[0001] This invention relates to bleaching compositions containing an oxygen releasing bleach
system, a bleach catalyst, a crystalline layered silicate and preferably a flocculating
agent.
[0002] The satisfactory removal of bleachable soils/stains such as tea, fruit juice and
coloured vegetable soils from stained fabrics is a particular challenge to the formulator
of a bleaching composition for use in a laundry washing method.
[0003] Traditionally, the removal of such bleachable stains has been enabled by the use
of bleach components such as oxygen bleaches, including hydrogen peroxide and organic
peroxyacids. The organic peroxyacids are often obtained by the in situ perhydrolysis
reaction between hydrogen peroxide and an organic peroxyacid bleach precursor. More
recently, products containing bleach catalysts, particularly manganese bleach catalysts
have become of interest.
[0004] A problem which is encountered with bleaches containing bleach catalysts in laundry
washing methods is the propensity of these bleaches to damage the fabrics being washed.
Types of fabric damage can include fading of coloured dyes on the fabrics, or in more
extreme cases structural damage to the fibres of the fabric resulting for example,
in 'pin-hole' formation in the fabrics. The problem can, in particular, be encountered
when the detergent product is added in bulk to a bath containing a tightly compressed
fabric load during a pretreatment soaking method.
[0005] The detergent formulator thus faces the dual challenge of formulating a product which
maximises bleachable soil/stain removal but minimises the occurrence of any unwelcome
fabric damage effects of the catalytic bleaching system.
[0006] It is an object of the present invention to provide bleach catalyst containing bleaching
compositions suitable for use in laundry washing methods having good bleachable stain
removal wherein the compositions show reduced propensity to cause fabric damage.
[0007] The Applicants have found that the problem of fabric damage, and particularly of
fabric colour fading, can be reduced by the inclusion of a crystalline layered silicate
into a bleaching composition having a bleach system employing a transition metal bleach
catalyst. This reduction in fabric damage is enhanced by the inclusion additionally
of a flocculating agent into the composition.
[0008] The inclusion of the crystalline layered silicate and of any flocculating agent has
been found not to significantly compromise the bleachable stain removal ability of
the composition.
[0009] Laundry compositions including preferred flocculating agents, in combination with
clay mineral compounds for the purpose of providing fabric softening effects have
previously been disclosed in European Patent Applications No.s
EP-A-299,575 and
EP-A-313,146. Whilst these documents disclose that the compositions may contain optional bleaching
agents they contain no disclosure relating to the use of bleach catalysts. Furthermore,
they provide no teaching of the use of crystalline layered silicates, particularly
in combination with the flocculating agents described therein, to inhibit fabric damage,
including colour fading.
[0010] Bleach compositions including manganese containing bleach catalyst have been described,
for example, in European Patent Applications No.s
EP-A-549,271;
EP-A-549,272;
EP-A-544,490,
EP-A-544,440,
EP-A-458,397;
EP-A-458,398 and U.S. Patents No.s
US 4,430,243;
US 4,728,455;
US 5,114,606;
US 5,114,611,
US 5,153,161,
US 5,194,416;
US 5,227,084;
US 5,244,594;
US 5,246,621;
US 5,256,779;
US 5,274,147;
US 5,280,117; and
US 5,284,944. None of these documents disclose the use of crystalline layered silicates to inhibit
fabric colour fading associated with the manganese bleach catalyst component.
[0012] All documents cited in the present description are, in relevant part, incorporated
herein by reference.
Summary of the Invention
[0013] According to the present invention there is provided a bleaching composition adapted
for use in a laundry washing method containing
- (a) an oxygen-releasing bleach system;
- (b) a transition metal containing bleach catalyst; and
- (c) a crystalline layered silicate;
[0014] Most preferably, the composition contains a clay flocculating agent.
[0015] Preferably, the crystalline layered silicate is a crystalline layered sodium silicate
with the general formula
NaMSi
xO
2x+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.
[0016] Preferably, the crystalline layered silicate is present at a level of from 0.05%
to 40% by weight of the composition.
[0017] Preferably, the flocculating agent where present is an organic polymeric material
having an average molecular weight of from 100,000 to 10,000,000, preferably present
at a level of from 0.005% to 10% by weight of the composition.
[0018] Preferably, the weight ratio of the crystalline layered silicate to any flocculating
agent is from 300: 1 to 5:1.
[0019] The transition metal containing bleach catalyst is typically selected from the group
consisting of Mn
IV2(u-O)
3 (1,4,7-trimethyl-1,4,7-triazacyclononane)
2-(PF
6)
2; Mn
III2(u-O)
1 (u-OAch(1,4,7-tri-methyl-1,4,7-triazacyclononane)
2-(ClO
4)
2; Mn
IV4(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-triazacy-clononane)
2-(ClO
4)
3;Mn(1,4,7-trimethyl-1,4,7-triaza-cyclononane(OCH
3)
3-(PF
6); Co(2,2'-bispyridyi-amine)Cl
2; Di-(isothio-cyanato)bispyridylamine-cobalt (II); trisdipyridylamine-cobalt (II)
per-chlorate; Co(2,2-bispyridylamine)
2-O
2ClO
4; Bis-(2,2'-bispyridylamine) copper(II) per-chlorate; tris(di-2-pyridylamine) iron
(II) perchlorate; Mn gluconate; Mn(CF
3SO
3)
2; Co(NH
3)
5Cl; binuclear Mn complexed 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 and mixtures thereof.
[0020] According to another aspect of the present invention there is provided the use, in
a method for washing stained fabrics, of a bleaching composition containing an oxygen-releasing
bleach system and a transition metal containing bleach catalyst wherein said composition
contains a crystalline layered silicate to inhibit damage to the fabrics during the
wash.
Oxygen-releasing bleaching system
[0021] An essential feature of the invention is an oxygen-releasing bleaching system containing
essentially an oxygen bleaching species including for example, inorganic perhydrate
bleaches and organic peroxyacids.
[0022] In a preferred execution the bleaching system contains a hydrogen peroxide source
and a peroxyacid bleach precursor compound. The production of the 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.
Inorganic perhydrate bleaches
[0023] Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These 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.
[0024] 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.
[0025] 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.
[0026] Sodium percarbonate, which is a preferred perhydrate for inclusion in compositions
in accordance with the invention, is an addition compound having a formula corresponding
to 2Na
2CO
3.3H
2O
2, and is available commercially as a crystalline solid. The percarbonate is most preferably
incorporated into such compositions in a coated form which provides in product stability.
[0027] 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 form 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n
is from 0.2 to 0.5.
[0028] Other coatings which contain silicate (alone or with borate salts or boric acids
or other inorganics), waxes, oils, fatty soaps can alos be used advantageously within
the present invention.
[0029] Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the
detergent compositions herein.
Peroxyacid bleach precursor
[0030] Peroxyacid bleach precursors are preferably incorporated at a level of from 0.5%
to 20% by weight, more preferably from 1 % to 15% by weight, most preferably from
1.5% to 10% by weight of the compositions.
[0031] Suitable peroxyacid bleach precursors typically contain one or more N- or 0- acyl
groups, which precursors can be selected from a wide range of classes. Suitable classes
include anhydrides, esters, imides 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.
