AU723907B2

AU723907B2 - Fabric softening composition

Info

Publication number: AU723907B2
Application number: AU50510/98A
Authority: AU
Inventors: David Stephen Grainger; Abid Nadim Khan-Lodhi
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1996-10-16
Filing date: 1997-10-13
Publication date: 2000-09-07
Anticipated expiration: 2017-10-13
Also published as: WO1998016538A1; ZA979231B; AR009117A1; CN1240452A; AU5051098A; BR9711906A; EP0934328A1; EA001695B1; EA199900383A1; TR199900801T2; CN1293086C; TW577946B

Description

WO 98/16538 PCT/EP97/05762 FABRIC SOFTENING COMPOSITION Technical Field The present invention relates to fabric softening compositions. In particular the invention relates to fabric softening compositions that soften fabrics without affecting the absorbency of the fabric.

Background and Prior Art Rinse added fabric softener compositions are well known.

However, a disadvantage associated with conventional rinse conditioners is that although they increase the soft feel of a fabric they simultaneously decrease the fabric's absorbency. A decrease in the absorbency properties of a fabric means that its ability to take up water decreases.

This is particularly disadvantageous with towels where the consumer requires the towel to be soft, and yet, have a high absorbency.

Co-pending application GB 9518012.1 (Unilever) discloses liquid fabric conditioning compositions comprising a substantially water insoluble fabric softening compound.

The compositions have a phase structure with greater than one-dimensional long range order as defined by x-ray crystallography. The compositions are said to exhibit good softening and hydrophobicity.

WO 98/16538 PCT/EP97/05762 EP 0 380 406 (Colgate-Palmolive) discloses detergent compositions comprising a saccharide or reduced saccharide ester containing at least one fatty acid chain.

Bleaching detergent compositions comprising derivatives of pentoses or hexoses, having a long chain acyl or aroyl group and one or more short chain alkyl groups attached through a glycosidic bond are disclosed in WO 91/10719 (Novo).

Textile treatment compositions containing mixtures of cationic and nonionic surfactants are disclosed in GB 1 601 359 (Procter Gamble).

US 4 800 038 (Colgate-Palmolive) discloses the use of acylated sugar ethers as a bleach activator in nonionic detergent compositions.

WO 9500614 (Kao Corporation) discloses softening compositions comprising polyhydric alcohol esters and cationised cellulose.

JP 06264049 (Mitsubishi Kasei Corporation) discloses viscosity improving sucrose long chain fatty acid esters with an average degree of substitution of 4 to 7 in cosmetics and topical skin compositions.

US 5 447 643 (Hls) discloses acqueous fabric softeners comprising nonionic surfactant and mono,di or tri fatty acid esters of certain polyols.

LAJ D812 .j CRnk~ c ISeaS tay n_ e So -In I rg agen',7 deriv,,atives, which are so'iJd after esterification, ifl coboto n nJo nionic and cationic emuls'irs J-3 08 158258d Jc 1 o se s an t1410a ct e r, fa br-i C softLZe n Inrg cmO~SILIonS COMPris 7g aoyidl _yoolf~ acid estLef BE 827 986 discloses textile fabric sofreners comrising mno arc diesters.

The~~ vrsn ifVro is diece toad lei ng the proo -ems associated with the prlor art as referre-, to nereinaboye.

Th'e pri nc ipai1 advanta ces or Ft,_he pre sent invention are tha Crs, compositions 'when used to soften fabrics do so effectively without detriment to the absorbency of the rabrrc and that the comos-irions are easily manu'factured..

DeFin-ition of the invention Thus according to one aspect of the invention there i s Qorovided: A fabric softening composition comprising: a liquid or soft solid derivative of a cyclic polyol (CPE) or of a reduced saccharide (RSE) resulting from 35 to 100% of the hydroxyl groups in the cyclic polyol or reduced '.,~,saccharide being esterified or etherified, the derivative

AMCDEDSHEET

C3745 PCT oR S E ~'avn 111 C a, or nmore of S,0 esten grfoCs ir-I deo0e n dE :v 7- a Ci-d -o a C all'cxoL or 1 ('enli or higher esters anal; WO 98/16538 PCT/EP97/05762 ii) a deposition aid.

The invention also relates to a method of treating fabric comprising the step of treating the fabrics with a composition comprising a CPE or RSE wherein the CPE or RSE is a liquid or soft solid having a solid:liquid ratio between 50:50 and 0:100 at 20 0 C as determined by T 2 relaxaticn time NMR.

The invention also discloses the use of a CPE or RSE as a fabric softening aid that does not decrease the fabric's absorbency.

The invention further relates to a liquid or soft solid fatty acid ester of glucose having a solid:liquid ratio between 50:50 and 0:100 as measured above, the ester groups comprising a mixture of C 2

-C

22 alkyl or alkenyl chains and resulting from a cyclic polyol having 35 to 100% of the hydroxyl groups esterified. The use of a sorbitan mono ,di or trioleate as a hydrophilic softener is also provided. It has been found, surprisingly, that the above compositions provide an unexpected combination of simultaneous fabric softening and retention of absorbency.

Detailed Description of the Invention In the context of the present invention the initials CPE or RSE stand for a cyclic polyol derivative or a reduced saccharide derivative respectively which results from 35 to 100% of the hydroxyl groups of the cyclic polyol or reduced WO 98/16538 PCT/EP97/05762 saccharide being esterified and/or etherified and in which at least two or more of ester or ether groups are independently of one another attached to a C, to C 22 alkyl or alkenyl chain.

In the fabric softening compositions of the invention the ratio of CPE or RSE to deposition aid is preferably within the range of from 1:10 to 15:1, more preferably within the range from 1:5 to 10:1, most preferably 1:1 to 10:1.

