WO2005105969A1 - Compositions detergentes a lessive liquides a agents d'entretien des textiles silicone - Google Patents

Compositions detergentes a lessive liquides a agents d'entretien des textiles silicone Download PDF

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Publication number
WO2005105969A1
WO2005105969A1 PCT/US2005/001005 US2005001005W WO2005105969A1 WO 2005105969 A1 WO2005105969 A1 WO 2005105969A1 US 2005001005 W US2005001005 W US 2005001005W WO 2005105969 A1 WO2005105969 A1 WO 2005105969A1
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Prior art keywords
silicone
weight
blend
functionalized polysiloxane
laundry detergent
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PCT/US2005/001005
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English (en)
Inventor
Patrick Firmin August Delplancke
Jean-Pol Boutique
Stefano Scialla
Gregory Leo Jervier
Connie Lynn Sheets
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to MXPA06011880A priority Critical patent/MXPA06011880A/es
Priority to CA002561997A priority patent/CA2561997A1/fr
Priority to EP05705592A priority patent/EP1735420A1/fr
Priority to BRPI0509921-8A priority patent/BRPI0509921A/pt
Priority to JP2007507304A priority patent/JP2007532716A/ja
Publication of WO2005105969A1 publication Critical patent/WO2005105969A1/fr

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Classifications

    • 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
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • This invention relates to liquid laundry detergent compositions containing functionalized silicone materials as fabric care agents.
  • Such fabric care benefits to be imparted can be exemplified by one or more of reduction, prevention or removal of wrinkles; the improvement of fabric softness, fabric feel or garment, shape retention or recovery; improved elasticity; ease of ironing benefits; color care; anti-abrasion; anti-pilling; or any combination of such benefits.
  • Detergent compositions which provide both fabric cleaning performance and additional fabric care effects, e.g., fabric softening benefits are known as "2-in- 1 "-detergent compositions and/or as "softening-through-the-wash"-compositions.
  • quaternary ammonium fabric softening agents e.g., quaternary ammonium fabric softening agents
  • One such type of alternative fabric care agents comprises silicone, i.e., polysiloxane-based, materials. Silicone materials include nonfunctional types such as polydimethylsiloxane (PDMS) and functionalized silicones, and can be deposited onto fabrics during the wash cycle of the laundering process. Such deposited silicone materials can provide a variety of benefits to the fabrics onto which they deposit. Such benefits include those listed hereinbefore.
  • Non-functionalized silicones however good in their compatibility with detergents, have shortcomings. Such non-functionalized silicones can produce excellent fabric care benefits when directly applied to textiles, yet are found to work ineffectively in liquid laundry detergents. The problem is a complex one and includes inadequate deposition in the presence of surfactants, unsatisfactory spreading, inadequate emulsion stability and other factors. When such nonfunctional materials do not deposit effectively, a major proportion of the silicone is lost to the drain at the end of the wash, rather than being deposited evenly and uniformly on the fabrics, e.g., clothing, being washed.
  • amino and “ammonium” in this context most generally means that there is at least one substituted or unsubstituted amino or ammonium moiety covalently bonded to, or covalently bonded in, a polysiloxane chain and the covalent bond is other than an Si-N bond, e.g., as in the moieties - [Si]-O-CRVNR 3 , -[Si]-O-CR' 2 -NR 3 -[Si]-OCR' 2 -N + R 4 , -[Si]-OCR' 2 -N HR 2 -[Si]-O-CR' 2 - N + HR 2 -[Si]-CRVNR 3 etc.
  • Functionalized, nitrogen-containing silicones such as these can be used in and of themselves to impart a certain amount and degree of fabric care benefit.
  • functionalized silicones also have shortcomings. For example it is known that they can react chemically with components of detergents. Mechanisms of reaction have not been well documented but can in principle include reactions of aminofunctional groups themselves, as well as reactions of curable groups present within such functionalized polymers. The art is ambivalent on the possibility of successfully including reactive or curable silicones in detergents without stability problems.
  • references teaching desirablity of having curable or reactive moieties and on the other hand there are references teaching desirability of avoiding all reactive moieties (in this context including ammonium or aminofunctional moieties) in various cleaning compositions.
  • nitrogen-containing silicone materials useful as fabric care agents can be prepared from nitrogen-substituted alkoxysilanes or alkoxysiloxanes as starting materials. (See for example, the processes disclosed in EP-A-269,886 and US-A-6,093,841.) Such preparation can involve hydrolysis of the starting materials followed by catalytic equilibration and condensation with non-functionalized siloxanes. Depending on the process involved and conditions used, the resulting amino or ammonium functionalized silicones will contain reactive groups on the silicon atoms, and especially the terminal silicon atoms, of the siloxane chains in such reaction product material.
  • Such reactive groups can comprise -H, -OH, and -OR moieties originally present in the silane and siloxane starting materials.
  • synthesis routes such as the above, found desirable for manufacturing reasons, can be applied to the provision of improved fabric care detergents.
  • Processes which remove reactive groups from the functionalized silicone end product serve to render those end products "nonreactive.”
  • it is desirable to conduct such additional processes only to the minimum extent required for good liquid detergent fabric care benefit performance and stability, or the processes are wasteful and costly.
  • a silicone blend of preferably miscible silicones comprising certain amino and ammonium functionalized silicone material in combination with certain kinds of non-functionalized polysiloxanes.
  • the amino and ammonium functionalized silicones used are those which have been prepared in a manner to minimize the presence therein of certain types of reactive moieties.
  • These selected amino and ammonium functionalized silicones are also those which have a specific balance of amine and or ammonium functionality, as quantified by nitrogen content, and silicone viscosity and preferably molecular weight.
  • the nitrogen content is fundamentally linked to the ability to obtain miscibility of the functionalized and non-functionalized silicones, and the blend combination of the two acts synergistically. Moreover, while the levels of reactive group content needed are low, they do not need to be zero. This is believed to be due, at least in part, to the ability of the non- functionalized silicone to protect the functionalized silicone from interaction with other components of the detergent composition. Furthrmore, use of combinations of functionalized and non-functionalized silicones also permits formulation of liquid detergent products which do not need to contain a cationic deposition aid or a coacervate phase-forming polymer in order to promote deposition of the silicone materials onto fabrics.
  • the present invention therefore offers numerous advantages.
  • Fourth, the compositions are stable and effective for their intended industrial purposes. Other advantages include that the compositions are non-yellowing on white textiles and moreover, that they do not give uneven deposition or lead to unacceptable visual results on clothing.
  • the present invention is directed to aqueous (e.g., containing upwards of from 4% by weight water) liquid laundry detergent compositions which are suitable for cleaning and imparting fabric care benefits to fabrics laundered using such a composition.
