[0001] This invention relates to fabric-washing compositions. More particularly it relates
to an improved low temperature bleaching fabric-washing composition comprising a peroxide
compound, a peroxyacid bleach precursor and enzymes.
[0002] It is well known that active oxygen-releasing peroxide compounds are effective bleaching
agents. These compounds are frequently incorporated in detergent compositions for
stain and soil removal. They have, however, an important limitation: the activity
is extremely temperature-dependent. Thus, active oxygen-releasing bleaches are essentially
only practical when the bleaching solution is heated above 60°C. At a bleach solution
temperature of about 60°C, extremely high amounts of the active oxygen-releasing compounds
must be added to achieve any bleaching effect. This is both economically and practically
disadvantageous. As the bleach solution temperature is lowered below 60°C, peroxide
compounds, e.g. sodium perborate, are rendered ineffective, regardless of the level
of peroxide compound added to the system. The temperature dependency of peroxide compounds
is significant because such bleach compounds are commonly used as a detergent adjuvant
in textile wash processes that utilize an automatic household washing machine operating
at wash water temperatures of below 60°C. Such wash temperatures are utilized because
of textile care and energy considerations. Consequently, a constant need has developed
of substances which render peroxide compound bleaches more effective at bleach solution
temperatures below 60°C. These substances are generally referred to in the art as
bleach precursors, promoters or activators.
[0003] Typically, the precursor is a reactive compound of the N-acyl or O-acyl type such
as a carboxylic acid ester that in alkaline solution containing a source of hydrogen
peroxide, e.g. a persalt, such as sodium perborate, will generate the corresponding
peroxyacid, which is more reactive than peroxide compounds alone. The reaction involves
nucleophilic substitution on to the precursor molecule by perhydroxide anions (HOO⁻)
and is facilitated by precursors having good leaving groups. Often this reaction is
referred to as perhydrolysis. Numerous substances have been proposed in the art as
effective bleach precursors, promoters or activators, such as disclosed in a series
of articles by Allan H. Gilbert in Detergent Age, June 1967, pages 18-20, July 1967,
pages 30-33, and August 1967, pages 26-27 and 67; and further in GB patents 836,988;
907,356; 1,003,310 and 1,519,351; German patent 3,337,921; EP-A-0185522; EP-A-0174132;
EP-B-0120591; and US patents 4,412,934 and 4,675,393.
[0004] Normally, the precursor is also a hydrolysable material which can react with moisture
and alkaline components of the detergent compositions during storage, forming non-reactive
products. This reaction, referred to as hydrolysis, causes loss of precursor during
storage when incorporated in detergent compositions, the extent of which is highly
dependent upon the ease at which the precursor undergoes the hydrolysis reaction.
[0005] Various means have been proposed in the art to protect the precursor from the aqueous
and alkaline components of the detergent composition during storage. It should be
appreciated, however, that the less stable to hydrolysis the precursor is the more
difficult it will be to achieve adequate protection.
[0006] It is believed that this may be one reason why only a few of the large number of
proposed compounds have found commercial exploitation, of which N,N,N',N'-tetraacetylethylene
diamine (TAED), belonging to the type of N-acyl precursors, is the one most widely
used in practice.
[0007] One drawback of TAED, however, is the sluggishness of the peroxyacid release from
the reaction with the peroxide compound liberating hydrogen peroxide, such as sodium
perborate, sodium percarbonate, sodium persilicate, urea peroxide and the like, resulting
in a non-optimal bleaching effect. TAED can thus be classed as a slow-acting precursor,
which can be incorporated in enzymatic alkaline detergent compositions without undue
stability problems.
[0008] Another drawback of TAED is that its solubility in water is rather poor, i.e. somewhere
in the region of 1%, which is another reason for the non-optimal bleaching performance
of TAED/H₂O₂ systems.
[0009] With the trend towards still lower fabric-washing temperatures, to e.g. 40°C and
below, there is an incentive to improve on the bleaching performance of TAED/peroxide
compound systems. One option is to replace TAED by a more reactive precursor, such
as for example sodium p-acetoxybenzene sulphonate as disclosed in GB patent 846,798.
[0010] EP-A-0098129 is concerned with forming aliphatic peroxy acids in wash solution by
reaction of certain types of peroxyacid precursors with alkaline hydrogen peroxide.
The precursor is added in the form of a detergent additive product comprising the
precursor in combination with a non-particulate flexible substrate.