If a composition is required to give particularly high absorbency to fabrics it is advantageous if the ratio of CPE or RSE to deposition aid is at least 1:1 (especially if the deposition aid is a fabric softening compound).

If a highly softening composition is required it is advantageous if the ratio of a softening deposition aid to CPE or RSE is at least 2:3, preferably 1:1.

To give excellent softening and hydrophobicity to fabrics it is preferred if the ratio of softening deposition aid to CPE or RSE is from 3:2 to 1:10, more preferably from 2:3 to 1:10.

The CPE or RSE The liquid or soft solid (as hereinafter defined) CPEs or RSEs of the present invention result from 35 to 100% of the hydroxyl groups of the starting cyclic polyol or reduced saccharide being esterified or etherified. Typically the CPE's or RSE's have 3 or more ester or ether groups or WO 98/16538 PCT/EP97/05762 mixtures thereof for example 4 or more, example 5 or more.

It is preferred if two or more of the ester or ether groups of the CPE or RSE are independently of one another attached to a C 8 to C 22 alkyl or alkenyl chain. The C, to C 22 alkyl or alkenyl groups may be branched or linear carbon chains.

Preferably 40 to 100% of the hydroxyl groups, most preferably 50 to 100% are esterified or etherified.

CPEs are preferred for use with the present invention.

Inositol is a preferred example of a cyclic polyol.

Inositol derivatives are especially preferred.

In the context of the present invention the term cyclic polyol encompasses all forms of saccharides. Indeed saccharides are especially preferred for use with this invention. Examples of preferred saccharides for the CPE's or RSE's to be derived from are monosaccharides and disaccharides.

Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is especially preferred.

An example of a reduced saccharide is sorbitan.

Examples of disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred.

The liquid or soft solid CPE's or RSE's of the present invention can be prepared by a variety of methods well known WO 98/16538 PCT/EP97/05762 to those skilled in the art. These methods include acylation of the cyclic polyol or reduced saccharide with an acid chloride; trans-esterification of the cyclic polyol or reduced saccharide fatty acid esters using a variety of catalysts; acylation of the cyclic polyol or reduced saccharide with an acid anhydride and acylation of the cyclic polyol or reduced saccharide with a fatty acid.

Typical preparations of these martials are disclosed in US 4 386 213 (Procter and Gamble) and AU 14416/88 (Procter and Gamble).

It is preferred if the CPE or RSE has 4 or more ester or ether groups although for some compounds 3 ester or ether groups produce excellent results and are preferred. If the cyclic CPE is a disaccharide it is preferred if the disaccharide has 4 or more ester or ether groups.

Particularly preferred CPE's are esters with a degree of esterification of 4 or more, for example, sucrose esters.

It is advantageous if the saccharide or reduced saccharide has 3 or more ester groups.

Where the cyclic polyol is a reducing sugar it is advantageous if each ring of the CPE has one ether group, preferably at the Ci position, and the remaining hydroxyl groups are esterified. Suitable examples of such compounds include methyl glucose derivatives.

Examples of suitable CPEs include esters of alkyl(poly)glucosides, in particular alkyl glucoside esters having a degree of polymerisation from 1 to 2.

WO 98/16538 PCT/EP97/05762 It is preferable if the ester or ether groups of the cyclic polyol or reduced saccharide are independently of one another attached to a C 8 to C 22 alkyl or alkenyl chain or a C 2 to C. chain and in which the ratio of Ca to C 22 groups to C 2 to C, is from 5:3 to 3:5. This is because these products are in the main oils (liquids) and are thus easy to formulate.

It has also been found that excellent results are achieved with oils (liquids).

Examples of suitable saccharide esters include fatty acid esters of glucose, the ester groups comprising C 2

-C

18 alkyl or alkenyl chain and the degree of esterification being In particular saccharides having ester groups consisting essentially of a C 2 alkyl chain and a C 8 to C 12 straight alkyl chain, the molar ratio of short chain C 2 alkyl chains to C 8 to C12 straight alkyl chains being from 2:1 to 1:2, more preferably about 1:1 are suitable. It is further preferred if the degree of esterification is at least The liquid or soft solid CPE's or RSE's of the present invention are characterised as materials having a solid:liquid ratio of between 50:50 and 0:100 at 20 0 C as determined by T 2 relaxation time NMR, preferably between 43:57 and 0:100, most preferably between 40:60 and 0:100, such as, 20:80 and 0:100. The T 2 NMR relaxation time is commonly used for characterising solid:liquid ratios in soft solid products such as fats and margarines. For the purpose of the present invention, any component of the NMR signal with a T 2 of less than 100 Is is considered to be a solid WO 98/16538 PCTIEP97/05762 component and any component with T 2 100 (ts is considered to be a liquid component.

For the CPE's and RSE's the tetra, penta etc prefixes only indicate the averge degreees of esterification. The compounds exist as a mixture of materials ranging from the monoester to the fully esterified ester. It is the average degree of esterification which is used herein to define the CPE's and RSE's.

It has been found that CPE's and RSE's having unsaturated or mixed alkyl chain lengths show advantageous results.

Factors governing the suitability of the CPE's and RSE's are the presence and degree of branched chains, mixed chain lengths and the level of unsaturation.

The Deposition aid In the context of the present invention a deposition aid is defined as any material that aids deposition of the selected CPE or RSE onto a fabric during the laundering process.

The deposition aid may be selected from a fabric softening compounds, cationic compounds, nonionic surfactants, anionic surfactants, polymeric deposition aids or mixtures thereof.

It is preferred if the deposition aid is cationic in nature.

