CA1087352A - Fabric-softening compositions - Google Patents
Fabric-softening compositionsInfo
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- CA1087352A CA1087352A CA263,567A CA263567A CA1087352A CA 1087352 A CA1087352 A CA 1087352A CA 263567 A CA263567 A CA 263567A CA 1087352 A CA1087352 A CA 1087352A
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Abstract
Abstract of the Disclosure:
Solid and liquid wash-addable fabric-softening compositions contain as active softener a tertiary amine having an isoelectric point of from 8.3 to 9.8 and of the structure RR1R2N where R
is an alkyl group having from 1 to 6 carbon atoms and R1 and R2 are substantially linear alkyl or alkenyl groups having from 10 to 26 carbon atoms, for instance methyldi(hydrogenated tallow)amine.
Solid and liquid wash-addable fabric-softening compositions contain as active softener a tertiary amine having an isoelectric point of from 8.3 to 9.8 and of the structure RR1R2N where R
is an alkyl group having from 1 to 6 carbon atoms and R1 and R2 are substantially linear alkyl or alkenyl groups having from 10 to 26 carbon atoms, for instance methyldi(hydrogenated tallow)amine.
Description
108735~
This inventian relates to tertiary aminecompositions useful as fabric softeners.
In recent years compositions capable of improving the softness of laundered fabrics have been sold for damestic use. Usually such fabric-softening compositions have t~ken the form of an aqueous solution or dispersion of a campound which confers a softening effect on fabric, and these solutions or dispersions are added to the water in which the fabric articles are rinsed after washing. A camplete laundering process consists of a wash cycle in which a fabric is washed with an aqueous solution of a detergent camposition, follawed by removal of the bulk of the wash liquor fram the fabric, and a rinse cycle, in which the fabric is rinsed with water to remove residual detergent camposition, follawed by removal of the rinse liquor. The rinse cycle may be repeated before the laundered fabric is dried. m e need to add the softening camposition during the rinse cycle can be inconvenient, particularly with autamatic washing machines which would otherwise perform the camplete laundering without interruptian.
Attempts have therefore been made to develop a wash-cycle composition, that is, a camposition to be added in the wash cycle and which is capable of softening fabrics in the presen oe of detergent-active compounds so that the fabric can be cleaned and softened simultaneously. This pro-vides a difficult problem, for the active softening ingredient has to be capable of deposition in apposition to the action of the detergent whose function is to remove soil fram the fabric, and in an amount sufficient to soften the fabric, but not so great that the appearance of the fabric is impaired. Furthermore, the active softening ingredient should not depress the detergent activity of the detergent-active r
This inventian relates to tertiary aminecompositions useful as fabric softeners.
In recent years compositions capable of improving the softness of laundered fabrics have been sold for damestic use. Usually such fabric-softening compositions have t~ken the form of an aqueous solution or dispersion of a campound which confers a softening effect on fabric, and these solutions or dispersions are added to the water in which the fabric articles are rinsed after washing. A camplete laundering process consists of a wash cycle in which a fabric is washed with an aqueous solution of a detergent camposition, follawed by removal of the bulk of the wash liquor fram the fabric, and a rinse cycle, in which the fabric is rinsed with water to remove residual detergent camposition, follawed by removal of the rinse liquor. The rinse cycle may be repeated before the laundered fabric is dried. m e need to add the softening camposition during the rinse cycle can be inconvenient, particularly with autamatic washing machines which would otherwise perform the camplete laundering without interruptian.
Attempts have therefore been made to develop a wash-cycle composition, that is, a camposition to be added in the wash cycle and which is capable of softening fabrics in the presen oe of detergent-active compounds so that the fabric can be cleaned and softened simultaneously. This pro-vides a difficult problem, for the active softening ingredient has to be capable of deposition in apposition to the action of the detergent whose function is to remove soil fram the fabric, and in an amount sufficient to soften the fabric, but not so great that the appearance of the fabric is impaired. Furthermore, the active softening ingredient should not depress the detergent activity of the detergent-active r
- 2 -`~
.. '' , ~
... . .... . .
compound in the compositicn, and most compcunds which are knohfn to be fabric softeners are cationic and form insoluble af~dition products with conventional anionic detergent-active compounds. Proposals have been - made to solve this problem by using as softening agents certain betaines S which undergo a charge reversal when the pH changes from the alkalineconditions of a wash liquor where they are anionic to the less alkaline conditions of a rinse liquor in which they are cationic and their deposition on to fabric is prcmoted. Such a betaine is soluble in the wash liquor and the small proportion of that used which is in the wash liquor residue present in the first rinse cycle has to suffice to provide the softening.
It has been prcposed in German Patent 722,281 to use as textilè
softeners water-insoluble primary, secondary and tertiary fatty amunes in conjunction with detergents and inorganic salts, the only tertiary amine specifically mentioned being dimethyldodecylamine. British Patent 1,052,847 describes the use in the wash cycle of solid fabric softeners which are complexes of urea and primary, secondary and tertiary amines -having at least one straight-chain organic radical containing 12 to 18 carbon atoms, but no specific tertiary amines are mentioned.
, 20 It has now been discovered that a small group of tertiary fatty amines possess special advantages as wash-cycle fabric softeners because, like the betaines referred to above and unlike dimethyldodecylamine f and tertiary or other fatty amines in general, they are negatively charged under the relatively strong alkaline conditions present in a typical wash cycle and therefore do not complex with anionic detergent-active compounds, but are protonated and therefore cationic and fabric-substantive under the neutral or slightly alkaline conditions present in a rinse cycle. They can therefore be added to an alkaline detergent wash liquor without reducing its cleaning capacity, and as they are insoluble in the wash liquor, when this is discharged most of the amine is left behind entrapped in the fabric so that it is available for softening in the rinse; this residual amine becomes substantive to the fabric when the rinsing water is added, so that before the rinse liquor is discharged it is adsorbed on to the fabric.
m e isoe lectric point of such an amine lies within narrow limits, for the change in its electronic properties, or cllarge reversal, has to occur between the pH of the wash liquor and the pH of the first rinse liquor, which is still weakly alkaline due to residual wash liquor.
me pH of a wash liquor containing anionic detergent-active compounds is generally within the range from 8.0 to 9.9, depending on the detergency builder emplcyed. It has been found that where the isoelectric point of the amune is substantially below the pH of the wash liquor and at least 0.2 units above the pH of the rinse water the charge reversal occurs on addition of rinse water to the fabric after discharge of the wash liquor. The amines having the desired properties are ~j 20 tertiary amines having an isoelectric point of from 8.3 to 9.8 and the structure RRlR2N where R is an aIkyl group having fram l to 6 carbon atoms and R1 and R2 are substantially linear aIkyl or alkenyl groups having from 10 to 26 carbon atoms.
The isoelectric point of any given amine can be determined by measuring the electrophoretic mobility of an aqueous dispersion of the amine under standard conditions of concentration and temperature and ::: ~: :. ~: - : :
1~8~7352 at a series of pHs, with plotting of the mobilities against pH to determine the pH of zero m~bility. The isoelectric points of a series of fatty amines are given in khe following table, in which T and Co represent the nLLY~d aIkyl radical deriv2d frGm hydrogenated tallcw acid and COcGnUt oil acid, respectively. Fram this table it can be seen that those tertiary amines which are members of the above special group have the required isoelectric points, whereas the other amines do not.
T2NH 7.4 T3N 8.2 T2NCH3 8.8 T2N(CH2)3CH3 g.o Co2NcH3 9. 1 IN (CH3) 2 10. 0 INH2 10.9 kmines of the special group are in general old campounds, and their use has been described for purposes other than as fabric-softening agents. They can be prep æed by the processes described in Kirk-Othmer's Encyclo~aedia of Chemical Technology, Volume ~ under Fatty Amines, or in US Patent 3,471,562, which describes the prep æ ation of dioctadecylmethylamine and its use as an intermediate for the preparation of quaternary ammonium ca~pounds which æ e themselves cationic fabric softeners but do not possess the property of charge reversal. British Patent 1,286,054 and US Patent 3,696,056 describe the use of fatty amines in campositions for cantrolling fo~m generated by synthetic detergent campositions and make no mentian of fabric softening; the only tertiary amine having the structure given above that lS specifically mentioned is a substance - ~ ... ~ , .. . .. : .
1~8735Z
designated methyl dihydrcgenated tallcw amine. The only compositions disclosed containing that amine are ineffective for the purpose of providing fabric-softening, and in order to obtain the practical benefit of the present invention it has been found essential to formulate the fabric-softening amines in such a way as to provide compositions which are different from those described in British Patent 1,286,054 and US
- Patent 3,696,056.