N-acylated lactam precursor compound
[0032] N-acylated precursor compounds of the lactam class are disclosed generally in
GB-A-855735. Whilst the broadest aspect of the invention contemplates the use of any lactam useful
as a peroxyacid precursor, preferred materials comprise the caprolactams and valerolactams.
[0033] Suitable N-acylated lactam precursors have the formula:

wherein n is from 0 to about 8, preferably from 0 to 2, and R
6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons,
or a substituted phenyl group containing from 6 to 18 carbon atoms
[0034] Suitable caprolactam bleach precursors are of the formula:

wherein R
1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon
atoms, preferably from 6 to 12 carbon atoms, most preferably R
1 is phenyl.
[0035] Suitable valero lactams have the formula:

wherein R
1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon
atoms, preferably from 6 to 12 carbon atoms. In highly preferred embodiments, R
1 is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and
mixtures thereof.
[0036] The most preferred materials are those which are normally solid at <30°C, particularly
the phenyl derivatives, ie. benzoyl valerolactam, benzoyl caprolactam and their substituted
benzoyl analogues such as chloro, amino alkyl, alkyl, aryl and alkoxy derivatives.
[0037] Caprolactam and valerolactam precursor materials wherein the R
1 moiety contains at least 6, preferably from 6 to 12, carbon atoms provide peroxyacids
on perhydrolysis of a hydrophobic character which afford nucleophilic and body soil
clean-up. Precursor compounds wherein R
1 comprises from 1 to 6 carbon atoms provide hydrophilic bleaching species which are
particularly efficient for bleaching beverage stains. Mixtures of 'hydrophobic' and
'hydrophilic' caprolactams and valero lactams, typically at weight ratios of 1:5 to
5:1, preferably 1:1, can be used herein for mixed stain removal benefits.
[0038] Highly preferred caprolactam and valerolactam precursors include benzoyl caprolactam,
nonanoyl capro-lactam, benzoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl
caprolactam,3,5,5-trimethylhexanoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam,
decanoyl caprolactam, decanoyl valerolactam, undecenoyl caprolactam, undecenoyl valerolactam,
(6-octanamidocaproyl)oxybenzene-sulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate,
(6-decanamidocaproyl)-oxybenzenesulfonate, and mixtures thereof. Examples of highly
preferred substituted benzoyl lactams include methylbenzoyl caprolactam, methylbenzoyl
valerolactam, ethylbenzoyl caprolactam, ethylbenzoyl valerolactam, propylbenzoyl caprolactam,
propylbenzoyl valerolactam, isopropylbenzoyl caprolactam, isopropylbenzoyl valerolactam,
butylbenzoyl caprolactam, butylbenzoyl valerolactam, tert-butylbenzoyl caprolactam,
tert-butylbenzoyl valerolactam, pentylbenzoyl caprolactam, pentylbenzoyl valerolactam,
hexylbenzoyl caprolactam, hexylbenzoyl valerolactam, ethoxybenzoyl caprolactam, ethoxybenzoyl
valerolactam, propoxybenzoyl caprolactam, propoxybenzoyl valerolactam, isopropoxybenzoyl
caprolactam, isopropoxybenzoyl valerolactam, butoxybenzoyl caprolactam, butoxybenzoyl
valerolactam, tert-butoxybenzoyl caprolactam, tert-butoxybenzoyl valerolactam, pentoxybenzoyl
caprolactam, pentoxybenzoyl valerolactam, hexoxybenzoyl caprolactam, hexoxybenzoyl
valerolactam, 2,4,6-trichlorobenzoyl caprolactam, 2,4,6-trichlorobenzoyl valerolactam,
pentafluorobenzoyl caprolactam, pentafluorobenzoyl valerolactam, dichlorobenzoyl caprolactam,
dimethoxybenzoyl caprolactam, 4-chlorobenzoyl caprolactam, 2,4-dichlororbenzoyl caprolactam,
terephthaloyl dicaprolactam, pentafluorobenzoyl caprolactam, pentafluorobenzoyl valerolactam,
dichlorobenzoyl valerolactam, dimethoxybenzoyl valerolactam, 4-chlorobenzoyl valerolactam,
2,4-dichlororbenzoyl valerolactam, terephthaloyl divalerolactam, 4-nitrobenzoyl caprolactam,
4-nitrobenzoyl valerolactam, and mixtures thereof.
Perbenzoic acid precursor
[0039] Essentially any perbenzoic acid precursors are suitable herein, including those of
the N-acylated lactam class, which are preferred.
[0040] Suitable O-acylated perbenzoic acid precursor compounds include the substituted and
unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene
sulfonate:

[0041] Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides
with benzoylating agents, including for example:

[0042] Preferred 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.
[0043] Preferred perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl
tetraacyl peroxides, and the compound having the formula:

[0044] Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:

Perbenzoic acid derivative precursors
[0045] Suitable perbenzoic acid derivative precursors include any of the herein disclosed
perbenzoic precursors in which the perbenzoic group is substituted by essentially
any functional group including alkyl groups.
Cationic peroxyacid precursors
[0046] Cationic peroxyacid precursor compounds are also suitable herein. Typically such
cationic peroxyacid precursors are formed by substituting the peroxyacid part with
an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
[0047] 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.
[0049] 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.
[0050] A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl
ammonium) methyl derivative of benzoyl oxybenzene sulfonate:

[0051] A preferred cationically substituted alkyl oxybenzene sulfonate is the methyl ammonium
derivative of 2,3,3-trimethyl hexanoyloxybenzene sulfonate.
[0052] Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include
the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium
methylene benzoyl caprolactam:

[0053] Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl
sodium 4-sulphophenyl carbonate chloride.
Alkyl fatty peroxyacid bleach precursors
[0054] Alkyl fatty peroxyacid bleach precursors form alkyl fatty peroxyacids on perhydrolysis.
Preferred precursors of this type give rise to peracetic acid on perhydrolysis.
[0055] Preferred alkyl fatty peroxyacid 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.
Amide substituted peroxyacid bleach precursors
[0056] Another preferred class of peroxyacid bleach activator compounds are the amide substituted
compounds of the following general formulae:

wherein R
1, is an alkyl or aryl 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 I 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, 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. L may be selected from any
of the leaving groups described hereinbefore for the analogues having R
1 as an aryl or alkaryl group. Amide substituted bleach activator compounds of this
type are described in
EP-A-0170386.
[0057] The L group must be sufficiently reactive for the 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 stabilize for use in a bleaching composition. These characteristics
are generally paralleled by the pKa of the conjugate acid of the leaving group, although
exceptions to this convention are known. Ordinarily, leaving groups that exhibit such
behaviour are those in which their conjugate acid has a pKa in the range of from 4
to 13, preferably from 6 to 11 and most preferably from 8 to 11.
[0058] Preferred bleach precursors are those wherein R
1, R
2 and R
5 are as defined for the amide substituted compounds and L is 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, and Y is H or a solubilizing group.
