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EP1706443A1 - Amino- et/ou ammoniumpolysiloxane exempt de groupes alcoxy et hydroxyle - Google Patents

Amino- et/ou ammoniumpolysiloxane exempt de groupes alcoxy et hydroxyle

Info

Publication number
EP1706443A1
EP1706443A1 EP04805013A EP04805013A EP1706443A1 EP 1706443 A1 EP1706443 A1 EP 1706443A1 EP 04805013 A EP04805013 A EP 04805013A EP 04805013 A EP04805013 A EP 04805013A EP 1706443 A1 EP1706443 A1 EP 1706443A1
Authority
EP
European Patent Office
Prior art keywords
formulation according
component
group
groups
amino
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.)
Withdrawn
Application number
EP04805013A
Other languages
German (de)
English (en)
Inventor
Horst Lange
Roland Wagner
Christopher Roos
Annette MÖLLER
Anita Witossek
Karl-Heinz Stachulla
Karl-Heinz Sockel
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
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
Priority claimed from DE102004012877A external-priority patent/DE102004012877A1/de
Application filed by GE Bayer Silicones GmbH and Co KG filed Critical GE Bayer Silicones GmbH and Co KG
Publication of EP1706443A1 publication Critical patent/EP1706443A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions

Definitions

  • the invention relates to amino and / or ammonium polysiloxanes free of alkoxy and hydroxyl groups, processes for their preparation and their use.
  • Unmodified and quatmodified bentonites significantly influence the incrustation during the washing process (R.Bercovici, H.Kr withmann, Tenside, Surfactants, Detergents 22 (1985), pp.62-66).
  • siloxanes containing quaternary ammonium groups as plasticizers in anionic detergent formulations.
  • These can be, for example, monoquaternary compounds (WO 02/10256), diquaternary compounds (WO 02/10257, DE-OS 10036533, US 20020068689), polyquaternary compounds (WO 02/10259, US 20020103094), betaines (DE 10036522, DE 10036532), siloxanes containing oligomerized quat structures (DE10251524), branched siloxane polyquats (DE1021274) or reactive structures containing siloxane polyquats (DE10316662).
  • Aminosiloxane-polyether block copolymers are also said to act as plasticizers from anionic detergent formulations (US 20010056059).
  • anionic detergent formulations US 20010056059
  • the use of pure aminosiloxanes in formulations for softening textiles in a separate step after washing with detergent formulations containing anionic surfactants is well known.
  • Combinations with hydrocarbon-based quats are often proposed to reinforce the softening and refreshing effect (US 5064544, US 5174911, US 5300238, US 6255271, US 6376456, CA patent 1102511, WO 95/24460, DE-OS 2631419).
  • Pure aminosiloxanes have also been proposed in order to improve the substantivity of lipophilic components on solid substrates, for example from anionic washing formulations (US 6024891, US 6153567). A direct softening effect is not mentioned.
  • aminosiloxanes with an amino substitution degree of 0.01 to 0.7, based on dimethylsiloxy units, should be able to develop such a softening effect from anionic formulations.
  • aminosiloxanes are proposed as a softening component for powdered detergent formulations.
  • the question of the content of reactive, crosslinkable Si structures, such as silanol or alkoxysilane units, is not dealt with in the latter two publications, although technically available aminosiloxanes regularly have a significant content of silanol and alkoxysilane structures.
  • the present invention relates to complex anionic surfactant formulations, by means of which the special aminosiloxanes mentioned in the treatment of textiles and other natural and synthetic fibrous materials, such as, for example, paper fibers and hair, an excellent softening effect, a reduction in the tendency to creasing, an improvement in fiber elasticity and shape retention and maintain this ability to develop a softening effect, a reduction in the tendency to creasing, an improvement in fiber elasticity and shape retention over long periods of contact and storage with the anionic detergent formulation. It is a further object of the invention to provide a method for producing the special aminosiloxanes and the formulations produced therewith.
  • formulations according to the invention in formulations containing anionic detergents. It has surprisingly been found that formulations which contain special aminosiloxanes with a defined proportion of reactive groups, such as hydroxy or alkoxy groups, have an excellent softening effect, a reduction in the creasing tendency to show an improvement in fiber elasticity and shape retention, especially from complex anionic surfactant formulations, and surprisingly this ability to develop a softening effect, a reduction in creasing tendency, an improvement in fiber elasticity and shape retention is maintained over long periods of time.
  • the present invention thus relates to a formulation comprising: a) amino and / or ammonium polysiloxanes, in which the molar ratio of hydroxyl- and alkoxy-containing silicon atoms to non-hydroxyl- or alkoxy-containing terminal silicon atoms is less than 30%, and at least one component selected from the group , which consists of b) one or more surfactants, c) one or more nitrogen-free polysiloxanes and d) one or more coacervate phase formers.
  • Component a) is preferably straight-chain, branched or cyclic polysiloxane compounds which contain amino or ammonium groups only in the side groups (D or T groups) or at the chain end (M groups) and in which the molar ratio of hydroxy - and alkoxy-containing silicon atoms to non-hydroxy or alkoxy-containing terminal silicon atoms is less than 30%.
  • the molar ratio of hydroxyl and alkoxy-containing silicon atoms to non-hydroxy or alkoxy-containing terminal silicon atoms is preferably less than 20%, more preferably less than 10%, more preferably less than 5%, more preferably less than 1%, even more preferably 0%.
  • Hydroxy and alkoxy-containing silicon atoms means all M, D, T and Q groups which have a Si-OH or Si-OR grouping.
  • the "non-hydroxy or alkoxy-containing terminal silicon atoms” all mean M groups that have neither Si-OH nor SiOR groups.
  • the stated molar ratio of hydroxyl- and alkoxy-containing silicon atoms to non-hydroxyl- or alkoxy-containing terminal silicon atoms is advantageously determined according to the invention by NMR spectroscopic methods, preferably by ** H-NMR and 29 Si-NMR, particularly preferably by 29 Si-NMR.
  • the stated molar ratio of hydroxyl- and alkoxy-containing silicon atoms to non-hydroxyl or alkoxy-containing terminal silicon atoms expediently the ratio of the peak intensities as an integral of the corresponding signals in ⁇ Si-NMR.
  • R 1 methyl, aminopropyl and methoxy
  • Ratio (L ⁇ t ppm + I-i3 PP m) / l7 pm
  • the person skilled in the art is able to assign the corresponding chemical shifts in the case of differently substituted siloxy units. It is also possible to use the 1 H-NMR method in addition to the 29 Si-NMR. The 1 H-NMR method is also used to confirm the 29 Si-NMR signals.
  • the hydrogen atoms in the CH 3 -0-SiR 2 -0 groups are used using CDC1 3 as solvent and internal standard in the " ⁇ - NMR at +3.4 ppm and the H atoms in the -CH 2 -Si groups of the aminoalkylsiloxanes were found at +0.5 ppm
  • the change from CDC1 3 to CöD5-CD 3 shifts the position of the H signals in the CH 3 -0-SiR 2 -0 group to +3.2 ppm, those from the -CH 2 -Si groups of the aminoalkylsiloxanes remain unchanged
  • the IR method can also be used as a supplement (eg for SiOH determination) ,
  • not only the molar ratio of hydroxyl- and alkoxy-containing silicon atoms to non-hydroxyl- or alkoxy-containing terminal silicon atoms is less than 20%, but also the molar ratio of all reactive groups carrying silicon atoms to the non-reactive M Groups is less than 20%.
  • the limit value 0% means that suitable analytical methods, such as NMR spectroscopy or infrared spectroscopy, can no longer detect silicon atoms containing hydroxyl and alkoxy, preferably silicon atoms containing no reactive groups.
  • non-reactive chain-terminating M groups mean, in particular, structures which, in the environment of a detergent formulation, are unable to re-establish stable chemical bonds or coordination with an increase in molecular weight.
  • the substituents R 1 include, for example, Si-C-linked alkyl, alkenyl, alkynyl and aryl radicals, which can optionally be substituted by N, O, S and halogen.
  • the substituents are preferably C1 to C1 alkyl radicals, such as methyl, ethyl, vinyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, ethylcyclohexyl.