According to the present invention, a fabric-softening ccmposition oonprises a tertiary amine having an isoe lectric point of from 8.3 to 9.8 and of the structure RRlR2N where R is an aLkyl group having from 1 to 6 carbon atoms and Rl and R2 are substantially linear alkyl or aIkenyl groups having from 10 to 26 carbon atomsl and a diluent, in which the diluent is water or a water-soluble non-surface-active salt;
and where the diluent is water the composition is liquid and comprises from 2to 50% of the amine dispersed in from 98 to 50% of water, by weight of the total amount of the amine and wat~r~ and where the diluent is a water-soluble non-surface-active salt, the composition is solid and ccmprises from 6.3 to 90% of the amine and from 10 to 93.7~ of the -~
salt by weight of the composition.
The tertiary amine softeners are preferably those where R has from 1 to 4 carbon atoms, and especially those where R is a methyl group.
R will normally be a primary alkyl grcup. Preferably R1 and R2 each have from 12 to 22, and especially from 16 to 18, carbon atoms.
By "substantially linear alkyl or alkenyl group" is meant a group which is a substantially unbranched primary aLkyl or alkenyl group; the presence of minor amounts of branching insufficient to destroy the softening ; - 6 -properties which are conferred by the long chain is not excluded.
Mixtures of amines can be employed, for instance commercial mixtures of compounds in which the aIkyl or aIkenyl grou~s are derived from the fatty acids of natural fats, as when coconut and hydrogenated tallow acids are converted to their nitriles and these are subsequently hydrogenated and aIkylated. In accordance with usage in the fatty amine art, such mixed amines are here referred to as "coco" and "hydrogenated tallcw" amines. Rl and R2 can be similarly derived from soyabean oil fatty acid. Preferably Rl and R2 are groups derived from a ccmmon source so that in single compounds they are the same group, and in com~: rcial mixtures of ocmpounds they represent the same individual groups in the same proportion.
Examples of suitable amines for use as wash-cycle softeners are:
Methyldidecylamine Methyldicocoamine Methyldilaurylamine Methyldi(hydrogenated tallow) amine Methyldimyristylamine Ethyldilaurylamine Methyldicetylamine Ethyldi oe tylamine Methyldimargarylamine Propyldistearylamine Methyldistearylamine Butyldistearylamine Methyldiarachidylamine Ethyldicocoamine Methyldidocosylamine Ethyldi(hydrogenated tallow)amine Methyditetracosylamine Butyldi(hydrogenated tallow)amine Methyldicociamine and methldi(hydrogenated tallow)amine are particularly suitable.
The inVention provides a process for preparing an aqueuos amine dispersion of the invention, in which the amine is dispersed in water ,, .
~ 7 , .: , : .: ........... : .. , ..... ... :- ., , ~ ! ; : ' ' ', ' ' ' ' . , , .- . , , ' . ' ' ' .';','. . . _ . ; .' . ' . ,', ' ' ' ., , ' .
l~B735Z
in the presence of an emulsifier, preferably at a temperature at which the am m e is in the liquid form. Suitable emulsifiers are listed in Kirk-Othmers' Encyclopaedia of Chemical Technology, Volume 8, page 128-130. The resulting emulsion may on cool m g beccme a suspension due to solidification of the amine. Most dispersions thus prepared have a short life because they are unstable, and if stored before use are liable to separate into an aqueous phase and a solid amine phase: the successful preparation of dispersions that are stable for many weeks has presented a problem, for it has been found that the use of the standard procedures of emulsion technology for choosing an emulsifier system having the optimum hydrophiliclipophilic balance (HLB) fails to produce stable emulsions. It has hcwever been discovered that satisfactorily stable dispersions can be prepared by introducing an emulsifier with a hydrophobic group similar to the hydrophobic groups of the amine; this appears to function by enabling the formation of amine particles having at their surface the anianic polar head group of emulsifier carrying a negative charge, thus altering the effective isoelectric point of the amine, while the packing of the hydrophobic group of the emulsifier with the corresponding groups of the amine enables retention of this group within the particles. .
Accordingly a liquid composition of the invention preferably contains as emulsifier an anionic surface-active agent having a hydrophobic grc~p that is a substantially linear alkyl or alkenyl group having an average chain length within 2 1/2 carbon atoms of the average chain length of the groups Rl and R2 in the amine. Particularly suitable are emMlsifiers having a hydrophobic group distribution that is substantially ;~ - 8 -.:, . . .. . : . , ,. ;. . . . .
10873~iiZ
the same as that of the am m e. The anionic head group of the emulsifier can be carboxylate, sulphate, sulphonate, phosphate or phosphonate.
Suitable emulsifiers can be chosen frcm sodium laurate, myristate, palmitate and stearate, disalium hexadecenyl succinate (which has an effective hydrophobic chain length of 16 carbon atoms), sodium N-tallow acyl glutamate (where the "tallow acyl" is a mlxture of the acyl groups of tallcw fatty acids, and the emulsifier has an effective hydrophobic chain length of 17 carbon atoms), sodium C16-C18 ~-olefin sulphonate (having an effective hydrophobic chain length of 17 carbon atoms), sodium tallow fatty acid sulphonate (having an effective hydrophobic chain length of 17 carbon atams) and sodi~m C16-C20 n- alkyl phosphate (having an effective hydrophobic chain length of 18 carbon atoms). Other emulsifiers which can be used are sodium hexyIbenzene sulphonate and sodium - octadecylbenzene sulphonate. Instead of sodium salts the salt of any equivalent cation providing wat~r-solubility~ for instance lithium, potassium or ammcnium, can be used.
Where the amine employed is methldicoc3amine, the em~lsifier is preferably sodium laurate, and especially the sodium salt of coconut oil fatty acid. Where the amine is methyldi(hydrogenated tallow)amine the emLlsifier is preferably sodium stearate and especially the sodium salt of hydrogenated tallow acid.
~ `'''' .
~ Preferably the liquid amine composition contains from 5 to 30%, ; .
and especially from 7 to 25%, of the amine by weight of the total amount of amine and water, as such concentrations confer practical advantages in terms of correspondence to existing habits of users of liquid fabric conditioners having regard to the need to dispense a reasonable buIk of liquid in standard amounts and to provide an effective ;i am~unt ofamune in the wash liquor. An effective amount of the emwlsifier :':
_g_ : ~
. ;., : :; .,,: ~ . : . ... .. . .
~08735Z
is chosen from within the range of 0.002 to 10% by weight of the dispersion, and generally frcm 0.1 to 20% by weight of the disperse phase is employed.
Preferably the solid amine composition contains at least 6.5, and expecially at least 7%, of the am m e. The amount of the salt present will usually be less than 75% by weight of the co~position.
As water-soluble non-surface-active salts there are preferably used detergency builder salts. By "detergency builder salt" in this specification is meant a salt that possesses the power of increasing the detergent activity of a detergent-active compound Suitable detergency builder salts are inorganic buil~rs such as sodium ortho-, pyro-, trimeta- and tripoly-phosphates, sodium carbonate and sodium silicate.
Examples of organic builders are salts or organic acids such as sodium citrate, sodium oxydiacetate, sodium carboxymethyloxysuccinate, sodium nitrilotriacetate and sodium ethylenediam me tetraacetate.
15Non-surface-active salts other than detergency builders which can be used in solid compositions of the invention are sodium perborate or percarbonate which provide a bleaching function, and sodium sulphate.
Preferably where the ccmposition contains a detergency builder salt, it also contains an anionic detergent-active campound, especially a ~ 20 non-soap (or synthetic) anionic detergent-active compound. Such a - composition is preferably one containing fram 6.5 to 35% of amine, from
.. '' , ~
... . .... . .
compound in the compositicn, and most compcunds which are knohfn to be fabric softeners are cationic and form insoluble af~dition products with conventional anionic detergent-active compounds. Proposals have been - made to solve this problem by using as softening agents certain betaines S which undergo a charge reversal when the pH changes from the alkalineconditions of a wash liquor where they are anionic to the less alkaline conditions of a rinse liquor in which they are cationic and their deposition on to fabric is prcmoted. Such a betaine is soluble in the wash liquor and the small proportion of that used which is in the wash liquor residue present in the first rinse cycle has to suffice to provide the softening.
It has been prcposed in German Patent 722,281 to use as textilè
softeners water-insoluble primary, secondary and tertiary fatty amunes in conjunction with detergents and inorganic salts, the only tertiary amine specifically mentioned being dimethyldodecylamine. British Patent 1,052,847 describes the use in the wash cycle of solid fabric softeners which are complexes of urea and primary, secondary and tertiary amines -having at least one straight-chain organic radical containing 12 to 18 carbon atoms, but no specific tertiary amines are mentioned.