[0059] 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. It should be noted that bleach activators with a leaving
group that does not contain a solubilizing groups should be well dispersed in the
bleaching solution in order to assist in their dissolution.
Organic peroxyacids
[0060] The compositions may contain as components of the bleaching system organic peroxyacids,
typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by
weight of the composition.
[0061] 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.
[0062] Other organic peroxyacids include diperoxydodecanedioc acid, diperoxytetradecanedioc
acid, diperoxyhexadecanedioc acid, mono- and diperazelaic acid, mono- and diperbrassylic
acid.
Bleach catalyst
[0063] The compositions contain a transition metal containing bleach catalyst.
[0064] One suitable type of bleach catalyst is a catalyst system comprising a heavy metal
cation of defined bleach catalytic activity, such as copper, iron or manganese cations,
an auxiliary metal cation having little or no bleach catalytic activity, such as zinc
or aluminum 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.
[0065] Other 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
IV4(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-triazacydononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane,
and mixtures thereof.
[0066] 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).
[0067] 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, mesoinositol, lactose, and mixtures thereof.
[0068] 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.
[0069] Other examples include binuclear Mn complexed 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.
[0070] 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 (metalloporphyrin 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).
[0071] The bleach catalyst is typically used in a catalytically effective amount in the
compositions and processes herein. By "catalytically effective amount" is meant an
amount which is sufficient, under whatever comparative test conditions are employed,
to enhance bleaching and removal of the stain or stains of interest from the target
substrate. The test conditions will vary, depending on the type of washing appliance
used and the habits of the user. Some users elect to use very hot water; others use
warm or even cold water in laundering operations. Of course, the catalytic performance
of the bleach catalyst will be affected by such considerations, and the levels of
bleach catalyst used in fully-formulated detergent and bleach compositions can be
appropriately adjusted. As a practical matter, and not by way of limitation, the compositions
and processes herein can be adjusted to provide on the order of at least one part
per ten million of the active bleach catalyst species in the aqueous washing liquor,
and will preferably provide from about 1 ppm to about 200 ppm of the catalyst species
in the wash liquor. To illustrate this point further, on the order of 3 micromolar
manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate
and a bleach precursor. An increase in concentration of 3-5 fold may be required under
U.S. conditions to achieve the same results.
Crystalline layered silicate
[0072] The compositions of the invention contain a crystalline layered silicate, preferably
present at a level of from 0.05% to 40%, more preferably from 0.5% to 30%, most preferably
from 2% to 20% by weight of the composition.
[0073] The weight ratio of crystalline layered silicate to any peroxyacid bleach precursor
compound is preferably from 10: 1 to 1:5, more preferably from 5:1 to 1:2, most preferably
from 3:1 to 1 :1.
[0074] Preferred are the crystalline layered sodium silicates having the general formula
NaMSi
xO
2x+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 are disclosed in
EP-A-0164514 and methods for their preparation 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. The most preferred material is δ-Na
2Si
2O
5, available from Hoechst AG as NaSKS-6.
[0075] 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. WO 92/18594. The solid, water-soluble ionisable material is selected from organic acids, organic
and inorganic acid salts and mixtures thereof, with citric acid being preferred.
Flocculating agent
[0076] The compositions of the invention preferably contain a flocculating agent, preferably
present at a level of from 0.005% to 10%, more preferably from 0.05% to 5%, most preferably
from 0.1 % to 2% by weight of the composition.
[0077] The weight ratio of crystalline layered silicate to flocculating agent is preferably
from 300: 1 to 1:1, more preferably from 80:1 to 10:1, most preferably from 60:1 to
20:1.
[0078] The flocculating agent functions such as to bring together particles of crystalline
layered silicate in the wash solution and hence to aid their deposition onto the surface
of the fabrics in the wash. This functional requirement is hence different from that
of dispersant compounds which are commonly added to laundry detergent compositions
to aid the removal of clay soils from fabrics and enable their dispersion within the
wash solution.
[0079] Preferred as flocculating agents herein are organic polymeric materials having an
average weight of from 100,000 to 10,000,000, preferably from 150,000 to 5,000,000,
more preferably from 200,000 to 2,000,000.
[0080] Suitable organic polymeric materials comprise homopolymers or copolymers containing
monomeric units selected from alkylene oxide, particularly ethylene oxide, acrylamide,
acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Homopolymers of
ethylene oxide, acrylamide and acrylic acid are preferred.
[0081] European Patents No.s
EP-A-299,575 and
EP-A-313,146 in the name of the Procter and Gamble Company describe preferred organic polymeric
flocculating agents for use herein.
[0082] Inorganic flocculating agents are also suitable herein, typical examples of which
include lime and alum.
Additional detergent components
[0083] The detergent compositions of the invention may also contain additional detergent
components. The precise nature of these additional components, and levels of incorporation
thereof will depend on the physical form of the composition, and the precise nature
of the laundering operation for which it is to be used.
[0084] The compositions of the invention may for example, be formulated as hand and machine
laundry detergent compositions, including laundry additive compositions and compositions
suitable for use in the pretreatment of stained fabrics.
[0085] The compositions of the invention preferably contain one or more additional detergent
components selected from surfactants, builders, organic polymeric compounds, additional
enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition
agents and corrosion inhibitors.
Surfactant
[0086] The detergent compositions of the invention preferably contain as an additional detergent
component a surfactant selected from anionic, cationic, nonionic ampholytic, amphoteric
and zwitterionic surfactants and mixtures thereof.
[0087] The surfactant is typically present at a level of from 0.1 % to 60% by weight. More
preferred levels of incorporation of surfactant are from 1% to 35% by weight, most
preferably from 1% to 20% by weight.
[0088] Atypical 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. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and
II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given
in
U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
[0089] Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used
in combination with one or more anionic and/or nonionic surfactants.
Anionic surfactant
[0090] Essentially any anionic surfactants useful for detersive purposes can be included
in the compositions. 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.
[0091] 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
[0092] Anionic sulfate surfactants suitable for use herein include the linear and branched
primary 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).
[0093] Alkyl ethoxysulfate surfactants are preferably selected from the group consisting
of the C
6-C
18 alkyl sulfates which have been ethoxylated with from about 0.5 to about 20 moles
of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant
is a C
6-C
18 alkyl sulfate which has been ethoxylated with from about 0.5 to about 20, preferably
from about 0.5 to about 5, moles of ethylene oxide per molecule.
Anionic sulfonate surfactant
[0094] 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
[0095] Anionic carboxylate surfactants suitable for use herein include the alkyl ethoxy
carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl
carboxyls'), especially certain secondary soaps as described herein.
[0096] Preferred alkyl ethoxy carboxylates for use herein include those with the formula
RO(CH
2CH
2O)
x CH
2C00
-M
+ wherein R is a C
6 to C
18 alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that,
on a weight basis, the amount of material where x is 0 is less than about 20 %, and
the amount of material where x is greater than 7, is less than about 25 %, the average
x is from about 2 to 4 when the average R is C
13 or less, and the average x is from about 3 to 10 when the average R is greater than
C
13, and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium,
mono-, di-, and tri-ethanol-ammonium, most preferably from sodium, potassium, ammonium
and mixtures thereof with magnesium ions. The preferred alkyl ethoxy carboxylates
are those where R is a C
12 to C
18 alkyl group.