[0011] EP-A-0241137 is concerned with forming a storage-stable liquid laundry bleach formulation
containing peracid precursors.
[0012] A disadvantage of such more reactive precursors, however, is that they tend to (per)hydrolyse
more readily than tetraacetylethylene diamine (TAED), and hence suffer from a more
severe decomposition problem during storage.
[0013] Another disadvantage of more reactive precursors is that they tend to more readily
attack enzymes, especially proteolytic enzymes, which as a class is an essential ingredient
in the majority of current household fabric-washing compositions.
[0014] Consequently, a constant need has developed of possibly new and better substances
which render peroxide compound bleaches more effective at bleach solution temperatures
in the region of from ambient to about 40°C, without the above drawbacks and disadvantages.
[0015] It has now been found that specific carboxylic acid esters as hereinafter defined
are more reactive bleach precursors than TAED and yet they are surprisingly more stable
to hydrolysis than sodium p-acetoxybenzene sulphonate and more enzyme-friendly, thereby
rendering them suitable for use in enzymatic alkaline fabric-washing detergent compositions.
[0016] The invention therefore provides an improved alkaline fabric-washing composition
comprising a surface-active material, detergency builders, a peroxide compound bleach,
a peroxyacid bleach precursor and a proteolytic enzyme, characterized in that said
peroxyacid bleach precursor is a carboxylic acid ester of the following specific structural
formulae:

wherein R is an unsubstituted alkyl group containing 1 to 4 carbon atoms or a phenyl
group; and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkyl or
hydroxyalkyl substituted ammonium cation.
[0017] Advantageously, the alkaline fabric-washing compositions of the invention comprising
the peroxyacid bleach precursor described herein will have a 2-5 g/l solution pH of
8.5-10.5.
[0018] The use of these carboxylic acid esters in bactericidal compositions is disclosed
in German Patent Application N° 2 701 133. It cannot, however, be expected that these
specific esters are effective bleach precursors usable and of excellent stability
in enzymatic alkaline fabric-washing compositions in conjunction with a peroxide compound
bleach providing improved bleaching performance upon fabrics in the lower wash temperature
region of from ambient to about 40°C.
[0019] The compounds of the invention are much more reactive than TAED and are surprisingly
stable upon storage both alone and when mixed with additional components in alkaline
fabric-washing detergent compositions.
[0020] The following compounds are illustrative of precursors within the present invention:
(I) sodium 4-acetoxy benzoate;
(II) sodium 3-acetoxy benzoate;
(III) sodium 3-benzoyloxy benzoate;
(IV) sodium 4-benzoyloxy benzoate.
[0021] Hydrogen peroxide sources are well known in the art. They include the alkali metal
peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic
persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates
and persulphates. Mixtures of two or more such compounds may also be suitable. Particularly
preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate.
Sodium perborate monohydrate is preferred because it has excellent storage stability
while also dissolving very quickly in aqueous bleaching solutions. Rapid dissolution
is believed to permit formation of higher levels of percarboxylic acid which would
enhance surface bleaching performance.
[0022] Typically, the molar ratio of hydrogen peroxide (or a peroxide compound generating
the equivalent amount of H₂O₂) to precursor will range from 0.5:1 to about 20:1, preferably
1:1 to 15:1, most preferably from 2:1 to 10:1.
[0023] A detergent formulation of the invention containing a bleach system consisting of
an active oxygen-releasing material and the specific carboxylic acid ester as herein
defined will, in addition to surface-active materials, detergency builders and enzymes,
usually also contain other known ingredients of such formulations.
[0024] In the formulation of the invention, the peroxyacid bleach precursor may be present
at a level ranging from about 0.1% to 20% by weight, preferably from 0.5% to 10% by
weight, particularly from 1% to 7.5% by weight, together with a peroxide bleaching
compound, e.g. sodium perborate mono- or tetrahydrate, the amount of which is usually
within the range of from about 2% to 40%, preferably from about 4% to 30%, particularly
from about 10% to 25% by weight.
[0025] The surface-active material may be naturally derived, such as soap, or a synthetic
material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives
and mixtures thereof. Many suitable actives are commercially available and are fully
described in literature, for example in "Surface Active Agents and Detergents", Volumes
I and II, by Schwartz, Perry and Berch. The total level of the surface-active material
may range up to 50% by weight, preferably being from about 1% to 40% by weight of
the composition, most preferably 4% to 25%.
