Note: Descriptions are shown in the official language in which they were submitted.
' , CA 02248476 1998-09-28
C 7479 (C)
BLEACH ACTIVATION
Field of the Invention
5 The invention relates to activation of bleaches employing peroxy compounds including
hydrogen peroxide or hydrogen peroxide adducts, which liberate hydrogen peroxide in
aqueous solution, and peroxy acids (or precursors thereof); to compounds that activate
or catalyse peroxy compounds; to bleach compositions, including detergent bleachcompositions, which contain a catalyst for peroxy compounds; and to processes for
10 bleaching and/or washing substrates using the aforementioned types of compositions.
In particular, the present invention is concerned with the novel use of iron compounds
as catalysts for the bleach activation of peroxy compounds.
15 Back~round of the Invention.
Peroxide bleA.~hing agents for use in laundering have been known for many years. Such
agents are effective in removing stains, such as tea, fruit, and wine stains, from clothing
at or near boiling temperatures. The efficacy of peroxide bleachin~. agents drops off
sharply at temperatures below 60~C.
Previous patent applications dealt with environmentally acceptable mAngAnese ions and
complexes. US-A-4,728,455 ~ c~l~sçs the use of Mn(III)-gluconate as peroxide bleach
catalyst with high hydrolytic and oxidative stability; relatively high ratios of ligand
(gluconate) to Mn are, however, needed to obtain the desired catalytic system.
25 Moreover, the performance of these Mn-based catalysts is inadequate when used for
bleaching in the low-temperature region of about 20~-40~C, and they are restricted in
their efficacy to remove a wide range of stains.
In several patent documents, for instance EP-A~58,379, novel triazacyclononane-
' ~ CA 02248476 1998-09-28
based manganese complexes are disclosed, which display a high catalytic oxidation
activity at low temperatures that is particularly suitable for bleaçhing purposes. A major
improvement of the bleaching activity could be obtained by virtue of the fact that these
compounds are stable under washing conditions, e.g. high alkalinity and oxidizing
5 environment (as a result of the presence of hydrogen peroxide or peroxy acids).
In addition to the above-mentioned stain removal, dye transfer is a well-known problem
in the art and has been addressed in various ways. For instance, an improved dyetransfer inhibition has been obtained by using Fe-porphyrin and Fe-phthalocyanine
complexes (seeEP-A-537,381, EP-A-553,607, EP-A-538,228).
It is well known that the stability of Fe-co-ordination complexes in alkaline aqueous
media in the presence of peroxide compounds is very poor. In EP-A-537,381 and
EP-A-553,607, methods are disclosed for Improvement in this respect.
This poor stability of Fe-co-ordination species has resulted in the necessity of very low
concentrations of peroxide and, additionally, the use of polymers (see EP-A-538,228).
These measures, however, only reduce the negative effects of the above-indicated poor
stability to some extent and do not provide a complete solution to this problem.
In WO-A-9534628, it has been shown that the use of iron compounds containing
pentadentate nitrogen-containing ligands, in particular the use of N,N-bis(pyridin-2-
ylmethyl)-bis(pyridin-2-yl)methylamine, as blea~hing and oxidation catalysts, resulted
in a favourable bleaçhing activity, dye bleaching activity and oxidation activity in
25 general.
We have now surprisingly found that a significantly improved catalytic oxidationactivity of the Fe-coordination complex can be obtained by substituting the H-atom of
' , CA 02248476 1998-09-28
the C-H group of the methylamine moiety present in the ligands according to WO-A-
9534628, by other groups.
As a consequence, these new iron compounds were found to provide favourable stain
5 removal in the presence of hydrogen peroxide or peroxy acids. Furthermore, an
improved bleaching activity has been particularly noted in alkaline agueous solutions
containing peroxy compounds at concentrations generally present in the wash liquor
during the fabric washing cycle.
10 Additionally, these new iron compounds exhibit remarkable dye transfer inhibition
properties, and, alternatively, oxidation of organic substrates such as olefins, alcohols
and unactivated hydrocarbons.
Definition of the Invention
15 In one aspect, the present invention provides a bleach and oxidation catalyst comprising
an Fe-complex having formula (A):
[LFeXn] Yq (A)
20 or precursors thereof, in which
Fe is iron in the II, III,IV or V oxidation state;
X represents a coordin~tin~ species such as H20, ROH, NR3, RCN, OH, OOH,
OOR, RS, RO, RCOO, OCN, SCN, N3, CN, F-, Cl, Br, r, o2-, NO3, NO2, So42,
So32, PO43 or aromatic N donors such as pyridines, pyrazines, pyrazoles, imidazoles,
25 benzimidazoles, pyrimidines, triazoles and thiazoles with R being H, optionally
substituted alkyl or optionally substituted aryl;
n is an integer ranging from 0-3;
Y is a counter ion, the type of which is dependent on the charge of the complex;
, .