[0097] Alkyl polyethoxy polycarboxylate surfactants suitable for use herein 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, wherein at least
one R
1 or R
2 is a succinic acid radical or hydroxysuccinic acid radical, 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.
Anionic secondary soap surfactant
[0098] Preferred soap surfactants are secondary soap surfactants which contain a carboxyl
unit connected to a secondary carbon. The secondary carbon can be in a ring structure,
e.g. as in p-octyl benzoic acid, or as in alkylsubstituted cyclohexyl carboxylates.
The secondary soap surfactants should preferably contain no ether linkages, no ester
linkages and no hydroxyl groups. There should preferably be no nitrogen atoms in the
head-group (amphiphilic portion). The secondary soap surfactants usually contain 11-15
total carbon atoms, although slightly more (e.g., up to 16) can be tolerated, e.g.
p-octyl benzoic acid.
[0099] The following general structures further illustrate some of the preferred secondary
soap surfactants:
- A. A highly preferred class of secondary soaps comprises the secondary carboxyl materials
of the formula R3 CH (R4)COOM, wherein R3 is CH3(CH2)x and R4 is CH3(CH2)y, wherein y can be O or an integer from 1 to 4, x is an integer from 4 to 10 and the
sum of (x + y) is 6-10, preferably 7-9, most preferably 8.
- B. Another preferred class of secondary soaps comprises those carboxyl compounds wherein
the carboxyl substituent is on a ring hydrocarbyl unit, i.e., secondary soaps of the
formula R5-R6-COOM, wherein R5 is C7-C10, preferably C8-C9, alkyl or alkenyl and R6 is a ring structure, such as benzene, cyclopentane and cyclohexane. (Note: R5 can be in the ortho, meta or para position relative to the carboxyl on the ring.)
- C. Still another preferred class of secondary soaps comprises secondary carboxyl compounds
of the formula CH3 (CHR)k-(CH2)m-(CHR)n-CH(COOM)(CHR)o-(CH2)p-(CHR)q-CH3, wherein each R is C1-C4 alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that the total
number of carbon atoms (including the carboxylate) is in the range of 10 to 18.
[0100] In each of the above formulas A, B and C, the species M can be any suitable, especially
water-solubilizing, counterion.
[0101] Especially 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.
Alkali metal sarcosinate surfactant
[0102] 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.
Nonionic surfactant
[0103] Essentially any anionic surfactants useful for detersive purposes can be included
in the compositions. Exemplary, non-limiting classes of useful nonionic surfactants
are listed below.
Nonionic polyhydroxy fatty acid amide surfactant
[0104] Polyhydroxy fatty acid amides suitable for use herein are those having the structural
formula R
2CONR
1Z wherein : R1 is H, C
1-C
4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferable
C1-C4 alkyl, more preferably C
1 or C
2 alkyl, most preferably C
1 alkyl (i.e., methyl); and R
2 is a C
1-C
31 hydrocarbyl, preferably straight-chain C
5-C
19 alkyl or alkenyl, more preferably straight-chain C
9-C
17 alkyl or alkenyl, most preferably straight-chain C
11-C
17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain,
or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably
will be derived from a reducing sugar in a reductive amination reaction; more preferably
Z is a glycityl.
Nonionic condensates of alkyl phenols
[0105] The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols
are suitable for use herein. In general, the polyethylene oxide condensates are preferred.
These compounds include the condensation products of alkyl phenols having an alkyl
group containing from about 6 to about 18 carbon atoms in either a straight chain
or branched chain configuration with the alkylene oxide.
Nonionic ethoxylated alcohol surfactant
[0106] The alkyl ethoxylate condensation products of aliphatic alcohols with from about
1 to about 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 about 2 to about 10 moles of ethylene oxide per mole of alcohol.
Nonionic ethoxylated/propoxylated fatty alcohol surfactant
[0107] 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
[0108] 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
about 1500 to about 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
[0109] 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 about 2500 to about
3000. Examples of this type of nonionic surfactant include certain of the commercially
available Tetronic™ compounds, marketed by BASF.
Nonionic alkylpolysaccharide surfactant
[0110] Suitable alkylpolysaccharides for use herein are disclosed in
U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably
from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside,
hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3
to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing
saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and
galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the
hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose
or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds
can be, e.g., between the one position of the additional saccharide units and the
2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
[0111] The preferred alkylpolyglycosides have the formula
R
2O(C
nH
2nO)t(glycosyl)
x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10
to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; t is from 0 to 10, preferably
0, and X is from 1.3 to 8, preferably from 1.3 to 3, most preferably from 1.3 to 2.7.
The glycosyl is preferably derived from glucose.
Nonionic fatty acid amide surfactant
[0112] Fatty acid amide surfactants suitable for use herein are those having the formula:
R
6CON(R
7)
2 wherein R
6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and
each R
7 is selected from the group consisting of hydrogen, C
1-C
4 alkyl, C
1-C
4 hydroxyalkyl, and - (C
2H
4O)
xH, where x is in the range of from 1 to 3.
Amphoteric surfactant
[0113] Suitable amphoteric surfactants for use herein include the amine oxide surfactants
and the alkyl amphocarboxylic acids.
[0114] A suitable example of an alkyl aphodicarboxylic acid for use herein is Miranol(TM)
C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
Amine Oxide surfactant
[0115] Amine oxides useful herein 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, preferably 8 to 18 carbon
atoms; R
4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably
2 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and
each R
5 is an alkyl or hydyroxyalkyl group containing from 1 to 3, preferably from 1 to 2
carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable 1,
ethylene oxide groups. The R
5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to
form a ring structure.
[0116] These amine oxide surfactants in particular include C
10-C
18 alkyl dimethyl amine oxides and C
8-C
18 alkoxy ethyl dihydroxyethyl amine oxides. Examples of such materials include dimethyloctylamine
oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine
oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl
dimethylamine oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, tallow
dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide. Preferred are C
10-C
18 alkyl dimethylamine oxide, and C
10-18 acylamido alkyl dimethylamine oxide.
Zwitterionic surfactant
[0117] 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.
Betaine surfactant
[0118] The betaines useful herein are those compounds having the formula R(R')
2N
+R
2COO- wherein R is a C
6-C
18 hydrocarbyl group, preferably a C
10-C
16 alkyl group or C
10-16 acylamido alkyl group, each R
1 is typically C
1-C
3 alkyl, preferably methyl,m and R
2 is a C
1-C
5 hydrocarbyl group, preferably a C
1-C
3 alkylene group, more preferably a C
1-C
2 alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl
betaine; hexadecyl dimethyl betaine; C
12-14 acylamidopropylbetaine; C
8-14 acylamidohexyldiethyl betaine; 4[C
14-16 acylmethylamidodiethylammonio]-1-carboxybutane; C
16-18acylamidodimethylbetaine; C
12-16acylamidopentanediethyl-betaine; [C
12-16acylmethylamidodimethylbetaine. Preferred betaines are C
12-18 dimethyl-ammonio hexanoate and the C
10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants
are also suitable for use herein.