  • N-containing aminoalkyl substituents such as aminopropyl- and aminoethylaminopropyl-based units, imidazole- and pyrazole-containing alkyl substituents, units which are formed by reaction of epoxy functions or carboxylic acid functions or acrylate or methacrylate functions with primary, secondary or tertiary mono-di- or polyamines can be.
  • the N-containing aminoalkyl substituents can be primary, secondary, tertiary amino structures or quaternary ammonium structures. Also preferred are N-containing amidoalkyl substituents which are accessible by reaction of Si-C-linked amino or carboxylic acid functions with corresponding carboxylic acid derivatives or amines. The combination of amino and amide functions in the N-containing substituents is also possible.
  • the Si-C linked O-containing substituents are preferably esters, ethers and polyether units, especially units containing polyethylene oxide and / or polypropylene oxide.
  • the Si-C-linked S-containing substituents are preferably sulfonamide and thiourea units.
  • the Si-C-linked halogen-containing substituents are preferably fluorinated units, for example trifluoropropyl.
  • reactive M, D, T and Q groups are, in particular, structures which, in the environment of a detergent formulation, are able to re-establish chemical bonds or coordination with an increase in molecular weight.
  • the predominant reactive units are the Si-OH and SiOR- Units and can also include ⁇ SiH, acyloxysilyl groups, and Si-NC linked silylamines or Si-N-Si linked silazanes.
  • alkoxy-containing silicon units examples include ResSiOCH 3 , ⁇ SiOCH 2 CH 3 , ⁇ SiOCH (CH 3 ) 2 , ⁇ SiOCH 2 CH 2 CH 2 CH 3 and ⁇ SiOC 6 H 5 .
  • An example of acyloxysilyl residues is ⁇ SiOC (0) CH 3 .
  • the primary reaction of the aforementioned reactive groups in component c) used according to the invention is the hydrolysis with subsequent formation of SiOSi bonds.
  • the detergent formulations for example, strong interactions with non-volatile polyhydroxy compounds, polycarboxy compounds or their salts, sulfonic acids or their salts, monoalkyl sulfates, monoalkyl ether sulfates, carboxylic acids or their salts and carbonates occur, which lead to an uncontrolled reaction or coordination of the Aminosiloxane with reaction of the reactive groups mentioned, such as in particular the SiOH and SiOR groups, with an increase in molar mass.
  • Component a) preferably contains amino and / or ammonium groups in the side groups or the terminal groups of a main polysiloxane chain.
  • the side groups or terminal groups mentioned are particularly preferably bonded to a silicon atom via a carbon atom.
  • Component a) can also have functional organic radicals containing amino or ammonium groups which combine at least two siloxane radicals.
  • Component a) used according to the invention is preferably straight-chain, branched or cyclic amino and / or ammonium polysiloxane compounds, which are preferably in the side groups primary and / or secondary and / or wear tertiary amino groups, in which the amino groups are optionally protonated or quaternized, and which may optionally contain additional hydrophilic groups.
  • the amino or ammonium groups mentioned are preferably bonded to the siloxane skeleton via carbon.
  • the amino and / or ammonium-polysiloxane compounds mentioned are preferably polyalkylsoxanes with aminoalkyl or aminoarylsiloxane units.
  • the aminoalkyl units can be bound both to the difunctional, trifunctional or monofunctional end groups and can be part of other oxygen-containing side groups, in particular of polyether side groups.
  • the optionally present additional hydrophilizing groups are preferably those derived from polyalkylene oxides and saccharides.
  • Component a) is more preferably composed of siloxy units which are selected from the group consisting of:
  • R 1 represents organic radicals which may be the same or different from one another, with the proviso that at least one of the radicals R 1 contains at least one amino and / or ammonium group.
  • R 1 is preferably selected from optionally substituted, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals.
  • R 1 in component a) used according to the invention is particularly preferably selected from the group consisting of: al) straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals, which optionally have one or more groups selected from -O-, -NR 2 -, wherein R 2 is hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms, which may contain one or more groups selected from -O-, -NH-, -C (0) -, -C (S) - and -S0 2 -, and optionally by one or more substituents selected from the group consisting of a hydroxyl group, an optionally substituted heterocyclic group, preferably containing one or more nitrogen atoms, amino, alkylamino, dialkyla
  • -C (O) -, -C (S) - and -S0 2 - can contain, and said hydrocarbon radicals optionally by one or more substituents selected from all) hydroxyl, al2) nitrogen-containing groups, al3) halogen, al4) polyether radicals . a 15) residues containing sugar groups and al6)
  • R al61 is a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 200 carbon atoms, which optionally has one or more groups selected from -O-, —NR 2 -, wherein R 2 is as defined above,
  • hydrocarbon radical can be substituted by one or more substituents selected from the group consisting of hydroxyl, alkoxy having up to 20 carbon atoms, halogen , Groups containing nitrogen atoms, residues containing sugar groups and residues containing polyether groups, and in which m and m2 are each ⁇ 1, l62) hydroxy, al63) alkoxy having up to 20 carbon atoms, al64) optionally substituted polyether group-containing hydrocarbon radicals which are about Carbon or oxygen are bound to the silicon atom, al65) or two substituents R 1 from different of the siloxy units mentioned together can form a straight-chain, branched or cyclic alkanediyl radical having 2 to 12 carbon atoms between two silicon atoms, a2) hydroxy, a3) alkoxy with up to 20 carbon atoms, a4) optionally substituted Hydrocarbon radicals containing polyether groups which are bonded to the group consisting of hydroxyl, alkoxy having up to 20 carbon atoms,
  • R 1 is preferably alkyl, in particular methyl.
  • Preferred radicals R 1 which have nitrogen are, for example:
  • the nitrogen atoms contained in these residues can optionally also be protonated or quaternized.
  • amino- or ammonium-containing radicals R 1 are, for example:
  • the nitrogen-containing radical R 1 is preferably aminopropyl or aminoethylaminopropyl. Further preferred nitrogen-containing radicals R 1 are formed from the reaction of glycidyloxypropylsiloxanes with mono- or dialkylamines. Preferred compounds are therefore, for example, aminopolysiloxanes which result from the reaction of epoxyalkylsiloxanes with ammonia, primary or secondary amines, such as, for example, the reaction of glycidyloxypropylsiloxanes with mono- or dialkylamines.
  • Preferred polyether radicals having up to 20,000 carbon atoms in the definitions of the substituent R 1 of component a), which may optionally carry one or more amino, mono- or dialkylamino or arylamino groups, include:
  • R " Cl to C20 alkyl, preferably Cl to C12 alkyl, particularly preferably Cl to C8 alkyl, especially methyl, ethyl, propyl, butyl, hexyl, ethylhexyl and v + w-> 1.
  • Sugar-containing radicals for R 1 include, in particular, saccharide-containing organic radicals, such as, for example:
  • the production of such saccharide-containing polysiloxanes can be found, for example, in DE 4 318 536, DE 4318 537.
  • the average degree of polymerization of the polysilox portion of the aminopolysiloxanes used according to the invention, which results from Mn, is advantageously from 1 to 3000, preferably from 30 to 1000, especially from 100 to 1000, very particularly from 200 to 1000.
  • the ratio of the nitrogen-free polyorganosiloxane units to the nitrogen-containing polyorganosiloxane units in the aminopoly- Expediently, siloxanes is from 1: 1 to 500: 1, preferably 10: 1 to 500: 1, particularly preferably 20: 1 to 500: 1, especially 20: 1 to 400: 1, very particularly 40: 1 to 400: 1.
  • the ratio of the polyether- or saccharide-containing polyorganosiloxane units to the other polyorganosiloxane units can be from 0 to 1.
  • the typical nitrogen content of the aminopolysiloxanes used according to the invention is, for example, between 0.005% by weight to 18% by weight, preferably 0.02% by weight to 5% by weight, particularly preferably 0.02% by weight to 1, 5% by weight, especially 0.02% by weight to 1% by weight, very particularly 0.05% by weight to 1% by weight.
  • the aminopolysiloxanes used can be solid or liquid at 20 ° C.
