 for a remainder of the formulas CH 3 (CH 2 ) nl-
CH3(CH2)n2CHCH2- CH3(CH2)n3CH2 CH3 (CH2) n2CHCH 2 - CH 3 (CH2) n3CH 2
CH3(CH2)7CH=CH(CH2)8-CH 3 (CH2) 7CH = CH (CH 2 ) 8-
mitWith
nl = 9 bis 23,nl = 9 to 23,
n2 = 3 bis 23, bevorzugt 6 bis 23n2 = 3 to 23, preferably 6 to 23
n3 = 0 bis 18, wobei bevorzugt n2+ n3 < 31 ist,n3 = 0 to 18, preferably n2 + n3 <31,
n4 = 7 bis 23,n4 = 7 to 23,
n5 = 3 bis bis 15,n5 = 3 to 15,
steht,stands,
R für einen Rest der Formeln OR for a rest of the formulas O
CH3(CH2)n6 l'CH 3 (CH 2 ) n6 l '
mitWith
n6 = 8 bis bis 28,n6 = 8 to to 28,
steht,stands,
R3 für Ci-Cis -Alkyl oder C6-Cι0-Aryl steht,R 3 represents Ci-Cis-alkyl or C 6 -Cι 0 -aryl,
R für einen Rest R oder für einen Rest der FormelnR for a radical R or for a radical of the formulas
oder or
-CH2CH2CH2- -[CH2CH2O]q-[CH2CH(CH3)O]rJE-CH 2 CH 2 CH 2 - - [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r JE
steht,stands,
für 25 bis 60 steht,stands for 25 to 60,
ql und q2 unabhängig voneinander für 25bis 60 stehen, q3, q4, q5 und q6 unabhängig voneinander für 25 bis 60 stehen,ql and q2 independently represent 25 to 60, q3, q4, q5 and q6 independently represent 25 to 60,
wobei die Summe von q3 + q4 + q5 + q6 = q ist,where the sum of q3 + q4 + q5 + q6 = q,
r für 0 bis 10 steht,r represents 0 to 10,
rl und r2 unabhängig voneinander für 0 bis 10 stehen,rl and r2 are independently 0 to 10,
wobei die Summe von rl + r2 = r ist,where the sum of rl + r2 = r,
r3, r4, r5 und r6 unabhängig voneinander für 0 bis 10 stehen,r3, r4, r5 and r6 independently of one another represent 0 to 10,
wobei die Summe von r3 + r4 + r5 + r6 = r ist, undwhere the sum of r3 + r4 + r5 + r6 = r, and
das Verhältnis von r : q < 0.25 ist, und für die Formel (9') gilt:the ratio of r: q is <0.25, and the following applies to formula (9 '):
0,01 < Σ Alkylreste R3: Σ q < 0,10.01 <Σ alkyl radicals R 3 : Σ q <0.1
Ganz besonders bevorzugt sind erfmdungsgemäße Formulierungen, die als Verbindung (a) den Ester aus Stearinsäure und 40 mol EO enthalten.Formulations according to the invention which contain the ester of stearic acid and 40 mol of EO as compound (a) are very particularly preferred.
Die erfindungsgemäßen Formulierungen enthalten mindestens eine am Stickstoff quaternierte Ammoalkylsiloxan- Verbindung (Silikonquat). Derartige Verbindungen und deren Herstellung sind bekannt, z.B. aus WO 02/10 256, WO 02/10 257, WO 02/10 259, EP 282 720, EP 17 121, DE-A 100 36 533, DE-A 100 36 539, DE-A 100 36 532, DE-A 100 36 522 und DE -A 102 12 470.The formulations according to the invention contain at least one ammoalkylsiloxane compound (silicone quat) quaternized on nitrogen. Such compounds and their preparation are known, e.g. from WO 02/10 256, WO 02/10 257, WO 02/10 259, EP 282 720, EP 17 121, DE-A 100 36 533, DE-A 100 36 539, DE-A 100 36 532, DE- A 100 36 522 and DE -A 102 12 470.
Bevorzugt entsprechen die in den erfindungsgemäßen Formulierungen enthaltenen quaternierten Ammoalkylsiloxan- Verbindungen linearen oder cyclischen Poly- siloxanpolymeren der WO 02-10259 mit sich wiederholenden wesentlichen Struktur- einheiteή der Formeln (10) und (11)The quaternized ammoalkylsiloxane compounds contained in the formulations according to the invention preferably correspond to linear or cyclic poly- siloxane polymers of WO 02-10259 with repeating essential structural units of the formulas (10) and (11)
CH3 CH, R16 R16 CH 3 CH, R 16 R 16
X- SiO)— Si X-N-M-N- (1 1)X- SiO) - Si X-N-M-N- (1 1)
CH3 CH3 worinCH 3 CH 3 wherein
X ein zweiwertiger Kohlenwasserstoffrest mit mindestens 4 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweisen kann und bevorzugt eine Hydroxylgruppe aufweist und der durch ein Sauerstoffatom unterbrochen sein kann, und die Gruppen X in den Wiederholungseinheiten gleich oder verschieden sein können,X is a divalent hydrocarbon radical with at least 4 carbon atoms, which may have a hydroxyl group and preferably has a hydroxyl group and which may be interrupted by an oxygen atom, and the groups X in the repeating units may be the same or different,
Y ein zweiwertiger Kohlenwasserststoffrest mit mindestens 2 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweisen und der durch ein oder mehrere Sauerstoff- oder Stickstoffatome unterbrochen sein kann,Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by one or more oxygen or nitrogen atoms,
R11, R12, R13 und R1"* gleich oder verschieden sind und Alkylreste mit 1 bis 4 Kohlenstoffatomen oder Benzylreste bedeuten oder jeweils die Reste R11 und R13 oder R12 und R14 Bestandteile eines verbrückenden Alkylenrestes sein können, R16 H oder ein Alkylrest mit 1 bis 20 Kohlenstoffatomen ist, der sauerstoffsubstituiert sein kann,R 11 , R 12 , R 13 and R 1 "* are identical or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals or the radicals R 11 and R 13 or R 12 and R 14 can each be constituents of a bridging alkylene radical, R 16 is H or an alkyl radical with 1 to 20 carbon atoms, which may be oxygen-substituted,
M die Struktur -B-O-(EOx)v(POx)w-B-, worinM the structure -BO- (EOx) v (POx) w -B-, wherein
EOx eine Ethylenoxideinheit und POx eine Propylenoxideinheit ist,EOx is an ethylene oxide unit and POx is a propylene oxide unit,
B gradkettiges oder verzweigtes C2 bis C6 Alkylen,B straight-chain or branched C 2 to C 6 alkylene,
v 0 bis 200,v 0 to 200,
w 0 bis 200,w 0 to 200,
v+w > 1 entspricht,v + w> 1 corresponds,
n 2 bis 1000, worin die n in den Wiederholungseinheiten gleich oder verschieden sein können, undn 2 to 1000, in which the n in the repeating units can be the same or different, and
A- ein anorganisches oder organisches Anion bedeutet.A- means an inorganic or organic anion.
Die erfindungsgemäßen Formulierungen enthalten gegebenenfalls auch beliebige Mischungen der oben bezeichneten quaternierten Aminoalkylsiloxan- Verbindungen mit den entsprechenden nicht quaternierten Verbindungen. Bei diesen nicht quaternierten Verbindungen fehlt somit in der Formel (10) an den Stickstoffatomen in der Hauptkette jeweils einer der Reste R11 oder R12 bzw. R13 oder R14 The formulations according to the invention optionally also contain any mixtures of the above-mentioned quaternized aminoalkylsiloxane compounds with the corresponding non-quaternized compounds. In these non-quaternized compounds, one of the radicals R 11 or R 12 or R 13 or R 14 is therefore missing in the formula (10) on the nitrogen atoms in the main chain
Die erfindungsgemäß bevorzugten quaternierten Aminoalkylsiloxan-Verbindungen sind Gegenstand der WO 02/10 259 und dort allgemein und speziell beschrieben. Der Inhalt der WO 02/10 259 soll hiermit durch die vorliegende Anmeldung in vollem Umfang umfasst werden. In einer bevorzugten Ausführungsform der Erfindung stehen die Mengen an hydrophilen, nichtionogenen grenzflächenaktiven Verbindungen (a) und/oder hydrophilen Dispergiermitteln (b) und/oder Salzen (c) zu den Mengen an quaternierten Aminoalkylsiloxan- Verbindungen in einem Gewichtsverhältnis Ω von Ω = 0.05 bis 10, bevorzugt Ω = 0.05 bis 5, speziell Ω ■= 0.05 bis 3, ganz speziell Ω = 0.05 bis 1. Ω bildet nur das Verhältnis von Gesammtmenge Komponente (a) bis (c) zu Menge an Silikonquat ab. Bei Verwendung zu geringer Mengen an Zusatz (a) und/oder (b) und/oder (c) erschöpft sich die wirksame Stabilisierung bei der Faserausrüstung, d.h. z.B., dass die Scherstabilität unter Umständen bei starker mechanischer Scherung, hohen Temperaturen, langen Ausrüstungszyklen nicht immer aufrecht erhalten werden kann. Sehr große Zusatzmengen sind unökonomisch und können den Weichgriff des Textils in unerwünschter Weise verändern.The quaternized aminoalkylsiloxane compounds preferred according to the invention are the subject of WO 02/10 259 and are described there generally and specifically. The content of WO 02/10 259 is hereby fully encompassed by the present application. In a preferred embodiment of the invention, the amounts of hydrophilic, nonionic surface-active compounds (a) and / or hydrophilic dispersants (b) and / or salts (c) to the amounts of quaternized aminoalkylsiloxane compounds are in a weight ratio Ω of Ω = 0.05 to 10, preferably Ω = 0.05 to 5, especially Ω ■ = 0.05 to 3, very specifically Ω = 0.05 to 1. Ω only represents the ratio of the total amount of components (a) to (c) to the amount of silicone quat. If the amounts of additive (a) and / or (b) and / or (c) used are too small, the effective stabilization in the fiber equipment is exhausted, that is to say, for example, that the shear stability may not always be the case under strong mechanical shear, high temperatures, and long equipment cycles can be maintained. Very large additional quantities are uneconomical and can undesirably change the soft feel of the textile.