, 20 It has now been discovered that a small group of tertiary fatty amines possess special advantages as wash-cycle fabric softeners because, like the betaines referred to above and unlike dimethyldodecylamine f and tertiary or other fatty amines in general, they are negatively charged under the relatively strong alkaline conditions present in a typical wash cycle and therefore do not complex with anionic detergent-active compounds, but are protonated and therefore cationic and fabric-substantive under the neutral or slightly alkaline conditions present in a rinse cycle. They can therefore be added to an alkaline detergent wash liquor without reducing its cleaning capacity, and as they are insoluble in the wash liquor, when this is discharged most of the amine is left behind entrapped in the fabric so that it is available for softening in the rinse; this residual amine becomes substantive to the fabric when the rinsing water is added, so that before the rinse liquor is discharged it is adsorbed on to the fabric.
m e isoe lectric point of such an amine lies within narrow limits, for the change in its electronic properties, or cllarge reversal, has to occur between the pH of the wash liquor and the pH of the first rinse liquor, which is still weakly alkaline due to residual wash liquor.
me pH of a wash liquor containing anionic detergent-active compounds is generally within the range from 8.0 to 9.9, depending on the detergency builder emplcyed. It has been found that where the isoelectric point of the amune is substantially below the pH of the wash liquor and at least 0.2 units above the pH of the rinse water the charge reversal occurs on addition of rinse water to the fabric after discharge of the wash liquor. The amines having the desired properties are ~j 20 tertiary amines having an isoelectric point of from 8.3 to 9.8 and the structure RRlR2N where R is an aIkyl group having fram l to 6 carbon atoms and R1 and R2 are substantially linear aIkyl or alkenyl groups having from 10 to 26 carbon atoms.
The isoelectric point of any given amine can be determined by measuring the electrophoretic mobility of an aqueous dispersion of the amine under standard conditions of concentration and temperature and ::: ~: :. ~: - : :
1~8~7352 at a series of pHs, with plotting of the mobilities against pH to determine the pH of zero m~bility. The isoelectric points of a series of fatty amines are given in khe following table, in which T and Co represent the nLLY~d aIkyl radical deriv2d frGm hydrogenated tallcw acid and COcGnUt oil acid, respectively. Fram this table it can be seen that those tertiary amines which are members of the above special group have the required isoelectric points, whereas the other amines do not.
T2NH 7.4 T3N 8.2 T2NCH3 8.8 T2N(CH2)3CH3 g.o Co2NcH3 9. 1 IN (CH3) 2 10. 0 INH2 10.9 kmines of the special group are in general old campounds, and their use has been described for purposes other than as fabric-softening agents. They can be prep æed by the processes described in Kirk-Othmer's Encyclo~aedia of Chemical Technology, Volume ~ under Fatty Amines, or in US Patent 3,471,562, which describes the prep æ ation of dioctadecylmethylamine and its use as an intermediate for the preparation of quaternary ammonium ca~pounds which æ e themselves cationic fabric softeners but do not possess the property of charge reversal. British Patent 1,286,054 and US Patent 3,696,056 describe the use of fatty amines in campositions for cantrolling fo~m generated by synthetic detergent campositions and make no mentian of fabric softening; the only tertiary amine having the structure given above that lS specifically mentioned is a substance - ~ ... ~ , .. . .. : .
1~8735Z
designated methyl dihydrcgenated tallcw amine. The only compositions disclosed containing that amine are ineffective for the purpose of providing fabric-softening, and in order to obtain the practical benefit of the present invention it has been found essential to formulate the fabric-softening amines in such a way as to provide compositions which are different from those described in British Patent 1,286,054 and US
- Patent 3,696,056.
According to the present invention, a fabric-softening ccmposition oonprises a tertiary amine having an isoe lectric point of from 8.3 to 9.8 and of the structure RRlR2N where R is an aLkyl group having from 1 to 6 carbon atoms and Rl and R2 are substantially linear alkyl or aIkenyl groups having from 10 to 26 carbon atomsl and a diluent, in which the diluent is water or a water-soluble non-surface-active salt;
and where the diluent is water the composition is liquid and comprises from 2to 50% of the amine dispersed in from 98 to 50% of water, by weight of the total amount of the amine and wat~r~ and where the diluent is a water-soluble non-surface-active salt, the composition is solid and ccmprises from 6.3 to 90% of the amine and from 10 to 93.7~ of the -~
salt by weight of the composition.
The tertiary amine softeners are preferably those where R has from 1 to 4 carbon atoms, and especially those where R is a methyl group.
R will normally be a primary alkyl grcup. Preferably R1 and R2 each have from 12 to 22, and especially from 16 to 18, carbon atoms.
By "substantially linear alkyl or alkenyl group" is meant a group which is a substantially unbranched primary aLkyl or alkenyl group; the presence of minor amounts of branching insufficient to destroy the softening ; - 6 -properties which are conferred by the long chain is not excluded.
Mixtures of amines can be employed, for instance commercial mixtures of compounds in which the aIkyl or aIkenyl grou~s are derived from the fatty acids of natural fats, as when coconut and hydrogenated tallow acids are converted to their nitriles and these are subsequently hydrogenated and aIkylated. In accordance with usage in the fatty amine art, such mixed amines are here referred to as "coco" and "hydrogenated tallcw" amines. Rl and R2 can be similarly derived from soyabean oil fatty acid. Preferably Rl and R2 are groups derived from a ccmmon source so that in single compounds they are the same group, and in com~: rcial mixtures of ocmpounds they represent the same individual groups in the same proportion.
Examples of suitable amines for use as wash-cycle softeners are:
Methyldidecylamine Methyldicocoamine Methyldilaurylamine Methyldi(hydrogenated tallow) amine Methyldimyristylamine Ethyldilaurylamine Methyldicetylamine Ethyldi oe tylamine Methyldimargarylamine Propyldistearylamine Methyldistearylamine Butyldistearylamine Methyldiarachidylamine Ethyldicocoamine Methyldidocosylamine Ethyldi(hydrogenated tallow)amine Methyditetracosylamine Butyldi(hydrogenated tallow)amine Methyldicociamine and methldi(hydrogenated tallow)amine are particularly suitable.
The inVention provides a process for preparing an aqueuos amine dispersion of the invention, in which the amine is dispersed in water ,, .
~ 7 , .: , : .: ........... : .. , ..... ... :- ., , ~ ! ; : ' ' ', ' ' ' ' . , , .- . , , ' . ' ' ' .';','. . . _ . ; .' . ' . ,', ' ' ' ., , ' .
l~B735Z
in the presence of an emulsifier, preferably at a temperature at which the am m e is in the liquid form. Suitable emulsifiers are listed in Kirk-Othmers' Encyclopaedia of Chemical Technology, Volume 8, page 128-130. The resulting emulsion may on cool m g beccme a suspension due to solidification of the amine. Most dispersions thus prepared have a short life because they are unstable, and if stored before use are liable to separate into an aqueous phase and a solid amine phase: the successful preparation of dispersions that are stable for many weeks has presented a problem, for it has been found that the use of the standard procedures of emulsion technology for choosing an emulsifier system having the optimum hydrophiliclipophilic balance (HLB) fails to produce stable emulsions. It has hcwever been discovered that satisfactorily stable dispersions can be prepared by introducing an emulsifier with a hydrophobic group similar to the hydrophobic groups of the amine; this appears to function by enabling the formation of amine particles having at their surface the anianic polar head group of emulsifier carrying a negative charge, thus altering the effective isoelectric point of the amine, while the packing of the hydrophobic group of the emulsifier with the corresponding groups of the amine enables retention of this group within the particles. .
Accordingly a liquid composition of the invention preferably contains as emulsifier an anionic surface-active agent having a hydrophobic grc~p that is a substantially linear alkyl or alkenyl group having an average chain length within 2 1/2 carbon atoms of the average chain length of the groups Rl and R2 in the amine. Particularly suitable are emMlsifiers having a hydrophobic group distribution that is substantially ;~ - 8 -.:, . . .. . : . , ,. ;. . . . .
10873~iiZ
the same as that of the am m e. The anionic head group of the emulsifier can be carboxylate, sulphate, sulphonate, phosphate or phosphonate.
Suitable emulsifiers can be chosen frcm sodium laurate, myristate, palmitate and stearate, disalium hexadecenyl succinate (which has an effective hydrophobic chain length of 16 carbon atoms), sodium N-tallow acyl glutamate (where the "tallow acyl" is a mlxture of the acyl groups of tallcw fatty acids, and the emulsifier has an effective hydrophobic chain length of 17 carbon atoms), sodium C16-C18 ~-olefin sulphonate (having an effective hydrophobic chain length of 17 carbon atoms), sodium tallow fatty acid sulphonate (having an effective hydrophobic chain length of 17 carbon atams) and sodi~m C16-C20 n- alkyl phosphate (having an effective hydrophobic chain length of 18 carbon atoms). Other emulsifiers which can be used are sodium hexyIbenzene sulphonate and sodium - octadecylbenzene sulphonate. Instead of sodium salts the salt of any equivalent cation providing wat~r-solubility~ for instance lithium, potassium or ammcnium, can be used.