[0026] Synthetic anionic surface actives are usually water-soluble alkali metal salts of
organic sulphates and sulphonates having alkyl radicals containing from 8 to 22 carbon
atoms, the term alkyl being used to include the alkyl portion of higher aryl radicals.
[0027] Examples of suitable synthetic anionic detergent compounds are sodium and ammonium
alkyl sulphates, especially those obtained by sulphating higher (C₈-C₁₈) alcohols
produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C₉-C₂₀)
benzene sulphonates, particularly sodium linear secondary alkyl (C₁₀-C₁₅) benzene
sulphonates; sodium alkyl glyceryl ether sulphates, especially those esters of the
higher alcohols derived from tallow or coconut oil and synthetic alcohols derived
from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates;
sodium and ammonium salts of sulphuric acid esters of higher (C₉-C₁₈) fatty alcohol
alkylene oxide, particularly ethylene oxide, reaction products; the reaction products
of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized
with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine;
alkane monosulphonates such as those derived by reacting alphaolefins (C₈-C₂₀) with
sodium bisulphite and those derived by reacting paraffins with SO₂ and Cl₂ and then
hydrolyzing with a base to produce a random sulphonate; sodium and ammonium C₇-C₁₂
dialkyl sulphosuccinates; and olefin sulphonates, which term is used to describe the
material made by reacting olefins, particularly C₁₀-C₂₀ alpha-olefins, with SO₃ and
then neutralizing and hydrolyzing the reaction product. The preferred anionic detergent
compounds are sodium (C₁₁-C₁₅) alkylbenzene sulphonates, sodium (C₁₆-C₁₈) alkyl sulphates
and sodium (C₁₆-C₁₈) alkyl ether sulphates.
[0028] Examples of suitable nonionic surface-active compounds which may be used, preferably
together with the anionic surface-active compounds, include in particular the reaction
products of alkylene oxides, usually ethylene oxide, with alkyl (C₆-C₂₂) phenols,
generally 5-25 EO, i.e. 5-25 units of ethylene oxide per molecule; the condensation
products of aliphatic (C₈-C₁₈) primary or secondary linear or branched alcohols with
ethylene oxide, generally 6-30 EO, and products made by condensation of ethylene oxide
with the reaction products of propylene oxide and ethylene diamine. Other so-called
nonionic surface actives include alkyl polyglycosides, long chain tertiary amine oxides,
long chain tertiary phosphine oxides and dialkyl sulphoxides.
[0029] Amounts of amphoteric or zwitterionic surface-active compounds 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 detergent compounds are used,
it is generally in small amounts in compositions based on the much more commonly used
synthetic anionic and nonionic actives.
[0030] As stated above, soaps may also be incorporated in the compositions of the invention,
preferably at a level of less than 25% by weight. They are particularly useful at
low levels in binary (soap/anionic) or ternary mixtures together with nonionic or
mixed synthetic anionic and nonionic compound. Soaps which are used are preferably
the sodium, or, less desirably, potassium salts of saturated or unsaturated C₁₀-C₂₄
fatty acids or mixtures thereof. The amount of such soaps can be varied between 0.5%
and 25% by weight, with lower amounts of 0.5% to 5% being generally sufficient for
lather control. Amounts of soap between 2% and 20%, especially between 5% and 10%,
are used to give a beneficial effect on detergency. This is particularly valuable
in compositions used in hard water when the soap acts as a supplementary builder.
[0031] The detergent compositions of the invention also contain a detergency builder. Builder
materials may be selected from 1) calcium sequestrant materials, 2) precipitating
materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
[0032] Examples of calcium sequestrant builder materials include alkali metal polyphosphates,
such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts;
the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic
acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid;
and polyacetal carboxylates as disclosed in US patents 4,144,226 and 4,146,495.
[0033] Examples of precipitating builder materials include sodium orthophosphate, sodium
carbonate and long chain fatty acid soaps.
[0034] 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.
[0035] In particular, the compositions of the invention may contain any one of the organic
or inorganic builder materials, such as sodium or potassium tripolyphosphate, sodium
or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or
sodium carbonate/calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium
citrate, carboxymethyl malonate, carboxymethyloxy succinate and the water-insoluble
crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
[0036] These builder materials may be present at a level of, for example, from 5% to 80%
by weight, preferably from 10% to 60% by weight.