, CA 02248476 1998-09-28
q = z/[charge Y];
z denotes the charge of the complex and is an integer which can be positive,
zero or negative; if z is positive, Y is an anion such as F, Cl 7 Br~, I, NO3, BPh4, CIO4
, BF4, PF6, RSO3, RSO4, So42, CF3SO3 or RCOO; if z is negative, Y is a common
5 cation such as an alkali metal, alkaline earth metal or (alkyl)ammonium cation; and
L represents a ligand of general formula (B):
R2 R4
R~ (B)
1~3 R5
10 which contains at least five nitrogen atoms and in which the substituent groups Rl-R5
are independently selected from hydrogen, hydroxy, halogen, nitroso, formyl, carboxyl,
and esters and salts thereof, carbamoyl, sulfo, and esters and salts hereof, sulfamoyl,
nitro, amino, C0-C20-alkyl-hydroxy, C0-C20-alkyl-halogen, C0-C20-alkyl-nitroso, Co-C
alkyl-formyl, C0-C20-alkyl-carboxyl, and esters and salts thereof, C0-C20-alkyl-
carbamoyl, C0-C20-alkyl-sulfo, and esters and salts hereof, C0-C20-alkyl-sulfamoyl, C0-
C20-alkyl-amino, C0-C20-alkylaryl, C0-C20-alkylheteroaryl~ Co-C20 alkyl, C0-C8 alkoxy,
carbonyl-CO-C6-alkoxy, and aryl-(~O-CP6-alkyl, ~
provided that R~ does not represent hydrogen.
20 In another aspect, the present invention provides a bleaçhin~ composition comprising a
peroxy compound bleach preferably selected from hydrogen peroxide, hydrogen
peroxide-liberating or -generating compounds, peroxyacids and their salts, and mixtures
thereof, optionally together with peroxyacid bleach precursors, and a catalyst according
to the present invention.
Detailed Description of the Invention
, ' , CA 02248476 1998-09-28
Generally, the Fe-complex catalyst of the invention may be used in a bleaching system
comprising a peroxy compound or a precursor thereof, and may be suitable for use in
the washing and bleaching of substrates including laundry, dishwashing and hard
surface cleaning. Alternatively, the Fe-complex catalyst of the invention may be used
5 for bleaching in the textile, paper and woodpulp industries, as well as in waste water
treatment.
As already stated, an advantage of the Fe-complex catalysts according to the present
invention is that they exhibit a remarkably high oxidation activity in alkaline aqueous
10 media in the presence of peroxy compounds.
A second advantage of the new Fe-complex catalysts of the invention is that they show
good bleaching activity at a broader pH range (generally pH 6~ than those observed
for the previously disclosed iron complexes. Their performance was especially
15 improved at pH of around 10. This advantage may be particularly beneficial in view of
the current detergent formulations that employ rather alkaline conditions, as well as the
tendency to shift the pH during fabric washing from alkaline (typically, a pH of 10) to
more neutral values. Furthermore, this advantage may be beneficial when using the
present iron complex catalyst in machine dishwash formulations.
An additional advantage is that such compounds are active as dye-transfer inhibition
agents, as shown in Example 5.
Another advantage is that the catalysts of the invention have a relatively low molecular
25 weight and, consequently, are very weight-effective.
Precursors of the active Fe-complex catalysts of the invention can be any iron co-
ordination complex, which, under fabric washing conditions, is transformed into the
, , CA 02248476 1998-09-28
active iron complex of general formula (A). Alternatively, the precursor of the Fe-
complex of the invention can be a mixture of an iron salt, such as Fe(NO3)3, and the
ligand L.
A preferred class of ligands is that of compounds of general formula (B), in which R2,
R3, R4, R5 are independently chosen from Co-C5 alkyl substituted with nitrogen-
containing heterocyclic aromatic groups, such as pyridines, pyrazines, pyrazoles,
imidazoles, benzimidazoles, thiazoles, triazoles and pyrimidines, in particular pyridines,
and in which the substituent group Rl represents any group other than hydrogen, e.g.
hydroxy, halogen, nitroso, formyl, carboxyl, and esters and salts thereof, carbamoyl,
sulfo, and esters and salts hereof, sulfamoyl, nitro, amino, C0-C20-alkyl-hydroxy, C0-
C20-alkyl-halogen, CO-C20-alkyl-nitroso, CO-C20-alkyl-formyl, CO-C20-alkyl-carboxyl,
and esters and salts thereof, C0-C20-alkyl-carbamoyl, C0-C20-alkyl-sulfo, and esters and
salts hereof, C0-C20-alkyl-sulfamoyl, C0-C20-alkyl-amino, C0-C20-alkylaryl, Co-C20-
alkylheteroaryl, Co-C20 alkyl, Co-C8 alkoxy, carbonyl-C0-C6-alkoxy, aryl-C0-C6-alkyl,
whereby the carbamoyl, sulfamoyl and amino groups are optionally further substituted
by any other group.
A more preferred class of ligands is that of compounds of general formula (B), in which
the substituent group R~ is selected from Co-C20 alkylaryl, Co-C20 alkylheteroaryl, and
Co-C20 alkyl, and in which the substituent groups R2, R3, R4, and R5 are independently
chosen from Co-C5 alkyl substituted with a pyridine ring.