Sultaine surfactant
[0119] The sultaines useful herein are those compounds having the formula (R(R
1)
2N+R
2SO
3- wherein R is a C
6-C
18 hydrocarbyl group, preferably a C
10-C
16 alkyl group, more preferably a C
12-C
13 alkyl group, each R
1 is typically C
1-C
3 alkyl, preferably methyl, and R
2 is a C
1-C
6 hydrocarbyl group, preferably a C
1-C
3 alkylene or, preferably, hydroxyalkylene group.
Ampholytic surfactant
[0120] Ampholytic surfactants can be incorporated into the detergent compositions herein.
These surfactants can be broadly described as aliphatic derivatives of secondary or
tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines
in which the aliphatic radical can be straight chain or branched.
Cationic surfactants
[0121] Cationic surfactants can also be used in the detergent compositions herein. 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.
Water-soluble builder compound
[0122] The detergent compositions of the present invention preferably contain a water-soluble
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.
[0123] 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,
silicates and mixtures of any of the foregoing.
[0124] The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type
although monomeric polycarboxylates are generally preferred for reasons of cost and
performance.
[0125] 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.
[0126] 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.
[0127] 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.
[0128] Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up
to three carboxy groups per molecule, more particularly citrates.
[0129] 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.
[0130] 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 about 50°C, especially less than about
40°C.
[0131] 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.
[0132] 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 about 6 to 21, and salts of phytic acid.
[0133] Suitable silicates include the water soluble sodium silicates with an Si0
2: Na
20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0
ratio being most preferred. The silicates may be in the form of either the anhydrous
salt or a hydrated salt. Sodium silicate with an SiO
2: Na
20 ratio of 2.0 is the most preferred silicate.
[0134] Silicates are preferably present in the detergent compositions in accord with the
invention at a level of from 5% to 50% by weight of the composition, more preferably
from 10% to 40% by weight.
Partially soluble or insoluble builder compound
[0135] The detergent compositions of the present invention may contain a partially soluble
or insoluble 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% weight of the
composition.
[0136] Examples of largely water insoluble builders include the sodium aluminosilicates.
Suitable aluminosilicate zeolites have 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.
[0137] 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, Zeoilte
MAP, Zeolite HS and mixtures thereof. 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.
Heavy metal ion sequestrant
[0138] The detergent compositions of the invention preferably 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.
[0139] 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.
[0140] 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.
[0141] 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.
[0142] Preferred among the above species are diethylene triamine penta (methylene phosphonate),
ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene
phosphonate) and hydroxyethylene 1,1 diphosphonate.
[0143] 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.
[0144] 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. Examples of such preferred sodium salts of EDDS include Na
2EDDS and Na
3EDDS. Examples of such preferred magnesium complexes of EDDS include MgEDDS and Mg
2EDDS.
[0145] Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid,
described in
EP-A-317,542 and
EP-A-399,133.
[0146] The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl
N-2-hydroxypropyl-3-sulfonic acid sequestrants described in
EP-A-516,102 are also suitable herein. The β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic
acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described
in
EP-A-509,382 are also suitable.
[0147] EP-A-476,257 describes suitable amino based sequestrants.
EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-
1,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS)
is also suitable.
Enzyme
[0148] Another preferred ingredient useful in the detergent compositions is one or more
additional enzymes.
[0149] Preferred additional enzymatic materials include the commercially available lipases,
amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases
and peroxidases conventionally incorporated into detergent compositions. Suitable
enzymes are discussed in
US Patents 3,519,570 and
3,533,139.
[0150] Preferred commercially available protease enzymes include those sold under the tradenames
Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark),
those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those
sold by Genencor International, and those sold under the tradename Opticlean and Optimase
by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance
with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the
composition.
[0151] Preferred amylases include, for example, α-amylases obtained from a special strain
of B licheniformis, described in more detail in
GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under
the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl
and BAN by Novo Industries A/S. Amylase enzyme may be incorporated into the composition
in accordance with the invention at a level of from 0.0001% to 2% active enzyme by
weight of the composition.
[0152] Lipolytic enzyme (lipase) may be present at levels of active lipolytic enzyme of
from 0.0001% to 2% by weight, preferably 0.001 % to 1% by weight, most preferably
from 0.001 % to 0.5% by weight of the compositions.
[0153] The lipase may be fungal or bacterial in origin being obtained, for example, from
a lipase producing strain of
Humicola sp.,
Thermomyces sp. or
Pseudomonas sp. including
Pseudomonas pseudoalcaligenes or
Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also
useful herein.
[0154] A preferred lipase is derived from
Pseudomonas pseudoalcaligenes, which is described in Granted European Patent,
EP-B-0218272.
[0155] Another preferred lipase herein is obtained by cloning the gene from
Humicola lanuginosa and expressing the gene in
Aspergillus oryza, as host, as described in European Patent Application,
EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under
the trade name Lipolase. This lipase is also described in
U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Organic polymeric compound
[0156] Organic polymeric compounds are preferred additional components of the detergent
compositions in accord with the invention. By organic polymeric compound it is meant
herein essentially any polymeric organic compound commonly used as dispersants, and
anti-redeposition and soil suspension agents in detergent compositions, but excluding
any of the high molecular weight organic polymeric compounds described as flocculating
agents herein.
[0157] 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.
[0158] Examples of organic polymeric compounds include the water soluble organic homo- or
co-polymeric polycarboxylic acids 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 MWt 2000-5000 and their copolymers with
maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000,
especially 40,000 to 80,000.
[0159] Other suitable organic polymeric compounds include the copolymers of acrylamide and
acrylate having a molecular weight of from 3,000 to 100,000, and the acrylate/fumarate
copolymers having a molecular weight of from 2,000 to 80,000.
[0161] Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic
acid and vinyl alcohol, particularly those having an average molecular weight of from
5,000 to 10,000, are also suitable herein.
[0162] Other organic polymeric compounds suitable for incorporation in the detergent compositions
herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose
and hydroxyethylcellulose.
[0163] Further useful organic polymeric compounds are the polyethylene glycols, particularly
those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably
about 4000.
Suds suppressing system
[0164] The detergent compositions of the 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.
[0165] 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.
[0166] By antifoam compound it is meant herein any compound or mixtures of compounds which
act such as to depress the foaming or sudsing produced by a solution of a detergent
composition, particularly in the presence of agitation of that solution.
[0167] Particularly preferred antifoam compounds for use herein are silicone antifoam compounds
defined herein as any antifoam compound including a silicone component. Such silicone
antifoam compounds also typically contain a silica component. The term "silicone"
as used herein, and in general throughout the industry, encompasses a variety of relatively
high molecular weight polymers containing siloxane units and hydrocarbyl group of
various types. Preferred silicone antifoam compounds are the siloxanes, particularly
the polydimethylsiloxanes having trimethylsilyl end blocking units.
[0168] Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble
salts thereof. These materials are described in
US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically
have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon
atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and
lithium salts, and ammonium and alkanolammonium salts.