Where the amine employed is methldicoc3amine, the em~lsifier is preferably sodium laurate, and especially the sodium salt of coconut oil fatty acid. Where the amine is methyldi(hydrogenated tallow)amine the emLlsifier is preferably sodium stearate and especially the sodium salt of hydrogenated tallow acid.
~ `'''' .
~ Preferably the liquid amine composition contains from 5 to 30%, ; .
and especially from 7 to 25%, of the amine by weight of the total amount of amine and water, as such concentrations confer practical advantages in terms of correspondence to existing habits of users of liquid fabric conditioners having regard to the need to dispense a reasonable buIk of liquid in standard amounts and to provide an effective ;i am~unt ofamune in the wash liquor. An effective amount of the emwlsifier :':
_g_ : ~
. ;., : :; .,,: ~ . : . ... .. . .
~08735Z
is chosen from within the range of 0.002 to 10% by weight of the dispersion, and generally frcm 0.1 to 20% by weight of the disperse phase is employed.
Preferably the solid amine composition contains at least 6.5, and expecially at least 7%, of the am m e. The amount of the salt present will usually be less than 75% by weight of the co~position.
As water-soluble non-surface-active salts there are preferably used detergency builder salts. By "detergency builder salt" in this specification is meant a salt that possesses the power of increasing the detergent activity of a detergent-active compound Suitable detergency builder salts are inorganic buil~rs such as sodium ortho-, pyro-, trimeta- and tripoly-phosphates, sodium carbonate and sodium silicate.
Examples of organic builders are salts or organic acids such as sodium citrate, sodium oxydiacetate, sodium carboxymethyloxysuccinate, sodium nitrilotriacetate and sodium ethylenediam me tetraacetate.
15Non-surface-active salts other than detergency builders which can be used in solid compositions of the invention are sodium perborate or percarbonate which provide a bleaching function, and sodium sulphate.
Preferably where the ccmposition contains a detergency builder salt, it also contains an anionic detergent-active campound, especially a ~ 20 non-soap (or synthetic) anionic detergent-active compound. Such a - composition is preferably one containing fram 6.5 to 35% of amine, from
3 to 60% of anionic detergent-active compound, and from 5 to 75% of detergency builder salt, by weight of the ccmposition.
~i h~lere a compositicn contains an anionic detergent-active compound, it can be a water-soluble or water-dispersible alkali metal salt of an organic acid, especially a sodium or potassium salt, or a corresponding - ammonium or substituted ammonium salt. Examples of suitable organic , . , . . ~ , :.
- ,, - , .. .. . , :, :
., .: , . . .
. .~ : , . : :
1~873~iZ
acids are alk~lbenzene sulphonic acids whose alkyl groups contain from 8 to 20 carbon atoms, for instance linear C10-Cl5 alkylbenzene sulphonic acids; alkyl and alkenyl sulphonic acids of from 8 to 22 carbon atoms, for instan oe those known as olefin sulphonates which can be derived by reaction of sulphur trioxide with linear and branched olefins, especially "cracked wax" or "Ziegler" alpha-olefins, or those ~rived by reaction of aIkanes with sulphur dioxide and chlorine and subsequent hydrolysis, or by reaction of olefins with bisulphites; alkyl sulphosuccinates derived by reacting maleic acid esters with bisulphites; alkyl sulphuric acids of from 8 to 22 carbon atcms obtained by reaction of alcohols and sulphur trioxide; alkylether sulphuric acids obtained by reaction of molar quantities of alcohols of from 6 to 18 carbon atoms with 1 to 15 mols of ethylene oxide or mixtures of ethylene oxide and propylene oxide, and subsequently reacting the condensatian product with sulphur trioxide; natural or synthetic aliphatic carbcxylic acids of frcm 10 to 22 carbon atoms, especially the soaps obtained by splitting of triglyceride oils; and N-acylated isethionic and sarcosinic acids, where the acyl groups are those derived from such aliphatic carbaxylic acids. Other suitable anionic detergent-active compounds are described in "Surfaoe Active ' Agents", Volume I by Schwarz and Perry and "Surface Active Agents and Detergents", Volume II by Schwartz, Perry and ~erch.
Cb~positions of the invention can contain other fabric-washing detergent ccmposition ingredients, for instance lather boosters, such as coconut mon oethanolamide; lather controllers; chlorine-releasing bleaching agents, for instance trichloroisocyanuric acid and sodium and potassium dichloro-isocyanurates; ant;redeposition agents, such as sodium carboxymethylcellulos; and perfumes, colourants, fluorescers, corrosion inhibitors, germicides and enzymes.
. .
' .. '. '` , ,.,': ,'~ ' ' . " ' :
.,, ' ' '' ' ,' ", ' . ' ' :' ' : ' " '' ~ . . .'.'. .. : :.:.' . , 11~873S2 The invention provides a process for preparing a solid ccmpositian of the invention in which the amine is mixed with the non-surface-active salt and anionic detergent-active compound where present and, if required, the mix*ure is formed into granules. Preferably the solid composition is prepared as a spray-dried p3wder. Such a powder can be obtained by preparing an aqueous slurry cantaining the ingredient of the camposition and heating the slurry to 80C, at which the amine will be liquid and can with adequate mixing be distributed uniformly throughaut the slurry, which is then spray-dried to give a powder cantaining evenly-distributed amine.
For domestic use, a liquid camposition of the inventian can be added in small quantities sufficient to provide softening, for in5tance ~` from a bottle or a sealed sachet, for example from 10 to 100 ml, to a fabric load in a washing machine, together with a suitable detergent compositian, for instance a washing powder. Solid campositions of the invention without the necessary detergent for a wash are added in the same . ~ .
way, and solid compositians containing detergent-active compound for a wash are used in the same way as normal detergent compositions. In -~
`; order to get good results the pH of the wash liquor should be at least 0.2 pH units above the isoelectric point of the amine employed. This can be achieved by selection of a suitable amine for a given wash liquor, ~` if required. The pH of the wash liquor is preferably belcw 9.8 in order to avoid taa great a buffering effect to enable the necessary reduction of pH in the rinse liquor to be made without having to lower the pH of natural rinse water: however, a wash liquor of high pH can be diluted with water after washing and before wash liquor discharge if it is desired to reauce the ccntributicn of the residual wash liquor to the alkalirity -- 1.2 --.
~, , .
~87352 of the first rinse liquor. For practical purposes the wash liquor pH
should be above 8.5, so that scope is given for use of an amine whose isoelectric point is at least 0.2 units abcve the pH of the first rinse liquor.
The invention includes a process for the softening of fabries, in which an aqueous anionic detergent wash liquor is prepared from a co~position of the invéntio~ the liquor having a pH above the isoeleetric point of the amine, fabric is washed with the wash liquor, and the pH of the wash liquor in eontact with the washed fabric is then redueed to below the isoelectrie point of the amine to attach the amine to the surfa oe of the fabric. Preferably the bulk of wash liquor present during the washing step is separated from the washed fabrie and the pH reduetian is effeeted by the addition of rinse water to the fabric containing the residual wash liquor.
m e invention also ineludes a softened fabrie having a surface-coating of from 0.0005 to 0.01, and preferably from 0.001 to 0 005, parts by weight of the fabrie, of a tertiary anine of the speeial group defined above.
me inventian is illustrated by the following Examples, in whieh all t2mperatures are in C.
. .
, : .
Tb a solution in water (84.85g) of sodium laurate (0.15g) at 80 was added molten methyldieoeoamine (15g) and the mixture stirred and subjeeted to ultrasonie dispersion until it was homogeneous.
, ',,,' , : - ' " ' ' ,' ; " . .. ~, ' ` ~ ' "" .'' .. ." '. ' -` ` ' "
' ,' - ' -- .' ,, ' ' ' ',, ,, ; ` ' ' ' j, .' ' . '., , , '' ',' '. '', ~ ' ~ ~ . ; ' ' ' ' ' '1 '; ' Soiled laundry (2.7 kg) and 16 pieces (20.3 cm square) of clean cotton tcwelling were placed in a front-loading automatic drum washing machine, fol-lowed by water (20 litres) at 50, the amine dispersion (75 ml) and a detergent product (100 g) having the following composition in parts by weight:
Sodium dodecylkenzene sulphonate 7.5 Condensa~e of tallow fatty acid amine with 11 molæ equivalents of ethylene oxide 3-5 H æ dened tallow sodium soap 1.0 ;;
Sodium tripolyphosphate 64.9 Alkaline sodium silicate 1.0 Sodium sulphate 9-5 - Sodium car~oxymethyl cellulose 1.0 Sodium chloride 1.4 Fluorescer 0.2 Water 10.0 ~ me resulting load had a liquor : cloth ratio of 7:1 with the wash liquor at pH 9.3. The fabrics were washed with a standard programme in which the load ~; was heated to 95 with drum agitation during 35 min and then drained, lea-~ing about 20% of residual wash liquor, and rinsed four times with cold water (20 litres, pH 7.5, giving pH 8.7 in the first rinse liquor), with spin-drying afterthe third and fourth rinse. m e cloth was then allowed to dry in the atmosphere m e dried cloth had a surfaoe-coating of about 0.002 p æ ts of amine by weight of the fabric.
