Note: Descriptions are shown in the official language in which they were submitted.
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Deter~ent compositions
Technical field
The present invention relates to detergent compositions cont~ining a
cationic ester surfactant and a grease dispersing agent, which are suitable
for use in laundry and dish w~hing methods.
Background -to the invention
The satisfactory removal of greasy soils/stains, that is soils/stains having a
high proportion of triglycerides or f.~tty acids, is a challenge faced by the
form~ tor of detergent compositions for use in laundry and dish washing
methods. Surfactant components ha~e traditionally been employed in
detergent products to facilitate the removal of such greasy soils/stains. In
particular, surfactant systems comprising cationic esters have been
described for use in greasy soil/stain removal.
A challenge faced in laundry and dish washing is not just the removal of
greasy soils and stains from the soiled/ stained substrate, but dispersion of
the greasy stain/ soil components, thereby preventing their (re)deposition
onto the substrates. Grease dispersing agents can be employed in
detergents to achieve prevention of l re)deposition of greasy stains/soils.
Examples of grease dispersing agenls are polymers with hydrophobic side
- chains and hydrophilic monomer units in the backbone.
EP-B-21,491 discloses detergent compositions cont~ining a
nonionic/cationic surfactant mixture and a builder mixture comprising
aluminosilicate and polycarboxylate builder. The cationic surfactant may
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be a cationic ester. Improved particulate and greasy/oily soil removal is
described.
US-A-4,228,042 discloses biodegradable cationic surfactants, including
cationic ester surfactants for use in detergent compositions to provide
greasy/oily soil removal. The combination of these cationic surfactants
with nonionic surfactants in compositions designed for particulate soil
removal is also described.
US-A-4,260,529 discloses laundry detergent compositions having a pH of
no greater than 11 cont~ining cationic ester surfactant and nonionic
surfactant at defined weight ratios.
WO 91/08281 discloses dispersing polymers for dispersion of detergent
droplets, with a hydrophilic backbone and hydrophobic side chains.
It has now been found that the performance of certain grease dispersingagents in the traditional detergents is affected by the washing conditions,
such as water hardness. Essential for the performance of grease dispersing
agents is their affinity for and absorbance onto the (greasy) stain/ soil
components on the fabric. However, absorbance onto the stained fabric
can be problematic when 'limesoaps' (formed by the alkali and earth
alkali metals of the water hardness with fatty acids) are present on the
fabric. This problem is believed to cause the re~ ce~ performance of the
dispersing agents.
The Applicants have now found that this problem can be ameliorated by
the inclusion of cationic ester surfactants in detergents cont~inin~ grease
dispersing agents, which are polymers with a hydrophilic backbone and
hydrophobic side chain(s). Detergent compositions employing both
components have shown to deliver a surprisingly better cleaning
performance.
Two mechanisms are believed to be responsible for these benefits. Firstly,
the cationic ester surfactant is can reduce deposition of 'lime soaps' on the
fabric. The reduction of deposition will facilitate the absorbance of the
grease dispersing agent onto the greasy soils or stains. Thereby, an
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improvement of their dispersing performance is achieved. Secondly, it is
believed that dle cationic ester surfactant can act to facilitate solubilisationof greasy soil/ st~in components. This will aid the grease dispersing
agent's dispersal of the soil/ stain components. Thus, an overall
improved cle~ning of the detergent is achieved.
All documents cited in the present description are, in relevant part,
incol~orated herein by re~elellce.
S~mm~ry of the Invention
The detergent coln~ ion of the ~rescll~ invention com~ises
(a) a cationic ester surf~rt~nt; and
(b) a grease dispersing agent.
Plefelably the grease dispersing agent is present at a level of from 0.1%
to 15 ~ by weight of the deterg~nt co.nl,osilion.
In a preferred aspect, the cationic ester surfactant is selected from those
having the formula:
R2
R
, +
Rl-- C~ (CH)no _ (X)u--( C H2 )m--(Y)v--(C H2 )t N- R3 M
-a
R4
wherein Rl is a Cs-C31 linear or branched alkyl, alkenyl or alkaryl chain
or M-. N+(R6R7Rg)(CH2)S; X and Y, independently, are selected from
the group conci~tin~ of COO, OCO, O, CO, OCOO, CONH, NHCO,
OCONH and NHCOO wherein at least one of X or Y is a COO, OCO,
OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R7, and R8 are
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independently selected from the group consisting of alkyl, alkenyl,
hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4
carbon atoms; and Rs is independently H or a C 1-C3 alkyl group;
wherein the values of m, n, s and t independently lie in the range of from
0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u
and v independently are either 0 or 1 with the proviso that at least one of
u or v must be 1; and wherein M is a counter anion.
Detailed description of the invention
Cationic ester surfactant
An essential element of the detergent compositions of the invention is a
cationic ester surfactant. The cationic ester surfactant is preferably present
at a level from 0.1~ to 20.0~, more preferably from O.S% to 10%, most
preferably from 1.0% to 5.0% by weight of the detergent composition.
The cationic ester surfactant of the present invention is a, preferablywater dispersible, compound having surfactant properties comprising at
least one ester (i.e. -COO-) linkage and at least one cationically charged
group.
Suitable cationic ester surfactants, including choline ester surfactants,
have for example been disclosed in US Patents No.s 4228042, 4239660
and 4260529.
In one preferred aspect the ester linkage and cationically charged group
are separated from each other in the surfactant molecule by a spacer
group consisting of a chain comprising at least three atoms (i.e. of three
atoms chain length), preferably from three to eight atoms, more
preferably from three to five atoms, most preferably three atoms. The
atoms forming the spacer group chain are selected from the group
consisting of carbon, nitrogen and oxygen atoms and any mixtures
thereof, with the proviso that any nitrogen or oxygen atom in said chain
connects only with carbon atoms in the chain. Thus spacer groups
having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages
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s
are excluded, whilst spacer groups having, for example -CH2-O- CH2-
and -CH2-NH-CH2- linkages are included. In a preferred aspect the
spacer group chain comprises only carbon atoms, most preferably the
chain is a hydrocarbyl chain.
Preferred cationic ester surf~ct~nt~e are those having the formula:
R2
R5 1 +
Rl-- (3 (cH)no --(X)u--( C H 2 )m--(Y)v--(C H 2 )t--N--R3 M
- a R4
wherein Rl is a Cs-C31 linear or branched alkyl, alkenyl or alkaryl chain
or M-. N+(~6R7R8)(CH2)S; X and Y, independently, are selected from
the group con~ictin~ of COO, OCO, O, CO, OCOO, CONH, NHCO,
OCONH and NHCOO wherein at least one of X or Y is a COO, OCO,
OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R7, and R8 are
independently selected from the group consisting of alkyl, alkenyl,
hydroxyalkyl and hydroxy-alkenyl groups having from 1 to 4 carbon
atoms and alkaryl groups; and Rs is inde~elldently H or a Cl-C3 alkyl
group; wherein the values of m, n, s and t independently lie in the range
of from 0 to 8, the value of b lies in the range from 0 to 20, and the
values of a, u and v in~ependently are either 0 or 1 with the proviso that
at least one of u or v must be 1; and wherein M is a counter anion.
r~efe~ably M is selected from the group con.~i~tin~ of halide, methyl
sulfate, sulf~te, and nitrate, more preferably methyl s~llf~te, chloride,
bromide or iodide.
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In a preferred aspect, the cationic ester surfactant is selected from those
having the formula:
R,2
R5
R1 ~--(CH)nO (X) (CH2)m--N--R3 M-
a
R4
wherein ~1 is a Cs-C31 linear or branched alkyl, alkenyl or alkaryl
chain; X is seleceed from the group consisting of COO, OCO, OCOO,
OCONH and NHCOO; R2, R3, and R4 are independently selected from
the group con~ist~n~ of allyl and hydroxyalkyl groups having from 1 to 4
carbon atoms; and Rs is independently H or a Cl-C3 allyl group;
wherein the value of n lies in the range of from 0 to 8, the value of b lies
in the range from 0 to 20, the value of a is ei~er 0 or 1, and ~e value of
misfrom3to8.
