CA2238620C - Composition for treating stains on laundry items and method of treatment - Google Patents

Abstract

The present invention relates to a cleaning composition which is an oil-in- water or water-in-oil emulsion or a solution comprising non-aqueous hydrophobic solvent; first anionic or nonionic surfactant having an alkyl chain, the length of the alkyl chain being C11 or less; and second anionic or nonionic surfactant having an alkyl chain, the length of the alkyl chain being C12 or more. The cleaning composition has a pH greater than 8. The invention also relates to a method for treating a spot or stain on a textile fabric using the cleaning composition.

Description

COMPOSITION FOR TREATING STAINS ON LAUNDRY ITEMS AND METHOD
OF TREATMENT
The present invention relates to compositions for treating stains on laundry items. Laundry items can be treated either before or after a conventional laundering process by application of the composition in the region of the stain so that the stain is at least partially released and removal of the stain is made easier.
Emulsions of solvent-aqueous systems are known to be effective as spot pretreating compositions on both hydrophobic and hydrophilic stains.
GB-A-2 194 547, published on 9th March 1988, discloses TM
mixtures of n-dodecane with both short-chain (Neodol 91-6) and long chain (Neodol 45-1) nonionics. The compositions are in the form of liquid solutions; water-in-oil or ail-in-water microemulsions, or gels. However this application does not disclose compositions which comprise alkali material.

US-A-4 093 418, issued on 6th June 1978, and US-A-4 178 262, issued on 11th December 1979, disclose isoparaffin (C11-C14) in combination with long-chain (Clp-C18) nonionics.
i The present invention relates to a cleaning composition which is an-oil-in-water or water-in-oil emulsion or a solution comprising non-aqueous hydrophobic solvent; first anionic or nonionic surfactant having an alkyl chain, the length of the alkyl chain being C11 or less; and second anionic or nonionic surfactant having an alkyl chain, the length of the alkyl chain being C12 or more.
It is the objective of the present invention to improve the cleaning performance of stain treatment compositions particularly on fatty or greasy stains, including cosmetics and food stains such as cream, milk, sauces.
Another object of the present invention is to improve the removal of bleachable stains through the application of the composition of the present invention and the application of a bleaching compound, preferably a peroxide compound.
Summary of the Invention ' Y

