Technical Field
[0001] The present invention relates to the field of laundry additive products, designed
to be used in conjunction with a conventional laundry detergent. Such laundry additives
are usually designed to boost the performance of the conventional detergent. The present
laundry additive are provided in the form of a water-soluble sachet comprising at
least two compartments.
Background
[0002] Laundry additive products are well known in the art. Such products have commonly
been used to boost the performance of the conventional, main wash detergent, most
commonly by providing an additional bleaching performance. Conventional laundry additives
are in the form of powders, liquids or gels, however more recently additives in the
form of tablets have been introduced onto the market. Tablets are found to be attractive
to consumers because more precise dosing is possible and wasteful overdosing or underdosing
are reduced. Moreover consumers are attracted to such single dose products because
they are less likely to result in spillage or dripping. However the Applicants have
found that whilst such tablets are preferred by consumers the desire still exists
for a product where the user does not have to come into direct contact with the ingredients
of the composition.
[0003] Thus an object of the present invention is to provide a unit dosage laundry additive
composition, where the user does not come into direct contact with the ingredients
of the composition. This objective is met by a laundry additive sachet comprising
a liquid laundry additive composition.
[0004] A particular problem of using a liquid composition as opposed to a particulate composition
to fill the sachet is that ingredients, especially aggressive ingredients such as
bleaching agents, can either dissolve or damage the materials making up the sachet,
resulting in the premature dissolution of the sachet and release of the liquid laundry
additive composition. Furthermore, some liquid ingredients can simply leak through
the sachet wall, draining the composition from the sachet such that at the time of
use, the amount of laundry additive composition is not the correct dose.
[0005] It has also been the objective of the present invention to provide a laundry additive
product that provides more than one benefit. This objective is achieved by incorporating
different ingredients to provide the different benefits. However it has been found
that these ingredients are not always compatible. In fact in some instances the ingredients
react with each other to the extent that at least one of the ingredients is entirely
consumed prior to use by the consumer. In such instances the performance of the laundry
additive is, of course, aversely affected.
[0006] Hence is has been the object of the present invention to provide a laundry additive
in the form of a sachet comprising at least two compartments and comprising at least
one liquid composition.
Summary of the Invention
[0007] According to the present invention there is provided a laundry additive sachet comprising
one or more liquid compositions, wherein the sachet comprises two or more compartments
made of substantially water-soluble film or sheet material.
[0008] According to a second aspect of the present invention there is provided a process
of treating fabrics with a laundry additive sachet according to the present invention
in conjunction with a conventional laundry detergent in the presence of water.
[0009] According to a further aspect of the present invention there is provided the use
of a sachet according to according to the present invention as a laundry additive.
In addition there is provided the use of a sachet according to the present invention
to clean and/or soften fabric. Finally, there is provided the use of sachet according
to the present invention to clean and/or provide and easy ironing benefit.
Detailed Description of the Invention
Laundry Additive Sachet
[0010] The present invention relates to a laundry additive sachet comprising one or more
liquid compositions, described in more detail later. The sachet comprises at least
two compartments and is made from a substantially water-soluble film or sheet material.
[0011] Sachets comprising liquid or particulate compositions, have been discussed in the
prior art. However the sachets were typically either insoluble such that they could
be removed after the end of the wash, or were unsatisfactorily water-soluble. The
most commonly discussed water-soluble sachets of the prior art are made using polyvinyl
alcohol (PVA). However sachets made using PVA are sensitive to bleaching agents, such
that if a composition, especially a liquid composition comprising a bleaching agent
were to be filled into the sachet, the sachet would degrade and burst prior to use
by the consumer due to the effect of the bleaching agent on the PVA. The Applicants
have addressed this problem by using particulate, bleaching agents in either a particulate
but preferably a liquid matrix.
[0012] The Applicants have also addressed the known problem of PVA sachets gelling on contact
with water. This gelling phenomenon occurs where the outer surface of the PVA sachet
dissolves in water, but instead of dissipating into the surrounding water, it forms
a gel surrounding the sachet, preventing the further dissolution on the sachet. The
result is that the sachet does not totally dissolve, leaving residues of sachet on
the fabrics. The Applicants have found that by using a sachet made using a hydrophobically
modified cellulose polymer for example and most preferably hydroxy propyl methyl cellulose
(HPMC), the problems associated with PVA can be circumvented. HPMC is not only more
bleach stable but also does not produce the gelling phenomenon as seen with PVA and
for these reasons it is preferred to prepare the sachet using HPMC.
[0013] Sachets can be prepared according to the known methods in the art. More specifically,
the sachets are prepared by first cutting an appropriately sized piece of film/sheet.
The fold the sheet to form the necessary number and size of compartments and seal
the edges using any suitable technology, for example heat sealing.
Laundry Additive Composition
[0014] The sachet as described above comprises at least two compartments. At least one of
the compartments is filled, at least to some extent, with at least one liquid laundry
additive composition. The other compartment may be filled with the same or a different
liquid composition, or alternatively a particulate composition. Most preferably the
compartments are filled, at least to some extent with different composition. By the
term "different composition" it is meant that the first and/or second compositions
comprise at least one ingredient that is not preset in the other composition.
[0015] In the embodiment wherein the sachet comprises a third or subsequent compartment,
the compartment(s) may be filled at least to some extent with a third or subsequent
composition which is different to any of the other composition, for example the first
or second composition, in the case where a third composition exists.
[0016] In one preferred embodiment the first composition is a liquid or particulate, preferably
particulate composition comprising ingredients selected from the group listed under
laundry Additive Ingredients.
The second composition comprises a bleaching agent, different from that in the first
composition if present, and is in liquid form. Bleaching agents are described in more
detail below, however the preferred bleaching agent for use in the second composition
of this embodiment is a particulate peracid. In an even more preferred embodiment
the peracid is selected from the range of pre-formed mono peroxycarboxylic acid described
in more detail below. In an even more preferred embodiment the pre-formed peracid
is phthaloyl amido peroxyhexanoic acid, known as PAP. The pre-formed peracid is preferably
used in particulate form, and is then suspended in a liquid matrix. The liquid matrix
where present is substantially non-aqueous meaning that it does not comprise a level
of water that would result in the dissolution of the material making up the sachet.
The Applicants have found that the preferred ingredients used to suspend the PAP (suspending
agents) are solvents which do not either dissolve or damage the material making up
the sachet over time. More preferably the suspending agent is a long chain, low polarity
solvent. By long chain it is meant solvents comprising a carbon chain of greater than
6 carbon atoms and by low polarity it is meant a solvent having a dielectric constant
of less than 40. Preferred solvents include C12-14 paraffin and more preferably C12-14
isoparaffin. The benefit of the present embodiment is the significant improvement
in bleachable soil removal provided by the laundry additive.
[0017] In an alternative and equally preferred embodiment the second composition is the
same as that described above, however the first composition is a fabric softening
composition, comprising an ingredient which softens fabric and also renders the fabrics
treated easier to iron. The first composition of this embodiment may be in liquid,
but is preferably in particulate form. The softening ingredient can be present in
an amount of from 20% to 80% by weight of the first composition. Remaining ingredients
can be selected from any of those listed under Laundry Additive Ingredients.
[0018] Equally it is envisaged that the preceding embodiment may be altered such that the
performance delivering ingredient in the first composition instead of a softening
ingredient is for example, one or more enzymes, especially carezyme, an organic polymeric
compound, soil suspending polymer, dye transfer inhibitor a brightener and mixtures
thereof.
[0019] In a further alternative embodiment it is also preferable to manufacture a sachet
laundry additive following the same compositional structure as that described in the
first embodiment above, in which an additional element other than a softening ingredient,
for example as defined in the preceding paragraph may be added to the first, second
or first and second compositions.
[0020] The liquid composition of the present invention, where used to suspend a particulate
component, may also comprise other structuring ingredients in order to stabilise the
matrix. A preferred structuring agent is a combination of sodium alkyl benzene sulphonate
(LAS) and sodium sulphate which has been dehydrated to form a crystalline structure.
[0021] Fabrics treated with the compositions of the present inventions comprising a softening
ingredient not only improve the softness of the fabrics, but also make the fabrics
easier to iron. This easy ironing benefit is perceived as the fabrics not only having
less wrinkles, but also as the wrinkles being easier to remove for example when ironing.
Laundry Additive Ingredients
[0022] The compositions used may include a variety of different ingredients including builder
compounds, surfactants, enzymes, bleaching agents, alkalinity sources, colourants,
perfume, lime soap dispersants, organic polymeric compounds including polymeric dye
transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants,
metal ion salts, enzyme stabilisers, corrosion inhibitors, suds suppressers, solvents,
fabric softening agents, optical brighteners and hydrotropes.
Builder compound
[0023] The compositions of the present invention preferably contain a builder compound,
typically present at a level of from 1% to 80% by weight, preferably from 10% to 70%
by weight, most preferably from 20% to 60% by weight of the composition of active
detergent components.
Water-soluble builder compound
[0024] Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates,
or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which
the polycarboxylic acid comprises at least two carboxylic radicals separated from
each other by not more that two carbon atoms, carbonates, bicarbonates, borates, phosphates,
and mixtures of any of the foregoing.
[0025] The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type
although monomeric polycarboxylates are generally preferred for reasons of cost and
performance.
[0026] Suitable carboxylates containing one carboxy group include the water soluble salts
of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing
two carboxy groups include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic
acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
Polycarboxylates containing three carboxy groups include, in particular, water-soluble
citrates, aconitrates and citraconates as well as succinate derivatives such as the
carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates
described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands
Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane
tricarboxylates described in British Patent No. 1,387,447.
[0027] Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed
in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent
Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed citrates described in British Patent No. 1,439,000.
[0028] Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates,
cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates,
2,5-tetrahydrofuran - cis-dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates,
1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols
such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic
acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent
No. 1,425,343.
[0029] Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up
to three carboxy groups per molecule, more particularly citrates.
[0030] The parent acids of the monomeric or oligomeric polycarboxylate chelating agents
or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures
are also contemplated as useful builder components.
[0031] Borate builders, as well as builders containing borate-forming materials that can
produce borate under detergent storage or wash conditions can also be used but are
not preferred at wash conditions less that 50°C, especially less than 40°C.
[0032] Examples of carbonate builders are the alkaline earth and alkali metal carbonates,
including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine
calcium carbonate as disclosed in German Patent Application No. 2,321,001 published
on November 15, 1973.
[0033] Highly preferred builder compounds for use in the present invention are water-soluble
phosphate builders. Specific examples of water-soluble phosphate builders are the
alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium
and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium
polymeta/phosphate in which the degree of polymerisation ranges from 6 to 21, and
salts of phytic acid.
[0034] Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates,
sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate,
sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree
of polymerization ranges from 6 to 21, and salts of phytic acid.
Partially soluble or insoluble builder compound
[0035] The compositions of the present invention, especially those in particulate form,
may contain a partially soluble or insoluble builder compound. Examples of partially
water soluble builders include the crystalline layered silicates as disclosed for
example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043. Preferred are the crystalline
layered sodium silicates of general formula
NaMSi
xO
2+1 .yH
2O
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from
0 to 20. Crystalline layered sodium silicates of this type preferably have a two dimensional
'sheet' structure, such as the so called δ-layered structure, as described in EP 0
164514 and EP 0 293640. Methods for preparation of crystalline layered silicates of
this type are disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the present
invention, x in the general formula above has a value of 2,3 or 4 and is preferably
2.
[0036] The most preferred crystalline layered sodium silicate compound has the formula δ-Na
2Si
2O
5, known as NaSKS-6 (trade name), available from Hoechst AG.
[0037] The crystalline layered sodium silicate material is preferably present in granular
detergent compositions as a particulate in intimate admixture with a solid, water-soluble
ionisable material as described in PCT Patent Application No. WO92/18594. The solid,
water-soluble ionisable material is selected from organic acids, organic and inorganic
acid salts and mixtures thereof, with citric acid being preferred.
[0038] Examples of largely water insoluble builders include the sodium aluminosilicates.
Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell
formula Na
z[(AlO
2)
z(SiO
2)y]. xH
2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and
x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate
material are in hydrated form and are preferably crystalline, containing from 10%
to 28%, more preferably from 18% to 22% water in bound form.
[0039] The aluminosilicate zeolites can be naturally occurring materials, but are preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials
are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite
HS and mixtures thereof.
[0040] A preferred method of synthesizing aluminosilicate zeolites is that described by
Schoeman et al (published in Zeolite (1994) 14(2), 110-116), in which the author describes
a method of preparing colloidal aluminosilicate zeolites. The colloidal aluminosilicate
zeolite particles should preferably be such that no more than 5% of the particles
are of size greater than 1µm in diameter and not more than 5% of particles are of
size less then 0.05 µm in diameter. Preferably the aluminosilicate zeolite particles
have an average particle size diameter of between 0.01µm and 1µm, more preferably
between 0.05 µm and 0.9 µm, most preferably between 0.1µm and 0.6µm.
[0041] Zeolite A has the formula
Na
12 [AlO
2)
12 (SiO
2)
12]. xH
2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na
86 [(AlO
2)
86(SiO
2)
106]. 276 H
2O. Zeolite MAP, as disclosed in EP-B-384,070 is a preferred zeolite builder herein.
[0042] Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. When
employed as a component of a detergent composition colloidal aluminosilicate zeolites,
especially colloidal zeolite A, provide enhanced builder performance in terms of providing
improved stain removal. Enhanced builder performance is also seen in terms of reduced
fabric encrustation and improved fabric whiteness maintenance; problems believed to
be associated with poorly built detergent compositions.
[0043] A surprising finding is that mixed aluminosilicate zeolite detergent compositions
comprising colloidal zeolite A and colloidal zeolite Y provide equal calcium ion sequestration
performance versus an equal weight of commercially available zeolite A. Another surprising
finding is that mixed aluminosilicate zeolite detergent compositions, described above,
provide improved magnesium ion sequestration performance versus an equal weight of
commercially available zeolite A.
Surfactant
[0044] Suitable surfactants are selected from anionic, cationic, nonionic ampholytic and
zwitterionic surfactants and mixtures thereof. The surfactant is typically present
at a level of from 0.2% to 30% by weight, more preferably from 0.5% to 10% by weight,
most preferably from 1% to 5% by weight of the composition of active detergent components.
[0045] A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and
species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and
Heuring on December, 30, 1975. A list of suitable cationic surfactants is given in
U.S.P. 4,259,217 issued to Murphy on March 31,1981. A listing of surfactants typically
included in laundry detergent compositions is given for example, in EP-A-0414 549
and PCT Applications No.s WO 93/08876 and WO 93/08874.
Nonionic surfactant
[0046] Essentially any nonionic surfactants useful for detersive purposes can be included
in thecompositions. Preferred, non-limiting classes of useful nonionic surfactants
are listed below.
Nonionic ethoxylated alcohol surfactant
[0047] The alkyl ethoxylate condensation products of aliphatic alcohols with from 1 to 25
moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic
alcohol can either be straight or branched, primary or secondary, and generally contains
from 6 to 22 carbon atoms. Particularly preferred are the condensation products of
alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to
10 moles of ethylene oxide per mole of alcohol.
End-capped alkyl alkoxylate surfactant
[0048] A suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped poly(oxyalkylated)
alcohols represented by the formula:

wherein R
1 is a linear or branched, aliphatic hydrocarbon radical having from 4 to 18 carbon
atoms; R
2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon
atoms; x is an integer having an average value of from 0.5 to 1.5, more preferably
1; and y is an integer having a value of at least 15, more preferably at least 20.
[0049] Preferably, the surfactant of formula I, at least 10 carbon atoms in the terminal
epoxide unit [CH
2CH(OH)R
2]. Suitable surfactants of formula I, according to the present invention, are Olin
Corporation's POLY-TERGENT® SLF-18B nonionic surfactants, as described, for example,
in WO 94/22800, published October 13, 1994 by Olin Corporation.
Ether-capped poly(oxyalkylated) alcohols
[0050] Preferred surfactants for use herein include ether-capped poly(oxyalkylated) alcohols
having the formula:
R
1O[CH
2CH(R
3)O]
x[CH
2]
kCH(OH)[CH
2]
jOR
2
wherein R
1 and R
2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon
radicals having from 1 to 30 carbon atoms; R
3 is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms;
x is an integer having an average value from 1 to 30, wherein when x is 2 or greater
R
3 may be the same or different and k and j are integers having an average value of
from 1 to 12, and more preferably 1 to 5.
[0051] R
1 and R
2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic
hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18 carbon atoms being
most preferred. H or a linear aliphatic hydrocarbon radical having from 1 to 2 carbon
atoms is most preferred for R
3. Preferably, x is an integer having an average value of from 1 to 20, more preferably
from 6 to 15.
[0052] As described above, when, in the preferred embodiments, and x is greater than 2,
R
3 may be the same or different. That is, R
3 may vary between any of the alklyeneoxy units as described above. For instance, if
x is 3, R
3may be be selected to form ethlyeneoxy(EO) or propyleneoxy(PO) and may vary in order
of (EO)(PO)(EO), (EO)(EO)(PO); (EO)(EO)(EO); (PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO).
Of course, the integer three is chosen for example only and the variation may be much
larger with a higher integer value for x and include, for example, mulitple (EO) units
and a much small number of (PO) units.
[0053] Particularly preferred surfactants as described above include those that have a low
cloud point of less than 20°C. These low cloud point surfactants may then be employed
in conjunction with a high cloud point surfactant as described in detail below for
superior grease cleaning benefits.
[0054] Most preferred ether-capped poly(oxyalkylated) alcohol surfactants are those wherein
k is 1 and j is 1 so that the surfactants have the formula:
R
1O[CH
2CH(R
3)O]
xCH
2CH(OH)CH
2OR
2
where R
1, R
2 and R
3 are defined as above and x is an integer with an average value of from 1 to 30, preferably
from 1 to 20, and even more preferably from 6 to 18. Most preferred are surfactants
wherein R
1 and R
2 range from 9 to 14, R
3 is H forming ethyleneoxy and x ranges from 6 to 15.
[0055] The ether-capped poly(oxyalkylated) alcohol surfactants comprise three general components,
namely a linear or branched alcohol, an alkylene oxide and an alkyl ether end cap.
The alkyl ether end cap and the alcohol serve as a hydrophobic, oil-soluble portion
of the molecule while the alkylene oxide group forms the hydrophilic, water-soluble
portion of the molecule.
[0056] These surfactants exhibit significant improvements in spotting and filming characteristics
and removal of greasy soils, when used in conjunction with high cloud point surfactants,
relative to conventional surfactants.
[0057] Generally speaking, the ether-capped poly(oxyalkylene) alcohol surfactants of the
present invention may be produced by reacting an aliphatic alcohol with an epoxide
to form an ether which is then reacted with a base to form a second epoxide. The second
epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of
the present invention. Examples of methods of preparing the ether-capped poly(oxyalkylated)
alcohol surfactants are described below:
Nonionic ethoxylated/propoxylated fatty alcohol surfactant
[0058] The ethoxylated C
6-C
18 fatty alcohols and C
6-C
18 mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein,
particularly where water soluble. Preferably the ethoxylated fatty alcohols are the
C
10-C
18 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably
these are the C
12-C
18 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. Preferably
the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from
10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation
of from 1 to 10.
Nonionic EO/PO condensates with propylene glycol
[0059] The condensation products of ethylene oxide with a hydrophobic base formed by the
condensation of propylene oxide with propylene glycol are suitable for use herein.
The hydrophobic portion of these compounds preferably has a molecular weight of from
1500 to 1800 and exhibits water insolubility. Examples of compounds of this type include
certain of the commercially-available Pluronic™ surfactants, marketed by BASF.
Nonionic EO condensation products with propylene oxide/ethylene diamine adducts
[0060] The condensation products of ethylene oxide with the product resulting from the reaction
of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic
moiety of these products consists of the reaction product of ethylenediamine and excess
propylene oxide, and generally has a molecular weight of from 2500 to 3000. Examples
of this type of nonionic surfactant include certain of the commercially available
Tetronic™ compounds, marketed by BASF.
Anionic surfactant
[0061] Essentially any anionic surfactants useful for detersive purposes are suitable. These
can include salts (including, for example, sodium, potassium, ammonium, and substituted
ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate,
sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are
preferred.
[0062] Other anionic surfactants include the isethionates such as the acyl isethionates,
N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates 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), N-acyl sarcosinates. 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 tallow oil.
Anionic sulfate surfactant
[0063] Anionic sulfate surfactants suitable for use herein include the linear and branched
primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol
sulfates, alkyl phenol ethylene oxide ether sulfates, the C
5-C
17 acyl-N-(C
1-C
4 alkyl) and -N-(C
1-C
2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described
herein).
[0064] Alkyl sulfate surfactants are preferably selected from the linear and branched primary
C
10-C
18 alkyl sulfates, more preferably the C
11-C
15 branched chain alkyl sulfates and the C
12-C
14 linear chain alkyl sulfates.
[0065] Alkyl ethoxysulfate surfactants are preferably selected from the group consisting
of the C
10-C
18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene
oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C
11-C
18, most preferably C
11-C
15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to
5, moles of ethylene oxide per molecule.
[0066] A particularly preferred aspect of the invention employs mixtures of the preferred
alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed
in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactant
[0067] Anionic sulfonate surfactants suitable for use herein include the salts of C
5-C
20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C
6-C
22 primary or secondary alkane sulfonates, C
6-C
24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty
acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Anionic carboxylate surfactant
[0068] Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the
alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially
certain secondary soaps as described herein.
[0069] Suitable alkyl ethoxy carboxylates include those with the formula RO(CH
2CH
20)
x CH
2C00
-M
+ wherein R is a C
6 to C
18 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that,
on a weight basis, the amount of material where x is 0 is less than 20 % and M is
a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having
the formula RO-(CHR
1-CHR
2-O)-R
3 wherein R is a C
6 to C
18 alkyl group, x is from 1 to 25, R
1 and R
2 are selected from the group consisting of hydrogen, methyl acid radical, succinic
acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R
3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon
having between 1 and 8 carbon atoms, and mixtures thereof.
[0070] Suitable soap surfactants include the secondary soap surfactants which contain a
carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants
for use herein are water-soluble members selected from the group consisting of the
water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic
acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also
be included as suds suppressors.
Alkali metal sarcosinate surfactant
[0071] Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON
(R
1) CH
2 COOM, wherein R is a C
5-C
17 linear or branched alkyl or alkenyl group, R
1 is a C
1-C
4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and
oleoyl methyl sarcosinates in the form of their sodium salts.
Amphoteric surfactant
[0072] Suitable amphoteric surfactants for use herein include the amine oxide surfactants
and the alkyl amphocarboxylic acids.
[0073] Suitable amine oxides include those compounds having the formula R
3(OR
4)
xN
0(R
5)
2 wherein R
3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group,
or mixtures thereof, containing from 8 to 26 carbon atoms; R
4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures
thereof; x is from 0 to 5, preferably from 0 to 3; and each R
5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide
group containing from 1 to 3 ethylene oxide groups. Preferred are C
10-C
18 alkyl dimethylamine oxide, and C
10-18 acylamido alkyl dimethylamine oxide.
[0074] A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc. manufactured
by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
[0075] Zwitterionic surfactants can also be incorporated into the detergent compositions
hereof. These surfactants can be broadly described as derivatives of secondary and
tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives
of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine
and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
[0076] Suitable betaines are those compounds having the formula R(R')
2N
+R
2COO-wherein R is a C
6-C
18 hydrocarbyl group, each R
1 is typically C
1-C
3 alkyl, and R
2 is a C
1-C
5 hydrocarbyl group. Preferred betaines are C
12-18 dimethylammonio hexanoate and the C
10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants
are also suitable for use herein.
Cationic surfactants
[0077] Cationic ester surfactants used in this invention are preferably water dispersible
compound having surfactant properties comprising at least one ester (i.e.-COO-) linkage
and at least one cationically charged group. Other suitable cationic ester surfactants,
including choline ester surfactants, have for example been disclosed in US Patents
No.s 4228042, 4239660 and 4260529.
[0078] Suitable cationic surfactants include the quaternary ammonium surfactants selected
from mono C
6-C
16, preferably C
6-C
10 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted
by methyl, hydroxyethyl or hydroxypropyl groups.
Softening Ingredient
[0079] The softening ingredients of the present invention may be selected from any known
ingredients that provides a fabric softening benefit.
[0080] Clay minerals used to provide the softening properties of the instant compositions
can be described as expandable, three-layer clays, i.e., alumino-silicates and magnesium
silicates, having an ion exchange capacity of at least 50 meq/100g. of clay. The term
"expandable" as used to describe clays relates to the ability of the layered clay
structure to be swollen, or expanded, on contact with water. The three-layer expandable
clays used herein are those materials classified geologically as smectites.
[0081] There are two distinct classes of smectite-type clays; in the first, aluminum oxide
is present in the silicate crystal lattice; in the second class of smectites, magnesium
oxide is present in the silicate crystal lattice. The general formulas of these smectites
are Al
2(Si
2O
5)
2(OH)
2 and Mg
3(Si
2O
5) (OH)
2 for the aluminum and magnesium oxide type clay, respectively. It is to be recognised
that the range of the water of hydration in the above formulas can vary with the processing
to which the clay has been subjected. This is immaterial to the use of the smectite
clays in the present invention in that the expandable characteristics of the hydrated
clays are dictated by the silicate lattice structure. Furthermore, atom substitution
by iron and magnesium can occur within the crystal lattice of the smectites, while
metal cations such as Na
+, Ca
++, as well as H+, can be co-present in the water of hydration to provide electrical
neutrality. Except as noted hereinafter, such cation substitutions are immaterial
to the use of the clays herein since the desirable physical properties of the clays
are not substantially altered thereby.
[0082] The three-layer, expandable alumino-silicates useful herein are further characterised
by a dioctahedral crystal lattice, while the expandable three-layer magnesium silicates
have a trioctahedral crystal lattice.
[0083] As noted herein above, the clays employed in the compositions of the instant invention
contain cationic counterions such as protons, sodium ions, potassium ions, calcium
ion, magnesium ion, and the like. It is customary to distinguish between clays on
the basis of one cation predominantly or exclusively absorbed. For example, a sodium
clay is one in which the absorbed cation is predominantly sodium. Such absorbed cations
can become involved in exchange reactions with cations present in aqueous solutions.
A typical exchange reaction involving a smectite-type clay is expressed by the following
equation:
smectite clay (Na) + NH
4OH → smectite clay (NH
4) + NaOH.
[0084] Since in the foregoing equilibrium reaction, one equivalent weight of ammonium ion
replaces an equivalent weight of sodium, it is customary to measure cation exchange
capacity (sometimes termed "base exchange capacity") in terms of milliequivalents
per 100 g. of clay (meq./100 g.). The cation exchange capacity of clays can be measured
in several ways, including by electrodialysis, by exchange with ammonium ion followed
by titration or by a methylene blue procedure, all as fully set forth in Grimshaw,
"The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971). The cation
exchange capacity of a clay mineral relates to such factors as the expandable properties
of the clay, the charge of the clay, which, in turn, is determined at least in part
by the lattice structure, and the like. The ion exchange capacity of clays varies
widely in the range from about 2 meq/100 g. for kaolinites to about 150 meq/100 g.,
and greater, for certain clays of the montmorillonite variety. Illite clays have an
ion exchange capacity somewhere in the lower portion of the range, i.e., around 26
meq/100 g. for an average illite clay.
[0085] Illite and kaolinite clays, with their relatively low ion exchange capacities, are
preferably not used as the clay in the instant compositions. Indeed, such illite and
kaolinite clays constitute a major component of clay soils and, as noted above, are
removed from fabric surfaces by means of the instant compositions. However, smectites,
such as nontonite, having an ion exchange capacity of around 70 meq/100 g., and montmorillonite,
which has an ion exchange capacity greater than 70 meq/100 g., have been found to
be useful in the instant compositions in that they are deposited on the fabrics to
provide the desired softening benefits. Accordingly, clay minerals useful herein can
be characterised as expandable, three-layer smectite-type clays having an ion exchange
capacity of at least about 50 meq/100 g.
[0086] While not intending to be limited by theory, it appears that advantageous softening
(and potentially dye scavenging, etc.) benefits of the instant compositions are obtainable
and are ascribable to the physical characteristics and ion exchange properties of
the clays used therein. That is to say, experiments have shown that non-expandable
clays such as the kaolinites and the illites, which are both classes of clays having
an ion exchange capacities below 50 meq/100 g., do not provide the beneficial aspects
of the clays employed in the instant compositions.
[0087] The smectite clays used in the compositions herein are all commercially available.
Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite,
saponite, sauconite, and vermiculite. The clays herein are available under various
tradenames, for example, Thixogel #1® and Gelwhite GP® from Georgia Kaolin Co., Elizabeth,
New Jersey; Volclay BC® and Volclay #325®, from American Colloid Co., Skokie, Illinois;
Black Hills Bentonite BH450®, from International Minerals and Chemicals; and Veegum
Pro and Veegum F, from R.T. Vanderbilt. It is to be recognised that such smectite-type
minerals obtained under the foregoing tradenames can comprise mixtures of the various
discrete mineral entities. Such mixtures of the smectite minerals are suitable for
use herein.
[0088] While any of the smectite-type clays having a cation exchange capacity of at least
about 50 meq/100 g. are useful herein, certain clays are preferred. For example, Gelwhite
GP® is an extremely white form of smectite clay and is therefore preferred when formulating
white granular detergent compositions. Volclay BC®, which is a smectite-type clay
mineral containing at least 3% of iron (expressed as Fe
2O
3) in the crystal lattice, and which has a very high ion exchange capacity, is one
of the most efficient and effective clays for use in laundry compositions and is preferred
from the standpoint of product performance.
[0089] Appropriate clay minerals for use herein can be selected by virtue of the fact that
smectites exhibit a true 14Å x-ray diffraction pattern. This characteristic pattern,
taken in combination with exchange capacity measurements performed in the manner noted
above, provides a basis for selecting particular smectite-type minerals for use in
the granular detergent compositions disclosed herein.
[0090] The clay is preferably mainly in the form of granules, with at least 50%, preferably
at least 75%, and more preferable at least 90% being in the form of granules having
a size of at least 0.1 mm up to 1.8 mm, preferably up to 1.18 mm, preferably from
0.15 mm to 0.85 mm. Preferably the amount of clay in the granules is at least 50%,
more preferably at least 70% and most preferably at least 90% by weight of the granules.
[0091] Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632
and 4,062,647. European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of
the Procter and Gamble Company describe suitable organic polymeric clay flocculating
agents.
[0092] Other suitable softening ingredients are long chained polymers and copolymers derived
from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl
methacrylate, vinyl alcohol, vinyl pyrrolidone and ethylene imide. Preferred are polymers