More preferably R2, R3 and R4 are independently selected from a Cl-C4
alkyl group and a C1-C4 hydroxyalkyl group. In one preferred aspect at
least one, preferably only one, of R2, R3 and R4 is a hydroxyalkyl group.
The hydroxyallyl ~refeldbly has from 1 to 4 carbon atoms, more
plefel~bly 2 or 3 call,oll atoms, most preferably 2 carbon atoms. In
al~otllcr preferred aspect at least one of R2, R3 and R4 is a C2-C3 alkyl
group, more preferably two C2-C3 alkyl groups are present.
Highly p~felle~ water disl,ersible cationic ester surf~ct~nt~ are the esters
having the formula:
O CH3
1~
R1--C--O--(CH2)m--N+--CH3 M-
CH3
where m is from 1 to 4, preferably 2 or 3 and wherein Rl is a C1 1-Clg
linear or branched alkyl chain.
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Particularly preferred choline esters of this type include the stearoylcholine ester quaternary methylammonium halides (R1=C17 alkyl),
palmitoyl choline ester quaternary methylammonium halides (R1=C1s
alkyl), myristoyl choline ester quaternary methylammonium halides
(Rl=C13 alkyl), lauroyl choline ester methylammonium halides
(R1 =C1 1 alkyl), cocoyl choline ester quaternary methylammonium
halides (Rl =Cl 1 C13 alkyl), tallowyl choline ester quaternary
methylammonium halides (Rl =C 15 C 17 alkyl), and any mixtures thereof.
Other suitable cationic ester surfactants have the structural formulas
below, wherein d may be from 0 to 20.
Rl- O - C -(CH2)d C - O - CH2CH2- 1 - CH3 M
M CH3- N - CH2 - CH2- O - C -(CH2)- C - O - CH2- CH2- N - CH3M
CH3 CH3
In a preferred aspect the cationic ester surfactant is hydrolysable under the
conditions of a laundry wash method.
The particularly preferred choline esters, given above, may be preparedby the direct esterification of a fatty acid of the desired chain length with
dimethylArninoethanol, in the presence of an acid catalyst. The reaction
product is then quaternized with a methyl halide, preferably in the
presence of a solvent such as ethanol, water, propylene glycol or
preferably a fatty alcohol ethoxylate such as C1o-C1g fatty alcohol
ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups
per mole forming the desired cationic material. They may also be
prepared by the direct esterification of a long chain fatty acid of the
desired chain length together with 2-haloethanol, in the presence of an
acid catalyst material. The reaction product is then quaternized with
trimethyl~rnine, forming the desired cationic material.
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Grease dispersin~ agent
An essential element of the present invention is a grease dispersing agent.
By grease dispersing agent is meant herein a component capable of
dispersing or suspending greasy stain/ soil components into the (wash)
solution. The grease dispersing agents in accord with the present invention
are typically polymers, which have a hydrophilic backbone and at least
one hydrophobic side chain. The hydrophobic side chain acts functionally
to provide affinity of the grease dispersing agent for greasy soil/stain
components. The hydrophilic backbone acts functionally to provide
affinity of the grease dispersing agent for a~ueous environments.
Generally the hydrophilic backbone of the polymer is predomin~ntly
linear (the main chain of the backbone constitutes at least 50%, preferably
more than 75 %, most preferred more than 90% by weight of the
backbone), suitable monomer constituents of the hydrophilic backbone are
for example ~ln~ rated C1-C6 acids, ethers, alcohols, aldehydes, ketones
or esters, sugar units, alkoxy units, maleic anhydride and saturated
polyalcohols such as glycerol. Examples of suitable monomer units are
acrylic acid, methacrylic acid, maleic acid, vinyl acetic acid, glucosides,
ethylene oxide and glycerol. The hydrophilic backbone made from the
backbone constituents in the absence of hydrophobic side-groups is
relatively water-soluble at ambient temperatures and a pH of between 6.5
and 14Ø
Preferably the solubility is more than 1 g/l, more preferably more than S
g/l, most preferably more than 10 g/l.
Preferably the hydrophobic sidegroups are composed of alkoxy groups forexample butylene oxide and/or propylene oxide and/or alkyl or alkenyl
chains having from 5 to 24 carbon atoms. The hydrophobic groups may
be connected to the hydrophilic backbone via relatively hydrophilic bonds
for example a poly ethoxy linkage.
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Preferred grease dispersing agents are the polymers of the formula:
R8 R7
H CH2 C C~2 C Q1 Q2 H
R10 R9 - r - - v
q p
- n
Formula I
wherein:
Q2 is a molec~ r entity of formula (Ia):
- - - R6
CH2--CH CH CH - CH C
j I R1
C02A1 C02A2 Co2A3 , R~ 1 2
- x - ~ Y L R3
R4
, z
Formula Ia
wherein:
R1 represents -COO-O-, -O-, -O-CO-, -CH2-, CO-NH-, or is absent:
R2 represents from 1 to 50 independently selected alkyleneoxy groups
preferably e~ylene oxide or propylene oxide groups, or is absent,
provided that when R3 is absent and R4 represents hydrogen or contains
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no more than 4 carbon atoms, then R2 must contain an alkyleneoxy group
preferably more than S alkyleneoxy groups with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C 1-24 alkyl or C2 24 alkenyl group, with the
provisos that
(a) when Rl represents -O-CO-, R2 and R3 must be absent and R4
must contain at least 5 carbon atoms;
(b) when R2 is absent, then R4 is not hydrogen and when also R3 is
absent, then R4 must contain at least 5 carbon atoms;
R5 represents hydrogen or a group of formula -CooA4;
R6 represents hydrogen or C1 4 alkyl; and
A1, A2, A3 and A4 are independently selected from hydrogen, alkali
metals, ~lk~line earth metals, ammonium and amine bases and C1=4, or
(C2H4O)tH wherein t is from 1-50, and wherein the monomer units may
be in random order.
Q1 is a multifunctional monomer, allowing the branching of the polymer,wherein the monomers of the polymer may be connected to Q1 in any
direction, in any order, therewith possibly resulting in a branched
polymer. Preferably Ql is trimethyl propane triacrylate (TMPTA),
methylene bisacrylamide or divinyl glycol.
z and v are 1; n is at least 1; x is at least 1; (x + y + p + q + r): z is
from 4: 1 to 1,000: 1, preferably from 6: 1 to 250: 1; in which the
monomer units may be in random order; and preferably p and q are zero
and/or r is zero; most preferably p, q, y and r are zero.
R7 and R8 represents -CH3 or is a hydrogen;
R9 and R10 represent substituent groups such as amino, amine, amide,
sulphonate, sulphate, phosphonate, phosphate, hydroxy, carboxyl and
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11
oxide groups, preferably they are selected from -SO3Na, -CO-O-C2H4-
OSO3Na, -CO-O-NH-C(CH3)2-SO3Na, -CO-NH2, -O-CO-CH3, -OH;
It must be noted that the monomers of the polymer may be variable in
direction and position along the polymer backbone and along the side
chain(s).
P~eferably, polymeric grease dispersing agents for use in compositions of
the invention which are of relatively high pH (say 10 or more) are
subst~nti~lly free of hydrolysable groups such as carbonyl groups for
increased polymer stability at high pH values. Particularly preferred
polymeric grease dispersing agents for use in high pH compositions of the
invention comprise hydrophilic backbones conctit~te~ by acid groups such
as acrylic acid and at least one hydrophobic side chain which is
con.~titl-ted of from S to 75 relatively water-insoluble alkoxy groups such
as propoxy units optionally linked to the hydrophilic backbone via a poly-
alkoxy linkage con~ti~lter~ of from 1-10 relatively water soluble alkoxy
groups such as ethoxy units.
