[0001] The present invention relates to cleaning compositions suitable for use in various
laundry applications including hand and machine laundry methods, comprising a radical
scavenger.
Background of the invention
[0002] Cleaning compositions are well known in the art. Such compositions generally comprise
a number of active components that provide the cleaning function of the composition.
When selecting components of the composition, it is therefore preferred that the components
are stable in the composition so as not to lose cleaning effectiveness. In certain
instances however, some ingredients of a cleaning composition for example oxidising
agents can decompose leading to a reduction in the concentration of oxidising agent
over time and consequently to the reduction of the cleaning and whitening performance
of the composition.
[0003] Cleaning compositions can also comprise, in addition to the oxidising agent, a number
of other components that provide additional cleaning and whitening performance benefits.
When selecting components of the composition, it is preferred that the components
are stable in the composition, i.e., do not react with the oxidising agent, further
reducing the concentration of oxidising agent in the composition. In certain instances
however, the reaction or interaction of components of the composition with the oxidising
agent is inevitable. As a consequence of this, the premature decomposition of the
oxidising agent and the other actives present in the composition occurs, leading to
the reduction of the cleaning and/or whiteness effectiveness of the composition.
[0004] Although not wishing to be bound by theory, it is believed that decomposition of
the oxidising agent and the interaction or reaction of the different ingredients of
the composition with the oxidising agent can proceed via one electron and/or two electron
chemistry. One electron chemistry reactions are initiated by the formation of radicals
from the parent oxidising agent. Generally, the radicals formed are more reactive
and better oxidising species than the parent and thus accelerate the decomposition
kinetics of the oxidising agents and its reaction or interaction with the other actives
ingredients present in the composition. Thereby enhancing the decomposition of the
oxidising agent and the other actives ingredients. For example, where brighteners
are components of the composition, decomposition thereof can be initiated by one and/or
two electron processes, resulting in the loss or decreased of whiteness performance
benefit, normally expected when incorporating a brightener. The brightener oxidation
via one electron processes is believed to proceed faster than the two electron oxidation.
To improve the compatibility of the oxidising agent with the other actives, it is
therefore important to reduce, slow down or completely suppress one electron oxidation
chemistry reactions.
[0005] The Applicant has thus now surprisingly found that this problem is solved by formulating
a liquid bleaching composition according to the present invention. EP-A-668345 discloses
hypochlorite-containing compositions comprising a source of strong alkalinity, a pH
buffering means (silicate/carbonate) and radical scavengers. The radical scavengers
of the present invention are not disclosed therein. Furthermore, it has been found
that compositions of the present invention are stable on storage and provide improved
whiteness and cleaning performance in any laundry application even on ageing of the
composition, i.e. when used after prolonged periods of storage, as compared to the
whiteness and cleaning performance delivered by the same composition under the same
conditions but without any radical scavenger. More particularly, it has been found
that the stability of the oxidising agent and/or the other actives ingredients (where
present), are improved when the radical scavenger of the present invention is present
versus when it is not.
[0006] A further advantage of the compositions of the present invention is that they are
suitable for the cleaning of different types of fabrics including natural fabrics
(e.g., fabrics made of cotton, viscose, linen, silk and wool), synthetic fabrics such
as those made of polymeric fibers of synthetic origin as well as those made of both
natural and synthetic fibers.
[0007] Yet, another advantage of the liquid bleaching compositions of the present invention
is that said bleaching compositions are suitable for various laundry cleaning applications
both when used in diluted conditions, e.g. as a detergent additive or a fully formulated
laundry detergent composition, and when used in neat condition, e.g. as a liquid pretreater
(spotter).
[0008] GB 2,217,119 and US 5,135,075 describe compositions comprising sodium hypochlorite
and polystyrene sulfonated polymer.
[0009] WO 98/06814 describes hypohalite bleaching compositions comprising a pH buffering
compound and an ingradient having the ability to prevent the precipitation of the
salts of said buffering component upon dilution of the composition in water.
[0010] WO 99/35227 (relevant for novelty only) describes an acidic composition comprising
up to 5% of hydrogen peroxide and up to 0.5% of polystyrene sulfonate.
Summary of the invention
[0011] The present invention relates to a liquid cleaning composition comprising an oxidising
agent and a radical scavenger which is selected from the group consisting of: 2,3,4,5
tetramethoxy benzoic acid; 2,3,4,5,6 pentamethoxy benzoic acid; polystyrene; styrene:maleic
acid copolymer; styrene:acrylic acid copolymer; styrene:ethylene glycole graft polymers;
poly(ethyleneglycol) di-toluene sulfonate; poly hydroxy styrene; poly methyl stryrene;
polystyrene divinyl benzene; poly vinyl phenol; and mixtures thereof.
[0012] In a preferred embodiment the compositions of the present invention further comprise
one or more surfactants and/or a brightener.
Detailed description of the invention
Liquid cleaning compositions:
[0013] The compositions according to the present invention are in liquid form. Preferably,
the compositions of the present invention are thickened. Thickening can be achieved
by the addition of thickening components for example surfactants, more particularly
anionic surfactants. Preferably the compositions are in aqueous form. More preferably,
they comprise water in an amount of from 60% to 98% by weight, more preferably of
from 80% to 97% and most preferably of from 85% to 97% by weight of the total aqueous
liquid bleaching composition.
Oxidising agent
[0014] The oxidising agent of the present invention can be any known oxidising agent. Suitable
oxidising agent include peroxygen or hypohalite bleaching agent.
[0015] Suitable peroxygen bleaches to be used herein are hydrogen peroxide, water soluble
sources thereof, or mixtures thereof. As used herein a hydrogen peroxide source refers
to any compound that produces perhydroxyl ions when said compound is in contact with
water. Suitable water-soluble sources of hydrogen peroxide for use herein include
percarbonates, persilicates, persulphates such as monopersulfate, perborates, peroxyacids
such as diperoxydodecandioic acid (DPDA), perphtalic acid, perlauric acid, perbenzoic
and alkylperbenzoic acids, hydroperoxides, aliphatic and aromatic diacyl peroxides,
and mixtures thereof. Preferred peroxygen bleaches herein are hydrogen peroxide, hydroperoxide
and/or diacyl peroxide. Hydrogen peroxide is the most preferred peroxygen bleach herein.
[0016] Suitable hydroperoxides for use herein are tert-butyl hydroperoxide, cumyl hydroperoxide,
2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene-monohydroperoxide, tert-amyl
hydroperoxide and 2,5-dimethyl-hexane-2,5-dihydroperoxide. Such hydroperoxides have
the advantage to be particularly safe to fabrics and color while delivering excellent
bleaching performance when used in any laundry application.
