Field of the invention
[0001] The present invention relates to a cleaning composition for providing effective stain
removal.
[0002] The invention has been developed primarily for use in detergent compositions and
will be described hereinafter with reference to this application. However, it will
be appreciated that the invention is not limited to this particular field of use.
Background of the invention
[0003] Any discussion of the prior art throughout the specification should in no way be
considered as an admission that such prior art is widely known or forms part of the
common general knowledge in the field.
[0004] Peroxygen bleach compounds are well known for their ability to remove stains from
substrates. Such bleaching agents include hydrogen peroxide, or substances that can
generate perhydroxyl radical, such as inorganic or organic peroxides. Generally, the
peroxygen bleach compound or hydrogen peroxide must be activated.
[0005] One method of activation is to employ wash temperatures greater than 60 °C. High
temperatures required for activation of the peroxygen bleach compound often damage
the fabric dyes, and can also cause premature damage to the substrate or fabric. Another
known approach of activation is the use of organic precursor compounds along with
peroxygen bleach compound. Addition of the organic precursors, often also referred
to as bleach activators, into compositions having peroxygen bleach compound improves
bleaching activity at lower wash temperatures, e.g. 40 to 60 °C. Examples of bleach
activators are tetraacetylethylenediamine (TAED) and sodium nonanoyloxybenzenesulphonate(NOBS).
[0006] The bleach activators react with the perhydroxide anion (OOH-) of the hydrogen peroxide
released by the peroxygen bleach compound in the aqueous solution to form a peroxyacid
which is more reactive as a bleaching agent than the peroxide bleach alone.
[0007] Using a single bleach activator along with peroxygen bleach compound show limited
action on stains depending on whether such stains are hydrophobic or hydrophilic.
A hydrophobic bleach activator used with the peroxygen bleach compound is effective
on hydrophobic bleachable stains, such as burnt fat (like butter), tomato-sauce, cosmetics
(like lipstick), but have limited performance on hydrophilic bleachable stains, such
as tea or red wine stains. Similarly, a hydrophilic bleach activator when used with
peroxygen bleach compound is effective on hydrophilic bleachable stains, but shows
limited performance on hydrophobic bleachable stains. Two or more bleach activators
are often used together to activate peroxygen bleach compounds in order to make the
bleach composition effective towards hydrophilic as well as hydrophobic stains.
[0008] Various attempts have been made to improve the overall bleaching performance on fabrics
over a wide range of stains by using bleach activator combinations.
[0009] One such attempt was done in
WO11117617A1 (Reckitt & Colman, 2011) which discloses a cleaning composition having a dispersion of a particle in acidic
aqueous phase for providing stability before use and performance in use. The particle
includes an admixture of tetraacetylethylenediamine (TAED) and decanoyloxybenzenecarboxylic
acid (DOBA) coated with an acid stable coating.
[0010] US 2009130224 A1 (Borchers et.al., 2009) discloses an improved bleach activator and bleach activator compositions in the
form of granules having TAED and DOBA for use in washing, cleaning and disinfectant
compositions. The application discloses a granular bleach activating mixture of TAED
and DOBA in which the mixture is free of binders.
[0011] US 2008113036 A1 (Reinhardt et al. 2008) discloses an improved bleach activator and bleach activator compositions having
synergistic effects on difficult to remove stains such as grass and curry. The application
discloses a mixture of bleach activators based on hydroxybenzoic acids and particular
peracetic acid-releasing activators. This further discloses washing composition, cleaning
composition and disinfectant having the activator mixtures in the form of co-granules
of bleach component together with hydrogen peroxide-generating substance.
[0012] However there is still a need for cleaning composition which can provide for effective
removal of tough stains like fruity stains, sebum stains, tomato and sunflower oil
stains. Especially fruity stains are particularly difficult to remove. Tough stains
like fruity stains require a significant amount of bleaching agent for their removal,
which might also bleach the colour of the garment.
[0013] With growing trend towards eating healthier, people consume several servings of fruits
or fruit juices and other fruit based products between meals at work as well as at
home. As a result, incidents of fruity stains are on the rise. Thus there is a need
for cleaning composition providing effective removal of the fruity stains from fabric
especially from the white fabrics.
[0014] It is thus an object of the present invention to provide a cleaning composition which
is effective against fruity stains which are otherwise considered to be difficult
to remove.
[0015] It is another object of the present invention to provide a cleaning composition which
can be used at lower wash temperatures.