  • aqueous e.g., containing upwards of from 4% by weight water
  • Such compositions comprise:
  • At least one detersive surfactant selected from anionic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, and combinations thereof;
  • the specific amino and/or ammonium functionalized polysiloxane materials used are those which have been prepared by a process which intrinsically leaves reactive/curable groups in the functionalized polysiloxane material which is produced.
  • a process which intrinsically leaves reactive/curable groups in the functionalized polysiloxane material which is produced.
  • a process comprises hydrolysis of nitrogen-containing alkoxysilane and or alkoxysiloxane starting materials and catalytic equilibration and condensation of these hydrolyzed starting materials. Notwithstanding the tendency of the process used to leave reactive/curable groups within the resulting functionalized polysiloxane materials, such materials must be further processed in a manner which reduces and minimizes the amount of such reactive/curable groups which remain.
  • the amino and/or ammonium functionalized polysiloxane materials used must have a molar ratio of curable/reactive group-containing silicon atoms to terminal silicon atoms containing no reactive/curable groups which is less than 30%. Syntheses of the functionalized silicones are adapted herein to secure appropriate curable/reactive group contents, which can theoretically be zero or, more economically, can be non-zero while remaining at low and compatible levels.
  • Such amino and or ammonium functionalized polysiloxane materials also have a nitrogen content ranging from 0.05% to 0.5% by weight and a viscosity at 20 °C ranging from 0.00002 m 2 /s to 2.0 m 2 /s.
  • the nitrogen-free, non-functionalized polysiloxane material which forms part of the silicone blend has a viscosity which ranges from 0.01m 2 /s to 2 i 0m 2 /s. It is present in an amount such that the weight ratio of functionalized to non-functionalized siloxanes within the silicone blend ranges from 100:1 to 1:100.
  • the functionalized silicone and nitrogen-free, non- functionalized polysiloxane materials are preferably fully miscible at the specified nitrogen content of the functionalized silicone. This leads to droplets of the resulting blend which are more effective for providing fabric care benefits, e.g., softness or feel of textiles on the skin, than either of the materials alone.
  • compositions are essentially free of any coacervate phase-forming polymers. Likewise such compositions are essentially free of any cationic deposition aids.
  • liquid laundry detergent compositions herein as well as composition form, preparation and use, are described in greater detail as follows: In this description, all concentrations and ratios are on a weight basis of the liquid laundry detergent unless otherwise specified. Percentages of certain compositions herein, such as silicone emulsions prepared independently of the liquid laundry detergent, are likewise percentages by weight of the total of the ingredients that are combined to form these compositions. Elemental compositions such as percentage nitrogen (%N) are percentages by weight of the silicone referred to.
  • %N percentage nitrogen
  • Particle size ranges are ranges of median particle size.
  • a particle size range of from 0.1 micron to 200 micron refers to the median particle size having a lower bound of 0.1 micron and an upper bound of 200 microns.
  • Particle size may be measured by means of a laser scattering technique, using a Coulter LS 230 Laser Diffraction Particle Size Analyser from Coulter Corporation, Miami, Florida, 33196, USA.
  • Viscosity is measured with a Cammed CSL2 Rheometer at a shear rate of 21 sec "1 . Viscosity expressed in m 2 /sec can be multiplied by 1,000,000 to obtain equivalent values in Centistokes (Cst). Viscosity expressed in Cst can be divided by 1,000,000 to obtain equivalent values in m 2 /sec. Additionally, Kinematic viscosity can be converted to Absolute viscosity using the following conversion: multiply kinematic viscosity given in centistokes by density (grams/cm 3 ) to get absolute viscosity in centipoise (cp or cps).
  • the present compositions comprise as one essential component at least one surfactant selected from the group consisting anionic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, and combinations thereof.
  • the surfactant component can be employed in any concentration which is conventionally used to effectuate cleaning of fabrics during conventional laundering processes such as those carried out in automatic washing machines in the home. Suitable surfactant component concentrations include those within the range from 5% to 80%, preferably from 7% to 65%, and more preferably from 10% to 45%, by weight of the composition.
  • any detersive surfactant known for use in conventional laundry detergent compositions may be utilized in the compositions of this invention.
  • Such surfactants for example include those disclosed in "Surfactant Science Series", Vol. 7, edited by W. M. Linfield, Marcel Dekker.
  • Non- limiting examples of anionic, nonionic, zwitterionic, amphoteric or mixed surfactants suitable for use in the compositions herein are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co., and in U.S. Patent Nos. 5,104,646; 5,106,609; 3,929,678; 2,658,072; 2,438,091; and 2,528,378.
  • Preferred anionic surfactants useful herein include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or un-alkoxylated alkyl sulfate materials. Such materials will generally contain form 10 to 18 carbon atoms in the alkyl group.
  • Preferred nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials which correspond to the general formula:
  • R ⁇ is a Cg - Cjg alkyl group
  • m is from 2 to 4
  • n ranges from about 2 to 12.
  • R* is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
  • Silicone Component -
  • the present compositions essentially contain droplets of a blend of certain types of silicone materials.
  • This blend of silicone materials comprises both amino and/or ammonium group-containing functionalized polysiloxane materials and nitrogen- free, non-functionalized polysiloxane materials.
  • polysiloxane and “silicone” can be and are herein used interchangeably.
  • Both the functionalized and non-functionalized polysiloxanes used in the silicone blend are built up from siloxy units which are chosen from the following groups:
  • R substituents represent organic radicals, which can be identical or different from one another.
  • at least one of the R 1 groups essentially comprises nitrogen in the form of an amino or quaternary moiety, and optionally and additionally may comprise nitrogen in the form of an amide moiety so as to form an amino-amide.
  • none of the R 1 groups are substituted with nitrogen in the form of an amino or quaternary ammonium moiety.
  • the R 1 groups for each type of polysiloxanes correspond to those defined more particularly in one or more of the additional general formulas set forth hereinafter for these respective types of polysiloxane materials.
  • these Q, T, D and M designations for these several siloxy unit types will be used in describing the preparation of the functionalized polysiloxanes in a manner which minimizes the content of reactive groups in these functionalized materials.
  • These Q, T, D and M designations are also used in describing the NMR monitoring of the preparation of these materials and the use of NMR techniques to determine and confirm reactive group concentrations.
  • the functionalized silicone is a polymeric mixture of molecules each having a straight, comb - like or branched structure containing repeating SiO groups.
  • the molecules comprise functional substituents which comprise at least one nitrogen atom which is not directly bonded to a silicon atom.
  • the functionalized silicones selected for use in the compositions of the present inventions include amino-functionalized silicones, i.e., there are silicone molecules present that contain at least one primary amine, secondary amine, or tertiary amine. Quatemized amino-functionalized silicones, i.e. quaternary ammonium silicones, are also encompassed by the definition of functionalized silicones for the purpose of the present invention.
