EP0849354A1 - Softening compositions - Google Patents
Softening compositions Download PDFInfo
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- EP0849354A1 EP0849354A1 EP96309419A EP96309419A EP0849354A1 EP 0849354 A1 EP0849354 A1 EP 0849354A1 EP 96309419 A EP96309419 A EP 96309419A EP 96309419 A EP96309419 A EP 96309419A EP 0849354 A1 EP0849354 A1 EP 0849354A1
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- composition according
- nonionic surfactant
- nonionic
- composition
- surfactants
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Classifications
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- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
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- 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
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
- C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/667—Neutral esters, e.g. sorbitan esters
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
Definitions
- This invention relates to compositions for use in softening of fabrics during the laundry process.
- fabric softening compositions When fabrics are washed they acquire a rougher texture which feels harsh to the skin. Cotton fabrics are particularly affected. To counteract this, many consumers add fabric softening compositions to the rinse water. These fabric softening compositions generally contain a material with a cationic head group and 1 or 2 alkyl chains which are attached to the head group and are of sufficient length to make the cationic material insoluble in water. This cationic material is then deposited on the fabric, and causes the fabric to display a softer feel.
- lactobionamides which are nonionic surfactant materials, may be used as softening agent in a rinse conditioner composition.
- GB-A-2185991 teaches a detergent composition in which fabric softening is provided by the incorporation of an alkyl glycoside as the sole softening agent.
- the composition also contains an anionic surfactant and a nonionic surfactant other than an alkyl glycoside.
- GB-A-2185992 discloses detergent compositions which also contain an alkyl glycoside jointly with a quaternary ammonium compound, a nonionic surfactant which is not an alkyl glycoside and an anionic surfactant.
- this nonionic surfactant may be a fatty alcohol containing 8 to 18 carbon atoms ethoxylated with 5 to 30 moles of ethylene oxide.
- EP-A-380406 discloses a detergent composition containing anionic and nonionic surfactants together with a sugar ester as a fabric softening agent.
- the nonionic detergent (apart from the sugar ester) is preferably a fatty alcohol containing 8 to 22 carbon atoms alkoxylated with 3 to 20 moles of lower alkylene oxide. Among such materials it is stated to be preferred that the fatty alcohol has 11 to 15 carbon atoms and is alkoxylated with 5 to 13 lower alkoxy groups.
- EP-A-325184 discloses detergent compositions containing acetylated sugar ether. This is stated to provide a fabric softening function as well as acting as a bleach activator and detergency booster.
- a number of other documents teach detergent compositions in which an alkyl glycoside is used as one of the surfactants in a surfactant mixture. These documents generally recommend that a detergent composition includes anionic surfactant but in some experimental examples a composition is used which contains alkyl glycoside together with ethoxylated fatty alcohol.
- cationic fabric softener which is deposited from rinse water onto the fabric. While these cationic materials are effective and widely used, one problem with them is that they tend to render the softened fabric hydrophobic with the result that the water absorbency of fabrics such as cotton towels is reduced.
- An advantage of the nonionic materials used in the present invention is that they do not render the softened fabrics hydrophobic to the same extent as cationic fabric softeners and thus provide a better combination of properties.
- Rinse conditioner formulations which contain a cationic fabric softening material are generally formulated as aqueous dispersions. It is not a simple matter to formulate an aqueous dispersion which will be stable during storage under varying temperatures, possibly even including exposure to temperatures below freezing. For some markets it is desired or required to use a fabric softening agent which is biodegradable. For cationic fabric softeners this has been achieved by the use of materials containing an ester linkage but it is then necessary to guard against hydrolytic instability of the ester linkage, which is the subject of European Patent 239910).
- composition based on nonionic surfactants can avoid interfering with detergency when the fabrics are next washed with a detergent composition containing anionic detergent; can assist perfume delivery, and can facilitate the preparation of concentrated products with good physical stability, even when subjected to frost or high ambient temperature.
- the present invention provides a composition containing
- the HLB value of this material is less than 5, e.g. 4.9 and below. It may in particular lie in a range from 0.5 to 5.
- the mole ratio of (i) to (ii) is preferably in a range from 5:1 to 1:5. Usually it will be desirable that the mole ratio is from 3:1 to 1:5, and often the second nonionic surfactant will be in molar excess, e.g. a ratio of 1:1 to 1:4.
- compositions of this invention will be used as rinse conditioner compositions, although it is also possible to formulate a composition within this invention as a detergent composition for washing fabrics, and giving a softening benefit during this washing step.
- this invention provides a method of washing and conditioning fabrics by steps of
- the washing and rinsing of fabrics may be carried out in an automatic washing machine which pumps a majority of the wash liquor away from the fabrics before contacting them with the rinse water.
- a machine may mix the rinse conditioner composition with the rinse water as that water is drawn into the machine - and therefore just before it is brought into contact with the fabrics.
- the above method could also be carried out using a different type of machine, or by hand, such that the wet fabrics are taken out of the wash liquor and allowed to drain before immersion in the rinse water.
- the first nonionic surfactant (i) is required to have an aliphatic radical, especially an alkyl or alkenyl chain of at least 10 better at least 12 carbon atoms attached to a head group on which there are at least three hydroxyl groups. These are able to participate in hydrogen bonding, notably hydrogen bonding to cellulosic fabric.
- head groups with a plurality of hydroxyl groups can be provided by residues of sugars e.g. glucose, mannose, galactose, maltose and lactose, or by residues of the reduced counterparts of sugars e.g. mannitol and sorbitol.
- This head group may be provided by a single saccharide or reduced saccharide residue or it may be provided by residue of more than one saccharide in which case of course the head group will have a greater number of hydroxyl groups remaining free and able to participate in hydrogen bonding.
- the head group may be provided by a mixture of saccharides, notably a mixture of mono and disaccharides so that the average number of saccharide residues is not an integer, but lies between 1 and 2.
- the head group has an average of at least four hydroxyl groups free and able to participate in hydrogen bonding.
- the head group is derived from saccharide.
- saccharides and reduced saccharides are a convenient source of chemical structures with multiple hydroxyl groups in proximity to one another.
- Alkyl and alkenyl chain lengths up to 18 carbon atoms maximum are likely to be used. Chain lengths up to 22 and 24 carbon atoms are possible. Even longer chains are less easy to provide, but can be provided as shorter carbon chains connected through heteroatoms, thus providing a longer alkyl or alkenyl aliphatic chain interrupted by a heteroatom(s) such as in an
- a nonionic surfactant having a head group and an alkyl or alkenyl chain in accordance with the parameters indicated above will generally have an HLB value of at least 7. It is preferred that it has an HLB value of at least 8, better at least 10 and the HLB value may well be greater than 12 or 13.
- a number of types of nonionic material can serve as the first surfactant.
- One significant category of materials which may be used as this first nonionic surfactant are alkyl polyglycosides which have the formula RO(R'O) y (A) x in which R denotes an alkyl or alkenyl group containing from 8 to 22 carbon atoms; each (R'O) contains from 2 to 4 carbon atoms, and is preferably an ethoxy, propoxy, or glyceryl group; each A is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; y is from 0 to 12, and x is a number from 1 to 5.
- y is from 0 to 3 and will usually be zero; preferably x ranges from 1 or 1.2 up to 2.7 or 3, more preferably from 1.2 up to 1.6 or 2.0.
- Alkyl polyglycosides are discussed in a number of documents including European Patents 70074, 75995 and 317614 (WO 88/9369), GB 2185991, US 3598865, US 4011389 and US 4565647. Processes for their preparation are disclosed in US 3598865.
- nonionic surfactants having multiple hydroxy groups at the head are the glyceroglycolipid surfactants of formulae where A is a saccharide residue, B is OH or NRR', R is an alkyl or alkenyl group having from 8 to 24 carbon atoms, and R' is hydrogen or a C 1 to C 4 alkyl group or C 3 to C 7 cycloalkyl.
