Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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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.
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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
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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
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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
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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
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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
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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
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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
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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
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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;
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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
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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
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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
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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. .
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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
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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 -
C12-15E03 - - - 5
C9-11E06 22 34.2 7.5 -
C8E04 - - 5
Sodium 1 1 1 1
hydroxide
Butyl carbitol - 0.8 - -
Water balance balance balance balance
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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
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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
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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.
