SOIL RELEASE AGENT AND ITS USE IN FABRIC CONDITIONING COMPOSITIONS

Abstract: Use as a soil release agent of compounds of formula (I), wherein X is an anion, A is an (m + n) valent radical remaining after the removal of (m + n) hydroxy groups from an aliphatic polyol having p hydroxy groups and an atomic ratio of carbon to oxygen in the range of 1.0 to 3.0 and up to 2 groups per hydroxy group selected from ethylene oxide and propylene oxide, m is 0 or an integer from 1 to p-n, n is an integer from 1 to p-m, and p is an integer of at least 2, B is an alkylene or alkylidene group containing 1 to 4 carbon atoms, R<1>, R<2>, R<3> and R<4> are, independently from each other, straight or branched chain C1-C48 alkyl or alkenyl groups, optionally with substitution by one or more functional groups and/or interruption by at most 10 ethylene oxide and/or propylene oxide groups, or by at most two functional groups selected from (a), (b), (c), (d) and (e) or R<2> and R<3> may form a ring system containing 5 or 6 atoms in the rings, with the proviso that the average compound either has at least one R group having 22-48 carbon atoms, or at least two R groups having 16-20 carbon atoms, or at least three R groups having 10-14 carbon atoms.

Description: SOII. RELEASE AGENT AND ITS USE IN FABRIC CONDITIONING COMPOSITIONS The present invention relates to the use of a biodegradable quaternary ammonium material as a soil release agent, for example, in a fabric conditioning composition. Rinse added fabric softener compositions are well known. Typically such compositions contain a water insoluble quaternary ammonium fabric softening agent dispersed in water at a level of softening agent up to 7% by weight in which case the compositions are considered dilute, or at levels from 7% to 50% in which case the compositions are considered concentrates. In addition to softening, fabric softening compositions desirably have other benefits. One is the ability to confer soil release properties to fabrics, particularly those woven from polyester or cotton fibres. Soil release properties are generally imparted to fabrics by the use of a separate soil-release agent, usually a high molecular weight polymer, in a detergent composition or separate treatment. For example in EP 0 398 133A (Procter & Gamble) there is disclosed a cationic polymeric soil release agent for use in a fabric conditioning composition. A disadvantage of such compositions is that the soil release agent increases the number of components in the formulation, increasing cost and making the product less environmentally acceptable. EP 0,234,311A (Henkel) describes the use of insoluble polyfunctional quaternary ammonium compounds as soil collectors, to regenerate soil-laden detergent solutions. The document contains no specific mention of the quaternary ammonium materials to which the present invention relates. EP 0,309,052 (Procter and Gamble) describes the use of quaternary ammonium salts containing at least one ester linkage as softeners in shelf-stable and biodegradable fabric softening compositions. The compositions also include a linear alkoxylated alcohol. EP 0,506,312 (Unilever) discloses the use as a soil release agent of a quaternary ammonium material comprising a compound having two C 12 . 18 alkyl or alkenyl groups connected via an ester link to a hydrocarbon chain which is connected to the quaternary nitrogen atom. The use of polyol ester quats as fabric softening compounds is disclosed in EPO 638639 (Akzo) . According to the present invention there is provided the use as a soil release agent of a compound of formula I O O R 2 II II I (R^C-O- ) ^ ( -0-C-B-KT-R 3 ) ., n χ- I R 4 Formula I wherein X is an anion, A is an (m + n) valent radical remaining after the removal of (m + n) hydroxy groups from an aliphatic polyol having p hydroxy groups and an atomic ration of carbon to oxygen in the range of 1,0 to 3,0 and up to 2 groups per hydroxy group selected from ethylene oxide and propylene oxide. is 0 or an integer from 1 to p-n, n is an integer from 1 to p-m, and p is an integer of at