- Aldobionamides are another category of nonionic surfactants with multiple hydroxy groups in a head group. These compounds may be represented by a general formula ANR 1 R 2 where A is a sugar-based moiety which is a residue of an aldobionic acid and NR 1 R 2 replaces the OH group normally extending from the carbonyl group on the aldobionic acid; R 1 is an alkyl or alkenyl group having from 8 to 24 carbon atoms, and R 2 is hydrogen, C 1 to C 4 alkyl or C 3 to C 7 cycloalkyl. In preferred compounds R 2 is hydrogen.
- Aldobionic acids are disaccharides or polysaccharides in which the aldehyde group (generally found at the C 1 position of the sugar) has been replaced by a carboxylic acid. Upon drying they cyclise to aldobionolactones.
- Aldobionamides are amides of an aldobionic acid (or aldobionolactone).
- An aldobionamide may be based on compounds comprising two saccharide units or on compounds comprising more than two saccharide units, as long as the terminal sugar in the polysaccharide has an aldehyde group. Disaccharide compounds are preferred.
- aldobionamide which may be used for purposes of the invention is the disaccharide lactobionamide set forth below: wherein R 1 and R 2 are as specified above.
- Another preferred aldobionamide is maltobionamide of the following formula: wherein R 1 and R 2 are as specified above.
- aldobionamides (disaccharides) which may be used include cellobionamides, melibionamides and gentiobionamides.
- R 1 is hydrogen, C 1 -C 4 hydroxyalkyl such as 2-hydroxy ethyl or 2-hydroxy propyl, C 1 -C 4 alkyl or mixture thereof
- R 2 is a C 7 -C 23 alkyl or alkenyl group
- Z is an aliphatic radical having at least one carbon chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative of such a chain.
- Z is preferably derived from a reducing sugar in a reductive amination reaction.
- Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose.
- high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup can be utilised as well as individual sugars listed above. It should be understood that these corn syrups may yield a mixture of sugar components for Z.
- a further possibility for the first nonionic surfactant is a sugar ester consisting of a mono, di or polysaccharide esterified on one of its hydroxyl groups with a fatty acid of 8 to 24 carbon atoms. Esters of this general structure are mentioned in WO 89/01480.
- any of the above nonionic surfactants may be ethoxylated, because of course when an ethylene oxide molecule adds on to a hydroxyl group, it also provides a new hydroxyl group able to take part in hydrogen bonding.
- a category of ethoxylated surfactants which can be used as the first nonionic surfactant are the ethoxylated sorbitol esters. These are formed by ethoxylation of sorbitol or its cyclic derivative sorbitan, followed by esterification on one of the available hydroxy groups to introduce one long chain alkyl or alkenyl group, leaving the remaining hydroxy groups free. Compounds of this type are included in the range commercially available under the Registered Trade Mark TWEEN from Aldrich and from ICI United States Inc, but are also available from other suppliers.
- alkyl polyglycosides glyceroglycolipids or one of the various bionamides. None of these incorporate an ester linkage which could be vulnerable to hydrolysis.
- the second nonionic surfactant (ii) must be of low HLB.
- the second nonionic surfactant will have a polar group (which may be as small as a single hydroxyl group) attached to a lipophilic hydrocarbyl radical, especially a radical of 10 to 40 carbon atoms incorporating an aliphatic chain of at least 10 carbon atoms.
- the hydrocarbyl radical may be an alkyl or alkenyl chain, of at least 10, better at least 12 carbon atoms up to 24 carbon atoms.
- a preferred material is a fatty alcohol containing 11, better at least 12 up to 18 carbon atoms. It is also possible to use an ethoxylated or partially ethoxylated fatty alcohol provided the average degree of ethoxylation is low so as to give an overall low HLB value.
- Chain lengths longer than 24 carbon atoms can be provided as shorter carbon chains connected through heteroatoms, thus providing a longer chain (preferably aliphatic) interrupted by a heteratom such as in an
- HLB surface active material examples include sorbitan esters devoid of ethoxylation such as sorbitan monostearate, HLB 4.7; glycerol esters such as glycerol monostearate, esters of diglycerol and polyglycerol and monoesters of fatty acids with ethylene glycol (HLB typically 2.7-3.6).
- sorbitan esters devoid of ethoxylation such as sorbitan monostearate, HLB 4.7
- glycerol esters such as glycerol monostearate, esters of diglycerol and polyglycerol and monoesters of fatty acids with ethylene glycol (HLB typically 2.7-3.6).
- Sorbitan esters which do not include ethoxy groups and which are of low HLB are marketed under the trade mark SPAN by ICI United States.
- the second nonionic surfactant can be provided by a material with nitrogen in its head group, such as a fatty amine, fatty amide or slightly ethoxylated fatty amide, coconut monoethanolamide is an example of such a material.
- this second, low HLB, material does include some ethylene oxide residues, it will generally be the case that the average degree of ethoxylation is below 3, (e.g. 2.5 or below) so as to give an HLB value below 7; preferably the average degree of ethoxylation is less, such as below 1.8 so as to give an HLB value below 5.
- Fatty acids containing 8 or more carbon atoms are also materials of low HLB. However, we have found it difficult to make formulations with them, so we prefer that more than half, better more than 75% of the nonionic detergent of low HLB is other than fatty acid.
- neither of the surfactants includes residues of propylene oxide or any higher alkylene oxide.
- the molar ratio of the first nonionic surfactant to the second, low HLB nonionic surfactant lies in the range from 5:1 to 1:5, more preferably from 1:1 to 1:4 for most combinations of first and second surfactants.
- the two categories of nonionic surfactant should interact with each other to form a fabric-substantive liquid crystalline phase which is not simply micellar in nature.
- This liquid crystalline phase may be such as to be described as hydrated solid, lamellar (L ⁇ and L ⁇ ), hexagonal, cubic or some combination of these possibilities. Particularly preferred are the hydrated solid phase and the L ⁇ phase.
- the nonionic non-micellar liquid crystalline phase should exist at the concentration of use. In practice the combination of nonionic surfactants should form liquid crystalline phase(s) at an overall concentration of 5% by weight in water at 20°C.
- a liquid crystalline phase can be formed with a wide variety of nonionic surfactants as the first nonionic surfactant (incorporating at least three hydroxy groups in head group) provided the second nonionic surfactant is chosen to have a sufficiently low HLB.
- the formation of a suitable non-micellar liquid crystal phase can be checked by optical microscopy and other phase behaviour characterisation techniques as described by Small D M, Handbook of Lipid Research, Vol 4: The Physical Chemistry of Lipids " Plenum Press NY, 1986.
- the first nonionic surfactant, the second nonionic surfactant or both of them should have an alkyl or alkenyl group of at least 16 carbon atoms.
- one or both surfactants may contain tallow alkyl chains rather than coconut alkyl chains or similar synthetic alkyl chains of 11 to 15 carbon atoms.
- the second nonionic surfactant will contain an alkyl or alkenyl chain of at least 16 carbon atoms.
- the first nonionic surfactant will desirably be a material which forms an L ⁇ or hydrated solid phase in a system consisting of 2.5% by weight of first nonionic surfactant, 2.5% by weight of stearyl alcohol and 95% by weight of water.
- a characteristic of surfactant combinations which provide the preferred L ⁇ or hydrated solid phases is that, an aqueous mixture, containing the nonionic surfactants at a total concentration of 5% by weight, undergoes an endothermic phase transition at a temperature above 0°C, better above 5°C or 10°C. This phase transition is detectable by differential scanning calorimetry and is attributable to "melting" the hydrated solid or the hydrocarbon chains of the L ⁇ phase.