If a cationic surfactant or cationic softening aid is not present in the formulation it is preferred if a cationic polymeric deposition aid is present. Most preferably the WO 98/16538 PCT/EP97/05762 deposition aid is both cationic in nature and is a fabric softening compound.

Mixtures of deposition aids may be used, for example, a mixture of a cationic surfactant and a nonionic surfactant, or a fabric softening compound and a polymeric deposition aid.

Suitable cationic deposition aids include water soluble single chain quaternary ammonium compounds such as cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, or any of those listed in European Patent No. 258 923 (Akzo).

However, it is preferred if the deposition aid is a fabric softening compound. In particular substantially water insoluble quaternary ammonium materials comprising a single alkyl or alkenyl chain having an average length equal to or greater than C 20 are preferred. Even more preferable are compounds comprising a polar head group and two alkyl or alkenyl chains each having an average chain length equal to or greater than C 14 Preferably the fabric softening deposition aid of the invention has two long alkyl or alkenyl chains with an average chain length equal to or greater than C 14 More preferably each chain has an average chain length greater than C 1 i. Most preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of C 18 I L WO 98/16538 PCT/EP97/05762 It is preferred if the long chain alkyl or alkenyl groups of the fabric softening deposition aid are predominantly linear.

The fabric softening deposition aids used in the compositions of the invention are molecules which provide excellent softening, and are characterised by a chain melting -L to La transition temperature greater than 25 0

C,

preferably greater than 35 0 C, most preferably greater than 45 0 C. This L to La transition can be measured by DSC as defined in "Handbook of Lipid Bilayers, D Marsh, CRC Press, Boca Raton Florida, 1990 (Pages 137 and 337).

"Substantially insoluble" fabric compounds in the context of this invention are defined as fabric compounds having a solubility less than 1 x 10-3 wt% in demineralised water at 0 C. Preferably the fabric softening deposition aids have a solubility less than 1 x 10 4 Most preferably the fabric softening deposition aids have a solubility at 20 0 C in demineralised water from 1 x 10 8 to 1 x 10 6 Preferred fabric softening deposition aids are quaternary ammonium compounds, preferably those with at least one ester link.

It is especially preferred if the fabric softening deposition aid is a water insoluble quaternary ammonium material which comprises a compound having two C 12 1 alkyl or alkenyl groups connected to the molecule via at least one ester link. It is more preferred if the quaternary ammonium material has two ester links present. An especially WO 98/16538 PCT/EP97/05762 preferred ester-linked quaternary ammonium material for use in the invention can be represented by the formula R 1 N+ (CHI) n-T-R' Formula (I) 2 (CHO. -T-R wherein each R' group is independently selected from C, 4 alkyl, hydroxyalkyl or C 2 4 alkenyl groups; and wherein each R 2 group is independently selected from C,- 2 alkyl or alkenyl groups; T is orxC0- X_ is any suitable anion and n is an integer from Di(tallowoyloxyethyl) dimethyl aumonium chloride is especially preferred.

A second preferred type of quaternary ammnonium material can be represented by the formula (II): 00CR 2 (CI) nCli Forumula (II) CH'OOCR 2 WO 98/16538 PCT/EP97/05762 wherein R 1 n, X- and R 2 are as defined above.

It is advantageous for environmental reasons if the quaternary ammonium material is biologically degradable.

Preferred materials of this class such as 1,2 bis[hardened tallowoyloxy]-3- trimethylammonium propane chloride and their method of preparation are, for example, described in US 4 137 180 (Lever Brothers). Preferably these materials comprise small amounts of the corresponding monoester as described in US 4 137 180 for example 1-hardened tallowoyloxy -2-hydroxy 3-trimethylammonium propane chloride.

The fabric softening deposition aid of the composition may also be compounds having the formula (III): 0 0 R 4

I

(R -R )n X Formula (III)

I

R

wherein X is an anion, A is an valent radical remaining after the removal of 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, WO 98/16538 PCT/EP97/05762 B is an alkylene or alkylidene group containing 1 to 4 carbon atoms,

R

3

R

4

R

5 and R 6 are, independently from each other, straight or branched chain Ci-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 0 0 0 0 0 II II II I I II II and -0-C-0or R 1 1 and R 12 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. Preferred compounds of this type are described in EP 638 639 (Akzo).

The deposition aid may also be a nonionic surfactant.

Preferred nonionic ethoxylated surfactants have an HLB of from about 10 to about 20. It is advantageous if the surfactant alkyl group contains at least 12 carbon atoms.

Suitable polymeric deposition aids for use with the invention include cationic and nonionic polymeric deposition aids.

14 I WO 98/16538 PCTIEP97/05762 Suitable cationic polymeric deposition aids include cationic guar polymers such as Jaguar (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats (ex National Starch), Flocaid (ex National Starch), cationic potato starch such as SoftGel (ex Aralose), cationic polyacrylamides such as PCG (ex Allied Colloids). Cationic polymeric aids are particularly preferred in the absence of any other cationic material in the composition.

Suitable nonionic deposition aids include Pluronics (ex BASF), dialkyl PEGs, cellulose derivatives as described in GB 213 730 (Unilever), hydroxy ethyl cellulose, starch, and hydrpohobically modified nonionic polyols such as Acusol 880/882 (ex Rohn Haas).

Mixtures of any of the aforementioned deposition aids may be used.

Composition pH The compositions of the invention preferably have a pH from to 7, more preferably from 1.5 to Other Ingredients The compositions of the present invention can also contain fatty acids, for example C 8

C

24 alkyl or alkenyl monocarboxylic acids, or, polymeric carboxylic acids.