least 2, B is an alkylene or alkylidene group containing 1 to 4 carbon atoms, R 1 , R 2 , R 3 and R 4 are, independently from each other, straight or branched chain C α - C 48 alkyl or alkenyl groups, optionally with substitution by one ore more functional groups and/or interruption by at most 10 ethylene oxide and/or propylene oxide groups, or by at most two functional groups selected from O O O O O II II II I I II II -C-0-, -0-C-, -C-N-, -N-C-, and -O-C-O- or R 2 and R 3 may form a ring system containing 5 or 6 atoms in the ring, with the proviso that the average compound either has at least one R group having 22-48 carbon atoms, or at least two R groups having 16-20 carbon atoms, or at least three R groups having 10-14 carbon atoms. The invention also provides the use as a soil release agent of a hydrolysis product of a compound of formula I. The invention further provides a fabric conditioning composition comprising: (i) a quaternary ammonium fabric conditioning compound having a solubility in water at pH 2.5 and 20°C of less than lOg/1 and (ii) a compound of formula I or a zwitterionic hydrolysis products thereof. O O R 2 II II I (R 1 -C-0-) m A (-O-C-B-ir-R 3 ),, nX " I R 4 Formula I wherein X is an anion, A is an (m+n) valent radical remaining after the removal of (m+n) hydroxy groups from an aliphatic polyol having p hydroxy groups and an atomic ratio of carbon to oxygen in the range of 1,0 to 3,0 and up to 2 groups per hydroxy group selected from ethylene oxide and propylene oxide, m is 0 or an integer from 1 to p-n, n is an integer from 1 to p-m, and p is an integer of at least 2, B is an alkylene or alkylidene group containing 1 to 4 carbon atoms, R 1 , R 2 , R 3 and R 4 are, independently from each other straight or branched chain C -C 48 alkyl or alkenyl groups, optionally with substitution by one or more functional groups and/or interruption by at most 10 ethylene oxide and/or propylene oxide groups or by at most two functional groups selected from -C-0-, -0-C-, -C-N-, -N-C-, and -0-C-O-, or R 2 and R 3 may form a ring system containing 5 or 6 atoms in the ring, with the proviso that the average compound has at least one R group having 22-48 carbon atoms, or at least two R groups having 16-20 carbon atoms, or at least three R groups having 10-14 carbon atoms. Preferably, X " represents a halide anion, more particularly a chloride, sulphate, methosulphate, carboxylate or sulphonate anion. It is advantageous if the value of (m + n) in formula I is at least 2. It is preferred if the compound of formula I is composed of: a) 1 equivalent of an aliphatic polyol having p hydroxy groups. b) m equivalents of an aliphatic carboxylic acid of the formula R I COOH, and c) n equivalents of a C 1-4 halocarboxylic acid, d) n equivalents of a tertiary amine of the formula R 2 R 3 R 4 N or n equivalents of a secondary amine of the formula R 2 R 3 H, converted with n equivalents of a quaternizing agent. Within the scope of the invention preference is given to compositions comprising compounds corresponding to the first structural formula obtainable by reaction of a polyol having 2 to 8 hydroxy groups. Optimum results are obtained when the polyol is selected from the group of ethyleneglycol, glycerol, pentaerythritol, sorbitol, glucose, saccharose, methylglucoside, and/or condensed derivatives thereof. The polyol may be partially etherified and/or esterified. Good results can be obtained when the ester forming derivative of the polyol or the carboxylic acid is a natural fat, preferably a glyceride. Examples of condensed derivatives according to the invention are diglycerol, triglycerol, and dipentaerythritol. Use may also be made of natural polyols such as starch, degraded starch, and oligomers and/or polymers containing repeating units of vinyl alcohol. Compositions comprising compounds corresponding to the first structural formula are obtainable by reacting of an aliphatic carboxylic acid of the formula R 1 -COOH or an ester thereof. Optimum results are obtained when said acid is tallow acid and/or at least partially hydrogenated