[0037] The proteolytic enzymes which are suitable for use in the present invention are normally
solid, catalytically active protein materials which degrade or alter protein types
of stains when present as in fabric stains in a hydrolysis reaction. They may be of
any suitable origin, such as vegetable, animal, bacterial or yeast origin.
[0038] Proteolytic enzymes or proteases of various qualities and origins and having activity
in various pH ranges of from 4-12 are available and can be used in the composition
of the present invention. Examples of suitable proteolytic enzymes are the subtilisins
which are obtained from particular strains of
B.
subtilis and
B.
licheniformis, such as the commercially available subtilisins Maxatase®, as supplied by Gist-Brocades
N.V., Delft, Holland, and Alcalase®, as supplied by Novo Industri A/S, Copenhagen,
Denmark.
[0039] Particularly suitable is a protease obtained from a strain of Bacillus having maximum
activity throughout the pH range of 8-12, being commercially available e.g. from Novo
Industri A/S under the registered trade names Esperase® and Savinase®. The preparation
of these and analogous enzymes is described in British Patent Specification N° 1,243,784.
[0040] Other examples of suitable proteases are pepsin, trypsin, chymotrypsin, collagenase,
keratinase, elastase, papain, bromelin, carboxypeptidases A and B, aminopeptidase
and aspergillopeptidases A and B.
[0041] The amount of proteolytic enzymes normally used in the composition of the invention
may range from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, depending
upon their activity. They are generally incorporated in the form of granules, prills
or "marumes" in an amount such that the final washing product has proteolytic activity
of from about 2-20 Anson units per kilogram of final product.
[0042] Apart from the components already mentioned, the detergent compositions of the invention
can contain any of the conventional additives in the amounts in which such materials
are normally employed in fabric-washing detergent compositions. Examples of these
additives include lather boosters, such as alkanolamides, particularly the monoethanol
amides derived from palmkernel fatty acids and coconut fatty acids; lather depressants,
such as alkyl phosphates and silicones; anti-redeposition agents, such as sodium carboxymethyl
cellulose and alkyl or substituted alkyl cellulose ethers; peroxide stabilizers, such
as ethylene diemine tetraacetic acid, ethylene diamine tetra (methylene phosphonic
acid) and diethylene triaminepenta (methylene phosphonic acid); fabric-softening agents
including clays, inorganic salts, such as sodium sulphate, and, usually present in
very small amounts, fluorescent agents, perfumes, other enzymes, such as cellulases,
lipases and amylases, germicides and colorants.
[0043] Other useful additives are polymeric materials, such as polyacrylic acid, polyethylene
glycol and the copolymers (meth)acrylic acid and maleic acid, which may also be incorporated
to function as auxiliary builders together with any of the principal detergency builders
such as the polyphosphates, aluminosilicates and the like.
[0044] Generally, for reasons of improving stability and handling, the bleach precursors
will advantageously be presented in the form of particulate bodies comprising said
bleach precursor and a binder or agglomerating agent. Many and diverse methods of
preparing such precursor particulates have been described in various patent literature
documents, such as e.g. in Canadian Patent N° 1,102,966; GB Patent N°1,561,333; US
Patent N° 4,087,369; EP-A-0,240,057; EP-A-0,241,962; EP-A-0,101,634 and EP-A-0,062,523.
Each of these methods may be selected and applied to the bleach precursor of the invention.
[0045] Particulates incorporating the precursors of the present invention are normally added
to the spray-dried portion of the detergent composition with the other dry-mix ingredients,
such as enzymes, inorganic peroxygen bleaches and suds depressants. It will be appreciated,
however, that the detergent composition to which the precursor particulates are added
may itself be made in a variety of ways, such as dry-mixing, agglomeration extrusion,
flaking, etc., such ways being well known to those skilled in the art and not forming
part of the present invention.
[0046] In one specific embodiment, the peroxyacid precursors herein described are particularly
suitable for incorporation in so-called non-aqueous liquid laundry detergent compositions
containing an enzyme together with a peroxide bleaching compound, e.g. sodium perborate,
to impart an effective cleaning and stain-removing capacity to the products on fabrics
and textiles.
[0047] Non-aqueous liquid detergent compositions including paste-like and gelatinous detergent
compositions in which the precursor compounds can be incorporated are known from the
art and various formulations have been proposed, e.g. in US Patents 2,864,770; 2,940,938;
4,772,412; 3,368,977; GB-A-1,205,711; 1,270,040; 1,292,352; 1,370,377; 2,194,536;
DE-A-2,233,771; and EP-A-0,028,849.