[0016] It is yet another object of the present invention to provide a cleaning composition
which is effective against sebum stains.
[0017] It is yet another object of the present invention to provide a cleaning composition
which is particularly effective at cleaning fabrics.
[0018] Surprisingly it has been found that a cleaning composition having a combination of
two specific bleach activators and a mixture of specific enzymes removes tough stains,
which are otherwise considered to be difficult to be removed, especially fruity stains.
Summary of the invention
[0019] According to the first aspect, the present invention provides for a cleaning composition
comprising:
- (i) hydrogen peroxide or a peroxygen bleach compound capable of yielding hydrogen
peroxide in aqueous solution;
- (ii) a first bleach activator comprising a precursor of peracetic acid; and,
- (iii) a second bleach activator comprising a precursor of C8 to C11 peroxyacid;
wherein the composition comprises:
- (i) a protease; and,
- (ii) a lipase or an amylase or mixtures thereof.
[0020] According to the second aspect, the present invention provides for a method of bleaching
a bleachable substrate comprising the steps of:
- (i) applying to the substrate a neat or diluted form of the composition of the first
aspect;
- (ii) optionally applying to the substrate a detergent composition; and, rinsing the
substrate.
[0021] According to the third aspect disclosed is a use of the cleaning composition of the
first aspect for bleaching stains.
[0022] According to a fourth aspect disclosed is a use of the cleaning composition of the
first aspect for bleaching fruity or sebum stains on fabrics.
[0023] The invention will now be explained in more details.
Detailed description of the invention
[0024] According to the first aspect disclosed cleaning composition includes hydrogen peroxide
or a peroxygen bleach compound capable of yielding hydrogen peroxide in aqueous solution,
a first bleach activator, a second bleach activator, a protease and a lipase or an
amylase or mixtures thereof.
Cleaning composition:
[0025] Disclosed cleaning composition may be in different forms including but not limited
to powders, tablets, liquids, bars, crystals, gels, capsules or in the form of non-aqueous
liquids or carried on sheets or other substrates or in pouches.
[0026] The cleaning composition described herein can be used to make any cleaning preparation
which can be used for the purpose of bleaching any suitable substrate, for example,
laundry cleaning, laundry bleaches, bleach pre-treaters, hard surface cleaning (including
cleaning of lavatories, kitchen work surfaces, floors, mechanical ware washing etc.)
or automatic dishwashing compositions.
[0027] Preferably the disclosed cleaning composition is a granular detergent composition.
When the cleaning composition is a granular detergent composition it may be of a low
to moderate bulk density. The known methods for manufacturing a granular detergent
composition includes spray-drying, drum drying, fluid bed drying, and scraped film
drying preferably using the wiped film evaporator.
[0028] Alternatively, the granular detergent composition may be in a 'concentrated' or 'compact'
form. Such detergent composition may be prepared by mixing and granulating process,
for example, using a high-speed mixer or granulator, or other non-tower process.
[0029] When the cleaning composition is a granular detergent composition the first bleach
activator and the second bleach activator may be post dosed as particulates.
[0030] Preferably the pH of the aqueous solution on dissolution of the detergent composition
is 6 to 12 and more preferably from 7 to 10.5.
Peroxygen bleach compound:
[0032] Suitable peroxygen bleach compounds include hydrogen peroxide or any of its solid
adducts such as organic peroxides example; urea peroxide and inorganic persalts such
as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates.
Mixtures of two or more such compounds may also be suitable. Preferred inorganic persalts
are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate. Hydrogen
peroxide is especially preferred in liquid cleaning compositions.
[0033] Percarbonate is stable during storage and dissolves quickly in the cleaning liquor
and is especially preferred. It is believed that such rapid dissolution results in
the formation of higher levels of percarboxylic acid and, thus, enhances substrate
bleaching performance. Highly preferred percarbonate is in uncoated or coated form.
Preferably the average particle size of uncoated and coated percarbonate ranges from
about 400 to about 1200 µm, most preferably from about 400 to about 600 µm. If coated
percarbonate is used, the preferred coating materials include mixtures of carbonate
and sulphate, zeolite, precipitated silica, waxes, borates, polymers, citrates, silicate,
borosilicate or fatty acids.
[0034] Preferably the disclosed cleaning composition has 4 to 35 wt% of the peroxygen bleach
compound. When the disclosed cleaning composition is in the form of a bleach additive
for addition at the point of use either to wash liquor or to a non-bleaching detergent
composition, the peroxygen bleach compound may be present at even higher levels of
up to 90wt% of the composition. When the cleaning composition is a detergent composition
the composition has 5 to 20 wt % more preferably 10 to 15 wt% of the peroxygen bleach
compound.