  • the amino and / or ammonium polysiloxanes according to component a) used according to the invention are expediently available by means of a process in which organofunctional AUcoxysilanes or alkoxysiloxanes are first hydrolyzed and then equilibrated and condensed in the presence of at least one catalyst.
  • the process which is preferred according to the invention is explained in more detail below.
  • a preferred formulation according to the invention contains components a) and b).
  • a further preferred formulation according to the invention contains the components components a) and c)
  • a further preferred formulation according to the invention contains components a) and d).
  • the formulation additionally contains component e), at least one carrier substance.
  • a preferred formulation of this type contains components a), c) and e).
  • Component c) used according to the invention is preferably a straight-chain, cyclic, branched or partially crosslinked polydiorganosiloxane which is composed of siloxy units which are selected from the group consisting of:
  • R 3 has the same meaning as R 1 with the proviso that R 3 contains no nitrogen.
  • the meaning of the radicals R 3 in component c) in a given formulation can be the same or different from the meaning of the radicals R 1 in component a).
  • the substituent R 3 is preferably selected from the group consisting of: straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 200 carbon atoms, which optionally have one or more groups selected from -O-, -C ( O) - and - C (S) -, and optionally substituted by one or more substituents selected from hydroxy, alkoxy having up to 20 carbon atoms and polyether group-containing hydrocarbon radicals which are bonded to the silicon atom via carbon or oxygen , - Hydroxy, - alkoxy with up to 20 carbon atoms, - polyether group-containing hydrocarbon radicals which are bonded to the silicon atom via carbon or oxygen, or - two substituents R 3 from different of the siloxy units mentioned together form a straight-chain, branched or cyclic alkanediyl radical 2 to 12 carbon atoms between between egg silicon atoms.
  • the substituent R 3 is particularly preferably selected from the group consisting of: methyl, ethyl, butyl phenyl, optionally terminally etherified or esterified poly (ethyleneoxy) alkyl and copoly (ethyleneoxy) (propyleneoxy) alkyl groups.
  • component c) is the molar ratio of hydroxyl- and alkoxy-containing silicon atoms to non-hydroxy- or alkoxy-containing terminal silicon atoms similar to component a) less than 30%, preferably less than 20%, more preferably 10%, more preferably less than 5%, even more preferably less than 1%, such components c) can be produced by processes similar to those of component a).
  • Component c) is particularly preferably selected from the group consisting of: ⁇ , G> dihydroxy-terminated polydimethylsiloxanes, silicone polymers of the formulas (II) and (III)
  • R 4 is in each case selected independently of one another from the group consisting of: linear, branched or cyclic alkyl groups having 1 to 22 carbon atoms; linear, branched or cyclic alkenyl groups with 2 to 22 carbon atoms; phenyl; Alkylaryl groups of 7 to 20 carbon atoms; Arylalkyl groups with 7 to 20 carbon atoms, a poly (ethylene oxide / propylene oxide) copolymer group of the general formula (TV): -R 5 -0 (C 2 H 4 0) c (C 3 H 6 0) d -R 6
  • R 5 is a straight-chain, branched or cyclic alkanediyl group having 3 to 22 carbon atoms, optionally substituted by one or more Oxygen atoms can be interrupted
  • R 6 is independently selected from the group consisting of hydrogen, alkyl having 1 to 16 carbon atoms, alkanoyloxy having 1 to 16 carbon atoms, in which the index a is advantageously chosen so that the viscosity of the nitrogen-free Siheon polymer Formula 01) for the liquid at 20 ° € between 1 to 20 mPa-s with an S-hgoschwindigkeilsgdaUe of D - is " 'Hegi and the index' b 'is so selected that the viscosity of the nitrogen-free polyssloxane of the formula (ü ⁇ ) at 2 ⁇ ° C between
  • the index is a ah medium Polymerisauonsgrad P ⁇ orzugt 3 to east, the index b as the mean Pefyme ⁇ sat 'onsgrad P ,. preferably at 300 to 3000 with c -rd "•• - 1 to 20000 and c ⁇ - 0 to 10000 and d - 0 to 10000.
  • the Ethyicnoxy- and Propyle ⁇ oxy- groups are random or block axially, preferably statistically arranged in the Component c) is preferably also straight-chain, cyclic, branched or partially crosslinked polydiorganoailoxanes, that is to say more generally M, D, optionally T and Q-hooked polyorganisms "os" loxa ⁇ e, in which the organo group is preferably selected from: d to C " Alky crepe, polyalkyleneoxy groups, the end groups of which can be hydroxyl, i ⁇ tl ⁇ er- or ester groups, and which are preferably alkylene or alkylene groups attached to the SiJic, and aryl groups, and wherein the polydiorganosiloxanes on Silicon may optionally have functional groups, such as, in particular, hydroxyl and alkoxy groups, with the exception of nitrogen-containing groups.
  • the organo groups are particularly preferably selected from methyl, ethyl, butyl, phenyl, poly (ethyleneoxy) and copoly (ethyleneoxy) (propyleneoxy) groups.
  • Most preferred are polydialkylsiloxanes, especially polydimethylsiloxanes.
  • the nitrogen-free, functionalized or unfunctionalized polysiloxane compounds, in particular the polydimethylsiloxanes advantageously have a viscosity in the range from 100 to 50,000,000 mPa.s, preferably from 10,000 to 20,000,000 mPa.s, more preferably from 10,000 to 10,000,000 mPa.
  • Polysiloxane compounds which have functional groups are, for example, ⁇ dihydroxy-terminated polydimethylsiloxanes Further examples of the polysiloxane compounds as defined are described, for example, in "Silicone Surfactants”, ed.: R M. Hill, Surfactant Science Series, Vol 86, Marcel Dekker, Inc., 1999.
  • Examples of the nitrogen-free silicone polymers of the formula (HI) are the so-called Silwet® compounds from GE Specialty Materia ls, Waterford, NY, USA, or Tegostab from Goldschmidt, Essen or the SF PU foam stabilizer types that can be obtained from GE Bayer Silicones GmbH & Co KG, Leverkusen.
  • Further examples of the compounds of the formulas (H) and (TU) are polydimethylsiloxane oils, for example from GE Bayer Silicones GmbH & Co. KG from the Baysilone M series or silicone oils from the 200 series from Dow Corning.
  • the amount of nitrogen-free siloxane component c), based on the total amount of the formulation preferably containing component b), is 0 to 30% by weight, preferably 0 to 10% by weight, particularly preferably 0.1 to 10% by weight. %, especially 0.1 to 5% by weight, very particularly 0.5 to 5% by weight.
  • the total amount of amino siloxane and nitrogen-free siloxane component according to the invention, based on the total amount of the detergent formulation is preferably 0.1 to 65% by weight, preferably 0.1 to 30% by weight, more preferably 0.1 to 10% by weight, particularly preferably 0.1 to 5% by weight, especially 0.5 to 5% by weight.
  • Preferred formulations according to the invention contain components a) to e) in the following amounts: a): 1 to 95, preferably 1 to 30, more preferably 1 to 20, b): 0 to 65, preferably 1 to 20, c): 5 to 99, 10 to 80, d): 0 to 1, preferably 0.1 to 1, e): 0 to 70, preferably 20 to 70, the amounts given being% by weight, based on the total amount of the formulation.
  • Such formulations which contain relatively high proportions of the siloxane components a) and c), preferably serve as so-called pre-emulsions which are incorporated into the products for end use, such as cosmetic formulations, detergent formulations, textile finishing formulations, finishes, etc. ., as will be explained in more detail below.
  • the present invention therefore also relates to a method for producing ready-to-use end products (ie products which are used by the end user without further mixing), which comprises the use of the pre-emulsion.
  • Formulations for the end use have lower proportions of the siloxane components a) and c) in accordance with the dilution accompanying the end formulation.
  • Such formulations have, for example, the following composition: a): 0.1 to 50, preferably 1 to 10, more preferably 0.5 to 5, b): 0.1 to 65, preferably 1 to 40, c): 0.1 to 10, preferably 0.5 to 5, d): 0 to 1, preferably 0.1 to 1, e): 0 to 70, preferably 30 to 70, the amounts given being% by weight, based on the total amount of the formulation are.
  • Component e) is expediently selected from carrier substances el) solid at 20 ° C. and / or carrier substances e2) liquid at 20 ° C.