Examples of preferred ligands in their simplest forms are:
N,N-bis(pyridin-2-yl-methyl)- 1,1 -bis(pyridin-2-yl)- 1 -aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-1-aminoethane;
N,N-bis(pyrazol- 1 -yl-methyl)- 1,1 -bis(pyridin-2-yl)- 1 -aminoethane;
N,N-bis(pyrazol- 1 -yl-methyl)- 1,1 -bis(pyridin-2-yl)-2-phenyl- 1 -aminoethane;
~ CA 02248476 1998-09-28
N,N-bis(imidazol-2-yl-methyl)- 1,1 -bis(pyridin-2-yl)- 1 -aminoethane;
N,N-bis(imidazol-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-1-aminoethane;
N,N-bis( 1 ,2,4-triazol- 1 -yl-methyl)- 1,1 -bis(pyridin-2-yl)- 1 -aminoethane;
N,N-bis(1,2,4-triazol-1-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-1-aminoethane;N,N-bis(pyridin-2-yl-methyl)- 1,1 -bis(pyrazol- 1 -yl)- 1 -aminoethane;
N,N-bis(pyridin-2-yl-methyl)- 1,1 -bis(pyrazol- 1 -yl)-2-phenyl- 1 -aminoethane;N,N-bis(pyridin-2-yl-methyl)-1, 1 -bis(imidazol-2-yl)-1-aminoethane;
N,N-bis(pyridin-2-yl-methyl)- 1,1 -bis(imidazol-2-yl)-2-phenyl- 1 -aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1, 1 -bis(1 ,2,4-triazol-1 -yl)-1 -aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1, 1-bis(1,2,4-triazol-1-yl)-1-aminoethane;
More preferred ligands are:
N,N-bis(pyridin-2-yl~methyl~-1, 1 -bis(pyridin-2-yl)-1-aminoethane,
N,N-bis(pyridin-2-yl-methyl)- 1,1 -bis(pyridin-2-yl)- 1 -aminohexane,
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-1-aminoethane,
N,N-bis(pyridin-2-yl-methyl)- 1,1 -bis(pyridin-2-yl)-2-(4-sulfonic acid-phenyl)- 1-
aminoethane,
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(pyridin-2-yl)-1-aminoethane,
N,N-bis(pyridin-2-y!-methyl)-1, 1 -bis(pyridin-2-yl)-2-(pyridin-3-yl)-1-aminoethane,
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(pyridin-4-yl)-1-aminoethane,
N,N-bis(pyridin-2-yl-methyl)- 1,1 -bis(pyridin-2-yl)-2-( 1 -alkyl-pyridinium-4-yl)- 1-
aminoethane,
N,N-bis(pyridin-2-yl-methyl)- 1,1 -bis(pyridin-2-yl)-2-( 1 -alkyl-pyridinium-3 -yl)- 1-
aminoethane,
N,N-bis(pyridin-2-yl-methyl)- 1,1 -bis(pyridin-2-yl)-2-( 1 -alkyl-pyridinium-2-yl)- 1-
aminoethane.
The most preferred ligands are:
, CA 02248476 1998-09-28
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane, hereafter referred to
as MeN4Py,
N,N-bis(pyridin-2-yl-methyl)- 1,1 -bis(pyridin-2-yl)-2-phenyl- 1 -aminoethane, hereafter
referred to as BzN4Py.
Suitable counter ions are those which give rise to the formation of storage-stable solids.
Combination of the preferred iron complexes with the counter ion Y preferably
involves counter ions selected from RCOO-, BPh4-, CIO4-, BF4, PF6-, RSO3, RSO4,
So42, NO3, F, Cl, Br, r wherein R=H, optionally substituted phenyl, naphthyl or Cl-
10 C4 alkyl. Preferred co-ordinating species X are selected from CH3CN, pyridine, H2O,
Cl, OR, and OOH, wherein R=H, optionally substituted phenyl, naphthyl or C~-C4
alkyl.
The effective level of the Fe-complex catalyst, expressed in terms of parts per million
15 (ppm) of iron in an aqueous ble~çl-ing solution, will normally range from 0.001 ppm to
100 ppm, preferably from 0.01 ppm to 20 ppm, most preferably from 0.1 ppm to 10
ppm. Higher levels may be desired and applied in industrial ble~çlling processes, such
as textile and paper pulp ble~ ing The lower range levels are preferably used indomestic laundry operations.
The deter~ent bleach composition
The bleaching composition of the invention has particular application in detergent
25 formulations, to form a new and improved detergent bleach composition within the
purview of the invention comprising a peroxy compound bleach as defined above, the
aforesaid Fe-complex catalyst having general formula (A), a surface-active material and
a detergency builder.
CA 02248476 1998-09-28
The Fe-complex catalyst will be present in the detergent bleach composition of the
invention in amounts so as to provide the required level in the wash liquor. Generally,
the Fe-complex catalyst level in the detergent bleach composition corresponds to an
iron content of from 0.0005% to 0.5% by weight. When the dosage of detergent bleach
composition is relatively low, e.g about 1-2 g/l, the Fe content in the formulation is
suitably 0.0025 to 0.5%, preferably 0.005 to 0.25% by weight. At higher product
dosages, as used e.g by European consumers, the Fe content in the formulation issuitably 0.0005 to 0.1%, preferably 0.001 to 0.05% by weight.
Detergent bleach compositions of the invention are effective over a wide pH-range of
between 7 and 13, with optimal pH-range Iying between 8 and 11.