[0017] Suitable aliphatic diacyl peroxides for use herein are dilauroyl peroxide, didecanoyl
peroxide, dimyristoyl peroxide, or mixtures thereof. Suitable aromatic dicayl peroxide
for use herein is for example benzoyl peroxide. Such diacyl peroxides have the advantage
to be particularly safe to fabrics and color while delivering excellent bleaching
performance when used in any laundry application.
[0018] Preferably the oxidising agent of the invention is a hypohalite bleach. Hypohalite
bleaches may be provided by a variety of sources, including bleaches that are oxidative
bleaches and subsequently lead to the formation of positive halide ions as well as
bleaches that are organic based sources of halides such as chloroisocyanurates.
[0019] Suitable hypohalite bleaches for use herein include the alkali metal and alkaline
earth metal hypochlorites, hypobromites, hypoiodites, chlorinated trisodium phosphate
dodecahydrates, potassium and sodium dichloroisocyanurates, potassium and sodium trichlorocyanurates,
N-chloroimides, N-chloroamides, N-chloroamines and chlorohydantoins.
[0020] Particularly preferred oxidising agents of the present invention are the alkali metal
and/or alkaline earth metal hypochlorites selected from the group consisting of sodium,
potassium, magnesium, lithium and calcium hypochlorites, and mixtures thereof. Most
preferably the oxidising agent is sodium hypochlorite.
[0021] Preferably, the liquid compositions according to the present invention comprise said
oxidising agent such that the content of active oxidising agent in the composition
is from 0.1% to 20% by weight, more preferably from 0.25% to 8% by weight, most preferably
from 0.5% to 6% by weight of the composition.
The radical scavenger
[0022] The compositions of the present invention comprise a radical scavenger.
[0023] The radical scavengers herein are selected from the group consisting of 2,3,4,5 tetramethoxy
benzoic acid; 2,3,4,5,6 pentamethoxy benzoic acid; polystyrene; styrene:maleic acid
copolymer; styrene:acrylic acid copolymer; styrene:ethylene glycole graft polymers;
poly(ethyleneglycol) di-toluene sulfonate; poly hydroxy styrene; poly methyl stryrene;
polystyrene divinyl benzene; poly vinyl phenol; and mixtures thereof.
[0024] The compositions of the present invention may comprise from 0.001% to 10% by weight
of the total composition of a radical scavenger, or a mixture thereof, preferably
from 0.01% to 8%, more preferably from 0.1% to 6% and most preferably from 0.2% to
4%.
[0025] Alternatively, the compositions of the present invention may comprise a mixture of
the radical scavengers or a combination of at least one radical scavenger of the present
invention and another radical scavenger known in the art or those described in EP-A-0
905 224.
[0026] Advantageously, the compositions of the invention are stable on storage. By "stable
on storage", it is to be understood that the compositions of the present invention
typically do not undergo more than 25% loss of available oxidising agent after 5 days
of storage at 50°C ± 0.5°C and more preferably not more than 20%. The % loss of available
chlorine may be measured using the method described, for instance, in "Analyses des
Eaux et Extraits de Javel" by "La chambre syndicale nationale de L'eau de Javel et
des produits connexes", pages 9-10 (1984). Said method consists in measuring the available
oxidising agent in the fresh compositions, i.e. just after they are made, and in the
same compositions after 5 days at 50°C.
Brightener
[0027] A preferred optional component of the invention is a brightener. Any brightener known
in the art may be used herein including both hydrophobic and hydrophilic brighteners
and mixtures thereof.
[0028] Brighteners are compounds which have the ability to fluoresce by absorbing ultraviolet
wave-lengths of light and re-emitting visible light. Brighteners, also referred to
as fluorescent whitening agents (FWA), have been extensively described in the art,
see for instance EP-A-0 265 041, EP-A-0 322 564, EP-A-0 317 979 or "Fluorescent whitening
agents" by A.K. Sarkar, published by MERROW, especially page 71-72.
[0029] Commercial optical brighteners which may be useful in the present invention can be
classified into subgroups, which include, but are not necessarily limited to, derivatives
of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanine, dibenzothiophene-5,5-dioxide,
azole, 5- and 6-membered-ring heterocycle, and other miscellaneous agents. Examples
of such brighteners are disclosed in "The Production and Application of Fluorescent
Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
Further optical brighteners which may also be used in the present invention include
naphthlimide, benzoxazole, benzofuran, benzimidazole and any mixtures thereof. Particularly
preferred brighteners for use herein are the derivatives of stilbene and mixtures
thereof.
[0030] Examples of optical brighteners which are useful in the present compositions are
those identified in U.S. Patent 4,790,856. These brighteners include the PHORWHITE®
series of brighteners from Verona. Other brighteners disclosed in this reference include:
Tinopal-UNPA®, Tinopal CBS® and Tinopal 5BM® available from Ciba-Geigy; Artic White
CC® and Artic White CWD®; the 2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles; 4,4'-bis(1,2,3-triazol-2-yl)-stilbenes;
4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
[0031] Specific examples of brighteners useful herein include 4-methyl-7-diethylamino coumarin;
1,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;
2-styryl-naptho-[1,2-d]oxazole; 2-(stilbene-4-yl)-2H-naphtho[1,2-d]triazole, 3-phenyl-7-(isoindolinyl)
coumarin; 3-methyl-7-(isoindolinyl) coumarin; 3-chloro-7-(isoindolinyl) coumarin;
4-(isoindolinyl)-4'-methylstilbene; 4-(isoindolinyl)-4'-methoxystilbene; sodium 4-(isoindolinyl)-4'-stilbenesulfonate;
4-(isoindolinyl)-4'-phenylstilbene; 4-(isoindolinyl)-3-methoxy-4'-methylstilbene;
4-(2-chloroisoindolinyl)-4'-(2-methylisoindolinyl)-2,2'-stilbenedisosulfonic acid;
disodium 4,4'-diisoindolinyl-2,2'-stilbene disulfonate; 4,4'-diisoindolinyl-2,2'-stilbenedisulfonamide;
disodium 4,4'-(7,8-dichloro-1-isoindolinyl)2,2-stilbenedisulfonate; disodium 4,4'-(7-chloro-1-isoindolinyl)2,2-stilbenedisulfonate;
disodium 4,4'-(6-Isopropoxy-1-isoindolinyl)2,2-stilbenedisulfonate; disodium 4,4'-(7,8-diisopropyl-1-isoindolinyl)2,2-stilbenedisulfonate;
disodium 4,4'-(7-butoxy-1-isoindolinyl)2,2-stilbenedisulfonate; disodium 4,4'-(6-trifluoromethyl-1-isoindolinyl)2,2-stilbenedisulfonate;
disodium 4,4'-[6-(1,4,7-trioxanonyl)-1-isoindolinyl)]2,2-stilbenedisulfonate; disodium
4,4'-(7-methoxymethyl-1-isoindolinyl)2,2-stilbenedisulfonate; disodium 4,4'-(6-phenyl-1-isoindolinyl)2,2-stilbenedisulfonate;
disodium 4,4'-(6-naphthyl-1-isoindolinyl)2,2-stilbenedisulfonate; disodium 4,4'-(6-methylsulfonyl-1-isoindolinyl)2,2-stilbenedisulfonate;