- This invention may be embodied in various forms of fabric treatment product. Particularly envisaged is a rinse conditioner formulation for addition to water used for rinsing fabrics after washing. However, the invention can also be embodied in other product forms as will be mentioned again below.
- Rinse conditioner compositions of this invention preferably do not include any substantial amount of synthetic anionic detergent because such detergent may dissolve the desired liquid crystalline phase.
- Water soluble soaps, with chain lengths of 14 or less carbon atoms should be avoided for the same reason.
- the total amount of synthetic anionic detergent or water-soluble soap (if any) should preferably not exceed 10% by weight of the total amount of the required nonionic surfactants, indeed preferably not exceed 10% by weight of the total softener content.
- rinse conditioner compositions of this invention do not include other non-bionic surfactants, so that these cannot interfere with the interaction between the specified nonionic surfactants.
- the amount of ethoxylated fatty alcohols with five or more ethylene oxide residues may be no more than 10% (better not over 8%) weight of the amount of the said second non-ionic surface active material (ii).
- a composition of the present invention when a composition of the present invention is a rinse conditioner, it may contain the aqueous surfactants as a dispersion or solution in water at a total concentration in the range from 2% to 30% by weight.
- Rinse conditioners can also be embodied in other forms such as powders and pastes.
- a composition which is for use as a rinse conditioner will generally not include any significant amount of detergency builders.
- the total amount of insoluble aluminosilicate and water soluble tripolyphosphate will generally be less than 5% by weight of the composition. Usually these will be entirely absent.
- a rinse conditioner composition could include a cationic fabric softener, although certain forms of the present invention do not use cationic materials. Therefore, the total quantity of the required nonionic surfactants may be at least half, equal to or greater than the total quantity of cationic softeners, if any. Indeed, the total quantity of the required nonionic surfactants may be more than 3 or 4 times the total quantity, if any, of cationic softeners.
- ком ⁇ онентs which may be incorporated into such a rinse conditioning composition are perfumes, perfume carriers, polymeric thickeners, drape imparting agents, antistatic agents, germicides, fungicides and ironing aids.
- a rinse conditioning composition may be manufactured by making a melt of the surfactant materials, adding this to hot water e.g. at a temperature of 70 - 85°C, with mixing, and then mixing the composition with high shear until it is homogenous.
- the invention can also be utilised in compositions used on an industrial scale for finishing newly manufactured fabric.
- Another possible application is products for spraying directly onto fabric, for example when ironing the fabric after it has been dried.
- Yet another application is in products to be placed in a tumble dryer jointly with the fabrics, so that the nonionic surfactants transfer to the fabrics in their molten state.
- Conventional products in this category take the form of porous sheets impregnated with cationic fabric softener(s).
- This invention could be embodied as similar sheets impregnated with the solid surfactants of this invention.
- the conditioning composition of the present invention may be coated onto a flexible substrate which is capable of releasing the composition in a tumble dryer.
- a product can be designed for single usage or for multiple uses.
- One such multi-use article comprises a sponge material releasably enclosing enough of the conditioning composition to effectively impart fabric softness during several drying cycles.
- the multi-use article can be made by filling a porous sponge with the composition. In use, the composition melts and leaches out through the pores of the sponge to soften and condition fabrics.
- a single use sheet may comprise the inventive compositions carried on a flexible substrate such as a sheet of paper or woven or non-woven cloth substrate.
- Another possible form of product embodying the invention is a detergent composition which is formulated to give fabric softening jointly with fabric washing.
- the composition of the invention is a detergent composition for fabric washing
- the composition will usually contain one or more detergency builders, suitably in an amount of from 5 to 60 or 80 wt%, preferably from 20 to 60 wt%.
- detergency builders are well known.
- One well known class of builders is the alkali metal (preferably sodium) aluminosilicates. These may suitably be incorporated in amounts of from 5 to 60% by weight (anhydrous basis) of the composition, and may be either crystalline or amorphous or mixture thereof. These materials have the general formula: 0.8 - 1.5 Na 2 O.Al 2 O 3 . 0.8 - 6 SiO 2 contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
- the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above).
- Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1429143 (Proctor & Gamble).
- the preferred sodium aluminosilicates of this type are the well known commercially available zeolites A and X, and mixtures thereof.
- Also of interest is the novel zeolite P described and claimed in EP 384070 (Unilever).
- Water-soluble builders may be organic or inorganic.
- Inorganic builders that may be present include alkali metal (generally sodium) carbonate, orthophosphate, pyrophosphate and tripolyphosphate.
- Organic builders include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphorates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates; and organic precipitant builders such as alkyl- and alkenylmalonates and succinates.
- polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphorates
- monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates
- organic precipitant builders such as alkyl-
- Especially preferred supplementary builders for use jointly with aluminosilicate are polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, especially from 1 to 10 wt%; and monomeric polycarboxylates, more especially citric acid and its salts, suitably used in amounts of from 3 to 20 wt%, more preferably from 5 to 15 wt% by weight of the composition.
- Detergent compositions for fabric washing are customarily formulated using anionic surfactant as at least part of the detergent active.
- compositions are known in which the detergent active is wholly or largely nonionic. It is envisaged that the present invention may in particular be embodied in a built detergent composition where nonionic surfactants (including the nonionic surfactants required by this invention) are over 50%, probably at least 80% by weight of all surfactants present. Synthetic anionic surfactants may well be omitted entirely.
- the total amount of surfactant will generally lie in a range from 5 to 50%, more usually 5 to 40% by weight of the composition.
- Detergent compositions according to the invention may also contain a bleach system.
- a bleach system preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve bleaching action at low wash temperatures. If any peroxygen compound is present, the amount is likely to lie in a range from 10 to 25% by weight of the composition.
- Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, advantageously employed together with an activator.
- Bleach activators also referred to as bleach precursors
- Preferred examples include peracetic acid precursors, for example, tetraacetylethylene diamine (TAED), now in widespread commercial use in conjunction with sodium perborate.
- TAED tetraacetylethylene diamine
- the quaternary ammonium and phosphonium bleach activators disclosed in US 4751015 and US 4818426 (Lever Brothers Company) are also of interest.
- Another type of bleach activator which may be used, but which is not a bleach precursor is a transition metal catalyst as disclosed in EP-A-458397, EP-A-458398 and EP-A-549272.
- Detergent compositions of the invention may also contain one or more of the detergency enzymes known in the art for their ability to degrade and aid in the removal of various soils and stains.
- Suitable enzymes include the various proteases, cellulases, lipases, amylases, and mixtures thereof.
- ingredients which can optionally be employed in a detergent composition of the invention include antifoams, fluorescers, anti-redeposition agents such as sodium carboxymethylcellulose, heavy metal sequestrants such as EDTA; perfumes; pigments, colorants or coloured speckles; and inorganic salts such as sodium and magnesium sulphate.
- formulations were prepared, as set out in tables below.
- the formulations all contained 1.33% by weight of the carbohydrate-based first nonionic surfactant.
- Each formulation was prepared by adding the nonionic surfactant(s) to water at 80-85°C, and allowing the mixture to equilibrate with occasional agitation, after which it was subjected to high shear mixing until homogenous.
- formulations were tested to evaluate their fabric softening efficacy, diluting the formulations with tap water (10°FH) so that they contained a total of 7.52 grams of the formulation per litre of water. This provided 0.1 g/litre by weight of the first nonionic surfactant.
- Comparative data were provided by formulations containing one of the carbohydrate-based first nonionic surfactants without a second nonionic surfactant. Here the concentration of each first nonionic surfactant in water was 0.1 g/litre or greater.
- a control was provided by HT TMAPC formulated at a concentration of 2.5% by weight, and then used at a concentration of 4 g/litre, so as again to provide 0.1 g/litre by weight in the treatment liquor. Another control was water only.