Preferably saturated fatty acids are used, in particular, hardened tallow Ci,-C, 8 fatty acids.

WO 98/16538 PCT/EP97/05762 The composition can also contain one or more optional ingredients, selected from electrolytes, non-aqueous solvents, pH buffering agents, perfumes, perfume carriers, fluorescers, colorants, hydrotropes, antifoaming agents, antiredeposition agents, polymeric and other thickeners, enzymes, optical brightening agents, opacifiers, antishrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, anti-oxidants, anti-corrosion agents, drape imparting agents, antistatic agents, sunscreens, colour care agents and ironing aids.

If the product is a liquid it may be advantageous if a viscosity control agent is present. Any viscosity control agent used with rinse conditioners is suitable for use with the present invention, for example biological polymers such as Xanthum gum (Kelco ex Kelsan and Rhodopol ex Rhone- Poulenc), Guar gum (Jaguar ex Rhone-Poulenc), starches and cellulose ethers. Synthetic polymers are useful vicosity control agents such as-polyacrylic acid, poly vinyl pyrolidone, polyethylene, carbomers, cross linked polyacrylamides such as Acosol 880/882 polyethylene and polyethylene glycols.

Also suitable as viscosity modifires are decoupling polymers and defloccculating polymers.

Product Form The compositions may be in any physical form conventionally used for fabric softening compositions for example, powder, WO 98/16538 PCT/EP97/05762 paste, gel or liquid. It is preferred if the product is a liquid and especially preferred if it is an emulsion.

Examples The invention is illustrated by the following non-limiting examples. Further examples within the scope of the present invention will be obvious to the man skilled in the art.

Examples of the invention are illustrated by a number while comparative examples are illustrated by a letter.

A. Preparation of CPE's and RSE's Compound 1 Preparation of a glucose penta ester, where 50% (approx) of the ester groups are acetyl groups and 50% (approx) are decanoyl groups.

a-D glucose (0-111M) was added to pyridine at room temperature. Acetyl chloride (0.254M) and decanoyl chloride (0.278M) were mixed together and the acid chloride mixture added drop-wise to the glucose solution. The acid chlorides were added slowly over a period of about 1.5 hours. As the reaction proceeded, large amounts of a thick white precipitate were formed and ethyl acetate was added to maintain the fluidity of the reacton mixture.

WO 98/16538 PCT/EP97/05762 The reaction mixture was stirred overnight (>16 hours) at room temperature. The reaction mixture was filtered to remove the solid pyridine hydrochloride salt and stripped under vacuum to remove the excess pyridine. The remaining produce was taken back up in ethyl acetate, and combined with water in a separating funnel. The mixture was shaken and allowed to separate.

The organic layer was washed with water, dilute hydrochloric acid (to remove residual pyridine), saturated sodium bicarbonate (to remove the residual carboxylic acids), water (twice) and saturated sodium chloride. The organic layer was dried over magnesium sulphate (anhydrous) overnight, filtered and stripped under high vacuum with heating to leave a pale brown oily residue.

The IR spectrum showed only a single sharp peak at 1749 cm' in the carbonyl region. This confirms that there is no fatty acid chloride nor fatty acid remaining in the product.

In addition, there is no intensity in the 3000-3500cm-1 region due to un-reacted hydroxyl groups.

An analysis of the 1H NMR spectrum gives an a:P anomer ratio of 34:66. The integrals give a ring proton (3.5-6.5 ppm) to alkyl chain proton (0.8-2.5ppm) ratio of 0.127. This is agreement with a theoretical ratio of 0.127 for a glucose molecule esterified with an average of 2.5 acetyl groups and decanoyl groups per ring.

WO 98/16538 PCTIEP97/05762 Hydroxyl value Density 1.0300g/cm 3 Viscosity 810 mPa.s Compound 2 Preparation of a glucose penta ester, where 50% (approx) of the ester groups are acetyl groups and 50% (approx) are dodecanoyl groups.

The same procedure was followed as for Compound 1 with replacement of the decanoyl chloride with dodecanoyl chloride.

The IR spectrum showed only a single sharp peak at 1748 cm- 1 in the carbonyl region. This confirms that there is no fatty acid chloride nor fatty acid remaining in the product.

In addition, there is no intensity in the 3000-3500 cm' region due to un-reacted hydroxyl groups.

An analysis of the 1H NMR spectrum gives an cx: anomer ratio of 67:33. The integrals also give a ring proton (3.5-6.5 ppm) to alkyl chain proton (0.8-2.5 ppm) ratio of 0.1039.

This is in agreement with theoretical ratio of 0.1076 for a glucose molecule esterified with an average of 2.5 acetyl groups and 2.5 dodecanoyl groups per ring.

Hydroxyl value 19.5 Density 1.0078g/cm 3 Viscosity 693 mPa.S WO 98/16538 PCT/EP97/05762 Compound 3 Preparation of a glucose penta ester, where 50% (approx) of the ester groups are acetyl groups and 50% (approx) are octanoyl groups.

The same procedure was followed as for Compound 1 with replacement of decanoyl chloride with octanoyl chloride to give a dark brown viscous oil.

The IR spectrum showed only a strong sharp peak at 1748 cm-l and a much smaller peak at 1674 cm 1 in the carbonyl region.

Again, this confirms that there is no fatty acid chloride nor fatty acid remaining in the product. There is no intensity in the 3000-3500cm 1 region due to un-reacted hydroxyl groups.

Hydroxyl value undetectable Density 1.0535g/cm 3 Viscosity 3500 mPas.S Compound 4 Preparation of a glucose penta ester, where 70% (approx) of the ester groups are acetyl groups and 30% (approx) are octanoyl groups.