The peroxy blea~.hin~ compound
15 The peroxy bleaching compound may be a compound which is capable of yielding
hydrogen peroxide in aqueous solution. Hydrogen peroxide sources are well known in
the art. They include the alkali metal peroxides, organic peroxides such as ureaperoxide, and inorganic persalts, such as the alkali metal perborates, percarbonates,
perphosphates persilicates and persu!phates. Mixtures of two or more such compounds
20 may also be suitable.
Particularly preferred are sodium perborate tetrahydrate and, especially, sodiumperborate monohydrate. Sodium perborate monohydrate is preferred because of its high
active oxygen content. Sodium percarbonate may also be preferred for environmental
25 reasons. The amount thereof in the composition of the invention usually will be within
the range of about 5-3 5 % by weight, preferably from 10-25 % by weight.
, . CA 02248476 1998-09-28
Another suitable hydrogen peroxide generating system is a combination of a Cl-C4alkanol oxidase and a Cl-C4 alkanol, especially a combination of methanol oxidase
(MOX) and ethanol. Such combinations are disclosed in WO-A-9507972, which is
incorporated herein by reference.
s
Alkylhydroxy peroxides are another class of peroxy blea~hing compounds. Examples of
these materials include cumene hydroperoxide and t-butyl hydroperoxide.
Organic peroxyacids may also be suitable as the peroxy bleachin~ compound. Such
10 materials normally have the general formula:
1~l
Y--R--C--O--OH
wherein R is an alkyl- or alkylidene- or substituted alkylene group cont~inin~ from 1 to
about 20 carbon atoms, optionally having~an internal amide linkage; or a phenylene or
substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic
15 or non-aromatic group, a COOH or COOOH group or a quaternary ammonium group.
Typical monoperoxy acids useful herein include, for example:
(i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g. peroxy-a-
naphthoic acid;
20 (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, e.g. peroxylauric
acid, peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP); and
(iii) 6-octylamino-6-oxo-peroxyhexanoic acid.
Typical diperoxyacids useful herein include, for example:
25 (iv) 1,12-diperoxydodecanedioic acid (DPDA);
(v) 1,9-diperoxyazelaic acid;
(vi) diperoxybrassylic acid; dipe-oxysebacic acid and diperoxyisophthalic acid;
CA 02248476 1998-09-28
(vii) 2-decyldiperoxybutane-1,4-dioic acid; and
(viii) 4,4'-sulphonylbisperoxybenzoic acid.
Also inorganic peroxyacid compounds are suitable, such as for example potassium
5 monopersulphate (MPS). If organic or inorganic peroxyacids are used as the peroxygen
compound, the amount thereof will normally be within the range of about 2-10 % by
weight, preferably from 4-8 % by weight.
All these peroxy compounds may be utilized alone or in conjunction with a peroxyacid
10 bleach precursor and/or an organic bleach catalyst not cont~inin~ a transition metal.
Generally, the bleaçhin~ composition of the invention can be suitably formulated to
contain from 2 to 35%, preferably from 5 to 25% by weight, of the peroxy ble~ching
- agent.
15 Peroxyacid bleach precursors are hlown and amply described in literature, such as in
GB-A-836988; GB-A-864,798; GB-A-907,356; GB-A-1,003,310 and GB-A-1,519,351;
DE-A-3,337,921; EP-A-0,185,522; EP-A-0,174,132; EP-A-0,120,591; and US-A-
1,246,339; US-A-3,332,882; US-A~,128,494; US-A-4,412,934 and US-A-4,675,393.
20 Another useful class of peroxyacid bleach precursors is that of the cationic i.e.
quaternary ammonium substituted peroxyacid precursors as disclosed in US-A-
4,751,015 and US-A-4,397,757, in EP-A-0,284,292 and EP-A-331,229. Examples of
peroxyacid bleach precursors of this class are:
2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphophenyl carbonate chloride -
25 (SPCC);
N-octyl,N,N-dimethyl-N~0-carbophenoxy decyl ammonium chloride - (ODC);
3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and
N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.
CA 02248476 1998-09-28
A further special class of bleach precursors is formed by the cationic nitriles as
disclosed in EP-A-303,520; EP-A-458,396 and EP-A-464,880.
5 Any one of these peroxyacid bleach precursors can be used in the present invention,
although some may be more preferred than others.
Of the above classes of bleach precursors, the preferred classes are the esters, including
acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl-amides; and the
10 quaternary ammonium substituted peroxyacid precursors including the cationic nitriles.
Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-
benzoyloxy benzene sulphonate (SBOBS); N,N,N'N'-tetraacetyl ethyl.ene diamine
(TAED); sodium-l-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-
15 benzoloxy bçn7oate; 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphophenyl
carbonate chloride (SPCC); trimethyl ammonium toluyloxy-benzene sulphonate;
sodium nonanoyloxybenzene sulphon~te (SNOBS); sodium 3,5,5-trimethyl hexanoyl-
oxybenzene sulphonate (STHOBS); and the substituted cationic nitriles.
The precursors may be used in an amount of up to 12 %, preferably from 2-10 % byweight, of the composition.
As an alternative to the above described peroxide generating systems, molecular oxygen
may be used as the oxidant.