- the second nonionic surfactants are of such low HLB (i.e. non-polar) that they could not be dispersed in water. Consequently, if an attempt was made to use them without the first nonionic surfactant, the result was the same as with water alone.
- the test fabric was terry towelling which had previously been washed to remove any filler or dressing applied during manufacture.
- the fabric was treated in Tergotometer pots. Three pieces of terry towelling (8cm x 8cm, 40g total weight) were added to each tergotometer pot. The treatment liquor was then dosed onto the cloths which were treated for 5 minutes while the agitator in the tergotometer rotated at 65 rpm, then spin dried to remove excess liquor and line dried overnight.
- Softening of the fabrics was assessed by an expert panel of 4 people. Each panel member assessed cloths treated with test or comparative formulations, together with control cloths respectively treated with HT TMAPC or water only. Panel members were asked to assess softness on an 8 point scale, where a score of 8 represents unsoftened fabric and a score of 2 represents extremely soft fabric. Thus, lower values are indicative of better softening. Softness scores were calculated by averaging the scores of the individual panellists.
- pairs of first and second nonionic surfactants were tested at varying concentrations in the rinse liquor. Softness and wicking height were assessed as described for the Examples above. The results were: Dose (g/l) in rinse liquor Softness Ranking Wicking Height (cm) HTLB:GMS (1:1.5 mole ratio) 0.05 4 10.0 0.1 2.5 10.0 0.2 2 9.2 HTLB: ROH (1:1.5 mole ratio) 0.05 4.5 11.3 0.1 3 10.5 0.2 2 10.5 TLB: ROH (1:1.33 mole ratio) 0.05 7 14.4 0.1 5.5 14.4 0.02 3.25 12.0 CLB: ROH (1:2 mole ratio) 0.05 4.5 14.2 0.1 3 12.7 0.2 2 11.8
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Abstract
A fabric softening composition contains a first
nonionic surfactant which has a head group bearing at least
three hydroxyl groups and is preferably from carbohydrate
source and a lipophilic aliphatic tail of 10 to 40,
especially 16 to 24 carbon atoms, plus a second nonionic
surfactant of HLB not above 7, which may incorporate an
aliphatic chain of 10 to 40, especially 16 to 24 carbon
atoms.
Description
This invention relates to compositions for use in
softening of fabrics during the laundry process.
When fabrics are washed they acquire a rougher texture
which feels harsh to the skin. Cotton fabrics are
particularly affected. To counteract this, many consumers
add fabric softening compositions to the rinse water.
These fabric softening compositions generally contain a
material with a cationic head group and 1 or 2 alkyl chains
which are attached to the head group and are of sufficient
length to make the cationic material insoluble in water.
This cationic material is then deposited on the fabric, and
causes the fabric to display a softer feel.
US 5401426 discloses that lactobionamides, which are
nonionic surfactant materials, may be used as softening
agent in a rinse conditioner composition.
There have also been proposals to formulate a
detergent composition so that a fabric softening effect is
provided during the washing of the fabrics rather than
during a rinsing step. Such softening can be accomplished
using certain clays which have ion exchange properties. It
has also been proposed to use certain nonionic materials to
give fabric softening during washing.
More specifically, GB-A-2185991 teaches a detergent
composition in which fabric softening is provided by the
incorporation of an alkyl glycoside as the sole softening
agent. The composition also contains an anionic surfactant
and a nonionic surfactant other than an alkyl glycoside.
GB-A-2185992 discloses detergent compositions which also
contain an alkyl glycoside jointly with a quaternary
ammonium compound, a nonionic surfactant which is not an
alkyl glycoside and an anionic surfactant. In both of
these documents this nonionic surfactant may be a fatty
alcohol containing 8 to 18 carbon atoms ethoxylated with 5
to 30 moles of ethylene oxide.
EP-A-380406 discloses a detergent composition
containing anionic and nonionic surfactants together with a
sugar ester as a fabric softening agent. The nonionic
detergent (apart from the sugar ester) is preferably a
fatty alcohol containing 8 to 22 carbon atoms alkoxylated
with 3 to 20 moles of lower alkylene oxide. Among such
materials it is stated to be preferred that the fatty
alcohol has 11 to 15 carbon atoms and is alkoxylated with 5
to 13 lower alkoxy groups.
EP-A-325184 discloses detergent compositions
containing acetylated sugar ether. This is stated to
provide a fabric softening function as well as acting as a
bleach activator and detergency booster.
A number of other documents teach detergent
compositions in which an alkyl glycoside is used as one of
the surfactants in a surfactant mixture. These documents
generally recommend that a detergent composition includes
anionic surfactant but in some experimental examples a
composition is used which contains alkyl glycoside together
with ethoxylated fatty alcohol.
We have now discovered that a surprisingly high degree
of fabric softening can be achieved by means of a
composition which contains two kinds of nonionic surface
active materials (ie. surfactants). The present invention
is thus able to provide alternative compositions in which
fabric softening can be achieved without the use of
cationic materials. Alternatively, the combination of
nonionic softeners could be used jointly with cationic
softener.
As mentioned above, fabric softening is frequently
carried out using a cationic fabric softener which is
deposited from rinse water onto the fabric. While these
cationic materials are effective and widely used, one
problem with them is that they tend to render the softened
fabric hydrophobic with the result that the water
absorbency of fabrics such as cotton towels is reduced. An
advantage of the nonionic materials used in the present
invention is that they do not render the softened fabrics
hydrophobic to the same extent as cationic fabric softeners
and thus provide a better combination of properties.
Rinse conditioner formulations which contain a
cationic fabric softening material are generally formulated
as aqueous dispersions. It is not a simple matter to
formulate an aqueous dispersion which will be stable during
storage under varying temperatures, possibly even including
exposure to temperatures below freezing. For some markets
it is desired or required to use a fabric softening agent
which is biodegradable. For cationic fabric softeners this
has been achieved by the use of materials containing an
ester linkage but it is then necessary to guard against
hydrolytic instability of the ester linkage, which is the
subject of European Patent 239910).
The use of a combination of nonionic materials in
accordance with the present invention can assist in the
formulation of a product which is storage stable. Some
forms of this invention can provide biodegradability
without problems of hydrolytic instability.
Further advantages of a composition based on nonionic
surfactants is that it will avoid interfering with
detergency when the fabrics are next washed with a
detergent composition containing anionic detergent; can
assist perfume delivery, and can facilitate the preparation
of concentrated products with good physical stability, even
when subjected to frost or high ambient temperature.
In a first aspect, therefore, the present invention
provides a composition containing
In preferred forms of the invention the HLB value of
this material is less than 5, e.g. 4.9 and below. It may
in particular lie in a range from 0.5 to 5.
The mole ratio of (i) to (ii) is preferably in a range
from 5:1 to 1:5. Usually it will be desirable that the
mole ratio is from 3:1 to 1:5, and often the second
nonionic surfactant will be in molar excess, e.g. a ratio
of 1:1 to 1:4.
It is particularly envisaged that the compositions of
this invention will be used as rinse conditioner
compositions, although it is also possible to formulate a
composition within this invention as a detergent
composition for washing fabrics, and giving a softening
benefit during this washing step.
In another aspect, this invention provides a method of
washing and conditioning fabrics by steps of
The washing and rinsing of fabrics may be carried out
in an automatic washing machine which pumps a majority of
the wash liquor away from the fabrics before contacting
them with the rinse water. Such a machine may mix the
rinse conditioner composition with the rinse water as that
water is drawn into the machine - and therefore just before
it is brought into contact with the fabrics. However, the
above method could also be carried out using a different
type of machine, or by hand, such that the wet fabrics are
taken out of the wash liquor and allowed to drain before
immersion in the rinse water.