tallow acid. Other examples of suitable quaternary ammonium compounds corresponding to the first structural formula are obtained by replacing tallow acid with, e.g., coconut acid, palmitic acid, lauric acid, oleic acid, stearic acid, or the like. The R 2 , R 3 , and R 4 groups are, independently from each other, straight or branched chain C 1 -C 48 alkyl or alkenyl groups, optionally with substitution by one or more functional groups and/or interruption by at most 10 ethylene oxide and/or propylene oxide groups, or by at most two functional groups selected from: O O O I I O O II II II I I II II -C-0-, -O-C-, -C-N-, -N-C-, and -O-C-O- or R 2 and R 3 may form a ring system containing 5 or 6 atoms in the ring . Typical combinations of R 2 /R 3 /R 4 are : CH 3 /CH 3 /CH 3 , CH 3 /CH 3 /C 16/18 al ( en ) yl , CH 3 /CH 3 /CH 2 CH 2 00CC 15/17 alk ( en) yl , CH 3 /CH 3 /CH 2 , COOC 16/18 alk ( en) yl , CH 3 /CH 3 /CH 2 CH 2 CH 2 NHCOC 15/17 alk ( en)yl . The R 2 , R 3 and R 4 groups can be introduced into the molecule by the use of appropriate tertiary amines such as trimethylamine, (hydrogenated) tallow fatty acid ester of N,N-dimethylethanolamine, (hydrogenated) tallow alcohol ester of N,N-dimethylglycine, (hydrogenated) tallow fatty acid amide of N,N-dimethylaminopropylamine, and dimethyl (hydrogenated) tallowamine. The R 2 and R 3 groups can also be introduced by the use of appropriate secondary amines such as dimethylamine. The R 4 group can then be introduced by quaternization of the thus obtained tertiary amine with halogenating agents such as methyl chloride and dimethylsulphate. Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material. Examples of suitable polyolesterquats (PEQs) as claimed by the invention are given in EP 0638 639 (Akzo) . As indicated previously, the invention also provide the use of hydrolysis products of compounds of formula I as soil release agents. Examples of preferred hydrolysis products are: Hydrophobic surfactants of general formula II: (R 1 CO-) m A(OH) n Formula II Zwitterionic materials of general formula III: R 2 R 3 R 4 N + -B-CO.O " Formula III where R 2 , R 3 , R 4 , m, n, A and B are as defined for formula I. Preferred hydrolysis products are glycerol and pentaerythritol partial esters, especially glycerol mono-/di- stearate. It is also advantageous if the following hydrolysis products of formula I are used. RCO.NH(CH 2 ).^(CH^-CO.O- (Illb) where RCO. is a C 12 -C 18 fatty acyl group (optionally unsaturated) R(CH 3 ) 2 N + - (CH 2 ) y CO.O ~ (IIIc) where R is C λ to C 22 alk(en)yl branched or straight chain radical and y=l or 2. Preferably, R is C 12 to C 18 . It is especially preferred if the hydrolysis products of formula I are zwitterionic. The invention works particularly well when the PEQs and the hydrolysis products thereof are used in rinse conditioners. It is preferred if the rinse conditioners are liquids. The invention may contain more conventional cationic softening compounds. It is advantageous if the cationic softening compound is a quaternary ammonium softening compound having a solubility in water at pH 2.5 and 20°C of less than lOg/1. It is particularly advantageous if the cationic softening compound is a quaternary ammonium compound in which at least one long chain alkyl group is connected to the quaternary ammonium group via at least one ester link. Preferred cationic softening compounds for use with the invention are compounds of formula (IV) Rs R 5 _ N * _(CH 2 ) n -T-R 6 (CH 2 ) n -T-R 6 formula IV wherein each R 5 group is independently selected from C^ alkyl, alkenyl or hydroxalkyl groups; and wherein each R 6 group is independently selected from C 8 , 28 alkyl or alkenyl groups; O O II II T is - O - C - or - C - O - ; n is an integer from 0-5; and Y " is an anion. Also preferred are fabric conditioning compounds of formula (V) R 8 OOCR 9 I I I I R 8 CH 2 OOCR 9 Formula V wherein each R 8 is independently selected from C^,, alkyl, alkenyl or hydroxyalkyl groups; each R 9 is independently selected from C 8-28 alkyl or alkenyl groups; n is an integer from 0-5; and