Especially preferred grease dispersing agents of this type are the polymers
of the forrnula:-
R4 R3
H CH2 CH CH2 C H
R2 R2
Ra R1
-- Z
Rb
I' C
- -x - n
Formula II
wherein: x, z and n are as above;
. _ . ~
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- R3 and R4 represent hydrogen or Cl 4 alkyl;
- R2 represents -CO-O-, -O-, -O-CO-, CH2-, -CO-NH-, or is absent;
- R 1 represents -C3H6-N + -(CH3)3 (C 1 ~), -C2H4-OSO3 -(Na + ),
-SO3-(Na + ), -C2H4 N + (CH3)3 Cl-, -C2H4 N + (C2H6)3 Cl-
~-CH2 N+ (CH3)3 Cl-, -CH2 N+ (C2H6)3 Cl- or benzyl-SO3- (Na+) or
hydrogen;
- Ra is CH2, C2H4, C3H6 or is absent;
- Rb represents form 1 to 50 independently selected alkylene oxide
groups, preferably ethylene oxide groups or is absent;
Rc represents -OH or -H; and wherein if R2, Ra and Rb are absent, then
Rc is not -H.
Other preferred polymeric grease dispersing agents have the formula:
R5 R5 R6 R3 R4
G~l CH ~H O CH CH
,
HO---GH HC ~----CH HC~ 0- ~H HC --O--H
'~--O 6~- CH 6:~ o
R6 R5 R5 R1
- -X1- _ x2_ _z
- R2 - n
Formula III
wherein:
-x = Xl + X2
- x, z and n are as defined above
R1 represents -CH20- or -O-;
- R2 represents -CH2COO~Na+, -C3H60N+(CH3)3Cl- or -C3H3N+
(cH3)3cl-
- R3 and R4 represents -OH, CH20H, -O(C3H60)p-H,
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13
-CH2-O(C3H6O)p-H or -OCH2COO-Na + or -O-C3H6ON + (CH3)3CI-
or
-O- C3H6N + (CH3)3Cl-
- R5 represents -OH, ONH-CO-CH3 or -O(C3H6O)p-H
- R6 represents -OH, -CH2OH, -CH2-OCH3, -O(C3H6O)p-H or
-CH2-0-(C3H60)p-H
- p is from 1 - 10.
Preferably grease dispersing agents for use in compositions have a
molecular weight of between 500 and 100,000, more preferred from
1,000 to 20,000, especially preferred from 1,500 to 10,000 most
preferred from 2,800 to 6,000. Grease dispersing agents for use in
compositions of the invention may for example be prepared by using
conventional aqueous polymerisation procedures, suitable methods are for
example described in GB 89 24477, GB 89 24478 and GB 89 24479.
Generally the grease dispersing agent will be used at from 0.1 % to 15 ~,
morepreferablyfromO.5% to8.0%, especiallypreferredfrom 1.0% to
5.0% by weight of the detergent composition.
Additional detergent components
The detergent compositions of the invention may also contain additionaldetergent 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 washing operation for which it
is to be used.
The compositions of the invention preferably contain one or more
additional detergent components selected from additional surfactants,
bleaches, builders, additional enzymes, suds suppressors, lime soap
dispersants, and corrosion inhibitors.
,
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Additional surfactant
The detergent compositions of the invention preferably contain an
additional surfactant selected from anionic, nonionic, non-ester cationic,
ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
A typical listing of anionic, nonionic, ampholytic, and zwitterionic
classes, and species of these surfactants, is given in U.S.P. 3,929,678
issued to T ~lghlin 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.
Where present, ampholytic, amphoteric and zwitteronic surfactants are
generally used in combination with one or more anionic and/or nonionic
surfactants.
Anionic surfactant
The detergent compositions in accord with the present invention
preferably comprise an additional anionic surfactant. Essentially any
anionic surfactants useful for detersive purposes can be comprised in the
detergent composition. These can include salts (including, for example,
sodium, potassium, ammonium, and substituted ammonium salts such as
mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate,
carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are
preferred.
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 ~lnc~hlrated C12-C18 monoesters) diesters of sulfosuccinate
(especially saturated and lln~ lrated C6-C14 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.
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Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty
oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the
Cs-C17 acyl-N-(Cl-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) gll~c~min~
sulfates, and sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
herein).
Alkyl sulfate surfactants are preferably selected from the linear and
branched primary C1o-C1g alkyl sulfates, more preferably the Cl 1-C1s
branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the C1o-C1g alkyl sulfates which have been ethoxylated with
from 0.5 to 20 moles of ethylene oxide per molecule. More preferably,
the alkyl ethoxysulfate surfactant is a C 1 1-C 18, most preferably C 1 1 -C 15
alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably
from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures
have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surf~ct~nt~ suitable for use herein include the salts of
Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22
primary or secondary alkane sulfonates, C6-C24 olefin sulfonates,
sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures
thereof.
Anionic carboxylate surfactant
.. . .. . .. ..
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16
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the
soaps ('alkyl carboxyls'), especially certain secondary soaps as described
herem.
Suitable alkyl ethoxy carboxylates include those with the formula
RO(CH2CH20)X CH2COO-M+ wherein R is a C6 to Clg alkyl group, x
ranges from O to 10, and the ethoxylate distribution is such that, on a
weight basis, the amount of material where x is 0 is less than 20 % and
is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include
those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is a C6 to
Clg alkyl group, x is from 1 to 25, R1 and R2 are selected from the
group consisting of hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected
from the group consisting of hydrogen, substituted or unsubstituted
hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof
Suitable soap surfactants include the secondary soap surfactants which
contain a carboxyl unit connected to a secondary carbon. Preferred
secondary soap surfactants for use herein are water-soluble members
selected from the group consisting of the water-soluble salts of 2-methyl-
l-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-
butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may
also be included as suds suppressors.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates offormula R-CON (Rl) CH2 COOM, wherein R is a Cs-C17 linear or
branched alkyl or alkenyl group, Rl is a C1-C4 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.
Alkoxylated nonionic surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated and propoxylated nonionic surfactants are preferred.
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Preferred alkoxylated surfactants can be selected from the classes of the
nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols,
nonionic ethoxylated/propoxylated fatty alcohols, nonionic
ethoxylate/propoxylate condensates with propylene glycol, and the
nonionic ethoxylate condensation products with propylene oxide/ethylene
mine adducts.
Nonionic alkoxylated alcohol surfactant
The condensation products of aliphatic alcohols with from 1 to 25 molesof alkylene oxide, particularly ethylene oxide and/or propylene 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 cont~ining from 8 to 20 carbon
atoms with from 2 to lO moles of ethylene oxide per mole of alcohol.
Nonionic polyhydroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural formula R2CONR1Z wherein: R1 is H, C1-C4 hydrocarbyl, 2-
hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof,
preferable C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably
C1 alkyl (i.e., methyl); and R2 is a Cs-C31 hydrocarbyl, preferably
straight-chain Cs-C1g alkyl or alkenyl, more preferably straight-chain
Cg-C 1 7 alkyl or alkenyl, most preferably straight-chain C 1 1 -C 1 7 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 ~n~in~tion reaction; more preferably Z is a glycityl.
Nonionic fatty acid amide surfactant
Suitable fatty acid amide surfactants include those having the formula:R6CoN(R7)2 wherein R6 is an alkyl group cont~ining from 7 to 21,
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preferably from 9 to 17 carbon atoms and each R7 is selected from the
group consisting of hydrogen, Cl-C4 alkyl, Cl-C4 hydroxyalkyl, and -
(C2H40)XH, where x is in the range of from 1 to 3.
Nonionic alkylpolysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647, Llenado~ issued January 21, 1986, having a hydrophobic
group cont~ining from 6 to 30 carbon atoms and a polysaccharide, e.g., a
polyglycoside, hydrophilic group cont~ining from 1.3 to 10 saccharide
units.
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Preferred alkylpolyglycosides have the formula
R~O(CnH2nO)t(glYC~sYl)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 carbon atoms; n is 2 or 3; t is from O
to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from
glucose.