WO 98/16538 PCT/EP97/05762 The same procedure was followed as for Compound 1 using acetyl chloride (0.388 m) and octanoyl chloride (0.156m) to give an extremely viscous dark brown oil.

The IR spectrum showed only a strong sharp peak at 1749cm 1 and a much smaller peak at 1673cm in the carbonyl region.

Again, this confirms that there is no fatty acid chloride nor fatty acid remaining in the product. There is no intensity in the 3000-3500cm" 1 region due to un-reacted hydroxyl groups.

Viscosity 11450 mPa.s Density 1.1034g/cm 3 Compound Preparation of sucrose octa ester, where all of the ester groups are oleate groups.

Oleic acid (0.40M) (90% technical grade) was mixed with dichloromethane in a large round bottom flask to which Oxalyl chloride (0..44M) in dichloromethane was added. The residual dichloromethane and the excess oxalyl chloride were stripped off under high vacuum to leave 120g of oleoyl chloride.

In a separate flask, sucrose (0.044M) was added to a mixture of pyridine, ethyl acetate and dimethyl formamide. The oleoyl chloride prepared above was added dropwise to the WO 98/16538 PCT/EP97/05762 mixture and the mixture was stirred overnight at 80 0 C with a small amount of 4-dimethylamino pyridine catalyst.

The clear dark brown solution was stripped under vacuum and taken back up in diethyl ether. The organic layer was washed with water (twice), dilute hydrochloric acid, saturated sodium bicarbonate, water (four more times) and saturated brine after which the organic layer was dried over magnesium sulphate overnight. The magnesium sulphate was filtered off and the diethyl ether removed under high vacuum to leave a yellow oil.

The IR spectrum showed a sharp peak at 1740 cm' 1 in the carbonyl region. This confirms that there is no fatty acid chloride nor fatty acid remaining in the product.

Hydroxyl value undetectable Viscosity 568 mPa.s Density 0.9446 g/cm 3 Compound 6 Preparation of cellobiose octaester, where all of the ester groups are oleate groups.

A similar procedure was followed as for compound 5 with the replacement of the sucrose by cellobiose. The only minor changes to the precedure were that the reaction solvent comprised a mixture of pyridine and dimethyl formamide only ;22 WO 98/16538 PCT/EP97/05762 and the final reaction was heated with activated charcoal prior to drying with magnesium sulphate.

The IR spectrum showed a sharp peak at 1744 cm 1 in the caronyl region, confirming that there is no residual fatty acid nor fatty acid chloride remaining in the product.

Gel permeation chromatography shows only one sharp signal.

This indicates nearly all the material is the octaester.

Hydroxyl value: undetectable Viscosity: 1040 mPa.s Density: 0.9459 g/cm 3 Compound 7 Preparation of methyl a-D-glucopyranoside tetraester where 37.5% (approx) of the ester groups are acetyl groups and 62.5% (approx) are dodecanoyl groups.

A similar procedure was followed as for compound 2 with replacement of the glucose with methyl a-D-glucopyranoside.

The IR spectrum showed only a single sharp peak at 1747 cm-1 in the carbonyl, region confirming that there is no residual fatty acid, nor, fatty acid chloride remaining in the product.

WO 98/16538 PCT/EP97/05762 Hydroxyl value: Viscosity: 225 mPa.s Density: 0.9930 g/cm 3 Compound 8 Preparation of myo-inositol hexaester where 50% (approx) of the ester groups are acetyl groups and 50% (approx) are dodecanoyl groups.

A similar procedure was followed as for compound 2 with replacement of the glucose with myo-inositol.

The IR spectrum showed only a single sharp peak at 1755cm' 1 in the carbonyl region, confirming that there is no residual fatty acid nor fatty acid chloride remianing in the product.

Hydroxyl value: 0.04 Viscosity: 20,500 mPa.s Density: 1.0227 g/cm 3 B. Examples of Compositions In table 1 selected compounds above were placed in an ethanol or acetone solution (0.9g/l) and padded onto fabric to give deposition of 0.2% of compound by weight on the fabric.

WO 98/16538 Table 1 PCT/EP97/05762 Example Softening Active Solvent 1 Glucose perester 50:50 C 2

:C

10 Ethanol Compound 1 (oily liquid) 2 Glucose perester 50:50 C 2

:C

12 Ethanol Compound 2 (oily liquid) 3 Glucose perester 50:50 C 2

:C

8 Ethanol Compound 3 (oily liquid) 4 Sucrose octaoleate Acetone Compound 5 (oily liquid) Sucrose pentaoleate (Ryoto 0-170) Acetone (oily liquid) 6 Sucrose pentaester (Ryoto POS-135*) Acetone (soft solid) 7 Sucrose pentataurate (Ryoto L-195) Acetone (soft solid) A Sucrose tetrastearate (Ryoto S-270) Ethyl (white powder) Acetate Contains a mixture of palmitate, stearate and oleate ester groups.

Examples 8 to 21 (Table 2) below were prepared by mixing the listed components together in water. All Examples contain active material.

I Table 2; mixtures with CTAC (fabric softeningr co nound) Example cetyl trimethyl amnmonium chloride (CTACI Glucose perester 50:50 C 2

:C

1 Compound 2 (oily liquid) Glucose perester 50:50 C 2

:C

1 0 Compound l(oily liquid) Sucrose pentaoleate (Ryoto 0-170) Sucrose pen-taester (Ryoto POS-l3S) Sucrose pentalaurate (Ryoto L-195) Sucrose tetrastearate (Ryoto S-270) Sucrose tetraoleate (oily liquid) Sucrose perltaerucate (Ryoto ER-190) (soft liquid) Sucrose tetraeurate (Ryoto ER-290) (soft liquid) Sorbitan moiioleate (Span 80) (oily liquid)I Sorbitan trioleate (Span 85) (oily l iqu id) Water CTAC:oil ratio Span 80 and Span 85 are available from ICI surfactants.