Die Zugabe der beschriebenen Zusätze a) bis c) kann auf zwei Arten erfolgen. Es ist einerseits möglich, dass die erfindungsgemäßen Zusätze in die Formulierungen direkt eingebracht werden. Andererseits kann es unter Praxisbedingungen bevorzugt sein, die Formulierungen zunächst auf Anwendungskonzentration zu verdünnen und anschließend die erfindungsgemäßen Zusätze in die bereitete Flotte zu geben.The additives a) to c) described can be added in two ways. On the one hand, it is possible for the additives according to the invention to be introduced directly into the formulations. On the other hand, it may be preferred under practical conditions to first dilute the formulations to the application concentration and then to add the additives according to the invention to the prepared liquor.
Die erfindungsgemäßen Formulierungen können neben den Komponenten (a) und/oder (b) und oder (c) noch weitere grenzflächenaktive Komponenten (f), die eine Emulgierung bzw. Microemulgierung ermöglichen, enthalten.In addition to components (a) and / or (b) and or (c), the formulations according to the invention can also contain further surface-active components (f) which enable emulsification or microemulsification.
Bei diesen Komponenten (f) handelt es sich um übliche, dem Fachmann bekannte Formulierungsagentien zur Herstellung der Silikon(mikro)emulsionen, die jedoch allein nicht gegen hohen Energieeintrag stabil sind. Als solche bevorzugten Komponenten sind fl) bis f6) zu nennen: (fl) Oxalkylierungsprodukte, die durch Alkoxylierung mit Ethylenoxid oder Propylenoxid von Kondensationsprodukten phenolischer OH-gruppenhaltiger Aromaten mit Formaldehyd und NH-funktionellen Gruppen erhältlich sind. f2) nicht-ionische oder ionisch modifizierte Verbindungen aus der Gruppe der Alkoxylate, Alkylolamide, Ester, Aminoxide und Alkylpoly- glykoside, insbesondere Umsetzungsprodukte von Alkylenoxiden mit alkylierbaren Verbindungen, wie z.B. Fettalkoholen, Fettaminen, Fettsäuren, Phenolen, Alkyl- phenolen, Carbonsäureamiden und Harzsäuren. Hierbei handelt es sich z.B. um Ethylenoxidether aus der Klasse der Umsetzungsprodukte von Ethylenoxid mit gesättigten und/oder ungesättigten Fettalkoholen mit 6 bis 25 C-Atomen (kommerziell erhältlich beispielsweise in Form der Produktreihe Renex®) oder Alkylphenolen mit 4 bis 12 C-Atomen im Alkylrest oder gesättigten und/oder ungesättigten Fettaminen mit 14 bis 20 C-Atomen oder gesättigten und/oder ungesättigten Fettsäuren mit 14 bis 22 C-Atomen oder aus natürlichen oder modifizierten, gegebenenfalls hydrierten Rizinusölfettkörper hergestellte Veresterungs- und/oder Arylierungsprodukte, die gegebenenfalls durch Veresterung mit Dicarbonsäuren zu wiederkehrenden Struktureinheiten verknüpft sind. £3) ionische oder nicht-ionische Verbindungen aus der Gruppe der Umsetzungsprodukte von Alkylenoxid mit Sorbitanester [Tween, ICI], oxalkylierte Acetylendiole und glykole, oxalkylierte Phenole, insbesondere Phenol/Styrol-Polyglykolether. f4) ionische oder nichtionische polymere oberflächenaktive Mittel aus der Gruppe der Homo- und Copolymerisate, Pfropf- und Pfropfcopolymerisate sowie statistische und lineare Blockcopolymerisate. £5) anionische oberflächenaktive Mittel wie beispielsweise Alkylsulfate, Ethersulfate, Ethercarboxylate, Phosphatester, Sulfosuccinatamide, Paraffinsulfonate, Olefinsulfonate, Sarcosinate, Isothionate und Taurate f6) amphotere oberflächenaktive Mittel wie Betaine und Ampholyte, insbesondere Glycinate, Propionate und Imidazoline.These components (f) are customary formulation agents known to those skilled in the art for the preparation of the silicone (micro) emulsions, but these alone are not stable against high energy input. Examples of such preferred components are f1 to f6): (f1) oxyalkylation products which can be obtained by alkoxylation with ethylene oxide or propylene oxide from condensation products of phenolic OH group-containing aromatics with formaldehyde and NH-functional groups. f2) non-ionic or ionically modified compounds from the group of alkoxylates, alkylolamides, esters, amine oxides and alkyl poly- glycosides, in particular reaction products of alkylene oxides with alkylatable compounds, such as, for example, fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, carboxamides and resin acids. These are, for example, ethylene oxide ethers from the class of the reaction products of ethylene oxide with saturated and / or unsaturated fatty alcohols with 6 to 25 C atoms (commercially available, for example in the form of the Renex® product series) or alkylphenols with 4 to 12 C atoms in the alkyl radical or saturated and / or unsaturated fatty amines with 14 to 20 carbon atoms or saturated and / or unsaturated fatty acids with 14 to 22 carbon atoms or esterification and / or arylation products prepared from natural or modified, optionally hydrogenated castor oil fatty substances, which may be by esterification with Dicarboxylic acids are linked to recurring structural units. 3) Ionic or non-ionic compounds from the group of the reaction products of alkylene oxide with sorbitan esters [Tween, ICI], oxalkylated acetylenediols and glycols, oxalkylated phenols, in particular phenol / styrene polyglycol ethers. f4) ionic or nonionic polymeric surface-active agents from the group of homopolymers and copolymers, graft and graft copolymers and statistical and linear block copolymers. £ 5) anionic surfactants such as alkyl sulfates, ether sulfates, ether carboxylates, phosphate esters, sulfosuccinatamides, paraffin sulfonates, olefin sulfonates, sarcosinates, isothionates and taurates f6) amphoteric surfactants such as betaines and ampholytes, especially glycinates, propionates and imidazolines.
Besonders bevorzugte Formulierungsbestandteile (f) sind alkoxylierte Fettalkohole, verzweigte Fettalkohole und Fettsäuren mit 4 bis 14 Alkoxydeinheiten, ganz besonders bevorzugte Formulierungsbestandteile (f) sind alkoxylierte Fettalkohole, verzweigte Fettalkohole mit 6 bis 12 Alkoxydeinheiten, speziell Formulierungen, die den Ether von Tridecylalkohol mit 12 mol EO, den Ether von Tridecylalkohol mit 6 mol EO enthalten. Die Formulierungsbestandteile werden im allgemeinen in üblichen Mengen der erfindungsgemäßen Formulierung zugesetzt. Bevorzugt werden die Komponenten (f) in Mengen von 1 bis 200 Gew.%, bevorzugt 10 bis 80 Gew.-% , besonders bevorzugt 10-50 Gew.-% bezogen auf das quatemierte Aminoalkylsiloxan zugesetzt.Particularly preferred formulation constituents (f) are alkoxylated fatty alcohols, branched fatty alcohols and fatty acids with 4 to 14 alkoxide units, very particularly preferred formulation constituents (f) are alkoxylated fatty alcohols, branched fatty alcohols with 6 to 12 alkoxide units, especially formulations which contain the ether of tridecyl alcohol with 12 mol EO, the ether of tridecyl alcohol containing 6 mol EO. The formulation constituents are generally added to the formulation according to the invention in customary amounts. Components (f) are preferably added in amounts of 1 to 200% by weight, preferably 10 to 80% by weight, particularly preferably 10-50% by weight, based on the quaternized aminoalkylsiloxane.
Die Formulierungen können neben den Komponente(n) (a) bis (c) jeweils allein oder in Kombination und den Zusätzen (f) auch noch weitere Hilfsmittel in den für diese Hilfsmittel üblichen Mengen enthalten.In addition to component (s) (a) to (c), the formulations may in each case, alone or in combination, and additives (f) also contain other auxiliaries in the amounts customary for these auxiliaries.
Übliche Hilfsmittel im Sinne der Erfindung sind u.a. Egalisiermittel, Netzmittel, Glanzausrüstungsmittel, Faserschutzmittel, Schiebefestmittel und weitere Hilfsmittel nach Stand der Technik. Eine gute Übersicht der erfindungsgemäßen Hilfsmittel findet sich in Chwala/Anger, Handbuch der Textilhilfsmittel, Verlag Chemie, Weinhein 1977. Darüberhinaus können Puffersysteme zur Einstellung eines optimalen pH- Wertes während der Ausrüstung eingearbeitet werden.Usual aids in the sense of the invention include Leveling agents, wetting agents, gloss finishes, fiber protection agents, anti-slip agents and other auxiliaries according to the prior art. A good overview of the auxiliaries according to the invention can be found in Chwala / Anger, Handbuch der Textilhilfsmittel, Verlag Chemie, Weinhein 1977. In addition, buffer systems can be incorporated to adjust an optimal pH during the finishing.
Zur Herstellung der erfindungsgemäßen Formulierungen können die quaternierten Aminoalkylsiloxan-Verbindungen mit den Komponenten (a), (b) und/oder (c), gegebenenfalls unter Zusatz weiterer, oben genannter Bestandteile, gemischt werden, bevorzugt im Temperaturbereich von 20 bis 90°C, besonders bevorzugt bei 25 bis 70°C, ganz besonders bevorzugt bei 30 bis 60°C.To prepare the formulations according to the invention, the quaternized aminoalkylsiloxane compounds can be mixed with components (a), (b) and / or (c), if appropriate with the addition of further components mentioned above, preferably in the temperature range from 20 to 90 ° C. particularly preferably at 25 to 70 ° C, very particularly preferably at 30 to 60 ° C.
Die quaternierten Aminoalkylsiloxane werden dabei bevorzugt zu der/den Verbindungen) (a), (b) und/oder (c) gegeben; besonders bevorzugt wird das quatemierte Aminoalkylsiloxan (Silikonquat) vorgelegt und die Emulsionsbildung durch Zugabe der Verbindung(en) (a), (b) und/oder (c) und gegebenenfalls weiterer Zusätze vervollständigt.The quaternized aminoalkylsiloxanes are preferably added to the compound (s) (a), (b) and / or (c); The quaternized aminoalkylsiloxane (silicone quat) is particularly preferably introduced and the emulsion formation is completed by adding the compound (s) (a), (b) and / or (c) and, if appropriate, further additives.
Die erfindungsgemäßen Formulierungen eignen sich hervorragend als Textilweichmacher bei der Ausrüstung von textilen Flächengebilden, insbesondere solchen aus Baumwolle, Keratinfasern, bevorzugt Wolle, Seide oder Synthesefasern oder spielsweise sehr gut für die Ausrüstung von textilen Flächengebilden aus Mischungen von Baumwolle mit Polyester, Polyamid, Polyacrylnitril, Wolle oder Seide einsetzen. Exzellente Ergebnisse werden gleichermaßen bei der Ausrüstung textiler Flächengebilde aus Synthesefasern, insbesondere aus Polyester, Polyamid, Polypropylen oder Mischungen daraus erzieltThe formulations according to the invention are outstandingly suitable as textile softeners when finishing textile fabrics, in particular those made of cotton, keratin fibers, preferably wool, silk or synthetic fibers or for example, very good for finishing textile fabrics made from blends of cotton with polyester, polyamide, polyacrylonitrile, wool or silk. Excellent results are also achieved when finishing textile fabrics made of synthetic fibers, especially polyester, polyamide, polypropylene or mixtures thereof
Unter textilen Flächengebilden sind bevorzugt Gewebe, Gewirke, Maschenware und Vliese zu verstehen.Textile fabrics are preferably fabrics, knitted fabrics, knitwear and nonwovens.
Als besonders vorteilhaft hat sich die Verwendung der erfindungsgemäßen Formulierungen für die Ausrüstung von Baumwolle oder baumwoUhaltigen Textilien, die mit anionischen Weißtönern vorbehandelt wurden, nach dem Jet- Verfahren erwiesen.The use of the formulations according to the invention for finishing cotton or textiles containing cotton, which have been pretreated with anionic white toners, according to the jet method, has proven to be particularly advantageous.
Beim Einsatz der erfmdungsgemäßen Formulierungen können nicht nur hervorragende Weichmacher-Ergebnisse erreicht werden, vielmehr werden auch andere Eigenschaften des Textils, wie die Vernähbarkeit, verbessert oder der Glanz erhöht.When using the formulations according to the invention, not only excellent plasticizer results can be achieved, but also other properties of the textile, such as sewability, are improved or the gloss is increased.
Die Ausrüsung erfolgt im allgemeinen nach dem Kontinue-Verfahren (Foulard- oder Lisseuse- Verfahren) oder nach dem Ausziehverfahren (Jet- Verfahren). Bei Anwendung der erfindungsgemäßen Formulierungen nach einem dieser Ausrüstungsverfahrenen hat es sich als vorteilhaft erwiesen, die folgenden technologischen Parameter einzuhalten:The equipment is generally carried out by the continuous process (padding or lisseuse process) or by the exhaust process (jet process). When using the formulations according to the invention using one of these finishing methods, it has proven to be advantageous to comply with the following technological parameters:
• Kontinue (z.B. Foulard, Lisseuse)• Continuity (e.g. foulard, lisseuse)
1. Bei 1 l%iger Silikonkonzentration: 5-50 g/1, bevorzugt 10-40 g/1 und speziell1. With 1 l% silicone concentration: 5-50 g / 1, preferably 10-40 g / 1 and especially
10-25 g/1 Formulierung SQ (= Silikonquat) + a) bis c)10-25 g / 1 formulation SQ (= silicone quat) + a) to c)
2. Ausrüstungstemperatur: Raumtemperatur2. Equipment temperature: room temperature
3. Trocknungstemperatur: 75-105°C im Umlufttrockenschrank oder3. Drying temperature: 75-105 ° C in a convection oven or
10-60 sec auf dem Spannrahmen bei 150°C, besonders 30-45 sec10-60 sec on the stenter at 150 ° C, especially 30-45 sec
4. Zeit im Umlufttrockenschrank: 10-20 Minuten • Ausziehverfahren (z.B. Jet, Haspelkufe)4. Time in a forced air drying cabinet: 10-20 minutes • pull-out procedure (eg jet, reel runner)
1. Bei 11 %iger Silikonkonzentration: 1,0-5,0 %), bevorzugt 1,5-3,5 % und speziell 1,5-2,5 %1. With 11% silicone concentration: 1.0-5.0%), preferably 1.5-3.5% and especially 1.5-2.5%
Ausrüstungstemperatur: 30-60°C, bevorzugt 35-50°C und speziell 35-45°CEquipment temperature: 30-60 ° C, preferably 35-50 ° C and especially 35-45 ° C
3. Aufheizrate: 2-4°C/Minute 4. Ausrüstungszeit: 15-25 Minuten 5. Flottenverhältnis : 1 :5 bis 1:50, besonders 1:10 bis 1:30 6. Trocknungstemperatur 75-105 °C im Umlufttrockenschrank oder 10-60 sec auf dem Spannrahmen bei 150°C, besonders 30-45 sec3. Heating rate: 2-4 ° C / minute 4. Finishing time: 15-25 minutes 5. Fleet ratio: 1: 5 to 1:50, especially 1:10 to 1:30 6. Drying temperature 75-105 ° C in a circulating air oven or 10-60 sec on the stenter at 150 ° C, especially 30-45 sec
7. Zeit im Umlufttrockenschrank: 10-20 Minuten 7. Time in a forced air drying cabinet: 10-20 minutes
BeispieleExamples
In den nachstehenden Formulierungen wurde ein gemäß WO 02/10259, Beispiel 1 synthetisiertes Silikonquat (SQ) eingesetzt, welches folgende Strukturelemente aufweist und folgendermaßen hergestellt wird:A silicone quat (SQ) synthesized according to WO 02/10259, Example 1, which has the following structural elements and is produced as follows, was used in the formulations below:
la) In einem 1 Liter Dreihalskolben wurden 24 g Wasser und 4,18 g (0,048 mol tertiäre Aminogruppen) N,N,N',N'-Tetramethyl-l,6-hexandiamin und 3,8 g (0,012 mol primäre Aminogruppen ) eines unter dem Handelsnamen Jeffamin® ED 600 erhältlichen Alkylenoxidderivates der Strukturla) 24 g of water and 4.18 g (0.048 mol of tertiary amino groups) of N, N, N ', N'-tetramethyl-l, 6-hexanediamine and 3.8 g (0.012 mol of primary amino groups) were placed in a 1 liter three-necked flask. an alkylene oxide derivative available under the trade name Jeffamine ® ED 600 of the structure
H2NCH(CH3)CH2[OCH2CH(CH3)]a(OCH2CH2)9[OCH2CH(CH3)]bNH2 mit a+b = 3,6H 2 NCH (CH 3 ) CH 2 [OCH 2 CH (CH 3 )] a (OCH 2 CH 2 ) 9 [OCH 2 CH (CH 3 )] b NH 2 with a + b = 3.6
bei Raumtemperatur vorgelegt. Innerhalb von 5 Minuten wurden 12,0 g (0,03 mol) Dodecansäure in Form einer 50 %igen Lösung in 2-Propanol und 1,8 g (0,03 mol) Essigsäure zugesetzt. Nach Erwärmung des Ansatzes auf 50°C wurden innerhalb von 30 Minuten 194,1 g (0,06 mol Epoxygruppen) eines Epoxysiloxans der durchschnittlichen Zusammensetzungsubmitted at room temperature. 12.0 g (0.03 mol) of dodecanoic acid in the form of a 50% strength solution in 2-propanol and 1.8 g (0.03 mol) of acetic acid were added within 5 minutes. After the batch had been heated to 50 ° C., 194.1 g (0.06 mol epoxy groups) of an epoxysiloxane of the average composition were obtained within 30 minutes
und 30 ml 2-Propanol zugetropft. Die gelbe, trübe Mischung wurde 6 Stunden auf Rückflußtemperatur erhitzt. Nach Entfernung aller bis 100°C und bei 2 mmHg im Vakuum flüchtigen Bestandteile werden 204 g eines leicht gelben, trüben Materials erhalten, welches folgende Strukturelemente enthält and 30 ml of 2-propanol were added dropwise. The yellow, cloudy mixture was heated to reflux temperature for 6 hours. After removal of all components volatile up to 100 ° C and at 2 mmHg in a vacuum, 204 g of a slightly yellow, cloudy material are obtained, which contains the following structural elements
Ausgehend von diesem Silikonmaterial wurden drei Microemulsionskonzentrate folgender Zusammensetzung hergestellt: Based on this silicone material, three microemulsion concentrates with the following composition were produced:
Diese drei Microemulsionskonzentrate (etwa 40 %ig bezüglich SQ) werden mit Wasser einheitlich auf jeweils 11 % Silikonquatgehalt verdünnt. Von diesen 11 %igen transparenten Microemulsionen werden jeweils 6 g (absolute Silikonquatmenge 0.66 g) abgenommen, mit 6000 ml Wasser und ggf. Zusätzen intensiv vermischt und unter folgenden Randbedingungen zur Jetausrüstung benutzt: Jettyp: Mathis Labor- Jumbo- Jet Jetpumpe: Stufe 6 (höchstmögliche Scherung) Wassermenge im Jet: 6000 ml Ausrüstung: 15 Minuten bei 40°C Trocknung: 80°CThese three microemulsion concentrates (about 40% based on SQ) are uniformly diluted with water to 11% silicone quat content. 6 g (absolute silicone quat quantity 0.66 g) of each of these 11% transparent microemulsions are taken, mixed intensively with 6000 ml of water and any additives and used for jet equipment under the following boundary conditions: Jet type: Mathis Laboratory Jumbo-Jet jet pump: Level 6 ( highest possible shear) Water volume in the jet: 6000 ml Equipment: 15 minutes at 40 ° C drying: 80 ° C
Textil: 300g gebleichtes und mit optischem Aufheller (z.B. Blankophor® BA behandeltes Baumwolljersey). In der nachfolgenden Tabelle sind die Ergebnisse der Ausrüstversuche zusammen- gefasst.Textile: 300g bleached and treated with optical brightener (e.g. Blankophor® BA treated cotton jersey). The results of the equipment tests are summarized in the table below.
* Abscheidung an Glas- und Stahlteilen des Jets* Deposition on glass and steel parts of the jet
* * silikonartig weich mit Volumengewinn *** Tropfenemsinkzeit < 3 Sekunden* * silicone-like soft with volume gain *** drop sink time <3 seconds
Renex® 36 Handelsname der ICI Surfactants; Tridecylalkohol-(EO)12-OH Renex® 30 Handelsname der ICI Surfactants; Tridecylalkohol-(EO)6-OH Crodet® S40 Handelsname der Croda GmbH; Stearinsäure-(EO)4o-OHRenex® 36 trade name of ICI surfactants; Tridecyl Alcohol- (EO) 12 -OH Renex® 30 trade name of the ICI surfactants; Tridecyl alcohol- (EO) 6 -OH Crodet® S40 trade name of Croda GmbH; Stearic acid (EO) 4 o-OH
Versuch 1 beschreibt das inakzeptable Ergebnis eines nicht erfindungsgemäßen Versuchs gemäß dem Stand der Technik. Eine Verdoppelung der Tensidmenge beider Renex-Typen führt nicht zu einer Verhinderung der Ausfallung (Versuch 2, nicht erfindungsgemäß) . Die Versuche 3 und 4 belegen, dass durch einen erfindungsgemäßen Zusatz von Salzen mehrwertiger Kationen eine Ausfällung sicher verhindert werden kann. Aluminiumsalze sind effektiver als Magnesiumverbindungen.Experiment 1 describes the unacceptable result of an experiment according to the prior art which is not according to the invention. A doubling of the amount of surfactant of both Renex types does not prevent the failure (test 2, not according to the invention). Experiments 3 and 4 prove that precipitation can be reliably prevented by adding salts of polyvalent cations according to the invention. Aluminum salts are more effective than magnesium compounds.
Versuch 5 zeigt, dass durch einen erfindungsgemäßen Einbau von hydrophilen grenzflächenaktiven Verbindungen direkt in die Formulierung eine Ausfällung zuverlässig verhindert wird. Dies trifft auch auf eine ebenfalls erfindungsgemäße partielle nachträgliche Hinzufügung (Versuch 6) oder erfindungsgemäße vollständige Hinzufügung (Versuch 7) dieser hydrophilen grenzflächenaktiven Verbindung zu. Experiment 5 shows that by incorporating hydrophilic surface-active compounds directly into the formulation, precipitation is reliably prevented. This also applies to a partial subsequent addition (experiment 6) or complete addition (experiment 7) according to the invention of this hydrophilic surface-active compound.

Claims

Patentansprücheclaims
1. Formulierungen enthaltend mindestens ein quatemiertes Aminoalkylsiloxan und mindestens eine Verbindung aus der Reihe1. Formulations containing at least one quaternized aminoalkylsiloxane and at least one compound from the series
a) der hydrophilen, nichtionogenen grenzflächenaktiven Verbindungen, b) der hydrophilen Dispergiermittel und c) der Salze von zwei- oder dreiwertigen Metallen mit anorganischen Säuren.a) the hydrophilic, nonionic surface-active compounds, b) the hydrophilic dispersants and c) the salts of divalent or trivalent metals with inorganic acids.
2. Formulierungen gemäß Anspruch 1, dadurch gekennzeichnet, dass es sich bei den hydrophilen, nichtionogenen grenzflächenaktiven Verbindungen (a) um Ethylen/Propylenoxid (EO/PO) modifizierte Verbindungen, gegebenenfalls ungesättigt und/oder verzweigt, aus der Gruppe der Fettalkohole, Fettsäuren, Alkohole, Säuren, Alkylarylderivate, Fettamine, Glyceride und Sorbitanester, handelt, bei denen die Anzahl der EO/PO Einheiten zwischen 15 und 150 liegt, wobei das Verhältnis von PO Einheiten zu EO-Einheiten bei gleich oder unter 0.25 liegt, und bei denen die Anzahl der Ethylenoxideinheiten (EO-Teil) größer oder gleich der Anzahl der Kohlenstoffatome im Nicht-EO Teil ist, und um Alkylpolyglykoside, Ethylenoxid/Propylenoxid Copolymere und Polyethersiloxane handelt.2. Formulations according to claim 1, characterized in that the hydrophilic, nonionic surface-active compounds (a) are ethylene / propylene oxide (EO / PO) modified compounds, optionally unsaturated and / or branched, from the group of fatty alcohols, fatty acids, Alcohols, acids, alkylaryl derivatives, fatty amines, glycerides and sorbitan esters, in which the number of EO / PO units is between 15 and 150, the ratio of PO units to EO units being equal to or less than 0.25, and in which the Number of ethylene oxide units (EO part) is greater than or equal to the number of carbon atoms in the non-EO part, and is alkyl polyglycosides, ethylene oxide / propylene oxide copolymers and polyether siloxanes.
3. Formulierungen gemäß mindestens einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass es sich bei den hydrophilen Dispergiermitteln (b) um wasserlösliche Polysaccharide aus der Gruppe der substituierten Cellulosen handelt.3. Formulations according to at least one of claims 1 to 2, characterized in that the hydrophilic dispersants (b) are water-soluble polysaccharides from the group of substituted celluloses.
4. Formulierungen gemäß mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es sich bei den Salzen (c) um solche der Metalle Calcium, Magnesium und Aluminium mit Salzsäure, Schwefelsäure oder Phosporsäure handelt, wobei die Salze auch in in Form ihrer Hydrate vorliegen können.4. Formulations according to at least one of claims 1 to 3, characterized in that the salts (c) are those of the metals calcium, magnesium and aluminum with hydrochloric acid, sulfuric acid or Phosphoric acid is involved, and the salts can also be present in the form of their hydrates.
5. Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 4, dadurch gekennzeiclinet, dass es sich bei der Verbindung (a) um eine Verbindung der Formeln (1) bis (9)5. Formulations according to at least one of claims 1 to 4, characterized in that the compound (a) is a compound of the formulas (1) to (9)
R1-O-[CH2CH2O]q-[CH2CH(CH3)O] E (1),R 1 -O- [CH 2 CH 2 O] q - [CH2CH (CH3) O] E (1),
R2-NH-[CH2CH(CH3)O]r-[CH2CH2O]q-E (3),R 2 -NH- [CH 2 CH (CH 3 ) O] r - [CH 2 CH 2 O] q -E (3),
(5), R2-NH-CH(CH3)CH2-[OCH2CH(CH3)]m7-[OCH2CH2]q-[OCH2CH(CH3)]m8-NH-R2 (5) R 2 -NH-CH (CH 3 ) CH2- [OCH 2 CH (CH 3 )] m 7- [OCH 2 CH 2 ] q - [OCH 2 CH (CH 3 )] m8 -NH-R 2
(7),(7)
E-O-[CH2CH2O]s-[CH2CH(CH3)O]t-E (8), oderEO- [CH 2 CH 2 O] s - [CH 2 CH (CH 3 ) O] t -E (8), or
handelt,These,
worinwherein
für einen Rest R , Wasserstoff, geradkettiges oder verzweigtes, gesättigtes oder ein- oder mehrfach ungesättigtes Cι-Cι8- Alkyl welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, C1-C4- Alkoxycarbonyl oder Carbonyl substituiert ist, oder für Cs-Cio-Cyclo- alkyl steht, welches jeweils gegebenenfalls ein- oder mehrfach durch Cι-C4-Alkyl, -OH, Cι-C -Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,for a radical R, hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 8 -alkyl which, if appropriate, one or more times by -OH, -C-C 4 alkoxy, C 1 -C 4 alkoxycarbonyl or carbonyl is substituted, or is Cs-Cio-cycloalkyl, which is in each case optionally substituted one or more times by C 1 -C 4 -alkyl, -OH, C 1 -C -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl,
R1 für geradkettiges oder verzweigtes, gesättigtes oder ungesättigtes C8- C4o-Alkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C -Alkoxy, Cι-C -Alkoxycarbonyl oder Carbonyl, Amino, mono- oder di- Cι-C4- Alkylamino substituiert ist, oder für C5 -Cio-Cycloalkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- ein- oder mehrfach durch Cι-C4-Alkyl, -OH, Cι-C4-Alkoxy, Cι-C4- Alkoxycarbonyl oder Carbonyl, Amino, mono- oder di-C1-C -Alkyl- amino substituiert ist,R 1 stands for straight-chain or branched, saturated or unsaturated C 8 - C 4 o -alkyl, the alkyl chain of which may be interrupted one or more times by oxygen and / or nitrogen atoms and which may be one or more times by -OH, -CC -Alkoxy, -CC -alkoxycarbonyl or carbonyl, amino, mono- or di- -C-C 4 - alkylamino is substituted, or represents C 5 -Cio-cycloalkyl, the alkyl chain of which may be one or more times by oxygen is substituted one or more times by C 1 -C 4 -alkyl, -OH, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl, amino, mono- or di-C 1 -C -alkylamino,
R für geradkettiges oder verzweigtes, gesättigtes oder ein- bis mehrfach ungesättigtes C8-C4o-Alkyl steht, welches gegebenenfalls ein- oder mehfach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,R represents straight-chain or branched, saturated or mono- to polyunsaturated C 8 -C 4 o-alkyl, which is optionally mono- or poly-substituted by -OH, -CC 4 alkoxy, -C 4 -alkoxycarbonyl or carbonyl .
R für geradkettiges oder verzweigtes Ci-C26 Alkyl oder C6-Cιo-Aryl steht,R represents straight-chain or branched Ci-C 26 alkyl or C 6 -Cιo-aryl,
R4 für R3 oder für einen Rest der FormelnR 4 for R 3 or for a rest of the formulas
-CH2CH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E ,-CH 2 CH 2 -O- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E,
-CH2CH2CH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E -CH2CH2CH2-O-CH2CHOHCH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E -Z-[CH2CH2O]q-[CH2CH(CH3)O]r-E-CH 2 CH 2 CH 2 -O- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E -CH 2 CH 2 CH 2 -O-CH 2 CHOHCH 2 -O- [ CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E -Z- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E
worinwherein
Z ein geradkettiger oder verzweigter Alkyl- oder Cycloalklyrest ist, der jeweils durch -O- und /oder -CO- unterbrochen und gegebenenfalls durch mindestens eine OH-Gruppe substituiert sein kann,Z is a straight-chain or branched alkyl or cycloalkyl radical which can in each case be interrupted by -O- and / or -CO- and optionally substituted by at least one OH group,
oder steht,or stands,
q für 15 bis 150 steht,q represents 15 to 150,
ql und q2 unabhängig voneinander für 0 bis 150 stehen,ql and q2 are independently 0 to 150,
wobei die Summe von ql + q2 = q ist,where the sum of ql + q2 = q,
q3, q4, q5 und q6 unabhängig voneinander für 0 bis 150 stehen,q3, q4, q5 and q6 independently of one another represent 0 to 150,
wobei die Summe von q3 + q4 + q5 + q6 = q ist,where the sum of q3 + q4 + q5 + q6 = q,
r für 0 bis 50 steht,r represents 0 to 50,
rl und r2 unabhängig voneinander für 0 bis 50 stehen,rl and r2 independently of one another represent 0 to 50,
wobei die Summe von rl + r2 - r ist,where the sum of rl + r2 - r is
r3, r4, r5 und r6 unabhängig vonemander für 0 bis 50 stehen,r3, r4, r5 and r6 independently of one another represent 0 to 50,
wobei die Summe von r3 + r4 + r5 + r6 = r ist, undwhere the sum of r3 + r4 + r5 + r6 = r, and
das Verhältnis von r : q < 0.25 ist,the ratio of r: q <0.25,
m für 1 bis 50 steht. m7 und m8 unabhängig voneinander für 1 bis 50 stehen,m stands for 1 to 50. m7 and m8 independently of one another represent 1 to 50,
wobei 2 < m7+m8, und die Summe von m7 + m8 = m +1 ist, undwhere 2 <m7 + m8, and the sum of m7 + m8 = m +1, and
das Verhältnis von q : m > 4 ist,the ratio of q: m> 4,
s für 5 bis 150 steht,s stands for 5 to 150,
t für 5 bis 150 steht,t stands for 5 to 150,
wobei 0.05 < s : t < 20,where 0.05 <s: t <20,
0< zl < 2000,0 <zl <2000,
0 < z2 < 2000,0 <z2 <2000,
mindestens ein R4 ≠ R3 , undat least one R4 ≠ R3, and
0,01 < Σ Alkylreste R3 : Σ q+r < 10.01 <Σ alkyl radicals R 3 : Σ q + r <1
6. Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass es sich bei der Verbindung (a) um eine Verbindung der Formeln (1) bis (9) gemäß Anspruch 5 handelt, wobei6. Formulations according to at least one of claims 1 to 5, characterized in that the compound (a) is a compound of the formulas (1) to (9) according to claim 5, wherein
E für Wasserstoff, geradkettiges oder verzweigtes, gesättigtes oder ein- oder mehrfach ungesättigtes Cι-C4-Alkyl welches gegebenenfalls 1 bis zweifach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist, oder für C5-C6 -Cycloalkyl steht, welches jeweils gegebenenfalls ein- bis mehrfach durch Cι-C4-Alkyl, -OH, C - C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist, R1 für geradkettiges oder verzweigtes, gesättigtes oder ungesättigtes o- C36-Alkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls em- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxy carbonyl oder Carbonyl, Amino, mono- oder di- Cι-C4- Alkylamino substituiert ist, oder für Cs-Cβ-Cycloalkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch Cι-C4- Alkyl, -OH, Cι-C4-Alkoxy, Cι-C4- Alkoxycarbonyl oder Carbonyl, Amino, mono- oder di-Cι-C4-Alkyl- amino substituiert ist,E for hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 4 -alkyl which is optionally 1 to 2 times substituted by -OH, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl, or for C 5 -C 6 cycloalkyl, which is in each case optionally substituted one to more times by C 1 -C 4 -alkyl, -OH, C - C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl, R 1 stands for straight-chain or branched, saturated or unsaturated o- C 36 -alkyl, the alkyl chain of which is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which may be em- or multiple times by -OH, -CC 4 - Alkoxy, -C-C 4 alkoxy carbonyl or carbonyl, amino, mono- or di- -C -C 4 - alkylamino is substituted, or represents Cs-Cβ-cycloalkyl, the alkyl chain of which may be one or more times by oxygen and / or Nitrogen atoms is interrupted and which is optionally one or more times by C 1 -C 4 alkyl, -OH, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl or carbonyl, amino, mono- or di-C 1 -C 4 alkyl - is amino substituted,
R für geradkettiges oder verzweigtes, gesättigtes oder ein- bis mehrfach ungesättigtes Cιo-C36-Alkyl steht, welches gegebenenfalls ein- oder mehrfach durch -OH, C!-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,R represents straight-chain or branched, saturated or mono- to polyunsaturated C 1 -C 36 -alkyl, which may be mono- or polysubstituted by -OH, C ! -C 4 alkoxy, -C-C 4 alkoxycarbonyl or carbonyl is substituted,
R für geradkettiges oder verzweigtes Cι-Cι8 -Alkyl oder C6-Cιo-Aryl steht,R represents straight-chain or branched C 1 -C 8 alkyl or C 6 -C 8 aryl,
R für einen Rest R oder für einen Rest der FormelnR for a radical R or for a radical of the formulas
-CH2CH2-O-[CH2CH2θ]q-[CH2CH(CH3)O]r-E ; -CH 2 CH 2 -O- [CH 2 CH 2 θ] q - [CH 2 CH (CH 3 ) O] r -E ;
oderor
-CH2CH2CH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E-CH 2 CH 2 CH 2 -O- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E
steht, ql und q2 unabhängig voneinander für 20 bis 100 stehen,stands, ql and q2 independently represent 20 to 100,
wobei die Summe von ql + q2 - q ist,where the sum of ql + q2 - q is
q3, q4, q5 und q6 unabhängig voneinander für 20 bis 100 stehen,q3, q4, q5 and q6 independently represent 20 to 100,
wobei die Summe von q3 + q4 + q5 + q6 = q ist,where the sum of q3 + q4 + q5 + q6 = q,
r für 0 bis 20 steht,r stands for 0 to 20,
rl und r2 unabhängig voneinander für 0 bis 20 stehen,rl and r2 independently of one another represent 0 to 20,
wobei die Summe von rl + r2 = r ist,where the sum of rl + r2 = r,
r3, r4, r5 und r6 unabhängig voneinander für 0 bis 20 stehen,r3, r4, r5 and r6 independently of one another represent 0 to 20,
wobei die Summe von r3 + r4 + r5 + r6 = r ist, undwhere the sum of r3 + r4 + r5 + r6 = r, and
das Verhältnis von r : q < 0.25 ist,the ratio of r: q <0.25,
m für 1 bis 7 steht,m represents 1 to 7,
m7 und m8 unabhängig voneinander fürl bis 7 stehen,m7 and m8 are independently from 1 to 7,
wobei 2 < m7+m8, und die Summe von m7 + m.8 = m ist, undwhere 2 <m7 + m8, and the sum of m7 + m.8 = m, and
das Verhältnis von q : m > 4 ist,the ratio of q: m> 4,
s . für 5 bis 100 steht. t für 5 bis 100 steht,s. stands for 5 to 100. t stands for 5 to 100,
wobei 0.05 < s : t < 20,where 0.05 <s: t <20,
0 < zl < 20000 <zl <2000
0 < z2 < 2000,0 <z2 <2000,
mindestens ein R4 ≠ R3at least one R4 ≠ R3
undand
0,01 < Σ Alkyheste R3: Σ q+r < 0,5.0.01 <Σ alkyl residues R 3 : Σ q + r <0.5.
7. Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es sich bei der Verbindung (a) um eine Verbindung der Formeln (1 ') bis (9')7. Formulations according to at least one of claims 1 to 4, characterized in that the compound (a) is a compound of the formulas (1 ') to (9')
R1 θ-[CH2CH2O]q-[CH2CH(CH3)O] E (1 '),R 1 θ- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] E (1 '),
R2-NH I--{tcCHH22CCHH((CCHH33))OO]]rr--[[CCHH22CCHH22θθ]3;IE (3 '), R 2 -NH I - {tcCHH 22 CCHH ((CCHH 33 )) OO]] rr - [[CCHH 22 CCHH 22 θθ] 3; IE (3 '),
R2-NH-CH(CH3)CH2|[OCH2CH(CH3)]m-[OCH2CH2]q O-E (6'),R 2 -NH-CH (CH 3 ) CH 2 | [OCH 2 CH (CH 3 )] m - [OCH2CH 2 ] q OE (6 '),
R2-NH-CH(CH3)CH2|iθCH2CH(CH3)]m7-[OCH2CH2]q-[OCH2CH(CH3)]πιS-to-R2 R 2 -NH-CH (CH 3 ) CH 2 | iθCH 2 CH (CH 3 )] m7 - [OCH 2 CH 2 ] q - [OCH 2 CH (CH 3 )] πιS -to-R 2
(70,(70,
E-O^CH2CH2O]s-[CH2CH(CH3)O]tJE (8 '),EO ^ CH 2 CH 2 O] s - [CH 2 CH (CH 3 ) O] t JE (8 '),
oder ein Polyethersiloxan (9')or a polyether siloxane (9 ')
handelt, worin die in den Formeln (l ')-(8') dargestellten Klammerausdrücke „{" und „}" Ethylenoxid- bzw. Propylenoxid-Einheiten entweder wie dargestellt blockweise angeordnet sein können oder aber auch beliebig statistisch angeordnet sein können,in which the parentheses "{" and "}" shown in the formulas (1 ') - (8') Ethylene oxide or propylene oxide units can either be arranged in blocks as shown or can also be arranged randomly,
E für einen Rest R1, Wasserstoff, geradkettiges oder verzweigtes, gesättigtes oder ein- oder mehrfach ungesättigtes Cι-C18-Alkyl welches gegebenenfalls ein- oder mehrfach durch -OH, CrC4-Alkoχy, Cι-C - Alkoxycarbonyl oder Carbonyl substituiert ist, oder für C5-C10- Cycloalkyl steht, welches jeweils gegebenenfalls ein- oder mehrfach durch Cι-C4-Alkyl, -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,E for a radical R 1 , hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 18 -alkyl which is optionally substituted one or more times by -OH, CrC 4 -alky, C 1 -C 4 -alkoxycarbonyl or carbonyl , or represents C 5 -C 10 - cycloalkyl, which is in each case optionally substituted one or more times by C 1 -C 4 alkyl, -OH, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl or carbonyl,
R1 für geradkettiges oder verzweigtes, gesättigtes oder ungesättigtes C8- C4o-Alkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch -OH, Ci-C4-Alkoxy, Ct-GrAlkoxy carbonyl oder Carbonyl, Amino, mono- oder di- Cι-C4- Alkylamino substituiert ist, oder für C5-Cιo-Cycloalkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch C1-C4-Alkyl, -OH, Cι-C4-Alkoxy, Cι-C4- Alkoxycarbonyl oder Carbonyl, Amino, mono- oder di-Cι-C - Alkylamino substituiert ist, oder für C6-Cιo Aryl steht, welches gegebenfalls substituiert, insbesondere durch C3-Cι5.Alkyl substituiert ist.R 1 represents straight-chain or branched, saturated or unsaturated C 8 - C 4 o -alkyl, the alkyl chain of which is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which is optionally one or more times by -OH, Ci-C 4 -alkoxy, C t -Gralkoxy carbonyl or carbonyl, amino, mono- or di- -C-C 4 - alkylamino is substituted, or represents C 5 -Cιo-cycloalkyl, the alkyl chain of which may be one or more times by oxygen and / or nitrogen atoms is interrupted and which is optionally one or more times by C 1 -C 4 alkyl, -OH, -C-C 4 alkoxy, -C-C 4 - alkoxycarbonyl or carbonyl, amino, mono- or di-Cι-C - Alkylamino is substituted, or stands for C 6 -C aro, which is optionally substituted, in particular substituted by C 3 -C 5 alkyl.
R für geradkettiges oder verzweigtes, gesättigtes oder ein- bis mehrfach ungesättigtes C8-C4o-Alkyl steht, welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist, R für geradkettiges oder verzweigtes Cι-C26 Alkyl oder Cö-Cio-Aryl steht,R represents straight-chain or branched, saturated or mono- to polyunsaturated C 8 -C 4 o-alkyl, which is optionally mono- or polysubstituted by -OH, -CC 4 -alkoxy, -C-C 4 alkoxycarbonyl or carbonyl . R represents straight-chain or branched Cι-C 26 alkyl or C ö -Cio-aryl,
R für R3 oder für einen Rest der FormelnR for R 3 or for a rest of the formulas
-CH2CH2-O CH2CH2θ]q-[CH2CH(CH3)O]r-p ,-CH 2 CH 2 -O CH 2 CH 2 θ] q - [CH 2 CH (CH 3 ) O] r -p,
-CH2CH2CH2-O [CH2CH2θ]q-[CH2CH(CH3)O] E-CH 2 CH 2 CH 2 -O [CH 2 CH 2 θ] q - [CH 2 CH (CH 3 ) O] E
-CH2CH2CH2-O-CH2CHOHCH2-CH[CH2CH2O]q-[CH2CH(CH3)O]r-E-CH 2 CH 2 CH 2 -O-CH 2 CHOHCH 2 -CH [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E
-Z-[CH2CH2O]q-[CH2CH(CH3)O]r-E-Z- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E
wobeiin which
Z ein geradkettiger oder verzweigter Alkyl- oder Cycloalklyrest ist, der jeweils durch -O- und /oder -CO- unterbrochen und gegebenenfalls durch mindestens eine OH-Gruppe subsiruiert sein kannZ is a straight-chain or branched alkyl or cycloalkyl radical which can in each case be interrupted by -O- and / or -CO- and optionally be subsumed by at least one OH group
oderor
steht, stands,
q für 15 bis 150 steht,q represents 15 to 150,
q 1 und q2 unabhängig voneinander für 0 bis 150 stehen, wobei die Summe von ql + q2 = q ist,q 1 and q2 are independently 0 to 150, where the sum of ql + q2 = q,
q3, q4, q5 und q6 unabhängig voneinander für 0 bis 150 stehen,q3, q4, q5 and q6 independently of one another represent 0 to 150,
wobei die Summe von q3 + q4 + q5 + q6 = q ist,where the sum of q3 + q4 + q5 + q6 = q,
r für 0 bis 50 steht,r represents 0 to 50,
rl und r2 unabhängig voneinander für 0 bis 50 stehen,rl and r2 independently of one another represent 0 to 50,
wobei die Summe von rl + r2 = r ist,where the sum of rl + r2 = r,
r3, r4, r5 und r6 unabhängig voneinander für 0 bis 50 stehen,r3, r4, r5 and r6 independently of one another represent 0 to 50,
wobei die Summe von r3 + r4 + r5 + r6 = r ist, undwhere the sum of r3 + r4 + r5 + r6 = r, and
das Verhältnis von r : q < 0.25 ist,the ratio of r: q <0.25,
m für 1 bis 50 steht,m represents 1 to 50,
m7 und m8 unabhängig voneinander für 1 bis 50 stehen,m7 and m8 independently of one another represent 1 to 50,
wobei 2 < m7+m8, undwhere 2 <m7 + m8, and
das Verhältnis von q : m > 4 ist,the ratio of q: m> 4,
s für 5 bis 150, bevorzugt 15-150 steht,s represents 5 to 150, preferably 15-150,
t für 0 bis 150, bevorzugt 5 bis 150 und insbesondere 5 bis 20 steht, 0 < zl < 2000t represents 0 to 150, preferably 5 to 150 and in particular 5 to 20, 0 <zl <2000
0 < z2 < 20000 <z2 <2000
mindestens ein R4 ≠ R3 , undat least one R4 ≠ R3, and
für Formel (9') gilt:the following applies to formula (9 ' ):
0,01 < Σ Alkylreste R3 : Σ q < 1.0.01 <Σ alkyl radicals R 3 : Σ q <1.
Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 4 oder 7, dadurch gekennzeichnet, dass es sich bei der Verbindung (a) um eine Verbindung der Formeln (1 ') bis (9') gemäß Anspruch 7 handelt, wobeiFormulations according to at least one of claims 1 to 4 or 7, characterized in that the compound (a) is a compound of the formulas (1 ') to (9') according to claim 7, wherein
E für Wasserstoff, geradkettiges oder verzweigtes, gesättigtes oder ein- oder mehrfach ungesättigtes C1-C4- Alkyl welches gegebenenfalls 1 bis zweifach durch -OH, Cι-C4-Alkoxy, CrCj-Alkoxycarbonyl oder Carbonyl substituiert ist, oder für C5-C6 -Cycloalkyl steht, welches jeweils gegebenenfalls ein- bis mehrfach durch Cι-C - Alkyl, -OH, C1-C4- Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,E for hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C 1 -C 4 alkyl which is optionally 1 to 2 times substituted by -OH, -CC 4 alkoxy, CrCj-alkoxycarbonyl or carbonyl, or for C 5 -C 6 cycloalkyl, which is in each case optionally substituted one to more times by C 1 -C 4 -alkyl, -OH, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl or carbonyl,
R1 für geradkettiges oder verzweigtes, gesättigtes oder ungesättigtes Cιo-C36- Alkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C4- Alkoxycarbonyl oder Carbonyl, Amino, mono- oder di- C1-C4- Alkylamino substituiert ist, oder für C5-C6-Cycloalkyl steht, dessen Alkylkette gegebenenfalls ein- oder mehrfach durch Sauerstoff- und/oder Stickstoffatome unterbrochen ist und welches gegebenenfalls ein- oder mehrfach durch Ci-d-AlkvL -OH. Cι-C_ι-Alkoxv_ Ci-d-Alkoxvcarbonvl oder für C6-Cιo Aryl steht, welches gegebenfalls substituiert, insbesondere durch C3-C15.Alkyl substituiert ist.R 1 stands for straight-chain or branched, saturated or unsaturated C 1 -C 36 -alkyl, the alkyl chain of which is optionally interrupted one or more times by oxygen and / or nitrogen atoms and which may be one or more times by -OH, -C-C 4 - Alkoxy, -CC 4 - alkoxycarbonyl or carbonyl, amino, mono- or di- C 1 -C 4 alkylamino is substituted, or represents C 5 -C 6 cycloalkyl, the alkyl chain of which may be one or more times by oxygen and / or nitrogen atoms and which is optionally one or more times by Ci-d-AlkvL -OH. Cι-C_ι-Alkoxv_ Ci-d-Alkoxvcarbonvl or stands for C 6 -C aro, which is optionally substituted, in particular substituted by C 3 -C 15 alkyl.
R für geradkettiges oder verzweigtes, gesättigtes oder ein- bis melirfach ungesättigtes Cιo-C36-Alkyl steht, welches gegebenenfalls ein- oder mehrfach durch -OH, Cι-C4-Alkoxy, Cι-C4-Alkoxycarbonyl oder Carbonyl substituiert ist,R represents straight-chain or branched, saturated or mono- to melir-unsaturated C 1 -C 36 -alkyl, which is optionally substituted one or more times by -OH, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl or carbonyl,
R für geradkettiges oder verzweigtes Cι-Cι8 -Alkyl oder C6-Cιo-Aryl steht,R represents straight-chain or branched C 1 -C 8 alkyl or C 6 -C 8 aryl,
R4 für einen Rest R3 oder für einen Rest der FormelnR 4 for a radical R 3 or for a radical of the formulas
-CH2CH2-O -[CH2CH2Ojq-[CH2CH(CH3)O]lE ,-CH 2 CH 2 -O - [CH 2 CH 2 Oj q - [CH 2 CH (CH 3 ) O] lE,
oderor
-CH2CH2CH2-θJcH2CH2O]q-[CH2CH(CH3)OUE-CH 2 CH 2 CH 2 -θJcH 2 CH 2 O] q - [CH 2 CH (CH 3 ) OUE
steht,stands,
q für 20 bis 100 steht,q stands for 20 to 100,
ql und q2 unabhängig voneinander für 20 bis 100 stehen,ql and q2 independently represent 20 to 100,
wobei die Summe von ql + q2 = q ist,where the sum of ql + q2 = q,
q3, q4, q5 und q6 unabhängig voneinander für 20 bis 100 stehen,q3, q4, q5 and q6 independently represent 20 to 100,
wobei die Summe von q3 + q4 + q5 + q6 = q ist, rl und r2 unabhängig voneinander für 0 bis 20 stehen,where the sum of q3 + q4 + q5 + q6 = q, rl and r2 independently of one another represent 0 to 20,
wobei die Summe von rl + r2 = r ist,where the sum of rl + r2 = r,
r3, r4, r5 und r6 unabhängig voneinander für 0 bis 20 stehen,r3, r4, r5 and r6 independently of one another represent 0 to 20,
wobei die Summe von r3 + r4 + r5 + r6 = r ist, undwhere the sum of r3 + r4 + r5 + r6 = r, and
das Verhältnis von r : q < 0.25 ist,the ratio of r: q <0.25,
m für 1 bis 7 steht,m represents 1 to 7,
m.7 und m8 unabhängig voneinander fürl bis 7 stehen,m.7 and m8 are independently from 1 to 7,
wobei 2 < m7+m8, undwhere 2 <m7 + m8, and
das Verhältnis von q : m > 4 ist,the ratio of q: m> 4,
s für 5 bis 100, bevorzugt 15 bis 100 steht,s represents 5 to 100, preferably 15 to 100,
t für 5 bis 100, bevorzugt 5 bis 20 steht,t represents 5 to 100, preferably 5 to 20,
wobei t: s < 0,25where t: s <0.25
0 < zl < 20000 <zl <2000
0 < z2 < 20000 <z2 <2000
mindestens ein R4 ≠ R3 , undat least one R4 ≠ R3, and
für die Formel (9') gilt:the following applies to formula (9 '):
0,01 < Σ Alkylreste R3: Σ q < 0,5.0.01 <Σ alkyl radicals R 3 : Σ q <0.5.
Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Verbindung (a) den Formeln (1) bis (9) gemäß Anspruch 5 entspricht, wobeiFormulations according to at least one of claims 1 to 6, characterized in that the compound (a) corresponds to the formulas (1) to (9) according to claim 5, wherein
E für H, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2- oder CH3C(O)-E for H, CH 3 -, CH 3 CH 2 -, CH 3 CH 2 CH 2 -, (CH 3 ) 2 CH-, CH 3 CH 2 CH 2 CH 2 - or CH 3 C (O) -
steht,stands,
R1 für einen Rest der FormelnR 1 for a remainder of the formulas
CH3(CH2)nl-CH 3 (CH 2 ) nl-
CH3(CH2)n2CHCH2- CH3 CH 3 (CH2) n2 CHCH 2 - CH 3
CH3(CH2)n2CHCH2- CH3(CH2)n3CH2CH3 (CH2) n2CHCH 2 - CH 3 (CH 2 ) n3CH2
CH3(CH2)7CH=CH(CH2)8- CH 3 (CH 2 ) 7CH = CH (CH2) 8-
nl = 9 bis 23,nl = 9 to 23,
n2 = 3 bis 23,n2 = 3 to 23,
n3 = 0 bis 18,n3 = 0 to 18,
n4 = 7 bis 23,n4 = 7 to 23,
n5 = 3 bis bis 15,n5 = 3 to 15,
steht,stands,
für einen Rest der Formelnfor a rest of the formulas
n6 = 8 bis bis 28,n6 = 8 to to 28,
steht, R3 für Ci-Cis -Alkyl oder C6-C10-Aryl steht,stands, R 3 represents Ci-Cis alkyl or C 6 -C 10 aryl,
R4 für einen Rest R3 oder für einen Rest der FormelnR 4 for a radical R 3 or for a radical of the formulas
-CH2CH2-0-[CH2CH2O]q-[CH2CH(CH3)O]r-E ,-CH 2 CH 2 -0- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E,
oderor
-CH2CH2CH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E-CH 2 CH 2 CH 2 -O- [CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r -E
steht,stands,
q für 25 bis 60 steht,q represents 25 to 60,
ql und q2 unabhängig voneinander für 25bis 60 stehen,ql and q2 independently represent 25 to 60,
wobei die Summe von ql + q2 = q ist,where the sum of ql + q2 = q,
q3, q4, q5 und q6 unabhängig voneinander für 25 bis 60 stehen,q3, q4, q5 and q6 independently represent 25 to 60,
wobei die Summe von q3 + q4 + q5 + q6 = q ist,where the sum of q3 + q4 + q5 + q6 = q,
r für 0 bis 10 steht,r represents 0 to 10,
rl und r2 unabhängig voneinander für 0 bis 10 stehen,rl and r2 are independently 0 to 10,
wobei die Summe von rl + r2 = r ist,where the sum of rl + r2 = r,
r3, r4, r5 und r6 unabhängig voneinander für 0 bis 10 stehen, das Verhältnis von r : q < 0.25 ist, und für die Formel (9) giltr3, r4, r5 and r6 independently of one another represent 0 to 10, the ratio of r: q is <0.25 and applies to formula (9)
0,01 < Σ Alkylreste R3: Σ q+r < 0,10.01 <Σ alkyl radicals R 3 : Σ q + r <0.1
10. Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 4 und 7 bis 8, dadurch gekennzeichnet, dass die Verbindung (a) den Formeln (1 ') bis (9') gemäß Anspruch 7 entspricht, wobei10. Formulations according to at least one of claims 1 to 4 and 7 to 8, characterized in that the compound (a) corresponds to the formulas (1 ') to (9') according to claim 7, wherein
E für H, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2- oder CH3C(O)-E for H, CH 3 -, CH 3 CH 2 -, CH 3 CH 2 CH 2 -, (CH 3 ) 2 CH-, CH 3 CH 2 CH 2 CH 2 - or CH 3 C (O) -
steht,stands,
R für einen Rest der FormelnR for a rest of the formulas
CH3(CH2)nl-CH 3 (CH 2 ) nl-
CH3(CH2)n2CHCH2- CH3(CH2)n3CH2 CH3 (CH 2 ) n2CHCH2-CH3 (CH2) n3CH 2
CH3(CH2)7CH=CH(CH2)8- nl = 9 bis 23,CH 3 (CH 2 ) 7CH = CH (CH 2 ) 8- nl = 9 to 23,
n2 = 3 bis 23, bevorzugt 6 bis 23n2 = 3 to 23, preferably 6 to 23
n3 = 0 bis 18, wobei bevorzugt n2+ n3 < 31 ist,n3 = 0 to 18, preferably n2 + n3 <31,
n4 = 7 bis 23,n4 = 7 to 23,
n5 = 3 bis bis 15,n5 = 3 to 15,
steht,stands,
R für einen Rest der FormelnR for a rest of the formulas
OO
CH3(CH2)n6 l! CH3 (CH2) n6 l !
mitWith
n6 = 8 bis bis 28,n6 = 8 to to 28,
steht,stands,
R3 für Ci-Cig -Alkyl oder C6-Cι0-Aryl steht, R für einen Rest R3 oder für einen Rest der FormelnR 3 represents Ci-Cig-alkyl or C 6 -Cι 0 -aryl, R for a radical R 3 or for a radical of the formulas
-CH2CH2-θ|[CH2CH20]q-[CH2CH(CH3)O]rJE-CH 2 CH 2 -θ | [CH 2 CH 2 0] q - [CH 2 CH (CH 3 ) O] r JE
oderor
-CH2CH2CH2-O CH2CH2O]q-[CH2CH(CH3)O]r|-CH 2 CH 2 CH 2 -O CH 2 CH 2 O] q - [CH 2 CH (CH 3 ) O] r |
steht,stands,
q für 25 bis 60 steht,q represents 25 to 60,
ql und q2 unabhängig voneinander für 25bis 60 stehen,ql and q2 independently represent 25 to 60,
wobei die Summe von ql + q2 - q ist,where the sum of ql + q2 - q is
q3, q4, q5 und q6 unabhängig voneinander für 25 bis 60 stehen,q3, q4, q5 and q6 independently represent 25 to 60,
wobei die Summe von q3 + q4 + q5 + q6 = q ist,where the sum of q3 + q4 + q5 + q6 = q,
r für 0 bis 10 steht,r represents 0 to 10,
rl und r2 unabhängig voneinander für 0 bis 10 stehen,rl and r2 are independently 0 to 10,
wobei die Summe von rl + r2 = r ist,where the sum of rl + r2 = r,
r3, r4, r5 und r6 unabhängig voneinander für 0 bis 10 stehen,r3, r4, r5 and r6 independently of one another represent 0 to 10,
wobei die Summe von r3 + r4 + r5 + r6 = r ist, und für die Formel (9') gilt:where the sum of r3 + r4 + r5 + r6 = r, and the following applies to formula (9 '):
0,01 < Σ Alkylreste R3: Σ q < 0,1.0.01 <Σ alkyl radicals R 3 : Σ q <0.1.
11. Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass es sich bei den Verbindungen (b) um Carboxymethyl- cellulose, Hydroxyethylcellulose, Methylhydroxypropyl-cellulose oder um eine Verbindung der Formel11. Formulations according to at least one of claims 1 to 10, characterized in that the compounds (b) are carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose or a compound of the formula
worinwherein
x für 1.5 bis 20, bevorzugt 1,5 bis 10 stehtx stands for 1.5 to 20, preferably 1.5 to 10
handelt.is.
12. Formulierung gemäß wenigstens einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass es sich bei den quaternierten Ammoalkylsiloxanen um lineare oder cyclische Polysiloxanpolymere mit sich wiederholenden Struktureinheiten der Formeln (10) und (11) 12. Formulation according to at least one of claims 1 to 11, characterized in that the quaternized ammoalkylsiloxanes are linear or cyclic polysiloxane polymers with repeating structural units of the formulas (10) and (11)
16 ,1616, 16
CH, CH, RCH, CH, R
X-(SiO)— Si X-N-M-N- (11)X- (SiO) - Si X-N-M-N- (11)
CH3 CH3 CH 3 CH 3
worinwherein
X ein zweiwertiger Kohlenwasserstoffrest mit mindestens 4 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweisen kann, bevorzugt eine Hydroxylgruppe aufweist und der durch ein Sauerstoffatom unterbrochen sein kann, und die Gruppen X in den Wiederholungseinheiten gleich oder verschieden sein können,X is a divalent hydrocarbon radical with at least 4 carbon atoms, which may have a hydroxyl group, preferably has a hydroxyl group and which may be interrupted by an oxygen atom, and the groups X in the repeating units may be the same or different,
Y ein zweiwertiger Kohlenwasserststoffrest mit mindestens 2 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweisen und der durch ein oder mehrere Sauerstoff- oder Stickstoffatome unterbrochen sein kann,Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by one or more oxygen or nitrogen atoms,
R11, R12, R13 und R14 gleich oder verschieden sind und Alkylreste mit 1 bis 4 Kohlenstoffatomen oder Benzylreste bedeuten oder jeweils die Reste R1 und R3 oder R2 und R4 Bestandteile eines verbrückenden Alkylen- restes sein können,R 11 , R 12 , R 13 and R 14 are the same or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals or the radicals R 1 and R 3 or R 2 and R 4 can each be constituents of a bridging alkylene radical,
R .16 H oder ein Alkylrest mit 1 bis 20 Kohlenstoffatomen ist, der sauerstoffsubstituiert sein kann, M die Struktur -B-O-(EOx)v(POx)w-B-, worinR .16 is H or an alkyl radical with 1 to 20 carbon atoms, which may be oxygen-substituted, M the structure -BO- (EOx) v (POx) w -B-, wherein
EOx eine Ethylenoxideinheit und POx eine Propylenoxideinheit ist,EOx is an ethylene oxide unit and POx is a propylene oxide unit,
B gradkettiges oder verzweigtes C2 bis C6 Alkylen,B straight-chain or branched C 2 to C 6 alkylene,
v 0 bis 200,v 0 to 200,
w 0 bis 200,w 0 to 200,
v+w > 1 entspricht,v + w> 1 corresponds,
n 2 bis 1000, worin die n in den Wiederholungseinheiten gleich oder verschieden sein können,n 2 to 1000, in which the n in the repeating units can be the same or different,
A" ein anorganisches oder organisches Anion bedeutet,A "represents an inorganic or organic anion,
handelt.is.
13. Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 12 enthaltend mindestens ein quatemiertes Aminoalkylsiloxan und mindestens eine Verbindung aus der Reihe der hydrophilen, nichtionogenen grenzflächenaktiven Verbindungen (a).13. Formulations according to at least one of claims 1 to 12 containing at least one quaternized aminoalkylsiloxane and at least one compound from the series of hydrophilic, nonionic surface-active compounds (a).
14. Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass als Verbindung (a) der Ester aus Stearinsäure und 40 mol EO enthalten ist. 14. Formulations according to at least one of claims 1 to 13, characterized in that the ester (stearic acid and 40 mol EO) is present as compound (a).
15. Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass als weitere Komponente mindestens eine Verbindung (f) aus der Reihe der grenzflächenaktiven Verbindungen und Emulgatoren enthalten ist.15. Formulations according to at least one of claims 1 to 14, characterized in that at least one compound (f) from the series of surface-active compounds and emulsifiers is contained as a further component.
16. Formulierungen gemäß Anspruch 15, dadurch gekennzeichnet, dass als grenzflächenaktive Substanzen f) der Ether von Tridecylalkohol mit 12 mol EO und der Ether von Tridecylalkohol mit 6 mol EO enthalten ist.16. Formulations according to claim 15, characterized in that the surface-active substances f) contain the ether of tridecyl alcohol with 12 mol EO and the ether of tridecyl alcohol with 6 mol EO.
17. Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass die Mengen an hydrophilen, nichtionogenen grenzflächenaktiven Verbindungen (a) und/oder hydrophilen Dispergiermitteln (b) und/oder Salzen (c) zu den Mengen an quaternierten Aminoalkylsiloxan- Verbindungen in einem Mengenverhältnis Ω von Ω = 0.05 bis 10 stehen.17. Formulations according to at least one of claims 1 to 16, characterized in that the amounts of hydrophilic, nonionic surface-active compounds (a) and / or hydrophilic dispersants (b) and / or salts (c) to the amounts of quaternized aminoalkylsiloxane compounds have a quantity ratio Ω of Ω = 0.05 to 10.
18. Verwendung der Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 17 als Textilweichmacher bei der Ausrüstung von textilen Flächengebilden nach dem Kontinue- oder Ausziehverfahren.18. Use of the formulations according to at least one of claims 1 to 17 as a textile softener in the finishing of textile fabrics by the continuous or exhaust process.
19. Verwendung gemäß Anspruch 18 zur Ausrüstung von textilen Flächengebilden aus Baumwolle, Keratinfasern, bevorzugt Wolle, Seide, Synthesefasern oder Mischungen der vorgenannten Typen.19. Use according to claim 18 for finishing textile fabrics made of cotton, keratin fibers, preferably wool, silk, synthetic fibers or mixtures of the aforementioned types.
20. Verwendung gemäß Anspruch 18 zur Ausrüstung von textilen Flächengebilden aus Mischungen von Baumwolle mit Polyester, Polyamid, Polyacrylnitril, Wolle oder Seide.20. Use according to claim 18 for finishing textile fabrics made from blends of cotton with polyester, polyamide, polyacrylonitrile, wool or silk.
21. Verwendung gemäß Anspruch 18 zur Ausrüstung von textilen Flächengebilden aus Polyester, Polyamid, Polypropylen oder Mischungen daraus. 21. Use according to claim 18 for finishing textile fabrics made of polyester, polyamide, polypropylene or mixtures thereof.
22. Verwendung gemäß wenigstens einem der Ansprüche 19 bis 20 , dadurch gekennzeichnet, dass mit anionischen Weißtönern vorbehandelte textile Flächengebilde aus Baumwolle oder aus Mischungen von Baumwolle mit Polyester, Polyamid, Polyacrylnitril, Wolle oder Seide in einem Jet- Färbeapparat ausgerüstet werden.22. Use according to at least one of claims 19 to 20, characterized in that textile fabrics made of cotton or from mixtures of cotton with polyester, polyamide, polyacrylonitrile, wool or silk which have been pretreated with anionic white toners are equipped in a jet dyeing machine.
23. Verfahren zur Herstellung der Formulierungen gemäß wenigstens einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass man mindestens ein quatemiertes Aminoalkylsiloxan mit mindestens einer Verbindung aus der Reihe23. A process for the preparation of the formulations according to at least one of claims 1 to 17, characterized in that at least one quaternized aminoalkylsiloxane with at least one compound from the series
(a) der hydrophilen, nichtionogenen grenzflächenaktiven Verbindungen,(a) the hydrophilic, nonionic, surface-active compounds,
(b) der hydrophilen Dispergiermittel und(b) the hydrophilic dispersant and
(c) der Salze von zwei- oder dreiwertigen Metallen mit anorganischen Säuren, und gegebenenfalls weiteren Hilfs- und/oder Zusatzstoffen im Temperaturbereich von bevorzugt 20 bis 90°C mischt. (c) the salts of divalent or trivalent metals with inorganic acids, and optionally other auxiliaries and / or additives in the temperature range of preferably 20 to 90 ° C.
EP20030749889 2002-05-14 2003-05-13 Softening silicone formulations for textile finishing Expired - Lifetime EP1506336B1 (en)

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DE10221521 2002-05-14
DE2002121521 DE10221521A1 (en) 2002-05-14 2002-05-14 Formulations of silicone softeners for textile finishing
PCT/EP2003/004965 WO2003095735A2 (en) 2002-05-14 2003-05-13 Softening silicone formulations for textile finishing

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EP1506336A2 true EP1506336A2 (en) 2005-02-16
EP1506336B1 EP1506336B1 (en) 2011-05-04

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CN100368467C (en) 2008-02-13
AU2003232759A1 (en) 2003-11-11
JP4381299B2 (en) 2009-12-09
US7718268B2 (en) 2010-05-18
ATE508222T1 (en) 2011-05-15
EP1506336B1 (en) 2011-05-04
KR101032177B1 (en) 2011-05-02
AU2003232759A8 (en) 2003-11-11
WO2003095735A2 (en) 2003-11-20
JP2005533934A (en) 2005-11-10
CN1665981A (en) 2005-09-07
US20060100396A1 (en) 2006-05-11
DE10221521A1 (en) 2003-12-04
KR20040111607A (en) 2004-12-31
WO2003095735A3 (en) 2004-04-08
DE50313668D1 (en) 2011-06-16

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