Y " is an anion. Preferably the level of ester linked quaternary ammonium compounds is at least 1% by weight of the composition, more preferably more than 3% by weight of the composition; especially interesting are concentrated compositions which comprise more than 7% of ester-linked quaternary ammonium compound. The level of ester-linked quaternary ammonium compounds preferably is between 1% and 80% by weight, more preferably 3% to 50%, most preferably 8% to 50%. The composition can also contain one or more optional ingredients, selected from non-aqueous solvents, pH buffering agents, perfumes, perfume carriers, fluorescers, colorants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, anti- shrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, anti-oxidants, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids. The composition may also contain nonionic fabric softening agents such as lanolin and derivatives thereof. The softening composition may be stabilised at low temperatures by the addition of nonionic stabilisers. Suitable nonionic stabilisers which can be used include the condensation products of C β -C 22 primary linear alcohols with 10 to 20 moles of ethylene oxide. The alcohols may be saturated or unsaturated. In particular Genapol T-110, Genapol T-150, Genapol T-200 Genapol C-200 (all Trade Marks; all ex Hoechst Ag) , Lutensol ATI8 (Trade Mark) ex BASF, Genapol 0-100. Preferably, the level of nonionic stabiliser is within the range from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, most preferably from 1 to 4% by weight. The mole ratio of the quaternary ammonium compound to the nonionic stabilising agent is within the range from 40:1 to about 1:1, preferably within the range from 18.1 to about 3:1. The composition can also contain fatty acids for example C 8 - C 24 alkyl or alkenyl monocarboxylic acids or polymers thereof. Preferably saturated fatty acids are used, in particular, hardened tallow C 16 -C 18 fatty acids. Preferably the fatty acid is non-saponified, more preferably the fatty acid is free for example oleic acid, lauric acid or tallow fatty acid. The level of fatty acid material is preferably more than 0.1% by weight, more preferably more than 0.2% by weight. Especially preferred are concentrates comprising from 0.5 to 20% by weight of fatty acid, more preferably 1% to 10% by weight. The weight ratio of quaternary ammonium material to fatty acid material is preferably from 50:1 to 1:10. The compositions of the invention preferably have a pH in the range 1.2 to 5, more preferably a pH from 1.5 to 4. The invention will now be illustrated by the following examples. In the examples all percentages are expressed by weight. Examples according to the invention are illustrated by a number whilst comparative Examples are illustrated by a letter. Examples Liquid fabric softening compositions were made as follows. The following materials were made up as 1% w/w dispersions of active material in demineralised water by heating the mixtures at 70°C, with occasional agitation, until homogeneous. Asterisks indicate Trade Marks. DEEDMAC* - di (hardened tallowoyloxyethyl)dimethylammonium chloride, ex Hoechst. Raw material contained 85% quat. , 2% fatty acid, and 13% isopropanol. Arquad* 2HT - di (hardened tallowyl)dimethylammonium chloride, ex Akzo. Raw material contained 80% quat., 20% solvent. Accosoft* 460 - ethoxylated amidomaine quaternary, ex Stepan. Raw material contained 85% quat., 15% solvent. Stepantex* VRH90 - di (hardened tallowoyloxyethyl) - hydroxyethyl-methylammonium methosulphate, ex Stepan. Raw material contained 90% quat., 10% solvent. HT TMAPC - 1.2 bis [hardened tallowoyloxy] -3- trimethylammonium propane chloride recrystallised raw material (ex Hoechst), containing 98% quat., 2% fatty acid. PEQ 4 - glycerol -derived polyester quat., ex Akzo: /(OH) 0 . 5 Glyc- (OCO.RJ LO WOCO.CHalTfCHaϊaCHaCHaOCO.RΪ L s where RCO = hardened tallowoyl and the counter-ion is chloride. PEQ 5 - pentaerythritol-derived polyester quat., ex Akzo: /(OH) 0 . 3 Penta- (OCO.R) 2 0 \ (OCO.CH 2 N + (CH 3 ) 3 ) 1 . 