The first nonionic surfactant (i) is required to have
an aliphatic radical, especially an alkyl or alkenyl chain
of at least 10 better at least 12 carbon atoms attached to
a head group on which there are at least three hydroxyl
groups. These are able to participate in hydrogen bonding,
notably hydrogen bonding to cellulosic fabric. Such head
groups with a plurality of hydroxyl groups can be provided
by residues of sugars e.g. glucose, mannose, galactose,
maltose and lactose, or by residues of the reduced
counterparts of sugars e.g. mannitol and sorbitol.
This head group may be provided by a single saccharide
or reduced saccharide residue or it may be provided by
residue of more than one saccharide in which case of course
the head group will have a greater number of hydroxyl
groups remaining free and able to participate in hydrogen
bonding. The head group may be provided by a mixture of
saccharides, notably a mixture of mono and disaccharides so
that the average number of saccharide residues is not an
integer, but lies between 1 and 2. Preferably the head
group has an average of at least four hydroxyl groups free
and able to participate in hydrogen bonding.
It may not be essential that the head group is derived
from saccharide. However, saccharides and reduced
saccharides are a convenient source of chemical structures
with multiple hydroxyl groups in proximity to one another.
Alkyl and alkenyl chain lengths up to 18 carbon atoms
maximum are likely to be used. Chain lengths up to 22 and
24 carbon atoms are possible. Even longer chains are less
easy to provide, but can be provided as shorter carbon
chains connected through heteroatoms, thus providing a
longer alkyl or alkenyl aliphatic chain interrupted by a
heteroatom(s) such as in an
A nonionic surfactant having a head group and an alkyl
or alkenyl chain in accordance with the parameters
indicated above will generally have an HLB value of at
least 7. It is preferred that it has an HLB value of at
least 8, better at least 10 and the HLB value may well be
greater than 12 or 13.
A number of types of nonionic material can serve as
the first surfactant. One significant category of
materials which may be used as this first nonionic
surfactant are alkyl polyglycosides which have the formula
RO(R'O)y(A)x
in which R denotes an alkyl or alkenyl group containing
from 8 to 22 carbon atoms; each (R'O) contains from 2 to 4
carbon atoms, and is preferably an ethoxy, propoxy, or
glyceryl group; each A is a moiety derived from a reducing
saccharide containing 5 or 6 carbon atoms; y is from 0 to
12, and x is a number from 1 to 5. Preferably y is from 0
to 3 and will usually be zero; preferably x ranges from 1
or 1.2 up to 2.7 or 3, more preferably from 1.2 up to 1.6
or 2.0.
Alkyl polyglycosides are discussed in a number of
documents including European Patents 70074, 75995 and
317614 (WO 88/9369), GB 2185991, US 3598865, US 4011389 and
US 4565647. Processes for their preparation are disclosed
in US 3598865.
Another category of nonionic surfactants having
multiple hydroxy groups at the head, are the
glyceroglycolipid surfactants of formulae
where A is a saccharide residue, B is OH or NRR', R is an
alkyl or alkenyl group having from 8 to 24 carbon atoms, and
R' is hydrogen or a C1 to C4 alkyl group or C3 to C7
cycloalkyl.
These surfactants and their synthesis are disclosed in
EP-A-550279 and 550280.
Aldobionamides are another category of nonionic
surfactants with multiple hydroxy groups in a head group.
These compounds may be represented by a general formula
ANR1R2
where A is a sugar-based moiety which is a residue of
an aldobionic acid and NR1R2 replaces the OH group normally
extending from the carbonyl group on the aldobionic acid;
R1 is an alkyl or alkenyl group having from 8 to 24 carbon atoms, and R2 is hydrogen, C1 to C4 alkyl or C3 to C7 cycloalkyl. In preferred compounds R2 is hydrogen.
R1 is an alkyl or alkenyl group having from 8 to 24 carbon atoms, and R2 is hydrogen, C1 to C4 alkyl or C3 to C7 cycloalkyl. In preferred compounds R2 is hydrogen.
Aldobionic acids are disaccharides or polysaccharides
in which the aldehyde group (generally found at the C1
position of the sugar) has been replaced by a carboxylic
acid. Upon drying they cyclise to aldobionolactones.
Aldobionamides are amides of an aldobionic acid (or
aldobionolactone).
An aldobionamide may be based on compounds comprising
two saccharide units or on compounds comprising more than
two saccharide units, as long as the terminal sugar in the
polysaccharide has an aldehyde group. Disaccharide
compounds are preferred.
A specific example of an aldobionamide which may be
used for purposes of the invention is the disaccharide
lactobionamide set forth below:
wherein R1 and R2 are as specified above.
Another preferred aldobionamide is maltobionamide of
the following formula:
wherein R1 and R2 are as specified above.
Other examples of aldobionamides (disaccharides) which
may be used include cellobionamides, melibionamides and
gentiobionamides.
Aldobionamides and their preparation are described in
EP-A-550278.
Another category of surfactants with hydroxyl groups
in their head group is the polyhydroxy fatty acid amides
discussed in WO 95/30729. These have a general formula
wherein R1 is hydrogen, C1-C4 hydroxyalkyl such as 2-hydroxy
ethyl or 2-hydroxy propyl, C1-C4 alkyl or mixture
thereof, R2 is a C7-C23 alkyl or alkenyl group and Z is an
aliphatic radical having at least one carbon chain with at
least 3 hydroxyl groups directly connected to the chain, or
an alkoxylated derivative of such a chain. Z is preferably
derived from a reducing sugar in a reductive amination
reaction. Suitable reducing sugars include glucose,
fructose, maltose, lactose, galactose, mannose and xylose.
As raw materials to provide the group Z, high dextrose corn
syrup, high fructose corn syrup and high maltose corn syrup
can be utilised as well as individual sugars listed above.
It should be understood that these corn syrups may yield a
mixture of sugar components for Z.
A further possibility for the first nonionic
surfactant is a sugar ester consisting of a mono, di or
polysaccharide esterified on one of its hydroxyl groups
with a fatty acid of 8 to 24 carbon atoms. Esters of this
general structure are mentioned in WO 89/01480.
Any of the above nonionic surfactants may be
ethoxylated, because of course when an ethylene oxide
molecule adds on to a hydroxyl group, it also provides a
new hydroxyl group able to take part in hydrogen bonding.
A category of ethoxylated surfactants which can be
used as the first nonionic surfactant are the ethoxylated
sorbitol esters. These are formed by ethoxylation of
sorbitol or its cyclic derivative sorbitan, followed by
esterification on one of the available hydroxy groups to
introduce one long chain alkyl or alkenyl group, leaving
the remaining hydroxy groups free. Compounds of this type
are included in the range commercially available under the
Registered Trade Mark TWEEN from Aldrich and from ICI
United States Inc, but are also available from other
suppliers.
Among these various possible compounds useful as the
first nonionic surfactant, it is preferred to employ alkyl
polyglycosides, glyceroglycolipids or one of the various
bionamides. None of these incorporate an ester linkage
which could be vulnerable to hydrolysis.
The second nonionic surfactant (ii) must be of low
HLB. Generally, the second nonionic surfactant will have a
polar group (which may be as small as a single hydroxyl
group) attached to a lipophilic hydrocarbyl radical,
especially a radical of 10 to 40 carbon atoms incorporating
an aliphatic chain of at least 10 carbon atoms. The
hydrocarbyl radical may be an alkyl or alkenyl chain, of at
least 10, better at least 12 carbon atoms up to 24 carbon
atoms. A preferred material is a fatty alcohol containing
11, better at least 12 up to 18 carbon atoms. It is also
possible to use an ethoxylated or partially ethoxylated
fatty alcohol provided the average degree of ethoxylation
is low so as to give an overall low HLB value.