The surface-active material
The detergent bleach composition according to the present invention generally contains
a surface-active material in an amount of from 10 to 50% by weight.
CA 02248476 1998-09-28
Said surface-active material may be naturally derived, such as soap, or a synthetic
material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and
mixtures thereof. Many suitable actives are commercially available and are fully5 described in the literature, for example in "Surface Active Agents and Detergents",
Volumes I and II, by Schwartz, Perry and Berch.
Typical synthetic anionic surface-actives are usually water-soluble alkali metal salts of
organic sulphates and sulphonates having alkyl radicals cont~ining from about 8 to
10 about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher
aryl radicals. Examples of suitable synthetic anionic detergent compounds are sodium
and ammonium alkyl sulphates, especially those obtained by sulphating higher (C8-CI8)
alcohols producedj for example, from tallow or coconut oil; sodium and ammonium
alkyl (Cg-C,O) benzene sulphonates, particularly sodium linear secondary alkyl (C,0-
C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethersof the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride
sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters ofhigher (C9-C,8) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction
products; the reaction products of fatty acids such as coconut fatty acids esterified with
20 isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of
fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by
racting alpha-olefins (C8-C20) with sodium bisulphite and those derived by reaction
paraffins with SO2 and Cl2 and then hydrolysing with a base to produce a random
sulphonate; sodium an ammonium C7-CI2 dialkyl sulphosuccinates; and olefin
25 sulphonates which term is used to describe material made by reacting olefins,particularly C~o-C20 alpha-olefins, with SO3 and then neutralising and hydrolysing the
reaction product. The preferred anionic detergent compounds are sodium (Clo-C,5)alkylbenzene sulphonates, sodium (C,6-C,8) alkyl ether sulphates.
CA 02248476 1998-09-28
14
Examples of suitable nonionic surface-active compounds which may be used,
preferably together with the anionic surface-active compounds, include, in particular,
the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22)
phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; and the
condensation products of aliphatic (C8-CI8) primary or secondary linear or branched
alcohols with ethylene oxide, generally 2-30 EO. Other so-called nonionic surface-
actives include alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides,
long-chain tertiary phosphine oxides and dialkyl sulphoxides.
Amphoteric or zwitterionic surface-active compounds can also be used in the
compositions of the invention but this is not normally desired owing to their relatively
high cost. If any amphoteric or zwitterionic detergent compQunds are used, it isgenerally in small amounts in compositions based on the much more commonly used
15 synthetic anionic and nonionic actives.
As disclosed by EP-A-544,490, the performance of the hereinbefore described bleach
catalyst may be dependent upon the active detergent system and the builder system
present in the detergent bleach composition of the invention.
The detergent bleach composition of the invention will preferably comprise from 1-15
% wt of anionic surfactant and from 10-40 % by weight of nonionic surfactant. In a
further preferred embodiment the detergent active system is free from Cl6-C~2 fatty
acids soaps.
The deter~ency builder
~ CA 02248476 1998-09-28
The composition of the invention normally and preferably also contains a detergency
builder in an amount of from about 5-80 % by weight, preferably from about 10-60 %
by weight.
Builder materials may be selected from l) calcium sequestrant materials, 2)
precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
Examples of calcium sequestrant builder materials include alkali metal polyphosphates,
such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts; the
alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid,
oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and
polyacetal carboxylates as disclosed in US-A-4,144,226 and US-A-4,146,495.
Examples of precipilaling builder materials include sodium orthophosphate and sodium
carbonate.
Examples of calcium ion-exchange builder materials include the various types of water-
insoluble crystalline or amorphous al-lmino~ilicates, of which zeolites are the best
known representatives, e.g. zeolite A, zeolite B (also know as zeolite P), zeolite C,
zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0384070.
In particular, the compositions of the invention may contain any one of the organic and
inorganic builder materials, though, for environmental reasons, phosphate builders are
preferably omitted or only used in very small amounts.
25 Typical builders usable in the present invention are, for example, sodium carbonate,
calcite/carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate,
carboxymethyloxy malonate, carboxymethyloxy sucçin~te and the water-insoluble
crystalline or amorphous aluminosilicate builder material, each of which can be used as
', CA 02248476 1998-09-28
16
the main builder, either alone or in admixture with minor amounts of other builders or
polymers as co-builder.
It is preferred that the composition contains not more than 5% by weight of a carbonate
5 builder, expressed as sodium carbonate, more preferable not more than 2.5 % by weight
to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
Other in~redients
Apart form the components already mentioned, the detergent bleach composition of the
10 invention can contain any of the conventional additives in amounts of which such
materials are normally employed in fabric washing detergent compositions. Examples
of these additives include buffers such as carbonates, lather boosters, such as
alkanolamides, particularly the monoethanol amides derived from palmkernel fattyacids and coconut fatty acids; lather depressants, such as alkyl phosphates and silicones;
15 anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl orsubstituted alkyl cellulose ethers; stabilizers, such as phosphonic acid derivatives (i.e.
Dequest g) types); fabric softening agents; inorganic salts and alkaline buffering agents,
such as sodium sulphate and sodium silicate; and usually in very small amounts,
fluorescent agents; perfumes, enzymes, such as proteases, cellulases, lipases, amylases
20 and oxidases; germicides and colourants.