7 where RCO = hardened tallowoyl and the counter-ion is chloride. PEQ 1 - glycerol-derived polyester quat., ex Akzo: Glyc - (OCO.CH 2 N * (CH 3 ) 2 CH 2 CH 2 OCO.R) 2 . 0 where RCO = tallowoyl and the counter-ion is chloride. The soil release benefits of the various treatments were determined using the following method. Pre-treatment 16 3" x 3" cotton sheeting or knitted polyester squares were treated in a tergotometer pot (ambient temperature, 60 rpm) with 10 ml of a 1% w/w dispersion of the required material in IL of water. After 10 minutes, the fabric squares were removed and spun and line dried. Staining Each fabric square was stained with 0.1 ml of olive oil (highly refined, ex Signa Diagnostics) containing a small amount of solvent violet dye. The stains were allowed to wick out for 4 days prior to measurement of reflectance spectra and washing. ashin Each set of 16 fabric squares was washed in a tergotometer pot (40°C, 70 rpm, 15 min) with 2.5g Persil Micro Liquid in 500ml of water. After washing, the fabrics were rinsed in fresh water for 5 minutes and then line dried. Deterαencv Measurement After drying, reflectance spectra were again measured and percentage detergencies were calculated based on the reflectance values at the reflectance minimum (580 nm) via the Kubelka-Munk (K/S) function. Detergencies quoted are the mean values for the 16 fabric squares in each set. Percentage detergency was calculated using the equation: %Det. = 100x(K/S B - K/S A ) (K/S B- K/S C ) where K/S = (1-R) 2 /2R and where the B, A, and C subscripts refer to values obtained from before wash (stained) fabric, after wash (dried) fabric, and clean (untreated) fabric, respectively. Table 1 shows the detergency results of the fabric softening compounds of the prior art. Results are for removal of oily soil from cotton. Table 1 Pre-treatment Detergency Example A DEEDMAC 61.4 Example B Arquad 2HT 64.8 Example C Accosoft 460 57.6 Example D Stepantex VRH90 59.1 Example E HT TMAPC 64.6 Soil release test of PEQ softening actives on oily soil from cotton is shown in Table 2. Table 2 Pre-treatment Detergency Example 1 PEQ 4 70.2 Example 2 PEQ 5 78.5 Example 3 HT TMAPC 64.6 Example F water 58.7 Oily soil release from polyester by PEQ's is shown in Table 3. Table 3 Pre-treatment Detergency Example 4 PEQ 1 85.9 Example 5 PEQ 4 75.0 Example 6 PEQ 5 79.3 Example G HT TMAPC 66.6 PEQs have thus been shown to have a soil release benefit when compared with both no treatment and when compared with conventional ester quats.

Claims: CLAIMS 1. Use as a soil release agent of compounds of formula I. O O R 2 II II I (R 1 -C-0-) m A (-0-C-B-N + -R 3 ) n nX " I R 4 Formula I wherein X is an anion, A is an (m + n) valent radical remaining after the removal of (m + n) hydroxy groups from an aliphatic polyol having p hydroxy groups and an atomic ratio of carbon to oxygen in the range of 1.0 to 3.0 and up to 2 groups per hydroxy group selected from ethylene oxide and propylene oxide, m is 0 or an integer from 1 to p-n, n is an integer from 1 to p-m, and p is an integer of at least 2, B is an alkylene or alkylidene group containing 1 to 4 carbons atoms, R 1 , R 2 , R 3 and R 4 are, independently from each other, straight or branched chain C^C^ alkyl or alkenyl groups, optionally with substitution by one or more functional groups and/or interruption by at most 10 ethylene oxide and/or propylene oxide groups, or by at most two functional groups selected from O O O O O II II II I I II II -C-0- , -0-C- , -C-N- , -N-C- , and -O-C-O- or R 2 and R 3 may form a ring system containing 5 or 6 atoms in the rings, with the proviso that the average compound either has at least one R group having 22-48 carbon atoms, or at least two R groups having 16-20 carbon atoms, or at least three R groups having 10-14 carbon atoms. 2. Use as a soil release agent of a hydrolysis product of compounds according to claim 1. 3. Use of compound according to claim 1 or claim 2 in a fabric conditioning composition. 4. Use of a compound according to any preceding claim in a liquid composition. 