Chain lengths longer than 24 carbon atoms can be
provided as shorter carbon chains connected through
heteroatoms, thus providing a longer chain (preferably
aliphatic) interrupted by a heteratom such as in an
Other possibilities for a low HLB surface active
material include sorbitan esters devoid of ethoxylation
such as sorbitan monostearate, HLB 4.7; glycerol esters
such as glycerol monostearate, esters of diglycerol and
polyglycerol and monoesters of fatty acids with ethylene
glycol (HLB typically 2.7-3.6).
Sorbitan esters which do not include ethoxy groups and
which are of low HLB are marketed under the trade mark SPAN
by ICI United States.
The second nonionic surfactant can be provided by a
material with nitrogen in its head group, such as a fatty
amine, fatty amide or slightly ethoxylated fatty amide,
coconut monoethanolamide is an example of such a material.
If this second, low HLB, material does include some
ethylene oxide residues, it will generally be the case that
the average degree of ethoxylation is below 3, (e.g. 2.5 or
below) so as to give an HLB value below 7; preferably the
average degree of ethoxylation is less, such as below 1.8
so as to give an HLB value below 5.
Fatty acids containing 8 or more carbon atoms are also
materials of low HLB. However, we have found it difficult
to make formulations with them, so we prefer that more than
half, better more than 75% of the nonionic detergent of low
HLB is other than fatty acid.
Generally it will be desirable that neither of the
surfactants includes residues of propylene oxide or any
higher alkylene oxide.
In this invention it is desirable that the molar ratio
of the first nonionic surfactant to the second, low HLB
nonionic surfactant, lies in the range from 5:1 to 1:5,
more preferably from 1:1 to 1:4 for most combinations of
first and second surfactants.
The two categories of nonionic surfactant should
interact with each other to form a fabric-substantive
liquid crystalline phase which is not simply micellar in
nature. This liquid crystalline phase may be such as to be
described as hydrated solid, lamellar (Lα and Lβ),
hexagonal, cubic or some combination of these
possibilities. Particularly preferred are the hydrated
solid phase and the Lβ phase. The nonionic non-micellar
liquid crystalline phase should exist at the concentration
of use. In practice the combination of nonionic
surfactants should form liquid crystalline phase(s) at an
overall concentration of 5% by weight in water at 20°C.
We have found that a liquid crystalline phase can be
formed with a wide variety of nonionic surfactants as the
first nonionic surfactant (incorporating at least three
hydroxy groups in head group) provided the second nonionic
surfactant is chosen to have a sufficiently low HLB. The
formation of a suitable non-micellar liquid crystal phase
can be checked by optical microscopy and other phase
behaviour characterisation techniques as described by Small
D M, Handbook of Lipid Research, Vol 4: The Physical
Chemistry of Lipids" Plenum Press NY, 1986.
For formation of the liquid crystalline phase it has
proved desirable that either the first nonionic surfactant,
the second nonionic surfactant or both of them should have
an alkyl or alkenyl group of at least 16 carbon atoms.
Thus one or both surfactants may contain tallow alkyl
chains rather than coconut alkyl chains or similar
synthetic alkyl chains of 11 to 15 carbon atoms.
Frequently the second nonionic surfactant will contain
an alkyl or alkenyl chain of at least 16 carbon atoms.
Thus, the first nonionic surfactant will desirably be a
material which forms an Lβ or hydrated solid phase in a
system consisting of 2.5% by weight of first nonionic
surfactant, 2.5% by weight of stearyl alcohol and 95% by
weight of water.
A characteristic of surfactant combinations which
provide the preferred Lβ or hydrated solid phases is that,
an aqueous mixture, containing the nonionic surfactants at
a total concentration of 5% by weight, undergoes an
endothermic phase transition at a temperature above 0°C,
better above 5°C or 10°C. This phase transition is
detectable by differential scanning calorimetry and is
attributable to "melting" the hydrated solid or the
hydrocarbon chains of the Lβ phase.
This invention may be embodied in various forms of
fabric treatment product. Particularly envisaged is a
rinse conditioner formulation for addition to water used
for rinsing fabrics after washing. However, the invention
can also be embodied in other product forms as will be
mentioned again below.
Rinse conditioner compositions of this invention
preferably do not include any substantial amount of
synthetic anionic detergent because such detergent may
dissolve the desired liquid crystalline phase. Water
soluble soaps, with chain lengths of 14 or less carbon
atoms should be avoided for the same reason. Thus the
total amount of synthetic anionic detergent or water-soluble
soap (if any) should preferably not exceed 10% by
weight of the total amount of the required nonionic
surfactants, indeed preferably not exceed 10% by weight of
the total softener content.
Preferably, rinse conditioner compositions of this
invention do not include other non-bionic surfactants, so
that these cannot interfere with the interaction between
the specified nonionic surfactants. In particular, the
amount of ethoxylated fatty alcohols with five or more
ethylene oxide residues may be no more than 10% (better not
over 8%) weight of the amount of the said second non-ionic
surface active material (ii).
When a composition of the present invention is a rinse
conditioner, it may contain the aqueous surfactants as a
dispersion or solution in water at a total concentration in
the range from 2% to 30% by weight. Rinse conditioners can
also be embodied in other forms such as powders and pastes.
A composition which is for use as a rinse conditioner
will generally not include any significant amount of
detergency builders. Thus, the total amount of insoluble
aluminosilicate and water soluble tripolyphosphate (two
common detergency builders) will generally be less than 5%
by weight of the composition. Usually these will be
entirely absent.
A rinse conditioner composition could include a
cationic fabric softener, although certain forms of the
present invention do not use cationic materials.
Therefore, the total quantity of the required nonionic
surfactants may be at least half, equal to or greater than
the total quantity of cationic softeners, if any. Indeed,
the total quantity of the required nonionic surfactants may
be more than 3 or 4 times the total quantity, if any, of
cationic softeners.
Other constituents which may be incorporated into such
a rinse conditioning composition are perfumes, perfume
carriers, polymeric thickeners, drape imparting agents,
antistatic agents, germicides, fungicides and ironing aids.
Materials which enhance deposition on fabric may
usefully be included. Such materials are often polymeric:
GB-A-2266100 (case C3443) discloses certain cellulose
ethers for this purpose and mentions earlier documents
which proposed other materials able to bring about
deposition.
A rinse conditioning composition may be manufactured
by making a melt of the surfactant materials, adding this
to hot water e.g. at a temperature of 70 - 85°C, with
mixing, and then mixing the composition with high shear
until it is homogenous.
The invention can also be utilised in compositions
used on an industrial scale for finishing newly
manufactured fabric. Another possible application is
products for spraying directly onto fabric, for example
when ironing the fabric after it has been dried. Yet
another application is in products to be placed in a tumble
dryer jointly with the fabrics, so that the nonionic
surfactants transfer to the fabrics in their molten state.
Conventional products in this category take the form of
porous sheets impregnated with cationic fabric softener(s).
This invention could be embodied as similar sheets
impregnated with the solid surfactants of this invention.
The conditioning composition of the present invention
may be coated onto a flexible substrate which is capable of
releasing the composition in a tumble dryer. Such a
product can be designed for single usage or for multiple
uses. One such multi-use article comprises a sponge
material releasably enclosing enough of the conditioning
composition to effectively impart fabric softness during
several drying cycles. The multi-use article can be made
by filling a porous sponge with the composition. In use,
the composition melts and leaches out through the pores of
the sponge to soften and condition fabrics. A single use
sheet may comprise the inventive compositions carried on a
flexible substrate such as a sheet of paper or woven or
non-woven cloth substrate. When such an article is placed
in an automatic laundry dryer, the heat, moisture,
distribution forces and tumbling action of the dryer
removes the composition from the substrate and deposits it
on the fabrics. Substrate materials for single use and
multiple use articles, and methods of impregnating or
coating them are discussed in US-A-5254269 and elsewhere.