  • the amino groups can be modified, hindered or blocked in any known manner which prevents or reduces the known phenomenon of aminosilicone fabric care agents to cause yellowing of fabrics treated therewith if, for example, materials too high in nitrogen content are employed.
  • the functionalized silicone component of the silicone blend will generally be straight- chain, or branched polysiloxane compounds which contain amino or ammonium groups in the side groups (i.e., the amino or ammonium groups are present in groups having general structures designated D or T) or at the chain ends (i.e., the amino or ammonium groups are present in groups having general structures designated M).
  • the molar ratio of curable/reactive group-containing silicon atoms to non-curable/reactive group-containing terminal silicon atoms is from 0% to no more than 30%, i.e., 0.3 mole fraction.
  • this low level of reactive groups, as determined on the neat (undiluted, not yet formulated) functionalized silicone dissolved at a concentration of, for example, 20% by weight in a solvent such as deuterated chloroform is from about the practical analytical detection threshold (nuclear magnetic resonance) to no more than 30%.
  • Hydroxyl- and alkoxy-containing silicon atoms in this context means all M, D, T and Q groups which contain an Si-OH or Si-OR grouping. (It should be noted that D groups which contain -OH or -OR substituents on the silicon atom will generally comprise the terminal Si atoms of the polysiloxane chain.)
  • the "non-hydroxyl- or alkoxy-containing terminal silicon atoms” means all M groups which contain neither a Si-OH nor a Si-OR group.
  • This molar ratio of hydroxyl- and alkoxy-containing silicon atoms to non-hydroxyl- or alkoxy-containing terminal silicon atoms is expediently determined according to the present invention by nuclear magnetic resonance (NMR) spectroscopy methods, preferably by l H-NMR and 29 Si-NMR, particularly preferably by 29 Si-NMR. According to this invention, this molar ratio of hydroxyl- and alkoxy- containing silicon atoms to non-hydroxyl- or alkoxy-containing terminal silicon atoms is expediently the ratio of the integrals of the corresponding signals in 29 Si-NMR.
  • NMR nuclear magnetic resonance
  • Ratio (L ⁇ PP m + I- ⁇ 3 p P m) l 7 ppm x 100%. (For purposes of this invention, this molar ratio is expressed as a percentage which is referred to as the percent content of curable/reactive groups in the functionalized silicone.)
  • the limit value of 0% in the context of the invention means that preferably silicon atoms containing reactive groups can no longer be detected by suitable analytical methods, such as NMR spectroscopy or infra-red spectroscopy. It should be noted that, in view of the preparative methods for the functionalized silicone materials, having no reactive groups or having them at very limited levels does not follow automatically from mere presentation of chemical structures not having such reactive groups. Rather, reactive group content must be practically secured at the specified levels by adapting the synthesis procedure for these materials, as is provided for herein.
  • non-reactive chain-terminating M groups represent structures which, in the environment of the detergent formulations herein, are not capable of forming covalent bonds with a resulting increase in the molecular weight of materials formed.
  • the substituents R 1 include, for example, Si-C-linked alkyl, alkenyl, alkynyl and aryl radicals, which optionally can be substituted by N, O, S and halogen.
  • the substituents are preferably to C ⁇ 2 alkyl radicals, such as methyl, ethyl, vinyl, propyl, isopropyl, butyl, hexyl, cyclohexyl and ethylcyclohexyl.
  • M, D, T and Q structures with curable/reactive groups mean and represent, in particular, structures which do not contain the amino or quaternary nitrogen moieties and which, in the environment of the detergent formulations herein, are capable of forming covalent bonds, thereby creating material of increased molecular weight.
  • the predominant curable/reactive units are the Si-OH and SiOR units as mentioned, and can furthermore also include epoxy and or sSiHand/or acyloxysilyl groups, and or Si-N-C- linked silylamines and/or Si-N-Si-linked silazanes.
  • alkoxy-containing silicon units are the radicals ⁇ SiOCH 3 , ⁇ SiOCH 2 CH 3 , ⁇ SiOCH(CH 3 ) 2 , sSiOCH 2 CH 2 CH 2 CH 3 and ⁇ SiOC 6 H 5 .
  • An example of an acyloxysilyl radical is ⁇ SiOC(O)CH 3 .
  • the functionalized silicones used herein and having the requisite levels of reactive groups can be prepared by a process which involves: i) hydrolysis of alkoxysilanes or alkoxysiloxanes; ii) catalytic equilibration and condensation; and iii) removal of the condensation products from the reaction system, for example with anentraining agent such as an inert gas flow.
  • the functionalized silicones herein can be prepared for example, on the one hand from organofunctional alkoxysilanes or alkoxysiloxanes, and on the other hand with non-functional alkoxysilanes or alkoxysiloxanes.
  • organofunctional alkoxysilanes or the non-functional alkoxysilanes other silanes containing hydrolysable groups on the silicon, such as, for example, alkylaminosilanes, alkylsilazanes, alkylcarboxysilanes, chlorosilanes etc. can be subjected to the combined hydrolysis/equilibration process.
  • amino-functional alkoxysilanes, water, corresponding siloxanes containing M, D, T and Q units and basic equilibration catalysts initially can be mixed with one another in appropriate ratios and amounts. Heating to 60 °C to 230 °C can then be carried out, with constant thorough mixing. The alcohols split off from the alkoxysilanes and subsequently water can be removed stepwise. The removal of these volatile components and the substantial condensation of undesirable reactive groups can be promoted by using a reaction procedure at elevated temperatures and/or by applying a vacuum.
  • a further process step which comprises the removal of the vaporizable condensation products, such as, in particular, water and alcohols, from the reaction mixture by means of an entraining agent.
  • Entraining agents which can be employed to prepare functionalized polysiloxanes to be used according to this invention are: carrier gases, such as nitrogen, low- boiling solvents or oligomeric silanes or siloxanes.
  • carrier gases such as nitrogen, low- boiling solvents or oligomeric silanes or siloxanes.
  • Suitable entraining agents for these azeotropic distillations include, for example, entraining agents with a boiling range from about 40 to 200 °C. under (normal pressure (1 bar)).
  • Higher alcohols such as butanol, pentanol and hexanol, halogenated hydrocarbons, such as, for example, methylene chloride and chloroform, aromatics, such as benzene, toluene and xylene, or siloxanes, such as hexamethyldisiloxane and octamethylcyclotetrasiloxane, are preferred.
  • the preparation of the desired aminosiloxanes can be monitored by suitable methods, such as NMR spectroscopy or FTIR spectroscopy, and is concluded when a content of reactive groups which lies within the scope according to the invention is determined.