5. Use of a compound according to any preceding claim characterised in that (m + n) in the formula I is at least 2. 6. Use of a compound according to any preceding claim wherein the compound of formula I is derived from a) 1 equivalent of an aliphatic polyol having p hydroxy groups. b) m equivalents of an aliphatic carboxylic acid of the formula RICOOH, and c) n equivalents of a C 1-4 halocarboxylic acid, followed by treatment with d) n equivalents of a tertiary amine of the formula R 2 R 3 R 4 N or n equivalents of a secondary amine of the formula R 2 R 3 NH converted with n equivalents of a quatemizing agent. 7. Use of a compound according to claim 6, in which the polyol contains 2 to 8 hydroxy groups. 8. Use of a compound according to claim 7, in which the polyol is selected from the group of ethylene glycol, glycerol, pentaerythritol, sorbitol, glucose, saccharose, methyl glucoside, and/or condensed derivatives thereof. 9. Use of a compound according to claim 8 in which the polyol is selected from the group consisting of diglycerol, triglycerol, and dipentaerythritol. 10. Use of a compound according to claim 6 in which the polyol is selected from the group of natural polyols such as starch, degraded starch and oligomers and/or polymers containing repeating units of vinyl alcohol. 11. Use of a compound according to claim 6 in which the aliphatic acid of the formula R 1 -COOH is tallow acid and/or at least partially hydrogenated tallow acid. 12. Use of a compound according to claim 6 in which the tertiary amine is trimethylamine. 13. A fabric conditioning composition comprising (i) a quaternary ammonium fabric conditioning compound having a solubility in water at pH 2.5 and 20°C of less than lOg/1 and (ii) a compound of the formula I or a zwitterionic hydrolysis product thereof: O O R 2 II II I (R 1 -C-0-) m A (-0-C-B-N + -R 3 ) n nX " I R 4 Formula I wherein X is an anion, A is an (m+n) valent radical remaining after the removal of (m+n) hydroxy groups from an aliphatic polyol having p hydroxy groups and an atomic ratio of carbon to oxygen in the range of 1.0 to 3.0 and up to 2 groups per hydroxy group selected from ethylene oxide and propylene oxide, is 0 or an integer from 1 to p-n, n is an integer from 1 to p-m, and p is an integer of at least 2, B is an alkylene or alkylidene group containing 1 to 4 carbon atoms, R 1 , R 2 , R 3 and R 4 are, independently from each other straight or branched chain C 1 -C 48 alkyl or alkenyl groups, optionally with substitution by one or more functional groups and/or interruption by at most 10 ethylene oxide and/or propylene oxide groups or by at most two functional groups selected from O -C-O- -0-C-, -C-N-, -N-C-, and -O-C-O- or R 2 and R 3 may form a ring system containing 5 or 6 atoms in the ring, with the proviso that the average compound has at least one R group having 22-48 carbon atoms, or at least two R groups having 16-20 carbon atoms, or at least three R groups having 10-14 carbon atoms. 14. A fabric conditioning composition according to claim 13 in which the fabric conditioning compound (i) is selected from compounds of formula (IV) R * R,_ N + _(CH 2 ) -T-R (CH 2 ) n -T-R 6 formula IV wherein each R 5 group is independently selected from C α _ 4 alkyl, alkenyl or hydroxalkyl groups; and wherein each R 6 group is independently selected from C 8-28 alkyl or alkenyl groups; T is - O - C - or - C - 0 - ; n is an integer from 0-5; and Y " is an anion. 15. A fabric conditioning composition according to claim 13 in which the fabric conditioning compound (i) is selected from compounds of formula (V) R 8 OOCR 9 I I KT _ (CH 2 ) n -CH R 8 CH 2 OOCR 9 Formula V wherein each R 8 is independently selected from C^ alkyl, alkenyl or hydroxyalkyl groups; each R 9 is independently selected from C 8-28 alkyl or alkenyl groups; n or O is an integer from 1-5; and Y " is an anion.

Inventors: KHAN-LODHI ABID NADIM, WHALEY CHRISTOPHER, KHAN-LODHI, ABID, NADIM, WHALEY, CHRISTOPHER
Applicants: UNILEVER NV, UNILEVER PLC, UNILEVER N.V.
Application year: 1996
Main classification: C11D3
IPC codes: C11D1, C11D3