Bleach activator:
[0035] Disclosed composition includes a first bleach activator and a second bleach activator.
Preferably the ratio of the first bleach activator to the second bleach activator
is from 5:1 to 1:5, preferably from 3:1 to 1:3 and further preferably from 2:1 to
1:2, and most preferably 1:1.
[0036] The bleach activator may be in the form of a powder or as particulate bodies having
the bleach activator, a binder or agglomerating agent. It is preferred for reasons
of stability and handling, that bleach activator is in the form of particulate bodies.
[0037] Preferably the weight ratio of bleach activator to hydrogen peroxide or peroxygen
bleach compound capable of yielding hydrogen peroxide in aqueous solution is from
1:2 to 1:20 more preferably from 1:2 to 1:15 and still preferably from 1:5 to 1:10.
First bleach activator:
[0038] Disclosed cleaning composition includes a first bleach activator having a precursor
of peracetic acid. The first bleach activator is preferably a compound from the class
of polyacylated alkylenediamines. Preferably the compound from the class of polyacylated
alkylenediamines is tetraacetylethylenediamine (TAED).
[0039] Disclosed cleaning composition include 0.1 wt% to 20 wt%, preferably from 0.5 wt%
to 10 wt% and optimal composition include 1 wt% to 5 wt% of the first bleach activator.
Second bleach activator:
[0040] Disclosed cleaning composition includes a second bleach activator having a precursor
of C
8 to C
11 peroxyacid. Preferably the second bleach activator is hydroxybenzoic acid derivative
of the formula (I)
in which R is C
8-C
11 alkyl group.
[0041] Preferably the second bleach activator is decanoyloxybenzoic acid (DOBA) and derivatives
thereof.
Enzyme:
[0042] Disclosed composition includes a protease and a lipase or amylase or a mixture thereof.
Protease:
[0043] Disclosed cleaning composition includes a protease. Suitable protease includes those
of animal, vegetable or microbial origin. Protease from microbial origin is preferred.
Protease may also be chemically modified or protein engineered mutant. Preferably
the protease is a serine protease or a metallo protease, preferably an alkaline microbial
protease or a trypsin-like protease. Examples of alkaline proteases are subtilisins,
especially those derived from Bacillus, examples include subtilisin Novo, subtilisin
Carlsberg, subtilisin 309, subtilisin147 and subtilisin 168 (described
WO8906279A1). Examples of trypsin-like proteases are trypsin from porcine or bovine origin and
the Fusarium protease described in
WO8906270A1 and
WO9425583A1. The protease is preferably from B.subtilis. Preferred commercially available protease
includes Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™, Esperase™, Everlase™,
Polarzyme™, and Kannase™, Maxatase™, Maxacal™, Maxapem™, Properase™, Purfast®, Effectenz®,
Purafect™, Purafect OxP™, FN2™, and FN3™ (Genencor International Inc.).
[0044] Protease from a strain of Bacillus having maximum activity throughout the pH range
of 8 to 12 is highly preferred and includes commercially available Esperase™ and Savinase™.
[0045] Preferably the cleaning composition of the present invention include 0.001 wt% to
10 wt% more preferably from 0.01 wt% to wt% of protease depending upon their activity.
Lipase:
[0046] Disclosed cleaning composition includes a lipase. Lipase catalyses hydrolysis of
ester bonds of edible fats and oils, i.e. triglycerides, into free fatty acids, mono-
and diglycerides and glycerol.
[0047] Preferred lipases include those of bacterial or fungal origin. Chemically modified
or protein engineered mutants are included. Examples of useful lipases include lipases
from Humicola species (incl. Thermomyces. species) which includes lipase from H. lanuginosus
(T. lanuginosus) as described in
EP0258068B1 and
EP0305216B1 or from H. insolens as described in
WO9613580A1 or lipases from Pseudomonas species which includes lipase from P. alcaligenes or
P. pseudoalcaligenes (
EP0218272 A1), P. cepacia (
EP0331376B1), P. stutzeri (
GB 1 ,372,034), P. fluorescens, Pseudomonas species strain SD 705 (
WO95/06720 and
WO96/27002), P. wisconsinensis (
WO96/12012) or lipases from Bacillus species which includes lipases from B. subtilis (
Dartois et al. (1993), Biochemica et Biophysica Acta, 1131 , 253-360), B. stearothermophilus (
JP64/744992) or B. pumilus (
WO 91/16422). Other examples include lipase variants such as those described in
WO92/05249,
WO94/01541,
EP407225,
EP260105,
WO95/35381,
WO96/00292,
WO95/30744,
WO94/25578,
WO95/14783,
WO95/22615,
WO97/04079 and
WO97/07202.