CTAC is availbie from Aldrich (25% solution).

The Ryoto products are available from Mitsibushi-IKagku Food Corporation.

I 0 '0 00

U'

00 The examples listed in Table 3 below were prepared by heating the ingredients together at 80 0 C, and mixing at high shear.

TahTh 3! mixtures with 1~EO (fabric softenina comoound) Table 3: mixtures with HEO (fabric softenina comnound) Example 22 23 f 4 25 J 26 27 f C 28 29 30 T 31 32 D HE~Q 12.57 1.71 0.86 2.57 1.71 0.86 4.28 0.86 0.86 0.86 2.57 1.71 0.86 Fatty Acid 0.43 0.39 0.14 0.43 0.29 0.14 0.72 0.14 0.14 0.14 0.43 0.39 0.14 1 Glucose perester 2 3 4 50:50 Compound 2 (oily liquid) I Glucose peresier 2 3 4 50:50 C2:C 30 Compound 1 (oily liquid) Sucrose pentaoleate (Ryoto 4 2 3 0-110) (oily liquid) Sucrose pentaester (Ryoto 4 P05-1351 (soft liquid) Scose pentalaurate (Ryoto 4 L-195) (soft solid) Sucrose tetrastearate 4 (Ryoto0 S-270) (hit e powder)____ Water 95 95 95 95 95 95 95 95 95 95 95 95 HEQ:oil. ratio 1.285:1 1,.1.45 1:4.65 L -1175 1:1.75 1:4.65 1:4 1:4 1:4 3:2 2:3 HEQ' is 1,2 binthardened tallowoyloxyl t rime thyl ammonium propane chloride available from Hoechst.

WO 98/16538 PCT/EP97/05762 The examples listed in Table 4 prepared by heating the ingredients together at 80 0 C, and mixing at high shear.

Table 4; mixtures with Prapagen 34452 The examples listed in Table ingredients together at 80 0

C

4 were prepared by heating the and mixing at high shear.

Example 33 3.4 35 36 37 38 E Prapagen 3445 2 3 2 1 3 2 1 Glucose perester 2 3 4 50:50 C 2

:C

12 Compound 2 (oily liquid) Glucose perester 2 3 4 50:50 C 2

:C

1 i Compound 1 (oily liquid) Water 95 95 95 95 95 95 Prapagen:oil 3:2 2:3 1:4 3:2 2:3 1:4 ratio 2 Dimethyl ditallow ammonium chloride.

WO 98/16538 WO 9816538PCT/EP97/05762 Table 5; mixtures with Accosoft 460 HC The examples listed in Tables 5, 6 and 7 were prepared by heating the ingredients together at 80 0 C and mixing at high shear.

Example 39 140 41 F Accosoft 460 HC 3 2 1 Sucrose pentaoleate 2 3 4 0 Ryoto 0-170 (oily liquid)_____ Water 95 95 95 Accosoft:oil 3:2--T2.:3 11:4- Table 6; mixtures with-Accosoft 550 HC Examiple.:42 43 4 Accosoft 550 HC 3 2 1 Sucrose pentacleate 2 3 4 0 Ryoto 0-170 (oily Water 95 95 195 Accosoft:oil 3:2 12:3 11:4- Accosoft 460 and Accosoft 550 HC are available from Stepan.

WO 98/16538 PCT/EP97/05762 Table 7: mixtures with Arouad HT Example 45 46 47 Arquad HT 1 1 1 Sucrose Tetraoleate 4 (oily liquid) Sucrose pentaeurueate 4 (Ryoto ER-190) (oily liquid) Sucrose tetraeureate 4 (Ryoto ER-290) (oily liquid) Water 95 95 Arquad HT:oil 1:4 1:4 1:4 Softness Evaluation Softening performance was evaluated by adding 0.lg of fabric softening compound (2ml of a 5% a.d. dispersion for liquids) to 1 litre of tap water, at ambient temperature in a tergotometer. Three pieces of terry towelling (8cm x 8cm, total weight) were added to the tergotometer pot. The cloths were treated for 5 minutes at 65 rpm, spin dried to remove excess liquor and line dried overnight and conditioned at 21 0 C/65 C/ for 24 hours.

For Examples 1 to 7 and A the terry towelling was treated by padding the composition directly onto the fabric as described above.

Softening of the fabrics was assessed by an expert panel of 4 people using a round robin paired comparison test protocol. Each panel member assessed four sets of test 7o WO 98/16538 PCT/EP97/05762 cloths. Each set of test cloths contained one cloth of each test system under a evaluation. Panel members were asked to assess softness on a 8 point scale. Softness scores were calculated using an "Analysis of Variance" technique. Lower values are indicative of better softening.

Absorbency Evaluation The absorbency was measured using the textile and paper industry wicking (Klemm) test. A strip of treated fabric is held vertically with a clip whilst the free end is weighed down with a piece of rubber. The strip is lowered into a tray containing a 0.02% diphenyl red dye solution such that the rubber weight is just below the surface. The height to which the liquid rises up the strip in one hour is measured (unless stated otherwise). Six fabric strips are measured for each treatment. "Active in Table 8 is the deposition aid.