of ethylene oxide, acrylamide and acrylic acid. These polymers preferably have average
molecular weight in the range of from 100 000 to 10 million, more preferably from
150 000 to 5 million. Average molecular weight of a polymer can be easily measured
using gel permeation chromatography, against standards of polyethylene oxide of narrow
molecular weight distributions. The most preferred polymers are polyethylene oxides.
[0093] Other suitable softening ingredients include cationic fabric softening agents can
also be incorporated into compositions in accordance with the present invention which
are suitable for use in methods of laundry washing. Suitable cationic fabric softening
agents include the water insoluble tertiary amines or dilong chain amide materials
as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
Enzymes
[0094] Where present said enzymes are selected from the group consisting of cellulases,
hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, lipases,
phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases,
phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases,
β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.
[0095] Preferred enzymes include protease, amylase, lipase, peroxidases, cutinase and/or
cellulase in conjunction with one or more plant cell wall degrading enzymes.
[0096] The cellulases usable in the present invention include both bacterial or fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 12 and an activity above
50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent
4,435,307, Barbesgoard et al, J61078384 and W096/02653 which disclose fungal cellulases
produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases
are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95/26398.
[0097] Examples of such cellulases are cellulases produced by a strain of Humicola insolens
(Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. Other
suitable cellulases are cellulases originated from Humicola insolens having a molecular
weight of 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a
~43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase
activity; a preferred endoglucanase component has the amino acid sequence disclosed
in PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGIII
cellulases from Trichoderma longibrachiatum described in WO94/21801, Genencor, published
September 29, 1994. Especially suitable cellulases are the cellulases having color
care benefits. Examples of such cellulases are cellulases described in European patent
application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme
(Novo Nordisk A/S) are especially useful. See also WO91/17244 and WO91/21801. Other
suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092,
WO96/17994 and WO95/24471.
[0098] Said cellulases are normally incorporated in the detergent composition at levels
from 0.0001% to 2% of active enzyme by weight of the detergent composition.
[0099] Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate,
perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching",
i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations
to other substrates in the wash solution. Peroxidase enzymes are known in the art,
and include, for example, horseradish peroxidase, ligninase and haloperoxidase such
as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are
disclosed, for example, in PCT International Application WO 89/099813, WO89/09813
and in European Patent application EP No. 91202882.6, filed on
[0100] November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is
the laccase enzyme.
[0101] Preferred enhancers are substitued phenthiazine and phenoxasine 10-Phenothiazinepropionicacid
(PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid
(POP) and 10-methylphenoxazine (described in WO 94/12621) and substitued syringates
(C3-C5 substitued alkyl syringates) and phenols. Sodium percarbonate or perborate
are preferred sources of hydrogen peroxide.
[0102] Said cellulases and/or peroxidases are normally incorporated in the detergent composition
at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
[0103] Other preferred enzymes that can be included in the detergent compositions of the
present invention include lipases. Suitable lipase enzymes for detergent usage include
those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri
ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those
which show a positive immunological cross-reaction with the antibody of the lipase,
produced by the microorganism
Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,
under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P". Other
suitable commercial lipases include Amano-CES, lipases ex
Chromobacter viscosum, e.g.
Chromobacter viscosum var.
lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and
lipases ex
Pseudomonas gladioli. Especially suitable lipases are lipases such as M1 Lipase
R and Lipomax
R (Gist-Brocades) and Lipolase
R and Lipolase Ultra
R(Novo) which have found to be very effective when used in combination with the compositions
of the present invention. Also suitables are the lipolytic enzymes described in EP
258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381
and WO 96/00292 by Unilever.
[0104] Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind
of lipase, namely lipases which do not require interfacial activation. Addition of
cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor);
WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).
[0105] The lipases and/or cutinases are normally incorporated in the detergent composition
at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
[0106] Suitable proteases are the subtilisins which are obtained from particular strains
of B.
subtilis and
B. licheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of
Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE®
by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme
and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases
include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE®
and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades. Proteolytic enzymes
also encompass modified bacterial serine proteases, such as those described in European
Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages
17, 24 and 98), and which is called herein "Protease B", and in European Patent Application
199,404, Venegas, published October 29, 1986, which refers to a modified bacterial
serine protealytic enzyme which is called "Protease A" herein. Suitable is what is
called herein "Protease C", which is a variant of an alkaline serine protease from
Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position
104, serine replaced asparagine at position 123, and alanine replaced threonine at
position 274. Protease C is described in EP 90915958:4, corresponding to WO 91/06637,
Published May 16, 1991. Genetically modified variants, particularly of Protease C,
are also included herein.
[0107] A preferred protease referred to as "Protease D" is a carbonyl hydrolase variant
having an amino acid sequence not found in nature, which is derived from a precursor
carbonyl hydrolase by substituting a different amino acid for a plurality of amino
acid residues at a position in said carbonyl hydrolase equivalent to position +76,
preferably also in combination with one or more amino acid residue positions equivalent
to those selected from the group consisting of +99, +101, +103, +104, +107, +123,
+27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216,
+217, +218, +222, +260, +265, and/or +274 according to the numbering of
Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C. Ghosh,
et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No. 08/322,677,
filed October 13, 1994.
[0108] Also suitable for the present invention are proteases described in patent applications
EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants
described in WO 95/23221.
[0109] See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140
A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and
a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired,
a protease having decreased adsorption and increased hydrolysis is available as described
in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents
suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are
described in EP 516 200 by Unilever.
[0110] Other preferred protease enzymes include protease enzymes which are a carbonyl hydrolase
variant having an amino acid sequence not found in nature, which is derived by replacement
of a plurality of amino acid residues of a precursor carbonyl hydrolase with different
amino acids, wherein said plurality of amino acid residues replaced in the precursor
enzyme correspond to position +210 in combination with one or more of the following
residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132,
+135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the
numbered positions correspond to naturally-occurring subtilisin from
Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins
(such as
Bacillus lentus subtilisin). Preferred enzymes of this type include those having position changes
+210, +76, +103, +104, +156, and +166.
[0111] The proteolytic enzymes are incorporated in the detergent compositions of the present
invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably
from 0.005% to 0.1% pure enzyme by weight of the composition.
[0112] Amylases (α and/or β) can be included for removal of carbohydrate-based stains. WO94/02597,
Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which
incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April
20, 1995. Other amylases known for use in cleaning compositions include both α- and
β-amylases. α-Amylases are known in the art and include those disclosed in US Pat.
no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341;
and British Patent specification no. 1,296,839 (Novo). Other suitable amylases are
stability-enhanced amylases described in WO94/18314, published August 18, 1994 and
WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional
modification in the immediate parent available from Novo Nordisk A/S, disclosed in
WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216,
W095/26397 and W096/23873 (all by Novo Nordisk).
[0113] Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and
Termamyl® , Ban® ,Fungamyl® and Duramyl® , Natalase ® all available from Novo Nordisk
A/S Denmark. WO95/26397 describes other suitable amylases : α-amylases characterised
by having a specific activity at least 25% higher than the specific activity of Termamyl®
at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10,
measured by the Phadebas® α-amylase activity assay. Suitable are variants of the above
enzymes, described in WO96/23873 (Novo Nordisk). Other amylolytic enzymes with improved
properties with respect to the activity level and the combination of thermostability
and a higher activity level are described in WO95/35382.
[0114] Preferred amylase enzymes include those described in WO95/26397 and in co-pending
application by Novo Nordisk PCT/DK96/00056.
[0115] The amylolytic enzymes are incorporated in the detergent compositions of the present
invention a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably
from 0.00024% to 0.048% pure enzyme by weight of the composition
[0116] In a particularly preferred embodiment, the compositions of the present invention
comprise amylase enzymes, particularly those described in WO95/26397 and co-pending
application by Novo Nordisk PCT/DK96/00056 in combination with a complementary amylase.
[0117] By "complementary" it is meant the addition of one or more amylase suitable for detergency
purposes. Examples of complementary amylases (α and/or β) are described below. WO94/02597
and WO95/10603, Novo Nordisk A/S describe cleaning compositions which incorporate
mutant amylases. Other amylases known for use in cleaning compositions include both
α- and β-amylases. α-Amylases are known in the art and include those disclosed in
US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610;
EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other suitable
amylases are stability-enhanced amylases described in WO94/18314, and W096/05295,
Genencor and amylase variants having additional modification in the immediate parent
available from Novo Nordisk A/S, disclosed in WO 95/10603. Also suitable are amylases
described in EP 277 216 (Novo Nordisk). Examples of commercial α-amylases products
are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl® , all
available from Novo Nordisk A/S Denmark. WO95/26397 describes other suitable amylases
: α-amylases characterised by having a specific activity at least 25% higher than
the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a
pH value in the range of 8 to 10, measured by the Phadebas® α-amylase activity assay.
Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk).
Other amylolytic enzymes with improved properties with respect to the activity level
and the combination of thermostability and a higher activity level are described in
WO95/35382. Preferred complementary amylases for the present invention are the amylases
sold under the tradename Purafect Ox Am
R described in WO 94/18314, WO96/05295 sold by Genencor; Termamyl® , Fungamyl® , Ban®
Natalase® and Duramyl® , all available from Novo Nordisk A/S and Maxamyl® by Gist-Brocades.
[0118] Said complementary amylase is generally incorporated in the detergent compositions
of the present invention a level of from 0.0001% to 2%, preferably from 0.00018% to
0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.
Preferably a weight of pure enzyme ratio of specific amylase to the complementary
amylase is comprised between 9:1 to 1:9, more preferably between 4:1 to 1:4, and most
preferably between 2:1 and 1:2.
[0119] The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal,
bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic
(psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic,
halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also
included by definition, are mutants of native enzymes. Mutants can be obtained e.g.
by protein and/or genetic engineering, chemical and/or physical modifications of native
enzymes. Common practice as well is the expression of the enzyme via host organisms
in which the genetic material responsible for the production of the enzyme has been
cloned.
[0120] Said enzymes are normally incorporated in the detergent composition at levels from
0.0001% to 2% of active enzyme by weight of the detergent composition. The enzymes
can be added as separate single ingredients (prills, granulates, stabilized liquids,
etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates
).
[0121] Other suitable detergent ingredients that can be added are enzyme oxidation scavengers
which are described in Copending European Patent application 92870018.6 filed on January
31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene
polyamines.
[0122] A range of enzyme materials and means for their incorporation into synthetic detergent
compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International,
WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes
are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219,
Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations,
and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora
et al, April 14, 1981. Enzymes for use in detergents can be stabilised by various
techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S.
3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986,
Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570.
A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described
in WO 9401532 A to Novo.
Bleaching agent
[0123] Suitable bleaching agents include chlorine and oxygen-releasing bleaching agents,
preferably oxygen-releasing bleaching agent containing a hydrogen peroxide source
and an organic peroxyacid bleach precursor compound. The production of the organic
peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen
peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
In a preferred aspect a pre-formed organic peroxyacid is incorporated into the composition
in a liquid matrix as a suspended particulate as described above. Compositions containing
mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination
with a preformed organic peroxyacid are also envisaged.
Inorganic perhydrate bleaches
[0124] Particulate compositions preferably include a hydrogen peroxide source, as an oxygen-releasing
bleach. Suitable hydrogen peroxide sources include the inorganic perhydrate salts.
[0125] The inorganic perhydrate salts are normally incorporated in the form of the sodium
salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight
and most preferably from 5% to 25% by weight of the compositions.
[0126] Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate,
persulfate and persilicate salts. The inorganic perhydrate salts are normally the
alkali metal salts. The inorganic perhydrate salt may be included as the crystalline
solid without additional protection. For certain perhydrate salts however, the preferred
executions of such granular compositions utilize a coated form of the material which
provides better storage stability for the perhydrate salt in the granular product.
[0127] Sodium perborate can be in the form of the monohydrate of nominal formula NaBO
2H
2O
2 or the tetrahydrate NaBO
2H
2O
2.3H
2O.
[0128] Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates
for inclusion in compositions in accordance with the invention. Sodium percarbonate
is an addition compound having a formula corresponding to 2Na
2CO
3.3H
2O
2, and is available commercially as a crystalline solid. Sodium percarbonate, being
a hydrogen peroxide addition compound tends on dissolution to release the hydrogen
peroxide quite rapidly which can increase the tendency for localised high bleach concentrations
to arise. The percarbonate is most preferably incorporated into such compositions
in a coated form which provides in-product stability.
[0129] A suitable coating material providing in product stability comprises mixed salt of
a water soluble alkali metal sulphate and carbonate. Such coatings together with coating
processes have previously been described in GB-1,466,799, granted to Interox on 9th
March 1977. The weight ratio of the mixed salt coating material to percarbonate lies
in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most
preferably from 1 : 49 to 1 : 19. Preferably, the mixed salt is of sodium sulphate
and sodium carbonate which has the general formula Na
2SO
4.n.Na
2CO
3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n
is from 0.2 to 0.5.
[0130] Another suitable coating material providing in product stability, comprises sodium
silicate of SiO
2 : Na
2O ratio from 1.8 : 1 to 3.0 : 1, preferably 1.8:1 to 2.4:1, and/or sodium metasilicate,
preferably applied at a level of from 2% to 10%, (normally from 3% to 5%) of SiO
2 by weight of the inorganic perhydrate salt. Magnesium silicate can also be included
in the coating. Coatings that contain silicate and borate salts or boric acids or
other inorganics are also suitable.
Peroxyacid bleach precursor
[0131] Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in
a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors
may be represented as