Amphoteric surfactant
Suitable amphoteric surf~ct~nt.~ for use herein include the amine oxidesurfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(0R4)XNO(R5)2 wherein R3 is selected from an alkyl, hydroxyallcyl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containin~
from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group
cont~inin~ from 2 to 3 carbon atoms, or mixtures thereof; x is from O to
5, preferably from O to 3; and each R5 is an alkyl or hydroxyalkyl group
con~inin~ from l to 3, or a polyethylene oxide group con~inin~ from 1
to 3 ethylene oxide groups. Preferred are Clo-Clg alkyl dimethyl~mine
oxide, and C10-l8 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM)
C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
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.
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Suitable betaines are those compounds having the formula
R(R')2N+R2COO- wherein R is a C6-C1g hydrocarbyl group, each Rl
is typically C1-C3 alkyl, and R2 is a C1-Cs hydrocarbyl group. Preferred
betaines are C12 18 dimethyl-ammonio hexanoate and the C10-l8
acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex
betaine surfactants are also suitable for use herein.
Cationic surfactants
Additional cationic surfactants can also be used in the detergent
compositions herein. Suitable cationic surfactants include the quaternary
ammonium surfactants selected from mono C6-C16, preferably C6-C1o
N-alkyl or alkenyl ammonium surfactants wherein the rem~inin~ N
positions are substituted by methyl, hydroxyethyl or hydroxypropyl
groups.
~lk~linity
In the detergent compositions of the present invention preferably a
alkalinity system is present to achieve optimal cationic ester surfactant
performance. The ~lk~linity system comprises components capable of
providing ~lk~linity species in solution. By alkalinity species it is meant
herein: carbonate, bicarbonate, hydroxide, the various silicate anions,
percarbonate, perborates, perphosphates, persulfate and persilicate.
Such ~lk~linity species can be formed for example, when ~lk~line salts
selected from alkali metal or alkaline earth carbonate, bicarbonate,
hydroxide or silicate, including crystalline layered silicate, salts and
percarbonate, perborates, perphosphates, persulfate and persilicate salts
and
any mixtures thereof are dissolved in water.
Examples of carbonates are the ~lk~line earth and alkali metal carbonates,
including sodium carbonate and sesqui-carbonate and any mixtures thereof
with ultra-fine calcium carbonate such as are disclosed in Gerrnan Patent
Application No. 2,321,001 published on November 15, 1973.
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Suitable silicates include the water soluble sodium silicates with an SiO2:
Na20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 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 SiO2: Na20 ratio of 2.0 is the most preferred silicate.
Preferred crystalline layered silicates for use herein have the generalformula
NaMSix02x+1 YH20
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. Herein, x in the general
formula above preferably has a value of 2, 3 or 4 and is preferably 2. The
most preferred material is ~-Na2Si20s, available from Hoechst AG as
NaSKS-6.
Water-soluble builder compound
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.
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, borates, phosphates, and mixtures of any
of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or
oligomeric in type although monomeric polycarboxylates are generally
preferred for reasons of cost and performance.
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Suitable carboxylates cont~inin~ one carboxy group include the water
soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
Polycarboxylates cont~ining 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
cont~ining 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.
Polycarboxylates cor~t~ining 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 cont~ining 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. Preferred
polycarboxylates are hydroxycarboxylates cont~ining up to three carboxy
groups per molecule, more particularly citrates.
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.
Borate builders, as well as builders cont~ining borate-forrning materials
that can produce borate under detergent storage or wash conditions are
useful water-soluble builders herein.
Suitable 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
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degree of polymerization ranges from about 6 to 21, and salts of phytic
acld.
Partially soluble or insoluble builder compound
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.
Examples of largely water insoluble builders include the sodium
aluminosilicates .
Suitable aluminosilicate zeolites have the unit cell formula
Nazl(AlO2)z(SiO2)y]. xH2O 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, cont~ining from 10% to
28%, more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably synthetically derived. Synthetic crystalline aluminosilicate ion
exchange materials are available under the designations Zeolite A, Zeolite
B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has
the formula
Na 12 [Al~2) 12 (sio2)l2]. xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula
Na86 [(Alo2)86(sio2)lo6]. 276 H2O.
Or~anic peroxyacid bleaching system
A preferred feature of detergent compositions of the invention is an
organic peroxyacid bleaching system. In one preferred execution the
bleaching system contains a hydrogen peroxide source and an orgarlic
peroxyacid bleach precursor compound. The production of the organic
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24
peroxyacid occurs by an in situ reaction of the precursor with a source of
hydrogen peroxide. Preferred sources of hydrogen peroxide include
inorganic perhydrate bleaches. In an alternative preferred execution a
preformed organic peroxyacid is incorporated directly into the
composition. Compositions cont~inin~ mixtures of a hydrogen peroxide
source and organic peroxyacid precursor in combination with a preformed
organic peroxyacid are also envisaged.
Inor~anic perhydrate bleaches
Inorganic perhydrate salts are a preferred source of hydrogen peroxide.These salts are normally incorporated in the form of the alkali metal,
preferably 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.
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 cryst~lline 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.
Suitable coatings comprise inorganic salts such as alkali metal silicate,
carbonate or borate sa~ts or mixtures thereof, or organic materials such as
waxes, oils, or fatty soaps.
Sodium perborate is a preferred perhydrate salt and can be in the form of
the monohydrate of nominal formula NaB02H202 or the tetrahydrate
NaB02H202 3H20
Alkali metal percarbonates, particularly sodium percarbonate are
preferred perhydrates herein. Sodium percarbonate is an addition
compound having a formula corresponding to 2Na2C03.3H202, and is
available commercially as a crystalline solid.
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Potassium peroxymonopersulfate is another inorganic perhydrate salt of
use in the detergent compositions herein.
Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen
peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally
peroxyacid bleach precursors may be represented as
i !
X-C-L
where L is a leaving group and X is essentially any functionality, such
that on perhydroloysis the structure of the peroxyacid pro~h~ced is
o
X-C -OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a
level of from 0.5~ to 20% by weight, more prefelably from 1 % to 15%
by weight, most preferably from 1.5% to 10~ by weight of the detergent
collll.ositions .
Suitable peroxyacid bleach precursor compounds typically contain one ormore N- or O-acyl groups, which precursors can be selected from a wide
range of classes. Suitable classes include anhydrides, esters, imides,
lart~mc 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.
Leavln~ groups
The leaving group, hereinafter L group, must be sufficiently reactive for
the perhydrolysis reaction to occur within the optimum time frame (e.g., a
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wash cycle). However, if L is too reactive, this aetivator will be difficult
to stabilize for use in a bleaching composition.
Preferred L groups are selected from the group consisting of:
--0~ --O~Y , and --~~
Il ~ 11
R3 --N N --N--C--CH--R4
R3 r
-O--C H=C--C H=C H2 --O--C H=C--C H=C H2
O ,CH~C, ,> C~NR4
Il 11
O O
R3 0 Y
--~C=CHR4 , and N--lv--CH--R4
R3 o
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
cont~ining from 1 to 14 carbon atoms, R3 is an alkyl chain cont~ining
from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing
group. Any of R1, R3 and R4 may be substituted by essentially any
functional group including, for example alkyl, hydroxy, alkoxy, halogen,
amine, nitrosyl, amide and ammonium or alkyl ~mmmonium groups
The preferred solubilizing groups are -S03-M+, -C02-M+, -S04-M+,
-N +(R )4X- and O < --N(R )3 and most preferably -S03-M + and
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27
-CO2-M + wherein R3 is an alkyl chain cont~inin~ 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, amrnonium or substituted ammonium
cation, with sodium and potassium being most preferred, and X is a
halide, hydroxide, methylsulfate or acet~te anion.
Alkyl percarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis. Preferred precursors of this type provide peracetic acid on
perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of ~e imide type
include the N-,N,NlNl tetra acetylated alkylene diqminPs wherein the
alkylene group contains from 1 to 6 carbon atoms, particularly those
compounds in which the alkylene group contains l, 2 and 6 carbon atoms.
Tetraacetyl ethylene ~ mine (TAED) is particularly preferred.
Od~er preferred alkyl percarboxylic acid precursors include sodium 3,5,5-
tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium
nonanoyloxybenzene sulfonate tNOBS), sodium acetoxybenzene sulfonate
(ABS) and pent~cetyl glucose.
Amide substitl~te~ allyl peroxyacid precursors
Amide substi~te~l alkyl peroxyacid precursor compounds are suitable
herein, including ~ose of ~e following gelleral formulae:
R1 C--N R2--C--L R1_--N C R2 C L
O R5 O or R5 O O
wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an
alkylene group cont~ining from 1 to 14 carbon atoms, and R5 is H or an
alkyl group cont~ining 1 to 10 carbon atoms and L can be essentially any
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28
leaving group. Amide substituted bleach activator compounds of this type
are described in EP-A-0170386.
Perbenzoic acid precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on
perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds
include the substituted and unsubstitl~te~l benzoyl oxybenzene sulfonates,
and the benzoylation products of sorbitol, glucose, and all saccharides
with benzoylating agents, and those of the imide type including N-benzoyl
succinimide, tetrabenzoyl ethylene ~ min~ and the N-benzoyl substituted
ureas. Suitable imidazole type perbenzoic acid precursors include N-
benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl
group-cont~inin~ perbenzoic acid precursors include N-benzoyl
pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Cationic peroxyacid precursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids
on perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the
peroxyacid part of a suitable peroxyacid precursor compound with a
positively charged functional group, such as an ammonium or alkyl
~mmmonium group, preferably an ethyl or methyl ammonium group.
Cationic peroxyacid precursors are typically present in the solid detergent
compositions as a salt with a suitable anion, such as a halide ion:
The peroxyacid precursor compound to be so cationically substituted maybe a perbenzoic acid, or substituted derivative thereof, precursor
compound as described hereinbefore. Alternatively, the peroxyacid
precursor compound may be an alkyl percarboxylic acid precursor
compound or an amide substituted alkyl peroxyacid precursor as described
hereinafter
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;
.
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29
5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in
JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in UK
Patent Application No. 9407944.9 and US Patent Application Nos.
08/298903, 08/298650, 08/298904 and 08/298906.
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. Preferred cationic peroxyacid precursors of the N-acylated
caprol~t~m class include the trialkyl ammonium methylene benzoyl
caprolactams and the trialkyl ammonium methylene alkyl caprol~ct~m~.
Benzoxazin organic peroxyacid precursors
Also suitable are precursor compounds of the benzoxazin-type, as
disclosed for example in EP-A-332,294 and EP-A-482,807, particularly
those having the formula:
[~(N"C R~
wherein Rl is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed or~anic peroxyacid
The organic peroxyacid bleaching system may contain, in addition to, oras an alternative to, an organic peroxyacid bleach precursor compound, a
preformed organic peroxyacid, typically at a level of from 1 % to 15 % by
weight, more preferably from 1 % to 10~ by weight of the composition.
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A preferred class of organic peroxyacid compounds are the amide
substituted compounds of the following general formulae:
R1---C--N R2--C--OOH R1--N C R2 C OOH
O R5 O or R5 O O
wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon
atoms, R2 is an alkylene, arylene, and alkarylene group cont~inin~ from 1
to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group
cont~inin~ 1 to 10 carbon atoms. Amide substituted organic peroxyacid
co~ ,ounds of this type are described in EP-A-0170386.
Other organic p;eroxyacids include diacyl and tetraacylperoxides,
especially diperoxy~lo(lec~n~lioc acid, diperoxytetr lec~n~ioc acid and
diperoxyhex~ec~nç~lioc acid. Mono- and diper~ ic acid, mono- and
diperbrassylic acid and N-phthaloyl~min~peroxicaproic acid are also
suitable herein.
Bleach catalyst
The compositions optionally contain a transition metal cont~inin~ bleach
catalyst. 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 .~ pn~~e cations, an auxiliary metal cation having
little or no bleach catalytic activity, such as zinc or al~ nllm cations, and
a se~ strant having defined stability conct~nts for the catalytic and
ry metal cations, particularly ethylen~ min~tet~cetic acid,
ethylell~li~min~tetra(methylenephosphonic acid) and water-soluble salts
thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the ~ nPse-based complexes
disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Plefel,~,d
examples of these catalysts include MnIV2(u-O)3(1,4,7-trime~yl-1,4,7-
triazacyclononane)2-(PF6)2, MnIII2(u-O) 1 (u-OAc)2( 1,4, 7-trimethyl-
1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-0)6(1,4,7-
triazacyclononane)4-(ClO4)2, MnIIlMnIV4(u-o) 1 (u-OAc)2 ( 1 ,4, 7-
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31
trimethyl-1,4,7-triazacyclononane)2-(Cl04)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-triazacyclodo~lec~ne, 2-methyl-1,4,7-triazacyclononane, 2-methyl-
1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane,
and mixtures thereof.
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 te~ches
mononuclear m~n~n~ose (IV) complexes such as Mn(1,4,7-trimethyl-
1,4,7-triazacyclononane)(OCH3)3 (PF6). Still another type of bleach
catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex
of m~n~nese (III), and/or (IV) with a ligand which is a non-carboxylate
polyhydroxy compound having at least three consecutive C-OH groups.
Other examples include binuclear Mn complexed with tetra-N-dentate and
bi-N-dentate ligands, including N4MnIII(u-O)2MnIVN4)+and
[Bipy2MnIII(u-0)2MnIVbipy2]-(C104)3 .
Further suitable bleach catalysts are described, for example, in European
patent application No. 408,131 (cobalt complex catalysts), European
patent applications, publication nos. 384,503, and 306,089 (metallo-
porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand
catalyst), U.S. 4,711,748 and European patent application, publication
no. 224,952, (absorbed m~n~nese on aluminosilicate catalyst), U.S.
4,601,845 (aluminosilicate support with m~n~nese and zinc or
m~n~sium salt), U.S. 4,626,373 (m~np~nese/ligand catalyst), U.S.
4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019
(cobaltchelantcatalyst) C~n~ n 866,191 (transitionmetal-cont~inin&
salts), U.S. 4,430,243 (chelants with m~n~nese cations and non-catalytic
metal cations), and U.S. 4,728,455 (manganese gluconale catalysts).
Heavy metal ion sequestrant
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
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32
m~nesium chelation capacity, but preferentially they show selectivity to
binding heavy metal ions such as iron, m~n~nese and copper.
Heavy metal ion se~uestrants 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.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such as the amino alkylene poly (alkylene phosphonates),
alkali metal ethane l-hydroxy disphosphonates and nitrilo trimethylene
phosphonates.
Preferred among the above species are diethylene tri~mine penta
(methylene phosphonate), ethylene ~ mine tri (methylene phosphonate)
hexamethylene cli~mine tetra (methylene phosphonate) and hydroxy-
ethylene 1,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and polyaminocarboxylic acids such as
ethylene~i~minotetracetic acid, ethylenetriamine pentacetic acid,
ethylene~ mine disuccinic acid, ethylene~ mine diglutaric acid, 2-
hydroxypropylen~ mine disuccinic acid or any salts thereof. Especially
preferred is ethylene~ min~o-N,N'-disuccinic acid (EDDS) or the alkali
metal, ~ lin-o earth metal, ammonium, or substituted ammonium salts
thereof, or mixtures thereof.
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. 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 ~-
~l~nin~?-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.
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33
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331
describes suitable se~uestrants 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), ethylenedi~mine-N-
N'-diglutaric acid ~EDDG) and 2-hydroxypropylene~ minç-N-N'-
disuccinic acid (HPDDS) are also suitable.
Enzyme
Another preferred ingredient useful in the detergent compositions is one
or more additional enzymes.
Preferred additional enzymatic materials include the commercially
available lipases, cutinases, amylases, neutral and ~lk~line proteases,
cellulases, endolases, esterases, pectinases, lactases and peroxidases
conventionally incorporated into detergent compositions. Suitable
enzymes are discussed in US Patents 3,519,570 and 3,533,139.
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.
Preferred amylases include, for example, a-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.
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34
Lipolytic enzyme may be present at levels of active lipolytic enzyme offrom 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.
The lipase may be fungal or bacterial in origin being obt~ine~l~ for
example, from a lipase producing strain of Humicola sp., Thermomyces
sp. or Pseudomonas sp. including Pseudomonas pseudoalcali~enes or
Pseudomas fluorescens. Lipase from chemically or genetically modified
mutants of these strains are also useful herein A preferred lipase is
derived from Pseudomonas pseudoalcali~enes, which is described in
Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from
Humicola l~ inosa and expressing the gene in Aspergillus orvza, 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.
Non-grease-dispersing organic polymeric compound
Non-grease-dispersing organic polymeric compounds are suitable
additional components of the detergent compositions in accord with the
invention, and are preferably present as components of any particulate
components where they may act such as to bind the particulate component
together.
By non-grease-dispersing organic polymeric compound it is meant herein
essentially any polymeric organic compound which is not a grease
dispersing agent in accord with the present invention and which is
commonly used as dispersants, and anti-redeposition and non-greasy soil
suspension agents in detergent compositions, including any of the high
molecular weight organic polymeric compounds described as clay
flocculating agents herein.
Non-grease-dispersing organic polymeric compound is typically
incorporated in the detergent compositions of the invention at a level of
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from 0.15~o to 30%, preferably from 0.5% to 15%, most preferably from
1 % to 10% by weight of the compositions.
Examples of suitable organic polymeric compounds for use herein are
polyamino compounds, including those derived from aspartic acid such as
those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers cont~ining monomer units selected from maleic acid, acrylicacid, polyaspartic acid and vinyl alcohol, particularly those having an
average molecular weight of from 5,000 to 10,000, are also suitable herein.
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
The detergent compositions of the invention, when formulated for use inmachine washing compositions, preferably comprise a suds suppressing
system present at a level of from 0.01 % to 15 ~, preferably from 0.05 % to
lO ~, most preferably from 0.1 % to 5 % by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially
any known antifoam compound, including, for example silicone antifoam
compounds and 2-alkyl alcanol antifoam compounds.
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.
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 l'silicone" as used herein, and in
general throughout the industry, encompasses a variety of relatively high
molecular weight polymers cont~ining siloxane units and hydrocarbyl group
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36
of various types. Preferred silicone antifoam compounds are the siloxanes,
particularly the polydimethylsiloxanes having trimethylsilyl end blocking
units.
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 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.
Other suitable antifoam compounds include, for example, high molecular
weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of
monovalent alcohols, aliphatic C1g-C40 ketones (e.g. stearone) N-alkylated
amino triazines such as tri- to hexa-alkylmelamines or di- to tetra
alkyl~ mine chlortriazines forrned as products of cyanuric chloride with
two or three moles of a primary or secondary amine cont~ining 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.
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;
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37
wherein said silica/silicone antifoam compound is incorporated at a level
of from 5% to 505~, 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 Corning
under the tradename DCO544;
(c) an inert carrier fluid compound, most preferably comprising a C16-
C1g 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;
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 cont~inin~ 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 cont~ining from 12 to 20 carbon atoms, or
a mixture thereof, with a melting point of from 45~C to 80~C.
Clay softening system
The detergent compositions may contain a clay softening system
comprising a clay mineral compound and optionally a clay flocc~ tin~
agent.
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. European Patents No.s EP-A-
299,575 and EP-A-313,146 in the name of the Procter and Gamble
Company describe suitable organic polymeric clay flocculatin~ agents.
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38
Polymeric dye transfer inhibitin~ a~ents
The detergent compositions herein may additionally comprise from 0.01%
to 10 %, preferably from 0.05 % to 0.5 ~ by weight of polymeric dye
transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolymers or combinations thereof.
a) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
Suitable herein are copolymers of N-vinylimidazole and N-
vinylpyrrolidone having an average molecular weight range of from 5,000
to 50,000. The preferred copolymers have a molar ratio of N-
vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
b) Polyvinylpyrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone("PVP") having an average molecular weight of from 2,500 to 400,000.
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 ~SP Corporation. Other
suitable polyvinylpyrrolidones which are commercially available from
BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
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c) Polyvinyloxazolidone
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.
d) Polyvinylimidazole
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.
Optical bri~htener
The detergent compositions herein also optionally contain from about
0.005% to 5 % by weight of certain types of hydrophilic optical
brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
R, R2
N~O~ I ~C=C~ N
R2 So3M SO3M R~
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 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.
When in the above formula, Rl is anilino, R2 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
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marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy
Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical
brightener useful in the detergent compositions herein.
When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-
bis[(4-~nilino-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
SBM-GX by Ciba-Geigy Corporation.
When in the above forrnula, R1 is anilino, R2 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.
Cationic fabric softening agents
Cationic fabric softening agents can also be incorporated into
compositions in accordance with the present invention. Suitable cationic
fabric softening agents include the water insoluble tertiary amines or
dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0
011 340.
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 in~redients
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.
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41
pH of the compositions
The present compositions preferably have a pH measured as a 1%
solution in distilled water of at least 8.5, preferably from 9.0 to 12.5,
most preferably from 9.S to 11Ø
Form of the compositions
The compositions in accordance with the invention can take a variety ofphysical forms including granular, tablet, bar and liquid forms. The
compositions are particularly the so-called concentrated granular detergent
compositions adapted to be added to a washing machine by means of a
dispensing device placed in the machine drum with the soiled fabric load.
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.
The mean 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 .7mm in diameter and not more than 5
of particles are less than 0.15mm in diameter.
The term mean particle size as defined herein is calculated by sieving a
sample of the composition into a number of fractions (typically 5
fractions) on a series of Tyler sieves. The weight fractions thereby
obtained are plotted ~g~in~t the aperture size of the sieves. The mean
particle size is taken to be the aperture size through which 50~ by weight
of the sample would pass.
The bulk density of granular detergent compositions in accordance with
the present invention typically have a bulk density of at least 600 g/litre,
more preferably from 650 g/litre to 1200 g/litre. Bulk density is measured
by means of a simple funnel and cup device consisting of a conical funnel
moulded rigidly on a base and provided with a flap valve at its lower
extremity to allow the contents of the funnel to be emptied into an axially
aligned cylindrical cup disposed below the funnel. The funnel is 130 mm
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42
high and has internal diameters of 130 mm and 40 mm at its respective
upper and lower extremities. It is mounted so that the lower extremity is
140 mm above the upper surface of the base. The cup has an overall
height of 90 mm, an internal height of 87 mm and an internal diameter of
84 mm. Its nominal volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand
pouring, the flap valve is opened and powder allowed to overfill the cup.
The filled cup is removed from the frame and excess powder removed
from the cup by passing a straight edged implement eg; a knife, across its
upper edge. The filled cup is then weighed and the value obtained for the
weight of powder doubled to provide a bulk density in g/litre. Replicate
measurements are made as required.
Surfactant a~glomerate particles
The cationic ester surfactant herein, preferably with additional
surfactants, is preferably present in granular compositions in the form of
surfactant agglomerate particles, which may take the form of flakes,
prills, marumes, noodles, ribbons, but preferably take the form of
granules. The most preferred way to process the particles is by
agglomerating powders (e.g. aluminosilicate, carbonate) with high active
surfactant pastes and to control the particle size of the resultant
agglomerates within specified limits. Such a process involves mixing an
effective amount of powder with a high active surfactant paste in one or
more agglomerators such as a pan agglomerator, a Z-blade mixer or more
preferably an in-line mixer such as those manufactured by Schugi
(Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and
Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1,
Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high
shear mixer is used, such as a Lodige CB (Trade Name).
A high active surfactant paste comprising from 50% by weight to 95 % byweight, preferably 70% by weight to 85 % by weight of surfactant is
typically used. The paste may be pumped into the agglomerator at a
temperature high enough to m~i~t~in a pumpable viscosity, but low
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43
enough to avoid degradation of the anionic surfactants used. An operating
temperature of the paste of 50~C to 80~C is typical.