[0048] Preferred commercially available lipases are available under the trademarks Lipoclean®,
Lipolase®, Lipolase® Ultra and Lipex®. LIPEX® is particularly preferred, and LIPEX®
100 T is further particularly preferred. The activity of commercial lipase is commonly
expressed as Lipase Units or LU. Different lipase preparations may have different
activities. For fungal lipases these may range from 2,000 to 2,000,000 LU per gram.
Preferred compositions include lipase having 5 to 20000LU/g.
[0049] In order to prevent accidents and to alleviate safety concerns, commercial lipases
are always coated with an inert material. Therefore, commercial lipases that are used
for detergent powders, bars and tablets are in granular form containing very low amount
of active lipase and balance of adjunct materials. Such granulates contain lipase
concentrate, inorganic salt, binders and coating materials. They are free-flowing
so that there is no lumping, and the granulate dissolve faster. Lipases are also available
in liquid form, example LIPEX ® 100 L.
[0050] Preferred cleaning composition has 0.0001wt% to 0.3wt% lipase, more preferably from
0.0001 to 0.1wt% lipase and further preferably 0.0009wt% to 0.00186 wt% lipase.
Amylase:
[0051] Disclosed cleaning composition includes an amylase. Suitable amylases (alpha-amylase
and/or beta-amylase) include those of bacterial or fungal origin. Chemically modified
or protein engineered mutants are included. Examples of amylase suitable for the present
invention includes alpha-amylase obtained from Bacillus species which includes special
strain of B. licheniformis, described in more detail in
GB 1,296,839, or the Bacillus species strains disclosed in
WO 95/026397 or
WO 00/060060. Other suitable examples of amylases are the variants described in
WO 94/02597,
WO 94/18314,
WO 96/23873,
WO 97/43424,
WO 01/066712,
WO 02/010355 and
WO 02/031124 (which references all incorporated by reference).
[0052] Commercially available amylases are Duramyl(TM), Termamyl(TM), Termamyl Ultra(TM),
Natalase(TM), Stainzyme(TM), Stainzyme Plus(TM), Fungamyl(TM) and BAN(TM) (Novozymes
A/S), Rapidase(TM) and Purastar(TM) (from Genencor International Inc.).
Mannanase:
[0053] Preferably the disclosed composition includes mannanase. Examples of suitable mannanase
include those of bacterial or fungal origin. Preferably the mannanase is derived from
a strain of a filamentous fungus genus Aspergillus, preferably Aspergillus niger or
Aspergillus aculeatus (
WO 94/25576).
WO 93/24622 disclosing a mannanase isolated from Trichoderma reese is also preferred. Mannanases
have also been isolated from several bacteria, including Bacillus species. For example,
Talbot et al.,Appl. Environ. Microbiol., Vol.56, No. 11, pp. 3505-3510 (1990) describes a beta-mannanase derived from Bacillus stearothermophilus.
Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551 -555 (1994) describes a beta-mannanase derived from Bacillus subtilis.
JP-A-03047076 discloses a beta-mannanase derived from Bacillus sp.
JP-A-63056289 describes the production of an alkaline, thermostable beta- mannanase.
JP-A-63036775 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and
beta-mannosidase.
JP-A-08051975 discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM-001. A purified
mannanase from Bacillus amyloliquefaciens is disclosed in
WO 97/11164.
Examples of preferred commercially available mannanases include Mannaway(TM) available
from Novozymes A/S Denmark.
Surfactant:
[0054] Disclosed cleaning composition preferably includes a surfactant. The surfactant may
be a soap or an anionic, nonionic, amphoteric, zwitterionic or cationic surfactant
or mixtures thereof. In general, the nonionic and anionic surfactant may be chosen
from the surfactants described in "
Surface Active Agents" Vol. 1, by Schwartz and Perry, Interscience 1949,
Vol. 2 by Schwartz, Perry and Berch, Interscience 1958, in the current edition of "
McCutcheon ' s Emulsifiers and Detergents" published by Manufacturing Confectioners
Company or in "
Tenside-Taschenbuch", H.Stache, 2nd Edn., Carl Hauser Verlag, 1981.