WO 98/16538 Table 8 PCTIEP97/05762 Example Oil J Active Wicking S oftness Height Score 1 (cm) 1 Compound 1 13.50e 3.83 2 Compound 2 13.52~' 4.00 3 Compound 3 13.12' 5.00 4 Compound 5 14.83' 4.00 Ryoto 0-170 -20.00 2.81 6 Ryoto POS-135 -10.41 2.25 7 Ryoto L-175 -8.53 2.75 A Ryoto S-270 -4.91 2.37 8 Compound 2 CTAC 14.55 4.17 9 Compound 1 CTAC 15.64 3.83 Compound 2 CTAC 16.25 3.67 11 Compound 1 CTAC 15.06 4.83 12 Compound 1 CTAC 16.39 13 Compound 1 CTAC 17.08 3.83 14 Ryoto 0-170 CTAC 15.88 3.07 Ryoto POS-135 CTAC 8.82 3.05 16 Ryoto L-195 CTAC 7.18 3.57 17 Sucrose CTAC 14.04 4.00 tetraoleat e 18 Ryoto ER-190 CTAC 15.21 3.90 WO 98/16538 PCT/EP97/05762 Example Oil Active fWicking Softness IHeight Score 19 Ryoto ER-290 CTAC 13-35 3.75 Span 80 CTAC 13.43 4.56 21 Span 85 CTAC 13.70 4.25 B Ryoto S-170 CTAC 6.33 3.17 22 Compound 2 HEQ 5.33 2.67 23 Compound 2 HEQ 8.50. 2.70 24 Compound 2 HEQ 11.59 3.29 Compound 2 HEQ 3.12 3.325 26 Compound 2 HEQ 5.79 3.875 27 Compound 2 HEQ 11.79 4.75 28 Ryoto 0-170 HEQ 11.04 3.08 29 Ryoto POS-135 REQ 9.41 4.50 Ryoto L-195 REQ 9.95 4.25 31 Ryoto 0-170 HEQ 8-.19 2.31 32 Ryoto 0-170 REQ 9.89 2.65 C REQ 2.20 D Ryoto S-270 HEQ 6.25 3.75 33 Compound 2 Prapagen 3445 11.25 4.12 34 Compound 2 Prapagen 3445 11.83 4.87 Compound 2 Prapagen 3445 13.08 4.87 36 Compound 1 Prapagen 3445 13.21 4.37 37 Compound 1 Prapagen 3445 13.75 4.75 38 Compound 1 Prapagen 3445 15.12 4.625_ WO 98/16538 PCT/EP97/05762 Example Oil Active Wicking Softness Height Score (cm) E T Prapagen 34452 12.71 5.38 39 Ryoto 0-170 Accosoft, 460HC 6.78 3.67 Ryoto 0-170 Accosoft 460HC 9.3 41 Ryoto 0-170 Accosoft, 460HC 13.01 3.87 F Ryoto 0-170 Accosof t 460HC 3.34 4.17 42 Ryoto 0-170 Accosoft, 550HC 10.97 3.92 43 Ryoto 0-170 Accosoft 550HC 12.76 3.8 44 Ryoto 0-170 Accosoft, 550HC 15.23 4.17 G Ryoto 0-170 Accosoft, 550HC 9.9 5.15 Sucrose Arquad HT 14.00 3.94 tetraoleate 46 Ryoto ER-190 Arquad HT 14.73 4.25 47 Ryoto ER-290 Arquad HT 13.58 4.00 Desized 20.00 towelling ILThese wicking heights were measured after only minutes.

The above softness and absorbency results demonstrate that the examined compounds except excellent hydrophilic softening properties when compared to the compounds of the prior art.

WO 98/16538 PCT/EP97/05762 Examples 48 and 49 Examples 48 and 49 were prepared as 5% total active emulsions/dispersion in water of a 1:4 fabric softener:sucrose ester mixture. 0.3% of a perfume was included in the compositions which were then tested for perfume longevity. See Table 11 below.

Table 11 Sucrose pentaoleate (Ryoto 0- 170) liauid accept- accept- acceptable able able 49 HEQ Sucrose 3.0 2.4 1.76 pentasteate as above H HEQ 3.1 1.9 1.19 Perfume intensity was measured by a trained panel except for example 48 which was measured separately. A value of 0.5 is given for a cloth immersion in fabric. Five represents a very strong smell and 0 an undetable smell. The perfume intensity is assessed after application (when the cloth is wet), after 5 hours and after 24 hours.

It can be seen that the presence of the oil increases prefume longevity.

WO 98/16538 PCT/EP97/05762 Example Example 50 was prepared as a series of a 5% total active emulsions/dispersions in water of 4.5% sucrose tetraerucate (oily liquid, Ryoto ER 290), 0.5% CTAC and 0.2% of a polymer deposition aid (some of which are cationic) as given below:- Example 50a Example 50b Example 50c Example 50d Example 50e Example 50f Example 50g Celquat SC240 Coltide HQS Crodacel QS FlocAid 34 Bermacoll CST Merquat 100 Softgel BDA (ex National Starch Chemical) (ex Croda Coloids) (ex Croda Coloids) (ex National Starch) 035 (ex Berol Nobel) Nonionic (ex Chemviron) (ex Avebe) Example 51 Example 51 was prepared as a series of 5% total active emulsions/dispersions in water of 4.5% sucrose tetraerucate (as in Example 55), 0.5% of a nonionic surfactant deposition aid (Synperonic A7) and 0.2% of the following deflocculating polymers (all of which are cationic).

Example 51a Example 51b Example 51c Example 51d Celquat SC240 Coltide HQS Coltide QS Poly DMDAAC:EHA (ex National Starch Chemical) (ex Croda Colloids) (ex Croda Colloids) (ex National Starch) 10:1 molar ratio copolymer (Mwt 2400 approx) 74 WO 98/16538 PCT/EP97/05762 Example 52 Example 52 was prepared as a 1:4 emulsion/dispersion total active) of DEEDMAC:sucrose pentaoleate (Ryoto 0-170) by mixing at high temperatures.