[0169] Other suitable antifoam compounds include, for example, high molecular weight fatty
esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols,
aiiphatic C
18-C
40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines
or di- to tetra alkyldiamine chlortfiazines formed as products of cyanuric chloride
with two or three moles of a primary or secondary amine containing 1 to 24 carbon
atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g.
sodium, potassium, lithium) phosphates and phosphate esters.
[0170] Copolymers of ethylene oxide and propylene oxide, particularly the mixed ethoxylated/propoxylated
fatty alcohols with an alkyl chain length of from 10 to 16 carbon atoms, a degree
of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10, are
also suitable antifoam compounds for use herein.
[0171] Suitable 2-alky-alcanols antifoam compounds for use herein have been described in
DE 40 21 265. The 2-alkyl-alcanols suitable for use herein consist of a C
6 to C
16 alkyl chain carrying a terminal hydroxy group, and said alkyl chain is substituted
in the a position by a C
1 to C
10 alkyl chain. Mixtures of 2-alkyl-alcanols can be used in the compositions according
to the present invention.
[0172] A preferred suds suppressing system comprises
- (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone
antifoam compound comprising in combination
- (i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by
weight of the silicone antifoam compound; and
- (ii) silica, at a level of from 1 % to 50%, preferably 5% to 25% by weight of the
silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of from
5% to 50%, preferably 10% to 40% by weight;
- (b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer
with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide
ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1 % to 10%
by weight; a particularly preferred silicone glycol rake copolymer of this type is
DCO544, commercially available from DOW Coming under the tradename DCO544;
- (c) an inert carrier fluid compound, most preferably comprising a C16-C18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to
15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
[0173] A preferred particulate suds suppressor system useful herein comprises a mixture
of an alkylated siloxane of the type hereinabove disclosed and solid silica.
[0174] The solid silica can be a fumed silica, a precipitated silica or a silica, made by
the gel formation technique. The silica particles suitable have an average particle
size of from 0.1 to 50 micrometers, preferably from 1 to 20 micrometers and a surface
area of at least 50m
2/g. These silica particles can be rendered hydrophobic by treating them with dialkylsilyl
groups and/or trialkylsilyl groups either bonded directly onto the silica or by means
of a silicone resin. It is preferred to employ a silica the particles of which have
been rendered hydrophobic with dimethyl and/or trimethyl silyl groups. A preferred
particulate antifoam compound for inclusion in the detergent compositions in accordance
with the invention suitably contain an amount of silica such that the weight ratio
of silica to silicone lies in the range from 1:100 to 3:10, preferably from 1:50 to
1:7.
[0175] Another suitable particulate suds suppressing system is represented by a hydrophobic
silanated (most preferably trimethyl-silanated) silica having a particle size in the
range from 10 nanometers to 20 nanometers and a specific surface area above 50m
2/g, intimately admixed with dimethyl silicone fluid having a molecular weight in the
range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica
of from about 1:1 to about 1:2.
[0176] A highly preferred particulate suds suppressing system is described in
EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having
a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises
a monoester of glycerol and a fatty acid having a carbon chain containing from 12
to 20 carbon atoms.
EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic
carrier material is a fatty acid or alcohol having a carbon chain containing from
12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to
80°C.
[0177] Other highly preferred particulate suds suppressing systems are described in copending
European Application
91870007.1 in the name of the Procter and Gamble Company which systems comprise silicone antifoam
compound, a carrier material, an organic coating material and glycerol at a weight
ratio of glycerol : silicone antifoam compound of 1:2 to 3:1. Copending European Application
91201342.0 also discloses highly preferred particulate suds suppressing systems comprising silicone
antifoam compound, a carrier material, an organic coating material and crystalline
or amorphous aluminosilicate at a weight ratio of aluminosilicate : silicone antifoam
compound of 1:3 to 3:1. The preferred carrrier material in both of the above described
highly preferred granular suds controlling agents is starch.
[0178] An exemplary particulate suds suppressing system for use herein is a particulate
agglomerate component, made by an agglomeration process, comprising in combination
- (i) from 5% to 30%, preferably from 8% to 15% by weight of the component of silicone
antifoam compound, preferably comprising in combination polydimethyl siloxane and
silica;
- (ii) from 50% to 90%, preferably from 60% to 80% by weight of the component, of carrier
material, preferably starch;
- (iii) from 5% to 30%, preferably from 10% to 20% by weight of the component of agglomerate
binder compound where herein such compound can be any compound, or mixtures thereof
typically employed as binders for agglomerates, most preferably said agglomerate binder
compound comprises a C16-C18 ethoxylated alcohol with a degree of ethoxylation of from 50 to 100; and
- (iv) from 2% to 15%, preferably from 3% to 10%, by weight of C12-C22 hydrogenated fatty acid.
Polymeric dye transfer inhibiting agents
[0179] The detergent 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.
[0180] 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.
a) Polyamine N-oxide polymers
[0181] Polyamine N-oxide polymers suitable for use herein contain units having the following
structure formula:

wherein P is a polymerisable unit, whereto the R-N-O group can be attached to, or
wherein the R-N-O group forms part of the polymerisable unit or a combination of both.
A is

-O-, -S-, -N-; x is O or 1;
[0182] R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups
or any combination thereof whereto the nitrogen of the N-O group can be attached or
wherein the nitrogen of the N-O group is part of these groups.
[0183] The N-O group can be represented by the following general structures :

wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups
or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of
the N-O group can be attached or wherein the nitrogen of the N-O group forms part
of these groups. The N-O group can be part of the polymerisable unit (P) or can be
attached to the polymeric backbone or a combination of both.
[0184] Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable
unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic
or heterocyclic groups. One class of said polyamine N-oxides comprises the group of
polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine,
pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
[0185] Another class of said polyamine N-oxides comprises the group of polyamine N-oxides
wherein the nitrogen of the N-O group is attached to the R-group.
[0186] Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group
is attached to the polymerisable unit.
[0187] Preferred class of these polyamine N-oxides are the polyamine N-oxides having the
general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein
the nitrogen of the N-O functional group is part of said R group. Examples of these
classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine,
pyrrole, imidazole and derivatives thereof.
[0188] Another preferred class of polyamine N-oxides are the polyamine oxides having the
general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein
the nitrogen of the N-O functional group is attached to said R groups. Examples of
these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.
[0189] Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble
and has dye transfer inhibiting properties. Examples of suitable polymeric backbones
are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates
and mixtures thereof.
[0190] The amine N-oxide polymers of the present invention typically have a ratio of amine
to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide groups
present in the polyamine oxide polymer can be varied by appropriate copolymerization
or by appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide
is from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, most preferably from
1:7 to 1:1000000. The polymers of the present invention actually encompass random
or block copolymers where one monomer type is an amine N-oxide and the other monomer
type is either an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides
has a PKa < 10, preferably PKa < 7, more preferred PKa < 6.