[0055] Suitable anionic surfactant includes water-soluble alkali metal salts of organic
sulphates and sulphonates having alkyl radicals containing from about 8 to about 22
carbon atoms, the term alkyl includes the alkyl portion of higher acyl radicals. Examples
of suitable synthetic anionic surfactant are sodium and potassium alkyl sulphates.
Especially preferred are the sodium and potassium sulphates obtainable by sulphating
higher C
8 to C
18 alcohols for example from tallow or coconut oil. Other preferred anionic surfactant
include sodium and potassium alkyl C
9 to C
20 benzene sulphonates, particularly sodium linear secondary alkyl C
10 to C
15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those
ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols
derived from petroleum.
[0056] Most preferred anionic surfactants are sodium lauryl ether sulfate (SLES), particularly
preferred are anionic surfactant with 1 to 3 ethoxy groups, sodium C
10 to C
15 alkyl benzene sulphonates (LAS) and sodium C
12 to C
18 alkyl sulphates (PAS). Alkyl ester suphonates such as methyl ester sulphonates (MES)
may be preferably used for replacing a portion or completely replacing the anionic
surfactant.
[0057] Other suitable surfactants are those described in
EP-A-328 177 (Unilever), which shows resistance to salting-out, the alkyl polyglycoside surfactants
described in
EP-A-070 074 and alkyl monoglycosides. The surfactant chain may be branched or linear.
[0058] Suitable nonionic surfactants include the reaction products of compounds having a
hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids,
amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone
or with propylene oxide. Preferred nonionic surfactants are C
6 to C
22 alkyl phenol-ethylene oxide condensates, generally having 5 to 25 EO, i.e. 5 to 25
units of ethylene oxide per molecule, and the condensation products of aliphatic C
8 to C
18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5
to 50 EO. Preferably, the non-ionic is 10 to 50 EO, more preferably 20 to 35 EO. Alkyl
ethoxylates are particularly preferred.
[0059] Soaps may also be present. The fatty acid soap used preferably contains from about
16 to about 22 carbon atoms, preferably in a straight chain configuration. Preferred
soap may be derived from saturated and non-saturated fatty acids obtained from natural
sources and synthetically prepared. Examples of such fatty acids include capric, lauric,
myristic, palmitic, stearic, oleic, linoleic and linolenic acid. The anionic contribution
from soap is preferably from 0 to 30 wt% of the total anionic.
[0060] Preferred surfactant systems are mixtures of anionic with nonionic surfactant, in
particular the groups and examples of anionic and nonionic surfactants pointed out
in
EP-A-346 995 (Unilever).
[0061] Amounts of amphoteric or zwitterionic surfactants can also be used in the compositions
of the invention but this is not normally desired owing to their relatively high cost.
If any amphoteric or zwitterionic surfactants are used, it is generally in small amounts
in combinations with anionic and nonionic surfactants.
[0062] The compositions according to the invention include 2 wt% to 70wt% of surfactant
more preferably 10 to 30wt%. Preferred compositions include anionic or non-ionic surfactants.
More preferred compositions include a mixture of the two.
Builders and Sesquestrants:
[0063] Disclosed cleaning composition may include builders.
Builders may be selected from 1) calcium sequestrant materials, 2) precipitating materials,
3) calcium ion-exchange materials and 4) mixtures thereof.
[0064] Examples of calcium sequestrant materials include alkali metal polyphosphates, such
as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetraacetic
acid.
[0065] Examples of precipitating builder materials include sodium orthophosphate and sodium
carbonate.
[0066] Examples of calcium ion-exchange builder materials include the various types of water-insoluble
crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives
and includes zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X,
zeolite Y and also the zeolite P-type as described in
EP-A-O, 384, 070. It is preferred that when an insoluble inorganic builder for example zeolite is
used, the size is in the range 0.1 to 10 µm (as measured by The Mastersizer 2000 particle
size analyzer using laser diffraction ex Malvern™).
[0067] When the cleaning composition is a detergent composition in the form of granular,
spray- dried or dry-blended powder, the level of builder is preferably from 1 to 40
wt%.
[0068] Preferably the detergent composition includes zeolite and carbonate (including bicarbonate
and sesquicarbonate) builders. The composition may also contain other builders including
crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably
sodium aluminosilicate. Alternatively, or additionally to the aluminosilicate builders,
phosphate builders may be used. The term phosphate includes diphosphate, triphosphate,
and phosphonate species.