A similar operation was also carried out without the amine dispersion. The cloth pieces were assembled in pairs, one washed with amine and one without, anddirectly compared by a test panel of 5 operators who allotted an order of .- 1~
- . .,: . i. , : : , , .
,: ' ' ' ` ' , ' , .. ~ . .
1087~5Z
softening preference to each pair. In 77 out of 80 pair comparisons the cloth - treated with the amine dispersion was selected as softer.
EXAMæLE 2 An amine dispersion was prepared as in Example 1, but using as amine methyldi(hydrogenated tallow) amine and as emulsifier sodium stearate.
Soiled laundry (2.7 kg) and 16 pie oe s (20.3 cm square) of cotton tcwelling was placed in a tcp-loading paddle washing machine, follcwed by water (68 litres) at 50, the amine dispersion (50 ml) and a detergent product (100 g) having the following composition in parts by weight:
Sodium dodecylbenzene sulphonate 6.0 Condensate of hardened tallow fatty alcohol with r 18 molar equivalents of ethylene oxide 4.0 Mardened tallow sodium soap 8.0 Sodium tripolyphosphat,e 33.0 Alkaline sodium silicate 8.0 Sodium sulphate 3.1 Sodium carboxymethyl cellulose 1.0 ;~
.. ,, ~ .
S~;um perborate 25.0 Fluorescer and perfume 0.7 Water 11.2 The resulting load had a liquor : cloth ratio of 25:1, with the wash liquor at pH 9.7. The fabrics were washed with a stan~rd programme in which the load was heated to 95 with paddle agitation during 40 min and was drained and ex oe ss water removed b~ spinning, leaving about 10% of residual wash liquor, and rinsedtwice with cold water (60 litres, pH 7.5, giving pH 8.2 in the first rinse liquor), with spin-drying after the final rinse, and the cloth allcwed to dry inthe atmosphere. m e dried cloth had a surface-coating of about 0.0015 parts of ;' ., , , ' . , `. " . , ,,, .. ,, .. ,,.. ~
amine by weight of the fabric.
The procedure was repeated using 32 pie oe s of towelling and no amune dis- L
persion : 16 were removed and dried and the machine set for one more rinse and spin cycle, and 50 ml of a commercial rinse conditioner containing 6% by weight of a mixture of dimethyldicocoammanium chloride and dimethyldi(hydrogenated tallcw)ammonium chloride as softener was added and the 16 remaining pieces dried.
$he 16 pieces from each treat~ent were arranged in triplets and submitted to a softness co~,parison by a 5-membered test panel. Each triplet was allotted a score of 1 for the softest piece, 2 for the next softest and 3 for the harshest.
The total softness scores were as follcws.
Cloths treated with ' amine dispersion 130 commercial rinse ccnditioner 113 i detergent cnly 237 :, ;~ 15 m is demonstrates that softening with the amine dispersion used as a wash cycle softener was not significantly poorer ~han that with the commercial quater-nary ammonium salt composition when used as a rinse cycle softener, both showingmarked softening.
EX~MæLE 3 :' ; 20 An amine dispersion was prepared as in Example 1, but using as aminemethyldistearylamine (isoe lectric point 8.7) and as emulsifier sodium stearate.As detergent there was used a composition having the following ingredients in parts by wèight:
Sodium dodecylbenzene sulphonate - 14.0 Coconut ethanolamide 2.0 Sodium tripolyphosphate 33.0 Alkaline sodium silicate 6.0 ., . .
.: . .. . . . . . . .
- ~ , . .. , - , ;: ~, .; -l~
Sodium sulphate 17.0 Sodium car~oxymethylcellulose 0.5 Sodium perborate 20.0 Fluorescer and perfume 0.2 Water 7.3 In a Tergotometer were placed 4 pieces of clean cotton towelling (20.3 cm `~ square), water (800 ml), amine dispersion ~2 ml) and detergent ccmposition (3.2 g), giving a liquor : cloth ratio of 20:1, with the wash liquor at pH 9.7. ~I ' The cloth was washed or 15 min at 80, the wash li~uor discharged, leaving about 10% as residue, the cloth rinsed twice in cold water (800 ml, 24H, pH 7.5, giving pH 8.2 in the first rinse liquor), and dried. m e dried cloth had a sur-;'~ face-coating of about 0.002 parts of amine by weight of the fabric.
me procedure was also carried out using no amine dispersion. The sets of ; cloths were tested for softness in pairs as in Example 1. ~very member of the panel found that the cloth treated with amine dispersion was softer than that ,; . . .
~, treated with detergent alone.
., ~ .
EX~MPLES 4 and 5 An amine dispersion ~Example 4) was prepared as in Example 2, except that the amine used was a methyldiaIkylamine of isoe lectric point 9.3, each of whoseaIkyl groups was derived fram a commercial mixture of C20 and C22 straight chainsaturated fatty acids in which the C20 acid predominated.
Similar dispersions were prepared for ccmparison using as amine tri(hydro-genated tallcw)amine whose isoe lectric points are 8.2 and 10.0 respectively.
The amine dispersion of Example 2 was also used (Example 5).
; 25 The washing prooedure of Example 3 was carried out with each em~lsion, (with wash liquor pH 9.7 and first rinse liquor pH 8.2). The cloths were divided into 16 sets of 4 pieces including one washed with each emulsion, and graded by a test ~, .
~08735Z
panel of 5 persons for softness, with scores allotted as 1 for the softest and
~i h~lere a compositicn contains an anionic detergent-active compound, it can be a water-soluble or water-dispersible alkali metal salt of an organic acid, especially a sodium or potassium salt, or a corresponding - ammonium or substituted ammonium salt. Examples of suitable organic , . , . . ~ , :.
- ,, - , .. .. . , :, :
., .: , . . .
. .~ : , . : :
1~873~iZ
acids are alk~lbenzene sulphonic acids whose alkyl groups contain from 8 to 20 carbon atoms, for instance linear C10-Cl5 alkylbenzene sulphonic acids; alkyl and alkenyl sulphonic acids of from 8 to 22 carbon atoms, for instan oe those known as olefin sulphonates which can be derived by reaction of sulphur trioxide with linear and branched olefins, especially "cracked wax" or "Ziegler" alpha-olefins, or those ~rived by reaction of aIkanes with sulphur dioxide and chlorine and subsequent hydrolysis, or by reaction of olefins with bisulphites; alkyl sulphosuccinates derived by reacting maleic acid esters with bisulphites; alkyl sulphuric acids of from 8 to 22 carbon atcms obtained by reaction of alcohols and sulphur trioxide; alkylether sulphuric acids obtained by reaction of molar quantities of alcohols of from 6 to 18 carbon atoms with 1 to 15 mols of ethylene oxide or mixtures of ethylene oxide and propylene oxide, and subsequently reacting the condensatian product with sulphur trioxide; natural or synthetic aliphatic carbcxylic acids of frcm 10 to 22 carbon atoms, especially the soaps obtained by splitting of triglyceride oils; and N-acylated isethionic and sarcosinic acids, where the acyl groups are those derived from such aliphatic carbaxylic acids. Other suitable anionic detergent-active compounds are described in "Surfaoe Active ' Agents", Volume I by Schwarz and Perry and "Surface Active Agents and Detergents", Volume II by Schwartz, Perry and ~erch.
Cb~positions of the invention can contain other fabric-washing detergent ccmposition ingredients, for instance lather boosters, such as coconut mon oethanolamide; lather controllers; chlorine-releasing bleaching agents, for instance trichloroisocyanuric acid and sodium and potassium dichloro-isocyanurates; ant;redeposition agents, such as sodium carboxymethylcellulos; and perfumes, colourants, fluorescers, corrosion inhibitors, germicides and enzymes.
. .
' .. '. '` , ,.,': ,'~ ' ' . " ' :
.,, ' ' '' ' ,' ", ' . ' ' :' ' : ' " '' ~ . . .'.'. .. : :.:.' . , 11~873S2 The invention provides a process for preparing a solid ccmpositian of the invention in which the amine is mixed with the non-surface-active salt and anionic detergent-active compound where present and, if required, the mix*ure is formed into granules. Preferably the solid composition is prepared as a spray-dried p3wder. Such a powder can be obtained by preparing an aqueous slurry cantaining the ingredient of the camposition and heating the slurry to 80C, at which the amine will be liquid and can with adequate mixing be distributed uniformly throughaut the slurry, which is then spray-dried to give a powder cantaining evenly-distributed amine.