disodium 4,4'-(7-cyano-1-isoindolinyl)2,2-stilbenedisulfonate; and disodium 4,4'-[7-(1,2,3-trihydroxypropyl)-1-isoindolinyl)]2,2-stilbenedisulfonate;
disodium 4-isoindolinyl-4'-ethoxy-2,2'-stilbenedisulfonate; disodium 4-isoindolinyl-4'-methoxy-2,2'-stilbenedisulfonate;
disodium 4-isoindolinyl-4'-ethoxy-2,2'-stilbenedisulfonamide; disodium 4-isoindolinyl-4'-methyl-2,2'-stilbenedisulfonamide;
disodium 4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2 disulphonate,
disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino)-stilbene-2:2'-disulphonate,
disodium 4,4'-bis-(2,4-dianilino -s-triazin-6-ylamino)-stilbene-2-sulphonate, monosodium
4,4"-bis-(2,4-dianilino -s-triazin-6-ylamino)-stilbene-2:2'-disulphonate, disodium
4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2'-disulphonate,
disodium 4,4'-bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2' disulphonate, disodium
4,4'-bis-(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)-stilbene-2,2'-disulphonate,
sodium 2-(stilbyl-4"-(naphtho-1',2':4,5)-1,2,3-triazole-2"-sulphonate, 4,4'-bis-(2-sulphostyryl)-biphenyl,
4,4'-bis(4-phenyl-2H-1,2,3-triazol-2-yl)-2,2'-stilbenedisulfonic acid and mixture
thereof. See also U.S. Patent 3,646,015, U.S. Patent 3,346,502 and U.S. Patent 3,393,153
for further examples of brighteners useful herein.
[0032] Indeed one of the functionally equivalent derivative salts of 4,4'-bis(4-phenyl-2H-1,2,3-triazol-2-yl)-2,2'-stilbenedisulfonic
acid, namely its sodium salt is available from Mobay Chemical Corporation, a subsidiary
of Bayer AG under the name Phorwite® CAN. The amine salt is available from Molay under
the name Phorwite® CL solution. The potassium salt is available under the name Phorwite®
BHC 766.
[0033] Specific examples of hydrophilic optical brighteners useful in the present invention
are those having the structural formula:
wherein R
1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R
2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino,
chloro and amino; and M is a salt-forming cation such as sodium or potassium.
[0034] When in the above formula, R
1 is anilino, R
2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic
acid and disodium salt. This particular brightener species is commercially marketed
under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is
the preferred hydrophilic optical brightener useful in the detergent compositions
herein.
[0035] When in the above formula, R
1 is anilino, R
2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener
is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid disodium salt. This particular brightener species is commercially marketed under
the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
[0036] When in the above formula, R
1 is anilino, R
2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid, sodium salt. This particular brightener species is commercially marketed under
the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
[0037] Another preferred brightener is Optiblanc BRB available from 3V sigma.
[0038] Other substituted stilbene 2,2'-disulfonic acid derivatives also include 4-4'-bis
(2-2' styryl sulfonate) biphenyl, commercially available from Ciba-Geigy under the
trade name Brightener 49® or other hydrophilic brighteners like for example Brightener
3® or Brightener 47®, also commercially available from Ciba-Geigy.
[0039] Specific examples of hydrophobic brighteners useful in the present invention include
the polycyclic oxazole derivatives such as benzo-oxazole derivatives, or mixtures
thereof and particularly preferred herein the benzo-oxazole derivatives. An example
of such a brightener is benzoxazole,2,2'-(thiophenaldyl)bis having the following formula
C18H10N2O2S, commercially available from Ciba-Geigy under the trade name Tinopal SOP®.
This brightener is almost insoluble in water, i.e. it has a solubility being lower
than 1 gram per liter. Another example of such a brightener is bis(sulfobenzofuranyl)biphenyl,
commercially available from Ciba-Geigy under the trade name Tinopal PLC®.
[0040] By "hydrophobic brighteners", it is to be understood herein any brightener whose
solubility in water is lower than 10 grams per liter at 25°C. By "solubility" of a
given compound, it is to be understood herein the amount of said compound solubilized
in deionized water at 25°C. Thus, a compound having a solubility being lower than
10 grams per liter means that when less than 10 grams of said given compound is incorporated
in deionized water at 25°C said compound is entirely dissolved in said water, i.e.
a clear and stable solution is obtained. In other words, incorporating 10 grams per
liter or more of said given compound in water will result in a precipitation of said
compound in said medium. Accordingly, by "hydrophilic brighteners", it is to be understood
herein any brightener whose solubility in water is higher or equal to 10 grams per
liter at 25°C.
[0041] Where present, brightener is incorporated at a level of from 0.001% to 1.0%, preferably
from 0.005% to 0.5%, more preferably from 0.005% to 0.3% and most preferably from
0.008% to 0.1%, by weight of the composition.
[0042] Where hydrophobic brighteners are present in the compositions herein they may both
be solubilized or suspended in the compositions of the present invention. Such brighteners
solubilisation can be for example achieved by means of a surfactant or a mixture thereof
as described herein after. Various surfactants may be used for this purpose like C8-C20
alkyl aryl sulphonates as described for example in U.S. Patent 4, 623,476 or amine
oxides as described for example in EP-A-186386. Preferred surfactants also called
"co-surfactants" to solubilise and/or suspend such a hydrophobic brightener are anionic
surfactants including alkyl sulphates or alkylalkoxy sulphates having from 4 to 30
carbon atoms in the alkyl chain, or alkylethoxycarboxylates having from 6 to 30 carbon
atoms in the alkyl chain such as Akyposoft® 100 NV from Chemy or Sandosan LNCS from
Sandoz. Preferred are C12-C14 alkyethoxysulphates. Such co-surfactants herein should
be used in amounts required to solubilize the hydrophobic brightener in need thereof.
[0043] Generally, when a co-surfactant is used, the liquid compositions of the present inventions
are prepared in a process wherein the hydrophobic brightener and the co-surfactant
are first mixed to form a premix, before the premix is then mixed with the remainder
of the composition which has been separately prepared.
[0044] Alternatively, the hydrophobic brightener may be suspended by means of a specific
suspending agent, like polymers and/or colloidal particulate silicate. Any polymers
known to those skilled in the art as having suspending properties are suitable for
use herein including those described for example in EP-A-206718.