WO 97/20094 PCT/fJS96/I4766 The objective of the present invention is achieved by providing a cleaning composition which has a pH greater than 8, thereby enhancing cleaning performance for both fatty stains and bleachable stains. Preferably the pH is greater than 9, and more preferably greater than 10.
The cleaning composition preferably comprises water from 5~
to 95~ by weight of the composition.
The invention also relates to a method for treating a spot or stain on a textile fabric using the cleaning compositions of the invention.
Detailed description of the invention Hydrophobic solvents are an essential feature of the compostions of the present invention. Preferred hydrophobic solvents are defined in terms of Hansen parameters. A hydrophobic solvent as defined herein is considered to be a solvent having Hansen hydrogen bonding cohesion parameter dH below 18 (Joule/cm3)0.5 , preferred hydrophobic solvents have a Hansen hydrogen bonding cohesion parameter dH below 12 (Joule/cm3)0.5 and a Hansen polar parameter dP below 8 (Joule/cm3)0.5 .
Preferred solvents for use comprise mixtures of hydrocarbons with a flash point no lower than 70°C, an initial boiling point no lower than 130°C, preferably no lower than 145°C, and a solidification point not above 20°C
and aliphatic fatty acid esters. More preferred solvents would be alkanes or alkenes with a chain length above C7, and particularly alkanes and alkenes with an average of C8 to C20 atoms. Particularly preferred hydrophobic solvents are deodorised kerosene; solvent naphtha; chlorinated hydrocarbons; and terpenes. Even more preferred are paraffins; isoparaffins; naphthenes; aromatics; olefins;
1,1,1-trichloroethane perchloroethylene; methylene chloride; Shellsol SS° mixture (Ce-C11 isoparaffin + 5%
aliphatic C7 ester); D-Limonene; and Glidsafe~ supplied by Glidsol. Solvents are used in the detergent compositions of the present invention preferably at a level of from 3%
to 90%, more preferably from 4% to 45%, and most preferably from 5% to 25% by weight of the detergent composition.
Other solvents having a Hansen parameter of dH less than 18 (Joule/cm3)0.5 include glycol ethers, more preferably glycol ethers based upon ethylene oxide, propylene oxide, or mixtures thereof. Particularly preferred are ethylene glycol monoethyl ether; Propylene glycol monomethyl ether;
2-butoxy ethanol; butyl diethylene glycol ether ethanol;
butoxytriglycol; butylene glycol; hexylene glycol; and propyl propanol. Such solvents are used in combination with mixtures of short chain surfactants and long chain surfactants.
By "short-chain" what is meant herein is surfactants which comprise a C6-C1~ alkyl chain as their hydrophobic portion.
Such short-chain surfactants are accordingly those conventionally used in this field, but with a shorter alkyl chain, and can be of any type. Accordingly, suitable short chain surfactants for use herein include C6-C11 alkyl sulfates (C6-C11S04), alkyl ether sulfates (C6-CZ1 (OCH2CH2)eS04), alkyl sulfonates (C~-C11S03), alkyl succinates (C6-C1100CCH2CH2COOZ), alkyl carboxylates (C6-C11COOM), alkyl ether carboxylates (C6-C11 {OCH2CH2)eCOOM), alkyl sarcosinates (C6-C~1CON(CH3)R), alkyl sulfo succinates (C6-C1100CCH(S03M)CH2COOZ), amine oxides (Cg-C11RR'NO), glucose amides (C6-C11CONR " X), alkylpyrrolidones (C6-C21(C4H60N), alkylpolysaccharides (Cg-CliOGg), alkyl alkoxylates (C6-C11 {OCH2CH2)e(OCH2CH2CH2)pOH) and betaines (C6-Cl~N+(CH3)2CH2C00-). In the formulae in brackets, a and p are independently from 0 to 20 and a+p>0, Z is M or R,M is H or any counterion such as those known in the art, including Na, K,Li, NH4, amine, X is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof, R, R' and R " are C1-C5 alkyl groups, possibly functionalized with hydroxyl groups, R and R~ are preferably Cl-C3, most preferably methyl, R « is preferably 2-hydroxyethyl or 2 ~ hydroxypropyl, G is saccharide, preferably glucose, and g is of from 1.5 to 8. AlI these surfactants are well known in the art. A more complete disclosure of conventional glucose amides can be found for instance in WO 92-06154 and a more complete disclosure of conventional alkyl polysaccharides can be found for instance in US 4,536,329.
The compositions according to the present invention may comprise any of the above surfactants alone, or any combination thereof.
Preferred short chain nonionic surfactants for use herein are alkyl alkoxylates according to the formula C6-C11(OCH2CH2) a (OCH2CH2CH2)pOH, where a and p representing respectively the degree of ethoxylation and propoxylation, are independently of from 0 to 20, and that a+p>0. Most preferred short chain nonionic surfactants for use herein are those where a and p are such that a+p is from 3 to 10;
particularly those where p is 0 and a is 3 to 8. Also, most preferred short chain nonionic surfactants for use herein are those where said short chain is a hydrocarbon chain comprising from 7 to 11 carbon atoms. Said preferred short chain nonionic surfactants for use herein can be manufactured by the processes well known to the man skilled in the art, such as condensation of the corresponding alcohol and alkylene oxide, but such short chain surfactants are more conveniently commercially available for instance from Sidobre under the trade mark Mergital C4 (C8E04), from Kolb under the trade marks Imbentin~
AG/810/050 and AG/810/080 (respectively CS-10E05 and C8-10E08); from Shell under the trade mark Dobanol 91-2.5 (Cg-C11 E02.5), Dobanol 91-6 (Cg-C11 E06), Dobanol 91-4-6; from TM
Vista Chemicals Vista 1012-52, from EXXON Asopol 91-4.6.
Another preferred class of short chain nonionic surfactants are secondary alcohol ethoxylates according to the formula CH3-(CH2)X-CH-(CH2)y-CH3 O
(CH2-CH2-O)n-H
wherein (X+Y) is from 2 to 10 and the number of ethoxylate groups n is from 1 to 7. Example of commercially available TM
surfactants of this type include the Tergitol S series from Union Carbide.
Preferred short chain anionic surfactants for use herein are C6-C11 alkyl sulfates and C6-C11 alkyl sulfonates, C6-C11 betaines, C6-C11 amine oxides and mixtures thereof.
Most preferred are the C6-Cg alkyl sulfates and sulfonates.
Such short chain anionic surfactants can be made by well known sulphation or sulphonation processes followed by neutralization, but said anionic short chain surfactants are more conveniently commercially available, for instance from Rhone Poulenc under the trade mark Rhodapon ~ OLS, or from Witco under the trade mark Witconate~.
Any alkaline materials is suitable for use in the present invention. Preferred alkaline materials are selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, ammonium silicate, sodium bicarbonate, borax, monoethanolamine borate, monoethanolamine triethanolamine, and mixtures thereof.
In general the spot treating composition comprises from O.lo to 100, preferably 0.5°s to 3% by weight of the alkaline material. The pH is greater than 8, more preferably greater than 9, and most preferably greater than 10. pH of the neat compositions was measured by means of a rM
portable pH meter from Knick (Portamess 752).
By "long-chain" what is meant herein is surfactants having an alkyl chain, the alkyl chain comprising 12, or more than 12 carbon atoms.
Non-limiting examples of long-chain surfactants useful herein include the conventional C12-C18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C12-C20 alkyl sulfates ("AS"), the C12-C18 secondary (2,3) alkyl sulfates of the fomula CH3(CH2)x(CHOS03-M+) CH3 and WO 97/20094 PCT/US9b/14766 CH3 (CH2)y(CHOS03-M+)CH2CH3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated a sulfates such as oleyl sulfate, the C12-C18 alkyl alkoxy ~ sulfates ("AExS"; especially EO 1-7 ethoxy sulfates), C12-C1g alkyl alkoxy carboxylates (especially the EO 1-S
ethoxycarboxylates), the C12-Z8 glycerol ethers, the C12-Clg alkyl polyglycosides and their corresponding sulfated polyglycosides the C12-C1g alpha-sulfonated fatty acid esters methyl ester sulphonate (MES), and oleyol sarcosinates. The conventional nonionic and amphoteric surfactants such as the C12-C1g alkyl ethoxylates ("AE") particulary preferred are C12-C16 fatty alcohol polyglycol ethers or ethoxylated primary alcohols with EO 2-7 (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C12-C1g amine oxides, and the like, can also be included in the overall compositions. The C12-C1g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C1g N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhhydroxy fatty acid amides, such as C12-C1g N-(3-methoxypropyl) glucamide.
The N-propyl through N-hexyl C12-C1g glucamides can be used for low sudsing. C12-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C12-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
A particularly preferred composition according to the present invention comprises from 5% to 50% by weight of a mixed nonionic system comprising first, short-chain nonionic surfactant and second, long-chain nonionic surfactant. More preferably the composition comprises from 10% to 40% by weight of the mixed nonionic surfactant, and most preferably from 15% to 30%. The nonionic system preferably has an overall HLB value of from 2 to 16, more preferably from 8 to 14, most preferably from 9 to 10.
Furthermore it is preferred that the ratio of first surfactant to second surfactant is from 1:10 to 10:1, more preferably from 1:3 to 3:1, and most preferably about 1:1.
Bleaching agents may also be useful in the method of the present invention for treating bleachable stains. The bleaching agents may be incorporated into the compositions described above, or may be added as separate bleaching compositions. Peroxide bleaching agents are most preferred.
The detergent composition of the present invention is useful in various known and conventional cleaning methods. ' However a preferred cleaning method comprises the steps of applying the detergent composition to the spot or stain;