For domestic use, a liquid camposition of the inventian can be added in small quantities sufficient to provide softening, for in5tance ~` from a bottle or a sealed sachet, for example from 10 to 100 ml, to a fabric load in a washing machine, together with a suitable detergent compositian, for instance a washing powder. Solid campositions of the invention without the necessary detergent for a wash are added in the same . ~ .
way, and solid compositians containing detergent-active compound for a wash are used in the same way as normal detergent compositions. In -~
`; order to get good results the pH of the wash liquor should be at least 0.2 pH units above the isoelectric point of the amine employed. This can be achieved by selection of a suitable amine for a given wash liquor, ~` if required. The pH of the wash liquor is preferably belcw 9.8 in order to avoid taa great a buffering effect to enable the necessary reduction of pH in the rinse liquor to be made without having to lower the pH of natural rinse water: however, a wash liquor of high pH can be diluted with water after washing and before wash liquor discharge if it is desired to reauce the ccntributicn of the residual wash liquor to the alkalirity -- 1.2 --.
~, , .
~87352 of the first rinse liquor. For practical purposes the wash liquor pH
should be above 8.5, so that scope is given for use of an amine whose isoelectric point is at least 0.2 units abcve the pH of the first rinse liquor.
The invention includes a process for the softening of fabries, in which an aqueous anionic detergent wash liquor is prepared from a co~position of the invéntio~ the liquor having a pH above the isoeleetric point of the amine, fabric is washed with the wash liquor, and the pH of the wash liquor in eontact with the washed fabric is then redueed to below the isoelectrie point of the amine to attach the amine to the surfa oe of the fabric. Preferably the bulk of wash liquor present during the washing step is separated from the washed fabrie and the pH reduetian is effeeted by the addition of rinse water to the fabric containing the residual wash liquor.
m e invention also ineludes a softened fabrie having a surface-coating of from 0.0005 to 0.01, and preferably from 0.001 to 0 005, parts by weight of the fabrie, of a tertiary anine of the speeial group defined above.
me inventian is illustrated by the following Examples, in whieh all t2mperatures are in C.
. .
, : .
Tb a solution in water (84.85g) of sodium laurate (0.15g) at 80 was added molten methyldieoeoamine (15g) and the mixture stirred and subjeeted to ultrasonie dispersion until it was homogeneous.
, ',,,' , : - ' " ' ' ,' ; " . .. ~, ' ` ~ ' "" .'' .. ." '. ' -` ` ' "
' ,' - ' -- .' ,, ' ' ' ',, ,, ; ` ' ' ' j, .' ' . '., , , '' ',' '. '', ~ ' ~ ~ . ; ' ' ' ' ' '1 '; ' Soiled laundry (2.7 kg) and 16 pieces (20.3 cm square) of clean cotton tcwelling were placed in a front-loading automatic drum washing machine, fol-lowed by water (20 litres) at 50, the amine dispersion (75 ml) and a detergent product (100 g) having the following composition in parts by weight:
Sodium dodecylkenzene sulphonate 7.5 Condensa~e of tallow fatty acid amine with 11 molæ equivalents of ethylene oxide 3-5 H æ dened tallow sodium soap 1.0 ;;
Sodium tripolyphosphate 64.9 Alkaline sodium silicate 1.0 Sodium sulphate 9-5 - Sodium car~oxymethyl cellulose 1.0 Sodium chloride 1.4 Fluorescer 0.2 Water 10.0 ~ me resulting load had a liquor : cloth ratio of 7:1 with the wash liquor at pH 9.3. The fabrics were washed with a standard programme in which the load ~; was heated to 95 with drum agitation during 35 min and then drained, lea-~ing about 20% of residual wash liquor, and rinsed four times with cold water (20 litres, pH 7.5, giving pH 8.7 in the first rinse liquor), with spin-drying afterthe third and fourth rinse. m e cloth was then allowed to dry in the atmosphere m e dried cloth had a surfaoe-coating of about 0.002 p æ ts of amine by weight of the fabric.
A similar operation was also carried out without the amine dispersion. The cloth pieces were assembled in pairs, one washed with amine and one without, anddirectly compared by a test panel of 5 operators who allotted an order of .- 1~
- . .,: . i. , : : , , .
,: ' ' ' ` ' , ' , .. ~ . .
1087~5Z
softening preference to each pair. In 77 out of 80 pair comparisons the cloth - treated with the amine dispersion was selected as softer.
EXAMæLE 2 An amine dispersion was prepared as in Example 1, but using as amine methyldi(hydrogenated tallow) amine and as emulsifier sodium stearate.
Soiled laundry (2.7 kg) and 16 pie oe s (20.3 cm square) of cotton tcwelling was placed in a tcp-loading paddle washing machine, follcwed by water (68 litres) at 50, the amine dispersion (50 ml) and a detergent product (100 g) having the following composition in parts by weight:
Sodium dodecylbenzene sulphonate 6.0 Condensate of hardened tallow fatty alcohol with r 18 molar equivalents of ethylene oxide 4.0 Mardened tallow sodium soap 8.0 Sodium tripolyphosphat,e 33.0 Alkaline sodium silicate 8.0 Sodium sulphate 3.1 Sodium carboxymethyl cellulose 1.0 ;~
.. ,, ~ .
S~;um perborate 25.0 Fluorescer and perfume 0.7 Water 11.2 The resulting load had a liquor : cloth ratio of 25:1, with the wash liquor at pH 9.7. The fabrics were washed with a stan~rd programme in which the load was heated to 95 with paddle agitation during 40 min and was drained and ex oe ss water removed b~ spinning, leaving about 10% of residual wash liquor, and rinsedtwice with cold water (60 litres, pH 7.5, giving pH 8.2 in the first rinse liquor), with spin-drying after the final rinse, and the cloth allcwed to dry inthe atmosphere. m e dried cloth had a surface-coating of about 0.0015 parts of ;' ., , , ' . , `. " . , ,,, .. ,, .. ,,.. ~
amine by weight of the fabric.
The procedure was repeated using 32 pie oe s of towelling and no amune dis- L
persion : 16 were removed and dried and the machine set for one more rinse and spin cycle, and 50 ml of a commercial rinse conditioner containing 6% by weight of a mixture of dimethyldicocoammanium chloride and dimethyldi(hydrogenated tallcw)ammonium chloride as softener was added and the 16 remaining pieces dried.
$he 16 pieces from each treat~ent were arranged in triplets and submitted to a softness co~,parison by a 5-membered test panel. Each triplet was allotted a score of 1 for the softest piece, 2 for the next softest and 3 for the harshest.
The total softness scores were as follcws.
Cloths treated with ' amine dispersion 130 commercial rinse ccnditioner 113 i detergent cnly 237 :, ;~ 15 m is demonstrates that softening with the amine dispersion used as a wash cycle softener was not significantly poorer ~han that with the commercial quater-nary ammonium salt composition when used as a rinse cycle softener, both showingmarked softening.
EX~MæLE 3 :' ; 20 An amine dispersion was prepared as in Example 1, but using as aminemethyldistearylamine (isoe lectric point 8.7) and as emulsifier sodium stearate.As detergent there was used a composition having the following ingredients in parts by wèight:
Sodium dodecylbenzene sulphonate - 14.0 Coconut ethanolamide 2.0 Sodium tripolyphosphate 33.0 Alkaline sodium silicate 6.0 ., . .
.: . .. . . . . . . .
- ~ , . .. , - , ;: ~, .; -l~
Sodium sulphate 17.0 Sodium car~oxymethylcellulose 0.5 Sodium perborate 20.0 Fluorescer and perfume 0.2 Water 7.3 In a Tergotometer were placed 4 pieces of clean cotton towelling (20.3 cm `~ square), water (800 ml), amine dispersion ~2 ml) and detergent ccmposition (3.2 g), giving a liquor : cloth ratio of 20:1, with the wash liquor at pH 9.7. ~I ' The cloth was washed or 15 min at 80, the wash li~uor discharged, leaving about 10% as residue, the cloth rinsed twice in cold water (800 ml, 24H, pH 7.5, giving pH 8.2 in the first rinse liquor), and dried. m e dried cloth had a sur-;'~ face-coating of about 0.002 parts of amine by weight of the fabric.
me procedure was also carried out using no amine dispersion. The sets of ; cloths were tested for softness in pairs as in Example 1. ~very member of the panel found that the cloth treated with amine dispersion was softer than that ,; . . .