[0069] Other forms of builder include silicates, such as soluble silicates, metasilicates,
layered silicates (e.g. SKS-6 from Hoechst). Builders or complexing agent as ethylenediaminetetraacetic
acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic
acid may also be included. Many builders are also bleach- stabilising agents by virtue
of their ability to complex metal ions.
Other ingredients:
[0070] Disclosed cleaning composition may include one or more of other ingredients selected
from bleach stabiliser, polymers, perfumes, fluorescers, soil release polymers, germicides,
colourants and coloured speckles such as blue speckles. This list is not intended
to be exhaustive.
[0071] Disclosed composition may include a bleach stabiliser. Suitable bleach stabilisers
include ethylenediamine tetraacetate (EDTA), ethylenediamine disuccinate (EDDS), and
the aminopolyphosphonates such as ethylenediamine tetramethylene phosphonate (EDTMP)
and diethylenetriamine pentamethylene phosphonate (DETPMP).
[0072] When present the composition may include one or more polymers. Examples include carboxymethylcellulose,
poly (ethylene glycol), poly (vinyl alcohol), polycarboxylates such as polyacrylates,
maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers. Suitable
commercially available polymer includes Sokalan CP5 (ex BASF) which is a polyacrylate,
namely maleic acid-acrylic acid copolymer, with a sodium salt.
[0073] Disclosed cleaning composition may also include perfumes. When present the perfumes
could be of natural origin or synthetic. They include single compounds or mixtures
of compounds. By perfume in this context is not only meant a fully formulated product
delivering fragrance, but includes selected components of that fragrance, particularly
those which are prone to loss, such as the so-called top notes. The perfume may be
used in the form of neat oil or in an encapsulated form.
[0074] Disclosed composition may also include fluorescent agent (optical brightener). Fluorescent
agents are well known and many fluorescent agents are commercially available. Usually,
these fluorescent agents are supplied and used in the form of their alkali metal salts,
for example, the sodium salts. The total amount of the fluorescent agent or agents
used in the composition is generally from 0.005 to 2 wt%, more preferably 0.01 to
0.1 wt%. Preferred fluorescent agent includes but not limited to distyryl biphenyl
compounds, e.g. Tinopal (Trade Mark) CBS-X, diamine stilbene disulphonic acid compounds,
e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH and pyrazoline compounds,
e.g. Blankophor SN. Preferred fluorescers are: sodium 2- (4-styryl-3-sulfophenyl)
-2H-napthol [I,2-d]triazole, disodium 4, 4'-bis {[(4-anilino-6- (N methyl-N-2 hydroxyethyl)
amino 1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2' disulfonate and disodium 4,4'-
bis (2-sulfoslyryl) biphenyl. Tinopal® DMS is the disodium salt of disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}
stilbene-2-2' disulfonate. Tinopal® CBS is the disodium salt of disodium 4,4'-bis(2-sulfostyryl)biphenyl.
[0075] Disclosed composition may include a soil release polymer, for example sulphonated
and unsulphonated PET/PEOT polymers, both end-capped and non-end-capped, and polyethylene
glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22. Especially
preferred soil release polymer are the sulphonated non-end-capped polyesters described
and claimed in
WO9532997A (Rhodia Chimie).
[0076] The invention will now be explained in details with the help of non-limiting exemplary
embodiments.
Examples
[0077] Evaluation of the preferred and the comparative compositions in removal of blackberry
stain and tomato-sunflower stain:
a) Measurement of Soil Release Index (SRI)
[0078] Soil release index (SRI) is a measure of the amount of a stain present on fabric
that is removed during a washing process. The intensity of any stain after washing
is measured by means of a spectrophotometer and expressed in terms of the difference
between the stained fabric and a clean fabric giving ΔE* for each stain. It is defined
as ΔE* and is calculated as:
[0079] L*, a*, and b* are the coordinates of the CIE 1976 (L*, a*, b*) colour space, determined
using a standard spectrophotometer. ΔE* can be measured before and after the stain
is washed, to give ΔE*bw (before wash) and ΔE*aw (after wash).
[0080] ΔE after wash is the difference in L a b colour space between the clean (unwashed)
fabric and the stained fabric after wash. So a ΔE after wash of zero means that a
stain is completely removed.
[0081] SRI is defined as:
[0082] A SRI of 100 means complete removal of a stain. The higher the SRI value, the greater
is the stain removal potential.