[0191] The polyamine oxides can be obtained in almost any degree of polymerisation. The
degree of polymerisation is not critical provided the material has the desired water-solubility
and dye-suspending power. Typically, the average molecular weight is within the range
of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to
30,000, most preferably from 3,000 to 20,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
[0192] Preferred polymers for use herein may comprise a polymer selected from N-vinylimidazole
N-vinylpyrrolidone copolymers wherein said polymer has an average molecular weight
range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from
10,000 to 20,000. The preferred N-vinylimidazole N-vinylpyrrolidone copolymers have
a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably
from 0.8 to 0.3, most preferably from 0.6 to 0.4.
c) Polyvinylpyrrolidone
[0193] The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP" having
an average molecular weight of from 2,500 to 400,000, preferably from 5,000 to 200,000,
more preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000. Suitable
polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY
and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight
of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular
weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is
also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are
commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP
12.
[0194] Polyvinylpyrrolidone may be incorporated in the detergent compositions herein at
a level of from 0.01% to 5% by weight of the detergent, preferably from 0.05% to 3%
by weight, and more preferably from 0.1 % to 2% by weight. The amount of polyvinylpyrrolidone
delivered in the wash solution is preferably from 0.5 ppm to 250 ppm, preferably from
2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
d) Polyvinyloxazolidone
[0195] The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric
dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular
weight of from 2,500 to 400,000, preferably from 5,000 to 200,000, more preferably
from 5,000 to 50,000, and most preferably from 5,000 to 15,000.
[0196] The amount of polyvinyloxazolidone incorporated in the detergent compositions may
be from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, and more preferably
from 0.1% to 2% by weight. The amount of polyvinyloxazolidone delivered in the wash
solution is typically from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm,
more preferably from 5 ppm to 100 ppm.
e) Polyvinylimidazole
[0197] The detergent compositions herein may also utilize polyvinylimidazole as polymeric
dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average
molecular weight of from 2,500 to 400,000, more preferably from 5,000 to 50,000, and
most preferably from 5,000 to 15,000.
[0198] The amount of polyvinyl im idazole incorpoarted in the detergent compositions may
be from 0.01 % to 5% by weight, preferably from 0.05% to 3% by weight, and more preferably
from 0.1 % to 2% by weight. The amount of polyvinylimidazole delivered in the wash
solution is from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably
from 5 ppm to 100 ppm.
Optical brightener
[0199] The detergent compositions herein may also optionally contain from about 0.005% to
5% by weight of certain types of hydrophilic optical brighteners which also provide
a dye transfer inhibition action. If used, the compositions herein will preferably
comprise from about 0.01% to 1% by weight of such optical brighteners.
[0200] 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.
[0201] 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.
[0202] Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent
compositions herein.
[0203] 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.
[0204] 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.
[0205] The specific optical brightener species selected for use in the present invention
provide especially effective dye transfer inhibition performance benefits when used
in combination with the selected polymeric dye transfer inhibiting agents hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX
and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous
wash solutions than does either of these two detergent composition components when
used alone. Without being bound by theory, it is believed that such brighteners workthis
way because they have high affinity for fabrics in the wash solution and therefore
deposit relatively quick on these fabrics. The extent to which brighteners deposit
on fabrics in the wash solution can be defined by a parameter called the "exhaustion
coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener
material deposited on fabric to b) the initial brightener concentration in the wash
liquor. Brighteners with relatively high exhaustion coefficients are the most suitable
for inhibiting dye transfer in the context of the present invention.
[0206] Of course, it will be appreciated that other, conventional optical brightener types
of compounds can optionally be used in the present compositions to provide conventional
fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such
usage is conventional and well-known to detergent formulations.
Clay mineral compound
[0207] The compositions of the invention may contain as a fabric softening component a clay
mineral compound, preferably present at a level of from 0.05% to 40%, more preferably
from 0.5% to 30%, most preferably from 2% to 20% by weight of the composition. For
clarity, it is noted that the term clay mineral, as used herein, excludes sodium aluminosilicate
builder compounds.
[0208] The weight ratio of clay mineral compound to any peroxyacid bleach precursor compound
is preferably from 10:1 to 1:5, more preferably from 5:1 to 1:2, most preferably from
3:1 to 1:1.
[0209] The clay mineral compound is preferably a smectite clay compound. Smectite clays
are disclosed in the
US Patents No.s 3,862,058 3,948,790,
3,954,632 and
4,062,647 and European Patents No.s
EP-A-299,575 and
EP-A-313,146 all in the name of the Procter and Gamble Company.
[0210] The term smectite clays herein includes both the clays in which aluminium oxide is
present in a silicate lattice and the clays in which magnesium oxide is present in
a silicate lattice. Typical smectite clay compounds include the compounds having the
general formula Al
2(Si
2O
5)
2(OH)
2·nH
2O and the compounds having the general formula Mg
3 (Si
2O
5)
2(OH)
2·nH
2O. Smectite clays tend to adopt an expandable three layer structure.
[0211] Specific examples of suitable smectite clays include those selected from the classes
of the montmorillonites, hectorites, volchonskoites, nontronites, saponites and sauconites,
particularly those having an alkali or alkaline earth metal ion within the crystal
lattice structure. Sodium or calcium montmorillonite are particularly preferred.
[0212] Suitable smectite clays, particularly montmorillonites, are sold by various suppliers
including English China Clays, Laviosa, Georgia Kaolin and Colin Stewart Minerals.
[0213] Clays for use herein preferably have a largest particle dimension of from 0.01µm
to 800µm, more preferably from 1 mm to 400 mm, more preferably from 5mm to 200 mm.
[0214] Particles of the clay mineral compound may be included as components of agglomerate
particles containing other detergent compounds. Where present as such components,
the term "largest particle dimension" of the clay mineral compound refers to the largest
dimension of the clay mineral compound refers to the largest dimension of the clay
mineral component as such and not to the agglomerated particle as a whole.
[0215] Substitution of small cations, such as protons, sodium ions, potassium ions, magensium
ions and calcium ions, and of certain organic molecules inlcuding those having positively
charged functional groups can typically take place within the crystal lattice structure
of the smectite clays. A clay may be chosen for its ability to preferentially absorb
one cation type, such ability being assessed by measurements of relative ion exchange
capacity. The smectite clays suitable herein typically have a cation exchange capacity
of at least 50 meq/100g.
U.S. Patent No. 3,954,632 describes a method for measurement of cation exchange capacity.
[0216] The crystal lattice structure of the clay mineral compounds may have, in a preferred
execution, a cationic fabric softening agent substituted therein. Such substituted
clays have been termed 'hydrophobically activated' clays. The cationic fabric softening
agents are typically present at a weight ratio, cationic fabric softening agent to
clay of from 1: 200 to 1:10, preferably from 1:100 to 1:20. Preferred 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.
Cationic fabric softening agents
[0217] Cationic fabric softening agents can also be incorporated into compositions in accordance
with the present invention. These may be present as distinct components or as components
of the, hereinbefore described, hydrophobically activated clay materials. 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 011340.
[0218] Cationic fabric softening agents are typically incorporated at total levels of from
0.5% to 15% by weight, normally from 1% to 5% by weight.