T.~lln-lry washing method
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. 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.
In a preferred use aspect a dispensing device is employed in the washing
method. The dispensing device is charged with the detergent product, and
is used to introduce the product directly into the drum of the washing
machine before the commencement of the wash cycle. Its volume
capacity should be such as to be able to contain sufficient detergent
product as would normally be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing
device cont~ining 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 cont~inment 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 contact with the wash water.
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
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44
high concentrations of product in the drum of the washing machine at this
stage of the wash cycle.
Preferred dispensing devices are reusable and are designed in such a way
that container integrity is m~int~ine-l in both the dry state and during the
wash cycle. Especially preferred dispensing devices for use with the
composition of the invention have been described in the following patents;
GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345
and EP-A-0288346. An article by J.Bland published in Manufacturing
Chemist, November 1989, pages 41-46 also describes especially preferred
dispensing devices for use with granular laundry products which are of a
type commonly know as the "granulette". Another preferred dispensing
device for use with the compositions of this invention is disclosed in PCT
Patent Application No. WO94/11562.
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 m~cking 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.
Alternatively, the dispensing device may be a flexible container, such as a
bag or pouch. The bag may be of fibrous construction coated with a
water impermeable protective material so as to retain the contents, such as
is disclosed in European published Patent Application No. 0018678.
Alternatively it may be formed of a water-insoluble synthetic polymeric
material provided with an edge seal or closure designed to rupture in
a~ueous media as disclosed in European published Patent Application
Nos. 0011500, OOllS01, 0011502, and 0011968. A convenient for~n of
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water frangible closure comprises a water soluble adhesive disposed along
and sealing one edge of a pouch formed of a water impermeable
polymeric film such as polyethylene or polypropylene.
Pack~in~ for the compositions
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 l~min~tes A
preferred pack~ging execution is described in European Application No.
94921505.7.
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Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications
have the following me~nin~s:
LAS : Sodium linear C12 alkyl benzene sulfonate
TAS : Sodiumtallow alkyl sulfate
C45AS : Sodium C 14-C 15 linear alkyl sulfate
CxyEzS : Sodium C1x-Cly branched alkyl sulfate
condensed with z moles of ethylene oxide
C45E7 : A C14 15 predomin~ntly linear primary alcohol
condensed with an average of 7 moles of
ethylene oxide
C25E3 : A C12 15 branched primary alcohol condensed
with an average of 3 moles of ethylene oxide
C25E5 : A C12 15 branched primary alcohol condensed
with an average of 5 moles of ethylene oxide
CEQ I : R1COOCH2CH2.N+(CH3)3 with Rl =
Cl l-C13
CEQ II : RlcoocH2cH2cH2N + (CH3)3 with ~1 =
Cl l-C13
CEQ III R1COO CH2CH2 N+(CH3)2(CH2CH2OH)
with Rl=cll-cl3
CEQ IV : R1COOCH2CH2N+(CH3CH2)2(CH3) with
Rl =Cl l-C13
QAS : R2.N+(CH3)2(C2H4OH) with R2 = C12 ~ C14
Soap : Sodium linear alkyl carboxylate derived from an
80/20 mixture of tallow and coconut oils.
TFAA : C16-Clg alkyl N-methyl glucamide
TPKFA : C12-C14 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
Zeolite A : Hydrated Sodium Aluminosilicate of forrnula
Na12(A102SiO2)12. 27H20 having a primary
particle size in the range from 0.1 to 10
micrometers
NaSKS-6 : Crystalline layered silicate of formula
~ -Na2Si205
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47
Citric acid : Anhydrous citric acid
Carbonate : Anhydrous sodium carbonate with a particle size
between 200~m and 900~1m
Bicarbonate : Anhydrous sodium bicarbonate with a particle
size distribution between 400~m and 1200,um
Silicate : Amorphous Sodium Silicate (SiO2:Na2O; 2.0
ratio)
Sodium sulfate: Anhydrous sodium sulfate
Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size distribution between
425,um and 850,um
GDP : polymer of (CH2CHCOONa)25-
CH(CH3)COOC12H2s, average molecular
weight about 35,000
MA/AA : Copolymer of 1 :4 maleic/acrylic acid, average
molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose
Protease : Proteolytic enzyme of activity 4KNPU/g sold by
NOVO Industries A/S under the tradename
Savinase
Alcalase : Proteolytic enzyme of activity 3AU/g sold by
NOVO Industries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold
by NOVO Industries A/S under the tradename
Carezyme
Amylase : Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the tradename
Termamyl 60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold by
NOVO Industries A/S under the tradename
Lipolase
Endolase : Endoglunase enzyme of activity 3000 CEVU/g
sold by NOVO Industries A/S
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48
PB4 : Sodium perborate tetrahydrate of nominal
formula NaBO2 .3H2o.H2o2
PB1 : Anhydrous sodium perborate bleach of
nominal formula NaB~2-H2~2
Percarbonate : Sodium Percarbonate of nominal formula
2Na2C03 ~3H2~2
NOBS : Nonanoyloxybenzene sulfonate in the form of the
sodium salt.
TAED : Tetraacetylethylen.odi~mine
DTPMP : Diethylene tri~mine penta (methylene
phosphonate), marketed by Monsanto under the
Trade name Dequest 2060
Photoactivated: Sulfonated Zinc Phthlocyanine encapsulated in
bleach dextrin soluble polymer
Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 : Disodium 4,4'-bis(4-~nilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1,1-hydroxyethane diphosphonic acid
PVNO : Polyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrolidone and
vinylimidazole
SRP 1 : Sulfobenzoyl end capped esters with oxyethylene
oxy and terephtaloyl backbone
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate)
short block polymer
Silicone antifoam: Polydimethylsiloxane foam controller with
siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller to said
dispersing agent of 10:1 to 100:1.