[0083] The clean (or virgin) fabric is an "absolute standard" which is not washed. For each
experiment, it refers to an identical piece of fabric to that to which the stain is
applied. Therefore, its point in L a b colour space stays constant.
b) Preparation of the preferred and control detergent composition
[0084] A control detergent composition (Control) was prepared with a ratio between first
bleach activator (TAED) to second bleach activator (DOBA) of 1:1. Control composition
was formulated with no enzymes. Other standard laundry detergents were also included.
The composition of Control is provided in Table 1.
[0085] Preferred detergent composition Ex 1 and Ex 2 had a ratio between first bleach activator
(TAED) to second bleach activator (DOBA) of 1:1. Ex 1 was formulated with a combination
of protease and amylase. Ex 2 was formulated with a combination of protease and lipase.
The composition of preferred detergent compositions is provided in Table 1.
c) Washing protocol for determining SRI-values
[0086] For the determination of the SRI-values, a standard protocol was used, called the
machine wash protocol.
[0087] Said machine wash protocol is as follows:
- (a) A set of 6 cotton swatches were taken.
- (b) Each cotton swatch was stained at two different and marked locations with a blackberry
fruit stain and a Tomato sunflower oil stain.
- (c) Colour of the two stains on the cotton swatches were measured before washing to
get ΔE*bw (before wash).
- (d) 7gpl of the control composition was added to a Miele Washing machine Softronic
W4165.
- (e) A normal white wash cotton intensive cycle 1 hour 56 minutes was selected with
water temperature of 40°C. The total wash liquor used was 6 liters. The water used
had a hardness 24° French hardness. The wash load was 1.5 kg.
- (f) The wash load included the stained cotton swatches and two SBL soil strips and
the liquor to cloth ratio was 4:1. The stained cotton swatches were not soaked before
washing.
- (g) Post washing the cotton swatches was dried overnight.
- (h) The after wash reading of the stain on the 6 cotton swatches were recorded.
[0088] Similarly the stained cotton swatches were prepared and washed as described in the
above steps (a) to (h) with a preferred composition and the reading of the swatches
before and after wash was recorded.
d) Measurement of the delta SRI values
[0089] The delta SRI value after wash was determined as the difference between the absolute
SRI value for a stained cotton swatch washed with the preferred composition and absolute
SRI value for a stained cotton swatch washed with the control composition.
[0090] A delta SRI value higher than the LSD (Least significant difference) value indicates
a statistically significant difference between the absolute SRI values of stained
swatch washed with the preferred composition and the absolute SRI value of stained
swatch washed with control composition.
[0091] The SRI and the delta SRI values of the cotton swatches stained with blackberry fruit
stain and tomato - sunflower oil stain and thereafter washed with the control or the
preferred compositions with the machine wash protocol described above are provided
in Table 2.
Table1
|
Control |
Ex 1 |
Ex 2 |
Ingredients |
(wt%) |
(wt%) |
(wt%) |
Na-LAS |
11.69 |
11.69 |
11.69 |
Non-Ionic 7EO |
1.17 |
1.17 |
1.17 |
Sodium Soap |
0.63 |
0.63 |
0.63 |
Na disilicate |
6.60 |
6.60 |
6.60 |
Soda Ash |
20.64 |
20.64 |
20.64 |
Sodium Sulphate |
34.579 |
34.129 |
34.309 |
SOKLAN CP5 (ex BASF, polymer of maleic acid and acrylic acid) |
0.39 |
0.39 |
0.39 |
SCMC(sodium carboxy methyl cellulose) |
0.23 |
0.23 |
0.23 |
Tinopal CBSx |
0.02 |
0.02 |
0.02 |
Zeolite |
2.613 |
2.613 |
2.613 |
TAED |
1.35 |
1.35 |
1.35 |
DOBA |
1.35 |
1.35 |
1.35 |
Sodium Percarbonate |
12.00 |
12.00 |
12.00 |
EDTMP Ca/Na salt (Dequest 2047) |
0.369 |
0.369 |
0.369 |
Citric Acid anhydrous |
1.90 |
1.90 |
1.90 |