  • the desired aminoalkylalkoxysilanes can be prepared in a prior reaction from halogenoalkyl-, epoxyalkyl- and isocyanatoalkyl-functionalized alkoxysilanes. This procedure can be employed successfully if the aminoalkylalkoxysilanes required are not commercially available.
  • halogenoalkylalkoxysilanes are chloromethylmethyldimethoxysilane and chloropropylmethyldimethoxysilane
  • an example of epoxyalkylalkoxysilanes is glycidylpropylmethyldmethoxysilane
  • examples of isocyanate-functionalized silanes are isocyanatopropylmethyl-diethoxysilane and isocyanatopropyltriethoxysilane. It is also possible to carry out the functionalization to amino-functional compounds at the stage of the silanes or the equilibrated siloxanes.
  • Ammonia or structures containing primary, secondary and tertiary amino groups can be used in the preparation of the amino-functionalized silanes and siloxanes.
  • Diprimary amines are of particular interest, and here in particular 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 Corp.) can be used.
  • Primary-secondary diamines, such as aminoethylethanolamine are furthermore preferred.
  • Primary-tertiary diamines such as N,N-dimethylpropylenediamine, are also preferred.
  • Secondary- tertiary diamines such as N-methylpiperazine and bis-(N,N-dimethylpropyl)amine, represent a further group of preferred amines.
  • Tertiaryamines 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 advantageously be employed. After the synthesis has been carried out, these aminoalkylalkoxysilanes are used in the combined hydrolysis/equilibration process hereinbefore described.
  • a siloxane precursor high in amino groups is prepared in a separate first step. It is essential that this siloxane precursor is substantially free from reactive groups, for example silanol and alkoxysilane groups.
  • the synthesis of this siloxane precursor high 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 as well as basic equilibration catalysts are first mixed with one another in appropriate ratios and amounts.
  • composition of this siloxane precursor high in amino groups can be determined by suitable methods, such as titration, NMR spectroscopy or FTIR spectroscopy.
  • the actual target product can be prepared from this siloxane precursor high in amino groups and siloxanes containing M, D, T and Q units under base or acid catalysis. According to requirements for minimization of the end contents of reactive groups, this can again be carried out, as already described, at elevated temperature and/or with vacuum and with azeotropic distillation.
  • the essential advantage of this two-stage method is that the final equilibration proceeds with substantial exclusion of e.g. water and alcohols and the contents of reactive groups in the starting substances are small and known. It is possible to carry out the aminoalkylalkoxysilane synthesis described above in series with the two-stage synthesis.
  • the functionalized silicones used herein must also have a % amine/ammonium functionality, i.e., nitrogen content or %N by weight, in the range of from 0.05% to 0.50%. More preferably, nitrogen content ranges from 0.10% to 0.45% by weight. Most preferably, ntrogencontent ranges from 0.3% to 0.4%. Nitrogen content can be determined by conventional analytical techniques such as by direct elemental analysis or by NMR.
  • the functionalized silicone materials used herein must also have certain viscosity characteristics.
  • the functionalized polysiloxane materials used herein will have a viscosity from 0.00002 m 2 /s (20 centistokes at 20 °C) to 0.2 m 2 /s (200,000 centistokes at 20 °C), preferably from 0.0015 m 2 /s (1500 centistokes at 20 °C) to 0.1 m 2 /s (100,000 centistokes at 20 °C), and more preferably from 0.002 m 2 /s (2000 centistokes at 20 °C) to 0.01 m 2 /s (10,000 centistokes at 20 °C).
  • the preferred functionalized silicones will also have a molecular weight in the range of from 2,000 Da to 100,000 Da, preferably from 15,000 Da to 50,000 Da, most preferably from 20,000 Da to 40,000 Da, most preferably, from 25,000 Da to 35,000 Da.
  • Examples of preferred functionalized silicones for use in the compositions of the present invention include but are not limited to, those which conform to the general formula (A):
  • G is phenyl, or C j -Cg alkyl, preferably methyl; a is 0 or an integer having a value from
  • R* is a monovalent radical conforming to the general formula CqH2qL, wherein q is an integer having a value from 2 to 8 and L is selected from the following groups: -N(R2)CH2-CH2-N(R2)2; -N(R2)2; wherein R ⁇ is hydrogen, phenyl, benzyl, hydroxyalkyl or a saturated hydrocarbon radical, preferably an alkyl radical of from C to C20
  • R is independently selected from C ⁇ to C4 alkyl, hydroxyalkyl and combinations thereof, preferably from methyl and wherein n and m are hereinbefore defined.
  • R groups are methyl, the above polymer is known as "trimethylsilylamodimethicone".
  • a non-functionalized silicone is a polymer containing repeating SiO groups and substitutents which comprise of carbon, hydrogen and oxygen.
  • the non-functionalized silicones selected for use in the compositions of the present invention include any nonionic, non-cross linked, nitrogen-free, non-cyclic silicone polymer.
  • the non-functionalized silicone is selected from nonionic nitrogen-free silicone polymers having the Formula (I): 1 R 1 R 1
  • each R! is independently selected from the group consisting of linear, branched or cyclic alkyl groups having from 1 to 20 carbon atoms; linear, branched or cyclic alkenyl groups having from 2 to 20 carbon atoms; aryl groups having from 6 to 20 carbon atoms; alkylaryl groups having from 7 to 20 carbon atoms; arylalkyl and arylalkenyl groups having from 7 to 20 carbon atoms and combinations thereof, selected from the group consisting of linear, branched or cyclic alkyl groups having from 1 to 20 carbon atoms; linear, branched or cyclic alkenyl groups having from 2 to 20 carbon atoms; aryl groups having from 6 to 20 carbon atoms; alkylaryl groups having from 7 to 20 carbon atoms; arylalkyl; arylalkenyl groups having from 7 to 20 carbon atoms and wherein the index w has a value such that the viscosity of the nitrogen-free silicone polymer is
  • the non-functionalized silicone is selected from linear nonionic silicones having the Formulae (I), wherein R! is selected from the group consisting of methyl, phenyl, and phenylalkyl, most preferably methyl.
  • Non-limiting examples of nitrogen-free silicone polymers of Formula (I) include the Silicone 200 fluid series from Dow Corning and Baysilone Fluids M 600,000 and 100,000 from Bayer AG.
  • the blend of functionalized and non-functionalized silicones can be formed by simply admixing these two types of silicones together in the appropriate desired ratios. Silicone materials of these two essential types are preferably miscible liquids when their compositions are as specified herein. The silicone blend then can then be added as is to the detergent compositions herein under agitation to form droplets of the silicone blend within the detergent composition.