Chelating agents
[0045] In the compositions of the present invention, the presence of a chelating agent in
addition to radical scavenger is not compulsory, but is highly preferred.
[0046] It is believed that the presence of a chelating agent in the compositions of the
present invention further contributes to the brightener stability upon prolonged periods
of storage, and thus to the effective whiteness performance of these compositions
upon ageing.
[0047] Suitable chelating agents may be any of those known to those skilled in the art such
as the ones selected from the group comprising phosphonate chelating agents, phosphate
chelating agents, polyfunctionally-substituted aromatic chelating agents, ethylenediamine
N,N'- disuccinic acids, or mixtures thereof.
[0048] Chelating agents may be desired in the compositions of the present invention, preferably
phosphate chelating agents like phytic acid, as they further contribute to the benefit
delivered by the radical scavengers herein by further improving the stability of the
brighteners, thus delivering effective whiteness performance in any laundry application
upon ageing of the compositions, i.e. after prolonged periods of storage.
[0049] Suitable phosphonate chelating agents for use herein may include alkali metal ethane
1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as
amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP),
nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates,
and diethylene triamine penta methylene phosphonates (DTPMP). The phosphonate compounds
may be present either in their acid form or as salts of different cations on some
or all of their acid functionalities. Preferred phosphonate chelating agents to be
used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane
1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially
available from Monsanto under the trade name DEQUEST®.
[0050] Suitable phosphate chelating agents are as following: Phosphonic acid can be condensed
in the reaction :
[0052] All such phosphate ingredients are suitable for use herein, and preferred are linear
phosphate ingredients (i.e. R is M) where n is 1 (pyrophosphate) and n is 2 (tripolyphosphate
(STPP)), most preferably where n is 2. The most commonly available form of these phosphate
is where M is Sodium.
[0053] Phytic acid, which is particularly suitable for use herein, is a hexa-phosphoric
acid that occurs naturally in the seeds of many cereal grains, generally in the form
of the insoluble calcium-magnesium salt. It may also be derived from corn steep liquor.
Commercial grade phytic acid is commercially available from J.T.Baker Co., e.g. as
a 40% aqueous solution. It is intended that the present invention covers the acidic
form of phytic acid as well as alkali metal salt derivatives thereof, particularly
sodium or potassium salts thereof. Sodium phytate is available from Jonas Chemical
Co (Brooklyn, N.Y.). In fact since the typical pH of the compositions of the present
invention are in the alkaline pH range, the phytic acid component exists primarily
as the ionized salt in the liquid compositions herein even if it is added in its acidic
form. Mixtures of such salts of phytic acid are also covered.
[0054] Polyfunctionally-substituted aromatic chelating agents may also be useful in the
compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et
al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such
as 1,2-dihydroxy -3,5-disulfobenzene.
[0055] A preferred biodegradable chelating agent for use herein is ethylene diamine N,N'-
disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium
salts thereof or mixtures thereof. Ethylenediamine N,N'- disuccinic acids, especially
the (S,S) isomer have been extensively described in US patent 4, 704, 233, November
3, 1987, to Hartman and Perkins. Ethylenediamine N,N'- disuccinic acids is, for instance,
commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
[0056] Particularly preferred chelating agents for use herein are phosphate chelating agents
like sodium pyrophosphate, sodium tripolyphosphate, phytic acid, and mixtures thereof.
[0057] Typically, the compositions according to the present invention comprise up to 10%,
preferably from 0.01% to 5% by weight, more preferably from 0.05% to 2% and most preferably
from 0.1% to 1.5% by weight of the composition.
pH
[0058] The pH of the liquid compositions according to the present invention, as is, is typically
from 12 to 14 measured at 25°C. The liquid compositions of the invention have a pH
of from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5, when
diluted into 1 to 500 times its weight of water. It is in this alkaline range that
the optimum stability and performance of the hypohalite as well as fabric whiteness
and/or safety are obtained. The pH range is suitably provided by a buffering component.
[0059] Suitable sources of alkalinity are the caustic alkalis such as sodium hydroxide,
potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such
as sodium and/or potassium oxide. A preferred strong source of alkalinity is a caustic
alkali, more preferably sodium hydroxide and/or potassium hydroxide. Typical levels
of such caustic alkalis, when present, are of from 0.1% to 1.5% by weight, preferably
from 0.5% to 1.5% by weight of the composition.
Optional pH buffering components
[0060] In the compositions of the present invention, the presence of a pH buffering component
is not compulsory, but is preferred.
[0061] It is believed that the presence of a pH buffering component in the compositions
of the present invention further contributes to the effective whiteness performance
of these compositions as well as to the fabric safety. Indeed, the pH buffering component
allows to control the alkalinity in the bleaching solution, i.e. maintain the pH of
the bleaching solution at a pH of at least 7.5, preferably at least 8.5, and more
preferably at least 9.5 for a longer period of time starting from the moment at which
the dilution is completed (e.g. when the bleaching composition of the present invention
is diluted in the bleaching solution at a dilution level of 200:1 (water:composition)).
It is believed that the pH buffering component may also contribute to brightener stability,
where present, and thus to the effective whiteness performance of the compositions
herein.
[0062] The pH buffering component ensures that the pH of the composition is buffered to
a pH value ranging from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5
to 11.5 after the composition has been diluted into 1 to 500 times its weight of water.
[0063] Suitable pH buffering components for use herein are selected from the group consisting
of alkali metal salts of carbonates, polycarbonates, sesquicarbonates, silicates,
polysilicates, boron salts, phosphates, stannates, alluminates and mixtures thereof.
More preferably alkali metal salts of carbonate, silicate and borateThe preferred
alkali metal salts for use herein are sodium and potassium.
[0064] Suitable boron salts or mixtures thereof for use herein include alkali metal salts
of borates and alkyl borates and mixtures thereof. Examples of boron salts include
boric acid, alkali metal salts of metaborate, tetraborate, octoborate, pentaborate,
dodecaboron, borontrifluoride and alkyl borate containing from 1 to 12 carbon atoms,
preferably from 1 to 4. Suitable alkyl borate includes methyl borate, ethyl borate
and propyl borate. Particularly preferred boron salts herein are the alkali metal
salts of metaborate, such as sodium metaborate, potassium metaborate, and the alkali
metal salts of borate, such as sodium borate, or mixtures thereof. Boron salts like
sodium metaborate and sodium tetraborate are commercially available from Borax and
Societa Chimica Larderello under the name sodium metaborate and Borax®.
[0065] Particularly preferred pH buffering components are selected from the group consisting
of sodium carbonate, sodium silicate, sodium borate, sodium metaborate and mixtures
thereof.
[0066] The raw materials involved in the preparation of hypohalite bleaches usually contain
by-products, e.g. calcium carbonate resulting in an amount of up to 0.4% by weight
of by-product within the hypohalite composition. However, at such amount, the by-product
will not have the buffering action defined above.
[0067] Liquid bleaching compositions herein will contain an amount of pH buffering component
of from 0.5% to 9% by weight, preferably from 0.5% to 5% by weight, and more preferably
in an amount of from 0.6% to 3% by weight of the composition.
[0068] The composition according to the invention may comprise other optional components
such as bleach-stable surfactants, organic or inorganic alkalis, builders, thickening
agents, polymers, pigments, dyes, solvents, perfumes, and mixtures thereof.
Surfactants
[0069] The liquid compositions of the present invention may comprise a surfactant as a desirable
optional ingredient. Said surfactants may be present in the compositions according
to the present invention in amounts of from 0.1% to 50%, preferably from 0.1% to 40%
and more preferably from 1% to 30% by weight of the composition.
[0070] Surfactants suitable for use herein include anionic surfactants, nonionic surfactants,
cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures
thereof.
[0071] In a particularly preferred embodiment the surfactant is selected from the group
consisting of alkyl sulphate, alkyl ether sulphate and mixtures thereof.
[0072] Suitable anionic surfactants for use in the compositions herein include water-soluble
salts or acids of the formula ROSO
3M wherein R preferably is a C
10-C
24 hydrocarbyl, preferably linear or branched alkyl having a C
10-C
20 alkyl component, more preferably a C
12- C
18 linear or branched alkyl, and M is H or a cation, e.g., an alkali metal cation (e.g.,
sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-,
and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium
and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines
such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
[0073] Other suitable anionic surfactants for use herein are water-soluble salts or acids
of the formula RO(A)
mSO
3M wherein R is an unsubstituted C
6-C
24 linear or branched alkyl group having a C
6-C
24 alkyl component, preferably a C
10-C
20 linear or branched alkyl, more preferably C
12-C
18 linear or branched alkyl, A is an ethoxy or propoxy unit, m is greater than zero,
typically between about 0.5 and about 30, more preferably between about 0.5 and about
5, and M is H or a cation which can be, for example, a metal cation (e.g., sodium,
potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated
herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-,
trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium,
dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine,
triethylamine, mixtures thereof, and the like. Exemplary surfactants are C
12-C
18 alkyl polyethoxylate (1.0) sulfate, C
12-C
18E(1.0) sulfate, C
12-C
18 alkyl polyethoxylate (2.25) sulfate, C
12-C
18E(2.25) sulfate, C
12-C
18 alkyl polyethoxylate (3.0) sulfate, C
12-C
18E(3.0) sulfate, and C
12-C
18 alkyl polyethoxylate (4.0) sulfate, C
12-C
18E(4.0) sulfate, wherein the counterion is conveniently selected from sodium and potassium.
[0074] In a particularly preferred embodiment of the present invention the surfactant system
used is an anionic surfactant system, namely alkyl alkoxy (preferably ethoxy) sulphate
alone for example alkyl (ethoxy) 3 sulphate or in combination with a co-surfactant,
preferably a C2-C10 alkyl sulphate and/or a C8-C22 alkyl or aryl sulphonate like C8-C22
benzene sulphonate and/or another alkyl alkoxy sulphate apart the 3 ethoxylated one.
Indeed the presence of said alkyl (ethoxy) 3 sulphate alone or in combination with
a cosurfactant provides the desired viscosity to the present compositions and delivers
excellent stain removal properties to said compositions especially when used in any
laundry application.
[0075] Typically such compositions according to the present invention have a viscosity between
25 cps and 1500 cps, preferably between 50 cps and 1100 cps, depending from the ratio
between AE
3S and the co-surfactant, when measured with a rheometer like carri-med CSL2-100® at
the following viscosity parameters : angle : 1°58, gap : 60, diameter : 4.0 cm, iner
: 63.60 at a temperature of 25°C and a shear rate of 30 1/sec.
[0076] Other anionic surfactants useful for detersive purposes can also be used herein.
These can include salts (including, for example, sodium, potassium, ammonium, and
substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap,
C
9-C
20 linear alkylbenzenesulfonates, C
8-C
22 primary or secondary alkanesulfonates, C
8-C
24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the
pyrolyzed product of alkaline earth metal citrates, e.g., as described in British
patent specification No. 1,082,179, C
8-C
24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl
ester sulfonates such as C
14-16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates,
isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and
sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated
C
12-C
18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C
6-C
14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside
(the nonionic nonsulfated compounds being described below), branched primary alkyl
sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH
2CH
2O)
kCH
2COO-M
+ wherein R is a C
8-C
22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin
acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated
rosin, and resin acids and hydrogenated resin acids present in or derived from tall
oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I
and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally
disclosed in U.S. Patent 3,929,678, issued December 30, 1975, to Laughlin, et al.
at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
[0077] Other suitable anionic surfactants for use herein also include acyl sarcosinate or
mixtures thereof, in its acid and/or salt form, preferably long chain acyl sarcosinates
having the following formula:
wherein M is hydrogen or a cationic moiety and wherein R is an alkyl group of from
11 to 15 carbon atoms, preferably of from 11 to 13 carbon atoms. Preferred M are hydrogen
and alkali metal salts, especially sodium and potassium. Said acyl sarcosinate surfactants
are derived from natural fatty acids and the aminoacid sarcosine (N-methyl glycine).
They are suitable to be used as aqueous solution of their salt or in their acidic
form as powder. Being derivatives of natural fatty acids, said acyl sarcosinates are
rapidly and completely biodegradable and have good skin compatibility.
[0078] Accordingly, suitable long chain acyl sarcosinates to be used herein include C
12 acyl sarcosinate (i.e., an acyl sarcosinate according to the above formula wherein
M is hydrogen and R is an alkyl group of 11 carbon atoms) and C
14 acyl sarcosinate (i.e., an acyl sarcosinate according to the above formula wherein
M is hydrogen and R is an alkyl group of 13 carbon atoms). C
12 acyl sarcosinate is commercially available, for example, as Hamposyl L-30® supplied
by Hampshire. C
14 acyl sarcosinate is commercially available, for example, as Hamposyl M-30® supplied
by Hampshire.
[0079] Suitable nonionic surfactants for use herein include a class of compounds which may
be broadly defined as compounds produced by the condensation of alkylene oxide groups
(hydrophilic in nature) with an organic hydrophobic compound, which may be branched
or linear aliphatic (e.g. Guerbet or secondary alcohol) or alkyl aromatic in nature.
The length of the hydrophilic or polyoxyalkylene radical which is condensed with any
particular hydrophobic group can be readily adjusted to yield a water-soluble compound
having the desired degree of balance between hydrophilic and hydrophobic elements.
Accordingly suitable nonionic synthetic surfactants include:
(i) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products
of alkyl phenols having an alkyl group containing from 6 to 20 carbon atoms in either
a straight chain or branched chain configuration, preferably from 8 to 12 carbon atoms,
with ethylene oxide, the said ethylene oxide being present in amounts equal to 10
to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such
compounds may be derived from polymerized propylene, diisobutylene, octane, and nonane;
(ii) Those derived from the condensation of ethylene oxide with the product resulting
from the reaction of propylene oxide and ethylene diamine products which may be varied
in composition depending upon the balance between the hydrophobic and hydrophilic
elements which is desired. Examples are compounds containing from about 40% to about
80% polyoxyethylene by weight and having a molecular weight of from about 5000 to
about 11000 resulting from the reaction of ethylene oxide groups with a hydrophobic
base constituted of the reaction product of ethylene diamine and excess propylene
oxide, said base having a molecular weight of the order of 2500 to 3000;
(iii) The condensation product of aliphatic alcohols having from 6 to 22 carbon atoms,
in either straight chain or branched chain configuration, preferably from 8 to 18
carbon atoms, with from 2 to 35 moles of ethylene oxide, preferably from 4 to 25 and
more preferably from 5 to 18. Example of this type of material are a coconut alcohol
ethylene oxide condensate having from 5 to 18 moles of ethylene oxide per mole of
coconut alcohol, the coconut alcohol fraction having from 9 to 14 carbon atoms;
(iv) Trialkyl amine oxides and trialkyl phosphine oxides wherein one alkyl group ranges
from 10 to 18 carbon atoms and two alkyl groups range from 1 to 3 carbon atoms; specific
example is tetradecyl dimethyl phosphine oxide;
(v) The condensation products of ethylene oxide with a hydrophobic base formed by
the condensation of propylene oxide with propylene glycol; The hydrophobic portion
of these compounds will preferably have a molecular weight of from about 1500 to about
1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties
to this hydrophobic portion tends to increase the water solubility of the molecule
as a whole, and the liquid character of the product is retained up to the point where
the polyoxyethylene content is about 50% of the total weight of the condensation product,
which corresponds to condensation with up to about 40 moles of ethylene oxide.
[0080] Particularly suitable nonionic surfactants for use herein are capped nonionic ethoxylated
surfactants according to the formula:
R
1(OR
2)
nOR
3
wherein R
1 is a C
8-C
18 linear or branched alkyl or alkenyl group, aryl group, alkaryl group, preferably,
R
1 is a C
10-C
15 alkyl or alkenyl group, more preferably a C
10-C
15 alkyl group;
R
2 is a C
2-C
10 linear or branched alkyl group, preferably a C
4 group;
R
3 is a C
1-C
10 alkyl or alkenyl group, preferably a C
1-C
5 alkyl group, and
n is an integer ranging in the range of from 1 to 20, preferably from 1 to 10, more
preferably from 1 to 5;
or mixtures thereof.
[0081] These surfactants are commercially available from BASF under the trade name Plurafac®,
from HOECHST under the trade name Genapol® or from ICI under the trade name Symperonic®.
Preferred capped nonionic ethoxylated surfactant of the above formula are those commercially
available under the tradename Genapol® L 2.5 NR from Hoechst, and Symperonic® LF/CS
1100 from ICI.
[0082] Other suitable nonionic surfactants for use herein include the amine oxides corresponding
to the formula:
wherein R is a primary alkyl group containing 6-24 carbons, preferably 10-18 carbons,
and wherein R' and R" are, each, independently, an alkyl group containing 1 to 6 carbon
atoms. The arrow in the formula is a conventional representation of a semi-polar bond.
The preferred amine oxides are those in which the primary alkyl group has a straight
chain in at least most of the molecules, generally at least 70%, preferably at least
90% of the molecules, and the amine oxides which are especially preferred are those
in which R contains 10-18 carbons and R' and R" are both methyl. Exemplary of the
preferred amine oxides are the N-hexyldimethylamine oxide, N-octyldimethylamine oxide,
N-decyldimethylamine oxide, N-dodecyl dimethylamine oxide, N-tetradecyldimethylamine
oxide, N-hexadecyl dimethylamine oxide, N-octadecyldimethylamine oxide, N-eicosyldimethylamine
oxide, N-docosyldimethylamine oxide, N-tetracosyl dimethylamine oxide, the corresponding
amine oxides in which one or both of the methyl groups are replaced with ethyl or
2-hydroxyethyl groups and mixtures thereof. A most preferred amine oxide for use herein
is N-decyldimethylamine oxide.
[0083] Other suitable nonionic surfactants for the purpose of the invention are the phosphine
or sulfoxide surfactants of formula :
wherein A is phosphorus or sulfur atom, R is a primary alkyl group containing 6-24
carbons, preferably 10-18 carbons, and wherein R' and R" are, each, independently
selected from methyl, ethyl and 2-hydroxyethyl. The arrow in the formula is a conventional
representation of a semi-polar bond.
[0084] Suitable zwitterionic detergents for use herein comprise the betaine and betaine-like
detergents wherein the molecule contains both basic and acidic groups which form an
inner salt giving the molecule both cationic and anionic hydrophilic groups over a
broad range of pH values. Some common examples of these detergents are described in
U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.
Preferred zwitterionic detergent compounds have the formula
wherein R1 is an alkyl radical containing from 8 to 22 carbon atoms, R2 and R3 contain
from 1 to 3 carbon atoms, R4 is an alkylene chain containing from 1 to 3 carbon atoms,
X is selected from the group consisting of hydrogen and a hydroxyl radical, Y is selected
from the group consisting of carboxyl and sulfonyl radicals and wherein the sum of
R1, R2 and R3 radicals is from 14 to 24 carbon atoms.
[0085] Amphoteric and ampholytic detergents which can be either cationic or anionic depending
upon the pH of the system are represented by detergents such as dodecylbeta-alanine,
N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate
according to the teaching of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids
such as those produced according to the teaching of U.S. Pat. No. 2,438,091, and the
products sold under the trade name "Miranol", and described in U.S. Pat. No. 2,528,378,
said patents being incorporated herein by reference. Additional synthetic detergents
and listings of their commercial sources can be found in McCutcheon's Detergents and
Emulsifiers, North American Ed. 1980, incorporated herein by reference.
[0086] Cationic surfactants suitable for use in compositions of the present invention are
those having a long-chain hydrocarbyl group. Examples of such cationic surfactants
include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those
surfactants having the formula:
[R
2(OR
3)
y][R
4(OR
3)
y]
2R
5N
+X
-
wherein R
2 is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain,
each R
3 is selected from the group consisting of -CH
2CH
2-, -CH
2CH(CH
3)-, -CH
2CH
2CH
2-, and mixtures thereof; each R
4 is selected from the group consisting of C
1-C
4 alkyl, benzyl ring structures formed by joining the two R
4 groups, and hydrogen when y is not 0; R
5 is the same as R
4 or is an alkyl chain wherein the total number of carbon atoms of R
2 plus R
5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values
is from 0 to about 15; and X is any compatible anion.
[0087] Quaternary ammonium surfactant suitable for the present invention has the formula
(I):
whereby
R1 is a short chainlength alkyl (C6-C10)
y is 2-4, preferably 3.
whereby R2 is H or a C1-C3 alkyl,
whereby x is 0-4, preferably 0-2, most preferably 0,
whereby R3, R4 and R5 are either the same or different and can be either a short chain
alkyl (C1-C3) or alkoxylated alkyl of the formula II,
whereby X- is a counterion, preferably a halide, e.g. chloride or methylsulfate.
R6 is C1-C4 and z is 1 or 2.
[0088] Preferred quat ammonium surfactants are those as defined in formula I whereby
R1 is C8, C10 or mixtures thereof, x=o,
R3, R4, R5 = CH3.
[0089] Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds
useful in the present composition having the formula :
R
1R
2R
3R
4N
+X
- (i)
wherein R
1 is C
8-C
16 alkyl, each of R
2, R
3 and R
4 is independently C
1-C
4 alkyl, benzyl, and -(C
2H
40)
XH where x has a value from 2 to 5, and X is an anion. Not more than one of R
2, R
3 or R
4 should be benzyl.
[0090] The preferred alkyl chain length for R
1 is C
12-C
15 particularly where the alkyl group is a mixture of chain lengths derived from coconut
or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols
synthesis. Preferred groups for R
2R
3 and R
4 are methyl and the anion X may be selected from halide, methosulphate, acetate and
phosphate ions.
Examples of suitable quaternary ammonium compounds of formulae (i) for use herein
are :
coconut trimethyl ammonium chloride or bromide;
decyl triethyl ammonium chloride;
C12-15 trimethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is
alkyl and R2R3R4 are methyl).
di-alkyl imidazolines
[0091] Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044,
Cambre, issued October 14, 1980 and in European Patent Application EP 000,224.
Polymers
[0092] An optional component of the compositions herein is a polymer. Suitable polymers
for use herein comprise monomeric units selected from the group consisting of unsaturated
carboxylic acids, polycarboxylic acids, sulphonic acids, phosphonic acids and mixtures
thereof. Co-polymerisation of the above monomeric units among them or with other co-monomers
such as styrenesulfonic acid is also suitable.
[0093] Preferred examples of such polymers are the polymers and co-polymers of monomeric
units selected from the group consisting of acrylic acid, maleic acid, vinylsulphonic
acid and mixtures thereof. Also suitable for use herein are the above mentioned polymers
and co-polymers which are modified in order to contain other functional groups such
as aminophosphonic and/or phosphonic units. More preferred polymers are selected from
the group consisting of polyacrylate polymers, co-polymers of acrylic and maleic acid,
co-polymers of styrene sulphonic acid and maleic acid, and mixtures thereof, preferably
modified with aminophosphonic and/or phosphonic groups.
[0094] The molecular weight for these polymers and co-polymers is preferably below 100,000,
most preferably between 500 and 50,000. Most suitable polymers and co-polymers for
use herein will be soluble in an amount up to 0.1% by weight, in an aqueous composition
comprising 5% by weight of sodium hypochlorite with its pH adjusted to 13 with sodium
hydroxide.
[0095] Commercially available such polymers, suitable for use herein, are the polyacrylate
polymers sold under the tradename Good-Rite® from BF Goodrich, Acrysol® from Rohm
& Haas, Sokalan® from BASF, Norasol® from Norso Haas. Also suitable for use herein
are the co-polymers of styrene sulphonic acid and maleic acid, commercially available
under the tradename Versaflex® from National Starch such as Versaflex 157, as well
as Acumer® terpolymers from Rohm and Haas, in particular Acumer® 3100. Preferred commercially
available polymers are the polyacrylate polymers, especially the Norasol® polyacrylate
polymers and more preferred are the polyacrylate polymer Norasol® 410N (MW 10,000)
and the polyacrylate polymer modified with phosphonic groups Norasol® 440N (MW 4000)
and its corresponding acid form Norasol® QR 784 (MW 4000).
[0096] A preferred polymer for use herein is a polyacrylate polymer modified with phosphonic
groups commercially available under the tradename Norasol® 440N (MW 4000) and its
corresponding acid form Norasol® QR 784 (MW 4000) from Norso-Haas.
[0097] Mixtures of polymers as herein described may also be used in the present invention.
[0098] Polymers herein are preferably present in low amounts, i.e. in amounts of up to 10%,
preferably up to 1%, more preferably up to 0.5% by weight, even more preferably from
0.001% to 0.3% by weight, and most preferably from 0.005% to 0.2% by weight of the
composition.
Method of bleaching fabrics:
[0099] Particularly preferred surfaces to be bleached with the compositions herein are fabrics
including for example clothes, curtains, drapes, bed linens, bath linens, table cloths,
sleeping bags, tents, upholstered furniture and the like, and carpets.
[0100] Thus, the present invention further encompasses a method of bleaching fabrics which
comprises the step of contacting said fabrics with a bleaching composition according
to the present invention. In a preferred embodiment, the compositions used in said
method of bleaching fabrics are liquid hypochlorite-containing compositions that may
further comprise a chelating agent and/or a pH buffering component as defined hereinbefore.
Said method according to the present invention delivers effective whiteness performance
upon ageing of the compositions.
[0101] The compositions according to the present invention are applied to fabrics in a liquid
form. Indeed, by "in a liquid form", it is meant herein the liquid compositions according
to the present invention per se in neat or diluted form.
[0102] The compositions according to the present invention are typically used in diluted
form in a laundry operation. By "in diluted form", it is meant herein that the compositions
for the bleaching of fabrics according to the present invention may be diluted by
the user, preferably with water. Such dilution may occur for instance in hand laundry
applications as well as by other means such as in a washing machine. Said compositions
can be diluted up to 500 times, preferably from 5 to 200 times and more preferably
from 10 to 80 times.
[0103] More specifically, the method of bleaching fabrics according to the present invention
comprises the steps of first contacting said fabrics with a bleaching composition
according to the present invention, in its diluted form, then allowing said fabrics
to remain in contact with said composition, for a period of time sufficient to bleach
said fabrics, typically 1 to 60 minutes, preferably 5 to 30 minutes, then rinsing
said fabrics with water. If said fabrics are to be washed, i.e., with a conventional
composition comprising at least one surface active agent, said washing may be conducted
together with the bleaching of said fabrics by contacting said fabrics at the same
time with a bleaching composition according to the present invention and said detergent
composition, or said washing may be conducted before or after that said fabrics have
been bleached.
[0104] In another embodiment of the present invention the method of bleaching fabrics comprises
the step of contacting fabrics with a liquid bleaching composition according to the
present invention, in its neat form, and allowing said fabrics to remain in contact
with said bleaching composition for a period of time sufficient to bleach said fabrics,
typically 5 seconds to 30 minutes, preferably 1 minute to 10 minutes before rinsing
said fabrics with water. If said fabrics are to be washed, i.e., with a conventional
composition comprising at least one surface active agent, said washing may be conducted
before or after that the fabrics have been bleached with the composition herein. In
the embodiment of the present invention wherein the liquid bleaching composition of
the present invention, is applied to the fabrics in its neat form, it is preferred
that the level of hypohalite bleach, is from 0.01% to 5%, preferably from 0.1% to
3.5%, more preferably from 0.2% to 2% and most preferably from 0.2% to 1%.
[0105] It is preferred to perform the bleaching methods herein before said fabrics are washed.
Indeed, it has been observed that bleaching said fabrics with the compositions according
to the present invention (diluted and/or neat bleaching methods) prior to washing
them with a detergent composition provides superior whiteness and stain removal with
less energy and detergent than if said fabrics are washed first, then bleached.
[0106] Alternatively instead of following the neat bleaching method as described herein
above (pretreater application) by a rinsing step with water and/or a conventional
washing step with a liquid or powder conventional detergent, the bleaching pre-treatment
operation may also be followed by the diluted bleaching method as described herein
before either in bucket (hand operation) or in a washing machine.
Examples
[0107]
|
I |
II
Comparative |
III
Comparative |
IV
Comparative |
NaOCl (as % w/w AvCl2) |
3 |
3 |
3 |
3 |
NaOH (% w/w) |
0.5 |
1 |
1 |
1 |
Na2CO3 (% w/w) |
0 |
0 |
1 |
1.5 |
Silicate (% w/w SiO2) |
0 |
0.5 |
0 |
0.5 |
Borate (% w/w) |
0 |
0 |
1 |
1 |
NaC12/14E3S |
0 |
0 |
0 |
0 |
C12/14dimethyl amine oxide |
0 |
0 |
0 |
0 |
NaC12/14S |
0 |
0 |
0 |
0 |
Tinopal PLC® |
0 |
0 |
0 |
0 |
Optiblanc BRB® |
0 |
0 |
0 |
0 |
tetramethoxy benzoic acid |
0.5 |
0 |
0.5 |
0.5 |
Polystyrene sulfonate |
0 |
1.0 |
0.5 |
0.5 |
Fragrance |
0.1 |
0.1 |
0.1 |
0 |
|
V |
VI
Comparative |
VII
Comparative |
VIII
Comparative |
NaOCl (as % w/w AvCl2) |
5 |
5 |
5 |
5 |
NaOH (% w/w) |
0.5 |
1 |
1 |
1 |
Na2CO3 (% w/w) |
0 |
0 |
1 |
1.5 |
Silicate (% w/w SiO2) |
0 |
0.5 |
0 |
0.5 |
Borate (% w/w) |
0 |
0 |
1 |
1 |
NaC12/14E3S |
0 |
0 |
0 |
0 |
C12/14dimethyl amine oxide |
0.5 |
0.5 |
0.5 |
0.5 |
NaC12/14S |
0 |
0 |
0 |
0 |
Tinopal PLC® |
0 |
0.01 |
0 |
0.1 |
Optiblanc BRB® |
0 |
0 |
0 |
0 |
tetramethoxy benzoic acid |
0.5 |
0 |
0.5 |
0.5 |
Polystyrene sulfonate |
0 |
1.0 |
0.5 |
0.5 |
Fragrance |
0.1 |
0.1 |
0.1 |
0 |
|
IX |
X
Comparative |
XI
Comparative |
XII
Comparative |
NaOCl (as % w/w AvCl2) |
5 |
5 |
5 |
5 |
NaOH (% w/w) |
0.5 |
1 |
1 |
1 |
Na2CO3 (% w/w) |
0 |
0 |
1 |
1.5 |
Silicate (% w/w SiO2) |
0 |
0.5 |
0 |
0.5 |
Borate (% w/w) |
0 |
0 |
1 |
1 |
NaC12/14E3S |
5 |
5 |
5 |
5 |
C12/14dimethyl amine oxide |
0 |
0.5 |
0 |
0 |
NaC12/14S |
0.5 |
0 |
0.5 |
0.5 |
Tinopal PLC® |
0.01 |
0.01 |
0 |
0 |
Optiblanc BRB® |
0 |
0.01 |
0 |
0 |
tetramethoxy benzoic acid |
0.5 |
0 |
0.5 |
0.5 |
Polystyrene sulfonate |
0 |
1.0 |
0.5 |
0.5 |
Fragrance |
0.1 |
0.1 |
0.1 |
0 |
|
XIII |
XIV
Comparative |
XV
Comparative |
XVI
Comparative |
NaOCl (as % w/w AvCl2) |
5 |
5 |
5 |
5 |
NaOH (% w/w) |
0.5 |
1 |
1 |
1 |
Na2CO3 (% w/w) |
0 |
0 |
1 |
1.5 |
Silicate (% w/w SiO2) |
0 |
0.5 |
0 |
0.5 |
Borate (% w/w) |
0 |
0 |
1 |
1 |
NaC12/14E3S |
0 |
5 |
5 |
0 |
C12/14dimethyl amine oxide |
0 |
0.5 |
0 |
2 |
NaC12/14S |
5.0 |
0 |
0.5 |
0.5 |
Tinopal PLC® |
0.01 |
0 |
0.01 |
0.05 |
Optiblanc BRB® |
0 |
0.01 |
0.01 |
0 |
tetramethoxy benzoic acid |
0.5 |
0 |
0.5 |
0.5 |
Polystyrene sulfonate |
0 |
1.0 |
0.5 |
0.5 |
Fragrance |
0.1 |
0.1 |
0.1 |
0 |
Wherein:
NaC12/14E3S is a C12/14 alkyl ethoxy (3) sulfate sodium salt, e.g., Empicol ESC3®
from Albright & Wilson.
C12/14 dimethylamine oxide is for example industrially available from Albright & Wilson
NaC12/14S is C12/14 alkyl sulphate
Tinopal PLC® available from Ciba Geigy
Optiblanc BRB® available from 3V sigma
Tetramethoxy benzoic acid is for example available as reagent grade from Aldrich
Polystyrene sulphonate is available as Versaflex® from National Starch
Fragrances can contain terpenes, esters, ethers and alcohols
[0108] These examples of the present invention are not intended to limit the scope of the
claimed invention in any way.