When using a hydrogen peroxide source, such as sodium perborate or sodium
percarbonate, as the bleaching compound, it is preferred that the composition contains
not more than 5 % by weight of a carbonate buffer, expressed as sodium carbonate,
25 more preferable not more than 2.5% by weight to substantially nil, if the composition
pH lies in the lower alkaline region of up to 10.
', CA 02248476 1998-09-28
Of the additives, transition metal sequestrants such as EDTA and the phosphonic acid
derivatives, e.g. ethylene diamine tetra-(methylene phosphonate)-EDTMP- are of
special importance, as not only do they improve the stability of the catalyst/H2O2
system and sensitive ingredients, such as enzymes, fluorescent agents, perfumes and the
like, but also improve the bleach performance, especially at the higher pH region of
above 10, particularly at pH 10.5 and above.
The invention will now be further illustrated by way of the following non-limiting
examples:
Example 1
Preparation of MeN4Py ligand
The precursor N4Py.HClO4 was prepared as follows:
To pyridyl ketone oxim (3 g, 15.1 mmol) was added ethanol (15 ml), concentrated
ammonia solution (15 mL) and NH40Ac (1.21 g, 15.8 mmol). The solution was
warmed until reflux. To this solution was added 4.64 g Zn in small portions. After the
addition of all Zn, the mixture was refluxed for 1 hour and allowed to cool to ambient
temperature. The solution was filtered and water (15 ml) was added. Solid NaOH was
added until-pH'~10 and the solution-w&s extracted-with-CH2CI2 (3 x20 ~1). The
organic layers were dried over Na2SO4 and evaporated until dryness. Bis(pyridin-2-
yl)methylamine (2.39 g, 12.9 mmol) was obtained as a colourless oil in 86% yield,
showing the following analytical characteristics:
~H NMR (360 MHz, CDCI3): o 2.64 (s, 2H, NH2), 5.18 (s, lH, CH), 6.93 (m, 2H,
pyridine), 7.22 (m, 2H, pyridine), 7.41 (m, 2H, pyridine), 8.32 (m, 2H, pyridine); 13C
NMR (CDCI3): o 62.19 (CH), 121.73 (CH), 122.01 (CH), 136.S6 (CH), 149.03 (CH),
162.64 (Cq).
CA 02248476 1998-09-28
To picolylchloride hydrochloride (4.06 g, 24.8 mmol) was added, at 0~C, 4.9 ml of a
5N NaOH solution. This emulsion was added by means of a syringe to bis(pyridin-2-
yl)methylamine (2.3 g, 12.4 mmol) at 0~C Another 5 ml of a 5N NaOH solution was
added to this mixture. After warming to ambient temperature, the mixture was stirred
vigorously for 40 hrs. The mixture was put in an ice bath and HCI04 was added until
pH<l, whereupon a brown solid precipitated. The brown precipitate was collected by
filtration and recrystallized from water. While stirring, this mixture was allowed to cool
to ambient temperature, whereupon a light-brown solid precipitated which was
collected by filtration and washed with cold water and air-dried (1.47 g).
From 0.5 g of the perchlorate salt of N4Py prepared as described above, the free amine
was obtained by precipitating the salt with 2N NaOH and subsequently by extraction
with CH2CI2. To the free amine was added- under argon 20 ml of dry tetrahydrofuran
freshly distilled from LiAlH4. The mixture was stirred and cooled to -70 ~C by an
15 alcohol / dry ice bath. Now 1 ml of 2.5 N butyllithium solution in hexane was added
giving an immediate dark red colour. The mixture was allowed to warm to -20 ~C and
now 0.1 ml of methyl iodide was added. The temperature was kept to -10 ~C for 1 hour.
Subsequently 0.5 g of ammonium chloride was added and the mixture was evapo~aledin vacuo. To the residue water was added and the aqueous layer was extracted with
20 dichloromethane. The dichloromethane layer was dried on sodium sulfate, filtered and
evaporated giving 0.4 g residue. The residue was purified by crystallisation from ethyl
acetate and hexane giving 0.2 g of creamish powder (50% yield) showing the following
analytical characteristics:
~H NMR (400 MHz, CDCI3): o (ppm) 2.05 (s, 3H, CH3), 4.01 (s, 4H, CH2), 6.92 (m,
25 2H, pyridine), 7.08 (m, 2H, pyridine), 7.39 (m, 4H pyridine), 7.60 (m 2H, pyridine),
7.98 (d, 2H, pyridine), 8.41 (m, 2H pyridine), 8.57 (m, 2H, pyridine). '3C NMR
(100.55 MHz, CDCI3): ~ (ppm) 21.7 (CH3), 58.2 (CH2), 73.2 (Cq), 121.4 (CH), 121.7
CA 02248476 1998-09-28
19
(CH), 123.4 (CH), 123.6 (CH), 136.0 (CH), 148.2 (Cq), 148.6 (Cq), 160.1 (Cq), 163.8
(Cq).