  • the weight ratio of functionalized polysiloxane material to non-functionalized polysiloxane material in the silicone blend will range from 100:1 to 1:100. More preferably the blend will contain functionalized and non-functionalized silicones in a weight ratio of from 1:25 to 5:1, even more preferably from 1:20 to 1:1, and most preferably from 1:15 to 1:2.
  • the blends of functionalized and non-functionalized polysiloxanes used in the detergent compositions herein are preferably also “miscible.”
  • such silicone blends are “miscible” if they mix freely and exhibit no phase separation at 20 °C when admixed within the broad weight ratio range of from 100:1 to 1:100.
  • the silicone blends present as droplets in the liquid detergent can get into the liquid detergent composition formulation in a number of different ways provided that the two essential silicones are mixed before adding them to the balance of the liquid detergent composition. They can be mixed "neat” to form the blend, or, more preferably, the silicone blends can be introduced into the liquid detergent being added as "silicone emulsions".
  • Silicone emulsions herein, unless otherwise made clear, refers to combinations of the blended essential silicones with water plus other adjuncts such as emulsifiers, biocides, thickeners, solvents and the like.
  • the silicone emulsions can be stable, in which case they are useful articles of commerce, practically convenient to handle in the detergent plant, and can be transported conveniently.
  • the silicone emulsions can also be unstable.
  • a temporary silicone emulsion of the blended silicones can be made from the neat silicones in a detergent plant, and this temporary silicone emulsion can then be mixed with the balance of the liquid detergent provided that a dispersion of the droplets having the particle sizes specified herein is the substantially uniform result.
  • percentages of ingredients in the liquid detergents the convention will be used herein of accounting only the essential silicones in the "silicone blend" part of the composition, with all minor ingredients e.g., emulsifiers, biocides, solvents and the like, being accounted for in conjunction with recital of the non-silicone component levels of the formulation.
  • the silicone blend is emulsified with water and an emulsifier to form an emulsion which can be used as a separate component of the detergent composition.
  • an emulsifier to form an emulsion which can be used as a separate component of the detergent composition.
  • Such a preformed oil-in-water emulsion can then be added to the other ingredients to form the final liquid laundry detergent composition of the present invention.
  • the weight ratio of the silicone blend to the emulsifier is generally between 500:1 and 1:50, more preferably between 200:1 and 1:1, and most preferably greater than 2:1.
  • the concentration of the silicone blend in the oil-in-water emulsion will generally range from 5% to 60% by weight of the emulsion, more preferably from 35% to 50% by weight of the emulsion.
  • Preferred silicone blend emulsions for convenient transportation from a silicone manufacturing facility to a liquid detergent manufacturing facility will typically contain these amounts of silicone, with the balance of suitable transportation blends being water, emulsifiers and minor components such as bacteriostats. In such compositions the weight ratio of the silicone blend to water will generally lie in the range from 1:50 to 10:1, more preferably from 1:10 to 1:1.
  • any emulsifier which is chemically and physically compatible with all other ingredients of the compositions of the present invention is suitable for use therein and in general the emulsifier can have widely ranging HLB, for example an HLB from 1 to 100. Typically the HLB of the emulsifier will lie in the range from 2 to 20.
  • Cationic emulsifiers, nonionic emulsifiers and mixtures thereof are useful herein.
  • Emulsifiers may also be silicone emulsifiers or non-silicone emulsifiers.
  • Useful emulsifiers also include two- and three-component emulsifier mixtures. The invention includes embodiments wherein two emulsifiers or three emulsifiers are added in forming the silicone blends.
  • Nonionic emulsifiers are nonionic emulsifiers:
  • nonionic emulsifier suitable for use herein comprises the "common" polyether alkyl nonionics. These include alcohol ethoxylates such as Neodol 23-5 ex Shell and Slovasol 458 ex Sasol.
  • suitable nonionic emulsifiers include alkyl poly glucoside-based emulsifiers such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, preferably from 8 to 16 carbon atoms, more preferably from 10 to 12 carbon atoms, and a polysaccharide, e.g.
  • a polyglycoside, hydrophilic group containing from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • Preferred alkylpolyglycosides have the formula
  • R ⁇ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and combinations thereof in which the alkyl groups contain from 6to 30, preferably from 8 to 16, more preferably from 10 to 12 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7.
  • the glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position).
  • the additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2-position.
  • Compounds of this type and their use in detergents are disclosed in EP-B 0070077, 0075 996, 0 094 118, and in WO 98/00498.
  • Nonionic emulsifiers for making silicone blend emulsions include other polyol surfactants such as sorbitan esters (e.g. Span 80 ex Uniqema, Crill 4 ex Croda) and ethoxylated sorbitan esters.
  • sorbitan esters e.g. Span 80 ex Uniqema, Crill 4 ex Croda
  • Polyoxyethylene fatty acid esters e.g. Myrj 59 ex Uniqema
  • ethoxylated glycerol esters may also be used as can fatty amides/amines and ethoxylated fatty amides/amines.
  • Cationic emulsifiers suitable for use in the silicone blends of the present invention have at least one quatemized nitrogen and one long-chain hydrocarbyl group. Compounds comprising two, three or even four long-chain hydrocarbyl groups are also included. Examples of such cationic emulsifiers include alkyltrimethylammonium salts or their hydroxyalkyl substituted analogs, preferably compounds having the formula R1R2R3R ]SJ+X-.
  • R1 ⁇ R2 ⁇ R3 ⁇ R4 ⁇ g independently selected from C1-C26 alkyl, alkenyl, hydroxyalkyl, benzyl, alkylbenzyl, alkenylbenzyl, benzylalkyl, benzylalkenyl and X is an anion.
  • the hydrocarbyl groups R 1 , R 2 , R 3 and R4 can independently be alkoxylated, preferably ethoxylated or propoxylated, more preferably ethoxylated with groups of the general formula (C2H4 ⁇ ) x H where x has a value from
  • R 2 , R 3 or R ⁇ should be benzyl.
  • the hydrocarbyl groups R , R2, R3 and R ⁇ can independently comprise one or more, preferably two, ester- ([-O-C(O)-]; [-C(O)-O-]) and/or an amido-groups ([O-N(R)-]; [-N(R)-O-]) wherein R is defined as R* above.
  • the anion X may be selected from halide, methysulfate, acetate and phosphate, preferably from halide and methylsulfate, more preferably from chloride and bromide.
  • the R1, R 2 , R3 and R ⁇ hydrocarbyl chains can be fully saturated or unsaturated with varying Iodine value, preferably with an Iodine value of from 0 to 140. At least 50% of each long chain alkyl or alkenyl group is predominantly linear, but also branched and/or cyclic groups are included.
  • the preferred alkyl chain length for R* is C12-C15 and preferred groups for R 2 , R3 and R* are methyl and hydroxyethyl.