The softening and absorbency was measured as before. The composition was stable and the results are given below:- Softening 4.00 Wicking height 11.74 cm Example 53 A fully formulated fabric softening composition as according to the present invention was prepared as below: Cetyl trimethyl ammonium chloride Sucrose ester oil Cationic polymer deposition aid Dye Perfume Minors Water by weight 0.2 0.0025 0.3 0.02 balance The sucrose ester oil was Ryoto ER290 available from Mitsubishi Kagaku Foods Corporation. The deposition aid was Floc Aid 34 available from National Starch Chemical.

WO 98/16538 PCT/EP97/05762 Example 54 Table 9 below shows the T 2 NMR solid:liquid ratio of CPE's and RSE's used according to the present invention. A comparative crystalline solid sugar ester is also included.

The ratios were measured at 20 0 C. The degree of esterification letherification is stated.

Table 9 Material Solid:Liquid Degree and of Physical Form ratio at 20 0 C esterification Ryoto S270 96:4 4/8 50% crystalline (comparative) solid. Liquid Ryoto 0-170 0:100 5/8 62.5% liquid Ryoto ER-290 0:100 4/8 50% liquid Ryoto ER-190 0:100 5/8 50% soft solid Ryoto POS-135 30:70 5/8 62.5% soft solid Ryoto L-195 43:57 5/8 62.5 liquid Sucrose 0:100 4/8 50% liquid tetraoleate Compound 1 0:100 5/5 100% liquid oleate Compound 2 0:100 5/5 100% liquid Compound 3 0:100 5/5 100% liquid Compound 4 0:100 5/5 100% liquid Compound 5 0:100 8/8 100% liquid Compound 6 0:100 8/8 100% liquid Compound 7 0:100 4/4 100% liquid Compound 8 0:100 6/6 100% liquid Span 80 0:100 1/4 25% liquid Span 85 0:100 3/4 75% liquid The Ryoto materials have previously been described.

Compounds 1 to 8 are described herein above. Span 80 and are Sorbitan monoleate and trioleate oily liquids respectively, available from ICI surfactants.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

i* *oo* *oo* 0

Claims

Claims

1) A fabric softening composition comprising:

i) a liquid or soft solid derivative of a cyclic polyol (CPE) or of a reduced saccharide (RSE) resulting from 35 to 100% of the hydroxyl groups in the cyclic polyol or reduced saccharide being esterified or etherified, the derivate (CPE or RSE) having at least 2 or more of ester or ether groups independently attached to a C₈-C₂₂ alkyl or alkenyl chain or mixtures thereof, and containing at least 35% tri or higher esters.;

ii) a deposition aid.

2) A fabric softening composition according to claim 1 wherein the CPE or RSE results from a cyclic polyol or a reduced saccharide having 40-70% of the hydroxyl groups esterified and/or etherified.

3) A fabric softening composition according to either of claims 1 or 2 wherein the CPE or RSE results from a cyclic polyol or reduced saccharide having 4 or more hydroxyl groups etherified or esterified.

4) A fabric softening composition according to any preceeding claim in which CPE or RSE is derived from a monosaccharide or disaccharide .

5) A fabric softening composition according to any one of the preceeding claims in which the CPE is a saccharide

f< polyester, a saccharide polyether or a saccharide polyester/polyether .

6) A fabric softening composition according to any preceeding claim wherein the CPE is a selected from sucrose pentalaurate, sucrose tetraoleate, sucrose pentaerucate and sucrose tetraerucate.

7) A fabric softening composition according to any preceding claim in which the ester or ether groups of the CPE or RSE are independently of one another attached to a C₈ to C₂₂ alkyl or alkenyl chain or a C₂ to C₈ chain and in which the ratio of C₈ to C₂₂ groups to C₂-C₈ is from 5:3 to 3:5.

8) A fabric softening composition according to any preceding claim in which the deposition aid is selected from a cationic surfactant, a nonionic surfactant, an anionic surfactant, a polymeric deposition aid, a fabric softening compound or mixtures thereof.

9) A fabric softening composition according to any preceding claim in which the fabric softening compound has a solubility of less than 1 x 10^"3 wt% in demineralised water at 20°C.

10) A fabric softening composition according to claim 9 in which the fabric softening compound is a quaternary ammonium compound. 11) A fabric softening composition according to any preceding claim in which the ratio of CPE or RSE to deposition aid is within the range from 1:10 to 15:1.

12) A fabric softening composition according to any preceding claim which is in liquid form or emulsion form.

13) A fabric softening composition according to claim which further comprises a viscosity control agent.

14) Use of a CPE or RSE as defined in any of the preceeding claims within a fabric softening composition as a fabric softening aid that does not decrease the fabrics absorbency.

15) A liquid or soft solid fatty acid ester of glucose having a solid: liquid ratio of between 50:50 and 0:100 as measured by T₂ relaxation time NMR at 20°C, the ester groups comprising a mixture of C₂-C₂₂ alkyl or alkenyl chains and resulting from a cyclic polyol having 35-100% of the hydroxyl groups esterified.

16) A fatty acid ester of glucose according to claim 15, the ester groups consisting essentially of a C_2-C₈ alkyl chain and a C₈ to C₁₂ straight alkyl chain, the molar ratio of C₂ alkyl chain to C₈ to C₁₂ straight alkyl chain being from 2:1 to 1:2.

17) Use of a sorbitan mono,di or trioleate as a hydrophilic fabric softener.

4z.