Other optional ingredients
[0219] Other optional ingredients suitable for inclusion in the compositions of the invention
include perfumes, colours and filler salts, with sodium sulfate being a preferred
filler salt.
Form of the compositions
[0220] The detergent compositions of the invention can be formulated in any desirable form
such as powders, granulates, pastes, and tablets.
Solid compositions
[0221] The detergent compositions of the invention are preferably in the form of solids,
such as powders and granules.
[0222] The particle size of the components of granular compositions in accordance with the
invention should preferably be such that no more that 5% of particles are greater
than 1.4mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.
[0223] The bulk density of granular detergent compositions in accordance with the present
invention typically have a bulk density of at least 450 g/litre, more usually at least
600 g/litre and more preferably from 650 g/litre to 1200 g/litre.
Making processes - granular compositions
[0224] In general, granular detergent compositions in accordance with the present invention
can be made via a variety of methods including dry mixing, spray drying, agglomeration
and granulation.
Laundry washing methods
[0225] The compositions of the invention may be used in essentially any washing or cleaning
method, including machine laundry washing methods.
[0226] Machine laundry methods herein typically comprise treating soiled laundry with an
aqueous wash solution in a washing machine having dissolved or dispensed therein an
effective amount of a machine laundry detergent composition in accord with the invention.
The detergent can be added to the wash solution either via the dispenser drawer of
the washing machine or by a dispensing device. By an effective amount of the detergent
composition it is meant from 40g to 300g of product dissolved or dispersed in a wash
solution of volume from 5 to 65 litres, as are typical product dosages and wash solution
volumes commonly employed in conventional machine laundry methods.
[0227] In a preferred washing method herein a dispensing device containing an effective
amount of detergent product is introduced into the drum of a front-loading washing
machine before the commencement of the wash cycle.
[0228] The dispensing device is a container for the detergent product which is used to deliver
the product directly into the drum of the washing machine. Its volume capacity should
be such as to be able to contain sufficient detergent product as would normally be
used in the washing method.
[0229] Once the washing machine has been loaded with laundry the dispensing device containing
the detergent product is placed inside the drum. At the commencement of the wash cycle
of the washing machine water is introduced into the drum and the drum periodically
rotates. The design of the dispensing device should be such that it permits containment
of the dry detergent product but then allows release of this product during the wash
cycle in response to its agitation as the drum rotates and also as a result of its
immersion in the wash water.
[0230] To allow for release of the detergent product during the wash the device may possess
a number of openings through which the product may pass. Alternatively, the device
may be made of a material which is permeable to liquid but impermeable to the solid
product, which will allow release of dissolved product. Preferably, the detergent
product will be rapidly released at the start of the wash cycle thereby providing
transient localised high concentrations of product in the drum of the washing machine
at this stage of the wash cycle.
[0232] Especially preferred dispensing devices are disclosed in European Patent Application
Publication Nos.
0343069 &
0343070. The latter Application discloses a device comprising a flexible sheath in the form
of a bag extending from a support ring defining an orifice, the orifice being adapted
to admit to the bag sufficient product for one washing cycle in a washing process.
A portion of the washing medium flows through the orifice into the bag, dissolves
the product, and the solution then passes outwardly through the orifice into the washing
medium. The support ring is provided with a masking arrangemnt to prevent egress of
wetted, undissolved, product, this arrangement typically comprising radially extending
walls extending from a central boss in a spoked wheel configuration, or a similar
structure in which the walls have a helical form.
Packaging for the compositions
[0233] Commercially marketed executions of the bleaching compositions can be packaged in
any suitable container including those constructed from paper, cardboard, plastic
materials and any suitable laminates. A preferred packaging execution is described
in copending European Application No.
93970141.4.
Abbreviations used in Examples
[0234] In the detergent compositions, the abbreviated component identifications have the
following meanings:
XYAS : |
Sodium C1X - C1y alkyl sulfate |
25EY : |
A C12-15 predominantly linear primary alcohol condensed with an average of Y moles of ethylene
oxide |
XYEZ : |
AC1x-C1y predominantly linear primary alcohol condensed with an average of Z moles of ethylene
oxide |
XYEZS : |
C1X-C1Y sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole |
TFAA : |
C16-C18 alkyl N-methyl glucamide. |
Silicate : |
Amorphous Sodium Silicate (SiO2:Na2O ratio =2.0) |
NaSKS-6 : |
Crystalline layered silicate of formula 6-Na2Si2O5 |
Carbonate : |
Anhydrous sodium carbonate |
Polycarboxylate : |
Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000 |
Zeolite A : |
Hydrated Sodium Aluminosilicate of formula Na12(AlO2SiO2)12. 27H2O having a primary particle size in the range from 1 to 10 micrometers |
Citrate : |
Tri-sodium citrate dihydrate |
Percarbonate : |
Anhydrous sodium percarbonate bleach coated with a coating of sodium silicate (Si2O: Na2O ratio = 2:1) at a weight ratio of percarbonate to sodium silicate of 39:1 |
TAED : |
Tetraacetylethylenediamine particle formed by agglomerating TAED with citric acid
and polyethylene glycol (PEG) of Mw=4,000 with a weight ratio of components of TAED:citric
acid:PEG of 75:10:15, coated with an external coating of citric acid at a weight ratio
of agglomerate: citric acid coating of 95:5. |
Benzoyl Caprolactam : |
Benzoyl caprolactam particle formed by agglomerating benzoyl caprolactam (BzCl) with
citric acid and polyethylene glycol (PEG) of Mw=4,000, with a weight ratio of components
of BzCl:citric acid: PEG of 63:21:16, coated with an external coating of citric acid
at a weight ratio of agglomerate:citric acid coating of 95:5 |
Protease : |
Proteolytic enzyme sold under the tradename Savinase by Novo Industries A/S with an
activity of 13 KNPU/g. |
Amylase : |
Amylolytic enzyme sold under the tradename Termamyl 60T by Novo Industries A/S with
an activity of 300 KNU/g |
Cellulase : |
Cellulosic enzyme sold by Novo Industries A/S with an activity of 1000 CEVU/g |
Lipase : |
Lipolytic enzyme sold under the tradename Lipolase by Novo Industries A/S with an
activity of 165 KLU/g |
CMC : |
Sodium carboxymethyl cellulose |
HEDP : |
1,1-hydroxyethane diphosphonic acid |
EDDS : |
Ethylenediamine -N, N'- disuccinic acid, [S,S] isomer in the form of the sodium salt. |
PVNO : |
Poly (4-vinylpyridine)-N-oxide copolymer of vinylimidazole and vinylpyrrolidone having
an average molecular weight of 10,000. |
Flocculant |
Homopolymer of ethylene oxide having an average molecular weight of 1,000,000 |
Mn catalyst |
MnIV2(m-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, as described in U.S. Pat. Nos. 5,246,621 and 5,244,594. |
Granular Suds Suppressor: 12% Silicone/silica, 18% stearyl alcohol,70% starch in granular
form |
Example 1
[0235] The following laundry detergent compositions A to D were prepared in accord with
the invention:

Example 2
[0236] The following laundry detergent compositions E to H were prepared in accord with
the invention:
