WO2017191462A1 - Composition - Google Patents

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Publication number
WO2017191462A1
WO2017191462A1 PCT/GB2017/051252 GB2017051252W WO2017191462A1 WO 2017191462 A1 WO2017191462 A1 WO 2017191462A1 GB 2017051252 W GB2017051252 W GB 2017051252W WO 2017191462 A1 WO2017191462 A1 WO 2017191462A1
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WIPO (PCT)
Prior art keywords
percent
units
residues
formula
moles
Prior art date
Application number
PCT/GB2017/051252
Other languages
French (fr)
Inventor
Arianna BAU
Sylvie FERDINAND
Raquel LAFUENTE SERRA
Sara Quaggia
Alberto Simionato
Luca Spadoni
Original Assignee
Reckitt Benckiser Vanish B.V.
Reckitt Benckiser (Brands) Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Reckitt Benckiser Vanish B.V., Reckitt Benckiser (Brands) Limited filed Critical Reckitt Benckiser Vanish B.V.
Priority to EP17723480.4A priority Critical patent/EP3452568B1/en
Priority to CN201780041800.XA priority patent/CN109415657B/en
Priority to AU2017259313A priority patent/AU2017259313B2/en
Publication of WO2017191462A1 publication Critical patent/WO2017191462A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • C11D3/0015Softening compositions liquid
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742Nitrogen containing silicones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/12Soft surfaces, e.g. textile

Definitions

  • the present invention relates to liquid laundry compositions comprising silicone additives. More particularly the present invention relates to the use of silicone additives in
  • liquid laundry compositions to increase the whiteness of laundered fabrics, as well as to improve their ease of ironing, hydrophilicity, and softness.
  • Clothing is a background feature of modern life. A principie issue with the use of clothing is that in wears no: it attracts dirt / soil: both frorn 3 wearer and their surroundinas.
  • Laundry detergent compositions that both clean and soften fabric during a laundering process are known and have been developed and sold by laundry detergent manufacturers for many years.
  • these laundry detergent compositions comprise components that are capable of providing a fabric-softening benefit to the laundered fabric; these fabric-softening components include silicones.
  • washing is of course beneficial but one major issue is that whilst washing cleans and refreshes clothes; soiling in use is stlil inevitable. It would be greatly beneficial if there could be found a way to prevent / slow soiling of garments when they are worn, it would be supremely beneficial if one single composition could be identified which could address this prevention concern as well as providing excellent washing.
  • composition comprising:
  • the liquid detergent product may comprise a laundry detergent product, a carpet detergent product, a hard surface (such as dishware) detergent product.
  • the present invention is directed to a method for washing an item comprising washing said item in the presence of the above composition.
  • the present invention is directed to a method for laundering a textile fabric comprising washing said fabric in the presence of the above composition.
  • the present invention relates to the inclusion of a silicone additive in a liquid laundry product to impart increased whiteness, ease of ironing, and softness to the laundered article.
  • the benefits are delivered to the laundered items either during the wash cycle or the rinse cycle of the wash procedure.
  • the silicone additives improve the properties of detergent compositions and rinse cycle additives. Such additives render the fabric, especially 100 percent cotton will and terry cloth, whiter and brighter than fabrics treated with liquid laundry compositions that do not contain these silicone additives. This increase in whiteness can be detected both visually and spectrophotometrically (reflectance) as measured by a Hunter Colorimeter.
  • fabrics treated with these silicone additives in liquid laundry compositions require less effort to iron, and are softer to the touch than do those treated with liquid laundry compositions that do not contain these additives.
  • the amount of silicone additive employed in the composition of this invention is from 0.01 wt. percent to 25 wt. percent, and more preferably, from 0.1 wt. percent to 10 wt. percent.
  • the silicone additive is selected from the group below. One or more silicone may be used.
  • a silicone resin is a mixture of polyorganosiloxane- silicone resins, where each of the one or more silicone resins of the polyorganosiloxane- silicone resin mixture contains at least about 80 mole percent of units selected from the group consisting of units of the general formulas 3, 4, 5, 6:
  • R is selected from H, -OR 10 , or -OH residues or monovalent hydrocarbon residues with 1 to 40 carbon atoms, optionally substituted with halogens, where at least 20 mole percent of the units are selected from the group consisting of units of the general formulas 5 and 6, and a maximum of 10 wt. percent of the R residues are -OR 10 and -OH residues.
  • the silicone resins may preferably be MQ silicon resins (MQ) comprising at least 80 mole percent of units, preferably at least 95 mole percent and particularly at least 97 mole percent of units of the general formulae 3 and 6.
  • MQ MQ silicon resins
  • the average ratio of units of the general formulae 3 to 6 is preferably at least 0.25, particularly at least 0.5, preferably at most 4, and more preferably at most 1.5.
  • the silicon resins may also preferably be DT silicone resins (DT) comprising at least 80 mole percent of units, preferably at least 95 mole percent and particularly at least 97 mole percent of units of the general formulae 4 and 5.
  • DT silicone resins comprising at least 80 mole percent of units, preferably at least 95 mole percent and particularly at least 97 mole percent of units of the general formulae 4 and 5.
  • the average ratio of units of the general formulae 4 to 5 is preferably at least 0.01 , particularly at least 0.2, preferably at most 3.5, and more preferably at most 0.5.
  • Preferred halogen substituents of the hydrocarbon residues R are fluorine and chlorine.
  • Preferred monovalent hydrocarbyl radicals R are methyl, ethyl, phenyl.
  • Preferred monovalent hydrocarbyl radicals R 10 are methyl, ethyl, propyl and butyl.
  • Suitable aminosiloxane polymers are represented by of one or more liquid aminoalkyl- containing polyorganosiloxanes (P) comprising at least 80 mole percent of units selected from units of the general formulae 7, 8, 9 and 10 R 1 2 SiO 2 / 2 (7)
  • a has the value 0 or 1
  • b has the value 1 or 2
  • a+b has a value of 2
  • R 1 represents monovalent hydrocarbyl radicals having 1-40 carbon atoms and optionally substituted with halogens
  • R 2 represents either a) aminoalkyl radicals of the general formula 11
  • R 5 represents divalent hydrocarbyl radicals having 1-40 carbon atoms
  • R 6 represents monovalent hydrocarbyl radicals having 1-40 carbon atoms, H,
  • R 7 represents a radical of the general formula 12
  • x has the value 0 or an integer value from 1 to 40, and represents a divalent radical of the general formula:
  • R 9 represents H or hydrocarbyl radicals having 1-40 carbon atoms, or
  • R 3 represents hydrocarbyl radicals having 1-40 carbon atoms and optionally substituted with halogens
  • R 4 represents -OR or -OH radicals, and wherein, in the polyorganosiloxanes (P), the average ratio of the sum of units of the general formulae 7 and 8 to the sum of units of the general formulae 9 and 10 is in the range from 0.5 to 500, the average ratio of units 9 to 10 being in the range from 1.86 to 100, and the polyorganosiloxanes (P) have an average amine number of at least 0.01 mequiv/g.
  • the monohydric hydrocarbyl radicals R, R 1 , R 3 , R 6 , R 9 and R 10 may be halogen substituted, linear, cyclic, branched, aromatic, saturated or unsaturated.
  • the monovalent hydrocarbyl radicals R, R 1 , R 3 , R 6 , R 9 and R 10 each have 1 to 6 carbon atoms, and particular preference is given to alkyl radicals and phenyl radicals.
  • Preferred halogen substituents are fluorine and chlorine.
  • Particularly preferred monovalent hydrocarbyl radicals R, R 1 , R 3 , R 6 , R 9 and R 10 are methyl, ethyl, phenyl.
  • the divalent hydrocarbyl radicals R 5 may be halogen substituted, linear, cyclic, branched, aromatic, saturated or unsaturated.
  • the R 5 radicals have 1 to 10 carbon atoms, and particular preference is given to alkylene radicals having 1 to 6 carbon atoms, in particular propylene.
  • Preferred halogen substituents are fluorine and chlorine.
  • R 5 radicals are alkyl and alkanoyl radicals.
  • Preferred halogen substituents are fluorine and chlorine.
  • Particularly preferred substituents R 6 are methyl, ethyl, cyclohexyl, acetyl and H. It is particularly preferable for the R 6 and R 7 radicals to have the meaning H.
  • Preferred cyclic organic radicals formed from R 6 and R 7 in the general formula 11 together with the attached nitrogen atom are the five and six rings, in particular the residues of pyrrolidine, pyrrolidin-2-one, pyrrolidine-2, -dione, pyrrolidin-3 -one, pyrazol-3-one, oxazolidine, oxazolidin-2 -one, thiazolidine, thiazolidin-2-one, piperidine, piperazine, piperazine-2, 5-dione and morpholine.
  • R 2 radicals are -CH 2 NR 6 R 7 , -(CH 2 ) 3 NR 6 R 7 and -(CH 2 ) 3 N(R 6 )
  • R 2 radicals are aminoethylaminopropyl and cyclohexylaminopropyl.
  • mixtures (M) wherein at least 1 mole percent, more preferably at least 5 mole percent, particularly at least 20 mole percent and at most 90 mole percent, more preferably at most 70 mole percent and particularly at most 60 mole percent of the R 6 and R 7 radicals are acetyl radicals and the remaining R 6 and R 7 radicals have the meaning H.
  • b is 1.
  • a+b has an average value from 1.9 to 2.2.
  • x has the value 0 or a value from 1 to 18, more preferably 1 to 6.
  • y has the values of 1 , 2 or 3.
  • the polydiorganosiloxanes (P) comprise at least 3 and particularly at least 10 units of the general formulae 7 and 8.
  • liquid aminoalkyl-containing polyorganosiloxanes (P) comprise at least 95 mole percent, more preferably at least 98 mole percent and particularly at least 99.5 mole percent of units selected from units of the general formulae 7, 8, 9 and 10.
  • polyorganosiloxanes (P) can be selected for example from units selected from units of the general formulae 3, 4, 5, 6.
  • the ratio of a to b is chosen such that the polyorganosiloxanes (P) preferably have an amine number of at least 0.1 , in particular at least 0.3 mequiv/g of polyorganosiloxane (P).
  • the amine number of the polyorganosiloxanes (P) is preferably at most 7, more preferably at most 4.0 and particularly at most 3.0 mequiv/g of polyorganosiloxane (P).
  • the amine number designates the number of ml of IN HCI which are required for neutralizing 1 g of
  • the viscosity of the polyorganosiloxanes (P) is preferably at least 1 and particularly at least 10 mPa-s and preferably at most 100 000 and particularly at most 10 000 mPa-s at 25 degrees centigrade
  • the ratio of the units of the general formulae 7 and 8 to the sum total of 9 and 10 is preferably at least 10, particularly at least 50 and preferably at most 250, particularly at most 150.
  • the ratio of units 9 to 10 is preferably at least 1.9 and particularly at least 2.0 and preferably at most 70 and particularly at most 50.
  • the polyorganosiloxanes (P) are obtainable via known chemical processes such as, for example, hydrolysis or equilibration.
  • silicones include a Polyorganosiloxane-Silicone Resin Mixture
  • the polyorganosiloxane-silicone resin mixture comprises between about 50 percent to about 99.9 percent by weight of the mixture, of one or more polyorganosiloxane fluid compounds, at least about 0.01 percent by weight of the mixture, of one or more silicone resins, and a maximum of about 5 percent by weight of the mixture, of water. Certain embodiments of the polyorganosiloxane-silicone resin mixture may comprise between about 75 percent to about 98 percent of the polyorganosiloxane fluid compounds. Other embodiments may comprise between about 80 percent to about 90 percent, or alternatively between about 80 percent to about 87 percent of the polyorganosiloxane fluid compounds.
  • certain embodiments of the polyorganosiloxane-silicone resin mixture may comprise between about 0.1 percent and 50 percent, or between about 2 percent and about 30 percent of the silicone resins. Other embodiments of the mixture may comprise between about 5 percent and about 20 percent of the silicone resins.
  • Each of the one or more polyorganosiloxane fluid compounds contains at least 80 mol percent of units selected from the group consisting of units of the general formulae la, lb, II and III:
  • R 1 means monovalent hydrocarbon residues with 1 to 40 carbon atoms, optionally substituted with halogens.
  • R 2 means either a) aminoalkyl residues of the general formula IV: -R 5 -NR 6 R 7 (IV),
  • R 5 means divalent hydrocarbon residues with 1 to 40 carbon atoms
  • R 6 means monovalent hydrocarbon residues with 1 to 40 carbon atoms
  • H hydroxymethyl or alkanoyl residues
  • R 7 means a residue of the general formula V
  • y has an integer value from 1 to 6, and R 9 means H or monovalent hydrocarbon

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A composition comprises : A) a liquid detergent product; and B) asilicone additive

Description

COMPOSITION
The present invention relates to liquid laundry compositions comprising silicone additives. More particularly the present invention relates to the use of silicone additives in
liquid laundry compositions to increase the whiteness of laundered fabrics, as well as to improve their ease of ironing, hydrophilicity, and softness.
Clothing is a background feature of modern life. A principie issue with the use of clothing is that in wears no: it attracts dirt / soil: both frorn 3 wearer and their surroundinas.
Laundry detergent compositions that both clean and soften fabric during a laundering process are known and have been developed and sold by laundry detergent manufacturers for many years. Typically, these laundry detergent compositions comprise components that are capable of providing a fabric-softening benefit to the laundered fabric; these fabric-softening components include silicones.
Such washing is of course beneficial but one major issue is that whilst washing cleans and refreshes clothes; soiling in use is stlil inevitable. It would be greatly beneficial if there could be found a way to prevent / slow soiling of garments when they are worn, it would be supremely beneficial if one single composition could be identified which could address this prevention concern as well as providing excellent washing.
It is an on object of the present invention to address these problems.
According to a first aspect of the invention there is provided a composition comprising:
A) a liquid detergent product; and B) a silicone additive preferably selected from the group outlined below.
The liquid detergent product may comprise a laundry detergent product, a carpet detergent product, a hard surface (such as dishware) detergent product.
In another aspect, the present invention is directed to a method for washing an item comprising washing said item in the presence of the above composition.
In a preferred aspect, the present invention is directed to a method for laundering a textile fabric comprising washing said fabric in the presence of the above composition.
In the most preferred aspect the present invention relates to the inclusion of a silicone additive in a liquid laundry product to impart increased whiteness, ease of ironing, and softness to the laundered article.
The benefits are delivered to the laundered items either during the wash cycle or the rinse cycle of the wash procedure. The silicone additives improve the properties of detergent compositions and rinse cycle additives. Such additives render the fabric, especially 100 percent cotton will and terry cloth, whiter and brighter than fabrics treated with liquid laundry compositions that do not contain these silicone additives. This increase in whiteness can be detected both visually and spectrophotometrically (reflectance) as measured by a Hunter Colorimeter. In addition, fabrics treated with these silicone additives in liquid laundry compositions require less effort to iron, and are softer to the touch than do those treated with liquid laundry compositions that do not contain these additives.
Further benefits include the facilitation of removal of greasy stains; especially on synthetic fabrics. This is postulated to be due to the higher oil repellency given by the formula; particularly on synthetic fibres. A yet further benefit includes colour fixing. In this regard it has been observed that when formula is applied directly (e.g. on a coloured fibrous material) and left for a period such as 24hrs, the colour of the garment is darkened (revived very visibly). It has also been found that a similar effect can be obtained after 10 repeated washing cycles using the formulation in the rinse cycle.
Similar benefits have also been noticed when the composition has been used when applied to carpets, hard surfaces (such as dishware).
The amount of silicone additive employed in the composition of this invention is from 0.01 wt. percent to 25 wt. percent, and more preferably, from 0.1 wt. percent to 10 wt. percent.
The silicone additive is selected from the group below. One or more silicone may be used.
An example of a silicone resin is a mixture of polyorganosiloxane- silicone resins, where each of the one or more silicone resins of the polyorganosiloxane- silicone resin mixture contains at least about 80 mole percent of units selected from the group consisting of units of the general formulas 3, 4, 5, 6:
Figure imgf000003_0001
in which R is selected from H, -OR10, or -OH residues or monovalent hydrocarbon residues with 1 to 40 carbon atoms, optionally substituted with halogens, where at least 20 mole percent of the units are selected from the group consisting of units of the general formulas 5 and 6, and a maximum of 10 wt. percent of the R residues are -OR10 and -OH residues.
The silicone resins may preferably be MQ silicon resins (MQ) comprising at least 80 mole percent of units, preferably at least 95 mole percent and particularly at least 97 mole percent of units of the general formulae 3 and 6. The average ratio of units of the general formulae 3 to 6 is preferably at least 0.25, particularly at least 0.5, preferably at most 4, and more preferably at most 1.5.
The silicon resins may also preferably be DT silicone resins (DT) comprising at least 80 mole percent of units, preferably at least 95 mole percent and particularly at least 97 mole percent of units of the general formulae 4 and 5. The average ratio of units of the general formulae 4 to 5 is preferably at least 0.01 , particularly at least 0.2, preferably at most 3.5, and more preferably at most 0.5.
Preferred halogen substituents of the hydrocarbon residues R are fluorine and chlorine. Preferred monovalent hydrocarbyl radicals R are methyl, ethyl, phenyl.
Preferred monovalent hydrocarbyl radicals R10 are methyl, ethyl, propyl and butyl.
Suitable aminosiloxane polymers are represented by of one or more liquid aminoalkyl- containing polyorganosiloxanes (P) comprising at least 80 mole percent of units selected from units of the general formulae 7, 8, 9 and 10 R1 2SiO2/2 (7)
R1aR2bSiO(4-a-b)/2 (8),
R33SiO{1/2) (9),
R3 2RSiO{1/2) (10),
where a has the value 0 or 1 , b has the value 1 or 2, a+b has a value of 2,
R1 represents monovalent hydrocarbyl radicals having 1-40 carbon atoms and optionally substituted with halogens,
R2 represents either a) aminoalkyl radicals of the general formula 11
-R5-NR6R7 (11)
where
R5 represents divalent hydrocarbyl radicals having 1-40 carbon atoms,
R6 represents monovalent hydrocarbyl radicals having 1-40 carbon atoms, H,
hydroxymethyl or alkanoyl radicals, and
R7represents a radical of the general formula 12
- (R8-NR6)xR5 (12)
where
x has the value 0 or an integer value from 1 to 40, and represents a divalent radical of the general formula:
- (CRV)y (13)
where y has an integer value from 1 to 6,
and R9 represents H or hydrocarbyl radicals having 1-40 carbon atoms, or
b) in the general formula 11 R6 and R7 combine with the nitrogen atom to form a cyclic organic radical having 3 to 8 -CH2- units, although nonadjacent -CH2- units may be replaced by units selected from -C(=O)-, -NH-, -O- and -S-,
R3 represents hydrocarbyl radicals having 1-40 carbon atoms and optionally substituted with halogens,
R4 represents -OR or -OH radicals, and wherein, in the polyorganosiloxanes (P), the average ratio of the sum of units of the general formulae 7 and 8 to the sum of units of the general formulae 9 and 10 is in the range from 0.5 to 500, the average ratio of units 9 to 10 being in the range from 1.86 to 100, and the polyorganosiloxanes (P) have an average amine number of at least 0.01 mequiv/g. The monohydric hydrocarbyl radicals R, R1 , R3, R6, R9 and R10 may be halogen substituted, linear, cyclic, branched, aromatic, saturated or unsaturated. Preferably, the monovalent hydrocarbyl radicals R, R1 , R3, R6, R9 and R10 each have 1 to 6 carbon atoms, and particular preference is given to alkyl radicals and phenyl radicals. Preferred halogen substituents are fluorine and chlorine. Particularly preferred monovalent hydrocarbyl radicals R, R1 , R3, R6, R9 and R10 are methyl, ethyl, phenyl.
The divalent hydrocarbyl radicals R5 may be halogen substituted, linear, cyclic, branched, aromatic, saturated or unsaturated. Preferably, the R5 radicals have 1 to 10 carbon atoms, and particular preference is given to alkylene radicals having 1 to 6 carbon atoms, in particular propylene. Preferred halogen substituents are fluorine and chlorine.
Preferred R5 radicals are alkyl and alkanoyl radicals.
Preferred halogen substituents are fluorine and chlorine.
Preferred alkanoyl radicals are -C(=O)R11, where R11 has the meanings and preferred meanings of R1. Particularly preferred substituents R6 are methyl, ethyl, cyclohexyl, acetyl and H. It is particularly preferable for the R6 and R7 radicals to have the meaning H.
Preferred cyclic organic radicals formed from R6 and R7 in the general formula 11 together with the attached nitrogen atom are the five and six rings, in particular the residues of pyrrolidine, pyrrolidin-2-one, pyrrolidine-2, -dione, pyrrolidin-3 -one, pyrazol-3-one, oxazolidine, oxazolidin-2 -one, thiazolidine, thiazolidin-2-one, piperidine, piperazine, piperazine-2, 5-dione and morpholine.
Particularly preferred R2 radicals are -CH2NR6R7, -(CH2)3NR6R7 and -(CH2)3N(R6)
(CH2)2N(R6)2. Examples of particularly preferred R2 radicals are aminoethylaminopropyl and cyclohexylaminopropyl.
Preference is also given to mixtures (M) wherein at least 1 mole percent, more preferably at least 5 mole percent, particularly at least 20 mole percent and at most 90 mole percent, more preferably at most 70 mole percent and particularly at most 60 mole percent of the R6 and R7 radicals are acetyl radicals and the remaining R6 and R7 radicals have the meaning H.
Preferably, b is 1. Preferably, a+b has an average value from 1.9 to 2.2.
Preferably, x has the value 0 or a value from 1 to 18, more preferably 1 to 6. Preferably, y has the values of 1 , 2 or 3.
Preferably, the polydiorganosiloxanes (P) comprise at least 3 and particularly at least 10 units of the general formulae 7 and 8.
Preferably, the liquid aminoalkyl-containing polyorganosiloxanes (P) comprise at least 95 mole percent, more preferably at least 98 mole percent and particularly at least 99.5 mole percent of units selected from units of the general formulae 7, 8, 9 and 10.
Further units of the polyorganosiloxanes (P) can be selected for example from units selected from units of the general formulae 3, 4, 5, 6.
The ratio of a to b is chosen such that the polyorganosiloxanes (P) preferably have an amine number of at least 0.1 , in particular at least 0.3 mequiv/g of polyorganosiloxane (P). The amine number of the polyorganosiloxanes (P) is preferably at most 7, more preferably at most 4.0 and particularly at most 3.0 mequiv/g of polyorganosiloxane (P). The amine number designates the number of ml of IN HCI which are required for neutralizing 1 g of
polyorganosiloxane (P).
The viscosity of the polyorganosiloxanes (P) is preferably at least 1 and particularly at least 10 mPa-s and preferably at most 100 000 and particularly at most 10 000 mPa-s at 25 degrees centigrade
The ratio of the units of the general formulae 7 and 8 to the sum total of 9 and 10 is preferably at least 10, particularly at least 50 and preferably at most 250, particularly at most 150.
The ratio of units 9 to 10 is preferably at least 1.9 and particularly at least 2.0 and preferably at most 70 and particularly at most 50.
The polyorganosiloxanes (P) are obtainable via known chemical processes such as, for example, hydrolysis or equilibration.
Other silicones may also be present.
Other silicones include a Polyorganosiloxane-Silicone Resin Mixture
The polyorganosiloxane-silicone resin mixture comprises between about 50 percent to about 99.9 percent by weight of the mixture, of one or more polyorganosiloxane fluid compounds, at least about 0.01 percent by weight of the mixture, of one or more silicone resins, and a maximum of about 5 percent by weight of the mixture, of water. Certain embodiments of the polyorganosiloxane-silicone resin mixture may comprise between about 75 percent to about 98 percent of the polyorganosiloxane fluid compounds. Other embodiments may comprise between about 80 percent to about 90 percent, or alternatively between about 80 percent to about 87 percent of the polyorganosiloxane fluid compounds. Additionally, certain embodiments of the polyorganosiloxane-silicone resin mixture may comprise between about 0.1 percent and 50 percent, or between about 2 percent and about 30 percent of the silicone resins. Other embodiments of the mixture may comprise between about 5 percent and about 20 percent of the silicone resins.
Each of the one or more polyorganosiloxane fluid compounds contains at least 80 mol percent of units selected from the group consisting of units of the general formulae la, lb, II and III:
R1 2SiO(2/2) (la),
R1aR2bSiO(2/2) (lb),
R33SiO(1/2) (II),
R3 2R4SiO(1/2) (III),
in which a has the value 0, 1 or 2, b has the value 1 or 2, and the sum of a and b is equal to 2. R1 means monovalent hydrocarbon residues with 1 to 40 carbon atoms, optionally substituted with halogens. R2 means either a) aminoalkyl residues of the general formula IV: -R5-NR6R7 (IV),
wherein R5 means divalent hydrocarbon residues with 1 to 40 carbon atoms, R6 means monovalent hydrocarbon residues with 1 to 40 carbon atoms, H, hydroxymethyl or alkanoyl residues, and R7 means a residue of the general formula V
-(R8-NR6)xR6 (V),
wherein x has the value 0 or an integer value from 1 to 40, and R8 means a divalent residue of the general formula VI
-(CR92-)y- (VI),
wherein y has an integer value from 1 to 6, and R9 means H or monovalent hydrocarbon

Claims

residues with 1 to 40 carbon atoms, or b) aminoalkyl residues of the general formula IV wherein R6 and R7 together with the N atom forms a cyclic organic residue with 3 to 8 -CH2- units, and where nonadjacent -CH2- units can be replaced by units that are chosen from -C(- O)-, -NH-, -0-, and -S-. R3 means monovalent hydrocarbon residues with 1 to 40 carbon atoms optionally substituted with halogens. R4 means the residues -OR -OH, wherein R means monovalent hydrocarbon residues with 1 to 40 carbon atoms, optionally substituted with halogens. Additionally, the average ratio of the sum of units of formulae la and lb to the sum of units of formulae II and III within the one or more polyorganosiloxane fluid compounds may range from about 0.5 to about 500. The average ratio of units of formula II to the units of formula III within the one or more polyorganosiloxane fluid compounds may range from about 1.86 to about 100. The one or more polyorganosiloxane fluid compounds have an average amine number of at least about 0.01 meq/g of polyorganosiloxane fluid compounds. The monovalent hydrocarbon residues R, R1, R3, R6, R9 and R10 can be halogen-substituted, linear, cyclic, branched, aromatic, saturated or unsaturated. Some embodiments of the monovalent hydrocarbon residues R, R1 , R3, R6, R9 and R10 have from 1 to 6 carbon atoms, including alkyl residues and phenyl residues. Certain embodiments have halogen substituents such as fluorine and/or chlorine. Monovalent hydrocarbon residues R, R1 , R3, R6, R9 and R10methyl, ethyl and phenyl are useful in the present compositions. The divalent hydrocarbon residues R5 can be halogen substituted, linear, cyclic, branched, aromatic, saturated or unsaturated. The residues R5 may have from 1 to 10 carbon atoms. Alkylene residues with 1 to 6 carbon atoms, including propylene, are especially useful embodiments. If R5 is halogenated, the halogen substituents may be fluorine and chlorine.Residues R5 may be alkyl and/or alkanoyl residues. Embodiments of R6 may contain halogen substituents such as fluorine and chlorine. Embodiments of R^/vhich are alkanoyl residues may have the general formula -C(-O)OR11 , where R11 has the meanings and preferred meanings of R1 described above. Especially preferred substituents R6 are methyl, ethyl, cyclohexyl, acetyl and hydrogen. Cyclic organic residues may be formed from the connection of R6 and R7 in the general formula IV together with the bonded N atom. These cyclic residues include pentacycles and hexacycles, such as the residues of pyrrolidine, pyrrolidin-2-one, pyrrolidin-2,4-dione, pyrrolidin-3-one, pyrazol-3-one, oxazolidine, oxazolidin-2-one, thiazolidine, thiazolidin-2-one, piperidine, piperazine, piperazin-2,5-dione and morpholine. Embodiments of the residues R2 include -CH2NR6R7, -(CH2)3NR6R7, -(CH2)3N(R6), and - (CH2)2N(R6)2. Examples include the aminoethylaminopropyl and cyclohexylaminopropyl residues. In certain embodiments of the polyorganosiloxane fluid b has the value 1 or 2. Some embodiments have the sum of a+b having an average value of from about 1.9 to about 2.2.In some useful embodiments the ratio of a to b is chosen so that the polyorganosiloxane fluid compounds have an amine number of at least about 0.1 , and some at least 0.3, meq/g polyorganosiloxane fluid compound. The amine number designates the number of millilitres of 1 N hydrochloric acid which are required for neutralizing 1 gram of polyorganosiloxane fluid. Some embodiments have the amine number of the polyorganosiloxane fluid is being a maximum of about 7. Others have a maximum of about 2.0, and yet others have a maximum of 1.0 meq/g polyorganosiloxane fluid, x may have the value of 0 or a value from 1 to 18. Certain embodiments have x being from 1 to 6. Certain embodiments of the fluid have y having a value of 1 , 2 or 3. The polydimethylsiloxane fluids contain at least 3, especially at least 10 units of the general formula I. The viscosity of the polyorganosiloxane fluid compounds is at least about 1 mPa-s at 25 degrees centigrade, especially at least about 10 mPa-s, and has a maximum of about 100,000, especially at least about 10,000 mPa s, Certain embodiments of the polyorganosiloxane fluid compound have a viscosity of at least about 100 mPa-s and a maximum of 5,000 mPa-s, at 25 degrees centigrade The average ratio of the units of the general formula I to the sum of units II and III may range from about 0.5 to about 500. In certain embodiments the ratio may be at least about 10, particularly at least about 50 and range to a maximum of about 250, particularly a maximum of about 150. The ratio of the units II to units III may range from about 1.86 to about 100. Useful embodiments may have this ratio being at least about 3 and may range to a maximum of about 70. Other embodiments may have this ration being at least about 6 or at least about 10, and may range to a maximum of about 50. Each of the one or more silicone resins of the polyorganosiloxane-silicone resin mixture contains at least 80 mol percent of units selected from the group consisting of units of the general formulas VII, VIII, IX and X in which R10 means H, -OR or -OH residues or monovalent hydrocarbon residues with 1 to 40 carbon atoms, optionally substituted with halogens. Certain useful embodiments of the polyorganosiloxane-silicone resin mixture may comprise silicone resins comprising at least about 90 percent, at least about 95 percent, or at least about 98 percent of units selected from the group consisting of units of the general formulas VII, VIII, IX and X. The silicone resins are preferably MQ silicone resins (MQ) comprising at least 80 mol percent of units, preferably at least 95 mol percent and particularly at least 97 mol percent of units of the general formulae VII and X. The average ratio of units of the general formulae VII to X is preferably at least 0.25, particularly at least 0.5 and preferably 4, more preferably at most 1.5. The silicone resins (S) are also preferably DT silicone resins (DT) comprising at least 80 mol percent of units, preferably at least 95 mol percent and particularly at least 97 mol percent of units of the general formulae VIII and IX. The average ratio of units of the general formulae VIII to IX is preferably at least 0.01 , particularly at least 0.02 and preferably at most 3.5, more preferably at most particularly at most 0.5. At least 20 mol percent of the units of the silicone resins are selected from the group consisting of units of the general formulas IX and X. Other embodiments comprise silicone resins have at least 40 percent or even 50 percent of units selected from the group consisting of units of the general formulas IX and X, A maximum of 10 wt. percent of the R10 residues in the one or more silicone resins are -OR and -OH residues. In other useful embodiments a maximum of 3 percent or even 1 percent may be desired. The carrier of the surface treatment composition may be any known material, generally, but not necessarily, a liquid useful in delivering the polyorganosiloxane-silicone resin mixture to the surface which is desired to be treated. The carrier may be as simple as a single component delivery vehicle such as water or alcohol which would allow the mixture to be sprayed onto a surface. Alternatively, the carrier may be complex such as a cleaning composition such as a laundry detergent where the mixture would be applied in conjunction with the other beneficial uses of the complex carrier. Preferred examples of silicones includes the following:- with a molecular weight of ~35000; and and Preferably the composition comprises a wax component. it has been observed that the wax component is able io improve the performance of the composition, especially with regard to stain repeiiency performance. Without wishing to be bound by theory it is postulated thai the presence of the wax component aids the deposition and / or integration of the silicone component into/onto the fabric. Preferably the wax component is present in the composition in an amount of from 0.1 to 20wt%, more preferably from 1 to 15wt%, more preferably from 2 to 10wt% and most preferably from 4 to 8 wt%. Preferably the wax component is present In a ration of from 10:1 to 1 : 10; more preferably from 5:1 to 1 :5, more preferably from 3:1 to 1 :3: most preferably from 2: 1 to 1 :2; by weight with reference to the silicone component Preferred wax components Include hydrocarbon oils and edible oils such as vegetable and / or nut oils such as olive oil, sunflower oil, maize oil, rape oil, soya oil, peanut oil, meadowfoam seed oil. linseed oil, walnut oil, sesame oil and thistle oil. Mixtures of more than wax component may be used. Generally the wax component is modified / derivatized such that it is not completely apolar. Preferred moeities for use in derivatization include anionic and / or cationic groups. The wax component may contain one or more derivatization moieties. Preferred derivatisation moieties include ammonium, carboxylate, sulphate, sulphite, sulphonate, nitrate, halogen groups. As certain wax components have poor solubility in water the wax component may be employed in the formulation in a form that aids its incorporation. Preferred forms include one or more of suspension, encapsulation and / or emulsification. To achieve this incorporation auxiliary agents such as solvents and / or surfactants may be employed. Most preferably the hydrophobic component comprises a derivatized paraffin oil (a hydrocarbon having a boiling range of 140 to 300 degrees centigrade - otherwise known as kerosene). A preferred ingredient comprises melaminic paraffin (a melamine and / or derivative thereof (such as an alkylated derivative) in paraffin oil). A preferred example of this is Freepel 1200 BASE (available from Emerald Performance Materials). Another example of this is a fatty acid melamine and paraffin wax emulsion and a polyvinyl alcohol) (such as described in In WO 02/14426). A yet further preferred example includes Arkophob FL 2150 available from Clariant. Optionally the composition comprises from 0.001 percent to 99.99 percent, preferably 0.001 percent to 20 percent, preferably 4 percent to 18 percent, e.g. most preferably about 4.5 percent or 13 percent, by weight, of bleach. The bleach is preferably peroxide bleach, most preferably hydrogen peroxide. Peroxide sources other than H2O2 can be used. Preferably the composition comprises a surfactant. Where present the composition comprises from 0.001 percent to 99.99 percent, preferably 0.05 percent to 40 percent, preferably 10 percent to 30 percent, e.g. about 25 percent, by weight of surfactant. The surfactant is, for example, an anionic or nonionic surfactant or mixture thereof (most preferably a nonionic surfactant). The nonionic surfactant is preferably a surfactant having a formula RO (CH2CH2O)nH where- in R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of repeating units and is a number of from about 1 to about 12. Examples of other non-ionic surfactants include higher aliphatic primary alcohol containing about twelve to about 16 carbon atoms which are condensed with about three to thirteen moles of ethylene oxide. Other examples of nonionic surfactants include primary alcohol ethoxylates (available under the Neodol trade name from Shell Co.), such as Cn alkanol condensed with 9 moles of ethylene oxide (Neodol 1-9), Ci2-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12-i3 alkanol with 9 moles of ethylene oxide (Neodol 23- 9), C12-15 alkanol condensed with 7 or 3 moles ethylene oxide (Neodol 25-7 or Neodol 25-3), C14-15 alkanol con densed with 13 moles ethylene oxide (Neodol 45-13), Cg-n linear ethoxylated alcohol, averaging 2.5 moles of ethylene oxide per mole of alcohol (Neodol 91-2.5), and the like. Other examples of nonionic surfactants suitable for use in the present invention include ethylene oxide condensate products of secondary aliphatic alcohols containing 1 1 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available non-ionic detergents of the foregoing type are Cn-15 secondary alkanol condensed with either 9 moles of ethylene oxide (Tergitol 15-S-9) or 12 moles of ethylene oxide (Tergitol 15-S-12) marketed by Union Carbide, a subsidiary of Dow Chemical. Octylphenoxy polyethoxyethanol type nonionic surfactants, for example, Triton X-100, as well as amine ox ides can also be used as a nonionic surfactant in the present invention. Other examples of linear primary alcohol ethoxylates are available under the Tomadol trade name such as, for ex ample, Tomadol 1-7, a Cn linear primary alcohol ethoxylate with 7 moles EO; Tomadol 25-7, a C12-C15 linear pri mary alcohol ethoxylate with 7 moles EO; Tomadol 45-7, a C14-C15 linear primary alcohol ethoxylate with 7 moles EO; and Tomadol 91-6, a Cg-Cn linear alcohol ethoxylate with 6 moles EO. Other examples of linear primary alcohol ethoxylates are available under the Lutensol trade name such as, for ex ample, Lutensol A3N, a C13-15 linear primary alcohol eth- oxylate with 3 moles EO; Lutensol LA60, a C13-15 linear primary alcohol ethoxylate with 7 moles EO. Also Ge- napol such as, for example, Genapol LA3, a C13-15 linear primary alcohol ethoxylate with 3 moles EO; Genapol LA070, a C13-15 linear primary alcohol ethoxylate with 7 moles EO Tomadol 45-7, a C14-C15 linear primary alcohol ethoxylate with 7 moles EO; and Tomadol 91-6, a Cg-Cn linear alcohol ethoxylate with 6 moles EO. Other nonionic surfactants are amine oxides, alkyl amide oxide surfactants. Preferred anionic surfactants are frequently provided as alkali metal salts, ammonium salts, amine salts, amino- alcohol salts or magnesium salts. Contemplated as useful are one or more sulfate or sulfonate compounds including: alkyl benzene sulfates, alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl pol- yether sulfates, monoglyceride sulfates, alkyl- sulfonates, alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarconsinates, acyl isethionates, and N-acyl taurates. Generally, the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms.Other surfactants which may be used are alkyl naphtha lene sulfonates and acyl / oleoyl sarcosinates and mixtures thereof. Preferably the composition comprises a fabric softening active (FSA) or a mixture of more than one FSAs. In one embodiment, the composition comprises at least about 1 percent, alternatively at least about 2 percent, alternatively at least about 3 percent, alternatively at least about 4 percent, alternatively at least about 5 percent, alternatively at least about 6 percent, alternatively at least about 7 percent, alternatively at least about 8 percent, alternatively at least about 9 percent, alternatively at least about 10 percent, and alternatively at least about 12 percent, and less than about 90 percent, alternatively less than about 40 percent, alternatively less than about 30 percent, alternatively less than about 20 percent, alternatively less than about 18 percent, alternatively less than about 15 percent, of said FSA, by weight of the composition. In one embodiment, the FSA is cationic. (all percentages by weight). Without wishing to be bound by theory it is postulated that the fabric softening active aids silicone deposition (as we!i as providing a softening function). One suitable FSA comprises compounds of the formula {R4-m-N+-[(CH2)n-Y-R1 ]m}X- (1) wherein each R substituent is either hydrogen, a short chain CrCe, suitably Ci-C3 alkyl or hydroxyalkyl group, e.g., methyl, ethyl, propyl, hydroxyethyl, and the like, poly(C2-3 alkoxy), suitably polyethoxy, benzyl, or mixtures thereof, each m is 2 or 3; each n is from 1 to about 4, suitably 2; each Y is -0-(O)C-, -C(O)-0-, -NR-C(O)-, or -C(O)-NR-; the sum of carbons in each R\ plus one when Y is -0-(O)C- or -NR-C(O)-, is C12-C22, suitably C14-C20, with each R1 being a hydrocarbyl, or substituted hydrocarbyl group, and X" can be any softener- compatible anion, such as chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate. [0022] A second suitable FSA has the general formula: [R3N+CH2CH(YR1)(CH2YR1)]X- wherein each Y, R, R1 , and X" have the same meanings as before. Such compounds include those having the formula: wherein each R is a methyl or ethyl group and suitably each R1 is in the range of Cisto C19. When the diester is specified, it can include the monoester that is present. These types of agents and general methods of making them are disclosed in U.S. Pat. No. 4,137,180, Naik et al, issued Jan. 30, 1979. An example of a suitable DEQA (2) is the "propyl" ester quaternary ammonium fabric softener active having the formula 1 ,2- di(acyloxy)-3-trimethylammoniopropane chloride. A third suitable FSA has the formula: [R4-m-N+-R1 m]X (3) A fourth suitable FSA has the formula: wherein each R, R , and A- have the definitions given above; each R2 is a C1-6alkylene group, suitably an ethylene group; and G is an oxygen atom or an -NR- group. A fifth suitable FSA has the formula: wherein R1, R2 and G are defined as above. A sixth suitable FSA comprises condensation reaction products of fatty acids with dialkylenetriamines in, e.g., a molecular ratio of about 2: 1 , said reaction products containing compounds of the formula: R1-C(O)-NH-R2-NH-R3-NH-C(O)R1 (6) wherein R1, R2 are defined as above, and each R3 is a C1-6 alkylene group, suitably an ethylene group and wherein the reaction products may optionally be quaternized by the additional of an alkylating agent such as dimethyl sulfate. Such quaternized reaction products are described in additional detail in U.S. Pat. No. 5,296,622, issued Mar. 22, 1994 to Uphues et al. A seventh suitable FSA has the formula: [R1-C(O)-NR-R2-N(R)2-R3-NR-C(O)-R1]+A- (7) wherein R, R1, R2, R3 and A- are defined as above. An eighth suitable FSA comprises reaction products of fatty acid with hydroxyalkylalkylenediamines in a molecular ratio of about 2:1 , said reaction products containing compounds of the formula: R1-C(O)-NH-R2-N(R3OH)-C(O)-R1 (8) wherein R1, R2 and R3 are defined as above. A ninth suitable type of FSA has the formula: wherein R, R1, R2, and A- are defined as above. Non-limiting examples of compound (1) are N,N-bis(stearoyl-oxy-ethyl) N,N-dimethyl ammonium chloride, N,N-bis(tallowoyl-oxy-ethyl) Ν,Ν-dimethyl ammonium chloride, N,N- bis(stearoyl-oxy-ethyl) N-(2 hydroxyethyl) N-methyl ammonium methylsulfate, Bis (acyloxyethyl) hydroxyethyl Methyl ammonia Methyl sulphate Non-limiting examples of compound (2) is 1 ,2di(stearoyl-oxy) 3 trimethyl ammoniumpropane chloride. Non-limiting examples of compound (3) are dialkylenedimethylammonium salts such as dicanoladimethylammonium chloride, di(hard)tallowedimethylammonium chloride dicanoladimethylammonium methylsulfate. An example of commercially available dialkylenedimethylammonium salts usable in the present invention is dioleyldimethylammonium chloride available from Witco Corporation under the trade name Adogen(R) 472 and dihardtallow dimethylammonium chloride available from Akzo Nobel Arquad 2HT75. A non-limiting example of compound (4) is 1-methyl-1-stearoylamidoethyl-2- stearoylimidazolinium methylsulfate wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, G is a NH group, R5 is a methyl group and A- is a methyl sulfate anion, available commercially from the Witco Corporation under the trade name Varisoft(R). A non-limiting example of compound (5) is 1-tallowylamidoethyl-2-tallowylimidazoline wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, and G is a NH group. A non-limiting example of compound (6) is the reaction products of fatty acids with diethylenetriamine in a molecular ratio of about 2:1 , said reaction product mixture containing Ν,Ν-dialkyldiethylenetriamine with the formula: R1-C(O)-NH-CH2CH2-NH-CH2CH2-NH-C(O)-R wherein R1-C(O) is an alkyl group of a commercially available fatty acid derived from a vegetable or animal source, such as Emersol(R) 223LL or Emersol(R) 7021 , available from Henkel Corporation, and R2 and R3 are divalent ethylene groups. A non-limiting example of compound (7) is a difatty amidoamine based softener having the formula: [R1-C(O)-NH-CH2CH2-N(CH3)(CH2CH2OH)-CH2CH2-NH-C(O)-R1]+CH3S04- wherein R1-C(O) is an alkyl group, available commercially from the Witco Corporation e.g. under the trade name Varisoft(R) 222LT. A non-limiting example of compound (8) is the reaction products of fatty acids with N-2- hydroxyethylethylenediamine in a molecular ratio of about 2:1 , said reaction product mixture containing a compound of the formula: R1-C(O)-NH-CH2CH2-N(CH2CH2OH)-C(O)-R1 wherein R1-C(O) is an alkyl group of a commercially available fatty acid derived from a vegetable or animal source, such as Emersol(R) 223LL or Emersol(R) 7021 , available from Henkel Corporation. A non-limiting example of compound (9) is the diquaternary compound having the formula: wherein R1 is derived from fatty acid, and the compound is available from Witco Company.It will be understood that combinations and mixtures of any of the above types of FSAs disclosed above are suitable for use in this invention. In the cationic nitrogenous salts