  • the preferred overall chain length is Cjg, though combinations of chain lengths having non-zero proportions of lower, e.g., Cj2 C14, C ⁇ and some higher, e.g., C20 chains can be quite desirable.
  • Preferred ester-containing emulsifiers have the general formula
  • each R5 group is independently selected from Ci .4 alkyl, hydroxyalkyl or C2.4 alkenyl; and wherein each Rg is independently selected from Cg_28 alkyl or alkenyl groups; E is an ester moiety i.e., -OC(O)- or -C(O)O-, n is an integer from 0 to 5, and X ' is a suitable anion, for example chloride, methosulfate and combinations thereof.
  • a second type of preferred ester-containing cationic emulsifiers can be represented by the formula: ⁇ (R5) 3 N(CH 2 ) n CH(O(O)CR6)CH2O(O)CR 6 ⁇ + X " wherein R 5 , Rg, X, and n are defined as above.
  • This latter class can be exemplified by 1,2 bis[hardened tallowoyloxy]-3- trimethylammonium propane chloride.
  • the cationic emulsifiers, suitable for use in the blends of the present invention can be either water-soluble, water-dispersible or water-insoluble.
  • Silicone emulsifiers useful herein are nonionic, do not include any nitrogen, and do not include any of the non-functionalized silicones described hereinbefore. Silicone emulsifiers are described for example in “Silicone Surfactants” in the Surfactant Science Series, Volume 86 (Editor Randal M. Hill), Marcel Dekker, NY, 1999. See especially Chapter 2, “Silicone Polyether Copolymers: Synthetic Methods and Chemical Compositions and Chapter 1, "Siloxane Surfactants”.
  • Especially suitable silicone emulsifiers are polyalkoxylated silicones corresponding to those of the structural Formula I set forth hereinbefore wherein R 1 is selected from the definitions set forth hereinbefore and from poly(ethyleneoxide/propyleneoxide) copolymer groups having the general formula (II):
  • R 1 being such a poly(ethyleneoxy/propyleneoxy) copolymer group, and each R ⁇ is independently selected from the group consisting of hydrogen, an alkyl having 1 to 4 carbon atoms, and an acetyl group; and wherein the index w has a value such that the viscosity of the resulting silicone emulsifier ranges from 0.00002 m 2 /sec to 0.2 m 2 /sec.
  • Emulsifier Diluents are Emulsifier Diluents:
  • the emulsifier may also optionally be diluted with a solvent or solvent system before emulsification of the silicone blend.
  • a solvent or solvent system before emulsification of the silicone blend.
  • the diluted emulsifier is added to the pre-formed silicone blend.
  • Suitable solvents can be aqueous or non-aqueous; and can include water alone or organic solvents alone and/or combinations thereof.
  • Preferred organic solvents include monohydric alcohols, dihydric alcohols, polyhydric alcohols, ethers, alkoxylated ethers, low- viscosity silicone-containing solvents such as cyclic dimethyl siloxanes and combinations thereof.
  • glycerol glycols, polyalkylene glycols such as polyalkylene glycols, dialkylene glycol mono C j -Cg ethers and combinations thereof. Even more preferred are diethylene glycol mono ethyl ether, diethylene glycol mono propyl ether, diethylene glycol mono butyl ether, and combinations thereof. Highly preferred are combinations of solvents, especially combinations of lower aliphatic alcohols such as ethanol, propanol, butanol, isopropanol, and/or diols such as 1,2- propanediol or 1,3-pro ⁇ anediol; or combinations thereof with dialkylene glycol mono Cj-Cg ethers and/or glycols and or water. Suitable monohydric alcohols especially include C1-C4 alcohols.
  • the silicone blend as hereinbefore described will generally comprise from 0.05% to 10% by weight of the liquid detergent composition. More preferably, the silicone blend will comprise from 0.1% to 5.0%, even more preferably from 0.25% to 3.0%, and most preferably from 0.5% to 2.0%, by weight of the liquid detergent composition.
  • the silicone blend will generally be added to some or all of the other liquid detergent composition components under agitation to disperse the blend therein.
  • the silicone blend either having added emulsifiers present or absent, will be present in the form of droplets.
  • such droplets will generally have a median silicone particle size of from 0.5 ⁇ m to 300 ⁇ m, more preferably from 0.5 ⁇ m to 100 ⁇ m and even more preferably from 0.6 ⁇ m to 50 ⁇ m.
  • particle size may be measured by means of a laser scattering technique, using a Coulter LS 230 Laser Diffraction Particle Size Analyser from Coulter Corporation, Miami, Florida, 33196, USA). Particle sizes are measured in volume weighted % mode, calculating the median particle size.
  • Another method which can be used for measuring the particle size is by means of a microscope, using a microscope manufactured by Nikon® Corporation, Tokyo, Japan; type Nikon® E-1000 (enlargement 700X).
  • liquid detergent compositions of the present invention must contain water as well as an additional non-silicone laundry adjunct selected from detersive enzymes, dye transfer inhibiting agents, optical brighteners, suds suppressors, and combinations thereof.
  • the liquid detergent compositions herein are aqueous in nature. Accordingly, the detergent compositions herein will contain at least 4% by weight of water. More preferably such compositions will contain at least 20% by weight of water, even more preferably at least 50% by weight of water.
  • the laundry adjuncts may also comprise one or more detersive enzymes. Suitable detersive enzymes for use herein include: Proteases like subtilisins from Bacillus [e.g. subtilis, lentus, licheniformis, amyloliquefaciens (BPN, BPN'), alcalophilus,] e.g.
  • Suitable cellulases include those produced by Pseudomonas and Chromobacter groups. Preferred are e.g. Lipolase ⁇ , Lipolase
  • Carbohydrases e.g. mannanase (US6060299), pectate lyase (WO99/27083) cyclomaltodextringlucanotransferase (WO96/33267) xyloglucanase (WO99/02663).
  • Bleaching enzymes eventually with enhancers include e.g. peroxidases, laccases, oxygenases, (e.g. catechol 1,2 dioxygenase, lipoxygenase (WO 95/26393), (non-heme) haloperoxidases .
  • these enzymes are typically present at concentrations from 0.0001% to 2.0%, preferably from 0.0001% to 0.5%, and more preferably from 0.005% to 0.1%, by weight of pure enzyme (weight % of composition).
  • Enzymes can be stabilized using any known stabilizer system like calcium and/or magnesium compounds, boron compounds and substituted boric acids, aromatic borate esters, peptides and peptide derivatives, polyols, low molecular weight carboxylates, relatively hydrophobic organic compounds [e.g.