~, treated with detergent alone.
., ~ .
EX~MPLES 4 and 5 An amine dispersion ~Example 4) was prepared as in Example 2, except that the amine used was a methyldiaIkylamine of isoe lectric point 9.3, each of whoseaIkyl groups was derived fram a commercial mixture of C20 and C22 straight chainsaturated fatty acids in which the C20 acid predominated.
Similar dispersions were prepared for ccmparison using as amine tri(hydro-genated tallcw)amine whose isoe lectric points are 8.2 and 10.0 respectively.
The amine dispersion of Example 2 was also used (Example 5).
; 25 The washing prooedure of Example 3 was carried out with each em~lsion, (with wash liquor pH 9.7 and first rinse liquor pH 8.2). The cloths were divided into 16 sets of 4 pieces including one washed with each emulsion, and graded by a test ~, .
~08735Z
panel of 5 persons for softness, with scores allotted as 1 for the softest and
4 for the harshest. .
The ccmbined softness scores obtained were:
Cloths treated with dispersions of methyldi(C -C aIkyl)amlne (Example 4) 136 met~yldi(hydrogenated tallow)amine 167 - (Example 5) tri(hydrogenated tallow)amine 301 dimethyl(hydrogenated tallow)amine 196 m e scores with the amine dispersions of Examples 4 and 5 demonstrate a softening effect in comparison with those with the other dispersions. m e cloths washed with the last dispersion had greasy deposits due to a precipitate formed from the amine and the anionic detergent used.
m e amine dispersion of Example 2 was used as a wash cycle softener as in Example 3, in oomparison with a ccmmercial wash cycle softener containing 14%
by weight of a quaternary imidazoline methyl sulphate, with the commercial quat~r nary ammonium salt rinse conditioner of Example 2, and also with the detergent composition of Example 3 with no added softener. me procedure used was similar to that in Example 3 except that 1 ml of the amine emulsion of Example 2 and 1 ml of the quaternary imidazoline salt softener were used as wash cycle softeners, and washed were also carried out with the detergent composition with no softenerboth with and without the commercial rinse conditioner of Example 2 (1 ml) addedto the last rinse liquor. m e resulting dried cloths were panel-tested as before, and the following softness scores obtained.
.. . . . .. . . . , _ , . . .
., ., :
:: , ,,,:, :., : . , - : . .. :, . :. .. ' .. . . ~.
Cloths treated with dispersi~n of methyldi(hydrogenated 10 tallow)amine commercial wash cycle softener 270 ccmmercial rinse conditioner 142 detergent only 280 EXAMPT.F~ 7 to 15 ; Amine dispersions were prepared as in Example 2, but using a range of a~lne - concentrations, namely 5,10,20,25,30,35,40,45 and 50% of methyldi(hydrogenated tallow)amine by weight of the dispersion and sodium stearate as emulsifier. me emulsions were found to be stable for at least 6 weeks at ambient temperature.
` The proc~ess of Example 3 using an am~ne dispersion but with the amine dis-; persion repla~ed by 1 ml of the 30% dispersion above (Example 11) was carried out and softened cotton fabric produced.
EXAMPIES 16 to 20 Anine dispersions were prepared as in Example 2, but using a range of em~lsifier concentrations~ namely 0.015, 0.45, 0.75, 1.5 and 3% of sodium stearate by weight of the dispersion. m e dispersions were found to be stable for at least 6 weeks at a~bient temperature, and that with 0.45% emulsifier was stable for atleast 6 manths.
EXAMPLES 21 to 30 kmine dispersions were prepared as in Example 2, but using a series of dif-ferent emulsifiers, and the period of stability of each emulsion at 20 was observed, as follows.
Example Emulsifier Stability 21 sodium laurate 10 days 22 sodium myristate 2 weeks ~L08735Z
r Example Em~lsifier Stability 23 sodium palmitate at least 6 weeks -24 sodium hexadecenyl succinate at least 10 weeks sodium N-tallow acyl glutamate 4 weeks 26 sodium cl6-cl8~<-olefin sulphonate 4 weeks 27 sodium hexylbenzene sulphonateat least 10 weeks 28 sodium octadecyIbenzene sulphonate4 weeks : 29 sodium tallow fatty acid sulphonateat least 10 weeks sodium C16-C20 n-alkyl phosphate 6 weeks EXAMPLES 31 and 32 : Stable amine dispersions are prepared as in Example 1 but using as amine and em~lsifier respectively methyldicocoamine and the sodium salt of coconut oil fatty acid : and methyldi-(hydrogenated tallcw)amine and the sodium salt of hydrogenated tallow fatty acid.
A solid fabric-softening composition having the following ingredients in parts by weight was prepared.
Sodium dodecylbenzene sulphonate 14.0 Cooonut ethanolamide 2.0 Sodium tripolyphosphate 33.0 Sodium sulphate 6.9 Alkaline sodium silicate 6.0 Methyldi(hydrogenated tallow)am m e 10.0 Sodium carboxymethyloe llulose 0.5 Fluorescer 0.4 Sodium perborate 20.0 Water 7.2 ~` iO8735Z
All the ingredients except the amine and the perborate were ~ixed together with - an additional amcunt of water (62 parts) to provide a slurry, and heated to 80, the amine was added in the molten state and the mixture thoroughly stirred and spray-dried to give a dry free flowing powder, with which the perborate was finally mixed.
m e composition was used to wash cotton pieces in a Tergotometer at 0.4%
i concentration as in Example 3, with a wash liquor pH of 9.7 and a first rinse ` liquor pH of 8.3. The dried cloth had a surface-ccating of about 0.004 parts of amine by weight of the fabric. A control wash was also carried out using a , 10 similar ccmposition in which the amine was replaced by the same amount of addi-tional sodium sulphate. Comparison by a test panel as before was made and the cloth treated with amine was chosen as softer in every instance.
EX~MPLE 34 A solid fabric-softening composition was prepared having the same ingredients as the detergent product of Example 1 except that 7.5 parts of methyldi(hydro-genated tallow)amine was substituted for the same amount of sodium sulphate. The~ composition was prepared by mixIng together all the ingredients except the amine - and a portion (23 parts) of the sodium tripolyphosphate, together with an addi-tional amount of water (60 parts) to provide a slurry, heating the mixture to 80, adding the molten amine, stirring the m~xture thoroughly and spray-drying to give a dry free-flcwing powder, with which the remaining tripolyphosphate was mixed.
The composition was used to wash cotton pieces in a Tergotcmeter as in Example 3 at 0.2, 0.4 and 0.6% concentrations, with a wash liquor pH of 9.3 and a first rinse liquor pH of 8.1, and control washes were also carried out using the detergent product of Example 1. Ccmparison by a test panel as before showed that the amine-treated cloth was softer than the control in every instance.
~ 10873~2 :-'' A composition is prepared as in Example 34, except that the amlne employed . is methyldicocoamine : 100 g of the composition is used in a front-loading auto-matic washing machine in a laundering process similar to that described in Example ~ 1, with a wash liquor pH of 9.3 and a first rinse liquor pH of 8.7, to provide : softe m ng of the cotton fabric.
~, ,,, ,: l .
The ccmbined softness scores obtained were:
Cloths treated with dispersions of methyldi(C -C aIkyl)amlne (Example 4) 136 met~yldi(hydrogenated tallow)amine 167 - (Example 5) tri(hydrogenated tallow)amine 301 dimethyl(hydrogenated tallow)amine 196 m e scores with the amine dispersions of Examples 4 and 5 demonstrate a softening effect in comparison with those with the other dispersions. m e cloths washed with the last dispersion had greasy deposits due to a precipitate formed from the amine and the anionic detergent used.
m e amine dispersion of Example 2 was used as a wash cycle softener as in Example 3, in oomparison with a ccmmercial wash cycle softener containing 14%
by weight of a quaternary imidazoline methyl sulphate, with the commercial quat~r nary ammonium salt rinse conditioner of Example 2, and also with the detergent composition of Example 3 with no added softener. me procedure used was similar to that in Example 3 except that 1 ml of the amine emulsion of Example 2 and 1 ml of the quaternary imidazoline salt softener were used as wash cycle softeners, and washed were also carried out with the detergent composition with no softenerboth with and without the commercial rinse conditioner of Example 2 (1 ml) addedto the last rinse liquor. m e resulting dried cloths were panel-tested as before, and the following softness scores obtained.
.. . . . .. . . . , _ , . . .
., ., :
:: , ,,,:, :., : . , - : . .. :, . :. .. ' .. . . ~.