WO 97/20094 PCTlI7S96l14766 placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain; and applying heat, ~ pressure, or heat and pressure to the textile fabric in the region of the spot or stain; so that some or all of the ~ spot or stain is absorbed into the absorbent layer.
A still more preferred cleaning method comprises the steps of .
(a) applying the detergent composition to a spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain and a first means for transferring some or all of the spot or stain into the absorbent layer; optionally also applying a peroxide bleaching agent and subsequently (b) applying a hydrophilic solvent or water, to the textile fabric in the region of the spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain and the step of applying heat to the textile fabric in the region of the spot or stain.
The application of heat or pressure, or both, may be achieved by any means, but is most preferably achieved by a hand-held device such as an iron. A conventional iron having a hot-plate fixed to a body is a highly preferred hand held device. The hot-plate is heated most commonly by electrical means, and may have a means for controlling the ' temperature. A supply of water or steam may also be provided by the iron. Most preferably the absorbent layer is placed on a flat surface, such as an ironing board, and the stained or soiled textile fabric is laid flat on top of, and in contact with, the absorbent layer. The iron can then be easily applied to the textile fabric in the region of the stain or spot in order to ensure complete, or substantially complete, transfer of the stain or spot into -the absorbent layer. The iron is preferably operated at a temperature of from 40°C to 200°C, more preferably from 40°C to I80°C.
An alternative device for applying heat or pressure is a heated roller or any other heated applicator. The roller or applicator may also be provided with a supply of the detergent composition.
Suitable applicators include a steam iron with suction brush attachment, such as that disclosed in EP-A-0 493 348, and a thermoelectric applicator, such as that disclosed in EP-A-0 552 397. Also suitable is a steam iron with atomiser, such as that disclose in EP-A-0 629 736 wherein the detergent composition may optionally be stored in the iron and delivered directly onto the textile fabrics by means of the atomiser.
Without wishing to be bound by theory it is believed that hydrophobic stains are first rendered hydrophilic by ' applying a detergent composition, optionally with a gentle rubbing action. Greasy stains which contain hydroxyl WO 97/20094 PCTlUS96/14766 groups are deprotoneated at high pH and are thus rendered more easy to solubilize in the detergent solution. Higher pH can also induce soll peptization on some food stains.
The stains are in effect broken down, and rendered easier to remove. The benefits of high pH can be particularly observed when before or after application of the detergent composition, another composition containing a bleaching species is applied on the stain. Indeed, conventional peroxide bleaching technologies have an increased reactivity with pH. Water is then applied to the stain, again, optionally with a gentle rubbing action. The stain is removed by laying the stained fabric adjacent to an absorbent layer. The stain, which has been rendered more hydrophilic by the treatment, is transferred to the absorbent layer.
Textile fabrics are any materials made from cloth, including garments such as shirts, blouses, socks, skirts, trousers, jackets, underwear etc, and also including tablecloths, towels, curtains etc. The definition of textile fabrics as used herein does not include carpets and similar floor coverings.
' Textile fabrics which are to be used in the present invention are commonly made by weaving or knitting. Many different fibres may be used to produce woven, knitted or WO 97/20094 PCTlUS96/14766 other types of textile fabric including synthetic fibres (such as polyester, polyamide, etc.) and natural fibres from plants (such as cotton, hemp) and from animals (such as wool, angora, silk). Blends of different fibres are also commonly used. .