  • esters dialkyl glycol ethers, alcohols or alcohol alkoxylates], alkyl ether carboxylate in addition to a calcium ion source, benzamidine hypochlorite, lower aliphatic alcohols and carboxylic acids, N,N-bis(carboxymethyl) serine salts; (meth)acrylic acid-(meth)acrylic acid ester copolymer and PEG; lignin compound, polyamide oligomer, glycolic acid or its salts; poly hexamethylene bi guanide or N,N-bis-3-amino-propyl- dodecyl amine or salt; and combinations thereof.
  • the degradation by the proteolytic enzyme of second enzymes can be avoided by protease reversible inhibitors [e.g. peptide or protein type, in particular the modified subtilisin inhibitor of family VI and the plasminostrepin; leupeptin, peptide trifluoromethyl ketones, peptide aldehydes.
  • protease reversible inhibitors e.g. peptide or protein type, in particular the modified subtilisin inhibitor of family VI and the plasminostrepin; leupeptin, peptide trifluoromethyl ketones, peptide aldehydes.
  • the laundry adjuncts may also comprise one or more materials effective for inhibiting the transfer of dyes from one fabric to another.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and combinations thereof. If used, these agents typically are present at concentrations from 0.01% to 10%, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%, by weight of the composition.
  • polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-A x -Z; wherein Z is a polymerizable unit to which an
  • N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units;
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-O group can be represented by the following general structures:
  • R ⁇ , R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water- soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and combinations thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1:4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpyrrolidone (“PVP”) having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
  • compositions herein may comprise from 0.01% to 2.0% by weight of an optical brightener.
  • Suitable optical brighteners include stilbene brighteners.
  • Stilbene brighteners are aromatic compounds with two aryl groups separated by an alkylene chain.
  • Optical brighteners are described in greater detail in U.S. Patents 4,309,316; 4,298,490; 5,035,825 and 5,776,878.
  • compositions may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.1% to 5% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise any known antifoam compound, including silicone-based antifoam compounds and 2-alkyl alcanol antifoam compounds.
  • Preferred silicone antifoam compounds are generally compounded with silica and include the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof, which are described in US 2,954,347.
  • a preferred particulate suds suppressing system is described in EP-A-0210731.
  • a preferred suds suppressing system in particulate form is described in EP-A-0210721.
  • the liquid laundry detergent compositions of the present invention must be essentially free of any coacervate phase-forming polymer or cationic deposition aid. Essentially free means less than 0.01%, preferably less than 0.005%, more preferably less than 0.001% by weight of the composition, and most preferably completely or totally free of any coacervate phase-forming polymer and of any cationic deposition aid.
  • a coacervate phase-forming polymer is any polymer material which will react, interact, complex or coacervate with any of the composition components to form a coacervate phase.
  • coacervate phase includes all kinds of separated polymer phases known by the person skilled in the art such as disclosed in L. Piculell & B. Lindman, Adv. Colloid Interface Sci., 41 (1992) and in B. Jonsson, B. Lindman, K. Holmberg, & B. Kronberb, "Surfactants and Polymers In Aqueous Solution", John Wiley & Sons, 1998.
  • a cationic deposition aid is a polymer which has cationic, functional substituents and which serve to enhance or promote the deposition onto fabrics of one or more fabric care agents during laundering operations.
  • Many but not all cationic deposition aids are also coacervate phase-forming polymers. Whether or not a cationic deposition aid forms a coacervate or whether or not a coacervate phase-forming polymer acts as a deposition aids, neither of these two polymer types can be significantly present in the detergent compositions of this invention.
  • compositions may optionally comprise one or more optional composition components, such as liquid carriers, detergent builders and chelating agents including organic carboxylate builders such as citrate and fatty acid salts, stabilizers and structurants such as hydrogenated castor oil and its derivatives, coupling agents, fabric substantive perfumes, cationic nitrogen-containing detersive surfactants, pro-perfumes, bleaches, bleach activators, bleach catalysts, enzyme stabilizing systems, soil release polymers, dispersants or polymeric organic builders including water-soluble polyacrylates, acrylate / maleate copolymers and the like, dyes, colorants, filler salts such as sodium sulfate, hydrotropes such as toluenesulfonates, cumenesulfonates and naphthalenesulfonates, photoactivators, hydrolyzable surfactants, preservatives, anti-oxidants, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, color speckles,
  • liquid detergent compositions of the present invention can be prepared in any suitable manner and can, in general, involve any order of combining or addition as known by the person skilled in the art. As indicated, the silicone blend is generally preformed and then added to the balance of the liquid detergent components.
  • the final liquid laundry detergent composition is formulated by combining a pre-formed silicone blend, which is optionally emulsified with an emulsifier, with at least one surfactant and further at least one additional requisite non-silicone laundry adjunct.
  • the surfactant and the laundry adjunct may optionally pre-mixed prior to combination with the, optionally emulsified, pre-formed silicone blend.
  • 1,003.3 g (3.86 mol) of aminoethylaminopropylmethyldimethoxysilane, 1,968 g of a siloxane of the composition M2D25 and 29.7 g of a 10% strength solution of KOH in methanol are mixed with one another in a four-necked flask at room temperature, while stirring.
  • 139 g (7.72 mol) of deionized water are added dropwise to the cloudy mixture, and the temperature rises to 46 °C.
  • the temperature is increased stepwise to 125 °C in the course of 3 hours, with a methanol- containing distillate (363 g) being removed from 80 °C.
  • the product obtained is analyzed for reactive group content using NMR spectroscopy methods.
  • NMR spectroscopy methods involve the following parameters:
  • Such a material has a nitrogen content of 0.34% by weight and a percent ratio of terminal curable/reactive groups of essentially 0%.
  • a final 7.14g water is added and the stirring speed is increased to 400RPM. The mixture is stirred at this speed for 40 minutes.
  • Step 2 aminosilicone 15.0 g of the Step 2 aminosilicone are added to 45.0 g of PDMS 0.6 m/s 2 (600,000 centistokes at 20 °C; GE® Visc-600M) and mixed with a normal laboratory blade mixer (type: IKA Labortechnik Eurostar power control-vise lab mixer) for at least 1 hour.
  • 30.0g of the blend of Step 2 aminosilicone with PDMS 0.6m/s 2 are added to 4.30g of Crill 4 sorbitan oleate ex Croda and mixed with a normal laboratory blade mixer at 300RPM for 15 minutes.
  • Neodol 25-3 ex Shell and 4.6g of Slovasol 458 ex Sasol (ethoxylated alcohol nonionic) and stirred for 10 minutes at 300RPM. lO.Og water is added and the mixture is stirred for 30 minutes at 300 RPM.
  • premix El 104.9g is added to 1500 g of either premixes Al or A2 or A3 and stirred for 15 min at 350RPM with a normal laboratory blade mixer.
  • premix E2 78.0g of premix E2 is added to 1500 g of either premixes Al or A2 or A3 and stirred for 15 min at 350RPM with a normal laboratory blade mixer.
  • the mean particle size in the Al, A2 or A3 products is in the 2 ⁇ m- 20 ⁇ m range.
  • the liquid laundry detergent compositions of composition Entries 1 to 12 all demonstrate excellent product stability as fully formulated composition as well as in diluted form during a laundering cycle.
  • the liquid laundry detergent compositions of composition Entries 1 to 12 all provide excellent fabric cleaning and fabric care performance when added to the drum of an automatic washing machine wherein fabric are there and thereinafter laundered in conventional manner.
  • compositions of Entries 1 to 12 are particularly advantageous with respect to fabric softening benefits imparted to fabrics treated therewith; this is especially true for colored fabrics on which the observed fabric softening benefits are even more enhanced in comparison to the fabric softening benefits provided onto white fabrics.
  • the compositions of Entries 1, 2, 3, 10, 11, and 12 are also advantageous with respect to anti-abrasion benefits and to anti-pilling benefits provided for fabrics treated therewith.
  • the compositions of Entries 1, 2, 3, 10, 11, and 12 are particularly advantageous with respect to color care benefits imparted to fabrics treated therewith.

Abstract

Cette invention concerne des compositions détergentes à lessive liquides aqueuses servant à nettoyer et à entretenir les textiles lavés avec ces compositions . Ces compositions comprennent (A) au moins un tensioactif détergent; (B) quelques gouttes d'un mélange de silicone comprenant un polysiloxane fonctionnalisé ammonium ou amino contenant de l'azote et un polysiloxane fonctionnalisé dépourvu d'azote; et (C) au moins un additif de lessive non silicone supplémentaire sélectionné parmi des enzymes détergentes, des agents inhibiteurs de transfert de colorants, des azurants optiques, des suppresseurs d'eau savonneuse, ainsi que des combinaisons de ceux-ci. Le composant polysiloxane fonctionnalisé du mélange silicone présente une teneur relativement faible, autrement dit inférieure à 30 % en mol, en groupes réactifs/durcissables, une teneur en azote comprise entre 0,05 % et 0,50 % en poids et une viscosité comprise entre 0,00002 m2/s et 0,2 m2/s. Le matériau polysiloxane non fonctionnalisé dépourvu d'azote présente une viscosité comprise entre 0,01 m2/s et 2,0 m2/s. Ces compositions ne peuvent pas aussi contenir des polymères de formation de phase coacervée et/ou des agents cationiques facilitant le dépôt.
PCT/US2005/001005 2004-04-16 2005-01-12 Compositions detergentes a lessive liquides a agents d'entretien des textiles silicone WO2005105969A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
MXPA06011880A MXPA06011880A (es) 2004-04-16 2005-01-12 Composiciones detergentes liquidas para lavanderia con agentes de siliconas para el cuidado de las telas.
CA002561997A CA2561997A1 (fr) 2004-04-16 2005-01-12 Compositions detergentes a lessive liquides a agents d'entretien des textiles silicone
EP05705592A EP1735420A1 (fr) 2004-04-16 2005-01-12 Compositions detergentes a lessive liquides a agents d'entretien des textiles silicone
BRPI0509921-8A BRPI0509921A (pt) 2004-04-16 2005-01-12 composições detergentes lìquidas para lavagem de roupas com agentes de silicone para tratamento de tecidos
JP2007507304A JP2007532716A (ja) 2004-04-16 2005-01-12 シリコーン布地ケア剤を含む液体洗濯洗剤組成物

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US8038729B2 (en) 2007-06-15 2011-10-18 Ecolab Usa Inc. Liquid fabric conditioner composition and method of use
WO2014079622A1 (fr) * 2012-11-20 2014-05-30 Unilever Plc Ingrédient destiné à être utilisé dans une composition de lessive
WO2014079620A1 (fr) * 2012-11-20 2014-05-30 Unilever Plc Compositions pour lessive
US9506015B2 (en) 2014-11-21 2016-11-29 Ecolab Usa Inc. Compositions to boost fabric softener performance
US9688945B2 (en) 2014-11-21 2017-06-27 Ecolab Usa Inc. Compositions to boost fabric softener performance
US9725679B2 (en) 2014-11-21 2017-08-08 Ecolab Usa Inc. Compositions to boost fabric softener performance

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CA2560587C (fr) * 2004-04-16 2011-09-13 The Procter & Gamble Company Compositions detergentes liquides pour le lavage du linge, presentant des melanges de silicones servant d'agents adoucissants
CN105199107A (zh) * 2015-11-09 2015-12-30 齐齐哈尔大学 一种新型氨基硅油的合成方法
CN111057624A (zh) * 2019-12-19 2020-04-24 威莱(广州)日用品有限公司 一种杀菌护色防串色浓缩洗衣液及其制备方法

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US8038729B2 (en) 2007-06-15 2011-10-18 Ecolab Usa Inc. Liquid fabric conditioner composition and method of use
US9150819B2 (en) 2007-06-15 2015-10-06 Ecolab Usa Inc. Solid fabric conditioner composition and method of use
US10113139B2 (en) 2007-06-15 2018-10-30 Ecolab Usa Inc. Solid fabric conditioner composition and method of use
US10233407B2 (en) 2007-06-15 2019-03-19 Ecolab Usa Inc. Liquid fabric conditioner composition and method of use
WO2014079622A1 (fr) * 2012-11-20 2014-05-30 Unilever Plc Ingrédient destiné à être utilisé dans une composition de lessive
WO2014079620A1 (fr) * 2012-11-20 2014-05-30 Unilever Plc Compositions pour lessive
US9506015B2 (en) 2014-11-21 2016-11-29 Ecolab Usa Inc. Compositions to boost fabric softener performance
US9688945B2 (en) 2014-11-21 2017-06-27 Ecolab Usa Inc. Compositions to boost fabric softener performance
US9725679B2 (en) 2014-11-21 2017-08-08 Ecolab Usa Inc. Compositions to boost fabric softener performance
US10415003B2 (en) 2014-11-21 2019-09-17 Ecolab Usa Inc. Compositions to boost fabric softener performance
US10947481B2 (en) 2014-11-21 2021-03-16 Ecolab Usa Inc. Compositions to boost fabric softener performance
US11466233B2 (en) 2014-11-21 2022-10-11 Ecolab Usa Inc. Compositions to boost fabric softener performance

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EP1735420A1 (fr) 2006-12-27
BRPI0509921A (pt) 2007-09-18
CA2561997A1 (fr) 2005-11-10
JP2007532716A (ja) 2007-11-15
CN1942572A (zh) 2007-04-04

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