Cloths treated with dispersi~n of methyldi(hydrogenated 10 tallow)amine commercial wash cycle softener 270 ccmmercial rinse conditioner 142 detergent only 280 EXAMPT.F~ 7 to 15 ; Amine dispersions were prepared as in Example 2, but using a range of a~lne - concentrations, namely 5,10,20,25,30,35,40,45 and 50% of methyldi(hydrogenated tallow)amine by weight of the dispersion and sodium stearate as emulsifier. me emulsions were found to be stable for at least 6 weeks at ambient temperature.
` The proc~ess of Example 3 using an am~ne dispersion but with the amine dis-; persion repla~ed by 1 ml of the 30% dispersion above (Example 11) was carried out and softened cotton fabric produced.
EXAMPIES 16 to 20 Anine dispersions were prepared as in Example 2, but using a range of em~lsifier concentrations~ namely 0.015, 0.45, 0.75, 1.5 and 3% of sodium stearate by weight of the dispersion. m e dispersions were found to be stable for at least 6 weeks at a~bient temperature, and that with 0.45% emulsifier was stable for atleast 6 manths.
EXAMPLES 21 to 30 kmine dispersions were prepared as in Example 2, but using a series of dif-ferent emulsifiers, and the period of stability of each emulsion at 20 was observed, as follows.
Example Emulsifier Stability 21 sodium laurate 10 days 22 sodium myristate 2 weeks ~L08735Z
r Example Em~lsifier Stability 23 sodium palmitate at least 6 weeks -24 sodium hexadecenyl succinate at least 10 weeks sodium N-tallow acyl glutamate 4 weeks 26 sodium cl6-cl8~<-olefin sulphonate 4 weeks 27 sodium hexylbenzene sulphonateat least 10 weeks 28 sodium octadecyIbenzene sulphonate4 weeks : 29 sodium tallow fatty acid sulphonateat least 10 weeks sodium C16-C20 n-alkyl phosphate 6 weeks EXAMPLES 31 and 32 : Stable amine dispersions are prepared as in Example 1 but using as amine and em~lsifier respectively methyldicocoamine and the sodium salt of coconut oil fatty acid : and methyldi-(hydrogenated tallcw)amine and the sodium salt of hydrogenated tallow fatty acid.
A solid fabric-softening composition having the following ingredients in parts by weight was prepared.
Sodium dodecylbenzene sulphonate 14.0 Cooonut ethanolamide 2.0 Sodium tripolyphosphate 33.0 Sodium sulphate 6.9 Alkaline sodium silicate 6.0 Methyldi(hydrogenated tallow)am m e 10.0 Sodium carboxymethyloe llulose 0.5 Fluorescer 0.4 Sodium perborate 20.0 Water 7.2 ~` iO8735Z
All the ingredients except the amine and the perborate were ~ixed together with - an additional amcunt of water (62 parts) to provide a slurry, and heated to 80, the amine was added in the molten state and the mixture thoroughly stirred and spray-dried to give a dry free flowing powder, with which the perborate was finally mixed.
m e composition was used to wash cotton pieces in a Tergotometer at 0.4%
i concentration as in Example 3, with a wash liquor pH of 9.7 and a first rinse ` liquor pH of 8.3. The dried cloth had a surface-ccating of about 0.004 parts of amine by weight of the fabric. A control wash was also carried out using a , 10 similar ccmposition in which the amine was replaced by the same amount of addi-tional sodium sulphate. Comparison by a test panel as before was made and the cloth treated with amine was chosen as softer in every instance.
EX~MPLE 34 A solid fabric-softening composition was prepared having the same ingredients as the detergent product of Example 1 except that 7.5 parts of methyldi(hydro-genated tallow)amine was substituted for the same amount of sodium sulphate. The~ composition was prepared by mixIng together all the ingredients except the amine - and a portion (23 parts) of the sodium tripolyphosphate, together with an addi-tional amount of water (60 parts) to provide a slurry, heating the mixture to 80, adding the molten amine, stirring the m~xture thoroughly and spray-drying to give a dry free-flcwing powder, with which the remaining tripolyphosphate was mixed.
The composition was used to wash cotton pieces in a Tergotcmeter as in Example 3 at 0.2, 0.4 and 0.6% concentrations, with a wash liquor pH of 9.3 and a first rinse liquor pH of 8.1, and control washes were also carried out using the detergent product of Example 1. Ccmparison by a test panel as before showed that the amine-treated cloth was softer than the control in every instance.
~ 10873~2 :-'' A composition is prepared as in Example 34, except that the amlne employed . is methyldicocoamine : 100 g of the composition is used in a front-loading auto-matic washing machine in a laundering process similar to that described in Example ~ 1, with a wash liquor pH of 9.3 and a first rinse liquor pH of 8.7, to provide : softe m ng of the cotton fabric.
~, ,,, ,: l .
Claims (14)
IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A fabric-softening composition comprising a tertiary amine having an isolectric point of from 8.3 to 9.8 and of the structure RR1R2N where R
is an alkyl group having from 1 to 6 carbon atoms and R1 and R2 are substan-tially linear alkyl or alkenyl groups having from 10 to 26 carbon atoms, and a diluent, in which the diluent is water or a water-soluble non-surface-active salt; and where the diluent is water the composition is liquid and comprises from 2 to 50% of the amine dispersed in from 98 to 50% of water, by weight of the total amount of amine and water, and where the diluent is a water-soluble non-surface-active salt, the composition is solid and comprises from 6.3 to 90% of the amine and from 10 to 93.7% of the salt by weight of the composition.
is an alkyl group having from 1 to 6 carbon atoms and R1 and R2 are substan-tially linear alkyl or alkenyl groups having from 10 to 26 carbon atoms, and a diluent, in which the diluent is water or a water-soluble non-surface-active salt; and where the diluent is water the composition is liquid and comprises from 2 to 50% of the amine dispersed in from 98 to 50% of water, by weight of the total amount of amine and water, and where the diluent is a water-soluble non-surface-active salt, the composition is solid and comprises from 6.3 to 90% of the amine and from 10 to 93.7% of the salt by weight of the composition.
2. A composition according to Claim 1, in which the diluent is water and the composition contains from 7 to 25% of the amine dispersed in from 93 to 75% of water, by weight of the total amount of amine and water.
3. A composition according to Claim 2, and containing an emulsifying amount of an anionic surface-active agent having a hydrophobic group that is a substantially linear alkyl or alkenyl group having an average chain length within 2? carbon atoms of the average chain length of the groups R1 and R2 in the amine.
4. A composition according to Claim 1, in which the diluent is a water-soluble non-surface-active salt and the composition contains from 6.5 to 35% of the amine, from 3 to 60% of an anionic detergent-active compound, and as water-soluble non-surface-active salt from 5 to 75% of detergency builder salt, by weight of the composition.
5. A composition according to any one of Claims 1, 2 and 4 where R has from 1 to 4 carbon atoms.
6. A composition according to any one of Claims 1, 2 and 4, where R is a methyl group.
7. A composition according to any one of Claims 1, 2 and 4, where R has from 1 to 4 carbon atoms and R1 and R2 each have from 12 to 22 carbon atoms.
8. A composition according to any one of Claims 1, 2 and 4, where R is a methyl group and R1 and R2 each have from 16 to 18 carbon atoms.
9. A composition according to any one of Claims 1, 2 and 4, where the amine is methyldicocohmine.
10. A composition according to any one of Claims 1, 2 and 4, where the amine is methyldi(hydrogenated tallow)amine.
11. A composition according to Claim 3, where the amine is methyl-dicocoamine and the anionic surface-active agent is sodium laurate.
12. A composition according to Claim 3, wherein the amine is methyldi-(hydrogenated tallow)amine and the anionic surface-active agent is sodium stearate.
13. In a process for the softening of fabrics, the steps of preparing an aqueous anionic detergent wash liquor from a composition according to Claim 1, the liquor having a pH above the isoelectric point of the amine, washing fabric with the wash liquor, and reducing the pH of the wash liquor in contact with the washed fabric to below the isoelectric point of the amine to attach the amine to the surface of the fabric.
14. A process according to Claim 13, in which the bulk of wash liquor present during the washing step is separated from the washed fabric and the pH reduction is effected by the addition of rinse water to the fabric con-taining the residual wash liquor.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB43336/76 | 1975-10-22 | ||
| GB4333676A GB1520969A (en) | 1975-10-20 | 1976-10-19 | Process for the preparation of a,w-diamines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1087352A true CA1087352A (en) | 1980-10-14 |
Family
ID=10428346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA263,567A Expired CA1087352A (en) | 1975-10-22 | 1976-10-18 | Fabric-softening compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1087352A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4514444A (en) * | 1984-02-03 | 1985-04-30 | The Procter & Gamble Company | Fabric cleaning/conditioning compositions |
-
1976
- 1976-10-18 CA CA263,567A patent/CA1087352A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4514444A (en) * | 1984-02-03 | 1985-04-30 | The Procter & Gamble Company | Fabric cleaning/conditioning compositions |
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