Subsequently [(MeN4Py)Fe(CH3CN)](ClO4)2, hereinafter referred to as Fe(MeN4Py),
5 was prepared as follows:
To a solution of 0.27 g of MeN4Py in 12 ml of a mixture of 6 ml acetonitrile and 6 ml
methanol was added 350 mg Fe(ClO4)2.6H2O immediately a dark red colour formed. To
the mix was added now 0.5 g of sodium perchlorate and a orange red precipitate formed
10 immediately. After 5 minutes stirring and ultrasonic treatment the precipitate was
isolated by filtration and dried in vacuo at 50~C. In this way 350 mg of an orange red
powder was obtained in 70% yield showing the following analytical characteristics:
'H NMR (400 MHz, CD~CN): o (ppm) 2.15, (CH3CN), 2.28 (s, 3H, CH3), 4.2 (ab, 4H,
CH2), 7.05 (d, 2H, pyridine), 7.38 (m, 4H, pyridine), 7.71 (2t, 4H pyridine), 7.98 (t,
2H, pyridine), 8.96 (d, 2H pyridine), 9.06 (m, 2H, pyridine).
W/Vis (acetonitrile) [~max, nm (~, Ml cm-l)]: 381 (8400), 458 nm (6400).
Anal.Calcd for C25H26CI2FeN6O8: C, 46.11; H, 3.87; N, 12.41; Cl, 10.47; Fe, 8.25.
Found: C, 45.49; H, 3.95; N, 12.5; Cl, 10.7; Fe, 8.12.
Mass-ESP (cone voltage 17V in CH3CN): m/z 218.6 [MeN4PyFe]2 ; 239.1
[MeN4PyFeCH3C~2t.~
Example 2
Preparation of BzN4Py ligand
To 1 g of the N4Py ligand prepared as described above, 20 ml of dry tetrahydrofuran
freshly distilled from LiAlH4, was added under argon. The mixture was stirred and
cooled to -70 ~C by an alcohol / dry ice bath. Now 2 ml of 2.5 N butyllithium solution
in hexane was added giving an immediate dark red colour. The mix was allowed to
CA 02248476 1998-09-28
warm to -20~C and now 0.4 ml of benzyl bromidide was added. The mixture was
allowed to warm up to 25 ~C and stirring was continued over night. Subsequently 0.5 g
of ammonium chloride was added and the mixture was evaporated in vacuo. To the
residue water was added and the aqueous layer was extracted with dichloromethane.
S The dichloromethane layer was dried on sodium sulfate, filtered and evaporated giving
1 g brown oily residue. According to NMR spectroscopy, the product was not pure but
contained no starting material (N4Py). The residue was used without further
purification.
Subsequently [(BzN4Py)Fe(CH3CN)](CI04)2 hereinafter referred to as Fe(BzN4Py),
was prepared as follows:
To a solution of 0.2 g of the residue obtained by the previous described procedure in 10
ml of a mixture of 5 ml acetonitrile and 5 ml methanol was added 100 mg
Fe(ClO4)2.6H2O immediately a dark red colour formed. To the mix was added now
0.25 g of sodium perchlorate and ethylacetate was allowed to diffuse into the mixture
overnight. Some red crystals were formed which were isolated by filtration and washed
with methanol. In this way 70 mg of a red powder was obtained showing the following
analytical characteristics:
lH ~MR-(-4~0 ~z,-CD3(~N~: ~-(ppm-)-~ 2,-(~, 3H, C~-H3CN~, 3 65 *-4.1-(ab, 4H,- - --. . - . .
CH2), 4.42 (s, 2H, CH2-benzyl), 6.84 (d, 2H, pyridine), 7.35 (m, 4H, pyridine), 7.45
(m, 3 H, benzene) 7.65 (m, 4H benzene + pryidine), 8.08(m, 4H, pyridine), 8.95 (m,
4H pyridine).
W/Vis (acetonitrile) [~max, nm (~, M-lcm'l)]: 380 (7400), 458 nm (5500).
Mass-ESP (cone voltage 17V in CH3CN): mJz 256.4 [BzN4Py]2+; 612
[BzN4PyFeCI04]
' CA 02248476 1998-09-28
Example 3
The bleaching activity of the Fe-catalysts prepared according to Example 1 and 2, was
demonstrated in the presence of hydrogen peroxide on standard tea-stained (BC-1)cotton test cloths.
s
The experiments were carried out at 40~C and at a pH of 10 in a temperature-controlled
glass beaker equipped with a magnetic stirrer, thermocouple and a pH electrode.
Two pieces of test cloth were stirred for 30 minutes in 1 liter of a 8.6xlO 3 mol/l
10 hydrogen peroxide solution in millipore water, containing concentrations of the
compounds as indicated in Table 1. After rinsing with demineralised water, the test
cloths were dried for 7 minutes in a microwave oven. The reflectance (R460*) of the test
cloths was measured on a Minolta(~ CM-3700d spectrophotometer including UV-filter
before and after treatment. The difference (~R460*) between both reflectance values
15 thus obtained gives a measure of the bleachin~ performance, i.e. higher ~R460* values
correspond to an improved blea~hin~ performance.
TABLE 1
conc. Fe ~R460*
(mol/l) (at pH=10)
blank - 6.5
Fe(NO3)3 lOxlO-6 6.2
Fe(N4Py) loxlo-6 12.0
Fe(MeN4Py) lOx1o-6 15.8
Fe(BzN4Py) loxlo-6 17.3
~ CA 02248476 1998-09-28
In Table 1, Fe(MeN4Py) and Fe(BzN4Py) refer to the Fe-catalysts prepared according to
Examples 1 and 2, and Fe(N4Py) to the non-methylated analogue as described in WO-
A-9534628. The blank and Fe(NO3)3 experiment were used as control.
S These measurements show that significantly improved bleaching performance is
obtained with Fe(MeN4Py) and Fe(BzN4Py) as compared to Fe(N4Py) as catalyst.
Example 4
The bleaching activity of the Fe(MeN4Py) catalyst prepared according to Example 1
10 was demonstrated in the presence of a detergent formulation on standard tea-stained
(BC-1) cotton test cloths.
The detergent formulation contained the following ingredients and was dosed (in water)
as indicated in Table 2.
TABLE 2
Detergent formulation used for the ble~ching experiments with Fe(MeN4Py)
Ingredient Dosage (g/l)
Sodium linear alkylbenzene sulphonate (LAS) 0.60
Sodium triphosphate (STP) 0.36
Sodium carbonate 0.44
Sodium disilicate 0.20
Sodium sulphate 0.67
Sodium perborate monohydrate 0.20
Tetraacetyleneethylene diamine (TAED) 0.06l)
Fe(MeN4Py) <o.ol2)
enzymes, fluorescer, SCMC, minors, moisture 0.19
' CA 02248476 1998-09-28
I) Only for experiment A
2) Only for experiment B
5 The experiments were carried out at 25~C and at a pH of around 10 (pH of the wash
liquor) by using water of 4 ~F (Ca:Mg= 4:1) in a temperature-controlled glass beaker
equipped with a magnetic stirrer, thermocouple and a pH electrode.
Two pieces of test cloth were stirred for 30 minllt~s in 1 liter of the above detergent
10 formulation yielding in situ:
*in experiment A: 1.5 x 10-3 mol/l hydrogen peroxide and
0.5 x 10 3 mol/l peroxyacetic acid; and
*in experiment B: 2 x 10 3 mol/l hydrogen peroxide
containing 1 x 10 5 mol/l Fe(MeN4Py).
After rinsing with demineralised water, the test cloths were dried for 7 minutçc in a
microwave oven. The reflectance (R460*) of the test cloths was measured on a Minoltat~
CM-3700d spe~ ophotometer -including W-filter before and after treatment. The
difference (~R460*) between both reflectance values thus obtained gives a measure of
20 the bleaçhin~ performance, i.e. higher ~R460* values correspond to an improved
bleaching performance.
Experiment A: 4.0 ~R460* bleachin~ units
Experiment B: 6.7 QR460* bleaç~inp units
These measurements show that significantly improved bleaching performance is
obtained with ~e(MeN4Py)/H202 in representative detergent formulation, compared to
peroxyacetic acid/H202 in the same detergent formulation.
CA 02248476 1998-09-28
24
Example S
The dye oxidation activity of the Fe-catalysts prepared according to Examples 1 and 2
was demonstrated in the presence of hydrogen peroxide on a dye known as Acid Red5 88
The experiments were carried out at 40 C at pH=10 in a 1 cm cuvet in the presence of
8.6x10 3 mol/l hydrogen peroxide and 6xlO 5 mol/l Acid Red 88. The absorbance at 503
nm (A503), which is the maximum of the characteristic visible absorption of the dye in
aqueous media, was measured at P0 and t=30 minutes. The ~A503 value given in thetable is a measure of the dye ble~ching activity: ~A503= 1 - (As03(t=30)/A503(t=0 min)),
expressed in %.
A higher AA503 va~ue represent a better dye ble~chin~. activity.
TABLE 3
pH 10 pH 8
conc.(mol/l) aA503 aA5o3
blank - 15% 2%
Fe(NO3)3 5x10-6 16 % 2 %
Fe(MeN4Py) 5xlo-6 26 % 79 %
Fe(BzN4Py) 5x10-6 35 % 86 %
Fe(MeN4Py) and Fe(BzN4Py) in Table 2 refer to the Fe-catalyst prepared according to
Examples 1 and 2. The blank and Fe(NO3)3 experiment were used as controls.
These measurements show that improved dye oxidation performance is obtained whenFe(MeN4Py) and Fe(BzN4Py) are used as catalysts, especially at pH 8.
CA 02248476 1998-09-28
Example 6
The oxidation activity of Fe(MeN4Py) catalyst, prepared according to example 1, was
demonstrated in the presence of hydrogen peroxide on a range of organic substrates.
The experiments were carried out at ambient temperature in acetone. The concentration
of the Fe catalyst was 7.7x10-4 M and the ratio catalyst/H202/substrate was 1/100/1000.
The turnover numbers indicated in Table 4 represent the number of molecules formed
per molecule of catalyst as determined after the indicated time of the reaction by using
gas chromatography. In a blank experiment or in the presence of Fe(NO3)3, essentially
no oxidation products could be detected.
TABLE 4
substrate product (turnover number) reaction time
2-cyclohexen-1-ol (9)
cyclohexene 2-cyclohexen-1-one (3) 30 minutes
cyclohexene epoxide (0)
cyclohexane cyclohexanol (11) 30 minutes
cyclohexanone (6)