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49
In the following Examples all levels are quoted as 5~ by weight of the
composition:
Example 1
The following laundry detergent compositions A to F were prepared in
accord with the invention:
A B C D E F
LAS 8.0 8.0 8.0 8.0 8.0 8.0
C25E3 3.4 3.4 3.4 3.4 3.4 3.4
CEQ I 0.8 0.8 2.0 2.0 1.0 0.7
CEQ II 0.2 0.5 0.5 0.7 2.0 0.8
QAS - - 0.8 - - 0.8
Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1
Carbonate 13.0 13.0 13.0 27.0 27.0 27.0
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
Sodium sulfate 26.1 26.1 26.1 26.1 26.1 26.1
PB4 9.0 9.0 9.0 9.0 9.0 9.0
TAED 1.5 1.5. 1.5 1.5 1.5 1.5
DETPMP 0.25 0.25 0.25 0.25 0.25 0.25
HEDP 0.3 0.3 0.3 0.3 0 3 0 3
Protease 0.26 0.26 0.26 0.26 0.26 0.26
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Amylase 0.1 0.1 0.1 0.1 0.1 0.1
GDP 0.5 0.8 2.0 1.0 3.0 3.0
MA/AA 0.3 0.3 0.3 0.3 0.3 0.3
CMC 0.2 0.2 0.2 0.2 0.2 0.2
Photoactivated 15 15 15 15 15 15
bleach (ppm) ppm ppm ppm ppm ppm ppm
Brightener 1 0.09 0.09 0.09 0.09 0.09 0-09
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5
Misc/minors to
100~
Density in g/litre 850 850 850 850 850 850
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51
Example 2
The following granular laundry detergent compositions G to I of bulk
density 750 g/litre were prepared in accord with the invention:
G H
LAS 5.25 5.61 4.76
TAS 1.25 1.86 1.57
C45AS - 2.24 3.89
C25AE3S - 0.76 1.18
C45E7 3.25 - 5.0
C25E3 - 5.5
CEQ II 0.8 2.0 2.0
CEQ III 0.4 1.0 0.5
STPP 19.7 - -
Zeolite A - 19.5 19.5
NaSKS-6/citric acid - 10.6 10.6
(79:21)
Carbonate 6.1 21.4 21.4
Bicarbonate - 2.0 2.0
Silicate 6.8
Sodium sulfate 39.8 - 14.3
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PB4 5.0 12.7
TAED 0.5 3.1
DETPMP 0.25 0.2 0.2
HEDP 0.3 0 3
Protease 0.26 0.85 0.85
Lipase 0.15 0.15 0.15
Cellulase 0.28 0.28 0.28
Amylase 0.1 0.1 0.1
GDP 0.8 2.0 0.2
MA/AA 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Photoactivated bleach 15 ppm 27 ppm 27 ppm
(ppm)
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Perfume 0.3 0.3 0.3
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 1005~
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Example 3
The following detergent formulations, according to the present invention
were prepared, where J is a phosphorus-cont~ining detergent composition,
K is a zeolite-cont~ining detergent composition and L is a compact
detergent composition:
J K L
Blown Powder
STPP 24.0 - 24.0
Zeolite A - 24.0
C45AS 9.0 6.0 13.0
MA/AA 2.0 4.0 2.0
LAS 6.0 8.0 11.0
TAS 2.0
C E Q I - - 2.0
CEQ II - 2.0
C E Q III 2.0
Silicate 7.0 3.0 3.0
CMC 1.0 1.0 0.5
GDP 1.5 0.5 1.5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DTPMP 0.4 0.4 0.2
Spray On
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate 6.0 13 .0 15 .0
PB4 18.0 18.0 10.0
PB1 4.0 4.0 0
TAED 3.0 3.0 1.0
Photoactivated bleach 0.02 0.02 0.02
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
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Amylase 0.25 0.30 0.15
Dry mixed sodium 3.0 3.0 5.0
sulfate
Balance (Moisture ~ 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
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Example 4
The following nil bleach-cont~inin~ detergent formulations of particular
use in the washing of colored clothing, according to the present invention
were prepared:
M N O
Blown Powder
Zeolite A 15.0 15.0
Sodium sulfate 0.0 5.0
LAS 3.0 3.0
CEQ I 0.5
CEQ II 1.0 3.0
CEQ IV 0.5 - 3.0
DTPMP 0.4 0.5
GDP 1.0 3.0 5.0
CMC 0.4 0.4
MA/AA 4.0 4.0
Agglomerates
C45AS - - 11.0
LAS 6.0 5.0
TAS 3.0 2.0
Silicate 4.0 4.0
Zeolite A 10.0 15.0 13.0
CMC - - 0.5
MA/AA - - 2.0
Carbonate 9.0 7.0 7.0
Spray On
Perfume 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
C25E3 2.0 2.0 2.0
Dry additives
MA/AA - - 3.0
NaSKS-6 - - 12.0
Citrate 10.0 - 8 .0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
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Alcalase 0.5 0.3 0.9
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 9.0 0.0
R~l~n~e (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 700 700 700
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Examp~e 5
The following detergent formulations, according to the present invention
were prepared:
P Q R S
LAS 20.0 14.0 24.0 22.0
QAS 0.7 1.0 - 0.7
CEQ III 0.4 0.4 3.8
CEQ IV 1.5 0.7 - 3.4
TFAA - 1.0 - -
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5 - -
STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13 .0 7.5 - 5 .0
Bicarbonate - 7.5
DTPMP 0.7 1.0
SRP 1 0.3 0.2 - 0.1
GDP 0.8 2.2 3.4 5.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.8 1.0 0.5 0.5
Amylase 0.8 0.4 - 0.25
Lipase 0.2 0.1 0.2 0.1
Cellulase 0.15 0.05
Photoactivated 70ppm 45ppm - 10ppm
bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
PB1 6.0 2.0
NOBS 2.0 1.0
B~l~nre 100 100 100 100
(Moisture and
Miscellaneous)
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Example 6
The following detergent formulations, according to the present invention
were prepared:
T U V
Blown Powder
Zeolite A 30.0 22.0 6.0
Sodium sulfate 19.0 5.0 7.0
M A/A A 3.0 3.0 6.0
G D P 1.0 2. 8 4.1
L A S 14.0 12.0 22.0
C45A S 8.0 7.0 7.0
C E Q II - 0.4 1.5
C E Q IV 1.5 1.5 1.5
Silicate - 1.0 5.0
Soap - - 2.0
Brightener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0
D TP M P - 0.4 0.4
Spray On
C45E7 1.0 1.0 1.0
Dry additives
P V P VI/P V N O 0.5 0.5 0.5
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0 4
Amylase 0.1 0.1 0.1
Cellulase 0.1 0.1 0.1
N O BS - 6.1 4.5
PBl 1.0 5.0 6.0
Sodium sulfate - 6.0
R~l~nce (Moisture 100 100 100
and Miscellaneous)
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Example 7
The following high density and bleach-con~inin~ detergent formulations,according to the present invention were prepared:
W X Y
Blown Powder
Zeolite A 15.0 15.0 15.0
Sodim sulfate 0.0 5.0 0.0
LAS 3.0 3.0 3.0
QAS - 1.5 1.5
CEQ II 0.5 0.5 1.2
CEQ III 0.9 1.2 0.5
DTPMP 0.4 0.4 0.4
GDP 3.2 1.4 5.8
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 - -
Dry additives
Citrate 5.0 - 2.0
Bicarbonate - 3.0
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PB1 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Protease 1.0 1.0 1.0
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Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 850
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Example 8
The following high density detergent formulations, according to the
present invention were prepared:
Z AA
Agglomerate
C45AS 11.0 14.0
CEQ III 1.8 2.2
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
GDP 2.8 3.3
MA/AA 4.0 2.0
CMC 0.5 0.5
DTPMP 0.4 0.4
Spray On
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Protease 1.4 1.4
Lipase 0.4 0.4
Cellulase 0.6 0.6
Amylase 0. 6 0. 6
Silicone antifoam 5.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2
Balance (Moisture and 100 100
Miscellaneous)
Density (g/litre) 850 850
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Example 9
The following liquid detergent formulations, according to the present
invention were prepared:
AB AC AD AE AF AG AH AI
LAS 10. 13.0 9.0 - 25.0 - - -
o
C25AS 4.0 1.0 2.0 10. - 13.0 18.0 15.0
o
C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0C25E7 6.0 8.0 13. 2.5 - - 4.0 4.0
o
CEQ I 0.4 1.0 0.8 0.4 2.0 2.5 3.5
CEQ II 0.6 1.2 0.7 0.4 1.2 - - 3.5
TFAA - - - 4.5 - 6.0 8.0 8.0
QAS - - - - 3.0 1.0
TPKFA 2.0 - 13. 2.0 - 15.0 7.0 7.0
o
Rapeseed fatty acids - - - 5.0 - - 4.0 4.0
Citricacid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0
Dodecenyl/tetradecenyl 12. 10.0 - - 15 .0
succinic acid 0
Oleic acid 4.0 2.0 1.0 - 1.0
Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0
1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-
Mono Ethanol Amine - - - 5.0 - - 9.0 9.0
Tri Ethanol Amine - - 8
NaOH up to pH 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2
Ethoxylated 0.5 - 0.5 0.2 - - 0.4 0.3tetraethylene
pent~min~
DTPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0
GDP 0.4 0.6 0.9 1.6 2.2 3.1 2.8 1.8
SRP 2 0.3 - 0.3 0.1 - - 0.2 0.1PVNO
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Protease 0.5 0.5 0.4 0.2 - 0.5 0.3 0.6
s
Alcalase - - - - 1.5
Lipase - 0.10 - 0.0 - - 0.15 0.15
Amylase 0.2 0.25 0.6 0.5 0.25 0.9 0.6 0.6
Cellulase - - - 0.0 - - 0.15 0.15
s
Endolase - - - 0.1
0 0.07
Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5
Na formate - - 1.0 - - - - -
Ca chloride - 0.015 - 0.0
Bentonite clay - - - - 4.0 4.0
Suspending clay SD3 - - - - 0.6 0.3
Balance (Moisture and 100 100 100 100 100 100 100 100
Miscellaneous)