herein, the anion A-, which is any softener compatible anion, provides electrical neutrality. Most often, the anion used to provide electrical neutrality in these salts is from a strong acid, especially a halide, such as chloride, bromide, or iodide. Other anions can also be used, such as chloride, methylsulfate, ethylsulfate, sulfate, carbonate, and the like. The anion can also carry a double charge in which case A- represents half a group. The composition may include various optional ingredients, such as enzymes, builders, solvents, dye transfer inhibition agents, dye catchers, preservatives, antioxidants, anti-static agents, fragrances, odour absorbing components, optical brighteners, stain release agents, acidifying agents, radical scavengers, alkalizing agents, thickeners (e.g. hydroxyethylcellulose and / or xanthan gum). The compositions of the invention may include one or more organic solvents. Without wishing to be bound by theory it is postulated that the solvent aids silicone deposition and / or stain removal. Such further organic solvents may include one or more of: alcohols, glycols, acetates, ether acetates, glycerols, as well as polyethylene glycols and glycol ethers. Mixtures of these organic solvents can also be used. Non-limiting examples of useful glycol ethers and examples Include those glycol ethers having the general structure wherein y or alkenyl, or a cyclic alkane group of at least 6 carbon atoms, which may be fully or partially unsaturated or aromatic; n Is an Integer from 1 to 10, preferably from 1 to 5; each R is selected from H or CH3; and a is the Integer 0 or 1 Specific and preferred solvents are selected from propylene glycol methyl ether, dlpropylene glycol methyl ether, trlpropylene glycol methyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether, dlethylenegiycol n-butyl ether, diethylene glycol methyl ether, propylene glycol, ethylene glycol, diethylene glycol monoethyl ether acetate and the like. When present such one or more organic solvents may be present In any effective amount, preferably in amounts of between about 0.001-10 percent wt. , and preferably between about 0.01-5 percent wt. of the composition. The invention is illustrated with reference to the following non-limiting examples. Examples A mix of 3.5kg of cotton and polyester/cotton swatches washed in a European washing machine with a standard cotton 40°C cycle, dosing various solutions during the rinse cycle.All examples use parts by weight unless stated otherwise. A - Paraffin Inclusion The following solutions were tested using the cycle above with 68g of detergent dosed into the wash cycle and 60ml of the formula below added to the rinse cycle. Repellency test method
1. Put 75 μL_ of water with a micropipette on the surface of the textile gently forming a drop on point 1. Start the timer.
2. Successively, put other 6 drops around the garment (see picture)
3. Record total time when drop is completely absorbed
4. Mean value is done with calculation on standard deviation
Results
Figure imgf000017_0001
Here a synergy is seen between the silicone and the paraffin.
B - Variation of Paraffin Ratio
The following solutions were tested (as in last example)
Figure imgf000017_0002
Repellency test Results
Figure imgf000017_0003
C - Addition of Solvent
The following solutions were tested (as in last examples) using the cycle above with 68g of detergent dosed into the wash cycle and 60ml of the formula below added to the rinse cycle.
Figure imgf000018_0001
Repellency test Results
Figure imgf000018_0002
Stain release
Parity and Superiority versus detergent alone.
Figure imgf000018_0003
Figure imgf000019_0001
Improved performance on greasy stains: Chocolate syrup, French mustard, Lipstick and Mud and also some bleachable like Coffee and Tea thanks to the propyleneglycol. It is seen how also the formula without propyleneglycol performs well on water based stains while having some superiorities on greasy stains (make up and mustard) which it is believed are thanks to the contribution of the paraffin.
These results are particularly surprising. In separate tests the silicone and paraffin did not perform so well (see below).
A mix of cotton and polyester/cotton swatches washed in a European washing machine with a standard cotton 40°C cycle, dosing the following solutions during the rinse cycle under ideal conditions:
Figure imgf000019_0002
Repellency results on water:
Figure imgf000019_0003
Stain release results after having stained pre-conditioned swatches and washed again only with detergent:
Polyester-Cotton
Figure imgf000019_0004
Figure imgf000020_0003
Cotton
Figure imgf000020_0002
Conclusion: Silicone helps on waterbased stains but fixes oily stains, on cotton but also on cotton / PES (fixing is seen by the inferiorities). Paraffin looks to perform well across a wide range of stains (waterbased and oily stains) no matter the kind of swatch. Particularly looks to work well on greasy stains on cotton / PES swatch.
D - Softness evaluation
A mix of 3.5kg of cotton swatches washed in a European washing machine with a standard cotton 40°C cycle, dosing 68 g of detergent dosed into the wash cycle and 60 ml of various solutions during the rinse cycle.
The softness was evaluated by a panel of 10 people giving a softness score of 1-10 (1 harsh; 10 soft)
Softness Results
Figure imgf000020_0001
D - Colour evaluation
A mix of 3.5kg of coloured swatches washed in a European washing machine with a standard cotton 40°C cycle, dosing 65g pf detergent into the wash cycle and 60 ml of various solutions during the rinse cycle. AISE coloured fabrics used for the test
Figure imgf000021_0001
Formulation A5 was used as the inventive composition. The comparative results were achieved using detergent alone.
The swatches conditioned with the inventive formulation show in 58% of the cases from the AISE Dye set a lower value of dL * (greyness index scale 1/100) which demonstrates that colours become more brilliant and seem to be enhanced and revitalized.
Results from instrumental evaluation after 10 washes with detergent + inventive formulation or detergent alone:
Figure imgf000021_0002
Figure imgf000022_0001
1. A composition comprising:
A) a liquid detergent product; and B) a silicone additive.
2. A composition according to claim 1 wherein the silicone additive comprises
Figure imgf000023_0001
3. A composition according to claim 1 or 2, wherein the silicone additive is present in an amount of from 1-10wt%, preferably about 5wt%.
4. A composition according to any one of the proceeding claims wherein the composition comprises a wax component.
5. A composition according to claim 4, wherein the hydrophobic component is present in an amount of from 0.1 to 20wt%.
6. A composition according to claim 1 or 2, wherein the hydrophobic component comprises a derivatized paraffin.
7. A composition according to any one of the proceeding claims wherein the composition comprises a cationic surfactant.
8. A composition according to claim 7 wherein the composition comprises about 8wt% cationic surfactant.
9. A composition according to any one of the proceeding claims wherein the composition comprises one or more organic solvents.
10. A method for laundering a textile fabric comprising washing said fabric in the presence of a composition according to claims 1 to 9.
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