EHDP (Dequest 2016D) |
0.246 |
0.246 |
0.246 |
Antifoam |
0.40 |
0.40 |
0.40 |
Savinase 24GTT (protease) |
0 |
0.173 |
0.173 |
Lipex 100TB (lipase) |
0 |
0 |
0.10 |
Stainzyme Plus 12GT (amylase) |
0 |
0.10 |
0 |
Repelotex SF2 |
0.123 |
0.123 |
0.123 |
Dimorpholino Fluorescer Granular |
0.20 |
0.20 |
0.20 |
Blue Carbonate Speckles |
1.00 |
1.00 |
1.00 |
Moisture, Salts, NDOM |
2.87 |
2.87 |
2.87 |
TOTAL |
100.00 |
100.00 |
100.00 |
Table 2
|
SRI |
Delta SRI |
LSD95p |
LSD95n |
Tomato-sunflower oil stain |
Control |
88.0292 |
0.0000 |
3.9490 |
-3.9490 |
Ex 1 |
92.0873 |
4.0582 |
3.9490 |
-3.9490 |
Ex 2 |
89.9515 |
1.9224 |
3.9490 |
-3.9490 |
Blackberry fruit stain |
Control |
88.9981 |
0.0000 |
4.4120 |
-4.4120 |
Ex 1 |
94.6586 |
4.6605 |
4.4120 |
-4.4120 |
Ex 2 |
95.1835 |
5.1854 |
4.4120 |
-4.4120 |
[0092] The results in Table 2 clearly shows that the delta SRI of the preferred compositions
(Ex 1 and Ex 2) having a combination of TAED, DOBA and enzymes protease and amylase
(Ex 1) or protease and lipase (Ex 2) shows statistically significant improvement in
removal of blackberry fruit stain when compared to the control composition. It is
also clear from Table 2 that preferred composition (Ex2) is comparatively better than
control composition in removal of tomato-sunflower oil stain and the preferred composition
(Ex 1) shows statistically significant improvement in removal of tomato and sunflower
oil stain when compared to the control composition.
Evaluation of the preferred and the comparative compositions in removal of sebum stains:
[0093] Commercially available detergent powder ArielTM Actilift UK (ex Proctor and Gamble)
was used as Control.
[0094] The preferred granular detergent composition Comp 3 was prepared with a ratio between
first bleach activator (TAED) to second bleach activator (DOBA) of 1:1 and having
the enzymes protease, amylase and lipase. Other standard laundry detergents were also
included. The formulation of Comp 3 is provided in Table 3.
[0095] One set of 6 cotton swatches stained with sebum stain was rinsed in the machine wash
protocol as described above. The SRI values for the stained cotton swatch after wash
were determined with the procedure as described above and the results were provided
in Table 3. The Delta SRI value were also determined and provided in Table 4.
Table 3
Ingredients |
Comp 3 (wt%) |
Na-LAS |
11.69 |
sNon-Ionic 7EO |
1.17 |
Sodium Soap |
0.63 |
Na disilicate |
6.23 |
Soda Ash |
20.64 |
Sodium Sulphate |
34.129 |
CP5 |
0.39 |
SCMC |
0.23 |
Tinopal CBSx |
0.02 |
Zeolite 4 A |
2.613 |
TAED |
1.35 |
DOBA |
1.35 |
Sodium Percarbonate |
12.00 |
EDTMP Ca/Na salt (Dequest 2047) |
0.369 |
Citric Acid anhydrous |
1.90 |
EHDP (Dequest 2016D) |
0.246 |
GAG |
0.40 |
Savinase 24GTT (protease) |
0.173 |
Lipex 100TB (lipase) |
0.10 |
Mannaway 4T (mannanase) |
0.082 |
Stainzyme Plus 12GT (amylase) |
0.100 |
Repelotex SF2 |
0.123 |
Dimorpholino Fluorescer Granular |
0.20 |
Blue Carbonate Speckles |
1.00 |
Moisture, Salts, NDOM |
2.87 |
TOTAL |
100.00 |
Table 4
|
SRI |
Delta SRI |
LSD95p |
LSD95n |
Sebum stain |
|
|
|
|
Ariel™ Actilift UK |
88.41 |
0 |
4.872 |
-4.872 |
Comp 3 |
93.39 |
4.979 |
4.872 |
-4.872 |
[0096] The results in Table 4 clearly shows that the preferred composition (Comp 3) having
a combination of bleach activators TAED, DOBA and enzymes protease, lipase and amylase
shows statistically significant improvement in removal of sebum stain when compared
to the commercially available comparative composition (ArielTM Actilift UK ).
[0097] It will be appreciated that the illustrated examples provide for a detergent compositions
having specific bleach activators and enzymes.
[0098] It should be understood that the specific forms of the invention herein illustrated
and described are intended to be representative only as certain changes may be made
therein without departing from the clear teachings of the disclosure.