VVO 97120094 PCTlL1S96/14766 EXAMPLES
Example 1 Example 2 Example 3 Example 4 Shellsol 20 20 20 20 Dobanol 25E03 5 5 5 -Alkyl sulphate 5 - 5 5 CBAS

Dehydol C8E04 - 5 - 5 Sodium hydroxide 1 1 - -Monoethanolamine - - 3 3 Water 69 69 67 67 In the examples, Shellsol ~ is a mixture of Cg-C11 isoparaffins with 5~ aliphatic C7 ester.
Dehydol ° is a fatty alcohol polyglycol ether octyl with an average of 4E0, supplied by Henkel.
Dobanol ° is a ethoxylated primary alcohol with an average of 3E0, supplied by Shell.
Alkyl sulphate, C8AS, has an average of 8 carbon atoms in the alkyl chain.
These emulsions were prepared by mixing the components in the following order . Dobanol 25E3 was first mixed with the ' Shellsol solvent. The short-chain surfactant (alkyl sulphate or Dehydol) was then added followed by an aqueous solution of sodium hydroxide. Mixing was continued until a stable oil-in-water emulsion was formed.
Example 5 Example 6 Example 7 Limonene 18.3 18.3 23.5 HLAS 10.5 - -Dehydol C8E04~ 6 16.5 -Alkyl Sulphate C8A5 _ - ~.8 Monoethanolamine 3 3 5.8 Butyl carbitol 10 10 11.7 Oleic acid - -Water balance balance balance Example 8 Example 9 Example 10 Example 11 Dodecane 22 48.2 - -Hexadecane - - 10 -Tridecane - - - 20 C14-15E01 5.5 14.8 10 -C9-11E06 22 34.2 7.5 -Sodium 1 1 1 1 hydroxide Butyl carbitol - 0.8 - -Water balance balance balance balance In example 11, the tridecane was replaced by .
Isopar K~ which is a C10-C12 isoparaffinic hydrocarbon from Exxon TM
Glidsol 66-2 which is a mixture of terpene hydrocarbon from Glidoc Glidsol 100 which is a mixture of terpene hydrocarbon from Glidoc rM
Invert 2000 which is a citrus terpene/water emulsion from Dow Example 12 Example 13 TM

Shellsol 20 20 Dobanol 25-3 (C12E03) 0.2 5.2 C8 Alkyl sulphate 5 5 C10 Alkyl sulphate 0.2 0.2 n~