  • a preferred formulation contains 1 to 1500 parts by weight selected from the group of components b), d) and e), based on 100 parts by weight of components a) and c).
  • the amount of component b) is from 0.1 to 70 parts by weight per 100 parts by weight of the total amount of components a) and c).
  • the amount of component d) is 0.01 to 10 parts by weight per 100 parts by weight of the total amount of components a) and c).
  • the amount of component e) is from 1 to 1420 parts by weight per 100 parts by weight of the total amount of components a) and c). In a further preferred formulation, the amount of component el) is from 1 to 710 parts by weight per 100 parts by weight of the total amount of components a) and c).
  • the amount of component e2) is from 1 to 710 per 100 parts by weight of the total amount of components a) and c).
  • Component b) used according to the invention is preferably a silicon-free surfactant, which is preferably selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants and cationic surfactants.
  • Anionic surfactants include, for example, those mentioned in DE 69901211 T2. Essentially all anionic surfactants which are useful for washing purposes are suitable. These can include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.
  • anionic surfactants include the isethionates, such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (in particular saturated and unsaturated C12-C18 monoesters), diesters of sulfosuccinate (in particular saturated and unsaturated C6- C14-diesters), N-acyl sarcosinate.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and resin acids and hydrogenated resin acids which are present in or derived from tallow oil.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched, primary and secondary Alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17-acyl-N- (Cl-C4-alkyl> and -N- (Cl-C2-hydroxyalkyl) glucamine sulfates, and sulfates of alkyl polysaccharides, such as the sulfates of Alkyl polyglucoside (the nonionic, non-sulfated compounds are described herein.)
  • Alkyl sulfate sides are preferably selected from the linear and branched, primary C10-C18-alkyl sulfates, more preferably the branched chain C1-C15-alkyl sulfates and the linear-chain C 12-14 alkyl
  • Alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulfates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule, more preferably the alkyl ethoxy sulfate surfactant is a C11-C18, most preferably C11 -C15 alkyl sulfate which has been ethoxylated with 0.5 to 7, preferably 1 to 5, moles of ethylene oxide per molecule, mixtures of the preferred are preferred Alkyl sulfate and alkyl ethoxy sulfate surfactants used. Such mixtures have been described in PCT Patent Application No. WO 93/18 124.
  • anionic sulfonate surfactants can include: the salts of linear C5-C20-alkylbenzenesulfonates, alkyl ester sulfonates, primary or secondary C6-C22-alkanesulfonates, C6-C24-01efinsulfonates, sulfonated polycarboxylic acids, alkylglycerolsulfonates, fatty acylglycerylsulfonols, mixtures of these, fattyols.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ("alkyl carbo .xyls"), especially certain secondary soaps, as described herein.
  • Suitable alkyl ethoxy carboxylates include those having the formula R 12 0 (CH 2 CH 2 0) x ⁇ CH 2 C00 " M, where R 12 is a C6-C18 alkyl group, xl is in the range from 0 to 10, and the ethoxylate distribution, on a weight basis such that the amount of material wherein xl is 0 is less than 20% and M is a cation.
  • Suitable alkyl polyethoxypolycarboxylate surfactants include those of the formula R 13 0- (CHR 14 -CHR 15 -0) -R 16 , wherein R 13 is a C6-C18 alkyl group, x2 is 1 to 25, R 14 and R 15 are selected from the group consisting of hydrogen, methyl radical, succinic acid residue, hydroxy succinic acid residue and mixtures thereof, and R 16 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having 1 to 8 carbon atoms and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary Soap surfactants for use herein are water-soluble representatives selected from the group consisting of water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps can also be included as foam suppressants.
  • alkali metal sarcosinates of the formula R 17 -CON (CR 18 ) CH 2 - COOM in which R 17 is a linear or branched C5-C17 alkyl or alkenyl group, R 18 is a Cl -C6 alkyl group and M is an alkali metal ion.
  • R 17 is a linear or branched C5-C17 alkyl or alkenyl group
  • R 18 is a Cl -C6 alkyl group
  • M is an alkali metal ion.
  • Anionic surfactants particularly preferred according to the invention include: fatty acid salts, alkoxylated fatty acid salts, fatty alcohol sulfates, fatty alcohol ether sulfates, alkyl sulfonates, alkyl aryl sulfonates.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include the compounds having the formula R 19 (OR 20 ) x3 N (O) (R 21 ) 2 , wherein R 19 is selected from alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl groups or mixtures thereof containing 8 to 26 carbon atoms ;
  • R 20 is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; x3 is 0 to 5, preferably 0 to 3; and each R 21 is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, or a polyethylene oxide group having 1 to 3 ethylene oxide groups.
  • amphoteric surfactants also include conventional zwitterionic surfactants which are incorporated into detergent compositions. In the broadest sense, these surfactants can be described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
  • Betaine and Sultain surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are the compounds having the formula R 2 (R 23 ) 2 N ⁇ R 2 COO ** wherein R 22 is a C6-C18 hydrocarbyl group, each R 23 is typically Cl-C3 alkyl, and R 24 is a divalent Cl -C5 hydrocarbyl group.
  • Preferred betaines are C12-18 dimethylammoniohexanoate and the C10-C18 acyl amidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • component b) is one or more silicone-free, cationic surfactants, preferably of the following formula:
  • R 7 , R 8 , R 9 and R 10 are independently selected from the group consisting of: C ⁇ -C28 alkyl, C2-C28 alkenyl, hydroxy C ⁇ -C28 alkyl, C8-C28 arylalkyl, C7-C28 alkylaryl, Cg-C28 alkylarylalkyl, C9-C28 alkenylarylalkyl, C8-C28 arylalkenyl, and X is an anion
  • component b) are tetraorgano-substituted quaternary ammonium compounds with one or two long-chain C8 to C28 hydrocarbon radicals and two or three short-chain Cl to C6 hydrocarbon radicals.
  • the long-chain radicals C12 to C20 are preferably chains and the short-chain radicals are methyl, ethyl, propyl, butyl, hexyl, phenyl and hydroxyethyl, 2-hydroxypropyl.
  • Preferred counterions are Cl “ , Br " , CH 3 OS0 3 ; C 2 H 5 OS0 3 " , M, HCOO " and CH3COO " .
  • Examples include: dodecyl-ethyl-dimethyl-ammonium bromide Didodecyl-dimethyl-ammonium bromide.
  • the chain length of the long chain hydrocarbon group is preferably 12 to 15 carbon atoms, and the short-chain radicals R 8 , R 9 and R 10 are preferably methyl and hydroxyethyl.
  • the chain length of the long-chain hydrocarbon groups is preferably from 12 to 28 carbon atoms.
  • Preferred ester-containing surfactants have the formula:
  • R 25 is independently selected from C ⁇ _4 alkyl, hydroxyalkyl or C2.4 alkenyl; and wherein R 26 is independently selected from C8-28 alkyl or alkenyl groups;
  • E is an ester group ie, -OC (O) - or -C (0) 0-, z is an integer from 0 to 8, and X "is as defined above.
  • fatty acids of lengths C8 to C26, preferably CIO to C20, especially C12 to C18
  • the fatty acids or the cuts in the chain length ranges mentioned can be saturated fatty acids, unsaturated fatty acids, hydroxy-substituted act fatty acids or mixtures thereof.
  • examples of the t. abovementioned acids are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and ricinoleic acid.
  • Other examples are Taigfett Textre- and coconut fatty acid segments.
  • oxyethyl, 2-oxypropyl - or 1,2-dioxypropyl or oligooxyethylene spacers the short-chain radicals preferably being methyl, ethyl, propyl, butyl, hexyl, phenyl and hydroxyethyl , 2-hydroxypropyl.
  • Preferred counterions are Cf, Bf, CH 3 OS0 3 7 C 2 H 5 OS0 3 " , N0 3 7 HCOO- and CH 3 COO " . Examples are mentioned
  • Another group of cationic surfactants as component b) are those of the formula R 27 A (CH 2 ) M NR 28 R 29 where R 27 is C 6 -C 2 alkyl; A is a divalent group selected from - NH- -CONH-, -COO- or -O—, or A may be absent; R 28 and R 29 are independently selected from the group consisting of H, -CC 4 alkyl or (CH 2 -CH 2 -0 (R 30 )) where R 30 is H or methyl.
  • surfactants of this type are decylamine, Dodecylamine, C 8 -C 2 bis (hydroxyethyl) amine, C 8 -C 2 bis (hydroxypropyl) amine, C 8 -C 2 amidopropyldimethyl amine or salts thereof
  • Other surfactants include: fatty acid amides of the formula R 31 C (0 ) N (R 32 ) 2 wherein
  • R 31 is an alkyl group with 8 to 28 carbon atoms and R 32 is in each case a short-chain radical, preferably selected from hydrogen, Cj-Cg alkyl and hydroxyalkyl. Also Cg-
  • C28 N alkyl polyhydroxy fatty acid amides can be used. Typical examples include: C ⁇ 2 "C ⁇ 8 N-methylglucamides (see WO 92/06154). Other sugar derivatives include, for example, Cg-C2g N - (3-methoxypropyl) glucamide. These also have two or three short-chain Cl to C6 hydrocarbon radicals. The one or two long alkyl radicals per molecule are derived from fatty acids of lengths C8 to C26, preferably C10 to C20, especially C12 to C18. The fatty acids or the cuts in the chain length ranges mentioned can also be saturated fatty acids, unsaturated fatty acids, Hydroxy-substituted fatty acids or mixtures thereof.
  • acids mentioned are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and rhicinoleic acid. Further examples are tallow fatty acid and coconut fatty acid cuts.
  • Their connection to the quaternized nitrogen is preferably via amidoethyl and 3-amidopropyl spacers for the short chain residues methyl, ethyl, propyl, butyl, Hexyl, phenyl and hydroxyethyl, 2-hydroxypropyl.
  • it can be are cyclic radicals, such as imidazolinium radicals, into which fatty alkyl substituents may also be incorporated.
  • Preferred counterions are Cl ⁇ Br “ , CH 3 OSO3 " , C 2 H 3 OS0 3 " , NO3 " , HCOO " and CH3COO " .
  • Examples include: (undecylenic acid amidopropyl) trimethyl-ammonium methosulfate (rhicinoleic acid amidopropyl) trimethyl-a monium methosulfate 1-methyl-1-tallow fatty acid amidoethyl 1-2-tallow fatty alkyl-imidazolinium methosulfate l-methyl-l-2-oleylamidoethyl imidazolinium methosulfate l, l-emylene bis (l-methyl-2-tallow fatty alkyl imidazolinium) methosulfate.
  • amine salts can also be used. These are salts of primary, secondary or tertiary amines with inorganic or organic acids.
  • the nitrogen in these amine salts is substituted by one or two long-chain C8 to C28 hydrocarbon residues, one to three hydrogen atoms and optionally one or two short-chain Cl to C6 hydrocarbon residues.
  • the one or two long alkyl radicals per molecule are derived, for example, from fatty amines or fatty acids of lengths C8 to C26, preferably C10 to C20, especially C12 to C18.
  • Preferred counterions are Cl “ , Br “ , CH3OSO3” , C 2 H 5 OS0 3 “ , N0 3 “ , HCOO " and CH3COO " .
  • the fatty amines used can be ethoxylated to increase the hydrophilicity.
  • One example is the ethoxylated stearlyamine derivative CH 3 ( CH 2 ) ⁇ 7 N + H [(CH 2 CH 2 0) 5 H] 2 Cl " .
  • the fatty acids or the cuts in the chain length ranges mentioned can be the already described saturated fatty acids, unsaturated fatty acids, hydroxy-substituted ones Act fatty acids or their mixtures.
  • Examples of the acids mentioned are lauric acid, myristic acid, pahnitic acid, stearic acid, oleic acid and rhicinoleic acid. Other examples are high fat and coconut fatty acid cuts.
  • their attachment to the amine salt nitrogen is preferably via oxyethyl, 2-oxypropyl, 1,2-dioxypropyl and in the case of amides preferably via amidoethyl and 3-amidopropyl spacer.
  • the short-chain radicals are preferably methyl, ethyl, propyl, butyl, hexyl, phenyl and hydroxyethyl, 2-hydroxypropyl.
  • Preferred counterions are Cl “ , Br " , CH3OSO3 " , C 2 H 5 OS0 3 7 N0 3 " , HCOO " and CH 3 COO " .
  • Examples include stearic acid triethanolamine derivative:
  • the amount of the optional Component b) used, based on the total amount of the formulation, is expediently from 0 to 30% by weight, preferably 0 to 10% by weight If the component b) is present in the formulation, the amount is preferably between 0.01% by weight. -% and 15% by weight, more preferably 1 to 10% by weight Component b) in the formulations according to the invention has the function of improving the emulsifiability of component c) and, if appropriate, of increasing the substantivity the formulations according to the invention are prepared in such a way that component a) is added to a mixture of the other components Add components b) to e) in succession in any order to component a).
  • the aminosiloxanes a) used according to the invention are first mixed with the nitrogen-free siloxane component (s) c) and this mixture is added to the other constituents. It is also possible to add the components one after the other to the mixture of aminosiloxane (s) / nitrogen-free siloxane component (s) (a) + c)). It is also preferred to premix the mixture of aminosiloxane (s) / nitrogen-free siloxane component (s) with individual or more matrix components and to add these premixes to the residual matrix.
  • the aminosiloxanes a) used according to the invention are first introduced into multi-component formulations based on polysiloxane, which can be flexibly adjusted to the type of substrates to be treated and the treatment conditions by simply varying the composition ratios of the components they contain. It should also be this Formulations make it possible to optimize the amounts of the aminosiloxanes a) used according to the invention in order to achieve the desired properties of the substrates to be treated, without the desired properties of the substrates to be treated deteriorating.
  • These multicomponent formulations preferably contain, based on the total amount of Components c) and a) 5 to 99% by weight of component c) and 1 to 95% by weight of component a).
  • the amount of component c) is more preferably 20 to 90% by weight and the amount of component a) is 10 to 80% by weight, particularly preferably the amount of component c) is 30 to 90% by weight and the amount of Component a) 10 to 70 wt .-%, each based on the total amount of components c) and a).
  • the optionally present carrier substances of component e) are preferably selected from solid carrier substances el) and / or liquid carrier substances e2), which are described in more detail below.
  • the formulations according to the invention preferably contain 0 to 1500, more preferably 0 to 1000, more preferably 0 to 500, more preferably 0 to 300 and most preferably 0 to 150 parts by weight of the optionally present components b), d) and e), based on 100 parts by weight of components c) and a).
  • Component b) is preferably added in amounts of 0 to 70, more preferably 0 to 50 and particularly preferably 0 to 30 parts by weight per 100 parts by weight of the total amount of components c) and a). If component b) is present in the formulation, it is present in amounts of> 0 parts by weight, preferably> 0.1 part by weight per 100 parts by weight of the total amount of components c) and a).
  • Component d) is preferably present in amounts of 0 to 10 , more preferably 0 to 3, particularly preferably 0 to 1.5 and most preferably from 0 to 0.9 parts by weight per 100 parts by weight of the total amount of components c) and a). If component d) is present in the formulation, it is present in amounts of> 0, preferably> 0.01 parts by weight, preferably at most up to 1 part by weight, per 100 parts by weight of the total amount of components c) and a).
  • Component e ie component el) and / or e2
  • Component el is preferably used in amounts of 0 to 1420, more preferably 0 to 600 and particularly preferably 0 to 200 Parts by weight per 100 parts by weight of the total amount of components c) and a) added.
  • Component el) is preferably added in amounts of 0 to 710, more preferably 0 to 300 and particularly preferably from 0 to 100 parts by weight per 100 parts by weight of the total amount of components c) and a). If component el) is present in the formulation, it is contained in amounts of> 0 parts by weight, preferably> 5 parts by weight per 100 parts by weight of the total amount of components c) and a).
  • Component, e2) is preferably added in amounts of 0 to 710, more preferably 0 to 300 and particularly preferably from 0 to 100 parts by weight per 100 parts by weight of the total amount of components c) and a). If component e2) is present in the formulation, it is present in amounts of> 0 parts by weight, preferably> 5 parts by weight per 100 parts by weight of the total amount of components c) and a).
  • Component c) optionally used is one or more silicone-free, preferably cationic, surfactants.
  • component d) is expediently cationic copolymers which are based on natural or synthetic polymer structures. This differs from the surfactants of component b), which are not based on polymer structures. Combinations of natural and synthetic polymers are also possible.
  • Coacervate generator means complex charged anions or cations, each of which forms a complex salt with an altered solubility behavior with a polymer or colloid particle charged in opposite directions.
  • coacervate phase includes all types of discontinuous phases, as described for example in “L. Piculell & B. Lindman, Adv. CoUoid Interface Sci., 41 (1992) "and in” B. Jonsson, B. Lindman, K. Holmberg, & B. Kronberb, "Surfactants and Polymers In Aqueous Solution,” John Wiley & Sons, 1998 ".
  • the mechanism of coacervation and its specific forms are fully described in” Interfacial Forces in Aqueous Media “, CJ van Oss, Marcel Dekker, 1994, pages 245 to 271.
  • coacervate phase is used in the literature occasionally also referred to as “complex coacervate phase” or as "associated phase separation".
  • the coacervate phase former optionally contained in the formulation according to the invention according to component d) leads, for example, when encountering anionic surfactants or anionic groups of any other components, for example when using the formulation according to the invention, such as in detergent formulations, fiber treatment formulations or in the treatment of pretreated substrate surfaces (anionic auxiliaries or dirt particles), to form coacervate phases ch visible using dyes.
  • anionic generally refers to protonated amino compounds or quaternary ammonium compounds (tetraorganoammonium compounds).
  • Natural copolymers are preferably derived from cellulose, starch or chitosan. Quaternary ones are particularly advantageous Ammonium group-modified guar gum derivatives, which are commercially available as JAGUAR types from Rhone-Poulenc. Synthetic copolymers are preferably based on cationic structures such as polyvinylamines, polyethyleneimines and polydimethyldiallylammonium halides. Alternatively, cationically modified materials based on polyvinylpyrrolidone,
  • Polyacrylamide, polymethylacrylamide, polyvinylimidazole and aminoalkylimidazole copolymers are used.
  • High-molecular poly (vinylamine-vinylformamide) copolymers and high-molecular polyethyleneimines are particularly advantageous within this group.
  • high molecular weight natural or synthetic coacervate formers are preferable to low molecular weight structure-analogous compounds.
  • a third group of materials are complexes of polycationic and polyanionic compounds, ie complex salts.
  • Combinations of natural polymers and synthetic polymers are preferred. Specifically, these are combinations of anionic natural polymers with cationic synthetic polymers. The pairing of cationic natural polymer with anionic synthetic polymer is also possible.
  • Examples of preferred combinations are carboxymethyl cellulose, polyethyleneimine, carboxymethyl cellulose / polyvinylamine, chitosan polystyrene sulfonic acid, chitosan polyacrylic acid, chitosan polymethacrylic acid. Combinations of two oppositely charged natural polymers or synthetic polymers are also preferred. Examples include the combinations carboxymethyl cellulose / chitosan, polyethyleneimine / polyacrylic acid and polyvinylamine / polystyrene sulfonic acid.
  • the polycationic compounds can be used in the form of the bases or salts of monovalent anions.
  • the polyanionic compounds can be used in the form of the acids or salts of monovalent cations.
  • Synthetic polycationic and polyanionic compounds can be used in the form of their copolymers, so that their charge density can be varied. If the complexes treated above are used, their net charge should appropriately be cationic. This means that, regardless of the specific substance pairing, there is an excess of amino or ammonium groups over the anionic groups, such as carboxylic acid, sulfonic acid, sulfuric acid semiesters or their salts. As a result of the complexation of polycationic and polyanionic compounds of the type described above, the molecular weight of the coacervate former increases in the desired manner.
  • coacervate former d) is contained in the formulation according to the invention, its preferred amount is 0.001 to 5% by weight, more preferably 0.1 to 1% by weight, based on the total amount of the formulation.
  • Component e) used in the formulation according to the invention is one or more carrier substances. These are preferred from solid Carrier substances el) and / or liquid carrier substances e2) are selected. In the context of the present invention, this means that the liquid carriers are liquid at 40 ° C., the solid carriers are solid at 40 °.
  • Preferred liquid carriers e2) include aqueous and non-aqueous, and can include: water alone or organic solvents, preferably water-soluble organic solvents alone and / or mixtures thereof with water.
  • Preferred organic solvents include: monoalcohols, diols, polyols such as glycerin, glycol, polyethers such as polyalkylene glycols such as polyethylene glycols and mixtures thereof, also with water.
  • Mixtures of solvent in particular mixtures of lower aliphatic alcohols, such as ethanol, propanol, butanol, isopropanol, and or diols, such as 1,2-propanediol or 1,3-propanediol, are particularly preferred; or mixtures thereof with glycerin.
  • Suitable alcohols include, in particular, -C-alcohols. 1,2-Propanediol is preferred.
  • the liquid carrier e2) is expediently present in the formulation according to the invention, based on the total amount of the formulation, in an amount of 0 to 95% by weight, preferably 0 to 65% by weight, more preferably 0 to 55% by weight. If the liquid carrier e2) is present in the formulation according to the invention, its preferred amount is more than 5, more preferably more than 10, most preferably more than 30 to 70, more preferably up to 60% by weight.
  • the solid support el) used as component e) is preferably selected from
  • Particularly preferred are compounds that are selected from the group of water-soluble compounds that have a solubility in water of at least 100 grams / liter at 20 ° C. Appropriately, these are not components b), c) or d).
  • the solid carriers include: inorganic or organic salts, polyhydroxy compounds, saccharides, amides, such as urea, and higher molecular weight polyethylene oxides.
  • the solid supports el) are preferably compounds which have no significant surface-active effect in the sense of surfactants.
  • inorganic salts are sodium chloride, potassium chloride, sodium carbonate and sodium sulfate.
  • An example of an organic salt is sodium acetate.
  • polyhydroxy Compounds and saccharides are pentaerythritol, sorbitol, glucamine, N-methylglucamine.
  • Amide derivatives which can be used according to the invention are, for example, urea and highly hydrophilic, saccharide-modified amide derivatives such as ethylenediamine-bisgluconamide, 1,3-propylenediamine-bisgluconamide, 1,2-propylenediamine-bisgluconamide, diethyletriamine-bisgluconamide, dipropylenetriamentryl-bisgluconamide bisgluconamide, N, N-dimethyl-ethylenediamine-gluconamide N, N-dimethyl-propylenediamine-gluconamide.
  • saccharide-modified amide derivatives are accessible by regioselective reaction of the primary amino groups of the corresponding amines with saccharide carboxylic acid lactones, such as gluconic acid lactone or glucopyranosylarabinonic acid lactone (DE 4 318 536, DE 4 318 537).
  • the solid carrier el) is expediently present in the formulation according to the invention, based on the total amount of the formulation, in an amount of 0 to 95% by weight, preferably 0 to 65% by weight, more preferably 0 to 55% by weight , If the solid carrier el) is contained in the formulation according to the invention, its preferred amount is more than 5, more preferably more than 10, most preferably more than 30 to 70, more preferably up to 60% by weight.
  • the solid carrier el) and the liquid carrier e2) can be in any ratio to one another. The choice of the ratio depends on whether liquid, pasty or solid compositions of the formulation are desired.
  • the formulation can also be present in encapsulated form in a liquid or solid matrix.
  • the formulation according to the invention may contain, in addition to the components a) to e) described above, further other ingredients or auxiliaries, depending on the areas of application.
  • so-called builders such as zeolites, silicates, polyphosphates, alkali metal citrates, -2,2-oxydisuccinates, -carboxymethyloxysuccinates, -nitrilotriacetates, and sodium carbonate
  • enzymes, defoamers such as silicone compounds and stabilizers
  • the stabilizers serve, for example, to stabilize component a) by preventing their coagulation and sedimentation.
  • the stabilizers are, for example, ' gums' and other polysaccharides, such as carrageen gum, other thickeners or rheology additives.
  • the stabilizer is preferably a crystalline hydroxyl-containing compound, such as trihydroxystearin, a hydrogenated oil or a derivative thereof.
  • Further auxiliaries which can be contained in particular in detergents are coupling agents, such as hexylamine, octylamine, nonylamine, their C1-C3 secondary or tertiary analogs and alkanediols.
  • Further auxiliaries, which can be contained in particular in detergents are fragrances adhering to the substrates, chelating agents, other surface-active substances.
  • the preparation of the formulation can include, for example, the production of a homogeneous mixture of c) + a) and the introduction of optional components b), d) and e).
  • components c) and a) are first mixed homogeneously to form a premix, optionally with the addition of parts of the carrier substance e).
  • homogeneous means largely dissolved or else dispersed in transparent, finely divided form.
  • the optional component b) can, for example, be subsequently introduced into this homogeneous premix.
  • this introduction can in turn lead to a homogeneous mixture or else a visibly coarser disperse distribution of b) in the premix c) + a).
  • d), (optionally further) e), ie el) and / or e2) can be introduced into this mixture.
  • a solution of b) in water e) or a solution of d) in water e) or a mixture of b) and d) is introduced into the premix c) + a).
  • b) + d) + e) to the premix c) + a) is also within the scope of the invention.
  • These various mixing strategies can influence the microscopic distribution of the components in the multi-component formulation and thus ultimately the behavior in the formulation according to the invention.
  • the pre-emulsions obtained can then be introduced into final formulations, such as detergents, shampoos, cleaning agents, etc.
  • one or more of the components a) to e) can be present in the formulation according to the invention in encapsulated form or in a form drawn onto a carrier.
  • the encapsulation can be a coating with water-soluble polymers, surfactants or salts or include a conglomerate of the components according to the invention with a carrier.
  • the encapsulation can take place, for example, by spray granulation.
  • the present invention further relates to a process for the preparation according to the invention that the preparation of component a) by the steps: i) hydrolysis of alkoxysilanes or alkoxysiloxanes ii) catalytic equilibration and condensation, and iii) removal of the condensation products with an entrainer Reaction system includes.
  • the present invention relates to a process for the preparation of amino and / or ammonium polysiloxanes, in which the molar ratio of hydroxyl- and alkoxy-containing silicon atoms to non-hydroxyl- or alkoxy-containing terminal silicon atoms is less than 30%, which comprises the steps: i) hydrolysis of alkoxysilanes or alkoxysiloxanes ii) catalytic equilibration and condensation, and iii) removal of the condensation products with an entrainer from the reaction system.
  • the invention further relates to amino and / or ammonium polysiloxanes which have been prepared by the above process and in particular to the use of the amino and / or ammonium polysiloxanes mentioned (component a)) in formulations comprising anionic surfactants, such as, for example, cosmetic formulations, detergent formulations, plasticizer formulas, Surface treatment formulas, laundry finishes, such as ironing aids, textile finishing formulas, etc.
  • anionic surfactants such as, for example, cosmetic formulations, detergent formulations, plasticizer formulas, Surface treatment formulas, laundry finishes, such as ironing aids, textile finishing formulas, etc.
  • Component a) used according to the invention can be produced, for example, on the one hand from organofunctional alkoxysilanes or alkoxysiloxanes, on the other hand with non-functional alkoxysilanes or alkoxysiloxanes by means of the combined hydrolysis / equilibration process mentioned above.
  • organofunctional acoxysilanes or the non-functional alkoxysilanes others can use am Silanes containing silicon hydrolyzable grapples, such as, for example, alkylaminosilanes, alkylsilazanes, alkylcarboxysilanes, chlorosilanes, etc., are subjected to the combined hydrolysis / equilibration process.
  • amino-functional alkoxysilanes, water, corresponding M, D, T and Q units containing siloxanes and basic equilibration catalysts are first mixed together in defined proportions. This is followed by constant mixing, heating to expediently from 60 to 230 ° C., the alcohols split off from the alkoxysilanes and subsequently water being removed step by step.
  • the removal of these volatile components and the extensive condensation of undesirable reactive groups can be promoted by carrying out the reaction at elevated temperatures and / or by applying a vacuum.
  • Suitable entraining agents for these azeotropic distillations are, for example, entraining agents with a boiling range of about 40 to 200 ° C. at (normal pressure (1 bar)).
  • Higher alcohols such as butanol, pentanol, hexanol, halogenated hydrocarbons, such as, for example, methylene chloride, chloroform, aromatics, such as benzene, toluene, xylene, or siloxanes, such as hexamethyldisiloxane and octamethylcyclotetrasiloxane, are preferred.
  • the production of the aminosiloxanes a) used according to the invention is monitored by suitable methods such as NMR spectroscopy or FTIR spectroscopy and is complete when a content of reactive groups is found which is within the scope of the invention.
  • the desired aminoalkylalkoxysilanes are formed in a preceding reaction from haloalkyl-, epoxyalkyl- and isocyanatoalkyl-functionalized alkoxysilanes manufactured. This procedure can be used successfully if the required aminoalkylalkoxysilanes are not commercially available.
  • haloalkylalkoxysilanes examples include chloromethylmethyldimethoxysilane and chloropylmethyldimethoxysilane, epoxyalkylalkoxysilanes glycidylpropylmethyldimethoxysilane and isocyanate-functionalized silanes isocyanatopropylmethyldiethoxysilane and isocyanato-propyl. It is also possible to carry out the functionalization to give amino-functional compounds at the level of the silanes or the equilibrated siloxanes. In the production of the amino-functionalized silanes or siloxanes, for example, structures containing ammonia, primary, secondary and tertiary amino groups can be used.
  • diprimary amines especially diprimary alkylamines, such as 1,6-diaminohexane and 1,12-diaminododecane, and diprimary amines based on polyethylene oxide-polypropylene oxide copolymers, such as Jeffamine® from the D and ED series (Huntsman Corp. ).
  • Primary-secondary diamines such as aminoethylethanolamine, are also preferred.
  • Primary tertiary diamines such as N, N-dimethylpropylenediamine are also preferred.
  • Another group of preferred amines are secondary tertiary diamines, such as N-methylpiperazine and bis (N, N-dimethylpropyl) amine.
  • Tertiary amines such as trimethylamine, N-methylmorpholine and N, N-dimethylethanolamine, are also preferred.
  • Aromatic amines such as imidazole, N-methylimidazole, aminopropylimidazole, aniline and N-methylaniline can also be used with advantage.
  • these aminoalkylalkoxysilanes are used in the combined hydrolysis / equilibration process described above.
  • a two-stage process control can be followed. In a separate first step, a siloxane precursor rich in amino groups is produced.
  • this siloxane precursor is largely free of reactive groups, for example silanol and alkoxysilane groups.
  • the synthesis of this siloxane precursor rich in amino groups is carried out using the hydrolysis condensation / equilibration concept already described.
  • a relatively large amount of the amino-functional alkoxysilane, water and relatively small amounts of siloxanes containing M, D, T and Q units, and basic equilibration catalysts are first mixed together in defined proportions. Subsequently, with constant mixing, there is a heating mung to 60 to 230 ° C, wherein the alcohols split off from the alkoxysilanes and subsequently water are gradually removed as described above.
  • composition of this siloxane precursor rich in amino groups is determined by suitable methods such as titration, NMR spectroscopy or FTJR spectroscopy.
  • the actual target product can be produced from this siloxane precursor rich in amino groups and siloxanes containing M, D, T and Q units with base or acid catalysis.
  • a major advantage of this two-stage method is that the final equilibration takes place with the extensive exclusion of, for example, water and alcohols, and the contents of reactive groups in the starting materials are small and known. It is possible to precede the two-stage synthesis with the aminoalkylalkoxysilane synthesis described above. In a further embodiment of the invention, it is possible to obtain aminosiloxanes according to the invention by equilibration, subsequent hydrosilylation and optionally alkylation. Here, in a manner known per se, an acid-catalyzed equilibration takes place with the participation of SiH functionalized IV ⁇ D units.
  • Amino-functional alkenes or alkynes for example allylamine or N, N-dimethylallylamine, can be added directly to the hydrogen siloxanes obtained by hydrosilylation.
  • amine-reactive olefins and acetylenes such as haloalkenes, halocarboxylic acid esters of alkenols, halocarboxylic acid esters of alkynols, halogen alcohol esters of unsaturated carboxylic acids, epoxy-substituted alkenyl or alkenyl ether structures, by hydrosilylation.
  • Examples are allyl chloride, allyl bromide, allyl chloroacetate, propyl chloroacetate, allyl chloropropionate, propynyl chloropropionate, butindiyl chlorodiacetate, chloropro-pionic butynediyl diester, undecenoic acid chloroethanol ester, undanoloxylyl ester, undecylglycol ester, undecylglycidyl ether. Then, depending on ability of the target product to react with the nitrogen-containing compounds ammonia, primary, secondary and tertiary amines already mentioned.
  • diprimary amines especially diprimary alkylamines, such as 1,6-diaminohexane and 1,12-diaminododecane, and diprimary amines based on polyethylene oxide-polypropylene oxide copolymers, such as Jeffamine® of the D and ED series (Huntsman Co ⁇ .).
  • Primary-secondary diamines such as aminoethylethanolamine, are also preferred.
  • Primary tertiary diamines such as N, N-dimethylpropylenediamine are also preferred.
  • Another group of preferred amines are secondary tertiary diamines such as N-methylpiperazine and bis (N, N-dimethylpropyl) amine.
  • Tertiary amines such as trimethylamine, N-methylmopholine and N, N-dimethylethanolamine are also preferred.
  • Aromatic amines such as imidazole, N-methylimidazole and aminopropylimidazole can also be used with advantage.
  • the general advantage of this concept based on equilibration, hydrosilylation and possibly alkylation is the extensive exclusion of water from the reaction cycle. In this way, the formation of undesired silanols can be largely suppressed.
  • the present invention further relates to the use of the formulation according to the invention for the treatment of natural and / or synthetic fibrous materials.
  • the present invention further relates to the use of the formulation according to the invention for use in detergents.
  • the present invention further relates to the use of the formulation according to the invention for the initial textile finishing of natural and / or synthetic fibers, including paper and textiles.
  • the present invention further relates to the use of the formulation according to the invention for the production of cosmetic products.
  • the present invention further relates to the use of the formulation according to the invention for the production of a cosmetic composition for the treatment of skin and / or hair.
  • the present invention further relates to the use of the formulation according to the invention as a textile plasticizer.
  • the present invention further relates to the use of the formulation according to the invention for the production of agents for ironing aid and agents for preventing or reversing textile creases.
  • the present invention further relates to the use of the formulation according to the invention for the production of detergents.
  • the present invention further relates to cosmetic compositions containing at least one formulation according to the invention.
  • the present invention further relates to detergents containing at least one formulation according to the invention.
  • Formulations represent systems which are suitable for treating textiles and other natural and synthetic fibrous materials, in particular in the presence of nonionic and / or anionic surfactants, from detergent formulations or agents for fiber pretreatment.
  • the amino and / or ammonium polysiloxanes or their mixtures and formulations can be incorporated directly into detergents or can be metered separately into the ongoing washing process.
  • the treated substrates are given a silicone-typical softness, improved elasticity and reduced tendency to wrinkle.
  • the described amino and / or ammonium polysiloxanes or their mixtures and formulations can be used as a component of separate plasticizer systems after the washing of fibers and textiles.
  • the aminosiloxanes described or their mixtures and formulations can be used for the surface treatment of substrates, such as natural and synthetic fibers, including paper and textiles, as a component of systems for initial textile finishing, as an ironing aid and as a means of preventing or reversing textile creasing. It is also possible to introduce the amino and / or ammonium polysiloxanes or their mixtures and formulations into cosmetic systems for the treatment of hair and skin. Examples
  • Example 1 la) Production of an aminosiloxane precursor rich in amino groups with a small proportion of reactive groups corresponding to component a)
  • the viscosity of a sample taken at this point in time is 2940 mPa.s, 20 ° C.). It is applied at 180 ° C water jet vacuum, so that D 4 boils at reflux for 10 minutes. 60 g of D4, which contains enclosed water drops, are removed in a water separator. This procedure is repeated after 2, 4 and 6 hours. After cooling back to 30 ° C., 0.36 g of acetic acid are added to neutralize the catalyst. Then all the components boiling up to 150 ° C. are removed in an oil vacuum. 5957 g of a colorless aminosiloxane with a viscosity of 4470 mPa.s (20 ° C.) and the composition determined by NMR spectroscopy are removed
  • Example 3 The following formulations are produced:
  • formulations FI to F4 To prepare formulations FI to F4, the heavy-duty liquid detergent is initially introduced and the aminosiloxane is metered in dropwise with very vigorous stirring. After the end of the metering range, transparent formulations FI to F4 are available. additionally a 1% aqueous solution of a cationic guar gum (MW 425,000; 0.7 mmol / g N + ) as component d) is prepared and stored at 4 ° C.
  • Example 4 To test the softening properties, washing tests are carried out in a drum washing machine.

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Abstract

L'invention concerne des formulations comprenant : a) un amino- et/ou ammonium-polysiloxane, dont le rapport molaire des atomes de silicium renfermant un hydroxy et un alcoxy, aux atomes de silicium terminaux non hydroxy ou alcoxy, ne dépasse pas une valeur limite déterminée, et au moins un autre constituant choisi dans le groupe comprenant b) un ou plusieurs agents tensio-actifs, c) un ou plusieurs polysiloxanes exempts d'azote, et d) un ou plusieurs générateurs de phase coacervée. L'invention concerne en outre l'utilisation des formulations pour le traitement de matériaux fibreux. L'invention concerne également un procédé particulier de préparation des composants a).
EP04805013A 2003-12-23 2004-12-22 Amino- et/ou ammoniumpolysiloxane exempt de groupes alcoxy et hydroxyle Withdrawn EP1706443A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10361533 2003-12-23
DE102004012877A DE102004012877A1 (de) 2003-12-23 2004-03-16 Alkoxy- und hydroxylgruppenfreie Amino- und/oder Ammoniumpolysiloxane
DE102004018392 2004-04-16
PCT/EP2004/053682 WO2005063855A1 (fr) 2003-12-23 2004-12-22 Amino- et/ou ammoniumpolysiloxane exempt de groupes alcoxy et hydroxyle

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ATE526365T1 (de) 2004-12-23 2011-10-15 Dow Corning Vernetzbare saccharid-siloxan-zusammensetzungen und daraus gebildete netzwerke, überzüge und artikel
EP1885331A2 (fr) 2005-05-23 2008-02-13 Dow Corning Corporation Compositions d'hygiene personnelle a copolymeres de saccharide-siloxane
CN101228311A (zh) * 2005-05-23 2008-07-23 陶氏康宁公司 含糖-硅氧烷共聚物的表面处理组合物
EP2019678A4 (fr) 2006-05-23 2012-05-02 Dow Corning Nouvel agent filmogène en silicone pour la libération de principes actifs
US8268975B2 (en) 2009-04-03 2012-09-18 Dow Agrosciences Llc Demulsification compositions, systems and methods for demulsifying and separating aqueous emulsions
KR101858022B1 (ko) 2010-08-23 2018-05-16 다우 실리콘즈 코포레이션 수성 환경에서 안정한 당 실록산 및 그러한 당 실록산의 제조 및 사용 방법
CN112538334B (zh) * 2020-12-09 2022-05-27 成都硅宝科技股份有限公司 一种光伏组件用有机硅封装材料及其制备方法

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DE19628035A1 (de) * 1996-07-11 1998-01-15 Wacker Chemie Gmbh Wäßrige Cremes von Organosiliciumverbindungen für Hydrophobierung von Baustoffen
US6649692B2 (en) * 2001-02-20 2003-11-18 Crompton Corporation Organopolysiloxane composition, emulsion-forming concentrates and aqueous emulsions formed therefrom and use of the emulsions in the treatment of textiles
DE10221521A1 (de) * 2002-05-14 2003-12-04 Ge Bayer Silicones Gmbh & Co Formulierungen von Silikonweichmachern für die textile Ausrüstung

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