where L is a leaving group and X is essentially any functionality, such that on perhydrolysis
the structure of the peroxyacid produced is

[0132] Peroxyacid bleach precursor compounds are preferably incorporated at a level of from
0.5% to 20% by weight, more preferably from 1% to 10% by weight, most preferably from
1.5% to 5% by weight of the compositions.
[0133] Suitable peroxyacid bleach precursor compounds typically contain one or more N- or
O-acyl groups, which precursors can be selected from a wide range of classes. Suitable
classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles
and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
Leaving groups
[0134] The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis
reaction to occur within the optimum time frame (e.g., a wash cycle). However, if
L is too reactive, this activator will be difficult to stabilise for use in a bleaching
composition.
[0135] Preferred L groups are selected from the group consisting of:

and mixtures thereof, wherein R
1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R
3 is an alkyl chain containing from 1 to 8 carbon atoms, R
4 is H or R
3, R
5 is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a solubilizing
group. Any of R
1, R
3 and R
4 may be substituted by essentially any functional group including, for example alkyl,
hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.
[0136] The preferred solubilizing groups are -SO
3-M
+, -CO
2-M
+, -SO
4-M
+, -N
+(R
3)
4X
- and O<--N(R
3)
3 and most preferably -SO
3-M
+ and -CO
2-M
+ wherein R
3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides
solubility to the bleach activator and X is an anion which provides solubility to
the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium
cation, with sodium and potassium being most preferred, and X is a halide, hydroxide,
methylsulfate or acetate anion.
Perbenzoic acid precursor
[0137] Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
[0138] Suitable O-acylated perbenzoic acid precursor compounds include the substituted and
unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene
sulfonate:

[0139] Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides
with benzoylating agents, including for example:

[0140] Perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide,
tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole
type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole
and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl
pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
[0141] Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl
tetraacyl peroxides, and the compound having the formula:

[0142] Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:

[0143] Suitable N-acylated lactam perbenzoic acid precursors have the formula:

wherein n is from 0 to 8, preferably from 0 to 2, and R
6 is a benzoyl group.
Perbenzoic acid derivative precursors
[0144] Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.
[0145] Suitable substituted perbenzoic acid derivative precursors include any of the herein
disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially
any non-positively charged (i.e.; non-cationic) functional group including, for example
alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
[0146] A preferred class of substituted perbenzoic acid precursor compounds are the amide
substituted compounds of the following general formulae:

wherein R
1 is an aryl or alkaryl group with from 1 to 14 carbon atoms, R
2 is an arylene, or alkarylene group containing from 1 to 14 carbon atoms, and R
5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can
be essentially any leaving group. R
1 preferably contains from 6 to 12 carbon atoms. R
2 preferably contains from 4 to 8 carbon atoms. R
1 may be aryl, substituted aryl or alkylaryl containing branching, substitution, or
both and may be sourced from either synthetic sources or natural sources including
for example, tallow fat. Analogous structural variations are permissible for R
2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical
substituent groups or organic compounds. R
5 is preferably H or methyl. R
1 and R
5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator
compounds of this type are described in EP-A-0170386.
Cationic peroxyacid precursors
[0147] Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
[0148] Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid
part of a suitable peroxyacid precursor compound with a positively charged functional
group, such as an ammonium or alkyl ammonium group, preferably an ethyl or methyl
ammonium group. Cationic peroxyacid precursors are typically present in the compositions
as a salt with a suitable anion, such as for example a halide ion or a methylsulfate
ion.
[0149] The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic
acid, or substituted derivative thereof, precursor compound as described hereinbefore.
Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid
precursor compound or an amide substituted alkyl peroxyacid precursor as described
hereinafter
[0150] Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594;
EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
[0151] Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium
substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl
glucose benzoyl peroxides.
[0152] A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl
ammonium) methyl derivative of benzoyl oxybenzene sulfonate:

[0153] A preferred cationically substituted alkyl oxybenzene sulfonate has the formula:

[0154] Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include
the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium
methylene benzoyl caprolactam:

[0155] Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class
include the trialkyl ammonium methylene alkyl caprolactams:

where n is from 0 to 12, particularly from 1 to 5.
[0156] Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl
sodium 4-sulphophenyl carbonate chloride.
Alkyl percarboxylic acid bleach precursors
[0157] Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
[0158] Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N
1N
1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to
6 carbon atoms, particularly those compounds in which the alkylene group contains
1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
[0159] Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethyl
hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS),
sodium acetoxybenzene sulfonate (ABS) and penta acetyl glucose.
Amide substituted alkyl peroxyacid precursors
[0160] Amide substituted alkyl peroxyacid precursor compounds are also suitable, including
those of the following general formulae:

wherein R
1 is an alkyl group with from 1 to 14 carbon atoms, R
2 is an alkylene group containing from 1 to 14 carbon atoms, and R
5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any
leaving group. R
1 preferably contains from 6 to 12 carbon atoms. R
2 preferably contains from 4 to 8 carbon atoms. R
1 may be straight chain or branched alkyl containing branching, substitution, or both
and may be sourced from either synthetic sources or natural sources including for
example, tallow fat. Analogous structural variations are permissible for R
2. The substitution can include alkyl, halogen, nitrogen, sulphur and other typical
substituent groups or organic compounds. R
5 is preferably H or methyl. R
1 and R
5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator
compounds of this type are described in EP-A-0170386.
Benzoxazin organic peroxyacid precursors
[0161] Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example
in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

including the substituted benzoxazins of the type

wherein R
1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R
2, R
3, R
4, and R
5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl,
aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR
6 (wherein R
6 is H or an alkyl group) and carbonyl functions.
[0162] An especially preferred precursor of the benzoxazin-type is:

Preformed organic peroxyacid
[0163] The organic peroxyacid bleaching system may contain, in addition to, or as an alternative
to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid
, typically at a level of from 0.5% to 25% by weight, more preferably from 1% to 10%
by weight of the composition.
[0164] A preferred class of organic peroxyacid compounds are the amide substituted compounds
of the following general formulae:

wherein R
1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R
2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and R
5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. R
1 preferably contains from 6 to 12 carbon atoms. R
2 preferably contains from 4 to 8 carbon atoms. R
1 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing
branching, substitution, or both and may be sourced from either synthetic sources
or natural sources including for example, tallow fat. Analogous structural variations
are permissible for R
2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical
substituent groups or organic compounds. R
5 is preferably H or methyl. R
1 and R
5 should not contain more than 18 carbon atoms in total. Amide substituted organic
peroxyacid compounds of this type are described in EP-A-0170386.
[0165] Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc
acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid. Dibenzoyl peroxide
is a preferred organic peroxyacid herein. Mono- and diperazelaic acid, mono- and diperbrassylic
acid are also suitable herein.
[0166] Pre-formed monoperoxycarboxylic acids (hereafter referred to as peracid) suitable
for use herein are mono peracids, meaning that the peracid contains one peroxygen
group. Preferably the peracid is in solid form.
[0167] In a preferred embodiment of the present invention the peracid has the general formula
X-R-C(O)OOH
wherein R is a linear or branched alkyl chain having at least 1 carbon atom and X
is hydrogen or a substituent group selected from the group consisting of alkyl, especially
alkyl chains of from 1 to 24 carbon atoms, aryl, halogen, ester, ether, amine, amide,
substituted phthalic amino, imide, hydroxide, sulphide, sulphate, sulphonate, carboxylic,
heterocyclic, nitrate, aldehyde, phosphonate, phosphonic or mixtures thereof.
[0168] More particularly the R group preferably comprises up to 24 carbon atoms. Alternatively,
the R group may be a branched alkyl chain comprising one or more side chains which
comprise substituent groups selected from the group consisting of aryl, halogen, ester,
ether, amine, amide, substituted phthalic amino, imide, hydroxide, sulphide, sulphate,
sulphonate, carboxylic, heterocyclic, nitrate, aldehyde, ketone or mixtures thereof.
[0169] In a preferred peracid the X group, according to the above general formula, is a
phthalimido group. Thus, particularly preferred peracids are those having general
formula:

where R is C1-20 and where A, B, C and D are independently either hydrogen or substituent
groups individually selected from the group consisting of alkyl, hydroxyl, nitro,
halogen, amine, ammonium, cyanide, carboxylic, sulphate, sulphonate, aldehydes or
mixtures thereof.
[0170] In a preferred aspect of the present invention R is an alkyl group having from 3
to 12 carbon atoms, more preferably from 5 to 9 carbon atoms. Preferred substituent
groups A, B, C and D are linear or branched alkyl groups having from 1 to 5 carbon
atoms, but more preferably hydrogen.
[0171] Preferred peracids are selected from the group consisting of phthaloyl amido peroxy
hexanoic acid, phthaloyl amido peroxy heptanoic acid, phthaloyl amido peroxy octanoic
acid, phthaloyl amido peroxy nonanoic acid, phthaloyl amido peroxy decanoic acid and
mixtures thereof.
[0172] In a particularly preferred aspect of the present invention the peracid has the formula
such that R is C
5H
10 i.e. phthaloyl amido peroxy hexanoic acid or PAP. This peracid is preferably used
as a substantially water-insoluble solid or wetcake and is available from Ausimont
under the trade name Euroco.
[0173] The peracid is preferably used at a level of from 0.1% to 30%, more preferably from
0.5% to 18% and most preferably 1% to 12% by weight of the composition.
Metal-containing bleach catalyst
[0174] The compositions described herein which contain bleach as detergent component may
additionally contain as a preferred component, a metal containing bleach catalyst.
Preferably the metal containing bleach catalyst is a transition metal containing bleach
catalyst, more preferably a manganese or cobalt-containing bleach catalyst.
[0175] The compositions of the present invention may comprise an effective amount of a bleach
catalyst. The term "an effective amount" is defined as "an amount of the transition-metal
bleach catalyst present in the present invention compositions, or during use according
to the present invention methods, that is sufficient, under whatever comparative or
use conditions are employed, to result in at least partial oxidation of the material
sought to be oxidized by the composition or method."
[0176] Preferably the compositions of the present invention comprise from 1 ppb (0.0000001%),
more preferably from 100 ppb (0.00001%), yet more preferably from 500 ppb (0.00005%),
still more preferably from 1 ppm (0.0001%) to 99.9%, more preferably to 50%, yet more
preferably to 5%, still more preferably to 500 ppm (0.05%) by weight of the composition,
of a metal bleach catalyst as described herein below.
[0177] A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation
of defined bleach catalytic activity, such as copper, iron cations, an auxiliary metal
cation having little or no bleach catalytic activity, such as zinc or aluminium cations,
and a sequestrant having defined stability constants for the catalytic and auxiliary
metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic
acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
[0178] Preferred types of bleach catalysts include the manganese-based complexes disclosed
in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts
include Mn
IV2(u-O)
3(1,4,7-trimethyl-1,4,7-triazacyclononane)
2-(PF
6)
2, Mn
III2(u-O)
1(u-OAc)
2(1,4,7-trimethyl-1,4,7-triazacyclononane)
2-(ClO
4)
2, Mn
lV4(u-O)
6(1,4,7-triazacyclononane)
4-(ClO
4)
2, Mn
IIIMn
IV4(u-O)
1(u-OAc)
2-(1,4,7-trimethyl-1,4,7-triazacyclononane)
2-(ClO
4)
3, and mixtures thereof. Others are described in European patent application publication
no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane,
2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane,
and mixtures thereof.
[0179] The bleach catalysts useful in the compositions herein may also be selected as appropriate
for the present invention. For examples of suitable bleach catalysts see U.S. Pat.
4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear
manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH
3)
3-(PF
6).
[0180] Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a
water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate
polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands
include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol,
meso-inositol, lactose, and mixtures thereof.
[0181] U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition
metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands
are of the formula:

wherein R
1, R
2, R
3, and R
4 can each be selected from H, substituted alkyl and aryl groups such that each R
1-N=C-R
2 and R
3-C=N-R
4 form a five or six-membered ring. Said ring can further be substituted. B is a bridging
group selected from O, S. CR
5R
6, NR
7 and C=O, wherein R
5, R
6, and R
7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups.
Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole,
and triazole rings. Optionally, said rings may be substituted with substituents such
as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine.
Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine
complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl
2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate,
Co(2,2-bispyridylamine)
2O
2ClO
4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II)
perchlorate, and mixtures thereof.
[0182] Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-dentate
ligands, including N
4Mn
III(u-O)
2Mn
IVN
4)
+and [Bipy
2Mn
III(u-O)
2Mn
IVbipy
2]-(ClO
4)
3.
[0183] While the structures of the bleach-catalyzing manganese complexes of the present
invention have not been elucidated, it may be speculated that they comprise chelates
or other hydrated coordination complexes which result from the interaction of the
carboxyl and nitrogen atoms of the ligand with the manganese cation. Likewise, the
oxidation state of the manganese cation during the catalytic process is not known
with certainty, and may be the (+II), (+III), (+IV) or (+V) valence state. Due to
the ligands' possible six points of attachment to the manganese cation, it may be
reasonably speculated that multi-nuclear species and/or "cage" structures may exist
in the aqueous bleaching media. Whatever the form of the active Mn·ligand species
which actually exists, it functions in an apparently catalytic manner to provide improved
bleaching performances on stubborn stains such as tea, ketchup, coffee, wine, juice,
and the like.
[0184] Other bleach catalysts are described, for example, in European patent application,
publication no. 408,131 (cobalt complex catalysts), European patent applications,
publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455
(manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application,
publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845
(aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373
(manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat.
specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing
salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations),
and U.S. 4,728,455 (manganese gluconate catalysts).
[0185] Other preferred examples include cobalt (III) catalysts having the formula:
Co[(NH
3)
nM'
mB'
bT'
tQ
qP
p] Y
y
wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5 (preferably
4 or 5; most preferably 5); M' represents a monodentate ligand; m is an integer from
0 to 5 (preferably 1 or 2; most preferably 1); B' represents a bidentate ligand; b
is an integer from 0 to 2; T' represents a tridentate ligand; t is 0 or 1; Q is a
tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n +
m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected counteranions present
in a number y, where y is an integer from 1 to 3 (preferably 2 to 3; most preferably
2 when Y is a -1 charged anion), to obtain a charge-balanced salt, preferred Y are
selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate,
acetate, carbonate, and combinations thereof; and wherein further at least one of
the coordination sites attached to the cobalt is labile under laundry detergent use
conditions and the remaining co-ordination sites stabilise the cobalt under laundry
detergent conditions such that the reduction potential for cobalt (III) to cobalt
(II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts)
versus a normal hydrogen electrode.
[0186] Preferred cobalt catalysts of this type have the formula:
[Co(NH
3)
n(M')
m] Y
y
wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M' is
a labile coordinating moiety, preferably selected from the group consisting of chlorine,
bromine, hydroxide, water, and (when m is greater than 1) combinations thereof; m
is an integer from 1 to 3 (preferably 1 or 2; most preferably 1); m+n = 6; and Y is
an appropriately selected counteranion present in a number y, which is an integer
from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to
obtain a charge-balanced salt.
[0187] The preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride
salts having the formula [Co(NH
3)
5Cl] Y
y, and especially [Co(NH
3)
5Cl]Cl
2.
[0188] More preferred are the present invention compositions which utilize cobalt (III)
bleach catalysts having the formula:
[Co(NH
3)
n(M)
m(B)
b] T
y
wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is one
or more ligands coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably
1); B is a ligand co-ordinated to the cobalt by two sites; b is 0 or 1 (preferably
0), and when b=0, then m+n = 6, and when b=1, then m=0 and n=4; and T is one or more
appropriately selected counteranions present in a number y, where y is an integer
to obtain a charge-balanced salt (preferably y is 1 to 3; most preferably 2 when T
is a -1 charged anion); and wherein further said catalyst has a base hydrolysis rate
constant of less than 0.23 M
-1 s
-1 (25°C).
[0189] Preferred T are selected from the group consisting of chloride, iodide, I
3-, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide,
PF
6-, BF
4-, B(Ph)
4-, phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof.
Optionally, T can be protonated if more than one anionic group exists in T, e.g.,
HPO
42-, HCO
3-, H
2PO
4-, etc. Further, T may be selected from the group consisting of non-traditional inorganic
anions such as anionic surfactants (e.g., linear alkylbenzene sulfonates (LAS), alkyl
sulfates (AS), alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g., polyacrylates,
polymethacrylates, etc.).
[0190] The M moieties include, but are not limited to, for example, F
-, SO
4-2, NCS
-, SCN
-, S
2O
3-2, NH
3, PO
43-, and carboxylates (which preferably are mono-carboxylates, but more than one carboxylate
may be present in the moiety as long as the binding to the cobalt is by only one carboxylate
per moiety, in which case the other carboxylate in the M moiety may be protonated
or in its salt form). Optionally, M can be protonated if more than one anionic group
exists in M (e.g., HPO
42-, HCO
3-, H
2PO
4-, HOC(O)CH
2C(O)O-, etc.) Preferred M moieties are substituted and unsubstituted C
1-C
30 carboxylic acids having the formulas:
RC(O)O-
wherein R is preferably selected from the group consisting of hydrogen and C
1-C
30 (preferably C
1-C
18) unsubstituted and substituted alkyl, C
6-C
30 (preferably C
6-C
18) unsubstituted and substituted aryl, and C
3-C
30 (preferably C
5-C
18) unsubstituted and substituted heteroaryl, wherein substituents are selected from
the group consisting of -NR'
3, -NR'
4+, -C(O)OR', -OR',-C(O)NR'
2, wherein R' is selected from the group consisting of hydrogen and C
1-C
6 moieties. Such substituted R therefore include the moieties -(CH
2)
nOH and -(CH
2)
nNR'
4+, wherein n is an integer from 1 to 16, preferably from 2 to 10, and most preferably
from 2 to 5.
[0191] Most preferred M are carboxylic acids having the formula above wherein R is selected
from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched
C
4-C
12 alkyl, and benzyl. Most preferred R is methyl. Preferred carboxylic acid M moieties
include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic,
succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate,
tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic,
lactic, malic, and especially acetic acid.
[0192] The B moieties include carbonate, di- and higher carboxylates (e.g., oxalate, malonate,
malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (e.g.,
glycine, alanine, beta-alanine, phenylalanine).
[0193] Cobalt bleach catalysts useful herein are known, being described for example along
with their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-Metal
Complexes",
Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. For example, Table 1 at page 17, provides the base hydrolysis
rates (designated therein as k
OH) for cobalt pentaamine catalysts complexed with oxalate (k
OH= 2.5 x 10
-4 M
-1 s
-1 (25°C)), NCS
- (k
OH= 5.0 x 10
-4 M
-1 s
-1 (25° C)), formate (k
OH= 5.8 x 10
-4 M
-1 s
-1 (25°C)), and acetate (k
OH= 9.6 x 10
-4 M
-1 s
-1 (25°C)). The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate
salts having the formula [Co(NH
3)
5OAc] T
y, wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate
chloride, [Co(NH
3)
5OAc]Cl
2; as well as [Co(NH
3)
5OAc](OAc)
2; [Co(NH
3)
5OAc](PF
6)
2; [Co(NH
3)
5OAc](SO
4); [Co(NH
3)
5OAc](BF
4)
2; and [Co(NH
3)
5OAc](NO
3)
2 (herein "PAC").
[0194] These cobalt catalysts are readily prepared by known procedures, such as taught for
example in the Tobe article hereinbefore and the references cited therein, in U.S.
Patent 4,810,410, to Diakun et al, issued March 7,1989,
J. Chem. Ed. (1989),
66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly
(Prentice-Hall; 1970), pp. 461-3;
Inorg. Chem.,
18, 1497-1502 (1979);
Inorg. Chem.,
21, 2881-2885 (1982);
Inorg. Chem.,
18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and
Journal of Physical Chemistry, 56, 22-25 (1952); as well as the synthesis examples provided hereinafter.
[0195] Cobalt catalysts suitable for incorporation into the detergent compositions of the
present invention may be produced according to the synthetic routes disclosed in U.S.
Patent Nos. 5,559,261, 5,581,005, and 5,597,936, the disclosures of which are herein
incorporated by reference.
[0196] Other suitable bleach catalysts include transition-metal bleach catalyst comprising
:
i) a transition metal selected from the group consisting of Mn(II), Mn(III), Mn(IV),
Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I),
Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV),
Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV), preferably
Mn(II), Mn(lll), Mn(IV), Fe(II), Fe(III), Fe(IV), Cr(II), Cr(III), Cr(IV), Cr(V),
Cr(VI), and mixtures thereof;
ii) a cross-bridged macropolycyclic ligand being coordinated by four or five donor
atoms to the same transition metal, said ligand comprising:
a) an organic macrocycle ring containing four or more donor atoms (preferably at least
3, more preferably at least 4, of these donor atoms are N) separated from each other
by covalent linkages of 2 or 3 non-donor atoms, two to five (preferably three to four,
more preferably four) of these donor atoms being coordinated to the same transition
metal atom in the complex;
b) a cross-bridged chain which covalently connects at least 2 non-adjacent donor atoms
of the organic macrocycle ring, said covalently connected non-adjacent donor atoms
being bridgehead donor atoms which are coordinated to the same transition metal in
the complex, and wherein said cross-bridged chain comprises from 2 to about 10 atoms
(preferably the cross-bridged chain is selected from 2, 3 or 4 non-donor atoms, and
4-6 non-donor atoms with a further donor atom); and
iii) optionally, one or more non-macropolycyclic ligands, preferably selected from
the group consisting of H2O, ROH, NR3, RCN, OH-, OOH-, RS-, RO-, RCOO-, OCN-, SCN-, N3-, CN-, F-, Cl-, Br-, I-, O2-, NO3-, NO2-, SO42-, SO32-, PO43-, organic phosphates, organic phosphonates, organic sulfates, organic sulfonates,
and aromatic N donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles,
pyrimidines, triazoles and thiazoles with R being H, optionally substituted alkyl,
optionally substituted aryl.
[0197] The preferred cross-bridged macropolycyclic ligands are is selected from the group
consisting of:
a) a cross-bridged macropolycyclic ligand of formula (I) having denticity of 4 or
5:

b) a cross-bridged macropolycyclic ligand of formula (II) having denticity of 5 or
6:

c) the cross-bridged macropolycyclic ligand of formula (III) having denticity of 6
or 7:

wherein each E unit represents the moiety having the formula:
(CRn)a-X-(CRn)a'
wherein X is selected from the group consisting of oxygen, sulfur, -NR-, phosphorous,
or X represents a covalent bond wherein E has the formula:
(CRn)a-(CRn)a'
for each E units the sum of a + a' is independently selected from 1 to 5; each G unit
is a moiety (CRn)b; each R unit is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl,
and heteroaryl, or two or more R units are covalently bonded to form an aromatic,
heteroaromatic, cycloalkyl, or heterocycloalkyl ring; each D unit is a donor atom
independently selected from the group consisting of nitrogen, oxygen, sulfur, and
phosphorous, and at least two atoms which comprise D units are bridgehead donor atoms
coordinated to the transition metal; B units are a carbon atom, a D unit, or a cycloalkyl
or heterocyclic ring; each n is an integer independently selected from 1 and 2, completing
the valence of the carbon atoms to which the R units are covalently bonded; each n'
is an integer independently selected from 0 and 1, completing the valence of the D
donor atoms to which the R moieties are covalently bonded; each n" is an integer independently
selected from 0, 1, and 2 completing the valence of the B atoms to which the R moieties
are covalently bonded; each a and a' is an integer independently selected from 0 to
5, wherein the sum of all a + a' values in the ligand of formula (I) is within the
range of from about 8 to about 12; the sum of all a + a' values in the ligand of formula
(II) is within the range of from about 10 to about 15; and the sum of all a + a' values
in the ligand of formula (III) is within the range of from about 12 to about 18; each
b is an integer independently selected from 0 to 9, or in any of the above formulas,
one or more of the (CRn)b moieties covalently bonded from any D to the B atom is absent as long as at least
two (CRn)b covalently bond two of the D donor atoms to the B atom in the formula, and the sum
of all b indices is within the range of from about 2 to about 5.
[0198] A further description of the bleach catalysts of the present invention can be found
in WO 98/39406 A1, published September 11, 1998, WO 98/39098 A1, published September
11, 1998, and WO 98/39335 A1, published September 11, 1998, all of which are included
herein by reference.
[0199] The nomenclature herein to describe the transition-metal bleach catalysts is the
same nomenclature style used in the above-identified references. However, the chemical
names of one or more of the herein described ligands may vary from the chemical name
assigned under the rules of the International Union of Pure and Applied Chemistry
(IUPAC). For example, a preferred ligand for the purposes of the present invention,
5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane, has the IUPAC name 4,11-dimethyl-1,4,8,11-tetraaza-bicyclo[6.6.2]hexadecane.
A further preferred ligand is 5,12-diethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane.
[0200] Metal bleach catalysts useful in the invention compositions can in general include
known compounds where they conform with the invention definition, as well as, more
preferably, any of a large number of novel compounds expressly designed for the present
laundry use. Suitable bleach catalysts for use in the compositions herein further
include for example:
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II);
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) Hexafluorophosphate;
Aquo-hydroxy-5,12-dimethyl-15,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III)
Hexafluorophosphate;
Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II) Hexafluorophosphate;
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) Tetrafluoroborate;
Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II) Tetrafluoroborate;
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III) Hexafluorophosphate;
Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Iron(II);
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Iron(II);
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Copper(II);
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Copper(II);
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Cobalt(II);
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Cobalt(II);
Dichloro 5,12-dimethyl--4-phenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-4,10-dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II);
Dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II);
Dichloro-5,12-dimethyl-2,11-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-4,10-dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II);
Dichloro-2,4,5,9,11,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-2,3,5,9,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-2,2,4,5,9,9,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-2,2,4,5,9,11,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-3,3,5,10,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-3,5,10,12-tetramethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-3-butyl-5,10,12-trimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II);
Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Iron(II);
Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Iron(II);
Aquo-chloro-2-(2-hydroxyphenyl)-5,12-dimethy1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II);
Aquo-chloro-10-(2-hydroxybenzyl)-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane
Manganese(II);
Chloro-2-(2-hydroxybenzyl)-5-methy1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Chloro-10-(2-hydroxybenzyl)-4-methyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II);
Chloro-5-methyl-12-(2-picolyl)-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Chloride;
Chloro-4-methyl-10-(2-picolyl)-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II)
Chloride;
Dichloro-5-(2-sulfato)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(III);
Aquo-Chloro-5-(2-sulfato)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II);
Aquo-Chloro-5-(3-sulfonopropyl)-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II);
Dichloro-5-(Trimethylammoniopropyl)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(III) Chloride;
Dichloro-5,12-dimethyl-1,4,7,10,13-pentaazabicyclo[8.5.2]heptadecane Manganese(II);
Dichloro-14,20-dimethyl-1,10,14,20-tetraazatriyclo[8.6.6]docosa-3(8),4,6-triene Manganese(II);
Dichloro-4,11-dimethyl-1,4,7,11-tetraazabicyclo[6.5.2]pentadecane Manganese(II);
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[7.6.2]heptadecane Manganese(II);
Dichloro-5,13-dimethyl-1,5,9,13-tetraazabicyclo[7.7.2]heptadecane Manganese(II);
Dichloro-3,10-bis(butylcarboxy)-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II);
Diaquo-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
Chloro-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.13,7.111,15.]pentacosa-3,5,7(24),11,13,15(25)-hexaene manganese(II) Hexafluorophosphate;
Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaazatetracyclo[7.7.7.13,7.111,15.]pentacosa-3,5,7(24),11,13,15(25)-hexaene Manganese(II) Trifluoromethanesulfonate;
Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaazatetracyclo[7.7.7.13,7.111,15.]pentacosa-3,5,7(24),11,13,15(25)-hexaene Iron(II) Trifluoromethanesulfonate;
Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadecane Manganese(II)
Hexafluorophosphate;
Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecane Manganese(II)
Hexafluorophosphate;
Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadecane Manganese(II)
Chloride;
Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecane Manganese(II)
Chloride;
Dichloro 5,12,15,16-tetramethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II);
and
Chloro 5-methyl-12-(2'-oxybenzyl)-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II).
[0201] Further suitable complexes useful as transition-metal bleach catalysts further include
not only monometallic, mononuclear kinds such as those illustrated hereinabove but
also bimetallic, trimetallic or cluster kinds. Monometallic, mononuclear complexes
are preferred. As defined herein, a monometallic transition-metal bleach catalyst
contains only one transition metal atom per mole of complex. A monometallic, mononuclear
complex is one in which any donor atoms of the essential macrocyclic ligand are bonded
to the same transition metal atom, that is, the essential ligand does not "bridge"
across two or more transition-metal atoms.
[0202] Further examples of manganese transition metal complexes are the manganese(III) and
manganese(IV) complexes having the general formula:

wherein X is independently a coordinating or bridging species non-limiting examples
of which are H
2O, O
22-, O
2-,
-OH, HO
2-, SH
-, S
2-, >SO, Cl
-, SCN
- , N
3-, N
3-, RSO
3-, RCOO-, NH
2-, and NR
3, wherein R is H alkyl, aryl, each of which is optionally substituted, and R
1COO, wherein R
1 is an alkyl, aryl unit, each of which may be optionally substituted;
L is a ligand which is an organic molecule containing a number of nitrogen atoms which
co-ordinate via all or some of said nitrogen atoms to the manganese centers;
z denotes the charge of the complex and is an integer which can have a positive or
negative value;
Y is a monovalent or multivalent counter-ion, which provides charge neutrality, which
dependent upon the charge z of the complex; and q is z/Y.
[0203] Preferred of these manganese complexes are those wherein said coordinating or bridging
group X is either CH
3COO
-, O
2-, and mixtures thereof, preferably when said manganese atom is in the (IV) oxidation
state and X is O
2-. Ligands which are preferred are those which contain at least three nitrogen atoms
and which coordinate via three nitrogen atoms to one of the manganese centers and
are preferably of a macrocyclic nature.
[0204] Preferred ligands have the formula:

wherein t is an integer having the value 2 or 3; s is an integer having the value
3 or 4; q is an integer having the value 0 or 1, R
1 and R
2 are each independently selected from hydrogen, alkyl, aryl, each of which can be
optionally substituted; R
3 is independently selected from hydrogen, alkyl, aryl, each of which can be optionally
substituted.
[0205] Non-limiting examples of preferred ligands are 1,4,7-trimethyl-1,4,7-triazacyclononane
(Me
3-TACN), and 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me
4-TACN).
[0206] The selection of the counter ion Y for establishing charge neutrality is not critical
for the activity of the complex. Non-limiting examples of said counter ions are chloride,
sulphate, nitrate, methylsulphate, surfactant-ions, such as long chain alkylsulphates,
alkylsulphonates, alkylbenzenesulphonates, tosylate, trifluoromethylsulphonate, perchlorate,
BPh
4-, PF
6-, and mixtures thereof.
[0207] Examples of manganese complexes of this type include:
i) [(Me3-TACN)MnIV(m-O)3MnIV(Me3-TACN)]2+(PF6-)2;
ii) [(Me4-TACN)MnIV(m-O)3MnIV(Me4-TACN)]2+(PF6-)2;
iii) [(Me3-TACN)MnIII(m-O)(m-OAc)2MnIII(Me3-TACN)]2+(PF6-)2;
iv) [(Me4-TACN)MnIII(m-O)(m-OAc)2MnIII(Me4-TACN)]2+(PF6-)2;
[0208] Further manganese complex catalysts are the mononuclear complexes having the formula:
[LMn
IV(OR)
3] Y
wherein manganese, Mn, is in the +4 oxidation state; R is C
1-C
20 radical selected from the group-consisting of alkyl, cycloalkyl, aryl, benzyl, and
radical combinations thereof; at least two R radicals may also be connected to one
another so as to form a bridging unit between two oxygens that coordinate with the
manganese; L is a ligand selected from a C
3-C
60 radical having at least 3 nitrogen atoms coordinating with the manganese; and Y is
an oxidatively-stable counterion dependent upon the charge of the complex.
[0209] Non-limiting examples of preferred complexes are those wherein L is 1,4,7-trimethyl-1,4,7-triazacyclononane,
and 2 methyl-1,4,7-trimethyl-1,4,7-triazacyclononane, and R is C
1 alkyl.
[0210] Further examples of mononuclear manganese complex catalysts which are capable of
bleaching in the absence of a source of hydrogen peroxide or other peroxygen bleaching
agent include those having the formula:
[LMnX
p]
zY
q
wherein manganese can be in any of the II, III, or IV oxidation sates; each X independently
represents a coordinating species with the exception of RO-, such as Cl
-, Br
-, I
-, F
-, NCS-, N
3-, I
3-, NH
3, RCOO-, RSO
3-, RSO
4-, in which R is alkyl or aryl wherein each can be optionally substituted, OH
-, O
22-, HO
2-, H
2O, SH, CN
-, OCN
-, S
42-, and mixtures thereof; p is an integer from 1 to 3; z denotes the charge of the complex
and is an integer which can be positive, zero, or negative; Y is a counter-ion the
selection of which dependent upon the charge z of the complex; q = z/Y; and L is a
ligand having the formula:

wherein t is 2; s is 3; R
1, R
2 and R
3 are each independently selected from hydrogen, C
1-C
6 alkyl, aryl, each of which can be optionally substituted.
[0211] A particularly useful metal bleach catalyst is [Mn(Bcyclam)Cl2]:

"Bcyclam" (5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane) is prepared
according to J. Amer. Chem. Soc., (1990), 112, 8604.
[0212] The bleach catalysts herein may be co-processed with adjunct materials so as to reduce
the colour impact if desired for the aesthetics of the product, or to be included
in enzyme-containing particles as exemplified hereinafter, or the compositions may
be manufactured to contain catalyst "speckles".
Organic polymeric compound
[0213] Organic polymeric compounds may be added as preferred components of the compositions
in accord with the invention. By organic polymeric compound it is meant essentially
any polymeric organic compound commonly found in detergent compositions having dispersant,
anti-redeposition, soil release agents or other detergency properties.
[0214] Organic polymeric compound is typically incorporated in the detergent compositions
of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most
preferably from 1% to 10% by weight of the compositions.
[0215] Examples of organic polymeric compounds include the water soluble organic homo- or
co-polymeric polycarboxylic acids, modified polycarboxylates or their salts in which
the polycarboxylic acid comprises at least two carboxyl radicals separated from each
other by not more than two carbon atoms. Polymers of the latter type are disclosed
in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight 2000-10000
and their copolymers with any suitable other monomer units including modified acrylic,
fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid
or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene
and any mixtures thereof. Preferred are the copolymers of acrylic acid and maleic
anhydride having a molecular weight of from 5000 to 100 000, more preferably from
20,000 to 100,000.
[0216] Preferred commercially available acrylic acid containing polymers having a molecular
weight below 15,000 include those sold under the tradename Sokalan PA30, PA20, PA15,
PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 45N,
480N, 460N by Rohm and Haas.
[0217] Preferred acrylic acid containing copolymers include those which contain as monomer
units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid or its
salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted
acrylic monomer or its salts having the general formula-[CR
2-CR
1(CO-O-R
3)]- wherein at least one of the substituents R
1, R
2 or R
3, preferably R
1 or R
2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R
1 or R
2 can be a hydrogen and R
3 can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer
wherein R
1 is methyl, R
2 is hydrogen (i.e. a methacrylic acid monomer). The most preferred copolymer of this
type has a molecular weight of 3500 and contains 60% to 80% by weight of acrylic acid
and 40% to 20% by weight of methacrylic acid.
[0218] The polyamine and modified polyamine compounds are useful herein including those
derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and
EP-A-351629.
[0219] Other optional polymers may polyvinyl alcohols and acetates both modified and non-modified,
cellulosics and modified cellulosics, polyoxyethylenes, polyoxypropylenes, and copolymers
thereof, both modified and non-modified, terephthalate esters of ethylene or propylene
glycol or mixtures thereof with polyoxyalkylene units.
[0220] Suitable examples are disclosed in US patent Nos. 5,591,703 , 5,597,789 and 4,490,271.
Soil Release Agents
[0221] Suitable polymeric soil release agents include those soil release agents having:
(a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene
segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene
segments with a degree of polymerization of from 2 to 10, wherein said hydrophile
segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties
at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising
oxyethylene and from 1 to 30 oxypropylene units, said hydrophile segments preferably
comprising at least 25% oxyethylene units and more preferably, especially for such
components having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or
(b) one or more hydrophobe components comprising (i) C
3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise
oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C
3 oxyalkylene terephthalate units is 2:1 or lower, (ii) C
4-C
6 alkylene or oxy C
4-C
6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably
polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) C
1-C
4 alkyl ether or C
4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are
present in the form of C
1-C
4 alkyl ether or C
4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, or a combination of
(a) and (b).
[0222] Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization
of from 200, although higher levels can be used, preferably from 3 to 150, more preferably
from 6 to 100. Suitable oxy C
4-C
6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric
soil release agents such as MO
3S(CH
2)
nOCH
2CH
2O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580,
issued January 26, 1988 to Gosselink.
[0223] Polymeric soil release agents useful herein also include cellulosic derivatives such
as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate
or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate,
and the like. Such agents are commercially available and include hydroxyethers of
cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also
include those selected from the group consisting of C
1-C
4 alkyl and C
4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol,
et al.
[0224] Soil release agents characterized by poly(vinyl ester) hydrophobe segments include
graft copolymers of poly(vinyl ester), e.g., C
1-C
6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones,
such as polyethylene oxide backbones. See European Patent Application 0 219 048, published
April 22, 1987 by Kud, et al.
[0225] Another suitable soil release agent is a copolymer having random blocks of ethylene
terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of
this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S.
Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur
issued July 8, 1975.
[0226] Another suitable polymeric soil release agent is a polyester with repeat units of
ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units
together with 90-80% by weight of polyoxyethylene terephthalate units, derived from
a polyoxyethylene glycol of average molecular weight 300-5,000.
[0227] Another suitable polymeric soil release agent is a sulfonated product of a substantially
linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and
oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
These soil release agents are described fully in U.S. Patent 4,968,451, issued November
6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release
agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December
8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent
4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric
compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink. Other polymeric
soil release agents also include the soil release agents of U.S. Patent 4,877,896,
issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl,
end-capped terephthalate esters.
[0228] Another soil release agent is an oligomer with repeat units of terephthaloyl units,
sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat
units form the backbone of the oligomer and are preferably terminated with modified
isethionate end-caps. A particularly preferred soil release agent of this type comprises
one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy
units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
Heavy metal ion sequestrant
[0229] The compositions of the invention may contain as an optional component a heavy metal
ion sequestrant. By heavy metal ion sequestrant it is meant herein components which
act to sequester (chelate) heavy metal ions. These components may also have calcium
and magnesium chelation capacity, but preferentially they show selectivity to binding
heavy metal ions such as iron, manganese and copper.
[0230] Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%,
preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably
from 0.5% to 5% by weight of the compositions.
[0231] Heavy metal ion sequestrants, which are acidic in nature, having for example phosphonic
acid or carboxylic acid functionalities, may be present either in their acid form
or as a complex/salt with a suitable counter cation such as an alkali or alkaline
metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof. Preferably
any salts/complexes are water soluble. The molar ratio of said counter cation to the
heavy metal ion sequestrant is preferably at least 1:1.
[0232] Suitable heavy metal ion sequestrants for use herein include organic phosphonates,
such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy
disphosphonates and nitrilo trimethylene phosphonates. Preferred among the above species
are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene
phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene
1,1 diphosphonate.
[0233] Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic
acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine
pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid,
2-hydroxypropylenediamine disuccinic acid or any salts thereof.
[0234] Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali
metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures
thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium
salt or complex thereof.
[0235] Organo diphosphonic acid, which does not contain nitrogen as part of its chemical
structure. This definition therefore excludes the organo aminophosphonates, which
however may be included in compositions of the invention as heavy metal ion sequestrant
components.
[0236] The organo diphosphonic acid is preferably a C
1-C
4 diphosphonic acid, more preferably a C
2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane
1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or fully ionized
form, particularly as a salt or complex.
Water-soluble sulfate salt
[0237] The compositions optionally contains a water-soluble sulfate salt. Where present
the water-soluble sulfate salt is at the level of from 0.1% to 40%, more preferably
from 1% to 30%, most preferably from 5% to 25% by weight of the compositions.
[0238] The water-soluble sulfate salt may be essentially any salt of sulfate with any counter
cation. Preferred salts are selected from the sulfates of the alkali and alkaline
earth metals, particularly sodium sulfate.
Alkali Metal Silicate
[0239] An alkali metal silicate is a preferred component of the compositions of the present
invention. A preferred alkali metal silicate is sodium silicate having an SiO
2:Na
2O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0. Sodium
silicate is preferably present at a level of less than 20%, preferably from 1% to
15%, most preferably from 3% to 12% by weight of SiO
2. The alkali metal silicate may be in the form of either the anhydrous salt or a hydrated
salt.
[0240] Alkali metal silicate may also be present as a component of an alkalinity system.
[0241] The alkalinity system also preferably contains sodium metasilicate, present at a
level of at least 0.4% SiO
2 by weight. Sodium metasilicate has a nominal SiO
2 : Na
2O ratio of 1.0. The weight ratio of said sodium silicate to said sodium metasilicate,
measured as SiO
2, is preferably from 50:1 to 5:4, more preferably from 15:1 to 2:1, most preferably
from 10:1 to 5:2.
Colourant
[0242] The term 'colourant', as used herein, means any substance that absorbs specific wavelengths
of light from the visible light spectrum. Such colourants when added to a detergent
composition have the effect of changing the visible colour and thus the appearance
of the detergent composition. Colourants may be for example either dyes or pigments.
Preferably the colourants are stable in composition in which they are to be incorported.
Thus in a composition of high pH the colourant is preferably alkali stable and in
a composition of low pH the colourant is preferably acid stable.
[0243] The first and/or second and/or subsequent compositions may contain a colourant, a
mixture of colourants, coloured particles or mixture of coloured particles such that
the various phases have different visual appearances. Preferably one of either the
first or the second phases comprises a colourant. Where both the first and second
and/or subsequent phases comprise a colourant it is preferred that the colourants
have a different visual appearance.
Enzyme Stabilizing System
[0244] Preferred enzyme-containing compositions herein may comprise from 0.001% to 10%,
preferably from 0.005% to 8%, most preferably from 0.01% to 6%, by weight of an enzyme
stabilizing system. The enzyme stabilizing system can be any stabilizing system which
is compatible with the detersive enzyme. Such stabilizing systems can comprise calcium
ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine
bleach scavengers and mixtures thereof. Such stabilizing systems can also comprise
reversible enzyme inhibitors, such as reversible protease inhibitors.
Suds suppressing system
[0245] The detergent tblets of the present invention, when formulated for use in machine
washing compositions, preferably comprise a suds suppressing system present at a level
of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5%
by weight of the composition.
[0246] Suitable suds suppressing systems for use herein may comprise essentially any known
antifoam compound, including, for example silicone antifoam compounds, 2-alkyl and
alcanol antifoam compounds. Preferred suds suppressing systems and antifoam compounds
are disclosed in PCT Application No. WO93/08876 and EP-A-705 324.
Polymeric dye transfer inhibiting agents
[0247] The compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05%
to 0.5% by weight of polymeric dye transfer inhibiting agents.
[0248] The polymeric dye transfer inhibiting agents are preferably selected from polyamine
N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers
or combinations thereof.
Optical brightener
[0249] The compositions suitable for use in laundry washing methods as described herein,
also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic
optical brighteners.
[0250] Hydrophilic optical brighteners useful herein include 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.
[0251] 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.
[0252] 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.
[0253] 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.
[0254] Other preferred optical brighteners are those known as Brightener 49 available from
Ciba-Geigy.
Other optional ingredients
[0255] Other optional ingredients suitable for inclusion in the compositions of the invention
include perfumes and filler salts, with sodium sulfate being a preferred filler salt.
pH of the compositions
[0256] The compositions of the present invention are preferably not formulated to have an
unduly high pH, in preference having a pH measured as a 1% solution in distilled water
of from 7.0 to 12.5, more preferably from 7.5 to 11.8, most preferably from 8.0 to
11.5.
Examples
[0257] The present example is representative of the laundry additive sachets as described
herein and are not meant to be limiting.
Compartment 1 |
Powder (15 g) |
Percarbonate |
15% |
|
|
TAED |
5% |
|
|
Clay softener |
67% |
|
|
Polyethlene oxide av. mol. Wt. 500 000 |
2% |
|
|
citric acid |
5% |
|
|
Bicarbonate |
5% |
|
|
Minors |
1% |
|
|
|
total |
100% |
|
Compartment 2 |
Liquid (15 g) |
Isoparaffin |
55% |
|
|
CLASS* |
5% |
|
|
PAP |
25% |
|
|
NOBS |
15% |
|
|
|
total |
100% |
*CLASS = crystalline linear alkyl benzene sulphonate (LAS) structure |