Dehydol 04 (C8E04) 5 -Sodium hydroxide 0.3 0.3 DTPMP 0.04 0.04 Dobanol 90 0.3 0.3 Hydrogen peroxide 1.4 1.4 Water balance balance pH = 9 pH = 9 WO 97!20094 PCT/US96/14766 DTPMP is diethylene triamine penta methylene phosphonic acid from Monsanto, bequest 2060.
A set of polycotton swatches (50mm square) were soiled with make-up, chocolate sauce and tomato sauce. The stain was ' left to age for a day, in the dark, at normal room temperature (c.a. 20oC, 60%RH). Each soiled swatch was cleaned by the following method:
1. The stained area was placed directly upon a strip of absorbent paper (the paper used was the absorbent core of a diaper) .
2. 1 ml of the composition of Example 1 was dripped on to the stained area.
3. The stained area was brushed with a conventional electrical toothbrush for IO seconds (the toothbrush used, a Braun~ dental d3, was one normally intended for daily oral care).
4. The steps 2. and 3. were repeated one more time.

5. 1 ml of distilled water was dripped on to the stained area, and pressure and heat were applied using an iron set at a temperature of 120°C for 10 seconds. A typical ironing WO 97/20094 PCTlUS96/14766 pressure, as normally used for removing wrinkles in fabrics, was used.
f 6. Step 5. was repeated with a further 2m1 of distilled - water.

7. The swatch was dried and smoothed.
The method of cleaning was repeated on stained swatches using the compositions of Examples 2 to 13 in place of the composition of Example 1.

Claims (14)

20

1. A cleaning composition which is an oil-in water or water-in-oil emulsion, or a solution, comprising (i) non-aqueous hydrophobic solvent;
(ii) first anionic or nonionic surfactant having an alkyl chain, the length of the alkyl chain being C11 or less;
(iii) second anionic or nonionic surfactant having an alkyl chain, the length of the alkyl chain being C12 or more; and characterised in that the cleaning composition has a pH of at least 8.

2. A cleaning composition according to claim 1 comprising from 0.1 to 10% by weight of an alkaline material, wherein the alkaline material is selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, ammonium silicate, sodium bicarbonate, borax, monoethanolamine borate, monoethanolamine, triethanolamine, and mixtures thereof.

3. A cleaning composition according to claim 1 further comprising from 5 to 95% by weight of water.

4. A cleaning composition according to claim 1 wherein the pH at 1% solution in distilled water of at least 9.

5. A cleaning composition according to claim 1 wherein the pH at la solution in distilled water of at least 10.

6. A cleaning composition according to claim 1 comprising from 3% to 90% by weight of the non-aqueous hydrophobic solvent having a Hansen hydrogen bonding cohesion parameter dH below 18 (Joule/cm3)0.5 and a Hansen polar parameter dP
below 8 (Joule/cm3)0.5.

7. A cleaning composition according to claim 6 wherein the solvent comprises hydrocarbons with a flash point of not less than 70°C, an initial boiling point of greater than 145°C, and a solidification point of less than 20°C.

8. A cleaning composition according to claim 7 wherein the solvent is selected from the group consisting of C10-C18 linear or branched alkanes, terpene or mixtures thereof.

9. A cleaning composition according to claim 1 wherein the second surfactant is selected from the group consisting of C12-C16 fatty alcohol polyglycol ethers or ethoxylated primary alcohols with 2 to 7 ethoxylation.

10.A cleaning composition according to claim 9 comprising from 5% to 50% by weight of a mixed nonionic surfactant system comprising the first and second surfactants, the mixed nonionic surfactant system having an overall HLB
value of from 2 to 16.

11. A cleaning composition according to claim 10 wherein the molar ratio of first surfactant to second surfactant is from 1:10 to 10:1.

12. A method of treating a spot or stain on a textile fabric comprising the steps of :
applying the detergent composition as defined in any one of claims 1 to 11 to the spot or stain;
placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain; and applying heat, pressure, or heat and pressure, to the textile fabric in the region of the spot or stain, so that some or all of the spot or stain is absorbed into the absorbent layer.

13. A method according to claim 12 comprising the steps of :
(a) applying the detergent composition to the spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain and a first means for transferring some or all of the spot or stain into the absorbent layer; and subsequently (b) applying a hydrophilic solvent, or water, to the textile fabric in the region of the spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain and a second means for transferring some or all of the spot or stain into the absorbent layer.

14. A method according to claim 13 wherein the second means for transferring some or all of the spot or stain, comprises the step of applying heat to the textile fabric in the region of the spot or stain using a hand-held iron.