[0048] These are compositions which normally comprise a nonaqueous liquid medium with or
without a solid phase dispersed therein. The non-aqueous liquid medium may be a liquid
surfactant, preferably a liquid nonionic surfactant; a non-polar liquid medium, e.g.
liquid paraffin; a polar solvent, e.g. polyols, such as glycerol, sorbitol, ethylene
glycol, optionally combined with low-molecular monohydric alcohols, e.g. ethanol or
isopropanol; or mixtures thereof.
[0049] The solid phase can be builders, alkalis, abrasives, polymers, clays, other solid
ionic surfactants, bleaches, enzymes, fluorescent agents and other usual solid detergent
ingredients.
EXAMPLE I
[0050] The hydrolysis of various bleach precursors was measured by using the following technique.
[0051] 1 gram of sodium lauryl sulphate and 2 grams of sodium metaborate tetrahydrate were
dissolved in 1000 ml of double-distilled deionised water; this solution was used in
the reference cell of the spectrophotometer. To 800 ml of the stirred solution was
added sufficient precursor to give an optical density of 0.4 to 0.8, and the solution
was passed through a flow-cell in the spectrophotometer. The decomposition (hydrolysis)
of the precursor was monitored by measuring the decrease in optical density at the
wavelength of maximum absorbance.
[0052] The following bleach precursors were used:
1) Sodium 1-benzoyloxybenzene-4-sulphonate (BOBS).
2) Sodium p-acetoxybenzene sulphonate (SABS).
3) Sodium 3-benzoyloxy benzoate (S-3-BOB).
4) Sodium 4-benzoyloxy benzoate (S-4-BOB).
[0053] The results are tabulated below:
Table I
Precursor |
Hydrolysis rate constant (/ min.) |
% loss after 60 min. |
1) BOBS |
0.0038 |
20 |
2) SABS |
0.0154 |
57 |
3) S-3-BOB |
0.0022 |
12 |
4) S-4-BOB |
0.0023 |
13 |
[0054] These results confirm that the bleach precursors 3) and 4) as used in the invention
are more stable to hydrolysis than the reactive esters BOBS and SABS.
EXAMPLE II
[0055] The following granular detergent composition was prepared by spray-drying an aqueous
slurry:
Composition |
Parts by weight |
sodium alkyl benzene sulphonate |
6.0 |
C₁₄-₁₅ alcohol / 7 ethylene oxide |
7.0 |
sodium soap |
1.6 |
zeolite |
24.0 |
alkaline silicate |
0.5 |
polyacrylate |
4.0 |
sodium carbonate |
8.0 |
sodium carboxymethyl cellulose |
0.5 |
ethylene diamine tetraacetate |
0.2 |
fluorescer |
0.2 |
salts |
0.7 |
[0056] To this base powder were added 15 parts of sodium perborate monohydrate, an amount
of precursor at a molar ratio of precursor to perborate of 1:9, and 1% by weight of
a proteolytic enzyme (Savinase® T40 marumes).
[0057] Bleaching tests were carried out with the finished powder formulation using different
precursors, in a Tergotometer heat-up wash to 40°C in 24°FH water at a dosage of 5
g/l. Tea-stained test cloths were used as the bleach monitor. The bleaching efficiencies
were determined using an Elrepho reflectometer and the results expressed as ΔR 460*
are shown in the following Table II.
Table II
Precursor |
ΔR 460* |
1) S-4-BOB |
5.3 |
2) S-3-BOB |
6.7 |
3) TAED |
4.5 |
[0058] These results show that both compositions of the invention containing the precursors
1) S-4-BOB and 2) S-3-BOB are superior to TAED in removing tea stains from fabrics
at 40°C.
EXAMPLE III
[0059] Samples of the finished powder formulations of Example II containing perborate, enzyme
and unprotected precursors were stored in open phials at 25°C and 81% R.H. for seven
days.
[0060] Enzyme activities were determined in the stored samples after seven days and compared
with the freshly made samples. The results presented in Table III as percentage loss
of enzyme activity were the average of duplicate storage tests:
Table III
Precursor |
% loss of enzyme activity |
S-4-BOB |
20 |
S-3-BOB |
14 |
TAED |
33 |
[0061] These test results show that the precursors used in the invention are even more compatible
with the enzyme Savinase® T40 than TAED.