Another possible form of product embodying the
invention is a detergent composition which is formulated to
give fabric softening jointly with fabric washing.
If the composition of the invention is a detergent
composition for fabric washing, the composition will
usually contain one or more detergency builders, suitably
in an amount of from 5 to 60 or 80 wt%, preferably from 20
to 60 wt%. Various classes of detergency builders are well
known.
One well known class of builders is the alkali metal (preferably sodium) aluminosilicates. These may suitably be incorporated in amounts of from 5 to 60% by weight (anhydrous basis) of the composition, and may be either crystalline or amorphous or mixture thereof. These materials have the general formula:0.8 - 1.5 Na2O.Al2O3. 0.8 - 6 SiO2
contain some bound water and are required to have a calcium
ion exchange capacity of at least 50 mg CaO/g. The
preferred sodium aluminosilicates contain 1.5-3.5 SiO2
units (in the formula above).
One well known class of builders is the alkali metal (preferably sodium) aluminosilicates. These may suitably be incorporated in amounts of from 5 to 60% by weight (anhydrous basis) of the composition, and may be either crystalline or amorphous or mixture thereof. These materials have the general formula:
Suitable crystalline sodium aluminosilicate ion-exchange
detergency builders are described, for example, in
GB 1429143 (Proctor & Gamble). The preferred sodium
aluminosilicates of this type are the well known
commercially available zeolites A and X, and mixtures
thereof. Also of interest is the novel zeolite P described
and claimed in EP 384070 (Unilever).
Other builders may also be included in a detergent
composition, as necessary or desired. Water-soluble
builders may be organic or inorganic. Inorganic builders
that may be present include alkali metal (generally sodium)
carbonate, orthophosphate, pyrophosphate and
tripolyphosphate. Organic builders include polycarboxylate
polymers, such as polyacrylates, acrylic/maleic copolymers,
and acrylic phosphorates, monomeric polycarboxylates such
as citrates, gluconates, oxydisuccinates, glycerol mono- di- and
trisuccinates, carboxymethyloxysuccinates,
carboxymethyloxymalonates, dipicolinates,
hydroxyethyliminodiacetates; and organic precipitant
builders such as alkyl- and alkenylmalonates and
succinates.
Especially preferred supplementary builders for use
jointly with aluminosilicate are polycarboxylate polymers,
more especially polyacrylates and acrylic/maleic
copolymers, suitably used in amounts of from 0.5 to 15 wt%,
especially from 1 to 10 wt%; and monomeric
polycarboxylates, more especially citric acid and its
salts, suitably used in amounts of from 3 to 20 wt%, more
preferably from 5 to 15 wt% by weight of the composition.
Detergent compositions for fabric washing are
customarily formulated using anionic surfactant as at least
part of the detergent active. However, compositions are
known in which the detergent active is wholly or largely
nonionic. It is envisaged that the present invention may
in particular be embodied in a built detergent composition
where nonionic surfactants (including the nonionic
surfactants required by this invention) are over 50%,
probably at least 80% by weight of all surfactants present.
Synthetic anionic surfactants may well be omitted entirely.
In a detergent composition for fabric washing the
total amount of surfactant will generally lie in a range
from 5 to 50%, more usually 5 to 40% by weight of the
composition.
Detergent compositions according to the invention may
also contain a bleach system. This preferably comprises
one or more peroxy bleach compounds, for example, inorganic
persalts or organic peroxyacids, which may be employed in
conjunction with activators to improve bleaching action at
low wash temperatures. If any peroxygen compound is
present, the amount is likely to lie in a range from 10 to
25% by weight of the composition.
Preferred inorganic persalts are sodium perborate
monohydrate and tetrahydrate, and sodium percarbonate,
advantageously employed together with an activator. Bleach
activators, also referred to as bleach precursors, have
been widely disclosed in the art. Preferred examples
include peracetic acid precursors, for example,
tetraacetylethylene diamine (TAED), now in widespread
commercial use in conjunction with sodium perborate. The
quaternary ammonium and phosphonium bleach activators
disclosed in US 4751015 and US 4818426 (Lever Brothers
Company) are also of interest. Another type of bleach
activator which may be used, but which is not a bleach
precursor, is a transition metal catalyst as disclosed in
EP-A-458397, EP-A-458398 and EP-A-549272.
Detergent compositions of the invention may also
contain one or more of the detergency enzymes known in the
art for their ability to degrade and aid in the removal of
various soils and stains. Suitable enzymes include the
various proteases, cellulases, lipases, amylases, and
mixtures thereof.
Further ingredients which can optionally be employed
in a detergent composition of the invention include
antifoams, fluorescers, anti-redeposition agents such as
sodium carboxymethylcellulose, heavy metal sequestrants
such as EDTA; perfumes; pigments, colorants or coloured
speckles; and inorganic salts such as sodium and magnesium
sulphate.
A number of experiments were carried out with the
following materials:
- CLB = Cocolactobionamide
- }all
- TLB = Tallow lactobionamide
- }of
- HTLB = Hardened tallow lactobioamide
- }formula
Various formulations were prepared, as set out in
tables below. The formulations all contained 1.33% by
weight of the carbohydrate-based first nonionic surfactant.
Each formulation was prepared by adding the nonionic
surfactant(s) to water at 80-85°C, and allowing the mixture
to equilibrate with occasional agitation, after which it
was subjected to high shear mixing until homogenous.
After cooling, formulations were tested to evaluate
their fabric softening efficacy, diluting the formulations
with tap water (10°FH) so that they contained a total of
7.52 grams of the formulation per litre of water. This
provided 0.1 g/litre by weight of the first nonionic
surfactant. Comparative data were provided by formulations
containing one of the carbohydrate-based first nonionic
surfactants without a second nonionic surfactant. Here the
concentration of each first nonionic surfactant in water
was 0.1 g/litre or greater. A control was provided by HT
TMAPC formulated at a concentration of 2.5% by weight, and
then used at a concentration of 4 g/litre, so as again to
provide 0.1 g/litre by weight in the treatment liquor.
Another control was water only. The second nonionic
surfactants are of such low HLB (i.e. non-polar) that they
could not be dispersed in water. Consequently, if an
attempt was made to use them without the first nonionic
surfactant, the result was the same as with water alone.
The test fabric was terry towelling which had
previously been washed to remove any filler or dressing
applied during manufacture. The fabric was treated in
Tergotometer pots. Three pieces of terry towelling (8cm x
8cm, 40g total weight) were added to each tergotometer pot.
The treatment liquor was then dosed onto the cloths which
were treated for 5 minutes while the agitator in the
tergotometer rotated at 65 rpm, then spin dried to remove
excess liquor and line dried overnight.
Softening of the fabrics was assessed by an expert
panel of 4 people. Each panel member assessed cloths
treated with test or comparative formulations, together
with control cloths respectively treated with HT TMAPC or
water only. Panel members were asked to assess softness on
an 8 point scale, where a score of 8 represents unsoftened
fabric and a score of 2 represents extremely soft fabric.
Thus, lower values are indicative of better softening.
Softness scores were calculated by averaging the scores of
the individual panellists.
The results are tabulated below:
Ex. No | Formulations providing 0.1g APG per litre in rinse | |||
APG (wt%) | ROH (wt%) | APG:ROH (molar ratio) | Softness Ranking | |
1 | 1.33 | 1.42 | 1:1.75 | 3 |
2 | 1.33 | 1.63 | 1:2 | 3.25 |
3 | 1.33 | 1.85 | 1:2.25 | 3.75 |
4 | 1.33 | 2.05 | 1:2.5 | 4.25 |
C | 1.33 | None | 7.0 |
Ex. No | Formulations providing 0.1g CLB per | litre in rinse | ||
CLB (wt%) | ROH (wt%) | CLB:ROH (molar ratio) | Softness Ranking | |
5 | 1.33 | 1.17 | 1:2 | 3.25 |
6 | 1.33 | 1.34 | 1:2.25 | 3.75 |
7 | 1.33 | 1.49 | 1:2.5 | 3.5 |
8 | 1.33 | 1.79 | 1:3 | 3.5 |
CLB (wt%) | GMS (wt%) | CLB:GMS (molar ratio) | Softness Ranking | |
9 | 1.33 | 1.46 | 1:1.75 | 4.5 |
10 | 1.33 | 1.67 | 1:2 | 5.25 |
11 | 1.33 | 2.09 | 1:2.5 | 5.25 |
12 | 1.33 | 2.50 | 1:3 | 6.25 |
Ex. No | Formulations providing 0.1g TLB per litre in rinse | |||
TLB (wt%) | Second nonionic | Molar Ratio | Softness Ranking | |
13 | 1.33 | ROH | 1:1.33 | 2.75 |
14 | 1.33 | GMS | 1:0.5 | 3.25 |
F | 1.33 | None | 7.25 |
Ex. No | Formulations providing 0.1g HTLB per litre in rinse | |
HTLB:GMS (molar ratio) | Softness Ranking | |
15 | 1:0.5 | 3.5 |
16 | 1:1 | 3.75 |
17 | 1:1.5 | 2.2 |
18 | 1:2 | 3.5 |
HTLB:ROH | Softness Ranking | |
19 | 1:0.5 | 3.5 |
20 | 1:1 | 3.75 |
21 | 1:1.5 | 2.25 |
22 | 1:2 | 3.5 |
Ex. No | Formulation provides in rinse | Softness Ranking |
Control A | 0.1g HT TMAPC per litre | 2.75 |
Control B | Water only | 8 |
D | 0.2g CLB per litre | 6.5 |
E | 2.0g CLB per litre | 6.5 |
In a second experiment some of the treated test cloths
were divided into strips 3cm wide. These were tested for
water absorbency by dipping an end portion in demineralised
water and measuring the height of water rise up the strips
after 15 minutes. The results are in the following table
and show a dramatic difference from the HT TMAPC control.
Ex. No | Formulation | Wicking Height (mm) | |
provides 0.1g/litre in rinse | Second nonionic | ||
1 | 1.33% APG | 1.42% ROH | 52 |
5 | 1.33% CLB | 1.17% ROH | 66 |
Control A | HT TMAPC | none | 3 |
In further experiments, pairs of first and second
nonionic surfactants were tested at varying concentrations
in the rinse liquor. Softness and wicking height were
assessed as described for the Examples above. The results
were:
Dose (g/l) in rinse liquor | Softness Ranking | Wicking Height (cm) |
HTLB:GMS (1:1.5 mole ratio) | ||
0.05 | 4 | 10.0 |
0.1 | 2.5 | 10.0 |
0.2 | 2 | 9.2 |
HTLB:ROH (1:1.5 mole ratio) | ||
0.05 | 4.5 | 11.3 |
0.1 | 3 | 10.5 |
0.2 | 2 | 10.5 |
TLB:ROH (1:1.33 mole ratio) | ||
0.05 | 7 | 14.4 |
0.1 | 5.5 | 14.4 |
0.02 | 3.25 | 12.0 |
CLB:ROH (1:2 mole ratio) | ||
0.05 | 4.5 | 14.2 |
0.1 | 3 | 12.7 |
0.2 | 2 | 11.8 |
Claims (12)
- A composition containing(i) a first nonionic surfactant or mixture of surfactants, having a head group bearing at least three free hydroxyl groups, and having a lipophilic aliphatic radical of 10 to 40 carbon atoms attached to that head group, and(ii) a second nonionic surfactant or mixture of surfactants with an HLB value which is not above 7.
- A composition according to Claim 1 wherein the HLB value of the second nonionic surfactant is less than 5.
- A composition according to claim 1 or claim 2 wherein the head group of the first nonionic surfactant bears at least four free hydroxyl groups.
- A composition according to claim 1, claim 2 or claim 3 wherein the aliphatic radical of the first nonionic surfactant is an alkyl or alkenyl chain of 12 to 24 carbon atoms.
- A composition according to any one of the preceding claims wherein the mole ratio of (i) to (ii) is in a range from 5:1 to 1:5.
- A composition according to claim 3 wherein the surface active materials (i) and (ii) when at a total concentration of 5% by weight in water at 20°C form a liquid crystalline phase.
- A composition according to any one of the preceding claims wherein the first nonionic surface active material (i) has an HLB exceeding 11.
- A composition according to any one of claims 1 to 7 which is an aqueous suspension for use as a rinse conditioner.
- A composition according to claim 8 which contains from 2 to 30% of the said nonionic surfactants.
- A porous sheet impregnated with a composition according to any one of claims 1 to 7.
- A composition according to any one of claims 1 to 7 which is a detergent composition containing builder.
- A method of washing and conditioning fabrics by steps of(i) washing the fabrics in an aqueous wash liquor containing detergent, then(ii) rinsing the fabrics with water characterised by adding a composition according to any one of claims 1 to 7 to the rinse water.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96309419A EP0849354A1 (en) | 1996-12-20 | 1996-12-20 | Softening compositions |
CA002275876A CA2275876A1 (en) | 1996-12-20 | 1997-12-11 | Softening compositions |
EP97953864A EP0946696A1 (en) | 1996-12-20 | 1997-12-11 | Softening compositions |
BR9713607-7A BR9713607A (en) | 1996-12-20 | 1997-12-11 | Fabric softener composition, porous sheet, and fabric washing and conditioning process |
AU57608/98A AU5760898A (en) | 1996-12-20 | 1997-12-11 | Softening compositions |
PCT/EP1997/007145 WO1998028390A1 (en) | 1996-12-20 | 1997-12-11 | Softening compositions |
ARP970106107 AR009841A1 (en) | 1996-12-20 | 1997-12-22 | A SOFTENING COMPOSITION FOR FABRICS, A POROUS LEAF IMPREGNATED WITH SUCH SOFTENING COMPOSITION FOR FABRICS AND A METHOD FOR WASHING AND CONDITIONING FABRICS |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96309419A EP0849354A1 (en) | 1996-12-20 | 1996-12-20 | Softening compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0849354A1 true EP0849354A1 (en) | 1998-06-24 |
Family
ID=8225203
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96309419A Withdrawn EP0849354A1 (en) | 1996-12-20 | 1996-12-20 | Softening compositions |
EP97953864A Withdrawn EP0946696A1 (en) | 1996-12-20 | 1997-12-11 | Softening compositions |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97953864A Withdrawn EP0946696A1 (en) | 1996-12-20 | 1997-12-11 | Softening compositions |
Country Status (6)
Country | Link |
---|---|
EP (2) | EP0849354A1 (en) |
AR (1) | AR009841A1 (en) |
AU (1) | AU5760898A (en) |
BR (1) | BR9713607A (en) |
CA (1) | CA2275876A1 (en) |
WO (1) | WO1998028390A1 (en) |
Families Citing this family (2)
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US11925730B2 (en) * | 2016-07-13 | 2024-03-12 | Council Of Scientific & Industrial Research | Method for preventing rectraction of aqueous drops and a medical device coated with hydrophilic coating |
GB2589993A (en) * | 2018-06-28 | 2021-06-16 | Kimberly Clark Co | Lotion treated tissue product |
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Also Published As
Publication number | Publication date |
---|---|
CA2275876A1 (en) | 1998-07-02 |
EP0946696A1 (en) | 1999-10-06 |
WO1998028390A1 (en) | 1998-07-02 |
AU5760898A (en) | 1998-07-17 |
BR9713607A (en) | 2000-04-11 |
AR009841A1 (en) | 2000-05-03 |
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